Composites: Part B 43 (2012) 3436–3444

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Composites: Part B
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Hybrid polymeric composites reinforced with sisal fibres and silica microparticles
Leandro José da Silva a, Túlio Hallak Panzera a,⇑, Vânia Regina Velloso a, André Luis Christoforo a,
Fabrizio Scarpa b
a
Department of Mechanical Engineering, Federal University of São João Del Rei, UFSJ, Brazil
b
Advanced Composites Centre for Innovation and Science, University of Bristol, UK

a r t i c l e i n f o a b s t r a c t

Article history: Polymeric composites reinforced with natural fibres have been developed in recent years, showing signif-
Received 7 October 2011 icant potential for various engineering applications due to their intrinsic sustainability, low cost, low
Received in revised form 2 December 2011 weight and mechanical strength. The interfacial adhesion between natural fibres and polymeric matrices
Accepted 2 January 2012
is critical to the composite performance. In order to improve the physical adhesion of polymeric compos-
Available online 9 January 2012
ites, micro and nanoparticles have been added to synthetic fibres in the past. This work investigates the
effect of silica microparticles, volume fraction of sisal and maleic anhydride on the mechanical properties
Keywords:
of polymeric composites reinforced with unidirectional sisal natural fibres. A full factorial design (2231)
A. Lamina/ply
B. Mechanical properties
was carried out to identify the effect of these factors on the responses: bulk density, apparent density,
C. Statistical properties/methods apparent porosity, water absorption, mechanical strength and modulus of elasticity. A microstructure
D. Electron microscopy analyses was conducted to verify the interface condition. The volume fraction of fibres, silica addition,
and the interaction between silica particles and maleic anhydride additions exhibited significant effects
on the tensile strength and modulus of elasticity of the composites. The microsilica addition did not affect
significantly the flexural strength; while the interaction between fraction of fibres, silica particles and
maleic anhydride addition played a major role not only on the flexural strength, but also on the flexural
modulus. The volume fraction of sisal fibres exhibited significant effects on the bulk density, apparent
density, apparent porosity and water absorption of the composites.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction dealing with natural fibre composites is the adhesion between

Polymeric composites reinforced with natural fibres have been
developed during the last decade as a sustainable alternative for
some engineering applications. According to Silva [1], the interest
towards biocomposites development became more effective due
to the growing demand for low cost materials from renewable
sources that could substitute traditional ones. A significant amount
of research and development activities on natural composites has
been generated also in response to the requirements from certifica-
tion and legal entities on the use and final destination of synthetic
fibres and resins derived from petroleum. In addition, the high cost
of synthetic fibres and the public awareness and sensitivity to the
preservation of the natural environment contribute to the develop-
ment of new research activities in this area [2].
Sisal fibres have been investigated as a dispersive phase in
polymeric composite materials due to their intrinsic low cost,
acceptable mechanical properties from a structural engineering
perspective, and market availability. According to Maldas and
Kokta [3] and Lyons and Ahmed [4], one of the main difficulties
⇑ Corresponding author.
E-mail address: panzera@ufsj.edu.br (T.H. Panzera).
the fibres and the matrices. The chemical affinity between the cel-
lulose and the polymeric matrix can be improved by the modifica-
tion of the fibre surface or the polymer, using chemical additives,
for instance, the maleic anhydride [5]. The addition of modified
polymers such as maleic anhydride into polymeric composites
reinforced with natural fibres has been studied [6–8] to improve
the interfacial adhesion, consequently, enhancing the mechanical
properties of the composites.
Mishra et al. [9] and Naik and Mishra [10], studied the effect of
the maleic anhydride on sisal fibres and banana fibres. The water
absorption was significantly decreased by the chemical treatment.
The mechanical properties, such as modulus of elasticity, hardness
and impact resistance increased with maleic anhydride addition,
demonstrating its capacity as a compatibilizing agent.
Not only chemical addictive, but also ceramic minerals have
been added into the epoxy matrix to enhance the mechanical per-
formance of laminated composites. Several works [11–21] have
been focusing on nanoparticle additions into epoxy/glass fibre
composites. The epoxy matrix exhibits low viscosity and long gel
time, which contributes to the mixing procedure of nanoparticles.
Mahrholz et al. [12] investigated the addition of silica nanopar-
ticles into epoxy resin matrix. The weight fraction of 25% improved

