Composites Science and Technology 69 (2009) 10091015

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Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Biodegradable green composites made using bamboo micro/nano-brils

and chemically modied soy protein resin
Xiaosong Huang *, Anil Netravali
Fiber Science Program, Cornell University, Ithaca, NY 14853, USA

a r t i c l e

i n f o

Article history:
Received 16 October 2008
Received in revised form 10 January 2009
Accepted 14 January 2009
Available online 23 January 2009
Keywords:
A. Polymermatrix composites (PMCs)
A. Short-bre composites
B. Mechanical properties
B. Thermomechanical properties
B. Environmental-friendly
Biodegradable
Green composites
Soy protein
Plant-based bres

a b s t r a c t
Micro/nano-sized bamboo brils (MBF) and a modied soy protein resin were used to fabricate environmentally friendly composites. With the incorporation of MBF the fracture stress and Youngs modulus of
the soy protein concentrate (SPC) increased signicantly. With the addition of 30 parts of MBF (SPC is 100
parts, based on weight), the fracture stress and Youngs modulus were increased from 20.2 MPa to
59.3 MPa and from 596 MPa to 1816 MPa, respectively. The addition of MBF, however, did not show signicant decrease in the fracture strain of the specimens. As a result, the toughness of the MBF reinforced
SPC increased. The toughness of the SPC based composites containing 30 parts of MBF was 6.0 MPa compared to 2.7 MPa for SPC without MBF. MBF reinforced SPC was then cross-linked using a silane, (3-isocyanatopropyl)triethoxysilane (ITES). Although the fracture strength and Youngs modulus did not show
signicant increase, the modication using ITES showed signicant increase in the fracture toughness.
SPC containing 30 parts of MBF, 10 parts of ITES and 2 parts of glycerol showed fracture stress of
82 MPa, Youngs modulus of around 3.2 GPa and toughness of 4.3 MPa. The environment-friendly, fully
biodegradable green composites, based on MBF and modied SPC resins, have excellent properties and
great potential to replace the traditional petroleum-based materials in many applications.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Petroleum-based polymers and ber reinforced composites are
widely used in different elds due to their low density and high
mechanical and physical properties. However, most of the resins
and bers made from petroleum are non-degradable and in the
composite form they are non-recyclable. With double digit growth
in the use of these materials in the past few years, their disposal
has become a critical issue. Further, petroleum is a fossil fuel which
is estimated to last for another 5060 years at the current rate of
consumption [1].
Petroleum is not sustainable or renewable resource. In addition,
there are a signicant environmental concerns caused by the use of
non-degradable petroleum-based polymers and composites. As a
result, fully sustainable and biodegradable materials have attracted the attention of many researchers and corporations [1].
Some biodegradable, petroleum-based polymers, such as polyvinyl
alcohol, and some polyesters and polyurethanes, possess excellent
mechanical properties [24]. However, since they are non-renewable petroleum-based resource, more attention is being given to
plant-based polymers and bers that are yearly renewable and
fully sustainable [5,6]. Bamboo, for example, used in this study
grows so fast that it can be harvested three or even four times a
* Corresponding author. Tel.: +1 607 379 3213.
E-mail address: xh29@cornell.edu (X. Huang).
0266-3538/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2009.01.014

year. Protein, starch, cellulose, etc. have been used to prepare the
biodegradable resins or composites [5,6].
Soy protein has been used to fabricate biodegradable green
plastics and composites due to its low cost and worldwide availability [711]. Soy beans are grown widely around the world and
many different soy protein grades are commercially available. For
example, defatted soy our containing about 50% protein, soy protein concentrate (SPC) with about 70% protein and soy protein isolates (SPI) containing about 90% protein are commonly available
[12]. Based on their ultracentrifugal sedimentation rates, soy
proteins can be sorted into four main categories, 2S, 7S, 11S and
15S [1214]. Out of them, 7S and 11S are the largest and the most
important fractions. Soy protein contains 18 amino acids including
those that contain polar functional groups, such as carboxyl, amine
and hydroxyl groups that are capable of chemically reacting
[1214]. These reactive groups can be utilized for chemical modication to improve the mechanical and physical properties of the
protein and thus improve the properties of the composites made
using them.
Plant-based bers are composed of nano- and micro-brils
[15,16]. Since the cellulose molecules in the brils are highly oriented and crystalline, micro-brils have excellent mechanical properties [1719]. Micro-brillated cellulose (MFC) can be obtained by
mechanical shearing of cellulose bers [1719]. The MFC has high
aspect ratio and high tensile properties and has been used for
fabrication of composites with excellent mechanical properties

