Journal of Elastomers and

Plastics
http://jep.sagepub.com/

Natural Weathering of Poly (Lactic Acid): Effects of Rice Starch and

Epoxidized Natural Rubber
G.H. Yew, W.S. Chow, Z.A. Mohd Ishak and A.M. Mohd Yusof
Journal of Elastomers and Plastics 2009 41: 369
DOI: 10.1177/0095244309103663

The online version of this article can be found at:

http://jep.sagepub.com/content/41/4/369

Published by:

http://www.sagepublications.com

Additional services and information for Journal of Elastomers and Plastics can be found at:

Email Alerts: http://jep.sagepub.com/cgi/alerts

Subscriptions: http://jep.sagepub.com/subscriptions

Reprints: http://www.sagepub.com/journalsReprints.nav

Permissions: http://www.sagepub.com/journalsPermissions.nav

Citations: http://jep.sagepub.com/content/41/4/369.refs.html

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

Natural Weathering of Poly
(Lactic Acid): Effects of Rice Starch
and Epoxidized Natural Rubber
G. H. YEW, W. S. CHOW* AND Z. A. MOHD ISHAK
School of Materials and Mineral Resources Engineering
Engineering Campus, Universiti Sains Malaysia
Seri Ampangan, 14300 Nibong Tebal, Penang, Malaysia

A. M. MOHD YUSOF
Department of Polymer Technology, Malaysian Institute of
Chemical & Bio-Engineering Technology, Universiti Kuala
Lumpur, Lot 1988, Kawasan Perindustrian Bandar Vendor
Taboh Naning, 78000 Alor Gajah, Melaka, Malaysia

ABSTRACT: Poly(lactic acid) (PLA) composites consisting of PLA, rice starch

(RS), and epoxidized natural rubber (ENR50) are compounded using a twin-
screw extruder followed by compression molding. Two types of thermoplastic
starch are prepared by mixing RS with glycerol and water. Natural weathering
tests are performed on the PLA/RS composites in Penang, Malaysia for
2 months. The average mean temperature and mean relative humidity are
298C and 70%, respectively. Tensile tests are performed to characterize the
mechanical properties of the weathered PLA/RS composites. Morphological
studies are performed by using scanning electron microscopy (SEM). The tensile
properties of weathered PLA/RS composites decreased slightly, on the other
hand, the tensile properties of weathered PLA/SG and PLA/SGW composites
decreased drastically. The retention-ability of the PLA composites are relatively
low, which may be attributed to the photo-degradation of PLA, chain scission of
PLA, oxidation degradation on ENR, moisture absorption of RS, and leaching of

*Author to whom correspondence should be addressed.

E-mail: [email protected]; [email protected]

JOURNAL OF ELASTOMERS AND PLASTICS Vol. 41July 2009 369

0095-2443/09/04 036914 $10.00/0 DOI: 10.1177/0095244309103663
The Author(s), 2009. Reprints and permissions:
http://www.sagepub.co.uk/journalsPermissions.nav

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

370 G. H. YEW ET AL.

RS particles. In addition, discoloration, surface roughness, surface cracking, and

embrittlement are observed for all PLA/RS composites. The extent of
degradation is increased by the addition of ENR, owing to the fact that ENR
is susceptible to oxygen attack, and consequently facilitates degradation.
The morphological properties of the weathered PLA/RS composites are
transformed to a more brittle behavior, indicating that severe degradation has
occurred on the PLA/RS composites.

KEY WORDS: polylactic acid (PLA), rice starch, epoxidized natural rubber
(ENR), natural weathering, composites.

