Polymer Testing 67 (2018) 533–544

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material Properties

Effects of sodium carbonate on the performance of epoxy and polyester coir- T

reinforced composites
Júlio Cesar dos Santosa,b, Renato Luiz Siqueirac, Luciano Machado Gomes Vieirad,
Rodrigo Teixeira Santos Freirea,b, Valdir Manob, Túlio Hallak Panzeraa,∗
a
Centre for Innovation and Technology in Composite Materials, Department of Mechanical Engineering, Federal University of São João Del Rei, Brazil
b
Department of Natural Sciences, Federal University of São João Del Rei, Brazil
c
Department of Materials Engineering, Center of Technological Education of Minas Gerais, Brazil
d
Department of Production Engineering, Federal University of Minas Gerais, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Surface modification induced by sodium carbonate on coir fibres was studied in view of its application as a
Composites reinforcing agent in polyester and epoxy polymer fibre-reinforced composites. Coir fibres were treated with a
Coir fibre 10 wt% sodium carbonate solution for different periods of time (24, 96 and 168 h) at room temperature. The
Chemical treatment surface treatment was evaluated by scanning electron microscopy, X-ray diffraction and thermogravimetric
Mechanical properties
analysis. Tensile, flexural and impact properties of treated and untreated coir fibre-reinforced composites were
TGA
compared. Coir-reinforced epoxy and polyester composites were manufactured by the uniform dispersion of
XRD
SEM randomly oriented coir fibres within the polymeric matrix. Tensile and flexural modulus of coir-reinforced
polyester composites increased nearly 28% and 25%, respectively after 96 h of coir treatment. An analogous
increase of 31% and 17% was obtained for coir-reinforced epoxy composites. In addition, coir-polyester com-
posites achieved superior tensile (∼17%) and flexural (∼5%) modulus and impact strength (∼193%) compared
with coir-epoxy-derived composites. In contrast, coir-epoxy composites led to superior tensile and flexural
strength. The experimental results revealed that sodium carbonate solution effectively removes hemicellulosic
compounds, promotes swelling and increases superficial roughness of the fibres, improving the mechanical
properties (modulus and strength) of the coir-reinforced composites studied.

1. Introduction
Natural fibres have been appraised as environmentally correct ma-
terials due to their renewability, biodegradability and low processing
energy demands [1,2]. Lignocellulosic fibres, in particular, are neutral
with respect to the emission of CO2, which is a very important char-
acteristic in view of the Kyoto protocol [3].
Natural fibres consist of thick-walled cells, referred to as elementary
fibres, which make the structure stiff and strong. The elementary fibre
is composed of multilayered cellulose-lignin/hemicellulose walls of
variable thickness, built on an array of cellulose-based crystalline
structures called microfibrils, arranged at a particular angle (the mi-
crofibrillar angle – MFA). Cell walls are composed of a primary and a
secondary wall layers, whose chemical composition (i.e., the content of
lignin, cellulose and hemicellulose) varies from fibre to fibre. The
physical and mechanical properties of natural fibres are determined by
their chemical composition, cell wall/lumen ratio and cellulose mi-
crofibrillar angle in the dominant cell wall layers [2,4,5]. There are, in
fact, thousands of different natural fibres in the world and only few of
these have been studied, which opens a vast field of research for fibre-
reinforced composites [1]. Natural fibres, however, present low re-
sistance to microbial attack and, owing to their hydrophilicity, are
susceptible to moisture absorption and incompatible with hydrophobic
macromolecular matrices, which impairs fibre-matrix adhesion. In spite
of these drawbacks, these materials are currently used in many appli-
cations due to their resistance to corrosion and abrasion, low density,
low cost and high specific mechanical properties. The selection of the
composite matrix phase is, however, limited by the temperature at
which natural fibres degrade. Most natural fibres are thermally unstable
above 200 °C, and thus thermoset polymers that can be cured below this
temperature are used, especially unsaturated polyester and epoxy types
[6]. Epoxy polymers are currently the dominant choice for low and
moderate temperatures (up to 135 °C) and the most common material
used in high-performance engineering composites. Despite their lower
cost and extensive use in commercial applications, polyesters, which
can be used at approximately the same temperatures as epoxy

∗
Corresponding author.
E-mail address: panzera@ufsj.edu.br (T.H. Panzera).

