Composites: Part B 68 (2015) 14–21

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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

The effect of alkaline treatment on mechanical properties of kenaf fibers

and their epoxy composites
V. Fiore a,⇑, G. Di Bella b, A. Valenza a
a
Department of ‘‘Ingegneria Civile, Ambientale, Aerospaziale, dei Materiali’’, University of Palermo, Viale delle Scienze, 90128 Palermo, Italy
b
CNR ITAE, Salita S. Lucia sopra Contesse 5, 98126 Messina, Italy

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

Article history: In this work, kenaf fibers were pre-treated in a NaOH solution (6% in weight) at room temperature for two
Received 19 May 2014 different periods (48 and 144 h). The chemical treatment of kenaf fibers for 48 h allowed to clean their
Received in revised form 4 August 2014 surface removing each impurity whereas 144 h of immersion time had detrimental effect on the fibers
Accepted 7 August 2014
surface and, consequently, on their mechanical properties.
Available online 17 August 2014
Untreated and NaOH treated kenaf fibers (i.e. for 48 h) were also used as reinforcing agent of epoxy
resin composites. The effect of the stacking sequence (i.e. using unidirectional long fibers or randomly
Keywords:
oriented short fibers) and the chemical treatment on the static mechanical properties was evaluated
A. Wood
B. Adhesion
showing that the composites exhibit higher moduli in comparison to the neat resin. As regards the
B. Fiber/matrix bond strength properties, only the composites reinforced with unidirectional layers show higher strength than
C. Statistical properties/methods the neat resin. Moreover, the alkali treatment increased the mechanical properties of the composites, due
D. Mechanical testing to the improvement of fiber–matrix compatibility.
The dynamic mechanical analysis showed that the storage and the loss moduli are mainly influenced
by the alkali treatment above the glass transition temperature. Moreover, the alkali treatment led to a
notable reduction of tan d peaks in addition to significant shifts of tan d peaks to higher temperatures
whereas the stacking sequence did not influence the trends of storage modulus, loss modulus and damp-
ing of the composites.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction and biodegradable characteristics of natural fibers help their ulti-

In the last few years, the depletion of petroleum resources, the
increasing awareness toward the environment and the great con-
cern for greenhouse effect have stimulated industries (i.e. automo-
tive, building, nautical) to replace conventional synthetic materials
using sustainable ones. In reference to this issues, green compos-
ites, made of renewable agricultural and forestry feedstock, repre-
sent a suitable alternative to synthetic fiber reinforced composites
[1].
If compared with conventional organic fibers (i.e. glass and car-
bon fibers), natural fibers provide many advantages, such as abun-
dance (and therefore low cost), biodegradability, flexibility during
processing thus reducing machine wear, minimal health hazards,
high sound absorption, fracture resistance, enhanced energy recov-
ery, carbon dioxide sequestration, low density, acceptable specific
properties and ease of separation [2,3]. Moreover, the renewable
⇑ Corresponding author. Tel.: +39 091 23863721; fax: +39 091 7025020.
E-mail addresses: vincenzo.fiore@unipa.it (V. Fiore), guido.dibella@itae.cnr.it
(G. Di Bella).
mate disposal by composting or incineration, which are not possi-
ble with most industrial fibers. In addition, they cause less dermal
and respiratory irritation than glass fibers.
Natural fibers reinforced composites are primarily used as low
cost materials that have useable structural properties [2]. They
have been used in applications such as automotive interior linings,
upholstery stuffing, egg-boxes and electronics packaging [4]. Thus,
the use of natural fibers in commercial composites has been lim-
ited to reinforcement of non-structural components.
The main drawbacks in use of natural fibers as reinforcement of
polymeric matrices are the poor compatibility between fibers and
matrix, and high moisture absorption of fibers. These features
result in a low ability to transfer stress from matrix to fiber in addi-
tion to dimensional changes of fibers that may lead to microcrack-
ing of composites, thus reducing their mechanical properties.
Surface treatments are often used to improve performances of
natural fiber reinforced composites by bridging the gap in compat-
ibility between hydrophilic fibers and hydrophobic matrices. Nat-
ural fibers can be modified either by physical or chemical means.
Physical treatments change structural and surface properties of

