A Review on Interface Modification and Characterization

of Natural Fiber Reinforced Plastic Composites

JAYAMOL GEORGE1, M. S . SREEKALA2, and SABU THOMAS2

'Department of Mechanical Engineering

Technical University of Eindhoven
Post Box 5 13,5600MB Eindhoven, The Netherlands
2School of Chemical Sciences, M a h a t m a GQndhi University
Priyadarshini Hills, P. O., Kottayam 686 560, Kerala, India

An important aspect with respect to optimal mechanical performance of fiber re-

inforced composites in general and durability in particular is the optimization of the
interfacial bond between fiber and polymer matrix. The quality of the fiber-matrix
interface is significant for the application of natural fibers as reinforcement for
plastics. Since the fibers and matrices are chemically different, strong adhesion at
their interfaces is needed for an effective transfer of stress and bond distribution
throughout a n interface. A good compatibikation between cellulose fibers and non-
polar matrices is achieved from polymeric chains that will favor entanglements and
interdiffusion with the matrix. This article gives a critical review on the physical
and chemical treatment methods that improve the fiber-matrix adhesion and their
characterizationmethods.

1. INTRODUCTION in applications such as boat hulls, bathtubs and

E cological concerns have resulted in a renewed in-
terest in natural materials, and therefore issues
such as recyclability and environmental safety are be-
coming increasingly important for the introduction of
new materials and products. At this moment, design-
ing for recycling or in a somewhat broader perspec-
tive, eco-design, is becoming a philosophy that is ap-
plied to more and more materials and products. I t is
for these reasons that natural fibers based on &no-
cellulose can be considered as an interesting - envi-
ronmentally safe - alternative for the use of glass
fibers as reinforcement in engineering polymeric ma-
terials. Natural fibers like flax, hemp, kenaf, jute and
sisal have a number of techno-economical and ecolog-
ical advantages over E-glass fibers. The combination
of interesting mechanical and physical properties to-
gether with their environmentally friendly character
has motivated a number of industrial sectors, notably
the automotive industry, to consider these fibers as
potential candidates to replace glass fibers in environ-
mentally safe products.
Natural fibers are undergoing a high-tech revolu-
tion that could see them replace synthetic materials
*lCorrespondhg author. Email: jayamolgeorge@email.com
archery bows. The synthetics being challenged by
this natural revolution are composite materials -
plastics reinforced with glass or carbon fibers. For
high performance materials, DuPont Kevlar and car-
bon are the fibers of choice. They are very strong,
highly temperature resistant, expensive and limited
to high performance applications such as in aero-
space. Glass fibers have many benefits like low cost,
high strength etc. But the main disadvantage is their
non-biodegradability. This is where natural fibers
come into their own. They are abundant, renewable,
cheap, recyclable and biodegradable..They exhibit low
density and the extent of environmental pollution
caused is less compared to synthetic fibers. They are
naturally designed to be incredibly tough. According
to Hills (11, natural fibers could turn up in everything
from cars to golf clubs. In Germany, car manufactur-
ers aim to make every component recyclable and
biodegradable. The door panels in the Mercedes have
been made from plastics reinforced with flax fibers.
Also Canadian companies are using the flax fibers in
a polypropylene matrix to create moldable material to
form the rear-shelf panel of the 2000 Chevrolet Im-
pala (2). The performance advantages of plant fibers
in polymer matrix composites (PMC) are their chemi-
cal properties, high specific stiffness, high specific
strength and sound absorption.

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9 1471
 Jayamol George, M.S. Sreekala and Sabu Thomas

2. CLASSIFICATIONAND STRUCTURE OF closeness of approach of the molecules to each other;

NATURAL FIBERS i.e., the crystallinity of the fiber. One practical feature
of the solubility of fibers is that the fiber molecules
Depending on the origin, vegetable fibers can be may degrade either because of the chemical reactivity
grouped into bast (jute, banana, flax, hemp, kenaf, of the solvent or because the separated fiber mole-
mesta) leaf (pineapple, sisal, screw pine) and seed or cules are more accessible than the molecules in the
fruit fibers (coir, cotton, oil palm). Mechanical proper-
solid fiber.
ties of some natural fibers are shown in Table 1. (3).
Textile fibers are crystalline and the degree of crys-
Cellulose is the main component of the vegetable
tallinity depends on the origin of the material. This
fibers. The elementary unit of a cellulose macromole-
crystallinity not only influences physical properties,
cule is anhydro d- glucose, which contains three hy- but also affects solubility very obviously. Cellulose
droxyl (-OH) groups. These hydroxyl groups form hy-
and its derivatives such as cellulose acetate, provide
drogen bonds inside the macromolecule itself
good examples of the influence of crystallinity on solu-
(intramolecular) and between other cellulose macro-
bility. The large number of hydroxyl groups in cellu-
molecules (intermolecular). Therefore all vegetable
lose would increase the affhity of polymer to water.
fibers are hydrophilic in nature. Conventional fibers
The hydroxyl groups in the amorphous regions com-
like glass, aramid. carbon etc. can be produced with a
bine with water to give the relatively high moisture re-
definite range of properties, whereas in natural fibers,
gain of cellulose fibers. The most satisfactory solvents
this will vary considerably. The cellulose of natural
for cellulose are alkaline and a common solvent is
fiber contains different natural substances such as
cuprammonium solution (5).The copper ions proba-
lignin and waxes. The fibers are made up of cellulose
bly form a complex with the hydroxyl groups of cellu-
microfibrills, which are bonded together by lignin.
lose and the ammonia, which in turn probably forms
Physical properties of natural fibers are basically in-
a complex with the copper, which is already joined to
fluenced by the chemical structure such as cellulose
the cellulose.
content, degree of polymerization, orientation and
crystallinity, which are affected by conditions during
4. NATURAL FIBER COMPOSITES
growth of plants as well as extraction methods used.
There is an enormous amount of variability in fiber The combination of a plastic matrix and reinforcing
properties depending upon whether the fibers are fibers gives rise to composites having the best proper-
taken from which part of the plant, the quality of ties of each component. Since the plastics are soft,
plant and location (4). Different fibers have different flexible and lightweight in comparison to fibers, their
lengths and cross-sectional areas and also different combination provides a high strength-to-weight ratio
defects such as micro compressions, or pits or cracks. to the resulting composite. A major disadvantage of
So one way to achieve the same flexibility using nat- cellulose fibers is their highly polar nature, which
ural fiber is to regenerate the cellulose and make it make them incompatible with non-polar polymers.
more uniform by dissolving the microfibrils in solvent Also, the poor resistance to moisture absorption
and then precipitating under controlled conditions. makes the use of natural fibers less attractive for ex-
terior applications. The properties of composites de-
3.REGENEWTED CELLULOSE pend on those of the individual components and on
their interfacial compatibility. Several types of poly-
The solubility of textile fibers and the properties of
mers have been used as matrices for natural fiber
solutions of fibers are important, not only in the pro-
composites (6-14). The most commonly used are ther-
duction process as such, but also in the control and
moset polymers such as polyester, epoxies and phe-
investigation of these processes. The ease with which
nolics. Thermoplastics like polyethylene (PE), poly-
a textile fiber dissolves depends on the chemical na-
styrene (PSI and polypropylene (PP) have also been
ture of the groups that hold the molecules and the
used (6-9).These polymers have a different af-fhity t o
wards the fiber owing to the difference in their chemi-
cal structure. It was reported that sisal/LDPE com-
Table 1. Mechanical Properties of Some Plant Fibers.
posites showed a better reinforcing effect because of
Fiber Initial Ultimate Elongation Flexural high matrix ductility and high strength/modulus ratio
modulus tensile strength at break modulus of sisal as compared to that of LDPE matrix (8).Nair,
(GWm2) (MN/mz) (%) (MN/m2) et al. (6)reported the tensile properties of polystyrene
Sisal 9-22 568-640 3-7 12.5-17.5 reinforced with short sisal fiber and benomylated sisal
Pineapple 34-82 413-1 627 0.8-1 0.24-0.40 fiber. The bemylation of sisal fiber was found to en-
Banana 7-20 54-754 1 -4 2-5 hance the tensile properties of resulting composites.
Jute 18 226 1.3 0.3-0.5 The incorporation of sisal fiber considerably reduced
Mesta - - 1 -2 0.35-0.65
Flax 27.6 780 2-4 0.18-0.25 the glass transition temperature (Tg)of polystyrene. It
Sunhemp - 760 2-4 12.5-17.5 was reported by Joseph, et al. (8)that among poly-
Palmyrah 4-6 180-27 5 7-1 5 - ester, epoxy and phenol formaldehyde composites of
Cotton - 200-400 6-7 0.03-0.10 sisal fiber, the phenolic type resin performed as a
Reference3 better matrix than epoxy and polyester resins with

