CHAPTER 1

INTRODUCTION

1.1 What is Bioplastic?

Bioplastics are plastics derived from renewable biomass sources, such as vegetable fats
and oils, corn starch, straw, woodchips, food waste, etc. Bioplastic can be made from
agricultural by-products and also from used plastic bottles and other containers using
microorganisms. Bioplastics are usually derived from sugar derivatives,
including starch, cellulose, and lactic acid [1]. Biodegradable plastics are of two types; one
is plastic materials which will be decomposed in natural aerobic (composting) process and
another is decomposed in anaerobic (landfill) environments. Degradation occurs when the
soil microbial consortia start consuming these polymers and eventual release of monomers
to the environment certainly has less hazardous effects on the landscape. These polymers
are either composed of bioplastics (PHA or PHB) or plastics which are derived from
renewable raw materials or petroleum based plastics which contains additives [2].
Bioplastics which are disposed in environment and can easily degrade through the
enzymatic actions of microorganisms. The degradation of biodegradable plastic produces
carbon dioxide (CO2), methane (CH4)), water (H2O), biomass, humic matter and various
other natural substances which can be readily eliminated. Due to its ability to degrade in
the biotic environment these types of materials are renamed as “Bioplastics.”

1.2 Why bioplastic?

The major sources of land pollution include plastics, metal and glass containers, food
wrapping, worn-out machinery, old furniture, garbage, etc. Plastics have become a large
environmental problem [2]. As the world need plastics for our daily purposes, about 265
million tonnes of plastics were produced worldwide in 2010 [3]. Plastics are degraded very
slowly, which can cause the original products to remain in the landfills for hundreds or
even thousands of years. The prominence of plastic pollution is correlated with plastics
being economical and durable, which lends to high levels of plastics used by humans [2].
However, it is slow to degrade and plastic pollution can unfavorably affect lands,
waterways and oceans. Living organisms, particularly marine organisms which includes
both the flora and fauna, can also be affected through entanglement, direct assimilation of
 plastic waste, or through contact with chemicals within the plastics and cause interruptions
in bio functions of the living organisms. Even humans are also not free from the hazardous
cause of plastic pollution; they suffer from the disruption of the thyroid hormone levels.
Due to the use of excessive chemical additives during plastic production, plastics have
potentially toxic and that could prove to be carcinogenic. Some of the principal additives
are used as phthalate plasticizers and brominated flame retardants. Therefore, nowadays
scientists are looking at potential alternative to the traditional plastics derived from
petrochemical source [2].

1.3 Application:

Bioplastics are used for disposable items, such as packaging, crockery, cutlery, pots, bowls,
and straws. Few commercial applications exist for bioplastics. In principle they could
replace many applications for petroleum-derived plastics, however cost and performance
remain problematic. As a matter of fact, their usage is favourable only if supported by
specific regulations limiting the usage of conventional plastics. Typical is the example of
Italy, where biodegradable plastic bags and shoppers are compuslory since 2011 with the
introduction of a specific law. Beyond structural materials, electroactive bioplastics are
being developed that promise to be used to carry electric current. Biopolymers are available
as coatings for paper rather than the more common petrochemical coatings.

1.4 Types of Bioplastics:

1.4.1 Starch-based plastics

Thermoplastic starch currently represents the most widely used bioplastic, constituting about
50 percent of the bioplastics market. Simple starch bioplastic can be made at home. Pure starch
is able to absorb humidity, and is thus a suitable material for the production of drug capsules
by the pharmaceutical sector. Flexibiliser and plasticiser such as sorbitol and glycerine can also
be added so the starch can also be processed thermo-plastically. The characteristics of the
resulting bioplastic (also called "thermo-plastical starch") can be tailored to specific needs by
adjusting the amounts of these additives.

Starch-based bioplastics are often blended with biodegradable polyesters to produce

starch/polylactic acid, starch/polycaprolactone or starch/Ecoflex (polybutylene adipate-co-
terephthalate produced by BASF) blends. These blends are used for industrial applications and
are also compostable. Other producers, such as Roquette, have developed other
starch/polyolefin blends. These blends are not biodegradable, but have a lower carbon footprint
than petroleum-based plastics used for the same applications.

