“Green” Composites Using Bioresins from Agro-Wastes
and Modified Sisal Fibers
Namrata V. Patil, Muhammad M. Rahman, Anil N. Netravali
Department of Fiber Science & Apparel Design, Cornell University, Ithaca, New York 14853
“Green” composites were fabricated using modified
sisal fibers and agro-waste derived resins from nonedi-
ble protein and starch in a simple and cost-effective
manner. Sisal fibers were modified using a novel com-
bination of mercerization followed by heat treatment
under a pre-determined tension which improved their
Young’s modulus by over 200% (from 5.5 to 16.7 GPa)
and tensile strength by about 50% (from 300 to 450
MPa). The non-edible protein and starch were
extracted from defatted karanja (Pongamia pinnata)
and mango (Mangifera indica) seed cake wastes,
respectively, to prepare the green resins. Composite
specimens were fabricated using as-received and
modified fibers and agro-waste derived resins using a
hand lay-up process followed by hot-pressing. The
tensile properties of the composites made with modi-
fied fibers showed significant improvement as com-
pared to the composites made with as-received fibers
as well as other edible starch or protein-based sisal
composites. POLYM. COMPOS., 00:000–000, 2017. V C
2017 Society of Plastics Engineers
INTRODUCTION
Increasing global environmental concerns and fast
depletion of petroleum resources have triggered research
in developing sustainable, environment-friendly, and bio-
degradable materials for use in various applications
including automotive, indoor housing, sports, and civil
structural sectors. As a consequence, fully renewable
plant-based polymers such as polysaccharides (starch, cel-
lulose, etc.) and proteins have received considerable
attention as “green” materials that satisfy the require-
ments stated above [1–3]. In addition, they are inexpen-
sive and widely available around the world [1–3]. Natural
fibers have already replaced some nondegradable syn-
thetic fibers in various applications such as textiles, pack-
aging as well as composites. Although natural fibers are
not as strong as some synthetic fibers, recent advances in
Correspondence to: A. N. Netravali; e-mail: ann2@cornell.edu
Contract grant sponsor: NSF-CREST; contract grant number: 1137681;
contract grant sponsor: Wallace Foundation.
DOI 10.1002/pc.24607
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2017 Society of Plastics Engineers
V sectors [26–28]. After extracting oil, the remaining
POLYMER COMPOSITES—2017
natural fiber development through surface treatments have
shown significant opportunities for improving the perfor-
mance of natural fibers [4, 5]. Sisal is one of the widely
used natural fibers as it is easy to cultivate. These fibers
are extracted from the leaves of Agave Sisalana plant.
The effect of various chemical modifications such as
alkali treatment, acetylation, silanization, etc., on the
structure-property characteristics have been investigated
in the past [6, 7]. Low density, along with excellent
mechanical properties of such fibers compared with com-
mon synthetic fibers can provide lighter and stronger eco-
friendly structures including composites [6].
Some “partially green” composites made by combining
natural fibers and petroleum-based resins have already
been commercialized and used in various applications [7,
8]. Like the fully synthetic composites, partially green
composites also face the same disposal problems at the
end of their useful life due to the presence of nondegrad-
able petroleum-based resins that cannot be separated from
fibers. As a result, the focus has been slowly shifting to
fabricating fully “green” composites using natural fibers
and biodegradable resins that can be composted rather
than putting them in the landfills [9].
A number of biodegradable resins have been devel-
oped from some commercially available edible proteins
such as soy and starches such as potato and corn for com-
posite materials [10–19]. A major concern about utilizing
these sources for technical applications is that they are
extracted from edible sources. Considering the increased
demand for edible proteins and starches in the future,
from human and livestock sectors, it is critical to explore
the nonedible sources for technical applications, which
will not compete with the edible ones in the food security
interest [20–22]. Some agro-seeds such as Pongamia pin-