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X. Huang, A. Netravali / Composites Science and Technology 69 (2009) 10091015

[1719]. The composites fabricated using MFC and phenolic resin

showed Young modulus of 19 GPa [17]. MFC has also been shown
to enhance the interfacial adhesion and toughness in bamboo composites by preventing the growth of micro-cracks [18,19].
Silanes have been used widely to form cross-linked (solgel)
structures [2023]. The alkoxy groups in silane can be hydrolyzed
in ethanol/water solution to form silanols. Silanols can further undergo condensation reactions with either other silanols or alkoxy
groups [20,21]. A solgel structure can be formed through the
hydrolysis and condensation reactions. The relative reaction rates
of hydrolysis and condensation can be inuenced by various factors such as pH, reaction temperature, and solvent. [2023]. As a
result, the microstructure of the solgel is controllable.
The objective of this study was to develop fully biodegradable
and environment-friendly green composites possessing moderate
strength and stiffness. Micro/nano-sized bamboo brils were used
as the reinforcement. SPC was rst reinforced with the micro/
nano-sized bamboo brils. The brils were uniformly dispersed
into the soy protein resin and formed into isotropic composite
sheets with high mechanical properties. The reinforced SPC composite was then chemically modied using ITES to further improve
the mechanical and physical properties.

The mechanical properties of the MBF modied SPC specimens

were further improved by chemical modication of SPC using ITES.
To study the effect of ITES on the properties of modied SPC, 2%,
5%, 7%, 10% and 12% of ITES, by weight of SPC, was added. To carry
out the reaction, the dried SPC was dispersed into THF which was
followed by the addition of predetermined amounts of ITES. This
mixture was stirred for 1 h to obtain a uniform dispersion. Ethanol
solution (20%) was then added to form a SPC suspension. The mix
ratio of ethanol solution: SPC was 1:15 by weight. Ethanol was
added to increase the solubility of ITES. The pH of the suspension
was controlled to be 8.5 by adding 1 M NaOH solution. The ITES
hydrolysis and condensation reactions were conducted at 75 C
while stirring for 2 h in the precuring step. Predetermined amounts
of MBF suspension were added 30 min before the end of the precuring step. The MBF and ITES modied SPC composite sheets were
then oven-dried at 40 C for 36 h to remove water and ethanol. The
dry composite sheets were cured using the same procedure as described above.
2.3. Specimen characterization

Soy protein concentrate (SPC) powder, under the brand name of

Arcon S, was provided by Archer Daniels Midland Company,
Decatur, IL. Micro/nano-sized bamboo brils (MBF) were obtained
from Doshisha University, Kyoto, Japan, in the form of a paste containing 510% MBF and 9095% water. Analytical grade NaOH,
glycerol, ethanol, anhydrous tetrahydrofuran (THF) and (3-isocyanatopropyl)triethoxysilane (ITES) were purchased from Fisher
Scientic, Pittsburg, PA. NaOH was dissolved into distilled and
deionized (DD) water to obtain a 1 M solution before using. ITES,
ethanol, THF and glycerol was used directly without further purication. SPC was vacuum-dried at 40 C and a vacuum of 710 mm of
mercury for 12 h.

