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Bioplastics- utilization of waste banana peels for synthesis of polymeric films

Thesis · April 2014

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A PROJECT REPORT ON
“BIOPLASTICS- UTILIZATION OF
WASTE BANANA PEELS FOR
SYNTHESIS OF POLYMERIC FILMS”

Submitted by:

ABHIJIT MOHAPATRA

SHRUTI PRASAD

HEMANT SHARMA

SHRI VILE PARLE KELAVANI MANDAL’S

D.J.SANGHVI COLLEGE OF ENGINEERING


VILE PARLE (W), Mumbai-400056

1
A PROJECT REPORT ON

“BIOPLASTICS- UTILIZATION OF WASTE


BANANA PEELS FOR SYNTHESIS OF

POLYMERIC FILMS ”
Submitted to
UNIVERSITY OF MUMBAI
At
Semester VIII of Academic Year 2013-2014
In partial fulfilment of the requirements for the degree of
B.E.CHEMICAL ENGINEERING
BY

Abhijit Mohapatra (60011100028)

Shruti Prasad (60011100034)

Hemant Sharma (60011100054)

SHRI VILE PARLE KELAVANI MANDAL’S


D.J.SANGHVI COLLEGE OF ENGINEERING
VILE PARLE (W), Mumbai-400056

2
Shri Vile Parle Kelvani Mandal’s
DWARKADAS J. SANGHVI COLLEGE OF ENGINEERING
VILE PARLE (WEST), MUMBAI- 400 056

CERTIFICATE
This is to certify that the following students whose names are given below have
successfully completed the B.E. (Chemical Engineering) project entitled

“Bioplastics-Utilization of Waste Banana Peels for Synthesis of Polymeric


Films”

At Dwarkadas J. Sanghvi college of Engineering, Mumbai as a partial fulfilment of


the requirement for the degree of Chemical Engineering (Semester VIII) of
University Of Mumbai in the year 2013-2014.

Submitted By: -

Abhijit Mohapatra 60011100028


Shruti Prasad 60011100034
Hemant Sharma 60011100054

Internal Guide External Examiner HOD


Prof. Sanjay Dalvi Chemical Engg Dept
Dr V Ramesh
3
Acknowledgement
We would like to take this opportunity to thank the Chemical Engineering Department for their
utmost support towards our final year project. We appreciate the immense help and guidance
offered by our mentor, Prof. Sanjay Dalvi. We would like to thank our HOD, Dr. V.Ramesh for
letting us use the laboratories and the equipments for our project work. We would also like to
take this opportunity to express our gratitude to Prof E. Narayanan (Mentor Prof- Production
Dept) Prof D. D. Kale (ex ICT Faculty), Mr Tushar Dongre (Sr Manager-Technical, Reliance
Industries) for their guidance. We also thank the Applied Chemistry Depart (MPSTME &
DJSCOE), Manuben Nanavati College of Pharmacy for being supportive of our work and
helping us with our project. Lastly we would like to thank Mrs. Jyotsna, Mr. Jaisingh and Mr.
Nitin, for providing us with the necessary help in the laboratories.

4
Abstract

The diminishing supply of petroleum along with the pollution caused due to the non-
biodegradability of petroleum based plastics, has led to an increased interest in the field of
bioplastics. The initial sections of this report begin with the history of plastics followed by
bioplastics. A brief economic study of bioplastic has also been discussed in this report.
Applications, advantages and disadvantages are also mentioned to give the reader a broader
understanding of the scenario.

The latter section of the project endeavours to study a novel method in the production of
biopolymers using waste banana peels. Variations in synthesis parameters like pH, plasticizer
choice and hydrolysis times were extensively tested and the optimum combination was obtained.

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Table of Contents

Chapter No Name Page No

1 Literature Survey 7
2 Plastics 9
3 Bioplastics 16
4 Experimental Procedure 38
5 Testing Procedure 44
6 Experimental Trials Conducted 47
7 Observations 53
8 Calculations 56
9 Analysis 61
10 Preliminary Process Scheme 68
11 Future Scope 71
12 References 73

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Chapter 1
Literature Survey

7
Literature survey

The Royal Society of Chemistry describes the generic process for the manufacture of starch
based bioplastics. This involves hydrolysis of the starch by using an acid. Abdorreza et al (2011)
have described in their paper the physiological, thermal and rheological properties of acid
hydrolyzed starch. This paper shows that the amylose content increases initially but continuous
hydrolysis causes a decrease in the amylose content. This fact is also corroborated in the paper
by Karntarat Wuttisela et al (2008). The amylose content is responsible for the plastic formation
in starch. Plasticizers are used to impart flexibility and mouldability to the bioplastic samples.
Thawien Bourtoom, of the Prince of Songkla University, Thailand, in his paper (2007) discusses
the effects of the common types of plasticizers used and their effects on various properties like
tensile strength, elongation at break and water vapour permeability of the bioplastic film.
Applications of bioplastics, especially in the packaging industry have been discussed in the paper
by Nanou Peelman et al (2013) where biobased polymers used as a component in (food)
packaging materials is considered, different strategies for improving barrier properties of
biobased packaging and permeability values and mechanical properties of multi-layered biobased
plastics is also discussed.

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Chapter 2
Plastics

9
2. Plastics
2.1 History

A plastic is a type of synthetic or man-made polymer; similar in many ways to natural resins
found in trees and other plants. Webster's Dictionary defines plastics as: any of various complex
organic compounds produced by polymerization, capable of being moulded, extruded, cast into
various shapes and films, or drawn into filaments and then used as textile fibres.

The development of artificial plastics or polymers started around 1860, when John Wesley Hyatt
developed a cellulose derivative. His product was later patented under the name Celluloid and
was quite successful commercially, being used in the manufacture of products ranging from
dental plates to men’s collars.

Over the next few decades, more and more plastics were introduced, including some modified
natural polymers like rayon, made from cellulose products. Shortly after the turn of the century,
Leo Hendrik Baekeland, a Belgian-American chemist, developed the first completely synthetic
plastic which he sold under the name Bakelite.

In 1920, a major breakthrough occurred in the development of plastic materials. A German


chemist, Hermann Staudinger, hypothesized that plastics were made up of very large molecules
held together by strong chemical bonds. This spurred an increase in research in the field of
plastics. Many new plastic products were designed during the 1920s and 1930s, including nylon,
methyl methacrylate, also known as Lucite or Plexiglas, and polytetrafluoroethylene, which was
marketed as Teflon in 1950.

Nylon was first prepared by Wallace H. Carothers of DuPont, but was set aside as having no
useful characteristics, because in its initial form, nylon was a sticky material with little structural
integrity. Later on, Julian Hill, a chemist at DuPont, observed that, when drawn out, nylon
threads were quite strong and had a silky appearance and then realized that they could be useful
as a fibre.

The World Wars also provided a big boost to plastic development and commercialization. Many
countries were struck by a shortage of natural raw materials during World War II. Germany was

10
cut off quite early on from sources of natural latex and turned to the plastics industry for a
replacement. A practical synthetic rubber was developed as a suitable substitute. With Japan’s
entry into the war, the United States was no longer able to import natural rubber, silk and many
metals from most Far Eastern countries. Instead, the Americans relied on the plastics industry.
Nylon was used in many fabrics, polyesters were used in the manufacturing of armour and other
war materials and an increase in the production synthetic rubbers occurred.

Advances in the plastics industry continued after the end of the war. Plastics were being used in
place of metal in such things as machinery and safety helmets, and even in certain high-
temperature devices. Karl Ziegler, a German chemist developed polyethylene in 1953, and the
following year Giulio Natta, an Italian chemist, developed polypropylene. These are two of
today’s most commonly used plastics. During the next decade, the two scientists received the
1963 Nobel Prize in Chemistry for their research of polymers.[1]

2.2 Classification, Structure and Uses

Plastics are essentially a by-product of petroleum refining. In plastics production, the


components of oil or natural gas are heated in a cracking process, yielding hydrocarbon
monomers that are then chemically bonded into polymers. Different combinations of monomers
produce polymers with different characteristics.

