Green Composites: An Overview
Elisa Zini, Mariastella Scandola
University of Bologna, Chemistry Department, G. Ciamician and INSTM, UdR Bologna, 40126 Bologna, Italy
The use of natural bers to reinforce polymers is a
well-established practice, and biocomposites are
increasingly used in sectors such as automotive and
construction. Green composites are a specic class of
biocomposites, where a bio-based polymer matrix is
reinforced by natural bers, and they represent an
emerging area in polymer science. This work discusses
the environmental benets deriving from the use of
natural bers in polymer composites and from substi-
tution of oil-derived polymers by bio-based polymers
as matrix material. New trends in the selection of natu-
ral bers, that is, from waste rather than from valuable
crops are described. Recently developed thermoplastic
and thermosetting bio-based polymers are reviewed,
and commercially available green composites obtained
thereof are discussed. POLYM. COMPOS., 32:19051915,
2011. 2011 Society of Plastics Engineers
INTRODUCTION
As early as in 1908, the rst natural-ber-based poly-
mer composites, constituted of phenol or melamine-form-
aldehyde resins reinforced with cotton or paper, appeared
[1]. Reinforced plastics, especially those reinforced with
glass bers (GRP), reached the commodity status in the
1940s due to their low cost and are largely diffused nowa-
days [2] in a variety of sectors, that is, automotive, con-
struction, electro/electronics, and sports (Fig. 1). In tech-
nologically demanding applications, such as aviation,
wind power, and sports, glass bers are often substituted
by highly performing, higher cost bers, such as carbon
or polymeric bers (aramids).
A problem associated with the use of glass bers in
composites for the transport sector is the high density of
glass (2.5 g/cm3) that signicantly increases the specic
weight of the polymer matrix, leading to materials that, in
automotive applications, have a negative environmental
impact in terms of energy consumption. Another draw-
back of GRPs is associated with their end-life disposal:
Correspondence to: Mariastella Scandola; e-mail: mariastella.scandola@
unibo.it
Contract grant sponsors: INSTM, MIUR (Ministero Istruzione, Universita`,
Ricerca).
DOI 10.1002/pc.21224
Published online in Wiley Online Library (wileyonlinelibrary.com).
V
C 2011 Society of Plastics Engineers
POLYMER COMPOSITES-2011
upon incineration of the composite, for example, glass
bers (typically present up to 50% by volume) remain as
unburned residues.
Vegetable bers, extensively explored since 1990 by
research institutions and automotive companies as an
environmentally friendly alternative to traditional glass
ber reinforcement, are characterized by low density
(
1.5 g/cm3) and they burn if incinerated. Moreover, they
are low cost, and they are intrinsically biodegradable. At
the beginning of this century, after intense research stud-
ies, polymers reinforced with natural bers (NFC), com-
monly named biocomposites, started to be industrially
applied not only in the automotive and building sectors,
but also in the broad area of consumer goods. A recent
work by La Mantia et al. [3] comprehensively reviewed
such type of NFCs with particular emphasis on strategies
to overcome composite processability problems and
improving composite performance. The polymers consti-
tuting the matrix in such new materials were mainly oil-
derived polyolens. Nowadays, however, public concern
about the environment and the availability of limited fos-
sil fuel resources has forced governments, companies, and
scientists to nd alternatives to crude oil and to develop
sustainable materials from renewable resources. Hence the
latest innovation in the eld of biocomposites is the sub-
stitution of oil-derived polymers with polymers from
renewable resources (bio-based polymers) as the matrix
component. Such materials are named green compo-
sites [1, 4], a term that indicates that the composite as a
whole (both matrix and reinforcement) originates from
renewable resources. Worth pointing out is that some
Authors label as green composites all NFCs [3], irre-
spective of the nature of the polymeric matrix (both bio-
and oil-based). In this work, we use the term green com-
posites onlyand specicallyfor wholly bio-based
composites, that is, both bers and matrix from renewable
resources.
In an economic situation, such as the present one,
where oil price increases, the use of green composites is
advantageous not only for the environment but also from
an economical viewpoint.
This work aims at providing an updated overview on
green composites, with attention both to their commercial
availability and to the latest research activities mainly

FIG. 1. Industrial application sectors of glass ber-reinforced compo-
sites in Europe (year 2010) [2].
oriented to mechanical properties optimization and to
exploring the potential of alternative natural ber resour-
ces. The waste management options of green composites
will be also described, and the environmental benets will
be specically pointed out. Bio-derived reinforcements
other than natural bers (cellulose whiskers, etc.) are
intentionally excluded from this work.
NATURAL FIBERS AS COMPOSITE
REINFORCEMENT
Natural bers can be classied into plant-based and
animal-based bers as shown in Figure 2. Vegetable bers
are mainly constituted of polysaccharides while animal
bers are proteins. To be used as reinforcement, pure
bers need to be extracted and separated from all cement-
ing substances that are present in the natural plant or ani-
mal raw material (hemicelluloses, lignin, wax, proteins,
etc.). Wood, that is, a brous composite in itself is com-
monly used in the form of wood pulp.
Table 1 compares some important physical properties
of the most extensively studied bers for polymer com-
posite applications. It is evident from the density data in
Table 1 that all natural bers possess lower density than
glass bers. This property makes natural bers particu-
FIG. 2. Classication of natural bers.
1906 POLYMER COMPOSITES-2011
larly suitable as glass ber substitutes for applications in
the automotive sector, where an equivalent ber loading
corresponds to an overall weight reduction of the compos-
ite. When ber mechanical properties are compared (Ta-
ble 1), it is clear that those of natural bers are lower
than those of glass, carbon, and aramid bers. However,
if the different density is taken into account, the specic
mechanical properties of natural bers come closer to
those of synthetic bers, and, in particular, the specic
tensile strength of ax bers is comparable with that of
glass bers. Additional advantages of the use of natural
bers in composites are their renewability, biodegradabil-
ity, nontoxicity, good insulation properties, low machine
wear, etc. A broad variety of bers with different thermal
and mechanical properties are abundantly synthesized in
nature and are available for the development of high-per-
formance biocomposites.
Vegetable Fibers
A number of reviews about the properties of natural
bers and their use in polymeric composites can be found
in the literature [1, 5, 7, 13, 14]. Most studies are focused
on vegetable bers and in particular on bast bers (ax,
hemp, jute, and kenaf). This choice is dictated by their
superior mechanical properties (Table 1) and by the possi-
bility to easily separate clean bers from the cementing
substances in the bast. However, unlike synthetic bers,
vegetable bers have signicantly greater variability in
their mechanical properties (Table 1) as a consequence of
age of the plant, geographical and climatic growth condi-
tions, harvesting methods, purication technology, etc.
Moreover, availability of large quantities of a specic
type of bast ber depends on the geographical area of cul-
tivation: in temperate regions, ax and hemp are domi-
nant, whereas, in tropical regions, the use of jute and
kenaf prevails [13]. Primary problems that must be over-
come for a sound industrial application of cellulosic bers
in biocomposites are variability of ber quality and
changing seasonal and geographical availability. Another
DOI 10.1002/pc
 TABLE 1. Physical properties of some natural and synthetic bers.

