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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

particle reinforcement. In these studies, an increase was


Three dimensional (3D) glass fiber epoxy composites rein- found in some properties of the composite, such as strength,
forced with nano-SiO2 particles at ratios of 0.5 wt.%, elasticity and elongation percentage [8 – 14]. In the studies
1 wt.%, 2 wt.% and 3 wt.%, were manufactured using the where the effects of nano-SiO2 particles added into epoxy
vacuum infusion method to improve the mechanical prop- resin were examined, it was confirmed that the elongation
erties. Differential scanning calorimetry, thermo-gravi- ratio decreased, whereas it was established that some prop-
metric analysis, particle dispersion detection by color mea- erties such as toughness, flexural strength, impact resis-
surement, scanning electron microscopy, energy dispersive tance and tensile strength improved [9, 15 – 18]. In studies
X-ray spectroscopy mapping, three point bending and ten- carried out to increase the mechanical properties of 3D
sile testing were performed to characterize the nano-parti- composites, laminated or filled composites were fabricated
cle-reinforced 3D composites. Mapping and color measure- [1, 8, 19 – 22]. However, no study on the reinforcement of
ment revealed good dispersion of the nano-particles. The 3D spacer glass fiber composites with nano-particles has
mechanical tests showed improvement rates of 52 % and been found. Therefore, this study considered whether the
64 % respectively on warp and weft directions compared properties of 3D glass fiber composites could be enhanced
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with the non-reinforced 3D composite. The tensile strength by adding nano-particles.


of the nano-SiO2 reinforced 3D woven composites also in- As 3D composite materials have strength limitations due
creased to 6 % and 10 % according to the warp and weft di- to their hollow structure, determining their behavior, da-
rections compared with the non-reinforced 3D composite. mage state and mechanical properties under load is impor-
tant to increase the areas where they can be used. In this re-
Keywords: Characterization; Glass fiber; Nano-particle re- gard, the objective of this study was specifically to enhance
inforcement; 3D hybrid composite 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].
1. Introduction
2. Experimental procedure
3D fibers are used in composite, reinforced materials whose
top and bottom faces are linked to each other and which 2.1. Materials
have channel-like voids. The weave in the channel direction
is called the warp, and the weave perpendicular to this direc- In this study, nano-particle-reinforced 3D epoxy glass fiber
tion is called the weft. 3D composite structures are used in composites were fabricated and their properties were inves-
automotive, aerospace and defense industries. The effect of tigated. The 3D glass fibers used in the study (Fig. 1) were
the pile height on the mechanical properties in 3D fibers fabricated from E-glass purchased from Parabeam B.V.
has been investigated [1 – 5], and it has been determined that The woven fibers had a total thickness of 3.3 mm (after re-
the compressive strength and the flexural strength decrease sined total thickness is 3 mm) and a density of 782 g m–2.
with an increase in the pile height [2, 3]. In studies where a The resin used as the matrix material in the system is an
varied number of piles with the same height were examined, epoxy resin commercially available under the trade name
it was observed that an increased number of piles improved of HEXION MGS L-160, and it was applied by mixing it
the compressive and flexural strengths [4]. A decrease in with a commercial hardener under the trade name MGS H-
the pile thickness with the same pile number and height re- 160, at a ratio of 5 : 1 (resin : hardener) by weight.
duced the compressive and flexural strengths [6]. In studies
carried out based on the weave direction, it was established 2.2. Composite manufacturing
that the warp direction demonstrated higher strength than
the weft direction [5]. It was also pointed out that the result- A vacuum infusion method was used to produce the compo-
ing damage mostly occurred in the areas where the piles sites in order to ensure uniform wetting and to avoid the for-
were linked to the top and bottom faces [3, 7]. mation of a resin pool [1, 3]. Materials that had been pre-
Some studies carried out on 2D composites examined the pared at 0.86 MPa vacuum in a closed system were
improvability of the composite’s mechanical properties via completely wetted with the resin, and then the vacuum bag

