relationship of moulding pressure and weight of …negara-negara membangun. cara-cara pelupusan sisa...
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RELATIONSHIP OF MOULDING PRESSURE AND WEIGHT OF GRANULATE
IN IMPROVING THE MECHANICAL AND CHARACTERISTICS OF
BIOPOLYMER FROM RENEWABLE RESOURCES
MOHD KHAIRUL ZAIMY BIN ABD GHANI
UNIVERSITI TUN HUSSEIN ONN MALAYSIA
RELATIONSHIP OF MOULDING PRESSURE AND WEIGHT OF GRANULATE
IN IMPROVING THE MECHANICAL AND CHARACTERISTICS OF
BIOPOLYMER FROM RENEWABLE RESOURCES
MOHD KHAIRUL ZAIMY B. ABD GHANI
A thesis submitted in
Fulfillment of requirement for the award of the
Degree of Master of Mechanical Engineering
Faculty of Mechanical and Manufacturing Engineering
University Tun Hussein Onn Malaysia
APRIL 2016
iii
ACKNOWLEDGEMENT
Special this dedication to my late father, my mother, siblings that helped a lot, Prof
Madya Dr Anika Zafiah Mohd Rus' supervisor, friends in E1 (Sustainable Polymer
Engineering Group) that a lot give ideas to resolve problem in conduct research and
all that had helped in completing this thesis.
iv
ABSTRACT
Waste cooking oils are problematic disposal especially in the developed countries.
Options for disposing of waste cooking oil are limited. Pouring waste cooking oil down
to the drain or sewers leads to clog and odour as well as damage wastewater leading
to problems for humanlife. Thus, in this research, vegetable waste cooking oil is used
as raw material to produce foam. This foam was crosslink with flexible isocyanate type
Polymethane Polyphenyl (Modify polymeric-MDI) and further processed into
granulate (powder) to be able to hot compress by hot compression moulding technique.
These fabricated samples were namely as biopolymer. The conversion process of bio-
monomer into BP was examined using Fourier Transform Infra-Red (FTiR) show the
complete conversion of BP from bio-monomer indicated by 3351 cm-1 of N-H and
carbonyls C=O functional groups at 1743 cm-1. Meanwhile the weight loss of BP as a
function of temperature was determined by using Linseis Thermal Analyser (STA)
(TG + DTA) indicating 3 distinct regions comprises of soft and hard segment
degradation region at 253 °C and 410 °C respectively. The moulding pressure of 31
bar to 44 bar was set with different weight of granulate of BP from 110 gm to 160 gm.
The compressed BP gives the highest tensile and flexural value of 4.89 MPa and 18.08
MPa respectively. Evidently, both compress BP of the highest tensile and flexural were
affected by the highest density of 1.42 g/cm3. In general, the higher the compression
moulding pressure the less void was examined, as well as the weight of granulates in
the mould. The Scanning Electron Microscope (SEM) of fracture morphology surface
of BP shows both ductile and brittle modes, and experiencing a ductile to brittle
transition. This is due to increase interfacial strength at higher moulding pressure with
good interfacial adhesion between granulates. Thus, the optimal combination of
compression moulding parameters is helpful for polymer manufacturing with better
mechanical properties such as tensile and flexural strength.
v
ABSTRAK
Pelupusan sisa minyak masak terbuang mempunyai pelbagai masalah terutamanya di
negara-negara membangun. Cara-cara pelupusan sisa minyak masak ini adalah sangat
terhad. Pembuangan sisa minyak masak ke dalam parit atau pembetung membawa
kepada masalah tersumbat dan bau serta kerosakan air sisa yang membawa kepada
masalah kepada kehidupan manusia. Oleh itu, dalam kajian ini, sisa minyak masak
sayuran digunakan sebagai bahan mentah untuk menghasilkan busa (foam). Busa ini
telah crosslink dengan flexible isocyanate daripada jenis Polymethane Polyphenyl
(Modify polymeric-MDI) seterusnya diproses menjadi granulat (serbuk) bagi
dimampatkan dalam acuan yang telah disetkan suhu pemanasan. Sampel ini
dinamakan sebagai biopolimer. Proses penukaran lengkap daripada bio-monomer
kepada BP disahkan melalui alatan spektrum infra merah (FTiR) yang dapat dilihat
pada gelombang 3351 cm-1 iaitu kumpulan berfungsi N-H dan C=O pada 1743 cm-1.
Sementara itu kehilangan jisim BP dikaji terhadap perubahan suhu melalui Linseis
Thermo balance Simultaneous Thermal Analysis (STA) (TG + DTA) menunjukkan
kehilangan jisim pada tiga kecerunan graf dengan bahagian degradasi pada segmen
lembut dan keras masing-masing pada suhu 253 OC dan 410 OC. Tekanan acuan pada
31 bar sehingga 44 bar telah diset dengan perbezaan jisim granulat BP daripada 110 g
kepada 160 g. Hasil daripada proses mampatan BP memberikan nilai kekuatan tegang
dan lenturan tertinggi masing-masing pada 4.89 MPa dan 18.08 MPa. Jelas
menunjukkan, kedua-dua kekuatan tegang dan lenturan mampatan BP dipengaruhi
oleh ketumpatan tertinggi pada 1.42 g/cm3. Secara asas, lebih tinggi tekanan mampatan
lebih kurang lubang-lubang pori, begitu juga jisim granulat dalam acuan. Dari
Scanning Electron Microscope (SEM) morfologi permukaan retakan BP menunjukkan
kedua-dua mod anjal dan rapuh dan peralihan anjal kepada rapuh. Ini disebabkan oleh
peningkatan kekuatan antara muka pada tekanan acuan yang tinggi dengan daya
lekatan yang bagus di antara granulat. Oleh itu. kombinasi optimum parameter
mampatan acuan membantu untuk menghasilkan polimer dengan ciri-ciri mekanikal
yang lebih baik seperti kekuatan tegang dan lenturan.
