CHAPTER 2

REVIEW AND RELATED LITERATURE

Society is facing important questions.  How do we live sustainably and enjoy a high quality
standard of living? How will our developed world function beyond cheap oil? Can we continue to throw
away so much of what we make? Bioplastics are part of the answer.

Conventional, oil based plastics are ubiquitous – many were invented in the early 20 th century
and they became part of everyday life from the 50s onwards.  Now, they can be found throughout our
homes and cars, in our workplaces and leisure activities.  They range from short life packaging products
that are used for a day and then discarded, through consumer durables and electronics to long life
physical infrastructure that endures for decades.  Oil based plastics have been so successful due to their
low cost related to their oil based origins and their ability to be processed rapidly in mass production.

Contemporary bioplastics are now challenging the dominance of their “petro” cousins.   Today’s
bioplastics are being developed with the functional capability to substitute in many existing plastic
applications and allowing them to be transformed on the existing infrastructure of conversion
equipment. 

Conventional perception regarding bioplastics sees them used in shopping bags, short-life
packaging and disposable items but this is changing as their attributes are enhanced.    Bioplastics can,
but don’t have to decompose rapidly.  Advances in science allow them to perform their required uses
for decades if required.
BIOPLASTICS

Plastics are distinguished by their enormous diversity which makes them so successful in
numerous applications. This is also true of bioplastics. They also cover an abundance of types, each with
its own individual profile.

Bioplastics from renewable origin are a new generation of plastics able to significantly reduce
the environmental impact in terms of energy consumption and green-house effect in specific
applications, to perform as traditional plastics when in use, and completely biodegrade within
composting cycle.

There are currently three bio-based polymer types on the market: starch materials, polylactic
acid (PLA, polyester) and cellulose materials. Polyhydroxy fatty acids (PHA) which are manufactured
using biological processes can also be included as a promising fourth class, despite the fact that this
polyester is only commercially available in very limited quantities. This will however soon change as
successions of companies have announced they will set up production facilities for PHA polymers.

Renewable raw materials already currently dominate the production of bioplastics, and
particularly with regard to commercial products, can no longer be overlooked. Many bioplastics are
however mixes or blends containing synthetic components. Synthetic polymer types and addititives are
frequently used, albeit in small quantities, to improve the functional properties of the finished product
and to expand the range of applications.
     Table 2.1 Types of Bioplastics and its Application

RENEWABLE BASE MANUFACTURER APPLICATION

Starch-based polymers Novamont (MaterBi) films, moulding, extrusion

Rodenburg (Solanyl)
Plantic Technologies
Bioplast (Biotec)
Biop
and other
Polyhydroxy-alkanoates Kaneka moulding, films
(PHA) Metabolix
Telles
PHB Industrial
Polylactic acid (PLA) NatureWorks PLA films, moulding, fibers
Pyramid Bioplastics
Synbra Technologies
Cellulose-derivatives Innovia Films (NatureFlex) films, injection moulding
FKuR

Today bioplastics and particularly starch-based plastics are used in specific industrial
applications where biodegradability is required such as the composting bags and sacks, fast food
serviceware (cups, cutlery, plates, straws etc.), packaging (soluble foams for industrial packaging, film
wrapping, laminated paper, food containers), agriculture (much film, nursery pots, plant labels), hygiene
(diaper back sheet, cotton swabs).

The market of starch-based bioplastics in 2001 has been estimated at about 30000ton/year,
with a strong incidence of soluble foams for packaging and films. Bioplastics from renewable origin,
either biodegradable or non biodegradable still comprise a niche market which requires high efforts in
the areas of material and application development; the technical and economical breakthroughs
achieved in the last three years, however, open new possibilities for such products in the mass markets
and specifically in the food packaging.
THERMOPLASTICS
A thermoplastic (sometimes written as thermo plastic) is a type of plastic made from polymer
resins that becomes a homogenized liquid when heated and hard when cooled. When frozen, however,
a thermoplastic becomes glass-like and subject to fracture. These characteristics, which lend the
material its name, are reversible. That is, it can be reheated, reshaped, and frozen repeatedly. This
quality also makes thermoplastics recyclable.

