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I hereby declare that the matter embodied in this dissertation entitled “Development of ginger
and Technology, Amity School of Applied Sciences, Amity University Gurugram, Haryana, for
the award of the degree of Master of Technology in Polymer Science and Technology is my
original work. I have not plagiarized or submitted the same work for the award of any other degree.
In case this undertaking is found incorrect, I accept that my degree may be unconditionally
withdrawn.
Gurugram
ii
CERTIFICATE
This is to certify that the work contained in this project report entitled “Development of ginger
reinforced polyvinyl alcohol biocomposites”, submitted by Kudzai Hamish Ruzvidzo, has been
carried out under the supervision of Prof. A.P. Gupta and Prof. Joydeep Dutta. The matter
embodied in this dissertation has not been submitted elsewhere for any degree.
iii
ACKNOWLEDGEMENT
I would like to thank my research supervisors, Prof. A.P Gupta, Head, Department of Polymer
Science and Technology, ASAS and Prof. Joydeep Dutta, Professor, Department of Applied
Chemistry, ASAS, for their kind assistance and dedication throughout the whole tenure of the
dissertation.
My sincere thanks also to the Amity University Haryana, for providing me an opportunity and
access to the laboratory and research facilities.
I must acknowledge as well the lab staff of Department of Chemistry supervised by Mr. Vijay
Kumar who offered unflagging support and wise advice throughout my work in laboratory.
Special mention goes to my parents, Mr. E Ruzvidzo and Mrs. B Ruzvidzo, my special friend
Miss. Rumbidzai Authentic Fungura, my colleagues Mr. Tapiwanashe Shumba and Miss. Pooja
Nehra for their support during the tenure of the dissertation.
Above all, I thank the Almighty God for guiding and protecting me throughout.
iv
ABSTRACT
Biocomposites of polyvinyl alcohol (PVA) reinforced with different weight percentages of ginger
(Zingiber officinale) and of thickness between 0.30mm to 0.35mm were developed and their
tensile strengths, water absorption capacity, water vapour transmission rate (WVTR),
biodegradation by soil burial tests and thermal analysis by Thermogravimetric analysis (TGA)
were evaluated. The fibres were extracted from ginger using water retting for 14 days. The
biocomposites were fabricated using hand lay-up method and the different weight percentages of
ginger fibres were 1%, 3% and 5%. The fibre orientations in the biocomposites were bidirectional,
unidirectional, diagonal and random. Water absorption analysis showed a high water uptake but
lower than that of pure PVA. Water vapour transmission rate of the PVA/ginger biocomposites
were high though lesser than those of pure PVA samples. For the soil burial test, the rate of
biodegradation increased with an increase in fibre content, with the 5wt% sample having the
highest rate of biodegradation. The thermal analysis showed that the biocomposite had a higher
degradation temperature of 310oC as compared to that of the PVA sample that was 290 oC. The
results of this study showed that the ginger reinforced polyvinyl alcohol biocomposite was
completely biodegradable thus; it can find applications in packaging.
v
TABLE OF CONTENTS
Acknowledgement (iv)
Abstract (v)
1. Introduction 1-6
3.1 Materials
6. References 55-59
vi
LIST OF FIGURES
Figure 1.1 Classification od matrix materials of composites
Figure 2.1 Structures of Zingiberene, gingerols and shogaols
Figure 2.2 Structures of farnesene and curcumene
Figure 2.3 Ginger productivity of India in last decade
Figure 2.4 Structures of some biodegradable polymers
Figure 2.5 Polymerization of polyvinyl alcohol
Figure 2.6 Hand lay-up composite fabrication process
vii
LIST OF TABLES
viii
LIST OF ABBREVIATIONS
ASTM American Society for Testing and Materials
TS Transverse Section
ix
CHAPTER 1: INTRODUCTION
1.1 Overview of composites
Some applications require a mix of different materials with unique and distinct properties to have
the best characteristics. Thus, nowadays it is essential to combine different materials as to produce
a final product with superior and unique properties over the individual materials1. For instance,
polymers are usually resistant to chemicals, lightweight, thermal insulators, electrical insulators,
processable in many ways etc., however their other mechanical properties, like tensile strengths,
are not that great. Plant fibres have great tensile strengths, thus a mix of a polymer with those plant
fibres will produce a product that has superior strength properties in addition to special individual
properties of these materials. Some include increased strength, toughness, stiffness, reduced
weight, increased durability, thermal insulation, resistance to corrosion, creep, fatigue, tear etc.