INTRODUCTION

EATHERING IS A science considered by many to be the exposure of

W polymeric materials to either a natural environment or a weath-
ering chamber of some sort [1]. Outdoor weathering results from a
combination of many environmental factors. The main agents of
weathering are sunlight (particularly ultraviolet radiation), tempera-
ture, thermal cycling, and moisture in various forms and wind [2].
Applications involving sunlight exposure are the most challenging
and the most stressful for commercial thermoplastic polymers. Most of
the thermoplastic polymers undergo loss of physical properties or color
changes to varying degrees when exposed to direct sunlight. The
incorporation of starch into plastics to enhance their fragmentation
and degradability in the environment has generated considerable
interest. In the open literature, few well-documented studies focus on
the natural weathering of starch-filled thermoplastics. Breslin and Li [3]
have reported the weathering properties of starch-polyethylene compo-
sites film in a marine environment. The corn starch-polyethylene
composites rapidly deteriorated during exposure in the strawline of a
marsh, attributed to the photodegradation of the films. Danjaji et al. [4]
have examined the effects of natural weathering of linear low-density
polyethylene (LLDPE)/sago starch composites. Embrittlement, surface
cracking, and total collapse of the matrix were observed for the weathered
LLDPE/sago starch samples.
Poly(lactic acid) (PLA) is a degradable thermoplastic polymer with
excellent mechanical properties which is now, beginning to be produced
on a large scale from fermentation of corn to lactic acid and subsequent
chemical polymerization. Starch is of interest as a naturally occurring
biodegradable material due to its cost effectiveness, abundance, renew-
ability, availability, good thermo-processability, using conventional
plastic processing equipment (extrusion, injection molding), and its

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

 Natural Weathering of Poly(Lactic Acid) 371

adequate thermal stability for melt blending with synthetic plastics

(i.e., aliphatic polyester, nonbiodegradable thermoplastics) [5].
Epoxidized natural rubber (ENR) with 50 mol% epoxidation has been
shown to be polar properties similar to those of acrylonitrile butadiene
rubber and butyl rubber. However, ENR vulcanizates exhibit poor aging
properties. The unstable nature of ENR is believed to be due to the
residual acidity that was inherited from the natural rubber modification
(epoxidation) with peroxide. Residual acidity has been claimed to be
responsible for the high gel content, high viscosity and poor storage
stability of ENR [6].
In our previous research, 20 wt% RS achieved a good balance of tensile
properties. The addition of ENR improved the tensile properties of PLA/
RS composites. In addition, it is found that the incorporation of RS and
ENR into PLA could facilitate its degradability when the composite are
being subjected to water absorption and a-amylase enzymatic treat-
ments [7]. This work is focused on the study of degradability for PLA/RS
composites in the natural weathering environment. In this study, the
natural weathering of PLA/RS composites was performed in tropical
climates. The hot and wet environments could be considered as an
extreme climate to study the degradation of PLA/RS/ENR composites.
It is expected that the incorporation of RS and ENR could again
contribute to the degradation of PLA when it is subjected to natural
weathering. The work presented in this article focuses on the studies of
the effects of natural weathering on the mechanical and morphological
properties of PLA/RS composites.

EXPERIMENTAL

Materials

PLA was supplied by Mitsui Chemicals Inc., Japan. Melt flow index
(MFI) and density of PLA were 64.8 g/10 min (at 1908C and 2.16 kg load)
and 1.23 g/cm3, respectively. Rice starch (RS) was obtained from TIGA
Gajah Cho Heng Sdn. Bhd., Malaysia. It was a fine white powder, which
is granular in form with particle size range from 2 to 8 mm and moisture
content of 11.5%. Two types of thermoplastic starch (TPS) were
prepared, i.e., rice starchglycerol mixture (SG) and rice starch
glycerolwater mixture (SGW). A standard mixture of rice starch and
glycerol (SG) (ratio 4/1) was prepared by using of a mechanical stirrer
(15 min, 100 rpm). The starch-glycerol mixture was left at room
temperature (25  38C) for 24 h to swell the RS granules. TPS was

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

372 G. H. YEW ET AL.

Table 1. Composition and designation of materials.

