Original Article

Journal of Reinforced Plastics

and Composites

Mechanical and biodegradable properties 2014, Vol. 33(22) 2034–2045

! The Author(s) 2014
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DOI: 10.1177/0731684414552684
polylactide composites jrp.sagepub.com

Wuchang Fu1, Xiaoqiang Xu2 and Hongwu Wu1

Abstract
Sisal fiber (SF) was grafted with low polymerization degree polylactide (PLA) according to the principle of coordinative
ring-opening polymerization of lactide, and then the lactide-grafted sisal fiber (SF-g-LA) was mixed with PLA to make
PLA/SF-g-LA composites. The mechanical properties, morphology, and biodegradability of PLA/SF-g-LA composites were
systematically investigated, comparing with untreated SF reinforced PLA (PLA/USF) and alkali-treated SF reinforced PLA
(PLA/ASF) composites. Results showed that the interfacial properties between SF-g-LA and PLA matrix showed dramatic
improvement. The PLA/SF-g-LA composites exhibited noticeably superior tensile and flexural properties; however, their
impact strength decreased slightly compared with pure PLA. All of the composites were buried in soil and different
degrees of degradation were achieved. Because of better interfacial adhesion between SF-g-LA and PLA matrix, the
degradation rate of PLA/SF-g-LA composite was lower than those of PLA/USF and PLA/ASF composites, although still
higher than that of pure PLA. The biodegradation of PLA/SF-g-LA composites was marked by appearance of cavities, the
exfoliation of fragmental materials, and the degradation of cellulose fibrils.

Keywords
Polymer–matrix composites, natural fiber, surface treatments, mechanical properties, environmental degradation

