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Poly(lactic acid)/starch composites: Effect of microstructure and morphology

of starch granules on performance

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DOI: 10.1002/app.45504

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Poly(lactic acid)/starch composites: Effect of microstructure and
morphology of starch granules on performance
Saud Khalid,1 Long Yu ,1,2 Linghan Meng,1 Hongsheng Liu,1 Amjad Ali,1 Ling Chen1
1
Center for Polymer from Renewable Resources, SFSE, South China University of Technology (SCUT), Guangzhou 510640, China
2
Sino-Singapore International Joint Research Institute, Knowledge City, Guangzhou 510663, China
Correspondence to: L. Yu (E - mail: felyu@scut.edu.cn)

ABSTRACT: Starches used to develop biodegradable composites belong to different botanical sources that exhibit different microstruc-
tures and morphologies. This results in confused relationship and no comparison of data for applications. In this work, the most
popular ten different starches were used as model materials to investigate the relationship between starch microstructure and the per-
formance of poly(lactic acid) (PLA)/starch composites. It was found that: (a) composites filled with either well-sized (small-sized and
non-agglomerated) starch granules or those containing high amylose content (G-50 and G-80) improves the reinforcing ability of
PLA, with least reduction in deformation; (b) aggregation tendency of small-sized starch granules can be controlled using surface
modification approach that not only reduces the phase-separation between starch and PLA but also improves the dispersion; and
(c) no discernible relationship exists between the starches, from different botanical sources, and the thermal performance of PLA/
starch composites. The results provide practical guidelines to develop starch-based biodegradable composites for commercial applica-
tions. V
C 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45504.

KEYWORDS: biodegradable; biopolymers and renewable polymers; nanostructured polymers; packaging; surfaces and interfaces

Received 27 March 2017; accepted 6 July 2017

DOI: 10.1002/app.45504

INTRODUCTION microstructures and morphologies of starches on the performan-

Compositing or blending is popular and important technique
from commercial point-of-view, particularly for the develop-
ment of new biodegradable materials, as many raw materials are
either of lower quality or higher cost. Composites of biodegrad-
able poly(lactic acid) (PLA), reinforced or filled by low cost
starch, are considered as one of the most promising biodegrad-
able materials and various commercial products (such as pack-
aging and mulch films, thermoforming containers, injection
molded items, extrusion sheet, etc.) are available in the market.
Many patents and articles have been published in this area.1–26
However, the starches used to develop composites or blends
come from different botanical sources, having different chemical
and physical microstructures, which results in confused relation-
ship, between microstructures and performances, and no com-
parison of data for applications.
Effect of microstructure of fillers on the polymeric blends and
composites has been studied extensively21,27–37 and even hand-
books are available.38–40 On the other hand, it is well known that
starches from different botanical sources have different chemical
(such as amylase/amylopectin ratio), physical (such as particles
size, shape), microstructures,13,41–44 and thermal properties.45–48
However, there is no systematic report on the effect of
ces of their blends or composites. Furthermore, it is well known
that PLA and starch are incompatible since the former is hydro-
phobic and the latter is hydrophilic. Various techniques and
methods have been developed to improve the interface between
hydrophobic PLA and hydrophilic starch,17,49,50 including grafting
hydrophilic group (maleic anhydrate)8,51,52 on PLA surface; or
grafting hydrophobic groups on starches,7,11,53,54 and crosslinking
between PLA and starch with methylenediphenyl diisocyanate
(MDI),6,18 etc. However, there is no commercial product available
in the market using these techniques, mainly because of high cost
(such as grafting reaction) or toxic concern (such as treatment
with MDI or other crosslinking agents, etc.), especially for food
packaging or short-life applications. Development of a simple
and low cost treatment will be greatly useful for commercial
applications.
In this work, the most popular starches from ten different
botanical sources (cereal, tuberous, vegetable, and legume), hav-
ing different chemical and physical microstructures, were used
as model materials to investigate the relationship between the
microstructures and performances of PLA/starch composites.
The effect of pre-treatment of starches on the composites was
also investigated. It was found that:

C 2017 Wiley Periodicals, Inc.

