COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 64 (2004) 13011310
www.elsevier.com/locate/compscitech

Environmental degradability of self-reinforced composites made

from sisal
Xun Lu
a

a,b,c

, Ming Qiu Zhang

b,*
,

Min Zhi Rong a, Da Lei Yue a, Gui Cheng Yang

Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Zhongshan University, Guangzhou 510275, PR China
b
Materials Science Institute, Zhongshan University, Guangzhou 510275, PR China
c
Institute of Polymers, School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, PR China
Received 24 March 2003; received in revised form 10 September 2003; accepted 20 October 2003
Available online 16 December 2003

Abstract
Self-reinforced sisal composites were prepared by molding slightly benzylated sisal bers. The environmental degradation behavior of the materials was evaluated in the present paper with reference to the eects of ageing in water, enzyme solution and soil,
respectively. It was found that the inherent biodegradability of plant bers is still associated with the composites. In contrast to plant
ber/synthetic polymer composites, however, water resistance of the current composites is greatly increased as characterized by the
insignicant variation in the mechanical properties of the composites before and after being aged in water. With the help of cellulase
and fungi, the self-reinforced sisal composites can be degraded leading to weight loss and decay of mechanical performance. In the
course of cellulase induced degradation, the insusceptibility of lignin to the enzyme decelerated the rate of deterioration, while the
soil burial resulted in an overall decomposition of the composites.
2003 Elsevier Ltd. All rights reserved.
Keywords: A. Fibers; A. Polymer-matrix composites (PMCs); Degradation; B. Mechanical properties; B. Surface treatments

1. Introduction
For keeping in step with societal concerns on energy
crisis and ecological problems, reduction in the usage of
materials made from fossil oil becomes more and more
important. In the eld of composite materials, for example, a series of works have been done to replace the
conventional synthetic ber composites by means of
natural vegetable ber composites [1,2]. So far, two
main technical routes have been developed. One deals
with the compounding of natural ber with traditional
petroleum based polymers, like thermosetting polymers
(unsaturated polyester [3], epoxy [4], phenol formaldehyde resin [5], etc.), or low processing temperature
thermoplastic polymers (polypropylene [6], polyethylene
[7], etc.). The other mixes plant bers with biodegrad-

Corresponding author. Tel.: +86-20-84036576; fax: +86-2084036576.

E-mail address: ceszmq@zsulink.zsu.edu.cn (M.Q. Zhang).
0266-3538/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2003.10.013

able polymers including poly(lactic acid) [8], starch

plastics [9], soybean plastics [10] and cellulosic plastics
[11]. Comparatively, the composites prepared in the
former way cannot be regarded as fully biodegradable
materials because of the nonbiodegradability of the
matrix polymers.
However, many biodegradable polymers are not costeective enough at present. Their potential application
as the matrices of structural composites has to be conned to some specic area with high value-added. For
manufacturing aordable and fully biodegradable
composites, matrix polymers derived from annually renewable resources except food and feed coupled with
low-cost processing techniques are critical. In this context, the authors proposed the concept of all-plant ber
composites, in which plasticized plant ber serves as
matrix while discontinuous or continuous plant ber
plays the role of reinforcement [12,13]. Since most
components of plant bers can be kept when they are
converted into thermally formable materials through
simple substitution reactions on the side chains of

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X. Lu et al. / Composites Science and Technology 64 (2004) 13011310