1359-8368/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesb.2012.01.026
 L.J. da Silva et al. / Composites: Part B 43 (2012) 3436–3444 3437

the characteristics of the matrix and increased the mechanical per- The modification of polymeric matrices or fibre surfaces with
formance of structural laminated composites. the addition of microparticles and nanoparticles of ceramic mate-
Rosso et al. [13] evaluated the mechanical strength of epoxy re- rials has also been evaluated for synthetic fibres, especially glass fi-
sin, adding 5% in volume of silica nanoparticles. The silica addition bres. This work investigates the effect of silica microparticles and
was able to improve the stiffness and tenacity of the polymer, con- maleic anhydride addition into polymeric matrix (epoxy resin) of
sequently, increasing the modulus of elasticity (20%) and the frac- composites with unidirectional sisal fibres, providing a thorough
ture tenacity (70%) of the composites. Design of Experiments (DOE) and Analysis of Variance (ANOVA)
Isik et al. [14] and Yasmin et al. [15], studied the effect of nano- to assess from a rigorous statistical point of view the influence of
clay addition from 0 to 10 wt.% into epoxy matrix. Isik et al. [14] the biocomposite components on the mechanical properties of
verified that the nanoclay addition of 1 wt.% provided higher im- the laminates.
pact resistance and tensile strength. However, the modulus of elas-
ticity was gradually increased with the nanoclay addition. Yasmin
2. Materials and methods
et al. [15] identified a percent increase of 80% on the modulus of
elasticity when 10 wt.% of nanoclay particles were added.
The polymeric composites were fabricated from modified and
Haque et al. [16] and Ávila et al. [17] concluded that the addi-
non-modified epoxy matrix, supplied by Resiqualy Company (São
tion of nanoclay particles between 1 and 2 wt.% into glass/epoxy
Paulo – Brazil), and from dispersive phase of unidirectional sisal fi-
composites enhanced the thermo mechanical properties; however
bres supplied by Sisalsul Company (São Paulo – Brazil). The fibres
the opposite behaviour was observed when high percent fractions
were extracted, washed and combed by the supplier, with no
(over 5 wt.%), were added. The interlaminar shear, the flexural
chemical treatment. The matrix phase was modified by the addi-
strength and the fracture tenacity exhibited a significant percent
tion of silica microparticles and maleic anhydride. The silica micro-
increase of 44%, 24%, and 23% respectively, when only 1 wt.% of
particles were supplied by Moinhos Gerais Company (Minas Gerais
nanoclay was added.
– Brazil), and classified by sieving process in monomodal range of
The addition of rigid nanoparticles into polymeric matrix can
size 0.037 mm. The resin and the hardener were combined first;
improve the mechanical performance of laminated composites,
afterwards the silica microparticles were added and hand-mixed
mainly under compressive loadings, when the matrix phase is af-
by 5 min at room temperature (22 °C).
fected by adding high stiff material. Subramaniyan and Sun [19]
Tensile tests were carried out according to ASTM D3822-07 [23]
investigated the effect of nanoclay additions (0, 3, 5 and 8 wt.%)
and ASTM D638-03 [24] standards to determine the tensile
into epoxy matrix. The longitudinal compressive strength of the
strength and modulus of elasticity of the fibres and matrix phase,
composites did increase by 22% and 36% with the addition of
respectively. The test speeds were set as 3 mm/min for sisal fibres
3 wt.% and 5 wt.% of nanoclay.
and 2 mm/min for polymeric matrices.
Nanosilica particles have been used to reinforce the matrix of
The elastic properties of the fibres and matrices where then
glass/epoxy composites. Jia-Lin and Yi-Lieh [20] observed that add-
used to determine the effective properties of the composites using
ing nanosilica particles (at 10, 20 and 30 wt.%) increased the com-
Eqs. (2)–(4). The fibre–matrix interface condition was also verified
pressive strength of laminated composites, with the highest value
by comparing the Halpi–Tsai relations to the experimental data ob-
reached for 30 wt.%.
tained by tensile tests on the biocomposites produced.
Cao and Cameron [21] evaluated the effect of silica particles on
The biocomposite laminates were fabricated manually by the
the glass fibres surface. The particles increased the mechanical
use of a metal frame in order to align and fix the fibres. The manual
strength of the composites minimizing the onset and rate of crack
moulding process was carried out upon a glass plate covered by a
propagation, as a result of the increase in interfacial area.
cloth parting (Armalon), providing good surface finishing of the
A micromechanical analysis based on the rule of mixtures can
lamina. The polymeric matrix (modified and non-modified) was
be performed to estimate the composite properties P⁄ by the indi-
spread on the fibres by the use of spatula and roller aerator. A glass
vidual properties of its components:
fibre composite was used to protect the specimen ends at the
P ¼ Pf  V f þ Pm  V m ð1Þ clamping area, avoiding premature cracking during the tensile
testing (see Fig. 1). A scanning electron microscope (SEM), Hitachi
In Eq. (1), the individual properties of the components Pf and Pm
T-3000 model, was used to observe the cross section of the com-
(fibres and matrix respectively) are then related to the homoge-
posites. The tensile and flexural testing of the composites was car-
nised property P through their volume fractions Vf and Vm. The rule
ried out based on the recommendations of British Standard 2747
of mixture assumes a perfect interface between phases, and does
[26] and ASTM D790 [27], respectively. The mechanical tests were
not take into account the characteristics of the fibre–matrix inter-
carried out in Autograph machine monitored by the software
face. Halpin and Tsai introduced two new coefficients to compen-
Topazium, using the loading cells of 2 kN (tensile) and 0.5 kN
sate the effect of the interface condition on the composite effective
(flexural).
properties [22], with the introduction of the coefficients n and g
depending on the individual phases and the effective property esti-
mated by rule of mixture model:
Pf ðP  Pm Þ  V f  P ðPf  Pm Þ
n¼ ð2Þ
Pm ðPf  P Þ  V m ðP f  Pm Þ