V

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Table I. Specimen Code and Composition

Surface treatment
Specimen Source of Supplier of of starcha Composition
Sr. no. code starch starch Yes/No PLA:Biomax:Starch
1. Ref N/A N/A N/A 95:5:0
2. A Corn Langfang, Heibei, China Yes 65:5:30
3. A-1 Corn Langfang, Heibei, China No 65:5:30
4. B Gelose-50 (G-50) Penford, Australia Yes 65:5:30
5. B-1 G-50 Penford, Australia No 65:5:30
6. C Gelose-80 (G-80) Penford, Australia Yes 65:5:30
7. D Potato Zhuanglang Nanhu Yes 65:5:30
Chenglinsanhao Co. Ltd.
8. E Cassava Huanglong Foods Co. Ltd. Yes 65:5:30
9. F Sweet potato Henan Tianfu Chemical Co. Ltd. Yes 65:5:30
10. G Wheat Anhui Ante Food Co., Ltd. Yes 65:5:30
11. H Rice Jiangxi Deli Foods Co. Ltd. Yes 65:5:30
12. I Pea Shandong Jianyuan Yes 65:5:30
Bioengineering Co., Ltd.
13. J Green bean Hebei JingxianHaichun Yes 65:5:30
Starch Co. Ltd.
a
Treated with 0.2% stearic acid on wt/wt basis.

(a) large-sized starch granules are more efficient in enhancing and the information related to their microstructures and molec-
the yield strength of PLA matrix while the small-sized gran- ular weights have been studied extensively.55–58
ules exhibit better deformability;
(b) aggregation tendency of small-sized starch granules can be Sample Preparation. Negative impact of moisture, in starch
controlled using surface modification approach that not granules, on interfacial bonding between starch and PLA is
only reduces the phase-separation between starch and PLA well-documented.6,59 For this reason, all the starches were dried
but also improves the dispersion of starch granules in the in a vacuum drier (Yingkou Liaohe Pharmaceutical & Chemical
PLA matrix; equipment co., Ltd., Yingkou, China) at a speed of 90 rpm,
(c) deformation of the composites can also be improved using 20.1 MPa of vacuum, 140 8C temperature for 4 h, followed by
starches with high amylose content; and
(d) no discernible relationship exists between starches, from dif-
ferent botanical sources, on the thermal performance of
PLA/starch composites.
The results provide a practical guideline for developing such
kind of biodegradable composites, and can also be used for
other composites or blends filled with starch particles.

EXPERIMENTAL
Materials and Sample Preparation
Materials. PLA (3251D; density 1.24 g m23; melt-flow index
(MFI) 5 30 g per 10 min at 190 8C) was supplied by Nature-
Works (Minnetonka, Minnesota) as a semi-crystalline grade.
Biomax (Strong 120) was supplied by Dupont while (Shanghai,
China), stearic acid (analytical grade) was purchased from Tian-
jin Chemical Reagent Factory (Tianjin, China). Native starches
(non-modified chemically), from 10 different botanical sources,
were procured from the local market. Name of the supplier for
each starch is mentioned in Table I. All the materials used in
this experimental work are available commercially. Additionally,
all the starches used in this work are popular food resources Figure 1. Schematic representation of sheet-extrusion line.

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Figure 2. SEM and OM images of starch granules from different botanical sources. [Color figure can be viewed at wileyonlinelibrary.com]

the addition of stearic acid (0.2% concentration on wt/wt 110 rpm without creating any vacuum pressure. PLA was dried
basis); vacuum drier was run again to coat the surface of starch in a vacuum drier (Model No. FZH-10 of Nanjing Colorway
granules with stearic acid at 140 8C for 1 h at a speed of Machinery and Equipment Co. Ltd., Nanjing, China) at 65 8C

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Table II. Morphology of Starch Granules

Average diameter (lm)