cellulose in association with partial removal of lignin,

the resultant thermoplastics dier from commercially
available cellulosic plastics and are characterized by
environmentally friendly and economic nature. The results indicated that sisal/cyanoethylated wood sawdust
and sisal/benzylated wood sawdust composites prepared
according to this idea exhibit mechanical properties
similar to those of glass ber reinforced composites
while possessing the biodegradability of the feedstock
[14]. Besides the above stated advantages, physical heterogeneity in the so-called all-plant ber composites
instead of chemical heterogeneity of conventional composites is also favorable for interfacial interaction as
well.
Recently, another type of all-plant ber composites
was developed in our laboratory, which takes the
advantages of gradient plasticization along the radial
direction of sisal bers [15,16]. That is, through slight
benzylation treatment, skin layers of sisal bers were
converted into thermoplastic material while the core of
the ber cells remained unchanged. Then self-reinforced
composites of sisal can be prepared using hot pressing,
in which the plasticized parts of sisal serve as matrix and
the unplasticized cores of the bers as reinforcement.
The inherent interfacial compatibility guarantees ecient stress transfer between the components. Fig. 1
summarizes the development possibilities of the all-plant
ber composites.
It is worth noting that although etherication or esterication that provides lignocellulosic substances with

certain thermoplasticity has been investigated in detail

[17,18], biodegradabilities of the resultants are not systematically documented to the authors knowledge.
Since the above chemical reaction takes place mostly at
the side chains of cellulose of plant bers, the backbone
structure of cellulose might not be aected in principle
so that the plasticized products can still be biodegraded
like the unmodied versions. Earlier studies of sisal reinforced benzylated wood composites [14] and phenolated wood-based molding materials [19] evidenced the
consideration.
As one of our serial works on all-plant ber composites, the research interest of the present paper is focused on the evaluation of the biodegradability of the
self-reinforced composites based on sisal. Unlike other
all-plant ber composites analyzed previously, these
self-reinforced composites are made from unitary raw
material sisal. The complexity of the composite system
is reduced accordingly. Therefore, it would be relatively
simple to discuss the observed results and to draw a
conclusion.
With respect to the assessment of materials biodegradability, structure analysis as well as characterization
of the variations in polymerization degree, weight and
mechanical properties of the deteriorated products are
common means [20]. Due to the chemical complexity of
plant bers, the present paper monitors the biodegradability of the self-reinforced composites from sisal predominately in terms of measuring weight loss and
mechanical performance decay.

PLANT FIBERS

PLASTICIZATION

THERMOFORMABLE
MATERIAL
(as matrix)

SURFACE MODIFCATION

SHORT OR CONTINUOUS
FIBERS WITH
PLASTICIZED SKIN
LAYERS

SHORT OR CONTINUOUS
FIBERS WITH CHANGED
SURFACE CHEMISTRY
(as reinforcement)

COMPOUNDING AS CONVENTIONAL
THERMOPLASTIC COMPOSITES TO PRODUCE
PLANT FIBER REINFORCED PLASTICIZED PLANT
FIBER COMPOSITES

THERMOFORMED AS
CONVENTIONAL
THERMOPLASTICS TO
PRODUCE SELF-REINFORCED
COMPOSITES

ALL-PLANT FIBER COMPOSITES

(cost effective, fully biodegradable, physically heterogeneous, )

Fig. 1. Concept of all-plant ber composites.