There are different kinds of thermoplastics, with each type varying in crystalline organization
and density. Some types that are commonly produced today are polyurethane, polypropylene,
polycarbonate, and acrylic. Celluloid, which is considered the first thermoplastic, made its appearance in
the mid-1800s and reigned in the industry for approximately 100 years. During its peak production, it
was used as a substitute for ivory. Today, it is used to make guitar picks.

Sometimes, thermoplastics are mystified with thermosetting plastics. Although they may sound
the same, they actually acquire very different properties. While thermoplastics can be melted to a liquid
and cooled to a solid, thermosetting plastics chemically depreciate when subjected to heat. Ironically,
however, thermosetting plastics tend to be more durable when allowed to cool than many
thermoplastics.

Thermoplastics also differ from elastomers, even though some are considered both. While many
thermoplastics can be stretched to a point, they generally tend to both resist, and stay in the shape they
are stretched to. Elastomers, as the name suggests, bounce back. On the other hand, the addition of
plasticizers to the melt can render a more pliable thermoplastic. In fact, this is usually the case when a
thermoplastic is being used for plastic injection molding or extrusion.

The specific action of a plasticizer is to lower the material’s glass transition temperature, which
is the point it becomes brittle when cooled and soft when heated. Temperature varies with each type of
thermoplastic and is dictated by its crystallization structure. Nevertheless, temperature can also be
adjusted by introducing a thermoplastic into a copolymer, such as polystyrene. Until the use of
plasticizers, some molded thermoplastic parts were prone to crack in cold weather.
RAW MATERIALS
a) CASSAVA

Cassava (Manihot esculenta) is a perennial shrub, which sometimes reaches the size of a
small tree. It stems vary in color from pale to dirty white to brown marked by numerous nodes
formed by scars left by fallen leaves. The flesh can be chalk-white or yellowish. Cassava is a staple
food in tropical countries and provides more than 10 percent of the daily dietary caloric intake to
about 300 million people in the world. Regardless of its importance, cassava is mostly grown by
small farmers on small plots of land. Urban consumers and factories obtain their cassava from rural
areas where it is grown. Cassava is usually processed immediately after it is taken from the ground
because it is highly perishable. Spoiling starts within 48 to 72 hours after harvest (West et al., 1988).

Figure 2.1 Cassava root crops

Roots of cassava plants are few and shallow and some become storage roots. These are
clustered around the base of the plant and extend about 60cm on all sides. It is for these roots that
contain from 15%-40% starch, that the crop is cultivated. Under favorable conditions, a single root
may weigh as much as 4kls. The number of roots per plant at harvest varies from 2 to 7 each
averaging from 27.7cm- 43.3cm long and 4.5cm -7.4cm in diameter. Cassava roots are very rich in
starch, and contain significant amounts of calcium (50 mg/100g), phosphorus (40 mg/100g) and
vitamin C (25 mg/100g).

Cassava is in fact the most widely grown of the root crops in the Philippines. The
average volume of production is close to 2.0 million tons. Of this volume, it is estimated that 75% is
 utilized for food, 20% for starch processing, and 5% for feed (BAS, 2000). Some areas in the country
though use cassava as cash crop and on a commercial scale in places such as ARMM, Bicol Region,
and Western Mindanao. Table 2.1 shows that the principal cassava growing areas are located in
Mindanao, which accounts for 59% of the area and 71% of the production in the Philippines.

Table 2.2 Cassava Statistics in various regions in the Philippines

Region Area Production Yield
1990 1999 1990 1999 1990 1999
Philippines 2113,653 221,618 1,853.38 1,793.59 8.67 8.09
1. CAR 276 134 2.36 1.92 8.56 14.33
2. Ilocos Region 1,806 1,944 10.73 13.95 5.94 7.18
3. Cagayan Valley 436 2,268 1.42 17.90 3.26 7.89
4. Central Luzon 1,247 1,027 7.99 7.65 6.41 7.45
5. Southern Tagalog 10,241 11,031 63.04 66.64 6.16 6.04
6. Bicol 32,113 30,548 263.03 189.73 8.19 6.21
7. Western Visayas 9,895 6,048 50.77 50.82 5.13 8.40
8. Central Visayas 20,405 16,322 167.46 115.41 8.21 7.05
9. Eastern Visayas 26,839 22,146 97.88 59.46 3.65 2.68
10. Western Mindanao 22,308 24,339 218.80 235.98 9.81 9.69
11. Northern Mindanao 9,499 8,053 92.20 81.68 9.71 10.14
12. Southern Mindanao 3,874 2,292 33.17 15.71 8.56 6.85
13. Central Mindanao 1,856 1,115 13.19 7.86 7.11 7.05
14. CARAGA 9,855 5,545 38.18 38.66 3.87 6.97
15. ARMM 63,003 88,806 793.18 890.47 12.59 10.03