Source of starch Particle shape Via SEMa Via OMb
Corn Polygon with pores on surface 11.59 6 4.22 13.18 6 3.82
G-50 Polygon (large granules) & oval (small granules) with 7.79 6 2.98 9.05 6 2.45
pores on surface and are aggregated
G-80 Oval, smooth surfaced and aggregated 7.64 6 2.35 9.07 6 1.83
Potato Oval& smooth surfaced 24.93 6 8.96 31.31 6 25.43
Cassava Flaky & irregular having internal grooves on surface 8.48 6 5.36 11.36 6 2.88
with pronounced edges
Sweet potato Spherical (large) & polygon (small) with internal 15.54 6 11.09 16.17 6 4.80
grooves on small granules
Wheat Spherical & lenticular with pores on surface and 7.72 6 6.09 12.25 6 7.22
are aggregated
Rice Polygon having pores on surface with pronounced 4.17 6 1.34 6.04 6 0.77
edges
Pea Oval with external appendages on surface 18.22 6 6.22 18.18 6 5.89
Green bean Oval & flaky 13.16 6 4.12 15.08 6 4.33
a
Scanning electron microscope.
b
Optical microscope.

for 4 h at 20.1 MPa. All the samples were hermetically sealed, of 5 kV was used in this part of the experimental work, to avoid
immediately after drying, and were stored in air-tight container damaging the surfaces.
under controlled conditions of temperature and humidity to
Optical Microscope. An optical microscope (OM, Axioskop 40
avoid any probability of moisture uptake. Five percent of biode-
Pol/40A Pol, ZEISS), equipped with 35-mm SLA camera, was
gradable toughness agent, DuPont Biomax strong 120, was
used to observe the morphology of different starch granules.
added in all the samples, prior to running them in the extrusion
Microscope was calibrated using stage micrometer slide; type
system, to improve the toughness as well as the processability of
C1 (1 div 5 0.01 mm) of XTZ Optical Instrument Factory
the materials.
(Shanghai, China). Slides for each sample were prepared and
Sheet Extrusion. The sheets of the PLA/starch composites were were viewed in microscope at a magnification of 350 while, the
prepared using compounding extrusion system [Model No. images were enlarged 1.3 times of their actual size.
KY35/45 of Jiangsu (Nanjing) Keya Co., China] with a sheet
die. Figure 1 shows the schematic representation of the process- Mechanical Properties
Tensile Testing. Tensile properties were evaluated in accordance
ing system. This system is comprised of three sections: (a) twin-
screw extruder (diameter 5 35 mm; L/D 5 40) with eight bar- with ASTM D882-12 guidelines. Tensile bar shaped specimens
rels; (b) single-screw extruder (diameter 5 60 mm; L/D 5 16)
with two barrels; and (c) a sheeting die (600 mm width). The
advantage of this one-step extrusion system is to minimize the
PLA degradation during multi-steps extrusion. Highest temper-
ature of screw barrels was set at 165 8C, while the temperature
of sheeting die was maintained at 155 8C. Each sample was
mixed manually and was assigned a unique specimen code,
based on the source of starch and the composition of extruded
specimen (see Table I). The thickness of the extruded sheets was
about 0.500 mm. All the extruded sheets were stored in room
temperature before characterization.
Microstructure Characterization
Scanning Electron Microscope. Scanning electron microscope
(SEM, ZEISS, Oberkochen, Germany) was used to investigate
the interface between the matrix and reinforcing particles of
broken tensile bar specimen as well as to study the microstruc-
ture of starch granules. All the samples were put on metal stubs, Figure 3. Effect of concentration of corn starch on tensile properties of
previously covered with double sided adhesive, and coated with PLA/starch composites. [Color figure can be viewed at wileyonlinelibrary.
gold using Eiko Sputter Coater under vacuum. A lower voltage com]