https://doi.org/10.1016/j.polymertesting.2018.03.043
Received 30 January 2018; Received in revised form 22 March 2018; Accepted 24 March 2018
Available online 27 March 2018
0142-9418/ © 2018 Elsevier Ltd. All rights reserved.
J.C. dos Santos et al.
Fig. 1. Treatment process: a) portions of coir fibres b) Na2CO3 bath treatment c) post treatment washing.
polymers, are rarely chosen for high-performance composites [7].
Coir, in particular, is a lightweight, strong type of fibre that has
lately attracted scientific and commercial interest owing to its specific
properties and availability [5,8–11]. Compared with other typical
natural fibres, coir has higher lignin and lower cellulose and hemi-
cellulose content which, along with its high microfibrillar angle, pro-
vides several valuable properties, such as resiliency, toughness, as well
as damping, abrasion, weather resistance and high enlongation at break
[11]. Hydrophilicity, however, limits the use of coir and other natural
fibres as reinforcement in hydrophobic polymers [12–14]. Chemical
modifications of the fibres have been proposed to improve the com-
posite mechanical performance and durability [6,12,13,15]. Several
studies indicate that, in order to improve physical and mechanical
properties, the surface of coir fibres can be modified by alkaline
treatment to enhance fibre-matrix compatibility. Karthikayen & Bala-
murugan [16] reported that the alkaline treatment of coir-reinforced
epoxy composites enhanced the impact resistance (∼78%), as well as
the tensile (∼18%) and flexural (∼17%) strength relative to untreated
composites. Similar behaviour is observed with other fibres. For in-
stance, Kumar et al. [14] have used NaOH to treat coconut-sheath fibres
in reinforced epoxy composites, achieving higher tensile (∼21%),
flexural (∼19%) and impact (∼24%) strength relative to non-treated
composites. Rout et al. [17] also reported the improvement of the fibre-
matrix interfacial adhesion in coir-polyester reinforced composites after
alkali treatment of the fibres. The higher tensile (∼26%) strength was
obtained after treatment with a 2 wt% NaOH solution, while flexural
strength and impact resistance were higher (∼17 and ∼41%, respec-
tively) for treatments with a 5% alkali NaOH solution.
Jayabal et al. [18] investigated woven coir fibre-reinforced polye-
ster composites and reported a 40% (42%) increase in tensile (flexural)
strength and 20% increase in impact resistance in comparison to un-
treated fibre composites. Enhanced mechanical properties were ob-
tained for the following NaOH concentration/soaking time combina-
tions: (2 wt%, 96 h), (5 wt%, 72 h) and (8 wt%, 24 h). However, the use
of chemical reagents such as sodium hydroxide have become less at-
tractive owing to their cost as well as operational and environmental
hazards, which affect the environmental acceptability and commercial
viability of biocomposites manufacturing [19,20].
New eco-friendly and cost-effective treatments based on sodium
bicarbonate have been proposed for kenaf, sisal and flax fibre-re-
inforced epoxy composites [1,20,21]. Such treatments enhance fibre
stiffness as well as fibre-matrix adhesion by removing hemicellulose
and superficial impurities of the fibres. However, the mildly alkaline
character of sodium bicarbonate demanded longer treatment periods
(about 120 h) compared to highly alkaline NaOH solution [19].
Sodium bicarbonate, NaHCO3, also known as sodium acid carbo-
nate, is frequently used as an antacid for medical purposes, as a lea-
vening agent to bake cakes and bread and in the manufacture of sodium
carbonate (Na2CO3). Sodium carbonate, Na2CO3, a comparatively
stronger alkali, is used in laundry detergents as a softening agent.
Sodium carbonate acts as a relatively strong alkali in aqueous so-
lution and has been previously studied for the pretreatment of
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Polymer Testing 67 (2018) 533–544
lignocellulosic materials [22]. The effectiveness of this salt is compar-
able to that of regular alkaline reagents, e.g., NaOH. Sodium carbonate
can also potentially overcome the major operational problems with
conventional alkaline pretreatments such as corrosion and environ-
mental hazards [22], as well as serve as an effective pretreatment of
natural fibres at reduced exposure times compared to sodium bicarbo-
nate. Such use, to the best of these authors' knowledge, has received
much less attention relative to other methods. This work, therefore,
aims to investigate the effects of the alternative, eco-friendly sodium
carbonate pretreatment on the properties of epoxy and polyester coir-
reinforced composites. Morphological and chemical characteristics of
treated and untreated coir were investigated through scanning electron
microscopy (SEM), X-Ray Diffraction (XRD), thermogravimetric ana-
lysis (TGA) and density. In order to investigate the effect of the pro-
posed treatment on the mechanical properties of coir-epoxy/polyester
composites, quasi-static tensile and flexural tests as well as flatwise
charpy impact tests were carried out.
2. Material and methods
2.1. Alkali treatment of coir fibres
Coir fibres in entangled mats were supplied by Deflor Bioengenharia
(Belo Horizonte – Brazil). Portions of manually removed coir fibres
(Fig. 1a) were soaked in 10 wt% Na2CO3 solution (Fig. 1b), with mea-
sured pH nearly 12 for 24, 96 or 168 h at room temperature. The coir
samples were washed in water and subsequently immersed in fresh
water for 30 min (post-treatment - Fig. 1c) and oven-dried at 50 C for
24 h. The average length of the fibres was 16 ± 5 cm.
2.2. Fabrication of the composites
The thermosetting polymers, epoxy and polyester, were supplied by
Hunstman-Brazil. The epoxy polymer consisted of Renlam M resin and
Aradur HY 956 hardener at a proportion of 5:1, respectively. An un-
satured orthophtalic polyester resin was mixed with 2 wt% of methyl-
ethyl-ketone as a catalyst. Composite samples were manufactured by
hand lay-up followed by cold uniaxial compaction. Randomly oriented
coir fibres were placed on an aluminium plate (0.5 mm thickness) in a
square steel mould frame, of dimensions 310 mm × 310 mm × 3 mm
(Fig. 2a). Based on preliminary experiments [23], the fibre grammage
was set at 900 g/m2. From the mean apparent density of coir fibres
obtained in this work, 0.86 ± 0.02 g/cm3, the fibre volume fraction of
approximately 30% was determined.
The polymer mixture was then poured into the mould and, once the
fibres were completely wet (Fig. 2b), a similar aluminium plate was
placed on the surface and the mould was closed with a steel lid
(Fig. 2c). Samples were cured for 60 h at room temperature under a
