Natural Fiber Eco-Composites

G. Bogoeva-Gaceva,
1
M. Avella,
2
M. Malinconico,
2
A. Buzarovska,
3
A. Grozdanov,
3
G. Gentile,
4
M.E. Errico
4
1
Faculty of Technology and Metallurgy, University St Cyril and Methodius, 1000 Skopje, Republic of
Macedonia
2
Institute for Chemistry and Technology of Polymers, ICTP-CNR, 80078 Pozzuoli, Naples, Italy
3
Faculty of Technology and Metallurgy, University St. Cyril and Methodius, 1000 Skopje, Republic of
Macedonia
4
Institute for Chemistry and Technology of Polymers, ICTP-CNR, 80078 Pozzuoli, Naples, Italy
The natural ber (NF) reinforced composites, so called
eco-composites, are subject of many scientic and re-
search projects, as well as many commercial programs.
The growing global environmental and social concern,
high rate of depletion of petroleum resources, and new
environmental regulations have forced the search for
new composites and green materials, compatible with
the environment. The aim of this article is to present a
brief review of the most suitable and commonly used
biodegradable polymer matrices and NF reinforcements
in eco-composites, as well as some of the already pro-
duced and commercialized NF eco-composites. POLYM.
COMPOS., 28:98107, 2007. 2007 Society of Plastics Engi-
neers
INTRODUCTION
One of the major environmental problems we are facing
today is the plastic waste problem. The tremendous produc-
tion and use of plastics in every segment of our life has
increased the plastic waste in huge scales. The waste dis-
posal problems, as well as strong European regulations and
criteria for cleaner and safer environment, have directed
great part of the scientic research to eco-composite mate-
rials that can be easily degraded or bio assimilated [1, 2]. As
a term, eco-composite is usually used to describe composite
material with environmental and ecological advantages over
conventional composites. By denition, an eco-composite
may contain natural ber (NF) and natural polymer. More-
over, eco-composites could be a combination of NF and
biodegradable polymer matrix. Using the last terminology,
i.e. biodegradable polymers, the number of polymer matri-
ces that could be used in eco-based composite formulations
is signicantly increased. The research eld of biodegrad-
able polymers is still in its early stages, but is growing in
popularity every day. Currently, a lot of polymer biodegrad-
able matrices have appeared as commercial products, of-
fered by various producers. The high price of these mate-
rials is the main restriction in their use (Table 1), in spite of
their unique physical and chemical properties [3, 4]. The
aim of this article is to present a brief review of the most
commonly used biodegradable polymers and NFs in eco-
composite materials.
BIODEGRADABLE MATRICES IN ECO-
COMPOSITES
The general division of biodegradable polymers, widely
accepted in numerous literature surveys, classies these
polymers into three categories, based on whether they po-
lymerize biologically or synthetically:
Biosynthetic
Semi-biosynthetic
Chemo-synthetic polymers
Biosynthetic are actually natural polymers, produced
from natural sources. Starch, as one of the commonly
used natural polymers, offers limited substitute for petro-
leum plastics. Starch is a polysaccharide that can be found
in numerous renewable resources as corn, potato, rice,
and others [5]. Starch is the least expensive biopolymer. It
becomes thermoplastic when properly plasticized with
water or other plasticizers. Starch formulations can be
processed by all common methods, used for synthetic
Correspondence to: Dr. A. Grozdanov; e-mail: anita@ian.tmf.ukim.edu.mk
Contract grant sponsor: EU FP6 INCO Program; contract grant number:
INCO-CT-2004509185.
DOI 10.1002/pc.20270
Published online in Wiley InterScience (www.interscience.wiley.com).
2007 Society of Plastics Engineers
POLYMER COMPOSITES2007
resins (extrusion, injection molding, thermoforming, etc.).
It can be used in its granular form, or as biodegradable
ller [6]. The main shortcomings, related to this material,
are low impact resistance, strong water absorption, and
very poor mechanical properties (lack of interfacial ad-
hesion). To improve some of the properties, starch is
usually blended with other thermoplastic polymers [7, 8].
In one of the earliest uses of starch in plastics, it was
blended with PE, with 2080% of starch content. Starch
can be blended with polyvinyl alcohol, as well: the blends
are thermoplastic and easily processible. Starch-based
blends biodegrade at rates that depend on composition
and crystallinity. The blends of starch with aliphatic poly-
esters, especially poly(-caprolactone) (PCL), were
widely studied [911].
The mechanical properties of starch as a polymer matrix
could be also signicantly improved in the presence of
NFs as reinforcements [12]. It was shown that the tensile
strength in eco-composites is strongly dependent on ber
content. Vazques et al. have studied the properties of
biodegradable composites based on PCL/starch blend ma-
trix, known under the commercial name MaterBi-Z and
NFs [13]. They showed signicant increase in elastic
modulus (E) up to 700 MPa and mechanical strength ()
up to 15 MPa of the composites when compared with the
polymer matrix (E 37 MPa and 7.3 MPa, respec-
tively).
