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Tomczak, Sydenstricker & Satyanarayana. Studies On Lignocellulosic Fibers of Brazil - Part II - Morphology and Properties of Brazilian Coconut Fibers
Tomczak, Sydenstricker & Satyanarayana. Studies On Lignocellulosic Fibers of Brazil - Part II - Morphology and Properties of Brazilian Coconut Fibers
www.elsevier.com/locate/compositesa
Received 1 June 2006; received in revised form 12 February 2007; accepted 13 February 2007
Abstract
Stressstrain curves for dierent diameters, tensile properties and thermal behaviour of Brazilian coir bers are presented. The tensile
strength (TS) and Youngs modulus (YM) of these coir bers were found to decrease, while the percentage (%) strain at break remained
constant as ber diameter increased. With bers (mean diameter of 0.225 mm), a decrease in TS and % strain at break but an increase in
YM with increasing test length of the ber, and a considerable increase in TS, constant YM and % strain at break with increasing strain
rate were observed. The results are discussed in terms of X-ray diraction and microscopic observations. Thermal behaviour of the bers
revealed degradation of dierent constituents in an N2 or O2 atmosphere. Thermo-mechanical analysis of the bers revealed increased
modulus and decreased tan d values.
2007 Elsevier Ltd. All rights reserved.
Keywords: A. Coconut ber; B. Tensile properties; B. Thermal analysis; D. Microstructure
1. Introduction
The use of lignocellulosic bers as reinforcements for
polymeric materials has been growing during the last decade or so to replace synthetic bers, especially glass bers
in composites, for dierent industrial sectors, such as packaging, automobiles [1,2] and even in the building sector [3].
This is mainly due to their unique characteristics, such as
abundance, biodegradability, low density, non-toxic nature, less abrasiveness to plastic processing equipment and
useful mechanical properties, not to mention their low cost
(1740% of glass ber) [4]. These have made them alternates to man-made bers for making composites [26]. In
Corresponding author. Tel.: +55 41 3361 3470; fax: +55 41 3361 3186.
E-mail address: kgs_satya@yahoo.co.in (K.G. Satyanarayana).
1359-835X/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2007.02.004
addition, there is a growing awareness of ecological concerns, particularly in the automotive uses of these bers,
due to stringent enforcement of laws, particularly in European countries [6]. These factors also encourage nding
new uses for these bers, which otherwise go to waste.
Also, these bers may provide important opportunities to
improve peoples standard of living by helping generate
additional employment, particularly in the rural sector.
Accordingly, every country that has these natural sources
has started to conduct R&D eorts with lignocellulosic
bers, seeking to take advantage of their potential social
advantages.
Brazil has a high potential for the production of vegetable bers and produces a number of lignocellulosic bers.
For example, it produces annually about 1.5 billion coconuts (Cocos nucifera L.) [7], mainly in the northeast region,
in a cultivated area of 273,810 ha. The annual yield of
1711
1712
ACrystalline
100
ATotal
3. Results
3.1. Eect of ber diameter
Stressstrain curves for bers of dierent diameters were
obtained. Fig. 1a shows a typical stressstrain curve of a
Brazilian coir ber of 0.131 mm diameter and gauge length
of 20 mm, tested at a strain rate of 5 mm/min. For comparison, that for an Indian coir ber of diameter 0.250 mm
and 50 mm test length, tested at 20 mm/min, is shown in
Fig. 1b. Using Fig. 1a, elastic modulus values were
obtained from the initial linear part of the curve, while
the nal strength was evaluated from the high plastic
region. The strength properties thus evaluated are presented as a function of diameter in Fig. 2. It can be seen
that both tensile strength and elastic modulus of bers
decrease with increasing diameter within the range studied
(0.040.40 mm), as observed in the case of pineapple bers
[57] and ax bers [58,59], but contrary to the values
observed for Indian coir bers [12]. On the other hand,
the strain at failure, although showing some variation,
may be considered as roughly constant at around 30%,
which is again opposite to that observed in the case of
Indian coir bers.