Compared with other manufactured materials, composites have the important characteristic that
the individual material will remain distinct2. A composite has two phases i.e. a matrix phase and a
dispersion phase3. The matrix phase is continuous material that encloses the composite. The matrix
can be a metal, polymer, ceramic or carbon4. Polymer matrix can be either a thermoset such as
epoxy or a thermoplastic such as polyphenylene sulphide. The matrix is a binder as it holds fibres
together and helps align them in the stress direction, helps transfer the load, protects the reinforcing
material from environmental damages like toxic chemicals, abrasion, oxidative attacks, moisture,
radiation, temperature etc., prevents formation of cracks in fibre and maintains geometry of
reinforcement5. The dispersion phase is responsible for the core of composites6. The connection to
the matrix is by bonding. Reinforcing materials are the solid constituent of the composite that
provide strength and stiffness. Reinforcements can be whiskers, flakes, fibres, particulates, solid
eutectics etc.7 Apart from providing strength in the composite, reinforcing materials can
additionally be used to provide resistance against heat, corrosion, electricity etc. while also
providing rigidity. Composite materials find applications in many sectors of industry like in the
automobile industries, marine applications, electronic circuit boards, aeronautical applications,
safety and security sectors, chemical plants, sporting equipment like tennis racquets, construction,
biomedical, musical instruments, aerospace etc.8
Matrices
Thermoplastics
or Thermosets
Polymer Matrix Composites (PMC) consist of reinforcing fibres bound together by either a
thermoplastic or a thermoset resin matrix9. These type of composites have low weight, are very
strong, are very stiff, cheap, have good resistance to both corrosion and abrasion and can be easily
made. However, Polymer matrix Composites have low thermal resistances, the coefficients of
thermal expansions are usually high, most are fabricated by lay-up method that is laborious and
slow10. Thus, a need arose for newer and faster automation fabrication methods for Polymer Matrix
Composites. Ceramic Matrix Composites (CMC) consist of a ceramic material being the matrix in
a composite11. A ceramic can be referred as an inorganic non-metallic solid material that has very
strong ionic bonding, is crystalline in nature and possess high moduli, high compressive strength,
12
high hardness, inert to most chemicals, their thermal conductivities are usually low etc.
However, ceramics have very low fracture toughness. Thus, Ceramic Matrix composites (CMC)
13
are vital to enhance toughness of composite materials. Unlike in Polymer matrix composites
where the aim of reinforcement is for enhancing how strong the composite is, in Ceramic Polymer
Matrix (CMC) the reinforcements used such as carbon, glasses, oxides and non-oxides adds to
how strong composites become. Metal Matrix composites (MMC), a composite material, in which
2
the matrix is a metal like aluminum, titanium, magnesium, iron, nickel, cobalt or silver14. MMCs
have the advantages of having low densities, excellent creep, excellent wear resistances, being
strong and able to sustain high temperatures etc.
3
Table 1: Classification of plant fibres
4
1.3 Advantages and disadvantages of composite materials
These composite materials offer many advantages over traditional materials like metals. These
advantages make the utilization of these materials more attractive in this ever growing and
competitive industrial market. Composite materials offer the following advantages i.e. reduced
weight, increased strength, rigidity, resistance to fatigue, resistance to toxic chemical substances
like acids, alkalis etc., resilience, cost saving, increased thermal and electrical insulation, increased
safety due to having low thermal and electrical conductivities. Other advantages include varied
design options or flexibility, high strength-to-weight ratios, corrosion resistance, high-impact
strengths, dimensional stability, radar transparency, durability and water resistance. However,
composite materials also have the following drawback i.e. special equipment are required, hot
curing is usually needed, as compared to wrought metals composites are more brittle. Thus,
composites damage easily. Raw materials have high costs, complex and labour intensive
fabrication process. Hot curing or cold curing involves plenty of time. Fortunately, many of the
above disadvantages can be minimized by proper design and material selection.
5
Analysis of the prepared composites using TGA
To determine the water absorption capacity, percentage biodegradability and water vapour
transmission rate (WVTR) of the biocomposite samples and analyze these properties with
respect to packaging applications.
The thesis consists of five chapters. Chapter I, “Introduction”, presents a general overview of
composites, their classifications, applications, advantages, drawbacks, plant fibre reinforced
polymers etc.
Chapter II includes a “Review of Literature” which gives information of the previous work
concerning biocomposites and ginger.
Chapter III is the “Materials and Methods” which gives the detailed experiments and tests adopted
during the research work. This includes the extraction of the fibres from ginger, production of
composite samples and ASTM standards testing methods.
Chapter IV comprises “Results and Discussions” which details results of the present research
work. Tensile strengths results, water absorption results, biodegradability test, water vapour
transmission rate, TGA and FTIR results are discussed in detail.
Chapter V highlights the “Summary and Conclusions”, which concludes the research work and
gives brief summary and major conclusions drawn from the study. The chapter also gives more
ideas on how to extend the research work in future for researchers.
6
CHAPTER 2: REVIEW OF LITERATURE
2.1 Natural fibres as reinforcements in composites
Ghazali et al. used harakeke and hemp fibres as reinforcements in biocomposites. They used
chemicals such as NaOH or together with sodium sulphate to extract the fibres. Analysis using
single fibre tensile testing, X-ray diffraction (XRD), scanning electron microscopy (SEM) and
Thermogravimetric analysis (TGA) of the fibres was conducted. Chemical treatment of the fibres
caused thermally stable fibres and higher crystallinity index. Hyper-branched polymers (HBP)
were used to plasticize the fibres which in turn enhanced composite ductility and impact
strengths17.