308 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 The epoxy resin was reinforced with nano-SiO2 at dif-
sprung back allowing the material to regain its 3D hollow ferent ratios: 0.5 wt.% (0.23 vol.%), 1 wt.% (0.46 vol.%),
form. The specimens were allowed to cure for 18 h at room 2 wt.% (0.94 vol.%), 3 wt.% (1.42 vol.%). The technical
temperature, and then they were subjected to post curing for specifications of the nano-SiO2 powder are shown in Ta-
2 h at 80 8C. The test specimens with warp and weft direc- ble 1. The mixture of nano-SiO2 and resin was prepared
tions were prepared from composite plates that had been se- using a Sonics Vibracell VCX-750 ultrasonic mixer. Ultra-
parately infused in the warp and weft directions, rather than sonication is an effective way to ensure maximum homoge-
from a single plate. Plates had been cut according to re- neity [8, 12, 17, 24 – 28]. The mix of the resin and nano-
quired specimen dimensions as given below. At least 5 spe- SiO2 was prepared by hand stirring for 5 min at room tem-
cimens were prepared from both nano-SiO2-reinforced and perature. The ultrasonication time was 20 min in total at a
non-reinforced 3D composites for each tensile and three 35 % frequency amplitude value. The ultrasonication pro-
point bending tests on both warp and weft directions. The cess was cooled using iced water to avoid both overheating
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thermo gravimetric analysis (TGA) tests were performed and the chemical decomposition of the resin. Production
on the warp direction only because of the warp direction was completed before the precipitation of particles. The
has been found the most effective direction on plates. All composite form of the 3D glass fiber after the fabrication
calculations are made by averaging the results of all 5 spe- is shown in Fig. 2.
cimens used in the experiments. The results were analyzed Three-point bending tests were carried out on 140 ·
in comparison with non-reinforced samples. 30 mm specimens that had been prepared in both the warp
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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 Surface Area True Density Morphology


(nm) (%) (m2 g–1) (g cm–3)

SiO2 30 99.9 440 2.2 – 2.6 Spherical

Fig. 2. Manufactured 3D composite and the section view of the wet piles.

Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4 309


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- improved the thermal degradation characteristics of the
dard test method for flexural properties, with a distance of composite and increased the operating temperature range.
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 3.2. Bending test results
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- As a result of the test, it was established that the nano-SiO2-
mens were initially sized at 250 · 40 mm and then their reinforced 3D composites had an increased flexural
middle sections were reduced to 25 mm, the standard size. strength compared to the non-reinforced 3D composites.
Larger edge sections of the specimens were filled with liq- As seen from the graph shown in Fig. 4 for the reinforced
uid paste and solidified, thus preventing the hollow material materials, the highest value was measured at 70.9 MPa with
from being crushed by the drawing jaws as a result of slid- an added 1 % SiO2, whereas the flexural strength of the pure
ing. material was measured to be 46.6 MPa in the warp direc-
Microstructural analyses were performed on different
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018

tion. This represented an increase of 52 %. In the weft direc-


sized images taken from both the surface and the damaged tion, the flexural strength was measured to be 55.3 MPa
region caused by the bending tests of the composite using with an added 1 % SiO2 again, whereas the flexural strength
an Insize ISM-PM200SB optical microscope and FEI Nova in the weft direction was measured to be 33.5 MPa for the
NanoSEM 650 scanning electron microscopy (SEM) de- pure material, which represented an increase of approxi-
vice. Furthermore, in the study where thermal properties mately 64 %. The reinforcement material/resin ratio is a de-
were examined using TGA investigations, energy-disper- cisive parameter in the strength properties of composite ma-
sive X-ray spectroscopy (EDX) analysis was used to try terials [29]. There is a threshold value of this ratio for all
and observe the distribution of the nano-particles in the composite materials. In other words, the maximum strength
composite structure. Because it is known that the nano- properties are obtained at certain proportional values,
SiO2 particles produce a color change in the 3D composite, which can also be referred to as the saturation point. It is
the dispersion stability was investigated by color changes evident that nano-SiO2 particles added to the composite
measured with a Mathai Color Striker device on the surface structure increase the reinforcement material/resin ratio in
of the composite according to the ASTM D-2244 standard. the structure. This indicates that the saturation level of the
reinforcement material/resin ratio is reached at a 1 % nano-
3. Result and discussion SiO2-reinforcement level by mass. In addition, it was
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thought that a 1 % nano-SiO2-reinforcement ratio forms


3.1. TGA analysis the ideal interface and improves the strength properties by
limiting the growth of nano-pores, as well as the propaga-
TGA analysis was performed on the composite material tion of cracks thanks to the mechanical locking formed by
with an added 1 % of nano-SiO2 particles in order to exam- the particles with the epoxy [25, 30 – 33]. Also, it is be-
ine the effect of the particle reinforcement on the thermal lieved that the spherical morphology of nano-SiO2 will con-
properties. As seen from the TG graph shown in Fig. 3, the tribute significantly to fewer knitting regions, fewer over-
degradation temperature of the nano-particle-reinforced laps and more ideal wetting. Thus, the ideal wetting and
composite increased by 18 8C compared to the pure epoxy distribution of matrix reinforcement material was obtained
composite. The fact that the TG curve has a very low slope at a 1 % reinforcement level. Overlapping, aggregation,
and the degradation temperature rose indicated that the in- and poor wetting regions particularly, increased at 2 % and
termolecular bond strength of the nano SiO2-reinforced 3 % SiO2-reinforcement levels. Further evidence for the im-
composite increased. A 45 8C increase was detected in the provement nano-SiO2 particles make to the distribution
extreme temperature value where the degradation was mechanism of the applied load by its positioning in the
ended. It was observed that the nano-particle reinforcement epoxy resin is the increase in the bending elasticity modulus