3.2. Eect of test length
Table 1 presents the results of the eect of test length
(varying from 5 to 25 mm) of coir bers of mean diameter
0.225 mm on their strength properties tested at a strain rate
of 5 mm/min. It can be seen that the tensile strength and
180
160
140
-2
Stress (MN.m )
120
100
80
60
40
20
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45
Strain
Fig. 1. Typical stressstrain curve for a coir ber: (a) present study and (b) Indian ber [12].
300
-1
4500
4000
250
Modulus (MPa)
1713
200
150
3500
3000
2500
2000
100
1500
50
1000
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50
0.05
0.10
0.15
0.20
0.25
0.30
Diameter (mm)
Diameter (mm)
Tensile strength
Modulus
0.35
0.40
0.45
35
30
25
20
15
10
5
0
0.05-0.1 0.1-0.15 0.15-0.20 0.20-0.25 0.25-0.30 0.30-0.35 0.35-0.40 0.40-0.45
Diameter (mm)
Strain at break
Fig. 2. Inuence of diameter on mechanical properties of coir bers (gauge length: 20 mm; strain rate: 5 mm/min).
Table 1
Tensile properties of coir bers of dierent guage length
Gauge length, L0
(mm)
SD tensile strength
(MPa)
Mean modulus
(GPa)
SD modulus
(GPa)
Mean strain at
break (%)
SD strain at break
(%)
5
10
20
25
142.6
135.4
128.7
118.3
53.26
44.8
47.4
35.56
1.269
1.966
2.302
2.734
0.386
0.393
0.707
0.912
59.87
34.04
29.91
25.01
23.80
15.86
12.09
12.50
SDstandard deviation.
1106 M N m3, which is lower than the earlier reported value of about 2320.4 M N m3 for Indian coir bers [61].
3.3. Eect of strain rate
Table 2 presents the results of the eect of strain rate (5,
10, 20 and 50 mm/min) on coir bers of gauge length of
20 mm and diameter 0.225 mm. It can be seen that the tensile strength increases from 128.7 MPa to 155.4 MPa, while
no signicant changes in the strain at failure and in
Youngs modulus are observed when the strain rate
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Table 2
Tensile properties of coir bers at dierent strain rate
Strain rate
(mm/min)
SD tensile strength
(MPa)
Mean modulus
(GPa)
SD modulus
(GPa)
Mean strain at
break (%)
SD strain at break
(%)
5
10
20
50
128.7
134.7
142.4
155.4
47.4
63.9
70.2
70.2
2.301
2.214
2.392
2.402
0.706
0.843
0.872
0.868
29.9
34.9
28.6
31.0
12.1
13.8
13.6
13.6
SDstandard deviation.
increased from 5 mm/min to 50 mm/min. These observations are similar to those observed with sisal bers of
Indian origin [61], but contrary to those of Indian coir
bers [12].
All the three above mentioned observations (Sections
3.13.3) are explained in the next section.
3.4. X-ray diraction studies
The X-ray diraction spectrum of the coir bers used in
this investigation is shown in Fig. 3, which is similar to
other natural bers, showing peak associated with the crystalline part at 2h = 22. The crystallinity index of coir bers
calculated using this spectrum is 57%, compared to 44%
reported earlier [46]. As methods for the rough estimation
of the microbrillar angle of lignocellulosic bers are available, the angle of the coir bers was calculated in the present study, following the equation given in [61,64]. It was
found to be 51, compared to other reported experimental
and estimated values of 3045 [12,64]. It should also noted
that support for the orientation of microbrils (cellulose)
was only available from X-ray studies [12] until direct evidence from microscopic studies was obtained in the eighties
and thereafter [12,50].
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Fig. 5. Scanning electron micrographs of coir ber at dierent strain rates: (a) fracture surface showing the defects and necking [1000, 5 mm/min];
(b) and (c): fractograph showing the end of ber with pull out of microbrils [500, 10 mm/min 1000, 50 mm/min].
