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1 ABOUT POLYMERIC THIN FILMS

Polymer is one of the most important classes of non-metallic materials. Various

types of polymeric materials occur in abundance as natural products. Proteins,

carbohydrates and shellac are some examples. Proteinaceous fibre (wool, silk) and

carbohydrate fibres (cotton, flax) have been in use for ages. Early efforts to widen the

application areas of polymers were mainly confined to chemically modifying the

natural materials. Modification of casein by formaldehyde, esterification of cellulose

and vulcanization of natural rubber are some examples of the development of more

useful products from naturally occurring polymeric materials.

Depending on the application, the ideal lifetime of a polymeric product could vary

from weeks to years. The stability and durability of polymeric materials during

thermo-or photo-oxidation or under other external influences is of outmost importance

in applications such as coatings, building materials, and automotive parts, whereas a

rapidly degradable material is preferable in temporary short-time applications. There

are considerable economic and environmental benefits if we can design polymers for

short or long lifetimes as well as prevent the release of harmful substances from the

materials during their lifetime.

Polymers with their tunable functionalities offer the ability to rationally design

micro- and nano-engineered materials. Their synthesis as thin films have significant
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advantages due to the reduced amounts of materials used, faster processing times

and the ability to modify the surface while preserving the structural properties of the

bulk. Furthermore, their low cost, ease of fabrication and the ability to be easily

integrated into processing lines, make them attractive alternatives to their inorganic
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thin film counterparts. Chemical vapour deposition (CVD) as a polymer thin-film

deposition technique offers a versatile platform for fabrication of a wide range of

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polymer thin films preserving all the functionalities. Solventless, vapour-phase

deposition enables the integration of polymer thin films or nanostructures into micro-

and nano devices for improved performance.

Even people who have never heard of polymer thin-films benefit nearly every day

from products made from these high-tech coatings. They are key ingredients in the

slow-release fertilizer they apply to their lawns and the timed-release pills in their

medicine cabinets. They are also used in multicolour photographic printing,

biomedical membranes, anti-reflective coatings, LCDs and other useful products.

Every day we are exposed to myriad of applications of polymeric thin films. This is

whether it occurs in food wrapping, the packaging of virtually any item that is sold, or

in protective coatings placed on the surface of furniture or glass.

Thin-film technologies have advanced significantly over the last several decades,

becoming one of the major components of electronic, medical or energy related

industries. As free-standing structures, two-dimensional thin films have advantages

over bulk materials due to their large surface-to volume ratios, desirable for

applications requiring enhanced surface interactions. Thin films can also be employed

as coatings over bulk materials to achieve application-specific properties that are

unattainable in the substrate material. With the advance of polymer thin-film

deposition techniques, polymer films continue to garner more recognition in the thin-

film industry that historically has been dominated by inorganic films.

A polymer is a long chain organic molecule composed of one or more types of

monomers. The organic nature of the polymer thin films makes them invaluable for

biomedical applications and the ability to tune the response of the films by

functionalization significantly expands the application areas of the polymer thin films.

Furthermore, the mechanical robustness, ease of processing and the low cost of

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polymer thin films are desirable characteristics for industrial applications. Coating

surfaces with polymeric thin films serves mainly two purposes: changing the surface

properties of the substrate for specific applications or creating a platform for further

functionalization.

1.2 CELLULOSE AND ITS MODIFICATION

The major constituents of higher plant cell walls area group of polymers with

backbones made up of ß- 1,4-linked monosaccharides. The dominant one among them

is cellulose, which is the ß -1,4-homopolymer of anhydroglucose. It is the primary

structural component responsible for much of the mechanical strength of the cell wall.

Its structural properties derive from its ability to retain a semicrystalline state of

aggregation even in an aqueous environment; this is unusual for a polysaccharide.

Figure 1.1 represents structure of cellulose.

OH OH OH
H O H O H O
H H H
OH H O OH H O O
OH H
H H H
H OH H OH H OH

Figure 1.1 Structure of Cellulose

Cellulose is a cheap, renewable, biodegradable and abundant natural polymer. In

addition to its exploitation in the native form for traditional industries like paper and

textile manufacturing, cellulose constitutes a chemical precursor for the production of

many organic materials. Chemical modification of cellulose expands its domains of

application, and provides film-like materials, which can be processed into a various

way such as spinning or casting. Cellulose has the potential to become a key resource

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in the development of sustainable biofuels and biomaterials. Although traditionally

employed for paper production and some key commodity polymers, the chemistry of

cellulose and its applications are undergoing a renaissance. Recent studies have

demonstrated its applicability as a value added material for improving the physical

properties of composites while addressing many life cycle analysis issues. As an

extension of these effects, cellulosic whiskers have been incorporated into several

polymeric matrixes and shown to enhance strength and surface properties.


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Environmental concerns have led to an increased demand for renewable

materials in many industrial applications. This trend has at the same time contributed

to a reconsideration of traditional biomaterials, such as native lignocellulosic fibres, in

applications in which these have been replaced by better performing synthetic

polymers. One such is an absorbent in hygienic products, in which the lignocellulosic

fibres initially used are partially replaced by super absorbing synthetic polymers.

Other areas are wiping and towel products, for which requirements for materials with

improved strength and controlled wettability caused a total or partial replacement of

biofibres with synthetic fibres. In the future, in addition to renewability,

biodegradability and low price, lignocellulosic fibres must offer improved

performance to be able to compete with very efficient generations of synthetic, tailor-

made polymers.

One very attractive feature of lignocellulosic fibres is their chemical composition,

with a large amount of relatively easily accessible hydroxyl units that can be used for

the attachment of a variety of functional groups. Chemical modifications of cellulosic

materials are commonly carried out to make cellulosic polymers such as cellulose

acetate, nitro-cellulose and carboxymethyl-cellulose. However, most derivatization

reactions are carried out under such conditions that the fibres inherent properties, such

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as strength and stiffness, are destroyed and the product obtained is a soluble and

processable polymer. During the latter part of the century, scientists have intensified

efforts to modify fibres in such a way that the inherent fibre properties are preserved.