nata (karanja), Azadirachta indica (neem), and Jatropha
curcus (jatropha) have received attention in the recent
past as the sustainable oil sources for medicinal or bio-
diesel production [20, 21, 23–25]. While some other fruit-
seeds such as Mangifera indica (mango), Citrullus lanatus
(watermelon), Cucumis melo (honeydew melon) are used
to extract oils for use in cosmetics and pharmaceutical
 FIG. 1. Chemical structure of (a) amino acid, (b) amylose, and (c) amylopectin.
defatted seed cake, rich in secondary metabolites consist-
ing mostly of starch and/or protein, remains as waste [21,
22]. Additional value can be easily obtained from these
seed cakes if starch and proteins in them can be extracted
and used as biodegradable resins for fiber-reinforced com-
posites [29]. Some of the seed wastes such as karanja,
neem, and mango contain toxins or anti-nutritional com-
pounds, which, in fact, may be beneficial if traces of the
toxins from these seed cakes are present in the resins and
composites as they can protect composites from micro-
bial, termite, or ant attacks [20].
The main goal of this study was to develop a process
to enhance the sisal fiber properties and fabricate low-
cost, fully “green” composites by combining modified
sisal fibers with starch and protein based bioresins
derived from agro-industrial wastes. Sisal fiber was
selected as reinforcement due to its abundant availability,
low-cost, high cellulose content, and good specific tensile
strength. For the first time, as-received sisal fibers were
modified using an optimum combination of chemical
(mercerization) and physical (heat) treatment under prede-
termined tension to further enhance their tensile proper-
ties. The effect of combination (chemical and heat)
treatment on fiber properties has been investigated in this
study. Karanja protein (KP) was extracted from defatted
karanja seed cake (DKSC) while mango starch (MS) was
extracted from defatted mango seed cake (DMSC). As-
received and chemical and heat treated (modified) sisal
fiber-reinforced unidirectional composites were fabricated
with KP and MS resins, separately, using hand lay-up and
hot-pressing processes. The mechanical properties and the
cost of manufacturing of the composites have been illus-
trated and compared with other green composites.
EXPERIMENTAL
Materials
DKSC was obtained from The Ahimsa Alternative,
Bloomington, MN, USA and DMSC was provided by
Manorama Industries, Raipur, Chhattisgarh, India. Sisal
fibers were purchased from Agroindustrias in Yucatan,
Mexico. These fibers had a density of 1.45 g/cm3 and
their diameters ranged between 200 and 400 mm. Analyti-
cal grade sodium hydroxide (NaOH) pellets, hydrochloric
acid (37%), glacial acetic acid, and reagent grade sorbitol
2 POLYMER COMPOSITES—2017
(98% purity) were purchased from Sigma-Aldrich
Chemical, Allentown, PA, and used as received.
Extraction of KP and MS
The protein content in DKSC was about 27% while
the starch content in DMSC was 43%. KP and MS
were extracted and purified from the DKSC and DMSC,
respectively, using the previously reported methods [22,
29].
In brief, KP was extracted using an alkaline extraction
and acid precipitation of DKSC [29]. At first, finely
ground DKSC powder was dispersed in alkaline medium
(pH 5 10.5 6 0.2) followed by magnetic stirring at 758C
for 60 min. The mixture was then centrifuged to discard
the insoluble residues from the supernatant. The superna-
tant was adjusted to acidic pH (4.5 6 0.2) for isoelectric
precipitation of KP. The resulting brown precipitate was
separated, freeze-dried, and ground to fine powder, which
is referred to as KP. The general chemical structure of
the amino acids in KP is shown in Fig. 1a. KP consists of
several polar and nonpolar amino acids, which are recog-
nized by the “R” group varies significantly depending on
the amino acid [29]. The amino acids within a single mol-
ecule are bound by peptide bonds formed by the reaction
between the carboxylic and amino groups.
For extracting MS, DMSC was passed through a
blender to obtain fine powder. This powder was passed
through a 250 mm sieve and stirred in water overnight by
magnetic stirring and then vacuum filtered. The washing
and filtration steps were repeated again to wash away
water-soluble sugars, leaving the starch-rich residue. This
residue was dried in an air circulating oven at 608C for
24 h. The dried starch-rich residue was ground in a
