F. Yildirim et al.
: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
Ferhat Yildirima , Mustafa Aydinb , Ahmet Avcic
a Department of Industrial Design Engineering, Faculty of Simav Technology, University of Dumlupınar, Simav, Kütahya, Turkey
b Department of Mechanical Engineering, Faculty of Engineering, University of Dumlupınar, Kütahya, Turkey
c Department of Mechanical Engineering, Faculty of Engineering, University of Selçuk, Konya, Turkey
Mechanical properties of nano-SiO2
reinforced 3D glass fiber/epoxy composites
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018
Three dimensional (3D) glass fiber epoxy composites rein-
forced with nano-SiO2 particles at ratios of 0.5 wt.%,
1 wt.%, 2 wt.% and 3 wt.%, were manufactured using the
vacuum infusion method to improve the mechanical prop-
erties. Differential scanning calorimetry, thermo-gravi-
metric analysis, particle dispersion detection by color mea-
surement, scanning electron microscopy, energy dispersive
X-ray spectroscopy mapping, three point bending and ten-
sile testing were performed to characterize the nano-parti-
cle-reinforced 3D composites. Mapping and color measure-
ment revealed good dispersion of the nano-particles. The
mechanical tests showed improvement rates of 52 % and
64 % respectively on warp and weft directions compared
For personal use only.
with the non-reinforced 3D composite. The tensile strength
of the nano-SiO2 reinforced 3D woven composites also in-
creased to 6 % and 10 % according to the warp and weft di-
rections compared with the non-reinforced 3D composite.
Keywords: Characterization; Glass fiber; Nano-particle re-
inforcement; 3D hybrid composite
1. Introduction
3D fibers are used in composite, reinforced materials whose
top and bottom faces are linked to each other and which
have channel-like voids. The weave in the channel direction
is called the warp, and the weave perpendicular to this direc-
tion is called the weft. 3D composite structures are used in
automotive, aerospace and defense industries. The effect of
the pile height on the mechanical properties in 3D fibers
has been investigated [1 – 5], and it has been determined that
the compressive strength and the flexural strength decrease
with an increase in the pile height [2, 3]. In studies where a
varied number of piles with the same height were examined,
it was observed that an increased number of piles improved
the compressive and flexural strengths [4]. A decrease in
the pile thickness with the same pile number and height re-
duced the compressive and flexural strengths [6]. In studies
carried out based on the weave direction, it was established
that the warp direction demonstrated higher strength than
the weft direction [5]. It was also pointed out that the result-
ing damage mostly occurred in the areas where the piles
were linked to the top and bottom faces [3, 7].
Some studies carried out on 2D composites examined the
improvability of the composite’s mechanical properties via
308
particle reinforcement. In these studies, an increase was
found in some properties of the composite, such as strength,
elasticity and elongation percentage [8 – 14]. In the studies
where the effects of nano-SiO2 particles added into epoxy
resin were examined, it was confirmed that the elongation
ratio decreased, whereas it was established that some prop-
erties such as toughness, flexural strength, impact resis-
tance and tensile strength improved [9, 15 – 18]. In studies
carried out to increase the mechanical properties of 3D
composites, laminated or filled composites were fabricated
[1, 8, 19 – 22]. However, no study on the reinforcement of
3D spacer glass fiber composites with nano-particles has
been found. Therefore, this study considered whether the
properties of 3D glass fiber composites could be enhanced
by adding nano-particles.
As 3D composite materials have strength limitations due
to their hollow structure, determining their behavior, da-
mage state and mechanical properties under load is impor-
tant to increase the areas where they can be used. In this re-
gard, the objective of this study was specifically to enhance
the mechanical and thermal properties of 3D spacer compo-
sites by applying nano-particle reinforcement, whose posi-
tive contributions to 2D composites and resin systems have
been proven [8, 9, 15 – 17, 19, 23].
2. Experimental procedure
2.1. Materials
In this study, nano-particle-reinforced 3D epoxy glass fiber
composites were fabricated and their properties were inves-
tigated. The 3D glass fibers used in the study (Fig. 1) were
fabricated from E-glass purchased from Parabeam B.V.
The woven fibers had a total thickness of 3.3 mm (after re-