Techapaitoon et al. explored the fracture toughness of natural fibre composites consisting of
digylycidyl ether of bisphenol-A (DGEBA) epoxy matrix and flax fibres in one composite and
plain-woven regenerated cellulose fibres in the other. Two methods were employed to fabricate
the composites i.e. resin infusion under flexible tooling (RIFT) and resin transfer molding (RTM).
Interlaminar fracture energies of 20J/m2 were determined for flax-fibre reinforced biocomposites
developed by RIFT process. For those developed using RTM process, the fracture energy was
963J/m2.19
7
Zhu et al. developed renewable flax composites using mimosa tannin resin and pine-oil derived
supersap epoxy resin. These composites were gauged for their usefulness in modern vehicle
applications. The flax/supersap composites were suitable for exterior structural uses and
flax/tannin composites were applicable for interior non-structural uses21.
Li et al. developed a composite consisting of flax fibre as reinforcement and polyethylene (PE) as
matrix using injection moulding and also investigated effects of material properties and processing
parameters. Treatments were done as to reduce the hydrophilicity of fibres and enhance the fibre-
matrix adhesion. The matrices used were mainly High Density Polyethylene (HDPE) and Linear
Low Density Polyethylene (LLDPE) 22.
Jabbar et al. studied developments of jute-based composites using green epoxy matrix. Composites
were developed using compression molding and hand lay-up methods. The fibres were treated with
alkalis and characterized using FTIR. Mechanical properties were also determined. Creep was
analyzed using three models23.
Wretfors et al. developed a renewable composite of wheat gluten plastic with hemp fibres as
reinforcement. Retting was used for fibre extraction. Effects of fibre on the mechanical strengths
were analyzed24.
Gupta S.K et al. investigated the mechanical behaviours of epoxy-based composites reinforced by
short bamboo fibres. They concluded that mechanical properties were greatly influenced by the
size of the fibres used. Excess fibres caused deterioration of mechanical properties due to lack of
proper bonding of the matrix and the fibre around the interface. Thus, the transfer of load to the
bonding fibres is disrupted25.
Kumar S et al. developed epoxy-based composites reinforced by banana fibres. Their main goal
was to examine the mechanical behaviour of the composites. The composites were developed
using the hand lay-up technique. They concluded that fibre loading and length had high effects on
the mechanical properties like hardness, flexural strength, tensile strength, impact strength etc26.
8
improved by the utilization of a compatibilizer. They also developed other biocomposites of
(PHBV-PBAT) matrix and various lignocellulosic fibres27.
9
reinforced with hemp
fibres
Gupta S.K et al.25 Epoxy-based Excess fibres caused deterioration of mechanical
composites reinforced properties due to lack of proper bonding of the matrix
with short bamboo and the fibre around the interface. Thus, the transfer of
fibres load to the bonding fibres is disrupted
Kumar S et al.26 Epoxy-based Fibre loading and length had high effects on the
composites reinforced mechanical properties like hardness, flexural strength,
with banana fibre tensile strength, impact strength etc.
Nagarajan et al.27 (PHBV-PBAT) matrix Increase of fibre loading led to deterioration of
and switchgrass mechanical strength of the composites. They also
developed other biocomposites of (PHBV-PBAT)
matrix and various lignocellulosic fibres
10
Table 3: Classification of ginger
Kingdom: Plantae
Subkingdom: Tracheobionata
Class: Liopsida
Clade: Angiosperms
Clade: Monocots
Genus: Zingiber
Order: Zingiberales
10% fats,
1-4% essential oils
5% fibers,
60% starch,
6% inorganic material,
10% proteins,
10% residual moisture,
11
Sahdeo Prasad and Amit K. Tyagi et al. (2015) reported the major compounds of ginger rhizomes
as 50–70% carbohydrates, 3–8% lipid, phenolic compounds and terpenes. Terpenes include
zingiberene, β-bisabolene, α-farnesene, β-sesquiphellandrene, and α-curcumene, and phenolics
include gingerol, shogaol and paradols. Zingiberene, C15H24, which makes the bulk of ginger oil,
is a monocyclic sesquiterpene. Zingiberene gives ginger the flavoring and makes up about 30% of
the oils. Gingerols contribute about 23–25% while shogaol contributes about 18–25%. These two,
shogaol and gingerols, contribute a greater quantity compared to others. Other constituents present
include raw fibre, minerals, amino acids, ash, vitamins such as nicotinic acid and vitamin A,
protein and phytosterols.
12
Constituents of ginger depend on where it originates as well as the physical state of the rhizome34.
Gingerols are responsible for pungency of fresh ginger. Two important groups of chemicals in
ginger are34:
Volatile oils give aroma as well as taste of ginger. Sesquiterpene hydrocarbons like zingeberene,
curcumene and farnesene, as well as bisabolene and b-sesquiphellandrene, are the volatile oil
constituents of ginger. Zingeberene is about 35%, curcumene about 18% and farnesene about 10%
34
.