blender and passed through a sieve to obtain fine MS
powder. MS consists of starch, which is a polysaccharide
composed of glucose units linked with a-(1!4) linkages
(amylose) and a-(1!6) linkages (amylopectin). The
chemical structure of amylose and amylopectin is shown
in Fig. 1b and c, respectively.
Preparation of KP and MS Resins
To prepare KP resin, KP powder was mixed with DI
water in the ratio of 1:10 (w/v) using a magnetic stirrer.
Sorbitol (10 wt% of KP) was added to the KP solution to
DOI 10.1002/pc
 FIG. 2. Schematic illustration of sisal fiber modification using chemical and heat treatment. [Color figure
can be viewed at wileyonlinelibrary.com]
overcome the brittleness of the protein resin and stirred
further for 10 min. After this, the pH of the KP solution
was adjusted to 11.5 6 0.2 and was stirred at 808C for 20
min. At this stage, KP resin was ready to use with sisal
fiber to fabricate composites.
To prepare MS resin, MS powder was mixed with DI
water in the ratio of 1:10 (w/v) at room temperature (RT)
and then gelatinized (without adding any plasticizer) by
increasing the temperature of the solution to 908C for 30
min. As the temperature increased, the viscosity of the starch
increased as a result of gelatinization. The gelatinized starch
was used as a resin to bind sisal fibers and form composites.
To test the tensile properties, the plasticized KP and
gelatinized MS were poured, separately, onto TeflonV R
coated glass plates and dried in an air-circulating oven at
408C and then hot–pressed in a hydraulic hot-press (Car-
ver, model 3891-4PROA00, Wabash, IN) at 1308C for 20
min to obtain KP and MS resin sheets. These resin sheets
were conditioned at 218C and 65% RH for 24 h prior to
their characterization.
Modification of Sisal Fibers
As-received sisal fibers were modified by chemical
treatment followed by a heat treatment process. Both
chemical and heat treatment processes were carried out
under constant tension. A bundle containing 40 oriented
sisal fibers was immersed in 2M NaOH solution at RT
while applying a tension of 50 g/fiber for 2 h in a
PlexiglasVR tank built for the treatment as shown in the
schematic in Fig. 2. In an earlier study, a tension of
50 g/fiber was shown to give the highest improvement in
the Young’s modulus and the tensile strength of the sisal
fibers [30]. One end of the fiber bundle was fixed with
the clamp to the tank and passed through the rollers onto
DOI 10.1002/pc
the other end where the fibers were held in tension by
applying the desired amount of load. After 2 h of soaking,
the fibers were rinsed several times with DI water, neu-
tralized with 1% acetic acid solution, and again rinsed
several times with the DI water to obtain neutral pH. The
fibers were then dried at 1408C in an air-circulating oven
for 1 h under the same tension kept during the chemical
treatment. These chemical and heat-treated fibers are
referred to as “modified fibers” in this study. As-received
and modified fibers were conditioned at 218C and 65%
RH for 24 h prior to their characterization.
Fabrication of Sisal Fiber-Reinforced Composites
A simple hand lay-up process was used for fabricating
the unidirectional composites. Continuous (with respect to
specimen size) sisal fibers (as-received and modified)
were immersed into plasticized KP and gelatinized MS
resins, separately, taken out and squeezed softly to
remove excess resin by hand. The immersion in the resin
solutions and squeezing steps of sisal fibers were repeated
several times to ensure complete resin impregnation of
the fibers. The wet fibers in the bundles were aligned uni-
directionally on the TeflonVR coated metal mold to prevent
any major distortion. After that, they were dried for 18 h
in an air-circulating oven maintained at 408C. Finally, the
dried (still containing small % of moisture) composites
were cured in a Carver Hydraulic hot press at 1308C for
20 min under a pressure of 6 MPa. All composites were
then conditioned at 218C and 65% RH for 24 h. Sisal
fiber reinforced KP composites are referred to as Sisal-
KP composites while sisal fiber reinforced MS compo-
sites are referred to as Sisal-MS composites. Modified
sisal fiber reinforced KP composites are referred to as
Modified Sisal-KP composites while modified sisal fiber
POLYMER COMPOSITES—2017 3
reinforced MS composites are referred to as Modified
Sisal-MS composites in this study.