Density Elongation Youngs Tensile Specic tensile Water

Fiber (g/cm3) (%) modulus (GPa) strength (MPa) strength absorption (%) References

E-glass 2.5 2.5 70 20003500 8001400 5

Aramide 1.4 3.33.7 6367 30003150 21402250 5, 6
Carbon 1.4 1.41.8 230240 4000 2860 5
Flax 1.5 1.23.2 2780 3451500 2301000 7 4, 5
Cotton 1.51.6 3.010.0 5.512.6 287800 190530 825 46
Jute 1.31.5 1.51.8 1055 393800 300610 12 46
Hemp 1.5 1.6 70 550900 370600 8 4
Sisal 1.31.5 2.02.5 9.428 511635 390490 11 46
Ramie 1.5 2.03.8 44128 400938 270620 1217 4, 5
Coir 1.2 1530 46 131220 110180 10 46
Soft wood kraft 1.5 40 1000 670 5
Chicken feathers 0.89 310 100200 112220 7, 8
Silkworm silk 1.31.4 15 0.5 8 9-11

potential drawback of vegetable bers is their tendency to sile, impact, and exural properties of the soy-based resin
absorb water (moisture content between 5 and 10% by were signicantly enhanced.
weight, Table 1) due to the high hydroxyl content of cel-
lulose. As a consequence, particular attention must be
paid during composite processing (i.e., through careful Animal Fibers
predrying) in order to avoid absorbed water evaporation
Recently, animal-based bers have attracted increasing
that leads to porous products. Moreover, the presence of
attention as potential high performance reinforcing bers.
hydrophilic groups at the ber surface does not favor
Animal-based bers that are traditionally used for the
compatibility between natural bers and typically hydro-
manufacture of garments (wool [17] and silk [9, 18])
phobic polymer matrices; hence, natural bers tend to
have been tested as reinforcements for biocomposites.
form aggregates during composite processing and attain a
Wool keratin bers, for example, are characterized by sur-
poor degree of dispersion. Notwithstanding the above-
face toughness, exibility, high aspect ratio, and are less
mentioned problems, the drawing force to the successful
hydrophilic than cellulose bers. Interestingly, feather
use of vegetable bers in polymer composites is their
keratin bers possess a hollow structure, so that a given
availability in large quantities at low cost, their good me-
volume of bers contains a signicant volume of air,
chanical properties, and a number of well-assessed proc-
resulting in a very low density (
0.9 g/cm3) and low-
essing protocols.
dielectric constant (k
1.7) that suggests their use in com-
In addition to the widely used bast bers, increasing
posites for electronic applications [19]. Cocoons of silk-
interest is presently directed toward other vegetable rein-
worm silk are made of a single continuous silk strand
forcements that may substitute valuable crops as ber raw
with length in the range of 10001500 m, where the -
materials (some of them are included in Fig. 2). In view
broin laments are cemented by sericin. Mechanical prop-
of better land saving, for example, perennial grasses such
erties of silk vary considerably with animal species and
as Indiangrass or switchgrass have been investigated as
with spinning conditions. The silkworm, for example, pro-
reinforcing agents. Switchgrass, which grows on marginal
duces stronger and more brittle bers at high spinning
lands, is a self-seeding crop, which requires low amounts
speeds, whereas when the spinning velocity decreases, the
of fertilizers. Switchgrass stems were studied to reinforce
produced bers are weaker and more extensible [10].
PP for industrial applications in the area of automotive
Thermal stability of silk bers is relatively low (\1408C),
interiors [15], and it was found that, compared to a jute-
but they resist oxidation and they display antibacterial
PP composite of the same density, the composite rein-
and UV-resistant properties. Biocomposites reinforced
forced by switchgrass stems had higher modulus, higher
with silk bers have been investigated in view of bioen-
exural strength, higher impact resistance, and similar
gineering applications such as scaffolds for tissue engi-
sound absorption properties. Another example is Indian-
neering and bone xators [4].
grass, a perennial native grass of North America that
readily invades sites with bare soil such as old abandoned
farm elds, reclaimed lands, and roadsides. Indiangrass
Fibers from Waste
was tested as reinforcement of a polymer matrix made of
a soy-based aliphaticaromatic copolyester [16], and it In the area of polymer composites reinforced with veg-
was found that, although raw Indiangrass improved tensile etable bers, an interesting approach to land preservation
and exural properties but not impact strength, by pre- is the extraction of bers from agricultural waste.
treating Indiangrass bers with an alkali solution, the ten- Attempts have been made to use sunower stalk [20], ba-