X. Lu et al. / Composites Science and Technology 64 (2004) 13011310

2.1. Preparation of self-reinforced sisal composites

Sisal bers with diameter ranging from 100 to 200 lm
were provided by Dongfanghong State Farm in
Guangdong Province, China. Chopped sisal bers that
had been extracted by benzeneethanol (v/v 2/1) were
added into NaOH solution of desired concentration
with stirring. After 11.5 h, the bers were transferred
into a ask containing benzyl chloride. Bezylation reaction was carried out under vigorous stirring at 115 C
for a period of time to get benzylated products with
various reaction extents [16]. Then, the products were
puried through washing with distilled water to remove
inorganic salts, and with ethanol to remove residues of
benzyl chloride and by-products, respectively. Finally
the treated sisal was dried under vacuum at 60 C until
constant weight was reached.
To produce self-reinforced sisal composites, the
benzylated short sisal bers were compressed by a hot
press at 160 C under 9.8 MPa. The molding conditions
were determined according to the owability measurements carried out in [16]. Since the present composites
are manufactured on the basis of slight benzylation of
the surface layers of the sisal bers, the characteristic
parameter of the materials is no longer volume fraction
of the reinforcement but the degree of benzylation of the
bers. However, the extent of benzylation reaction is
factually hard to be measured due to the chemical heterogeneity of sisal bers, which has to be evaluated by
the percentage weight gain after the benzylation treatment instead. It has explicit engineering meaning and
reects the incorporation of benzyl groups.
2.2. Characterization
To measure the moisture retention in sisal, the untreated bers were dried in an oven at 95100 C until a
constant weight was achieved. Then, they were transferred into a desiccator and the weight increase of the
bers was measured as a function of time [21]. Aging of
sisal composites in water was conducted by immersing
the sheets in water at room temperature for a period of
time. Time dependence of weight and dimensions of the
composites were measured. Before each measurement,
the samples were blotted using a piece of lter paper.
Enzymolysis of sisal and the composites was carried
out by using cellulase. The vacuum dried bers or
composite sheets were put together with cellulase into
the buer solution of acetic acid-sodium acetate
(pH 5.0) with stirring at 50 C. After a given time, the
specimens were taken out of the reactor, washed thoroughly, and dried in vacuum. Variations in weight (of
both sisal bers and the composite sheets) and mechanical properties (of the composites) before and after

the enzymolysis were then determined to show the eect

of enzyme-aided biodegradation. Microbiological deterioration of the composites was simulated in soil. That
is, the specimens were laid deep in soil for a period of
time and then taken out for further characterization.
Surface morphological changes due to biodegradation
tests were observed using a Hitachi S-520 scanning
electron microscope (SEM).
Tensile and exural properties of the composites were
determined by a LWK-5 universal tester at a crosshead
speed of 10 mm/min in accordance with GB3354-82
standard. Unnotched Charpy impact strength was
measured by an XJJ-5 impact tester. All the reported
data were the average of ve successful tests.

3. Results and discussion

3.1. Eect of water uptake
It has been known that either biodeterioration of
plant ber composites in soil or enzymolysis of the
materials has to proceed at the presence of water [14,19].
Since mechanical performance of sisal composites is also
a function of water uptake, e.g., when the composites
were aged in water their tensile and exural properties
decreased [14,21,22] while the impact toughness increased [21], the inuence of moisture absorption on the
present composites should be viewed prior to the analysis of the biodegradability data.
Like other untreated plant bers, sisal exhibits considerable moisture absorbability due to its hydrophilic
nature (Fig. 2). The straight line of the weight increment
against square root of time over most of the time range
investigated reveals that the moisture absorption kinetics follows Fikian law. Such a typical diusion controlled absorption behavior implies that water molecules

3.0

Relative variation in
sample weight [%]

2. Experimental

1303

2.5
2.0
1.5
1.0
0.5
0.0
0.0

0.5

1.0

1.5

2.0
1/2

Time

2.5

3.0

3.5

4.0

1/2

[h ]

Fig. 2. Moisture absorption behavior of sisal bers in a desiccator at

room temperature.