Pf  Pm
g¼ ð3Þ
Pf þ n  Pm
The Halpin–Tsai model to estimate the effective properties of
unidirectional composite materials adjusted to non-perfect inter-
face conditions is finally expressed by the following relation:
Pm ð1 þ n  g  V f Þ
P ¼ ð4Þ
1  g  Vf Fig. 1. Tensile test specimens.
3438 L.J. da Silva et al. / Composites: Part B 43 (2012) 3436–3444

Table 1
Experimental conditions, full factorial design (2231).

Conditions Type of Volume Maleic anhydride Silica addition

fibres fraction (%) (wt.%) (wt.%)
C1 Sisal 30 0 0
C2 Sisal 30 2 0
C3 Sisal 30 0 20
C4 Sisal 30 2 20
C5 Sisal 30 0 33
C6 Sisal 30 2 33
C7 Sisal 50 0 0
C8 Sisal 50 2 0
C9 Sisal 50 0 20
C10 Sisal 50 2 20
C11 Sisal 50 0 33
C12 Sisal 50 2 33

Fig. 2. Backscattering electron image (BSE) of sisal fibre surface.

The apparent density, apparent porosity and water absorption
of the composites were carried out according to recommendations
of British Standard BS EN ISO 10545-3 [28]. Apparent porosity is a
measure of the void spaces in a material, and is measured as a frac-
tion, between 0 and 1, or as a percent between 0% and 100%.
The experimental factors such as volume fraction of fibres (30%
and 50%), weight fraction of maleic anhydride (0 wt.% and 2 wt.%)
and weight fraction of silica particles (0 wt.%, 20 wt.% and
33 wt.%) were investigated, providing a full factorial design of
2231, resulting on 12 experimental conditions (see Table 1).
Preliminary tests were conducted in order to set the upper level
of fibre (50%) and silica particles (33 wt.%) in the system, which
provides a suitable surface finishing and lower porosity. A large
percent of natural fibres contributes to an overall lower cost (sisal
being less expensive than the thermoset matrix) and also a more
sustainable composite material in terms of recycling and sourcing. Fig. 3. Stress/strain curve for sisal fibres in tensile test.
Mixture time (5 min), cure time (7 days), room temperature
(22 °C) and the matrix (epoxy resin) were kept constants during analyses. Step (iii) shows a large elongation of fibres which can be
the experiment. The responses investigated during the analysis attributed to the initial fraying effect of fibres. Step (iv) features a
were: bulk density, apparent density, apparent porosity, water significant increase in tensile stress, achieving a maximum close to
absorption, tensile strength, flexural strength and modulus of 1100 MPa. The mean values of tensile strength and modulus
elasticity. of elasticity of the sisal fibres were 905 MPa and 16.4 GPa,
The randomization procedure was adopted during the sample respectively.
fabrication and the experimental tests. This randomization let an The mechanical behaviour of the epoxy resin under tensile
arbitrary ordering of the experimental conditions, avoiding that loading is shown in Fig. 4. The tensile strength and the modulus
non controlled factors affect the responses [25]. of elasticity of the matrix phase were identified as 32 MPa and
Five biocomposite specimens were fabricated for each experi- 0.92 GPa, respectively.
mental condition. Two replicates and 12 experimental conditions Fig. 5 shows the mechanical behaviour of a C1 composite, which
were performed running total of 120 specimens. The replicate con- corresponds to 30% volume fraction of sisal fibres, no silica
sists on the repetition of the experimental condition, which offers particles and addition of maleic anhydride. A similar stress/strain
the estimative of the experimental error of the individual response. curve is observed when compared to the epoxy matrix; however
The extension of this error is important to decide the existence or the tensile strength and the modulus of elasticity were increased
not of significant effects attributed to factor action [25]. The soft- nearly 490% and 622% respectively.
ware Minitab 14 was used to manipulate the data using the Design
of Experiment (DOE) and Analysis of Variance (ANOVA) tools.