DOI 10.1002/pc POLYMER COMPOSITES-2011 1907

gasse [20], rice husk [21], wheat straw [22, 23], soy stalk
[23], and cornhusk [24] as sources of cellulosic bers to
be used as reinforcement in biocomposites. Cellulose
bers having properties intermediate between those of
cotton and ax were successfully extracted from cornhusk
[24], a by-product of corn production that is worldwide
available and has limited commercial value. In addition,
modied and unmodied rice husk bers were investi- ber extraction, compatibilizer production, intermediate
gated by Favaro et al. [21] as reinforcement of postcon-
sumer high-density polyethylene (PE), while Habibi et al.
[25] used lignocellulosic bers extracted from Egyptian
agricultural residues (mainly cotton stalk, rice straw, ba-
gasse, and banana plant waste) to reinforce PE. The
results available to date suggest that the use of agricul-
tural by-products as a source of natural bers, by saving
land and natural resources required to grow new bers, is
benecial to agriculture and food production, and, in addi-
tion, it contributes solving the problem of agricultural
waste disposal.
Alternative potential sources of waste bers are some
animal-derived protein wastes, such as by-products from
the wool textile industry (poor quality raw wools not suit-
able for spinning), hair, and feather. In particular, chicken
feather bers can be obtained from the over four million
tons of waste generated by poultry industry worldwide ev-
ery year. The use of chicken feather bers (keratin bers)
as reinforcement in PE and in poly(lactic acid) (PLA) is
reported by Barone et al. [8] and by Cheng et al. [26],
respectively. The hollow structure of keratin bers, as
mentioned earlier, leads to an extremely low ber density
that can be exploited, for example, to obtain light-weight
materials for automotive applications. Another potential
application eld was explored by Hong and Wool who
developed a low-k dielectric composite, suitable for elec-
tronic applications, taking advantage of the low dielectric
constant of chicken feather bers (k
1.7) and using a
soybean-based resin as the polymer matrix [19]. Waste
wool bers were used in another study [27], where they
were successfully embedded in a polymeric lm-forming
matrix of cellulose acetate, obtaining a new composite
material, suitable for lm production, and lament spin-
ning with potential applications as compostable packag-
ing, agricultural lm, textile ber, etc.
Overall, the use of bers from waste (either agricul-
tural by-products or avian feathers) as reinforcement in
biocomposites offers a low cost and environmentally
friendly solution to waste disposal and a possibility for
farmers or poultry producers to gain a prot from waste.
Environmental Sustainability
Few studies are available in the literature concerning
the environmental advantages associated with the substitu-
tion of glass bers with natural bers that were reviewed
in an early study by Joshi et al. [28]. An interesting result
in this area concerns the cumulated energy demand that,
in the case of hemp ber production, was shown to be
1908 POLYMER COMPOSITES-2011
only 10% of that required for production of glass bers
[29]. A study by Corbiere-Nicollier et al. [30] reports the
life cycle assessment (LCA) of transport pallets made of
polypropylene (PP) reinforced with china reed ber in
comparison with the LCA of the same PP pallets rein-
forced with glass bers. The LCA study took into account
PP and glass ber production, china reed cultivation and
transport, pallet fabrication, use, and end of life disposal
through incineration. The comparison was made between
pallets with analogous mechanical properties in terms of
elastic modulus, that is, between a pallet containing 53%
by weight of china reed and another containing 42% by
weight of glass bers. Overall, the natural ber-reinforced
(NFR) pallet resulted in signicantly lower environmental
impacts compared to the glass ber-reinforced (GFR) pal-
let, except for nitrate and phosphate emissions in water
associated with china reed cultivation. The study was con-
ducted under different scenarios (recycling at various per-
centages, pallet life, plastic content, and changes in trans-
port distances), and the conclusion was that the NFR pal-
let was always environmentally superior, provided that
the pallet had a lifetime of at least 3 years. In case of
shorter lifetime, a higher number of pallets is required,
and the environmental advantages of the NFR pallet are
lost.
Another comparative study by Pervaiz et al. [31]
reports the environmental impacts evaluation, in particu-
lar, the carbon storage potential, of a specic molded
component for the automotive industry made of polypro-
pylene reinforced with either hemp or glass bers. The
study shows a net energy saving of 50,000 MJ (
3 ton of
CO2 emissions) per ton of composite when 30% by
weight of glass bers are replaced with 65% of hemp
bers. For automotive applications, another important as-
pect is the overall reduction in vehicle weight that results
in fuel saving. For the mentioned component, a 21%
weight reduction was calculated (PP/hemp vs. PP/glass
ber). This study estimated that 3.07 million ton of CO2
emissions (4.3% of total US industrial emissions) and
1.19 million cubic meter of crude oil could be saved if
natural ber composites would substitute 50% of the ber
glass plastics used in North America for automotive appli-
cations. In conclusion, the available data indicate that nat-
ural bers have a tremendous potential as a means not
only to save nonrenewable resources but also to control
greenhouse gas emissions.
However, the environmental advantages in term of
energy and CO2 balances illustrated earlier are partially
counterbalanced by problems associated with the produc-
tion of the most widely used bers in composites, that is,
bast bers. Indeed, fertilizers used to grow the crops have
a negative impact associated with the accumulation of
phosphate and nitrate in water. Moreover, the production
of such bers requires land and water, and it steals
resources for agricultural food production. For these rea-
sons, increasing interest is presently addressed, as men-
DOI 10.1002/pc
 TABLE 2. Commercially available (or expected) bio-based polymers.

Polymer Biobased polymer fraction Biobased content (%)a Status

Polyhydroxyalkanoates (PHAs) Whole polymer 100 Commercial

Polylactic acid (PLA) L-Lactic acid up to 100b Commercial
Polytrimethylene terephthalate (PTT) 1,3-Propanediol 30 Commercial
Polyacrylic acid 3-Hydroxypropionic acid 100 Expected
Polyethylene (PE) Ethanol 100 Commercial
Polybutylene succinate (PBS) Succinic acid
54 Pilot scale
Polyvinylchloride (PVC) Ethanol 100 Expected 2011
Polyamide 11 (PA11) Ricinoleic acid 100 Commercial
Cellulosics Cellulose Up to 100c Commercial
Thermoplastic starch (TPS) and Starch Up to 100 Commercial
starch derivatives
Polyisoprene Isoprene 100 Expected 2012
Aliphatic polyesters 1,3-Propanediol, succinic acid, Up to 100d Commercial
fatty acids
Polyethers 1,3-Propanediol, fatty acids Up to 100d Commercial
Polyurethane (PU) Fatty acids Up to 70 Commercial
Epoxy resins Triglycerides Up to 100d Commercial
Furan resins Xylose Up to 100 Commercial
Polyamide 6/10 Ricinoleic acid 66 Commercial

a
Calculated according to ASTM D6866.
b
Depends on D-lactic acid monomer content.
c
Depends on type of substituent and degree of substitution.
d
Depends on composition.