Starch is usually surface treated to improve the compat-
ibility between the starch and the synthetic polymer. For
example, different surface treatments of starch with in situ
-caprolactone or -valerolactone monomers are pro-
posed [14]. The role of the monomer is to promote cova-
lent grafting of the polyester chains into starch, resulting
in a material with good interfacial adhesion between the
two components. Other possibility to overcome the poor
mechanical properties of the starch is to obtain starch
graft copolymers having thermoplastic branches [15].
As a material, starch has very low decomposition temper-
ature, and cannot be simply melted. For these reasons this
natural polymer is often chemically modied by partial or
complete esterication of the hydroxyl groups in the side
chain. The modied commercial product is known as
SCONACELL A [16].
Cellulose is another natural polymer. It differs in some
respect from other polysaccharides produced by plants. Its
molecular chain is very long, consisting of only one
repeating unit, glucose, and occurs in crystalline state
[17]. Cellulose plastic has been a commercial product for
many years. The usefulness of cellulose as a starting
material can be also extended by chemical modication to
methyl cellulose (MC), hydroxypropylmethyl cellulose
(HPMC), hydroxypropyl cellulose (HPC), and carboxy-
methyl cellulose (CMC). These cellulose ether lms, cast
from aqueous or aqueous-ethanol solutions of MC,
HPMC, HPC, and CMC, tend to have moderate strength;
are resistant to oils and fats; and are exible, transparent,
odorless, tasteless, water-soluble, moderate barriers to
moisture and oxygen [17]. MC lms provide an excellent
barrier against migration of fats and oils. HPC is the only
edible and biodegradable cellulose-derived polymer that
is thermoplastic and, therefore, capable of injection mold-
ing and extrusion. Development of cellulose plastics as a
matrix in bio-composites requires properties such as per-
cent elongation, exibility, and impact behavior. The
chemical, physical, mechanical, and thermal properties of
cellulose are also inuenced by its modications. Mo-
hanty et al. used various eco-friendly plasticizers to obtain
a suitable polymer matrix for eco-composite application
[18]. They have shown at the same time that the plasti-
cizer content can improve stiffness and toughness prop-
erties of the cellulose plastics. Cellulose could be found in
eco-composites more as a ber, than as a polymer matrix
[19].
Polyhydrohyalkanoates belong to the biosynthetic class of
polymers, produced in the nature by fermentation of sug-
ars or lipids [20, 21]. More than a 100 different monomers
can be combined within this family to give materials with
extremely different properties. Polyhydroxy butyrate
(PHB), polyhydroxy valerate, and their copolymers
P(HB-V) are the commonly used polymer matrices in
numerous eco-composites [22, 23]. The interest for these
polymers has grown, since they are biodegradable, and at
the same time have very similar mechanical and thermal
properties to polyolens (propylene (PP) and PE) (Table
2).
PHB is highly crystalline, and prior to its melting has
higher decomposition level, resulting in a very brittle
material. These properties could be easily controlled by
the content of hydroxy valerate in the P(HB-V) copoly-
mers. The resulting copolymers are less crystalline and
more processible [24]. Depending on the HV content,
PHB-V can display physical properties and processing
behavior resembling PE or PP, and can range from brittle
plastic to an elastomer. P(HB-V) properties can be further
modied with additives. P(HB-V) has substantial water
resistance, greater than most polysaccharides and pro-
teins. P(HB-V) is thermoplastic and can be processed by
injection molding, extrusion, blow molding, lm and ber
forming as well as a variety of coating and lamination
techniques.
TABLE 1. Average cost of biodegradable polymers and some
traditional thermoplastic polymers [3, 4].
Polymer (eur/kg) biodegradable polymers (eur/kg)
HDPE 0.92 PLA 34
LLDPE 0.82 Starch 24
PP 0.80 Polyesters 3.55
PS 1.08 BAK 5.58
PVC 0.78 PCL 8.3
TABLE 2. Thermal and mechanical properties of some biodegradable
polymers.
Polymer T
g
(C) T
m
(C)
Tensile
strength
(MPa)
Tensile
modulus
(GPa)
El.
break
(%)
PLA 54 170 2848 3.5 6
PCL 62 57 16 0.4 80
PHB 5 171 40 3.5 7
PHB-V 2 to 8 162102 28 0.9 15
PP 10 176 38 1.7 40
DOI 10.1002/pc POLYMER COMPOSITES2007 99
The second class of biodegradable polymers, i.e. semi-
biosynthetic polymers, are polymers in which the mono-
mer unit is produced naturally or by a fermentation pro-
cess, and then the polymerization procedure is a classical
synthetic procedure. A representative of the semi-biosyn-
thetic polymers is polylactic acid (PLA). This polymer is
characterized by its transparency, humidity, and oil resis-
tance. It can be found in the D,L PLA or L PLA form. The
rst form of PLA is an amorphous polymer, while the
second one is a semi-crystalline polymer. PLA is polyes-
ter synthesized from LA. Condensation polymerization of
LA generally produces a low-molecular-weight polymer,
which is then treated with coupling reagents that act as
chain extenders to give high molecular-weight (M
w
) PLA.