http://dx.doi.org/10.1016/j.compositesb.2014.08.025
1359-8368/Ó 2014 Elsevier Ltd. All rights reserved.
 V. Fiore et al. / Composites: Part B 68 (2015) 14–21
fibers and thereby influence their mechanical bonding to polymers.
Chemical methods of altering natural fibers involve introducing a
material compatible with both fibers and matrix.
In particular, alkaline treatment, also called mercerization, is a
well-known method to increase interfacial bonding strength
between ligno-cellulosic fibers and thermoset resins [5]. Merceri-
zation reduces fiber diameter and removes lignin, hemicellulose,
wax and oils covering the surface of the fiber [6]. Moreover, it is
well-know that mercerization leads both to the development of a
rough surface topography that results in better fiber–matrix inter-
face adhesion and to increment of the number of cellulose exposed
on fiber surface, so that the number of bonding between fiber sur-
face and polymer increases too [7].
Several researchers employed different percentage of alkali
solution (5%, 7%, 10% and 15% in weight) and immersion times
(1, 3 and 24 h) to treated natural fibers [8–13]. In particular,
Edeerozey et al. [12] used different concentrations (i.e. 3%, 6%
and 9%) of NaOH to pre-treat kenaf fibers for 3 h at room temper-
ature. For the 6% NaOH concentration, two different conditions
were used (i.e. immersion at room temperature and immersion
in water bath at 95 °C). The authors reported that pre-treatment
of kenaf fibers in 6% NaOH solution in water bath leads to the best
results.
In the paper of Mahjoub et al. [13], kenaf fibers were pre-treated
in a NaOH solutions with different concentration (i.e. 5%, 7%, 10%
and 15% in weight), for 3 and 24 h at room temperature. They sta-
ted that the 5% alkali solution was the best for kenaf fiber treat-
ment because of causing no tension on fiber texture and
structure as compared to 10% and 15% alkali solutions.
There is a wide range of natural fibers which can be applied as
reinforcements or fillers thanks to their properties and availability;
i.e. flax, hemp, jute, kenaf and sisal. However, kenaf (Hibiscus cann-
abinus L.) offers advantages as a fiber crop including fast growth in
a variety of climatic conditions and subsequently fast accumula-
tion of carbon dioxide [14]. It has been cultivated since around
4000 BC for food and fiber extracting purposes. Kenaf belongs to
the Malvaceae, a family noteworthy for both its economic and hor-
ticultural importance. In particular, it has a high growth rate, up to
10 cm/day under optimum ambient conditions [15], rising to a
height of more than 3 m and a base diameter of 3–5 cm in
3 months [16]. It can then yield a dry weight of 6000–10,000 kg/
ha year (new varieties may reach 30,000 kg/ha year).
Kenaf fiber, obtained from processing the bark of the kenaf
plant, exhibits low density, non-abrasiveness during processing,
high specific mechanical properties and biodegradability. It is sim-
ilar to jute and can be used either as an alternative to, or in admix-
ture with jute. Moreover, kenaf was priced at $400 per tonne in
1995 and from $278 to $302 per tonne in 2000 [17] and, from
the viewpoint of energy consumption, it takes 15 MJ of energy to
produce 1 kg of kenaf; whereas it takes 54 MJ to produce 1 kg of
glass fiber [15]. It has been largely used as reinforcement of
thermoplastic polymers [18,19] and recently also of thermoset
polymers [20,21]. Moreover, kenaf fibers have been used as non-
woven mats in the automotive, textiles, fiberboard, civil and
electronic industries [22–26].
In the present work, kenaf fibers were treated with 6% NaOH
solution for two immersion times: 48 h and 144 h. The morpholog-
ical changes were examined using scanning electron microscopy
and the mechanical properties were evaluated through single fiber
tensile tests. A reliability analysis of the experimental data was
performed using a two-parameter Weibull distribution.
Untreated and NaOH treated kenaf fibers were also used as rein-
forcement of epoxy resins. In particular, two composites were real-