3. Results

Fig. 2 shows the backscattering electron image (BSE) at 250 of

magnification of the sisal fibre with no chemical treatment. The
bright area in BSE mode corresponds to denser area, while the dark
spots correspond to porous sections. The grey level variation of the
sisal fibre image shows its heterogeneity, which is an intrinsic
characteristic of natural fibres.
Fig. 3 exhibits the mechanical behaviour of the sisal fibre under
tensile loading. The mechanical behaviour can be approximately
divided in four steps (Fig. 3). At step (i), the stiffness reaches a
maximum of 200 MPa, increasing to 450 MPa during step (ii). The
450 MPa value was used during the following micromechanics Fig. 4. Stress/strain curve for resin epoxy in tensile test.
 L.J. da Silva et al. / Composites: Part B 43 (2012) 3436–3444
Fig. 5. Stress/strain curve for composite fabricated with non-modified epoxy
matrix.
Fig. 6 shows the back scattering electron image of the sisal fibre
composites, its cross section at 50 magnification before testing
(Fig. 6a), and a fractured section of a C1 composite at 180 magnifi-
cation after tensile loading (Fig. 6b). Several types of failure modes
(fibre failure, fibre pull-out and debonding) can be observed.
Fig. 7 exhibits the effective modulus of elasticity for the C1 and
C7 composites (see Table 1). Based on the micromechanics analy-
ses, it can be concluded that the interface condition for C1 can be
classified as quasi-perfect, since the experimental data are closer
to the rule of mixture model (see Fig. 7). However, the interface
condition of the C7 composite can be considered as imperfect, with
the data approaching the Halpin–Tsai approximation.
The results from the Analysis of Variance (ANOVA) are given in
Table 2. If the P-value is less than or equal to 0.05 the effect is con-
sidered significant [25]. An a-level of 0.05 for a level of significance
with a 95% probability indicates the effect being significant. The
main effect of a factor might be interpreted individually only if
there is no evidence that it does not interact with other factors
[25]. When one or more interaction effects of superior order are
significant, the interacting factors might be considered jointly
and not separately. All P-values less than or equal to 0.05 are
underlined in Table 2. The significant effects are shown on main ef-
fect plot or interaction plot. These graphics are not a typical ‘scat-
ter’ plot of data, but illustrate the statistical analysis and provide
the variation on the significant effects. The value of ‘R2 adjust’
shown in the ANOVA (Table 2) indicates the adjustment of the
models is satisfactory. Larger values of adjusted R2 suggest models
of greater predictive ability [25].
Fibre Matrix
(a)
Fig. 6. Backscattering electron images of sisal composite (a) before (b) after testing.
3439
Fig. 7. Experimental and estimated values for modulus of elasticity.
3.1. Bulk and apparent density
The bulk density data varied from 0.66 g/cm3 to 1.21 g/cm3. The
main factor volume fraction of fibre and the interaction of volume
fraction of fibres, silica addition and maleic anhydride were signifi-
cant, showing P-values of 0.000 and 0.035; respectively (Table 2).
The residual plot shown in Fig. 8 validates the normal condi-
tions required to the Analysis of Variance (ANOVA) for the bulk
density results. In general, the residual plots for all responses
investigated in this work showed similar behaviour attending the
normal conditions required. Therefore, the residual plots for the
other responses will not be discussed in this paper.
Fig. 9 shows the interaction effect plot for bulk density. A
percent reduction of 53% was verified when the fibre fraction is in-
creased from 30% to 50% (Fig. 9a). This behaviour can be attributed
to the lower density of the fibres in comparison to the matrix
phase. The maleic anhydride addition also reduced the bulk den-
sity of the composites (Fig. 9b and c), however the silica addition
did not promote significant changes to the bulk density values
(Fig. 9a and c).
The main factors volume fraction of fibres and silica addition sig-
nificantly affected the apparent density of the composites, exhibit-
ing P-values of 0.010 and 0.000; respectively.
Fig. 10 features the main effect plot of the volume fraction of fi-
bres for the apparent density. The increase in the amount of fibres
from 30% to 50% provides a 1.7% increase on apparent density. This
behaviour is opposite to the bulk density (Fig. 9) which shows the
reduction of density as the increase of fibres. This difference can be
explained by the higher porosity achieved when the composites
are manufactured with a large amount of fibres. Higher the
Fractured Debonding
fibre
Pull out
(b)
3440 L.J. da Silva et al. / Composites: Part B 43 (2012) 3436–3444