Recently, a catalyzed condensation polymerization has
been found to give high M
w
PLA, when carried out in a
high boiling point solvent at reduced pressure. Alterna-
tively, the low-M
w
prepolymer is depolymerized to pro-
duce lactide (the cyclic dimmer of LA), and then metal-
catalyzed ring opening polymerization of lactide is
performed to produce high-M
w
PLA with good mechan-
ical properties. Its mechanical properties can be modied
by varying its M
w
and its crystallinity. Its properties can
also be modied by copolymerization of the LA with
caprolactone or glycolic acid. PLA resins are being de-
veloped and marketed through a number of commercial
efforts for different applications. PLA is thermoplastic,
and can be processed by most common methods, includ-
ing ber spun. As a monomer, lactic acid can be produced
in chiral forms by fermentation of corn and other agricul-
tural resources [25]. The mechanical properties of PLA
have been extensively studied as a biomaterial in the
medicine, but only recently it has been used as a polymer
matrix in eco-composites [26]. Its applicability and use in
eco-composites is still limited by its high price when
compared with other biodegradable polymers.
Xia et al. [27] investigated the use of PLA resin rein-
forced with kenaf bers for the interior parts of its Prins
hybrid car. In 2002, Cargill-Dow LLC started up a com-
mercial polylactide plant, with the aim of production of
PLA bers for textiles and nonwovens, PLA lm pack-
aging applications, and rigid thermoformed PLA contain-
ers [28].
The chemosynthetic polymers are another large class of
degradable polymers, and are actually a family of poly-
esters. PCL is one of the representatives of this class of
polymers. PCL is hydrophobic, commercially available
thermoplastic aliphatic polyester with good mechanical
properties. It is prepared by ring opening polymerization
of -caprolactone. The degradable synthetic polyesters,
polyglucolic acid, and PCL are susceptible to hydrolytic
degradation, because the ester groups are separated by
CH
2
groups, which impart some exibility to the chain.
Even when they are in highly crystalline forms, the ex-
ibility allows penetration of water molecules [25].
Polyester amides that can be found commercially (BAK
1095 and BAK 2195) belong to the chemo-synthetic
biodegradable polymers as well. These polymers com-
mercially appeared in 1995 by Bayer AG. Mohanty et al.
have reported biodegradable jute/BAK 1095 composites
[29]. Novel eco-friendly bio-composites based on BAK
have been developed recently [30]. It was shown that the
efciency of BAK reinforcement is strongly dependent on
the surface modication, but it is also completely biode-
gradable. For these reasons, Bayer AG has recently quit
the production of BAK, since there is no economical
justication for continuing this costly effort.
The poly(itaconic acid esters) could also be an important
polymers, because of the fact that itaconic acid is not only
an oil-based product, but it can also be obtained by
fermentation process of molds and various carbohydrates.
Poly(dicyclohexyl itaconate) is especially interesting
polymer, with properties that could be signicantly mod-
ied when blended with other thermoplastic polymers
[31, 32]
It can be concluded that the last group of biodegradable
polymers, i.e. chemo-synthetic, are generally polyesters.
A common feature of all polyesters is the very reactive
ester functional group, which could have signicant role
in tailoring the interface between the polymer matrix and
NFs as reinforcement.
Another polymer, although not biodegradable, that could
be found as a polymer matrix in numerous eco-friendly
composites is PP. As an oil-based product, PP could not
be classied as a biodegradable polymer, but by introduc-
ing thermo-sensitive catalysts to increase the degradabil-
ity, PP takes an important place in eco-composite mate-
rials. For example, Mohanty et al. have demonstrated that
the NF reinforced PP composites have potential to replace
glass-PP composites [33]. It has also been reported that
PP can be effectively modied by maleic anhydride.
Maleic anhydride provides polar interactions and co-
valently links PP to the hydroxyl groups of the cellulose
ber [34]. Special attention has been paid to the modi-
cation of bers with specic chemical treatments to im-
prove the adhesion with polyolen matrices. Table 3
shows some of the mechanical properties reported in the
literature for several thermoplastic matrices, reinforced
with NFs.
NATURAL FIBERS AS REINFORCEMENTS FOR
ECO-COMPOSITES
In the last decade, there is a growing interest in NF
reinforced composites because of their high performance in
terms of mechanical properties, signicant processing ad-
vantages, chemical resistance, and low cost/low density
ratio [13, 35, 36]. On the other hand, for environmental
reasons, there is an increased interest in replacing reinforce-
ment materials (inorganic llers and bers) with renewable
organic materials.
TABLE 3. Tensile properties of polyolene composites with 20% of
natural bers.