constant uniaxial pressure at 645 kPa. This pressure level was set based
on several preliminary studies. The Tec Glaze-N mould release agent
was used on the surface of aluminium plates to ensure better surface
finish of the composite samples. Subsequently, the aluminium plates
J.C. dos Santos et al.
Fig. 2. Hand Lay-up manufacturing process.
were removed, and the composite panel with nearly 3 mm in thickness
was post-cured at room temperature for 2 weeks (according to the
manufacturer's recommendation).
2.3. Design of experiment
The Design of Experiment (DoE) and Analysis of Variance (ANOVA)
techniques involve arrays to organize the factors affecting the me-
chanical and physical properties studied and the levels at which they
should be set. A full factorial design (21∙31 = 6) with six experimental
conditions (E.C.) was established to investigate the effect of the factors
(levels) Treatment Time, TT (24, 96, 168 h) and Matrix Phase, MP
(epoxy and polyester), on the flexural and tensile modulus and strength,
charpy impact resistance and apparent density of the composites. The
treated (untreated) composites are identified with the sample codes E-
24, E-96 and E-168 (E-raw) for epoxy composites and P-24, P-96 and P-
168 (P-raw) for polyester composites. A randomization procedure was
also adopted during manufacturing and experimental tests, making the
whole numerical process more robust against non-controllable vari-
ables [25,26].
2.4. Morphological and chemical characterization of fibres
2.4.1. Scanning electron microscopy (SEM)
Raw and treated fibres were analysed by scanning electron micro-
scopy using a Philips XL-30 FEG microscope and Hitachi TM 3000
microscope model coupled to an energy dispersive X-ray spectrometer
(EDS).
2.4.2. Fibre apparent density
The apparent density of coir fibres was measured by the density-
gradient column method for 5 samples composed of a bunch of fibres
immersed in pure ethanol (ASTM D276 [24]).
2.4.3. X-ray diffraction - crystallinity index (Ic)
X-ray diffraction was used to evaluate the removal of superficial
compouds and exposure of cellulose molecules. The fibre bundles were
manually aligned and scissor-lacerated to micro-segments to be ana-
lysed by X-ray diffraction using a Rigaku Ultima IV X-ray diffractometer
operating with CuKα radiation (λ = 0.15418 nm). The diffraction pat-
terns were obtained for values of 2θ ranging from 5 to 40° in continuous
scan mode at 1°/min. The crystallinity index (Ic) of the samples was
calculated using the formula:
I − Iam ⎞
Ic = ⎛ 002
⎜ × 100,
⎟
⎝ I002 ⎠ (1)
where I002 is the maximum intensity of diffraction on the (002) crys-
tallographic plane at a 2θ angle between 22° and 23°, and Iam is the
intensity of diffraction of the amorphous material taken at a 2θ angle
between 18° and 19° where the intensity is at a minimum [23–25].
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Polymer Testing 67 (2018) 533–544
2.4.4. Thermogravimetric analysis (TG/DTG)
The thermal stability of the raw and treated fibres was evaluated by
thermogravimetry using a Shimadzu DTG-60H differential thermal
analyzer. The analyses were performed under nitrogen atmosphere at a
constant flow (∼100 ml/min), with a heating rate of 10 °C/min and
temperature ranging from 30 to 800 °C.
2.5. Mechanical tests
The uniaxial tensile and flexural tests were conducted on a
Shimadzu AGX-Plus Universal Testing Machine equipped with a 100 kN
load cell according to ASTM D3039 [30] and ASTM D790 [31], re-
spectively, at a crosshead speed of 2 mm/min. Samples of dimensions
250 mm × 25 mm were used for the tensile test and a video-ex-
tensometer was used for the elongation measurements. For each ex-
perimental condition, six (6) specimens were fabricated with two re-
plicates running a total of 96 specimens. A second composite plate was
manufactured to obtain a new set of samples (Replicate 2).
The flexural test was performed on samples whose length and width
were determined in accordance to ASTM D790, so that the length of the
support span was 16 times the specimen thickness. For each experi-
mental condition, ten (10) specimens were fabricated with two re-
plicates to total of 160 specimens. The impact test was carried out using
a Charpy Impact Tester (XJJ Series) equipped with an 8.04 Nm hammer
of 15 J of energy with samples of 80 mm × 10 mm of dimensions, ac-
cording to ISO 179-1 [32]. For each condition, ten (10) specimens were
fabricated with two replicates to a total of 160 specimens. Tests were
conducted at controlled temperature (23 °C) and humidity (55%).
3. Results
3.1. Morphological analysis
In addition to the removal of lignin from the fibre surface, sodium
carbonate also removes impurities, wax and fatty substances adsorbed
in the surface [19]. The mechanism of action of alkalis is the disruption
of hydrogen bonds on the fibre surface, thereby increasing its roughness
[5,16,28]. The native surface of the fibre (Fig. 3a) is smooth due to a
waxy layer [33]. A rougher fibre surface is achieved after 24 h of
treatment and roughness progressively increases up to 96 h, owing to
the removal of waxes, cuticles and globular particles, creating pits
(tyloses) on the fibre surface (Fig. 3b and c), as reported by Nam et al.
[34]. It is noteworthy, however, that longer periods of treatment pro-
duces a smoother surface owing to the complete removal of cuticles and
globular particles, as shown in Fig. 3d, for 168 h. Longer periods of
treatment also leads to degradation of the fibres [1], also observable in
Fig. 3d. This effect may account for the decrement of the tensile and
flexural strength obtained from the composite mechanical character-
ization, as commented in section 3.3.
3.2. Physical, chemical and thermal characterization
The physical, chemical and thermal properties of the fibres studied
are summarized in Table 1. It is possible to observe that raw coir fibres
have lower density and relatively higher thermal stability.
3.2.1. Apparent density and structure
The apparent density of coir fibres varied from 0.86 to 0.97 g/cm3,
higher values being associated with the sodium carbonate treatment. As
shown in Fig. 4a, the morphological analysis of the cross section of a
single untreated coir fibre reveals numerous elementary fibres, each
with its own lumen and pores (Fig. 4a). The apparent density was de-
termined considering, as mentioned above, the whole volume occupied
by the fibre, including the enclosed air volume. The fibre density is
affected by fibre length and porosity [2], since pores reduce the density.
Sodium carbonate increased the apparent density (see Table 1), owing
J.C. dos Santos et al. Polymer Testing 67 (2018) 533–544