Fig. 3. TG plot of 1 % nano-SiO2-reinforced


3D glass fiber composite.

310 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 force, flexural strength and modulus of elasticity of the 3D
were calculated in the warp direction – at a 1 % nano- composite material are shown in Fig. 4. The results were
SiO2-reinforcement ratio by mass – at 5 GPa and in the weft also statistically evaluated and expressed as error bars in
direction – also at a 1 % nano-SiO2 reinforcement ratio by the figures. In the analyses in which non-reinforced 3D
mass – at 3.6 GPa. The increased ratios of the bending elas- composites were taken as a reference, it was seen that the
ticity modulus of nano-SiO2-reinforced 3D composite were results obtained from reinforced 3D composites that exhibit
69 % in the warp direction and 81 % in the weft direction. improvements in mechanical properties were in the 95 %
The effects of the nano-SiO2-reinforcement on bending confidence interval.
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018
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Fig. 4. Bending test results of composites


with different SiO2 ratios: (a) bending force,
(b) bending strength, (c) bending modulus of
elasticity.

Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4 311


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

There was a decrease measured in the deflection proper- faces joined [3, 7]. The damage in the warp-direction speci-
ties of the SiO2-reinforced 3D composite materials. This mens tended to follow a weaving line in a zigzag pattern,
decrease was seen at all reinforcement rates of SiO2. While whereas the damage in the weft-direction specimens oc-
the deflection values of 3D composites with pure epoxy curred in a straight line. It was observed that, with increas-
were measured to be 4.8 mm for the warp direction and ing load, the weave layers became detached and the glass fi-
4.6 mm for the weft direction, the highest decreases were bers broke away from the matrix material. This condition is
measured to be 5.5 mm in the warp direction and 5.9 mm shown in the optical microscopy (OM) images of the da-
in the weft direction, with an added 3 % SiO2. The changes mage region in Fig. 6.
in deflection with reinforcement rates of nano-SiO2 parti-
cles are shown in Fig. 5. 3.3. Tensile test results
The fracture regions of the mechanical test specimens
were investigated after the tests. It was established that the Based on the results obtained from the tensile tests per-
damage, particularly in the weft-direction specimens, oc-
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formed on the composite materials, a significant increase


curred in the section where the pile and the top and bottom was determined in the maximum tensile force, tensile

Fig. 5. Deflection values of composites with


different SiO2 ratios.
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Fig. 6. OM pictures of the damage area of weft directed three point bending samples.

312 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 increases in the composite material’s tensile strength were
increase obtained in the tensile properties of the composite measured to be approximately 5 % in the warp direction
proves that an effective interface bonding forms among the and approximately 11 % in the weft direction. Figure 8
reinforcement material, nano-SiO2 and epoxy. The ultraso- shows the effects of changing the amount of SiO2 on the
nic mixing method ensured a homogeneous distribution of tensile properties of the composite material.
resin and nano-particles, and improved the formation of The strain ratio is the most affected property of the com-
the matrix–nano-particle interface. Furthermore, the fact posite as a result of SiO2 reinforcement. As can be seen in
that the selected nano-SiO2 has a specific surface area as Fig. 9, when compared with the non-reinforced composite
high as 440 m2 g–1 is considered to contribute to the forma- the increased ratio of the strain for the warp and weft direc-
tion of this robust interface. tion are 14 % and 7 % respectively. The highest strain val-
Figure 7 shows the stress–strain curves of the nano-SiO2 ues were obtained at 1 % SiO2 for the warp and weft direc-
reinforced and non-reinforced 3D woven glass fiber com- tions. The strain was measured as 2.4 % and 2.24 % on the
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018