sined total thickness is 3 mm) and a density of 782 g m–2.
The resin used as the matrix material in the system is an
epoxy resin commercially available under the trade name
of HEXION MGS L-160, and it was applied by mixing it
with a commercial hardener under the trade name MGS H-
160, at a ratio of 5 : 1 (resin : hardener) by weight.
2.2. Composite manufacturing
A vacuum infusion method was used to produce the compo-
sites in order to ensure uniform wetting and to avoid the for-
mation of a resin pool [1, 3]. Materials that had been pre-
pared at 0.86 MPa vacuum in a closed system were
completely wetted with the resin, and then the vacuum bag
Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
was opened to ensure that the crushed piles of the fiber
sprung back allowing the material to regain its 3D hollow
form. The specimens were allowed to cure for 18 h at room
temperature, and then they were subjected to post curing for
2 h at 80 8C. The test specimens with warp and weft direc-
tions were prepared from composite plates that had been se-
parately infused in the warp and weft directions, rather than
from a single plate. Plates had been cut according to re-
quired specimen dimensions as given below. At least 5 spe-
cimens were prepared from both nano-SiO2-reinforced and
non-reinforced 3D composites for each tensile and three
point bending tests on both warp and weft directions. The
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thermo gravimetric analysis (TGA) tests were performed
on the warp direction only because of the warp direction
has been found the most effective direction on plates. All
calculations are made by averaging the results of all 5 spe-
cimens used in the experiments. The results were analyzed
in comparison with non-reinforced samples.
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Fig. 1. Dry 3D glass fiber fabric and the piles in section view.
Table 1. Technical specifications of nano-SiO2 powder.
Material Particle Size Purity
(nm) (%)
SiO2 30 99.9
Fig. 2. Manufactured 3D composite and the section view of the wet piles.
Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
The epoxy resin was reinforced with nano-SiO2 at dif-
ferent ratios: 0.5 wt.% (0.23 vol.%), 1 wt.% (0.46 vol.%),
2 wt.% (0.94 vol.%), 3 wt.% (1.42 vol.%). The technical
specifications of the nano-SiO2 powder are shown in Ta-
ble 1. The mixture of nano-SiO2 and resin was prepared
using a Sonics Vibracell VCX-750 ultrasonic mixer. Ultra-
sonication is an effective way to ensure maximum homoge-
neity [8, 12, 17, 24 – 28]. The mix of the resin and nano-
SiO2 was prepared by hand stirring for 5 min at room tem-
perature. The ultrasonication time was 20 min in total at a
35 % frequency amplitude value. The ultrasonication pro-
cess was cooled using iced water to avoid both overheating
and the chemical decomposition of the resin. Production
was completed before the precipitation of particles. The
composite form of the 3D glass fiber after the fabrication
is shown in Fig. 2.
Three-point bending tests were carried out on 140 ·
30 mm specimens that had been prepared in both the warp
Surface Area True Density Morphology
(m2 g–1) (g cm–3)
440 2.2 – 2.6 Spherical
309
 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
and weft directions according to the ASTM D-7264 stan-
dard test method for flexural properties, with a distance of
80 mm between the supports and at a speed of 3 mm min–1
[3]. The tensile tests were performed in both the warp and
weft directions at a drawing speed of 0.5 mm min–1 accord-
ing to the ASTM D-3039 standard [4, 5]. The tensile speci-
mens were initially sized at 250 · 40 mm and then their
middle sections were reduced to 25 mm, the standard size.
Larger edge sections of the specimens were filled with liq-
uid paste and solidified, thus preventing the hollow material
from being crushed by the drawing jaws as a result of slid-
ing.
Microstructural analyses were performed on different
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sized images taken from both the surface and the damaged
region caused by the bending tests of the composite using
an Insize ISM-PM200SB optical microscope and FEI Nova
NanoSEM 650 scanning electron microscopy (SEM) de-
vice. Furthermore, in the study where thermal properties
were examined using TGA investigations, energy-disper-
sive X-ray spectroscopy (EDX) analysis was used to try
and observe the distribution of the nano-particles in the
composite structure. Because it is known that the nano-
SiO2 particles produce a color change in the 3D composite,
the dispersion stability was investigated by color changes