Composite
Modulus
(MPa)
Elongation
at break (%)
Strength
(MPa)
PP/Bamboo 2500 / 16
PP/sugar cane 600 8.0 17
LDPE/short sisal 453 10 12.5
LDPE/treat sisal 926 12 16.5
100 POLYMER COMPOSITES2007 DOI 10.1002/pc
NFs represent environmentally friendly alternatives to
conventional reinforcing bers (glass, carbon, kevlar). Ad-
vantages of NF over traditional ones are low cost, high
toughness, low density, good specic strength properties,
reduced tool wear (nonabrasive to processing equipment),
enhanced energy recovery, CO
2
neutral when burned, bio-
degradability. Because of their hollow and cellular nature,
NF perform as acoustic and thermal insulators, and exhibit
reduced bulk density [35, 37]. Depending on their perfor-
mance when they are included in the polymer matrix, ligno-
cellulosic bers can be classied in three categories: (1)
wood our particulate, which increases the tensile and ex-
ural modulus of the composites, (2) bers of higher aspect
ratio that contribute to improve the composites modulus and
strength when suitable additives are used to regulate the
stress transfer between the matrix and the bers, (3) long
NFs with highest efciency amongst the lignocellulosic
reinforcements. The most efcient NFs have been consid-
ered those that have high cellulose content coupled with a
low microbrile angle, resulting in high lament mechani-
cal properties.
Depending on their origin, NFs can be grouped into seed,
bast, leaf, and fruit qualities. The bast and leaf (hard ber)
types are the most commonly used in composite applica-
tions [38, 39]. Examples of bast bers include hemp, jute,
ax, ramie, and kenaf. Leaf bers include sisal, pineapple,
leaf ber, banana. The characteristic properties of NF vary
considerably, depending not only on their origin, but also on
the quality of plants location, the age of the plant, and the
preconditioning [38].
The strength characteristics (Tables 4 and 5) of NF
depend on the properties of the individual constituents, the
brillar structure, and the lamellae matrix [40]. For an
understanding of the mechanical properties and durability of
bers, the amount of major structural constituents of the
bers, cellulose, hemicellulose, and lignin should be known
[41]. Chemical composition and structural parameters of
some NFs are given in Table 6.
NFs exhibit considerable variation in diameter, along
with the length of individual laments (Table 7). The qual-
ity and overall properties of bers depend also on factors
such as size, maturity, and processing methods adopted for
the extraction of ber [42].
The properties such as density, electrical resistivity, ul-
timate tensile strength, and initial modulus are related to the
internal structure and chemical composition of bers. NFs
are complex in their chemical structure; generally they are
lignocellulosic, consisting of helically wound cellulose mi-
crobrils in an amorphous matrix of lignin and hemi-cellu-
lose. Mechanical properties are determined mainly by the
cellulose content and microbrillar angle. Youngs modulus
of NF decreases with the increase of diameter. A high
cellulose content and low microbril angle are desirable
properties of a ber to be used as reinforcement in polymer
composites [41] (Table 6). The mechanical properties of NF
are also signicantly related to the degree of polymerization
of cellulose in the ber.
The cells of ax ber consist mostly of pure cellulose,
being cemented as fascicle bundles by means of noncellu-
losic incrusting such as lignin, hemicellulose, pectin, pro-
tein or mineral substances, resins, tannins, dyers, and a
small amount of waxes and fat [38, 39]. A mature ax cell
wall consists of about 7075% cellulose, 15% hemicellu-
lose, and pectic materials. Cellulose is a natural polymer
with high strength and stiffness per weight, and it is the
building material of long brous cells. Selective removal of
noncellulosic compounds constitutes the main objective of
ber chemical treatment. Both the hemicellulosic and pectin
materials play important roles in ber bundle integration,
ber bundle strength, and individual ber strength as well as
water absorbency, swelling, elasticity, and wet strength. The
production of individual bers without the generation of
kink bands will generate bers with much higher intrinsic
ber strength, which is very useful for composite applica-
tion [41, 42].
Desirable properties for bers include excellent tensile
strength and modulus, high durability, low bulk density,
TABLE 4. Basic properties of some natural bers [40].
Fiber
Density
(g/cm
3
)
Elongation
at break
(%)
Fracture
stress
(MPa)
Young
modulus
(GPa)
Cotton 1.5 7.08.0 287597 5.512.6
Jute 1.31.46 1.51.8 393800 1030
Flax 1.41.5 2.73.2 3451500 1080
Hemp 1.48 1.6 270900 2070
Sisal 1.21.5 2.02.5 511700 3.098
Bamboo 0.8 / 3911000 4889
Soft wood 1.5 / 1000,0 40,0
Ramie 1.5 3.63.8 400938 44128
TABLE 5. Mechanical properties of natural bers when compared with conventional reinforcements [40].
Fiber
Specic
gravity
(g/cm
3
)
Tensile
strength
(GPa)
Tensile
modulus
(GPa)
Specic
strength
(GPa/g cm
3
)
Specic
modulus
(GPa/g cm
3
)
Cost
ratio
Sisal 1.20 0.080.5 398 0.070.42 382 1
Flax 1.20 2.00 85 1.60 71 1.5
E-Glass 2.60 3.50 72 1.35 28 3
Kevlar 1.44 3.90 131 2.71 91 18
Carbon (standard) 1.75 3.00 235 1.71 134 30
DOI 10.1002/pc POLYMER COMPOSITES2007 101
good moldability, and recyclability. NFs have an advantage
over conventional reinforcement bers in that they are less
expensive (Table 8), abundantly available from renewable
resources, and have a high specic strength. Application of
long NFs instead of short wood-bers, such as ax, kenaf,
and sisal, is reasonable in automobile sector because of the
specic modulus, close to that of glass-reinforced compos-
ites.
