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Research Paper v.11.2.2
Research Paper v.11.2.2
INTRODUCTION
The production and consumption of plastics have been increasing throughout the years
due to its versatility and very good properties [59]. It has replaced traditional materials
such as paper, aluminum, and steel in various applications because it is low-cost and
light-weight [25, 27]. However, many environmental problems have been associated with
the disposal of plastics because they are inert to microbial degradation and chemicals in
the environment making it non-biodegradable [29, 52, 65]. Since most polymers and
polymer products have a short shelf life (less than two years), a lot of them, are consumed
and just discarded into the environment after their utilization [28, 43, 71]. Petroleum-
based polymers are designed and developed to be durable and withstand all forms of
degradation [67].
Although recycling is an attractive solution, most still end up in landfills since only a
small portion of plastics are recyclable and it is difficult to collect and sort plastic wastes,
which in turn, causes a problem in finding available landfill sites [29, 52]. The use of
biodegradable plastics has been proposed to alleviate the impact of these non-
biodegradable petroleum-based polymers [22, 29]. Non-petroleum-based polymers have
been sought by a lot of researches in the quest for finding a viable replacement for non-
biodegradable products that causes pollution and environmental deterioration [63].
The race for biodegradable plastics started in the 1970’s and is continuing to grow further
around the globe. Biodegradable plastics can be defined as plastics that undergo
biodegradation – a process that occurs when bacteria and fungi degrade the polymer in
either aerobic or anaerobic environment to produce carbon dioxide, methane, and other
non-toxic by-products. They have similar properties to conventional properties but they
can be decomposed after disposal by the activity of microorganisms [28].
Polymeric materials such as natural resins are biodegradable and readily available [65].
Some common polymers are polycaprolactone, poly(hydroxyalkanoates), poly(vinyl)
alcohol, and poly(ethylene glycol). These polymers are rather expensive compared to the
non-biodegradable polyethylene and polypropylene [25]. Due to its large availability, low
cost, and inherent biodegradability, starch has been investigated as the most promising
materials for the purpose of biodegradable polymer production [28, 65]. Many
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researchers have focused on corn, wheat, potato starches and few reports are available for
sago starch. [58] However, there has been no literature citing on the use of banana
peelings for the purpose of plastic production. Banana is an inexpensive fruit rich in
starch content (14-23% on a fresh basis and 62% on a dry basis) [25].
The structure of starch-based materials, compared with fossil fuel based plastics, are
easily changed with surrounding humidity. The properties of starch films are influenced
by their molecular weights, structures, ratio of crystalline to amorphous region,
plasticizers and additives present, and polymer mobility. Strong films with low gas
permeability can be obtained from high-amylose starch. Grafting and copolymerization
of starches and the introduction of acetic/fatty acid moieties via esterification reduce
water absorption and water transmission of films. Films prepared with oxidized banana
starch have higher water vapor permeability and tensile strength than with the unmodified
starch [25].
The preparation of starch-based plastics involves the plasticizing of the starch under
heating to obtain a thermoplastic starch that can be processed using conventional plastic
processing techniques [57]. Various plasticizers and additives were evaluated for the
gelatinization of starch at thermal processing and among them water is the most
commonly used. However, the use of water alone results in poor mechanical properties
due to its fast retro gradation (recrystallization) [30]. Plasticizers used are polyols such as
glycerol, glycol, xylitol, and sorbitol. Urea, formaldehyde, and acetamide which contain
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and amide group can be also used. Sorbitol is an alcohol sugar that is commonly used as
humectant, texturizer and softener [57, 64].
1. How does the different amounts of Musa acuminata starch, peelings, and chitosan
affect the gelatinization time of the bioplastics?
2. What are the optimum amounts of banana starch, peelings, and chitosan to
produce the bioplastic with the most promising characteristics?
3. How does the model generated used to predict the gelatinization time of a
specified bioplastic formulation compare to the actual values obtained from the
experiment itself?
3
It aims to determine the effect of the different amounts of starch derived from Musa
acuminata starch, peelings, and chitosan on the rate of gelatinization of the bioplastics.
The bioplastics would be prepared by mixing different amounts of starch, chitosan,
glycerol, and water and molding into thin sheets.
This undertaking was found to be significant since the synthesis of a novel bioplastics
from banana peelings would provide a new route on the synthesis of biodegradable
plastics by using starch extracted from Musa acuminata starch and peelings.
Moreover, it can be justified that this is of high significance due to the following listed
reasons:
4
This may also serve as future reference for other researchers interested in
this field of investigation.
This research only entails to discuss the extraction of starch from Musa acuminata starch
and peelings and their utilization to synthesize biodegradable plastics. It covers the
investigation of the gelatinization time of the different bioplastic formulations.
Only the bioplastic formulation and its gelatinization time will be the parameters to be
investigated in the study. The optimum formulation will be determined based on the
contour graphs generated by the Design Expert software for the response that is
evaluated. D-Optimal design will be used to assess the effect of the formulations on the
gelatinization time of the different bioplastics.
The study is only limited to those stated parameters and conditions. It would not entail to
discuss the mechanism of biodegradation of the bioplastics derived from Musa acuminata
peelings. It will not tackle the investigation of its chemical properties as well as the
physical properties not so stated in this section. Furthermore, the researchers would not
study the effect of other varieties of bananas and the use of other additives in the rate of
biodegradation and gelatinization of the bioplastics. Lastly, it would not tackle other
parameters not so stated in the scope of the study.
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CHAPTER II
At the present time, our world is facing a lot of environmental problems, thus researchers
are looking for ways to innovate packaging materials for food production [1]. Through
the years, human has explored the earth’s natural resources without limits, finding raw
materials for industry [2] and one of the most amazing inventions are plastics. Synthetic
polymers are important in many branches, for example in the packaging industry [3].
Most of the products that we buy come in plastic bags, and almost all of them end up in
the landfill [4] and with this plastic consumption have been increasing worldwide
together with modern industrialization [5]. As we all know, synthetic plastics are resistant
to degradation, and consequently their disposal is becoming an international drive for the
development of biodegradable polymers [6]. For this reason, disposing of plastic waste
became a serious problem because plastics hardly decompose in the environment [7]. In
spite of this, the consumption of plastics still increased because of the growth in their use
as the resource material for objects that are disposable [8] and also many of the physical
and chemical properties of plastics make them ideal materials for a variety of products
and applications [9]; these properties include resistance to chemical reactions, especially
enzymatic reactions [10]. Worldwide production of plastics is more than 78 million tons
per year and almost half of that is rejected within a short period of time, becoming
garbage deposits and landfills for decades (more than 30 years) [11] and each year about
140 million tons of synthetic polymers are made [3].
In 1992, biodegradable polymer resins captured less than 5 million pounds or roughly
0.08 % of the plastic materials and resins market [12]. That is why the use of renewable
natural polymers in the manufacture of plastics increased in impulse and importance in
the last years of the 20th century [13]. Since last decades, many attempts have been
focused on grafting or blending plastic materials with cheap and biodegradable natural
biopolymers, such as starch, cellulose, chitin, etc., to create new materials with desired
properties [14]. Biodegradable polymers give an appealing method to material design
because their use in place of petroleum-based plastics materials and resins slows the
introduction of fossil fuel-derived carbon dioxide into the atmosphere [2]. Biodegradation
is the natural process in which the degradation of materials results from the action of
naturally-occurring microorganisms such as bacteria, fungi or algae [15]. One approach
to the synthesis of biodegradable plastics is to maximize the naturally occurring
biodegradable polymer, starch [16]. Starch is a polysaccharide that has contributing great
importance in the fields of new materials and environment [8] and can be found in plant
organs in the form of granules that are relatively dense, insoluble in cold water, and range
from 1 to 100 µm in size depending on the plant species [17] . It is most often used since
it is abundant, inexpensive, renewable, and fully biodegradable [18, 19].
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2.1 Plastics
Plastics are the newest packaging materials discovered in the 19 th century. Plastics
become very important materials that are developed and utilized over the past 170 years.
Several plastics were discovered like styrene in 1831, vinyl chloride in 1835 and celluloid
in the late 1860s. However, none of these became practical for packaging until the 20 th
century [22].
Styrene was first distilled from a balsam tree in 1831 but the early products were friable
and shivered easily. Germany refined the process in 1933 and by the 1950s styrofoam
was available worldwide. The insulation and cushioning materials as well as foam, boxes,
cups and meat trays for food industry became popular. Vinyl chloride in 1835 was
provided for further development of rubber chemistry. Molded deodorant bottles for
packaging were introduced in 1947 and in 1958. Heat shrinkable films were also
developed from blending styrene with synthetic rubber [22].
Nowadays containers are made from vinyl chloride. Another invention on plastics is
celluloid during the American Civil War. Due to shortage of ivory, United States offered
$10000 reward for an ivory substitute. John Wesley Hyaat, a New York engineer with
his bother Isaiah Smith Hyaat experimented several years before creating the new
material. Celluloid patented in 1870 could not be molded but rather carved and shaped
like ivory [22]. In 1990, cellulose acetate was first derived from wood pulp and
developed for photographic uses in 1909. Although cellophane is already manufactured
in New York in 1924, it wasn’t commercially used for packaging until the late 1950s and
early 1960s [22].
In 1933, films protected submarine telephone cables and drug tablet packaging. One of
the most common used plastics is polyethylene terephthalate (PETE). This material
became available for containers during the last two decades with its use for beverages
entering the market in 1977. Foods and other hit-fill products such as jams could also be
packaged in PETE by the year 1980 [22].
Plastics are widely used in everyday products. Common uses include food storage and
packaging, household items and furniture. Plastics in the environment are traditionally
made from petroleum, a non-renewable resource in the release of greenhouse gases that
contribute to global warming. When making and disposing of plastics, their by-products
create air and water pollution. Plastics create a waste disposal burden, especially single-
use plastics like product packaging and soft drink bottles [23].
Plastics can contain chemicals and metals, which are used as additives and stabilizers.
Some of these can be toxic such as lead. It can release chemicals into food and drink.
Some kinds of plastics are more likely to than polycarbonate, polyvinylchloride and
polystyrene. Plastics have been tied to a wide range of negative health effects on animals
including endocrine disruption and cancer but in human are not yet fully studied or
understood [23].
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The polyvinylchloride is one of the most common used types of plastics. It is present in
many things. Some of the substances added to PVC are the hormone-disrupting
chemicals that may pose hazards to human health and child development. PVC products
including certain toys may have chemicals which can flake, leach, causing the release of
these chemicals into our surroundings [23].
Phthalates is a class of chemicals used to make plastics flexible and can be used in many
products such as vinyl flooring, plastic clothing, detergents, adhesives, and personal-care
products and commonly found in vinyl plastic products. Bisphenol A is used when
making polycarbonate and other plastic products and used in consumer products (baby
bottles, protective coating in food cans, toys, containers and personal care products). It
can leach from these products and potentially cause harm to those in contact with them.
Lead is used to soften plastics or keep them more stable in heat [23].
Municipal wastes are dependent on governmental peripheries and may not only
encompass residential wastes and/or commercial wastes. Urban wastes, agricultural
wastes, and industrial wastes may also be taken into account depending on the discretion
of the government. Therefore, the term “municipal waste” is defined on the basis of the
existing policies, parameters, and customs in a specific geographical location. These laws
and practices are the determinant on the appropriate collection and proper disposal of
municipal wastes from different sectors such as those coming from the residential
communities [26].
Plastics, which are an integral and indispensable part of the wastes generated by different
sectors such as the residential, industrial, and commercial entities, are classified as a
municipal waste. With this discretion, the local or the national government claims the
responsibility in the collection and disposal of plastics. In most cases, however, plastic
collection is shouldered by the private sector. Furthermore, businesses and commercial
bodies using that use plastics can opt to segregate their wastes and sell the recyclable
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ones into recycling companies and waste facilities. This will help in estimating the
overall amount and quality of wastes generated by a company [26].
Statistical data and correlations and other sources of information regarding the
socioeconomic behavior in a particular location is essential in order to do assessments on
their impact on present waste plastics generation rate and its effect on the future trends.
There has been a strong correspondence between the status of the economy and/or the
industrialization rate to the rate at which plastics are produced and utilized within the
developing countries [26].
Plastics account for 11.3 percent by weight of the total municipal wastes disposed in
landfills in the United States. The Environmental Protection Agency reported that plastics
accounted for 26.1% by volume in 1997 (13.0% by weight). Among the wastes
discarded, 66% are biodegradable (comprised of food waste, yard trimmings, wood,
paper/board) and 31% are non-biodegradable or detrimental to the environment (plastics,
rubber, leather, textiles, metals, glass) while the remaining 3% are unclassified [27].
Most of the plastics came from packaging. As it can be seen from the figures, the
containers and plastics category has the largest share of plastics in municipal solid wastes
[27].
It was estimated that the amount of plastics entering the US landfills by 2003 to be about
20.65 million tons. 11.91 tons came from the utilization of plastics as a packaging
material. 8.39 million tons came from durable goods while 4.6 million tins came from
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nondurable goods. Plastics are recycled in a considerably lower rate than any other
material in the United States. From the figures that follow, the containers ad packaging
sector has the highest overall recycling rate with about 38.8 percent. Plastics are recycled
only at the rate of 8.9 percent. 3.9 percent of the plastics from durable goods are recycled
compared to 18.1 percent for the category as a whole. Plastics coming from the
nondurable goods are recycled at a negligible rate compared to the overall 31.0 percent
for this category [27].