measured with a Mathai Color Striker device on the surface
of the composite according to the ASTM D-2244 standard.
3. Result and discussion
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3.1. TGA analysis
TGA analysis was performed on the composite material
with an added 1 % of nano-SiO2 particles in order to exam-
ine the effect of the particle reinforcement on the thermal
properties. As seen from the TG graph shown in Fig. 3, the
degradation temperature of the nano-particle-reinforced
composite increased by 18 8C compared to the pure epoxy
composite. The fact that the TG curve has a very low slope
and the degradation temperature rose indicated that the in-
termolecular bond strength of the nano SiO2-reinforced
composite increased. A 45 8C increase was detected in the
extreme temperature value where the degradation was
ended. It was observed that the nano-particle reinforcement
310
improved the thermal degradation characteristics of the
composite and increased the operating temperature range.
3.2. Bending test results
As a result of the test, it was established that the nano-SiO2-
reinforced 3D composites had an increased flexural
strength compared to the non-reinforced 3D composites.
As seen from the graph shown in Fig. 4 for the reinforced
materials, the highest value was measured at 70.9 MPa with
an added 1 % SiO2, whereas the flexural strength of the pure
material was measured to be 46.6 MPa in the warp direc-
tion. This represented an increase of 52 %. In the weft direc-
tion, the flexural strength was measured to be 55.3 MPa
with an added 1 % SiO2 again, whereas the flexural strength
in the weft direction was measured to be 33.5 MPa for the
pure material, which represented an increase of approxi-
mately 64 %. The reinforcement material/resin ratio is a de-
cisive parameter in the strength properties of composite ma-
terials [29]. There is a threshold value of this ratio for all
composite materials. In other words, the maximum strength
properties are obtained at certain proportional values,
which can also be referred to as the saturation point. It is
evident that nano-SiO2 particles added to the composite
structure increase the reinforcement material/resin ratio in
the structure. This indicates that the saturation level of the
reinforcement material/resin ratio is reached at a 1 % nano-
SiO2-reinforcement level by mass. In addition, it was
thought that a 1 % nano-SiO2-reinforcement ratio forms
the ideal interface and improves the strength properties by
limiting the growth of nano-pores, as well as the propaga-
tion of cracks thanks to the mechanical locking formed by
the particles with the epoxy [25, 30 – 33]. Also, it is be-
lieved that the spherical morphology of nano-SiO2 will con-
tribute significantly to fewer knitting regions, fewer over-
laps and more ideal wetting. Thus, the ideal wetting and
distribution of matrix reinforcement material was obtained
at a 1 % reinforcement level. Overlapping, aggregation,
and poor wetting regions particularly, increased at 2 % and
3 % SiO2-reinforcement levels. Further evidence for the im-
provement nano-SiO2 particles make to the distribution
mechanism of the applied load by its positioning in the
epoxy resin is the increase in the bending elasticity modulus
Fig. 3. TG plot of 1 % nano-SiO2-reinforced
3D glass fiber composite.
Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
of 3D composites. The highest elasticity modulus values
were calculated in the warp direction – at a 1 % nano-
SiO2-reinforcement ratio by mass – at 5 GPa and in the weft
direction – also at a 1 % nano-SiO2 reinforcement ratio by
mass – at 3.6 GPa. The increased ratios of the bending elas-
ticity modulus of nano-SiO2-reinforced 3D composite were
69 % in the warp direction and 81 % in the weft direction.
The effects of the nano-SiO2-reinforcement on bending
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Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
force, flexural strength and modulus of elasticity of the 3D
composite material are shown in Fig. 4. The results were
also statistically evaluated and expressed as error bars in
the figures. In the analyses in which non-reinforced 3D
composites were taken as a reference, it was seen that the
results obtained from reinforced 3D composites that exhibit
improvements in mechanical properties were in the 95 %
confidence interval.
Fig. 4. Bending test results of composites
with different SiO2 ratios: (a) bending force,
(b) bending strength, (c) bending modulus of
elasticity.
311
 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
There was a decrease measured in the deflection proper-
ties of the SiO2-reinforced 3D composite materials. This
