Manufacturing of Natural

Fiber/Agrowaste Based Polymer

Composites

Debora Puglia, Fabrizio Sarasini, Carlo Santulli and José M. Kenny

Abstract Most recently, there has been an increasing interest for the production of
laminates for semi-structural applications using sustainable materials. In this field, a
possible option is the use of composites including ligno-cellulosic fibers, which are
normally obtained as by-products from the textile industry, therefore mainly in the
form of fabric or mats. Despite a reasonably large amount of studies on ther-
mosetting composites reinforced with vegetable fibers also exist, in the view to
replace fiberglass e.g., in the automotive industry, it is clear on the other side that
the evolution of natural fiber composites has a much stronger drive towards the use
of thermoplastic matrices and possibly biodegradable ones. Moreover, in terms of
life cycle analysis (LCA), it is recommendable that both matrix and fiber are
obtained from by-products or even better waste from an industrial or agricultural
process, so that their use may represent as such a reduction in the environmental
impact of the whole process. Therefore, this chapter discusses first the opportunities
offered and challenges encountered in the production of natural fiber composites,
then concentrating on the possibilities to obtain a polymer matrix alternative to
petrol-based ones, especially in the particular case of manufacturing biopolymers
by using agrowaste as received or with limited structural transformations rather than
simply as a monomer (e.g., dextrose) source for polymer synthesis.

Keywords Lignocellulosic fibers
Natural fiber composites
Thermoplastic

starch Biobased thermosets

D. Puglia
J.M. Kenny

Department of Civil and Environmental Engineering,
Università di Perugia, Strada di Pentima 4, 05100 Terni, Italy
F. Sarasini
Department of Chemical Engineering Materials Environment,
Sapienza Università di Roma, via Eudossiana 18, 00184 Rome, Italy
C. Santulli (&)
School of Architecture and Design, Università di Camerino,
viale della Rimembranza, 63100 Ascoli Piceno, Italy
e-mail: [email protected]

© Springer International Publishing AG 2017 125

M. Jawaid et al. (eds.), Green Biocomposites, Green Energy and Technology,
DOI 10.1007/978-3-319-46610-1_6
126 D. Puglia et al.

1 Natural Fiber/Agrowaste Based Thermosetting

Composites

1.1 General Considerations

Thermosetting resins play an important role in industry due to their high flexibility
for tailoring desired ultimate properties, leading to their high modulus, strength,
durability, and thermal and chemical resistances as provided by high cross-linking
density. Recent years have viewed an increasing demand of natural products in
industrial applications for environmental issues, waste disposal, and depletion of
non-renewable resources (Jenck et al. 2004; Raston 2005). Renewable resources
can provide an interesting sustainable platform to substitute partially, and to some
extent totally, petroleum-based polymers through the design of bio-based polymers
that can compete or even surpass the existing petroleum-based materials on a
cost-performance basis with high eco-friendliness values (Kaplan 1998; Stewart
2008b). In the case of thermosetting materials, the most widely applied renewable
resources include plant oils as the most important renewable raw material for the
production of bio-based polymer materials. Plant oils are triglycerides (triesters of
glycerol with long-chain fatty acids) with varying composition of fatty acid
depending on the plant, the crop, the season, and the growing conditions. Recent
reviews have focused on the development of cross-linked plant oils and their
derivatives for thermosetting applications, such as coating and resins (Biermann
et al. 2000; Derksen et al. 1996; Meier et al. 2007; Raquez et al. 2010; Sharma and
Kundu 2006). In addition to plant oils, other raw renewable materials of interest in
the design of bio-based thermosetting materials include lignin and proteins due to
their vast abundance and high functionality (Derksen et al. 1996; Stewart 2008a).
Due to its aromatic nature, lignin has been considered as a promising substitute for
phenol in phenol–formaldehyde-based resins. In non-food applications, the use of
plant proteins like soy proteins and wheat gluten may be also a promising way to
produce thermosetting (bio)materials with a large range of applications. In this
framework, there has been also overwhelming interest in using biobased ther-
mosetting polymers as matrix in natural fiber composites, not only because they are
from renewable sources, but also since they have comparable mechanical properties
to other conventional thermosetting polymers. Interestingly, many studies have
been performed as regards the use of natural fibers as reinforcements in composites,
but only quite a few investigations have been carried out on the possibilities of
using polymers from renewable resources as matrix (Herrmann et al. 1998;
Williams and Wool 2000). In the following paragraphs, the different thermosetting
materials obtained from agrowaste material will be considered, and special attention
will be given to composites containing natural macrofibers.
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 127

