HYBRID POLYMERIC COMPOSITES REINFORCED WITH SISAL FIBRES AND SILICA

MICROPARTICLES

Leandro José da Silva1, Túlio Hallak Panzera1*, Vânia Regina Velloso1, André Luis Christoforo1, Fabrizio
Scarpa2
1
Department of Mechanical Engineering, Federal University of São João Del Rei – UFSJ, Brazil.
2
Advanced Composites Centre for Innovation and Science, University of Bristol, UK.

*panzera@ufsj.edu.br

Abstract: Polymeric composites reinforced with natural fibres have been developed in recent years, ,
showing with significant potential for various engineering applications due to their intrinsic sustainability,
low cost, low weight and mechanical strength. The interfacial adhesion between natural fibres and
polymeric matrices is critical to the composite performance. In order to improve the physical adhesion of
polymeric composites, 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 of polymeric composites reinforced with unidirectional sisal natural fibres. A full
factorial design (2231) was carried out to identify the effect of these factors on the responses: bulk density,
apparent density, apparent porosity, water absorption, mechanical strength and modulus of elasticity. A
microstructure 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.

Keywords: Composites, natural fibres, sisal fibres, design of experiments (DOE).

1. Introduction

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 certification 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 development of new research activities in this
area [2].
The sisal fibres have been investigated as 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 Mallik [4], one of the main difficulties
dealing with natural fibre composites is the adhesion between the fibres and the matrices. The chemical
affinity between the cellulose and the polymeric matrix can be improved by the modification 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], 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 compatibilizing agent.
Not only chemical addictive, but also ceramic minerals have been added into matrix phase to enhance
the mechanical performance 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 nanoparticles into epoxy resin matrix. The weight
fraction of 25% improved the characteristics of the matrix and increased the mechanical performance of
structural laminated composites.
 Rosso et al. [13] evaluated the mechanical strength of epoxy resin, adding 5% in volume of silica
nanoparticles. The silica addition was able to improve the stiffness and tenacity of the polymer,
consequently, increasing the modulus of elasticity (20%) and the fracture tenacity (70%) of the composites.
Isik et al. [14] and Yasmin et al. [15], studied the effect of nanoclay addition from 0 to 10%wt into epoxy
matrix. Isik et al. [14] verified that the nanoclay addition of 1%wt provided higher impact resistance and
tensile strength. However, the modulus of elasticity was gradually increased with the nanoclay addition.
Yasmin et al. [15] identified a percent increase of 80% on the modulus of elasticity when 10%wt of nanoclay
particles were added.
Haque et al. [16] and Ávila et al. [17] concluded that the addition of nanoclay particles between 1 - 2%wt
into glass/epoxy composites enhanced the thermo mechanical properties; however the opposite behaviour
was observed when high percent fractions (over 5%wt), were added. The interlaminar shear, the flexural
strength and the fracture tenacity exhibited a significant percent increase of 44%, 24%, and 23%
respectively, when only 1%wt of nanoclay was added.
The addition of rigid nanoparticles into polymeric matrix can improve the mechanical performance of
laminated composites, mainly under compressive loadings, when the matrix phase is affected by adding
high stiff material. Subramaniyan and Sun [19] investigated the effect of nanoclay additions (0, 3, 5 and
8%wt) into epoxy matrix. The longitudinal compressive strength of the composites did increase by 22%
and 36% with the addition of f 3%wt and 5%wt of nanoclay
Nanosilica particles have been used to reinforce the matrix of glass/epoxy composites. Tsai and Cheng [20]
observed that adding nanosilica particles (at 10, 20 and 30%wt) increased the compressive strength of
laminated composites, with the highest value reached for 30%wt.
Cao and Cameron [21] evaluated the effect of silica particles on the glass fibres surface. The particles
increased the mechanical strength of the composites minimizing the onset and rate of crack propagation,
as a result of the increase in interfacial area.
A micromechanical analysis based on the rule of mixtures can be performed to estimate the composite
properties P* by the individual properties of its components:

P *  Pf  V f  Pm  Vm (1)

In Eq. (1), the individual properties of the components P f and Pm (fibres and matrix respectively) are
then related to the homogenised property P through their volume fractions V f and Vm. The rule of mixture
assumes a perfect interface between phases, and does not take into account the characteristics of the
fibre-matrix interface. Halpin and Tsai introduced two new coefficients to compensate the effect of the
interface condition on the composite effective properties [22] , with the introduction of the coefficients and
 depending on the individual phases and the effective property estimated by rule of mixture model:

Pf ( P *  Pm )  V f  P * ( Pf  Pm )
  (2)
Pm ( Pf  P * )  Vm ( Pf  Pm )

Pf  Pm
 (3)
Pf    Pm

The Halpin-Tsai model to estimate the effective properties of unidirectional composite materials
adjusted to non-perfect interface conditions is finally expressed by the following relation:

Pm (1  ξ  η  Vf )
P*  (4)
1  η  Vf

The modification of polymeric matrices or fibre surfaces with the addition of microparticles and
nanoparticles of ceramic materials has been so evaluated for synthetic fibres, especially glass fibres. This
work investigates the effect of silica microparticles and maleic anhydride addition into polymeric matrix
(epoxy resin) of composites with unidirectional sisal fibres, providing a thorough Design of Experiments
(DOE) and Analysis of Variance (ANOVA) to assess from a rigorous statistical point of view the influence of
the biocomposite components on the mechanical properties of the laminates.

2. Materials and methods

 The polymeric composites were fabricated from modified and non-modified epoxy matrix, supplied by
Resiqualy Company (São Paulo - Brazil), and from dispersive phase of unidirectional sisal fibres supplied
by Sisalsul Company (São Paulo – Brazil). The fibres were extracted, washed and combed by the supplier,
with no chemical treatment The matrix phase was modified by the addition of silica microparticles and
maleic anhydride. The silica microparticles were supplied by Moinhos Gerais Company (Minas Gerais –
Brazil), and classified by sieving process in monomodal range of size 0.037 mm. The resin and the
hardener were combined; afterwards the silica microparticles were added and hand-mixed by 5 min in
room temperature around 22oC.
Tensile tests were carried out according to ASTM D3822-07 [23] and ASTM D638-03 [24] standards to
determine the tensile strength and modulus of elasticity of the fibres and matrix phase, respectively. The
test speeds were set as 3 mm/min for sisal fibres and 2 mm/min for polymeric matrices.
The elastic properties of the fibres and matrices where then used to determine the effective properties
of the composites using Equations (2-4). The fibre-matrix interface condition was also verified by
comparing the Halpi-Tsai relations to the experimental data obtained by tensile tests on the biocomposites
produced.
The biocomposite laminates were fabricated manually by the use of a metal frame in order to align and
fix the fibres. The manual moulding process was carried out upon a glass plate covered by a cloth parting
(Armalon), providing good surface finishing of the lamina. The polymeric matrix (modified and non-
modified) was spread on the fibres by the use of spatula and roller aerator. A glass fibre composite was
used to protect the specimen ends at the clamping area, avoiding premature crack during the tensile
testing (see Figure 1). The scanning electron microscope (SEM), Hitachi T-3000 model, was used to
observe the cross section of the composites. The tensile and flexural testing was carried out based on the
recommendations of British Standard 2747 [26] and ASTM D790 [27], respectively. The mechanical tests were
carried out in Autograph machine monitored by the software namely Topazium, using loading cells of
0.5kN and 2kN.
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 fraction, between 0–1, or as a percent between 0–
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 2 231, 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.
Mixture time (5 minutes), cure time (7 days), room temperature (~22 oC) and the matrix (epoxy resin)
were kept constants during the experiment. The responses investigated during the analysis were: tensile
strength, flexural strength, modulus of elasticity, bulk density, apparent density, apparent porosity and
water absorption.