into carbon dioxide and water in just a few years.10

Introduction
Recently, with the looming crisis of environmental pol-
lution and petroleum resources shortage, the research
and development of non–petroleum-based degradable
polymer materials are imperative. In the last few dec-
ades, biobased polymers and biodegradable polymer
materials, such as polyhydroxyalkanoates, polyhydrox-
ybutyrate, polycaprolactone, and polylactide (PLA),
have become the focus of research studies not only in
the fundamental research but also in the chemical
industry.1–4 Among all of the biodegradable polymers,
PLA seems to be the most widely researched and devel-
oped and consequently the most applied polymer.5–8
PLA is a linear aliphatic thermoplastic polyester that
is made from renewable resources such as corn and
sugar beet commonly by ring-opening polymerization
and becomes a new, compostable, versatile polymer.9
In contrast with conventional plastics like polypropyl-
ene and polyethylene, which require hundreds or even
thousands of years to degrade, PLA can decompose
Besides, PLA has a series of excellent properties such
as good biocompatibility, biodegradability, transpar-
ency, and high strength and modulus.11–13 It can be
easily processed by conventional processing techniques
used for thermoplastics, such as injection molding,
blow molding, thermoforming, and extrusion.
Therefore, PLA is used in numerous fields, ranging
from the industrial packaging field to the biocompat-
ible/bioabsorbable medical device market.14–19
1
National Engineering Research Center of Novel Equipment for Polymer
Processing, South China University of Technology, China
2
The Key Laboratory of Polymer Processing Engineering, South China
University of Technology, China
Corresponding author:
Hongwu Wu, National Engineering Research Center of Novel Equipment
for Polymer Processing, South China University of Technology, 181
Wushan Road, Guangzhou, China.
Email: mmhwwu@scut.edu.cn
Fu et al.
However, the cost of PLA is relatively high, which
limits its extensive application. One of the available
methods to reduce the cost and to improve the quality
of PLA products is by blending PLA with natural bio-
materials. At present, composites reinforced by natural
fibers such as kenaf, flax, bamboo, sisal, and jute are
emerging as a viable alternative to synthetic fiber
reinforced composites and have been the subject of
many studies.7,20–24 Compared with synthetic fibers,
natural fibers offer several advantages such as low
cost, high specific mechanical strength, recyclability,
and biodegradability.25–27 Owing to the readily bio-
degradable reinforcement and matrix, natural fiber
reinforced degradable polymer composite is likely
more ecofriendly.1,28
Sisal fiber (SF) is extracted from the leaf of sisal, a
plant that initially grew in the east and southeast of
North America. As one of the most widely used and
easily cultivated natural fibers, its outstanding proper-
ties such as low cost, low density, and high specific
strength afford SF-reinforced composites good mech-
anical properties and cost of production is low. In add-
ition, composites consisting of biodegradable polymers
and natural fibers have been shown to completely
degrade in soil or when composted, thereby gaining
much attention.29–31
Unfortunately, the presence of hydroxyl and other
polar groups in natural fiber constituents makes the
fiber exhibit high hydrophilic nature, which leads to
incompatibility and poor wettability with the hydropho-
bic polymer matrix. The incompatibility can also cause
weak bonding in the interface between fiber and matrix
and thus have a great influence on the mechanical prop-
erties of the composite.32 To improve the interfacial
adhesion between natural fiber and matrix, chemical
modification methods such as alkali treatment, use of
coupling agents, and graft co-polymerization are
common.32–34 Joseph et al.35,36 studied the effect of
chemical treatment on the tensile properties of short
SF reinforced polyethylene composites and polypropyl-
ene composites and found that the treatments enhanced
the tensile properties of the composites considerably,
but to varying degrees. Islam et al.37 investigated the
influence of alkali treatment on the interfacial and phy-
sicomechanical properties of industrial hemp fiber
Table 1. Physical and mechanical properties of polylactide (3051D).
Tensile
Melt flow (190 C, Density strength Elongation at
2.16 kg) (g/10 min) (g/m3) (MPa) break (%)
10–30 1.24 64.5 5.2
2035
reinforced PLA composites. The results demonstrated
that interfacial bonding was increased by alkali treat-
ment of fibers, which led to improved composite mech-
anical properties. Yu et al.38 studied the effect of fiber