Materials compositions
Materials designation PLA (wt%) RS (wt%) SG (wt%) SGW (wt%) ENR (phr)

PLA 100
PLA/RS20 80 20
PLA/RS20/ENR5 80 20 5
PLA/RS20/ENR10 80 20 10
PLA/SG20 80 20
PLA/SG20/E5 80 20 5
PLA/SG20/E10 80 20 10
PLA/SGW20 80 20
PLA/SGW20/E5 80 20 5
PLA/SGW20/E10 80 20 10

extruded with a twin-screw extruder (Berstorff) with extrusion zone

temperature ranging from 808C to 958C. The extrudates were
immediately placed in a desiccator containing 95% H2SO4 to control
moisture absorption. Another TPS was also prepared by mixing RS,
glycerol, and water (SGW) (ratio 8/1/1) with the same method under
identical conditions. ENR-25 was supplied by Rubber Research Institute
of Malaysia (RRIM), Malaysia. The composition and designation of
materials was shown in Table 1.

Sample Preparation

Melt compounding of the PLA/RS composites was done in a twin-

screw extruder (Berstorff). The extrusion zone temperatures ranged
from 1808C to 1958C. Prior to extrusion, PLA pellets and RS were
dried by using a dehumidifier (ConAir Franklin) at 708C for 24 h.
The extrudates were pelletized with the Speecon 7200MA pelletizer. The
compounded samples were compression-molded in a Kao Tieh GoTech
compression molding machine at 1908C using a pressure of 10 MPa for
12 min and cooled under pressure for 3 min. Molded samples were cut
into dumbbell shaped specimens according to ASTM D638.

Natural Weathering

The weathering test of PLA/RS composites were conducted according

to ASTM D1435. Specimens were attached to a rack with a specimen
holder. The rack was adjusted to face the equator at an angle of 458.
The rack is situated at an open area whereby it is free from being

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

 Natural Weathering of Poly(Lactic Acid) 373

overshadowed by other objects. The samples were collected every 2 weeks

for a total of 8 weeks to determine the extent of degradation. Moisture at
the surface of the samples were removed with a clean towel and left in air
for 24 h at room temperature before mechanical tests were conducted and
fractured surface are being observed under SEM. A comprehensive
meteorological data supplied by Penang Meteorological Department,
Malaysia comprising measurements of mean temperature, mean relative
humidity (RH), rainfall, and solar radiation during the weathering
period. The average mean temperature and mean RH are 298C and 70%.
The average rainfall and solar radiation are 1.0 mm and 20 MJ/m2,
respectively.

Mechanical Properties

Tensile tests were performed according ASTM D638, by using an

Instron 3366 testing machine. The crosshead speed was set at 5 mm/min.
Samples for tensile measurements were conditioned at 30  2% RH for
24 h before testing. All these tests were conducted at ambient
temperature and an average value of five repeated tests was taken for
each composition. Tensile modulus, tensile strength, and elongation at
break were evaluated from stressstrain data.

Morphological Studies

Image analyzer and scanning electron microscopy (SEM; Cambridge

Stereoscan 2000) was used to study the surface morphology and mode of
failure of the PLA/RS samples. Test samples were first sputter-coated
with gold in order to prevent electrical discharge during examination.

RESULTS AND DISCUSSION

Mechanical Properties

Table 2 shows the tensile properties of PLA/RS20 composites after

being subjected to natural weathering for 8 weeks. Note that the values
presented in parenthesis in Table 2 refer to the percentage of retention
in the respective tensile properties. The tensile properties of PLA and
its composites were found to be highly deteriorated upon subjected to
natural weathering. The reduction of the tensile properties may be
attributed to the combination effects of sunlight, UV radiation, heat,
humidity, rainfall, moisture, atmosphere pollutants, microbes etc.

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

374 G. H. YEW ET AL.

Table 2. Tensile properties of PLA composites after exposure to natural weathering.