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CONTENTS
TITLE i
DECLARATION ii
ACKNOWLEDGEMENT iii
ABSTRACT iv
ABSTRAK v
CONTENTS vi
LIST OF TABLES ix
LIST OF FIGURES x
LIST OF ABBREVIATIONS xiv
CHAPTER 1 INTRODUCTION
1.1 Research background 1
1.2 Problem statement 3
1.3 Research objective 4
1.4 Research scope 4
1.5 Significant of research 5
1.6 Thesis organization 5
CHAPTER 2 LITERATURE REVIEW
2.1 Background of polymer 6
2.2 Polymer from renewable resources 7
2.3 Composites from oil-based polymers 9
2.4 Characterization of Thermoset 10
2.4.1 Type of application thermoset 13
2.5 Characterization of biopolymer 14
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2.6 Phase transitions 18
2.6.1 Glass transition (Tg) 18
2.6.2 DSC Analysis 18
2.7 Interrelationship between processing
parameters and property of polymer 20
2.7.1 Thermoplastic processing 21
2.7.2 Thermosetting processing 23
2.7.3 Others process 25
2.8 Compression moulding of polymer specimens 25
2.8.1 Mould designs 31
2.8.2 Specimen shapes 32
2.9 Influence strength and type of measurement
on void content of polymer 33
2.10 Fracture of polymer study 37
2.10.1 Brittle cleavage fracture 39
2.10.2 Ductile fracture 40
CHAPTER 3 METHODOLOGY
3.1 Introduction 43
3.2 Samples preparation of biopolymer
from waste cooking oil 45
3.2.1 Granulate production process 48
3.3 Hot compression technique 49
3.4 Characterization of granulate 51
3.4.1 Fourier Transform Infrared
spectroscopy (FTIR spectroscopy) 52
3.4.2 Differential Scanning Calorimetry
(DSC) analysis 53
3.4.3 Thermogravimetric (TGA) analysis 54
3.5 Physical and mechanical tests 55
3.5.1 Determination of tensile properties 55
3.5.2 Flexural testing of biopolymer 58
3.6.3 Morphology study of biopolymer 61
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3.5.4 Density test of biopolymer 62
CHAPTER 4 RESULT AND DISCUSSION
4.1 Introduction 63
4.2 Spectroscopy analysis of Biopolymer 64
4.3 DSC Analysis 67
4.4 Thermal properties of BP 69
4.5 Mechanical properties of biopolymer (BP) 72
4.6 Morphological surface of biopolymer by
scanning electron microscope observation 80
4.7 SEM morphological of tensile
facture surface biopolymer (BP) 87
4.8 SEM morphological of flexural
facture surface biopolymer (BP) 91
CHAPTER 5 CONCLUSION
Conclusion 94
Future Work 95
REFERENCES 97
APPENDICES 108
ix
LIST OF TABLES
1.1 Thesis organization description 5
2.1 Biopolymers Found in Nature and Their Functions 16
2.2 Raw materials used in compression moulding process 30
3.1 Formulation of biopolymer 48
3.2 Shows summary of operating conditions for
temperature, curing & cooling time,
weight of granulate and moulding pressure 50
3.3 Dimensions for specimens 56
4.1 Table of IR absorptions for the determination of
functional group in Biopolymer (BP) 65
4.2 Thermal decomposition of Biopolymer 70
x
LIST OF FIGURES
2.1 Schematic, two-dimensional representation of thermoset cure 11
2.2 Macroscopic development of rheological and
mechanical properties during network formation 12
2.3 Illustrating identified examples of applications for
each category of polyurethane 14
2.4 Example DSC analysis 19
2.5 Shows Interrelationship between
Processing and Property of polymer 20
2.6 Schematic of Extrusion 21
2.7 Schematic of Injection moulding 22
2.8 Schematic of Inflation film forming 22
2.9 Schematic of Fibre drawing 23
2.10 Schematic of vacuum forming 24
2.11 Schematic of Blow moulding 24
2.12 The four stages in compression-moulding 26
2.13 Compression moulding method 28
2.14 Critical process parameters of compression moulding method 29
2.15 Side view of the basic categories of moulds
for compression moulding 31
2.16 Failure of the bridge in Minnesota 37
2.17 (a) Ductile fracture (b) Brittle cleavage fracture both
are observed from tensile fracture surfaces 39
2.18 Cup and cone fracture 41
2.19 Microvoid coalescence in ductile fracture 42
2.20 Different characteristics of microvoids observed
under (a) Uniaxial tensile loading, (b) shear
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and (c) tensile tearing 42
3.1 Flow of process methodology 44
3.2 The Schematic Diagram of Biopolymer
Production Route using Hot Compression Moulding 47
3.3 Wabash Genesis Hyraulic Hot Press moulding machine
(a) hot compression moulding machine and
(b) schematic drawing of hot compression moulding
and its components 51
3.4 FTIR spectrometer-Perkin Elmer 52
3.5 (a) Shows DSC research instruments specification
DSC Q2000 thermal analysis system
(b) technique to put a sample on DSC holder 54
3.6 The (a) Linseis TGA machine and
(b) tweezers as the tool to transfer the sample into crucible 55
3.7 Shape and dimensions for specimens 56
3.8 (a) shows Universal Tensile Machine,
(b) Tensile samples for Biopolymer 57
3.9 Allowable Range of Loading Nose and
Support Radii in ISO 178-93 58
3.10 Flexural samples for Biopolymer 59
3.11 The (a) SEM machine and (b) Auto Fined Coater 61
3.12 Mettler Toledo Weighing for density test
of Biopolymer samples 62
4.1 FTIR spectra for Biopolymer (BP) 65
4.2 Shows DSC analysis of BP and the red line
as middle of the change in baseline which is
the inflection point 67
4.3 Thermogram TG and derivative weight loss
of Biopolymer (BP) 69
4.4 Graph density (g/cm3) of BP versus
moulding pressure (Bar) 72
4.5 Tensile strength of BP with different weight (gram)
of granulate and moulding pressure (Bar) 73
4.6 Flexural strength (MPa) of BP versus
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moulding pressure (Bar) 74