1.39 million tons of the total 20.65 million tons of plastics disposed are recycled in the
US in the year 2003. This accounts for about 6.7 percent of the total plastics in the US.
330 000 tons of these came from durable goods and 1.06 million tons from packaging and
containers. This is much less than the rates of recycling for other materials. Recycling of
plastics boomed in the 1980s and early 1990s but become stagnant and declined in the
recent years. This drawn an immediate environmental concern [27].
The falling plastics recycling industry sees that the decreased collection and increasing
competition in Asia particularly in China to be a threat to the survival of the industry.
Plastic processors faced a high cost for synthesizing recycled plastics due to the healthy
overseas markets but they cannot increase their prices because they cannot afford to
compete with virgin resins [27].
10
Figure 2.3: Recycling rates of plastics versus the overall recycling rates for each category
[27]
11
Table 2.2: Recovery of Materials in US Municipal Solid Waste [27]
As it can be seen from the tables, 5.2% of the plastics in the US MSW are recovered
which corresponds to around 1.38 million tones. Only 14.3 percent of the total
polyethylene terephthalates (PET) are processed and recycled. High density polyethylene
(HDPE) follows at a recycling rate of 9.1 percent, low density and linear low density
polyethylenes (LDPE/LLDPE) at 2.4% and others at 6.9%. LDPE and LLDPE are the
most prevalent plastics in the MSW followed by HDPE. The recycling rates for all resins
declined from 2000 to 2003 except for HDPE which rose from 8.7% in 2000 to 9.1% in
2003 [27].
12
Figure 2.4: Amount of plastics recycled and recycling rates for US MSW [27]
13
2.4 Overview and history of biodegradable plastics
In the ancient history, plant waxes i.e., amber and shellac were used in the manufacture
of various materials. Although there has been a widespread use of polymers from natural
resources, it is until the 1800s where the first mass production of these materials
occurred. In 1869, John Wesley Hyatt, an American inventor, used a bioplastics made
from cellulose to coat billiards balls. However, he later found out that the material is
flammable which made it inappropriate for use since many people smoke during those
times. Still persistent and optimistic, he refined the material which led him to produce
celluloid. Celluloid has drawn attention most especially in the photography and film
industry. Currently, it is still widely used in the film industry as film reels [22].
In 1920’s Henry Ford conducted an experiment using soybean-based plastics for auto-
parts. Since soy beans are very versatile and are present in excess during his times, he
used it to produce soybean-based bioplastics and used it instead of wood and metal in the
fabrication of automobiles’ steering wheel rim. He even built the idea of making a car
made up of plastic. However, since war is imminent over the European nations, his idea
was not noticed by people of his times [22].
During the 1900s, the plastic industry prospered with the discovery that they can be made
form petroleum products. Plastic production then became heavily dependent on the fossil
fuels since it is cheaper as compared to using natural materials. With the break-out of the
World War II, there was an urgent need to use affordable yet effective materials for use
in their war supplies. Because of this, plastics came to play and became widely used in
almost all products at the end of the war [22].
In the early 1970s, research is focused on preventing plastics to degrade in order to avoid
loss in performance as the plastic aged, exposed to sunlight, or exposed to chemicals. As
a rule of thumb, total degradation of plastics is achieved when there is 90 percent loss in
the tensile strength of the plastic. Thus, non-biodegradable plastics were synthesized
together wit the use of additives to enhance their properties [27].
This shifted in the early 1980s when interest in biodegradation of plastics bolstered as
many sees it as a solution to the growing landfill crisis. Plastics can actually be degraded
by microorganisms but the process is very slow to be noticed and usually takes hundreds
of years. Plastics may also undergo other forms of degradation. One of the methods
employed aside from biodegradation in photodegradation that occurs upon exposure to
UV rays of the sun. Another degradation mechanism is the hydrolytic reaction. In this
case, water undergoes chemical reactions within the polymer matrix to reverse
14
polymerization. Some polymers need to be hydrolyzed first to reduce molecular weight
before being amenable to microbial degradation. For these reasons, it has been blamed
for consuming landfill spaces throughout the ages [27].
Another area of interest that emerged in the later years is the production of bio-based
plastics. These are plastics derived from renewable materials and feedstock rather from
the commercially produced petroleum-based plastics. They may or may not be
biodegradable or compostable. By the year 2005, the United States began to set
guidelines for designating items as bio-based [27].
Many view that the use of biodegradable plastics instead of the non-biodegradable ones is
a promising solution to alleviate this global concern. Biodegradable plastics can be
advantageous in the sense that it can increase soil fertility; it can eliminate the problem of
accumulation of bulk plastic wastes into the environment; and it can lower the cost of
maintenance of waste facilities such as sanitary landfills. Furthermore, scientists believe
that these biodegradable materials can be also be further processed and recycled into
useful oligomers and alike through the use of biotechnology [30].
However, because of its large cost of production and inferior qualities, these materials
cannot compete with conventional plastics that are available in the market. Only
cellulose-based bioplastics gained considerable interest and as of these times, it has been
used for food packaging since biodegradable materials are sought for packaging
15
especially in the food industry [31]. Many environment-enthusiasts and researchers
whose interest is in polymer chemistry generate huge improvements in the field – mostly,
however, in a laboratory or pilot scale.
For around 100 years the American Society for Testing of Materials (ASTM) provides
mechanisms where the industry, government and other institutions joined forces to
develop unity standards. Through the standards provided by ASTM, safe and effective
operations are ensured to be delivered to the public by governments, industries, and other
agencies [32].
The ASTM set standards with the introduction of degradable and recyclable plastics as a
response to the ever growing demand for sustainable development and increasing
environmental awareness. This standard also helps to overcome the confusion and
misunderstanding in many institutions. They also provides a level, well defined rules and
standards where companies introduced new degradable materials and aid the government
in monitoring and confirming the degradability claims of companies. Furthermore, it
informs the consumers on the environmental benefits upon using those biodegradable
materials [32].
The terms sustainable development and eco-efficient got the attention of many companies
now a days. They insist the importance of biodegradability and recyclability in designing
new products. In addition by those designs they have pursue it will help to enhance the
environmental problems and the improper disposal of waste [32].
The following are the ASTM definitions of different types of degradable plastics:
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Oxidatively-degradable plastic: Degradable plastics which undergo the
oxidative route in the course of their degradation are classified as oxidatively-
degradable plastics [33].
An emerging trend in the field of plastic technology is the use of plastics of renewable
and biodegradable origin, called as bioplastics. This has gained a wide interest among
researchers and most are optimistic that it can reduce the environmental impact of using
traditional plastics significantly on the basis of energy consumption during its production
and its superior properties comparable to plastics currently available in the market [33].
ASTM standards have played major role in helping to grow a new degradable plastic
industry. It also evolves such establishments or companies to commercialized
biodegradable plastic worldwide. This helps in defining and developing new materials
and emerging technologies and services as well as creating future technologies [33].
There are two phase in the degradation process; the first phase is the formulation
breaks the molecular chains so that the material can be no longer considered a
plastic but a material with an entirely different molecular structure. The second
phase is the material will be consumed by the bacteria and fungi and which will
access the carbon and hydrogen after the formulation has reduced its molecular
weight level. This process is what we call biodegradation; this will be continued
until the material has been biodegraded to nothing more than carbon dioxide,
water and humus, then the carbon dioxide will be absorbed by plants [34].
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The oxo-biodegraded plastics degrade, and then biodegrade on sea or at land, in
the light or in dark, in heat or cold in whatever timescale is needed, resulting in
no harmful residues [34].
There are no additional cost involved in the products made with this technology,
thus it can be made with the same machinery and workplace as the normal
commercial plastics, and with the same low cost polymer [34].
Some plastic in this type have high starch content and it was merely called that
this justifies the claim that they are made from renewable resources. However,
many of them contain up to 50% of synthetic plastic derived from oil. Modified
crops also were used in manufacturing hydro-biodegradable plastics [34].
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c.) Photo-degradable plastic
This type of bioplastic, react to ultra-violet light, but unless they are also oxo-
biodegradable they won’t degrade on sewer, landfill or any same environment
[34].
Biodegradable plastics can’t be distinguished from the conventional plastic such as PE,
PP or PS. They just look like plastic and possess comparable properties. On the other
hand when it comes to chemical aspect they possess technical property which
distinguishes them from certain parameters. Whether this parameter can be an advantage
or disadvantage still it depends on its application and also for the perspective of the
viewer [35].
Bioplastic also showed good printability, with no pre-treatment needed. There are types
that possesses glossiness (PLA), high transparency (PLA), good aroma, high oxygen
barrier properties (starchy products). Furthermore, by the impact of certain polymers to
the special sound of PLA film products, they cover a broad spectrum ranging from its
mechanical properties [35].
A certain biodegradable polymer has its particular feature, through its eponymous
characteristics. Thus, these materials are amenable to degradation employing
microorganisms or they can be stored in a composting plant where microbes degrade
them in about twelve weeks without producing toxic and hazardous effects. Bioplastics
are needed to be developed; it’s still having its infancy compared to other. Then standards
plastics also is continued in improving for years, and upon examining this almost every
products emerges as a true high-tech product [35].
The management of steadily increasing amounts of solid waste has become one of the
serious global problems nowadays. Since most polymers and polymer products have a
short shelf life (less than two years), a lot of them, particularly polyolefins are consumed
and just discarded into the environment after their utilization. Petroleum-based polymers
are designed and developed to be durable and withstand all forms of degradation. The use
of biodegradable plastics has been proposed to alleviate the impact of these non-
biodegradable petroleum-based polymers. They are designed with the increasing
environmental awareness to be easily degraded by the enzymatic action of
microorganisms. Several efforts have been made to accelerate the biodegradation of
polymeric materials by using natural polymers in many applications to replace synthetic
19
polymers and minimize environmental problems caused by these. The use of
biodegradable materials based on renewable resources would help in the reduction of
plastics both in the industrial and household wastes [26].
The blending of biodegradable polymers is one approach of reducing the overall cost of
the material and modifying the desired properties and degradation rates. Compared to
copolymerization method, blending may be a much easier and faster way to achieve the
desired properties. More importantly, through blending, other less expensive polymers
could be incorporated with one another. Miscibility of blends is one of the most
important factors affecting the final polymer properties. Some of the advantages of
producing miscible blends are: single phase morphology and reproducibility of the
mechanical properties [36].
Products that are made from bioplastics like bags have strong pulling strength, soft and
convenient. Injections made also from this can endure high temperature, more than 90
degrees. Under proper conditions this Bioplastics can degrade to the point where
microorganisms can metabolize them. Aside from that, the oil-based biodegradable
plastics that degraded may release previously stored carbon as carbon dioxide. However,
products made from Bioplastics absorb moisture easily making it inconvenient to store
because it is needed to be kept dry and protected from air and sunshine. The
biodegradation time was not controllable. Bioplastics can’t be recycled because starch-
based bioplastic products will be biodegraded by microbes after disposal [37].
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Table 2.5: Production of plastics in the United States [21]
21
2.9 Production of biodegradable plastics
Because polymeric materials are used in almost all areas of life, we are then living in the
polymer age. They are used in construction, clothing, health, food, transportation, and
almost every aspect of our lives. Without synthetic polymers, technological
advancements must have gone too slow. Production of plastics and other polymers
continue to prosper and continue to be utilized in almost all industries around the globe.
Shown in the previous pages are the production of plastics and rubbers in the United
States, Europe, and Japan. Note that the fabrication of synthetic polymers continues to
increase as years pass by [21].
A process where a solid plastic (also called a resin), usually in the form of beads or
pellets, is continuously fed to a heated chamber and carried along by a feed screw within
is called extrusion. The feed screw is driven via drive/motor and tight speed and torque
control is critical to product quality. As it is conveyed it is compressed, melted, and
forced out of the chamber at a steady rate through a die. The immediate cooling of the
melt results in re-solidification of that plastic into a continually drawn piece whose cross
section matches the die pattern. This die has been engineered and machined to ensure that
the melt flows in a precise desired shape [38].
Casting processes are characterized by the use of a liquid or power starting material that
is shaped without the application of significant pressure. The absence of pressure is such
an important characteristic of casting process that all process for forming processes that
do not require pressure are called considered as casting processes. Therefore there are
numerous different casting processes [38]. These are:
Mold casting
Slush casting (this processing technique is closely related to rotational molding)
Static powder casting (very similar to slush molding, except the mold is filled
with powder)
Cell casting (uses a mold that is defined by two parallel plates – used to produce
sheets)
Continuous casting (This is another method for making plastic sheets. This time
the resin is poured between two continuous belts separated by a gasket)
Film (or solvent) casting (used for producing plastic films) [39]
Melt-mixing
Casting is a solidification process. Because of this, the microstructure can be finely tuned,
such as grain structure, phase transformations and precipitation. Yet, defects such as
shrinkage porosity, cracks and segregation are also intimately linked to solidification.
These defects can lead to lower mechanical properties. A subsequent heat treatment is
often required to reduce residual stresses and optimize mechanical properties [40].
These biodegradable plastics were derived from plants are now developed around the
world. In fact continents like United States, Europe, and Asia, which from renewable
22
materials like corns, wheat and potato starches as substitute for the petroleum-based
plastics [41].
