538

BIODEGRADABLE PLASTICS FROM CASSAVA STARCH IN THAILAND

Klanarong Sriroth
1
, Rungsima Chollakup
2
, Kuakoon Piyachomkwan
2

and Christopher G. Oates
3


ABSTRACT
The paper reviews the role of starch and biodegradable plastics production in Thailand,
emphasizing the potential contribution of cassava starch in these products. Types of biodegradable
plastics and their manufacturing processes are described. The major types of biodegradable plastics
discussed are directly-expanded starch products and various starch-polymer blends (PCL, PLA, PVA
and PHA). Research focusing on cassava starch incorporation into biodegradable plastics is
summarized.

INTRODUCTION
The world production of plastic is estimated to be more than 100 million tonnes per
year. The need for such large quantities of conventional plastics and their dominance over
other materials is due to their excellent long-life properties. These properties include
resistance to chemical reactions, specially enzymatic reactions. For example, it can take up
to one hundred years to degrade only a few grams of plastic (such as polyethylene) under
normal environmental conditions. Degradation at high temperature, such as in pyrolysis
(burning) tends to cause emission of toxic fumes. Plastic accumulation in the environment
thus creates tremendous problems for the world, presently and in the future. Environmental
problems caused by plastics include changes to the carbon dioxide cycle, problems in
composting, and increased toxic emissions. Stimulated by environmental concerns,
scientists are now concentrating on ways to develop plastic use more efficiently. Two
simple strategies are to recycle (reuse), or to produce plastics that will degrade when no
longer required.

Degradable plastics are grouped by the American Society for Testing and Materials
(ASTM D20.96) as:
a) Photodegradable plastics A degradable plastic in which the degradation
results from the action of natural daylight;
b) Oxidatively degradable plastics A degradable plastic in which the
degradation results from oxidation;
c) Hydrolytically degradable plastics A degradable plastic in which the
degradation results from hydrolysis; and
d) Biodegradable plastics A degradable plastic in which the degradation results
from the action of naturally occurring microorganisms such as bacteria, fungi
and algae.

As the plastics defined in categories a), b) and c) require additional inputs, such as
light (UV) or oxygen for degradation, the biodegradable plastics (d) offer the only products
which are naturally degradable.

1
Department of Biotechnology, Kasetsart University, Bangkok, Thailand.
2
National Center for Genetic Engineering and Biotechnology (BIOTEC), Bangkok, Thailand.
3
Agro Food Resources (Thailand) Co., Ltd.
539
Biodegradable plastics are polymers or polymer blends, which in addition to
possessing properties similar to conventional plastics are susceptible to natural enzyme
hydrolysis or other chemical attack. The plastic is therefore either broken down to
oligosaccharides or monomers, through depolymerization, or are degraded to gaseous
components through mineralization. Starch, a natural polymer, is biodegradable and as
such can play an important role in the biodegradable plastic manufacturing process. It is
also inexpensive and renewable. In tropical countries cassava starch offers opportunities
due to its purity, clearness of its paste and low cost of production. This starch also posseses
properties that enable it to be blended with other expensive polymers required for
producing biodegradable plastic. Projections for the requirement of biodegradable plastic,
by the year 2000, is 1.68 million tonnes (Table 1).

Table 1. Projections of world consumption of biodegradable plastics in the year 2000.

Application Quantity
(million tonnes)
Trash bags
Agricultural
Food containers/utensils
Oneway packaging
Food packaging
1.00
0.09
0.18
0.27
0.14
Total 1.68
Source: Chemical Week, October 27, 1993.

The CradleToGrave concept (Figure 1) has been designed by the Michigan
Biotechnology Institute (1994). As the end use of products from biodegradable plastic is
composting, it can serve as a reserve for carbon dioxide and as a means to return nutrients
back to the soil (as compost).