Gingerols, especially [6]-gingerol, which is the major one, are the most active constituent in fresh
ginger. Other gingerols include [8]-gingerol and [10]-gingerol. Nonvolatile pungent substances
comprises of [6]-gingerol, [8]-gingerol, [10]-gingerol, shogaols, zingerone and paradols35. As the
[6]-gingerol, [8]-gingerol and [10]-gingerol are thermally unstable, they form [6]-, [8]- and [10]
under high temperatures35. Gingerols dehydrate to form shogaols, and paradols are formed by
adding hydrogen to shogaol35. Generally, gingerols are similar to paradols35.
Other constituents found in ginger include carbohydrates, minerals, fats, minerals, waxes etc.
Zingibain or commonly named ginger protease is also found in ginger36. In addition, ginger has
13
about 3 to 8% lipids like oleic, capric, linoleic, palmitic, triglycerides etc. as well as about 50 to
70% carbohydrates present as starch37. Volatile oils contribute about 1-2% of ginger as well as 5
to 8% resinous matter. The oils consists of more than 50 constituents and exude the aroma of
ginger38. These volatile oils of ginger comprise of the sesiquiterpenes like β besabolene and
zingiberene, monoterpenes like β-phelandrene, cineol, borneol, citral as well as zingiberol39.
14
Ginger productivity of India in last decade
7 6.53 6.56
6
5.2
4.88 4.98 4.94
4.71
5
4 3.5 3.58
0
2008-09 2009-10 2010-11 2011-12 2012-13 2013-14 2014-15 2015-16 2016-17
Productivity (Tonnes/ha)
15
2.2 Biodegradable polymers
Polymers have extensive applications in packaging, textiles, automotive industries, construction,
medicine, electronics, plumbing, adhesives, aerospace, furniture, sporting equipment, music,
agriculture etc. Unfortunately, synthetic polymers are non-biodegradable thus; they tend to create
environmental pollution issues as they remain in landfills or oceans for long periods. This tends to
affect both humans and wildlife. A polymer is a macromolecule made up of joining many repeated
subunits called monomers42. Biodegradation is the putrefaction of substances by action of bacteria,
algae, fungi etc. ASTM as well as ISO have defined degradable plastics as “Those that undergo a
significant change in chemical structure under specific environmental conditions” 43
.
Biodegradation of polymers occurs either in oxygen (aerobic) or without (anaerobic). As reported
by Subramanian Senthilkannan Muthu in Assessing the Environmental Impact of Textiles and the
Clothing Supply Chain, the basic equations for the two processes can be simplified as:
Thus as shown, biodegradable polymers break down after use and produces gases such as carbon
dioxide, methane, nitrogen etc., biomass, water and inorganic salts.
Kucharczyk et al. dealt with latest advances in synthesis, modification and degradation of
biodegradable polyesters. Systems based on lactic acid – polylactides were mainly centred on. The
polyesters would have medical applications. Degradation studies of the polylactides produced
were also done under various conditions44.
16
Soleimani et al. developed new polymeric nanomaterials that would have biomedical uses. They
focused on the design, synthesis and evaluation of new biodegradable polymers and nanoscale
assemblies for drug delivery. Firstly they developed many poly(ester amides) composed of α-
amino acids, diols, and diacids. Then a poly(ester amide) - poly(ethylene oxide) conjugate was
developed and made into micelles as to achieve controlled release of PTX via hydrolysis of ester
linkages46.
Aydin et al. developed biodegradable polymer intended for bone plate applications. Biodegradable
fibres of Poly(L-lactide) and Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with hydroxyapatite
(HAP) nanoparticles were produced using extrusion method plus spinning to provide
reinforcements of polymeric bone plates47.
Moura et al. developed biodegradable copolymers of EVA and PLA using transesterification
reactions. They synthesized a maximum of 25% of the copolymer. ISO 14851 (1991) was used for
biodegradation tests. The results showed that the procedure allowed for development of
biodegradable copolymers with identical properties to those of conventional polymers48.
Díaz et al. developed and studied properties together with uses of biodegradable polymers
developed from diols and dicarboxylic acids. The uses of these biodegradable polymers include
hydrogels, soft tissue engineering, drug delivery systems and liquid crystals. They considered
usage of aromatic units and α-amino acids as the stiffness of molecular chains as well as
intermolecular interaction could be easily changed. They showed that poly(ester amide)s from
naturally occurring amino acids offered huge potential in biomedical uses as biodegradable
materials50.
