Iran J Ortho. 2018 March; 13(1):e9449. doi: 10.5812/ijo.9449.

Published online 2017 June 26. Original Article

The Effect of Weight Fraction, Silanization and Size of Fillers on the

Mechanical Properties of an Experimental SiO2 Dental Composite
Salman Khaje,1 and Masoud Jamshidi1,*
1
Polymer research Lab., School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
*
Corresponding author: Dr. Masoud Jamshidi, Polymer research Lab., School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran. Tel:
+98-2177240255, Fax: +98-2177240495, E-mail: mjamshidi@iust.ac.ir

Received 2016 October 23; Accepted 2017 June 06.

Abstract

Background: This research studied mechanical properties of silica-based nanocomposite as a strong restorative material through
flexural test method.
Objectives: The purpose of this study was to evaluate the effect of weight fraction, silanization and filler size on the flexural prop-
erties of silica-based dental nanocomposite.
Methods: The prepared composites were made of light-cured copolymer based on Bisphenol A glycolmethacrylate (Bis-GMA) and
Triethylene glycoldimethacrylate (TEGDMA) at proportion of 50:50 which reinforced by silica filler. The effect of silanization and
weight fraction of the filler was studied with samples containing 10 wt% (n (10)), 20 wt% (n (20)) and 30 wt% (n (30)) nanosilica filler.
Samples silanized with (γ -MPS) were also tested. Flexural properties were evaluated with Three-Point Bending test. Flexural strength
of the nano SiO2 based composites were also compared to micro silica glass composites. Flexural data were analyzed with one-way
analysis of the variance.
Results: The sample with 10 wt% (n (10)) had equal strength as the sample with 30 wt% (n (30)) nanosilica filler. Modulus of the
sample n (30) was higher than the other samples, but its toughness was significantly lower. Silanization had not expected positive
effect on the flexural properties.
Conclusions: Adding low amount of nanosilica improved mechanical properties of the resin composite. Silanization of the parti-
cles enhanced workability of the paste, but mechanical properties decreased significantly. Reduction in the size of the filler to nano
scale caused better flexural strength in comparison to micro glass silica composites.

Keywords: Nanosilica Composite, Flexural Strength, Modulus, Salinization

1. Background mercial dental composites has decreased from 8 - 30 µm

to the scale of nanometers (5). Nanomaterials have unique
Resin composite was introduced to dentistry practice properties such as small size, large surface area, high sur-
about 60 years ago by Dr. Bowen. During this past 60 face energy and a large proportion of surface atoms. Based
years, this technology developed well and today is one of on literature it is possible to enhance properties such as
the most popular restorative materials in the world (1). modulus of elasticity, surface hardness, polymerization
Resin composite is composed of polymeric matrix, shrinkage, and filler loading of dental resin composites by
filler and photoinitiation system. The resin is usually re- addition of nanomaterials (6).
inforced by addition of particles as fillers to promote its
In dentistry, silica nanoparticles are more preferred
physical and mechanical properties. Parameters such as
than the other particles as filler, because of their aesthet-
Nature, type, size distribution and surface properties of
ics and high biocompatibility, therefore in this study sil-
fillers have considerable effects on the mechanical proper-
ica particles were chosen to be added to reinforce the resin
ties of resin composite (2). Different kinds of fillers such
composite (7).
as silica, zirconia, titanium oxide and hydroxyapatite have
been used as a dispersed phase in various researches to en- To investigate the effect of spherical nanosilica on the
hance mechanical properties of this biomaterial (3, 4). flexural properties of dental composites, flexural strength,
With the advent of nanotechnology, nanomaterials ap- flexural modulus and toughness of an experimental den-
plication in biomedical sciences captured great attention. tal composite containing different amount of spherical
In recent years, the size of the added filler particles in com- nanosilica as filler were evaluated. Then surface of the sam-

Copyright © 2017, Iranian Journal of Orthodontics. This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial 4.0
International License (http://creativecommons.org/licenses/by-nc/4.0/) which permits copy and redistribute the material just in noncommercial usages, provided the
original work is properly cited.
 Khaje S and Jamshidi M

ples with the same amount of fillers was treated by silane

coupling agent to improve interactions between the fillers
and matrix resin, after that the mechanical tests were done
again to compare the effect of silanization. To investigate
the effect of size of fillers on Flexural strength, mechani-
cal properties of two nanocomposite samples were com-
pared with a silica glass resin composite with the same
filler weight fractions.