MANUFACTURING PROCESS TECHNOLOGY
1. Starch Puff
This kind of product is known also as Gelatinized starch puff or Plate expanded
by extrusion or Baking with water. The products are formed by the swelling and
expansion of starch through the action of high temperature and water vapor. The products
formed in the extruder are starch foam, snack, etc (Figures 2 and 3). Plate expansion or
baking give products such as waffles, which can be formed in tray shapes or other
packaging material.

Clean Green Company in Minneapolis, MN, USA, has produced starch foam
called peanut (American name of loose fill packing material) by extrusion of wheat
starch (90 portion) and polyvinyl alcohol (10 portion). EcoFoam, a product of National
Starch, uses waxy corn as raw material. In European countries, the baking technology is
also at a commercial scale. Packaging products, such as fast food utensils, are available in
the market using both cereal and potato starches. The marketing of biodegradable
packaging products are supported in the EU.
540


Figure 1. Design concept of biodegradable plastic from cradle to grave.
Source: Michigan Biotechnology Institute, 1994.



Figure 2. Extrusion of starch foam.
Cutter
Cassava foams
Extruder
high pressure
high temperature
controlled moisture content
541



(a) (b)

Figure 3. Starch foam: (a) Pesika Naturpack GmbH; (b) Suedstraerke GmbH.

Cassava starch has been successfully expanded under extrusion conditions. Due to
its low bulk density, a little modification is needed so that its moisture content is increased.
Twin screw extrusion is recommended for direct expansion of cassava starches. Cassava
starch can also be used as the raw material for plate expanded or baking products. Cassava
starch can be expanded in moulds, at 200-240C for 1-3 minutes, to form into package
utensils, such as bowls. About 10% additives, including calcium carbonate, agar, or
emulsifier are needed to improve the properties. The bulk density is reported in the range
of 0.15 to 0.176 g/cm
3
(Poovarodom and Praditduang, 1999)

Even though this group of products has been introduced to the market for some
time, and can be produced at reasonable cost, constraints to its wider adoption still exist.
First, special machinery is required, such as high shear extruder (not plastic extruder),
continuous molding machine with high temperature (continuous waffle moulds using high
pressure and temperature). Thus, the investment cost for the machinery is high.
Distribution of the products is limited, due to its rigidity and short shelf life. Further, these
products can not be applied to high moisture conditions. Lamination with other polymers,
to improve shelf life and tolerance to high moisture conditions, will increase production
cost, and such polymers have to be approved before using as a food packaging material.

2. Polymer/Starch Blends
The biodegradable polymers (polylactic acid, polyhydroxyl butyrate) are in this
group produced by fermentation (using starch hydrolysis products: glucose, maltose, etc.).
The blending of polymers with starch under controlled conditions leads to co-
polymerization that in turn results in high molecular polymers with thermoplastic
properties. Though the mixing or blending needs special machinery, such as an extruder,
the products (polymer blend) can be handled as easily as conventional plastic resin.
542
Polymer blends can be distributed or transported to normal plastic converters, which can
process the blends to products using normal injection or blow moulds.

2.1 Polymers
Though starch, such as that of cassava, is used as a polymer, other polymers are
frequently used in the blend:

a. Polycaprolactone

Mn =4x10
4
Tm =62
o
C

This polyester is manufactured by catalytic ring-opening polymerization of -
caprolactone. Union Carbide is the biggest manufacturer (Table 2). Polycaprolactone
blend is the most used polymer/starch blend because of its low melting temperature (Tm)
and high susceptibility to amylase and lipase hydrolyses (Tokiwa et al., 1990a; 1990b). A
number of patents of polycaprolactone/starch blend are held:

- Michigan Biotechnology International (MBI), USA (US 5,578,691 etc.)
- Chuo Kajuku Co., Ltd, J apan (US 5,256,711 etc)
- Bioplastics Inc., Suite, Ml.
- Daicel Chemical Industries Co., Ltd, J apan
- J apan Corn Starch, J apan
Most patents describe a generic starch, this includes cassava.