surface treatment on the mechanical properties of PLA/
ramie fiber composites and found that the fiber–matrix
interfacial adhesion was improved after silane treatment
of ramie fiber. Sreekala et al.39 treated oil palm fiber
with acrylonitrile in 1% H2SO4 solution after alkali
and KMnO4 oxidized pretreatment. However, the
expected increase in fiber–matrix adhesion of fiber-rein-
forced phenol formaldehyde composites after grafting
treatment was not observed.
In this study, SF grafted with low polymerization
degree PLA (SF-g-LA) was prepared according to the
principle of coordinative ring-opening polymerization
of lactide. Then, the mechanical properties, morph-
ology, and biodegradability of SF-g-LA–reinforced
PLA (PLA/SF-g-LA) composites were systematically
investigated, comparing with untreated SF reinforced
PLA (PLA/USF) composites and alkali-treated SF
reinforced PLA (PLA/ASF) composites.
Experimental
Materials
PLA (3051D, injection molding grade) was obtained
from Nature Works LLC, USA. Table 1 shows the
physical and mechanical properties of PLA obtained
from Nature Works. Prior to mixing, PLA was dried
at 50 C (223 K) for 8 h. The industrial SFs (GB/
T15031-94) were supplied by Dongfang Sisal Co.
(Guangdong, China). The physical and mechanical
properties of SF provided by supplier are shown in
Table 2. The fiber was cut to 10 mm average length
and dried in a vacuum drier at 50 C (223 K) for 5 h.
L-lactide with a purity of over 95% was purchased from
Esun Industrial Co. Ltd (Shenzhen, China). As the
catalyst, stannous octoate (Oct2Sn) was obtained
from Sinopharm Chemical Reagent Co. Ltd
(Shanghai, China). Chemicals and solvents like
sodium hydroxide (NaOH) and toluene were of analyt-
ical grade and were obtained from local commercial
sources.
Flexural Glass transition Crystallization Melting
strength temperature temperature temperature
(MPa) ( C) ( C) ( C)
86 55–65 95–120 150–180
2036
Table 2. Properties of sisal fiber.
Fiber Fiber Cellulose Hemicellulose
diameter density content content
(mm) (g/m3) (%) (%)
25–200 1.45 67–78 10–14
Fiber surface grafting modification
As a pretreatment process, alkali treatment is required
for SFs to remove residual lignin, pectin, wax, and low
polymerization degree hemicellulose covering on the
external surface of the fiber cell wall. First, the pre-
dried SFs were immersed in NaOH solution (18% wt/
vol) and stirred at ambient temperature (25 C) for 3 h.
After that, the fibers were washed with distilled water to
remove the excess of NaOH sticking to the fibers, fol-
lowed by drying in a vacuum oven at 50 C for 5 h.
The copolymerization principle of grafting L-lactide
onto SF and the schematic diagram of experimental
equipment are shown in Figure 1(a) and (b), respect-
ively. Generally, grafting copolymerization is a chain
reaction consisting of a sequence of four steps, namely
activation, initiation, propagation, and termination.
First, the oxygen atom of hydroxyl in the surface of
SF cellulose coordinates with the empty orbits of tin
atom in Oct2Sn, forming coordination compound.
Subsequently, as an initiator the coordination com-
pound attacks acyl-oxygen of L-lactide monomer
which leads to acyl-oxygen cleavage—ring opening
and therefore forms a linear chain segment. The linear
chain segment then inserts into the tin–oxygen bond of
initiator and the molecular chain begins to propagate.
The propagating polymer chain stops growing when the
temperature is lower than the reaction temperature.
In order to graft low polymerization degree PLA
onto SFs, a set of experimental apparatus was designed
(as in Figure 1(b)). A total of 500 ml toluene and 10 g
CaCl2 was added into a four-mouth flask. Then the
experimental temperature was raised to 111 C, as a
result of which the toluene reflux was boiling for
30 min, thereby removing moisture from the solution.
After that the reaction system was cooled down to
room temperature, and the above-mentioned pretreated
SFs (8 g) and L-lactide monomer (3 g) were added into
the four-mouth flask. Then the reaction system was
vacuumized to remove oxygen and was slowly inflated
with nitrogen. By repeating the vacuumizing and inflat-
ing operations thrice, a nitrogen atmosphere was estab-
lished. Finally, the reaction system was reheated to
140 C, and a catalytic amount of Oct2Sn (2 wt% of
the monomer) was added into the flask. Thus, grafting
reactions were allowed to progress under nitrogen
Journal of Reinforced Plastics and Composites 33(22)
Lignin Tensile Tensile
content strength modulus Elongation at
(%) (MPa) (GPa) break (%)
8–11 468–640 9–22 3–7
atmosphere and with intense stirring for 30 min. The
grafted SFs were then dried in the open air for
sample preparation.
Sample preparation
The pre-dried pure PLA was melt compounded with