17
Figure 2.4: Structures of some biodegradable polymers (Source: Gross R.A,
Kalra B, Biodegradable Polymers for the Environment)
2.2.1 Polyvinyl alcohol
Polyvinyl alcohol (PVA), [CH2CH(OH)]n, is a colourless, water-soluble, biodegradable synthetic
resin which surprisingly when compared with most vinyl polymers, is not made via polymerization
of the corresponding monomer51. Instead, PVA involves firstly polymerization of vinyl acetate
monomers by free radicals to form polyvinyl acetate (PVAc), which is then dissolved in an alcohol
such as methanol with a catalyst like sodium hydroxide52. Then a partial hydrolysis or complete
hydrolysis will remove the acetate group (CH3COO) from the polyvinyl acetate but does not
disrupt its long chain structure, thus PVA is a hydrophilic linear polymer. The synthesis of PVA
is summarized as shown below:
18
Figure 2.5: Polymerization of polyvinyl alcohol
Polyvinyl alcohol has chemical formula (C2H3OR)n where R = H or COCH3. The physical
description of polyvinyl alcohol can be described as being odourless, tasteless, translucent white
to cream-coloured granules or powders53. 4% aqueous solutions of polyvinyl alcohol have a pH
from 5 to 8 and it is also strongly hydrophilic53. The boiling point of polyvinyl alcohol is
approximately 644 degree Fahrenheit at 760 mm Hg54. The melting point of polyvinyl alcohol is
between 212 degrees Celsius to 267 degrees Celsius55. Polyvinyl alcohol is highly soluble in water
but solubility of polyvinyl alcohol in water increases with a decrease in molecular weight56.
Polyvinyl alcohol is insoluble in animal oils, vegetable oils, acetone, aromatic hydrocarbons,
chlorinated hydrocarbons, esters, and ether but slightly soluble in ethanol57. The density of
polyvinyl alcohol is between 1.19-1.31 g/cm³.58 When polyvinyl alcohol is heated to
decomposition, acrid smoke is emitted with irritating fumes also59. The viscosity of polyvinyl
alcohol ranges from above 4.8 to 5.8 mPa.s for a 4 % solution at 20 °C60. Polyvinyl alcohol is
unique in that it is made by alcoholysis or saponification or hydrolysis of polyvinyl acetate. The
acetate groups from the polyvinyl acetate are replaced with hydroxyl groups61.
19
2.2.2 Polyvinyl alcohol as a matrix in biocomposites
Jyoti et al. developed a biocomposite of polyvinyl alcohol and date palm leaf fibre (PVA/DPL) by
melt mixing fabrication method using various proportions of the fibres. The fibres were treated
with certain chemicals as to improve the dispersion and better compatibility of them with the PVA
matrix. The acrylic acid treated DPL fibres produced better qualities compared with other methods.
Properties were analyzed like morphology, tensile strength; Young’s modulus, elongation at break,
impact strength, flexural strength etc. and the results were compared to those of virgin PVA
matrix62.
Ching et al. developed and characterized a PVA/oil palm empty fruit bunch fibre composite by
casting evaporation technique. There was intimate contact between the empty fruit bunch fibre and
the polyvinyl alcohol. They showed that addition of 1 wt% of empty fruit bunch fibre led to an
increase in the tensile strength and modulus od the PVA/empty fruit bunch composite. Stiffness of
the PVA that was reinforced with 3 wt% of empty fibre bunch increased by 300% compared to the
neat polyvinyl alcohol63.
Tian et al. developed polyvinyl alcohol/modified silicon carbide (SiC) composites. The modified
silicon carbide was used as a filler because of its relatively good abrasive nature thus; it would be
able to improve the wear resistance of PVA. The composites were fabricated using a melt process
and then subjected to tensile tests. The suitability of the composites for tribological uses was being
analyzed. The interactions between the matrix and the filler were enhanced by the utilization of
coupling agents. The surface modified SiC particles were also well dispersed within the polyvinyl
alcohol which enhanced their compatibility with the matrix64.
Pron et al. developed a polyvinyl alcohol – polypyrrole conducting composite by the exposing the
solid polyvinyl alcohol films containing FeCl3 or K3Fe(CN)6 to the vapours of the pyrrole. They
showed that the distribution of the oxidant within the polyvinyl alcohol matrix is crucial for the
morphology and electrical properties of the developed composites65.
Ahmed et al. developed polyvinyl alcohol – iodine composites by addition of different weight
percentages i.e. 2,4 and 6% of the iodine to the polyvinyl alcohol matrix. The main use of the
developed composites were to treatment of wounds infected with diseases especially diabetes.
Injured mice were used to apply the solutions and films as to evaluate the healing action. They
showed that the drug was antibacterially active and healed the wounds well66.
20
Singha et al. developed biocomposite films of starch and polyvinyl alcohol. The reinforcement
was in the form of delignified Grewia optiva fibre as well as methyl methacrylate (MMA) grafted
fibres. Citric acid was the plasticizer and the cross-linker was glutaraldehyde. Tests were done for
their mechanical properties, biodegradability and antibacterial properties. Results from SEM
revealed great adhesion between starch and polyvinyl alcohol blend matrix and fibres. Results also
revealed the biocomposite films were suitable for food packaging applications67.