ized using vacuum bagging technique: i.e. the first one reinforced
by six MAT layers (i.e. randomly oriented short fibers); the second
one by six UD layers (i.e. oriented long fibers). Tensile and three
15
point bending tests were performed to evaluate the mechanical
properties of the composites.
Static mechanical properties were obtained by carrying out ten-
sile and three point bending tests. Dynamic characterization was
carried out in tensile mode at 1 Hz frequency by heating the com-
posites from room temperature to 140 °C. To evaluate the void con-
tent of the manufactured composites, their real and theoretical
densities were compared.
2. Materials and methods
2.1. Preliminary studies of kenaf fibers
2.1.1. Chemical pre-treatments
Table 1 reports the main properties of kenaf fibers, supplied by
Kenaf Eco Fibres Italia S.p.a., used in this work. Preliminary studies
on kenaf fibers were performed in order to evaluate the influence
of the alkali pre-treatment both on both the morphology and the
mechanical properties of the fibers. In particular, kenaf fibers were
pre-treated in a NaOH solution (6% in weight) at room temperature
for two immersion times: i.e. 48 h and 144 h. The fibers were
washed thoroughly with distilled water to remove the excess of
NaOH and then dried at room temperature for 48 h followed by
oven drying at 100 °C for 6 h.
Scanning electron microscopy (SEM) analysis was performed by
scanning the surfaces of the fibers using a SEM Phenom World
model Phenom Pro X. Before analysis, each fiber was cut to a height
of 10 mm, coated with gold and rubbed upon a 25 mm diameter
aluminum disc.
2.1.2. Mechanical characterization
In order to evaluate the effect of the chemical pre-treatments on
the mechanical properties of fibers, tensile tests were performed
on kenaf fibers treated in NaOH solution for 48 h and 144 h.
Untreated fibers (i.e. raw) were also tested as control.
For each condition investigated, forty fibers were mechanically
tested in tension, according to ASTM standard [27] using a Zwick-
Roell Universal Testing Machine (UTM) model Z005, equipped with
a load cell of 200 N. The strain rate was set equal to 1 mm/min and
gage length to 30 mm. The results were analyzed statistically using
an ad-hoc code developed in MatlabÒ environment, as suggested in
the literature about the mechanical tests of natural fibers. In fact, it
is well know that the results of the tensile tests on single lignocel-
lulosic fibers are difficult to analyze since a high scatter is
observed. This scatter can be mainly related to several factors as
test parameters/conditions, area measurements and plant charac-
teristics (i.e. the source and age of the plant, the processes of fiber
extraction and the presence of defects) [28]. For these reasons, a
statistical approach is required to evaluate the mechanical
properties.
Table 1
Characteristics of kenaf fibers.
Length (mm) 40 (short) 300 (long)
Diameter (lm) 55–60
Density (g/cm3) 1.2
Chemical composition
Lignin (%) 20.1
Cellulose (%) 44.4
Ash (%) 4.6
Mechanical properties
Tensile modulus (GPa) 40
Ultimate stress (MPa) 350–600
Elongation at break (%) 2.5–3.5
16 V. Fiore et al. / Composites: Part B 68 (2015) 14–21
Hence, the experimental data obtained by mechanical charac-
terization were statistically analyzed using a two-parameter Wei-
bull distribution, a method widely used to analyze mechanical
properties of lignocellulosic fibers [29–32].
2.2. Composite and layer preparation
Two kinds of layer, having areal weight equal to 450 g/m2, were
used as reinforcement of the composites. The first one (Fig. 1a), in
the next named MAT, consists of randomly oriented fibers with
length of 40 mm. The second one (Fig. 1 b), in the next UD, is made
of fibers, with length 300 mm, oriented along one direction. Each
layer was prepared with the following procedure:
– a specific amount of commercial fibers was weighted in order to
obtain the specific areal weight (i.e. 450 g/m2);
– the fibers were randomly dispersed (i.e. to produce a MAT layer)