Fig. 3. SEM surface analysis of coir fibres (a) raw (b) 24 h treated (c) 96 h treated (d) 168 h treated.

to cellulose swelling, which promotes the densification of cell walls and
reduces the lumen of the elementary fibres (compare Fig. 4b and c). The
low packed crystalline regions contributes to the diffusion of the Na+
ions through the structure [35]. Due to low cellulose content (micro-
fibrils) (∼45% of fibre structure [4]) the Na+ ions can easily diffuse
through the structure of raw coir fibres, since the amorphous regions
are more easily accessed by solvent molecules. The literature reports
that, after washing with water, the Na+ ions tend to be excluded from
the crystalline lattice [34,36,37]. However, EDS analysis reveals that
the post-treatment applied was not enough to remove all sodium ions
from inter- and intramolecular cellulose fibrils (Fig. 4c). Higher con-
centrations of alkali, however, may cause depolymerization of cellulose
molecules, damaging the cell wall and reducing the density [38]. Such
effect was not observed, which implies that the alkaline concentration
used did not cause cell wall damage.
Cellulose swelling is a complex phenomenon which affects both
molecular and supramolecular structures [1,36,39,40]. Cellulose mo-
lecules, which consist of a series of glucopyranose rings linked together
by valence bonds, are arranged parallel to the fibre axis in structures
called cellulosic chains or microfibrils linked by hydroxyls bonds. In
aqueous media, sodium carbonate dissociates into Na+ and CO32− ions.
Na+ ions do not participate in the hydrolysis reaction but, on the other
hand, the CO32− ions interact with H+ of the water releasing OH−.
Based on the Na2CO3 dissolution, Na+ ions released into the aqu-
eous medium in contact with cellulose form I disrupt hydroxyl bonds
and, having a favorable diameter to penetrate the interlattice space
between adjacent planes, diffuse into these planes and form a new Na-
cellulose I [41] lattice with relatively large distances between the cel-
lulose molecules which play a crucial role in widening even the smallest
pores. Considering that most of the hydroxyl groups (OH) present in the
fibres correspond to alcoholic hydroxyls, an interaction analogous to
that which occurs during a traditional mercerization treatment may be
proposed [1,27,34,42].
Coir-OH + Na+ + OH− → Coir-O-Na+ + H2O (2)
The OH groups of cellulose are converted into ONa groups [18] by
expanding the cellulose molecule dimensions, thereby increasing the
pore size. Cell wall swelling enables large molecules to penetrate
crystalline regions and exert very large forces on the weaker Na-cellu-
lose I lattice; thus, the lumen collapses resulting in a more compact
structure, leading to a closer packing of the chains of cellulose fibrils.
The swollen cell wall does not revert to the original shape after drying;
cell walls remain swollen and the lumen is permanently collapsed.

Table 1
Physical, chemical and thermal characterization of coir fibre.
Fibre treatment Apparent Density Crystallinity Index Weight loss Cellulose Thermal Stability

3
g/cm % Range (°C) % (°C)

None 0.86 ± 0.02 44.79 30–124 7.23 –

223–395 48.98 357
395–622 42.58 –
Na2CO3 24 h 0.91 ± 0.04 47.73 30–137 9.61 –
210–403 41.39 314
403–597 45.06 –
96 h 0.96 ± 0.02 47.84 30–140 13.59 –
208–421 38.83 312
421–600 44.51 –
168 h 0.97 ± 0.03 47.85 30–139 9.38 –
215–410 42.43 318
410–644 45.12 –