Polyvinyl alcohol has a variety of uses i.e. as a release agent, as a binder and thickener, to make
Vinylon, as a textile-sizing agent, for paper coatings, in packaging as water-soluble films, is useful
in PET bottles as a CO2 barrier. Polyvinyl alcohol is also used as PVA fibre that is utilized as
concrete reinforcement, as polyvinyl nitrate raw material, as surface-active agent, as protective
chemical-resistant gloves, as protective colloid in suspension polymerization. When polyvinyl
alcohol is doped with iodine, it polarizes light and polyvinyl alcohol finds application in medical
procedures.
21
Table 5: Summary of research on the soil burial biodegradability of some substances
22
2.3 Hand Lay-Up Composite Fabrication Method
Composites are made in three processes i.e. open molding, closed molding and cast polymer
molding.73 Open molding is a simple, low cost process which the resins, and fibre reinforcements
are exposed to air. Thus, the composites cure or harden. Hand lay-up, filament winding, casting
and spray-up are all open molding techniques.74 Hand lay-up is the easiest and popular open
molding composite manufacturing process. It also requires less amount of equipment compared
with other techniques.
23
Mikell P. Groover et al (2002) reported that hand lay-up composite manufacturing process can be
best explained in the steps shown in Figure 6. In step (1), the mold is treated with mold releasing
substance to avoid the sticking of polymer to the surface. In step (2) a thin gel coat is then put onto
the outside covering of molding. In step (3), when partial setting of the gel coat has occurred,
quantities of both resin and the fibre are then applied. Rollers thoroughly wet the reinforcement
and eliminate air. In step (4), the part is cured. Curing time is dependent on which polymer is
utilized. For example, epoxy based systems at room temperature cure in about 24 to 48 hours. In
step (5) the part which has now completely hardened is ejected. The hand lay-up composite
manufacturing method is usually utilized for thermosets like epoxy. It is the simplest of all
composite fabrication methods. It offers cheaper tooling and many part sizes. Hand lay-up
composite fabrication method is used in areas like making of aircraft components, boat hulls, large
container tanks, swimming pools, stage props, some automotive parts etc.75. The materials used as
matrix in this method include epoxy, unsaturated polyester, polyvinyl esters phenolic resin etc.
and the reinforcements are glass fibre, carbon fibre, aramid fibre and natural plant fibres like ginger
fibres.
24
CHAPTER 3: MATERIALS AND METHODS
3.1 Materials
Reagents of pure quality were extensively used for the experiments. Polyvinyl alcohol (Mol. Wt.
85,000 to 1,24,000) was purchased at the Central Drug House (CHD), Vardaan House, Daryaganj,
New Delhi, India. Distilled water was also used throughout for all experiments. Table 6
summarizes the properties of the polyvinyl alcohol.
The ginger was purchased from the local market at Amity University Haryana.
25
3.2 Extraction of fibre from ginger
Storage of
Washing Peeling of ginger in
of ginger ginger freezer for 3
days
Water
Washing and Stripping of retting of
drying of ginger ginger for
ginger fibres fibres 14 days
26
Figure 3.3 - Water retting and stripping of fibres from ginger
27
Figure 3.4: Unwashed ginger fibres (left) plus washed and
dried ginger fibres (right)
3.3 Biocomposite fabrication
3.3.1 Preparation of polyvinyl alcohol solution
10% polyvinyl alcohol solution was prepared. 10grams of polyvinyl alcohol powder was slowly
added to 100mL of deionized water in a volumetric flask. After full dispersion of the powder, the
mixture was then heated until the polymer became solubilized. After heating, the polyvinyl alcohol
solution was left to cool.
28
Figure 3.5: Initial stage in fabrication of biocomposites
Ginger fibres were then arranged into the polyvinyl alcohol solution.
29
Three different fibre content weight percentage classes of biocomposite samples were prepared.
The first class consisted of 1 wt% ginger fibre, the second 3 wt% ginger fibre and the third 5 wt%
ginger fibre.
30
Some of the ginger reinforced polyvinyl alcohol biocomposite samples developed are shown in
the images below:
31
32
33
Figure 3.7: Images of ginger reinforced polyvinyl alcohol
biocomposite samples produced
34
3.4 Testing and characterization methods
3.4.1 Water absorption test
A modified ASTM D570 procedure was employed for the water absorption test. In this test three
dried rectangular ginger reinforced polyvinyl alcohol biocomposites of length 28mm and width
25mm were first weighed. Samples were then emerged into water in a freezer for 24 hours. A
freezer was employed in this procedure because the ginger reinforced polyvinyl alcohol
biocomposite is greatly soluble in water, thus decreasing the temperature would reduce the rate of
solubility.79 After 24 hours samples were ejected, dried with a cloth and immediately weighed.
The water absorption is percentage change (gain) or increase in weight 80.
Where wet weight refers to the weight of the biocomposite samples after being emerged in water
for 24 hours, and dry weight refers to the initial weight of the biocomposite samples.
To determine the WVTR of biocomposite samples, two modified ASTM – E96 procedure D wet
cup methods were used.