1304

X. Lu et al. / Composites Science and Technology 64 (2004) 13011310

cannot induce viscoelastic response of the cellulosic

molecules.
When the bers have been chemically modied and
molded into sheet-like materials, the water sorption
curves change slightly, as illustrated by Fig. 3. The most
distinct variation lies in the appearance of the induction
period characterized by zero uptake at the initial stage
of ageing. It should be attributed to the dierence in
fusion of the plasticized sisal bers between the surface
and the bulk of the specimens resulting from the
molding procedure. The relatively higher temperature of
the material in contact with the surface of the mold than
that in the bulk would easily lead to better mold-packing
of the surface layer of the molded sheet. This provides
the composites specimens with certain resistance to
water permeation, giving rise to rather low water uptake
rate. So long as at least one diusion path is built up
throughout the composites, i.e., the so-called percolation eect takes place, the specimens start to absorb
water like their feedstock. The evident increase in the
absorption rates at around 96 h might be indicative of
the heterogeneous structure of the composites. That is,
the water uptake of the reinforcements-rich core region of
the composites is delayed by the hindrance eect of the
resin-rich surface portion. As demonstrated by Table 1,
the expansion rates in both thickness and width directions over the time range from 96 to 168 h is lower
than those from 0 to 96 h. Considering that when water
penetrates into the slits of the unplasticized parts of sisal, their volume expansions would not be necessarily in
proportion to the weight increment as a result of the
loosened structure, the above data evidence the estimation that the reinforcements play the leading role in
soaking up water within the latter period of time (i.e.,
from 96 to 168 h).
A quantitative comparison between the results shown
in Figs. 2 and 3 reveals that the water resistance of the
composites is greatly improved. It should be interpreted

Table 1
Variation in composites sizes due to water aging at room temperature
Composites

Self-reinforced sisal composites

made from benzylated sisal
with weight gain of 25.8 wt%
Self-reinforced sisal composites
made from benzylated sisal
with weight gain of 43.0 wt%
Self-reinforced sisal composites
made from benzylated sisal
with weight gain of 59.8 wt%

Relative
increase in
thickness
(%)

Relative
increase
in width
(%)

96

3.3

1.1

168
96

4.7
2.4

1.5
0.9

168
96

3.5
1.9

1.1
0.8

168

2.5

0.9

as the result of benzylation treatment, which changes the

cell structure of sisal bers. As stated in the Experimental part, hemicellulose is partially removed during
the pretreatment using NaOH, and then benzylation
occurs on the remaining hydroxyl groups on the cell
surface of sisal [16]. Benzyl groups act as masks and
block the slits between the cells, so that the probability
of moisture absorption is reduced accordingly. It explains that with a rise in the percentage weight gain due
to benzylation (i.e., the extent of benzylation), the increments in sample weights (Fig. 3) and sizes (Table 1)
are decreased when immersion time in water is identical.
Figs. 46 illustrate the mechanical properties of the
composites as a function of immersion time in water.
Roughly speaking, the variations as well as the variation
rates are not as signicant as those observed in sisal ber
reinforced synthetic polymers [21,22]. Such an insensitivity to water uptake not only reects the reduced hydroscopicity of the composites but also manifests the
inaccessibility of the reinforcements/matrix interface to

2.0

Flexural modulus [GPa]

3.5
1

Relative variation in
sample weight [%]

Aging
time (h)

1.5

2
3

1.0

0.5

3.0

2.5

2.0
3

0.0

9
1/2

Time

12

15

1/2

[h ]

Fig. 3. Moisture absorption behavior of self-reinforced sisal composites at room temperature. Weight gains of the benzylated sisal: (1) 25.8
wt%; (2) 43.0 wt%; (3) 59.8 wt%.

1.5

30

60

90

120

150

180

Time [h]
Fig. 4. Flexural modulus of self-reinforced sisal composites versus
aging time in water at room temperature. Weight gains of the benzylated sisal: (1) 25.8 wt%; (2) 43.0 wt%; (3) 59.8 wt%.

X. Lu et al. / Composites Science and Technology 64 (2004) 13011310

Flexural strength [MPa]

100

80

60

40

30

60

90

120

150

180

Time [h]
Fig. 5. Flexural strength of self-reinforced sisal composites versus aging time in water at room temperature. Weight gains of the benzylated
sisal: (1) 25.8 wt%; (2) 43.0 wt%; (3) 59.8 wt%.