The basic backbone of a hydrocarbon polymer is a chain of carbon atoms, with hydrogen atoms
branching off the carbon spine. Some plastics contain other elements as well. For example,
Teflon contains fluorine, PVC contains chlorine, and nylon contains nitrogen.

Plastics have vast applications in all walks of life. They are used from manufacturing of
packaging items, furniture, and fabrics to medical equipment and construction articles.

There are various reasons for the popularity of plastics. Some of them are

 Low cost
 Resistance to chemical solar and microbial degradation
 Thermal and chemically insulating properties
 Low weight

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Plastics can also be custom-designed for innumerable uses like prosthetic limbs, bullet proof
vest etc. The use of plastic materials in cars and airplanes reduces their weight and therefore
increases their fuel efficiency.

Plastics are broadly classified into two main categories. These are explained in the table below
which gives a broad overview of both the types. [4]

Plastics

Thermosets
Thermoplastics
1. Solidifies or sets irreversibly when
heated. 1. Softens when exposed to heat and returns
to original condition at room temperature.
2.The molecules of these plastics are cross
linked in three dimensions and this is why 2. Do not undergo significant chemical
they cannot be reshaped or recycled. change.
3.They are useful for their durability and 3. Weak bond, which becomes even more
strength. weak on reheating.
4. Used primarily in automobiles and 4. Thermoplastics can easily be shaped and
construction applications. Other uses are molded into products such as milk jugs, floor
adhesives, inks, and coatings. coverings, credit cards, and carpet fibers

2.3 Problems associated with plastics

Despite their many uses and desirable properties, petroleum based conventional plastics have
many disadvantages. The major reasons for looking at alternatives to plastics are because of the
following drawbacks:

1. Production Problems

Plastics are derivatives of petroleum, natural gas or similar substances. They are transformed into
a polymer resin, which is then shaped and formed into whatever object is desired. However, as a
petroleum by-product, plastics contribute to oil dependency, and in the present times it is
generally recognized that oil will not be available indefinitely. This points to a possible raw

12
material crisis in the future.

2. Plastic Recycling

Although many types of plastics could potentially be recycled, very little plastic actually enters
the recycling production process. The most commonly recycled type of plastic is polyethylene
terephthalate (PET), which is used for soft drink bottles. Approximately 15 to 27 percent of PET
bottles are recycled annually. The other type of plastic which is somewhat commonly recycled is
high-density polyethylene (HDPE), which is used for shampoo bottles, milk jugs and two thirds
of what are called rigid plastic containers. Approximately 10 percent of HDPE plastic is recycled
annually.

These figures show that most of the plastics manufactured do not get recycled and as production
continues unabated, this poses a serious problem.

3. Landfill Disposal

The vast majority of plastics, especially plastic bags, wind up in landfills. The fact that available
landfill space is becoming increasingly scarce and plastics are non biodegradable poses special
problems for landfills.

Compounding the issue is the survey (Zero Waste America. (1988-2008)) which found that 82
percent of the surveyed landfill cells had leaks, while 41 percent had a leak larger than 1 square
foot.

Also these leaks are detectable only if they reach landfill monitoring wells. Both old and new
landfills are usually located near large bodies of water, making detection of leaks and their
cleanup difficult.
All these issues point to the fact that landfill disposal of plastics is not a sustainable solution.

4. Incineration

Some industry officials have promoted the incineration of plastic as a means of disposal. A
similar process of pyrolysis breaks plastics into a hydrocarbon soup which can be reused in oil
and chemical refineries. However, both incineration and pyrolysis are more expensive than
recycling, more energy intensive and also pose severe air pollution problems. In 2007, the EPA

13
acknowledged that despite recent tightening of emission standards for waste incineration power
plants, the waste-to-energy process still “create significant emissions, including trace amounts of
hazardous air pollutants”.

Incinerators are a major source of 210 different dioxin compounds, plus mercury, cadmium,
nitrous oxide, hydrogen chloride, sulphuric acid, fluorides, and particulate matter small enough
to lodge permanently in the lungs. (U.S. Environmental Protection Agency. (2007, December
28). Air Emissions)

5. Adverse effect on Biodiversity

Plastic debris affects wildlife, human health, and the environment. Plastic pollution has directly
or indirectly caused injuries and deaths in 267 species of animals (including invertebrate groups)
that scientists have documented. These problems are because of various reasons which include
poisoning due to consumption of plastics, suffocation due to entanglement in plastic nets etc.

The millions of tons of plastic bottles, bags, and garbage in the world's oceans are breaking down
and leaching toxins posing a threat to marine life and humans. Some marine species, such as sea
turtles, have been found to contain large proportions of plastics in their stomach. When this
occurs, the animal typically starves, because the plastic blocks the animal's digestive tract. In
some cases small bits of plastics are accidently consumed by animals. Any such animal, if eaten
by another will cause the plastics to travel up the food chain. This may cause serious health
hazards in a wide array of creature.

6. The Carbon Cycle

When a plant grows, it takes in carbon dioxide, and when it biodegrades, it releases the carbon
dioxide back into the earth – it’s a closed loop cycle. When we extract fossil fuels from the earth,
we disrupt the natural cycle, and release carbon dioxide into the atmosphere faster than natural
processes can take it away. As a result, the atmosphere is getting overloaded with carbon
dioxide. Additionally, fossil fuels take millions of years to form, and are therefore non-renewable
resources. In other words, we are using our fossil resources faster than they can be replaced.

When we make products like plastics from fossil fuels, we are contributing to the imbalance in
the environment while depleting valuable fossil resources, thereby increasing the carbon

14
footprint of the product. Bioplastics, on the other hand, can replace nearly 100% of the fossil fuel
content found in conventional plastics, and require considerably less energy for production. [2], [3]

[5]

Plastics are so vital to our lives and so versatile in their usage, their use cannot be completely
stopped. Hence alternative solutions to this problem are being looked into. The most promising
answer seems to be coming in the form of bioplastics.

15
Chapter 3
Bioplastics

16
3. Bioplastics
3.1 Introduction

Plastics that are made from renewable resources (plants like corn, tapioca, potatoes, sugar and
algae) and which are fully or partially bio-based, and/or biodegradable or compostable are called
bioplastics.

European Bioplastics has mentioned 2 broad categories of bioplastics:

 Bio based Plastics: The term bio based means that the material or product is (partly)
derived from biomass (plants). Biomass used for bioplastics stems from plants like corn,
sugarcane, or cellulose.
 Biodegradable Plastics: these are plastics which disintegrate into organic matter and
gases like CO2, etc in a particular time and compost which are specified in standard
references (ISO 17088, EN 13432 / 14995 or ASTM 6400 or 6868).

However, it should be noted that the property of biodegradation does not depend on the resource
basis of a material, but is rather linked to its chemical structure. In other words, 100 percent bio
based plastics may be non-biodegradable, and 100 percent fossil based plastics can biodegrade.
[22]

17
The figure below explains the broad categories into which bioplastics are divided.

[22]

Thus all the highlighted regions in the graph represent bioplastics. They can thus be bio based-
biodegradable, non bio based-biodegradable and bio based-non biodegradable.

18
The table below gives a short comparison of various properties of both the plastics. [17]

19
3.2 History

Event Date: Event:

The First Man-made Plastic (Bioplastic) :


At the Great International Exhibition in London, Alexander Parkes (1813-
1890), a chemist and inventor, displayed a mouldable material made of
1st Jan, 1862 cellulose nitrate and wascalles called Parkesine. Parkesine was greeted
with great public interest, so Parkes began the Parkesine Company at
Hackney Wick, in London. However it wasn’t very successful
commercially.