Characterizations of Sisal Fibers, Sisal-KP, and Sisal-MS

Composites
Attenuated total reflectance-Fourier transform infrared
(ATR-FTIR) spectra of as-received and modified sisal
fibers were collected using a Nicolet Magna 560 FTIR
spectrometer with a split pea accessory. Each spectrum
was obtained by averaging 256 scans recorded from
2,000 to 800 cm21 wavenumbers.
Thermal degradation behaviors of the as-received and
modified sisal fibers were investigated using thermogravi-
metric analysis, TGA, (TGA-2050, TA Instruments, DE).
Specimens weighing (6 mg) were scanned from 30 to
6008C at a heating rate of 108C/min under a flow of
60 mL/min nitrogen gas.
X-ray diffraction (XRD) patterns of the as-received
and modified sisal fibers were recorded on an X-ray dif-
fractometer (Scintag theta-theta powder diffractometer,
PAD-X, Scintag, Cupertino, CA) equipped with CuKa1
radiation (k 5 0.154 nm) at 40 kV and 40 mA. Data were
collected from 208 to 508 Bragg angles (2h) at a scan rate
of 38/min and a step interval of 0.028. Average of three
different samples was used to calculate the crystallinity of
both as-received and modified fibers.
Tensile properties of single sisal fibers (as-received and
modified), KP and MS resin sheets (approx. 1 mm thick-
ness) and their composites were determined using an Instron
5566 universal testing machine (Canton, MA). Single sisal
fibers were individually mounted on rectangular paper tabs
and glued at two ends. The fiber diameter was measured at
five different locations along the gauge length using a cali-
brated optical microscope (Olympus BX51, Melville, NY).
The fibers were tested at a strain rate of 0.02 min21 and a
gauge length of 30 mm. At least 20 specimens were tested
to perform statistical evaluations of the data.
Resin specimens with dimensions of 10 3 60 mm2 were
tested at a strain rate of 0.6 min21 and a gauge length of
30 mm using the same Instron universal testing machine. At
least six specimens were tested to report the average values
with standard deviations. The composite specimens with
dimensions of 10 3 60 mm2 were tested at a strain rate of
0.6 min21 and a gauge length of 30 mm. A minimum of
six specimens were tested for each composition.
Surface morphologies of the as-received and treated sisal
fibers and fracture surfaces of the composites were charac-
terized using a LEO 1550 field emission scanning electron
microscope (Germany) at 3 kV accelerating voltage.
RESULTS AND DISCUSSION
Characteristics of as-Received and Modified Sisal Fibers
Figure 3 shows ATR-FTIR spectra of the as-received
and modified sisal fibers. As can be seen in Fig. 3, both
FIG. 3. ATR-FTIR spectra of as-received and modified sisal fibers.
major peaks at 1,736 and 1,240 cm21 seen in as-received
fibers diminished after the modification. The peak at
1,736 cm21 seen in as-received fibers is assigned to the
unconjugated stretching of carbonyl group from carbox-
ylic acids or esters. A similar peak was observed in hemi-
cellulose by Yang et al. [31]. The diminished peak at
1,736 cm21 in the modified sisal fiber can be attributed
to the removal of hemicellulose [32]. The peak at
1,240 cm21 represents the CAOAC stretching vibration
of aryl alkyl ether groups due to the presence of lignin in
as-received sisal fiber. This peak was also reduced in the
modified sisal fiber. Yang et al. also observed a peak at
1,240 cm21 for lignin, which was absent in pure cellulose
[31]. The ATR-FTIR results confirm the removal of most
of the hemicellulose and lignin from the surface of sisal
fiber (an insignificant little trace may be attached to the
fiber) and should result in an increase in the cellulose
content.
Figure 4 shows the TGA thermograms of as-received
(a) and modified sisal fibers (b) along with their deriva-
tive (DTG) curves. The TGA thermograms of as-received
sisal fibers in Fig. 4a show three distinct stages. The
weight loss below 1508C can be attributed to the evapora-
tion of any adsorbed water/moisture. In this case, this loss
was about 4–5%. As-received sisal fibers started to
degrade from 2258C and showed a weight loss of about
70% in the range of 225–4008C. The weight loss in this
range was observed in two stages. DTG curve shows two
distinct peaks at 300 and 3668C, indicating two step-
degradation of the as-received sisal fiber. Thermal degra-
dation of hemicellulose has been reported to occur
between 225 and 3408C [33]. About 23% weight loss was
observed during this stage. Thermal degradation of cellu-
lose component occurred at a higher temperature with
faster degradation rate seen within the range of 340–
4108C with a weight loss of about 42% [31]. The com-
plete carbonization of as-received sisal fibers occurred
from 450 to 6008C with 10–15% char yield remaining.