One of the key properties required for materials intended to be used in hygienic

products is their ability to absorb liquids. It has been pointed out that the absorption

properties of lignocellulosic materials are strongly dependent on the wetting

behaviour of single cellulosic fibres. The Wilhelmy plate technique has been found to

be an attractive tool for the evaluation of the adsorption characteristics of single

fibres.

In the synthesis of cellulose-based materials, cellulose fibres usually have to be

chemically functionalised in order to modify the interactions between the fibres or to

adjust compatibility with other materials. Nowadays, there is an emerging interest in

replacing non-renewable additives with carbon-neutral and biodegradable compounds

for such modifications. In the last few decades, science and technology have started to

move in the direction of renewable raw materials that are environmentally friendly

and sustainable. Biopolymers, such as cellulose, starch, chitin and chitosan have been

assessed, not only as sustainable resources, but also as attractive materials with

interesting properties and functionalities. Biopolymers or their derivatives can be

blended with other polymers (including biopolymers) resulting in a number of new

composite materials with enhanced properties and applications in several fields. The

use of natural cellulose fibres as a reinforcement in polymeric composite materials is

an example of this strategy. More recently, micro and nanofibrillated cellulose (MFC

and NFC) substrates have generated a great interest as reinforcement in composite

materials due to their high mechanical performance and to the fact that cellulose is

one of the most abundant natural resources. Several studies have been published

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dealing with the preparation and characterization of micro and nanofibrillated

cellulose based-composites with different polymeric matrices, such as Poly(vinyl

acetate), hydroxypropyl cellulose, viscous polysaccharide matrix in the form of a

50/50 amylopectinglycerol blends, Poly(lactic acid), Poly(vinyl alcohol) and

Polyurethane.

Lignocellulosic materials appear to be suitable fillers or reinforcing agents for

biodegradable matrices since they exhibit interesting properties such as a renewable

nature, wide variety of feed stocks available throughout the world, low cost, low

density, high specific strength and modulus, nonfood agricultural-based economy, low

energy consumption, high sound attenuation of lignocellulosic-based composites,

comparatively easy processability due to their nonabrasive nature, which allows high

filling levels and significant cost savings, and finally relatively high reactive surface,

which can be used for grafting specific groups. Thus, the use of lignocellulosic fibres

derived from annually renewable resources as a reinforcing phase in polymeric matrix

composites provides positive environmental benefits with respect to ultimate

disposability, and raw materials use. A major disadvantage of cellulose fibres is their

hydrophilic character that makes them, in principle, sparingly miscible with less polar

or nonpolar polymers. Therefore, to develop such a biocomposites with optimum

properties, it has been customary to decrease the hydrophilicity of the lignocellulosic

materials by chemical modification or to promote interfacial adhesion through the use

of compatibilizers. The chemical modification is usually obtained through the use of

reagents having functional groups that are capable of bonding to the hydroxyl groups

of the lignocellulosic materials. Another drawback of lignocellulosic fillers is their

high moisture absorption and the resulting swelling and decrease in mechanical

properties. Moreover, the processing temperature of composites is restricted to about

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2000C because lignocellulosic materials exhibit significant degradation processes

above this temperature. In spite of that, higher thermal stability, less colour, more

homogeneity and enhanced properties can be achieved by using highly purified

cellulose fibres. In the latter material, lignin and hemicellulose residues have been

virtually eliminated from the natural fibre and, therefore, more robust filler is thus

generated. Properties of fibre reinforced composites depend on many factors, for

instance fibre/matrix adhesion, volume fraction of fibre, fibre aspect ratio, fibre

orientation, and stress/transfer efficiency through the interface. Fibre size and

processing techniques have a significant incidence on the final properties of the

composites, because they define the degree of fibre dispersion and their impact on

matrix morphology. Fibre content in biodegradable polymers is also frequently

associated with the degree of dispersion or agglomeration of the fibres, because high

fibre contents in the matrix produce fibre agglomeration, caused by the tendency of

the filler to form hydrogen bonding with each other. As mentioned above, fibre

dispersion has a stronger effect in the mechanical properties of the composites, which

can ultimately be reflected on other potential properties such as barrier properties. The

presence of impermeable crystalline fibres is thought to increase the detour factor in

the materials leading to slower diffusion processes and, hence, to lower permeability.

To enhance barrier properties to gases and vapours the filler should be less permeable

or impermeable and have optimum dispersion and a high aspect ratio (filler

length/thickness ratio). Fibre size is also relevant because by reducing fibre size, high

surface to volume ratio of the filler in the matrix is achieved, and this makes possible

to strongly impact properties with low additions of the reinforcing elements without

detrimental impact on other important parameters such as crystallinity, optical

properties and material toughness. The literature results show that composites with a

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smaller particle size and good dispersion have higher properties compared to others of

greater size. Current technologies allow to reduce fibre cross-section surface to a

volume ratio of the filler in the matrix is achieved, and this makes possible to strongly

impact properties with low additions of the reinforcing elements without detrimental

impact on other important parameters such as crystallinity, optical properties and

material toughness. The literature results show that composites with a smaller particle

size and to the nanometer level as in the case of the so-called Micro Fibrillated

Cellulose (MFC) or in electrospun cellulose fibres.