1472 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Voi. 41, No. 9
 Review on Interace Modijkation and Characterization
respect to tensile and flexural properties owing to the
high interfacial bonding in phenolic composites.
Joseph et al. (91 found that the reinforcing ability of
sisal fiber in PP matrix is less. It was found that
kudzu fiber (Pueraria lobata) extracted from kudzu
vines and banana strands have potential economical
value with polyester to make a commercial fabric
woven on power looms (10, 11).The flexural behavior
of coir, straw and jute fibers in polyester have been
studied and analyzed by various workers (12-14). The
potential of sunhemp/polyester composites in terms
of tensile and impact properties has been investigated
by Rohatgi and co-workers (151.Zadorecki and Flodin
(16)used cellulose fiber in the form of paper sheets as
reinforcement in unsaturated polyester composites.
The reinforcing effect of sisal, jute and bamboo fiber
in epoxy composites is also reported (17-201. Several
studies have been carried out by Kokta and co-work-
ers using chemithermomechanical pulp in different
thermoplastics (21, 22). Crystallization kinetic studies
were carried out by Chen and Porter (231 on compos-
ites made of polyethylene and kenaf fiber, which is ex-
tracted from the bast of the plant Hibiscus cannabi-
nus. The environmental performance of flax fiber mat
reinforced polypropylene was investigated by monitor-
ing the moisture absorption and swelling and measur-
ing the residual mechanical properties of the samples
at different moisture levels (24). The effects of filler
content and size on the mechanical properties of
PP/oil palm wood flour composites were reported by
Zaini et aL (25).The stress transfer at the interface
between two different phases is determined by the de-
gree of adhesion. A strong adhesion at the interfaces
is needed for an effective transfer of stress and load
distribution through out the interface. This situation
calls for the development of strategies for the surface
modification of cellulosic surfaces, thereby an effec-
tive control over the fiber/polymer interface. In
order to improve the mechanical properties of com-
posites, a coating is applied, which generally con-
sists of coupling agents or compatibilizing agents
that introduce chemical bonds between the fiber
and matrix. Effects of coupling agents on cellulosic
fiber reinforced thermoplastic composites and their
influence on mechanical properties have been re-
ported (26-28).Vanna et aL (29) reported the effect
of various chemical treatments such as organoti-
tanate, zirconate, silane, N-substituted methacry-
lamide on the properties of sisal fibers reinforced
polyester composites. Reinforcing fibers can be
modified by physical and chemical methods.
5. FIBER HODIFICATION
6.1. Physical methods of modification
Physical methods involve surface fibrillation, elec-
tric discharge (30, 311 (Corona, cold plasma) etc.
Physical treatments change structural and surface
properties of the fiber and thereby influence the me-
chanical bonding with the matrix.
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
Surface modification by discharge treatment such
as low temperature plasma, sputtering and corona
discharge is of great interest in relation to the im-
provement in functional properties of vegetable fibers.
Low temperature plasma treatment causes mainly
chemical implantation, etching, polymerization, free
radical formation, crystallization, whereas sputter
etching brings about chiefly physical changes such as
surface roughness and this leads to increase in adhe-
sion and decreases light reflection (31). Low tempera-
ture plasma is a useful technique to improve the sur-
face characteristics of the fiber and polymeric
materials by utilizing the ingredients such as electron,
ion, radical and excited molecules produced by elec-
trical discharge. Low temperature plasma can be gen-
erated under atmospheric pressure in the presence of
helium (311.
The action of these plasmas involves abstraction of
protons and creation of unstable radicals that convert
functional groups such as alcohols, aldehydes, ke-
tones and carboxylic acids. Electrical discharge meth-
ods are used for cellulose fiber modification to de-
crease the melt viscosity of cellulose- polyethylene
composites (32) and to improve the mechanical prop-
erties of composites. Corona treatment is one of the
most interestmg techniques for surface oxidation acti-
vation. It changes the surface energy of the cellulosic
fibers, which in turn affects the melt viscosity of com-
posites (30).Mechanical and rheological properties of
cellulose-PPcomposites subjected to corona treatment
were reported by Sapieha et al. (33,34). Corona treat-
ment modifies the surface composition and therefore
the surface properties of the composite components.
S.2 Chemical Modification
Strongly polarized cellulose fibers me not inherently
compatible with hydrophobic polymers. The compati-
bility and dispersability of fiber and matrix can be im-
proved by developing a hydrophobic coating of a com-
patible polymer on the surface of filler before being
mixed with polymer matrix. Generally, coupling
agents facilitate the optimum stress transfer at the in-
terface between fiber and matrix. Coupling agents are
molecules possessing two functions. The first is to
react with OH groups of cellulose and the second is to
react with functional groups of the matrix. The selec-
tion of a coupling agent that can combine both
strength and toughness to a considerable degree is
important for a composite material. The most com-
mon coupling agents are silane, isocyanate and ti-
tanate based compounds, the chemical composition of
which allows them to react with the fiber surface,
which forms a bridge of chemical bonds between the
fiber and matrix. In the case of cellulosic fiber com-
posites, isocyanates were found to be reliable. It is ex-
pected that the formation of a primary type of bonds
- covalent bonds between cellulose and isocyanate -
and a secondary type of weak bonds between thermo-
plastics and isocyanates improve the mechanical prop-
erties of wood fiber filed thermoplastics. Pretreatment
1473
 Jayamol George,M. S . Sreekala and Sabu Thomas
of fibers by encapsulated coating with silanes or iso-
cyanates, grdting etc. provides better dispersion by
reducing the fiber-fiber interaction with the formation
of coating on the fiber surface.
5.2.1 Silane Treatments
Several theories have been proposed to explain the
interfacial bonding mechanisms of silane coupling
agents, which are responsible for the improvement of
mechanical performance and hygrothermal stability of
the composites. Among these, the most widely ac-
cepted is chemical bonding theory. In the chemical
bonding theory, the bifunctional silane molecules act
as a link between the resin and the cellulose by form-
ing a chemical bond with the surface of cellulose
through a siloxane bridge while its organofunctional
group bonds to the polymer resin. This co-reactivity
with both the cellulose and the polymer via covalent
primary bonds gives molecular continuity across the
interface region of the composite. A number of factors
affect the microstructure of the coupling agent, which
in turn controls the mechanical and physical proper-
ties of the composites (35).They are the silane struc-
ture, its organofunctionality, acidity, drying condi-
tions and homogeneity, the topology and the chemical
composition of fiber surface. The general chemical for-
mula of silane is X,Si-R, a multifunctional molecule
that reacts at one end with the cellulose fiber surface
and the other end with the polymer phase. R is a
group, which can react with the resin, and X is a
group, which can hydrolyze to form a silanol group in
aqueous solution, and these react with hydroxyl
group of the cellulose surface. R-groups may be vinyl,