posites. According to the graph, typical fiber reinforced warp and weft directions respectively.
polymer composite curves were obtained. Compared with It was thought that the improvements detected in tensile
the non-reinforced samples different degrees of improve- strength – just as those in bending properties – were asso-
ment on the tensile properties can be observed in the 3D ciated with the formation of an effective interface between
composites depending on the amount of nano-SiO2. It is the nano-particles and the epoxy resin. Due to the good wet-
clearly seen the nano-particles increase the tensile proper- ting obtained by nano-particles with the epoxy and the me-
ties. While the non-reinforced 3D glass fiber composite chanical locking, growth of nano-pores and propagation of
has a tensile strength of 55.2 MPa in the warp and cracks were limited and strength properties were improved
51.6 MPa in the weft directions, these values increased with [25, 30 – 33]. According to the tensile stress results in the
the nano-SiO2 reinforcement. The highest increases were weft direction, 2 % ratio value for the reinforcement materi-
determined for 1 % SiO2 with 58 MPa in the warp direction, al may increase the reinforcement material/resin ratio in
and for 2 % SiO2 with 57.2 MPa in the weft direction. The this direction.
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Fig. 7. Tensile curves of composites with dif-


ferent SiO2 ratios: (a) warp direction, (b) weft
direction.

Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4 313


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

Optical microstructural analysis was performed on the it can be seen that the fibers that break due to the load were
damaged regions of the specimens following the tensile scraped off the epoxy matrix. It was observed that surface
tests. Figure 10 shows the woven glass fibers deformed by cracks developed in the matrix structure outside the fracture
the tensile load. At higher magnification (inset of Fig. 10), zone.
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Fig. 8. Tensile properties of composites with


different SiO2 ratios: (a) tensile force, (b) ten-
sile strength.
For personal use only.

Fig. 9. Strain values of composite with dif-


ferent SiO2 ratios.

314 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 burn-out, it would stay with the glass fiber. Because the
TGA process gives the main mass loss of the composite
The volume fraction of fiber relative to the total volume of by burning the resin, vf was measured experimentally on
the composite is an important parameter in composite ma- TGA and theoretically calculated by using the following
terials and is called fiber volume fraction (vf), a number Eq. (1) [38]. Fiber volume fraction studies were carried
between 0 and 1 [34]. vf can be determined experimentally out on the non-reinforced 3D composites and 1 % of
by weighing the composite before and after the test when nano-SiO2-reinforced 3D composites which gives the
the resin is removed by ignition loss according to the highest mechanical strength.
ASTM 2584 standard [35]. The burning method (ASTM wf :qc
D2584-68 [35]) has been considered a simple and effective vf ¼ ð1Þ
way to determine the volume fraction of cured resin com- wc :qf
posite materials. Abdalla et al. [36] declared that in many Where, wf is the weight of the fiber (g), wc is the weight of the
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018

cases the burn-out process has shown some limitations composite (g), qc is the density of the composite (g cm–3), and
when extra fillers have been added to the composite mate- qf is the density of the fiber (g cm–3). For determining the ex-
rial. The fillers which may be partially burned out or not perimental fiber volume fraction, the density of nano-SiO2
burned out at all by the burn-out process stay with the was added to the glass fibers mass with the following conver-
glass fiber. This causes difficulties in determining the fiber sion, Eq. (2):
volume. Until now there has been no standard approach to
separate fillers from the resin and glass fiber of structural wSiO2 :qc
vSiO2 ¼ ð2Þ
composites [36, 37]. During the burning it was thought wc :qSiO2
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) 4 315


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 In the EDX analyses made on the fractured resin zones,
weight of the used SiO2, and qSiO2 is the density of the Si and O2 peaks are seen. This shows the presence of rein-
SiO2. According to the formulation theoretical vf results forcement powders in the structure (Fig. 12a). In addition,
for the 3D composites were found as 0.355 (35.5 %) for Ca and Al are seen due to the Al2O3 and CaO compounds
non-reinforced composite and 0.358 (35.8 %) for 1 % SiO2 found in the chemical composition of the glass fibers. With
reinforced 3D composite. The mass loss after the TGA ana- EDX mapping of the epoxy structure, the presence of SiO2,
lysis is given in Fig. 3. The weight ratio of the non-burned separate silicon (Si) and oxygen (O) and its homogeneous
particles to the main composite mass was 54.4 % for non re- distribution throughout the structure are seen (Fig. 12b).
inforced composite and 53.3 % for 1 % SiO2-reinforced Because of the epoxy’s chemical composition, high levels
composites. The calculated experimental vf results of the of oxygen (O) and carbon (C) are seen on the mapping.
3D composites were found as 0.338 (33.8 %) for non-rein-
forced composite and 0.348 (34.8 %) for 1 % SiO2-rein- 3.6. Dispersion detection on surfaces
forced 3D composite. When the vf results are compared be-
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with color measurement