tioned earlier, to bers such as indiangrass or switchgrass
as well as to bers from agricultural and animal wastes.
BIO-BASED POLYMERS
As stated in the Introduction section, a green compos-
ite is a natural-ber-reinforced biocomposite in which the
matrix is a bio-based polymer. Bio-based polymers have
been dened as man-made or man-processed organic mac-
romolecules derived from biological resources for plastic
and ber applications [32]. All bio-based materials con-
tain a certain amount of bio-based carbon that can be cal-
culated, as weight percent of the total C-content, from the
relative amount of isotope 14C in the material according
to the standard method ASTM D6866. A material fully
based on fossil carbon does not contain the 14C isotope,
whereas materials partially or entirely based on renewable
resources have a measurable 14C content. Today, many
bio-based thermosetting and thermoplastic polymers have
been developed. Table 2 collects presently commercially
available bio-based polymers as well as products close to
commercialization. The polymers reported in the table
spread a broad range of macromolecular compounds,
including polyesters, polysaccharide derivatives, polyur-
ethanes, and a variety of thermosetting resins with a car-
bon content that may cover wide intervals, up to 100%.
The global capacity by the end of 2007 of bio-based
plastics (comprising cellulose polymers and nonfood
starch) was estimated by the PRO-BIP 2009 Report [32]
at 20 Mt (million metric tons), that is, at
20% of the
worldwide production of plastics that is dominated by oil-
derived polymers. The report shows, however, that with a
global average annual growth rate of 38% (from 2003 to
the end of 2007), the market of bio-based plastics has
experienced a rapid growth.
Although a number of economic and technical aspects
must still be optimized to achieve a massive substitution
of oil-based plastics with bio-based polymers, it is worth
pointing out that geopolitical developments strongly affect
affordability and supply of fossil fuels, and they conse-
quentially inuence the price of crude oil, of natural gas,
and of oil-derived polymers. A recent study on bioplastics
suggests [33] that the bioroute may become economically
advantageous with respect to the oil-route if oil prices
continue raising and that bio-based polymers have the
potential not only to replace existing polymers in a num-
ber of applications, but also to provide new combinations
of properties for new applications.
At present, only a few bio-based polymers among
those developed have been studied and applied as the ma-
trix in green composites (reviewed in the following sec-
tion). However, the broad range of bio-based polymers
that are commercially available (Table 2) is expected to
stimulate further investigations on their potential use as
matrices in green composites.
GREEN COMPOSITES
Green composites are biocomposites where both matrix
and reinforcement derive from renewable resources.
Selection of a suitable ber, among those available in na-
ture, as reinforcement for a given polymer is guided by

DOI 10.1002/pc POLYMER COMPOSITES-2011 1909

the values of composite stiffness and strength required.
Besides intrinsic properties of each component (bers and
matrix), the mechanical properties of the composite are
expected to depend on ber aspect ratio, volume fraction
and orientation, and on adhesion at the ber-matrix inter-
face [34].
Softwood bers have generally a length of 1.55.0
mm, a diameter comprised between 15 and 80 lm and an
aspect ratio of around 100, while the aspect ratio of indi-
vidual bast ber cells is in the region of 10001200 [35].
Feather keratin bers have average diameter of 5 lm [8],
while silkworm silk bers have a diameter of 1015 lm
[9]. The latter are commercially available in a continuous
lament, so that they potentially have extremely high as-
pect ratio.
Fiber aspect ratio is inuenced by the way in which
bers are extracted and processed. Moreover, composite
manufacturing may strongly inuence both the aspect ra-
tio and ber orientation, so that the mechanical properties
of the composite are accordingly affected. However, a
crucial issue for high performance composites is good
interfacial ber/matrix adhesion that promotes good stress
transfer from the continuous phase to the bers that must
carry the load.
In general, hydrophilicity of natural bers does not
promote adhesion to the essentially hydrophobic polymers
used as composite matrix, so that during processing, poor
ber wetting causes a nonuniform distribution of bers in
the matrix and void formation. Many different ap-
proaches, reported in a number of reviews [3, 5, 12, 36
40], have been explored to improve ber/matrix interface.
They include ber modication before composite manu-
facture via chemical (esterication [4146], etherication
[41, 45, 46], treatment with silane [12, 36, 47], or isocya-
nates [48, 49]) or physical means (plasma [12, 37, 50, 51]
or corona treatments [50, 52]) as well as modication of
the polymer matrix [53, 54].
In particular, chemical modications of ber surface
through substitution of polar hydroxyls with apolar groups
have been demonstrated to be a successful route for
improving mechanical properties of natural ber compo-
sites. Among them, chemical grafting involves attaching
to the surface of the ber a suitable polymer with a solu-
bility parameter similar to that of the polymer matrix.
Such polymer acts as an interfacial agent and improves
adhesion between ber and continuous phase. An example
is PE glycol grafted on ax bers that improves the me-
chanical properties of ax ber-reinforced PLA compo-
sites [45]. Extensive studies have also been performed on
graft copolymerization of vinyl monomers such as methyl
methacrylate and acrylates, on both vegetable and animal
bers [55, 56]. In all cases, where a ber modication is
performed, it is essential that the reaction is conned to
the surface layer in order avoid loss of ber mechanical
properties.
An alternative strategy to improve ber-matrix adhe-
sion and ber dispersion is the addition of a compatibil-
1910 POLYMER COMPOSITES-2011
izer playing the role of adhesion promoter. This approach
has been widely used in NFCs with polyolen matrices
[3] and is been currently investigated in the eld of green
composites. For example, Wong et al. [57] showed that
hydrogen-bonding additives, such as glycerol triacetate
and 4,4-thiodiphenol, improve interfacial adhesion of ax
bers with PLA or PHB, respectively.
Thermosetting Green Composites
It is known that resins from natural oils (soybean, cas-
tor, linseed, etc.) can be used in substitution of petrochemi-
cal-derived thermosetting resins such as unsaturated poly-
esters, vinyl esters, and epoxy resins [58]. Natural oils are
cheap, abundant, and renewable. They are based on triglyc-
erides of fatty acids, and they can polymerize when chemi-
cal functionalities are added on their active sites (double
bonds, allylic carbons, ester groups, and carbons alpha to
the ester group). Epoxidation, ring opening reaction with
haloacids or alcohols, ozonolysis, and hydration are some
of the methods used to functionalize unsaturated plant oils
[58]. Newly developed oil-based plastics are being eval-
uated and tested by end-users and converters for high-vol-
ume reinforced applications in agricultural equipment,
automotive components, civil infrastructure (bridges and
highway components), marine structures (pipes and off-
shore equipment), rail infrastructure (carriages, box cars,
and grain hoppers), and construction industry (particle
board, ceilings, and engineered lumber).
Table 3 lists recent studies appeared in the literature
on green composites based on seed-oil derived thermoset-
ting resins. A broad range of bers and ber loadings (5
90%) have been investigated. The most used resins are
epoxidized natural oil, cross linked with anhydrides, and
polyurethanes made from natural polyols and diisocya-
nates from petrochemical feedstock. Lee et al. [48], for
example, used a polyol from castor oil in a mixture with
polycaprolactone diol to prepare castor oil-based polyur-
ethanes with controlled mechanical properties. Hemp
bers modied with isocyanate were used to reinforce the
polyurethane biocomposites [48]. Epoxidized natural oils
can be modied by the reaction of acrylic acid to form
acrylate epoxidized oils that in turn are used for the prep-
aration of composites. Hong and Wool [19] prepared
composites from avian bers and an acrylate epoxidized
soybean oil resin and obtained a low-k dielectric material
that can be applied in modern high-speed microelec-
tronics. Manufacturing techniques of thermoset biocompo-
sites are generally the same closed mold" techniques
(e.g., resin transfer molding, vacuum infusion, and com-
pression molding) as in the traditional composite industry
[34]. The resin formulation is rst infused into the ber
mats in a mold. Then, the curing of the matrix is per-
formed at selected temperature by compression molding
or alternatively by applying a vacuum. These composite
manufacturing techniques allow high ber loading; thanks
to the low-viscosity of resin formulation before curing.
DOI 10.1002/pc
 TABLE 3. Recently developed green composites based on natural oil derived thermosetting resins.