y-aminopropyl, y-methacreloxypropyne etc. The
X-group may be chloro, methoxy, ethoxy etc. The type
of organofunctional group and pH of the solution dic-
tates the composition of silane in dilute solution. It is
essential that the R-group and the functional group
be chosen so that they can react with the functional
group in the resin under given curing conditions. Fur-
thermore the X-group must be chosen that can hy-
drolyze to allow reactions to take place between the
silane and the OH-group on the cellulose surface.
When the treated fibers are dried, a reversible conden-
sation takes place between the silanol and -OH
groups on the cellulose fiber surface, forming a poly-
siloxane layer, which is bonded to the cellulose sur-
face. When the silane coated cellulose surface in con-
tact with the resin, the R-groups on the fiber surface
react with the functional groups present in the poly-
mer resin, forming a stable covalent bond with the
polymer. Once all these reactions occur, the silane
coupling agents may function as a bridge to bond the
cellulose fibers to the resin with a chain of primary
strong bond.
Apart from the chemical structure of silane, disper-
sion aids such as solvent and initiator (different or-
ganic peroxides) provide various chemical reactions as
well as physical interactions at the interface. In this
way they play important roles in the mechanical
1474 POLYMER ENG/NfER/#G AND SCIENCE, SEPTEMBER 2007, Yo/. 41, No. 9
properties of the composites (36). Treatment of fibers
with silane coupling agents significantly improves the
interfacial adhesion and therefore the mechanical
properties of the composites (28, 37, 381. The perfor-
mance of silane coupling agents in hard wood aspen
fiber in different polymeric systems was reported (26,
36). The coupling action of silanes is accelerated by
the presence of solvents and initiators.
5.2.2. Isocyanate treatment
Isocyanates, especially poly(methy1ene)poly(pheny1)
isocyanate (PMPPIC), are h o r n in wood chemistry as
wood binders with successful application in particle-
board in Europe. They are also used for the produc-
tion of oriented strand board, OSB, in North America.
Extensive experimental work on the application of iso-
cyanate as coupling agents for different types of cellu-
lose materials and polymers has been carried out by
Kokta and co-workers (36). Composites were manu-
factured with cellulosic material, which was either
precoated with an isocyanate polymer mixture, or the
isocyanate was added directly into the mixture of fiber
and polymer. Thomas et al. (28, 39) reported on the
mechanical properties of isocyanate treated fiber
reinforced thermoplastics composites. Urethane deriv-
atives of cardanol were treated with sisal fiber to im-
prove the compatibility between fiber and matrlx (39).
The urethane derivatives of cardanol (CTDIC) is the
reactive product of cardanol, the principal component
of cashew nut shell liquid and toluene di-isocyanate.
The long chain structure of CTDIC linked to the cellu-
lose fiber makes the fiber hydrophobic, compatible
and highly dispersible in the thermoplastic matrix.
The poly(methylene1poly(pheny1)isocyanate (PMPPIC)
treatment has significant influence on the properties
of composites, i.e., increased thermal stability, re-
duced water absorption etc (28, 40-42). PMPPIC is
chemically linked to the cellulose matrix through
strong co-valent bonds. The -N = C = 0 group of
PMPPIC is highly reactive with the -OH group of cellu-
lose and therefore a urethane linkage is formed.
0
II
R-N=C=O + H O - c e l l -+ R HN-C-0-cell
The urethane group results from the interaction of an
isocyanate and hydroxyl compound. The reaction
leads to polyurethane when multifunctional reactants
are used. When a di-isocyanate and a diol react to-
gether, a linear polyurethane is obtained, while a &-
isocyanate and a polyhydric compound lead to a
crosslinked polymer. Crosslinked polyurethane could
also be derived from a compound containing three or
more isocyanate groups. In the absence of a catalyst,
electron-withdrawing groups of the isocyanate mole-
cule and electron donating groups on the active
hydrogen molecule of cellulose increase the rate of re-
action. Joly et al. (43) studied the effect of alkyl iso-
cyanate treatment on the water absorption behavior of
 Review on lnterace Modification and Characterization
cotton cellulose-reinforced composites by varying the
length of alkyl chains. Their results showed the im-
portance of critical length of the alkyl chain for reduc-
ing the amount of sorbed water. Ni and Frazier (44)
reported the formation of urethanes and polyureas in
isocyanate /wood by 15N CP MAS, NMR studies. They
found that resin polymerization occurs via the reac-
tion of isocyanate with wood moisture to form
polyurea. Biuret formation and isocyanate dimeriza-
tion were also detected. In the presence of traces of
humidity, isocyanates will react preferably with water
instead of hydroxyl group of cellulose. This results in
disubstituted ureas on the fiber surface. Because of
their basicity they can react easily with further
isocyanates, which results in side chains that are
bonded to the hydroxyl group of cellulose. The main
reaction of isocyanates therefore consists of inclusion
or adhesion of alkyl or aryl ureas and their further re-
action products with isocyanates. Rench and Reid1
(45) modified chemithermomechanicalpulp (CTMP)
with various isocyanates such as n-butyl isocyanate
(BUI), phenyl isocyanate (PHI),hexamethylene di-iso-
cyanate (HMDI) and polyhnethylene) poly(pheny1) iso-
cyanate (PMPPIC) in DMF in the absence of catalyst,
and their effect on the thermoanalytical behavior of
CTMP was investigated. Aliphatic isocyanates such as
BUI and HMDI showed a low potential of reaction with
CTMP, compared to ammatic isocyanates with equal
functionality like MDI and PHI. The use of MDI and its
oligomeric modifcation PMPPIC as coupling agent re-
sulted in an increased thermal stability of modified
pulp compared to untreated pulp. FTIR studies of the
isocyanate modifled pulps showed urethane formation
as being the main component of these chemical pulp
modifcation processes. They also reported the pres-
ence of endothermic peak in DSC experiments with
the use of PHI at high concentrations due to a sec-
ondary reaction between isocyanate and humidity,
which yield urea, or to an isocyanate trimerization
product-an isocyanurate. The presence of this sec-
ondary reaction component is linked with a high re-
duction in water uptake of modified pulp.
5.2.3. Graft Copolymerization
Grafting is an effective method for the modifcation
of natural fibers. Grafting on the cellulose fiber may
take place before or during compounding. In the for-
mer case, pretreatment of fibers by compatibilizing
agents generally occurs in solution. The excess of (un-
reacted) compatibiling agent is eliminated by washing.
In the latter case, treatment during compounding oc-
curs at the mixing temperature of the matrix. Grafting
efficiency, grafting proportion and grafting frequency
determine the degree of compatibility of cellulose
fibers with a polymer matrix. The grafting parameters
are influenced by the type and concentration of initia-
tor, the monomer to be grafted and the reaction
conditions. Puig et al. (46) reported the effect of
methylmethacrylate (MMA) grafting on henequen
fibers and its applications in composites. The ratio of
POLYMER ENGINEERINGAND SCIENCE, SEPTEMBER2001, Vol. 41, No. 9
monomer/cellulose, initiator conceiitration and reac-
tion time are the grafting parameters varied. The
grafting of vinyl monomers onto cellulose and other
cellulosic fibers has been studied extensively by vari-
ous research workers (4749). This reaction is initi-
ated by free radicals of cellulose molecules. Reaction
can also be possible by ionic initiated processes. Free
radical sites may be formed on the cellulose molecules