ASF and SF-g-LA, respectively, to obtain composites
with fiber mass fractions of 10%, 20%, 30%, and 40%,
using a two-roll plastics mill at 180 C for 5 min. Then,
using a hot press (QLB-25D/Q, Wuxi no. 1 Rubber &
Plastic Co. Ltd, China), the composites were molded
into sheets with thickness of 4 mm and 1 mm at tem-
perature of 185 C and pressure of 10 MPa for 6 min,
followed by cooling down to room temperature. The
neat PLA and the untreated SF reinforced composites
were prepared in the same way as were the references.
These sheets were cut to standard sample dimensions
for further characterization and properties
measurements.
Characterization of grafted SFs
The mechanism of ring-opening polymerization of lac-
tide in the presence of Oct2Sn is not unique. According to
the research of Kricheldorf et al.,40 Oct2Sn combined
with alcohol establishes a rapid complexation equilib-
rium and this interaction is stronger than the interaction
between Oct2Sn and lactide. That is to say, the direct
initiation of Oct2Sn with lactide plays a minor role and
the co-initiation by other OH groups plays the major
role, when there exist compounds with OH groups. In
order to verify the occurrence of low polymerization
degree PLA grafted onto SF successfully, soxhlet extrac-
tion was used to remove the adsorbed but not chemically
bonded PLA. Two grams of the grafted fibers were
ground and put into a Soxhlet extractor, and 100 ml tolu-
ene was added into a round-bottom flask. The flask was
heated with oil bath at 110 C for 24 h. The remaining
solids were washed thrice with distilled water, dried in a
vacuum oven at 50 C for 5 h, and then characterized
using Fourier-transform infrared spectroscopy (FTIR).
Infrared spectra of SFs were acquired using a Nexus 670
FTIR spectrophotometer (Thermo Nicolet Co., USA)
with a range of 400–4000 cm1. The ground fibers were
mixed with KBr and pressed into flakes. Additionally,
Fu et al.
Figure 1. (a) Grafting copolymerization principle of L-lactide onto sisal fiber and (b) the schematic diagram of experimental
equipment.
Tr: reaction temperature.
the morphology of the fibers was observed using a scan-
ning electron microscope (SEM). The microstructures of
the surface of fibers were investigated using a Nova
NanoSEM 430 scanning microscope (FEI Co.,
Holland) to observe the variation of SFs before and
after grafting.
Mechanical testing
Tensile properties were tested according to ISO 527-
2:2012 standard. The measurements were done using
2037
an Instron 5566 electronic universal testing machine
(Instron Co., USA) at a crosshead speed of 2 mm/min
at room temperature. Flexural properties were deter-
mined in three-point bend mode, according to ISO
14125:1998 standard at a speed of 2 mm/min. The
measurements were performed at room temperature
using an Instron 5566 electronic universal testing
machine. The Izod unnotched impact measurements
were carried out using a PIT501B-2 pendulum impact
testing machine (Wance Technologies Ltd, Shenzhen,
China) at room temperature. The impact strength was
2038
determined by striking the bar-shaped specimen with a
hammer, as per ISO 180:2000. In total, five specimens
per composite sample were used for each analysis and
the average was taken as the reported value.
Composites morphology
The surface morphology of the specimens was observed
with the Nova NanoSEM 430. The sheets were frac-
tured in liquid nitrogen to obtain unaffected fractured
surfaces. Nova NanoSEM 430 was operated at 10 kV.
Prior to observation, the fractured surfaces were coated
with gold to achieve optimal imaging.
Biodegradation studies
Biodegradability of the samples was assessed by mea-
suring the rate of residual mass of composites buried in
the soil of a garden lawn. The composite samples pre-
pared in the mechanical tests were used for biodegrad-
ability testing. After drying and weighing, the samples
were buried in garden soil at a depth of 10 cm. The
environmental temperature and relative humidity were
recorded during the degradation period, and their aver-
age values were 20 C and 70%, respectively. The pH of
the garden soil was 6.5. The buried samples were dug
out after being buried for 10, 20, 35, 60, 90 days,
respectively. Then they were washed in distilled water
and dried to constant weight at 50 C in a vacuum oven.
The rate of residual mass
Wr (%) was calculated
using the formula
Wt
Wr ¼ 100%
W0
where W0 and Wt are the weights of specimens before
and after being buried in soil, respectively. The reported
values are the average of three measurements.
Results and discussion
FTIR analysis
The FTIR spectra of USF, ASF, and SF-g-LA (after
Soxhlet extraction) are shown in Figure 2. The charac-
teristic absorption peaks of SFs near 3415.0 cm1 rep-