or oriented along one direction (i.e. UD layer) between the
metal plates of a Carver laboratory press;
– finally, the fibers were slightly wetted and hot-pressed
(P = 300 bar, T = 150 °C, time = 10 min).
The composites studied in this work were constituted by six
MAT or UD layers of kenaf fibers in a matrix of epoxy resin (i.e.
SP 106). All the composites were produced with a single lamination
using the vacuum bagging technique. This method involves an ini-
tial hand lay-up phase and then the polymerization of the matrix in
a flexible bag in which negative pressure is reached by a vacuum
pump. The cure cycle was performed at room temperature for
24 h following by a post-cure step at 60 °C for 8 h.
2.2.1. Assessment of voids content
The real densities qr of the composites were measured using a
helium pycnometer. For each sample analyzed, ten measures were
carried out and average values of density were recorded. All devi-
ation standards measured were lower to 0.001 g/cm3.
On the other hand, the theoretical densities were calculated as
given by Eq. (1) [33]:
qm  qp
qt ¼ ð1Þ
wm  qp þ wp  qm
where qm and wm represent the density and the weight content of
epoxy matrix; qp and wp the density and the weight content of
kenaf fibers. The volume voids content (tv) of the manufactured
composites was calculated using the Eq. (2):
qt  qr
tv ¼ ð2Þ
qt
Voids are among the most common manufacturing-induced
defects in composites, mainly due to the air entrapment during
the composite manufacturing and to the moisture absorbed when
Fig. 1. Kenaf layers used in this work: (a) MAT; and (b) UD.
the material is stored and processed. Higher voids content bring to
low resistance to water penetration in addition to both increased
variation and poor strength properties of composites [34,35]. In
particular, a good composite should have less than 1% voids,
whereas a poorly made composite can have up to 5% voids content
[33].
2.2.2. Mechanical characterization
Tensile tests were carried out according to ASTM standards [36]
using a Zwick-Roell Universal Testing Machine model Z005,
equipped with a load cell of 5 kN, with a cross-head speed of
2 mm/min. For each composite, five prismatic samples with
dimensions 15 mm  250 mm were tested. Three point bending
tests were carried out according to ASTM standard [37] using a
LLOYD Instruments Universal Testing Machine model LR10K,
equipped with a 10 kN load cell. For each composite, five prismatic
samples with dimensions 100 mm  12.5 mm were tested. The
span length was equal to 80 mm and cross-head speed to 2 mm/
min.
Dynamic mechanical analysis was carried out using a Metravib
dynamic mechanical analyzers model DMA+150, equipped with a
load cell of 150 N. The experiments were performed under the ten-
sile mode at a frequency of 1 Hz. Prismatic samples of size
16 mm  4 mm  1 mm were used. The tests were conducted at
temperatures from room to 140 °C with heating rate of 2 °C/min,
under nitrogen atmosphere.
3. Results and discussion
3.1. Kenaf fibers
3.1.1. Morphology of kenaf fibers
Fig. 2 shows the SEM micrographs (750) of the kenaf fibers. It
is possible to observe that:
1. the untreated fibers clearly show impurities on the surface that
can influence the adhesion properties with the resin in the com-
posites manufacturing (see Fig. 2a);
2. the fibers, after 48 h in the NaOH solution, do not show impuri-
ties due to the cleaning effect of the NaOH solution (see Fig. 2b);
3. the fibers after 144 h are strongly damaged (see Fig. 2c): in
some zones there are cracks propagating along the axis of the
fiber. This phenomenon is due to the increase of the soaking
time in the NaOH solution that damages the surface of the
fibers, thus resulting in lower tensile strength [39].
3.1.2. Mechanical characterization
Fig. 3 shows the Weibull distributions for (a) tensile strength
and (b) Young’s of untreated kenaf fibers. It can be seen that this
model provides a good fitting of the data for both mechanical
properties.
 V. Fiore et al. / Composites: Part B 68 (2015) 14–21