by dehydrogenation, depolymerization, oxidation or
formation of unstable metal complexes, which may
lead to one electron transfer to the metal, and cleav-
age of the gluco pyranoside ring. Ionic processes usu-
ally involve the formation of an alkoxide of cotton cel-
lulose with which copolymerization of vinyl monomers
is initiated. The most commonly used methods of free-
radical initiator on cellulose are high-energy ionizing
radiation, ceric ion redox systems and oxidative
reagents (48).Then the cellulose molecules break and
radicals are formed.
Grafting of poly acrylonitrile on jute fibers was done
by aqueous polymerization of acrylonitrile in the pres-
ence of a NaIO, or (IOJ and C U +ions ~ combination
as the initiator (49).Ceric ion initiated grafting of alkyl
arylates such as methyl, ethyl, propyl and butyl or
methyl methacrylate to cotton, paper or other hard
cellulosic fibers have been reported (50).Ghosh and
Mohanty (51) have reported the effect of grafting on
the performance of unsaturated polyester based jute
composites. Chemical modifications were achieved
through graft copolymerization with acrylonitrile or
methyl methacrylate. It was reported that polyacry-
lonitrile (PAN) graflmg showed a higher improvement
in the strength of the composite in comparison with
polymethyl methacrylate (PMMA) grafting. Important
factors in initiating graft copolymerization reaction of
vinyl monomers with activated cellulose are the acces-
sibility of free radical sites to the monomers, the life-
time of free radical sites, and the interaction of the
monomer solutions or vapors with activated cellulose
to increase the accessibility of the free radical sites to
monomer. After radical formation, the radical sites of
the cellulose are treated with a suitable solution (com-
patible with the polymer matrix) e.g. vinyl monomer
(48)acrylonitrile (49)and polystyrene (52).The result-
ing copolymer possesses properties characteristic of
both fibrous cellulose and grafted polymer.
One of the important factors to be remembered dur-
ing the direct grafting to fiber is that the monomer
cannot diffuse into ordered regions such as the crys-
tallites, but only into amorphous or disordered re-
gions. Since the mechanical behavior of the fibers is
largely determined by the ordered structure, grafting
does not bring about any drastic changes in the prop-
erties (48).The distribution of MA moieties on PP is of
great importance in the coupling action if MAPP is
prepared at low temperature or in solution. The graft-
ing of MA onto PP occurs along the chain without
modifying the length of the initial PP. The reaction of
this comblike structure with cellulose may lead to a
coating of fiber with several anchoring points. At
1475
 Jayamol George,M. S . Sreekala and Sabu Thomas
higher temperatures, the scission of PP chain occurs
with the formation of MA prepolymers at the scission
end. The scission of chain is initiated by a decrease in
the molecular weight. Reactions with cellulose will
then produce a brushlike grafting on the fiber, which
is favorable for the entanglements with the matrix
chains. The MAF'P chains of different lengths grafted
to the cellulose surface is explained in terms of a
brush concept (53).When a long chain polymer is at-
tached to a surface or an interface, the mobility of the
chains is restricted. The grafted chains would adopt a
random walk configuration in order to maximize their
configurational entropy (54). Under certain condi-
tions, the grafted chains may stretch away from the
surface and form a brushlike structure. Important
factors that affect the stretching tendency are graft
density, the molecular weight of grafted chains and
the character of the surrounding medium (55).A high
graft density allows neighboring chains to overlap.
Thus they stretch away from the surface in order not
to overfii the space. The adopted conformations lead
to a brush height that grows faster than the typical
chain dimension when the molecular weight in-
creases. This brush formation is likely to occur in var-
ious systems such as in solutions or melt containing
block copolymers as surfactants or compatibilizers.
Joly et al. (43) found that partial masking of cellu-
losic fiber with maleic anhyride grafted PP reduced
the water absorption in cotton fiber composites. The
effectiveness of MAH-PP copolymers as coupling
agents in jute/PP composites was studied by Gassan
and Bledzki (56).They found that improved fiber-ma-
trix adhesion gives a higher damage resistance under
cyclic dynamic loading.
5.2.4 Impregnation ofjbrs.
A better combination of fiber and polymer i s
achieved by impregnation of the reinforcing fibers
with polymer matrices compatible with the polymer.
Fibers are impregnated in liquid monomer and then
these monomers are polymerized in-situ using cata-
lyst, heat or radiation (57).A wide range of composite
properties is possible by varying the monomer with
crosslinking agent, the monomer f??lingmethod and
the polymerization process. Improved dimensional
stability of wood polymer composite fwpc) using sol-
vent exchange technique of impregnation was re-
ported (57). It is known that the elevated viscosity of
the matrix during processing of the composite hinders
the complete impregnation of the fibers which results
in a low mechanical interaction with the matrix.
Monomer solutions of low viscosity are used for the
purpose (27). F'ranco et aL (58)reported the improved
interfacial properties of henequen/HDPE composites
by the impregnation method. The HDPE was de-
posited on the henequen fibers from a dilute solution
of xylene at 115°C.
1476 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
5.2.5. Alkali swelling and substitution reactions
An old method of cellulose fiber modification is mer-
cerization. Mercerization is an alkali treatment to cel-
lulose fiber that depends on the type and concentra-
tion of alkali solution, time of treatment and
temperature. The changes in the surface morphology
of alkali treated oil palm fiber for 48h can be seen in
Fig. 1. It was reported that when the fiber was im-
mersed in alkali for 48h, the globular pultrusions pre-
sent in the untreated fiber disappeared, leading to the
formation of a larger number of voids (59).These voids
promote mechanical interlocking between fiber and
matrix. Loss of cuticle by the rupture of alkali sensitive
bonds leads to a rough surface. Varma et d (60) stud-
ied the thermal stability of natural and chemically
treated coir-fiber including mercerization in the nitro-
gen atmosphere. Effects of NaOH treatment and
y-preirradiation on coconut fiber/ PF composites were
reported by Owolabi et al. (61). In general this treat-
ment reduces the cementing material followed by the
removal of volatile products with the rupture of bonds.
Optimal conditions of mercerization ensure the i m
provement of tensile properties. George et al. (28) re-
ported reduction of tensile properties of PALF/LDPE
composites at higher concentrationsof NaOH.
In substitution reactions, those that substitute OH
groups of cellulose molecules in the presence of alkali
can be utilized. By impregnating fiber with alkaline
swelling agents and by reacting with some chemical
agents that can be substituted for the hydroxyl groups
on cellulose molecules in the presence of alkali,highly
decrystalked fibers can be obtained (62).The effective
substitution reactions include acetylation by acetic an-
hydride and cyanoethylation. Richards found that
acetylation of wood increases the dimensional instabil-
ity and reduces the susceptibility to decay (63).In-
creased strength, rot resistance and hydrophobicity of
jute fiber after acetylation are reported by Anderson et
al. (641. In a review article, Bledzki and Gassan re-
ported the surface modification of natural fibers, the
processing and properties of natural fiber composites
and their technical applications (65).