4 POLYMER COMPOSITES—2017 DOI 10.1002/pc

 FIG. 4. TGA thermograms of (a) as-received and (b) modified sisal fibers along with their derivative
(DTG) curves. [Color figure can be viewed at wileyonlinelibrary.com]

The thermal degradation of modified sisal fibers showed
two distinct stages as can be seen in Fig. 4b. The initial
weight loss below 1508C of about 5–6% was due to the
evaporation of absorbed water/moisture. Cellulose decom-
position was observed between 260 and 3508C with a
weight loss of about 50%. DTG curve confirmed the
removal of hemicellulose at 3008C observed in as-
received sisal fibers. The complete carbonization of sisal
fibers occurred from 450 to 6008C with 25–30% char
yield remaining.
Figure 5 shows XRD patterns of the as-received and
modified sisal fibers. Two broad peaks were observed in
both as-received and modified fibers at around 15.08 and
22.08, which can be assigned to (110) and (220) crystal
planes of cellulose [34]. However, the XRD peak for the
as-received fibers was broad, which comes from the
amorphous phase of the lignin present in the fiber. The
crystallinity index for as-received sisal fibers was calcu-
lated to be 64%, which is close to the previously reported
values of around 61% [35]. Both mercerization and heat
treatment under tension increase the crystallinity index in
modified fibers. Particularly, mercerization under tension
reduced the amorphous lignin content of the fibers. A sig-
nificant improvement of crystallinity from 64 to 73% was
observed after the mercerization and heat treatment of
sisal fibers due to the removal of cementing materials,
primarily lignin, which is noncrystalline. This improve-
ment is statistically significant as the average of three
specimens from various parts of the as-received and mod-
ified sisal fibers used to calculate the crystallinity belongs
to the fibers from the same origin (source). The signifi-
cant increase in the crystallinity is also reflected in the
increase in the tensile properties such as strength and
modulus of the modified fibers. Both treatments also
allowed better packing of cellulose molecules due to
stress as shown earlier in the scheme shown in Fig. 2 [6].
A sharp peak at 24.58 was observed in as-received sisal
fibers, which can be attributed to inorganic impurities
such as silica or calcium carbonate [35]. However, this
peak disappeared after the modification, which indicates
increased purity of sisal fibers. Usually, mercerization
improved the purity of sisal fibers by removing hemicel-
lulose and lignin along with other inorganic impurities
[36].
Figure 6 shows SEM micrographs of as-received and
modified sisal fibers at two different magnifications. As
seen in Fig. 6a, the surface of the as-received fibers was
relatively smooth compared to that of the modified fibers
(Fig. 6b). As mentioned earlier, the mercerization process
helps in removing undesirable lignin and hemicellulose as
well as other impurities such as silica/CaCO3 from the
fibers (confirmed by ATR-FTIR, TGA, and XRD). As the
NaOH solution causes the swelling of the fibers, it
removes lignin and simultaneously dissolves the primary
cell wall; a grid-like rough surface appears for the modi-
fied fibers as the fibrils are exposed. This can be clearly
seen in Fig. 6b [37]. The rougher, grid-like surface leads
to higher specific surface area available for better key
and lock type mechanical bonding with the resin [36].
The removal of lignin, hemicelluloses, and other inor-
ganic impurities results in hydroxyl groups on the cellu-
lose molecules to be exposed (as shown in scheme in Fig.
2), which, in turn, provide significant opportunity to
enhance the fiber-resin adhesion through hydrogen bond-
ing. Both, surface roughness and hydroxyl groups, are
FIG. 5. XRD patterns of as-received and modified sisal fibers.

DOI 10.1002/pc POLYMER COMPOSITES—2017 5

 FIG. 6. SEM micrographs of (a) as-received and (b) modified sisal fibers. Inset images taken at higher
magnifications.