Due to the origin of its raw material, starch is cheap, abundant, and renewable. Starch based
plastics are complex blends of starch with compostable plastics such as Polylactic acid,
Polybutylene Adipate Terephthalate, Polybutylene Succinate, Polycaprolactone, and
Polyhydroxyalkanoates. These complex blends improve water resistance as well as processing
and mechanical properties.

Starch-based films (mostly used for packaging purposes) are made mainly from starch blended
with thermoplastic polyesters to form biodegradable and compostable products. These films
are seen specifically in consumer goods packaging of magazine wrappings and bubble films.
In food packaging, these films are seen as bakery or fruit and vegetable bags. Composting bags
with this films are used in selective collecting of organic waste.

Further, a new starch-based film was developed by Agricultural Research Service scientists can
even be used as a paper.

1.4.2 Cellulose-based plastics:

Cellulose bioplastics are mainly the cellulose esters, (including cellulose

acetate and nitrocellulose) and their derivatives, including celluloid.

Cellulose can become thermoplastic when extensively modified. An example of this is cellulose
acetate, which is expensive and therefore rarely used for packaging. However, cellulosic fibers
added to starches can improve mechanical properties, permeability to gas, and water resistance
due to being less hydrophilic than starch.

A group at Shanghai University was able to construct a novel green plastic based on cellulose
through a method called hot pressing.

1.4.3 Protein-based plastics:

Bioplastics can be made from proteins from different sources. For example, wheat gluten and
casein show promising properties as a raw material for different biodegradable polymers.

Additionally, soy protein is being considered as another source of bioplastic. Soy proteins have
been used in plastic production for over one hundred years. For example, body panels of an
original Ford automobile were made of soy-based plastic.
There are difficulties with using soy protein-based plastics due to their water sensitivity and
relatively high cost. Therefore, producing blends of soy protein with some already-available
biodegradable polyesters improves the water sensitivity and cost.

1.4.4 Some aliphatic polyesters

The aliphatic biopolyesters are mainly polyhydroxyalkanoates (PHAs) like the poly-3-
hydroxybutyrate (PHB), polyhydroxyvalerate (PHV) and polyhydroxyhexanoate (PHH).

1.4.4.1 Polylactic acid (PLA)

Mulch film made of polylactic acid (PLA)-blend bio-flex. Polylactic acid (PLA) is a transparent
plastic produced from corn or dextrose. Superficially, it is similar to conventional
petrochemical-based mass plastics like PS. It has the distinct advantage of degrading to
nontoxic products. Unfortunately it exhibits inferior impact strength, thermal robustness, and
barrier properties (blocking air transport across the membrane).[6] PLA and PLA blends
generally come in the form of granulates with various properties, and are used in the plastic
processing industry for the production of films, fibers, plastic containers, cups and bottles. PLA
is also the most common type of plastic filament used for home fused deposition modeling.

1.4.4.2 Poly-3-hydroxybutyrate

The biopolymer poly-3-hydroxybutyrate (PHB) is a polyester produced by certain bacteria

processing glucose, corn starch[24] or wastewater.[25] Its characteristics are similar to those of
the petroplastic polypropylene. PHB production is increasing. The South
American sugar industry, for example, has decided to expand PHB production to an industrial
scale. PHB is distinguished primarily by its physical characteristics. It can be processed into a
transparent film with a melting point higher than 130 degrees Celsius, and is biodegradable
without residue.

1.4.5 Bio-derived polyethylene

The basic building block (monomer) of polyethylene is ethylene. Ethylene is chemically similar
to, and can be derived from ethanol, which can be produced by fermentation of agricultural
feedstocks such as sugar cane or corn. Bio-derived polyethylene is chemically and physically
identical to traditional polyethylene – it does not biodegrade but can be recycled. The Brazilian
chemicals group Braskemclaims that using its method of producing polyethylene from sugar
cane ethanol captures (removes from the environment) 2.15 tonnes of CO2 per tonne of Green
Polyethylene produced.
1.4.6 Genetically modified bioplastics

Genetic modification (GM) is also a challenge for the bioplastics industry. None of the currently
available bioplastics – which can be considered first generation products – require the use of
GM crops, although GM corn is the standard feedstock.

Looking further ahead, some of the second generation bioplastics manufacturing technologies
under development employ the "plant factory" model, using genetically modified
crops or genetically modified bacteria to optimise efficiency.