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Figure 4. Effect of addition of starch granules, from different botanical
sources, on tensile properties of PLA matrix at 30% loading of starch
[(Ref) no starch; (A) corn; (A-1) non-modified corn; (B) G-50; (B-1):
non-modified G-50; (C) G-80; (D) potato; (E) cassava; (F) sweet potato;
(G) wheat; (H) rice; (I) pea; (J) green bean].
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of definite size were cut from the sheets along machine-
direction. Apparatus used for tensile testing (Instron 5565,
Grove city, Pennsylvania) was run at a cross-head speed of 12.5
mm min21 and room temperature (25 8C). All the specimens
were conditioned for 48 h before testing while the results given
are average of seven specimens.
Drop Impact Testing. Impact properties were evaluated in
accordance with ASTM D256 guidelines. Apparatus used for
impact testing (Instron Dynatup 9250G) was run at an impact
velocity of 125 m min21. Four different values of impact testing
are reported, including:
(a) peak load;
(b) deflection at peak load;
(c) energy to peak load or impact strength; and
(d) energy to failure.
These values were calculated using load–deflection curve; the
peak of the curve was used to determine the value of peak load
and the deflection at peak load, while the area underneath the
curve was used to determine the value of energy to peak load as
well as the energy to failure. All the samples were conditioned
for 48 h before testing, while the results reported are averages
of five specimens.
Thermal Properties
Differential Scanning Calorimeter. A differential scanning calo-
rimeter (DSC, PerkinElmer DSC 4000, Waltham, Massachu-
setts), equipped with a low-temperature accessory, was used to
study the thermal properties of the samples. About 8 mg of
each sample was weighed and hermetically sealed in an alumi-
num pan. The samples were scanned in N2 atmosphere from 20
to 220 8C at a heating rate of 5 8C min21. Values of enthalpy for
both cold-crystallization as well as melting were calculated for
all the specimens based on PLA content (%).
Dynamic Mechanical Analyzer. A Perkin Elmer Pyris Diamond
dynamic mechanical analyzer (DMTA), using single cantilever
beam in tensile mode, was used to investigate the dynamitic
mechanical properties of the composites. Rectangular tensile bar
specimens were used in this experimental work. Samples were
scanned from 220 to 120 8C using heating rate, strain value,
and frequency of 2 8C min21, 0.05% and 1 Hz, respectively.
RESULTS AND DISCUSSION
Morphology of Starch Granules
Particle Shape. Starch granules exhibit variable morphology
based on their botanical origin (see Figure 2 and Table II). In
terms of particle shape of starch granules, the granules tend
to vary from oval (G-80, potato, pea, and green bean) to
roughly-spherical (wheat and sweet potato); from polygon
(corn, G-50, and rice) to irregular (cassava). Some starches
have external appendages on their surfaces (pea) while others
have internal grooves (cassava and sweet potato). Some
starches appear in the form of agglomerates (G-50 and wheat)
while others tend to appear in the form of flakes (cassava and
green bean). Such variation in morphology of starch granules,
from different botanical sources, has been reported in several
reviews and articles.55–58,60 It was also observed that the
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45504
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Table III. Effect of Addition of Starch Granules, From Different Botanical Sources, on Tensile Properties of PLA/Starch Composites along Machine
Direction

Specimen Source of
code starch Thickness (mm) Eba (%) Eb (GPa) rysc (MPa) rutsd (MPa)
Ref No starch 0.565 6 0.090 21.15 6 2.73 1.52 6 0.18 43.10 6 1.61 46.35 6 1.41
A Corn 0.583 6 0.018 3.18 6 0.17 1.82 6 0.12 31.07 6 2.73 32.75 6 3.22
A-1 Non-modified Corn 0.693 6 0.005 2.86 6 0.23 1.66 6 0.17 29.65 6 2.70 31.16 6 2.50
B G-50 0.466 6 0.020 3.29 6 0.22 2.13 6 1.17 29.72 6 1.17 32.79 6 1.80
B-1 Non-modified G-50 0.666 6 0.001 2.75 6 0.33 1.47 6 0.07 28.05 6 3.78 28.71 6 3.99
C G-80 0.594 6 0.002 3.12 6 0.12 1.44 6 0.13 25.71 6 3.27 26.72 6 3.27
D Potato 0.826 6 0.007 3.85 6 0.44 1.47 6 0.13 38.09 6 2.09 40.34 6 3.77
E Cassava 0.469 6 0.019 2.90 6 0.11 1.42 6 0.23 32.10 6 1.71 32.69 6 1.43
F Sweet potato 0.634 6 0.007 2.94 6 0.14 1.57 6 0.15 30.34 6 3.46 31.44 6 2.80
G Wheat 0.781 6 0.030 3.30 6 0.28 1.43 6 0.05 25.41 6 1.39 26.71 6 1.18
H Rice 0.457 6 0.024 3.91 6 0.53 1.43 6 0.18 26.46 6 1.46 29.71 6 2.32
I Pea 0.716 6 0.044 2.95 6 0.23 1.45 6 0.07 26.62 6 2.24 28.85 6 3.38
J Green bean 0.723 6 0.009 2.96 6 0.20 1.49 6 0.06 24.75 6 1.63 26.37 6 2.16
a
Elongation at break.
b
Young’s modulus.
c
Yield offset at 0.2%.
d
Ultimate tensile strength.