Table 2.6: Examples of products using plant based bioplastics and the companies that
produce them [41]
Nowadays, the public has become increasingly concerned about the impact of toxic
chemicals on humans and the environment. These chemicals have been found in
consumer products, the air and water, and increasingly in humans. Consequently,
industry and researchers are shifting towards bio-based products manufacturing and green
chemistry in an effort to produce better, safer products, while providing for a cleaner and
more sustainable world [73].
The term biodegradable means that a substance is able to broken down in simpler
substances by the activities of living organisms. Plants-based plastics are providing
alternatives methods aside to traditional plastics, especially for polyvinyl chloride (PVC)
that has been relying on extremely toxic additives and feedstock that really made a
hilarious impact to the environment and of course in our health through their production,
23
use and disposal. In fact, many of the chemicals that have been used in PVC production
may be the cause in many health problems such as cancer, birth defects, and reproductive
illnesses. On the other hand, bio-based plastics are generally derived from renewable
materials such as potato, corn, cassava and other starchy foods crops [41].
The production of bio-based plastics use fewer fossil fuels compared to the petroleum-
based plastics. Plants- based plastic is also compostable, they can be put on a composted
large scale facility, where it will degrade with a given days, within 45 days. In contrast,
conventional or traditional plastics, can take 100 years to start their degradation process
[41].
Thermoplastics are polymers that can flow when heated above a melting temperature.
Starch is a neutral polymer with complex levels of structure that impinge upon
thermoplastic deformation. It is a semi-crystalline polymer that does not melt in the
traditional sense to form a liquid. Melting occurs in the presence of moderate 10-30%
water content. Starch crystals contain 9-10% bound water. Starches are applicable to
thermoplastic processing, unlike other polysaccharides such as cellulose and various
gums. Cellulose is a structural polymer forming cell walls in plants and it cannot be
melted at moderate temperatures [48].
Starch is a biopolymer that is biodegradable suitable for green packaging materials. It has
a unique microstructure phase transitions and rheological properties. Starch consists of
amylose and amylopectin – both of which are polymers. Starch is economically
competitive with polymers derived from petroleum for manufacture of packaging
materials [48].
Thermoplastic starch has attracted much attention due to its thermoplastic-like process
ability with temperature and shear. The structures being disrupted are more complex than
those synthetic thermoplastic. The aim of this review is to provide framework for the
transition from native starch from its primary, secondary and tertiary molecular structure
granules to thermoplastic starch with its properties that parallel and contrast with
synthesis thermoplastics [48].
24
days it will gradually become opalescent through milky. Because of the hydrogen bonds
within and between starch molecules the starch solutions are not stable [48].
Cassava starch has been successfully expanded under extrusion conditions. Due to low
density, a bit modification is needed so that its moisture content is increased. Cassava
starch can be used as raw material for plate expanded or baking products, can be also
expanded in moulds, at 200-240°C. 10% additives including calcium carbonate, agar or
emulsifier are needed to amend the properties. The biodegradable polymers are in this
group produced by fermentation. Merging of polymers with starch under controlled
conditions leads to co-polymerization resulting in high molecular polymers with
thermoplastic properties [49].
Gelatinisation of cassava and potato starches at low water levels in the presence of
sodium chloride caused a diminish in gelatinisation temperature. The retro gradation in
these high amylopectin molecules is due to reforming of the amylopectin double helix
[48].
Water is the main plasticiser. Plasticiser activity has been related to water sorption
isotherms that give molar sorption enthalpies of starch plasticizer systems. Plasticisers for
starch functions the same as plasticiser in synthetic polymers. Fatty acids such as stearic
acid are mostly hydrophobic. Hydrophobic chains preferentially reside inside of starch
helical coils forming a complex. Extrusion caused fragmentation of the starch that was
detected by size exclusion chromatography and cross-polarisation spectroscopy [48].
Before, fields of wheat and rows of potatoes were seldom destined for anything more
than a rumbling tummy. But bio-products have come a long way since people have been
aware about the impact of the traditional plastics in the environment. Aside from its
environmental help, this biodegradable potato starch based plastics are finding new life as
water bottles, thin packing film, bags, dinnerware, tableware, drink ware, knife and fork,
chopsticks, toothpicks, combs, pots, cake containers, golf tees, clothes hangers, toys,
other daily use articles, packing materials and some gadgets like laptop, cell phones and
the like [74].
In some countries, particularly in North America, corn is the preferred source for starches
used in bioplastics, but researchers with the biopotato Network believe that, due to the
plentiful nature of potatoes – which grow in every Canadian province and contribute
nearly $6 billion to the national economy – the starch-heavy crop makes an ideal
substitute. Dr.Qiang Liu, a food scientist at the Guelph Food Research Centre in Guelph,
Ontario said that the potato starch is converted into a plastic-like resin that can be heated
and shaped into a variety of products through an injection molding process. The resulting
material is completely degradable by composting and is an excellent material for food
packaging because it allows the food to breathe [74].
The potato starch by-product is already used by the food processing industry as a general
thickener, binder, texturizer, and anti-caking or gelatinization agent. It’s also used in
yeast filtration, and as additives in the cosmetics and pharmaceutical industries. All of
25
these characteristics, researchers believe, add up to make it an ideal component for a new
generation of bioplastics. However, scientists believe that further research with potato
starch can improve bioplastics, help broaden their applications, and create bioplastics
with greater water resistance, stronger mechanical properties and greater processability
[74].
Based on the researches they have conducted scientist confirmed that bio-based plastics
benefit both the economy & environment. It strengthen the economy, there are new
manufacturing jobs that will be required to produce bio-based plastics with additional
spin-off jobs for processing. It also creates market advantage, businesses that use
packaging and products from bio-based plastics can improve sales to the growing
environmentally conscious market. Then it promotes sustainable agriculture by producing
PLA from potatoes will expand markets, reduce pesticide use and improve soil fertility
through better rotation. It also protects environmental public health, bio-based plastics
avoid the health-threatening toxic chemical additives and by-products associated with
existing petrochemical derived plastics and most importantly it reduces waste, products
made from bio-based plastics can be composted at the end of their useful life, conserving
landfill space. Using waste potatoes as the feedstock to make PLA will avoid costly
disposal problems [74].
Sarka et. al. used wheat B-starch to produce a biodegradable plastic material. They
prepared starch acetate with a degree of substitution of 1.5-2.3. Acetylation of starch
considerably reduced the absorption of water of PCL/starch blends. Acetylation is
continued in a glass reactor which is submerged in an oil bath. The glass reactor has a
rotating paddle heated to 128°C where the acetic anhydride was placed to initiate
acetylation.170 grams of starch was added and is continuously mixed for 5 minutes; the
temperature of the oil bath being increased to 133-138 °C. 50 % NaOH solution was
added while mixing. When it is already cooled, the reaction blend was mixed with cold
distilled water and reduced into smaller particles using a liquidizer. pH is adjusted to 3.3
to 4.5 before drying at 43-44 °C. The starch is then reduced into fine particles using a
standard mill of 100-300 µm. Poly-(ε-caprolactone) (PCL) melts were mixed with each
of the starch fillers in 10, 20, and 40 wt % in the Brabender Plasti-Corder’s chamber
using 110 °C and 60 rpm within 8 minutes. After that, the material is removed and was
immediately compression-molded forming a 5 mm thick film [68].
In another study, Domenek et al. cast wheat gluten films. First step is the preparation of
the film forming solution. It was prepared with the use of wheat gluten and uses a
concentration of 0.2 gmL-1 in 1% acetic acid, 0.0004 gmL -1 Na2SO4, and 0.04 gmL-1
glycerol. Using a homogenizer all of the said components were mixed continuously.
After that, it was allowed to settle so that separation of the foam formed is possible. By a
thin-layer applicator, the film was extended onto a Plexiglas surface and is allowed to dry
at 60 °C for about half an hour in an oven which is ventilated. The next step consist of
making the hot-molded wheat gluten films composed of wheat gluten and glycerol (35
w/w %). They were mixed in a mortar and left for 20 minutes. In a pressing press, this
blend was then hot-molded using a pressure of 150 bars to become wheat gluten powder.
26
This powder is mixed with glycerol in a two-blade counter rotating measuring mixer to
produce mixed gluten blends [69].
Narayan et.al., studied the thermal properties and morphology of biodegradable poly-
(lactic acid) and starch blends compatibilized using maleic anhydride and maleated
thermoplastic starch. Compatibilizers are used to improve the interfacial adhesion in
preparing the plastic blends. They are prepared by varying the amounts of starch and
PLA and extruding them to produce the plastic sheets. Characterization was done using
differential scanning calorimetry to determine the thermal properties, scanning electron
microscopy to determine its surface morphology, gel permeation chromatography to
determine the molecular weight and molecular weight distribution within the blend, and
FTIR to investigate the infrared spectra of the blends. Biodegradability studies were
conducted in a controlled and reproducible environment [71].
It was found that the starch content of the blends do not affect the glass transition
temperature, melting point, and cold crystallization temperature of the blends. There is a
slight increase in heat of fusion values as the amount of starch is increased. Crystallinity
has been observed to increase drastically which accordingly, might be due to the
breakage of PLA chains and the presence of starch acts as a nucleating agent for the
formation of crystalline structure of the polymeric films. The increased crystallinity of
the samples is also attributed to the decrease in molecular weights as more starch is
loaded. The blends produced yielded poorer mechanical properties than that of pure PLA
due to the increase in polydispersity caused by the moisture content in starch which
hydrolyzes the PLA causing chain degradation [71].
Tg and Tc slightly decreased when using MATPS compatibilized blends which might be
caused by the migration of the plasticizer in the thermoplastic starch. Crystallinity is
higher than those of pure blend but lower that MA-compatibilized blends. Higher T m is
attributed to the increase in nucleation (starch and MATPS) while lower peaks are a
result of the plasticizing effect brought by the migration of the plasticizer in the MATPS
[71].
The morphology of the blends is related to its mechanical properties. The presence of
clear edges and cavities within the pure matrix showed the incompatibility of starch and
PLA which results to poor mechanical properties. Using MA as compatibilizer, these
edges and cavities were greatly reduced. The use of MATPS showed improved interfacial
adhesion. However, this is not yet sufficient as a compatibilizer because the
morphologies revealed the presence of voids, cavities, edges, and boundaries. MATPS
27
cannot penetrate the matrix well unlike in MA due to its high viscosity. Because of these,
MATPS is deemed ineffective as far as the purpose of compatibilizing PLA and starch
blends are concerned [71].
Various industrial processing techniques have been used to prepare starch plastics,
including kneading, extrusion, compression molding and injection molding [92].
Processing temperatures are in the range of 100-2000C although care has to be taken
at temperature above 175oC because of starch molecular breakdown [96-98].Most
research has been focused on water and glycerol as the most important additives. As melt
flow accelerators lection, glycerin monostearate and calcium stearate have been studied
[7]. Several native starches have been processed such as: wheat, rice, corn, waxy maize
starch, high amylose corn starch and potato starch [92].
The dimensions of molded objects from hydrophilic polymers such as starch depend on
their water content [95]. If precise dimensions are required, processing should be
carried out so that products are formed at approximately the equilibrium in-use water
content [73]. For potato starch, for example, this means water contents of around 14% for
use under ambient conditions (50%relative humidity, 20-25oC [95]. If higher
water contents are used in processing, distortion and shrinkage will occur as the
equilibrium water content is naturally achieved after processing. In addition, higher water
content can induce more hydrolytic degradation of the starch chains during processing
and also gelatinization rather than melt formation. If lower water contents are
used, thermal degradation can occur during processing, as well as swelling after
processing [73].
Another way of making plastic also was discovered then, which involves getting bacteria
granules of plastic called polyhydroxyalkanoate (PHA) inside their cells. These bacteria
are simple grown in culture in bioreactors and the plastic has been manufactured. Some
scientist also tries to take genes from this kind of bacteria and transferred it into corn
plants, which they manufacture plastics using their own cells. Unfortunately like PLA,
PHA failed also to fit the satisfaction of the consumers due to its high cost production
[41].
Under good conditions the polymer can amount to more than 50%-80% of cell dry
weight. The storage product is found as granular inclusion bodies within the cytoplasm.
28
However, many of these compounds represent in relatively small amounts or other
properties are unsuitable as potential bioplastics. Species synthesizing
polyhydroxybutyric acid and polyhydroxyvalerate acid are some archae including
Haloferax mediterranea, these halophilic bacteria might present advantages for
production. As their culture requirements of salinity and relatively high temperature
provide little opportunity for growth of contaminants. Simultaneous production of large
amounts of exopolysaccharide diverts substrate to alternative products and makes
recovery of polyhydroxybutyric acid difficult in species like Azotobacter vinelandii.
Development of high-yielding mutant strains resulted in conversion rates of 65% for
polyhydroxybutyric acid and eventually polyhydroxyalkanoate yields of 71% dry weight
[70].
29
PHAs are grouped into two – the small chain length PHA that consists of PHAs with C3-
C5 and the medium chain length PHA with C6-C14. The grouping is based on the
substrate specificity of its synthesis. All monomeric units of MCL PHAs are oxidized in
the third carbon other than a few exceptional cases. For SCL PHAs, the monomeric units
are oxidized other that the third carbon. Various functional groups can be incorporated
into the PHA structure such as aromatics, alkyls, halogens, and cyano groups which make
it useful in producing various polymers with different properties based on the functional
groups used [72].