Resin and composite specimens were characterized for their

tensile properties, such as Youngs modulus, fracture stress, fracture strain and toughness, using an Instron universal tester (model
5566). Tensile properties were characterized according to ASTM D
882-97. Specimen toughness was characterized as the area under
the stressstrain curve. Prior to testing, the specimens were conditioned at standard ASTM conditions (21 C and 65% RH) for three
days. At least ve specimens were tested to obtain the average values. The gauge length for the tensile test was 50 mm and the strain
rate was maintained at 0.5/min.
Moisture content was measured using a Brabender moisture
tester (model 1153) according to ASTM D 2654-89a after conditioning for three days. The oven chamber of the tester was maintained at 105 C. The specimens were dried in the test chamber
for 24 h before the measurements were conducted. The moisture
content (MC) was calculated from the weight of the conditioned
specimen (wc) and the dried specimen (wd) based on the equation
below.

2.2. Preparation of the modied SPC

MC %

The MBF paste was rst dispersed into DD water to form a uniform suspension. The mix ratio of dry MBF: water was 0.01 by
weight. 1 M NaOH was used to adjust the pH of the MBF suspension to 9. SPC powder was separately dispersed into DD water in
a weight ratio of 1:12 to form a suspension using a magnetic stirrer. Predetermined amounts of glycerol were added into the SPC
suspension as a plasticizer. For the specimens prepared to characterize the effect of MBF on the mechanical properties of the reinforced SPC, 15 parts of glycerol was added (SPC is 100 parts in
this study). Earlier study had revealed that 15 parts of glycerol
could provide appropriate processibility and mechanical performance. For convenience, 10%, 20%, 30% and 40% of MBF were added
to study the effect of MBF. MBF water suspension was mixed with
the SPC dispersion in water in varying amounts. The mixture was
mechanically stirred at room temperature until a uniform suspension was obtained. It was further stirred at 75 C for 30 min (this
process is called precuring) and then transferred onto a poly(tetrauoroethylene) coated plate mold to form sheets. Water was
evaporated by keeping the mold in an air-circulating oven at
40 C for 24 h. The dried composite sheets containing MBF were
hot-pressed in Carver Hydraulic hot press, model 3891-4PROA00,
at 120 C under a pressure of 8 MPa for 25 min to obtain the cured
MBF reinforced SPC composite sheets. The sheet thicknesses were
in the range of 0.14 mm.

The SPC cross-linking using ITES was characterized by sodium

dodecyl sulfate-polyacrylamide gel electrophoresis (SDSPAGE).
The precured ITES cross-linked SPC suspension (without MBF)
was dispersed in 0.30 M Tris-HC1 buffer containing 0.01 M 2mercaptoethanol (ME) with an 8.0 pH. A high range molecular
weight protein standard (Mark12TM, Invitrogen, USA) was used as
a molecular weight marker.
Leica scanning electron microscope (SEM), model 440X was
used to characterize the dimensions of the MBF used. A small
amount of MBF was dispersed into DD water to form a dilute
suspension. The suspension was spread onto a ake of mica
and dried in a vacuum oven. The dried specimens were sputtered
with goldpalladium before taking SEM photomicrographs. The
atomic force microscope (AFM) (Digital Instruments, model
DimensionTM 3100) was used in tapping mode to characterize
the MBF surface topography. Same specimen preparation technique was used as one used for the SEM. The surface roughness
was characterized using Rmax and RMS. Rmax is the difference in
height between the highest and the lowest points in the scanned
area and RMS is the standard deviation of the heights of all
points in the scanned area.
The specimens were also characterized for their thermal stability using a thermogravimetric analyzer (TGA), model 2050, (TA
Instruments, New Castle, DE). All specimens were scanned from

2. Experimental
2.1. Materials

wc  wd
 100
wd

X. Huang, A. Netravali / Composites Science and Technology 69 (2009) 10091015

25 C to 450 C at a ramp rate of 10 C/min. All TGA tests were

carried out in nitrogen environment.
The dynamic mechanical properties of the specimens were
characterized using dynamic mechanical analyzer (DMA, model2980, TA Instruments, Inc., New Castle, DE). The tests were
performed at 1 Hz frequency with an amplitude of 15 lm. The
specimens were scanned from 35 C to 250 C at a ramp rate of
5 C/min. The storage moduli were determined from the DMA plots
according to ASTM D4065-01.
3. Results and discussion
3.1. MBF characterization
Typical SEM photomicrographs showing the bril dimensions
are shown in Fig. 1. From these photomicrographs, it is clear that
the brils have a very broad size (diameter) distribution, ranging
from a few hundred nano-meters to the micron level. MBF used
in this study can be roughly categorized as a mixture of nano-brils and micro-brils based on their diameters. The bril lengths
also show a broad distribution. In addition, the brils, especially
the nano-brils, show entanglements and branchings that form a