tween the non-reinforced and nano SiO2 reinforced 3D
composites, an increase can be seen easily. Increase in fiber Emady et al. [44] studied the color concentration measure-
volume fraction improves the mechanical strength, as found ment of powders on composite surfaces. Their study was
by other researchers [39 – 42]. On the other hand, the theo- based on exposing the surface of a sample that was dyed
retical vf is higher than the experimental results because it with an unknown concentration of material to light in the
was assumed that theoretically there were no voids present visible spectrum. The intensity of the light reflected from
in the composite body. But in manufacturing, this theoreti- the surface was proportional to the concentration of dyed
cal assumption is not valid and there are voids in the com- material in the sample. The concentration of dyed material
posite structure. The differences between the theoretical on the surface was determined by calculation [45]. In re-
and experimental fiber volume fraction values give the void search literature, there are several methods for measuring
content of the composite [43]. The void volume fraction the distribution, including Zeta potential (f), dynamic light
(vv) of 3D composites were found as 0.017 (1.7 %) for scattering, transmission electron microscopy (TEM) and
non-reinforced composite and 0.01 (1.0 %) for 1 % SiO2-re- color concentration measurement [46]. All the methods
inforced 3D composite. The void content of the 3D com- have unique features and were available. Zeta potential (f)
posite was decreased with the addition of the 1 % SiO2. and TEM methods were used, especially for examining the
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Thus the mechanical properties of the 3D composites were dispersion, size and morphology of the internal structure
increased with the decrease in the void content. According of the material, and they require complex equipment. Sur-
to the results it can be thought that the nano-SiO2 helps face-based measuring equipment was simpler and more
close the voids or reduce the void formation in the compos- usable, and also provided the main reference points, includ-
ite during the resin infusion. Obtained fiber volume fraction ing concentrations. In this study, surface color measure-
and void volume fraction results are given in Table 2. ment was performed in addition to the EDX mapping analy-
sis for the determination of particle distribution.
3.5. SEM-EDX analysis The reinforcement material, nano-SiO2, changes the
color of the resin, thereby changing the composite color.
In microstructural analysis of SEM images, it was seen that Furthermore, some additives or pigments are especially
the fibers were completely surrounded by the matrix resin. preferred to obtain a particular product color. Even if the
Thus the vacuum infusion method is an effective way of en- color does not change, color density tone differences can
suring homogeneous wetting and a nonporous composite be obtained in liquid–solid compositions such as resin and
structure. The efficiency of the vacuum infusion method in fiber-mix structures. Ultrasonication is one of the best ways
the production of 3D composites has also been emphasized to obtain good powder dispersion in liquid [8, 12, 17, 24 –
by other researchers [1, 3, 20]. 28], and this provides the homogeneity of the particles in
Fracture surfaces are shown in Fig. 11. Figure 11a shows the liquid resin before the wetting of the woven glass fiber.
deep matrix cracks at the points where the piles are linked After the vacuum process, the particles that were attached
to the top and bottom faces. It was understood that the da- to the composite outer and inner surfaces were considered
mage occurring during the tensile test developed in a way to be homogeneous. The EDX mapping examination per-
that the fibers were scraped off the matrix resin (Fig. 11b formed on the fractured inner surfaces of the 3D composites
and c). Based on the analyses made, it was seen that the revealed good dispersion of the SiO2 particles. The main
piles become completely upright via the absorbed resin, strategy of the color measurement is to find color hue dif-
thus the resin fully wets the glass fiber. It was also observed ferences resulting from nano-SiO2 particles on the compos-
from OM images that the damage formation on the pile sur- ite outer surface. The parameter measured is the color
face was clearer in SEM images. change factor, DE. It gives the total deviation in tone com-

Table 2. Obtained fiber volume fraction (vf) and void volume fraction (vv) results.

Material Theoretical vf Experimental vf Void volume fraction (vv)