beneficial to obtain higher fiber/resin interfacial shear
strength, and can result in higher Young’s modulus and
strength of the composites [36].
Table 1 presents data from the tensile tests that include
Young’s modulus, tensile strength, and fracture strain of
as-received and modified sisal fibers. As can be seen in
Table 1, significant improvement of over 200% in
Young’s modulus was obtained after the chemical and
thermal treatments of the fibers. Similarly, the tensile
strength of the modified fibers also increased by about
50%. However, fracture strain decreased from 6.1% to
3.1% (by about 50%). These changes are related to the
reduction in hemicellulose, lignin, and pectin components
resulting in increased cellulose content, which provides
the strength to the fiber because of its crystalline form. It
is common to observe longitudinal shrinkage in the case
of alkali-treated or mercerized natural fibers if no tension
is applied during the treatment [30]. Mercerization under
tension allows much greater improvement of fiber
strength as it improves the molecular orientation, reduces
the microfibrillar angle as well as results in better packing
of the crystallites and, thus, reduces the weak links origi-
nated from voids in the cellulose microfibrils [30]. Kim
and Netravali have shown that mercerization of sisal fibers
under tension leads to an improvement of about 110% in
Young’s modulus of the treated fiber [30]. Additional
improvement in Young’s modulus (over 200%) was
observed in this study after the mercerized fibers were heat-
treated at 1408C under tension. The heat treatment under
tension further increases the tensile strength as it is assumed
that the spiral degree of microfibrils (microfibrillar angle)
decreases further due to tension during heat treatment. These
changes in structure and chemical composition lead to the
improvement of tensile strength and modulus of sisal fibers.
Due to nonuniformity in the sisal fiber diameters, high
variability in tensile strength of sisal fibers was observed.
Therefore, a more realistic two-parameter Weibull statisti-
cal model was used to evaluate the cumulative density
function for the fiber strength. Figure 7 shows the Wei-
bull plots for as-received and modified sisal fibers. Proba-
bility of failure P, of a fiber with
h length
 iL failed at a
r m
stress r is given by: P 5 12exp 2 LL0 r0 Þ ; where, m is
the dimensionless shape parameter or Weibull modulus,
r0 is the scale parameter or characteristic strength in
MPa, and L0 is the reference length. L0 is considered 1
for simplicity. By linear regression from the Weibull plot,
value of m can be determined from the slope of the fitted
straight line and r0 can be obtained from the X-axis
where the line intersects Y-axis at 0 (i.e., Y 5 0) as can
be seen from Fig. 6. The probability of failure P at ith
ranked specimen from a total of N specimens is obtained
from the equation: P5 N11 i
. The mean tensile strength of

TABLE 1. Tensile properties of as-received and modified sisal fibers.

Young’s Modulus Tensile strength Fracture strain

Specimens (GPa) (MPa) (%)

As-received 5.5 6 1.2 305 6 57 6.6 6 0.6

sisal fibers
Modified 16.7 6 3.0 459 6 74 3.1 6 0.7
sisal fibers FIG. 7. Weibull probability plots for tensile strength of as-received and
modified sisal fibers.

6 POLYMER COMPOSITES—2017 DOI 10.1002/pc

TABLE 2. Weibull parameters determined from tensile test of as-
received and modified sisal fibers.
Weibull Scale Mean tensile Regression
modulus parameter strength, coefficient
Specimens (m) r0 (MPa)  (MPa)
r R2
As-received 5.6 330 304 0.94
sisal fibers
Modified 6.6 493 460 0.94
sisal fibers
 
sisal fiber is determined as r 5r0 C 11 m1 ; where, C rep-
resents the Gamma function. It is noted here that the
larger Weibull modulus, the more uniform is the fiber
strength distribution. The Weibull distribution parameters
calculated using linear regression methods have been
listed in Table 2. The Weibull moduli for the as-received
and modified sisal fibers were calculated to be 5.6 and
6.6, respectively. The lower value of Weibull modulus for
as-received sisal fibers indicates higher and uneven defect
distribution, which causes larger variation in tensile
strength.
Characterization of Sisal-KP and Sisal-MS Composites
Unidirectional Sisal-KP composites were fabricated
using the two sisal fibers (as-received and modified) and
precured KP resin containing 10% (w/w) sorbitol as plas-
ticizer. Unidirectional Sisal-MS composites were also fab-
ricated using the same two sisal fibers (as-received and
modified) and precured MS resin. The fiber volume frac-
tion of 0.42 6 0.02 was maintained in all cases. Previ-
ously, it has been shown that KP and MS resins can
replace edible protein or starch based resins, respectively,
and even some of the petroleum-based resins such as
polyvinyl alcohol or polypropylene because of their
acceptable properties [22, 29]. Table 3 shows the experi-
mental tensile properties of the as-received and modified
sisal fiber reinforced composites using KP and MS resins.
As can be seen in the data presented in Table 3, tensile
strength and Young’s modulus of the modified fiber
reinforced composites are significantly higher than the
composites made using as-received fibers in case of both
resins. Tensile strength, Young’s modulus, and fracture
strain of as-received Sisal-MS composites were 102.0
MPa, 4.6 GPa, and 3.3%, respectively. Modified Sisal-
MS composites showed significant improvements of 55%
in strength (over 158 MPa) and just over 75% in modulus
(8.1 GPa) along with a small decrease of 12% (2.9%) in
fracture strain. Based on the fiber tensile properties,
improved composite properties for modified sisal fibers
were expected. A similar phenomenon was observed in
the case of Sisal-KP composites as shown in Table 3. The
other factors contributing to the increased strength of the
modified fiber composites are the increased surface
roughness and cellulose content of the modified fibers.
Increased surface roughness allows better lock and key
type mechanical bonding whereas higher cellulose content
allowed better wetting of the fibers by the resins and
higher hydrogen bonding at the fiber-resin interface. It is
also clear from data in Table 3 that Sisal-MS composites
have better tensile properties compared to Sisal-KP com-
posites. The reason can be attributed to better starch-sisal
fiber bonding compared to protein-sisal fiber bonding
because of the chemical similarity between starch and
cellulose that can result in significant hydrogen bonding
compared with protein-cellulose [28]. Table 3 also shows
the theoretical (expected) values of Young’s modulus
and strength of composites, at 55% fiber volume fraction,
calculated using the rule of mixture (ROM). As stated
earlier, the expected values for Young’s modulus
and fracture stress of as-received and modified fiber com-
posites were calculated using a simple ROM model
to compare with the experimental values (Table 3)
[27]. The ROM model was used to predict the Young’s
modulus and fracture stress of the composite:
Ec 5 Ef vf 1 Em ð12vf ), where Ec ; Ef ; and Em are
Young’s modulus values for composite, fibers, and resins,
respectively, and vf is the fiber volume fraction in the
composites. The tensile properties of KP and MS resins
used for ROM calculations have been taken from the pre-
viously published studies from our laboratory [22, 29]. As