1011

network by splitting at different locations along the length as can

be seen in Fig. 1a. Fibrils were randomly orientated. The interconnected bril network as seen in Fig. 1a and b can contribute to improve the mechanical properties of the composites due to the high
interlocking density facilitating load transfers among brils and
the excellent mechanical properties of the brils.
Bamboo ber has a brillar structure as most other plant-based
bers have [17,24]. The surface topographies of micro-brils were
observed using AFM. Fig. 2 shows a typical AFM image of the surface of micro-brils with a scan size of 500 nm  500 nm. The
surface was rough at nano-scale. Rough surface provides a large
surface area so as to increase the interfacial interaction with the
resin in a composite. Roughness can also increase mechanical
interlocking if the resin can occupy all the valleys. The Rmax value
for the scanned surface was 102 nm and the RMS value was 16 nm.
The interaction (interfacial adhesion) between bers and the resin is an important factor that can inuence the mechanical and
physical properties of a composite [25,26]. A high interaction. i.e.,
good adhesion between the ber and the resin makes the stress
transfer between bers more efciently resulting in high mechanical properties. Since both SPC and cellulose in bamboo have polar
groups and hydrophilic properties, strong interfacial interaction,
such as hydrogen bonding, can be formed between the two phases
by providing a large interfacial area. Also, for the same weight of
bers, the smaller the ber diameter, the larger surface area the ber can provide. In the present case, both the nano-brils and micro-brils provided a large surface area. The micro-brils also
showed high surface roughness, as seen in Fig. 2, which can provide mechanical interlocking. Generally, a good interfacial interaction can be expected between the MBF and SPC resin because of
their compatible chemistries.
3.2. Mechanical properties of the MBF reinforced SPC composites
The polar groups in proteins are capable of cross-linking reaction. Thiols in cysteine in the extended soy protein chains can be
re-organized and oxidized to form disulde bonds [27]. The active
groups, such as hydroxyl, amine and carboxyl, in protein can form
hydrogen bonding or undergo condensation reaction to form a
cross-linked structure during precuring and curing steps [811].
The cured soy protein resin lm is in a cross-linked form through
these reactions which contribute to their high stiffness.
The effect of MBF content on the Youngs modulus, fracture
stress, fracture strain and toughness of the SPC with 15 parts of

Fig. 1. SEM photomicrographs of the micro/nano-sized bamboo brils.

Fig. 2. AFM image of the micro-bril.

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X. Huang, A. Netravali / Composites Science and Technology 69 (2009) 10091015

glycerol as the plasticizer is shown in Fig. 3a and b. Youngs modulus and fracture stress of the SPC containing 30 parts of MBF increased signicantly to 1816 MPa and 59.3 MPa, respectively,
compared to the Youngs modulus of 596 MPa and fracture stress
of 20.2 MPa for the SPC with no MBF. Cellulose brils have very
high crystallinity and molecular orientation. Microbriliated cellulose has been estimated to have Youngs modulus of about 140 GPa
due to this high crystallinity and orientation of cellulose in the brils [17,18]. Mechanical properties of the MBF used in this study
can also be expected to be high. In addition, high strength bamboo
brils which form a network as shown in Fig. 1 also help the load
redistribution between different brils resulting in higher mechanical properties of the reinforced composites. In addition, strong
hydrogen bonds between bamboo brils and the resin were developed once water was evaporated in the precuring and curing processes, which also contributed to the high mechanical properties of
the reinforced SPC composite sheets through the increased interfacial adhesion. A good interfacial bonding is critical to obtain the
best possible mechanical properties of the modied SPC specimens. Nam and Netravali [26] have reported that the interfacial
shear strength (IFSS) of ramie/SPC can be as high as 23 MPa. Their
IFSS values were obtained using the microbead tests. Lodha and
Netravali [28] also used microbead tests and obtained an IFSS value
of 29.8 MPa for ramie/soy protein isolate (SPI) composites. Lodha
and Netravali [28] fabricated a natural ber reinforced composite
and reported that with 15 mm long ramie bers reinforcing (critical length was around 2.5 mm in this case), SPI composites showed
fracture strength of 33.4 MPa and modulus of 1.65 GPa. Keller [29]