surface of starches extracted from either tuberous crop
(potato, cassava, and sweet-potato), vegetables (pea), or
legumes (green bean) are smooth. On the other hand, the
starches from cereal crops (corn, G-50, G-80, wheat, and rice)
have pores on their surface. Presence and/or concentration of
such pores have been utilized to optimize the reactant for
chemical modification of starches from different botanical
sources.61,62
Particle Size. Like particle shape, particle size of starch granules
is also different for different starches. Granules from potato
starch are large (31.31 6 25.43 mm via OM). On the other hand,
rice starch has small granules (6.04 6 0.77 mm). Rice starch has
been reported to possess the smallest particle size,63 only after
amaranth starch.55,60 Difference in morphology of starch gran-
ules exists not only in starches from different botanical origin
but also in starch granules having same botanical origin. For
example, maximum and minimum particle size observed, via
OM, for granular microstructure of potato starch were 94.4 and
7.7 mm, respectively. Previous researchers have reported similar
variations in maximum and minimum particle size of potato
starch (15–75,55 10–110,64 and 8–13163 lm). Most of the
starches, particularly wheat starch, showed a clear distinction
between small (<15 lm) and large (>15 lm) particles. Small

Table IV. Effect of Addition of Starch Granules, From Different Botanical Sources, On Drop Impact Strength of PLA/Starch Composites

Specimen Source of Deflection at Energy to Energy to

code starch Peak load (kN) peak load (mm) peak load (J) failure (J)
Ref No starch 0.965 6 0.253 8.522 6 0.948 3.560 6 1.312 3.751 6 1.349
A Corn 0.210 6 0.011 1.790 6 0.187 0.237 6 0.008 0.155 6 0.009
A-1 Non-modified Corn 0.197 6 0.019 1.901 6 0.342 0.204 6 0.016 0.130 6 0.021
B G-50 0.273 6 0.027 2.872 6 0.294 0.361 6 0.060 0.410 6 0.065
B-1 Non-modified G-50 0.185 6 0.010 2.145 6 1.263 0.208 6 0.052 0.226 6 0.057
C G-80 0.274 6 0.023 3.648 6 0.289 0.471 6 0.067 0.522 6 0.069
D Potato 0.224 6 0.045 3.430 6 0.410 0.322 6 0.068 0.387 6 0.089
E Cassava 0.231 6 0.024 2.629 6 0.679 0.276 6 0.041 0.311 6 0.050
F Sweet potato 0.217 6 0.028 2.913 6 0.311 0.304 6 0.052 0.340 6 0.055
G Wheat 0.490 6 0.069 5.356 6 0.658 1.204 6 0.331 1.307 6 0.347
H Rice 0.543 6 0.015 2.620 6 0.222 1.199 6 0.035 1.225 6 0.041
I Pea 0.378 6 0.009 3.423 6 0.271 0.541 6 0.051 0.592 6 0.047
J Green bean 0.632 6 0.040 6.505 6 0.251 1.864 6 0.201 1.993 6 0.212