Table 1. Experimental conditions, full factorial design (2 231).

Type of Volume Maleic Silica addition
Conditions
fibres fraction (%) anhydride (%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
 The randomization procedure was adopted during the sample fabrication and the experimental tests.
This randomization let an arbitrary ordering of the experimental conditions, avoiding that non controlled
factors affect the responses [25].

Figure 1. Tensile test specimens.

Five bio composite specimens were fabricated for each experimental condition. Two replicates and 12
experimental conditions were performed running total of 120 specimens. The replicate consists on the
repetition of the experimental condition, which offers the estimative of the experimental error of the
individual response. The extension of this error is important to decide the existence or not of significant
effects attributed to factor action [25]. The software Minitab 14 was used to manipulate the data using the
Design of Experiment (DOE) and Analysis of Variance (ANOVA) tools.

3. Results

Figure 2 shows the backscattering electron image (BSE) at 250x 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 gray level variation of the sisal fibre image shows its heterogeneity,
which is an intrinsic characteristic of natural fibres.

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

Figure 3 exhibits the mechanical behaviour of the sisal fibre under tensile loading. The mechanical
behaviour can be approximately divided in four steps (Figure 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 analyses. Step (iii) shows a large elongation of fibres which can be attributed to
the initial fraying effect of fibres. Step (iv) features a significant increase in tensile stress, achieving a
maximum close to 1100 MPa. The mean values of tensile strength and modulus of elasticity of the sisal
fibres were 905 MPa and 16.4 GPa, respectively.
 (i) (ii) (iii) (iv)

Figure 3. Stress/strain curve for sisal fibres in tensile test.

The mechanical behaviour of the epoxy resin under tensile loading is shown in Figure 4. The tensile
strength and the modulus of elasticity of the matrix phase were identified as 32 MPa and 0.92 GPa,
respectively.

Figure 4. Stress/strain curve for resin epoxy in tensile test.

Figure 5 shows the mechanical behaviour of a C1 composite, which corresponds to 30% volume
fraction of sisal fibres, no silica particles and addition of maleic anhydride. A similar stress/strain curve is
observed when compared to the epoxy matrix; however the tensile strength and the modulus of elasticity
were increased nearly 490% and 622% respectively.

Figure 5. Stress/strain curve for composite fabricated with non-modified epoxy matrix.

Figure 6 shows the back scattering electron image of the sisal fibre composites, its cross section at 50x
magnification before testing (Figure 6a), and a fractured section of a C1 composite at 180x magnification
after tensile loading (Figure 6b). Several types of failure modes (fibre failure, fibre pull-out and debonding)
can be observed
 Fractured Debonding
Fibre Matrix fibre

Pull out

(a) (b)

Figure 6. Backscattering electron images of sisal composite (a) before (b) after testing.

Figure 7 exhibits the effective modulus of elasticity for the C1 and C7 composites (see Table 1). Based
on the micromechanics analyses, 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 Figure 7).
However, the interface condition of the C7 composite can be considered as imperfect, with the data
approaching the Halpin-Tsai approximation.

Figure 7. Experimental and estimated values for modulus of elasticity.

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 considered significant [25]. A α-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 effect plot or interaction plot. These graphics are not a typical ‘scatter’ plot of data, but
illustrate the statistical analysis and provide the variation on the significant effects. The value of ‘R 2 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].
 Table 2. Analysis of Variance (ANOVA).