2. Methods

2.1. Materials
The used resin system was based on triethyleneg-
lycol dimethacrylate (TEGDMA) and 2, 2 -Bis- (4-
(methacryloxypropoxy)-phenyl)-propane (Bis-GMA)
which were procured from Sigma- Aldrich company
(Germany). Photo initiation system which consisted of
Camphorquinone (CQ) and Ethyl4-(dimethylamino) ben-
zoate (4EDMAB) was also purchased from Sigma-Aldrich.
Silanization process was conducted by N-propylamine
and (3-Mercaptopropyl) trimethoxy silane (γ -MPS) which
was provided by Merck and Sigma-Aldrich companies,
respectively. Nanosilica particle was provided by Nutrino
(China). Glass silica was obtained by crushing quartz.
Figure 1 shows microscopic shape of both nanosilica and
glass silica. Properties of the used fillers are presented in
Table 1. Sample codes are provided in Table 2.

2.2. Silanization of Silica Nanoparticles

nanosilica particles were silanized with MPS with the
method presented by the reference (8). First, the fumed Figure 1. Microscopic Shape of Fillers a) TEM Image of Nanosilica b) SEM Image of
silica (5 ± 0.05 g), the silane (0.5 ± 0.01 g), 100 mL cyclo- Glass Silica

hexane and n- propylamine (0.1 ± 0.01 g) were stirred for

30 minutes at room temerature. Then, the mixture was
stirred at 60°C at atmospheric pressure for another 30 min- Finally, the paste was light-cured with the light curing de-
utes. To elucidate silanized powder and removal of byprod- vice.
ucts, the mixture was put in a rotary evaporator at 60°C for The Photo curing unit had LED lamp, which emitted ra-
30 minutes. The powder was then heated at 95 ± 5°C for 1 diation between 420 and 500 nm with a maximum peak
hour in a rotary evaporator. Finally, it was dried at 80°C by of 470 nm. The intensity of the lamp was 550 mWcm-2
a vacuum oven for 24 hours. (Panaloux, China). Samples were casted into 25 mm × 2
mm × 2 mm mould upon guidelines on dental polymers
2.3. Preparation of Composites from ISO 4049:2009 (9). Since stainless steel mould was
not appropriate for separating the specimens, it was re-
The resin matrix contained Bis-GMA/TEGDMA mixture
placed by a teflon one. Samples were light-cured by over-
(i.e. 50:50 by weight) including CQ (0.2 wt%) and 4EDMAB
lapping irradiations for a total of 40s on both sides.
(0.8 wt%) as the photo initiating system. To prepare the
resin, TEGDMA was added to viscose Bis-GMA to dilute the
polymer, causing incorporation of more filler. Then, the 2.4. Mechanical Properties
particles were added and mixed by spatula till the color of Five specimens for each group were prepared. The flex-
the paste turned into semi-transparent to assure well dis- ural modulus was measured using a three- point bending
persion of particles in the paste. Then, photo initiating sys- test according to the ISO-4049 specification. Samples were
tem was added and the composite was casted into moulds. tested by a Santam Machine (Santam 150, Iran) at a speed

2 Iran J Ortho. 2018; 13(1):e9449.

 Khaje S and Jamshidi M

Table 1. Fillers’ Properties

Filler Shape Size, nm Specific surface area, m2 /g Purity, %

Nanosilica Spherical 10 - 15 180 - 270 99.99

Silica Glass Irregular 5000 43 71.22

Table 2. Sample Code, Filler Type and Content 2.5. Data Analysis
Mechanical properties were analyzed to find outliers.
Sample Code Sample Description Each sample consisted of 5 specimens. Average and stan-
n (10) Bis-GMA/TEGDMA(50:50) containing 10 wt%, un-silanized dard deviation of these specimens were calculated. Then
nanosilica the numbers out of average ± standard deviation were re-
n (20) Bis-GMA/TEGDMA(50:50) containing 20 wt%, un-silanized moved. Average and standard deviation of the remaining
nanosilica
data were calculated and approved as a reliable data in the
n (30) Bis-GMA/TEGDMA(50:50) containing 30 wt%, un-silanized
nanosilica
paper.
n-s (10) Bis-GMA/TEGDMA(50:50) containing 10 wt%, silanized
nanosilica
3. Results
n-s (20) Bis-GMA/TEGDMA(50:50) containing 20 wt%, silanized
nanosilica
Figures 2 and 3 presents flexural strength and flexu-
n-s (30) Bis-GMA/TEGDMA(50:50) containing 30 wt%, silanized ral modulus of composites containing 10, 20 and 30 wt%
nanosilica
nanosilica respectively. Flexural strength decreased when
SG5 (10) Bis-GMA/TEGDMA(50:50) containing 10 wt%, 5 micrometer
silica glass filler amount increased from 10 to 20 wt%. Contrarily, it in-
creased when weight fraction increased from 20 to 30 wt%.
SG5 (30) Bis-GMA/TEGDMA(50:50) containing 30 wt%, 5 micrometer
silica glass Flexural modulus had the same trend.
SG14 (10) Bis-GMA/TEGDMA(50:50) containing 10 wt%14, micrometer
silica glass
40
SG14 (30) Bis-GMA/TEGDMA(50:50) containing 10 wt%, 14 micrometer
silica glass 35

