Journal of Materials Science and Engineering B 1 (2011) 239-245

Formerly part of Journal of Materials Science and Engineering, ISSN 1934-8959

A Review on Starch Based Nanocomposites for

Bioplastic Materials

Bruno Robert Mose and Stephen Moffat Maranga

Department of Mechanical Engineering, Jomo Kenyatta University of Agriculture & Technology, Nairobi, Kenya

Received: December 29, 2010 / Accepted: January 18, 2011 / Published: July 25, 2011.

Abstract: The use of nanoparticles as additives to enhance the performance of materials has attracted considerable interest and
investment in the past decade. Layered silicates such as clay are the most preferred nano reinforcing particles because of their
environmental advantages, natural abundance, low cost in addition to their contribution to improved properties. Toyota Company
became the first to fabricate nanocomposites based on layered silicates for automotive applications in the 1980s. In subsequent years,
nano based composites continued to attract increasing attention as a means to enhance the performance of materials. Recently, there has
been renewed interest to develop a new class of bioplastic materials reinforced with nanocomposites to replace conventional bioplastics
due to environmental concerns. In spite of the successes achieved in development of clay-based nanocomposites, their design and
fabrication are often met with numerous limitations. Moreover, their large scale applications are still at their infancy stages. This paper
presents a review of the advances made in use of nanoparticle additives in improving the performance of starch based bioplastics.
Suggestions on the direction for future research are also made.

Key words: Starch based bioplastics, nanocomposites, biodegradable materials, mechanical properties, plasticizers.

1. Introduction pressure, no biodegradable plastics combining all the

features, functionalities and economies have been
Plastics are widely used for packaging and other
developed [1]. Efforts to produce competitive
applications because of their several advantages
biodegradable materials are often frustrated by the
compared to other materials. For example, plastics are
problem of finding optimal balance between
inexpensive, light-weight and chemically inert.
mechanical properties, cost and acceptable level of
Moreover, they are heat-sealable, easy to print on and
biodegradability. Starch, which is a biodegradable
offer the flexibility of fabricating into various shapes.
natural polymer and produced in abundance at low cost
Unfortunately, conventional plastics have their origin
is reported to be one of the most promising candidates
in petrochemical industry making them
for fabrication of bioplastics [3]. Numerous studies
non-biodegradable and non-renewable [1, 2]. The
have been conducted to optimize the properties of
non-biodegradable and non-renewable nature of
starch based bioplastics. The most important properties
plastics has been a serious disadvantage to their
in bioplastic materials include mechanical and
application leading to huge municipal wastes and
thermoforming properties, gas and water vapor
environmental degradation.
permeability, transparency and availability [1].
Therefore, most users are faced with increasing
While encouraging results have been reported,
pressure to minimize non-degradable waste and to
development of a bioplastic material that possesses all
switch to biodegradable materials. Despite this
of the required properties has been an enormous
challenge. Especially, there has been the issue of
Corresponding author: Stephen Moffat Maranga, professor, product cost as well as technical challenges such as
research fields: materials science, metallurgy. E-mail:
smmaranga@yahoo.com. brittleness associated with high loads, and poor water
240 A Review on Starch Based Nanocomposites for Bioplastic Materials
and gas barrier properties. This in turn has limited the
wide application of renewable starch based bioplastic
materials. As a result, significant attention is being paid
to understand fully how to manipulate final material
properties for various applications. Therefore, most
research directed towards enhancing the functional
properties and bonding strength of starch based
bioplastics has focused on incorporating additives such
as plasticizers to alleviate the problem of brittleness of
the materials. Recently, Zhang et al. [2] reported that
bioplastic films obtained from treatment with various
plasticizers are not cost-effective and fall short of the
required material properties. Moreover, Huang et al. [3]
noted that when starch based bioplastics treated with
plasticizers are stored for a long time; their mechanical
properties significantly deteriorate due to
recrystallization.
Noting the high market potential for bioplastic
materials, it is evident that there are great opportunities
ahead. However, there are challenges that need to be
overcome to improve the competiveness of bioplastic
materials. This paper reviews some of the recent
advances made in enhancing the performance of starch
based bioplastics through the use of nanoparticles to beat
the limitations demonstrated by plasticized bioplastics.
Potential application areas as well as future markets for
bioplastic materials are discussed. Finally, suggestions
on the direction for future research are also made.
2. Nanocomposite Bioplastics
In recent years, significant attention has been given
to a new class of bioplastic materials represented by
nanocomposites as the promising alternative to
conventional plastics due to their superior properties.
Nanocomposites consist of a polymer matrix
reinforced with nano dimensional particles instead of
the conventional micro dimensional fillers. The interest
in nanocomposites has been inspired by the pioneering
work conducted by researchers at Toyota company in
the 1980s [2] where it was reported that presence of
nanoparticles in the matrix contributed to significant
improvement in both physical and mechanical
properties. In the years that followed, there was a great
deal of research efforts aimed at improving the
performance of materials through use of nanoparticles.
Zeng et al. [4] observed that clay particles such as
Montmorillonite (MMT), hectorite, saponite and
laponite can be effectively used as nanocomposites due
to their unique structure and properties. When added to
form nanocomposites, the clays significantly enhance
the mechanical performance of bioplastics, improve
their moisture resistance and significantly reduce the
release of plasticizer from starch [2]. This achievement
demonstrates how bioplastic nanococomposites would
play a leading role in fabricating bioplastics whose
properties are comparable to those of conventional
plastics.
2.1 Property Enhancement
Studies by Chen and Evans [5] showed that addition
of 5% sodium montmorillonite increased the tensile
strength of thermoplastic starch (TPS) from 2.6 to 3.3
MPa while percentage elongation increased from 47 to
57%. In the starch based nanocomposites prepared by
De Carvalho et al. [6] using Kaolin clay, it was noted
that the Young’s modulus (E) and tensile strength
increased by 50% and 135% respectively when the
Kaolin concentration was 50 phr. The starch/MMT
nanocomposites prepared by Huang et al. indicated that
the tensile strength and Young’s modulus increased
monotonously with increase in filler content up to 8%
after which it levels off. The tensile strain however,
decreased as filler loading increased but at 8% loading
the highest value of 145% was recorded. Others [5, 7]
noted that use of nanoclay in developing the new class
of bioplastics contributed to significant increase in
Young’s modulus and shear modulus. Fig. 1 shows
results obtained by Chen and Evans. Recently,
Majdzadeh-Ardakani and Nazari [8] introduced
polyvinyl (PVOH) to starch/clay nanocomposites and
observed significant improvement in mechanical
properties, namely tensile strength and modulus. The
 A Review on Starch Based Nanocomposites for Bioplastic Materials 241