1.2 Phenolic Resins

Among different renewable resources, cashew nut shell liquid, an agricultural

by-product abundantly available in tropical countries such as India, is one of the
major and economical resources of naturally occurring phenols. Cashew nut shell
liquid (CNSL) occurs as a reddish brown viscous fluid in the soft honeycomb
structure of cashew nut shell, containing four major components with an unsatu-
rated C15-chain, namely cardanol, cardol, anacardic acid and 2-methylcarbol
(Fig. 1) (Voirin et al. 2014). The phenolic nature of resulting cardanol makes it
possible to react with formaldehyde under a variety of conditions to form Novolac
or Resole resins. Compared with conventional phenolic resins, cardanol–
formaldehyde resins have improved flexibility (due to the internal plasticization
effect of the long chain), leading to better processability (Quirino et al. 2014). The
side chain imparts a hydrophobic nature to the polymer, making it water repellent
and resistant to weathering. There are examples in which an epoxy resin crosslinked
with a cardanol based novolac was used as matrix and jute fibers as reinforcement
(Barreto et al. 2010; Campaner et al. 2010; Maffezzoli et al. 2004), or cardanol
based composites containing sisal (Barreto et al. 2011), or buriti fibers (Da Silva
Santos et al. 2010). Other examples of natural fibers that have been used to
reinforce CNSL-based novalac or resole type resins include oil palm fibers
(Tiamiyu and Ibitoye 2012), kenaf and hemp bast fibers (Aziz and Ansell 2004),
coconut coir fibers (Barreto et al. 2012). Other renewable fillers include rice husks
(Ofem et al. 2012), coffee husks (Bisanda et al. 2003) and sawdust (Lubi and
Thachil 2007). Natural fiber reinforcements are frequently pretreated with an alkali
solution (i.e. 5–12 % sodium hydroxide solution), to increase the number of
hydroxyl groups on the surface of the fiber (Fig. 1).
As suggested above, due to its similar structure with phenol, lignin has been also
considered as another natural substitute for phenolic based resins. Traditionally,
lignin is viewed as a waste material available in large quantity derived from the
wood pulp in the paper industry. Only 1–2 % of overall lignin is utilized for more
specific applications, the remaining primary serving as a (bio)fuel. Similar to
phenol–formaldehyde resins, lignins have an aromatic and cross-linked structure,
together with a great variety of functional groups such as ether and hydroxyl
groups, depending on the origin of lignin and the extraction technology
(Laurichesse and Avérous 2014). Through the functionalization of its hydroxyl
groups, lignin becomes a good candidate as a building block unit for polymer
synthesis to elaborate innovative macromolecular architectures (Matyjaszewski and
Möller 2012). Several attempts have been made to integrate lignin into industrial
processes to emphasize its use as a renewable feedstock, for example for replace-
ment of synthetic phenols in binders and in epoxy or phenol-formaldehyde resins
formulations (Kouisni et al. 2011). Literature reports include several methods to
synthesize lignin based epoxy resins. They have been applied for polyesters and
phenolic resins applications, following different strategies (Mansouri et al. 2011),
such as (i) blending lignin with epoxy resins (Yin et al. 2012), or (ii) modifying
128 D. Puglia et al.

Fig. 1 Components in CNSL (Lochab et al. 2014) and flow chart of preparation of the
biocomposites: a synthesis of polymer resol and b chemical treatment employed in the sisal fibers

lignin by an epoxidation reaction, usually with epichlorohydrin (Sun et al. 2007).