6. CHARACTERIZATION METHODS
A clear understanding of the complex nature of cel-
lulose surfaces is needed to optimize surface modifca-
tion procedures and thus to increase the usefulness
of lignocellulose as a constituent of composites. Since
the fibers and matrices are chemically different,
strong adhesion at their interfaces is needed for an ef-
fective transfer of stress and bond distribution through
out an interface. Several theories describe adhesion
phenomena, which include chemical bonding, wetting
diffusion (mechanical or entanglement interlocking of
components), electrostatic and acid/base interaction,
which act as a driving force for interfacial bonding
(66). Fundamentally, adhesion is a thermodynamic
event, with the enthalpy of adhesion determining the
strength of adhesion at equilibrium (67).There is also
 Review on Interace Modijkation and Characterization
a thermodynamic need to decrease the interfacial ten-
sion at interfaces (681.Good wetting is a requisite for
these thermodynamic demands, and this can only
occur if the surface energy of the wetting substance is
lower than that of substrate (67).
6.1 Inverse Gas ChromatographyAnalysis (IGC)
Interfacial adhesion, wetting and mechanical prop-
erties of composites that depend on the interfacial
characteristics are functions of the acid/base, or elec-
tron acceptor/donor properties of the materials in-
volved (68).The IGC methodology is convenient for the
evaluation of acid/base interface potentials for a wide
range of polymers and reinforcing fibers (69).This al-
lows the determination of surface characteristics of
materials and it is a sensitive method to look at surface
modification. Concerning cellulose fiber, IGC allows the
determination of the dispersive component of surface
energy using non-polar probes and acid base character-
istics using polar probes. It was reported that grafting
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
of MAPP on cellulosic surface increases the surface
energy and significantly decreases both the acidic and
basic character (70). The increase in MA content of
MAPP enhances basic character because of the higher
number of ester m e s , while the increase in molec-
ular weight reduces both the hydrophilic and acidic
character of the fiber. When thermodynamic consider-
ations are applied to inverse gas chromatography at
infinite dilution, it can be shown that (71).
- AG, = R.T. In V,,t k (11
where V, is the retention volume of a vapor probe by
stationary phase and k is a constant for a given chro-
matographic column. G is related to the work of adhe-
sion Wa by (68)
AG = N.a. Wa (2)
where N is the Avogadro’s number and a is the cross-
sectional area of the adsorbed vapor molecule.
1477
 Jayamol George, M. S. Sreekala and Sabu Thomas
Combining Eq I and 2 leads to
R. 7’.In V, = N . a. Wa + constant (31
and since
R. T.In V,,= 2. (y$)’’2.a. (-yF)’/2+ C 151
If R. T. hV,,is plotted vs. a (yld)1/2,(ySd)can be ob-
tained from the slope of the linear function. That lin-
ear function can also be used as a reference for inter-
action with vapors that are able to interact with the
substrate by non-dispersion forces. The distance be-
tween the retention volume for such a vapor and the
reference line is the specific free energy change AGab
due to polar interactions. Then,
A Gd =A H d - TASd (6)
If G,/T is plotted vs. 1/T,AHab can be obtained
from the slope of straight line. G, H and S are the free
energy, enthalpy, and entropy term. The enthalpy
contribution may be expressed in terms of acid/base
interaction as follows (72):
AH* = U N + &AN (7)
Here AN and DN are the vapor phase acid/base
characteristics and K , and & are the acid/base inter-
action potentials of the solid. Then by dividing both
sides by AN, Eq 7 can be rewritten as
AHdAN = &(DN/AiV) + Kd (8)
If AHab is plotted vs. (DN/AN), then the acid and
base interaction parameters, K, and Kd are readily ob-
tained. The availability of K, and & for components of
a polymer system allows for an empirical evaluation of
an acid/base pair interaction parameters, ZP (72)from
Ip = & (f).
Kd(m) + &(m)*I(d cf) (9)
IP data are useful for the interpretation of the depen-
dence of specific interactions of composite perfor-
mance parameters.
6.2 X-RayPhoto Electron Spectroscopy
X-ray photoelectron spectroscopy provides an un-
derstanding of both the quality of interfacial bond and
the performance of the bond during service. Felix and
Gatenholm (27) used this method to characterize the
bonding in modified cellulose and PP/MAF’P copolymer.
This technique was applied to determine the surface
composition of cellulose and wood fibers by Doms and
Gray (73). They found that the observed chemical
shifts and peak shapes were in accordance with the
molecular structure of the components. X-ray photo-
electron spectroscopy (XPS) studies of surface modifi-
cation of cellulose fibers by chemisorption with stearic
acid are reported (74).XPS studies on cellulose showed
that extraction of samples with organic solvents
1478 POLYMER ENGINEERfNG AND SCIENCE, SEPTEMBER2001, Vol. 41, No. 9
caused a si@cant increase in the proportion of oxy-
gen atoms relative to carbon atoms on the surface.
Zadorecki and Ronnhult (75) used the XPS technique
to evaluate the cellulose surface modified with triazine
coupling agents. They found that coupling agents
were concentrated on the surface rather than uni-
formly distributed throughout the fiber. XPS spectra
provide the chemical composition of cellulose surface.
George et al. (76) used the XPS technique to study the
surface composition of flax fibers. Figure 2 shows the
electron intensity as a function of binding energy of
untreated flax fiber, silane treated fiber and iso-
cyanate treated fiber in the XPS survey spectra. For
lignocellulosic materials, oxygen and carbon are the
predominant species, as is evident from the absorp-
tions of 01s and Cls occurring at 531 ev and 280 ev,
respectively. Some other species, such as Ca, Si etc.,
are also observed in small concentrations at 340 and
105 ev. In the case of silane and isocyanate treated
fibers, absorption peaks are shifted to some extent. It
can be seen that 0,, and C,, are the predominant
species and occur at 50 and 281 ev, respectively.
Other species present in small amounts are Ca 2 p at
344 and Si 2p at 98 ev. Joly et aL (43)used XPS analy-
sis to study the C/O ratio for cellulosic fibers treated
with isocyanate.
6.3 Environmental Scanning Electron Microscopy
(ESEM)
ESEM has proven useful for investigating wood
polymer interactions at fracture surfaces and polymer
distributions in W C s (77). ESEM allows observation
of the monomer impregnated samples directly and
after cure to W C s to yield information on the interac-
tion of the polymer formed with the wood compo-
nents. The advantage of the ESEM instrument is that
it allows wet, oily and electrically nonconductive spec-
imens to be observed without special preparation and
at relatively high pressures.
6.4 Energy Dispersive Analysis of X - R a p
(EDAX)
Elemental composition can be determined using en-
ergy dispersive analysis of X-rays. An energy dispersive
X-ray analyzer attached to an ESEM works on the
principle that when an electron beam of sufficient en-
ergy bombards a specimen, X-rays characteristics of
each element present are emitted. From their energy
and intensity, the atomic number and relative concen-
tration of a particular element can be determined. The
presence of polymer within the wood cell walls of a
balsa WPC containing 1:1 copolymer of ethyl-(hydroxy
methyl) acrylate (EHMA)and ethyl(chloromethyl) acry-
late (ECMA) was determined by Wright and Mathias
using this method (771. This type of analysis is partic-
ularly useful in determining the depth of a chemical
used for wood modification and to ascertain if the
chemical is homogeneously distributed.
 Review on Interace Modification and Characterization