Composite manufacturing Fiber weight

process Fiber Matrix content References

Vacuum-assisted resin Chicken feather Acrylated epoxidized soybean oil styrene 520% 19
transfer molding
Vacuum-assisted resin Chicken feather Soybean oil pentaerythritol glyceride maleates 520% 19
transfer molding
Resin transfer molding Hemp Castor oil PCL diphenylmethane 5% 48
diisocyanate
Sheet molding compound Luffa Cylindrica Castor oil diphenylmethane diisocyanate 10% 59
Compression molding Flax Metacrylated soybean oil styrene 60% 60
Compression molding Jute Polyurethane and epoxy resins from 50% 61
Mesua Ferrea seed oil
Compression molding Hemp Epoxidized linseed oil methyl 065% 62
tetrahydrophthalic anhydride
Compression molding Wheat straw Linseed oil, maleic anhydride, and 5090% 22
divinylbenzene
Compression molding Flax Epoxidized soybean oil 015% 63
Compression molding Coconut, sisal Castor oil diphenylmethane diisocyanate 1430% 64
Resin transfer molding Kenaf Epoxidized soybean oil maleic anhydride 10% 47
Resin transfer molding Flax Acrylated epoxidized soybean oil styrene 2040% 65

Notwithstanding the high scientic interest in this area,
demonstrated by the data in Table 3, thermosetting green
composites have not yet gained signicant production vol-
umes due to the scarcity of suitable bio-based thermosets
in the market. Among those available, green composites
containing soybean oil-based resin have recently appeared
on the market. Jakob Winter (Germany), for example, has
developed Green LinE, a line of products made with ax
and hemp bers embedded in epoxidized natural-oil res-
ins. The composites are manufactured by soaking natural
ber eeces in the resin followed by compression mold-
ing. According to the manufacturer, these biocomposites
can be varnished and laminated. Environ biocomposites
Mfg (USA) sells different product lines, where a soy-bean
resin embeds waste bers such as recycled newsprint,
wheat straw, and sunower hulls. The biocomposites are
commercialized in the form of light-weight panels for
nonstructural indoor applications.
Thermoplastic Green Composites
One of the most studied and broadly commercialized
bio-based thermoplastic polymer is PLA, whose monomer
derives from starch fermentation. A number of studies
have shown the suitability of PLA to act as the matrix in
NFCs, and the work on PLA green composites has been
recently reviewed by Graupner et al. [66]. Table 4 sum-
marizes recent studies on thermoplastic green composites

TABLE 4. Recently developed green composites based on bio-based thermoplastic resins.

Manufacturing processing Kind of ber matrix Fiber mass proportion Reference

Compression molding ax PHB, thermoplastic starch, PLA 2030 v/v% 67

Injection molding Wood our PHB 030 w/w% 68
Compression molding Pineapple leaf PHBV 030 w/w% 69
Injection molding Wood PHBV 1040 w/w% 70
Injection molding Wood Thermoplastic starch 1030 w/w% 71
Melt mixing Wood our Thermoplastic starch blend 1560 w/w% 72
Injection molding Flax PHBH 25 v/v% 46
Compression molding and ax PHB, PHBV 840 v/v% 73
injection molding
Injection molding Straw PHB 050 w/w% 74
Injection molding Wood PHB, PHBV 2040 w/w% 75
Injection molding Flax, ramie, jute, PHBV, Thermoplastic 1025 w/w% 76
cellulose ber, starch blends,
and oil palm ber cellulose acetate
Injection molding Corn straw, wheat PHBV 1040 w/w% 23
straw, soy stalk
Injection molding Wood Thermoplastic starch 030 w/w% 71
Solution casting Wool Cellulose acetate 520 w/w% 27
Compression molding and Hemp Cellulose acetate 030 w/w% 77
injection molding