resent the vibration absorption peaks of free hydroxyl
group in SFs. Compared with USF, the peaks of ASF
and SF-g-LA at 3415.0 cm1 are more intense and dis-
tinct, which reveals that alkali treatment can lead to
more hydroxyl groups being exposed. The peak of
SF-g-LA at 3415.0 cm1 is less intense than that of
ASF. It is mainly because the hydroxyl groups with
high activity on the fiber surface initiated grafting reac-
tion, while the hydroxyl groups inside the fiber could
Journal of Reinforced Plastics and Composites 33(22)
Figure 2. Infrared spectra for: (a) USF, (b) ASF, and (c) SF-g-LA.
USF: untreated sisal fiber; ASF: alkali-treated sisal fiber; SF-g-LA:
lactide-grafted sisal fiber.
not participate in the grafting reaction but would be
exposed after grinding into powder. For USF, a char-
acteristic absorption peak appears at 1737.0 cm1 that
belongs to the stretching vibration of C ¼ O of the
aldehyde group in the non-cellulosic constituents
(lignin, hemicellulose, pectin, etc.) of the fiber.
However, in the case of ASF, no similar absorption
peak appears at around 1737.0 cm1, which demon-
strates that the non-cellulosic constituents were
removed from the fiber after alkali treatment. Also,
the disappearance of the peak at 1258.1 cm1 after
alkalization indicates the removal of hemicellulose
materials. It can be observed that there are two add-
itional characteristic peaks at 1772.1 and 1272.3 cm1
in the curve of SF-g-LA compared with those of USF
and ASF. The characteristic absorption peak at
1772.1 cm1 belongs to the stretching vibration of
C ¼ O ester of the carbonyl group, whereas the char-
acteristic absorption peak at 1272.3 cm1 belongs to the
antisymmetric stretching vibration of –C–O–C– of ester
group. This pattern of distinctive peaks indicated suc-
cessful grafting of low polymerization degree PLA onto
SFs under decompressive copolymerization condition.
Analysis of SF morphology
SEM micrographs of the surfaces of USF, ASF, and
SF-g-LA are shown in Figure 3(a)–(c), respectively.
It can be seen from Figure 3(a) that the USF had a
smooth surface with joined fiber bundle and ultimate
cells in parallel fashion arrangement. After alkali
treatment, the destruction of cells on the fiber surface
and the presence of smaller cellulose fibrils can be
observed (Figure 3(b)). Alkali treatment can remove
Fu et al.
Figure 3. SEM micrographs of surface for: (a) USF, (b) ASF, (c) and (d) SF-g-LA.
SEM: scanning electron microscope; USF: untreated sisal fiber; ASF: alkali-treated sisal fiber; SF-g-LA: lactide-grafted sisal fiber.
hemicellulose, lignin, and other soluble materials and
makes fibers susceptible to be easily broken down into
smaller fibrils. It can be seen clearly from Figure 3(c) that
the surfaces of SFs were coated with low polymerization
degree PLA and the grafting polymerization led to
microfiber fibrillation of SFs. This could reduce the
diameters of SFs and increase aspect ratios as well as
the effective surface areas available for contacting with
the matrix in the composites. Figure 3(d) represents the
polymerization details of the surface of a single micro-
fiber with magnification. The FTIR and SEM results
indicated that PLA was present and partly bonded on
the fiber surface.
Mechanical properties of composites
Tensile property. Figure 4 shows the variation of tensile
strength and tensile modulus with SF content for PLA/
USF, PLA/ASF, and PLA/SF-g-LA composites, and
error bars are set at 1 SD. It can be seen clearly that
the tensile strength and tensile modulus of PLA/SF-g-
LA composites are higher than those of PLA/USF and
2039
PLA/ASF composites. The tensile strength of PLA/SF-
g-LA composite with 30 wt% fiber content showed the
best result of 79.0 MPa, increased by 23% compared
with that of pure PLA; whereas the tensile modulus
of PLA/SF-g-LA composite with 40 wt% fiber content
is 3486.1 MPa, increased by 97% compared with that of
pure PLA. As for fiber-reinforced composite, fiber acts
as a reinforcing phase, transferring load and dispersing
stress, which requires the performance of the fiber to
match with that of the matrix in order to obtain the
best mechanical properties.41 For PLA/SF-g-LA com-
posites, besides the removal of the organic gum on the
SF surface, the graft of low polymerization degree PLA
onto SF induces better interfacial bonding and com-
patibility between PLA and SF. Furthermore, the
enhanced fibrillation of SF-g-LA can also improve the
stress transferring efficiency.
Flexural and impact properties. The flexural strength and
flexural modulus of PLA/USF, PLA/ASF, and PLA/
SF-g-LA composites as a function of SF content are
shown in Figure 5, and error bars are set at 1 SD.
2040 Journal of Reinforced Plastics and Composites 33(22)