c 1s
100000 -
0 1s
C KLL
-* 80000 =-I
untreated
z
"\
N 1s
60000 - 0 KLL Si 2p
.-c
rn
C siiane treated
Y I\ I I
$ 40000 -
c

-
20000 -

8.5 Solid State 13C Nllw Spectroscopy
Solid state 13C N M R spectroscopy using cross polar-
ization and magic angle spinning (CP/MAS) is useful
for characterizing WPCs since detailed information
can be obtained from solid samples (78). In general,
solid state N M R involves proton-carbon cross polariza-
tion to enhance the I3C signal, high power decoupling
to eliminate dipolar line broadening due to protons
and spinning of the sample about the magic angle of
54.74O, with respect to the static field to reduce the
chemical shift anisotropy effects. A spectrum of
Southern pinewood obtained using CP/h4AS spec-
trometer is shown in Fig. 3 (77). The peaks in the
spectral region, from 160 ppm to 1110 ppm,are due to
the aromatic ring carbons of lignin, while those be-
tween 1 6 0 ppm and 143 ppm are assigned to oxygen
substituted aromatic carbons. The peak at 56 ppm

Fig. 3. Solid state 13C iWW? spec-

trum of Southern pinewood and
structure of cellulose unit Source
Re3 76.

1 1 l l 1 4 l 1 1 l 1 1 1 1 1 1 1 1 1 1 f

00 150 too 50 0
P?M

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9 1479
 Jayamol George, M. S . Sreekala and Sabu Thomas
corresponds to lignin methoxy carbons, and the peaks
at 122 and 135 ppm correspond to unsubstituted and
alkylated aromatic carbons, respectively. The acetyl
groups from hemicellulose components yield peaks at
2 1 ppm (methyls)and 172 ppm (carbonyls).The single
peak at 105 ppm is assigned to the C-1 carbon of the
cellulose anhydroglucose repeat unit. Thus, chemical
shift data allow qualitative and quantitative identifica-
tion of the three major components of wood.
6.6 Atomic Force Microscopy (AFM)
Atomic force microscopy is a useful technique to de-
termine the surface roughness of fibers. Its advantages
such as high resolution and non-destructivity offer a
unique possibility for repetitive examinations. The
force modulation mode gives a qualitative statement
about the local sample surface elasticity using an os-
cillating cantilever tip, which indents into the sample
surface. The amplitude of this deflection is measured
as a function of tip position when cantilever tip intends
Fig. 4. AFM three-dimensionalim.
ages dmiufibers.
1480 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
cyclically into the surface. AFM utilizes much smaller
forces between the tip and specimen (typically0.1 pNl
and the smaller radius of curvature of the tip gives
better spatial resolution. Mai and co-workers (79) used
this technique to determine the physical properties of
the interphases. The microscopic image produced is
that of a surface, representing the locus of points of
constant force between the tip and the specimen. An
important feature of the AFM is its ability to image
non-conducting surfaces. The information collected
during a scan of the surface is quantitative in three di-
mensions. When presented as a topographic image,
the elevation of each point in the picture is encoded
according to a gray scale or false color scale. This vari-
ation is clearly understood from the three-dimensional
picture of untreated and silane treated fibers. Figures
4(a) and (b) show three-dimensional images of un-
treated and silane treated flax fibers (80).After fiber
treabent, the surface roughness of the fibers was in-
creased considerably compared to untreated fiber.
 Review on Interace Modification and Characterization

6.7 Ildicromechanical Studies

There are several micromechanical tests that are
useful for characterizing the composite interface
properties. These include the single fiber pullout test,
the microbond test, the single fiber fragmentation test
and the micro-indentation test. The shear strength of
the fiber/matrix interface in a fiber reinforced com-
posite can be determine by measuring the force
needed to pull a single fiber axially out of the single
matrix. The microbond pullout test is considered as a
modified single fiber pullout test: it consists of a single
fdament embedded in the matrix. This experiment in-
volves the deposition of small amount of resin onto
the fiber surface in the form of a droplet that forms
concentrically around the fiber in the shape of an el- Fig. 6. Photomicrographof a typical microdropkt on afiber.
lipsoid. In the case of microbond test, it is assumed
that the interfacial shear strength is uniformly distrib-
uted along the embedded length of the fiber. When the In the fragmentation test, a single fiber is totally en-
shearing force reaches a critical value, pullout occurs capsulated in a matrix coupon, which in turn is
and the droplet is displaced along the axis of the fiber. loaded in tension. Depending on the level of fiber-ma-
The force/displacement curve of a microbond test ob- trix adhesion, tensile forces were transferred from the
tained from debonding droplet of flax/PP is given in matrix to the fiber. The stronger the fiber, the higher
Rg. 5. (81).The average shear stress is calculated by the strain needed for the observation of the first rup-
dividing the maximum measured force of debonding ture. For specimens containg a straight fiber, the
by the embedded fiber length area. The bond strength strain at which the first fiber ruptures is also not
values can be used for investigating the dependence of identical from one specimen to another. It has been
composite performance on the energy absorbing char- observed that the later the first fiber rupture, the
acterization of the interface and to establish the ex- higher the fiber fragment length reached at satura-
tent to which the fiber surface treatment can alter tion. Fiber rupture in flax/epoxy composites during a
bonding. The reliability of the data is dependent on fragmentation test is shown in Rg. 7. Fiber fragment
the shape of the droplet. Symmetric, round droplets length or aspect ratio is obtained by dividing the
are easier to test and analyze than droplets with flat length of domain of investigation by the number of
surfaces. If the length of droplet exceeds a critical fiber ruptures added by one.
value, the fiber will fi-acture prior to debonding and The pullout experiment, believed to possess the
pullout. A photomicrograph of a typical droplet on a characteristics of fiber pullout in composites, consists of
filament is shown in Fig. 6 (82). a fiber embedded in a matrix block or thin disc normal

o.20 I
-z
Y
0.1 5
I
Fig. 5 . Force displacement curve
?.lo -
of microbond test obtained from
debonding a droplet ofJlax/PP. -

0.05 -

0.00
0.00 0.05 0.10 0.15 0.20

Vertical displacement [ mm ]