Exposure time
Tensile
Materials properties Control 2 weeks 4 weeks 6 weeks 8 weeks

PLA Tensile 3.3 3.1 (93.9) 3.0 (90.9) 2.8 (84.8) 2.6 (78.8)
modulus (GPa)
Tensile 57.8 46.5 (80.4) 43.3 (74.9) 39.6 (68.5) 33.1 (57.3)
strength (MPa)
Elongation 3.8 3.1 (81.6) 2.8 (73.7) 2.3 (60.5) 1.9 (50.0)
at break (%)
PLA/RS20 Tensile 3.8 3.0 (78.9) 2.9 (76.3) 2.8 (73.7) 2.5 (65.8)
modulus (GPa)
Tensile 44.0 34.9 (79.3) 32.4 (73.6) 29.5 (67.0) 25.0 (56.8)
strength (MPa)
Elongation 2.5 1.9 (76.0) 1.6 (64.0) 1.4 (56.0) 1.0 (40.0)
at break (%)
PLA/RS20/E5 Tensile 3.3 2.9 (87.8) 2.8 (84.8) 2.5 (75.7) 2.4 (72.7)
modulus (GPa)
Tensile 49.0 27.1 (55.3) 25.1 (51.2) 23.6 (48.2) 17.1 (34.9)
strength (MPa)
Elongation 3.4 2.1 (67.7) 1.8 (52.9) 1.6 (47.1) 0.9 (26.5)
at break (%)
PLA/RS20/E10 Tensile 2.8 2.5 (89.3) 2.4 (85.7) 2.2 (78.6) 2.1 (75.0)
modulus (GPa)
Tensile 37.2 16.7 (44.9) 14.6 (39.2) 12.8 (34.4) 12.0 (32.3)
strength (MPa)
Elongation 2.6 1.7 (65.4) 1.3 (50.0) 1.0 (38.5) 0.9 (34.6)
at break (%)
PLA/SG20 Tensile 3.7 2.5 (67.6) 2.3 (62.2) 2.1 (56.8) 2.0 (54.1)
modulus (GPa)
Tensile 37.0 15.8 (42.7) 13.9 (37.6) 10.4 (28.1) 8.8 (23.8)
strength (MPa)
Elongation 3.1 1.6 (51.6) 1.4 (45.2) 1.2 (38.7) 0.9 (29.0)
at break (%)
PLA/SG20/E5 Tensile 3.1 2.33 (75.2) 1.9 (61.3) 1.66 (53.5) 1.47 (47.4)
modulus (GPa)
Tensile 28.6 10.0 (34.9) 7.5 (26.2) 6.3 (22.0) 4.7 (16.4)
strength (MPa)
Elongation 3.5 1.3 (37.1) 1.2 (34.3) 1.1 (31.4) 0.8 (22.9)
at break (%)
PLA/SG20/E10 Tensile 3.0 2.0 (66.7) 1.7 (56.7) 1.5 (50.0) 1.3 (43.3)
modulus (GPa)
Tensile 23.4 8.0 (34.2) 6.3 (26.9) 4.6 (19.7) 4.1 (17.5)
strength (MPa)
Elongation 2.7 1.2 (44.4) 1.1 (40.7) 0.9 (33.3) 0.7 (25.9)
at break (%)
(Continued)

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

 Natural Weathering of Poly(Lactic Acid) 375

Table 2. Continued.

Exposure time
Tensile
Materials properties Control 2 weeks 4 weeks 6 weeks 8 weeks

PLA/SGW20 Tensile 3.6 2.8 (77.8) 2.4 (66.7) 1.7 (47.2) 1.3 (36.1)
modulus (GPa)
Tensile 34.9 16.4 (47.0) 14.3 (41.0) 14.0 (40.1) 13.5 (38.7)
strength (MPa)
Elongation 3.0 1.7 (56.7) 1.5 (50.0) 1.4 (46.7) 0.9 (30.0)
at break (%)
PLA/SGW20/E5 Tensile 3.1 2.5 (80.6) 1.9 (61.3) 1.8 (58.1) 1.7 (54.8)
modulus (GPa)
Tensile 29.1 13.7 (47.1) 12.4 (42.6) 10.9 (37.5) 9.0 (30.9)
strength (MPa)
Elongation 3.4 1.7 (50.0) 1.6 (47.1) 1.3 (38.2) 0.8 (23.5)
at break (%)
PLA/SGW20/E10 Tensile 2.8 2.0 (71.4) 1.8 (64.3) 1.6 (57.1) 1.5 (53.6)
modulus (GPa)
Tensile 25.3 11.5 (45.5) 9.5 (37.5) 8.5 (33.6) 7.5 (29.6)
strength (MPa)
Elongation 2.8 1.5 (53.6) 1.3 (46.4) 1.1 (39.3) 0.8 (28.6)
at break (%)