DOI 10.1002/pc POLYMER COMPOSITES-2011 1911

having different combinations of bio-based polymers and
natural bers. Composites using PLA as matrix polymer
are purposely not included in the table (for PLA-biocom-
posites refer to Ref. 66). It is clear from the data in Table
4 that, having excluded PLA-biocomposites, most studies
focus on the use of polyhydroxyalkanoates (PHAs) as
matrices. A recent work by Barkoula et al. [73] offers a
review on earlier work on PHA-biocomposites.
By comparing Tables 3 and 4, it is evident that, unlike
thermosetting composites, thermoplastic green composites
can be obtained only with limited ber loading (maximum
50%w/w). This is due to techniques available for thermo-
plastic composite manufacturing that hinder good ber
dispersion in a high viscosity matrix when the ber con-
tent is higher than 50%. Interestingly, thermoplastic green
composites can be processed by means of the standard
and economic equipments used for plastic manufacturing
such as compounding and injection molding. However,
these techniques have the limitation that only relatively
short bers (which impart limited reinforcing effect) can
be used. If longer bers are to be included, compression
molding methods need to be used. In the automotive
industry, for example, long natural bers are generally
mingled together with bers of the thermoplastic polymer
to form a nonwoven eece, which is subsequently hot
pressed in order to promote melting of the thermoplastic
bers [35].
To date, a number of composite manufacturers have
introduced in their product range PLA composites rein-
forced with natural bers, as illustrated by the following
examples. Jakob Winter (Germany) produces Green LinE
ax/hemp ber composites based on PLA by using com-
pression-molding techniques. FKuR (Germany) has devel-
oped wood-reinforced PLA compounds (FIBROLON1),
which can be injection molded into complex proles, pan-
els, and hollow proles and/or into components for auto-
motive interiors. Kareline1 PLMS is a biodegradable
ber-reinforced PLA composite developed by Kareline
Oy (Finland). Granules from injection moulded wood or
natural ber-reinforced PLA are produced by GreenGran
BV (Germany). The company FASAL WOOD KG (Aus-
tria) develops and markets granulates from PLA and
wood waste for injection molding under the brand name
Fasal1. Products of wood and biodegradable polyesters
are also developed by FuturaMat (France) under the trade-
name BioFibra1 in grades suitable for injection, extru-
sion, or thermoforming.
Applications
Notwithstanding the intense research at the academic
level, large-scale commercialization of green composites
is still at its early stage compared to the large volume of
biocomposites containing oil-derived polymers, mainly
due to the higher costs of bio-based matrices. Implemen-
tation of fast and efcient processing procedures might be
1912 POLYMER COMPOSITES-2011
the key to successful commercialization of green compo-
sites.
Historically, it was in 2003 that the rst green compos-
ite appeared in a commercial product, that is, on the spare
tire cover of a car, the Toyota Raum. The bioplastic used
was Toyotas PLA Eco-Plastic reinforced with kenaf
bers. Automotive applications represent the best opportu-
nity for natural ber-reinforced plastics, because their low
density allows production of light-weight materials with
the advantage of fuel and cost saving. Compared to the
glass bers, natural bers provide better crash absorbance
and better acoustic and heat insulation, which are impor-
tant properties in the automotive sector. Potential applica-
tions in this eld are interior structures (seatback lining,
package shelves, seat bottoms, seatback cushions, head
restraints, under-oor body panels, door panel inserts, arm
rests, etc.).
Thermoplastic green composites can also nd applica-
tions in a range of widely different elds such as toys, fu-
neral articles, packaging (boxes), musical instruments, and
cases for electronic devices. An example of the latter was
a mobile phone made of PLA reinforced with kenaf bers
launched in 2006 by NEC Corporation, using a modied
PLA developed by UNITIKA LTD. The composite
applied in the mobile phone production achieved a bio-
based content of around 90%.
Building is an important and expanding application
eld for thermoset green composites, especially those
containing wood as reinforcement (WPCs) [29]: terrace
ooring, outdoor decking, window and door frames, pan-
els for both indoor and outdoor uses, and a number of
structural parts in buildings. A signicant increment in
the use of WPCs is also expected in the furniture indus-
try, where some important companies such as IKEA al-
ready commercialize chairs and shelves made of WPC
[29, 35].
End-Life Disposal
As concerns the end-of-life disposal of green compo-
sites, it is worth pointing out that a bio-based material is
not by denition biodegradable, that is, bio-based and bio-
degradable are independent properties. The bio-based con-
cept refers to the environmentally friendly origin of the
material, while biodegradability is a nal property dened
by a number of international norms such as EN 13432
that indicate the requisites that plastic products must pos-
sess to be biodegradable and compostable. Hence,
although in green composites the natural ber component
is intrinsically biodegradable, the bio-based polymer ma-
trix can be either biodegradable or not, as schematically
illustrated for some exemplary polymers in Figure 3.
Green composites with a biodegradable matrix (either
bio-based or not) can be disposed of, in principle, via
composting thus contributing to mitigate waste disposal
problems typical of industrialized countries. Conversely,
when the matrix of a green composite is nonbiodegrad-
DOI 10.1002/pc
 FIG. 3. Biodegradability of oil-based, bio-based, and partially bio-based polymers (a limited number of
polymers are listed for exemplication purposes).

able, the composite disposal options are restricted to
incineration or landlling. Biodegradability is a property
that is not always required in green composites, as, for
example, in long-lasting building applications where dura-
ble composites are needed.
Policies to encourage the use of recycled and/or bio-
based products are active in many developed countries
that also enforce the producer pays" principle requiring
manufacturers to the take responsibility for their products
throughout their whole life cycle. Several actions, such as
the end-of-life vehicles EU-Directive 2000/53 [78] for the
automotive sector and the 2009 International Maritime
Organizations Convention for the Safe and Environmen-
tally Sound Recycling of Ships [79] for the marine sector

FIG. 4. Prototypes of completely green products containing green composites: (a) WorldFirst Formula 3
racing car (from: http://www2.warwick.ac.uk/newsandevents/pressreleases/racing_car/); (b) a kayak made
from PLA and ax bers (from: http://www.plasmor.fr/fr/kayak-bers-lin/Unkayakenberdelin/188.html).
[Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