536
J.C. dos Santos et al.
Fig. 4. SEM cross-sectional area analysis of coir fibres: a and c) raw b) 96 h treatment and d) 96 h treatment (EDS analysis). The EDS spectra of raw and treated fibres
are also presented.
3.2.2. X-ray diffraction - crystallinity index (Ic) of raw and treated coir
fibres
The X-ray diffractograms of the untreated and Na2CO3-treated fibres
for different times are shown in Fig. 5. They reveal that both untreated
and treated coir exhibit the same diffraction pattern of cellulose I, in
which the main intensity peaks are located at 2θ between 22 and 23°
(between 18 and 22° for cellulose II, a polymorphic form) [27,29,36].
This reveals that the treatment of coir fibre with 10 wt% Na2CO3 does
not completely transform cellulose I into cellulose II, but it is sufficient
to reduce the amorphous phase (including cementing components:
hemicellulose, lignin [43]), consequently, leading to a slight increase of
the crystallinity index of treated samples (see Table 1). The increase of
crystallinity may also be attributed to the enhanced packing of cellulose
chains (microfibrils) after swelling [44].
Liu and Hu [45] report that NaOH concentrations above 11 wt%
537
Polymer Testing 67 (2018) 533–544
have considerable effects on the regeneration of cellulose I to cellulose
II at room temperature, while lower concentrations result only in a
slight increase of crystallinity and a negligible amount of cellulose II.
This finding helps to explain the present results, since the pH resulting
from a 10 wt% Na2CO3 solution is approximately 12, whereas that of a
NaOH solution at the same concentration is much higher. Therefore, it
is reasonable to state that the treatment proposed here constitutes a
milder and unfavorable condition for the complete formation of cellu-
lose II.
When fibres contain large amounts of amorphous material (i.e
lignin, hemicellulose, pectins and amorphous cellulose), the intensity of
diffraction of the amorphous material seem to be smeared out and
appear as a single broad peak. However, when the crystalline content is
high these peaks are more pronounced [40]. Fig. 5 reveals that, for
treated fibres, an inflection point begins to appear, and the broad peak
J.C. dos Santos et al.
Fig. 5. X-ray diffractograms of raw and Na2CO3 treated coir fibres.
tends to resolve into two individual peaks. The peak at 2θ = 16° is al-
ready very pronounced and this phenomenon implies an increase in
crystalline cellulose, whereas the amorphous phase is reduced relative
to untreated fibres The increase of crystallinity induced by Na2CO3
solution may be thus attributed to two effects: 1) amorphous material
removal and exposure of surface crystallites [5], and 2) structural re-
arrangement of crystalline regions [27,36,44–46].
During swelling, interfibrillar regions become less dense and rigid,
thus more prone to structural rearrangements [44]. After washing with
water, some authors [36,41] report that Na-cellulose I undergoes
structural changes with complete removal of Na+ ions. Such removal
did not completely occur here, as shown in Fig. 4d. Na-cellulose I
contains in fact two coexisting phases - Na-cellulose II, which re-
generates to cellulose I, and Na-cellulose III, also called cellulose IV,
which regenerates to cellulose II [36,37,45].
3.2.3. Thermogravimetric analysis (TGA)
The TG and DTG curves of raw and treated coir fibres are shown in
Fig. 6 and Table 1 (weight loss and thermal stability columns).
Previous studies report that the thermal decomposition profile of
coir fibres is characterized by three peaks [14,15,47]. The first peak is
associated with moisture loss, which occurs up to approximately 100 °C.
Sodium carbonate induces a significant increase in moisture absorption
relative to untreated coir fibres in the range of 32.92% (24 h), 87.97%
Fig. 6. Thermal analysis curves (a) TG and (b) DTG for coir fibres.
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Polymer Testing 67 (2018) 533–544
(96 h) and 29.73% (168 h). These results indicate enhanced interaction
between water molecules and coir fibre components (specially hydroxyl
groups of cellulose chains) after the removal of the superficial cuticle
layer and other chemical modifications produced by the Na2CO3
treatment [47]. It is noteworthy that moisture absorption depends on
the extent of the alkali treatment, rising to 88% for 96 h with sub-
sequent decrease to 30%. Similar behaviour was reported by Silva. et al.
[47], who also observed an increase in the moisture absorption of 5 wt
% NaOH-treated coir fibres in the range of 50%, 100% and 50% for 24,
48 and 72 h, respectively. To the best of these authors' knowledge, no
explanation for this behaviour has been found in the literature. How-
ever, SEM images (Fig. 3) imply that tyloses are more exposed at 96 h
than at 24 h, indicating the progressive cuticle removal by sodium
carbonate, which may explain the initial increment in moisture ab-
sorption. On the other hand, Medronho et al. [35] note that cellulose,
consisting of glucopyranose monomers, bears an amphiphilic character,
being hydrophobic in the equatorial plane of the glucopyranose rings
and hydrophobic in the axial plane. Gassan and Bledzki [44] report
that, on alkali treatment and the subsequent removal of lignin and
hemicellulose, cellulose molecules are more susceptible to spatial re-
orientation. This mechanism could account for the progressively more
hydrophobic character of the fibres through the incremented exposure
of the axial plane of the glucopyranoses.
For the untreated fibres, the second stage of mass loss, which ap-
pears as a shoulder centred at 307 °C in DTG curves, can be associated
mainly with hemicellulose degradation [1]. This stage of mass loss was
not observed for all treated fibres, demonstrating that the treatments of
24, 96 and 168 h with 10 wt% Na2CO3 solution were efficient in re-
moving a considerable amount of their hemicellulose. These results
corroborate the X-ray analysis presented in Fig. 5, which revealed a
reduction in amorphous compounds (including hemicellulose) from
coir fibres promoted by Na2CO3.
The most intense mass loss occurred in the range of 320–400 °C for
untreated fibres, in which the maximum mass flow occurred from the
solid to the vapor phase at 358 °C, corresponding to the thermal de-
gradation of cellulose [14,15]. This temperature (358 °C) of maximum
degradation rate decreased to approximately 310 °C for treated fibres,
observed in DTG curves, showing that the alkaline treatment also de-
creased the thermal stability of the cellulose. Previously studies have
reported a similar effect for sisal [1] and coir [47] fibres treated with
NaHCO3 and NaOH solutions at room temperature, respectively.
Some authors have, however, reported an improvement of the
thermal stability after alkaline treatment of fibres (sisal, munguba and
coir) owing to cellulose II [42,48,49] – which was not observed in this
study with the proposed alkaline treatment (see Fig. 6). It is important
to note that, although the transformation of cellulose I to II has not
J.C. dos Santos et al. Polymer Testing 67 (2018) 533–544