ANOVA P-value ≤ 0.05

Modulus Modulus
Water
Bulk Apparent Apparent Tensile of Flexural of
Experimental absorptio
density density porosity strength elasticity strength elasticity
factors n
(g/cm3) (g/cm3) % (MPa) (tensile) (MPa) (flexural)
%
(GPa) (GPa)
Volume fraction
0.000 0.010 0.000 0.000 0.000 0.002 0.000 0.000
of fibres
factorsMain

Silica addition 0.912 0.000 0.043 0.447 0.005 0.011 0.840 0.002

Maleic anhydride 0.266 0.584 0.037 0.016 0.354 0.477 0.000 0.000

Fraction of
fibres*silica 0.814 0.893 0.015 0.492 0.187 0.168 0.011 0.470
addition
Interaction of factors

Fraction of
fibres*maleic 0.906 0.584 0.445 0.706 0.094 0.280 0.232 0.003
anhydride
Silica
addition*maleic 0.765 0.081 0.733 0.635 0.001 0.022 0.166 0.267
anhydride
Fraction of
fibres*silica
0.035 0.327 0.650 0.122 0.418 0.381 0.007 0.008
addition*maleic
anhydride

R2 (adjust) 96.71% 92.98% 94.15% 90.01% 89.08% 80.24% 93.21% 97.12%

3.1 Bulk density

The bulk density data varied from 0.66 g/cm 3 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 significant,
showing P-values of 0.000 and 0.035; respectively (Table 2).
The residual plot shown in Figure 8 validates the normal conditions required to the ANOVA (analysis of
Variance) 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.
99

95
90
80
Percent (%)

70
60
50
40
30
20
10
5

1
-0.10 -0.05 0.00 0.05 0.10
Residual

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

Figure 9 shows the interaction effect plot for bulk density. A percent reduction of 53% was verified when
the fibre fraction is increased from 30% to 50% (Figure 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 density of the composites (Figures 9b and 9c), however the silica addition did not promote significant
changes to the bulk density values (Figures 9a and 9c).

0 20 33 0 2

1,1 Volume
Volume Fraction (%) Fraction
30
0,9
50
53%
0,7
1,1 Silica
(a) (b) Addition
Silica Addition (%)
sa sa 0,9
0
20
33
0,7

Maleic Anhydride (%)

(c)
sa

Figure 9. Main effect plot of fraction of fibres on bulk density of the composites.

The main factors “volume fraction of fibres” and “silica addition” significantly affected the apparent
density of the composites, exhibiting P-values of 0.010 and 0.000; respectively.
Figure 10 features the main effect plot of the volume fraction of fibres for the apparent density. The
increase amount of fibres from 30% to 50% provides a percent increase of 1.7% on apparent density. This
behaviour is opposite to the bulk density (Figure 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 porosity, higher the open pores and, consequently,
lower the volume of the composites.
Mean of Apparent density (g/cm3)

1.350

1.345
1.7%
1.340

1.335

1.330

30 50
Volume Fraction (%)

Figure 10. Main effect plot of volume fraction of fibres on apparent density of the composites.

The effect of the silica microparticles on the apparent density can be observed in Figure 11. When the
silica particles were added, a general increase of 12.4% on density was observed. The silica particles 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.
 1.425

Mean of Apparent density (g/cm3)

1.400

1.375

1.350 12.4%

1.325

1.300

1.275

1.250
0 20 33
Silica Addition (%)

Figure 11. Main effect plot of silica addition on apparent density of the composites.

3.3 Apparent porosity

The apparent porosity data varied from 17.9% to 36.4%. The main factors and an interaction effect
significantly affected the response showing P-values lower than of 0.05 (see Table 2). The main effect plot
of maleic anhydride addition is exhibited in Figure 12. The addition of maleic anhydride in the matrix
provided an increase of 5.8% to the porosity, which implies that it affects the rheology of the system, with
the modification of the matrix viscosity.
27.8
Mean of Apparent porosity (%)

27.6

27.4

27.2
5.8%
27.0

26.8

26.6

26.4

26.2

26.0
0 2
Maleic Anhydride (%)

Figure 12. Main effect plot of maleic anhydride on apparent porosity of the composites.