decrease was seen at all reinforcement rates of SiO2. While
the deflection values of 3D composites with pure epoxy
were measured to be 4.8 mm for the warp direction and
4.6 mm for the weft direction, the highest decreases were
measured to be 5.5 mm in the warp direction and 5.9 mm
in the weft direction, with an added 3 % SiO2. The changes
in deflection with reinforcement rates of nano-SiO2 parti-
cles are shown in Fig. 5.
The fracture regions of the mechanical test specimens
were investigated after the tests. It was established that the
damage, particularly in the weft-direction specimens, oc-
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curred in the section where the pile and the top and bottom
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Fig. 6. OM pictures of the damage area of weft directed three point bending samples.
312
faces joined [3, 7]. The damage in the warp-direction speci-
mens tended to follow a weaving line in a zigzag pattern,
whereas the damage in the weft-direction specimens oc-
curred in a straight line. It was observed that, with increas-
ing load, the weave layers became detached and the glass fi-
bers broke away from the matrix material. This condition is
shown in the optical microscopy (OM) images of the da-
mage region in Fig. 6.
3.3. Tensile test results
Based on the results obtained from the tensile tests per-
formed on the composite materials, a significant increase
was determined in the maximum tensile force, tensile
Fig. 5. Deflection values of composites with
different SiO2 ratios.
Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
strength and percent elongation values of the material. The
increase obtained in the tensile properties of the composite
proves that an effective interface bonding forms among the
reinforcement material, nano-SiO2 and epoxy. The ultraso-
nic mixing method ensured a homogeneous distribution of
resin and nano-particles, and improved the formation of
the matrix–nano-particle interface. Furthermore, the fact
that the selected nano-SiO2 has a specific surface area as
high as 440 m2 g–1 is considered to contribute to the forma-
tion of this robust interface.
Figure 7 shows the stress–strain curves of the nano-SiO2
reinforced and non-reinforced 3D woven glass fiber com-
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posites. According to the graph, typical fiber reinforced
polymer composite curves were obtained. Compared with
the non-reinforced samples different degrees of improve-
ment on the tensile properties can be observed in the 3D
composites depending on the amount of nano-SiO2. It is
clearly seen the nano-particles increase the tensile proper-
ties. While the non-reinforced 3D glass fiber composite
has a tensile strength of 55.2 MPa in the warp and
51.6 MPa in the weft directions, these values increased with
the nano-SiO2 reinforcement. The highest increases were
determined for 1 % SiO2 with 58 MPa in the warp direction,
and for 2 % SiO2 with 57.2 MPa in the weft direction. The
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Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
increases in the composite material’s tensile strength were
measured to be approximately 5 % in the warp direction
and approximately 11 % in the weft direction. Figure 8
shows the effects of changing the amount of SiO2 on the
tensile properties of the composite material.
The strain ratio is the most affected property of the com-
posite as a result of SiO2 reinforcement. As can be seen in
Fig. 9, when compared with the non-reinforced composite
the increased ratio of the strain for the warp and weft direc-
tion are 14 % and 7 % respectively. The highest strain val-
ues were obtained at 1 % SiO2 for the warp and weft direc-
tions. The strain was measured as 2.4 % and 2.24 % on the
warp and weft directions respectively.
It was thought that the improvements detected in tensile
strength – just as those in bending properties – were asso-
ciated with the formation of an effective interface between
the nano-particles and the epoxy resin. Due to the good wet-
ting obtained by nano-particles with the epoxy and the me-
chanical locking, growth of nano-pores and propagation of
cracks were limited and strength properties were improved
[25, 30 – 33]. According to the tensile stress results in the
weft direction, 2 % ratio value for the reinforcement materi-
al may increase the reinforcement material/resin ratio in
this direction.
Fig. 7. Tensile curves of composites with dif-
ferent SiO2 ratios: (a) warp direction, (b) weft
direction.
313
 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
Optical microstructural analysis was performed on the