occurred, the alkaline treatment was sufficient to modify the structure matrix (Fig. 8b). Such behaviour was also observed in the flexural test
of the cellulose I, converting some OH-groups into ONa-groups. and will be discussed in the following section.
Cellulose II presents more intermolecular hydrogen bonds than It is well established by the theory of composites that the tensile
cellulose I which increases the thermal stability of fibres [40,50–52]. It modulus of fibre-reinforced composites depends on the tensile modulus
is worth noting that Liu and Hu [45] have observed that the poly- of the fibres and matrix, fibre-matrix volume fraction and fibre or-
morphic transition from cellulose I to cellulose II is thermodynamically ientation [34]. Coir fibres are linear elastic at low stress, and then show
favorable depending on the interaction of two factors: NaOH con- plastic behaviour until fibre failure at a very high strain [2]. As pre-
centration and treatment temperature [45]. These authors have in fact viously reported by other authors, alkali treatment significantly en-
observed a negligible amount of cellulose II at room temperature after hances the tensile modulus and strength of coir fibres [13,14,34],
treatment with 10 wt% NaOH. However, in this work the remaining owing to the denser packing of the chains of cellulose fibrils promoted
Na+ ions might have contributed to reduce the new intermolecular by swelling. This fact is corroborated by the experimental results de-
hydrogen bonds, consequently affecting the thermal stability of the scribed in Section 3.2.1. The increase in the tensile modulus of the
cellulose. natural fibre is due to interacting factors, [54]. Alkali treatments pro-
The thermal events above 400 °C may be attributed to (1) lignin mote the rupture of sensitive bonds between cellulose and hemi-
degradation, which starts at room temperature and proceeds up to cellulose. The removal of hemicellulose induces rearrangements of the
700 °C and beyond [1,15,43] or (2) aromatization involving dehy- cellulose chains with the formation of new hydrogen bonds. Hence, the
drogenation reactions [53]. fibres tend to get closely packed [1,54,55]. As a result, the fibre swells
making the fibre more homogeneous and contributing to stress transfer
3.3. Mechanical tests between interfibrillar regions [1,55].
The predominant loading mode in random fibre networks is the
Table 2 depicts the average values obtained for all mechanical tests transfer of axial stress directly from one fibre to another at their in-
with the respective standard deviation. tersection [56]. The increase in roughness provided by Na2CO3 (up to
Table 3 presents the mechanical properties of the epoxy and 96 h) can, therefore, improve the axial stress transfer, and hence the
polyester resins in pristine conditions. It can be observed that the epoxy composite strength (16.8 and 14.8%, for epoxy and polyester, respec-
matrix is better in strength while polyester is better in modulus and tively). However, even after alkali treatment, fibre-reinforced compo-
impact resistance. sites presented much lower tensile strength than their neat polymer
The analysis of variance for tensile, flexural and impact tests is counterparts (56.12 and 63.9% for epoxy and polyester, respectively)
described in Table 4. The underlined p-values represent the factors or (Table 3). In addition, longer periods of treatment (above 96 h) also
interaction of factors that were statistically significant to the responses. reduced the tensile strength owing to fibre degradation. The tensile
The Anderson-Darling normality test presented pAD-values greater than strength, for a given fibre content, depends on the fibre orientation and
0.05, and R2 was greater than 91.25%, indicating that the data is well the fibre-matrix interfacial adhesion [1,5,28]. Fibres are randomly
described by the underlying statistical model used for ANOVA. distributed in the matrix and only those oriented perpendicular to the
applied load offer reinforcement to the composite. Fibres aligned
3.3.1. Tensile test transversely to the load direction virtually do not offer any reinforce-
Fig. 7a and b presents the typical tensile stress/strain curves of ment and act as barriers that impair the homogeneity of the stress
polyester and epoxy coir-reinforced composites, respectively. As re- distribution throughout the matrix. Such high concentration regions
vealed by the statistical analysis presented below, it is clear from these result in fracture that usually occurs at very low stress [5,57], which
figures that sodium carbonate enhances the tensile modulus of the coir- reduces the tensile strength of the composite material, as also observed
reinforced composites. The tensile strength is also significantly en- by Yan et al. [5].
hanced for 96 h of alkaline treatment, especially for epoxy composites.
Table 2 displays the average values obtained for tensile modulus and 3.3.2. Three-point bending test
strength with the respective standard deviation. The tensile modulus Fig. 9a and b shows the typical flexural load/displacement curves of
varied from 2.32 to 3.13 GPa. Matrix Phase (MP) as well as Treatment the coir-polyester and coir-epoxy polyester derived composites, re-
Time (TT) significantly affected the tensile modulus (p-values < 0.05) spectively. These figures indicate that the flexural maximum load is
and their effect was analysed via the interaction plot presented in significantly enhanced for 96 h of alkaline treatment, especially for
Fig. 8a, revealing that higher tensile modulus was achieved when epoxy composites. Such observations are corroborated by the statistical
polyester was used. analysis presented below. The flexural modulus of the composites
The tensile strength varied from 12.57 to 20.75 MPa. Only the main varied from 2.27 to 2.87 GPa (Table 2). Both factors – Matrix Phase and
factors contributed significantly to the tensile strength. Tensile modulus Treatment Time – significantly contributed to the flexural modulus,
and strength both increased with treatment time up to 96 h. The tensile which was increased by the coir fibre inclusions. The main effect plots
strength, however, presents the opposite behaviour, and higher strength are shown in Fig. 10a. The sodium carbonate treatment also enhanced
was achieved when coir fibres were embedded in the epoxy polymer the flexural modulus, which was higher for 96 h. As reported in the
literature, the modulus of raw coir fibres varies from 4.9 to 6.0 GPa [2],
Table 4 and increases with alkali treatments [13,54,58]. Such enhancement is
Analysis of variance for – ANOVA (p ≤ 0.05). due to the incorporation of such rigid fibres. Since the flexural modulus
Experimental factors Tensile Flexural Impact
is measured at small strains, its dependence on the interfacial adhesion
is small. Polyester, which presents a slightly higher flexural modulus,
Modulus Strength Modulus Strength Flatwise provided also higher flexural modulus compared to epoxy composites.
The flexural strength, also affected by Matrix Phase and Treatment
Main MP 0.000 0.000 0.000 0.000 0.000
TT 0.000 0.007 0.000 0.003 0.031
Time, varied from 23.27 to 42.94 MPa (Table 2). Epoxy composites
presented higher flexural strength compared to polyester composites
Interaction 0.000 0.507 0.157 0.462 0.056 (Fig. 10b). This behaviour is the same reported for tensile tests and
(MP x TT) deserves further analysis.
Weak adhesion between coir fibres (hydrophilic) and thermosetting
R2 (Adj.,%) 99.57 93.90 96.94 91.25 99.59
pAD (pAD ≥ 0.05) 0.659 0.319 0.654 0.982 0.729 polymers (hydrophobic) affects the flexural strength, and better fibre-
matrix interaction occurs if the fibre is somehow more hydrophobic