Reinvention:
After the fall of the Parkesine Company, a new name in bioplastics
8th Aug, 1869 surfaced. In 1869, John Wesley Hyatt, in an effort to find a new material
for billiard balls other than ivory, invented a machine for the production of
stable bioplastic. He was able to patent the material as Celluloid.

Discovery of Conventional Plastics:


28th Mar,
The discovery of petroleum plastics. The beginning of a long road that is
1907
coming to a dead end.

Ford Goes Bioplastic:


In the 1920's, Henry Ford, in an attempt to find other non-food purposes
8th Sep, 1924 for Agricultural surpluses. Ford began making bioplastics for the
manufacturing of automobiles. The bioplastics were used for steering
wheels, interior trim and dashboards. Ford has been using them ever since.

The Discovery of Polyethylene :


In 1933, two chemists, E.W. Fawcett and R.O. Gibson discovered
12th Jun, 1933
polyethylene on accident. While experimenting with ethylene and
benzaldehyde, the machine that they were using sprang a leak and all that

20
Event Date: Event:

was left was polyethylene. They were credited with the discovery of the
polymerization process.

The First Bioplastic Car:


Henry Ford unveiled the first plastic car in 1941. This car had a bioplastic
13th Aug, 1941
body and parts consisting of 14 different bioplastics. There was a lot of
interest, but soon after, WWII started and attentions were diverted.

A British Company, Imperial Chemical Industries, developed a bioplastic,


9th Aug, 1990
Biopol, which is biodegradable. This was the beginning of the bioplastic
revolution.

[1]

21
3.3 Life Cycle

The figure below shows the lifecycle of a generic bioplastic.

[2]

22
3.4 Economic Scenario

Bioplastics are used in an increasing number of markets – from packaging, catering products,
consumer electronics, automotive, agriculture/horticulture and toys to textiles and a number of
other segments.

The world currently utilises approximately 260 million tonnes of plastics each year. Bioplastics
make up about 0.1% of the global market.

3.4.1 Market Size

Growing demand for more sustainable solutions is reflected in growing production capacities of
bioplastics: in 2011 production capacities amounted to approximately 1.2 million tonnes. Market
data of “European Bioplastics” forecasts the increase in the production capacities by fivefold by
2016 – to roughly 6 million tonnes.

The factors driving market development are both internal and external. External factors make
bioplastics the attractive choice. This is reflected in the high rate of consumer acceptance.
Moreover, the extensively publicised effects of climate change, price increases of fossil
materials, and the increasing dependence on fossil resources also contribute to bioplastics being
viewed favourably.

23
[13], [2]

COPA (Committee of Agricultural Organisation in the European Union) and COGEGA (General
Committee for the Agricultural Cooperation in the European Union) have made an assessment of
the potential of bioplastics in different sectors of the European economy:

24
Product Tonnes/ year (2001)

Catering products 450,000


Organic waste bags 100,000
Biodegradable mulch foils 130,000
Biodegradable diaper foils 80,000
Foil packaging 240,000
Vegetable packaging 400,000
Tyre components 200,000
Total 2,000,000

The market research institute Ceresana expects the global bioplastics market to reach revenues of
more than US$2.8 billion in 2018 - reflecting average annual growth rates of 17.8%. Bioplastics
are supposed to contribute to protecting the climate, provide a solution for the waste issue,
reduce the dependence on fossil raw materials, and improve the image of plastic products. With a
roughly 35% share, Europe was the largest outlet for bioplastics in 2010, followed by North
America and Asia-Pacific.

Gobal production capacity


of bioplastics in 2011 (by region)
Asia North America Australia South America Europe

18.5%
34.6%

32.8%
13.7%

0.4% [13]
Total: 1,161,200 tonnes

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Over the next eight years, shares in demand of the individual world regions will shift
significantly. Ceresana forecasts two regions to considerably influence the bioplastics market.
Because of dynamic growth in consumption and production, Asia-Pacific will expand its share of
bioplastics demand. As a result, Asia-Pacific will almost draw level with Europe and North
America. In addition, South America will see strong growth, mainly because of massive
increases in production in Brazil

Global production capacity of bioplastics in


2016( by region)
South America Asia Europe North America Australia

4.9% 3.5% 0.2%

45.1%

46.3%

. Total: 5,778,500 tonnes [13]

3.4.2 Cost

With the exception of cellulose, most bioplastic technology is relatively new and currently not
cost competitive with (petro plastics). Bioplastics do not reach the fossil fuel parity on fossil fuel
derived energy for their manufacturing, reducing cost advantage over petroleum-based plastic.

26
Bioplastics Market Share
Cellulose acetate Polylactic Acid (PLA)
Extruded Starch Thermoplastic Starch/ Blends
Polyhydroxyalkanoates (PHAs) and others

10% 15%

15%

40%
20%

[17]

Forecast market growth is predicted to be greatest in non-biodegradable bioplastics. Bioplastics


could also be used in more sophisticated applications such as medicine delivery systems and
chemical microencapsulation. They may also replace petrochemical-based adhesives and
polymer coatings. However, the plastics market is complex, highly refined and manufacturers are
very selective with regard to the specific functionality and cost of plastic resins. For bioplastics
to make market grounds they will need to be more cost competitive and provide functional
properties that manufacturers require.

27
3.5 Applications

[13]

Bioplastics are used in a wide variety of fields. Some of them are:

3.5.1 Packaging

Today, biopackaging can be found in many European supermarkets. Sainsbury in the UK may be
cited as a pioneer – who first recognised the opportunities for compostable plastics packaging.
Many Supermarket chains such as Delhaize (Belgium), Iper (belonging to the Carrefour group;
Italy), Albert Heijn (Netherlands) and Migros (Switzerland) are actively placing their trust in
biopackaging. Last year, the world`s largest retailer, Wal-Mart, introduced its first range of
products in corn-based PLA packaging throughout the USA.

For supermarkets, it is also an enormous advantage to be able to compost unsold perished food
products cheaply together with their packaging rather than have to separate the contents from the

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packaging at considerable cost. Food residues do not interfere in the slightest with this recycling.
The same applies to compostable service packs, such as trays, plates, cups or cutlery.

i. Bags

Concerns over litter, the perceived waste of a single use item and the management of bio-waste
have made this one of the fastest growing sectors for bioplastics in the early
21st century. Bioplastics form excellent replacements to conventional oil based materials in this
sector with great performance characteristics, strength, good contact clarity and proven high
speed production.

ii. Wraps

Bioplastics can be converted into waterproof and fat resistant film for a wide variety of wrapping
and packing eco-options. A great natural feel and appropriate barrier technology allows products
like cheese to breathe on the path to the consumer. Flexible materials with paper-like dead-fold
characteristics broaden the application range. [7], [9], [10], [16], [20], [23]

3.5.2 Agriculture & Horticulture

The usually inherent property of biodegradability offers specific advantages in agriculture and
horticulture.

i. Mulch film

Bioplastics can be converted into fully opaque or semi-transparent films that provide the ideal
growing environment yet can be ploughed into the ground at the end of the growth cycle,
providing soil nutrition for future seasons. Producing pure foods with a minimum of pesticide
use is a powerful sales argument in vegetable-growing or organic farming. Ploughing-in
mulching films after use instead of collecting them from the field, cleaning off the soil and
returning them for recycling, is practical and improves the economics of the operation.

29
Mulch Films made of PLA Bioplastics

ii. Tree protectors and Plant supports/stakes:

Bioplastics are being developed as an answer to forest litter, providing a guard that enables
young trees to get the best possible start. Protection from vermin and hostile environment is
assured early in the growing cycle but the material will bio-disintegrate as the tree passes into
maturity. Unsightly litter is removed and collection costs on managed woodland eliminated.