Impact strength [kJ/m ]

40

35

30
2

25

1305

hydrogen bonding between cellulose and water molecules

so that the amount of intermolecular hydrogen bonding
in cellulose bers is reduced accordingly. It means that
sisal bers full of water cannot eciently fulll the task of
load bearing. Returning to Fig. 4, it can be deduced that
both interfacial failure and ber softening account for the
decay of composites moduli.
It is interesting to examine the dependence of impact
strengths of the composites on ageing time in water,
which varies with the weight gain due to benzylation of
the bers (Fig. 6). As found in our previous studies, a
moderate interfacial bonding is desired in short sisal/
epoxy composites to increase the energy dissipation
through ber debonding and pull-out as well as extension and uncoiling of the spirally arranged microbrils
[24]. Therefore, the above-discussed weakening eect of
water diusion on interfacial adhesion facilitates the
improvement of impact strength of the composites with
slighter degree of benzylation (refer to curves 1 and 2 in
Fig. 6). With respect to the composites with higher degree of benzylation (refer to curve 3 in Fig. 6), the
plasticized skin layers of sisal constitutes the majority
within the bulk material. Consequently, the plasticization eect of the absorbed water on the matrix probably
decreases the impact strength of the composites.
3.2. Enzyme-aided biodegradation

20
3

15

30

60

90

120

150

180

Time [h]
Fig. 6. Impact strength of self-reinforced sisal composites versus aging
time in water at room temperature. Weight gains of the benzylated
sisal: (1) 25.8 wt%; (2) 43.0 wt%; (3) 59.8 wt%.

moisture from the environment. It is known that when

plant bers begin to swell in the composites exposed to
humidity, interfacial shear stress would be developed
owing to the increased osmotic pressure, leading to adhesive debonding. As a result, the deteriorated interface
could no longer provide sucient stress transfer ability,
and the static mechanical performance (like tensile and
exural strengths and moduli) decreases. In this context,
the general trend exhibited by Figs. 4 and 5 manifests that
the interfacial strength of the current self-reinforced
composites is superior to that of conventional plant ber
composites because of the chemical homogeneity and
the inborn compatibility of the reinforcements/matrix
interface.
In comparison with the strength plots given in Fig. 5,
the decline of modulus is more obvious (Fig. 4). Raj
et al. [23] reported that the stiness of cellulose bers
drops considerably after being aged in boiling water due
to the softening of the desorbed zones of microbrils.
Substantial water uptake would lead to the formation of

Cellulase is a specic enzyme that is able to hydrolyze

cellulose into digestible matters. As shown in the following scheme [25], cellulose (Cx ) is attacked by endo-glucanase (Ex ) leading to the scission of b-1,4-glucosidic
bonds and the generation of amorphous cellulose and
soluble oligosaccharide (Co ). Then, the resultant oligosaccharide (Co ) is either directly decomposed into glucose
(C1 ) by the action of exo-glucanase (Eo ) or hydrolyzed
into cellobiose (C2 ) by cellobiase (E2 ), which is subsequently hydrolyzed into glucose (C1 ) by b-glucosidase
(E1 ).

Since crystalline cellulose makes the majority of plant

bers and provides strength properties, decomposition
of cellulose would certainly result in catastrophic deterioration of plant bers and their derivations. This accounts for the employment of cellulase in the present
work to investigate the biodegradability of the self-reinforced sisal composites.
As dosage of cellulase determines the enzymolysis
rate of cellulose, weight loss of both untreated and
benzylated sisal bers resulting from enzymolysis is