damaged regions of the specimens following the tensile
tests. Figure 10 shows the woven glass fibers deformed by
the tensile load. At higher magnification (inset of Fig. 10),
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For personal use only.
314
it can be seen that the fibers that break due to the load were
scraped off the epoxy matrix. It was observed that surface
cracks developed in the matrix structure outside the fracture
zone.
Fig. 8. Tensile properties of composites with
different SiO2 ratios: (a) tensile force, (b) ten-
sile strength.
Fig. 9. Strain values of composite with dif-
ferent SiO2 ratios.
Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
3.4. Fiber volume fraction
The volume fraction of fiber relative to the total volume of
the composite is an important parameter in composite ma-
terials and is called fiber volume fraction (vf), a number
between 0 and 1 [34]. vf can be determined experimentally
by weighing the composite before and after the test when
the resin is removed by ignition loss according to the
ASTM 2584 standard [35]. The burning method (ASTM
D2584-68 [35]) has been considered a simple and effective
way to determine the volume fraction of cured resin com-
posite materials. Abdalla et al. [36] declared that in many
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cases the burn-out process has shown some limitations
when extra fillers have been added to the composite mate-
rial. The fillers which may be partially burned out or not
burned out at all by the burn-out process stay with the
glass fiber. This causes difficulties in determining the fiber
volume. Until now there has been no standard approach to
separate fillers from the resin and glass fiber of structural
composites [36, 37]. During the burning it was thought
that SiO2 would not burn at 700 8C and when the resins
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Fig. 10. OM images of the damage area of warp directed tensile samples.
Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
burn-out, it would stay with the glass fiber. Because the
TGA process gives the main mass loss of the composite
by burning the resin, vf was measured experimentally on
TGA and theoretically calculated by using the following
Eq. (1) [38]. Fiber volume fraction studies were carried
out on the non-reinforced 3D composites and 1 % of
nano-SiO2-reinforced 3D composites which gives the
highest mechanical strength.
wf :qc
vf ¼ ð1Þ
wc :qf
Where, wf is the weight of the fiber (g), wc is the weight of the
composite (g), qc is the density of the composite (g cm–3), and
qf is the density of the fiber (g cm–3). For determining the ex-
perimental fiber volume fraction, the density of nano-SiO2
was added to the glass fibers mass with the following conver-
sion, Eq. (2):
wSiO2 :qc
vSiO2 ¼ ð2Þ
wc :qSiO2
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 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
where vSiO2 is the nano-SiO2 volume fraction, wSiO2 is the
weight of the used SiO2, and qSiO2 is the density of the
SiO2. According to the formulation theoretical vf results
for the 3D composites were found as 0.355 (35.5 %) for
non-reinforced composite and 0.358 (35.8 %) for 1 % SiO2
reinforced 3D composite. The mass loss after the TGA ana-
lysis is given in Fig. 3. The weight ratio of the non-burned
particles to the main composite mass was 54.4 % for non re-
inforced composite and 53.3 % for 1 % SiO2-reinforced
composites. The calculated experimental vf results of the
3D composites were found as 0.338 (33.8 %) for non-rein-
forced composite and 0.348 (34.8 %) for 1 % SiO2-rein-
forced 3D composite. When the vf results are compared be-
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tween the non-reinforced and nano SiO2 reinforced 3D
composites, an increase can be seen easily. Increase in fiber
volume fraction improves the mechanical strength, as found
by other researchers [39 – 42]. On the other hand, the theo-
retical vf is higher than the experimental results because it
was assumed that theoretically there were no voids present
in the composite body. But in manufacturing, this theoreti-
cal assumption is not valid and there are voids in the com-
posite structure. The differences between the theoretical
and experimental fiber volume fraction values give the void
content of the composite [43]. The void volume fraction
(vv) of 3D composites were found as 0.017 (1.7 %) for
non-reinforced composite and 0.01 (1.0 %) for 1 % SiO2-re-
inforced 3D composite. The void content of the 3D com-
posite was decreased with the addition of the 1 % SiO2.
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Thus the mechanical properties of the 3D composites were