4.7 Relationship of moulding pressure and different of
weight granulate on tensile strength
and density properties of Biopolymer 75
4.8 Relationship of moulding pressure and different of
weight granulate on flexural strength
and density properties of Biopolymer 76
4.9 Relationship of moulding pressure with weight of
granulate on elongation and Young Modulus
of Biopolymer 77
4.10 Percentage increment of tensile based on influence
moulding pressure and weight of granulate
of Biopolymer 78
4.11 Percentage increment of flexural based on
influence moulding pressure and weight of granulate
of Biopolymer 79
4.12 SEM surface morphology of BP based on
110g granulate with moulding pressure of
(a) 3.4 Bar (b) 31 Bar (c) 34 Bar (d) 38 Bar
(e) 41 Bar and 44 Bar 81
4.13 SEM surface morphology of BP based on
120g granulate with moulding pressure of
(a) 3.4 Bar (b) 31 Bar (c) 34 Bar (d) 38 Bar
(e) 41 Bar and 44 Bar 82
4.14 SEM surface morphology of BP based on
130g granulate with moulding pressure of
(a) 3.4 Bar (b) 31 Bar (c) 34 Bar (d) 38 Bar
(e) 41 Bar and 44 Bar 83
4.15 SEM surface morphology of BP based on
140g granulate with moulding pressure of
(a) 3.4 Bar (b) 31 Bar (c) 34 Bar (d) 38 Bar
(e) 41 Bar and 44 Bar 84
4.16 SEM surface morphology of BP based on
150g granulate with moulding pressure of
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(a) 3.4 Bar (b) 31 Bar (c) 34 Bar (d) 38 Bar
(e) 41 Bar and 44 Bar 85
4.17 SEM surface morphology of BP based on
160g granulate with moulding pressure of
(a) 3.4 Bar (b) 31 Bar (c) 34 Bar (d) 38 Bar
(e) 41 Bar and 44 Bar 86
4.18 SEM of surface fracture morphology at 30x magnification
with moulding pressure of (a) 3.4 bar (b) 31 bar
(c) 34 bar (d) 38 bar (e) 41 bar and (f) 44 bar at 160 g 88
4.19 SEM of surface fracture morphology at 30x magnification
with moulding pressure of (a) 3.4 bar (b) 31 bar
(c) 34 bar (d) 38 bar (e) 41 bar and (f) 44 bar at 160 g 92
xiv
LIST OF ABBREVIATIONS
PU - Polyurethane
PET - Polyethylene Terephthalate
wt. - weight
BP - Biopolymer
SEM - Scanning Electron Microscopy
ASTM - American Society for Testing and Materials
MDI - Methylene Diphenyl Diisocyanate
TDI - Toluene Diisocyanate
IIR - Butyl Rubber
PP - Polypropylene
SDOF - Single Degree Of Freedom
UTHM - Universiti Tun Hussein Onn Malaysia
UTM - Universal Testing Machine
NaOH - Sodium Hydroxide
H - Hydrogen
C - Carbon
O - Oxygen
CH2 - Hydrocarbon
OH - Hydroxide
N - Nitrogen
NH2 - Amine
H2O - Water
CO2 - Carbon Dioxide
Rpm - revolutions per minute
CaCO3 - Calcium Carbonate or Calcite
xv
NA -MMT - Sodium Montmorillonite
Ca - Calcium
Cl - Chlorine
Fe - Iron
K - Potassium
Mg - Magnesium
Si - Silicon
Zn - Zinc
Al - Aluminum
Cu - Copper
Ti - Titanium
Comp. - Compression
Stand. Dev. - Standard Deviation
xvi
LIST OF APPENDICES
A Table Tensile 108
B Table Flexural 123
C Table Density 134
CHAPTER 1
INTRODUCTION
1.1 Research background
Biopolymers derived from renewable resources from the stand point of environmental
protection from plastic disposal problem and saving or substitute petroleum resources
have been gathering much attention now days. These fully biodegradable and eco-
friendly materials find their way in several structural and non-structural applications
where they are not subjected to high loads.
Meanwhile, waste cooking oil includes any vegetable oil (e.g., soybean oil,
peanut oil, sunflower oil, linseed oil, coconut oil, cottonseed oil, canola oil, corn oil,
safflower oil, walnut oil, castor oil, tung oil, etc.), animal fat (e.g., lard, fish oil, poultry
fat, tallow, etc.), or by product or any combinations that has been heated to a high
temperature and/or used in the preparation of food or other products.
Traditionally, these waste oils were used as an additive to animal feed.
However, many harmful compounds are produced during the frying of vegetable oils.
The European Union (EU), aware of this problem, banned the use of waste cooking
oils in the composition of animal feed in 2002. Most of the toxic compounds in the
waste cooking oil are oxidation products from fatty acids, especially from
polyunsaturated fatty acids (Bautista and Vicente, 2009).
2
Waste cooking oil can pose a pollution hazard if not handled properly. To
prevent pollution of waterways and clogging of private and municipal drain systems,
restaurants and other food preparation facilities typically save used cooking oil and
employ sewage traps to filter grease out of waste water streams. Yellow and brown
grease (also commonly referred to as trap grease, sewage grease, or black grease) are
two forms of waste cooking oil that are readily available in bulk quantities. Yellow
grease is of a slightly higher quality than brown grease and typically has a free fatty
acid (FFA) content of between about 4 and 15 weight percent, while brown grease
typically has a FFA content of up to about 60 weight percent. The current supply of
yellow and brown grease exceeds the demand for these feedstocks.
Therefore, suitable processing parameters must be carefully selected in order
to obtain the optimum products generated from waste cooking oil such as polymer end
products. Most importantly is the hot press forming parameters that influence the
mechanical properties such as the temperature, pressure and heating time. Other effect
of processing parameter is on the flexural strength of biocomposite with increasing
moulding pressure. The dependence of mechanical properties on the process pressure
will be observed based on the increase in tensile and flexural strength.