Until now, NFs were used in composites with unsatur-
ated polyesters, epoxides, and polyurethanes. Among them
epoxy resins are characterized with the best adhesion to-
ward NFs. The composites based on polyurethane matrices
and sisal are used for production of door panels in automo-
bile industry; they are characterized with increased strength
and sufcient stiffness to preserve their shape during ex-
ploitation. Thermoplastic polymers have signicant viscos-
ity, and therefore the bers wetting is difcult. On the other
hand, increasing the temperature to lower the viscosity
could cause some undesirable effects, such as damage and
destruction of the NFs. The application of appropriate com-
patibilizers in these systems is practically unavoidable,
since otherwise the bers will start to behave as ller,
instead of reinforcement. A well-known example is maleic
anhydride modied polypropylene in PP matrix, causing a
signicant improvement of the mechanical properties of the
material [43].
Natural Fibers Modication
Some of the disadvantages and limitations of NFs, when
used as reinforcement for composites, are related to the lack
of proper interfacial adhesion, poor resistance to moisture
absorption, limited processing temperature to about 200C,
and low dimensional stability (shrinkage, swelling).
The ber/matrix interface plays an important role in the
physical and mechanical properties of composites. To im-
prove the interfacial properties, NFs are subjected to chem-
ical treatments such as dewaxing, mercerization, bleaching,
cyanoethylation, silane treatment, benzoylation, peroxide
treatment, isocyanate treatment, acrylation, acetylation, la-
tex coating, steam-explosion [37, 38, 44]. Research on a
cost-effective modication of NFs is necessary, since the
main market attraction of eco-composites is the competitive
cost of NFs. Surface modication of NF prior to their use in
composite materials is also needed to facilitate ber disper-
sion and induce bond formation between the ber and the
polymer matrix. The ber-to-ber interaction in NF, result-
ing from intermolecular hydrogen bonding, usually restricts
the dispersion of bers in the polymer matrix. On the other
hand, the use of surface treatments has the disadvantage of
increasing the cost of the nal product.
Chemical modication can be dened as a chemical
reaction between some reactive constituents of the NF and
chemical reagent, with or without a catalyst, to form a
covalent bond between the two. As the NFs result from the
chemistry of cell wall components, modication of the
chemistry of cell wall polymers can change the basic prop-
erties of a ber. The chemicals to be used for chemical
modication must be capable of reacting with lignocellu-
losic hydroxyls under neutral, mild alkaline, or acid condi-
tions at temperatures below 150C. The chemical system
should be simple and capable of swelling the structure to
facilitate penetration. The complete molecule should react
quickly with the lignocelluloses components yielding stable
chemical bonds, and the treated lignocelluloses must still
possess the desirable properties of untreated lignocellu-
losics. Therefore, the ber strength should not be reduced,
TABLE 7. Dimensions of some natural bers [40].
Fiber Average length (mm) Width (mm)
Cotton 1060 0.02
Flax 560 0.0120.027
Hemp 555 0.0250.050
Juta 1.55 0.02
Straw 13.4 0.023
Kenaf 2.64 0.0180.024
TABLE 6. Chemical composition and structural parameters of natural bers
a
[41].
Fiber
Cellulose
(%)
Hemi-cellulose
(%)
Lignin
(%)
Extractives
(%)
Ash
(%)
Pectin
(%)
Wax
(%)
Microbril/spiral
angle ()
Moisture
content
(%)
Jute 6171 13.620.4 1213 / / 0.2 0.5 8.0 12.6
Flax 7178 18.620.6 2.2 2.3 1.5 2.2 1.7 10.0 10.0
Hemp 70.274.4 17.922.4 3.75.7 3.6 2.6 0.9 0.8 6.2 10.8
Kenaf 5357 1519 5.99.3 3.2 4.7 / / / /
Sisal 6778 1014.2 811 / 1 10 2.0 20.0 11.0
Cotton 82.7 5.7 / / / / 0.6 / /
a
Literature data on chemical composition of NF have been inconsistent, and for this reason the range of chemical constituents given in this table should
be viewed with caution.
TABLE 8. Comparison of the price of some synthetic and natural
bers.
Fiber Carbon Steel Glass Sisal Jute Coir
Cost (USD $/kg) 200 30 3.25 0.36 0.30 0.25
Modulus Cost (GPa kg/$) 2.0 6.7 21.5 41.7 43.3 20.0
102 POLYMER COMPOSITES2007 DOI 10.1002/pc
no change in color, good electrical insulation properties
should be retained, and the hydrophobic nature of reagent
should be selected accordingly.
1. Alkali treatment of NFs, also called mercerization, is the
usual method to produce high quality bers. By remov-
ing the natural and articial impurities, alkali treatment
leads to brillation of the ber bundle into smaller bers.
In other words, alkali treatment reduces the ber diam-
eter and thereby increases the aspect ratio [38, 42].