Weathering can thus encompass the effect of most of the degradation

phenomena and usually involves the combined effect of two or more
antagonistic factors. The result is often the deterioration of the polymer
mechanical properties, leading to embrittlement or catastrophic failure
(i.e., cracking) of the product [8].
From Table 2, it can be seen that the tensile modulus, tensile strength,
and elongation at break of PLA decreased significantly after exposure to
natural weathering. The tensile strength and elongation at break of PLA
reduced to 50% of its initial value after 8 weeks of natural weathering.
The reduction in tensile modulus may be attributed to the chain scissions
of PLA. The chain scission of PLA could be possibly explained by the
photo-oxidation of PLA by UV radiation; and hydrolysis of PLA by rain
water/moisture. Recall that PLA could absorb water. The maximum
moisture content (Mm) and diffusion constant (D) of PLA is 1.0% and
5.60  1013 m2/s, respectively [7]. This could causes hydrolysis of ester
linkages and subsequently leads to the breaking down of long
macromolecular chains in PLA [9,10]. In addition, the short wavelength
UV radiation could cause damage on polymeric materials due to its high
quantum energy. The energy (97 kcal/mol) of the shortest wavelength
(295 nm) of solar radiation is capable of breaking CC, CN, OO, CCl,

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

376 G. H. YEW ET AL.

CO, NH, and SiO types of polymer bonds [11]. In this study, cleavage
of the CO bonds in PLA backbone chain may be attributed to the
UV radiation. Copinet et al. [9] reported that UV treatment (via UV light
with 315 nm) could catalyze the hydrolysis of ester linkage of PLA.
Several radical may be formed as a result from the cleavage at CO of the
main chain and the breaking of ester bonds as well as the radicals
produced from the cleavage at CC bonds of the main PLA macro-
molecular chains upon UV degradation [9].
Photo-degradation of polymers is basically initiated at some point
in the polymer where UV light is absorbed. The basic structure of
PLA containing chromophoric groups (CO) that could absorb solar UV
radiation. This may enhanced the susceptibility of PLA to premature
outdoor failure via photo-degradation. Carbonyl photo-cleavage reac-
tions may be the major cause of photodegradation in a wide range of
carbonyl-containing polymers as well as in the polymer that always
contain at least traces of carbonyl function as a result of oxidation
during processing (e.g., formation of carbonyl, hydroxyl, aldehyde,
ketone, carboxylic acid, and ester functional groups).
Recall that the chemical structure of PLA containing tertiary
hydrogen atoms (i.e., hydrogen atom in the branching CH3 groups
where adjacent to the chain backbone), thus it may be prone to the
oxidation degradation. Oxidative degradation of polymers causes them
to become embrittled and decreases their impact strength due to chain
scission and crosslinking reactions. As a result of oxidation, there is
also a decrease in both tensile strength and elongation at break of the
polymer [8].
The effects of RS and modified RS (SG and SGW) on the tensile
properties of PLA upon subjected to natural weathering were also
studied. Tensile strength and elongation at break of the exposed PLA/
RS20 composites generally decreased with the duration of natural
weathering. Recall that RS containing abundance of hydroxyl group,
which could prone to moisture absorption due to its hygroscopic nature.
The rainfall is relatively frequent during the natural weathering tests.
This may enhance the susceptibility of the RS to absorb rain water. It is
believed that the water molecules will be absorbed by the RS particles,
which were located in the outer surface, followed by the penetration of
the water molecules into the inner layer of the exposed PLA/RS20
specimens. In addition, some RS particles on the skin layer of weathered
PLA/RS20 samples were leached out due to the effects of rainfall.
Preechawong et al. [12] suggested that starch is prone to moisture and
water absorption due to its hygroscopic nature. Our previous study on
the water absorption of PLA/RS composites showed that the diffusion

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

 Natural Weathering of Poly(Lactic Acid) 377

constant of PLA/RS20 composites is higher than that of PLA [7].