Horticulturalists now choose bioplastics to make functional plant holders that are strong, water
resistant, in a choice of colours and have the ability to decompose naturally into biomass. [7], [23],
[24]

3.5.3 Personal Care and Hygiene

Most personal care items like toothbrushes, razors etc can be manufactured from bioplastics.
Matt finishing of the bioplastics ensures that the plastic razor has good grip and gives a smooth
shave. The material surface characteristics ensure good grip performance whilst providing a
device that will withstand every day use. Testing for products in this sector has demonstrated
suitable thermal, moisture and fatigue performance.

Meanwhile bioplastics can be blown to form opaque, soft-feel bottles for the likes of shampoos
and creams. Complementing bioplastic caps can be injection or compression moulded.

30
These products are one time use and throw products, if bioplastics can be used here, it can solve
the problem of plastic as a gross waste to a large extent.[7],[23]

3.5.4 Electronics

In 2009, Japanese multinational, NEC has successfully developed and implemented a flame-
retardant bio-plastic that can be used in electronic devices due to its high flame retardancy and
processability. The new bioplastic includes more than 75% biomass components, and can be
produced using manufacturing and moulding processes that halve the CO2 emissions of
conventional processes used to make petroleum-based flame-retardant plastics (PC/ABS
plastics). NEC's new bioplastic is therefore one of the most environmentally friendly flame
retardant plastics used for casing of electronic devices in the world

In another case, Mitsubishi Plastics, Inc has already succeeded in raising the heat-resistance and
strength of polylactic acid by combining it with other biodegradable plastics and filler, and the
result was used to make the plastic casing of a new version of Sony Corp.'s Walkman. Mitsubishi
Plastics had previously looked at bioplastic as something that would mainly be used in the
manufacture of casings and wrappings, but the company now feels confident that this
revolutionary material has entered a new phase in its development in which more complex
applications will be found. [14]

3.5.5 Automobiles

Ford Motor Corp. was the first automaker in the world to use bioplastics in the manufacture of
auto parts way back in the 1920s. Recently, Toyota motor corp. employed them in the cover for

31
the spare tire in the Raum, a new model that went on sale this May. The bioplastic used here is
polylactic acid (PLA) is made from plants, such as sweet potatoes and sugarcane.

A spokesperson for Toyota Motor's Biotechnology and Afforestation Business Division


expresses high hopes for the future of bioplastics, saying, "The inside of a car gets very hot and
is exposed to shocks while the vehicle is running. If bioplastics can be used in this tough
environment, they can be used in ordinary household products or anywhere else."[15]

3.5.6 Food Packing

In a new study published on June 6, 2013 in the peer-reviewed scientific journal Trends in Food
Science and Technology, researchers from the University of Gent review the application of
bioplastics in food packaging (Peelman et al 2013). The main bioplastics are polylactide (PLA),
starch, polyhydroxyalkanoates (PHA) and cellulose. PLA is the most widely used bioplastics
with application for fresh foods, dry foods such as pasta and potato chips, fruit drinks, yoghurt,
and meat. Starch has been used as an alternative for polystyrene (PS) to package tomatoes and
chocolate. Cellulose is used to package dry foods and fresh produce. While all of these materials
are biodegradable, their functional limitations have so far restricted their widespread application
in food packaging. As outlined by Peelman and colleagues, the main limitations of the four
materials is their brittleness, thermal instability, low melt strength, difficult heat sealability, high
vapour and oxygen permeability, poor mechanical properties, stiffness and poor impact
resistance.

In their study Peelman and colleagues review three processes, which may be used to improve the
properties of bioplastics, namely coating, blends and chemical/physical modifications.

i. Coating

Coating comprises the application of a thin bio based or non-bio based layer to the bioplastics.
Such coatings can lower the oxygen and vapour permeability, increase tensile strength and result
in higher elastic properties.

ii. Blending

Blending bioplastics is another approach to improve functionality. Cellulose and other bio based
materials may be used to create improved blends. Most bioplastics are immiscible; however the

32
introduction of functional groups, chemical modification or esterification can enhance
compatibility. Blending can reduce brittleness, increasing vapour water barrier properties,
flexibility, and tensile strength.

iii. Chemical and/or physical modification

The third approach to improve functionality is chemical and/or physical modification. It can be
used to enhance compatibility between two polymers or to improve the functional properties
directly. Citric acid added to starch films improves water and vapour properties (WVP).
Crosslinking cellulose acetate with phosphates improves tensile strength and slows water uptake
and degradation. Epichlorohydrin-modified starch has an increased tensile strength and improved
elongation. Partially substituting wheat gluten with hydrolyzed keratin or soaking wheat gluten
film in CaCl2 and distilled water improves the water vapour and oxygen barrier properties of a
wheat gluten derived film.

Peelman and colleagues conclude that using coatings, blending and chemical/physical
modification can extend the use of bioplastics in food packaging to a wide variety of food other
than fresh produce and dry foods. [16]

3.5.7 Construction

The Institute of Building Structures and Structural Design (ITKE) at the University of Stuttgart
(Germany) has worked on fibre-reinforced polymers, bionics and the development of new
building materials. Architect Carmen Köhler is investigating the applicability of natural fibre-
reinforced biopolymers in the construction industry. In contrast to fibreglass-reinforced
polymers, natural fibre-reinforced polymers are considerably lighter, emission stable and
breathable. “Construction material that is breathable at the same time as preventing moisture
from penetrating, is also of major interest in architectural terms,” said Carmen Köhler explaining
that she finds the material suitable for facades and insulations.
The group of researchers are currently investigating polylactide, cellulose acetate and other
materials. Selection criteria are price, temperature stability and the potential use of additives
during processing. “We hope that the material will be classified as B2 or even B1 class
construction material,” said Köhler explaining that B1 and B2 refer to the degree of
imflammability of materials, which should be as low as possible.

33
Classification:
A1 (100% non-combustible)
A2 (~98% non-combustible)
B1 difficult to ignite
B2 normal combustibility (like wood)
B3 easily ignited

The testing of the material has shown that cellulose acetate and polylactide (PLA) are very
resistant to UV. The biopolymers did not become discoloured to the same extent as traditional
transparent polymers when exposed to sunlight.
Cellulose acetate is already used for transparent heat insulation.

But there are a lot more markets starting to use bioplastic materials such as buildings and
construction, household, leisure or fibre applications (clothing, upholstery).

Products that show vast growth rates include bags, catering products, mulching films or
food/beverage packaging. Functional properties are often crucial in the user decision. The
environmental aspect and the very high consumer acceptance are additional selling points. [8]

34
3.6 Advantages of Bioplastics

3.6.1 Eco Friendly

Traditional plastics are the petroleum based plastics which depend on fossil fuels which is an
unsustainable source. Also acquiring fossil fuels does a lot of harm to the natural environment.
Bioplastics on the other hand are made from bio mass like trees, vegetables, even waste which is
completely bio degradable. So bioplastics are made from completely renewable source. Even
during the manufacturing of plastics, a lot of pollution occurs, for example, during production,
PVC plants can release dioxins, known carcinogens that bio-accumulate in humans and wildlife
and are associated with reproductive and immune system disorders

3.6.2 Require less time to degrade

Traditional plastics take thousands of years to degrade, these plastics lie in the environment,
most notably on the ocean floor where they do the maximum damage for years. These plastics
hamper the growth and kill the natural habitats.

Bioplastics on the other hand, require considerably less time to biodegrade. This degradation can
be carried out at home for some bioplastics and even for the bioplastics which require specific
conditions, time required to degrade completely is considerably less. This reduces the huge
pressure on our existing landfills

3.6.3 Toxicity

Some of the plastics degrade rapidly in the oceans releasing very harmful chemicals into the sea,
thus harming the animals, plants and also harming the humans by entering the food chain.