increased with the decrease in the void content. According
to the results it can be thought that the nano-SiO2 helps
close the voids or reduce the void formation in the compos-
ite during the resin infusion. Obtained fiber volume fraction
and void volume fraction results are given in Table 2.
3.5. SEM-EDX analysis
In microstructural analysis of SEM images, it was seen that
the fibers were completely surrounded by the matrix resin.
Thus the vacuum infusion method is an effective way of en-
suring homogeneous wetting and a nonporous composite
structure. The efficiency of the vacuum infusion method in
the production of 3D composites has also been emphasized
by other researchers [1, 3, 20].
Fracture surfaces are shown in Fig. 11. Figure 11a shows
deep matrix cracks at the points where the piles are linked
to the top and bottom faces. It was understood that the da-
mage occurring during the tensile test developed in a way
that the fibers were scraped off the matrix resin (Fig. 11b
and c). Based on the analyses made, it was seen that the
piles become completely upright via the absorbed resin,
thus the resin fully wets the glass fiber. It was also observed
from OM images that the damage formation on the pile sur-
face was clearer in SEM images.
Table 2. Obtained fiber volume fraction (vf) and void volume fraction (vv) results.
Material Theoretical vf
Non-Reinforced 3D Composite 0.355
1 wt.% Nano-SiO2 Reinforced 3D Composite 0.358
316
In the EDX analyses made on the fractured resin zones,
Si and O2 peaks are seen. This shows the presence of rein-
forcement powders in the structure (Fig. 12a). In addition,
Ca and Al are seen due to the Al2O3 and CaO compounds
found in the chemical composition of the glass fibers. With
EDX mapping of the epoxy structure, the presence of SiO2,
separate silicon (Si) and oxygen (O) and its homogeneous
distribution throughout the structure are seen (Fig. 12b).
Because of the epoxy’s chemical composition, high levels
of oxygen (O) and carbon (C) are seen on the mapping.
3.6. Dispersion detection on surfaces
with color measurement
Emady et al. [44] studied the color concentration measure-
ment of powders on composite surfaces. Their study was
based on exposing the surface of a sample that was dyed
with an unknown concentration of material to light in the
visible spectrum. The intensity of the light reflected from
the surface was proportional to the concentration of dyed
material in the sample. The concentration of dyed material
on the surface was determined by calculation [45]. In re-
search literature, there are several methods for measuring
the distribution, including Zeta potential (f), dynamic light
scattering, transmission electron microscopy (TEM) and
color concentration measurement [46]. All the methods
have unique features and were available. Zeta potential (f)
and TEM methods were used, especially for examining the
dispersion, size and morphology of the internal structure
of the material, and they require complex equipment. Sur-
face-based measuring equipment was simpler and more
usable, and also provided the main reference points, includ-
ing concentrations. In this study, surface color measure-
ment was performed in addition to the EDX mapping analy-
sis for the determination of particle distribution.
The reinforcement material, nano-SiO2, changes the
color of the resin, thereby changing the composite color.
Furthermore, some additives or pigments are especially
preferred to obtain a particular product color. Even if the
color does not change, color density tone differences can
be obtained in liquid–solid compositions such as resin and
fiber-mix structures. Ultrasonication is one of the best ways
to obtain good powder dispersion in liquid [8, 12, 17, 24 –
28], and this provides the homogeneity of the particles in
the liquid resin before the wetting of the woven glass fiber.
After the vacuum process, the particles that were attached
to the composite outer and inner surfaces were considered
to be homogeneous. The EDX mapping examination per-
formed on the fractured inner surfaces of the 3D composites
revealed good dispersion of the SiO2 particles. The main
strategy of the color measurement is to find color hue dif-
ferences resulting from nano-SiO2 particles on the compos-
ite outer surface. The parameter measured is the color
change factor, DE. It gives the total deviation in tone com-
Experimental vf Void volume fraction (vv)
0.338 0.017
0.348 0.01
Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4
 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
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For personal use only.