X. Lu et al. / Composites Science and Technology 64 (2004) 13011310

examined rstly (Fig. 7). Evidently, there is a critical

value for the cellulase-to-specimen weight ratio. When
the cellulase-to-specimen weight ratio is less than 1%,
the degree of ber degradation increases with increasing
cellulase dosage. Afterwards, the weight loss of the
specimens keeps constant. It means insucient cellulase
leads to low enzymolysis rate and hence low level weight
loss of the materials, but overdose of cellulase is useless
due to the limited amount of the reaction sites. According to the data of Fig. 7, a cellulase-to-specimen
weight ratio of 1% is selected for the subsequent
experiments.
Fig. 8 exhibits the results of cellulase-aided degradation of sisal bers as a function of ageing time. The removal of materials proceeds rapidly early in the reaction
and becomes slowed down after 24 h. This drastic transition originates from the specic cell wall structure of
lignocellulosics. Because the degradation takes place
primarily in the cellulose component, the ber surface has
to be rich in lignin as cellulose degrades. As a result, the
resistance of lignin to cellulase decomposition and its
blocking eect on the diusion of cellulase towards cellulose reduce the production rate of enzymolytic substances with a rise in time. From Fig. 8, it is also seen that
an increase in the extent of benzylation corresponds to
increased rate of weight loss as well as the ultimate weight
loss of the bers. This reveals that the plasticization approach applied to the plant bers in the current work does
not decrease the enzymolysis rate. On the contrary, an
accelerative eect is acquired owing to: (i) partial removal
of lignin from sisal during the pretreatment by NaOH, (ii)
expansion of interstitial volume inside the rigid cellulose
microbibrils and (iii) decrystallization of the orderly arranged cellulose molecules due to the introduction of the
benzyl groups.
In comparison with the results observed in the brous
state of sisal, the enzymolytic behaviors of the self-re-

50
4

Weight loss [%]

1306

40
3

30

20
1

10

50

100

Fig. 8. Time dependence of weight loss of: (1) sisal bers; (24) benzylated sisal bers due to enzymolysis (cellulase-to-specimen weight
ratio 1%). Weight gains of the benzylated sisal: (2) 15.5 wt%; (3) 26.5
wt%; (4) 43.2 wt%.

inforced composites from sisal do not vary greatly except the quantity of weight loss (Fig. 9). That is, the
composites are less susceptible to enzyme-aided biodegradation than the bers. The signicantly increased
packing density of the molded composite sheet, characterized by the remarkably reduced water absorbability
(cf. Figs. 2 and 3), should be responsible for the phenomenon. The buer solution of cellulase can only immigrate into the sheets through the surface defects, and
hence the reaction probability is decreased.
To have a direct image of the eect of enzyme-aided
biodegradation, morphologies of sisal bers and the selfreinforced composites before and after enzymolysis are
given in Fig. 10. For both untreated and benzylated sisal, the attack of cellulase leaves splits and cavities on
the cell walls (cf. Fig. 10(a)(d)). However, the skeletons
of the cells still exist because of the hindrance of lignin,
which coincides with the results and analyses of Fig. 8.
In the case of molded composite sheets, there are a

8
2

30

Weight loss [%]

Weight loss [%]

200

Time [h]

40

20
1

10

150

Cellulase-to-specimen weight ratio [%]

Fig. 7. Eect of cellulase dosage (expressed in terms of cellulase-tospecimen weight ratio) on enzymolysis induced weight loss of: (1) sisal
bers; (2) benzylated sisal bers with weight gain of 43.2 wt%. Reaction time: 10 h.

2
1

50

100

150

200

Time [h]
Fig. 9. Time dependence of weight loss of self-reinforced sisal composites due to enzymolysis (cellulase-to-specimen weight ratio 1%).
Weight gains of the benzylated sisal: (1) 15.5 wt%; (2) 26.5 wt%; (3)
43.2 wt%.

X. Lu et al. / Composites Science and Technology 64 (2004) 13011310

1307

Flexural modulus [GPa]

5
Before enzymolysis
After enzymolysis

0
15.5

26.5

43.2

Weight gain [wt%]

Fig. 11. Enzymolysis induced deterioration of exural modulus of selfreinforced sisal composites. Enzymolysis conditions: cellulase-tospecimen weight ratio 1%; reaction time 192 h.