Processing of plastic composites using natural fibres as reinforcement has


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increased dramatically in recent years . Fibre-reinforced composites consist of

fibre as reinforcement and a polymer as a matrix. Plastic polymers including high

density polyethylene (HDPE), low density polyethylene (LDPE), polyether ether

ketone (PEEK), etc. have been reported as the matrices 11. Traditional fibre-reinforced

composites use various types of glass, carbon, aluminium oxide, and many others as

reinforcing component. Natural fibres, especially bast (bark) fibres, such as flax,

hemp, jute, henequen and many others were applied by some researchers as fibre
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reinforcement for composites in recent years . Advantages of natural fibres over

man-made fibres include low density, low cost, recyclability and biodegradability.

These advantages make natural fibres potential replacement for glass fibres in

composite materials. Mechanical properties of natural fibres, especially flax, hemp,

jute and sisal, are very good and may compete with glass fibre in specific strength and

modulus 13. A better understanding of the chemical composition and surface adhesive

bonding of natural fibre is necessary for developing natural fibre-reinforced

composites. The components of natural fibres include cellulose, hemicellulose, lignin,

pectin, waxes and water soluble substances. The composition may differ with the

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growing condition and test methods even for the same kind of fibre. Cellulose is a

semicrystalline polysaccharide made up of D glucopyranose units linked together by

β-(1-4)-glucosidic bonds. And the large amount of the hydroxyl group in cellulose

gives natural fibre hydrophilic properties when used to reinforce hydrophobic

matrices; the result is a very poor interface and poor resistance to moisture

absorption14. Hemicellulose is strongly bound to cellulose fibrils presumably by

hydrogen bonds. Hemi cellulosic polymers are branched, fully amorphous and have a

significantly lower molecular weight than cellulose. Because of its open structure

containing many hydroxyl and acetyl groups, hemicellulose is partly soluble in water

and hygroscopic. Lignins are amorphous, highly complex, mainly aromatic, polymers

of phenyl propane units but have the least water sorption of the natural fibre

components. Because the low interfacial properties between fibre and polymer matrix

often reduce their potential as reinforcing agents due to the hydrophilic nature of

natural fibres, chemical modifications are considered to optimize the interface of

fibres. Chemicals may activate hydroxyl groups or introduce new moieties that can

effectively interlock with the matrix. The development of a definitive theory for the

mechanism of bonding by chemicals in composites is a complex problem. Generally,

chemical coupling agents are molecules possessing two functions. The first function is

to react with hydroxyl groups of cellulose and the second is to react with functional

groups of the matrix. Bledzki and Gassan outlined several mechanisms of coupling in

materials, namely: (a) elimination of weak boundary layers; (b) production of a tough

and flexible layer; (c) development of a highly crosslinked interphase region with a

modulus intermediate between that of substrate and of the polymer; (d) improvement

of the wetting between polymer and substrate; (e) formation of covalent bonds with

both materials; and (f) alteration of acidity of substrate surface. Chemical

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modifications of natural fibres aimed at improving the adhesion with a polymer
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matrix were investigated by a number of researchers . However, different

chemicals were used and very limited papers took a partial review on the mechanism

and utilization of chemical treatments in fibre-reinforced composites. The chemical

modification of natural or synthetic polymers is an elaborate experimental task

resulting in improvements in the original surface properties of the materials for use in

academic and technological applications.

From the viewpoint of the chemical potential of some natural or synthetic

materials for useful applications, amorphous silica gel, chitosan, fruit peel, crystalline

lamellar talc-like, clay-like or inorganic phosphate, and others have been explored.

However, the richest natural raw material, cellulose, has been less exploited. This is

despite the fact that this polysaccharide is encountered everywhere in nature, displays

active potential functional groups available to react under appropriate conditions,

displays changes in the surface after convenient immobilization, and can embody a

diversity of functionalities. For modification, hydroxyl groups are available in the

main skeleton and also in the branched chain, which is the most reactive position in

the functionalization process.

The applicability of such materials depends upon the availability of the active

functions attached to the pendant chains covalently bonded to a given framework. As

the original structure is changed into a surface, the hydrophilic character of the new

material transforms its properties, leading eventually to a more hydrophobic

behaviour. Thus, these kinds of modified surface agents comprise a variety of organic

molecules displaying amines, ketones, carboxylic acids, or thiol functions, and also

inorganic groups such as phosphates or oxides. Moreover, in general more than one

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functional basic center attached to the pendant molecule covalently bonded to the

framework structure is desired.

1.2.1 Chemical treatments

Alkaline Treatment

Alkaline treatment is one of the most-used chemical treatments of natural fibres

when used to reinforce thermoplastics and thermosets. The important modification

done by alkaline treatment is the disruption of hydrogen bonding in the network

structure, thereby increasing surface roughness. This treatment removes a certain

amount of lignin, wax and oils covering the external surface of the fibre cell wall,

depolymerises cellulose and exposes the short length crystallites. Addition of aqueous

sodium hydroxide (NaOH) to natural fibre promotes the ionization of the hydroxyl

group to the alkoxide 18.

Fibre -OH + NaOH Fibre - O Na + H2O

Thus, alkaline processing directly influences the cellulosic fibril, the degree of

polymerization and the extraction of lignin and hemi cellulosic compounds. In

alkaline treatment, fibres are immersed in NaOH solution for a given period of time.