Fig. 11. SEM images of fractured nano-SiO2-

reinforced 3D glass fiber composite: (a) fail-
ure mechanism, (b) fracture line, (c) fiber–
matrix bonding.

Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4 317

 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites

pared to the three primary colors [47]. The measured and ta-
bulated results were checked to see whether they were with-
in the range or not of a standard database, and are shown in
Table 3 [47].
The color measurements of the 3D composites were
made on the lower, middle and upper edges of the surfaces.
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According to the measured values, all three points in both
surface directions show little difference and can be consid-
ered valid results. All measured color tones induced by the
particles on the surface fall in the range of 0 to 1 and the
measured point colors are the same. The small differences
obtained prove the well balanced distribution of nano-SiO2

Fig. 12. EDX mapping analysis of the nano-SiO2-reinforced 3D glass fiber composite: (a) EDX analysis of epoxy region, (b) EDX mapping of
epoxy region showing C, O and Si distribution.

318 Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4

 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites

Table 3. Color measurement parameter meanings.

Color measurement parameter meanings

DE Mean differences between measured materials

DL (+) Partial white DL (–) Black

Da (+) Partial red evolution Da (–) Partial green evolution
Db (+) Partial yellow evolution Db (–) Partial blue evolution

Color Compare Range Color Compare Meaning

0 – 0.25 DE Perfect match

0.25 – 0.5 DE Can be considered with small difference
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018

0.5 – 1 DE Can be considered with little difference

1 – 2 DE Can be considered on some sectors
2 – 4 DE Can be considered on special applications
4 DE Cannot be considered

Table 4. Obtained color measurement results.

Material Direction Reference Reference Reference DL Da Db DE

DL Da Db

Pure Epoxy weft-1 32.99 2.21 5.85

weft-2 32.99 2.21 5.85 33.10 2.60 5.95 0.37
weft-3 32.99 2.21 5.85 32.93 2.13 5.47 0.26
For personal use only.

warp-1 33.81 2.03 5.69

warp-2 33.81 2.03 5.69 33.81 2.32 5.37 0.30
warp-3 33.81 2.03 5.69 33.96 2.35 5.42 0.34
warp-1 0.47 –1.34 –0.65
warp-2 0.47 –1.34 –0.65 0.49 –1.26 –0.02 0.46
warp-3 0.47 –1.34 –0.65 0.18 –1.61 0.07 0.71

0.5 wt.% SiO2 weft-1 32.91 2.44 6.83

weft-2 32.91 2.44 6.83 33.19 2.12 6.67 0.43
weft-3 32.91 2.44 6.83 33.31 1.97 6.76 0.59
warp-1 33.57 2.18 6.39
warp-2 32.91 2.44 6.83 33.48 2.28 6.35 0.70
warp-3 32.91 2.44 6.83 33.25 2.04 6.16 0.65

1 wt.% SiO2 weft-1 31.66 2.31 6.95

weft-2 31.66 2.31 6.95 31.70 2.35 6.82 0.09
weft-3 31.66 2.31 6.95 31.69 2.11 6.69 0.25
warp-1 33.79 1.97 6.45
warp-2 33.79 1.97 6.45 33.00 2.00 6.34 0.87
warp-3 33.79 1.97 6.45 34.02 1.90 6.70 0.29

2 wt.% SiO2 weft-1 32.53 1.70 6.85

weft-2 32.53 1.70 6.85 32.72 1.52 6.65 0.30
weft-3 32.53 1.70 6.85 31.97 1.59 6.93 0.63
warp-1 34.06 1.88 6.61
warp-2 34.06 1.88 6.61 33.99 1.68 6.24 0.30
warp-3 34.06 1.88 6.61 34.43 2.27 6.71 0.53