b) CASSAVA STARCH

More than two-thirds of the total production of cassava is used as food for humans,
with lesser amounts being used for animal feed (Nwokoro et al. 2002) and industrial purposes. The
future demand for fresh cassava may depend on improved storage methods, but the markets for
cassava as a substitute for cereal flours in bakery products and as energy source in animal feed
rations are likely to expand.
 Starch is one of the most important plant products to man. It is an essential component
of food providing a large proportion of the daily calorific intake. In West Africa, cassava flour and
gari (a processed cassava product) are consumed in large quantities. Cassava starch is recommended
for use in extruded snacks for improved expansion. It is also used as a thickener in foods that are not
subject to rigorous processing conditions. Cassava starch, which is very bland in flavor, is used in
processed baby foods as a filler material and bonding agent in confectionary and biscuit industries.

Cassava is also used to produce starch for industrial use and other products used in
processed food. Starch is a multibillion dollar business worldwide and it is finding application in
several industries. Cassava starch can perform most of the functions where maize, rice and wheat
starch are currently used. Starch is utilized in sizing and dyeing in the textiles industries to increase
brightness and weight of the cloth. In the pharmaceutical industries, starch serves as a filler material
and bonding agent for making tablets.

Cassava starch also have several other numerous uses such as an additive in cement to
improve the setting time, and it is used to improve the viscosity of drilling muds in oil wells. It is also
used to seal the walls of bore holes and prevent fluid loss. Starch is also the main raw material in
glue and adhesive industries. In paper production, cassava starch is currently used as glue to achieve
brightness and strength. Starch is also an important raw material for powder in the cosmetics
industries. In detergent soap manufacture, starch is used to get better recovery and to improve the
shelf life of detergents. While in the rubber and foam industries, starch is employed for getting
better foaming and color.

PROCESS
I. EXTRUSION of PLASTICS

A process is disclosed for producing thermoplastic starch based on renewable raw

materials and for further processing it into a granulate. A low viscosity starch is modified under a
low shearing stress during extrusion process and leaves the extruder with the increased viscosity in
the form of strip, threads or in other geometrical shapes.
 Extrusion is a process used to create objects of a fixed cross-sectional profile. A material
is pushed or drawn through a die of the desired cross-section. The two main advantages of this
process over other manufacturing processes are its ability to create very complex cross-sections and
work materials that are brittle, because the material only encounters compressive and shear
stresses. It also forms finished parts with an excellent surface finish. Extrusion may be continuous
(theoretically producing indefinitely long material) or semi-continuous (producing many pieces). The
extrusion process can be done with the material hot or cold.

However, plastics extrusion is the particular process used in the production of

thermoplastic starch. Plastic extrusion is a high volume manufacturing process in which
raw plastic material is melted and formed into a continuous profile. Extrusion produces items such
as pipe/tubing, weather stripping, fence, deck railing, window frames, adhesive tape and wire
insulation.

Figure 2.2 Sectional view of a plastic extruder showing the components

Plastics extrusion commonly uses plastic chips or pellets, which are usually dried in a
hopper before going to the feed screw. The polymer resin is heated to molten state by a
combination of heating elements and shear heating from the extrusion screw. The screw forces the
resin through a die, forming the resin into the desired shape. The extrudate is cooled and solidified
as it is pulled through the die or water tank. In some cases (such as fibre-reinforced tubes) the
extrudate is pulled through a very long die, in a process called pultrusion.
II. DRYING PROCESS

Drying is just one of a myriad of industrial heat and mass transfer operations. Although
drying is classically defined as a process that removes a liquid (usually water) from a solid in
equipment termed a dryer, there remains a wide application of various technologies to moisture
removal. Drying is differentiated from dewatering in that in drying; the moisture leaves the product
as a vapor or gas. This is achieved by imparting energy to the moisture molecule or changing the
environment so that the molecule has sufficient latent energy to leave the product.