Therefore, the development of a rough surface topogra-
phy and enhancement in aspect ratio offer better ber
matrix interface adhesion and an increase in mechanical
properties. Alkali treatment increases surface roughness,
resulting in better mechanical interlocking and the
amount of cellulose exposed on the ber surface. This
increases the number of possible reaction sites and al-
lows better ber wetting [38]. As a result of alkali
treatment, the following reaction [Eq. (1)] takes place:
FiberOH NaOH 3FiberONa

H
2
O (1)
Moreover, alkali treatment inuences the chemical compo-
sition of the bers, the degree of polymerization, and mo-
lecular orientation of the cellulose crystallites, due to the
removal of cementing substances such as lignin and hemi-
cellulose. Consequently, mercerization has lasting effect on
the mechanical behavior of bers, especially on their
strength and stiffness. Several studies conducted on alkali
treatment reported that mercerization led to increase of the
amount of amorphous cellulose at the expense of crystalline
cellulose, and removal of hydrogen bonding in the network
structure [37, 38].
2. Acetylation of NFs is a well-known esterication method
of introducing plasticization to cellulosic bers. Acety-
lation has been extensively applied to wood cellulose to
stabilize the cell wall, improving dimensional stability
and environmental degradation. One of the modication
techniques employed by the Okura Company in Japan
was to produce esteried woods, which would be molded
into plastic sheets by hot pressing [38].
Acetylation is based on the reaction of cell wall hydroxyl
groups of lignocellulosic materials with acetic or propionic
anhydride at elevated temperature (usually without a cata-
lyst) [Eq. (2)]:
FiberOH (H3CCO)
2
O
3FiberOOCOCH
3
CH
3
COOH (2)
According to Rowell [43], the hydroxyl groups that react
with the reagent are those of lignin and hemicelluloses
(amorphous material), while the hydroxyl groups of cellu-
lose (crystalline material), being closely packed with hydro-
gen bonds, prevent the diffusion of the reagent and thus
result in very low extents of reaction. It has been shown that
esterication improves the dispersion of lignocellulosic ma-
terials in a polymer matrix, as well as the dimensional
stability and interface of the nal composites [38, 40, 43].
3. Another effective method of surface chemical modica-
tion of NFs is graft copolymerization. Optimized vinyl
grafted NFs, consisting of orderly arrangement of grafted
segments, act as compatible reinforcing bers with sev-
eral resin systems to obtain better bermatrix adhesion
of the resulting eco-composites [38].
4. Isocyanate has a functional group ONACAO, which is
very susceptible to reaction with the hydroxyl group of
cellulose and lignin in the bers, and forms strong co-
valent bonds, thereby creating better compatibility with
the polymer matrix in the composites [Eq. (3)]. Kokta et
al. have studied the performance of isocyanate as a
coupling agent. Isocyanates provided better interaction
with thermoplastics resulting in superior properties. Iso-
cyanates could act as a promoter, or as an inhibitor of the
interaction [45].
FiberOOHRONACAO 3FiberOOOCONHR
(3)
5. Peroxide-Induced adhesion in cellulose ber-reinforced
thermoplastic composites has attracted the attention of
various researchers because of easy processability and
improvement in mechanical properties [35]. Sapieha et
al. have found that addition of a small amount of benzoyl
peroxide or dicumyl peroxide to cellulosepolymer (LL-
DPE) systems during the processing improved the com-
posite mechanical properties [45]. The improvement of
mechanical properties is attributed to the peroxide-in-
duced grafting of polyethylene onto cellulose surfaces,
following the reaction [Eq. (4)]:
ROOOR 32RO. (4)
RO.OCelluloseOH 3ROOHOCellulose.
6. Several authors have investigated the effect of silane
coupling agent on the interface performance of NF rein-
forced composites. The ber-surface silanization re-
sulted in better interfacial load transfer efciency, be-
cause of the increased adhesion. Hydrogen and covalent
bonding mechanisms could be found in the NF-silane
system [Eq. (5)]. It was assumed that the hydrocarbon
chains provided by the silane application inuenced the
wettability of the bers, thus improving the chemical
afnity to the polymer matrix. Silane treatment also
enhanced the tensile strength of the composite [45],
minimized the effect of moisture on composite proper-
ties, increased the adhesion, and thereby the composite
strength.
FiberOH RSi(OH)3 3FiberO
OH
Si
OH
R (5)
DOI 10.1002/pc POLYMER COMPOSITES2007 103
7. Acrylation treatment, maleated polypropylene/maleic
anhydride treatment, and titanate treatment of cellulosic
bers have also been reported [46]. The acrylation treat-
ment resulted in high strain values of the composites.
The composites ability to withstand the applied exural
stress is manifested by higher strain values, which indi-
cate the elastic nature of the material. Maleic anhydride
grafted polypropylene (MAPP) has been widely used as
a coupling agent or as a compatibilizer in NF-reinforced
polypropylene composites. The treatment of NFs with
MAPP copolymer provides covalent bonds across the
interface. Through such a treatment, the surface energy
of the bers is increased, thereby providing better wet-
tability and high interfacial adhesion. Many other com-
pounds (such as chromium complexes and titanates) can
be used as coupling agents. The processing of compos-
ites with titanate coupling agents found that the deposi-
tion of a monolayer of organ functional titanate elimi-
nated the water of hydration, thus enhancing the
dispersion and compatibility at the interface.