different types of potato based nanocomposite samples
prepared by Park et al. [9] through reinforcing the
matrix with nanoclays indicated significant
improvement in tensile strength and outstanding barrier
properties against gases and water. Zeng et al. [4]
observed that the dramatic improvement in barrier
properties and reduction in permeability is attributed to
the high aspect ratio of clay platelets. Yano et al. [10]
also earlier noted that barrier properties against gases
and water are a function of the length of clay as
demonstrated in Fig. 2a. In their studies, Yano et al.
noted that addition of about 2 wt.% Montmorillonite
(MMT) reduced the permeability of various gases to
values less than half of those of ordinary polyimide and
attributed the decrease in permeability to the increase
of the total path of the gases (Fig. 2b). Improvements in
tensile strength and reduction in water absorption
abilities have also been reported when nanoclay is
added to corn starch [3]. Garcia et al. [11] showed that
addition of nanocrystals to a cassava starch matrix not
only improved the mechanical properties but also
reduced the water vapor permeability by 40%.
Improvement in thermal stability of nanoclay
composites was first reported by Blumstein [4].
Recently, Huang and Yu [12] noted that introduction of
inorganic particles improved the thermal stability and
thermal resistance of starch/MMT nanocomposites.
Studies by the Toyota research team also showed that
the heat distortion temperature (HDT) of nylon 6
nanocomposites increased from 65˚C to 145˚C [4].

(a) (b)
Fig. 1 Effect of clay content on (a) Young’s modulus and (b) shear modulus of thermoplastic starch (TPS)–clay composites
(Error bars represent 5% error inherent in the measurement) [5].