b. Polylactic acid
Mn =1.88 x 10
5
Tm =175
o
C


This polyester is manufactured by catalytic ring-opening polymerization of lactide
(dilactone of lactic acid). Cargill, Minneapolis, MN, USA is the biggest manufacturer
(Table 2). Polylactic acid is used because lactic acid can be produced by microorganisms
n
PC
CH
2
C
O
O
C
O
C
C
C
O
C
C
n
O
O C PL
543
through a fermentation process. Many research laboratories in J apan claim that polylactic
acid can be produced from a condensation-polymerization reaction of free lactic acid (from
fermentation of starch). Polylactic acid from direct condensation polymerization is on the
market under the names of Lacty (Shimadzu Corp. J apan) and Lacea (Mitsui
Chemicals, J apan). These products offers the opportunity for a polymer blend totally
derived from starch-based materials.

- Polybutylene succinate (PBS), and
- Polybutylene succinate/adipate (PBSA)

Mn =3x10
4
Tm =96
o
C

These products are derived from polycondensation of linear dicarboxylic acid with
glycols. In the market they are sold under the name of Bionolle (Showa Highpolymer
Inc., J apan); a wide range of molecular weights and properties are available.

c. Polyvinyl alcohol (PVA)

Mn =7x10
4
Tm =180
o
C


This is one of the most common synthetic polymers which can be easily
biodegraded (Sakai et al., 1987). However due to its solubility, applications are limited.

d. Polyhydroxyalkanoates (PHA)

This group of products are obtained from microorganisms through a fermentation
process. Properties can be thermoplastic to elastomeric depending on the monomers used.
The most popular product of this group is poly (3hydroxybutyrate) (PHV).

The manufacturers and prices of polymers are shown in Table 2.



- CH
2
- CH - CH
2
- CH -
OH OH
n
n
PBS
O
C
O
(CH
2
)
2
(CH
2
)
4
O
O
C
O
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Table 2. Manufacturers, capacity and cost of biodegradable polymers.

Company Base Polymer Feedstock Cost ( $/lb) Capacity
(10
6
million
lb/yr)
Cargill,
Minneapolis, MN
Polylactide (PLA) Renewable
resources,
Maize
1.00-3.00 10(94 scale
up) ;250(mid-
1996)
Ecochem,
Wilmington, DE
Polylactide Copolymers Renewable
resources,
Cheese whey,
Maize
<2.00 projd 0.15
(94 scale up)
Zeneca (business
unit of ICI)
Poly(hydroxybutyrate-
co-hydroxyvalerate),
PHBV
Renewable
resources,
Carbohydrates
(glucose),
organic acids
8.00-10.00;
4.00 projd
0.66, additional
capacity slated
for 96 is 11-22
Novamont,
Montedison, Italy
Starch-synthetic
polymer blend
containing approx. 60%
starch
Renewable
resources
Petrochemical
1.60-2.50 50, in Turni,
Italy
Novon Products
(Warner-
Lambert), Morris
Plains, NJ
Thermoplastic starch
polymer compounded
with 5-25% additives
Renewable
resources,
Starch
2.00-3.00 100
Union Carbide,
Danbury, CT
Polycarpolactone (Tone
polymer)
Petrochemical 2.70 <10
Air Products &
Chemicals,
Allentown, PA
Polyvinyl alcohol
(PVOH) &
Thermoplastic PVOH
alloys (VINEX)
Petrochemical 1.0-1.25
(PVOH);
2.50-
3.00(VINEX)
150-200 (water
sol, PVOH);
5(VINEX)
National Starch &
Chemicals,
Bridgewater, NJ
Low DS starch ester Renewable
resources, Starch
2.00-3.00 Not available
MI Biotech
Inst./GRT-J apan
Corn Starch J oint
Venture, MI
Water repellant,
thermoplastic modified
starches
Renewable
resources,
Starch
1.0-1.50 0.1 (pilot
scale); 150
slated for early
96
Showa
Highpolymer
Co.,Ltd.
Condensation polymer
of glycols with aliphatic
dicarboxylic acids
(BIONELLE)
Petrochemical approx. 3.00 0.2 (pilot);7
(semi-
commercial ,
end 94)
Shimadzu Corp.
Technology
Research Lab.
Poly (lactic acid)
(Lacty)
Not available
Mitsui Chemicals,
Inc.
Poly (lactic acid)
(Lacea)
Not available
Source: Narayan, 1994.
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2.2 Blending techniques
There are four ways to blend starch with polymer:

a. Starch in the granular form
Mixing or blending starch with limited moisture content causes less loss of
structure of the starch granule. Cassava starch can be completely gelatinized at 65-70C
with 45% moisture content, but the granule is maintained at a moisture content under 5%.
The melting point (Tm) of dry cassava starch (almost anhydrous) is about 170C. After
blending polymers with granular starch, the structure consists of a continuous polymer
phase with starch granules embedded and reinforcing the network. This increases the
strength, water absorption and vapor permeability, and decreases the production cost
(Figure 4).

b. Gelatinized starch
By controlling the moisture content, starch granule structure can be totally
gelatinized at the same melting temperature as the polymer; thus, the two are blended
together. This affords improved properties of elongation and tensile strength to the
polymer (Figure 4).

c. Thermoplastic starch
Under severe extrusion conditions, low moisture content, high temperature and
pressure, starch can be melted. This thermoplastic starch is then a single component
continuous phase. Thermoplastic starch was patented by Werner-Pfleiderer Co., Ltd,
Germany.

d. Modified starch
Modification of starch, such as addition of ester groups, to manipulate its properties
supports the blending mechanism.

The manufacturing process is shown in Figures 5 and 6

Cassava starch blended with polycaprolactone (PCL) was developed in 1996
(Pranamuda et al., 1996). Blended in the proportion of 50/50, the product exhibited a
tensile strength of 3.90.4 MPa and % elongation of 240.956.7. The effect of varying the
proportion of cassava starch to PCL has also been investigated (Chollakup et al., 1998).
The tensile strength and % elongation of these products are shown in Table 3. Other
attempts to improve final product quality, such as irradiation treatment (Chollakup et al.,
1999a, Table 4), inclusion of silk protein to the blend (Chollakup et al., 1999b, Figure 7)
and addition of sucrose ester (SE) as plasticizer (Sriroth et al., 1999; Table 5) have been
reported.

The Cassava and Starch Technology Research Unit, a research unit supported by
the National Center for Genetic Engineering and Biotechnology (BIOTEC), the Thai
Tapioca Development Institute (TTDI), and Kasetsart University (KU), conducts research
on modification of cassava starch for blending with polymers.

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(a) Granular starch



(b) Gelatinized starch
Figure 4. Characteristic of granular and gelatinized starch as blending material for
polymer blend.
Source: Gould et al.,1990.
547



Figure 5. Biodegradable starch plastic manufacturing process.







Granular starch form
Gelatinized starch form
Thermoplastic starch
Monomer
Additives
Mixer
Blender
Extruder
Starch/Polymer blend
Plastic Converter
Products
and/or
and/or
and/or
Polymer
Modified starch
and/or
Reaction
with/
without
548

549





























Starch/Water/Polymer
or Plasticizer
Blend in
single screw extruder
Molding by
heat press machine
Testing mechanical properties and biodegradability
550
Figure 6. Extrusion process of biodegradable plastic.
Table 3. Physical properties of cassava starch/PCL blends using granular (TS) and
gelatinized (GS) starch in various proportions.