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9 1481
 Jayamol George, M. S . Sreekala and Sabu Thomas
Fig. 7. Fiber breakage during
fmsmentation test
to the surface of the polymer. A steadily increasing
force is applied to the free end of the fiber in order to
pull it out of the matrix. Load and displacement are
monitored as the fiber is pulled axially until either
pullout occurs or the fiber fractures. The strength of
the Aber/matrix interface can be calculated to a first
approximation by balancing the tensile stresses (af)
on the fiber and the shear stress IT) acting on the
fiber/matrix interface, obtaining a simple relationship
of the form T = (9/2)(dll), where it is assumed that
the shear stress is uniformly distributed along the
embedded length and d is the diameter.
The micro-indentation test is conducted on real com-
posites and therefore has the advantage of reflecting
actual processing conditions. A compressive force is
applied to individually selected fibers in a polished
cross section of the composite to produce debonding.
The interfacial shear strength is then derived from the
debond length.
7. BIODEGRADATION
Biodegradation is considered to be desirable for dis-
posal of plastic products such as packaging for food-
stuffs and agricultural products. Biodegradability is
defined as the tendency of materials to suffer degra-
dation by living organisms present in the natural en-
vironment (bacteria, fungi). It occurs by reaction be-
tween the enzymes secreted by the organism and the
polymer chains or additives that make up the com-
pound. The three basic stages t h a t constitute
biodegradative molecular breakdown in plastics are
(83):i) Change in appearance due to slight chemical
change associated with the onset of decomposition.
This may be due to the formation of double bond con-
jugation in the polymer chain. ii) Significant change in
the range of physical properties as a result of a sub-
stantial degree of main chain scission resulting in a
much lower average molecular weight. iii) Visual dis-
appearance of the polymer when mechanical break-
down (fragmentation)is sufficiently advanced to dis-
perse the material to submicroscopic scale.
1482 POLYMER ENGINEERINGAND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
The majority of commercial plastics are not directly
biodegradable. In order to improve potential biode-
gradability, the following factors should be consid-
ered (83):i) The environment in which biodegradation
is to take place must be appropriate to the require-
ments of the mechanism. The organism must be able
to flourish and the natural elements (moisture, sun-
light) balanced accordingly. ii) A high surface area to
mass ratio is required, not only to accelerate the pas-
sage of liquids through the medium, but also to as-
sist in fragmentation, once decomposition is initiated.
iii) The molecules or additives in the compound must
possess particular groups of chemicals that can react
with the organism. iv) The chances of biodegradation
are reduced if the polymer is highly crystalline or is of
high molecular weight. Addition polymers are gener-
ally resistant to biodegradation, since the carbon-car-
bon bonds in the backbone are not very susceptible
to enzymatic attack. If an easily hydrolyzable group
can be introduced into an addition polymer by a free
radical process, a wide variety of biodegradable poly-
mers can be prepared. Chemical effects have not
been used to achieve the biodegradability of poly-
mers. However, activation of carbon chains by certain
functional groups can markedly increase the suscep-
tibility to chain cleavage.
Studies of degradation have been mainly done for
LDPE and HDPE by Albertsson et al. (84-88). They
pointed out that biodegradation of PE is affected by
preliminary irradiation with a UV source, by the
morphology and surface area of the material, by an-
tioxidants and by additives (84-89).The initial photo-
oxidation facilitates a n attack of polyethylene by
micro- organisms owing to a synergetic effect between
photo oxidation and biodegradation. The microbial
degradation of an ultra-high mo1e:wt PE/starch com-
posite film was studied by Nakashima and Matsuo
(90) using two kinds of filamentous fungi, Myrothe-
ciurn verrucarria and Chaetorniurn globosurn I t was
found that in both drawn and undrawn films, the num-
ber of starch particles between PE fine filaments became
 Review on Interace Modification and Characterization
much lower and the average size of the residual starch
particles was smaller, indicating their effective biodegra-
dation. With respect to biodegradable additives, the
most effectiveoption appears to be the incorporation of
naturally occurring materials such as starches (91).
The production of lignocellulosic enzymes has re-
ceived importance in recent years because of their
possible role in achieving effective bioconversion of lig-
nocellulosic waste into simple sugars, chemicals, al-
cohols etc. Nobuo et aL (921 produced sugar and etha-
nol from cellulosic resources like rice, straw, grass,
bagasse, sawdust and newsprint, after chemical delig-
nification with trichoderma cellulose. Cellulase pro-
duced from T. viride was capable of extensive degrada-
tion of cellulosic materials and this enzyme was very
stable (93).The physiochemical properties of lignocel-
lulosic wastes determine the rate of enzymatic degra-