The biosynthesis of PHAs is much simpler than the formation of most polysaccharides, as
only 3 enzymes are normally involved β-thioketolase, acetoacetyl coenzyme A reductase
and polyhydroxybutyric synthase. The genes involved have been studied in formerly
designated Alcaligenes eutrophus called Ralstonia eutropha and Pseudomonas
oleovorans as well as other species. Genetic control of the process is also relatively
simple; the 3 genes involved are arranged in an operon to form a sequence of 3 open
reading frames and these can be transferred easily to other bacterial species and to yield
transgenic plant species. An alternative pathway found in Rhodospirillum rubrum was
outlined by Steinbuchel and Fuchtenbusch. The PHA synthase gene products from
different bacteria have been grouped into 3 classes altering in their essential proteins and
their substrate specificity [70].
Sutherland said that previous studies using recombinant strains of E.coli into which the
PHA biosynthesis genes from R. eutropha had been inserted, conceded PHB with mass of
3-11 x 106 Daltons. The mechanical properties of films from this product were improved
by stretching over 400%. The enzymes for PHB synthesis are normally essential and
regulation of synthesis appears to occur at the enzyme level [70].
30
Figure 2.7: Biosynthetic pathway of P(HB-HV) and PHB in Alcaligenes eutrophus [72]
Ojumu et. al. presented the figure above which shows the biosynthetic pathway of P(HB-
HV) and PHB in the bacterium Alcaligenes eutrophus. PHA is synthesized through the
action of three enzymes. The first enzyme promotes the condensation of the two
acetylCoA moieties in a reversible manner which forms acetoacetyl-CoA via the
ketothiolase pathway. Acetoacetyl-CoA reductase reduces the acetoacetyl-CoA to R(-)-3-
hydroxybutynyl-CoA followed by polymerization to R(-)-3-hydroxybutyryl-CoA which
then turns into PHB. A.eutrophus can accumulate PHB up to 80% of its dry weight and
should be cultivated in an excess glucose medium containing limited nitrogen and
phosphate source. The addition of propionic acid or valeric acid into the culture media
causes the formation of the 3-hydroxybutyrate and a 3-hydroxyvalerate which are
copolymers. The biosynthetic pathway for that is also shown [72].
The product Biopol has been used to form biodegradable plastic bottles, together with
golf tees, disposable razors and other products. The highly cost of the product in relation
to chemically synthesized plastics has led to closure of production. Alternative
applications which have been proposed are as water impermeable coatings for
biodegradable packaging as temporary plates and pegs in repair of bone injuries [70].
31
According to Sutherland large numbers of microbial polysaccharides are potentially
available, there are relatively few have been commercially developed. The reasons are the
microbial source may be pathogenic, production costs may be very high, product quality
may be difficult to maintain and to guarantee, the product may not achieve regulatory
acceptability or there is no market niche. Despite such problems, several EPS recognized
products of biotechnology [70].
The glass transition temperature (Tg) of the dry starch to be in the range of 240-250 oC. It
is estimated the Tg of the dry starch to be in the range of 240-250 oC [75]. Native starch is
a non-plasticized material because of the intra- and intermolecular hydrogen bonds
between hydroxyl groups of starch molecules. During the thermoplastic process, in the
presence of plasticizer, a semi crystalline granule of starch is transformed into a
homogenous material with hydrogen-bond cleavage between starch molecules, leading to
loss crystallinity [76].
The physical property of thermoplastic starch is greatly influenced by the amount of
plasticizer present. In most literature for thermoplastic starch are greatly influenced by
the amount of plastizicer present. In most literature for thermoplastic starch, polyols were
usually used as plasticizers, of which glycerol is the major one. The effect of
plastification level on the glass transition of thermo plastic starch is presented in the table
below. [77]
The mechanical properties of a low and a high molecular mass thermoplastic starch were
monitored at water contents in the range of 5-30% (w/w). The stress-strain properties of
32
the materials were evaluated [77]. Above certain glycerol contents, dependent on starch
source, a lower glass transition temperature Tgr esulted in decreased modulus and tensile
strengths and increased elongations. For potato and other starchy crops (wheat, and waxy
maize starch) the Tg was 75oC, 143oC, 152oC and 158oC respectively [77].
The effect of the type and amount of plasticizer on the mechanical, thermal and water-
absorption properties of melt-processed starch has also been investigated and reported
elsewhere [78]. It was reported that, in general, monohydroxyl alcohols and high
molecular weight glycols failed to plasticize starch, whereas shorter glycols were
effective [77].
The mechanical properties of starch-based plastics of native corn, potato, waxy corn and
wheat starch, produced by compression moulding of native starch and glycerol in the
weight ratio 0 to 3 were strongly dependent on the water content and starch source [79].
The mechanical and melt flow properties of two thermoplastic potato starch materials
with different amylose contents were evaluated [86] after conditioning at 53% relative
humidity (RH) and 230C the glycerol-plasticized sheets with a high amylose
content (HAP) were stronger and stiffer than the normal thermoplastic starch with an
amylose content typical for common potato starch. The tensile modulus at 53% RH was
about 160 Mpa for the high amylose material and about 120 Mpa for the plasticized
NPS (native potato starch). The strain at break was about50% for both materials [77].
The effect of various cross linked or hydrophobic additives (aldehydes, plant tannins,
alcohols and fatty acids) on mechanical properties and water resistance of thermo-
molded films made from a sunflower protein isolate plasticized with glycerol were
studied [96]. The use of octanoic acid resulted in high tensile strength (7 MPa), whereas
the use of octanol resulted in a great increase in tensile elongation (54%) [97]. Several
polyalcohols (glycerol, ethylene glycol,diethylene glycol, triethylene glycol and
propylene glycol) were tested as sunflower proteins plasticizers [98]. However, these
films were only moderately resistant to water [97]. Glycerol and triethylene glycol were
proposed as the most suitable plasticizers for sunflower proteins [97]. With a worldwide
production estimated at about 33 million metric tons, cottonseed is the most
important source of plant proteins after soybeans [99]. The viscoelastic behavior of
cotton seed protein isolate, plasticized with glycerol, was characterized in order to
determine the temperature range within which cottonseed protein-based materials can be
formed by extrusion or thermo-molding [99]. The results indicated that cottonseed
proteins are thermoplastics with a T g ranging from 80 to 200 oCwhen the glycerol content
varies from 0% to 40% (w/w, dry basis) [97].
33
2.13 Bioplastics derived from protein – rich meals
Early research on soy protein-based plastics was conducted in the 1940s [1]. At that time,
soy protein was mainly used as a filler or extender to decrease the cost of petroleum-
based plastics [109].
Soy protein has been widely used in foods to provide flavour, texture, and other
functional properties [108]. Soy protein also has been used in many industrial products,
such as adhesives for wood and paper, emulsifiers in colloidal rubber products, and
binders in coatings and paints [117–121]. Soy protein can also be extrusion-blown or cast
into films. Soy protein-based films have been shown to be good oxygen barriers and UV-
blockers that are useful as packaging materials [109]. With proper processing, soy protein
can also be made into foam products [109]. With its biodegradable, nonflammable, and
no electrostatic properties, soy protein-based plastics provide unique and attractive
features [109].
The predominant industrial application of soy protein is for the coating paper and paper
products since soy protein has unusual adhesive properties [109]. Recent research work
has been aimed for the development of soy protein - based biodegradable plastics and the
experimental results has shown that it can be molded into different items such as
disposable containers, utensils, toys, and sporting goods and still have desirable
properties[109].
34
Soy protein plastics are rigid, but tend to be brittle and water sensitive [104, 105]. Water
resistance of soybean protein-based plastics can be improved by chemical modification of
the proteins, or blending, e.g., with polyesters [101]. The flexibility of soybean protein-
based plastics can be improved by adding various plasticizers [104, 105]. It was reported
that depending on the moisture and glycerol contents, soy protein plastic sheets displayed
properties from rigid to soft [100].
The glass transition temperature of the sheets is also investigates and varied from ca. -
7 to 50oC with moisture contents ranging from 26 to 2.8% and 30 parts of glycerol.
Among proteins, wheat gluten with its unique viscoelastic properties and its water
insolubility is of particular interest for the preparation of biodegradable polymeric
materials [97].
Thermal properties of corn gluten meal and its proteic components were investigated by
Di Giola et al. [104]. Processing, and modification routes to produce and improve
properties of biodegradable plastics from soy isolate were studied [105]. Soy isolates,
acid-treated and cross linked soy were subsequently compounded, extruded, and injection
moulded. The obtained plastics were rigid and brittle with stiffness
ranging from 1436MPa for soy, to 1229MPa for glyoxal cross linked soy, up to 2698
MPa for heat-treated soy [97].
Protein-based plastics have been used, alone or in mixtures, to obtain edible films and
coatings. They have been used to protect pharmaceuticals and to improve the shelf life of
food products. Some commercialization of protein films has been realized in collagen
sausage casing, gelatin pharmaceutical capsules and corn zein protective coatings for nut
meats and candies [106]. Soybean protein can be used to produce a wide variety of non-
food products, including plastic films, building composites, insulating foams, plywood
adhesives, and other wood bonding agents [107].
The thermoplasticity and good-film forming properties of wheat gluten may be used to
pro-duce natural adhesives [108]. Gluten's adhesive properties make it useful in pressure-
sensitive medical bandages and adhesive tapes. Gluten has the ability to provide edible
protection for food or food components from interactions with the environment as they
35
can serve as barriers to mass transfer (e.g. oxygen, water vapor, moisture, aroma, lipids)
[108].
There are two important processes are used to make protein-based films: a wet process
based on dispersion or solubilization of proteins, and a dry process based on
thermoplastic properties of proteins under low water conditions [55]. Effects of molding
temperature and pressure on properties on soy protein polymers were evaluated [108].
The maximum stress of 42.9 MPa and maximum strain of 4.61% of the specimen were
obtained when soy protein isolate was molded at 150oC Native soy protein was converted
into a thermoplastic material in a co-rotating twin-screw extruder in the presence of
35%water and 10% glycerol (w/w relative to the protein amount) [105]. The extrusion
was carried out at temperatures ranging from 70 to 80 oC (temperature necessary for the
splitting of the disulphide bridges and loss of the tertiary structure of the protein).
Glycerol plasticized wheat gluten sheet was produced by extrusion at the barrel and die
set temperature of 130oC [108].
The morphology of polymers greatly affects their rates of biodegradation. The degree of
crystallinity is a crucial factor affecting biodegradability, since enzymes mainly attack the
amorphous domains of a polymer. The molecules in the amorphous region are loosely
packed, and thus make it more susceptible to degradation. The crystalline part of the
polymers is more resistant than the amorphous region [30].
The aliphatic polyesters and polycarbonate are two typical plastic polymers that show
high potential for use as biodegradable plastics, owing to their awareness to lipolytic
36
enzymes and microbial degradation. Compared with aliphatic polyesters and
polycarbonates, aliphatic polyurethane and polyamides (nylon) have higher Tm values.
The high Tm value of polyurethane and polyamide (nylon) are caused by the large ΔH
value due to the presence of hydrogen bonds among polymer chains based on the
urethane bond and the amide bond [30].
Biodegradable plastic is an innovative means of solving the plastic disposal problem from
the standpoint of development of new materials. In general, plastics are water-insoluble,
thermo-elastic polymeric materials. Biodegradability of plastics is affected by both their
chemical and physical properties. The biodegradation mechanisms of plastics as shown in
this review can be applied to biomass that is composed of polymeric materials (i.e.,
cellulose, hemicellulose, lignin, chitin, silk fibroin, etc.) [30].
Lipolytic enzymes such as lipase and esterase can hydrolyze not only fatty acid esters and
triglycerides, but also aliphatic polyesters. Lipolytic enzyme has an important role in the
degradation of natural aliphatic polyesters such as cutin, suberin and esteroid in the
natural environment and animal digestive tract [30].
Less attention has been paid to the degradation of biodegradable polymers in landfill
sites. Ishigaki et.al. suggested that appropriate management of landfill sites might lead to
the stimulation of polymer-degrading microorganisms. They studied the degradability of
polyhydroxyvalerate, polycaprolactone, polyvinyl alcohol, and cellulose acetate within
landfill model reactors and the subsequent weight loss and surface changes attributed to
biodegradation. Different biodegradation behaviors were observed for each individual
biodegradable plastic in aerated and unaerated landfill models. Aeration of landfills can
stimulate aerobic polymer-degrading microorganisms. Volume reduction due to film
fragmentation was observed for polyhydroxyvalerate at aerated conditions. However, for
plastics derived from natural polymers, stimulation of polymer-degrading
microorganisms is insufficient; augmentation of selective microbes and/or enzymes
might be necessary to obtain film fragmentation [42].
37
Degradation is a very important process in the breakdown of polymeric substrates and
organic wastes into less complex substances. In this process, the organic wastes are
converted to humic substances which are valuable and can be used as high quality
fertilizer. Composting is an environment-friendly municipal solid waste disposal
technology since it reduces waste stream to landfills, saves energy, and allows organic
compounds to be utilized by the agricultural industry [43].
Composting kinetics of the decomposition of organic wastes can be used to estimate the
C mineralization of various organic materials. The degradation curve of the evolution of
carbon dioxide consists of the lag phase, growth phase, and stationary phase. The first-
stage involves the mineralization of carbon to carbon dioxide. Studies revealed that
degradation reactions are first-order in nature [43].
Sarka et. al. states that biodegradation of PCL-starch begins with the starch consumption
and increases with the content in natural filler. The sample thickness was carefully
monitored to attain accurate measurements of surface erosions. Also, with this the carbon
dioxide produced from the biodegradation of material can be measured. The wheat starch
plastic blend results during test can be degraded completely within 8 weeks [68]. In a
study by Domenek et. al., when the wheat gluten is buried it degraded within 50 days
completely [69].