80

2500

Modulus (GPa)

2000

70

Modulus

60

1500
50

Stress

1000

40

500

Stress (MPa)

30

20

10

20

30

40

MBF content (parts)

7

25

Toughness (MPa)

Toughness

20

5
15

4
3

Frature strain

10

2
5

1
0

Fracture strain (%)

10

20

30

40

MBF content (parts)

Fig. 3. Mechanical properties of the MBF reinforced SPC composites (containing 15
parts of glycerol): (a) Youngs modulus and fracture stress vs. MBF content, (b)
toughness and fracture stain vs. MBF content.

obtained fracture stress of around 30 MPa with hemp short ber

reinforced composites. The higher tensile properties, especially
the tensile strength, obtained in this research are due to the high
strength of the brils, high aspect ratio and the interlocking network that they form that helps bril-to-bril load transfer. The
fracture strain, as shown in Fig. 3b, did not change signicantly
with the incorporation of MBF. For SPC containing different
amounts (040 parts) of MBF, the fracture strains seemed to be
constant between 10% and 13%. The incorporation of high modulus
(stiff) short bers in a resin can usually decrease the fracture strain.
The unchanged strain in this case is probably due to the exibility
and the entangled morphology of the MBF. The toughness of the
reinforced SPC increased signicantly when 30 parts of MBF were
incorporated as shown in Fig. 3b. With 30 parts of MBF, the toughness increased from 2.7 MPa for SPC with 15 parts of glycerol and 0
part of MBF to around 6.0 MPa. Although the modulus kept
increasing slightly, further increase in the MBF content beyond
30 parts did not show signicant increase in the fracture stress
and toughness, most likely due to the lack of effective load transfer
among bers resulted from the insufcient amount of soy protein
resin penetrating in between the MBF.
Glycerol behaves as a plasticizer in SPC [811,30]. Glycerol can
form strong hydrogen bonds with soy protein molecules. This will
reduce the interaction between soy protein molecules. The effect of
glycerol content on the mechanical properties and moisture content of the SPC containing 30 parts of MBF is shown in Table 1. Both
Youngs modulus and fracture stress of the specimen increased
with decrease in the glycerol content as can be expected. Once
glycerol content reduced to 2 parts, the fracture stress of the SPC
containing 30 parts of MBF further increased to 76 MPa and the
Youngs modulus increased to around 3.0 GPa compared to the
fracture stress of 59.3 MPa and Youngs modulus of 1.8 GPa for
MBF reinforced SPC with 15 parts of glycerol. The increase in modulus can be expected with reduced glycerol content since glycerol
is a plasticizer for soy protein. It has also been reported by Nam
and Netravali [26] that reducing glycerol content increased the ber/resin interfacial shear strength (IFSS) in ramie/SPI composites
due to the lubricating effect of glycerol. In their study, by reducing
glycerol content from 60 parts to 0, the IFSS increased signicantly
from about 13 MPa to 23 MPa [26]. Therefore, the increased IFSS
with the decreased glycerol content can also contribute to the improved mechanical properties. As can be expected, the fracture
strain dropped signicantly from 13.2% to 4.9% with the decrease
in glycerol content from 15% to 2%. At the same time, the toughness of the specimen decreased from 6.0 MPa to 2.1 MPa. This is
primarily due to the increased specimen brittleness. The moisture
content of the specimen reduced from 13.9% to 11.9% when the
glycerol content decreased from 15 parts to 2 parts. Since glycerol
has three hydroxyl groups capable of forming strong hydrogen
bonding with water molecules, it is very hydrophilic. The decrease
in glycerol content reduced the specimen moisture content. The
reduced moisture content in the MBF reinforced SPC specimens
is another reason for the increased modulus and decreased fracture
strain due to the plasticization effect of water.
3.3. Effect of ITES modication
The MBF reinforced SPC composites were further modied with
(3-isocyanatopropyl)triethoxysilane (ITES). The chemical structure
of ITES is shown below.