dation of these cellulosic wastes. Both cellulose and
hemicellulose as such are highly susceptible to the
action of cellulolytic microbes. Bioconversion of tapi-
oca waste and water hyacinth into the production of
food products and fuel was studied (94).
'The DLR institute of structural mechanics devel-
oped biocomposites by embedding natural reinforcing
fibers, e.g. flax,hemp, ramie, etc. into a biopolymeric
matrix made of derivatives from cellulose, starch, lactic
acid, etc. Polymers of natural origin, e.g. starch and
cellulose have to be modified physically or chemically
to be suitable for processing as thermoplastic resins.
For example, the structure of starch can be made
thermoplastic using glycerol and water (95). A fre-
quently used option to improve the properties is to
add copolymers, which can even be of petrochemical
origin, or the partial or complete esterification of the
hydroxy groups in the side chains with short chained
organic acids such as acetic acids. The esterification
of the hydroxy groups at the side chain is preferred
for making cellulose a thermoplastic material while
keeping its cellulose chain structure (96).Applying
the methods of biotechnical synthesis, in many cases
by fermentation, polymers in particular built up by
microorganisms are obtained, using such polymers as
storage for energy. Compared with plants, here the
task of storing energy is done by the starch. Poly(hy-
Table 2. Properties of Biopolymers.
Properties PP Polylactic Biotec
acid starch
Density (gk) 0.9 1.25 1.2
Tensile 25-35 53 30
strength (MPa)
'Tensile 1.4-1.8 3.5 1 0.5
modulus (GPa)
Elongation at 400-500 5 10
break (Yo)
Charpy impact 46 -
notched (kJ/rn2)
MFf (gllornin) 35 - 8.7
Tm (OC) 160 55 73
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
droxybutyric acid) [PHBl and its copolyesters are the
most important example for fermented biopolymers,
e.g. Biopol (97).Biopol (a bacterially derived biode-
gradable polymer) is a thermoplastic and has tensile
strength comparable to that of polypropylene. Roper-
ties of some of the biodegradable polymers in compar-
ison with polypropylene are given in Table 2. Mohanty
et al. (98) reported the surface modification of jute
fibers on the performance of jute/biopol composites.
Properties of Bioceta and flax fibers were reported by
Riedel and Nickel (99).Peijs et aL (100) found that ad-
dition of flax fibers to the relatively cheap PHB matrix
offersthe possibility of obtaining cheaper products to-
gether with improved toughness while retaining the
biodegradability of the resulting polymer composites.
When modifying the resin systems more or less exten-
sively, biocomposites being completely made from bio-
logically renewable resources can be designed for dif-
ferent applications to be either biodegradable or not.
The composite Polymers Division of Ashland Special-
ity Chemical Co. and Cara plastics are jointly assess-
ing the viability of using technology based on the use
of soybean oil in resins across various processes
(101). Apart from reuse or recycling, this offers addi-
tional possibilities of a convenient removal after the
end of a lifetime, i.e. biodegradation or composting of
the biodegradable kinds of biocomposites or combus-
tion of any kinds of biocomposites, which is now car-
bon dioxide-neutral and completely slag-free. Thus
biocomposites are fully integrated into natural cycles
and can also meet the steadily increasing environ-
mental demands of legislative authorities.
With respect to mechanical properties, biocompos-
ites are comparable to the well-known glass fiber-rein-
forced plastics. The main motivation for developing
biocomposites has been to create new composites that
are completely environmentally compatible in terms of
production, usage and removal. Since raw materials
are entirely taken from biologically renewable re-
sources, biocomposites are fully integrated into nat-
ural cycles. Since natural fibers are biodegradable,
matrix systems c a n be designed to be either
biodegradable or not according to the specific demands
of a given application. Since biodegradation and/or
Novamont Biopol Paragon
starch PHB starch
1.28 1.25 1.4
16 20-30 30-35
0.4-1 .o 2.5-29
>goo 8-42 1 -5
2.5-3.0 8-1 2 -
- 162 -
1483
 J a y m l George, M. S. Sreekala and Sabu '?7ronuis
combustion is a relatively new and very interesting re-
covery option for fiber reinforced composites, the be-
havior of decomposition has to be analyzed in order to
obtain reliable data on the degree of biodegradation
within a certain time, and the total time for decompo-
sition ( 102).
8. CONCLUSION
The mechanical and physical properties of natural
fibers vary considerably depending on the chemical
and structural composition, fiber type and growth
conditions. The mechanical properties of composites
are influenced mainly by the adhesion between the
matrix and fibers. The adhesion properties can be var-
ied by pretreating the fibers. So, special processing
methods such as physical and chemical modification
methods are developed. Natural fibers are renewable
and recyclable. Since biodegradation and/or combus-
tion is a relatively new and very interesting recovery
option for fiber reinforced composites, the behavior of
decomposition has to be analyzed in order to obtain
reliable data on the degree of biodegradation and the
total time for decomposition.
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