Examples are also reported in literature in which lignin modified phenolics are used
as matrices in natural fiber composites based on jute (Sarkar and Adhikari 2001),
sisal (Faulstich de Paiva and Frollini 2006), flax and kenaf (Mahendran et al. 2013).
Tannin compounds, extracted from the wood, bark, leaves, and galls of plants
can be also considered as another raw renewable material in the design of phenolic
resin composites reinforced with natural fibers. Frollini et al. (2008) used tannin as
a partial substitute of phenol in the preparation of composites reinforced with bark
from the Acacia Mimosa tree (fibers and particles) and sisal (Fig. 2). The tannin
used as the substitute of phenol was also extracted from the bark of the Acacia
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 129

Mimosa tree, because this tree is rich in tannin. In a companion paper, Barbosa et al.
(2010) used the tannin–phenolic matrix in the preparation of composites reinforced
with coir fibers.

1.3 Epoxy and Polyurethane Resins

In the formation of sustainable epoxy monomers, epoxidized plants oils and fatty
acids have been largely utilized. Vegetable oils, such as linseed oil, soybean oil,
castor oil, appear as excellent renewable raw materials for thermosetting polymers
as they are expected to be inexpensive and abundant, they have been also studied as
bio-based precursors through their epoxidation for the synthesis of bio-based epoxy
prepolymers (Wang and Schuman 2013). Vegetable oil-based monomers contain-
ing reactive functional groups, such as conjugated double bonds, acrylates, and
norbornene groups, have been successfully synthesized. These monomers can be
polymerized by themselves or copolymerized with petroleum-based monomers
using different polymerization methods to afford biorenewable thermosetting
materials. Thermal and mechanical properties of these thermosetting materials can
be finely tuned by controlling structures of vegetable oil-based monomers or using
different kinds of co-monomers. Green vegetable oil-based composites can also be
obtained by adding fillers, including natural fibers, into these vegetable oil-based
thermosets to further improve their thermal and mechanical properties. Several
researchers have investigated the synthesis and mechanical characterization of
networks based on epoxidized vegetable oil epoxy monomers using various
approaches (Liu et al. 2006). Park et al. (2004) synthesized and characterized
epoxidized soybean oil (ESO) and epoxidized castor oil (ECO), which proved one
of the most important functionalization reaction involving C=C double bonds. Soy
based polyols derived from ESO have also been widely used to produce poly-
urethanes that are comparable in many aspects with polyurethanes obtained from
petrochemical polyols (Lligadas et al. 2010). While epoxidized vegetable oils could

Fig. 2 SEM images of impact fractured surfaces of tannin–phenolic composites (TPC) reinforced
with 50 wt% of sisal fibers (Ramires and Frollini 2012)
130 D. Puglia et al.

be interesting renewable materials for adhesives and plasticizers, they could not
lead to high performance materials if fiber reinforcement is not considered. Taking
into consideration this limit, most ESO industrial uses are thus limited to non-
structural, additive applications, such as plasticizers or stabilizers: in this context,
many attempts have been done to improve the properties of bio-based epoxy by
using natural reinforcements. Quite a few publications exist in the field of bio
thermoset-based natural fiber composites (Adekunle et al. 2010; Liu et al. 2007; Liu
and Erhan 2008; Müssig 2008). Examples can be found for natural fiber composites
manufactured with flax (Liu et al. 2006), jute (Masoodi and Pillai 2012), hemp fiber
(Boquillon 2006) or composites prepared from corn, soybean, fish, and linseed oils
using up to 75 wt% of different natural fibers, such as corn stover, wheat straw, and
switch-grass fibers (Pfister and Larock 2012). Large scale natural fiber composite
‘unit beams’ of sandwich construction were successfully manufactured at the
University of Delaware from flax mat, chicken feathers, recycled paper and
structural foam using epoxidized soy-bean oil and a modified vacuum assisted resin
transfer molding (VARTM) process (Dweib et al. 2006; Hu et al. 2007).
Vegetable oils can also be converted to polyols, which can further react with
diisocyanates to provide polyurethanes. In sustainable thermosetting materials,
polyurethanes are currently prepared starting from renewable polyols, while the
second partner, isocyanate, is mainly made from petroleum-resources.
Examples of biobased polyurethanes containing natural fibers can be found for
castor oil-based polyurethanes with banana fibers processed by hand lay-up of short
random fiber-mats, followed by compression molding at room temperature (Merlini
et al. 2011). A natural polyol of alcoholysed castor oil with triethanolamine-based
rigid polyurethane foam and wood flour composite was prepared and characterized,
revealing a decrease in compression modulus and yield strength with increasing
wood flour content, although good interaction of wood flour with isocyanate was
noticed (Mosiewicki et al. 2008) (Fig. 3).