Ray et al., 15 and Mishra et al., 16 treated jute and sisal fibres with 5% aqueous NaOH

solution for 2 h up to 72 h at room temperature. Similar treatments were attempted by


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Morrison et al., to treat flax fibre. Garcia et al., reported that 2% alkali solution

for 90 s at 2000C and 1.5 MPa pressure was suitable for degumming and defibrillation

to individual fibres. These researchers observed that alkali led to an increase in

amorphous cellulose content at the expense of crystalline cellulose. It is reported that

alkaline treatment has two effects on the fibre: (a) it increases surface roughness

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resulting in better mechanical interlocking; and (b) it increases the amount of

cellulose exposed on the fibre surface, thus increasing the number of possible reaction

sites. Consequently, alkaline treatment has a lasting effect on the mechanical

behaviour of flax fibres, especially on fibre strength and stiffness .Van de Weyenberg

et al.,21 reported that alkaline treatment gave up to a 30% increase in tensile properties

(both strength and modulus) for flax fibre–epoxy composites and coincided with the

removal of pectin. Alkaline treatment also significantly improved the mechanical,

impact fatigue and dynamic mechanical behaviours of fibre-reinforced composites


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Jacob et al., examined the effect of NaOH concentration for treating sisal fibre-

reinforced composites and concluded that maximum tensile strength resulted from the

NaOH treatment at room temperature. Mishra et al., 23 reported that 5% NaOH treated

sisal fibre-reinforced polyester composite had better tensile strength than 10% NaOH

treated composites. This is because at higher alkali concentration, excess

delignification of natural fibre occurs resulting in a weaker or damaged fibre. The

tensile strength of the composite decreased drastically after certain optimum NaOH

concentration.

Silane Treatment

Silane coupling agents may reduce the number of cellulose hydroxyl groups in the

fibre–matrix interface. Silane is a chemical compound with a chemical formula SiH4.

Silanes are used as coupling agents to let glass fibres adhere to a polymer matrix,

stabilizing the composite material. In the presence of moisture, hydrolysable alkoxy

group leads to the formation of silanols. The silanol then reacts with the hydroxyl

group of the fibre, forming stable covalent bonds to the cell wall. Therefore, the

hydrocarbon chains provided by the application of silane restrain the swelling of the

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fibre by creating a crosslinked network due to covalent bonding between the matrix

and the fibre. Most of the researchers applied silane treatment in surface modification
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of glass fibre composites . Silane coupling agents were also found to be effective

in modifying the natural fibre–polymer matrix interface and increasing the interfacial

strength. Rong et al.,26 soaked sisal fibre in a solution of 2% aminosilane in 95%

alcohol for 5 minutes at a pH value of 4.5–5.5 followed by 30 minutes air drying for

hydrolyzing the coupling agent. Silane solutions in a water and ethanol mixture with

concentration of 0.033% and 1% were also carried by Valadez et al.,27 and Agrawal et

al.,18 to treat heneque´n fibres and oil palm fibres. It was verified that the interaction

between the silane coupling agent modified fibre and the matrix was much stronger

than that of alkaline treatment, which led to composites with higher tensile strength

from silane treated than alkaline-treated fibre. Thermal stability of the composites was

also improved after silane treatment 18.

Acetylation of Natural Fibres

Acetylation of natural fibres is a well-known esterification method causing

plasticization of cellulosic fibres. Acetylation describes a reaction introducing an

acetyl functional group (CH3COO–) into an organic compound. The reaction involves

the generation of acetic acid (CH3COOH) as by-product, which must be removed

from the lignocellulosic material before the fibre is used. Chemical modification with

acetic anhydride substitutes the polymer hydroxyl groups of the cell wall with acetyl

groups, modifying the properties of these polymers so that they become

hydrophobic28. Acetylation was used in surface treatments of fibre for use in fibre-

reinforced composites 29. Acetylation treatment of sisal fibre was reported to improve

the fibre–matrix adhesion. The procedure included an alkaline treatment initially,

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followed by acetylation. Mishra et al.,23 investigated the acetylation of sisal fibres.

Nair et al., 30 treated raw sisal fibre in 18% NaOH solution, then in glacial acetic acid

and finally in acetic anhydride containing two drops of concentrated H2SO4 for a

period of 1 h. The treated surface of sisal fibre reportedly became very rough and had

a number of voids that provided better mechanical interlocking with the polystyrene

(PS) matrix. A hypothetical model of the interface between the sisal fibre and PS

composites has been postulated. It was also reported that acetylated natural fibre-

reinforced polyester composites exhibited higher bio-resistance and less tensile

strength loss compared to composites with silane treated fibre in biological tests 31.

Benzoylation Treatment

Benzoylation of fibre improves fibre matrix adhesion, thereby considerably

increasing the strength of composite, decreasing its water absorption and improving

its thermal stability. Benzoylation is an important transformation in organic

synthesis32. Benzoyl chloride is most often used in fibre treatment. Benzoyl chloride

includes benzoyl (C6H5C=O) which is attributed to the decreased hydrophilic nature

of the treated fibre and improved interaction with the hydrophobic PS matrix. Nair et

al., 30 used NaOH and benzoyl chloride (C6H5COCl) solution for surface treatment of

sisal fibres. A hypothetical model of the interface of PS benzoylated sisal fibre

composite has been postulated by Nair et al.,30 . It was observed that the thermal

stability of treated composites were higher than that of untreated fibre composites. A

similar method was also applied by Wang to improve the interfacial adhesion of flax

fibre and polyethylene (PE) matrix. The fibre was initially alkaline pre-treated in

order to activate the hydroxyl groups of the cellulose and lignin in the fibre; then the

fibre was suspended in 10% NaOH and benzoyl chloride solution for 15 minutes. The

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isolated fibres were then soaked in ethanol for 1 h to remove the benzoyl chloride and

finally was washed with water and dried in the oven at 800C for 24 h.

Acrylation and Acrylonitrile Grafting


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Acrylic acid (CH2=CHCOOH) can be graft polymerized to modify glass fibres
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. Sreekala et al.,35,36 used acrylic acid in natural fibre surface modification.