Method 1
Three circular biocomposite samples were put on top of beakers containing distilled water. The
open mouth of the beaker was then sealed but making sure that 37mm diameter of the biocomposite
sample would remain exposed such that it would become the test area.
35
Figure 3.8: Water vapour transmission rate (WVTR) test representation
The initial weight was measured and then the setup was put in an incubator at 500C for 24 hours.
Afterwards the final weight was measured.
Method 2
Rectangular specimen were used, the first had dimensions of 36𝑚𝑚 × 28𝑚𝑚 and the other
35𝑚𝑚 × 22𝑚𝑚. These samples were put on top of beakers containing distilled water, making
sure to leave about 1.8cm space between the distilled water and test area of specimen. The open
mouth of the beaker was then sealed but making sure that the dimensions of the rectangular
specimen used would remain exposed such that it would become the test area. A temperature of
600C and a testing time of 6 hours was used. The setup was periodically weighed at one-hour
intervals for 6 hours. The weight change, G, was measured every hour. A graph of weight
change, G, vs time t was then plotted. From the graph, the linear portion’s slope is the one useful
in WVTR calculations.
36
Slope of G vs t graph linear portion divided by the test specimen area determines the value of the
WVTR.
G
(t)
WVTR =
A
slope of G vs t graph
=
Test area of specimen
37
The meteorology data for the period from 13 June 2018 to 29 June 2018 when the test was done
at Amity University Gurgaon, Haryana, India were:
38
CHAPTER 4: RESULTS AND DISCUSSION
4.1 Thickness of samples
The thickness of the pure PVA samples were higher than that of the biocomposite samples. The
thickness of six PVA/ginger biocomposite samples were measured and the results are shown in
Table 9
39
% water absportion % Water absorption of biocomposite samples in 24 hours
40
4.3 Water vapour transmission rate (WVTR) test analysis
The results of the WVTR test performed on the ginger reinforced polyvinyl alcohol biocomposites
are:
Method 1 results
Table 11: WVTR results for circular sample
41
G vs t graph for biocomposite sample
0.16
0.14
0.12
Weight change,(G), grams
0.1
0.08
0.06
0.04
0.02
0
0 1 2 3 4 5 6 7
Time (t), hours
0 137.584 0
1 137.533 0.051
2 137.448 0.085
3 137.349 0.099
4 137.237 0.112
5 137.118 0.119
6 136.991 0.127
42
G vs t graph for biocomposite sample
0.14
0.12
Weight change,(G), grams
0.1
0.08
0.06
0.04
0.02
0
0 1 2 3 4 5 6 7
Time (t), hours
43
WVTR of pure PVA samples
466.3 459.3
434.9
WVTR (gm-2day-1)
Averaging the three values, the WVTR of PVA sample was 453.5 gm−2 day −1 .
WVTR is one of the critical parameters for assessing packaging materials. Lower values of WVTR
show that the material has good resistance to water vapor transmission. The results showed that
pure polyvinyl alcohol sample had a greater WVTR value as compared to that of the ginger
reinforced polyvinyl alcohol solution. Polyvinyl alcohol is hydrophilic and as such due to hydroxyl
group, it can readily interact with water molecules thus consequently increasing the WVTR as
compared to other less hydrophilic substances. In ginger reinforced polyvinyl alcohol
biocomposite samples, the WVTR decreases because as the percentage composition of ginger
increases the hydrophilicity in turn decreases. It is impossible to compare WVTR values with
literature as they were not done under the same conditions. However, Suki et al. determined
WVTR values of 8.6g/m2h, 9.2g/m2h, 9.7g/m2h, 10.3g/m2h for PVA/BFF blends of 90/10, 80/20,
70/30, 60/40 respectively82.
44
4.4 Biodegradability test results
The results for the biodegradability tests were
90
80
70
% weight loss
60
50
40
30
20
10
0
5 days 10 days 15 days
Time (days)
45
From the results, the rate of biodegradability of the ginger reinforced polyvinyl alcohol
biocomposites increased with an increase in fibre content or with a decrease in ratios of PVA.
Also, in the soil sorption of water by the biocomposites would promote the entry of
microorganisms which would enhance the biodegradability process. From literature, the weight
loss of pure PVA is lesser that those of biocomposite samples since the fibres would aid in the
absorption of water which would speed up the biodegradation. From the results, the 5wt.%
bidirectional ginger reinforced polyvinyl alcohol biocomposite samples showed highest
biodegradation rate, whilst the 1wt.% bidirectional ginger reinforced polyvinyl alcohol
biocomposite samples showed the least biodegradation rates. Comparing with pure PVA, from
literature, Ooi et al. 2011, reasoned that pure PVA will have lesser biodegradation rates compared
to PVA biocomposites because the C-C backbone linkage of the PVA. Guohua et al. 2006 reported
that pure PVA samples exhibit greater resistance to soil burial biodegradation. During the period
the samples were buried, there was rainfall in Haryana, thus the excess water may have permeated
into the ginger reinforced biocomposite specimens. Table 5 in review of Literature section also
has a summary of research results on the soil burial biodegradability of some other composite
materials constituting PVA.