Figure 4. Tensile properties of PLA/USF, PLA/ASF, and PLA/SF-g-LA composites versus SF content: (a) tensile strength and (b) tensile
modulus.
PLA/USF: untreated sisal fiber reinforced polylactide; PLA/ASF: alkali-treated sisal fiber reinforced polylactide; PLA/SF-g-LA: lactide-
grafted sisal fiber reinforced polylactide; SF: sisal fiber.

Figure 5. Flexural properties of PLA/USF, PLA/ASF, and PLA/SF-g-LA composites versus SF content: (a) flexural strength and (b)
flexural modulus.
PLA/USF: untreated sisal fiber reinforced polylactide; PLA/ASF: alkali-treated sisal fiber reinforced polylactide; PLA/SF-g-LA: lactide-
grafted sisal fiber reinforced polylactide; SF: sisal fiber.

It can be seen from Figure 5(a) and (b) that the flexural
strength and flexural modulus of PLA/SF-g-LA com-
posites significantly improved with increase in SF con-
tent. The flexural strength reached maximum value of
107.3 MPa with 30 wt% SF, and flexural modulus
reached up to 5974.6 MPa with 40 wt% SF, increased
by 25% and 102%, respectively, compared with that of
pure PLA; the flexural strength of PLA/USF and PLA/
ASF composites fluctuated and maintained at
80–88 MPa, and flexural modulus increased slightly.
This is mainly due to the good interfacial performance
between SF-g-LA and PLA matrix, which makes the
fibers difficult to be pulled out. Therefore, the stress
in interface layer transfers effectively, increasing the
ability to resist elastic deformation of the composites.
However, the flexural strength of PLA/SF-g-LA com-
posites declined when fiber content exceeded 30 wt%.
It is probably because of the agglomeration and uneven
Fu et al.
Figure 6. Impact strength of PLA/USF, PLA/ASF, and PLA/SF-g-
LA composites as a function of SF content.
PLA/USF: untreated sisal fiber reinforced polylactide; PLA/ASF:
alkali-treated sisal fiber reinforced polylactide; PLA/SF-g-LA: lac-
tide-grafted sisal fiber reinforced polylactide; SF: sisal fiber.
distribution of residual SF, thus causing defection and
stress concentration of the composites.
As for impact property, the impact strength of PLA/
USF and PLA/ASF composites decreased markedly
and continuously as SF content increased, while
that of PLA/SF-g-LA composites decreased slowly
(Figure 6). As it is known, SF belongs to the class of
brittle reinforcing materials with high modulus and low
elongation, which has little promoting effect on the
improvement of toughness of composite material.
Besides, the addition of SF may induce some more
stress concentration points inside the composites.
Therefore, the impact strength of the composites
decreased with increase in fiber content. However,
owing to the improved interfacial properties of PLA/
SF-g-LA composites and the increased contact area
between matrix and fibrillating SF-g-LA, and maybe
some other unidentified reasons as well, the fibers
need to absorb more energy to be broken, which in
turn tempers the downtrend of the impact strength of
PLA/SF-g-LA composites.
Composites morphology
In order to further investigate the mechanism of SF-g-
LA–reinforced PLA composites, the microstructures of
the fracture surfaces were studied using SEM. The
micrographs of the brittle fracture surfaces of PLA/
USF, PLA/ASF, and PLA/SF-g-LA composites are
shown in Figure 7(a)–(d), respectively. It can be seen
from Figure 7(a) that the USF tended to agglomerate
2041
into bundles, and interfacial gaps appeared on the
interface between the two phases. This poor wetting
was due to the formation of hydrogen bonds among
USF and the disparate hydrophilicities of USF and
PLA. From Figure 7(b), it can be seen that the diam-
eters of SFs decreased and relatively better wetting was
achieved with alkali pretreatment. After grafting
copolymerization modification, as seen in Figure 7(c),
the diameters of SFs decreased significantly, and the
fiber bundles were scattered, producing fibrillation of
fibers. The fibrils were homogeneously dispersed in the
matrix. This indicates that for the SF-g-LA–reinforced
PLA composites, the alkali pretreatment may break the
hydrogen bonds between the cellulose fibrils and dis-
perse the originally gathered fibrils, and with the fol-
lowing grafting copolymerization modification, the
interface adhesion between the two phases could be
enhanced significantly and better wetting of SF-g-LA
in the PLA matrix achieved as well, demonstrated
by the coverage of layers of matrix on the fiber
(Figure 7(d)). This improved interfacial adhesion was
due to the increased surface area of SF-g-LA and PLA
and to the minor differences between the hydrophilicity
of the two components.
Biodegradation in soil
The rates of residual mass of pure PLA and composites
with 20 wt% SF buried in soil at a depth of 10 cm at
different degradation periods are shown in Figure 8.
For pure PLA and all composites, the rate of residual
mass decreased with burial period, i.e. the weight loss
increased. The order of higher weight loss is PLA/
ASF > PLA/USF > PLA/SF-g-LA > PLA, as depicted
in Figure 8. As a kind of hydrophobic resin, PLA was
hard to be adhered by the soil moisture at the early
stage of degradation. With the time increasing, the
weak parts on the surface of PLA hydrolyzed grad-
ually. It can be found that PLA/USF and PLA/ASF
composites experienced a similar variation tendency of
the residual mass rate, whereas the mass loss rate of
PLA/ASF composites was faster than that of PLA/
USF composites. This is mainly due to the hydrophilic
SFs that accelerated the degradation of composites.
The alkali treatment of fibers created slight fibrillation
and thus increased the specific surface area. As a result,
the hydrophilicity of ASF was enhanced and the mass
loss rate of PLA/ASF composites increased. For PLA/
SF-g-LA composites, the variation of the residual mass
rate was not obvious during the early 35 days, but the
rate of descent began to increase subsequently. As men-
tioned above, grafting L-lactide onto SF can induce
good interfacial properties between fiber and matrix,
which hinders the hydrolytic degradation of SFs on
the surface of composites. Another reason which
2042 Journal of Reinforced Plastics and Composites 33(22)