Non-Reinforced 3D Composite 0.355 0.338 0.017


1 wt.% Nano-SiO2 Reinforced 3D Composite 0.358 0.348 0.01

316 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
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018
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- According to the measured values, all three points in both
bulated results were checked to see whether they were with- surface directions show little difference and can be consid-
in the range or not of a standard database, and are shown in ered valid results. All measured color tones induced by the
Table 3 [47]. particles on the surface fall in the range of 0 to 1 and the
The color measurements of the 3D composites were measured point colors are the same. The small differences
made on the lower, middle and upper edges of the surfaces. obtained prove the well balanced distribution of nano-SiO2
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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
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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
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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 colors are the same. These results are in agreement with
clear that the underlying causes for this were the ultrasonic EDX mapping and prove that a good balanced distribu-
mixing and the vacuum-assisted resin transfer manufactur- tion is obtained using nano-SiO2 particles, ultrasonic
ing system. The ultrasonic particle mixing is the best way mixing and vacuum infusion methods.
to eliminate any aggregate and obtain good dispersion [8,
12, 17, 24 – 28, 48]. Also, the wetting of the fibers with the This study was supported by the Dumlupınar University Scientific Re-
search Project Commission with the 2015/69 acceptance numbered
vacuum method eliminates operator mistakes, accumula- project. The authors also thank the Dumlupınar University Advanced
tion and resin pooling. Data for the measured color are Technologies Center for their contributions to the study.
given in Table 4.

4. Conclusions References

[1] C.Q. Zhao, D.S. Li, T.Q. Ge, L. Jiang, N. Jiang: Mater. Des. 56
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

(2014) 50 – 59. DOI:10.1016/j.matdes.2013.10.083


fusion method reinforced with nano-SiO2 powders with [2] H. Fan, F. Sun, L Yang, F. Jin, D. Zhao: Compos. Sci. Technol. 87
contents of 0.5, 1, 2 and 3 wt.%. When reinforced with 1 % (2013) 142 – 148. DOI:10.1016/j.compscitech.2013.07.028
SiO2, the bending force increased from 104.9 N to 159.7 N [3] D.S. Li, C.Q. Zhao, L. Jiang, N. Jiang: Compos. Struct. 111
(2014) 56 – 65. DOI:10.1016/j.compstruct.2013.12.026
for the warp direction and from 75.5 N to 124.4 N in the [4] M. Li, S. Wang, Z. Zhang, B. Wu: Appl. Compos. Mater. 16
weft direction, compared to the non-reinforced composite. (2009) 1 – 14. DOI:10.1007/s10443-008-9072-4
In tensile testing, the tensile force increased from 4 355 N [5] M. Sadighi, S.A. Hosseini: Compos. Part B 55 (2013) 158 – 166.
to 4 647 N in the warp direction at 1 % SiO2 reinforcement DOI:10.1016/j.compositesb.2013.06.030
[6] H. Fan, L. Zhao, H. Chen, N. Kuang, C. Yang, S. Huang, Y. Jiang:
and increased from 4 156 N to 4 580 N in the weft direction Compos. Sci. Technol. 72 (2012) 1338 – 1343.
at 2 % SiO2 reinforcement, which were the highest values. DOI:10.1016/j.compscitech.2012.04.017
The conclusions of this study are as follows: [7] H. Fan, Q. Zhou, W. Yang, Z. Jingjing: Compos. Part B 41 (2010)
686 – 692. DOI:10.1016/j.compositesb.2010.07.004
1. The bending and tensile strengths of the 3D glass fiber [8] K. Bilişik, G. Yolaçan: Dokuma E-Cam/Polyester Nano Silika
Kompozitlerin Eğilme Özellikleri. XIIIth International İzmir Tex-
composite are obviously increased with the addition of tile and Apparel Symposium, Antalya, Turkey (2014).
nano-SiO2. [9] R.K. Nayak, A. Dash, B.C. Ray: Procedia Mater. Sci. 2014; 6:
2. The strain to failure of the nano-SiO2-reinforced com- 1359 – 1364. DOI:10.1016/j.mspro.2014.07.115
For personal use only.