CH3

CH2

O Si

CH2

N C O

It contains reactive isocyanate group which can react with

amine, hydroxyl and carboxyl groups present in soy protein. Isocyanate carbon is an electrophilic center due to the high electro-

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X. Huang, A. Netravali / Composites Science and Technology 69 (2009) 10091015

Table 1
Effect of glycerol on the mechanical properties and moisture content of the MBF reinforced SPC composites.
SPC/MBF/glycerol (by weight)

Fracture stress (MPa)

Fracture strain (%)

Youngs modulus (MPa)

Toughness (MPa)

Moisture content (%)

100/30/15
100/30/10
100/30/5
100/30/2

59.3
65.7
78.3
75.7

13.2
8.5
6.5
4.9

1816
2095
2596
3019

6.0
4.1
3.0
2.1

13.9
13.1
12.6
11.9

negativity of both oxygen and nitrogen next to the isocyanate carbon. Therefore, isocyanates are very reactive with nucleophiles
(e.g. water and amine) even in the absence of catalysts [3133].
It has been reported that isocyanate has a higher reactivity with
amines than with hydroxyl and carboxyl groups at neutral pH
[3133]. As a result, ITES mainly reacts with the amine groups in
soy protein molecules. The scheme of the amine reaction with ITES
is shown in the equation below.

O H
N C O + H2N Protein

N C N Protein

of the resin. However, this was not observed in the study. The possible reason is the relatively low cross-link density in the specimen. The addition of ITES signicantly increased the molecular
weight of soy protein but resulted in slight cross-linking. ITES
was attached onto soy protein fast due to the high reactivity of isocyanate with protein. However, the three hydrolyzed silanol
groups condense to cross-link at a much lower rate. There are a
couple of possible reasons which can lead to the increased fracture

O
NH C NH Protein

The lone pair of electrons on the amine groups attacks carbon

atoms in isocyanate, followed by the electron re-organization between isocyanate carbon and nitrogen. A urea bond is formed with
this reaction. The reactions of hydroxyl and carboxyl groups with
isocyanate follow a similar mechanism at much slower rates
forming urethane and amide bonds as the products, respectively
[3133].
Once the ITES is attached onto the protein molecules through
the reaction of isocyanate, the three ASiAOAEt groups present in
ITES can hydrolyze and then condense to form a cross-linked
(solgel) structure [2023]. The cross-link density can be controlled by changing the pH of the medium.
Fig. 4 shows the SDSPAGE proles of the molecular weight
marker, SPC and SPC modied with 10 parts and 5 parts of ITES,
respectively. The molecular weight marker is shown in Lane 1. Different bands correspond to fractions with different molecular
weights with 200 kDa for the top one and 2.5 kDa for the bottom
one. Lane 2 shows the different molecular weight fractions in
SPC. The dissociated SPC showed different subunits as in Lane 2.
The SDSPAGE of SPC cross-linked with 10 parts and 5 parts of ITES
are shown in Lanes 3 and 4, respectively. It is clear from Lanes 3
and 4 that once reacted with ITES, the low molecular weight
fractions reduced signicantly, which is a direct indication of a
cross-linked system. However, the cross-link density can not be
determined accurately from SDSPAGE results.
The mechanical properties and moisture content of the ITES
modied MBF reinforced SPC as a function of ITES content are
shown in Table 2. The addition of ITES did not show any statistically signicant increase in both Youngs modulus and fracture
stress. Youngs modulus and fracture stress were constant in the
range from 3.0 GPa to 3.3 GPa and from 76 MPa to 82 MPa, respectively. However, fracture strain and toughness increased signicantly with the application of ITES. Specimen toughness
increased signicantly from 2.1 MPa for SPC containing 2 parts of
glycerol and 30 parts of MBF to 4.6 MPa for SPC containing 2 parts
of glycerol, 30 parts of MBF and 12 parts of ITES. At the same time,
fracture strain increased from 4.9% to 7.3%. As shown in Fig. 4, the
addition of ITES cross-linked soy protein intermolecularly resulting
in an increased molecular weight. Cross-linking most commonly
increases the Youngs modulus and decreases the fracture strain