99

Modulus of elasticity
95

(flexural) (GPa)
90
80

Percent (%)
70
60

97.12%
0.267
0.470
0.002

0.003

0.008
0.000

0.000
50
40
30
20
strength (MPa)

10
5
Flexural

93.21%
1

0.232
0.166
0.840

0.011

0.007
0.000

0.000

-0.10 -0.05 0.00 0.05 0.10

Residual

Fig. 8. Residual plots for the bulk density of the composites.

Modulus of elasticity
(tensile) (GPa)

porosity, higher the open pores and, consequently, lower the vol-
ume of the composites.
80.24%
0.477

0.168

0.381
0.011

0.280
0.022
0.002

The effect of the silica microparticles on the apparent density

can be observed in Fig. 11. When the silica particles were added,
a general increase of 12.4% on density was observed. The silica par-
strength (MPa)

ticles did not affect the bulk density results. This result suggests
that the addition of silica increases the porosity and, consequently,
the apparent density of the material.
Tensile

89.08%
0.354

0.187

0.418
0.094
0.005

0.001
0.000

3.2. Apparent porosity

absorption (%)

The apparent porosity data varied from 17.9% to 36.4%. The

main factors and an interaction effect significantly affected the re-
90.01%
Water

0.447

0.492

0.122
0.635
0.016

0.706
0.000

sponse showing P-values lower than of 0.05 (see Table 2). The main
effect plot of maleic anhydride addition is exhibited in Fig. 12. The
addition of maleic anhydride in the matrix provided an increase
porosity (%)

of 5.8% to the porosity, which implies that it affects the rheology

Apparent

of the system, with the modification of the matrix viscosity.

94.15%
0.445
0.733
0.043
0.037

0.015

0.650
0.000

The interaction effect plot of the factors fraction of fibres and sil-
ica addition is shown in Fig. 13. The increase of the volume fraction
of the fibres from 30% to 50% provided a significant enhancement
density (g/cm3)

of the composites porosity, which can be attributed to the increase

of the surface area, and the resultant deterioration of the perfect
Apparent

wetting of fibres. The porosity of the composites was increased

92.98%
0.584

0.893
0.584

0.327
0.081
0.010
0.000

when 20 wt.% of silica particles were added. The addition of silica

particles provided not only the increase of the surface area of the
system, but also the modification of the matrix viscosity, affecting
P-value 6 0.05
Bulk density

the presence of pores into the matrix and interface areas.

(g/cm3)

96.71%
0.912
0.266

0.814

0.765
0.906

0.035
0.000

3.3. Water absorption

Due to the hygroscopic behaviour of natural fibres, the water

Fraction of fibres  silica addition  maleic anhydride

absorption is one of the most relevant properties in biocomposite

material design. The high level of humidity directly affects the fab-
rication (adhesion between fibres and matrix) and the durability of
the composites reinforced with natural fibres.
The water absorption data varied from 1.6% to 40%. The main
Fraction of fibres  maleic anhydride
Silica addition  maleic anhydride

factors volume fraction of fibres and maleic anhydride were signifi-

Fraction of fibres  silica addition

cant, exhibiting P-values of 0.000 and 0.016, respectively (Table 2).