In addition, the surface of the weathered samples was rough-like and
some powder-like particles were observed on top of the weathered
specimens, which may be attributed to the leaching of the RS particle
(e.g., the starch granules which located on the outer surface of the
compression-molded specimens) by rainfall.
Compared to PLA/RS20, the deterioration of tensile properties of both
PLA/SG20 and PLA/SGW20 are more severe. From Table 2, it can be seen
that both PLA/SG20 and PLA/SGW20 lost almost 70% of their tensile
strength and elongation at break after being exposed to natural
weathering. This can be attributed to the effects of glycerol modification
on the RS. Recall that addition of glycerol could destructurize the RS
particles and thus lower the interaction of the starch molecules and widen
the distance between the starch macromolecules. Again, it can
be hypothesized that the RS macromolecules have been plasticized
by glycerol modification, which facilitates the water penetration.
In addition, it is believed that glycerol could contribute to the
enhancement of water absorption due to its basic structure which
containing three hydroxyl groups. Based on our previous finding [7], the
maximum moisture content (Mm) and diffusion constant (D) of PLA/
SGW20 is 7.8% and 7.10  1013 m2/s, respectively. For the PLA/SG20,
the Mm and D is much higher, which are 10.7% and 9.55  1013 m2/s,
respectively. This may lead to higher moisture/rain water absorption
during natural weathering tests. According to Choi and Takahashi [13],
water absorption of the skin layer of polyester specimen due to rain and/or
moisture would cause a material softening. It can be noted that, however,
most of the polymeric materials could absorb water from humid air
or directly get moistened by rain tends to swell (water absorption).
A subsequent dry period implies that water will be released (i.e.,
shrinkage due to water desorption). Recall that in this study the PLA/
RS composites were subjected to hot and wet tropical climate. Thus, it is
believed that the weathered PLA/RS samples have undergone consider-
able changes of stress in the form of swelling and shrinkage, which could
lead to surface cracking. Accordingly, the surface cracking will act as
stress concentration sites and is responsible for the reduction of the
tensile properties of both unmodified and modified PLA/RS composites.
Further deterioration of the tensile properties of weathered PLA/RS20
composites is observed upon the incorporation of ENR50. The presence
of ENR in the PLA/RS20 composites could acts as auto-oxidant by
initiating free radical reaction. The oxidation of ENR will generate free
radicals, which subsequently initiate oxidation of PLA. The elastomer
phase is the most oxidizable component, since it contain unsaturated

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

378 G. H. YEW ET AL.

bonds (double bond, CC) [14]. Poh and Lee [15] have investigated the
thermal oxidative aging of ENR and found that during thermal-
oxidative process, epoxide ring opening reaction takes place resulting
in the formation of free radicals. The radical will then form hydroper-
oxides which will subsequently react with ENR and generate further
by-products e.g., alcohol, carboxylic acid, and ketone groups. Thus it is
believed that the incorporation of ENR50 could further facilitate the
degradation of PLA/RS20 composites upon subjected to natural weath-
ering with a tropical climate condition.

Morphological Properties

Figure 1(a)(c) show the SEM micrographs taken from the tensile
fractured surface of un-weathered samples of PLA/RS20/E5, PLA/SG20/
E5, and PLA/SGW20/E5 (i.e., as control). Figure 2 (a)(c) show the SEM
micrographs taken from the tensile fractured surface of weathered
samples of PLA/RS20/E5, PLA/SG20/E5, and PLA/SGW20/E5 composites
for 8 weeks in natural environment. It can be seen that all weathered PLA
composites fractured in a brittle manner. Fibrillated structure and plastic
deformation was totally disappeared (c.f. Figure 2(a)(c)). Starch
detachment from the PLA matrix could be observed on the fractured
plane. In addition, inter-connected cracks were revealed on the fractured

50 m
1a

50 m 1b 50 m 1c

Figure 1. SEM micrographs taken from the tensile fractured surface of un-weathered
(a) PLA/RS20/E5, (b) PLA/SG20/E5, and (c) PLA/SGW20/E5.