30
Flexural Strength (MPa)

25
rate of 0.75 mm/min until fracture occurred. The load
20
and the corresponding deflection were recorded and used
to calculate the flexural modulus (GPa) and the strength 15
(MPa) (10): 10
3 3
Es = Fl /4bh d 5
where F, l, b and h are maximum load, length span, 0
sample width and sample height, respectively. d is deflec- n (10%) n (20%) n (30%)
tion corresponding to the load F. The flexural strength was Fillers Code
calculated using the following equation (11):
Figure 2. Flexural Strength of Un-Silanized Silica Nanocomposite
Flexural Strength = 3.F.l./2b.h2
Where F is maximum load at the point of fracture, l is Figure 4 shows toughness of the un-silanized samples.
length span, b is the width of the sample and h its height. By addition of the filler from 10 to 20 wt% the toughness
Fracture strength is the resistance of a material to frac- didn’t change, but for the sample n (30) it decreased sig-
ture and toughness is an indication of the amount of en- nificantly from 1.8 kj/m2 to 1 kj/m2 .
ergy necessary to cause fracture. The total area under the γ -MPS was used as silane coupling agent to bridge be-
elastic and plastic portions of a stress-strain curve repre- tween the matrix and inorganic nanosilica in the resin
sents the toughness of a material. Stress/Strain curve was and also to disperse the silica particles uniformly. Flexu-
already provided by three point bending test results (i.e. ral strength, flexural modulus and toughness of silanized
load deflection curve). samples are shown in Figures 5 - 7.

Iran J Ortho. 2018; 13(1):e9449. 3

 Khaje S and Jamshidi M

800 600

700 500

Flexural Modulus (MPa)

Flexural Modulus (MPa)

600
400
500
300
400

300 200

200 100

100 0
n-s (10) n-s (20) n-s (30)
0
n 10 n 20 n 30
Sample Code
Fillers Code
Figure 6. Flexural Modulus of Silanized Silica Nanocomposite
Figure 3. Flexural Modulus of Un-Silanized Silica Nanocomposi

1.4
2.5
1.2
Toughness, kj/m2
2 1
Toughness, kj/m2

0.8
1.5
0.6
1
0.4

0.5 0.2
0
0 n-s (10) n-s (20) n-s (30)
n (10) n-s (20) n-s (30) Sample Code
Sample Code
Figure 7. Toughness of Silanized Silica Nanocomposite

Figure 4. Toughness Un-Silanized Silica Nanocomposite

(10) to 17.73 MPa in the sample n (20). Flexural strength of

25 the sample n (30) almost had no change in comparison to
n (20).
20
Flexural Strength (MPa)

Flexural modulus of the sample n-s (20) had lowest

number in comparison to the other samples, though it had
15
better toughness than the other two samples. Toughness
of all the silanized samples was almost in the same order.
10
Figure 8 summarizes all the measured flexural proper-
ties of the silanized and un-silanized samples in one figure.
5
Silanization had negative effect on all the properties. It is
0
further explained in the Discussion section.
n-s (10) n-s (20) n-s (30) Figures 9 and 10 shows effect of size on flexural
Sample Code strength of the composite. Strength of the sample n (10) is
2 to 3 times more than glass silica samples and it shows in-
Figure 5. Flexural Strength of Silanized Silica Nanocomposite crease in the strength by reduction in the size of the fillers.
For the composite containing 30 wt% filler, based on Fig-
ure 11, the sample filled with nanosilica had better strength
By increasing the filler content from 10 to 20 wt%, the again, but the difference was not significant like the sam-
flexural strength decreased from 22.3 MPa in the sample n ples with 10 wt% filler. Silica glass samples with different

4 Iran J Ortho. 2018; 13(1):e9449.

 Khaje S and Jamshidi M

40
UnSilanized

Flexural Strength (MPa)

Silanized
30

20

10

0
n (10%) n (20%) n (30%)