Narayan et.al. also conducted biodegradation studies calibrated by using cellulose which
achieves 91% degradation after 42 days. A time lag of 13 days is noted for the
degradation of pure PLA. The hydrolysis of the polymer into its oligomers occurs during
this stage. Degradation occurs at a maximum after 20-25 days and then it proceeds at
almost constant rate thereafter. The time lag decreases as starch content is increased
which means that it has enhanced biodegradability. The addition of MA as a
compatibilizer accelerated the biodegradability of the blends. However, those with higher
crystallinity degrade a little bit slower than those with lower crystallinity values. MA
accelerates chain scission in the presence of large amounts of water in the compost via
hydrolysis reactions and by back biting which results in an enhanced biodegradability of
the polymer blends. These were confirmed by GPC data. No evidence of MA reaction
with PLA occurred as the IR spectra revealed. MA is present as is as shown by the peaks
in C=O region of the spectra [71].
38
Composting can be an alternative to the use of landfills for solid waste disposals. The use
of biodegradable plastics permits disposal via composting thereby reducing the problems
and resolving the issues behind landfilling. Their use can greatly reduce their longevity in
the environment after disposal. Unfortunately, some compostable plastics are resistant to
water which poses another problem when these materials reach bodies of water. Besides,
these materials require the high temperatures in the landfill to cause hydrolysis and
initiate degradation [27].
Composting is limited to yard waste in the United States unlike in Canada and European
countries where composting campaign as an alternative to landfilling reached full
maturity. The first composting plants in Europe date back in the early 1970s. Fees are
being imposed on the use of non-biodegradable plastics to ensure recycling. As a result,
bioplastic use has become more prevalent in Europe than in the US. Europe is solid in its
goal to achieve 75 percent reduction of the use of landfills as a means of municipal solid
waste disposal [27].
Four companies, namely Novamont, Rodenburg Biopolymers, BASF, and Cargill Dow,
which represent over 90 percent of the European market for biodegradable plastics,
signed a ten-year Environmental Agreement with the European Union last November
2004 committing themselves in the use of biodegradable and compostable polymers for
the synthesis of packaging materials. It is managed by the Biodegradable Polymers
Association & Working Groups (IBAW). The agreement includes a labeling plan to
facilitate waste handling and a certification plan for quality control. By the mid-2005, 38
percent of all biodegradable plastics were consumed by supermarket carrier bags [27].
Different organizations around the globe issued standards to determine and assess the
biodegradability or compostability of a particular polymer. EN 13432 tackles the
methodology for evaluating compostability of a polymer. “Compostable Logo” is
awarded to materials that are certified by the Biodegradable Products Institute and the US
Composting Council in United States. For Japan, testing and certification of
biodegradable plastics is managed by the Biodegradable Plastics Society. Another
common procedure is by the American Society of Testing and Materials’ ASTM D6400
which provides the standard specifications for compostable plastics [27].
Nowadays, there are new sectors that was growing outside biodegradability, they was
using improved technical performances versus traditional materials. It has been estimated
that the market of starch-based plastics in 2001 is ranging about 30000 ton/year, with a
strong incidence about packaging and films particularly in soluble foams [33].
Bioplastics and starch-based plastics are being currently used in the industry where
biodegradability is a requirement like in the manufacture of composting bags and sacks,
packaging in fast food service like cups, spoons, forks, straws and plates, in household
materials (plates, glass, ladles, containers and etc.), packaging (food containers, film
wrapping and etc.) agriculture (pots, plants labels and etc.) and in hygiene (soap and
perfume containers, diaper back sheets, cotton swabs ) [33].
39
2.16 Starch
40
Figure 2.8: Structure of Starch [45]
2.17 Starch safety
41
Starch exists as an odorless white amorphous powder in nature and is a non-toxic
and not hazardous material. It is not flammable, hence poses no flammability hazards. It
is soluble in hot water and melts at 256° to 258°C. It can be stored indefinitely as long as
it is held dry. Toxicological studies showed that this is not a toxic substance. No chronic
effects and organ failures are reported from ingestion and contact with starch both in
animals and human beings. This is a potential allergen to people allergic to dusts and
powders. No regulation has been imposed regarding its transport, purchase, and storage
[45].
2.18 Banana
Banana (Musa acuminata) is one of the most common and widely grown fruit crops in
the Philippines. It is also one of the country’s major dollar earners, and banana has
consistently ranked next to coconut oil. In 1993, banana topped local production of other
major fruits such as pineapple and mango [36].
Banana belongs to the genus Musa, order Zingiberales, family Musaceae. The genus
Musa contains 30-40 species, with all wild species being diploids (2n=2x= 14, 18, 20, 22)
and native to South East Asia. It is grouped into 5 sections. These 5 sections are:
Callimusa (chromosome number 10, 2n=20), Australimusa (chromosome number 10,
2n=20), Eumusa (chromosome number 11, 2n=22), Rhodochlamys (chromosome number
11, 2n=22) and Incertae sed. [42, 50, 51].
Banana is an inexpensive fruit rich in starch content (14-23% on a fresh basis and 62% on
a dry basis) [52]. The pulp: peel ratio of banana increases during the development of the
fruit, from 1:1 to 4:1, depending on the variety and maturity at harvest. During the
storage ripening the starch declines from 20–23 to 1-2% but starch amount can be as high
as 11% depending on variety and at the same time the soluble sugar increases from less
than 1 to 20%. When the mature fruit ripens, the pulp: peel ratio increases, partly as a
result of water movement from the peel to the pulp associated with an increase of osmotic
pressure in the pulp caused by the hydrolysis of starch [53, 54].
Banana is considered as the fourth largest horticultural crop in the world with an
estimated production of 64.6 million metric tons as of 2000. It is widely grown in
countries in Africa, Asia, Europe, Oceania, Latin America, and the Caribbean (ISAAA,
2001). India is reported as the largest producer of banana, accounting for about 21% of
total world production in 2000. In the Philippines, banana is currently grown in a total
area of about 350,000 ha, which is an estimated 3% of the country’s total arable land
[55].
Table 2.9: Annual production of bananas in different countries [55]
42
Country Production (1000t ) Percent Share
World 58,618 100.00
India 10,200 17.40
Ecuador 7,494 12.78
Brazil 5,551 9.47
Philippines 3,550 6.06
China 3,241 5.53
Indonesia 3,012 5.14
Costa Rica 2,200 3.75
Colombia 2,200 3.75
Mexico 2,041 3.48
Thailand 1,700 2.90
Others 17,429 29.73
Banana has variety uses. The most common is eating it as fresh fruit after a meal. The
ripe fruit is pureed, candied, and preserved in various forms when not eaten fresh. Its
extract is used in the manufacture of catsup, vinegar, and wine. The unripe fruit is powder
ed and chipped. Among the more popular varieties are the Bungulan (fruit is round, very
sweet, seedless, and easily rots; has thick peel that is green when unripe and remains
green when ripe; flesh is white when ripe; gestation period is 12 months), Lacatan
(grows to a height of five to nine feet; fruit is round, seedless; has thick peel that is green
when unripe ,yellow-orange when ripe; gestation period is 14 to 15 months.), Latundan
(grows from six to 10 feet tall: fruit is round; has thin peel that is green when unripe,
yellow when ripe; flesh is white when ripe; gestation period is 12 months)., Saba (grows
to as tall as 20 feet; fruit is angular; has thick peel that is green when unripe, yellow when
ripe; flesh is white when ripe; gestation period is 15 to 16 months)., and Cavendish
(reaches five to 10 feet high; fruit is bigger than Bungulan; peel is green when unripe,
yellow when ripe; flesh is yellow when ripe; export quality; gestation period is six to
eight months) [36].
43
44
Table 2.11: Ultimate analysis of Musa acuminata [36]
45
2.19 Chitin and chitosan
Chitin has been namedropped as the second most abundant polysaccharide that occurs in
nature, cellulose being the most abundant. It is composed of β-(1—4)-linked 2-
acetamido-2-deoxy- β-D-glucose (N-acetylglucosamine). Although it does not occur in
cellulose-producing organisms, it is commonly termed as a cellulose-derivative. It is
structurally similar to cellulose with the exception that it contains acetamide groups (-
NHCOCH3) at C-2 positions [37].
Chitin is produced annually in almost equal amounts with cellulose. Through the years,
chitin received immense attention since it is an under-utilized natural resource that poses
a wide variety of applications in a great number of fields such as in medicine,
biotechnology, and many more. This nitrogenous polysaccharide naturally occurs as a
white, hard, and inelastic material commonly seen in the exoskeletons and internal
structures of invertebrates [56].
46
Figure 2.10: Structure of partially deacetylated chitosan [57]
It is reported as a potent material for use in the food industry as packaging materials
because of its excellent film-forming properties. Chitosan contains reactive amino and
hydroxyl groups which makes it to be utilized as an excellent intra-molecular and inter-
molecular cross-linker in the preparation of polymer matrices for various purposes such
as in the production of starch-based plastics [57].
Because α-chitin is the most common existing polymorph of chitin, it is the most widely
studied structure for utilization in different applications. Consequently, β-chitin and γ-
chitin are the less studied forms. γ-chitin is believed to be only a distorted version of the
first two polymorphs and is claimed to be a false polymorphic form of chitin [58].
The chains of α-chitin molecules are arranged in the form of sheets or stacks in which the
chains in one sheet have a similar sense and the sheets are arranged parallel to each other.
In the case of β-chitin, the adjacent sheets face the same direction along a similar axis, the
sheets are arranged in a parallel order but the sheets are alternately reversing its direction.
Lastly, for γ-chitin, the sheets are arranged in such a way that the third sheet is having the
opposite direction as compared to the preceding two more sheets [58].
Figure 2.11: Different polymorphic configurations of various forms of chitin (a) α-chitin,
(b) β-chitin, and (c) γ-chitin [58]
On average, about sixty to eighty thousand tons of chitinous waste are available in India
alone. Proper utilization of these resources can bring economic and academic prosperity
47
of a nation. Currently, chitin and its derivatives, primarily chitosan are being
commercially synthesized in various countries such as India, Japan, USA, Poland,
Norway, and Australia [56].
Chitin is present in a wide variety of taxonomic groups such as crustaceans, insects, and
fungi. However, commercial production of chitin is from marine crustaceans due to the
large availability of wastes from food processing utilizing crustaceans [58].
Crustacean shells are mainly comprised of calcium carbonate which on average, ranges
from thirty to fifty percent. Chitin is usually present in the range of twenty to thirty
percent while thirty to forty percent are proteins. Pigments of the crustacean exoskeletons
are usually of lipid nature. Those pigments are of high market value and can be extracted
and purified to high extents. These include astaxanthin, astathin, canthaxanthin, lutein, β-
carotene, etc. Usually, the high presence of β-chitin in the exoskeleton means higher
protein content and lower carbonate content than the usual ranges stated in the preceding
passages. Chitin can be extracted through the use of acidic solutions, usually HCl, which
dissolves CaCO3 and forms the water soluble calcium chloride. Proteins are removed by
followed by alkaline treatment, normally with the use of alkali earth bases such as NaOH.
During the depigmentation step, colorants are removed to remove astaxanthin and other
pigments to obtain a colorless product. These pigments can be further processed and
purified as already stated [58].
The acetamide groups of the natural polymer chitin can be hydrolyzed to obtain a
deacetylated derivative of chitin, otherwise known as chitosan. Due to the presence of
nitrogenous groups in the C2 and C3 positions in its sugar ring, the entire molecule poses
resistance to normal conditions of hydrolysis. Thus, severe alkaline hydrolysis is
normally conducted. Partially deacetylated chitin or chitosan (DA<30%) can be obtained
under strong aqueous alkali conditions coupled with thermal treatments. Sodium and
potassium hydroxides are commonly used alkali bases at 30-50% concentration at high
temperatures, usually at 100°C [58].
48
mass, upon pre-swollen chitin as described earlier. The reaction is allowed to proceed at
25°- 40°C, the reaction of which ranges from twelve hours to one day [58].
Both methods make use of an aqueous solution of concentrated alkali and require long
reaction times (1-80 hours) depending on the processing conditions. The concentration of
alkali, particle size, density of chitin, and previous treatments affects the extent of
deacetylation of the chitin. A minimal DD can be achieved using single alkaline
treatments (75-85%) [58].
Oxygen scavengers and reducing agents such as thiophenol and sodium borohydride are
used to increase the viscosity of the product. Using 2-propanol, 2-methyl-2-propanol,
polyethylene glycol, acetone, and paraffin oil – all of which are water-miscible enables to
use reduced volumes of the alkali during processing by about 85%. Other methodologies
are used to reduce processing time and large amounts of alkali required. An example is
the use of a triphenol solution in dimethyl sulfonate (DMSO) and allowing the chitin to
undergo consecutive reactions with the solution in the presence of alkali or the treatment
of chitosan with saturated steam drastically [58].
Deacetylase enzymes can also be used for chitin deacetylation using enzymes which can
be derived from a variety of fungal species like Mucor rouxii, Aspergillus nidulans, and
Collettichum lindemuthianim. Their use, however, is limited by the chitin insolubility
[58].
The use of chitosan can be limited due to its low solubility and high viscosities at neutral
conditions. Hydrolysis of polymer chains can produce low molecular weight chitosans.