posite material is decreased under a bending load, but [10] V.C.S. Chandrasekaran, S.G. Advani, M.H. Santare: Carbon 48
(2010) 3692 – 3699. DOI:10.1016/j.carbon.2010.06.010
increased under tensile loads. So, while the samples [11] N.A. Siddiqui, R.S.C. Woo, J.K. Kim, C.C.K. Leung, A. Munir:
showed brittle fracture in bending tests, they were char- Compos. Part A 38 (2006) 449 – 460.
acterized by more elastic behavior, exhibiting higher DOI:10.1016/j.compositesa.2006.03.001
strain values under tensile testing. [12] Y. Zhou, F. Pervin, V.K. Rangari, S. Jeelani: Mater. Sci. Eng.
3. Generally, the warp-directed samples give higher force A 426 (2006) 221 – 228. DOI:10.1016/j.msea.2006.04.031
[13] F.H. Gojny, M.H.G. Wichmann, B. Fiedler, W. Bauhofer,
values due to the orientation in the weave compared K. Schulte: Compos. Part A 36 (2005) 1525 – 35.
with the weft-directed samples. However, when the DOI:10.1016/j.compositesa.2005.02.007
changes are investigated, the weft-directed results give [14] E. Beyakrova, E.T. Thostenson, A. Yu, H. Kim, J. Gao, J. Tang:
proportionally more improvement compared to the warp Langmuir 23 (2007) 3970 – 3974. DOI:10.1021/la062743p
[15] R. Zhao, W. Luo: Mater. Sci. Eng. A 483 (2008) 313 – 315.
direction. The improvements for the warp and weft di- DOI:10.1016/j.msea.2006.08.151
rection respectively were calculated to be 52 % and [16] C. Chen, R.S. Justice, D.W. Schaefer, J.W. Baur: Polymer 49
64 % in the bending test and 5 % and 11 % in the tensile (2008) 3805 – 3815. DOI:10.1016/j.polymer.2008.06.023
test. [17] B.B. Johnsen, A.J. Kinloch, R.D. Mohammed, A.C. Taylor,
4. The typical failure mechanism was obtained under S. Sprenger: Polymer 48 (2007) 530 – 541.
DOI:10.1016/j.polymer.2006.11.038
bending loads. The main fracture was detected between [18] T.H. Hsieh, A.J. Kinloch, K. Masania, A.C. Taylor, S. Sprenger:
the piles and the top–bottom face sheet-knitting region. Polymer 51 (2010) 6284 – 6294.
The matrix and the fibers separated with increasing load DOI:10.1016/j.polymer.2010.10.048
and brittle fiber breakage finally occurred. [19] H. Fan, W. Yang, Q. Zhou: Compos. Part B 42 (2011) 1151 –
1156. DOI:10.1016/j.compositesb.2011.03.008
5. Fiber volume fraction was increased from 0.355 to [20] A.S. Vaidya, U.K. Vaidya, N. Uddin: Mater. Sci. Eng. A 472
0.358 with the addition of nano-SiO2. Increased fiber (2008) 52 – 58. DOI:10.1016/j.msea.2007.03.064
volume fraction improves the mechanical strength with [21] A.W. Van Vuure, J.A. Ivens, I. Verpoest: Compos. Part A 31
addition of 1 wt.% nano-SiO2. Void volume fraction (2000) 671 – 680. DOI:10.1016/S1359 – 835X(00)00017 – 8
[22] J. Zheng, L. Zhao, H. Fan: Compos. Part B 43 (2012) 1516 – 1522.
was decreased from 0.017 to 0.01 with the addition of DOI:10.1016/j.compositesb.2011.08.034
nano SiO2. Decrease of void volume fraction improves [23] A. Farrah, M. Jaafar, S. Palaniandy, A.K. Azizi: Compos. Sci.
the mechanical strength with addition of 1 wt.% nano- Technol. 68 (2008) 346 – 353.
SiO2. DOI:10.1016/j.compscitech.2007.07.015
6. Good wetting without resin pooling was obtained from [24] J. Li, Z. Wu, C. Huang, L. Li: Compos. Sci. Technol. 104 (2014)
81 – 88. DOI:10.1016/j.compscitech.2014.09.007
the vacuum infusion manufacturing process. Also, [25] Y.X. Zhou, P.X. Wu, Z.Y. Cheng, J. Ingram, S. Jeelani: eXPRESS
SEM images show the good bonding interface between Polym. Lett. 2 (2008) 40 – 48.
the fiber and matrix material. DOI:10.3144/expresspolymlett.2008.6
7. According to the EDX analysis and mapping results, ul- [26] A. Patra, N. Mitra: Compos. Sci. Technol. 101 (2014) 94 – 101.
DOI:10.1016/j.compscitech.2014.07.006
trasonic mixing of the nano-powder and epoxy resin [27] N.A. Siddiqui, M.L. Sham, B.Z. Tang, A. Munir, J.K. Kim: Com-
gives good dispersion and homogeneity. According to pos. Part A 40 (2009) 1606 – 1614.
the color measurement results, all the measured point DOI:10.1016/j.compositesa.2009.07.005