Analysis of Variance (ANOVA).

The composites fabricated with higher percent of fibres (50%)

Volume fraction of fibres

showed superior water absorption values, due to the strong hydro-

Experimental factors

Interaction of factors

philic behaviour of the sisal fibres (see Fig. 14). This behaviour indi-
Maleic anhydride

cates an unsuitable wetting of fibres by the polymeric matrix,

Silica addition

leaving them more exposed.

Main factors

R2 (adjust)

Fig. 15 shows the effect of the maleic anhydride addition on the

ANOVA

water absorption. For a 2 wt.% of maleic anhydride added, the in-

Table 2

crease of water absorption observed was equal to 11.8%. The water

absorption enhancement can be attributed to the chemical
 L.J. da Silva et al. / Composites: Part B 43 (2012) 3436–3444 3441

0 20 33 0 2

1,1 Volume
Fraction
30
Volume Fraction (%) 0,9
50

(a) (b) 0,7

1,1 Silica
Addition
0
Silica Addition (%) 0,9 20
33
(c)
0,7
Maleic Anhydride (%)

Fig. 9. Main effect plot of fraction of fibres on bulk density of the composites.
Mean of Apparent density (g/cm3)

27.8

Mean of Apparent porosity (%)

1.350
27.6
27.4
1.345
27.2

1.340 27.0
26.8

1.335 26.6
26.4
1.330 26.2
26.0
30 50 0 2
Volume Fraction (%) Maleic Anhydride (%)

Fig. 10. Main effect plot of volume fraction of fibres on apparent density of the Fig. 12. Main effect plot of maleic anhydride on apparent porosity of the
composites. composites.

1.425 36
Mean of Apparent density (g/cm3)

1.400 34
Mean of Aparent porosity (%)

1.375 32
1.350
30
1.325
28 Volume
1.300 Fraction
26 30
1.275 50
24
1.250
0 20 33 22
Silica Addition (%)
20
Fig. 11. Main effect plot of silica addition on apparent density of the composites. 0 20 33
Silica Addition (%)
reaction between the epoxy resin and the maleic anhydride, which
leads to an increase of the matrix polarity. Fig. 13. Interaction effect plot for the volume fraction of fibres and silica addition
on apparent porosity of the composites.

3.4. Tensile strength

The tensile strength of the composites varied from 104.68 MPa
to 170.50 MPa. The main factors volume fraction of fibres and silica
addition were identified as significant, exhibiting P-values of 0.000
and 0.005 respectively (see Table 2). The silica addition and maleic
anhydride interaction was also significant, with a P-value of 0.001
(Table 2).
Fig. 16 shows the main effect plot of the volume fraction of fi-
bres on the tensile strength of the composites. A percent reduction
of 20.6% on strength was identified when the fraction of fibres was
increased from 30% to 50%. This behaviour is in accordance with
the porosity results, with an increase of pores when the volume
fraction was increased and subsequent reduction of the biocom-
posites mechanical strength.
From Fig. 17 it is possible to observe the interaction effect plot
of silica addition and maleic anhydride on the tensile strength re-
sponse. The maleic anhydride, as well as the microsilica addition
contributes to reduce the biocomposite strength. An exception
3442 L.J. da Silva et al. / Composites: Part B 43 (2012) 3436–3444

36 150 Silica
Mean of Water absorption (%)

Addition
34
0

Mean of Tensile strength (MPa)

145
32 20
33
30 140
28
135
26
24 130
22
125
20
30 50 120
Volume Fraction (%)
115
Fig. 14. Main effect plot of the volume fraction of fibres on water absorption of the
composites. Porosity of the composites. 0 2
Maleic Anhydride (%)

Fig. 17. Interaction effect plot of silica and maleic anhydride additions on tensile
strength of the composites.
29.5
Mean of Water absorption (%)

29.0

28.5 3.5. Modulus of elasticity (tensile testing)