Physical, chemical, and enzymatic depolymerization can be used to counteract these
limitations. Aqueous solutions of hydrochloric acid can be used during chemical
depolymerization via acidic hydrolysis route. Nitrous acid or aqueous H 2O2 can also be
used; in this case, the depolymerization occurs via mechanisms involving oxidation of the
amino groups in the D-units of the chitosan polymer, which in turn causes the glycosidic
bonds to break causing the break-up of the polymer chain. Low molecular weight and
high solubility chitosans can be produced by employing chitinase, chitosanase,
gluconase, and other proteases. Cellulase, lipase, amylase, pectinase, lysozyme, and other
non-specific enzymes can also be used for chitosan depolymerization allowing
regioselective depolymerizationunder mild conditions. The use of Co-60 gamma rays in
physical depolymerization yields dimmers, trimer, and tetramers [58].
49
Figure 2.12: Chemical depolymerization of chitosan [58]
Chitin and its derivatives, primarily chitosan are abundant natural polymeric materials
which can be found in nature that have superb and distinctive attributes. These molecules
are biodegradable, compatible for use in biological applications, safe and non-hazardous,
and can be employed for adsorptive purposes [56, 59, 60]. Since chitosan contains
reactive amino groups in its structure, its reactions occur more readily than using
cellulose for similar purposes. Chitosan is partially insoluble in water but it is soluble in
dilute aqueous solutions of acids [56].
There have been various attempts to synthesize chitin derivatives that are also soluble in
aqueous solutions and organic solvents though employing chemical modifications, ionic
interactions, graft reactions and though selective N-alkylidinations and N-acylations.
However, only few were synthesized that are soluble in organic solvents due to the
difficulty in meeting the conditions of the required methodologies for their synthesis [56].
Chitin, chitosan and their derivatives are highly basic polysaccharides, which is in
contrary with the usual acidic nature of other polysaccharides found in nature such as
cellulose, carrageenan, agar, pectin, and many others. Cellulose, chitin, and chitosan
contain the characteristic β-(1—4)-anhydroglucosidic bond. However, the properties of
chitin differ to a large extent with that of cellulose primarily due to the presence of its
nitrogen substituent. It is hydrophobic in nature and is insoluble in water and in most
organic solvents. It is however, soluble in hexachloroisopropanol, mineral acids dissolved
in water, and dimethylacetamide containing 5% LiCl [56].
50
Chitin contains about five to eight percent nitrogen by mass largely aliphatic amino
groups in the C2 or C3 positions depending on the degree of deacetylation. It undergoes
typical amine reactions such as N-acylation and Schiff reactions. At mild conditions,
chitosan glucans can readily be obtained. D-glucosamine, an amino sugar, can be
obtained via hydrolysis in the presence of concentrated acids. Amido groups can be
introduced into the chitosan molecule with the use of acyl halides and acid anhydrides
following the N-acylation mechanism. Whenever linear propionyl and higher groups are
used as the N-acyl substituent, a vigorous reaction occurs resulting in the acetylation of
its hydroxyl groups [56].
On reaction with aldehydes and ketones, chitosan produces aldimines and ketimines at
room temperature. Reaction of ketoacids with chitosan and immediate reaction with
reducing NaBH3 leads to the formation of the class of molecules called glucans (e.g., N-
carboxybenzyl chitosans are derived from chitosan that is made to react with o- and/or p-
phthalaldehydic acids) which has proteic and may or may not have non-proetic amino
acid groups [56].
Upon hydrogenation and reaction with simple aldehydes, chitosan produces N-alkyl
chitosan which swells in water due to the weakening of hydrogen bonds in chitosan in the
presence of more bulky substituents. Because chitosan contains reactive amino groups in
the C2 position, reactions involving chitosan are more versatile. Thus, the synthesis of
chitin derivatives is usually done by first forming chitosan before the introduction of new
functional groups such as amido and keto groups are introduced into the polymer
structure [56].
51
Figure 2.13: Preparation of chitin and chitosan from crustaceans and fungi [58]
52
2.24 Uses and Applications of Chitin and Chitosan
Due to its unique and excellent properties, chitosan has been utilized in various
applications in different fields ranging from the pharmaceutical industry to water
treatment [56]. The following are some of the applications and uses of this versatile
polymer:
Cosmetics
It can also be used in oral health care such as in toothpastes, mouthwashes, and
chewing gums. Chitosan freshens breathe, prevents plaque formation and tooth
decay and masks unpleasant taste of silicon dioxide. It can also be applied as
dental filler [56].
Water Engineering
Chitosan can be used as a flocculating agent and as a chelating agent for heavy
metals in wastewater. It agglomerates anionic wastes in the solution and form
floes which can be removed by sedimentation. It can compete effectively with
synthetic resins in terms of capturing heavy metals from processed water.
Regenerated chitin and chitosan could be used in process such as osmosis, reverse
osmosis, microfiltration, desalination, dialysis, and hemodialysis [56].
Chitin and chitosan can strengthen paper and paper products. Chitosan addition
on paper products produced a smoother surface and more resistant to moisture. It
is of great value in the production of toilet paper, wrapping paper, and cardboard.
It can be also used as biodegradable packaging material for foods and other
products [56].
53
Chitin derivatives can also be used to produce the antistatic and soil repellent
properties of textiles. Chitosan is used in the textile industry for its ability to
remove dyes from dye processing effluents [56].
Food Industry
Chitin and chitin derivatives such as chitosan are also used in other different industries. It
is used as a fixing agent in photography, solid support for chromatographic separations
due to the presence of –NH2, primary and secondary –OH groups in its structure and it
can be dissolved in acetic acid solutions to produce ionic conductivity. It is also used as
potential components in lasers and light emitting devices such as LED’s. For biomedical
applications, chitin and chitosan is used in kidney design systems as artificial kidney
membrane due to its semi-permeability and high tensile strength. It is also used in tissue
engineering and in drug delivery systems due to its biocompatibility, biodegradability,
and non-toxic properties. Chitosan is also utilized for wound healing, wound dressings,
and artificial skins. It produces a tough biocompatible film that has an acceleratory effect
on wound healing process [56].
54
CHAPTER III
55
Figure 3.2: Extraction of starch from banana fruit and peelings
56
3.2 Methodology
3.2a Materials
Banana peelings are obtained and collected from Blumentritt Market, Sta. Cruz, Manila.
Sodium hydroxide pellets, chitosan powder, glycerol, and hydrochloric acid are supplied
by Merck, Germany. 1 N HCl solution is then prepared for use in starch extraction.
Stainless steel knives will be used to cut the banana peelings into small pieces. 1 L
beakers are used to contain the banana peelings. Stirring rods will be used to agitate the
slurry manually. The water used throughout the experiment is distilled.
Glycerol will be used as the plasticizer for starch and chitosan. The bioplastic will be
prepared via melt-mixing method. The mixture is placed in a 1 L beaker (Pyrex™) and
heated in a magnetic hot plate stirrer. Stainless steel molds will be used to form the thin
bioplastics films.
All reagents used are of analytical grade as supplied by Merck™, Germany. All
glasswares (Pyrex™) are provided by the TIP-Manila Chemical Engineering laboratory.
3.2b Equipment
Analytical balance (Mettler-Toledo) was used to weigh the needed materials for the
experiments done. This is also provided by the TIP-Manila Chemical Engineering
laboratory.
Drying of the starch is conducted using an electric oven provided by the Technological
Institute of the Philippines – Manila. It is operated at 220 V and 60 Hz AC starting from
57
40°C at 2°C/min heating rate until 110°C. The temperature is held constant at 110°C and
operated for 3 more hours.
The banana peelings is cut into small pieces and suspended in freshly-prepared 1 N HCl
solutions. The solution is agitated mechanically at constant rate for 10 minutes and the
slurry is filtered. The starch is subjected to drying conditions as stated beforehand.
Similar procedures were done for banana fruit.
Weighed amounts of the starch from Musa acuminata peelings and fruit are dissolved in
appropriate amounts of water at 70°C and heated up to 95°C at 5°C/min at constant
agitation. Chitosan is dissolved in 2% w/w aqueous acetic acid solution, mixed into the
starch solution and agitated at 95°C for 5 minutes. Glycerol is added according to the
formulation and the entire solution is again agitated at similar conditions for until the
slurry gelatinized.
The gelatinized mixture is placed in stainless steel molds and allowed to dry in an electric
oven. The gelatinization time of the formulations were noted. Experiments were done in
three replicates and the mean are reported.
3.2d Procedures
Banana starch is extracted from its peelings collected from Blumentritt Market, Sta. Cruz,
Manila. Methods are adopted from the studies of Charoenkongthum [52] with major
modifications. The peelings are washed thoroughly with running water to eliminate the
adhering particulates and dirt.
The washed peelings are cut into small pieces and suspended in freshly-prepared 1 N HCl
solutions in a 2:1 mass/volume ratio. This is to modify the starch composition by
breaking the bonds and chains of amylopectin molecules into small fragments which tend
to hinder gelatinization and plasticization of the bioplastics. The solution is agitated
manually at constant rate for 10 minutes and the slurry is filtered through a filter. The
starch is washed in distilled water until the supernatant becomes clear. It is then dried in
an oven starting from 40°C at 2°C/min heating speed until 110°C. The temperature is
held constant at 110°C and operated for 3 more hours. The dried peelings are then
pulverized in a pulverizer provided by TIP- Manila Unit Operations laboratory. The
pulverized starch is then placed inside a desiccator until further use. Similar procedures
were done for the banana fruit itself.
The formulation of the bioplastics for processing was designed using Design Expert D-
Optimal mixture design. D-Optimal design was chosen since the researchers wish to
58
determine the effect of the different formulations of the bioplastics on the response
selected i.e., gelatinization time. 16 runs were determined for the three-component
product (banana starch, peelings, and chitosan) to optimize the bioplastic production
using a cubic model. Banana starch, peelings, and chitosan loading were varied from 70-
100%, 0-20%, and 0-10% respectively. The design created by the software is as follows:
A:Banana B:Banana
Std Run Block Starch % Peelings % C:Chitosan %
10 1 Block 1 89.28143 10.114174 0.6043956
4 2 Block 1 90 0 10
8 3 Block 1 77.23076 12.769236 10
3 4 Block 1 70.00279 20 9.9972081
9 5 Block 1 85.47975 4.5202533 10
15 6 Block 1 76.57971 20 3.4202899
1 7 Block 1 100 0 0
12 8 Block 1 100 0 0
7 9 Block 1 92.85764 5.3012898 1.8410715
5 10 Block 1 76.57971 20 3.4202899
16 11 Block 1 85.36876 8.8732273 5.7580096
6 12 Block 1 85.36876 8.8732273 5.7580096
11 13 Block 1 81.066 17.987277 0.9467275
14 14 Block 1 90 0 10
13 15 Block 1 70.00279 20 9.9972081
2 16 Block 1 85.29462 14.705376 0
59
accuracy of the selected model. This will be done using Design Expert v.10.7. Empirical
equation for a particular response is also obtained which shows how the formulations
affect the said response. Contour plots were generated to investigate the effects of the
different formulations on the stated parameters. Diagnostics are also done in order to
validate the selected model and to ensure that the model generated can be used to
navigate thorough the design space, i.e., the model can be used to predict the response
accurately. Optimization was done using the best model as determined by ANOVA and
regression analysis.
60
CHAPTER 1V
4.1 Results
Gelling
Run A:Banana B:Banana Time
Starch Peelings C:Chitosan (min)
1 89.2814 10.1142 0.6044 35.2800
2 90.0000 0.0000 10.0000 35.2000
3 77.2308 12.7692 10.0000 27.1700
4 70.0028 20.0000 9.9972 30.4500
5 85.4797 4.5203 10.0000 28.1900
6 76.5797 20.0000 3.4203 31.6200
7 100.0000 0.0000 0.0000 29.2300
8 100.0000 0.0000 0.0000 29.8500
9 92.8576 5.3013 1.8411 26.4700
10 76.5797 20.0000 3.4203 32.9000
11 85.3688 8.8732 5.7580 27.6100
12 85.3688 8.8732 5.7580 28.1700
13 81.0660 17.9873 0.9467 27.4100
14 90.0000 0.0000 10.0000 34.2600
15 70.0028 20.0000 9.9972 31.2900
16 85.2946 14.7054 0.0000 32.9700
Lack-of-fit test was conducted in order to determine what it the best model to use to
navigate along the design space. From the table above, it can be seen that the cubic model
has the greatest value of 0.8430. This value means that the model has an insignificant
lack-of-fit.
61
Table 4.3: Model summary statistics
Adjusted Predicted
Std. R- R- R-
Source Deviation Squared Squared Squared PRESS Notes
Linear 3.1677 0.0031 -0.1503 -0.4834 194.0956
Quadratic 2.8869 0.3631 0.0446 -0.3909 181.9976
Special
Cubic 2.6422 0.5198 0.1997 -0.1981 156.7671
Cubic 0.5744 0.9849 0.9622 0.8845 15.1193 Suggested
Table 4.3 summarizes the different statistical parameters of the given set of data. In this
segment of data analysis, it is desired to know and determine the model that she would
go. From the data presented, it was seen that the R-squared value is greatest for the cubic
model supporting the earlier claim that it should be the model to be used for the given set
of data. Thus, the cubic model was selected to represent the collected data.