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Figure 5. SEM images of the tensile-fractured interface between PLA and starch in PLA/starch composites.
particles tend to agglomerate with each other that make it difficult
to calculate particle size of such granules.38 Surface modification of
starches has been shown to be an effective approach to decrease
interparticle interaction that in turn reduces the tendency of small
particles to agglomerate.39,65–67 It was also noted that the average
particle size calculated via SEM was smaller than that of OM
because of different principles of measuring instruments.
Mechanical Properties
Effect of Concentration of Starch Granules on Tensile
Properties of PLA/Starch Composites. Figure 3 shows the typi-
cal effect of addition of starch granules at different concentra-
tions on the tensile properties of PLA/starch composites, using
corn starch as an example. It was observed that both modulus
and yield strength of PLA showed slightly increasing tendency
with the addition of corn starch up to 13% and then started
to decrease with further addition of starch granules. The
results agree with previous reports and are expected.12,14 The
effect of starches, from different botanical sources, on the
mechanical and thermal properties of extruded sheets was
investigated based on 30% starch content in the following
work. Although, the mechanical properties of composites at
such higher loading of starch (up to 30%) are lower than that
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of pure PLA, it provides a better window to compare the dif-
ferences by enhancing the performance difference of compo-
sites after filling with starches from different botanical sources.
Furthermore, the addition of 30% starch, as filler, offers an
acceptable balance between cost and materials performance
from commercial or application-oriented point of view.
Tensile Strength. Figure 4 and Table III present the tensile
properties of PLA composites filled with starches, from differ-
ent botanical sources, at 30% loading. It is seen that the starch
granules from different botanical sources affect the mechanical
properties differently. Generally, small-sized rice starch gran-
ules were the most efficient to resist the reduction in elonga-
tion of PLA composites. The phenomenon can be explained
by reduction in stress concentration sites by the incorporation
of small-sized starch particles in PLA matrix.37–43 Potato
starch, having the largest particle size, also exhibited reason-
ably good resistance to deform the PLA composites as com-
pared to starches from other botanical sources. There can be
multiple factors (including particle size) that play role in
resisting the deformation of PLA composites filled with starch
particles.38,39,65 Further research is required in this area to
fully understand the role of different factors in resisting the
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Figure 6. Photos of impact-fractured surface of PLA/starch composites. [Color figure can be viewed at wileyonlinelibrary.com]
deformation of PLA-based composites. On the other hand,
smooth-surfaced large-sized potato starch granules were found
to be more efficient in enhancing the yield strength of PLA/
starch composites; such granules are also found to be more
efficient in resisting the deformation of the polymer matrix.37
Generally, the composites prepared using tuberous starches
(potato, cassava, and sweet potato) exhibited superior yield
strength, while the composites prepared using cereal starches
(corn, G-50, G-80, wheat, and rice) showed better elongation.
It was also noticed that the composites prepared using either
flaky or aggregated starch granules exhibited lower strength
and elongation than that of segregated starches. Aggregated
granules act as crack initiating points that lead to pre-mature
failure of the matrix, this results in weak tensile properties of
such composites than their segregated counterparts.39 The
composite prepared using starch granules with external appen-
dages on their surfaces (sweet potato) exhibited superior
Young’s modulus; the value of which was even better than
other tuberous starches (potato-smooth surfaced, cassava-
pointed edges). It was also observed that the presence of either
pointed edges (cassava, rice) or internal grooves (pea) on
starch granules deteriorated the modulus of PLA/starch com-
posites. Effect of surface treatment of starch granules on
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tensile properties of PLA composites was also studied. It was
noticed that the composites that were prepared with surface-
treated starch granules reinforced the PLA matrix more effi-
ciently, with less reduction in their elongation, than their non-
treated counterparts.
Drop Impact Strength. Table IV presents the effect of addition
of starch granules from different botanical sources on drop
impact strength of PLA/starch composites. It was found that
the composites prepared using small-sized starch granules
absorb the energy, during impact, more efficiently than either
large-sized or aggregated granules. It is expected because the
small particles could reduce the stress concentration sites in
the polymeric matrix.37–43 Similar trend was observed during
tensile testing, whereby the composites prepared with small-
sized starch granules exhibited better elongation than their
large-sized counterparts. It was also noticed that the energy
absorbing capacity of the composites prepared using either
cereal or legume starches is higher than that of tuberous and
vegetable starches. Effect of surface treatment of starch gran-
ules on drop impact strength of PLA/starch composites was
also studied. It was found that the surface treatment of starch
granules increases the energy absorbing capacity as well as the
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Table V. Effect of Addition of Starch Granules, From Different Botanical Sources, On Thermal Properties of PLA/Starch Composites