Figure 7. SEM micrographs of brittle fracture of composites for: (a) PLA/USF, (b) PLA/ASF, and (c) and (d) PLA/SF-g-LA.
SEM: scanning electron microscope; PLA/USF: untreated sisal fiber reinforced polylactide; PLA/ASF: alkali-treated sisal fiber reinforced
polylactide; PLA/SF-g-LA: lactide-grafted sisal fiber reinforced polylactide.

cannot be ignored is that the grafting copolymerization

Figure 8. Rate of residual mass of pure PLA and composites
with 20 wt% sisal fiber after different burying periods.
PLA: polylactide; PLA/USF: untreated sisal fiber reinforced poly-
lactide; PLA/ASF: alkali-treated sisal fiber reinforced polylactide;
PLA/SF-g-LA: lactide-grafted sisal fiber reinforced polylactide.
of lactide weakened the hydrophilicity of SFs, to some
extent.
By further investigating the biodegradability of SF-
reinforced PLA composites, the changes in the surface
morphology of PLA/USF, PLA/ASF, PLA/SF-g-LA
composites buried in soil after 10, 35, 90 days are
shown in Figure 9. It can be found that the interfacial
gaps between matrix and USF as well as between matrix
and ASF became larger after 10 days, then the cellulose
fibrils of SFs degraded partly and left lamellar structures
like lignin, which was difficult to degrade. After 90 days,
only the fiber debris remained, and the uneven sheet
structures appeared on the matrix around USF
(Figure 9(a)–(c)). It seems that the degradation began
around the SFs. Meanwhile the ASF and USF near the
surface of the composites degraded mostly, which illu-
strated that the degradation of composites was grad-
ually from the surface to the inside (Figure 9(d)–(f)).
For PLA/SF-g-LA composites, a small amount of
cavities appeared on the fracture surface of composites
Fu et al. 2043

Figure 9. SEM micrographs of: (a, b, c) PLA/USF, (d, e, f) PLA/ASF, and (g, h, i) PLA/SF-g-LA composites during different degradation
periods (a, d, and g: 10 days; b, e, and h: 35 days; and c, f, and i: 90 days) in soil environment with a burial depth of 10 cm.
SEM: scanning electron microscope; PLA/USF: untreated sisal fiber reinforced polylactide; PLA/ASF: alkali-treated sisal fiber reinforced
polylactide; PLA/SF-g-LA: lactide-grafted sisal fiber reinforced polylactide.

in the early stages. Then the exfoliation of some frag-
mental materials appeared on the surface of fiber and
finally led to the degradation of the cellulose fibrils
(Figure 9(g)–(i)).
Conclusions
Biodegradable composite with good mechanical prop-
erties and considerable biodegradability could be suc-
cessfully developed using L-lactide-grafted SFs as a
reinforcing agent and PLA as a matrix. FTIR analyses
demonstrated the successful grafting of low polymeriza-
tion degree PLA onto SFs, which was revealed from the
appearance of C ¼ O ester of the carbonyl group and –
C–O–C– of ester group. Also, the SEM micrographs of
the fiber surfaces confirmed that PLA was present on
the fiber surface. Although the impact strength
decreased slightly, L-lactide grafting significantly
enhanced the tensile and flexural properties of the com-
posite, compared with the PLA matrix and the compos-
ites reinforced by untreated or alkali-treated SFs. The
SEM photographs of fiber surfaces and fracture sur-
faces of composites clearly indicated that improved
interfacial properties were achieved after grafting modi-
fication of SFs. The degree of biodegradation increased
with time. With superior interfacial adhesion, the
2044
biodegradation rate of PLA/SF-g-LA composites was
lower those that of PLA/USF and PLA/ASF compos-
ites, although still higher than that of pure PLA, when
incubated in soil. The biodegradation process of PLA/
SF-g-LA composites can be summarized as follows: the
appearance of cavities, the exfoliation of fragmental
materials, and the degradation of cellulose fibrils.
Conflict of interest
None declared.
Funding
This research was supported by Specialized Research Fund
for the Doctoral Program of Higher Education of China
(grant no. 20120172130004) and National Key Basic
Research Program of China (973 Program) (grant no.
2012CB025902).
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