Acrylation reaction is initiated by free radicals of the cellulose molecule. Cellulose

can be treated with high energy radiation to generate radicals together with chain

scission. Oil palm fibres were mixed with 10% NaOH for about 30 minutes and then

treated with a solution of acrylic acid at 500C for 1 h at various concentrations. The

fibres were washed with aqueous alcohol solution and dried. The tensile strength of

oil palm fibre–PE composites did not increase. However, it was reported by Li et al.,

that the tensile strength of acrylic acid treated flax fibre–HDPE composites was

improved and water absorption of composites was decreased. Acrylonitrile (AN) is

also used to modify fibres. Graft copolymerization of AN on sisal fibres was studied
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by Mishra et al., using a combination of NaIO4 and CuSO4 as the initiator in an

aqueous medium at temperatures between 50 and 700C. Reaction medium, treatment

time, initiator, AN concentration and even fibre loading influenced the graft effect. It

was found that untreated fibres absorbed the most water and 25% AN-grafted sisal

fibres absorbed the least water, suggesting that changes in chemistry of the fibre

surface reduced the affinity of fibres to moisture. It was also found that grafting of

chemically modified fibres with 5% AN brought a higher increase in tensile strength


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and Young’s modulus of fibres than grafting with 10 and 25% AN. Mishra et al.,

also concluded that optimum graft yield was obtained for treatment duration of 3 h.

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Sreekala et al. 36 treated oil palm fibre with AN in 1% H2SO4 solution after alkali and

KMnO4 oxidized pre-treatment.

Permanganate Treatment

Most permanganate treatments are conducted by using potassium permanganate

(KMnO4) solution (in acetone) in different concentrations with soaking duration from

1 to 3 minutes after alkaline pre-treatment. Permanganate treatment leads to the

formation of cellulose radical through MnO3- ion formation. Then, highly reactive

Mn3+ ions are responsible for initiating graft copolymerization. Paul et al., 37
dipped

alkaline treated sisal fibres in permanganate solution at concentrations of 0.033,

0.0625 and 0.125% in acetone for 1 minute. As a result of permanganate treatment,

the hydrophilic tendency of the fibres was reduced, and thus, the water absorption of

fibre-reinforced composite decreased. The hydrophilic tendency of fibre decreased as

the KMnO4 concentrations increased. But at higher KMnO4 concentrations of 1%,

degradation of cellulosic fibre occurred which resulted in the formation of polar

groups between fibre and matrix.

Peroxide Treatment

In organic chemistry, peroxide is a specific functional group or a molecule with

the functional group ROOR containing the divalent ion O–O. Organic peroxides tend

to decompose easily to free radicals of the form RO. ; RO. then reacts with the

hydrogen group of the matrix and cellulose fibres.

Benzoyl peroxide (BP) and dicumyl peroxide (DCP) are chemicals in the organic

peroxide family that are used in natural fibre surface modifications. In peroxide

treatment, fibres are coated with BP or DCP in acetone solution for about 30 minutes

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after alkali pre-treatment. Sreekala et al. observed that high temperature was

favoured for the decomposition of the peroxide; peroxide-treated oil palm fibre-

reinforced PF composites could withstand tensile stress to a higher strain level. Joseph
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and Thomas investigated BP and DCP treatment on short sisal fibre reinforced PE

composites. The tensile strength values of composites increased with the increase in

concentration of peroxide up to a certain level (4% for DCP and 6% for BP) and then

remained constant. As a result of peroxide treatment, the hydrophilicity of the fibres

decreased and the tensile properties increased.

1.3 MECHANICAL PROPERTIES AND MOISTURE ABSORPTION

BEHAVIOUR

The foremost requirement for a designer of a polymeric thin film product is the
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data on the mechanical properties . The mechanical properties can be broadly

classified as short-term, long-term and surface properties. The short-term properties

are measured at a constant rate of stress or strain in different modes like tension,

compression, flexural, shear etc. The long term properties are measurements of

deformation or stress decay with respect to time in static conditions e.g. creep and

stress relaxation. The mechanical properties of the surface include hardness, scratch,

friction and abrasion. Tensile testing comes under short-term mechanical properties.

The study of stress in relation to strain in tension depicts the tensile properties of the

material. Tensile test data are widely used for defining the quality of different lots of

polymeric materials. They are also useful for the purpose of engineering design and

understanding the characteristics of the materials.


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Mechanical properties and moisture absorption behaviour related to each

other. Films which absorb less water will show better mechanical properties. The

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sensitivity of plastic materials to water absorption depends on their chemical nature.

The process involved in the water absorption by plastic materials depends on two

parameters: the diffusion coefficient and the equilibrium uptake. The former governs

the kinetics of water absorption and is highly temperature-dependent. Equilibrium

uptake is unaffected by temperature. Figure 1.2 represents Universal Testing Machine

(UTM).

The standard methods for water absorption are mostly short-term tests; hence the

results obtained are limited only to surface diffusion phenomena and not equilibrium

throughout the thickness of the test specimen.

Figure 1.2 Universal Testing Machine (UTM) used to measure tensile strength.

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1.4 GAS BARRIER PROPERTIES

Other than safe storage and transportation, an important requirement for most of

packaging applications of plastics is that the packaging material used should prevent

loss of volatile constituents from the packed contents and prevent the ingress of gases,

water and vapours, particularly oxygen and water vapour. Measurement of the this

barrier property of packaging material to gases and vapours, therefore, becomes

important in assessing the likely suitability of the different kinds of packaging

material in any given application.

Permeability is governed by the extent to which the permanent dissolves and

diffuses in the polymer. It can be deduced from Fick’s law that

P= DS

Where P, D and S are the permeability, difffusion and solubility constant

respectively for a given permanent-polymer system.

A steady state is established after a gas has been diffusing through a homogeneous

film at a constant temperature for a period of time under a maintained differential

partial pressure. The quantity of gas (Q) that will then pass through the film is directly

proportional to the difference in the pressure exerted by the gas on each face of the

film (∆ ), area ( ) of the sample exposed and time ( ) for which permeation occurs. It

is inversely proportional to its film thickness ( ).

∝ (∆ /

Thus = (∆ /

Where is a constant value for a specific combination of gas and polymer under

specified conditions and is known as ‘the transmission factor’, ‘permeability factor’,

‘permeability constant’, or ‘permeability coefficient’.