TABLE 3. Tensile properties of KP, MS, Sisal-KP, and Sisal-MS composites.

Composite specimens Young’s Modulus (GPa) Tensile strength (MPa) Fracture strain (%)

As-received Sisal-KP 3.1 (1.2) 110.8 (14.2)a 6.1 (1.0)

Modified Sisal-KP 5.8 (0.8) 152.8 (12.8) 3.8 (0.9)
As-received Sisal-MS 4.6 (1.4) 101.7 (10.3) 3.3 (0.5)
Modified Sisal-MS 8.1 (0.5) 158.1 (12.6) 2.9 (0.3)
KP [29] 0.4 (0.07) 10.8 (0.6) 31.5 (6.7)
MS [22] 0.3 (0.06) 3.5 (0.06) 1.3 (0.05)
As-received Sisal-KP (expected)b 3.2 172.6 —
Modified Sisal-KP (expected) 9.4 257.3 —
As-received Sisal-MS (expected) 3.2 169.3 —
Modified Sisal-MS (expected) 9.3 254.0 —
a
The numbers in parentheses are standard deviations.
b
Expected values are based on 55% fiber Vohnne in composites.

DOI 10.1002/pc POLYMER COMPOSITES—2017 7

 FIG. 8. SEM micrographs of the fracture surfaces of as (a) received sisal-KP, (b) modified sisal-KP, (c) as
received sisal-MS, and (d) modified sisal-MS composites in the longitudinal direction.
shown in Table 3, there are some discrepancies between
the experimental and the expected values, which can be
attributed to the experimental flaws. For example, the
nonuniform tension during hand-fabrication of composites
causes misalignment of the fibers within composites and
voids created during hot pressing or bubbles in the resin
can lead to lower Young’s modulus and strength as com-
pared with that of the fibers. In addition, these defects
negate the enhancements obtained in the fibers, at least to
some extent. However, such difficulties observed in labo-
ratory scale processing would not exist on an automated
manufacturing system used in the industry [30]. As a
result, much better composite properties can be obtained.
Earlier researchers have shown that mercerized sisal
fiber-soy protein resin composites can have tensile strength
of 188 MPa and Young’s modulus of 3.8 GPa at 55% fiber
volume fraction [30]. However, based on the results
obtained in this study, ROM calculations show that the
Young’s modulus of modified Sisal-MS composites would
be around 9.3 GPa while the Young’s modulus of modified
Sisal-KP composites would be around 9.4 GPa at the same
fiber volume fraction (Table 3) indicating much better
8 POLYMER COMPOSITES—2017
stiffness compared with the previous study [30]. In another
study, Young’s modulus and tensile strength values of sisal
fiber-reinforced polyurethane composites with a 30% fiber
volume fraction were found to be 1.81 GPa and 119 MPa,
respectively [38]. At 55% fiber volume, these values would
be about 3.3 GPa and 220 MPa, still much lower that the
values obtained in this study for the modified sisal fiber
composites. Overall, the properties such as tensile strength
and Young’s modulus of the modified Sisal-KP and modi-
fied Sisal-MS composites are higher as compared to other
composites based on pure soy protein or polyurethane resins
mentioned above. The superior properties of modified of
sisal fiber composites can be attributed fully to their
enhanced tensile properties after the combination of chemi-
cal and heat treatments. Even after considering the expense
of fiber treatment, the cost of manufacturing these compo-
sites would be extremely low because of the resins derived
from agro-wastes. As compared to other synthetic and most
natural fibers, the price of sisal fibers is low (0.36 US$/Kg)
and the green resins, KP or MS, prepared in this study could
be available for free, as they are considered as waste by-
products at present [22, 39].
DOI 10.1002/pc
 Figure 8 shows SEM images of the fracture surfaces of
as-received Sisal-KP, modified Sisal-KP, as-received
Sisal-MS and modified Sisal-MS composites in the longi-
tudinal direction after tensile tests. The fracture surfaces
of the as-received sisal fiber reinforced composites (Fig.
8a and c) showed longer fiber pull out (protruding)