Fig. 3 Castor oil (chemical formula, seed and oil) and SEM image of flexible polyurethane foams
based on castor oil (Kozak and Lobko 2012; Spontón et al. 2013)
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 131

The same oil-based polyurethane composites of natural fibers such as sisal,

coconut short fibers and woven sisal fabric have been studied. The results showed
that the performance of coconut fiber composites is generally inferior to that of sisal
fiber and even to the neat polyurethane matrix, whereas the best performance was
displayed by the sisal fabric composite (Chen et al. 2006). Two types of environ-
mentally friendly jute fiber reinforced green composites have been studied. These
are based on Mesua ferrea L. seed oil based poly(urethane ester) and poly(urethane
amide) resin blends with commercially available partially butylated melamine–
formaldehyde and epoxy resins by solution impregnation and hot-curing methods
(Dutta et al. 2010).

1.4 Polyester Resins

Polyester resins currently used for decorative coatings and for a wide range of
commodity composite materials (in industrial equipment such as tanks, boat
building, truck roofs, and so on) are a class of unsaturated polyester derived from
the polycondensation of a polyol and a polyvalent acid or acid anhydride. These
building blocks can be substituted for renewable-based analogous, either partially,
or to some extent, totally. For example, fatty acids or oils can be used as polyacids,
while rigid carbohydrates, such as isosorbide, can be used as polyols. Isosorbide is a
sorbitol derivative obtained from starch through hydrolysis and subsequent
hydrogenation of the glucose into sorbitol.
Recently, lignin esters have been also proposed for use as unsaturated ester
thermosets: following a fast and simple procedure, kraft lignins were esterified with
anhydrides to render them more soluble in styrene, improving toughness and
connectivity in the polymer network (Raquez et al. 2010). Epoxidized vegetable
oils can be used as a replacement for polyester resins. Rösch et al. prepared
cross-linked partially bio-based polyesters by curing epoxidized soybean oil with
various dicarboxylic acid anhydrides (Rösch and Mülhaupt 1993). In the case of
composites, an example can be found in the work of Haq et al. (2008), where the
synergy between natural fibers (industrial hemp) and the biobased resins obtained
by partial substitution of unsaturated polyester (UPE) with epoxidized soybean oil
(EMS) was exploited. In Yeganeh and Mehdizadeh (2004), John et al. (2002)
methacrylated soybean oil, methacrylic anhydride modified soybean oil (MMSO)
and acetic anhydride modified soybean oil-based resins and flax fiber composites
were manufactured by a compression molding technique. The fiber to resin ratio
was 60:40, where air-laid fibers were stacked randomly, the woven fabrics were
stacked in a crosswise (0/90) configuration and impregnation was performed
manually. The resultant cured bio-based composites exhibited significantly
improved performance.
132 D. Puglia et al.