28.0
The modulus of elasticity for the composites varied from
27.5 4.53 GPa to 6.21 GPa. The main factors volume fraction of fibres, sil-
ica addition and the interaction between silica addition and maleic
27.0
anhydride were significant, showing P-values of 0.002, 0.011 and
26.5 0.022, respectively.
Fig. 18 shows the main effect plot of fraction of fibres on mod-
26.0 ulus of elasticity. A percent reduction of 9.4% was observed when
0 2
the level of volume fraction of fibres was increased to 50%. The
Maleic Anhydride (%)
stiffness of sisal fibres is superior to the one of the polymeric ma-
Fig. 15. Main effect plot of the maleic anhydride on the water absorption of the trix; however the increase of sisal fibres did not enhance the mod-
composites. ulus of elasticity of the composites, which can be attributed to
weak adhesion fibre–matrix when a high percent of fibres are
added. In addition, this result exhibits a correlation with the other
properties, such as density and mechanical strength, since the
composites manufactured with 30% of sisal fibres exhibited higher
145
Mean of Tensile strength (MPa)

values of density (Fig. 9) and tensile strength (Fig. 16).

140
Fig. 19 features the interaction effect plot for the modulus of
elasticity of the composites. It can be noted that the silica and
135
maleic anhydride additions reduced the overall stiffness of the
composites. However, a combination between 20 wt.% of silica par-
130
ticles and 2 wt.% of maleic anhydride showed an increase of the
elastic modulus. The highest modulus of elasticity was achieved
125 when no silica particles and maleic anhydride were added.

120
Mean of Modulus of elasticity (GPa)

30 50
5.6
Volume Fraction (%)

Fig. 16. Main effect of the volume fraction of fibres on the tensile strength of the 5.5
composites.
5.4

occurs when 20 wt.% of silica particles were added to the matrix 5.3
with 2 wt.% of maleic anhydride. This behaviour suggests a possi-
ble interaction between the silica particles and the maleic anhy- 5.2
dride, improving the matrix-particle interface and consequently
the composite strength. The addition of silica particles and maleic 5.1
30 50
anhydride into laminated composites could enhance the mechani-
Volume Fraction (%)
cal properties under compressive loadings, due to the high stiffness
of silica particles and the improved adhesion between particles and Fig. 18. Main effect plot of the volume fraction of fibres on modulus of elasticity of
matrix. the composites.
 L.J. da Silva et al. / Composites: Part B 43 (2012) 3436–3444 3443

5.9 The interaction effect plot for the flexural strength of the
composites is shown in Fig. 20. The silica particles (Fig. 20a)
Mean of Modulus of elasticity (GPa)

5.8
and maleic anhydride (Fig. 20b) additions decreased the flexural
5.7
Silica
strength of the composites for both fibres fractions. The interac-
Addition tion between 20 wt.% of silica and 2 wt.% of maleic anhydride
5.6
0 exhibited a lower strength decreasing, compared to the compos-
20
5.5 ites fabricated with 33 wt.% of silica and 2 wt.% of maleic anhy-
33
5.4
dride (Fig. 20c).

5.3 3.7. Flexural modulus

5.2
The flexural modulus of the composites varied from 1.29 GPa to
5.1 3.16 GPa. The main factors volume fraction of fibres, silica addition
5.0 and maleic anhydride were significant, exhibiting P-values lower
than 0.05. The interaction of volume fraction of fibres and maleic
0 2 anhydride and the interaction of volume fraction of fibres, silica
Maleic Anhydride (%) addition and maleic anhydride exhibited significant effects, with
P-values of 0.003 and 0.008 respectively.
Fig. 19. Interaction effect plot for the silica and maleic anhydride additions on
modulus of elasticity of the composites.
The interaction effect plot for the flexural modulus of elasticity
is shown in Fig. 21. The addition of silica particles to the polymeric
matrix increased the stiffness of the composites manufactured
with lower level of volume fraction of fibres (30%). A higher flex-
3.6. Flexural strength ural modulus was observed by adding 20 wt.% of silica to the ma-
trix phase. This stiffness increase can be attributed to the higher
The flexural strength data of the composites varied from modulus of elasticity of the matrix during compressive loading,
29.28 MPa to 62.50 MPa. The main factors volume fraction of fibres which was achieved by adding silica microparticles. According to
and maleic anhydride significantly affected the response, with Jia-Lin and Yi-Lieh [20], the addition of 30% of silica nanoparticles
P-values of 0.000. The interaction effect between fraction of fibres, improved the mechanical strength of glass fibre composites sub-
silica addition and maleic anhydride was significant, showing a jected to mechanical compressive state. The enhancement effect
P-value of 0.007. Although a second order interaction has been sig- provided by microsilica was not observed when the composite
nificant, only the third order interactions are analysed [25]. was fabricated with 50% of fibres. This can be explained by the