The reduction in the strength with the void content is justified on the basis
crack nucleation starts from the voids, which referring to Scanning Electron
Microscopy (SEM) an the observations the broken samples.
Mechanical properties of green composites are greater when processed using
hot press forming (film stacking) in comparison to injection moulding. Thermal
degradation of natural fibres occurs in injection moulding process, as they are
subjected to two heating cycles, one to create compound and the other one when it is
injected. Furthermore, these fibres are subjected to the high amount of shearing during
the injection process, which leads to fibre damage. During hot press forming process,
fibres are heated only once and are not subjected to any shearing. Consequently, it
becomes easier to limit the damage of the fibres (Bodros et al., 2007).
Hence hot press forming process has been used in this work which regards to
processing parameters significantly influences the properties and interfacial
characteristics of the biopolymer.
3
1.2 Problem statement
An option for disposing of waste cooking oil is limited. According to (Rozman
et al., 2005)) disposal is difficult because used cooking oil is usually in a liquid or
semi-solid form and the solid waste regulations restrict the disposal of liquids in
landfills. Waste cooking oil must not be poured down drains or sewers because this
inevitably leads to blockages and odour smell or vermin problems and may also pollute
watercourses leading to problems for wildlife. Other disposal methods can also be
problematic, open burning of used cooking oil causes black smoke, which is prohibited
by (Yacob 2007).
Furthermore, Malaysia as one of the largest producers and manufacturers of
palm oil products, generates a large amount of palm oil by-products, which can be
recycled into bio-monomer. If this bio-monomer is put to good use, in this case as a
main material in biopolymer compound base on recycle thermoplastics, then it will
greatly reduce the cost of high-performance composite (Ahmad et al., 2007). At the
same time, it will also reduce the amount of waste generated by the palm oil industry,
thus achieving a global aim of sustainable development. Not only does it reduce waste,
it also preserves nature by eliminating the need to harvest natural aggregates from
natural sources.
The conversion process of biopolymer is started by collecting renewable
resources of waste cooking oil from Small and Medium Industries (SMIs) and
chemically manipulated at laboratory scale using less tan 2L of waste cooking oil. The
monomer conversion begins with the catalyst preparation to generate the epoxies from
the unsaturated fatty compound, and second reaction is the acid-catalyst ring opening
of the epoxies to form polyols or bio monomer. Crosslinker with correct proportion
ratio of bio monomer is based on 1:0.5 to generated biopolymer.
Choosing the correct fabrication techniques process is vital for minimum
defect of biopolymer. This is indicated not only by the minimum void content value
measured, but also by void distribution across the material, pressing method,
temperature and density. Defects are introduced in the biopolymer in all manufacturing
processes, although the size and frequency of each type depends upon the processing
cycle. Typical defects found as a result of the manufacturing conditions are:
Void due to volatile resin components or to trapped air bubbles.
4
Bonding defects. Components may be bonded together (e.g. panels and
stringers) during manufacturing and defects in the bondline occur due to
incorrect adhesive or contamination of the surfaces to be bonded.
1.3 Research objective
1. To propose a preparation technique of Biopolymer (BP) by using hot
compression moulding technique.
2. To characterize polymer granulate by verify the completion curing reaction and
the presence of free isocyanate groups (NCO).
3. To compare the mechanical properties and morphology behaviour of BP
produced by different moulding pressure and weight of granulate.
1.4 Research scope
In this study, biopolymer (BP) produced based on renewable monomer of waste
cooking oil. Waste cooking oil was obtained from Small and Medium Industries
(SMIs). Fourier transforms infrared (FTIR) spectroscopy is used to provide valuable
information of functional groups which can be used to determine the conversion of
biomonomer into biopolymer. In addition, the samples were examine using,
Differential Scanning Calorimetry (DSC), Thermo Gravimetric Analysis (TGA),
tensile, flexural, density and morphology of surface samples and tensile fracture. The
analysis will be concluded by the significant effect of compression moulding pressure
and weight of granulate which influences the voids content and mechanical properties
such as tensile, flexural are significantly increase with the increases of density which
subsequently reduce void.
5
1.5 Significant of research
i. To improve the interfacial adhesion between granulate by evaluate the optimal
combination of hot press parameters.
ii. To find the relationship between void and mechanical properties.
1.6 Thesis organization
CHAPTER 1 has highlighted the general introduction on this research, background
of study, problem statement, objective, scope and its significance of research. It
discussed the reason of research aimed in relationship of moulding pressure of
Biopolymer. In CHAPTER 2, reviews of literature were focusing on production
polymer, parameter hot compression moulding. CHAPTER 3 shows the methodology
that used to conduct the whole study. The technique of Biopolymer preparation, the
physical and mechanical test is described in details. CHAPTER 4 covers the results
and discussion of the experimental carried out from this research. CHAPTER 5
summarized the results and discussion of all the experimental testing. At the end of
this chapter, the recommendations are list out for future study. The entire chapter is
illustrated as tabulated in Table 1.1.
Table 1.1: Thesis organization description
CHAPTER Description
CHAPTER 1 Introduction
CHAPTER 2 Literature Review
CHAPTER 3 Research Methodology
CHAPTER 4 Results of Biopolymer testing
CHAPTER 5 Conclusions and Recommendations
CHAPTER 2
LITERATURE REVIEW
2.1 Background of polymer
Polyethylene, polypropylene, polystyrene, polyethylene terephthalate, and polyvinyl
chloride are all derived from petrochemical feedstocks.