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

 Natural Weathering of Poly(Lactic Acid) 379

surface of both PLA/SG20/E5 and PLA/SGW20/E5 (shown by arrows).

This can be correlated to the more severe degradation of the glycerol
modified RS filled PLA. The combination effects of glycerol modified RS
(both SG and SGW) and ENR could enhance the degradability of the PLA
composites upon exposure to natural weathering. This is in harmony with
the embrittlement of the composites and explained the dramatic drop of
the elongation at break values (c.f. Table 2).
Figure 3(a) and (b) shows the SEM micrographs taken from the sample
surface of PLA/SG20 and PLA/SG20/E5 composites after being subjected

Starch detachment

2a

Inter-connected cracks

Inter-connected cracks

2b 2c

Figure 2. SEM micrographs taken from the tensile fractured surface of weathered
(a) PLA/RS20/E5, (b) PLA/SG20/E5, and (c) PLA/SGW20/E5.

3a 3b

10m 10m

Figure 3. SEM micrographs taken from the samples surface of weathered (a) PLA/SG20
and (b) PLA/SG20/E5 composites.

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

380 G. H. YEW ET AL.

to natural weathering for 8 weeks. It can be seen that severe surface

deterioration occurred on PLA/RS composites. It is interesting to note
that surface cracks and microbes (e.g., fungus growth) were observed
through SEM. The fungus growth on the sample surface is shown by
arrows. In addition, small cracks are widely spread throughout
the surface of the PLA/RS20/E5 composites. This correlates well with
the dramatic reduction in the tensile properties and brittle fracture
morphology of the PLA composites. A variety of microorganisms may
attack plastic products causing degradation of properties and product
failure, mostly in warm humid climates. Starch filled plastics products
sometimes fail because of attack by various biological organisms. Of the
microorganisms, the most important are the fungi, especially species
known as mold or mildew. There are some fungi, which are able to
assimilate the degradation products formed by the chemical hydrolysis of
PLA [16]. A similar observation has been reported by Danjaji et al. [4].
Large cracks appear on the surface of the LLDPE/sago starch composites,
which apparently resulted in its collapse, and exposure of the embedded
starch granules [4].

CONCLUSIONS

Based on this work devoted to studying the effect of natural weathering

on the mechanical and morphological properties of degradable PLA/rice
starch (RS)/ENR composites, the following conclusions can be drawn:
(1) Tensile properties of PLA/RS composites decreased upon subjected
to natural weathering. Furthermore, the retention-ability of the
tensile properties for PLA/RS composites is relatively higher than
that of the PLA/SG and PLA/SGW composites.
(2) Addition of ENR further increased the degradability of the PLA/RS
composites owing to the oxidation degradation and ozone attack on
the unsaturated sites of ENR.
(3) The incorporation of the SG and SGW further decreased the tensile
properties of PLA composites upon subjected to natural weathering,
as compared to the PLA/RS composites. Discoloration was revealed
on all the PLA/RS composites.
(4) The morphological properties of all PLA/RS composites were
transformed to brittle in manner (evidenced by SEM), indicates
that severe degradation has been occurred on the PLA/RS composites
after being exposed to natural weathering in the environment with an
average mean temperature and mean RH are 298C and 70% for 8
weeks.

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

 Natural Weathering of Poly(Lactic Acid) 381

ACKNOWLEDGMENTS

The authors would like to thank The Ministry of Science, Technology

and Innovation (MOSTI), Malaysia for the IRPA grant (Grant Number:
6012913/IRPA Grant), and USM Short Term Grant. We also thank
Dr Kitagawa (Kyoto Municipal Research Institute, Japan) and Mitsui
Chemicals Inc., Japan for supplying PLA used in this study.