Table 4.4 presents the analysis of variance of the data obtained. ANOVA was performed
by Design Expert in order to create a design model that will represent the data gathered
and to evaluate the coefficients that will fit the model selected. The "Model F-value" of
43.3925 implies the model is not significant relative to the noise. There is a 0.01 %
chance that a "Model F-value" this large could occur due to noise.
Values of "Prob > F" less than 0.0500 indicate model terms are significant. In this case,
AB, ABC, AC(A-C), BC(B-C) are significant model terms. Values greater than 0.1000
62
indicate the model terms are not significant. The "Lack of Fit F-value" of 0.04 implies
the Lack of Fit is not significant. There is a 84.30% chance that a "Lack of Fit F-value"
this large could occur due to noise. A non-significant lack of fit is desirable because it is
desired to fit the data gathered into the model.
Parameter Values
Std. Dev. 0.5744
Mean 30.504
C.V. % 1.8831
PRESS 15.119
R-Squared 0.9849
Adj R-Squared 0.9622
Pred R-Squared 0.8845
Adeq Precision 19.159
The values for the different statistical parameters are presented in Table 4.5. A low
standard deviation (0.5744) means that the data are close to its mean. This indicates that
the design points in the model are well-correlated. Hence, the model can be used to
estimate the gelling time of the formulations of the bioplastic as desired. The high values
for the adjusted and predicted r-squared connotes that the experimental points gathered fit
well to the model.
The equation presented is generated by Design Expert for a cubic model. This equation
can be used to navigate all throughout the design space as supported by the statistical
tests conducted. This equation cannot be used outside the design space. This equation is
empirical and was generated only to investigate the points lying within the design space
and create contour plots and iteraction maps that will facilitate understanding on the
effect of the process parameters on the desired response. Note that the experimental
points are very close to the predicted values (Figure 4.1).
63
Figure 4.1: Predicted vs. actual plot of values of the generated model
Figure 4.2: Interaction curve for banana starch and banana peelings against gelling time
64
In order to investigate the effect of the different formulations on the gelling time of the
bioplastics, interaction curves are generated. Figure 4.2 shows the interaction between
banana starch, peelings, and gelling time. As the amount of starch is increased, the
gelling time decreases while as the amount of banana peelings is increased, the gelling
time increases. This can be explained by the molecular interactions between the starch
and the peelings. The banana peelings hinder the formation of plastics because it contains
very large macromolecules such as cellulose and hghly-branched starch (amylopectin).
Branching of molecules tend to increase the resistance of the polymer solutions to
undergo polymerization.
Figure 4.3: Interaction curve for banana starch and chitosan against gelling time
Figure 4.3 relates the effect of addition of chitosan into the polymer mixture for the
manufacture of bioplastics. The plot shows that the addition od chitosan into the polymer
causes a dramatic effect on the gelatinization time of the bioplatic. Increasing the amount
of chitosan causes the gelling time to decrease as shown by the cubic curve in the figure.
This is explianed by the nature of chitosan itself. Chitosan acts as a cross-linking agent in
this case by causing the molecules to ‘cling’ to each other, hence enhancing the rate at
which they polymerize. Chitosan, when added into the polymer matrix, will most likely
cause the molecules to gelatinize faster than the normal. The addition of chitosan hence,
65
is very helpful in optimizing the gelling time and hence, the processing time for the
synthesis of bioplastics.
Figure 4.4: Interaction curve for banana peelings and chitosan against gelling time
The interaction curve for banana peelings and chitosan against gelling time further proves
the postulate presented in the preceding paragraphs. It was stated that the banana peelings
hinder the gelatinization of the polymer mix because of its complex molecular structure.
Figure 4.4 shows that the addition of chitosan reverses the process. The presence of
chitosn tends to counter-act the ‘hindering effect’ of the banana peelings through its
‘cross-linking’ action. Chitosan causes the agglomeration of the molecules present in the
mixture which increases the rate at which they gelatinize.
It is also interesting to note that as the chitosan loading is increased up to about 5.125%,
the gelling time increases and then decreases as more chitosan is loaded. That is contrary
to what has been postulated lately. This negation can be explained by the
‘acclimatization’ of the chitosan and the other molecules in the mixture. At the region
mentioned, the cross-linking capacity of the chitosan is low since there is only a very
little amount added as compared to the amount of materials, i.e., banana starch and
banana peelings to be processed. The inflection point can therefore be named as the
optimum loading at that particular formulation.
Contour curves are also generated by Design Expert to clearly visualize what has been
stated in the previous paragraphs. Figure 4.5 is the contour plot showing the effect of
formulation on the gelling time of the bioplastic mixtures. The red region signifies areas
66
that have high gelling time while those in blue are the regions with low gelling time. The
plot reveals that low gelling time can be expected for high banana starch formulations.
Formulations with high amounts of banana peelings have higher gelatinization time. It is
interesting to note that the addition of chitosan changes the contour from red to blue as its
loading in the formulation is increased.
Figure 4.5: Contour plot showing the effect of the formulation on the gelling time
Figure 4.6 shows the different surface plots of the model’s design space. The plots show
how the response i.e., the gelling time is affected by the different formulations of the
bioplastics. Red-colored regions are those having high gelatinization time while those in
blue exhibit the reverse. Regions in green and yellow show behaviors in between the
defined extremeties.
The generated surface plots support the postulates stated earlier in this section. It can be
seen that regions in blue are those that have high starch content and low banana peelings.
Optimum conditions could be deduced from the plots alone – high starch content, low
banana peelings and high chitosan contents
Optimization was done to determine what would be the best formulation based on the
gelatinization time of the synthesized bioplastics. Table 6 show the optimum
formulations as determined numerically by Design Expert, their desirability, and the
predicted gelling time based on the generated model.
67
Figure 4.6: Surface plots of the design space
68
Table 4.6: Optimum formulations of bioplastics
Banana Banana
Number Starch Peelings Chitosan Gelling Time Desirability Experimental
1 90.512 3.852 5.636 20.3956 1 20.26
2 87.968 4.853 7.179 23.7293 1 23.89
3 89.047 5.848 5.105 23.0446 1 23.05
4 81.481 8.549 9.969 26.4363 1 26.89
5 93.046 2.545 4.409 17.5667 1 17.76
6 85.92 5.311 8.769 26.3126 1 26.33
7 90.801 2.469 6.73 20.7368 1 20.67
8 82.153 17.847 0 25.6266 1 25.75
9 87.588 5.63 6.782 24.0194 1 24.23
10 87.377 7.893 4.729 26.2798 1 26.21
11 86.217 6.689 7.094 25.5317 1 25.59
12 91.744 4.703 3.553 21.6495 1 21.89
13 89.047 4.194 6.759 22.4116 1 22.56
14 80.037 9.973 9.99 26.4452 1 26.78
15 81.687 18.313 0 24.1860 1 23.97
16 85.912 7.589 6.499 26.2793 1 26.34
17 86.95 6.992 6.058 25.2144 1 25.32
18 86.506 5.517 7.977 25.3846 1 25.47
19 89.755 6.679 3.566 24.9248 1 25.05
20 88.506 7.014 4.48 24.9132 1 25.16
21 92.729 0.862 6.409 18.6005 1 19.13
22 92.617 6.362 1.021 31.2086 0.4621
23 70.215 19.914 9.871 31.5747 0.4206
In order to validate the results obtained and to show that the model can be used to predict
the gelling time of the bioplastics based on the amount of the components in the mixture,
the formulations are synthesized and the results are presented on the same table. The
experimental values are plotted against the predicted gelling time and the plot was shown
on Figure 4.7.
69
Figure 4.7: Plot of experimental values against predicted values for optimum
formulations
70
CHAPTER 5
This study was conducted in order to provide a route for the synthesis of bioplastics from
Musa acuminate starch (fruit and peelings) with the addition of chitosan and to optimize
the said process using gelatinization time of the polymer slurry before plasticization as
the parameter. Sixteen different runs were employed using a D-Optimal Mixture design
to optimize the synthesis and to investigate the effect of the formulation composition on
its processing characteristics.
During the said study, it was found out that the composition of the bioplastic significantly
affect the gelling time of the polymer slurry before it plasticizes. High gelling time was
observed for formulations having high percentages of banana peelings while the opposite
effect was observed for increasing the amount of starch. Banana peelings hinder the
formation of plastics due to its complex molecular structure and its dissimilarity to
banana starch which make it difficult for the polymer slurry to gel and plasticize.
The hindrance of banana peelings to the rate of gelatinization was offset by the addition
of chitosan into the mixture. Chitosan serves as a cross-linking agent that causes the
molecules to be bridged and aggregated together, which then accelerates the rate of
gelling and counter-acting the hindering effect of the presence of banana peelings.
Since it was well-established that the mixture formulation significantly affects the
processing characteristics of the polymer slurry, a model was generated by Design Expert
that allowed in depth analysis of the obtained data. Statistical tests show that the data are
fitted well into the generated model and thus, the model could be use to effectively
forecast the gelatinization time of a particular mixture with a given formulation. Plots of
the interaction of the three components against gelling time as well as the contour map
and surface plots reveal the real behavior of the slurry as affected by its composition.
It can be concluded that the gelatinization time of bioplastics is greatly affected by its
composition. Highly-desirable gelling time could be obtained at high banana starch and
low banana peelings content. When added into the slurry, chitosan acts as a cross-linking
agent that off-sets the hindering effect brought by the presence of banana peelings. The
optimum formulation was found to be 93.046 % banana starch, 2.545% banana peelings,
and 4.409% chitosan. This yielded a gelling time of 17.76 seconds which is close to the
predicted value of 17.5667 seconds.
71
CHAPTER VI
The researchers recommend future studies be conducted in order to assess the results
presented in this paper. Aside from this, the following recommendations for future works
are made:
72
REFERENCES
[1] Rossi, Marquez G., Han, J.H., Garcia, Almebdarez B., Castano, Tostado E., and
Regalado, Gonzalez C. Effect of pH and temperature on the release of Nisin from
Antimicrobial Edible Whey Protein Isolate- based films with Different Thicknesses. Food
Science and Food Biotechnology 3rd International Congress. 1 (2009).
[2] Fabio, D.S., Larotonda, Katia N. Matsui, Valdir Soldi and Laurindo, Joao B..
Biodegradable Films Made from Raw and Acetylated Cassava Starch. Brazilian Archives
of Biology and Technology. 47 (3) (2004) 477-484.
[4] Liu, Sicong, Moult, Ian, and Long, Boguslav. An Investigation into Compostable
Plastic Bags. UBC Social, Ecological Development Studies (SEEDS) Student Reports.
(2009).
[5] Lee, Eun-Jung, Kweon, Dong-Keon, Koh, Bong-Kyung and Lim, Seung-Taik.
Physical Characteristics of Sweet Potato Pulp/ Polucaprolactone Blends. (2003).
[6] Kumar, Ashwin A., Karthick K., and Arumugam, K.P. Properties of Biodegradable
Polymers and Degradation for Sustainable Development. International Journal of
Chemical Engineering and Applicatons. 2 (2011).
[7] Cho, H.S., Moon, H.S., and Kim, M. Biodegradability and biodegration rate of
poly(caprolactone)-starch blend and poly(butylene succinate) biodegradable polymer
under aerobic and anaerobic environment. Waste Management. 31 (2011) 475-480.
[8] de Lima, S.M., Lima, M.A.G.A., Sarmento, S.M., Vinhas, G.M., and de Almeida,
Y.M.B. Starch Selection for Biodegradable Blend Preparation. 2nd Mercosur Congress
on Chemical Engineering.
[9] Park, Hwan-Man, Lee Sang-Rock, Chowdhury, Subhendu R., Kang, Tae-Kyu, Park,
Seung-Hoon, and Ha, Chang-Sik. Tensile Properties, Morphology and Biodegradable of
Blends of Starch with Various Thermoplastics. Department of Polymer Science and
Engineering. (2002).
[11] Rahman, P. M. Dr. Wan Aizan Bt Wan Abd, Ali, Roshafima Rasit, Jamaluddin,
Jamarosliza and Mohamad, Ida Idayu. Development of Low Density Polyethylene/Sago
Based Biofilm via Blow Film Technique. (2009).
73
[12] Uri, Noel D., Beach, Douglas E., and Boyd, Roy. Expanding biodegradable polymer
resin use: Assessing the aggregate impact on the US economy. 20 (1996).
[13] Salmoral, E.M., Gonzalez, M.E., and Mariscal, M. P. Biodegradable plastic made
from bean products. Industrial Crops and Products. 11 (2000) 217-225.
[14] Sarka, Evzen, Krulis, Zdenek, Kotek, Jiri, Ruzek, Lubomir, Korbarova, Anna,
Bubnik, Zdenek, and Ruzkova, Michaela. Application of Wheat Starch in Biodegradable
Plastic Materials. Czech Journal of Food Science. 29 (2011) 232-242.
[16] Moghaddam, L. Rintoul, P.J. Halley, P.M. Fredericks. Infrared microscopic mapping
of the homogeneity extruded blends: Application to starch/polyester blends. 2006.
[17] Liu, Qiang. Understanding Starches and Their Role in foods. (2005)
[18] Wu, Ken-Jer, Wu, Chin-San, and Chang, Jo-Shu. Biodegradability and Mechanical
properties of polycaprolactone composites encapsulating phosphate-solubilizing
bacterium Bacillus sp. PG01. 42 (2007) 669-675.
[19] Kun-yu, Zhang, Xiang-hai, Ran, Xiang-hai, Zhuang Yu-gang, Yao Bin and Dong Li-
Song. Blends of Poly(lactic acid) with Thermoplastic Acetylated Starch. Chem. Res.