Biodegradable plastics are completely safe and do not have any chemicals or toxins. This plastic
harmlessly breaks down and gets absorbed into the earth. Such advantages of bioplastics are of
extreme importance, as the toxic plastic load on the earth is growing and at this rate will cause a
whole range of problems for future generations

3.6.4 Lower energy consumption

Companies still use fossil fuels for the manufacture of bioplastics; however, many bioplastics use
considerably less fuel for their manufacture. For example,

35
Polylactic acid production requires less energy than other plastics

3.6.5 Environmental protection

Burning fossil resources increases the share of CO2 in atmosphere, which causes an increase of
the average temperature (greenhouse effect). Scientists see a distinct connection between CO 2
increase in atmosphere and the increase of number of thunderstorms, floods and aridity. Climate
protection is nowadays a central part of environmental policy, due to the fact that climate change
can create far-reaching negative consequences. Governments and organisations work against this
threat with targeted measures. [3], [8], [11], [18]

36
3.7 Challenges for Bioplastics

3.7.1 Misconceptions

Even though bio degradable plastics are considered to be good for the environment, they can
harm the nature in certain ways. Emission of Greenhouse gases like methane and carbon dioxide,
while they are degrading, is very large at landfill sites.

This can be handled by designing plastics so that they degrade slowly or by collecting the
methane released and use it elsewhere as fuel.

Some bioplastics need specific conditions to bio degrade, these conditions may not be available
at all the landfills or consumers may not have access to landfills, in such case it becomes
important to design bioplastics which are bio degradable in a normal soil compost

3.7.2 Environmental Impact

Starch based bioplastics are produced generally from plants like corn, potatoes and so on. This
puts massive pressure on the agricultural crops as they have to cater the need of ever growing
population. To make plastics, crops have to be grown and this could lead to deforestation

Bioplastics are generally produced from crops like corn, potatoes, and soybeans. These crops are
often genetically modified to improve their resistance to diseases, pests, insects etc. and increase
their yield. This practise however carries a very high risk to the environment as such crops can
be toxic for humans as well as for animals. [17]

3.7.3 Cost

Bioplastics are a newer technology and require still more research and development to get
established. Bioplastics are not thus, comparable to plastics with respect to cost.

37
Chapter 4
Experimental
Procedure

38
4.1 Experimental Procedure

4.1.1 Preparation of Banana Skins

Step 1: Banana peels are boiled in water for about 30 minutes

Step 2: The water is decanted from the beaker and the peels are now left to dry on filter paper for
about 30 minutes

Step 3: 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.

4.1.2 Production of Polymer

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 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
till dry.

Step 6: The tile is allowed to cool and the film is scraped off the surface

4.1.3 Synthesis of plastics was carried out in two phases

Stage 1: In this stage, the process parameters pH and Hydrolysis time were changed over a range
of values. Each sample produced was then tested for the strength based on the testing procedure
mentioned in the following stage. The best combination was obtained and used for the 2nd stage
of testing

Stage 2: In this stage, the commonly available plasticizers are compared. Based on the values of
parameters finalized from the earlier stage, fresh samples were synthesized and tested.

39
4.2 Reaction Mechanism

4.2.1 Hydrolysis

Starch consists of two different types of polymer chains, called amylose and amylopectin, made
up of adjoined glucose molecules. 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.

Amylopectin

Amylose

Acid hydrolysis changes the physiochemical properties of starch without changing its granule
structure. A research by Kerr et al (1952) said that at the temperature below the gelatinization
temperature, the amylopectin region of starch gets hydrolysed preferentially than the amylose
region. Also, if the amylopectin content is higher in the starch, the recovery of starch decreases
i.e. more of the starch gets hydrolysed.

In a research by M.N. Abdorezza et al (2012), native starch obtained from the stem of palm trees
was hydrolysed using 0.14N HCl. During the initial stages of hydrolysis, the amylose content
increased, this can be attributed to the fact that due the hydrolysis of branched chains of
40
amylopectin, linear chained amylose were formed. However, if the hydrolysis time was
increased up to 6 hours, the amylose content decreased albeit slightly. If this hydrolysis time was
increased up to 12 hours, the analysis revealed significant drop in the amylopectin and amylose
content of starch.

4.2.2 Addition of NaOH

In a study conducted by Ya-Jane Wang et al (2003) Common corn starch was treated with
different concentrations of hydrochloric acid, 0.06, 0.14, and 1.0N. It was observed that as the
concentration of the acid increased, the rate and the extent of the hydrolysis increased
significantly. The 1.0N acid hydrolysed amylopectin as well as amylose to a very large extent.

A study was conducted by Karntarat Wuttisella et al (2008) on Analysis of shift of wavelength


maximum using rapid colorimetric method was used to determine the Amylose: Amylopectin
ratio in native tapioca starch before and after hydrolysis using HCl.

The Am:Ap ratio in native tapioca starch was approximately 22:78. The figure below shows that
the Am:Ap ratio obtained by an iodometry method at a single wavelength (λ610) measurement
decreased with hydrolysis time using 2 M HC1. but not with 0.7 M HC1. This change was seen
after 30 min of incubation.[27],[28]

41
4.2.3 Glycerine as a Plasticizer

Plasticizers are generally small molecules such as polyols like sorbitol, glycerol and
polyethylene glycol (PEG) that intersperse and intercalate among and between polymer chains,
disrupting hydrogen bonding and spreading the chains apart, which not only increases flexibility,
but also water vapour and gas permeabilities.

Thermoplastic starch (TPS) materials are obtained from granular starch mixed with plasticizers
to enable melting below the decomposition temperature.

According to a study conducted by A.L.M. Smits, P.H. Kruiskamp, J.J.G. van Soest, J.F.G.
Vliegenthart, on heating starch freshly mixed with plasticizers, a strong exothermal interaction
enthalpy of ∆H ~ –35 J/g was detected by Differential Scanning Colorimeter (DSC). The
transition enthalpy is proportional to the amounts of glycerol or ethylene glycol added,
suggesting that the plasticizer is responsible for the observed exothermic event

42
However, specific interactions between plasticizer and starch chains are difficult to elucidate. It
is generally accepted that plasticizers lower the number of physical cross- links between starch
chains, and consequently retard the rate of retrogradation.

The process is irreversible, since reheating of the samples showed no exothermal enthalpy peak.
Heat treatment gives rise to a strong starch-plasticizer interaction, most probably caused by H-
bond formation.

Plasticizers can be used to influence this ageing induced by retrogradation. For instance, in bread
the degree of retrogradation is strongly reduced by the addition of monoglycerides, which
interact with the initially amorphous amylopectin. Van Soest et al. showed that an increasing
glycerol concentration in a waxy maize starch gel reduces the rate of retrogradation. The
inhibiting effect of various saccharides on retrogradation has also repeatedly been reported.

A study by the Department of Material Product Technology, Prince of Songkla University,


Thailand shows the effect of various commonly used plasticizers viz. sorbitol, glycerol and
polyethylene glycol which are studied over a range of concentration from 20 to 60%.

The results of this study demonstrates that sorbitol plasticized films provided the films with
highest mechanical resistance, but the poorest film flexibility. In contrast, glycerol and
polyethylene glycol plasticized films exhibited flexible structure; however, the mechanical
resistance was low, while inversely affecting the water vapour permeability. Type and
concentration of plasticizers affected the film solubility. Increasing the plasticizer concentration
resulted in higher solubility. The colour of biodegradable blend film from rice starch-chitosan
was more affected by the concentration of the plasticizer used than by its type.

43
Chapter 5
Testing Procedure

44
5. Testing Procedure

The following procedure was adopted to test the tensile strength of the samples. The process has
the following steps:

Step 1. Visual Analysis of the sample to locate any defects in it. If the sample has no defects it
can be used for testing. The common forms of defects are

i) Perforations and tears in the sample.

ii) Very low thickness

Step 2. After the sample is approved for testing, a 2cm by 4cm rectangular slice is cut out of the
sample for testing. The slice dimensions are kept constant for all samples to ensure uniformity in
the testing procedure.

Step 3. The slice of sample obtained is the clamped between 2 clips. One end of the clip is
attached to a support and the other end has a suspended pan for placing weights in them.