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Permeability is a property of a material whereas permeance is a performance

evaluation and not a property of a material.

1.4.1 Oxygen transmission rate (OTR)


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Oxygen transmission rate (OTR) is the measurement of the amount of oxygen

gas that passes through a substance over a given period. It is mostly carried out on

non-porous materials, where the mode of transport is diffusion, but there is a growing

number of applications where the transmission rate also depends on flow through

apertures of some description. Figure 1.3 represents OX-TRAN instrument used for

measure the gas barrier properties of the films.

Figure 1.3 OX-TRAN instrument used for measure the gas barrier properties of the
films

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Principle

Mount the pre-conditioned specimen between the upper and lower testing chambers.

Oxygen or air flows on one side of specimen, high pure nitrogen flows into another

side of the specimen. Oxygen molecules permeate through the specimen and enter

into the high pure nitrogen side, which is then carried to the sensor by the flowing

nitrogen. Obtain the oxygen transmission rate by analyzing the oxygen condensation

detected by the sensor. For package test, high pure nitrogen flows in the package; air

or pure oxygen flows around the outer side of the package.

1.4.2 Water vapour transmission rate (WVTR)

The use of polymer membranes in modern sportswear and protective clothing has

become more and more common. Optimal selection of membrane structure and

physico-chemical properties is intended to ensure the directional transport of water

vapour, without its condensation, at a rate adapted to that of moisture release from the

human organism. For that reason, it is important to be familiar with the membrane’s

structure, porosity, pore size and shape distribution, as well as sorption and diffusion

properties. Such characteristics of membranes can be obtained by various methods,

more or less close to subsequent conditions of their use with variable temperature,

relative humidity and outer air flow rate. A method for membrane testing, based on

the water vapour transport forced by the relative humidity of air under isothermal

conditions, has been developed at the Institute of Textile Materials Engineering.

The driving force of water vapour diffusion through a membrane is the difference

between the partial pressures of water vapour in air on both its sides. In a stationary

state, equilibrium is established on both membrane sides between the water

concentration on the membrane surface and the water vapour concentration in air that

21
is dependent on the temperature of the membrane surface and its surroundings. If the

partial water vapour pressures on both membrane sides are different, a gradient of

water concentration is established in the membrane. In porous membranes, the water

transport consists of three processes: water diffusion in the polymer, water diffusion

in air that fills the pores of the membrane, and the sorption/desorption of water on the

external membrane surface and internal pore surface. It is the polymer type and

structure, i.e. the size, tortuosity and type of pores (closed/open), that is of decisive

importance in water transport through membranes. Based on the analysed effect of the
43,44
membrane structure on water vapour permeability , the water permeability

through polyurethane and polyester membranes of different structures has been

determined.

1.5 BIODEGRADABLE PROPERTIES

The ever-growing environmental pressure caused by the widespread consumption

of petroleum based polymers and plastics have spurred a thrust into the development

of biodegradable or environmentally acceptable materials. Biopolymers derived from

various natural botanical resources such as protein and starch have been regarded as

alternative materials to petroleum plastic because they are abundant, renewable,

inexpensive and biodegradable.

In order to reduce the environmental load generated from the disposal of used

plastic products, significant attention has been placed on biodegradable plastics.

Plastic materials are indispensable in our lives as they are used extensively in many

diverse fields including, but not limited to, stationery goods, electronic products and

sports goods. However, a great majority of these products are disposed into landfills

after usage. Clearly, this contributes to a high environmental load. Plastics can be

22
completely resolved into water and carbon dioxide by the action of the

microorganism, when disposed of in the soil. Moreover, there are no emissions of

toxic gases during incineration. Recently, biodegradable plastics have been used in

commercial products such as ball-point pens, toothbrushes, tennis racket strings,

garbage bags, fishing lines, wrapping paper and many others.

Natural fibres such as kenaf, flax, jute, hemp, sisal, and henequen fibre reinforced

composites are an attractive research area because natural fibres are eco-friendly,

sustainable, low cost, low density, with acceptable mechanical properties, ease of

separation, carbon dioxide sequestration and biodegradability.

Biodegradable polymers are designed to degrade upon disposal by the action of

living organisms. Extraordinary progress has been made in the development of

practical processes and products from polymers such as starch, cellulose, and lactic

acid. The need to create alternative biodegradable water-soluble polymers for down-

the-drain products such as detergents and cosmetics has taken on increasing

importance. Consumers have, however, thus far attached little or no added value to

the property of biodegradability, forcing industry to compete head-to-head on a cost-

performance basis with existing familiar products. In addition, no suitable

infrastructure for the disposal of biodegradable materials exists as yet.

Recently, biodegradable polymers have attracted much attention because

biodegradability is extremely significant properties for some applications of

biomedical polymers. They are widely used in numerous medical and pharmaceutical

applications because of their low immunogenicity and good biocompatibility.

With growing environmental awareness, this search has particularly focused on

eco-friendly materials, with terms such as “renewable”, “recyclable”, sustainable” and

“triggered biodegradable” becoming buzzwords. This underscores the emergence of a

23
new type of materials – a change from non-renewable, but difficult to degrade or non-

degradable, to renewable and easily degradable materials. The development or

selection of a material to meet the desired structural and design requirements calls for

a compromise between conflicting objectives. This can be overcome by resorting to

multi-objective optimization in material design and selection.