Flexural strength [MPa]

100
80

Before enzymolysis
After enzymolysis

60
40
20
0
15.5

26.5

43.2

Weight gain [wt%]

Fig. 10. SEM micrographs of: (a) untreated sisal bers; (b) untreated
sisal bers having been enzymolyzed for 192 h; (c) benzylated sisal
bers; (d) benzylated sisal bers having been enzymolyzed for 192 h;
(e) surface of self-reinforced sisal composites; (f) surface of self-reinforced sisal composites having been enzymolyzed for 192 h. Weight
gain of the benzylated sisal: 43.0 wt%. Cellulase-to-specimen weight
ratio for all the enzymolysis tests: 1%.

Fig. 12. Enzymolysis induced deterioration of exural strength of selfreinforced sisal composites. Enzymolysis conditions: cellulase-tospecimen weight ratio 1%; reaction time 192 h.

number of cracks on the surface of the composites experienced enzymolysis (cf. Fig. 10(e) and (f)). It implies
that the biodegradation is initiated at the sample surface
and then occurs inside the material with the diusion of
cellulase.
Considering that chain scission of cellulose due to enzymolysis weakens the lignocellulosic cell walls, the mechanical performance of the self-reinforced sisal
composites would certainly go to decay. Unexpectedly,
the reduction in exural stiness and strength as well as
impact toughness of the composites after enzymolysis is
not signicant (Figs. 1113). In addition, the decrement of
the mechanical properties induced by enzymolysis seems
not to vary with the extent of benzylation of the bers. It
not only manifests that the composites have high damage

Impact strength [kJ/m ]

50

40

Before enzymolysis
After enzymolysis

30

20

10

0
15.5

26 .5

43.2

Weight gain [wt%]

Fig. 13. Enzymolysis induced deterioration of impact strength of selfreinforced sisal composites. Enzymolysis conditions: cellulase-tospecimen weight ratio 1%; reaction time 192 h.

1308

X. Lu et al. / Composites Science and Technology 64 (2004) 13011310

tolerance, but also helps to understand the mechanism

involved. For the all-plant ber composites consisting of
sisal bers and benzylated r sawdust [14], decay in their
mechanical performance is related to the proportion of
the reinforcement because sisal bers suck cellulase solution preferentially and enzymolysis takes place rstly
inside sisal bundles. With regard to the current self-reinforced sisal composites, it can be deduced that enzymolysis of the plasticized skin layers of sisal bers (i.e., the
matrix) plays the leading role. Due to the inherently
compatible interface between the plasticized parts and
unplasticized parts of sisal, the reinforcements of the
composites are hard to be accessed by the cellulase solution and hence their hydrolysis has to proceed at a latter
stage.
3.3. Soil burial induced biodegradation
The components in plant bers can be degraded into
carbohydrate by numerous micro-organisms like fungi
and bacteria existing in nature. For example, brown rot
fungi are rather eective in decomposing cellulose and
hemicellulose, while white rot fungi are able to degrade
lignin [25]. Since the last section demonstrates that the
self-reinforced composites from slightly plasticized sisal
still keep biodegradability in the environment containing enzyme, it is worth examining the degradation performance of the composites using soil burial. It factually
simulates the situation when the used composites are
abandoned as garbage.
Owing to the diculty in isolating degraded bers from
soil particles, the weight loss of sisal induced by biodegradation in soil was not recorded. Instead, Fig. 14 shows
the biodeterioration behavior of the self-reinforced sisal
composites. The values of weight loss of the composites
after 6-month burial in soil are similar to those measured
from the phenolated wood-based molding materials experienced biodegradation in broth system containing

Fig. 15. SEM micrographs of the surface of self-reinforced sisal composite sheets having been biodeteriorated for 6 months in soil (from
September to March).