3 wt.% SiO2 weft-1 33.50 2.35 7.39

weft-2 33.50 2.35 7.39 33.29 2.36 7.43 0.23
weft-3 33.50 2.35 7.39 33.53 2.06 7.09 0.32
warp-1 34.04 1.93 7.62
warp-2 34.04 1.93 7.62 33.15 1.88 7.75 0.96
warp-3 34.04 1.93 7.62 33.95 2.11 7.26 0.26

Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4 319

 F. Yildirim et al.: Mechanical properties of nano-SiO2 reinforced 3D glass fiber/epoxy composites
particles on the outer surface of the 3D composites. It is
clear that the underlying causes for this were the ultrasonic
mixing and the vacuum-assisted resin transfer manufactur-
ing system. The ultrasonic particle mixing is the best way
to eliminate any aggregate and obtain good dispersion [8,
12, 17, 24 – 28, 48]. Also, the wetting of the fibers with the
vacuum method eliminates operator mistakes, accumula-
tion and resin pooling. Data for the measured color are
given in Table 4.
4. Conclusions
3D woven composites were manufactured by a vacuum in-
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018
fusion method reinforced with nano-SiO2 powders with
contents of 0.5, 1, 2 and 3 wt.%. When reinforced with 1 %
SiO2, the bending force increased from 104.9 N to 159.7 N
for the warp direction and from 75.5 N to 124.4 N in the
weft direction, compared to the non-reinforced composite.
In tensile testing, the tensile force increased from 4 355 N
to 4 647 N in the warp direction at 1 % SiO2 reinforcement
and increased from 4 156 N to 4 580 N in the weft direction
at 2 % SiO2 reinforcement, which were the highest values.
The conclusions of this study are as follows:
1. The bending and tensile strengths of the 3D glass fiber
composite are obviously increased with the addition of
nano-SiO2.
2. The strain to failure of the nano-SiO2-reinforced com-
For personal use only.
posite material is decreased under a bending load, but
increased under tensile loads. So, while the samples
showed brittle fracture in bending tests, they were char-
acterized by more elastic behavior, exhibiting higher
strain values under tensile testing.
3. Generally, the warp-directed samples give higher force
values due to the orientation in the weave compared
with the weft-directed samples. However, when the
changes are investigated, the weft-directed results give
proportionally more improvement compared to the warp
direction. The improvements for the warp and weft di-
rection respectively were calculated to be 52 % and
64 % in the bending test and 5 % and 11 % in the tensile
test.
4. The typical failure mechanism was obtained under
bending loads. The main fracture was detected between
the piles and the top–bottom face sheet-knitting region.
The matrix and the fibers separated with increasing load
and brittle fiber breakage finally occurred.
5. Fiber volume fraction was increased from 0.355 to
0.358 with the addition of nano-SiO2. Increased fiber
volume fraction improves the mechanical strength with
addition of 1 wt.% nano-SiO2. Void volume fraction
was decreased from 0.017 to 0.01 with the addition of
nano SiO2. Decrease of void volume fraction improves
the mechanical strength with addition of 1 wt.% nano-
SiO2.
6. Good wetting without resin pooling was obtained from
the vacuum infusion manufacturing process. Also,
SEM images show the good bonding interface between
the fiber and matrix material.
7. According to the EDX analysis and mapping results, ul-
trasonic mixing of the nano-powder and epoxy resin
gives good dispersion and homogeneity. According to
the color measurement results, all the measured point
320
colors are the same. These results are in agreement with
EDX mapping and prove that a good balanced distribu-
tion is obtained using nano-SiO2 particles, ultrasonic
mixing and vacuum infusion methods.
This study was supported by the Dumlupınar University Scientific Re-
search Project Commission with the 2015/69 acceptance numbered
project. The authors also thank the Dumlupınar University Advanced
Technologies Center for their contributions to the study.
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