Step 4. The clamping positions are also kept constant. The figure below shows the sample with
the clamping locations. Applying the thumb rule for tensile strength testing, the samples are
clamped such that 60% of the sample is between the clamps and is our testing region.
20%
60%

Sample
20%
4cm

2 cm

Step 5. Once the sample has been clamped, weights are added in steps of 10 grams each. A gap
of 20 seconds is provided between the addition of weights to allow the sample to stretch and tear.

45
Step 6. The final weight at which the sample tears is noted using an electronic balance.

Step 7. For tensile strength calculations, we use the following formula:

The weight is calculated from the electronic balance readings. Now for the cross-sectional area
we use a Vernier calliper (TOYO™ Instruments; Least Count = 0.02 mm) to measure the
thickness. 5 readings are taken across the length of the sample to consider local variations in
thickness and the average of all is computed. The product of the sample width (2 cm) and the
average thickness gives us the cross-sectional area of the sample. Thus using the above equation
we calculate the tensile strength for all samples.

Schematic Representation of testing Apparatus

46
Chapter 6
Experimental Trials
Conducted

47
6.1 Number of Trials:

6.1.1 Trial 1 conducted on 18/03/2014

Sample pH Residence Time Weight of the Weight of the


(minutes) final paste film (grams)
(grams)

18/03-1 Acidic 5 33.56 4.095


18/03-2 Acidic 10 32.45 3.72
18/03-3 Acidic 15 31.89 4.361
18/03-4 Acidic 20 32.51 4.133

Status of trial: Rejected


Reason: This trial was rejected due to the presence of perforations in the samples which
made them unsuitable for testing.

6.1.2 Trial 2 conducted on 19/03/2014

Sample pH Residence Time Weight of the Weight of the


(minutes) final film(grams)
paste(grams)

19/03-1 Neutral 5 45.205 3.598


19/03-2 Neutral 10 49.668 3.689
19/03-3 Neutral 15 45.365 3.128
19/03-4 Neutral 20 44.663 2.815

Status of trial: Rejected

48
Reason: This trial was rejected due to the presence of excess water in the paste which
made the samples very thin.

6.1.3 Trial 3 conducted on 25/03/2014

Sample pH Residence Time Weight of the Weight of the


(minutes) final film(grams)
paste(grams)

25/03-4 Basic 5 42.56 5.678


25/03-3 Basic 10 38.286 5.32
25/03-2 Basic 15 43.78 4.88
25/03-1 Basic 20 38.086 4.913

Status of trial: Rejected


Reason: This trial was rejected due to the incorrect concentration of NaOH taken for the
experiments. This made the sample set inconsistent with any standards of testing.

6.1.4 Trial 4 conducted on 26/03/2014

Sample pH Residence Time Weight of the Weight of the


(minutes) final film(grams)
paste(grams)

26/03-4 Basic 5 33.849 5.833


26/03-3 Basic 10 34.475 3.852
26/03-2 Basic 15 33.968 4.528
26/03-1 Basic 20 33.946 4.569

Status of trial: All except sample 26/03-3 were accepted and tested.

49
Reason: This sample 26/03-3 was badly damaged during the production and could not
be used for further testing.

6.1.5 Trial 5 conducted on 1/04/2014

Sample pH Residence Time Weight of the Weight of the


(minutes) final film(grams)
paste(grams)

1/04-4 Neutral 5 33.43 4.344


1/04-3 Neutral 10 33.066 4.409
1/04-2 Neutral 15 32.225 3.823
1/04-1 Neutral 20 32.881 4.197

Status of trial: All except sample 1/04-4 were accepted and tested.
Reason: This sample was rejected as it was not evenly baked.

6.1.6 Trial 6 conducted on 1/04/2014

Sample pH Residence Time Weight of the Weight of the


(minutes) final film(grams)
paste(grams)

1/04-8 Acidic 5 31.649 4.21


1/04-7 Acidic 10 31.365 3.711
1/04-6 Acidic 15 30.018 4.904
1/04-5 Acidic 20 29.997 3.853

Status of trial: All except sample 1/04-6 were accepted and tested.
Reason: This sample was rejected as it was not evenly baked.

50
6.1.7 Trial 7 conducted on 2/04/2014

Sample pH Residence Time Weight of the Weight of the


(minutes) final film(grams)
paste(grams)

2/04-3 Neutral 5 33.066 4.352


2/04-2 Basic 10 33.605 3.925
2/04-4 Acidic 15 30.661 3.806

Additional Notes: sample 2/04-2 was 26/03-3 performed again


Sample 2/04-3- was 1/04-4 performed again
Sample 2/04-4 was 1/04-6 performed again
Status of trial: Rejected
Reason: All were rejected as the baking was incomplete.

6.1.8 Trial 8 conducted on 3/04/2014

Sample pH Residence Time Weight of the Weight of the


(minutes) final film(grams)
paste(grams)

3/04-3 Neutral 5 33.73 4.61


3/04-4 Basic 10 34.268 4.78
3/04-2 Acidic 15 31.42 3.92

Additional Notes: sample 3/04-4 was 26/03-3 performed again


Sample 3/04-3- was 1/04-4 performed again
Sample 3/04-2 was 1/04-6 performed again
Status of trial: Accepted for testing.

51
6.1.9 Final Trial conducted on 16/04/2014 using the parameters decided from the initial
8 trials and the results of testing
Parameters fixed:
pH- Neutral
Residence Time-15 minutes
Baking temperature- 120o C

Sample Plasticizer Weight of the Weight of the


paste (grams) film
grams)

16/04-2 Glycerine 33.527 3.776


16/04-3 Sorbitol 33.558 3.46
16/04-4 PEG 32.511 3.866

52
Chapter 7
Observations

53
7.1 Stage 1: Initial Trial

7.1.1 Weights supported by the samples

pH Residence Time Sample Weight (grams)


(Minutes)

Acidic 5 1/04-8 341.41


10 1/04-7 351.89
15 3/04-2 200.94
20 1/04-5 271.53

Basic 5 26/03-4 331.2


10 3/04-4 160.9
15 26/03-2 240.89
20 26/03-1 131.15

Neutral 5 3/04-3 231.59


10 1/04-3 331.50
15 1/04-2 406.19
20 1/04-1 301.69

7.1.2 Thickness of the samples:

pH Sample Thickness (mm)


1 2 3 4 5 Mean

Acidic 1/04-8 0.94 0.9 0.8 0.8 0.74 0.836


1/04-7 0.66 0.62 0.6 0.64 0.62 0.628
3/04-2 0.72 0.6 0.48 0.48 0.5 0.556

54
1/04-5 0.5 0.52 0.54 0.56 0.42 0.508

Basic 26/03-4 0.62 0.6 0.68 0.7 0.62 0.644


3/04-4 0.9 0.84 0.7 0.78 0.94 0.832
26/03-2 0.66 0.66 0.7 0.7 0.84 0.712
26/03-1 0.6 0.52 0.54 0.48 0.58 0.544

Neutral 3/04-3 0.6 0.64 0.74 0.68 0.78 0.688


1/04-3 0.62 0.58 0.66 0.68 0.66 0.64
1/04-2 0.6 0.52 0.54 0.66 0.58 0.58
1/04-1 0.6 0.52 0.54 0.62 0.52 0.56

7.2 Stage 2: Final Trial

7.2.1 Weights supported by the samples

pH Plasticizer Residence Time Sample Weight (grams)


(Minutes)

Neutral Glycerine 15 16/04-2 456.2


Neutral Sorbitol 15 16/04-3 794.95
Neutral PEG 15 16/04-4 558.11

7.2.2 Thickness of the samples:

Plasticizer Sample Thickness (mm)


1 2 3 4 5 Mean

Glycerine 16/04-2 0.68 0.6 0.6 0.8 0.72 0.68


Sorbitol 16/04-3 0.48 0.5 0.5 0.5 0.6 0.516
PEG 16/04-4 1.1 0.94 0.82 0.8 0.7 0.872