Fig. 2. SEM analysis: (a) untreated fibers; (b) after 48 h in NaOH solution; and (c) after 144 h.
Weibull fitting was performed also for tensile properties of
NaOH treated kenaf fibers. Also in these two cases, Weibull distri-
bution provides a reasonable approximation of the experimental
data. For sake of conciseness, the Weibull distributions for the
mechanical properties of the treated fibers are not shown.
The characteristic statistical parameters for tensile properties of
the untreated and NaOH treated fibers are reported in Table 2. The
Weibull shape and scale parameters are the characteristic values of
the distribution. In particular, the shape parameter indicates the
reliability of the data. A shape of 3 approximates a normal curve.
A shape between 2 and 4 is still fairly normal. A low value for
shape, say 1.25, gives a right-skewed curve. A high value for shape,
say 10, gives a left-skewed curve. Moreover, higher shape parame-
ter is equivalent to lower coefficient of variation in a normal distri-
bution. The scale parameter, or characteristic life, is the 63.2
percentile of the data. The scale defines the position of the Weibull
curve.
Fig. 3. Weibull distribution for (a) tensile stress and (b) Young’s modulus of
untreated fibers.
17
From Table 2, it is evident that the fibers, after 48 h in the NaOH
solution, show tensile properties (i.e. both tensile strength and
modulus) slightly lower than untreated fibers. Vice versa, the ten-
sile properties of kenaf fibers strongly decrease after 144 h of alkali
treatment. Consequently, this duration of alkali treatment is not
recommended.
Moreover, it is worth noting that kenaf fibers treated in alkali
solution for 48 h show the highest values of the shape parameters
(i.e. both for tensile strength and modulus), thus evidencing the
lowest variability of the data among the fibers investigated.
Hence, the morphological observations and the mechanical
characterizations of kenaf fibers show that the pre-treatment of
fibers in 6% NaOH solution for 48 h represents the best choice.
For these reasons, only kenaf fibers pre-treated in NaOH solution
for 48 h were used in this work to manufacture the composites.
The composites reinforced with untreated fibers were also manu-
factured and tested, as control.
3.2. Composites
All the composites prepared in this study are presented in
Table 3. Designation of a composite includes two specifications:
i.e. regarding the kind of fabric used and the chemical pre-treat-
ment. For instance, ‘‘TK-MAT’’ means that this composite consists
of six MAT layer of kenaf fibers pre-treated in 6% NaOH solution
for 48 h (TK).
It is worth noting that the alkali treatment of the fibers does not
influence the thickness, the fibers weight fraction Pf, the real den-
sity and the void content of the composites.
On the other hand, the thickness and fibers weight fraction
slightly vary whereas the void content strongly decreases by
changing the kind of layer.
3.2.1. Tensile tests
Fig. 4 shows the tensile properties of composites. All of the com-
posites show higher tensile moduli than the neat epoxy resin. In
particular, the tensile modulus strongly increases using as rein-
forcement UD layers of kenaf fibers. In particular, the UTK-UD
and TK-UD composites show tensile moduli about 376% and
393% higher than epoxy resin, respectively.
The use of MAT layers as reinforcement of epoxy resin has a
lower influence on the composite stiffness: i.e. the UTK-MAT and
TK-MAT composites show tensile moduli about 73% and 93%
higher than epoxy resin, respectively.
Despite the positive effect on tensile modulus, the use of MAT
layers involves detrimental effects on tensile strength of compos-
ites: i.e. the UTK-MAT and TK-MAT composites show tensile
strength about 34% and 10% lower than epoxy resin, respectively.
On the other hand, the UTK-UD and TK-UD composites have tensile
strength about higher (i.e. 100% and 122% respectively) than the
epoxy resin.
18 V. Fiore et al. / Composites: Part B 68 (2015) 14–21