1.4.7 Lipid derived polymers

A number bioplastic classes have been synthesized from plant and animal derived fats and
oils.[29] Polyurethanes, polyesters, epoxy resins and a number of other types of polymers have
been developed with comparable properties to crude oil based materials. The recent
development of olefin metathesis has opened a wide variety of feedstocks to economic
conversion into biomonomers and polymers. With the growing production of traditional
vegetable oils as well as low cost microalgae derived oils, there is huge potential for growth in
this area.
 CHAPTER 2
LITERATURE SURVEY

2.1 Starch- A major source in bioplastic production:

A number of bioplastic based on cellulose, starch and poly lactic acid (PLA) are common now a days
[4]. Starch is one of the major sources in the development of bioplastic. Starch consists of a long chain
of two glucose units joined together, namely branched polymerized amylopectin and amylose, which
gives its granular structure. Starch can behave like a thermoplastic in the presence of plasticizer, with
application of heat and mechanical treatment [3]. Starch is an inexpensive material derived from corn
and other crops, and is an annually renewable source. By fermentation of starch from crops, commonly
cornstarch or sugarcane, lactic acid is produced which can be polymerized to produce PLA. Similarly,
cellulose based plastics require wood pulps. Apart from these plastics, a number of water-soluble
bioplastics are being developed like carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC),
pullulan, thermal polyaspartate (TPAs), etc. by modifying starch and cellulose. These are being
developed to replace the water-soluble polymers prepare from synthetic monomers like acrylic acid,
maleic anhydride, methacrylic acid and also by the combination of these chemically derived monomers.
Water-soluble polymers are not biodegradable, and persist in ocean, lakes, and other water depositories
resulting in water pollution. On the other hand, water soluble BPs derived from modification of starch
and cellulose have good moisture retention capacity and low oxygen permeability, so they easily
degrade under water [4].
One of the most common waste form of starch is the banana peels. The waste management problem is
also faced due to the disposal of tonnes of banana peels in some parts of the globe, especially in
developing countries. The disposal of these large amounts of wet organic waste can eventually harm
the environment and lead to health problems such as respiratory disorders [3]. Banana peels consists
high sources of starch, which is about 18.5%. As banana peels ripen, the glucose level increases.
However, if the peels are too ripe, the starch will be converted into glucose while the least ripened
peels, becomes too firm although high in starch molecules. Therefore, banana peels can be suggested
as a suitable source for the manufacturing of bioplastics.

2.2 Various testing methods

2.2.1 Biodegradability
Two 400 ml beakers and 1.1 grams of a preweighed piece of bioplastics were taken, the preweighed
bioplastic material prepared was placed under the beaker containing soil at a depth of 5cm from the
surface. Some amount of water was sprinkled on the soil so that bacterial enzymatic activities could be
enriched. These samples were kept in the beaker for about 15 days and each 3 days of interval we
observed the decrease in the weight of the bioplastic material and results were recorded accordingly,
each experiment was done in triplicate in order to ensure results [2].

2.2.2 Water Absorption Test:

A small piece of the sample was cut into 1 cm × 2 cm size. The initial weight of the sample was
recorded. The sample was then placed into a beaker containing 60 mL of water at room temperature
for 24 hours. The sample was then taken out from the water and wiped off. The final weight was
recorded. The amount of water uptake was calculated by using the following formula:

WA (%) = Final weight (g)-initial weight (g) X 100

initial weight (g)

2.2.3 Solubility test:

Two types of bioplastic were prepared and solubility studies were conducted to check persistence of
these bioplastic materials. Samples of bioplastic from banana peel were soaked in Sodium Meta
Bisulfite solution and samples of bioplastic of banana peel which was obtained by a direct squeezing
process were considered. All the samples were cut into small pieces and were inserted into a test tube
containing different solvents. This test tells us about different solubility pattern of bioplastic in different
solvents.