55
Chapter 8
Calculations

56
8.1 Stage 1: Initial Trial

8.1.1 Conversion of Weights into forces

SR.NO pH Sample Weight (grams) Force(N)

1 Acidic 1/04-8 341.41 3.349232


2 Acidic 1/04-7 351.89 3.452041
3 Acidic 3/04-2 200.94 1.971221
4 Acidic 1/04-5 271.53 2.663709

5 Basic 26/03-4 331.2 3.249072


6 Basic 3/04-4 160.9 1.578429
7 Basic 26/03-2 240.89 2.363131
8 Basic 26/03-1 131.15 1.286581

9 Neutral 3/04-3 231.59 2.271898


10 Neutral 1/04-3 331.50 3.252015
11 Neutral 1/04-2 406.19 3.984724
12 Neutral 1/04-1 301.69 2.959579

57
8.1.2 Calculation of tensile strengths

pH Sample Force (N) Mean Area Tensile


thickness of (mm2) Strength
the sample (MPa)
(mm)

Acidic 1/04-8 3.349232 0.836 16.72 0.200313


Acidic 1/04-7 3.452041 0.628 12.56 0.274844
Acidic 3/04-2 1.971221 0.556 13.76 0.177268
Acidic 1/04-5 2.663709 0.508 10.16 0.262176

Basic 26/03-4 3.249072 0.644 12.88 0.252257


Basic 3/04-4 1.578429 0.832 16.64 0.094858
Basic 26/03-2 2.363131 0.712 14.24 0.165601
Basic 26/03-1 1.286581 0.544 10.88 0.118252

Neutral 3/04-3 2.271898 0.688 13.76 0.164750


Neutral 1/04-3 3.252015 0.64 12.88 0.254064
Neutral 1/04-2 3.984724 0.58 14.24 0.343511
Neutral 1/04-1 2.959579 0.56 10.88 0.264248

58
8.1.3 Calculation of conversion:

Sample Weight of the final Weight of the film Conversion %


paste(grams) (grams)

1/04-8 31.649 4.21 13.3021


1/04-7 31.365 3.711 11.83165
3/04-2 31.42 3.92 12.4761
1/04-5 29.997 3.853 12.8446

26/03-4 33.849 5.833 17.2324


3/04-4 34.268 4.78 13.9488
26/03-2 33.968 4.528 13.3302
26/03-1 33.946 4.569 13.4596

3/04-3 33.73 4.61 13.6673


1/04-3 33.066 4.409 13.3339
1/04-2 32.225 3.823 11.8634
1/04-1 32.881 4.197 12.7642

8.2 Stage 2: Final Trial

Performing the final trial with different set of plasticizers, keeping the parameters pH, residence
time and baking temperature constant.

pH- neutral

Residence time- 15 minutes

59
8.2.1 Calculation of Tensile Strength:

Sample Plasticizer Mean Area (mm2)= Weight Force (N)=


thickness of mean (grams) weight*10-3*
the sample thickness*20 9.81
(mm)

16/04-2 Glycerine 0.68 13.6 456.2 0.329068


16/04-3 Sorbitol 0.516 10.32 794.95 0.753474
16/04-4 PEG 0.872 17.44 558.11 0.313937

8.2.2 Calculation of Conversion:

Plasticizer Weight of the final Weight of the film Conversion %


paste (grams) (grams)

Glycerine 33.527 3.776 11.2625


Sorbitol 33.558 3.649 10.8737
PEG 32.511 3.866 11.8913

60
Chapter 9
Analysis

61
9.1 Stage 1: Varying pH and Hydrolysis Time

9.1.1 Analysis of neutral sample

Tensile Strength Vs Residence Time


0.4
Tensile Strength (N/mm^2)

0.35
0.3
0.25
0.2
0.15 Neutral
0.1
0.05
0
0 5 10 15 20 25
Residence time (mins)

The tensile strength for neutral sample keeps increasing when the residence times are increased
from 5 minutes to 15 minutes and reaches a maximum of 0.3435N/mm2 at 15 minutes and then
starts decreasing when the time is increased to 20 minutes. This suggests that the optimum
hydrolysis time is 15 minutes for this sample set. According to the research paper
“Physicochemical, thermal, and rheological properties of acid-hydrolyzed sago starch” by M.N.
Abdorezza et al (2012) native starch obtained was hydrolysed using dilute HCl. During the initial
stages of hydrolysis, the amylose content increased, this was attributed to the fact that due the
hydrolysis of branched chains of amylopectin, linear chained amylose were formed. However, if
the hydrolysis time was increased further, the amylose content decreased albeit slightly. If this
hydrolysis time was continued uninterrupted for long durations, the analysis revealed significant
drop in the amylopectin and amylose content of starch. This was because once the amylopectin is
hydrolysed to amylase, further hydrolysis leads to formation of glucose monomers which do not
aid in polymer formation

62
9.1.2 Analysis of basic sample

Tensile strength Vs Residence Time


0.3
Tensile Strength (N/mm^2)

0.25

0.2

0.15
Basic
0.1

0.05

0
0 5 10 15 20 25
Residence time (mins)

The tensile strength for the basic samples keeps decreasing as the residence times are increased
from 5 minutes to 20 minutes. Based on the paper “The effect of sodium hydroxide treatment
and fibre length on the tensile property of coir fibre” by Karthikeyan et al (2013), the
experimental results showed that increasing the amount of NaOH leads to a decrease in fibre
diameter in a linear fashion. This reduction in diameter naturally ends up with reduced tensile
strength.

63
9.1.3 Analysis of acidic sample

Tensile Strength Vs Residence Time


Tensile Strength (N/mm^2) 0.3

0.25

0.2

0.15 Acidic

0.1

0.05

0
0 5 10 15 20 25
Residence time (mins)

Based on the paper by Abdorezza et al (2007), an increase in residence time for acidic samples
should lead to a lesser tensile strength because of excessive hydrolysis. However the graph above
shows that the values of tensile strength are fluctuating within a range. This result is a deviation
from expected values and needs further research.

9.1.4 Analysis of all the samples (Tensile Strength)

Tensile Strength Vs Residence Time


(Combined Plot)
0.4
0.35
0.3
0.25
Acidic
0.2
Neutral
0.15
Basic
0.1
0.05
0
0 5 10 15 20 25

64
9.1.5 Analysis of all samples (Conversion)

Conversion Vs Residence Time


50
(Combined)
45
40
35
% Conversion

30
25 Acidic
20 Basic
15 Neutral
10
5
0
0 5 10 15 20 25
Residence Time

The conversion being considered in the graph above is not the chemical conversion of the
process but a relation of the net mass of polymer obtained per unit mass of the reaction mixture
fed into the oven. We can see that these conversions are almost constant for all the samples and
are independent of the pH and the residence times. From this it can be inferred that the
conversion is predominantly a result of the water losses which take place from the samples. The
changes in the chemical compositions, if any, do not contribute to a significant extent

From the combined plot, we observe that the maximum tensile strength from all the samples is
obtained for the neutral sample which has a residence time of 15 minutes. The average strength
of the basic samples, is always lower than the neutral samples.

Since the conversion plot does not show much of a variation for any of the sample, the final
fixing of the parameters solely depends on the combined plot of tensile strength. Thus from
both the combined plots of tensile strength and conversion, we fix

 pH – Neutral
 Residence time- 15 minute

65
as constant parameters for our stage 2 trial, where we conduct the same experiment using
different plasticizer.