46
4.5 Tensile strength of biocomposites
The results from the tensile testing are shown
4.5
3.5
3
Standard force [MPa]
2.5
1.5
0.5
0
-5 0 5 10 15 20 25
Elongation [%]
6
Standard force [MPa]
0
-10 0 10 20 30 40 50 60 70 80
Elongation [%]
47
5wt% bidirectional sample
10
7
Standard force [MPa]
0
-10 0 10 20 30 40 50 60 70 80
Elongation [%]
6
5
4
3
2
1
0
-5 0 5 10 15 20 25 30 35 40
Elongation [%]
48
5wt% random sample
14
12
10
Standard force [MPa]
0
-10 0 10 20 30 40 50 60 70 80
Elongation [%]
10
Standard force [MPa]
0
-20 0 20 40 60 80 100
Elongation [%]
49
1wt% unidirectional sample
12
10
Standard force [MPa]
0
-10 0 10 20 30 40 50 60 70 80
Elongation [%]
5
Standard force [MPa]
0
-10 0 10 20 30 40 50 60 70 80
Elongation [%]
50
1wt% random sample
7
5
Standard force [MPa]
0
-10 0 10 20 30 40 50 60
Elongation [%]
51
4.6 Thermogravimetric analysis (TGA)
60 -1
50 -1.5
40 -2
30 -2.5
20 -3
10 -3.5
0 -4
0 100 200 300 400 500 600 700 800
Temperature (degrees celcius)
60
-1
50
-2
40
30 -3
20
-4
10
0 -5
0 100 200 300 400 500 600 700 800
Temperature (degrees celcius)
52
Figure 4.10 shows the weight percentage vs sample temperature of the PVA sample. Figure 4.11
shows the weight percentage vs sample temperature of the ginger reinforced polyvinyl alcohol
biocomposite. The TGA curves of both pure PVA samples and PVA/ginger showed three weight
loss stages. For the pure PVA sample, the initial weight loss occurred at temperature region of 40
to 110°C due to the evaporation or loss of moisture from the polymer matrix. The loss in weight
was about 5.88wt% in this stage. The major loss of weight occurred in the 150 to 380°C. This is
because of the degradation of the side chain i.e. O-H groups of the PVA. The loss of weight in
stage was about 55wt%. The third stage ranged from temperatures above 400°C and corresponded
to the cleavage or breakdown of the C–C backbone of the polyvinyl alcohol. The weight loss in
this stage was around 30%. The degradation temperature of the PVA sample was 290oC.
The PVA/ginger biocomposites also exhibited three major stages of weight losses. The initial
weight loss occurred in the region from region 40 to 110°C and was due to the loss of moisture in
the biocomposites. The weight loss was about 4.16wtpercentage. The greatest weight loss occurred
from temperatures of 160 to 400oC and this was due to the structural degradation of the PVA
matrix in the biocomposites. The weight loss at this stage was about 52wt%. The third stage was
for temperatures above 400oC and it corresponds to the cleavage or breakdown of the backbone of
PVA as well as the degradation of fibre. The degradation temperature of the PVA/ginger
biocomposite sample was 310oC.
The degradation temperature of the PVA/ginger biocomposite sample was higher than that of PVA
sample because an increase for fibre enhances interaction between fibre and matrix, which in turn
improves the thermal resistance.
53
CHAPTER 5: CONCLUSIONS
In the study of the development of PVA/ginger biocomposites, ginger fibres were successfully
extracted using the water retting method. The extracted ginger fibres showed good tensile strength,
with the tensile increasing with increasing fibre content up to the 5wt% biocomposite samples.
The PVA/ginger composites were successfully developed using the hand lay-up method and had
different fibre weight percentage. The fibre and matrix had good compatibility and all are
hydrophilic in nature. The results of the water absorption test showed that the PVA/ginger
biocomposites had high water absorption capabilities due to the hydrophilic nature of both the
polyvinyl alcohol polymer and the natural fibres. However, an increase in the ginger fibre content
caused a decrease in the water absorption. The water vapour transmission rates also showed the
high tendency of the biocomposites for moisture transmission. However, the WVTR was lesser as
compared to that of pure PVA samples showing that incorporation of fibres reduces the moisture
transmission. Soil biodegradation tests also showed that the PVA/ginger biocomposites had a great
biodegradation rate as compared to pure PVA and an increase in fibre content corresponded to an
increase in the biodegradability of the biocomposites. This is great as the biocomposites would
have applications in packaging and as such, the high rates of biodegradation are vital as to reduce
environmental pollution as caused by most non-biodegradable synthetic polymers. The thermal
analysis of the biocomposites by TGA showed that the degradation temperature of the PVA/ginger
biocomposite was higher than that of pure PVA because the presence of the fibres enhanced
interactions between fibre and matrix that in turn improved the thermal resistance of the
biocomposite. Considering the above properties of the biocomposite samples developed, they can
find applications in packaging.
54
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