The drying process is intended to remove moisture from a feed substance and thereby
condition the feed into a “dry” final product. This does not imply that the product will have no
moisture content -- only that it will be “dry” by the definition of the specification. Some dry
materials such as certain agricultural products may possess 12 to 17 percent moisture (wet basis)
and be considered dry. Typically, in drying, one does not physically or chemically change the
composition of the feed, other than by removing the moisture.

In plastics manufacturing, material must be free of moisture before it is processed to

ensure that the end product is defect free.  Many of today’s plastic resins are hygroscopic. If the
moisture is not properly removed it will boil off when heated during the molding or extrusion
process. This released vapor can cause both structural and cosmetic flaws in the finished product.

III. MILLING PROCESS

Milling is the most common form of machining, a material removal process, which can
create a variety of features on a part by cutting away the unwanted material. The milling process
requires a milling machine, work piece, fixture, and cutter. The work piece is a piece of pre-shaped
material that is secured to the fixture, which itself is attached to a platform inside the milling
machine. The cutter is a cutting tool with sharp teeth that is also secured in the milling machine and
 rotates at high speeds. By feeding the work piece into the rotating cutter, material is cut away from
this work piece in the form of small chips to create the desired shape. 

Milling is typically used to produce parts that are not axially symmetric and have many
features, such as holes, slots, pockets, and even three dimensional surface contours. Parts that are
fabricated completely through milling often include components that are used in limited quantities,
perhaps for prototypes, such as custom designed fasteners or brackets. Another application of
milling is the fabrication of tooling for other processes. For example, three-dimensional molds are
typically milled. Milling is also commonly used as a secondary process to add or refine features on
parts that were manufactured using a different process. Due to the high tolerances and surface
finishes that milling can offer, it is ideal for adding precision features to a part whose basic shape has
already been formed.

In manufacturing thermoplastic-like starch, hammer mill is used in milling process.

A hammer mill is a machine whose purpose is to shred or crush aggregate material into smaller
pieces. These machines have many sorts of applications in many industries. It is essentially a steel
drum containing a vertical or horizontal rotating shaft or drum on which hammers are mounted. The
hammers are free to swing on the ends of the cross, or fixed to the central rotor. The rotor is spun at
a high speed inside the drum while material is fed into a feed hopper. The material is impacted by
the hammer bars and is thereby shredded and expelled through screens in the drum of a selected
size.

PRODUCT
THERMOPLASTIC-LIKE STARCH
Plastics are ubiquitous in contemporary society. They are found in households as kitchen
ware, toys, and resilient flooring to name a few, and are extensively employed in many such key
industries as automobile, aerospace, electrical, and medical industries (Richardson,2005).
 Useful as they are, plastics are disposed constantly by people, and eventually accumulate
to large piles along with other wastes. Various efforts have been addressed in response to the
problem: the creation of sanitary landfills in strategically located places, adoption of selective
collecting and recycling programs, and active government and civic participation (Vilpoux and
Averous, 2004); still, people resort to quicker, short-term solutions such as incineration and waste
burning at household levels, aggravating the effects of global warming in the planet.

One effective procedure to address this global problem is the conception of

biodegradable plastics, based on thermoplastic-like starches which at present exist in the market.
Biodegradable plastics refer to degradable polymers that are consumed by microorganisms through
polymer chain breakdown and subsequent utilization (Garth and Kowal, 2001).

Thermoplastic starches, consisting of starch can be used for disposable products and
they form an interesting and economically attractive alternative for traditional packaging plastics.
Because of the economic viability the production of these thermoplastic starches should preferably
be restricted to of-the-shelf chemicals, which is especially the case if the products are used for single
use packaging. From production point of view the properties should be such that standard unit
operations can be used without the necessity to develop new equipment and new production
processes [Leszczy_ski 1999].

Thermoplastic starch, or TPS, can be made by cast-molding in dry drums, or a

continuous supply of thermo-mechanical energy. More often than not, this combination of thermal
and mechanical input can obtain by extrusion. In this process, starch, along with plasticizers such as
water, is fragmented, destructured, plasticized, melted, and partially depolymerized through high
temperature and shearing in an extruder, giving a homogenous molten product called the extrudate
(Averous, 2004).