Table 2
Characteristic statistical parameters for tensile properties of kenaf fibers.

Untreated fibers Treated NaOH 48 h fibers Treated NaOH 144 h fibers

r E r E r E
Shape parameter 3.75 4.94 6.09 6.65 1.59 1.86
Scale parameter 556.45 43.90 519.52 40.51 312.94 26.40
Mean value 501.56 40.32 483.16 37.82 280.56 23.56
Standard deviation 150.98 9.27 89.11 6.78 182.26 12.94
Median 471.71 41.84 480.98 38.23 240.32 23.13
IQR 248.70 9.22 126.10 7.67 233.16 23.44
Failure 30 30 30 30 30 30
Censor 0 0 0 0 0 0
Correlation 0.97 0.98 0.97 0.98 0.97 0.98

Table 3
Kenaf/epoxy laminates investigated.

Sample UTK-MAT TK-MAT UTK-UD TK48-UD

Thickness (mm) 4.70 ± 0.05 4.72 ± 0.08 4.57 ± 0.11 4.60 ± 0.18
Pf (%) 48.3 48.3 48.6 48.6
Theoretical density (g/cm3) 1.19336 1.19336 1.19340 1.19340
Real density (g/cm3) 1.10134 1.10213 1.17320 1.17515
Voids content (%) 7.71 7.65 1.69 1.53

Fig. 4. Tensile properties of composites.