REFERENCES

1. Jacques, L.F.E. (2000). Accelerated and Outdoor/Natural Exposure Testing

of Coatings, Prog. Polym. Sci., 25: 13371362.
2. Nicholson, J.W. (1991). The Chemistry of Polymers. UK, The Royal Society
of Chemistry.
3. Breslin, V.T. and Li, B. (1993). Weathering of Starch-polyethylene
Composite Films in the Marine Environment, J. Appl. Polym. Sci., 48:
20632079.
4. Danjaji, I.D., Nawang, R., Ishiaku, U.S., Ismail, H. and Mohd Ishak, Z.A.
(2002). Degradation Studies and Moisture Uptake of Sago-starch Filled
Linear Low-density Polyethylene Composites, Polym. Test., 21: 7581.
5. Garlotta, D., Doane, W., Shogren, R., Lawton, J. and Willett, J.L. (2003).
Mechanical and Thermal Properties of Starch-filled Poly(D,L-lactic Acid)/
Poly(hydroxy Ester Ether) Biodegradable Blends, J. Appl. Polym. Sci.,
88: 17751786.
6. Ishiaku, U.S. and Mohd Ishak, Z.A. (1999). Developments in Poly(vinyl
Chloride)/Epoxidized Natural Rubber Blends, In: Shonaike, G.O. and
Simon, G.P. (eds), Polymer Blends and Alloys, pp. 663718, New York,
Marcel Dekker.
7. Yew, G.H., Mohd Yusof, A.M., Mohd Ishak, Z.A. and Ishiaku, U.S. (2005).
Water Absorption and Enzymatic Degradation of Polylactic Acid/Rice Starch
Composites, Polym. Deg. Stab., 90: 488500.
8. Scheirs, J. (2000). Compositional and Failure Analysis of Polymers:
A Practical Approach, New York, John Wiley & Sons.
9. Copinet, A., Bertrand, C., Govindin, S., Coma, V. and Couturier, Y. (2004).
Effects of Ultraviolet Light (315 nm), Temperature and Relative Humidity
on the Degradation of Polylactic Acid Plastic Film, Chemosphere, 55:
763773.
10. Spychaj, T. (2002). Chemical Recycling of PET: Methods and Products, In:
Fakirov, S. (ed.), Handbook of Thermoplastic Polyesters, pp. 12511290,
Wiley-VCH, Weinheim.
11. Kockott, D. (1999). Weathering, In: Brown, R. (ed.), Handbook of Polymer
Testing, Physical Methods, pp. 697734, New York, Marcel Dekker.
12. Preechawong, D., Peesan, M., Supophol, P. and Rujiravanit, R. (2005).
Preparation and Characterization of Starch/Poly(L-lactic Acid) Hybrid
Foams, Carbohydrate Polym., 59: 329337.

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010

382 G. H. YEW ET AL.

13. Choi, N.S. and Takahashi, K. (2002). Fracture Behavior of Discontinuous

Fiber-reinforced Injection Molded Polyester Composites, In: Fakirov, S.
(ed.), Handbook of Thermoplastic Polyesters, pp. 11731217, Weinheim,
Wiley-VCH.
14. Sharma, N., Chang, L.P., Chu, Y.L., Ismail, H., Ishiaku, U.S. and Mohd
Ishak, Z.A. (2001). A Study on the Effect of Pro-oxidant on the Thermo-
oxidative Degradation Behaviour of Sago Starch Filled Polyethylene,
Polym. Deg. Stab., 71: 381393.
15. Poh, B.T. and Lee, K.S. (1993). FTIR Study of Thermal Oxidation of ENR,
Eur. Polym. J., 30: 1723.
16. Baum, B., Parker, C.H. and Deanin, R.D. (1982). Environmental Resistance,
In: Baijal, M.D. (ed.), Plastics Polymer Science and Technology, pp. 883937,
New York, John Wiley & Sons.

Downloaded from jep.sagepub.com by Diana Palma R. on September 26, 2010