Fillers

800 UnSilanized 2.5 UnSilanized

Flexural Modulus (MPa)

Silanized 2 Silanized

Toughness, Kj/m2
600
1.5
400
1
200
0.5

0 0
n (10%) n (20%) n (30%) n (10%) n (20%) n (30%)
Fillers Fillers

Figure 8. Comparison Between Mechanical Properties of Silanized and Un-Silanized Nanocomposite Containing 10, 20 and 30 wt% Nanosilica

micro size fillers (14 and 5 micrometer) had closed strength

relative to each other.
35

30
Flexural Strength (MPa)

25

20
35
15
30
Flexural Strength (MPa)

10
25
5
20
0
15 n (30) SG5 (30) SG14 (30)

10 Sample Code

5 Figure 10. Comparison Between Flexural Strength of the Samples Containing 30 wt%
Filler
0
n (10) SG5 (10) SG14 (10)
Sample Code 4. Discussion

Figure 9. Comparison Between Flexural Strength of the Samples Containing 10 wt% 4.1. Mechanical Properties
Filler
The main objective of this research was to investigate
the mechanical properties of dental composite in which
nanosilica was as the filler.

Iran J Ortho. 2018; 13(1):e9449. 5

 Khaje S and Jamshidi M

Figure 11. A, Nanocomposite containing 30 wt% nanosilica; B, Nanocomposite containing 20 wt% nanosilica ;C, Nanocomposite containing 10wt% nanosilica

The content of nanofiller and good dispersion of 4.2. Effect of Silanization

nanoparticles are the key parameters for improving the
For the silanized samples, flexural strength of the n-s
mechanical properties of the dental composite (12). Fig-
(10) was more than other samples. It shows better stress
ure 11 shows the physical state of the composites contain-
transfer between filler and the matrix in this sample. Mod-
ing 10, 20 and 30 wt% un-silanized nanosilica. When the
ulus had the same trend as the un-silanized ones. There
addition of filler was 10 wt%, due to semiliquid state of the
was not considerable difference between toughness of the
composite, the nano particles dispersed properly in the
silanized samples. It shows filler amount doesn’t play a
resin matrix and it was helpful for stress transfer between
role in the toughness here. Silanization caused same dis-
the regions. Besides, the free volume was reduced and
persion of particles in the sample.
the good interaction between the nanofiller and matrix re-
Figure 8 compares un-silanizaed and silanized me-
sulted in high mechanical properties. Decrease in flexural
chanical properties of the samples. Silanization did not af-
strength of the sample n (20) was probably due to inap-
ford logical and applicable outcome. Flexural properties
propriate dispersion, thus agglomeration of nanoparticles
of all the silanized samples are significantly lower than un-
and resulted concentration of forces caused lower flexural
silanized ones. This result is not in the same line with many
strength than the sample n (10). Increase in the mechanical
of previous studies. We used n-propylamine as a stabilizer
properties of the sample n (30) can be attributed to higher
of silane connections and cyclohexane as solvent. Chen
amount of filler. Flexural strength of the sample n (30) was
and Brauer, in there research on effect of different solvents
only slightly more than n (10), but the semiliquid state of
on silanization concluded that although the silanization
the sample n (10) makes it inapplicable in dentistry prac-
process would be more efficient using that method, but
tice.
the strength of the resulting composite would decrease
Flexural modulus had the same trend as flexural rapidly (13). Performing the tests on the samples after
strength. Modulus is proportional to crosslinking den- a long time, might be the reason for the weak result of
sity (8). Lower modulus of the sample n (20) shows lower silanization on mechanical properties of the sample.
plasticity resulted from concentration of agglomerated The flexural strength, flexural modulus and toughness
nanoparticles. of the sample FS-N are significantly lower than FS. Nano-
silica particles agglomeration and intervention between
Toughness of the sample n (10) and n (20) are almost fumed silica particles and the matrix caused discontinuity
equal, but the number decreased significantly for the sam- in the composite; therefore, the strength was lowered (14).
ple n (30). High amount of nanoparticles caused insuffi- Based on Figures 9 and 10, the nanocomposite samples
cient resin to wet the particles as it can be seen in Figure with 10 and 30 wt% filler both had better flexural strength
11. This lead to discontinuity in the matrix, thus crack grew than their micro glass silica counterparts. As the size of the
easier and toughness decreased significantly from 1.8 to 1 particles reduces, the specific surface area increases, thus
kj/m2 . higher surface energy at the interphase is expectable and

6 Iran J Ortho. 2018; 13(1):e9449.

 Khaje S and Jamshidi M

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