The interaction effect plot of the factors “fraction of fibres and silica addition” is shown in Figure 13. The
increase of the volume fraction of the fibres from 30% to 50% provided a significant enhancement of the
composite´s porosity, which can be attributed to the increase of the surface area, and the resultant
deterioration of the perfect wetting of fibres. The porosity of the composites was increased 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 the presence of pores into the
matrix and interface areas.
 36 Volume
Fraction

Mean of Aparent porosity (%)

34 30
50
32

30 75.7%
28

26

24

22

20
0 20 33
Silica Addition (%)

Figure 13. Interaction effect plot for the volume fraction of fibres and silica addition on apparent porosity of
the composites.

3.4 Water absorption

Due to the hygroscopic behaviour of natural fibres, the water absorption is one of the most relevant
properties in biocomposite material design. The high level of humidity directly affects the fabrication
(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 factors “volume fraction of fibres” and
“maleic anhydride” were significant, exhibiting P-values of 0.000 and 0.016, respectively (Table 2).
The composites fabricated with higher percent of fibres (50%) showed superior water absorption
values, due to the strong hydrophilic behaviour of the sisal fibres (see Figure 14). This behaviour indicates
an unsuitable wetting of fibres by the polymeric matrix, letting them more exposure to moisture.

36
Mean of Water absorption (%)

34

32

30 77.9%
28

26

24

22

20

30 50
Volume Fraction (%)

Figure 14. Main effect plot of the volume fraction of fibres on water absorption of the composites.

Figure 15 shows the effect of the maleic anhydride addition on the water absorption. For a 2 % wt of
maleic anhydride added, the increase of water absorption observed was equal to 11.8 %. The water
absorption enhancement can be attributed to the chemical reaction between the epoxy resin and the
maleic anhydride, which leads to an increase of the matrix polarity.
 29.5

Mean of Water absorption (%)

29.0

28.5
11.8%
28.0

27.5

27.0

26.5

26.0
0 2
Maleic Anhydride (%)

Figure 15. Main effect plot of the maleic anhydride on the water absorption of the composites.

3.5 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).
Figure 16 shows the main effect plot of the volume fraction of fibres 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 biocomposites
mechanical strength.

145
Mean of Tensile strength (MPa)

140

135 20.6%

130

125

120

30 50
Volume Fraction (%)

Figure. 16. Main effect of the volume fraction of fibres on the tensile strength of the composites.

From Figure 17 it is possible to observe the interaction effect plot of “silica addition and maleic
anhydride” on the tensile strength response. The maleic anhydride, as well as the micro silica addition
contributes to reduce the biocomposite strength. An exception occurs when 20%wt of silica particles were
added to the matrix with 2%wt of maleic anhydride. This behaviour suggests a possible interaction
between the silica particles and the maleic anhydride, improving the matrix-particle interface and
consequently the composite strength. The addition of silica particles and maleic anhydride into laminated
composites could enhance the mechanical properties under compressive loadings, due to the high
stiffness of silica particles and the improved adhesion between particles and matrix.
 150 Silica

Mean of Tensile strength (MPa)

Addition
145 0
20
33
140
29.5%
135

130
17.6%
125

120

115
0 2
Maleic Anhydride (%)

Figure 17. Interaction effect plot of silica and maleic anhydride additions on tensile strength of the
composites.

3.6 Modulus of elasticity (tensile testing)

The modulus of elasticity for the composites varied from 4.53 GPa to 6.21 GPa. The main factors
“volume fraction of fibres”, “silica addition” and the interaction between “silica addition and maleic
anhydride” were significant, showing P-values of 0.002, 0.011 and 0.022, respectively.
Figure 18 shows the main effect plot of fraction of fibres on modulus of elasticity. A percent reduction of
9.4% was observed when the level of volume fraction of fibres was increased to 50%. The stiffness of sisal
fibres is superior to the one of the polymeric matrix; however the increase of sisal fibres did not enhance
the modulus 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 values of density (Figure 9) and tensile strength (Figure 16).
Mean of Modulus of elasticity (GPa)

5.6

5.5

5.4

9.4%
5.3

5.2

5.1
30 50
Volume Fraction (%)

Figure 18. Main effect plot of the volume fraction of fibres on modulus of elasticity of the composites