0 20 33 0 2
60 Volume
Volume Fraction (%) Fraction
50 30
50
40

(a) (b)
60 Silica
Silica Addition (%) Addition
50
0
20
40
33
(c)
Maleic Anhydride (%)

Fig. 20. Interaction effect plot for the fraction of fibres, silica addition and maleic anhydride addition on flexural strength of the composites.

0 20 33 0 2

Volume
2.5 Fraction
Volume Fraction (%) 30
2.0 50

(a) (b) 1.5

Silica
2.5 Addition
Silica Addition (%) 0
2.0 20
33
(c) 1.5

Maleic Anhydride (%)

Fig. 21. Interaction plot for the fraction of fibres, silica addition and maleic anhydride addition on the flexural modulus of the composites.
3444 L.J. da Silva et al. / Composites: Part B 43 (2012) 3436–3444
weak adhesion between fibre/particles and matrix phase. The
addition of particles in the system provided the increase of
contact surface area, consequently increasing the matrix phase
consumption.
The addition of maleic anhydride did not show positive effects
on the flexural modulus of the composites (Fig. 21b), with a general
reduction of the composite stiffness when the volume fraction of
fibre and maleic anhydride were increased. A more relevant mod-
ulus decrease was observed at 33 wt.% of silica microparticles
added (Fig. 21c).
4. Conclusions
A full factorial design was used to investigate a hybrid compos-
ite reinforced with natural fibre and silica microparticles. The main
conclusions from this work are the following:
i. The low level of volume fraction of fibres (30%) provided
not only higher modulus of elasticity and mechanical
strength under tensile and flexural loadings, but also lower
values of apparent density, apparent porosity and water
absorption.
ii. The silica microparticles affected all composite responses,
except for the water absorption. The silica particles were
not efficient as a second reinforced phase under tensile load-
ings. However, the silica particles provided a small incre-
ment to the flexural modulus, which was attributed to the
positive effect under compressive loadings. The apparent
density was increased with the addition of the silica parti-
cles; however the porosity was not affected, mainly for those
composites fabricated with lower level of fibres (30%).
iii. The maleic anhydride addition affected the flexural strength,
flexural modulus, water absorption and apparent porosity of
the composites. The interaction ‘‘silica addition and maleic
anhydride’’ was significant on tensile strength and modulus
of elasticity, while the interaction ‘‘volume fraction of fibres, sil-
ica addition and maleic anhydride’’ was highly correlating with
flexural strength and flexural modulus. Nevertheless, the
additive was not able to enhance the matrix-particles and
matrix-fibres interface, reducing the mechanical strength
and increasing the porosity and water absorption levels of
the composites.
iv. The C4 composite (30% Fibres, 20 wt.% Silica, 2 wt.% Maleic
anhydride) showed superior physic-mechanical properties,
such as: tensile strength (166.4 MPa), modulus of elasticity
(6.2 GPa) and apparent density (1.34 g/cm3).
v. The C5 composite (30% Fibres, 33 wt.% Silica, 0 wt.% Maleic
anhydride) exhibited higher stiffness and mechanical
strength under flexural loadings, such as: flexural strength
(59.5 MPa), flexural modulus (3.3 GPa) and apparent density
(1.41 g/cm3).
vi. The C12 composite (50% Fibres, 33 wt.% Silica and 2 wt.%
maleic anhydride) featured higher porosity (35.95%) and
water absorption (39.7%) making it inadequate for structural
applications. On the opposite, lower values were achieved by
C5 composite (30% Fibres, 33 wt.% Silica, 0 wt.% Maleic anhy-
dride), exhibiting 19.8% of porosity and 17.6% of water
absorption, making it an alternative material for sustainable
engineering applications.
Acknowledgments
The authors would like to thank the financial support of CAPES
and the suppliers, Resiqualy (epoxy resin), Sisalsul (sisal fibres) and
Moinhos Gerais (silica particles).
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