The development of such materials has not only been a great motivating factor for

materials scientists, but also an important provider of opportunities to improve the

standard of living of people around the world. This is true, since many of the

renewable materials are based on agricultural products as a source of raw materials,

particularly to plastic industries, and these could generate a non-food source of

economic development for farming and rural areas in developing countries. This can

provide a potential for economic improvement based on these materials even though

major thrust for their use has been driven by the needs in industrialized countries. For

example, lignocellulosic fibres such as jute, sisal, pineapple, curaua, etc., whose

extraction is an important process that determines the properties of the fibres, can

generate rural jobs since these fibres have established their potential as reinforcing

fillers in many polymers, and products based on these have found increasing use on a

commercial scale in recent years. Another example for the generation of jobs by agro-

based materials is provided by the use of rice husk, which constitutes more than 10%

of a world rice production 45. A variety of inorganic materials such as silica, zeolites,

solar grade silicon, building and thermal insulating materials, polymer composites,

etc., can be produced using this most promising agro-waste. Similarly, straws of rice

and sugarcane (bagasse), often used as fuels in households or sometimes burned in the

fields as means of disposal, are utilized as fillers/reinforcements in polymer or cement

to develop new materials (composites) for the construction industry. Yet another

24
example is the use of sugar cane in Brazil for the production of

poly(hydroxyalkanoates),explored for medical applications. It is reported that

increasing use of renewable materials would create or secure employment in rural

areas, the distribution of which would be in agriculture, forestry, industry, etc. It is

also reported that estimated production of heat, electricity and fuels could be

increased by 90 million metric tons of oil equivalent corresponding to 14 million

hectares of land by 2010 from 40 million metric ton in 1995 by the agro based

renewable materials.

Biodegradable type composites are not new to mankind. Their use dates to

antiquity, such as the Great Wall of China whose construction started initially in 121

B.C. as earth works were connected and made strong by clay bricks made of local

materials initially using red willow reeds and twigs with gravel during the Han

dynasty (209 B.C.), and later with clay, stone, willow branches, reeds and sand during

the Qin dynasty (221–206 B.C.) Other examples include, bows made with adhesively

bonded laminates of animal horns and tendons, wood or silk used by the Mongolians

in 1200 A.D. Composite materials have gone through significant developments in

terms of use of different raw materials, processes and even applications. Similarly,

use of natural polymers is not new, since paper, silk, etc., have been used from

historical times.

The use of natural polymers was superseded in the 20th century as a wide-range of

synthetic polymers were developed based on raw materials from low cost petroleum.

However, since the 1990s, increased attention has been paid to the use of natural

polymers and lignocellulosic fibres. The reasons for this include: (a) growing interest

in reducing the environmental impact of polymers or composites due to increased

awareness to eco-friendliness; (b) finite petroleum resources, decreasing pressures for

25
the dependence on petroleum products with increasing interest in maximizing the use

of renewable materials; and (c) the availability of improved data on the properties and

morphologies of natural materials such as lignocellulosic fibres, through modern

instruments at different levels, and hence better understanding of their structure–

property correlations. These factors have greatly increased the understanding and

development of new materials such as biocomposites.

Lignocellulosic fibres have some unique attributes, such as being less abrasive to

tooling and not causing as many respiratory problems for workers. Furthermore,

because they are inexpensive and have load bearing potential, the use of natural fibre

based composites has spread to various sectors, including aircraft, construction, grain

and fruit storage and footwear.

In addition, some European countries, where greater environmental consciousness

exists, have already established the use of Lignocellulosic Fibre Incorporated Polymer

Composites (LCFIPC) in automotive applications 46, 47. In view of this, a good amount

of LCFIPC products have been exported to the U.S. and other countries despite these

materials being only partially biodegradable. Although these composites exhibit the

attractive attributes mentioned above, they are limited to non-degradable polymeric

matrices, such as polyester, epoxy and phenol formaldehyde (PF), which may not be

fully biodegradable, while the fibres are fully biodegradable. Fortunately, traditional

engineering thermoplastics (ETP) markets, such as those for exterior auto

components, noise shields and door panels, or as “wood ceramic” for electromagnetic

shielding, have been effectively taken over by the new commodity polymers and their

composites due to their improved performance. In addition, many of the

lignocellulosic materials, such as rice and wheat straw, sugarcane bagasse and rice

and coffee husks, which were either used as household fuels or sometimes burnt in

26
situ in the fields as a means of disposal, have also been tried as fillers/reinforcements

in polymer or cement to develop new materials for the construction industry. These

successful attempts have opened up a large range of raw materials for the

development of biodegradable materials. Besides this, the increasing focus on eco-

friendliness, such as the European Union’s directive that all new vehicles must use

95% recyclable materials to achieve the “end of life” required by 2015 has led to the

greater impetus for the development of commercially viable biodegradable

composites. Under this directive, about 85% of these materials recoverable through

reuse or mechanical recycling and about 10% through energy recovery or thermal

recycling. It is therefore not surprising to note that many leading plastics companies in

U.S. and other western countries are in the forefront in developing biodegradable

materials from natural materials, including “secondary resources”, to mitigate

environmental impacts. Furthermore, it is reported that by 2020, about 10% of the

basic chemical building blocks will come from renewable plant resources, expected to

rise to 50% by 2050 as hurdles to their use are reduced.

Textile engineering and modeling aspects have been used in composite fabrication
48
with a view to increase the use of these materials . In this context, textile

engineering has provided an opportunity for producing hybrid composites as evident

from studies on the effect of fibre content, fibre orientation and roving texture of

hybrid fabrics on the mechanical properties of polymer composites. Also, it has

provided different but commonly used weave styles, such as plain (each warp fibre

passing alternately over and under the weft fibre), twill (repeated weaving of one or

more warp fibres under or over the weft fibres), satin (twill weave but have fewer

intersections of the weft and warp), leno (weave pattern to improve stability of fabrics

having lower fibre content), etc., to prepare the required form of reinforcements. In a

27
reinforced woven fabric, the fibres are interlocked up to a certain degree depending on

the weave pattern, such that they deform into or drape in a stable, predictable and

reversible manner, leading to desirable use properties. While hybridization effect of

lignocellulosic fibres with synthetic fibres on various properties has been extensively

studied, very limited studies with hybrids of lignocellulosic fibres mainly with non

degradable matrices have been reported. Hence, more studies in lignocellulosic fibre

based hybrids are required, which not only could increase the amount of fibres used,

but also open new applications for these materials.