The utilization of fossil fuels in the manufacture of plastics accounts for about
7% of worldwide oil and gas. These resources will arguably be depleted within the
next one hundred years, and the peak in global oil production as estimated by some
will occur within the next few decades (Williams & Hillmyerb, 2008). With time,
stability and durability of plastics have been improved continuously, and hence this
group of materials is now considered as a synonym for materials being resistant to
many environmental influences. At present all the raw materials are derived from
petrochemicals, and the toxicity and volatility of starting materials such as
formaldehyde require careful environmental, health and safety monitoring. But there
could soon be a new, greener alternative on the market based on a new generation of
‘bio-resins’ – thermoset resins derived principally from vegetable oils such as rapeseed
(Shah et al., 2008).
7
Mohanty et al., (1999) described that when a bio-degradable material (neat
polymer, blended product or composite) is obtained completely from renewable
resources may call it a green polymeric material. Bio-polymers from renewable
resources have attached much attention in recent year. Renewable sources of
polymeric materials offer an answer to maintaining sustainable development of
economically and ecologically attractive technology. The innovations in the
development of materials from bio-polymers, the preservation of fossil-based raw
materials, complete biological degradability, the reduction of the volume garbage and
compost ability in the natural cycle, protection of the climate through the reduction of
the carbon dioxides released, as well as the application possibilities of agricultural
resources for the production of bio/green materials are some of the reasons why such
materials have attached the public interest (Mohanty et al., 1999).
2.2 Polymer from renewable resources
Plant oils are vegetable oils extracted from plant sources, as opposed to animal
fats; they are quite abundant in nature. Soybean, linseed, castor, sunflower, rape seed,
and palm oils are some examples of plant oils. Soybean oil, for example, has been used
extensively in the food processing industry in salad dressings, sandwich spreads,
margarine, and mayonnaise—and also in non-food applications such as inks,
plasticizers, crayons, paints, and soy candles (Wool & Sun 2005). Soybean oil is the
most readily available and one of the lowest-cost vegetable oils in the world
(Takahashi et al., 2008). Linseed oil has been used mainly in non-food applications as
an impregnator and varnish in wood finishing, as a pigment binder in oil paints, and
as a plasticizer and hardener in putty. Inedible vegetable oils include processed linseed
oil, tung oil, and castor oil, and they are widely used in lubricants, paints, coatings
cosmetics, and pharmaceuticals.
Plant oils are renewable raw materials for a wide variety of industrial products,
including coatings, inks, plasticizers, lubricants and paints (Shirikant et al., 2001;
Victor Kolot, 2004 and Zhu et al., 2004). Soybean oil is the most abundant of all plant
oils, and it is mainly grown in the USA. Plant oils are triglycerides and contain various
fatty acids (Wool & Sun, 2005) such as linoleic, linolenic, oleic, palmitic, and stearic
8
acid (Liu, 1997). These fatty acids differ in chain length, composition, distribution,
and location. Some are saturated and some are unsaturated, which results in differences
in the physical and chemical properties of the oil (Wool & Sun, 2005). Plant oils are
also relatively cheap (Kaplan, 1998).
Large amount of plastic waste generated by industries poses serious
environmental problems which may require up to hundred years for total degradation
(Mantia & Moreale, 2008). An approach to decrease the solid waste is to substitute
conventional material with biodegradable raw materials to reduce costs and to enhance
the degradation of the final product. By renewable resources is meant agricultural
products mainly from five principal crops: soybean, oil palm, rapseed, sunflower and
coconut where the materials are synthesized by sunlight. Many researchers have
provided overviews of various partially and completely biodegradable resins and
composites. Among various cellulose, protein and starch based materials, soy protein
has been studied extensively as a potential replacement for petroleum-based products
due to its low cost, easy availability and biodegradability.
Oil-based bio-polymers have many advantages compared to polymers prepared
from petroleum-based monomers. They are bio-degradable and in many cases, cheaper
than petroleum polymers (Guner et al., 2006). According to the previous researches
Long et al., (2006), generally polymers from renewable resources can be classified
into three groups which are natural polymers such as starch, protein and cellulose,
synthetic polymers from natural monomers, such as polylactic acid (PLA), and
polymers from microbial fermentation, such as polyhydroxybutyrate (PHB). Three
ways bio-polymer plastics can be produced are through converting plant sugars into
plastic, producing plastics inside microorganisms and growing plastics in corn and
other crops.
Vegetable oils are one of the most abundant biological sources and important
raw materials for the production of bio-based polyurethanes because of their numerous
advantages: low toxicity, inherent biodegradability, and high purity. As a result of the
hydrophobic nature of triglycerides, vegetable oils produce polyurethanes that have
excellent chemical and physical properties such as enhanced hydrolytic tendencies,
high tensile strength and elongation, high tear strength, and thermal stability (Oprea,
2006). On the other hand, these materials have relatively low thermal stability,
primarily due to the presence of urethane bonds. The onset of urethane bond
dissociation is somewhere between 150 and 220 °C, depending on the type of
9
substituents, on the isocyanate and polyol side. Saturated hydrocarbons are known to
have relatively good thermal and thermo-oxidative resistance compared to polyether
and polyester polyols derived from petrochemicals (Monteavaro, 2005).
Vegetable oils are generally considered to be the most important class of
renewable resources, because of their ready availability and numerous applications.
Recently, a variety of vegetable oil-based polymers have been prepared by free radical,
cationic, olefin metathesis, and condensation polymerization. The polymers obtained
display a wide range of thermo physical and mechanical properties from soft and
flexible rubbers to hard and rigid plastics, which show promise as alternatives to
petroleum-based plastics (Xia & Larock, 2010).
2.3 Composites from oil-based polymers
Composites based on environmentally degradable, eco-compatible synthetic and
natural polymeric materials have great potential as advanced environmentally
acceptable alternatives to petroleum-based materials.
Tsujimoto et al., (2010) studied the synthesis and properties of green
nanocomposites from epoxidized natural oils and silane coupling agents. Natural oil-
based composites with good mechanical properties were prepared from an acrylate-
modified soybean oil and natural fibres (flax and hemp fibres) (Bunker & Wool, 2002).