DOI 10.1002/pc POLYMER COMPOSITES-2011 1913

promote dismantling at end-life and recycling/disposal
without risks to human health and safety or to the envi-
ronment.
Following the mentioned directives, car manufacturers
began to use biocomposite materials in car interiors,
where traditional reinforcing bers like glass were substi-
tuted by natural bers. In this context, some research
groups have explored the possibility to produce cars
entirely made of bio-degradable, renewable, plant-based
materials: durable bioplastic fuel lines, car seat foams,
body panels, structural components, interior parts, and
tires have already been developed. For example, Ohio
State University and the University of Akron (Goodyear
Polymer Centre) have jointly designed a 90% biodegrad-
able vehicle (Agri-Car) [80] comprising bio-based poly-
mers for the body, polymers, and fabrics derived from
renewable feedstock for the interior and trim, alternative
natural sources of rubber for tires, crops, and other bio-
mass for lubricants and fuel, including ethanol and meth-
ane. Along this line, the rst prototype of a green car 15. Y. Zou, H. Xu, and Y. Yang, J. Polym. Environ., 18, 464
completely built on current environmentally sustainable
technologies was the World First Formula 3 racing car
[81] developed the University of Warwick in 2009
(Fig. 4a).
In parallel, also in the marine sector, a new interest to-
ward environmentally friendly ships/boats begins to
emerge both at academic and at industrial level. An
example is the project NavEcoMat [82] developed by
PoleMer Bretagne (France) together with companies and
research centers whose goal was to produce high-perform-
ance green composites to be used in small pleasure boats.
A kayak prototype made of PLA reinforced with ax
bers was fabricated (Fig. 4b), whose durability in sea-
water has been tested [83].
CONCLUSIONS
Green composites have a tremendous development
potential as light weight sustainable composites, espe-
cially if the exploitation of natural bers from waste will
be implemented. Key activities to reach the goal will be
the identication of new bio-derived polymers, their eco-
nomically and environmentally sound production, and the
implementation of composite interfacial properties
through ad hoc" chemical/physical treatments.
REFERENCES
1. M.J. John and S. Thomas, Carbohydr. Polym., 71, 343
(2008).
2. E. Witten, Composites Market: Market Developments, Chal-
lenges, and Chances, AVK Federation of Reinforced Plas-
tics, Germany (2010).
3. F.P. La Mantia and M. Morreale, Compos. A: Appl. Sci.
Manuf., 42, 579 (2011).
4. H.Y. Cheung, M.p. Ho, K.T. Lau, F. Cardona, and D. Hui,
Compos. B: Eng., 40, 655 (2009).
1914 POLYMER COMPOSITES-2011
5. A.K. Bledzki, S. Reihmane, and J. Gassan, J. Appl. Polym.
Sci., 59, 1329 (1996).
6. A.K. Mohanty, M. Misra, and G. Hinrichsen, Macromol.
Mater. Eng., 276277, 1 (2000).
7. D.N. Saheb and J.P. Jog, Adv. Polym. Technol., 18, 351 (1999).
8. J.R. Barone, W.F. Schmidt, and C.F.E. Liebner, Compos.
Sci. Technol., 65, 683 (2005).
9. S.M. Lee, D. Cho, W.H. Park, S.G. Lee, S.O. Han, and L.T.
Drzal, Compos. Sci. Technol., 65, 647 (2005).
10. Z. Shao and F. Vollrath, Nature, 418, 741 (2002).
11. T. Arai, G. Freddi, R. Innocenti, and M. Tsukada, J. Appl.
Polym. Sci., 89, 324 (2003).
12. A.K. Bledzki and J. Gassan, Prog. Polym. Sci., 24, 221 (1999).
13. J. Summerscales, N.P.J. Dissanayake, A.S. Virk, and W.
Hall, Compos. A: Appl. Sci. Manuf., 41, 1329 (2010).
14. J.A. Youngquist, Wood-based Composites and Panel Prod-
ucts, in Wood HandbookWood as an Engineering Mate-
rial, USDA Forest Service, Forest Products Laboratory,
Department of Agriculture, Madison, WI, 131 (1999).
(2010).
16. W. Liu, A.K. Mohanty, L.T. Drzal, and M. Misra, Indus.
Eng. Chem. Res., 44, 7105 (2005).
17. A. Blicblau, R. Coutts, and A. Sims, J. Mater. Sci. Lett., 16,
1417 (1997).
18. Y. Zhao, H.Y. Cheung, K.T. Lau, C.L. Xu, D.D. Zhao, and
H.L. Li, Polym. Degrad. Stab., 95, 1978 (2010).
19. C.K. Hong and R.P. Wool, J. Appl. Polym. Sci., 95, 1524
(2005).
20. A. Ashori and A. Nourbakhsh, Waste Manag., 30, 680
(2010).
21. S.L. Favaro, M.S. Lopes, A.G. Vieira de Carvalho Neto, R.
Rogerio de Santana, and E. Radovanovic, Compos. A: Appl.
Sci. Manuf., 41, 154 (2010).
22. D.P. Pster and R.C. Larock, Compos. A: Appl. Sci. Manuf.,
41, 1279 (2010).
23. S. Ahankari, A.K. Mohanty, and M. Misra, Compos. Sci.
Technol., 71, 653 (2011).
24. N. Reddy and Y. Yang, Green Chem., 7, 190 (2005).
25. Y. Habibi, W.K. El-Zawawy, M.M. Ibrahim, and A.
Dufresne, Compos. Sci. Technol., 68, 1877 (2008).
26. S. Cheng, K.T. Lau, T. Liu, Y. Zhao, P.M. Lam, and Y.
Yin, Compos. B: Eng., 40, 650 (2009).
27. A. Aluigi, C. Vineis, A. Ceria, and C. Tonin, Compos. A:
Appl. Sci. Manuf., 39, 126 (2008).
28. S.V. Joshi, L.T. Drzal, A.K. Mohanty, and S. Arora, Com-
pos. A: Appl. Sci. Manuf., 35, 371 (2004).
29. M. Carus and C. Gahle, Reinf. Plast., 52, 18 (2008).