strain of the specimen. When the silane reacted with the amine
groups on protein molecules, the number of hydrogen bonds
formed between two protein molecules decreased. Silane molecules separated protein molecules to some degree. Soy protein
molecules can obtain relatively more freedom of motion due to
the incompletely reacted ITES, which can increase the specimen
fracture strain. The exibility of the formed SiAOASi bond can also
contribute to the increased fracture strain. The incorporation of 12
parts of ITES in the SPC containing 2 parts of glycerol and 30 parts

kDa
200
55.4
36.5

21.5

2.5

Fig. 4. SDSPAGE proles of the molecular weight marker (Lane 1), SPC (Lane 2),
SPC with 10 parts of ITES (Lane 3) and SPC with 5 parts of ITES (Lane 4).

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X. Huang, A. Netravali / Composites Science and Technology 69 (2009) 10091015

Table 2
Effect of ITES on the mechanical properties and moisture content of the MBF reinforced SPC composites.
SPC/MBF/glycerol/ITES (by weight)

Fracture stress (MPa)

Fracture strain (%)

Youngs modulus (MPa)

Toughness (MPa)

Moisture content (%)

100/30/2/0
100/30/2/2
100/30/2/5
100/30/2/7
100/30/2/10
100/30/2/12

75.7
75.7
73.6
75.5
81.6
80.0

4.9
5.9
6.1
6.8
7.0
7.3

3019
3218
3271
3020
3184
3221

2.1
3.3
3.5
3.9
4.3
4.6

11.9
12.0
11.6
11.4
11.0
11.0

Thermal stability of the specimens was characterized using

TGA. Fig. 5 shows the TGA thermograms of MBF, SPC and SPC reinforced with different amounts of MBF. The decomposition temperature of the specimen increased with the addition of MBF.
Unmodied SPC with 15 parts of glycerol starts to decompose at
around 238 C, whereas the SPC with 30 parts of MBF and 15 parts
of glycerol has a decomposition temperature of around 258 C. As
expected, MBF was thermally more stable than SPC resin. With
the addition of MBF, the thermal stability of the modied SPC resin
increased. The composites incorporated the thermal behavior of
the cellulose brils as a result of the insulating effect of the
nano/micro-sized brils. Once the temperature increased to above
360 C, the residual weight for all specimens became almost the
same since at this temperature most of the cellulose in ber was
decomposed. Due to the relatively low cross-link density, the addition of ITES did not show signicant inuence in the thermal stability of the modied specimens. The TGA thermograms of MBF
reinforced SPC with different amounts of ITES have not been included here. Chabba and Netravali [9] have reported that the
decomposition temperature of SPC increased from 235 C to
270 C by glutaradehyde cross-linking. In their case, the cross-link
density was signicantly higher than what was obtained with ITES
in this study.
Fig. 6a and b shows the storage moduli of the SPC containing 15
parts of glycerol and varying amounts of MBF and SPC containing 2
parts of glycerol, 30 parts of MBF and varying amounts of ITES and
as a function of temperature, respectively. As observed in the case

100
SPC+30 parts of MBF

Weight (%)

90
80
70

SPC

MBF

SPC+10 parts of MBF

60
SPC+20 parts of MBF

50

SPC+40 parts of MBF

40
30
25

125

225

325

425

Temperature (C)
Fig. 5. TGA thermograms of MBF, SPC and MBF reinforced SPC.