320 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

[28] C. Fernandez, C. Medina, G. Pincheira, C. Canales, P. Flores: [44] H.N. Emady, M. Wittman, S. Koynov, W.G. Borghard, F.J. Muz-
Compos. Part B 55 (2013) 421 – 425. zio, B.J. Glasser, A.M. Cuitino: Powder Technol. 286 (2015)
DOI:10.1016/j.compositesb.2013.07.010 392 – 400. DOI:10.1016/j.powtec.2015.07.050
[29] S. Ülkü, B. Korkmaz: Farklı Kompozisyonlardaki Polyesterin [45] S. Koynov, Y. Wang, A. Redere, P. Amin, H.N. Emady, F.J. Muz-
Mekanik Özelliklerinin Yapıya Bağlı Olarak Deneysel ve Teorik zio, B.J. Glasser: Powder Technol. 292 (2016) 298 – 306.
Olarak İncelenmesi, Balıkesir Symposium, Turkey (1988). DOI:10.1016/j.powtec.2016.01.039
[30] F.H. Gojny, M.H.G. Wichmann, U. Köpke, B. Fiedler, K. Schulte: [46] B.D. Mattos, O.J. Rojas, W.L.E. Magalhães: Powder Technol.
Compos. Sci. Technol. 64 (2004) 2363 – 2371. 301 (2016) 25 – 64. DOI:10.1016/j.powtec.2016.05.052
DOI:10.1016/j.compscitech.2004.04.002 [47] http://mepteknik.com/bg/assets/images/kkilavuz/RENK%
[31] Y. Zhou, F. Pervin, L. Lewis, S. Jeelani: Mater. Sci. Eng. A 475 20OLCUM%20CIHAZI%20KULLANMA%20KILAVUZU.pdf
(2007) 157 – 165. DOI:10.1016/j.msea.2007.04.043 [48] http://www.horiba.com/fileadmin/uploads/Scientific/Documents/
[32] L. Liu, H.D. Wagner: Compos. Sci. Technol. 65 (2005) 1861 – PSA/Webinar_Slides/TR016.pdf
1868. DOI:10.1016/j.compscitech.2005.04.002
[33] M. Nadler, J. Werner, T. Mahrholz, U. Riedel, W. Hufenbach: (Received August 12, 2016; accepted December 13, 2016;
Compos. Part A 40 (2009) 932 – 937. online since February 2, 2017)
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Chalmers University of Technology on January 7, 2018

DOI:10.1016/j.compositesa.2009.04.021
[34] M.W. Hyer: Stress Analysis of Fiber Reinforced Composite Mate-
rials, The McGraw-Hill Companies Inc., USA (1998).
[35] ASTM D2584: Standard test method for ignition loss of cured re- Correspondence address
inforced resins, Annual Book of ASTM standards, Vol. 8, Ameri-
can Society for Testing and Materials, Philadelphia, (USA) (1968) Dr. Ferhat Yildirim
328 – 329. Department of Industrial Design Engineering
[36] F.H. Abdalla, M.H. Megat, M.S. Sapuan, B.B. Sahari: J. Eng. Faculty of Simav Technology
Appl. Sci. 4 (2008) 7 – 11. University of Dumlupinar
[37] S.Y. Binshan, A.L. Svenson, C.B. Lawrence: Composites 26 43500 Simav, Kutahya
(1995) 725 – 731. DOI:10.1016/0010-4361(95)91140-Z Turkey
Tel.: +90 274 513 7917
[38] R. Whitacre, A. Amiri, C. Ulven: Ind. Crops Prod. 77 (2015)
Fax: +90 274 513 7914
232 – 238. DOI:10.1016/j.indcrop.2015.08.056
E-mail: ferhat.yildirim@dpu.edu.tr
[39] L.A. Pothan, S. Thomas, J. George: Tensile and Impact Properties
of Banana Fiber/Glass Fiber Hybrid Polyester Composites, 12th
Int. Conf. Composite Materials, Paris, France (1999) 1267.
[40] S. Mishra, A.K. Mohanty, L.T. Drzal, M. Misra, S. Parija, S.K.
Nayak, S.S. Tripathy: Compos. Sci. Technol. 63 (2003) 1377 –
1385. DOI:10.1016/S0266 – 3538(03)00084 – 8 Bibliography
For personal use only.

[41] R. Velmurugan, V. Manikandan: Indian. J. Eng. Mater. Sci. 12 DOI 10.3139/146.111479


(2005) 563 – 570.
URL: http://nopr.niscair.res.in/handle/123456789/8464
Int. J. Mater. Res. (formerly Z. Metallkd.)
[42] S.P. Priya, S.K. Rai: J. Ind. Text. 35(2006) 217 – 226. 108 (2017) 4; page 308 – 321
DOI:10.1177/1528083706055754 # Carl Hanser Verlag GmbH & Co. KG
[43] I.M. Daniel, O. Ishai: Engineering Mechanics of Composite Mate- ISSN 1862-5282
rials, Oxford University Press, 2nd Ed., New York, USA (2006).

Int. J. Mater. Res. (formerly Z. Metallkd.) 108 (2017) 4 321