30. T. Corbie`re-Nicollier, B. Gfeller Laban, L. Lundquist, Y.
Leterrier, J.-A. E. Manson, and O. Jolliet, Resour. Conserv.
Recycl., 33, 267 (2001).
31. M. Pervaiz and M.M. Sain, Resour. Conserv. Recycl., 39,
325 (2003).
32. L. Shen, J. Haufe, and M.K. Patel, Product Overview and
Market Projection of Emerging Bio-Based Plastics, Euro-
pean Polysaccharide Network of Excellence, PRO-BIP
(2009). Available at: http://www.epnoe.eu.
DOI 10.1002/pc
33. J. Ravenstijn, The State of the Art on Bioplastics. Products,
Markets, Trends and Technologies, Ludenscheid, Germany
(2010).
34. R. Talreja and J.-A.E. Manson, Polymer Matrix Composites,
Elsevier, Amsterdam (2001).
35. P.A. Fowler, J.M. Hughes, and R.M. Elias, J. Sci. Food.
Agric., 86, 1781 (2006).
36. A. Arbelaiz, B. Fernandez, J.A. Ramos, and I. Mondragon,
Thermochim. Acta, 440, 111 (2006).
37. M.N. Belgacem and A. Gandini, Compos. Interf., 12, 41 (2005).
38. J. George, M.S. Sreekala, and S. Thomas, Polym. Eng. Sci.,
41, 1471 (2001).
39. S. Kalia, B.S. Kaith, and I. Kaur, Polym. Eng. Sci., 49, 1253
(2009).
40. D. Maldas, B.V. Kokta, R.G. Raj, and C. Daneault, Poly-
mer, 29, 1255 (1988).
41. M. Baiardo, G. Frisoni, M. Scandola, and A. Licciardello,
J. Appl. Polym. Sci., 83, 38 (2002).
42. M. Baiardo, E. Zini, and M. Scandola, Compos. A: Appl.
Sci. Manuf., 35, 703 (2004).
43. G. Frisoni, M. Baiardo, M. Scandola, D. Lednicka`, M.C.
Cnockaert, J. Mergaert, and J. Swings, Biomacromolecules,
2, 476 (2001).
44. E. Zini, M. Scandola, and P. Gatenholm, Biomacromole-
cules, 4, 821 (2003).
45. E. Zini, M. Baiardo, and M. Scandola, Macromol. Biosci., 4,
286 (2004).
46. E. Zini, M.L. Focarete, I. Noda, and M. Scandola, Compos.
Sci. Technol., 67, 2085 (2007).
47. P. Tran, D. Graiver, and R. Narayan, J. Appl. Polym. Sci.,
102, 69 (2006).
48. N. Lee, O.J. Kwon, B. Chun, J. Cho, and J.S. Park, Fibers
Polym., 10, 154 (2009).
49. K. Joseph, S. Thomas, and C. Pavithran, Polymer, 37, 5139
(1996).
50. N.M. Belgacem, P. Bataille, and S. Sapieha, J. Appl. Polym.
Sci., 53, 379 (1994).
51. Z.F. Li and A.N. Netravali, J. Appl. Polym. Sci., 44, 333
(1992).
52. J. Gassan and V.S. Gutowski, Compos. Sci. Technol., 60,
2857 (2000).
53. C.S. Wu, Polym. Degrad. Stab., 94, 1076 (2009).
54. R. Karnani, M. Krishnan, and R. Narayan, Polym. Eng. Sci.,
37, 476 (1997).
55. G. Canche-Escamilla, J.I. Cauich-Cupul, E. Mendizabal, H.
Vazquez-Torres, and P.J. Herrera-Franco, Compos A, 30,
349 (1999).
56. A.L. Martinez-Hernandez, C. Velasco-Santos, M. de Icaza,
and V.M. Castano, e-Polymers, 016, 1 (2003).
57. S. Wong, R.A. Shanks, and A. Hodzic, Compos. Sci. Tech-
nol., 67, 2478 (2007).
DOI 10.1002/pc
58. S.N. Khot, J.J. Lascala, E. Can, S.S. Morye, G.I. Williams,
G.R. Palmese, S.H. Kusefoglu, and R.P. Wool, J. Appl.
Polym. Sci., 82, 703 (2001).
59. B.N. Melo, C.G. dos-Santos, V.R. Botaro, and V.M.D. Pasa,
Polym. Polym. Compos., 16, 249 (2008).
60. K. Adekunle, D. Akesson, and M. Skrifvars, J. Appl. Polym.
Sci., 116, 1759 (2010).
61. S. Dutta, N. Karak, and S. Baruah, J. Appl. Polym. Sci.,
115, 843 (2010).
62. N. Boquillon, J. Appl. Polym. Sci., 101, 4037 (2006).
63. Z. Liu, S.Z. Erhan, D.E. Akin, and F.E. Barton, J. Agric.
Food Chem., 54, 2134 (2006).
64. R.V. Silva, D. Spinelli, W.W.B. Filho, S.C. Neto, G.O.
Chierice, and J.R. Tarpani, Compos. Sci. Technol., 66, 1328
(2006).
65. G.I. Williams and R.P. Wool, Appl. Compos. Mater., 7, 421
(2000).
66. N. Graupner, A.S. Herrmann, and J. Mussig, Compos. A:
Appl. Sci. Manuf., 40, 810 (2009).
67. E. Bodros, I. Pillin, N. Montrelay, and C. Baley, Compos.
Sci. Technol., 67, 462 (2007).
68. E.R. Coats, F.J. Loge, M.P. Wolcott, K. Englund, and A.G.
McDonald, Bioresour. Technol., 99, 2680 (2008).
69. S. Luo and A.N. Netravali, Polym. Compos., 20, 367 (1999).
70. S. Singh and A.K. Mohanty, Compos. Sci. Technol., 67,
1753 (2007).
71. L. Averous and N. Boquillon, Carbohydr. Polym., 56, 111
(2004).
72. M. Morreale, R. Scaffaro, A. Maio, and F.P. La Mantia,
Compos. A: Appl. Sci. Manuf., 39, 503 (2008).
73. N.M. Barkoula, S.K. Garkhail, and T. Peijs, Indus. Crops
Prod., 31, 34 (2010).
74. M. Avella, E. Martuscelli, B. Pascucci, M. Raimo, B. Focher,
and A. Marzetti, J. Appl. Polym. Sci., 49, 2091 (1993).
75. P. Gatenholm, J. Kuba`t, and A. Mathiasson, J. Appl. Polym.
Sci., 45, 1667 (1992).
76. M. Wollerdorfer and H. Bader, Indus. Crops Prod., 8, 105
(1998).
77. A.K. Mohanty, A. Wibowo, and L.T. Drzal, Compos. A:
Appl. Sci. Manuf., 35, 363 (2004).
78. European Commission, L269, Ofcial Journal of European
Commission, 21st October 2000 (Directive 2000/53/EC),
Life Focus (2004).
79. www.imo.org.
80. L. Irwin, Biomass Mag. Issue July 2007 (2007).
81. www2.warwick.ac.uk/newsandevents/pressreleases/racing_car
(2011).
82. www.pole-mer-bretagne.com/navecomat_0.php.
83. A. Le Duigou, P. Davies, and C. Baley, Polym. Degrad.
Stab., 94, 1151 (2009).
POLYMER COMPOSITES-2011 1915