(a) (b)
Fig. 2 (a) Effect of clay length on relative permeability coefficiency of different types of clay [10] (b) tortuous pathway of a gas
through clay based nanocomposite.
242 A Review on Starch Based Nanocomposites for Bioplastic Materials
Zeng et al. suggested that the platelet nature of clay
nanoparticles hinder the diffusion of volatiles and assist
in the formation of char after thermal decomposition and
contribute to improved thermal stability.
2.2 Limitations of Nanoparticles in Property
Enhancement
While reinforcement of the biopolymer matrix with
nano-particles often offer better performing bioplastics
in addition to the exciting and interesting features such
as improved biodegradability, nanoclay composites
have however been noted to demonstrate numerous
limitations. One of the limitations is that
nanocomposite samples may contain high levels of
glycerol plasticizer [9] which undermines their
practical applications in certain areas. In addition, the
problem of non uniform dispersion of nanoclay
particles within the matrix has also been reported. For
instance, TEM microscopy results obtained by
Majdzadeh-Ardakani and Nazari [8] showed that
addition of citric acid activated montmorillinite
(CMMT) resulted in agglomeration of clay particles
within the matrix. However, the degree of
agglomeration seemed to depend on level of CMMT as
demonstrated in Fig. 3.
Attempts to improve nanoparticle dispersion have
involved replacement of Na+ present in the clays using
organic cations such as stearyl dihydroxyethyl
ammonium chloride and distearyl dimethyl ammonium
chloride, etc. [13]. Chung and Lai [14] noted that
addition of layered double hydroxides (LDH) to acid
(a)
Fig. 3 TEM micrographs of starch/PVOH/CMMT nanocomposites (a) 4 wt.% CMMT and (b) 8 wt.% CMMT [8].
modified starch caused improvement in nanoparticle
dispersion in the matrix. However, until now
dispersion of nanoparticles in starch based
biocomposites remains a challenge.
Production of most starch-clay nanoclay composites
has been done on batch based processes. For instance,
nanocomposites have been compounded using mixers
while others have been cast in form of films. In a case
that involved continuous production, a single screw
extruder was applied to produce the samples [3]. A
single screw extruder however, does not yield optimal
shear that is required to fully disperse the nanoclay
platelets. To overcome the problem of a single screw
extruder, Chiou et al. [15] applied a twin screw
extruder to fabricate starch/nanoclay composites and
observed that nanoparticles in some samples still
retained their stacked structures while others were seen
to be clumped within the matrix. Zhang et al. [2] also
employed a twin screw extruder to prepare samples of
starch/clay nanocomposites. However, the presence of
peaks in the X-ray diffraction curves demonstrated that
the dispersion was not homogeneous. The authors
noted that compatibility between starch and clay may
also play a role in dispersion.
Recently, Zhang et al. [16] conducted preliminary
studies on the use of back pressure equal channel
angular consolidation (BP-ECAC) as a novel approach
for achieving severe shear deformation in production
of plastic from natural polymer material. This
approach however, is yet to be developed further to
include processing of nanocomposites.
(b)
 A Review on Starch Based Nanocomposites for Bioplastic Materials
3. Potential Applications and Future
Markets
Starch based bioplastic nanocomposites represent an
exciting and promising alternative to conventional
plastics owing to their markedly improved
performance in mechanical, thermal, barrier as well as
other physical and chemical properties. Many
companies and research institutions have taken a strong
interest and invested heavily in the development of
starch based bioplastic nanocomposites. Some
applications of these nanocomposites are described
below.
3.1 Applications in Automotive Components
Polymer nanocomposites are generally known to
offer better performance with significant weight
reduction and affordable materials for transport
industries such as automotive and aerospace. The first
commercial product of a polymer nanocomposite is the
timing belt cover which was made from nylon 6
nanocomposites by the Toyota Company. The timing
belt demonstrated good rigidity and excellent thermal
stability. The timing belt was shown to save up to 25%
weight due to the lower content of nanoclays used. In
addition, nylon 6 nanocomposites have been used to
fabricate engine covers, oil reservoir tank and fuel
hoses in the automotive industry due to their
remarkable increase in heat distortion temperature
(HDT) as well as their enhanced barrier properties and
mechanical properties. Thermoplastic olefin
nanocomposite reinforced with as little as 2.5% clay
particles has also been employed by General Motors. In
recent years, there has been increased use of
biopolymer nanocomposites by various vehicle
manufacturers to make both external and internal parts
such as mirror housings, door handles etc. The weight
advantage of polymer nanocomposites has a significant
impact on environmental protection.
3.2 Packaging Materials
Bioplastics made from starch reinforced with clay
243
particles have outstanding barrier properties that would
result in considerable enhancement of shell life for
many packaged foodstuff. These nanocomposites