Glass transition Cold-crystallization

temperature (8C) point (Tcc) Melting point
a b c
Specimen Source of To Tp Tc DHcd Tm e
DHmf
21
code starch Via DSC Via DMA (8C) (8C) (8C) (J g ) (8C) (J g21)
Ref No starch 60.71 69.54 80.41 89.89 98.39 223.46 166.48 45.43
A Corn 60.12 71.30 88.28 93.75 98.94 221.89 167.43 33.02
A-1 Non-modified corn 58.55 70.62 87.13 93.14 98.63 220.04 167.15 33.14
B G-50 60.26 71.42 86.91 93.38 98.71 219.93 167.88 36.72
B-1 Non-modified G-50 58.68 71.43 84.72 92.71 98.37 217.52 167.73 34.59
C G-80 59.77 71.63 85.22 92.98 99.02 221.40 167.48 39.21
D Potato 59.85 71.71 84.92 92.39 98.42 221.31 167.55 34.21
E Cassava 60.35 71.53 87.96 94.05 99.31 219.82 167.24 32.84
F Sweet potato 60.01 71.32 88.59 94.49 99.79 223.51 167.82 38.96
G Wheat 60.02 71.93 83.14 92.23 99.28 221.66 167.65 32.76
H Rice 59.85 71.53 86.6 93.14 98.43 219.83 167.31 38.72
I Pea 59.78 71.48 85.77 93.23 99.02 223.51 167.57 38.07
J Green bean 59.93 70.70 82.73 91.89 97.87 221.30 167.31 37.13
a
Onset temperature.
b
Peak temperature.
c
Conclusion temperature.
d
Cold-crystallization enthalpy.
e
Melting temperature.
f
Melting enthalpy.

fracture resistance of PLA matrix. Similar pattern was
observed in case of tensile testing, whereby, the composites
prepared using surface-treated starch granules showed higher
elongation than their non-treated counterparts. It should be
noted here that the plastic deformation is the main energy
absorbing process that decreases with the increase in strength.
The results indicate that the simple surface treatment by stea-
ric acid can improve the interface between hydrophilic starch
and hydrophobic PLA matrix. Generally, the strength of com-
posites, that exhibit higher fracture resistance, is low and vice-
versa.39
Fracture Analysis
Tensile Fracture. Starch granules, from different botanical sour-
ces, disperse differently in PLA matrix. Figure 5 shows the SEM
images of interface between PLA and starch in tensile fractured
specimen. It was observed that the starch granules acted as flaw
in the composites that were prepared using large-sized granules.
Debonding of large-sized starch granules is relatively easier and
cracks can be seen on the surface of such granules, this phe-
nomenon reduces the flexibility of the PLA matrix and deterio-
rates the elongation of such composites. On the other hand,
small-sized starches tend to agglomerate with each other that
result in stress concentration sites with poor deformation. It has
been observed (see Figure 2) that the extent of agglomeration in
starches, from different botanical sources, is different. It should
be noted here that the size and interaction among the starch
particles determine the strength of aggregates. Under the effect
of external force, the agglomerates rupture that lead to pre-
mature failure of the matrix.38 Surface modification is a
technique that improves the dispersion of starch granules in
PLA matrix by controlling the aggregation tendency of the
starches as it reduces the interaction among starch particles.39,65
Improved dispersion of the small-sized starch granules in the
matrix has resulted in better mechanical performance (higher
strength and better deformation) of the composites. For exam-
ple, in the PLA-G50 system, improving dispersion and interface
has resulted in better mechanical properties. However, the
amount of surfactant needs to be optimized, depending on the
morphology (particle size, particle shape, and size as well as
concentration of pores on the surface) of starch granules, in
future.
Impact Fracture. PLA composites, filled with starches from dif-
ferent botanical sources, exhibited different mode of impact fail-
ure (see Figure 6). Absence of stress-localization area in PLA/
starch composites shows that the toughness of PLA matrix was
deteriorated with the addition of starch granules. Brittle mode
of failure (appearance of large holes with sharp edges) was
observed for the composites that were filled with either large
sized (potato, sweet potato, pea, and green bean) or aggregated
(non-treated G-50, cassava, and wheat) starch granules. Aggre-
gates act as crack-initiating sites and reduce the fracture resis-
tance of the material.38 On the other hand, ductile mode of
failure (appearance of cracks without any hole) was observed
for the composites that were filled with either small-sized starch
granules (rice) or high amylose starches (G-50 and G-80). It
was also observed that the composites prepared using surface-
treated starch granules exhibited higher fracture resistance than
their non-treated counterparts. It can be concluded therefore