lengths compared to those of the modified fiber rein-
forced composites (Fig. 8b and d). While the pull-out
length for the modified fibers is much shorter, they still
seem to be held together by the resin after fracture.
Results of this study confirm the earlier observations
made by Kim and Netravali who reported that the fracture
in the as-received fiber composites occurs partially due to
debonding of the fibers from the resin first and then the
fibers are broken as opposed to composites with modified
fibers where the fibers break and then the debonding
occurs [30]. As stated earlier, mercerization (chemical)
treatment removes lignin from the sisal fibers and, thus,
increases the cellulose content. As shown in Fig. 1, the
chemical structure of MS consists of amylose and amylo-
pectin, both made of glucose monomer units, is similar to
that of the cellulose from the sisal fibers, which is also
made up of glucose monomer units. The large number of
hydroxyl groups present on the surface of both starch and
cellulose leads to the formation of strong hydrogen bonds
between MS resin and sisal fibers [40, 41]. KP is made
up of many amino acids that contain polar groups
(hydroxyl, carboxyl, and amine) such as arginine, lysine,
histidine, aspartic acid, and glutamic acid. It also has sev-
eral amino acids such as alanine, glycine, etc., with non-
polar groups. Typically, sisal fibers can form hydrogen
bonds with the polar groups in amino acids as well as the
peptide bonds and not with that amino acids which have
nonpolar groups in protein [42, 43]. This limits the hydro-
gen bonding capability between sisal fibers and KP resin
to some extent. As a result, the bonding between sisal
fibers and starch resin can be expected to be slightly
higher compared with the bonding between sisal fibers
and KP resin. Thus, modified sisal fibers with higher cel-
lulose content can not only provide hydroxyl groups for
better fiber wetting but also can hydrogen bond with MS
and KP resins. In addition, the surface of the as-received
fibers is smooth, which makes debonding from the resin
easier as opposed to the rough, grid-like surface of the
modified fibers. All these factors contribute to better
interfacial bonding in the modified sisal fiber composites
and manifests in higher tensile strength and Young’s
modulus compared with the as-received fiber composites.
CONCLUSIONS
This study has successfully demonstrated that the ten-
sile and thermal properties of sisal fibers can be signifi-
cantly enhanced using a novel combination of chemical
and heat treatments carried out under tension. These treat-
ments can be extended to other natural cellulosic fibers
such as ramie, flax, jute, etc. as well. The study also
DOI 10.1002/pc
demonstrated that agro-industrial by-products and wastes
can be potential sources of nonedible protein or starch
based resins, which can substitute many edible proteins
and starches used to obtain sustainable bioderived resins.
The modified sisal fibers showed increased affinity for
both protein and starch based bioresins due to better
physical and chemical bonding. The tensile strength and
Young’s modulus of the modified fiber-reinforced compo-
sites were found to be higher than the ones made with the
as-received fibers as a result of the improved fiber prop-
erties as well as enhanced fiber-resin interfacial bonding.
The resins used in this study are available for almost free
and sisal fibers are inexpensive as well. Low cost of raw
materials and the processing techniques makes such com-
posites environmentally friendly, economically viable,
and industrially scalable.
ACKNOWLEDGMENT
The use of Cornell Center for Materials Research shared
facilities supported through the NSF MRSEC program
(DMR-1120296) is also acknowledged.
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DOI 10.1002/pc