Modulus (MPa)

3.4. Thermal stability and storage moduli of the modied SPC

8000
7000

6000

5000

1 - SPC
2 - SPC+20 parts of MBF
3 - SPC+30 parts of MBF
4 - SPC+40 parts of MBF

4000
1

3000
2000
1000
0
0

50

100

150

200

250

Temperature (C )

b12000
Modulus (MPa)

of MBF decreased the moisture content from 11.9% to 11.0%. The

reduced moisture content in the composites contributed to the
apparently increased modulus due to the reduced plasticization
effect by water. The addition of more than 12 parts of ITES only
resulted in slight increase in toughness and fracture stress, most
likely due to the incomplete crosslink-linking reaction and the
plasticizing effect of ITES.

1 - SPC+30 parts of MBF

2 - SPC+30 parts of MBF+5 parts of ITES
3 - SPC+30 parts of MBF+10 parts of ITES

10000 3
2

8000 1
6000
4000
2000
20

50

80

110

140

Temperature (C)
Fig. 6. Storage moduli of (a) SPC containing 15 parts of glycerol and varying
amounts of MBF and (b) SPC containing 2 parts of glycerol, 30 parts of MBF and
varying amounts of ITES as a function of temperature.

of the Youngs modulus, the storage modulus of the specimen increased signicantly with the addition of the MBF (Fig. 6a). Once
40 parts of MBF was added, the storage modulus of the SPC specimen at room temperature increased from about 3 GPa to 7 GPa.
The storage modulus did not decrease signicantly until the temperature reached to about 140 C. This is most likely due to the
thermally stable cellulose bril network structure of the MBF in
the SPC resin. For the MBF reinforced specimens, the storage moduli at around 150 C were still comparable to the storage modulus
for the unmodied SPC at room temperature. Therefore, the MBF
reinforced SPC composites have the potential for application in
environments with moderately high temperatures. The effect of
ITES on the storage modulus of the 30 parts of MBF reinforced
SPC composites are shown in Fig. 6b. The modication (slight
cross-linking) by ITES increased the storage modulus of the modied SPC specimens slightly at a temperature below 140 C. This can
be explained by the cross-linking of soy protein molecules as discussed earlier for the tensile properties. However, similar to the
tensile Youngs modulus, the increase in storage modulus was
small. At a temperature above 70 C, ITES did not show any inuence on the storage modulus of the modied MBF reinforced SPC
specimens.

X. Huang, A. Netravali / Composites Science and Technology 69 (2009) 10091015

4. Conclusions
Micro/nano-sized bamboo bril (MBF) reinforced SPC resin
composites were prepared. The composites showed transversely
isotropic properties due to the random distribution of the brils
in 2-D. Addition of the MBF signicantly increased the fracture
stress and Youngs modulus of the reinforced SPC specimens. With
the incorporation of 30 parts of MBF, the SPC with 15 parts of glycerol showed fracture stress of 59.3 MPa and Youngs modulus of
1816 MPa compared to the fracture stress of 20.2 MPa and Youngs
modulus of 596 MPa obtained for SPC containing no MBF. The
toughness of the specimen also increased signicantly from
2.7 MPa for SPC with 15 parts of glycerol to 6.0 MPa after reinforcing with 30 parts of MBF. By adding 10 parts of ITES, the toughness
and fracture strain of the SPC with 2 parts of glycerol increased
from 2.1 MPa to 4.3 MPa and from 4.9% to 7.0%, respectively.
However, incorporation of up to 12 parts of ITES did not show signicant increase in the Youngs modulus and fracture stress.
Acknowledgements
The authors would like to take this opportunity to thank Cornell
Center for Materials Research and College of Human Ecology at
Cornell for test facilities and Professor Toru Fujii of Doshisha
University, Kyoto, Japan, for providing the MBF. The authors would
also like to thank the College of Human Ecology at Cornell University for partially funding this research.
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