various fungi species [19]. It suggests that the soil burial is

able to provide qualied fungi for microbiologically degrading the all-plant ber composites.
It is noted that the decelerating eect reected by the
curves in Fig. 9 is also perceivable in Fig. 14. However, it
should not be attributed to the dierence in biodegradability between cellulose and lignin as the case of enzymolysis because all the components in plant bers can be
rotten by means of proper fungi in soil. A reasonable
explanation of the above phenomenon might be the insucient supply of the composites with fungi. Besides, the
time dependences of weight loss of the composites with
dierent extents of benzylation are almost the same
(Fig. 14). This might result from the overall degradation
of both the matrix and the reinforcements. As evidenced
by the microphotos in Fig. 15, not only cracks on the
composites surfaces but also eroded ber-like objects can
be found.
On the other hand, the extensive defects formed as a
result of breakdown of cellulose and lignin of both the
matrix and the reinforcements would signicantly lower
the load bearing ability of the self-reinforced composites. Although the weight loss of the composites having
5

Flexural modulus [GPa]

Weight loss [%]

2
1

0
Sept.

Before microbiological deterioration

After microbiological deterioration

Oct.

Nov.

Dec.

Jan.

Feb.

Mar.

Time
Fig. 14. Time dependence of weight loss of self-reinforced sisal composites due to soil burial. Weight gains of the benzylated sisal: (1) 15.5
wt%; (2) 26.5 wt%; (3) 43.2 wt%.

15.5

26.5

43.2

Weight gain [wt%]

Fig. 16. Microbiological degradation in soil induced deterioration of
exural modulus of self-reinforced sisal composites. Biodegradation
time: 6 months (from September to March).

X. Lu et al. / Composites Science and Technology 64 (2004) 13011310

Flexural strength [MPa]

100

Before microbiological deterioration

After microbiological deterioration

80

60

40

20

0
15.5

26.5

43.2

Weight gain [wt%]

Fig. 17. Microbiological degradation in soil induced deterioration of
exural strength of self-reinforced sisal composites. Biodegradation
time: 6 months (from September to March).

Impact strength [kJ/m ]

50

40

Before microbiological deterioration

After microbiological deterioration

30

1309

themselves and the inaccessibility of the reinforcements/matrix interface to moisture.

2. Although some hydroxyl groups of the components
of sisal have been substituted by benzyl groups during the process that provides sisal with thermal formability, the inherent biodegradability associated with
plant bers still remains in the resultant self-reinforced composites. In the case of enzymolysis aided
by cellulase, degradation rate of the composites gradually slow down because of the hindrance of lignin
that cannot be hydrolyzed by cellulase. It is believed
that biodegradation of the composites would be accelerated by using a mixture of cellulase and ligninase
or an approach combining cellulase aided deterioration and ultraviolet light irradiation (which is responsible for the degradation of lignin [26]).
3. The self-reinforced sisal composites can also be decomposed by fungi as revealed by the soil burial tests.
Unlike cellulase induced biodegradation of the composites, in which cellulose degrades preferentially,
the microbiological deterioration takes place in all
the components, leading to more substantial decay
of the mechanical performance of the composites
when the weight loss due to composites degradation
is identical.

20

Acknowledgements
10

0
15.5

26.5

43.2

Weight gain [wt%]

Fig. 18. Microbiological degradation in soil induced deterioration of
impact strength of self-reinforced sisal composites. Biodegradation
time: 6 months (from September to March).

been enzymolyzed for 192 h is similar to that having

been microbiologically deteriorated in soil for 6 months
(cf. Figs. 9 and 14), the retention of the mechanical
properties illustrated in Figs. 1618 is considerably
lower than that in Figs. 1113. It is again indicative of
the dierent ways of degradation of the composites in
enzyme solution and in soil.

4. Conclusions
1. Similar to the case of untreated sisal bers, water uptake of the self-reinforced composites made from
slightly benzylated sisal follows Fickian law. Having
been aged in water, the mechanical properties, like
exural modulus, exural strength, and impact
strength, of the composites do not change greatly because of the reduced hydroscopicity of the composites

The nancial support by the National Natural Science Foundation of China (Grant: 50173032), the Team
Project of the Natural Science Foundation of Guangdong Province (Grant: 20003038), and the Talents
Training Program Foundation of the Higher Education
Department of Guangdong Province are gratefully
acknowledged.

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