Mosiewicki & Aranguren (2013) carried out review, which will concentrate on the use
of vegetable oils as the base-materials for the production of polymer composites that
incorporate inorganic and organic particles and fibres, both synthetic and natural in
origin, and sized from the macro to the micro and nanoscale.
Hong & Wool (2005) reported a novel bio-based composite material, suitable
for electronic as well as automotive and aeronautical applications, was developed from
soybean oils and keratin feather fibres (KF). This environmentally friendly, low-cost
composite can be a substitute for petroleum-based composite materials. Keratin fibres
are a hollow, light, and tough material and are compatible with several soybean (S)
resins, such as acrylated epoxidized soybean oil (AESO). Khot et al., (2001) utilized
an acrylated epoxidized soybean oil to produce glass fibre composites by resin transfer
moulding. Depending on the fibre content, Young’s moduli of 5.2 to 24.8 GPa were
10
measured for the composites bearing 35 and 50 wt% of GF, respectively, and tensile
strengths of 129 - 463 MPa, for the same samples.
Pfister & Larock (2012) presented an interesting comparison of the behaviour
of different cationically cured plant oils used as matrices of agricultural fibres. They
considered composites prepared from corn, soybean, fish, and linseed oils using up to
75 wt% of different natural fibres, corn stover, wheat straw, and switch-grass fibres.
The composites showed a largely increased rigidity with respect to the unfilled
thermosets, but they were also much more brittle. The Young’s moduli reported were
in the range of 1.6 - 2.3 GPa and the tensile strengths were between 5.5 and 11.3 MPa.
One interesting observation was that higher degree of unsaturation of the natural oil
lead to better thermal and mechanical properties of the composites, which can be
linked to the higher crosslinking density that can be achieved in these materials. On
the other hand, wheat straw fibres offered the best performance composites.
2.4 Characterization of thermoset
Thermosets are network-forming polymers. Unlike thermoplastics, chemical reactions
are involved in their use. As a result of these reactions the materials first increase in
viscosity and eventually cross-link and become set, and as a result they can no longer
flow or dissolve. Cure is most often thermally activated, which gives rise to the term
thermoset, but network-forming materials whose cure is light activated are also
considered to be thermosets. Some thermosetting adhesives cross-link by a dual cure
mechanism that is by either heat or light activation. The reader interested in more
detailed discussion of thermosets and their behaviour is directed to (Pascault et al.,
2001)
In the uncured state thermosets are mixtures of small reactive molecules, often
monomers. Catalysts are often added to accelerate cure. Most thermosets incorporate
particulate fillers or fibre reinforcement to reduce cost, to modify physical properties,
to reduce shrinkage during cure, or to improve flame retardance. Thermosets generally
possess good dimensional stability, thermal stability, chemical resistance and electrical
properties. Because of these attributes, they find widespread use in several applications
such as adhesives; primary and secondary structural members in aerospace;
11
countertops and floors for manufacturing facilities and homes; printed circuit boards,
conductive polymer elements, and encapsulation materials for electronic applications;
dental materials, especially adhesives; and recreational products such as tennis
racquets, bicycle frames, golf clubs and fishing rods.
Unlike thermoplastic polymers the processing of thermosets includes the
chemical reactions of cure. As illustrated in Figure 2.1 cure begins by the growth and
branching of chains. As the reaction proceeds, the increase in molecular weight
accelerates, causing an increase in viscosity, illustrated in Figure. 2.2, and reduction
in the total number of molecules. Eventually several chains become linked together
into a network of infinite molecular weight. The abrupt and irreversible transformation
from a viscous liquid to an elastic gel or rubber is called the gel point. The gel point
of a chemically cross-linking system can be defined as the instant at which the weight
average molecular weight diverges to infinity (Pascault et al., 2001)
Figure 2.1: Schematic, two-dimensional representation of thermoset cure. For
simplicity difunctional and trifunctional co-reactants are considered. Cure starts with
A-stage or uncured monomers and oligomers(a); proceeds via simultaneous linear
growth and branching to an increasingly more viscous B-stage material below the gel
point (b); continues with formation of a gelled but incompletely cross-linked network
(c); and ends with the fully cured, C-stage thermoset (d) (Van Mele et al., 2004)
12
The macroscopic progress of cure is illustrated in Figure 2.2. In the early stages
of cure the thermoset can be characterized by an increase in its viscosity η. The gel
point coincides with the first appearance of an equilibrium (or time-independent)
modulus as shown. Reaction continues beyond the gel point to complete the network
formation, where physical properties such as modulus build to levels characteristic of
a fully developed network. Gelation is the incipient formation of a cross-linked
network, and it is the most distinguishing characteristic of a thermoset. A thermoset
loses its ability to flow and is no longer process able above the gel point, and therefore
gelation defines the upper limit of the work life.
Figure 2.2: Macroscopic development of rheological and mechanical properties
during network formation, illustrating the increase in viscosity η, which tends toward
infinity at the gel point; the first appearance of an equilibrium modulus
Ge at the gel point; and the increase in modulus with completion
of the network (Gotro & Prime, 2004)
13
2.4.1 Type of application thermoset
a) Insulation
PU can be used for a wide range of applications. PU foam is commonly used
as building insulation (for walls, roofs, floors, pipes etc.) as its properties are well
suited for reducing heat losses in buildings as well as keeping them cool. The
material’s high durability can also extend the lifetime of buildings, and its low
weight makes it easy to work with. Furthermore, it is space efficient as building
insulation, as it has the lowest thermal conductivity compared to all other insulates
that are used on a large scale. Other areas of application where the material’s
excellent insulation capacity makes it a suitable choice are for example in
refrigerators and freezers, caravans and remote heating and cooling pipes.
b) Comfort and cushioning
PU is widely used for making shoe soles, both within sports and trekking as
well as in fashion oriented footwear. The greatest benefit of using PU in shoe soles
is the material’s high durability, which provides shoes with long lifespan. PU can
also be found in car bodies; for interior and for insulating noise and heat from the
engine. Seats and armrests are often stuffed with PU for high comfort and
durability. Similarly, it is also used as stuffing in furniture such as beds, sofas and
chairs. One special type of PU in beds is memory foam, which shapes after the
body and therefore provides support.
c) Coatings, adhesives and elastomeric components
Different from the previous examples, PU is also used in coatings for a range
of different applications; cables, vehicles, floors, wooden furniture, bridges and
roads. It protects the surface from for example weather, corrosion and pollutions.