Concerning the second drawback, moisture absorption,
NFs are hygroscopic in nature, and they absorb or release
moisture depending on environmental conditions. Major
limitations of using NFs in durable composite applications
are their high moisture absorption and poor dimensional
stability (swelling). Fiber swelling can lead to micro crack-
ing of the composites and degradation of their mechanical
properties. This problem can be overcome by treating these
bers with suitable chemicals to decrease the hydroxyl
group in the bers. According to Stamboulis et al. (2000),
moisture absorption and swelling of treated ax ber com-
posites is 30% lower than that of composites with un-
treated ax bers [47]. Strong intermolecular ber/matrix
bonding decreases the rate of moisture absorption in eco-
composites. It is difcult to eliminate totally the moisture
absorption without using expensive surface barriers on the
composite surface.
ECO-COMPOSITES
In this respect, NF-reinforced composites (so-called eco-
composites) are subject of many scientic and research
projects as well as many commercial programs [48, 49]. The
growing global environmental and social concern, high rate
of depletion of petroleum resources, and new environmental
regulations have forced the search for new composites and
green materials that are compatible with the environment,
since the preexisting technology and machinery for blend-
ing, forming, and processing of these composites offer easy
and cost-effective processes, so the market for eco-compos-
ites seems to be promising and realizable for double-digit
growth in the near future [4951].
Generally, production procedures for NF composites
(with certain adjustments) are quite similar to those for the
production of ber glass composites. During the processing,
temperature must not exceed 200C, and the retention time
of the material exposed to high temperatures should not be
too long, to avoid destruction of the bers. Very common
technologies for NF composite materials are resin transfer
molding, vacuum injection molding, structural reacting in-
jection molding, injection molding, and compression mold-
ing.
NFs are used in the form of nonwoven textile, fabrics,
mat (NMT-mat of thermoplastic matrices and NFs), SMC,
and BMC for compression molding, and hybrid mats (NF/
PP, for example) and sometimes as UD-reinforcing bers
[52].
Daimler Chrysler has nished the so-called EXPRESS
process for thermoplastic matrix/NFs composites that actu-
ally represents compression under pressure of NFs mat.
Thermoplastic matrices (in melt) are introduced into the
mold through the extruder, and mat layers are alternately
situated in the mold after each loading of polymer melt
together with the additives [53].
It is very important to note that the cycle time of one
NMT is comparable with the cycle time for production of
thermoplastics reinforced with long bers. (LFT-D/NF)
[54]. LFT-D process is developed for direct introduction of
glass bers in polymer melt of PP. LFT-D/NF represents
process of reinforcement of thermoplastic polymers with
direct introducing of long NFs, resulting in long reinforced
compound that could be processed and pressed in one
stadium.
During the processing of NFs, various composites pro-
duction procedures result in materials with various proper-
ties, because of the different degrees of ber damages and
distribution. The inuence of ber length on the mechanical
properties could be explained by the fact that long bers
tend to bend, entangle, and scratch during the processing
and pressing procedures. This causes a decrease of the
effective ber lengths below the critical length (l
c
) in certain
direction, thus resulting in deterioration of the mechanical
properties [55].
The German institute of agricultural engineering from
Potsdam has presented a simple technology, suitable for
processing unretted hemp, ax, coir, and other bast ber
plants into composites for heat and sound insulation panels,
furniture boards, and mats for the automotive industry. A
capacity of up to 3 t/h of raw materials input (with ber
yields efciency of up to 29%) ensures economical and
protable ber production and marketing [50].
Tipco Industries from India launched a commercial pro-
duction of TIPWOOD50EX eco-friendly building mate-
rial, applicable for door panels, trims, ofce cabinet, marine
ooring, furniture, mono-block chairs, and various articial
wood product [51].
The US company Phenix Biocomposites LLC uses
wheat straw in its Biober composites, and sunower
hulls in its Dakota Burl composites, both intended for fur-
niture applications [48].
Signicant research work on eco composites has been
done at the German Aerospace Center (DLR). Recently,
Riedel and Nickel have reported on the state-of-the art and
future perspectives of eco composites, mainly based on UD
104 POLYMER COMPOSITES2007 DOI 10.1002/pc
laminates of hamp and ax bers in thermoplastics (PHB-
Biopol, PCL-Capa, Starch based-SCONACELL A) [16].
Takagi and coworkers have reported composites based on
modied starch resin, hemp, and bamboo bers [56]. Uni-
directional composites of hemp ber and starch-based resin
have tensile strength in the range of 200 MPa, making them
useful for structural applications.
NEC Corp. (NEC, Tokyo, Japan) and UNITIKA (Tokyo,
Japan) announced March 2006 the joint development of
kenaf ber-reinforced PLA [57]. More recent research, car-
ried out by both companies, involved further improvement
of the characteristics of the kenaf ber/PLA composites, to
allow its application in cell phones. Its moisture resistance
and the fall impact durability were improved by using the
latters commercialized PLA TERRAMAC.