WWW.MATERIALSVIEWS.COM 45504 (9 of 12) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45504

ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 7. Effect of addition of starch granules, from different botanical sources, on damping co-efficient (A) and storage modulus (B) of PLA/starch
composites. [Color figure can be viewed at wileyonlinelibrary.com]
that the fracture resistance of the composites can be controlled
by dispersing the well-sized (small-sized and non-aggregated)
starch granules in the PLA matrix.
Thermal Properties
Differential Scanning Calorimeter. Table V summarizes the
effect of addition of starch granules, from different botanical
sources, on the thermal properties of PLA/starch composites.
No discernible difference was observed for the addition of
starches from different botanical sources on thermal properties
of PLA. Generally, the addition of starch granules increases the
glass transition temperature (Tg) and reduces the cold-
crystallization temperature (Tc), cold-crystallization enthalpy
(DHc), melting temperature (Tm) as well as the melting enthalpy
(DHm) of PLA matrix. Results for glass transition, as measured
using different instruments (DSC and DMA), are slightly differ-
ent because of different principles of the measuring instruments.
The results measured using DMA demonstrate that the addition
of starch granules increases the Tg of PLA matrix which is
expected since the incorporation of filler in the matrix reduces
the mobility of polymer chains. It should be noted that the
minute changes in Tg can be detected more efficiently by DMA
than that by DSC.68 Reduction in both the melting enthalpy
(DHm) as well as the cold-crystallization enthalpy (DHc) of PLA
demonstrates that the addition of starch granules hampers the
PLA crystallization; same trend has been reported elsewhere.59
Effect of surface modification of starch granules on thermal
properties of PLA composites is complex and further research is
required to fully understand this phenomenon.
Dynamic Mechanical Analyzer. The effect of starch granules on
dynamic–mechanical properties of the composites is shown in
Figure 7. It is seen that starch granules generally increase the
damping co-efficient and decrease the storage modulus of the
PLA matrix, at or near glass transition temperature. Reduction
in storage modulus of PLA matrix after filling it with starch
granules indicates lower thermal stability and stress-transfer effi-
ciency. The reduction in stress-transfer efficiency of PLA/starch
composites is in accordance with impact results (Figure 6), indi-
cated by the visual disappearance of stress localization area
WWW.MATERIALSVIEWS.COM 45504 (10 of 12)
from the fractured surface after filling PLA matrix with starch
granules. A small enhancement in peak height of tan d (damp-
ing coefficient) for PLA composite filled with surface modified
corn starch was observed, when compared to the non-modified
corn starch. This indicates that the separation of starch granules
in PLA matrix was improved because of the surface modifica-
tion. A small enhancement in tan d was considered due to rein-
forcement rather than interfacial adhesion.
CONCLUSIONS
Starches used to develop biodegradable composites belong to
different botanical sources that exhibit different microstructure
and morphology. Such differences can be used as a template to
tune the properties of biodegradable polymeric blends or com-
posites filled with starch particles. Composites prepared using
large-sized starch granules exhibited higher strength while the
composites prepared using well-sized starch granules (small-
sized and non-agglomerated) demonstrated higher resistance
toward deformation. On the other hand, aggregation of starch
granules acts as crack initiating sites that lead to pre-mature
failure of the matrix under the effect of external force; agglom-
eration of small-sized starches can be controlled using surface
modification approach that not only reduces the interaction
among starch particles but also improves the deformation of
the composites. The results were supported by dynamic
mechanical properties whereby it was confirmed that the
improvement in mechanical properties are due to reinforcement
rather than interfacial adhesion. By evaluating the performance
of composites filled with starches from different botanical sour-
ces, a biodegradable material, originally developed for one pur-
pose, can be made available for more demanding usage.
ACKNOWLEDGMENTS
The authors from SCUT, China, would like to acknowledge the
research fund NFSC (31571789). Saud Khalid and Amjad Ali
would like to thank the China Scholarship Council and South
China University of Technology for providing opportunity and
support during their stay in China.
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45504
ARTICLE WILEYONLINELIBRARY.COM/APP
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