PU can also be found as adhesives, as it can bind together a wide range of different
materials, and in paint. PU elastomers can be used for many different applications,
a few of which are wheels for trolleys and rollerblades, hoses, seals and gaskets.
Figure 2.6 summarizes some of the identified application areas for PU in its
different forms.
14
Figure 2.3: Illustrating identified examples of applications for
each category of polyurethane Li et al., (2013)
2.5 Characterization of biopolymer
Polymers play a central role both in the natural world and in modern industrial
economies. Some natural polymers, such as nucleic acids and proteins, carry and
manipulate essential biological information, while other polymers such as the
polysaccharides-nature’s family of sugars-provide fuel for cell activity and serve as
structural elements in living systems. With advances in chemistry and materials
science, a vast array of novel synthetic polymers has been introduced over the past
century. Synthetic polymers such as nylon, polyethylene, and polyurethane have
transformed daily life. From automobile bodies to packaging, compact discs to
clothing, and food additives to medicine, manmade polymers pervade virtually every
aspect of modern society (Fomin, 2001).
15
However, the growing reliance on synthetic polymers has raised a number of
environmental and human health concerns. Most plastic materials, for instance, are not
biodegradable and are derived from non-renewable resources. The properties of
durability and strength that make these materials so useful and their persistence in the
environment and complicate on it’s disposal. In addition, the synthesis of some
polymeric materials involves the use of toxic compounds or the generation of toxic by-
products (Johan et al., 2007).
These problems have generated increased attention on polymers that are
derived from biological precursors or are produced by using the methods of modern
biotechnology. Such biopolymers may prove to have a variety of environmental
benefits. Possible applications range from agriculturally or bacterially derived
thermoplastics or thermosetting that are truly biodegradable, to novel medical
materials that are biocompatible, to water treatment compounds that prevent mineral
build-up and corrosion. However, this polymers typically have many different
properties, in certain applications biopolymers may not necessarily provide
environmental advantages over conventional polymers. In practice, it is extremely
difficult to develop and the testing methods which assess to the environmental
characteristics of materials (Fredrik-Selin, 2002).
Biopolymers is diverse and versatile class of materials that have potential
applications in virtually all sectors of the economy. For example, they can be used as
adhesives, absorbents, lubricants, soil conditioners, cosmetics, drug delivery vehicles,
textiles, high-strength structural materials, and even computational switching devices.
Currently, many biopolymers are still in the developmental stage, but important
applications are beginning to emerge in the areas of packaging, food production, and
medicine. Some biopolymers can directly replace synthetically derived materials in
traditional applications, whereas others possess unique properties that could open up a
range of new commercial opportunities. Novel biopolymer compounds are being
investigated by established agricultural and chemical firms, as well as small
biotechnology enterprises.
16
Table 2.1: Biopolymers found in nature and their functions (Kokubo et al., 2003)
Polymer Monomers Function(s)
Nucleic acids (DNA and RNA) Nucleotides
Carriers of genetic
information universally
recognized in all organisms
Proteins Alpha-ammo acids
Biological catalysts
(enzymes), growth
factors, receptors, structural
materials (wool, leather, silk,
hair, connective tissue);
hormones (insulin); toxins;
antibodies
Polysaccharides
(carbohydrates) Sugars
Structural materials in plants
and some higher organisms
(cellulose, chitin);
energy storage materials
(starch, glycogen); molecular
recognition (blood types),
bacterial secretions
Polyhydroxyalkanoates Fatty acids Microbial energy reserve
materials.
Polyphenols Phenols
Structural materials in plants
(Iignin), soil structure
(humics, peat), plant defense
mechanisms (tannins)
Polyphosphates Phosphates Inorganic energy storage
materials
Polysulfates Sulfates Inorganic energy storage
materials
17
Johan et al., (2007) reported the term “biopolymers” is used to describe a variety of
materials. In general, however, biopolymers fall into two principal categories:
polymers that are produced by biological systems such as microorganisms,
plants, and animals; and
polymers that are synthesized chemically but are derived from biological
starting materials such as amino acids, sugars, natural fats, or oils.
Table 2.1 listed various types of naturally occurring biopolymers defined on
the basis of the chemical structure of their monomeric units, and indicates the functions
that these polymers serve in living organisms. Biopolymers are strings or sequences of
monomeric units or monomers for short. In many cases these strings are linear, but
sometimes they are closed and circular, branched or even cross-linked.
18
2.6 Phase transitions
Phase transitions depending on the physical and chemical structure of thermoset, the
following phase transitions will occur on increasing material temperature.
2.6.1 Glass transition (Tg)
Temperature below the glass temperature (Tg) the mobility of the molecules (Brown.s
macromobility) is strongly curbed by intermolecular interaction. There are no position
change processes and only restricted thermal induced movements of chain segments
or side chains. At the glass temperature Brown.s micromobility of chain segments and
side chains starts to occur and the plastic becomes softer but is still mechanical stable.
Before reaching the glass temperature second-order relaxation processes are possible,
single-molecule segments obtain a restricted mobility.
2.6.2 DSC Analysis
The DSC curve is shown in Figure 2.4. The dissociation of the blocked isocyanate
seems due to the fracture of -N H-CO- chemical bond. When endothermic fracture of
chemical bond happens, the temperature can be represented as the initial dissociation
temperature (Yin et al., 2009). In some process of reaction consist of endothermic and
exothermic. When the temperature of the sample is higher than that of the inert
material, the deflection of the thermal curve is upwards (exothermic), and when it is
lower, the deflection is downwards (endothermic). Endothermic process of melting
sublimation solid-solid transitions desolvation chemical reaction and exothermic
process of crystallization solid-solid transition decomposition chemical reaction. A
typical DSC we can identify the glass transition temperature shown as Tg, the bulk
crystallisation shown as Tb, the liquidus temperature shown as Tl, and minor
crystalline phases and other features occurring as other peaks or troughs in the graph.