Figure 19 features the interaction effect plot for the modulus of elasticity of the composites. It can be
noted that the silica and maleic anhydride additions reduced the overall stiffness of the composites.
However, a combination between 20%wt of silica particles and 2%wt of maleic anhydride showed an
increase of the elastic modulus. The highest modulus of elasticity was achieved when no silica particles
and maleic anhydride were added.
 5.9

Mean of Modulus of elasticity (GPa)

Silica
Addition
5.8
0
5.7 20
33
5.6
5.5
7.96%
5.4

5.3
5.2
5.1

5.0

0 2
Maleic Anhydride (%)

Figure 19. Interaction effect plot for the silica and maleic anhydride additions on modulus of elasticity of the
composites.

3.7 Flexural strength

The flexural strength data of the composites varied from 29.28 MPa to 62.50 MPa. The main factors
“volume fraction of fibres” and “maleic anhydride” significantly affected the response, with P-values of
0.000. The interaction effect between “fraction of fibres, silica addition and maleic anhydride” was
significant, showing a P-value of 0.007. Although a second order interaction has been significant, only the
third order interactions are analysed [25].
The interaction effect plot for the flexural strength of the composites is shown in Figure 20. The silica
particles (Figure 20a) and maleic anhydride (Figure 20b) additions decreased the flexural strength of the
composites for both fibres fractions. The interaction between 20%wt of silica and 2%wt of maleic anhydride
exhibited a lower strength decreasing, compared to the composites fabricated with 33%wt of silica and
2%wt of maleic anhydride (Figure 20c).

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

60 Silica
(a) (b) Addition
Silica Addition (%)
sa
50
sa 0
20
40
33

Maleic Anhydride (%)

(c)
sa

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

3.8 Flexural modulus

The flexural modulus of the composites varied from 1.29 GPa to 3.16 GPa. The main factors “volume
fraction of fibres”, “silica addition” and “maleic anhydride” were significant, exhibiting P-values lower than
0.05. The interaction of “volume fraction of fibres and maleic anhydride” and the interaction of “volume
fraction of fibres, silica addition and maleic anhydride” exhibited significant effects, with P-values of 0.003
and 0.008 respectively.
The interaction effect plot for the flexural modulus of elasticity is shown in Figure 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 flexural modulus was observed by adding 20%wt of silica
to the matrix phase. This stiffness increase can be attributed to the higher modulus of elasticity of the
matrix during compressive loading, which was achieved by adding silica microparticles. According to Tsai
and Cheng [20], the addition of 30% of silica nanoparticles improved the mechanical strength of glass fibre
composites subjected to mechanical compressive state. The enhancement effect provided by microsilica
was not observed when the composite was fabricated with 50% of fibres. This can be explained by the
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 (Figure 21b), with a general reduction of the composite stiffness when the volume fraction of
fibre and maleic anhydride (%wt) were increased. A more relevant modulus decrease was observed at
33wt% of silica microparticles added (Figure 21c).

0 20 33 0 2

Volume
2,5 Fraction
Volume Fraction (%) 30
2,0 50

1,5

(a) (b) Silica

2,5 Addition
sa
Silica Addition (%)
sa 0
2,0 20
33
1,5

(c)
Maleic Anhydride (%)
sa

Figure 21. Interaction plot for the fraction of fibres, silica addition and maleic anhydride addition on the
flexural modulus of the composites.

4. Conclusions

A full factorial design was used to investigate a hybrid composite reinforced with natural fibre and
silica microparticles. The main conclusions from this work are the following:
i. The lower level of volume fraction of fibres (30%) provided not only higher modulus of elasticity
and mechanical strength (on tensile and flexural tests), 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 loadings. However, the silica
particles provided a small increment 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 particles;
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,
silica 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 (166.4MPa), modulus of elasticity (6.2GPa) 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 (59.5MPa), flexural modulus
(3.3GPa) 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
anhydride), 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 powder).

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