demonstrate optical transparency in addition to
biodegradability which is impossible to achieve with
conventional synthetic polymer composites. Starch
based packaging plastics are odorless, non toxic and
display low permeability to oxygen especially at low
relative humidity [17]. These property advantages
make the new generation of nanocomposite bioplastics
widely acceptable in packaging industries as wrapping
films and beverage containers. Bayer research group
played a significant role in developing a new grade of
plastic films for food packaging made from nylon 6
nanocomposites [4]. InnoWare Atlanta, USA, recently
successfully developed starch based food packaging
containers with the ability to withstand high
temperature, which is especially important during
transport and storage [1]. Therefore, starch based
packaging materials have great potential in providing
proper packaging materials for safe, wholesome food
products which has been the focus of food packaging
industry for many years.
3.3 Nanocomposite for Drug Delivery
The classical drug administration by injection causes
the plasma levels to go up and fall drastically when the
drug has been metabolized; leading to a cyclical pattern
each time a dose is administered. Therefore, in classical
drug administration, most of the drug plasma levels can
be outside the optimal range. Due to this, the drug
permeates throughout the body and is not targeted to
the site where it is specifically required. To overcome
this problem, a controlled drug delivery mechanism in
which the drug is released at a constant, preset rate,
preferably close to the specific location is required.
One of the notable approaches is to contain the drug in
a polymer membrane, from which it diffuses out into
the tissue in which the membrane is implanted. Duncan
and Kapecek [18] reported that various polymers to
which certain drugs were attached could be used to
244 A Review on Starch Based Nanocomposites for Bioplastic Materials
release the drugs after cleavage of the bonds attaching
them to the backbone. Recently, attempts to use starch
based biodegradable plastics have indicated enhanced
drug delivery and eliminated the need for surgical
retrieval of the polymeric material after drug
administration. The differential rates of drug release
demonstrated by this method of drug delivery may be
beneficial in cases where increased drug dosage is
necessary at the beginning of therapy [1].
4. Conclusions
It is observed that clay nanoparticles are cost
effective and versatile raw materials for starch based
nanocomposites due to their unique layered structure,
abundance in nature and wide availability. When clay
based nanoparticles are applied to fabricate starch
based bioplastics, enhanced properties are
demonstrated. Moreover, the very low level of clay in
the matrix makes the overall density similar to that of
pure polymer. Clay based nanocomposites have found
wide use in production of environment-friendly
automotive parts and packaging materials. Their future
markets will further expand from the current
automotive and packaging industries to other industries
such as electro materials, sensors and biomedicine.
Other potential applications for starch-based
nanocomposites for bioplastic materials are also
currently being investigated.
However, in spite of the successes achieved in the
development of clay-based nanocomposites, their
design, manufacturing and applications are often
empirical and their large scale applications are still at
their infancy stages. The reasons may be due to the
limited theoretical knowledge on the novel
nanostructure materials and the modification of clays
for the purpose of targeted bioplastic, the mechanisms
for superior reinforcement as compared to their
micro-counterparts and the establishments of a simple
processing structure-property relationship. Further
developments of starch based bioplastic
nanocomposites will depend largely on the
understanding of the above fundamental concepts.
Most nanocomposite fabrication methods have
reported nanoparticle agglomeration causing formation
of irregularly shaped nanostructural features within the
composite. Noting that enhancement of properties of
nano biocomposites is achieved when clay particles are
well dispersed in the polymer matrix, improved
properties of these materials can only be attainable if
nanoparticle inclusions are of uniform size and shape
and of very good degree of dispersion.
5. Suggestions for Future Work
Future research is therefore expected to address the
following issues and challenges: develop a simple but
effective way to modify clay minerals and improve
their compatibility with desirable polymer matrix since
dispersion of clay platelets directly affects the final
structure and hence the final properties of bioplastic
nanocomposites, design an effective experimental
technique to effectively fabricate nanocomposite
bioplastics with uniformly dispersed nanoparticles and
to establish optimal processing-structure-property
relations to facilitate the design of nanocomposite
bioplastics for specific applications. It is also proposed
that future works should use carbon nanotubes in the
fabrication of nanocomposite bioplastics.
Acknowledgments
The authors acknowledge Jomo Kenyatta University
of Agriculture and Technology.
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