By comparing the fabrics used as reinforcement, it is clear that
the UD composites show better tensile properties than the MAT
ones, regardless of chemical treatment.
These results are due to the different kind of fabrics used in
addition to void contents within the manufactured composites.
In particular, the fibers, arranged along the load direction in the
UD composites, give higher stiffness and strength than those of
the MAT composites (i.e. reinforced with short fibers randomly
oriented).
Moreover, as widely known by literature [34,35], the strength
properties can be related to the voids content within the manufac-
tured composites. It is worth to note that both MAT composites
show void contents slightly higher than 7% (Table 3). On the other
hand, the UD composites are characterized by lower void contents
(i.e. between 1% and 2%), thus leading to reduction of their tensile
strength.
Moreover, it is worth noting that the treatment of kenaf fibers
in NaOH solution influences the tensile properties of composites
whichever fabric is used as reinforcement. In particular, the TK-
MAT composites show tensile strength and modulus 36% and
12% higher than UTK-MAT composites. On the other hand, the
chemical pre-treatment of kenaf fibers leads to increments of
11% and 3.5% in tensile strength and modulus of the UD compos-
ites, respectively. These results confirm that the treatment of
hydrophilic kenaf fibers in the 6% NaOH solution for 48 h improve
their compatibility with the hydrophobic polymer used as matrix.
Therefore, the slightly decrease of mechanical properties of the
treated fibers than the untreated ones, observed previously, is
widely compensated by the cleaner surface of the treated fiber that
promotes a better adhesion between reinforcement and matrix
with a consequent improvement of the mechanical properties of
the composite.
Nevertheless, as discussed above, the MAT composites show
lower tensile strength than neat resin even if fiber chemical treat-
ment was performed. This means that, if the fibers are randomly
dispersed in a polymer matrix, they act as stress concentrators
leading to premature failures of composites. Similar results have
been obtained for epoxy composites reinforced with lignocellulosic
particles [38]. Overall, the UD composites reinforced with chemical
treated kenaf fibers show the best tensile performance.
Regarding the failure modes of composites reinforced with
alkali treated fibers, both TK-UD and TK-MAT composites show
tensile yielding of all their layers at the same time, as evidenced
by the stress drop shown in Fig. 5. This is predominantly linear,
with the crack path following the plane perpendicular to the load
direction.
The composites reinforced with untreated kenaf fibers, regard-
less of fabric used, show same failure mode. The stress–strain
 V. Fiore et al. / Composites: Part B 68 (2015) 14–21
Fig. 5. Typical stress/strain curves of TK composites obtained from tensile tests.
curves of the UTK-MAT and UTK-UD composites are not reported
for sake of brevity.
3.2.2. Flexural tests
The flexural properties of composites are shown in Fig. 6. The
results revealed are similar to those of tensile test. In particular,
the three point bending tests lead to the following results:
– all the composites show higher flexural moduli than neat epoxy
resin;
– the flexural modulus strongly increases using UD layers as rein-
forcement whereas the use of MAT layers has a lower influence
on flexural stiffness;
– the use of MAT layers involves detrimental effects on flexural
strength of composites since the fibers randomly disposed act
as stress concentrators leading to premature failures of compos-
ites, regardless of chemical treatment;
– the alkali treatment of kenaf fibers influences the flexural prop-
erties of composites whichever fabric is used as reinforcement,
due to improvement of the fibers–matrix compatibility;
– the alkali treatment higher influences flexural strength than
flexural modulus;
– the UD composites reinforced with alkali pre-treated kenaf
fibers show the best flexural properties.
Also in this case, the results confirm how the treatment of the
fibers improves the compatibility between reinforcement and
matrix.
Regarding the failure modes of composites reinforced with
alkali treated fibers, the TK-UD composites show an initial tensile
failure of the lower layers of composites, as evidenced by the initial
stress drop (1) shown in Fig. 7, followed by several delamination
phenomena (2) occurred at interfaces between adjacent layers.
Fig. 6. Flexural properties of composites.
19
Fig. 7. Typical stress/strain curves of TK composites obtained from flexural tests.
On the other hand, three TK-MAT composites fail initially for
tensile yielding of lower layers and immediately the crack propa-
gates through the thickness up to reach the upper side of the struc-
ture, leading to a catastrophic collapse of composite. This failure
mechanism is evidenced by the sudden stress drop that character-
izes the stress–strain curve of TK-MAT (a) sample in Fig. 7.
Also the last two composites (i.e. those with the best flexural
properties among TK-MAT samples) show tensile yielding of lower
layers but in these cases, the crack remains localized in the lower
zone of structure. Then, as in the case of the TK-UD samples,
delamination failures happen. The stress–strain curve of TK-MAT
(b) sample evidences the mechanisms happened.
The composites reinforced with untreated kenaf fibers, regard-
less of fabric used, exhibit tensile yielding of lower layers with the
following propagation of crack through thickness. The stress–strain
flexural curves of the UTK-MAT and UTK-UD composites are not
showed for sake of brevity.
As in the tensile case, the better flexural properties shown by
the UD composites are due to the kind of fabric used and to the
void contents within composites. Both these parameters influence
mechanical performances and failure mode evidenced by
composites.
All the TK composites (i.e. both UD and MAT) show tensile