While discussing the textile engineering aspects in the development of

composites, two recent exciting examples are of interest. The first is the weaving of

super-tough carbon nanotubes to develop polymer nanocomposite (570 J g-1,

compared to 33 J g-1 for Kevlar fibre and 12 J g−1 for graphite fibre), with a special

spinning method being adopted to obtain about 100 m of solid nanotube composite of

50 nm diameter containing 60% single-walled nanotubes. The resulting textiles are

reported to have been potential for making electronic devices such as sensors,

connectors, antennas, etc. The second example is electro spinning of polymeric fibres,

one of the most efficient methods to produce nano-polymer fibres, which exhibit large

surface area useful for various applications, including composites.

1.5.1 Biodegradable materials

One well accepted definitions reads that “materials obtained from nature or by

synthetic route, whose chemical bonds are cleaved at least in one step by enzymes

from the biosphere”, to which one can add, ‘with appropriate pH and temperature

conditions and total processing time for completion’. The suitability for a specific

28
application of such materials will be dictated by their mechanical properties as well as

their degradation.

It is well known that renewable resources such as plants (e.g., cellulose or chitin,
49,50
vegetable oils, etc.), bacteria as well as non-renewable petroleum (e.g.,

aliphatic/aliphatic–aromatic co-polyester) are sources of a variety of polymeric


51
materials . Accordingly, biodegradable polymeric materials have been classified as

natural or synthetic depending on their origin. Also, biodegradable polymers

themselves can be classified depending upon their origin such as agro polymers

(starch or cellulose), microbial poly(hydroxyalkanoate), chemically synthesized from

agro based resource monomers poly(lactic acid) and chemically synthesized from

conventionally synthesized monomers. Figure 1.4 represents classification of

biopolymers and their nomenclature.

Figure 1.4 Classification of biopolymers and their nomenclature

29
Products made using such polymers are shown in Figure 1.5 (a–e). These include

a drinking cup (Figure1.5a ) similar to a polystyrene disposable cup both in

appearance and characteristics, but starch based using environmentally friendly water

steam foaming and pressing process; lawn cutting and leaf bags (Figure1.5b) made of

corn starch by blow moulding with the red symbol printed near the top of the bag

indicating the Danish mark for ecological products; “green pens” (Figure1.5c) based

on starch, developed by Novamont, produced by injection moulding (except the ink

refill); razors (Figure1.5d) manufactured using PHA by injection moulding (handle)

and insert moulding (razor head) by the Kay Razor Company and foamed trays

(Figure1.5e) made of thermoplastic starch by BIOTEC, Germany. While the bag

shown in Figure1.5b is reported to create rich organic humus, which can be used as

soil nutrients, the foamed trays shown in Fig. 4e are reported to possess a very good

permeability for water vapor along with excellent gas (oxygen and carbon dioxide)

barrier properties. There are other examples, such as dinnerware based on potato

starch and limestone, packing products for general purposes made with potato/corn

starch designed by Proterra BV, International Centre for Agro-based Materials and

shampoo bottles formerly made of PHBV by the Monsanto Company using injection

moulding (cap) and blow moulding (bottle). All these can be composted after use.

There is also a patent for manufacturing biodegradable starch based products.

30
Figure 1.5 Biopolymer products: (a) disposable cup; (b) compostable bag; (c) writing
“green” pens; (d) shaving razor heads; (e) foamed trays

Another example is the use of acrylated epoxidized soybean oil blended with

polystyrene whose storage modulus is improved more than five times by adding

recycled paper, a cheap source of cellulose 52. Many of these have been well reported

in reviews, in textbooks, as well as at many international conferences. These

biopolymers are presently available in the market through manufacturing companies

such as Mitsui Chemicals, Novamont, Dupont, Bayer, etc., while plant-derived

biodegradable polymers are commercially available in Japan and Brazil. The market

has been growing fast for these biopolymers, with sales increasing by 20–30% a year
53
in 2000 . In North America alone, it was projected to increase from about 9090

metric tons (20 million lbs.) in 2000 to about 17,500 metric tons (35 million lbs.) by

31
2005 54. This was expected to lead to increased sales from around US$ 150 million in

2000 to US$ 1.4 billion by 2005. The perspective for worldwide manufacturing

capacity of bioplastics from both renewable and non-renewable petrochemical

materials till 2010 is illustrated in Figure. 1.6, which underlines the growing

dependence on the renewable materials. Also, a growing market for biodegradable

plastics from almost zero tons per annum in nineties to 600,000 tons per annum to

date, has been reported, the majority of which are based on renewable materials. This

estimated to the consumption of biopolymers in Europe alone to expand to roughly 10

million metric tons/year by 2020.

Figure 1.6 Worldwide manufacturing capacity of bioplastics.

32
1.6 OBJECTIVES OF THE PRESENT STUDY

In recent years, increasing emphasis has been placed on environmental impact

minimisation and resulting from this range and capability of natural and prepared

materials capable of non-biodegradable removal has seen steady development. In

particular considerable work has been carried out on the use of natural material with

its modification. This thesis reviews the current state of research on the use of the

naturally occurring material cellulose, its modified forms and their efficacy to produce

‘eco-friendly’ products. This research work concentrated on the preparation of novel

biodegradable films from cellulose. For this purpose modified cellulose-PLA,

modified cellulose-PVA, modified cellulose-PVA-PLA, modified cellulose-PP and

modified cellulose-PVA-PP systems were selected. Various films at different

compositions were prepared and their Soil burial degradation experiments, Moisture

absorption experiments, Mechanical testing, Oxygen permeability test, Water vapour

permeability test and Morphology were studied.

33
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