Chinese Universities. 25 (5) (2009), 748-753.
[23] Healthy Environment for Child Care Pre-School Settings. <www.cehn.org> (2009)
1-4.
[25] Chung, Yi-Lin and Lai, His-Mei. Properties of Cast Films Made of HCl-Methanol
Modified Corn Starch. Starch. 59 (2007) 583-592.
[26] Converting Waste Plastics into a Resource. United Nation Environment Programme,
Division of Technology, Industry and Economics International Environmental
Technology Centre. (2009) 15-17.
74
[27] Selke, Susan E. Plastics Recycling and Biodegradable Plastics. Handbook of Plastics
Technology. 109 (8) (2006)1-8.
[28] Abdul Rahman, Wan Aizan Wan, Ali, Roshafima Rasit, and Zakaria, Naterah.
Studies on the Biodegradability, Morphology and Mechanical Properties of Low Density
Polyethylene/Sago Based Blends. Proceeding of the 1st International Conference on
Natural Resources Engineering & Technology. (2006) 434-444.
[31] Elmhirst, Peter. Who Invented the Bio-Plastics? A brief history of biodegradable
plastic. <http://peterelmhirst.hubpages.com/hub/Who-Invented-Bio-Plastics-A-Brief-
History-of-Biodegradable-Plastic> (2012).
[32] Narayan, Ramani, Pettigrow, Charles. ASTM Standards help define and grow a new
biodegradable plastic industry. ASTM Standardization News. (2009) 1-7.
[34] Scott, Geral, Lemaire, Jaques, Jakubowicz, Ignacy, Ojeda, Telmo, Pavkham, Chris.
Briefing Note on Biodegradable Plastic. Oxo-Biodegradable Association. (2011) 5-13.
75
[42] Ishigaki, Tomori, Sugano, Wataru, Nakanishi, Akane, Tateda, Masafumi, Ike,
Michihiko, and Fujita, Masanori. The Degradability of Biodegradable Plastics in Aerobic
and Anaerobic Waste landfill Model Reactors. Chemosphere 54 (2004) 225-233.
[44] Pei Lang, Adrina Tie. Physico-Chemical Properties of Starch in Sago Palm
(Methoxylon sagu) at Different Growth Stages. University Sains Malaysia. (2004) 33-34.
[45] Material Safety and Data Sheet: Starch MSDS. Flinn Scientific Inc. (2001) 1-2.
[46] Wei Lee, Lim. Development of a Multicomponent Degradable Plastics through the
combination of the Sago Starch and Polyethylene/Poly(Caprolactone) blends. (2007) 1-
24.
[47] Navia, Diana Paola and Villada, Hector Samuel. Thermoplastic Cassava Flour. 23-
31.
[53] Foster, Marcus, Rodriguez, Elena, Martin, Jacinto Darias, Romero, Carlos Diaz.
Distribution of Nutrients in Edible Banana Pulp. (2003) 167.
[54] Mohapatra, Debabandya, Mishra, Sabyasachi, and Sutar, Namrata. Banana and its
By-product Utilization: An Overview. Journal of Scientific and Industrial Research. 69
(2010) 323-329.
[55] Calderon, R.P., Rola, A.C. Assessing Benefits and Cost of Commercial Banana
Production in the Philippines. Institute of Strategic Planning and Policy Studies, College
of Public Affairs U.P Los Banos.
[56] Dutta, Pradip Kumar, Dutta, Joydeep, and Tripathi, V.S. Chitin and Chitosan:
Chemistry, Properties, and Applications. Journal of Scientific & Industrial Research. 63
(2004) 20-31.
[57] Akter, Nousin, Dussault, Dominic, Khan, Ruhul A., Lacroix, Monique, Salmieri,
Stephane, and Sharmin, Nusrat. Fabrication and Mechanical Characterization of
76
Biodegradable and Synthetic Polymeric Films: Effect of Gamma Irradiation. Radiation
Physics and Chemistry 81 (2012) 995-998.
[58] Aranaz, Inmaculada, Mengibar, Marian, Harris, Ruth, Panos, Ines, Miralles, Beatriz,
Acosta, Niuris, Galed, Gemma, and Heras, Angeles. Functional Characterization of
Chitin and Chitosan. Current Chemical Biology. 3 (2009) 203-230.
[59] Material Safety and Data Sheet: Chitosan MSDS. Sciencelab.com, Inc. (2010) 1-5.
[60] Chitosan MSDS. St. Laurent Gulf Products, Ltd. (2005) 1-3.
[61] Lu, Shaojie, Song, Xuefeng, Cao, Deyong, and Yao, Kangde. Preparation of Water-
soluble Chitosan. Journal of Applied Polymer Science. 91 (2004) 3497-3503.
[63] Munthoub, Dayangku Intan, and Abdul Rahman, Wan Aizan Wan. Tensile and
Water Absorption Properties of Biodegradable Composites Derived from Cassava
Skin/Polyvinyl Alcohol with Glycerol as Plasticizer. Sains Malaysia. 40 (7) (2011) 713-
718.
[64] Zuraida, A., Yusliza, Y., Anuar, H., and Mohn Khairul Muhaimin, R. The Effect of
Water and Citric Acid on Sago Starch Bio-plastics. International Food Research Journal.
19 (2) (2012) 715-719.
[65] Ramirez, Maria Guadalupe Lomeli, Bolzon de Muniz, Graciela I., Satyanarayana,
Kestur G., Tanobe, Valcineide, and Iwakiri, Setsuo. Preparation and Characterization of
Biodegradable Composites based on Brazilian Cassava Starch, Corn Starch and Green
Coconut Fibers. Revista Materia. 15 (2) (2010) 330-337.
[66] Rao Patnaik, K.S.K., Sirisha Devi, K., Kiran Kumar, V., and Sri Harsha, K.
Biodegradability Behavior on Sorbitol Modified Starch Blended with HDPE.
International Journal of Chemical Engineering and Applications. 2 4 (2011) 248-251.
[68] Šarka, Evžen, Kruliš, Zdeněk, Kotek, Jiří, Růžek, Lubomír, Korbařova, Anna,
Bubnik, Zdeněk, and Růžkova, Michaela. Application of wheat B-starch in biodegradable
plastic materials. Czech Journal of Food Science (2011) 29 232–242.
77
[69] Domenek, Sandra, Feuilloley, Pierre, Gratraud, Jean, Morel, Marie Helen, and
Guibert, Stephane. Biodegradability of wheat gluten based bioplastics. (2003)
[71] Narayan, Ramani, Lee, Tae Jin, Shin, Boo Young, and Jang, Woo Yeul. Thermal
Properties and Morphology of Biodegradable PLA/Starch Compatibilized Blends.
Journal of Industrial Engineering Chemistry. 13 (3) (2007) 457-464.
[73] Health, Nick (2007). Bio-plastics: Turning Wheat and Potatoes into Plastics.
[WWW] The Naked Scientist: Science Radio and Science Podcast. Available from:
http://www.thenakedscientists.com.html. [Accessed 08/26/2012]
[74] Starch Janssen, Leon and Moscicki, Leszek (eds) (2009)Thermoplastic Starch:
A green material for various industries. Germany: Wiley-VCH Verlag GmbH & Co.
[75] Poutanen, K., Forsell P. Modification of starch properties with plasticizers, TRIP 4
(1996) 128.
[76] Rudnick, Ewa. Compostable Polymer Materials. Radarweg 29, PO Box 211,
1000 AE Amsterdam, The Netherlands: Elsevier Ltd. (2008).
[77] Van Soest J.J.G., Benes K., de Wit D. The influence of starch molecular mass on the
properties extruded thermoplastic starch. Polymer 37 (1996) 3543.
[78] Da Roz, A.L., Carvalho, A.J.F., Gandini, A., Curvelo, A.A.S. The effect of
plasticizers on thermoplastic starch compositions obtained by melt processing.
Carbohydr.Polym. (2006) 63 417.
[79] Hulleman S.H.D., Janssen EH.P., Feil H.The role of water during plasticization
of native starches.Polymer.39 (1998) 2043.
[80] Von Soest J.J.G., de Wit D., Vliegenthart J.F.G. Mechanical properties of
thermoplastic maize starch, J. Appl. Polym. Sci. 29 (1996) 225.
[81] Von Soest J.J.G., de Wit D., Vliegenthart J.F.G. Mechanical properties of
thermoplastics maize satrch, J. Appl. Polym. Sci. 61 (1996) 1927.
[82] Forsell P.M., Mikkila J. M., Moates, G.K., Parker, R. Phase and glass transition
behaviour of concentrated barley starch-glycerol-water mixtures, a model for
thermoplastic starch, Carbohydrates Polym. 34 (1997) 275.
78
[83] Rodriguez-Gonzalez F.J., Ramsay, B.A., Favis, B.D. Rheological and thermal
properties of thermoplastic starch with high glycerol content, Carbohydr. Polym. 58
(2004) 139.
[84] De Graaf, R.A., Karman, A. P., Janssen, L.P.B.M. Material properties and
glass transition temperatures of different thermoplastic starches after extrusion
processing. Starch 55 (2003) 139.
[85] Huang, M., Yu J., Ma, X. Etanoloamine as a novel plasticizer for thermoplastic
starch. Carbohydr.Polym. 90 (2005) 501.
[86] Thunwall, M., Boldizar, A., Rigdahl, M. Compression molding and tensile
properties of thermo plastic potato starch materials. Biomacromolecules 7 (2006)
981.
[87]Ma, X., Yu, J. The plasticizers containing amide groups for thermoplastic
starch, Carbohydr.Polym. 57 (2004) 197.
[88] Ma, X., Yu, J., Ma, Y. Urea and formamide as a mixed plasticizer for
thermoplastic wheat flour. Carbohydr.Polym. 60 (2005) 111.
[89] Shogren R.L., Swanson C.L., Thompson A.R.Extrudates of corn starch with urea
and glycols structure/mechanical property relations. Starch. 44 (1992) 335
[90] Ma X., Yu J., Wan J. Urea and ethanoloamine as a mixed plasticizer for
thermoplastic starch. Carbohydr.Polym. 64 (2006) 267.
[91] Yang J., Yu J., Ma X. Study on the properties of ethylenebisformamide and sorbitol
plasticized corn starch.Carbohydr. Polym.66 (2006) 110.
[92] Van Soest J.J.G., Kortleve P.M. The influence of maltodextrins on the structure and
properties of compression-molded starch plastic sheets.J. Appl. Polym. Sci.74 (1999)
2207.
[93] Van Soest J.J.G., Vliegenthart LEG. Crystallinity in starch plastics: consequences
for material properties. TIBTECH.15 (1997) 208.
[94] Van Soest J.J.G. The development of fully biodegradable starch plastics: process-
structure-property relationships. Agro-Food Industry Hi-Tech(1997) 17.
[96] Orliac O., Rouilly A., Silvestre E, Riga! L.: Effects of additives on the mechanical
properties, hydrophobicity and water uptake of thermo-moulded films produced from
sunflower protein isolate, Polymer 43 (2002) 5417.
79
[97] Rudnick, Ewa (2008) Compostable Polymer Materials. Radarweg 29, PO Box 211,
1000 AE Amsterdam, The Netherlands: Elsevier Ltd.
[98] Orliac O., Rouilly A., Silvestre E, Rigal L.: Effects of various plasticizers on the
mechanical properties, water resistance and aging of thermo-moulded films made from
sunflower protein isolate, Polymer 18 (2003) 91.
[99] Grevellec J., Marqui6 C., Ferry L., Crespy A., Vialettes V.: Processability of
cottonseed proteins into biodegradable materials, Biomacromolecules 2 (2001) 1104.
[100] Zheng H., Tan Z., Zhan Y., Huang J. Morphology and properties of soy protein
plastics modified with chitin, J. Appl. Polym. Sci. 90 (2003) 3676
[101] Mo X., Sun X. Effects of storage time on properties of soy protein-based plastics.
Polymers Environment. 11 (2003) 15.
[102] Pommet M., Redl A., Guilbert S., Morel M.: Intrinsic influence of various
plasticizers on functional properties and reactivity of wheat gluten thermoplastic
materials, J Cereal Sci. 42 (2005) 81.
[103] Micard V., Guilbert S.: Thermal behaviour of native and hydrophobized wheat
gluten, gliadin and glutenin-rich fractions by modulated DSC, Int. d. Biol. Macromol. 27
(2000) 229.
[104] Di Gioia L., Cuq B., Guilbert S.: Thermal properties of corn gluten meal and its
proteic components, Int. J. Biol. Macromol. 24 (1999) 341.
[105] Vaz C.M., van Doeveren REN.M., Yilmaz G., de Graaf L.A., Reis R.L., Cunha
A.M.: Processing and characterization of biodegradable soy plastics: effects of
crosslinking with glyoxal and thermal treatment, d. Appl. Polym. Sci. 97 (2005) 604.
[106] Irissin-Mangata J., Bauduin G., Boutevin B., Gontard N.: New plasticizers for
wheat gluten films, Eur. PolymerJ. 37 (2001) 1533.
[107] Kumar R., Choudhary V., Mishra S., Varma I.K., Mattiason B.: Adhesives and
plastics based on soy protein products, Ind. Crops Prod. 16 (2002) 155.
[108] Day L., Augustin M.A., Batey I.L., Wrigley C.W.: Wheat-gluten uses and industry
needs, Trend. Food Sci. 17 (2006) 82.
80