yielding of lower layers as predominant failure mode: the crack
starts where principal stress rxx, which increases through thick-
ness from central zone to external sides, reaches maximum tensile
value. It is consistent that structures reinforced by long unidirec-
tional fibers along the direction of principal stress, are more stiff
than those reinforced with short fibers randomly oriented.
Overall, the TK-UD composites show the best flexural perfor-
mances (average values of failure stress and Young’s modulus
equal to 177.6 MPa and 18.8 GPa, respectively). These values are
comparable or higher (i.e. flexural modulus) to those of other
composites reinforced with unidirectional natural fibers [40].
20 V. Fiore et al. / Composites: Part B 68 (2015) 14–21
Consequently, these composites could be used to realize structural
components that need materials with high flexural stiffness.
On the other hand, the MAT composites, though showing lower
flexural properties, satisfy the minimum requirements (EN stan-
dard 312-2 and 312-3 [41]) for flexural strength and modulus of
panels for general purpose and interior fitments (i.e. 11.5 MPa
and 1.6 GPa, respectively [42,43]), regardless of alkali treatment.
3.2.3. Dynamic mechanical analysis
Fig. 8 shows the variation of storage modulus E’ with tempera-
ture of neat resin and UD composites at frequency of 1 Hz. The
value of E’ was found to be higher for UD composites (i.e. 9 GPa
and 10 GPa for UTK-UD and TK-UD composites, respectively)
than neat resin (i.e. 2.6 GPa) in the plastic region (i.e. at low
temperature).
At higher temperatures, due to loss in stiffness of both the fiber
and the matrix, the storage modulus drops. It is worth notice that
composites reinforced with NaOH treated fibers had a lower fall in
the value of E0 when temperature is increased compared both to
composites reinforced with untreated fibers and to neat resin. In
particular, the storage modulus at 120 °C of the TK-UD composites
was found to be about 270 MPa, notably higher than those of the
TK-UD composites (18.2 MPa) and neat resin (15.2 MPa),
respectively.
Overall, the alkali treatment of natural fibers slightly influences
E0 of the composites in the plastic region whereas, if the merceriza-
tion of the fiber was performed, the storage modulus greatly
increases in the rubbery region. This trend confirm that the treat-
ment of the hydrophilic kenaf fibers in the 6% NaOH solution for
48 h improve their compatibility with the hydrophobic polymer
used as matrix.
Fig. 8. Variation of storage modulus E0 with temperature for neat resin and UD
composites.
Fig. 9. Variation of loss modulus E00 with temperature for neat resin and UD
composites.
Loss modulus E00 represents the viscous response of the mate-
rial. Fig. 9 shows the variations of E00 of neat resin and UD compos-
ites, as function of temperature. It can be noted that loss modulus
increased in the plastic region and then decreased with increasing
temperature in the rubbery region.
The effect of chemical treatment are found to influence on the
value of E00 only above the glass transition temperatures (tempera-
ture at peak values of E00 ). In particular, in the plastic region neat
resin and both UD-composites show values of E00 in the range of
60–70 MPa. In the rubbery region, E00 of neat resin was found to
be lower than the UD composites. In particular, the mercerization
of kenaf fiber leads to improvement of the loss modulus of com-
posites at high temperature.
Tan d, also named damping, is determined by the ratio of loss
modulus E00 and storage modulus E0 . Incorporation of fibers in a
composite system affects the damping behavior of the composites,
which is due to shear stress concentrations in the fibers along with
viscoelastic energy dissipation in the matrix [44]. Tan d depends on
the filler–matrix adhesion: i.e. a weak filler–matrix adhesion leads
to higher values of tan d [38,44] while a good filler–matrix adhe-
sion limits the mobility of the polymer chains thus reducing the
damping. In particular, low damping means that the particular
composite has good load bearing capacity.
Fig. 10 shows that the presence of the treated kenaf fibers dra-
matically reduces tan d, thus indicating the presence of good adhe-
sion, resulting in low damping. Vice versa, the damping of UTK-UD
composites is found to be higher than neat resin, due to weak
adhesion between the hydrophilic untreated fibers and the hydro-
phobic polymer used as matrix. These results also confirm the good
effect of the mercerization performed on the fiber/matrix compat-
ibility, resulting in improved stress transfer and good interfacial
adhesion. The MAT composites (i.e. UTK-MAT and TK-MAT) show
similar trends of storage modulus, loss modulus and damping.
These graphs are not reported for sake of brevity.
The glass transition temperature Tg can be calculated as the
temperature at which the damping [38,44] or the loss modulus
[45] attain their maximum values. As shown in Table 4, the glass
transition temperature is slightly influenced by the presence of
untreated kenaf fibers in the epoxy matrix. In particular, the Tg var-
ies from 69.1 °C for neat resin to the range between 71.5 °C and
73.8 °C for UTK-MAT and UTK-UD composites, thus no shift of Tg
to higher temperatures can be attributed to the presence of
untreated kenaf fibers.
On the contrary, the Tg greatly improves for composites rein-
forced with mercerized fibers, regardless their orientation. In par-
ticular, the Tg is equal to 84.3 °C and 87 °C for the TK-MAT and the
UTK-UD composites. Hence, the presence of untreated kenaf fibers
do not reduce the mobility of the matrix chains whereas the mer-
cerization of kenaf fibers improves the fiber–matrix interfacial
adhesion thus reducing the mobility of the matrix chains.
Fig. 10. Variation of tan d with temperature for neat resin and UD composites.
 V. Fiore et al. / Composites: Part B 68 (2015) 14–21 21

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