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J.C. dos Santos et al. Polymer Testing 67 (2018) 533–544

Fig. 7. Typical tensile stress/strain curves of the a) coir-derived polyester and b) coir-derived epoxy composites.

[14,46,59]. The adhesion between two solids is directly related to their
surface energies and wetting is a requisite to get a good interfacial
adhesion [60]. Chemical treatments can in fact, to some extent, change
the nature of the fibre surface from hydrophilic to hydrophobic due to
condensation reactions which expose the fibre surface to compatible
chemical groups of the matrix, promoting better wetting by hydro-
phobic matrices such as epoxy polymer [1,5] and polyester [3,58,61].
As already discussed above (section 3.2), Na2CO3 deeply removes
hemicellulose exposing lignin. Lignin being a phenolic natural polymer
[62], should be chemically compatible with polyester [13]. However,
when a certain amount of lignin is removed, an increased amount of
hydroxyl groups present in the cellulose becomes available [16,46,63].
Epoxy polymers are characterized by the presence of more than two
epoxide groups per molecule, which react with the hydroxyl groups of
cellulose at the interface increasing chemical bonding [14,64]. As a
result, epoxy composites presented superior flexural (and tensile)
strength relatively to polyester composites.
It is also noteworthy that the fibre-matrix adhesion is also enhanced
by the alkali treatment owing to increased mechanical anchoring and
wetting, resulting from the superficial roughening of fibres.
3.3.3. Impact test
Charpy impact data obtained for raw and treated coir reinforced
composites are presented in Fig. 11a. Impact strength values varied
from 6.13 to 18.59 kJ/m2. Polyester composites presented higher im-
pact strength, which was 193% higher compared to epoxy polymer
composites (Fig. 11b). These results were expected, since impact
strength is deeply affected by fibre-matrix adhesion and, in general,
very strong interfaces have a detrimental effect on impact properties.
Fracture is usually associated with the formation of macro-cracks in the
matrix, followed by fibre failure. Most of the energy absorbed during
impact is related to fibre pull-out [57].
Crack formation takes place in the matrix, which is usually less
resistant than fibres. Behind the crack front, bridging fibres stretch
freely along the separating crack faces and, in analogy to Hook's law,
absorb energy that will otherwise be available at the crack tip. Fibres
also stretch along the debond length, where stretching is restricted by
friction, which dissipates additional (thermal) energy once sliding takes
place along the fibre-matrix interface. As the stress increases, if the fibre
failure occurs along the debond length, the fibre will pull-out and
thermal energy will be dissipated due to the development of shear
frictional forces during sliding. Considering the abundance of fibres
dispersed in the coir fibre composites and the vast surface area avail-
able for fibre sliding in various directions, pull-out is considered a
powerful energy dissipation mechanism. Fibre pull-out is evident in
polyester composites, as shown in Fig. 12a.

Table 2
Summary of the mechanical tests.
E.C. Tensile Flexural Impact

Modulus Strength Modulus (GPa) Strength (MPa) kJ/m2

(GPa) (MPa)

r1 r2 r1 r2 r1 r2 r1 r2 r1 r2

E-Raw 2.32 2.33 17.31 18.12 2.26 2.28 32.64 37.15 6.41 4.25
( ± 0.15) ( ± 0.14) ( ± 0.54) ( ± 0.6) ( ± 0.11) ( ± 0.08) ( ± 4.47) ( ± 4.98) ( ± 0.42) ( ± 0.17)
E-24 h 2.56 2.53 17.90 17.60 2.59 2.60 40.09 38.65 6.77 6.07
( ± 0.23) ( ± 0.19) ( ± 0.9) ( ± 1.08) ( ± 0.13) ( ± 0.10) ( ± 3.85) ( ± 4.56) ( ± 0.67) ( ± 0.84)
E-96 h 2.59 2.62 20.91 20.63 2.72 2.64 43.05 42.79 6.29 5.97
( ± 0.10) ( ± 0.20) ( ± 0.66) ( ± 1.86) ( ± 0.21) ( ± 0.08) ( ± 4.08) ( ± 4.40) ( ± 0.69) ( ± 0.30)
E-168 h 2.60 2.59 18.68 19.88 2.67 2.68 40.07 34.49 6.42 6.82
( ± 0.10) ( ± 0.08) ( ± 3.29) ( ± 1.75) ( ± 0.14) ( ± 0.18) ( ± 5.10) ( ± 4.35) ( ± 0.79) ( ± 1.17)
P-Raw 2.41 2.52 12.83 12.17 2.40 2.36 23.58 25.87 17.41 18.89
( ± 0.04) ( ± 0.05) ( ± 0.86) ( ± 1.25) ( ± 0.14) ( ± 0.12) ( ± 3.41) ( ± 3.60) ( ± 3.18) ( ± 2.46)
P-24 h 2.96 2.87 11.68 14.26 2.68 2.62 29.24 29.97 17.05 17.64
( ± 0.18) ( ± 0.31) ( ± 0.36) ( ± 0.67) ( ± 0.17) ( ± 0.08) ( ± 3.66) ( ± 3.68) ( ± 0.79) ( ± 1.90)
P-96 h 3.12 3.13 14.40 14.36 2.82 2.90 30.42 31.20 18.13 17.99
( ± 0.09) ( ± 2.95) ( ± 0.05) ( ± 2.27) ( ± 0.09) ( ± 3.37) ( ± 0.14) ( ± 5.28) ( ± 0.77) ( ± 2.61)
P-168 h 3.12 3.12 13.32 13.59 2.81 2.80 24.51 21.86 16.93 17.02
( ± 0.24) ( ± 0.31) ( ± 0.38) ( ± 1.01) ( ± 0.10) ( ± 0.11) ( ± 2.99) ( ± 4.34) ( ± 2.71) ( ± 2.24)