2.2.4 Fourier Transform Infrared Spectroscopy Characterization:

Infrared spectroscopy is an essential and crucial characterization technique to elucidate the structure of
matter at the molecular scale. The chemical composition and the bonding arrangement of constituents
in a homopolymer, copolymer, and polymer composite and polymeric materials in general can be
obtained using Infrared (IR) spectroscopy. The FTIR spectrum of the sample is to be obtained at the
wavelength in the range of 450-4000 cm-1[5]. The FTIR equipment is shown in Fig. 2.1.
 Fig. 2.1 Fourier Transform Infrared Spectrometer

2.2.5 X-ray powder Diffraction:

X-ray powder Diffraction is a technique used to determine the crystallographic structure of natural and
synthetic materials. A beam of monochromatic (single wavelength) X-rays are focused on to the surface
of a finely powdered sample. The X-rays are scattered (diffracted) as they interact with the sample
material, the angle of which is characteristic of the crystal lattice of the material analysed [2]. The X-
Ray powder diffraction equipment is shown in the fig. 2.2.

Fig. 2.2 X-Ray powder diffraction

CHAPTER 3
METHODOLOGY
3.1 Experimental Procedure:
1. Preparation of Banana Skins

Step 1: Banana peels are removed using stainless steel knife and converted into small pieces. Then
peels are dip in sodium metabisulphite (0.2M) solution for 45 minutes. It is used as antioxidant and
preservative. This would increase the biodegradation period of plastic.
Step 2: Banana peels are boiled in distilled water for about 30 minutes.
Step 3: The water is decanted from the beaker and the peels are now left to dry on filter paper for
about 30 minutes
Step 4: After the peels are dried, they are placed in a beaker and using a hand blender, the peels
are pureed until a uniform paste is formed.

2. Production of Plastic
Step 1: 25gm of banana paste is placed in a beaker
Step 2: 3ml of (0.5 N) HCl is added to this mixture and stirred using glass rod.
Step 3: 2ml Plasticizer (Glycerol) is added and stirred.
Step 4: 0.5 N NaOH is added according to pH desired, after a desired residence time.
Step 5: The mixture is spread on a ceramic tile and this is put in the oven at 120o C and is baked.
Step 6: The tile is allowed to cool and the film is scraped off the surface.

3.2 Reaction Mechanism:

A Bioplastic of 0.3 mm prepared successfully from above experimental procedure. It is emphasized
that presence of HCl and NaOH in proper concentration is consider to be a controlling factor for its
strength. The hydrochloric acid is used in the hydrolysis of amylopectin, which is needed in order to
aid the process of film formation due to the H-bonding amongst the chains of glucose in starch, since
amylopectin restricts the film formation. The sodium hydroxide in the experiment is simply used to
neutralize the pH of the medium. Acid hydrolysis changes the physiochemical properties of starch
without changing its granule structure. If the amylopectin content is higher in the starch, the recovery
of starch decreases.

3.2.1 Glycerol as a Plasticizer:

Plasticizers or dispersants are additives that increase the plasticity or fluidity of a material. The
dominant applications are for plastics, especially polyvinyl chloride (PVC) glycerol, sorbitol. The
properties of other materials are also improved when blended with plasticizers including concrete,
clays, and related products. Plasticizers make it possible to achieve improved compound processing
characteristics, while also providing flexibility in the end-use product. Glycerol (also called glycerin)
is a simple polyol (sugar alcohol) compound. It is a colorless, odorless, viscous liquid that is sweet-
tasting and non-toxic.

3.2.2 Sodium metabisulfite as an Antioxidant:

The sodium metabisulfite (Na2S2O5) is used as an antioxidant here. It prevents the microbial growth
in the peels. It is used as a disinfectant, antioxidant and preservating agent.it is very soluble in
ethanol and water.
 REFERENCES
1. Production of bioplastics from banana peels; 1M. R. Gaonkar, 3Prashant Palaskar, 3Rishikesh
Navandar.
2. Biodegradable Plastic Production from food waste material and its sustainable use for green
application; 1Jayachandra Yaradoddi, 2Vinay Patil, 3Sharanabasava Ganacharya, 4Nagraj
Banapurmath, 5Ananad Hunashyal, 6Ashok Shettar.
3. The development of banana peel/ corn starch bioplastic film: A preliminary study; 1Noor
Fatimah Kader Sultan, 2Wan Lutfi Wan Johari

4. Eco-friendly Bioplastic for Uncontaminated Environment; Raaz

Maheshwari1, Bina Rani2, Sangeeta Parihar3, Anju Sharma1

5. FTIR – An Essential Characterization Technique for Polymeric Materials; Vladimir A.

Escobar Barrios, José R. Rangel Méndez, Nancy V. Pérez Aguilar, Guillermo Andrade
Espinosa and José L. Dávila Rodríguez