100
5.4%
60
259.2C
40.1%
40
20
313.4C
0
200
400
600
Temperature (C)
20
0
7.9%
64C
-20
80
274C
-40
64.1%
60
-60
-80
40
-100
20
28%
348C
-120
Weight (%)
19.6%
Oxiygen Atmosphere
100
80 67.2C
2
1
0
-1
-2
-3
-4
-5
-6
-7
-8
-9
-10
-11
-12
-13
-14
-15
-16
-17
-18
-19
-20
800
Weight (%)
Nitrogen Atmosphere
-140
0
200
400
600
800
Temperature (C)
Fig. 6. Thermal analysis of coir ber in (a) nitrogen and (b) oxygen atmospheres.
1716
Modulus (MPa)
Fiber as received
Modulus
Tan
3000
Tan
323 K
2900
0.045
286 K
0.040
2800
0.035
2700
0.030
183 K
2600
0.025
2500
100
150
200
250
300
350
400
450
Temperature (K)
Modulus (MPa)
Dry Fiber
Modulus
Tan
6000
5500
Tan
0.040
330 K
5000
0.035
306 K
4500
186 K
0.030
4000
0.025
3500
0.020
3000
0.015
2500
0.010
100
150
200
250
300
350
400
450
Temperature (K)
these bers are lignocelluslosic, when subjected to deformation under load they behave as viscoelastic materials as
described elsewhere [12,14,57,6062]. According to the viscoelastic model [64], the applied load is shared initially by
both spring (represented by the crystalline region in the
ber) and dashpot (represented by amorphous regions of
the ber) [61]. The deformation mechanism of such helical
springy structures is well described see Ref. [12], according
to which the microbrils along with the non-crystalline
regions may elongate through uncoiling, with simultaneous
bending and twisting, as described elsewhere [12,18,19,64
66]. So, the extent to which such a ber resists deformation
in the low strain region depends on its microbrillar angle
and is called the initial modulus of the ber. Hence, this
modulus value varies depending on the age and origin of
the ber.
Further, since the ber is viscoelastic in nature, the following Equation was used to calculate the eective modulus (E) according to Mclaughlin and Tait [64] given by
E Ec W c Enc 1 W c
where Ec and Enc are the modulus values of crystalline (cellulose) and non-crystalline (lignin) regions respectively. Wc
h2
1:24
60
the present values of the strength properties are slightly different from those reported (TS: 95118 MPa, YM: 2.8 GPa
and % strain at break: 2351.4) for Brazilian bers by others [43,50], suggesting that although retting may not have
any signicant eect as reported for Indian coir bers
[12], the testing conditions used certainly do.
In the present study the initial linear part of the stress
strain curve was used to calculate Youngs modulus. The
linear portion in the stressstrain curve is then followed
by another linear portion with disproportionately higher
strain, showing a tendency for curvature just the opposite
of that observed in the Indian coir bers. This curvature
also indicates the viscoelastic nature of the bers as
expected following the two-element model of Maxwell
and derived for sisal bers [61], and therefore the applied
stress is shared between the crystalline and non-crystalline
molecules of the ber. Hence, the spiral-like structure of
the ber undergoes deformation as mentioned above, with
initial uncoiling of microbrils followed by matrix yielding
and slipping of molecules with increased applied stress,
through decohesion of crystalline and non-crystalline molecules mainly through weak-links and other imperfections.
When these two mechanisms operate individually or
together, the initial modulus can be calculated as a function
of the microbrillar angle, which the spiral structure possesses. The nature of the stressstrain curve reects all
these. There is also evidence of necking, as observed in
SEM studies (Fig. 5b), similar to that observed in sisal
bers [61].