Tensile strength (MPa) Elongation (%)
Granular starch (TS)
TS/PCL (0/100)
TS/PCL (10/90)
TS/PCL (20/80)
TS/PCL (30/70)
TS/PCL (40/60)
TS/PCL (50/50)

30.40 +4.6
19.40 +3.4
17.70 +0.6
15.10 +1.3
9.00 +0.6
8.30 +0.7

613.40 +108.5
435.50 + 24.2
401.60 + 45.1
406.60 + 43.5
297.80 + 37.3
276.80 + 61.5

Gelatinized starch (GS)
GS/PCL (0/100)
GS/PCL (10/90)
GS/PCL (20/80)
GS/PCL (30/70)
GS/PCL (40/60)
GS/PCL (50/50)

30.40 +4.60
19.44 +3.00
16.64 +0.95
16.74 +0.95
8.33 +0.47
2.91 +0.39

613.40 +108.50
388.97 + 98.95
394.19 + 44.35
396.65 + 36.36
132.48 + 11.83
2.20 + 0.36
Values are the average of eight determinations +SD.
Source: Chollakup et al., 1998


Table 4. Physical properties of starch/PCL blends in the ratio of 30:70 using either
granular (TS) or gelatinized starch (GS).

Tensile strength
(MPa)
Elongation
(%)
Irradiated starch* and irradiated PCL* blend
1. Before radiation
- PCL 53.6 972.8
- TS/PCL 16.5 403.8
- GS/PCL 8.9 166.1
2. After radiation
- PCL* 31.9 678.0
- (TS/PCL)* 8.2 27.1
- (GS/PCL)* 9.2 13.5

Irradiated starch* and PCL blend
1. Before radiation
- TS/PCL 16.5 403.8
- GS/PCL 8.9 166.1
2. After radiation
- TS*/PCL 12.0 383.6
- GS*/PCL 10.0 135.0
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Source: Chollakup et al., 1999a.
Figure 7. Physical properties, determined as tensile strength and % elongation, of
cassava starch and PCL blends with the inclusion of silk protein (silk
hydrolysis-SH or silk fibroin-SF) at various concentrations (0 to 20%).
Source: Chollakup et al., 1999b.


Table 5. Physical properties of PCL/partially hydrated starch (PS) and PCL/
Hydrated starch (HS) at the ratio of 70/30 with various contents of sucrose
ester (SE).

Tensile strength (MPa) Elongation (%)
PCL/PS
+0% SE
+10% SE
+15% SE
+20% SE

10.18 +0.95
7.82 +0.98
7.53 +0.58
7.73 +0.79

217.28 +38.52
176.94 +63.13
200.59 +22.08
197.39 +32.25

PCL/HS
+0% SE
+10% SE
+15% SE
+20% SE

8.39 +0.68
7.36 +0.82
6.58 +0.50
6.53 +0.28

125.22 +38.86
157.29 +47.66
124.59 +25.19
134.74 +15.10
Source: Sriroth et al., 1999.
0
2
4
6
8
10
0 5 10 15 20 25
Concentratio (%
T
e
n
s
i
l
e

s
t
r
e
n
g
(
M
P
a
)
0
20
40
60
80
100
120
140
E
l
o
n
g
a
t
i
o
(
%
SH- Tensile strengt
SF- Tensile strengt
SH- %Elongation
SF- %Elongation
552
CONCLUSIONS
Cassava starch is the cheapest carbon source in the region and can be applied for
the production of biodegradable plastics in the future in two different ways:
a) As polymers: cassava starch can serve as a carbon source in the fermentation
process leading to the formation of high molecular weight polymers, PHB etc.,
or organic acids such as succinic acid and lactic acid, which can subsequently
undergo direct condensation to high molecular weight polymers. The future
polymers will be from fermentation processes that give more consumer
confidence.
b) As the blending material cassava starch can be modified in different ways, so
that the properties of the starch in the polymer blend are the best possible. This
will lead to the most reasonable production cost.
c) Through genetic engineering some plants are reported to have the ability for
polymer production, such as a transgenic tobacco plant expressing a bioelastic
protein-based polymer (Daniell and Guda, 1997). If biodegradable polymers
could be synthesized in plants, like starch or lipid, the polymers cost should be
competitive with those from more conventional sources.

Despite the superior properties of conventional plastics, biodegradable plastics will
be required in increasing amounts in certain markets. Major polymer producers are
therefore increasing their research and development investments in this area.


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th
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th
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th
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