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J.C. dos Santos et al. Polymer Testing 67 (2018) 533–544

Fig. 8. Tensile testing: a) interaction plot for tensile modulus and b) main effect plots for tensile strength.

Table 3 surface, rendering them more prone to premature rupture.

Mechanical properties of the matrices.
Property (Unit) Type of Matrix
4. Conclusions
Epoxy Polyester
Sodium carbonate treatment of coir fibres efficiently removed ex-
Tensile Strength (MPa) 47.29 ± 2.02 39.80 ± 3.05
ternal amorphous compounds and increased the exposure of crystalline
Modulus (GPa) 2.24 ± 0.11 2.44 ± 0.14
cellulosic fibres. Moreover, the swelling of the internal structure led to a
Flexural Strength (MPa) 69.26 ± 3.96 55.85 ± 2.91 substantial densification of the fibres. These effects promoted a sa-
Modulus (GPa) 2.14 ± 0.04 2.19 ± 0.08 tisfactory increase of the tensile and flexural modulus of the fibre re-
inforced composites for both polymeric matrices-epoxy and polyester-
Impact Resistance (kJ/m2) 6.33 ± 0.41 5.29 ± 0.31
studied.
The alkali treatment also increased the superficial roughness of coir
However, if the fibre-matrix interface is too strong, the mechanisms fibres, which increased the tensile and flexural strength relative to
of energy dissipation described above - fibre-matrix debonding, brid- untreated coir composites.
ging, sliding and pull-out - are inhibited and the impact resistance drops The alkali treatment resulted more effective for 96 h, period after
as the impact energy is canalized to matrix cracking [56,65,66]. This is which the tensile and flexural properties tend to decrease.
the case for epoxy polymer composites in which enhanced fibre-matrix However, the tensile and flexural strength of the fibre reinforced
interaction results in fracture of fibres at the crack plane with little fibre composites were in fact lower in comparison to the neat polyester and
pull-out, as shown in Fig. 12b. It is worth noting that Na2CO3 also led to epoxy matrices. As discussed, such behaviour is due to the random
a significant reduction, albeit small, of impact strength (see Fig. 11b). orientation of the fibres in the matrix. Only those oriented perpendi-
This behaviour may be explained by the enhancement of mechanical cular to the applied load offer reinforcement to the composite. Fibres
interlocking produced by the alkali treatment, owing to the superficial aligned transversely to the load direction act as stress concentration
roughening of the fibres (as discussed in Section 3.3.2), which reduces centres, which reduce the tensile strength of the composite material.
fibre pull-out (Fig. 12c) and impact energy dissipation. In addition, It is noteworthy that epoxy composites presented superior flexural
Dassios [66] has observed that, in the event of fibre sliding, the in- (and tensile) strength relative to polyester composites, since epoxy
creased superficial roughness also causes the tearing of interlocking polymers are characterized by the presence of more than two epoxide
fibre-matrix blocks, which magnifies the effects of failures on the fibre groups per molecule, which react with the hydroxyl groups of cellulose
at the interface, increasing chemical bonding.

Fig. 9. Typical flexural force/displacement curves of the a) coir-derived polyester and b) coir-derived epoxy composites.

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J.C. dos Santos et al. Polymer Testing 67 (2018) 533–544

Fig. 10. Flexural tests: a) main effect plots for modulus and b) strength.

Fig. 11. Impact properties of coir fibre composites (a) strength variation of impact strength of epoxy and polyester composites and (b) main effect plots for impact
strength.

Fig. 12. Charpy impact test: fracture analysis of untreated (a) polyester, (b) epoxy; (c) 96 h treated polyester composites.

However, owing to this superior fibre-matrix interaction, the impact
strength was lower for epoxy fibre reinforced composites since pull-out,
the main mechanism for impact energy dissipation, is dramatically re-
duced. The same behaviour is observed, to a lesser extent, for alkaly
treated fibre reinforced polyester composites, as sodium carbonate in-
creases the superficial roughness of the fibres, and thus fibre-matrix
interlocking.
In summary, the sodium carbonate treatment of coir fibres for 96 h
provides significant enhancement of tensile (and flexural) modulus and
strength of coir fibre reinforced epoxy and polyester composites and
overcomes the major operational problems with conventional alkaline
treatments such as corrosion, extensive neutralization and environ-
mental hazards.
Acknowledgements
The authors would like to thank the Brazilian Research Agencies
FAPEMIG (CEX - PPM-00075-17), CAPES (PhD scholarship) and CNPq
(306767/2016-3) for the financial support provided.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://dx.
doi.org/10.1016/j.polymertesting.2018.03.043.
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