9.2 Stage 2- Varying the Plasticizer

9.2.1 Analysis of tensile strengths of all samples for different plasticizers

Tensile Strength for Different


Plasticizers

PEG 400

Tensile Strength for


Sorbitol Different Plasticisers
Tensile Strength
(N/mm^2)

Glycerine

0 0.2 0.4 0.6 0.8

9.2.2 Analysis of conversion of all the samples

Conversion For Different Plasticizers

PEG

Sorbitol

Conversion %
Glycerine

0 10 20 30 40 50

66
We can see from the graph that sorbitol exhibits maximum tensile strength followed by
Glycerine and PEG 400. This is also the observed data from the paper on“Plasticizer effect on
the properties of biodegradable blend film from rice starch-chitosan” by Bourtoom. (2007) from
Prince of Songkla University, Thailand. The table below shows the increasing concentration of
these plasticizers results in decreased tensile strength (TS)

Properties Sorbitol Glycerine PEG

Brittleness Least Flexible Flexible structure Flexible structure

Tensile strength Highest TS 14.31MPa 16.14MPa


:26.06MPa

67
Chapter 10
Preliminary Process
Scheme

68
Preliminary Process Scheme

69
Description:

Since this form of bioplastic product does not have a fixed, defined market, the production has to
be done in a batch process. The location of the plant should be next to a banana processing
facility which makes any value added product like banana chips, flour, puree etc. The large
amount of banana peel waste generated can be used to make bioplastics in situ.

The process for manufacturing the banana based bioplastic is as shown in the flowchart. The
banana peels are gathered in a temporary storage vessel for processing. The peels are then moved
via a screw conveyor to the washing section where the samples are sprayed with water mixed
with mild surfactant to remove the dirt and grit. The samples are then rinsed again to remove the
residual surfactants.

The peels are then transferred to an agitated vessel with a jacket for heating where the banana
peels are boiled. Peels are then filtered to remove excess water and are transferred to stacks of
trays to dry on for half an hour. The drying is done at ambient temperature at atmospheric
conditions.

The dried, boiled peels are then sent to an industrial grinder where they are ground to a paste.
This paste is then sent to a reaction chamber. In it the paste is mixed with dilute 0.5N HCl and a
suitable plasticizer (here sorbitol) for a residence time of 15 minutes. The reaction taking place
here involves acidic hydrolysis of starch. The addition of the plasticizer aids in plastic formation.
A tank with paddle type agitator is selected. Paddle agitator will scrape from the sides and not
allow for formation of pockets.

The reaction mixture is transferred into the neutralization tank to stop the reaction. Here
calculated amounts of 0.5N NaOH are added to the reaction mixture to neutralize the acid and
stop the reaction.

Finally the paste is spread into a thin film and baked in an oven at about 120 deg C. The thin film
is peeled off the base and is now ready to use.

70
Chapter 11
Future Scope

71
Further Research can be carried out for better understanding of the Process and thereby
improving the Quality of the Product.

Other commonly available starch sources can be explored. Food wastes like mango seeds and
corn kernels also have high starch content. Hence these can also be utilized as a raw material for
synthesis of polymeric films.

So far we have conducted the experiment using only one set of concentrations (0.5 N NaOH &
0.5N HCl). Varying the concentration of the reagents might alter the properties of the polymeric
films obtained.
This project focussed primarily on tensile strength measurement. Other standard tests like Izod
Impact Test, Dart Impact Test etc. should also be conducted.

Synthesis of polymeric films can also be carried out after extraction of starch from banana peels
instead of processing it as a whole to see if it improves the polymeric properties.

The banana peels consists of many different components apart from starch. Currently only the
reaction with starch has been considered. The interaction of all the other components with the
reagents may also have an effect which must also be quantified.

72
Chapter 12
References

73
Chapter 2

1. http://dwb.unl.edu/Teacher/NSF/C06/C06Links/qlink.queensu.ca/~6jrt/chem210/Page2.h
tml- Joanne & Stefanie's Plastics Website- “History Of Plastics”
2. http://eco.allpurposeguru.com/2011/06/plastic-and-environmental-problems/#.U1tq-
Fca0TU - David Guion- “Plastic and environmental problems”
3. http://www.ehow.com/about_5045721_environmental-problems-plastic.html- Chris
Blank- “Environmental Problems With Plastic”
4. http://en.wikipedia.org/wiki/Plastic
5. HGCA magazine 2013, Agriculture and Horticulture Department

Chapter 3

1. http://www.timetoast.com/timelines/65909- “The history of bioplastics”


2. http://htpoint.com/featured-news/bioplastics-material-future/ -Amy Taylor, “Bioplastics
Could Be The Material Of The Future”
3. Zero Waste America. (1988-2008). Waste and Recycling: Data, Maps, & Graphs.
http://zerowasteamerica.org/Statistics.htm
4. http://eco.allpurposeguru.com/2011/06/plastic-and-environmental-problems/#.U1tq-
Fca0TU - David Guion, “Plastic and environmental problems”
5. http://dwb.unl.edu/Teacher/NSF/C06/C06Links/qlink.queensu.ca/~6jrt/chem210/Page2.
html- Joanne & Stefanie's Plastics Website- “History Of Plastics”
6. http://www.ehow.com/about_5045721_environmental-problems-plastic.html- Chris
Blank- “Environmental Problems With Plastic”
7. HGCA, “Industrial uses for crops: Bioplastics”
8. http://www.huffingtonpost.com- Huffington Post, Susanne Rust -“Bioplastics Debate:
Could They Harm The Environment?”
9. http://www.natureworksllc.com- NatureWorks LLC
10. http://www.materbi.com/- Mater-Bi La Bioplastica
11. http://www.momscleanairforce.org/whats-plastic-got-to-do-with-clean-air/- Beth Terry,
“What’s Plastic Got To Do With Clean Air? “

74
12. http://news.nationalgeographic.co.in/news/2009/08/090820-plastic-decomposes-oceans-
seas.html- Carolyn Barry, National Geographic- “Plastic Breaks Down in Ocean, After
All -- And Fast”
13. European bioplastics 2013, facts and figures.
14. Introduction to bioplastics, Dr. Jim Lunt
15. http://en.european-bioplastics.org/standards/certification/- European Bioplastics
16. http://www.eurokamczech.com/Biokam/Biokam/web/Packaging%C2%A0.html
17. HGCA magazine 2013, Agriculture and Horticulture Department
18. http://www.nec.com/en/global/environment/featured/bioplastics/- NEC Research and
Development: Bioplastics
19. http://web-japan.org/trends/science/sci031212.html- Trends in Japan, Science &
Technology-“BIOPLASTIC, Eco-Friendly Material Has a Bright Future”
20. http://www.foodpackagingforum.org/Research/Extending-the-use-of-bioplastics-in-food-
packaging- Charlotte Wagner “Extending the use of bioplastics in food packaging”
21. bioplastics MAGAZINE [01/09] Vol. 4, Dr. Rainer Hagen
22. European bioplastics Factsheet, august 2012
23. http://www.biomebioplastics.com/- Biome Bioplastics
24. http://commons.wikimedia.org/wiki/File:Mulch_Film_made_of_PLA-Blend_Bio-
Flex.jpg- F. Kesselring, FKuR Willich- “Mulch Film made of PLA-Blend Bio-Flex”
25. Jung, Yu Kyung; Kim, Tae Yong (2009). "Metabolic Engineering of Escherichia coli for
the production of Polylactic Acid and Its Copolymers". Biotechnology and
Bioengineering 105
26. Bacterially Produced Polyhydroxyalkanoate (PHA): Converting Renewable Resources
into Bioplastics -Jiun-Yee Chee1, Sugama-Salim Yoga1, Nyok-Sean Lau1, Siew-Chen
Ling1, Raeid M. M. Abed2 and Kumar Sudesh1
27. Ya- Jane Wang, Van- Den Truong, Linfeng Wang(2002): Structures and rheological
properties of corn starch as affected by acid hydrolysis. Carbohydrate Polymers 52(
2003) 327-333
28. S.A.Roberts, R.E.Cameron (2001): The effects of concentration and sodium hydroxide
on the rheological properties of potato starch gelatinisation. Carbohydrate Polymers
50(2002) 133-142

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