4.1.2. Eect of diameter
The decrease in tensile strength and initial modulus and
constant strain at break with increasing ber diameter can
be understood from the fact that as the diameter of the
lignocerllulosic bers changes, the other structural parameters, such as microbrillar angle, volume of strength rendering cells in the ber and density of weak-links or
aws, also behave the same manner as reported elsewhere
[12,53,54,57,60,61]. The values observed for coir are found
to be similar to the values observed in the case of Indian
pineapple bers [57]. The changes in these parameters in
turn aect the strength properties. As reported elsewhere,
both the tensile strength and Youngs modulus of lignocellulosic bers decrease with microbrillar angle [66]. This,
along with the higher crystallinity index indicating lower
lignin content in the present study compared to reported
values elsewhere, may also be the cause for the observed
tensile strength and modulus values in this study. However,
it should be noted that the results of Silva et al. [50] also
showed a decrease in TS from 91 MPa to 59 MPa for bers
of dierent diameters (average diameter ranged between
0.25 and 0.41 mm), while both the YM (1.92.3) and %
strain at break (2534) remained constant. These authors
considered all of them to be constant due to the geometric
features (shape of the cells of the ber they used, which
were found to be mostly oblong) and the range of standard
deviation. We feel this may not be the case, but that other
1717
factors, such as immaturity of the bers, higher microbrillar angle, along with the test conditions and chemical composition, are responsible for the observed dierences.
4.1.3. Eect of test length
The decrease in tensile strength and strain at break with
increasing test length of the ber can be understood as due
to the increasing number of defects/weak-links in the bers
with their increasing length. The observations and the
interpretations are similar to earlier published reports on
various lignocellulosic bers of Indian origin [12,57,60
62]. The defect density of the bers calculated from the
slope of the plot of nal tensile strength vs test length in
this investigation is 1106 M N m3. The fact that this value
is lower than that reported for Indian bers [61] suggests
the bers used in this study are better regarding defect content than those of the Indian bers. On the other hand, the
increase in Youngs modulus with increasing test length
can be interpreted as due to multicellular structure and
structural non-homogeneity of the bers, as observed and
explained in the case of Indian sisal bers [61]. Also, longer
the bers length, the higher will be its lignin content, and
hence the higher will be its resistance to applied stress
(higher stiness or modulus). This in turn results in lower
elongation.
4.1.4. Eect of the strain rate
The increase in tensile strength and unchanged initial
modulus and strain at break with increasing strain rate
observed in the present study can be explained in terms
of the viscoelastic model of cellulose bers [61]. In short,
the lignocellulosic bers such as coir, when subjected to
mechanical testing, behave as an elastic body at higher
speeds, with the crystalline region sharing most of the
applied stress/load. This results in increased tensile
strength and Youngs modulus. But at lower test speeds
the ber behaves like a viscous liquid and hence the applied
load is shared mostly by the amorphous region, resulting in
a low modulus. Also, since the crystallinity index of the
coir bers in the present study is close to 50%, there is no
trend towards viscoelastic performance in the ber at
higher testing speeds, and thus both the modulus and strain
at break may not change with increasing speed. However,
tensile strength being much more sensitive to test speed
compared to Youngs modulus, the increase in this property can be explained as reported for sisal [61].
4.2. Thermal eects
The thermogravimetric analysis (TG) of the bers in
nitrogen and oxygen atmospheres is shown in Fig. 6. The
TG measurement gives information about the composition
and thermal stability of coir bers. The gure also shows
that although the bers were tested in an oxidative atmosphere, degradation occurred in a much more complex
way than in an inert atmosphere. The % mass losses in
the two atmospheres are, respectively, 5.4 with onset at
1718
Table 3
Dynamic mechanical properties of coir ber in natural and dried state
Natural state
Dried state
tan d
Tg (C)
Modulus (GPa)
tan d
Tg (C)
Modulus (GPa)
0.0275
0.040
0.045
90
13
50
2.650
2.900
3.000
0.0275
0.0375
0.0325
87
57
33
4.500
5.750
5.250
1719
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