Another group of research-attractive eco-composites are
plant ber based soy protein composites. Lodha and Ne-
travali have prepared composites of chopped ramie bers
and soy protein isolate, with signicant strength improve-
ment [58]. Nam and Netravali announced UD ramie -
ber/soy protein concentrate composites (65% of ber con-
tent) with strength of 275 MPa, suitable for indoor
applications in housing and transportation [48]. Chaba and
Netravali have worked on fabrication and characterization
of green UD composites, based on ax yarn and cross-
linked soy our resin. The composites specimens exhibited
fracture stress and Youngs modulus of 259.5 MPa and 3.71
GPa, respectively, and exura strength of 174 MPa in
longitudinal direction [48]. These properties seem to be
sufcient for considering these green composites for indoor
structural applications. Phoenix bio-composites commer-
cialized fully degradable Environ composite, based on
soy our with recycled paper. These eco-composite mate-
rials could be used for furniture and architectural nonstruc-
tural applications [58]. Chiellinis research group from the
University of Pisa reported their research on injection
molded eco-composites based on corn and orange bers and
poly(vinyl alcohol) [59]. These composites showed small
changes in their mechanical properties after conditioning at
variable relative humidity, and even after complete soaking
in water. Composites, tested after storage for 1 year at 50%
relative humidity and 23C, exhibited mechanical properties
similar to those of freshly prepared materials.
Signicant research efforts have been spent on eco-
composites based on recyclable polymer with NFs. Cur-
rently, the widely favored PP is used for great number of
recyclable eco-composites. Visteon and Technilin devel-
oped their own ax/PP material R-Flax, based on a low-
cost ber. Taking into account very high specications from
Opel, which include critical safety requirements, R-Flax
can be used for interior items (door panels), where its
aesthetic qualities can even add to its consumer appeal.
Tech-Wood International from the Netherlands announced
its Tech-Wood eco-composite, aimed for construction
elements [48]. Tech-Wood eco-composite material con-
tains 70% pine-wood bers and 30% compatibilized PP.
The textile Institute from Aachen, Germany, reported use of
recycled bers (including carpet trimmings) in the automo-
bile industry [60]. Headliners based on ax-PP were shred-
ded, granulated, and processed. Old carpet material was
sorted into two layers using IR spectroscopy and image
analysis, and PP secondary bers were extracted from the
shredded material with a recovery rate of about 50%. These
secondary bers were then used with ax bers to obtain a
hybrid ax-PP yarn by friction spinning. The nal products
were obtained by thermoforming. Composite mechanical
properties were satisfactory, as were product odor assess-
ments. The headliner is the costliest part of a vehicle inte-
rior, and it is perhaps questionable whether or not the
process is economical [60]. NFC Wageningen UR from
Germany has announced a patent and commercial produc-
tion of NF reinforced PP composite granules, GreenGran
NF30, 50, 70, by extrusion technology [61]. Because of its
high NF content, GreenGran NF30, 50, 70 granules have
better insulating properties (heat, sound), better ame retar-
dancy properties, improved dimension stability at higher
temperatures, and no sharp edges after a car crash (safety
requirements for automotive interior parts).
Yang et al. have studied the possibility of using ligno-
cellulosic rice-husk our (RHF) as the reinforcing ller in
polyolene composites [62]. They have designed RHF/
Polypropylene composites with four levels of ller loading
(10, 20, 30, and 40 wt%). The results of tensile test per-
formed at six levels of temperatures and various crosshead
speed have shown that tensile strength of the composites
slightly decreased as the ller load increased. Applying the
method used in the wood-based panel industry, composite
insulation boards were produced with rice straw [63]. Com-
posite boards with specic gravity of 0.8 have slightly better
bending modulus than wood particle board (as a control
board) at a rice straw content of 10 wt%, and show no
differences from the control boards at a 20 wt% rice straw
level.
At the last Eco-comp 2005 conference, prof. Nishino
from Kobe University, Japan, reported on all-cellulose
composites, prepared by partial dissolving of cellulose ber
surfaces [64]. By optimizing the immersing conditions of
cellulose bers into solvent, the bers (with partially dis-
solved surfaces) have been unied by compression, fol-
lowed by drying. These all-cellulose composites showed
excellent mechanical and thermal properties [64].
In the framework of ECO-PCCM project, supported by
the EU FP6-INCO program, eco-composites based on PLA,
PHBV, and PP reinforced with different NFs are aimed for
construction panels and different elements for eco-houses
[65], and some of the results were presented at Eco-com-
posites 2005 [66].
CONCLUSION
The future opportunities for further research on eco-
composites involve two basic routes. One is being con-
ducted to develop new pathways to synthesize inexpensive
biodegradable polymers with improved mechanical and
DOI 10.1002/pc POLYMER COMPOSITES2007 105
thermal properties. The second eld of research is on a cost
effective modication of NFs, since the main market at-
traction of eco-composites is the competitive cost of NFs.
The reports, related to the comparison of LCA assessment
of NF composites with glass ber reinforced composites,
have found that NF composites are superior in the specic
automotive industry applications, rst of all due to the lower
weight of NF composites. Further evaluation of the eco
performance of NF composites and LCA studies should
provide further conrmation of their green character [67].
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