19
The glass transition, Tg has been called the “melting of amorphous material”.
As the material warm it up, its heat capacity increases and at some point the heat
capacity have enough energy in the material that it can be mobile. This requires a fair
amount of energy compared to the baseline increase, although much less than the
melting point does. This energy normally appears as a step change in the instrument
baseline – pointing up in heat flow instruments and down in heat flux (PerkinElmer,
Inc., 2013).
In non-crystalline and semi-crystalline polymer of any type – synthetic high
polymers like polypropylene and polystyrene, natural polymers like rubber, or
biological polymers like proteins – the glass transition is the best indicator of material
properties. As the glass transition changes due to either different degrees of
polymerization or modification by additives, the physical properties of the material
change. The relationship of Tg to degree of polymerization changes with these
alterations. Similarly, material properties also change dramatically above the Tg. For
example, materials lose their stiffness and flow as is the case in molten glass, and their
permeability to gasses increases dramatically.
Figure 2.4: Example DSC analysis
Glass Transition (Tg)
Decomposition
Oxidation Melting
Endotherm
20
2.7 Interrelationship between processing parameters and property of polymer
Plastics are mouldable organic resins. These are either natural or synthetic, and are
processed by forming or moulding into shapes. Plastics are important engineering
materials for many reasons. They have a wide range of properties, some of which are
unattainable from any other materials, and in most cases they are relatively low in cost.
Polymeric materials are formed by quite many different techniques depending
on (a) whether the material is thermoplastic or thermoset, (b) melting/degradation
temperature, (c) atmospheric stability, and (d) shape and intricacy of the product.
Polymers are often formed at elevated temperatures under pressure. Thermoplastic are
formed above their glass transition temperatures while applied pressure ensures that
the product retain its shape. Thermosets are formed in two stages – making liquid
polymer, then moulding it. Figure 2.5 Shows interrelationship between processing and
property of polymer.
Figure 2.5: Shows interrelationship between
processing and property of polymer William D., (2004)
21
2.7.1 Thermoplastic processing
(a) Drawing and extrusion
Long products having an uniform cross section, such as pipes, wires and L-shaped
rods, are usually made through the process called "drawing" or "extrusion." In these
processes, molten material is drawn or extruded through a "die" which has the mouse
having the same shape as the cross section of the product, and then the material is
cooled down so as to fix the shape of product as shows Figure 2.6. In general, since
cooling at the die is not enough to solidify whole the material, the material pass through
the die is cooled by passing it under a water pool or by using a water spray.
Figure 2.6: Schematic of extrusion (JSPP ed., 1996)
(b) Injection moulding
Injection moulding as shows Figure 2.7 is the process that the molten material is
injected into a mould cavity, the shape of which is almost the same as the final product,
and is cooled down so as to fix the shape of the material. This moulding process has
flexibility for the shape of products, and thus the injection moulding process is
commonly used for manufacturing the wide-range of plastic products, from the daily
necessities having relatively simple shape to the products having complicated shape,
such as the cases and containers of electronic equipment. In this process, since the
polymer melt viscosity of which is quite large is injected into a mould cavity at high
flow rate, injection pressure becomes quite high, e.g. up to several hundred MPa, and
thus large cramping force of the mould halves is required for moulding large products.
In addition to this, by this process, limited number of products can be obtained through
22
one shot of the moulding. This means that the process should be speeded up if one
wants to produce the products at high productivity.
Figure 2.7: Schematic of injection moulding (JSPP ed., 1996)
(c) Film forming
Plastic films are usually formed by stretching the molten polymer extruded in a plate-
like shape. The stretching the polymer material is not only for making the material
thinner, but also for developing orientation of polymer molecules; molecular
orientation results in strengthening in tensile strength of film in the direction of
orientation. In the practical film forming process as shows Figure 2.8, stretching of the
material is achieved by using tenters or rollers, or by using pressure of air blown into
the cylindrical polymer material (inflation film forming).
Figure 2.8: Schematic of inflation film forming (JSPP ed., 1996)
23
(d) Fibre drawing
Most of all the synthetic fibres (mono-filament) are made by stretching the molten
polymer extruded as a thin rod as shows Figure 2.9. Note that generally used strings
are made by twisting some mono-filaments together. Stretched materials become
stronger in the stretching direction due to molecular orientation. Cross section of the
rod before stretching is chosen according to the functions intended the fibre to acquire.
Figure 2.9: Schematic of fibre drawing (JSPP ed., 1996)
2.7.2 Thermosetting processing
(a) Vacuum forming and hot-press forming
In these processes, polymer material preformed like a board or film is softened by
heating first, put it on the mould, and then is pushed against a mould by using a vacuum
pressure (vacuum forming) or an opponent mould (hot-press forming). Figure 2.10
processes require less forming force, and simpler mould than that of injection
moulding can be used. But the preciseness of products is generally inferior to the
injection moulding. Accordingly the vacuum forming and/or hot-press forming are
usually applied for producing simple-shaped products, such as tray of foods.
24
Figure 2.10: Schematic of vacuum forming (JSPP ed., 1996)
(b) Blow moulding
Blow moulding as shows Figure 2.11 is the process often used to produce hollow
products such as bottles. Molten polymer is extruded as a cylindrical shape first (this
material is called as "parison"), the material is clamped between a pair of female
moulds, and then is pushed against the mould by the pressure of gas blown into the
cavity of the material. The strongest point of this process is the ability to produce
hollow products. Nowadays, therefore this process is applied also for producing
functional parts, such as air-spoilers of automobiles.
Figure 2.11: Schematic of blow moulding (JSPP ed., 1996)
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