1.5 Natural Fiber/Agrowaste Based Thermosetting

Elastomers

Several works were carried out employing vegetable oils as precursors for the
synthesis of vegetable oil-based polymers, in which the resulting polymers had
elastomeric or rubbery properties (Visakh et al. 2013). In these works, the vegetable
oils such as linseed, tung, soybean, corn, castor oils and others, or the modified
vegetable oils, were crosslinked by vinyl monomers, such as styrene, a-methyl
styrene, divinyl benzene, cyclopentadiene and others. Moreover, a promising
alternative for the production of elastomeric polymers is also the use of furanic
molecules, such as furfural and hydroxymethyl furfural. From these two com-
pounds, furfural and hydroxymethylfurfural, many monomers can be produced
through their functionalization, can be polymerized and the resulting polymers may
have thermoplastic properties and even rubbery properties. However, except for
natural rubber, all other molecules from renewable sources by themselves or in a
polymerized form do not exhibit the characteristics of elastomers. The polymers
produced from these molecules are mostly thermoplastic, and to provide elas-
tomeric characteristics they need to be modified by grafting, copolymerization or
blending.
Extensive literature is present for the case of thermoplastic biobased elas-
tomers, especially in the case of polyurethanes (Ghassemi and Schiraldi 2014;
Tang et al. 2014), while very few examples can be found in the case of ther-
mosetting elastomers. In the paper of Gopalakrishnan and Linda (2011), novel
thermosetting polyurethanes from novolac type hydroxyalkylated cardanol-
formaldehyde resins, polypropylene glycols (PPG-1200 and PPG-2000) and
aliphatic diisocyanates, such as hexamethylene diisocyanate and isophorone
diisocyanate, were prepared in the form of thin sheets, while in Wang et al.
(2012), a novel cross-linkable, high molecular weight poly(diisoamyl
itaconate-co-isoprene) (PDII) elastomer was prepared by emulsion polymerization
based on itaconic acid, isoamyl alcohol, and isoprene. In Zhu and Wool (2006), a
new bio-based elastomer synthesized from soybean oil was filled with nanoclay to
generate an elastic nanocomposite, while Andjelkovic and Larock (2006) studied
the synthesis and characterization of novel rubbers from cationic copolymeriza-
tion of soybean oils and dicyclopentadiene. To the best of our knowledge, fully
green elastomeric composites have never been produced and studied, being the
production of elastomeric polymers from molecules from renewable sources, to be
used as a matrix in these composites, still a big challenge. This is an area in
which there are still many possibilities to explore and research efforts must be
concentrated on solving this problem and thus opening new opportunities in the
preparation of fully green elastomer composites, generating new applications for
them as replacements for conventional elastomer composites.
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 133

1.6 Natural Nanofillers in Biobased Thermosets

The use of nanofiller in bio-based polymers for fiber reinforced polymer composites
can provide value added properties to biocomposites. In such composites, the
natural fibers remain the main reinforcement for stiffness and strength, while the
nanofiller could enhance the matrix properties.
Few examples of nanocomposites in which the cellulosic nanostructure is used
in bio-based thermosets can be also found. Due to the fact that these environment
friendly composites suffer from several limitations, such as low mechanical prop-
erties due to low strength in reinforcement plus inadequate interfacial strength, and
that cellulose nanostructures have been shown to have significant potential as
reinforcement, the possibility of using cellulose nanofibers as reinforcements in a
bio-derived resin was revised. In Masoodi et al. (2012), cellulose nanofibers were
used as reinforcements in the forms of layered films, while in Lee et al. (2011) the
stability of the gas-soybean oil foam templates and the mechanical properties of the
polymer nanocomposite foams are enhanced upon the addition of bacterial cellulose
nanofibrils. Other examples of bio-based thermosets containing cellulosic nanore-
inforcements are the work of Shibata and Nakai (2010) in which the use of a
bio-based epoxy was revised, and systems in which cellulose nanocrystals are
incorporated in bio-based polyurethanes (Lin et al. 2013; Wik et al. 2011). Few
examples exist also in the literature on the polymerization of furfuryl alcohol in
presence of cellulosic nanoreinforcements (Pranger and Tannenbaum 2008); in
these papers, the authors established the feasibility of producing furfuryl alcohol
reinforced by cellulose nanowhiskers and montmorillonite using in situ polymer-
ization without using any solvent or surfactants. They found that sulfonic acid
residues at the cellulose nanowhiskers surface, which were left over from the acid
hydrolysis treatment, acted as catalyst for the polymerization reaction of furfuryl
alcohol. Results on the use of nanocellulose in fiber reinforced traditional ther-
mosets can be found in Phillips et al. (2013), where the infusion of an epoxy
reinforced with nanocellulose in presence of flax was studied.
Limited examples can be also found in which the biobased natural fiber com-
posite contains cellulosic nanostructures. A waterborne polyurethane synthesized
from castor oil and polyethylene glycol crosslinked with isophorone diisocyanate
was used as matrix in a cellulose nanocrystals (from Eucalyptus globulus) based
composite with concentrations from 0.2 to 5 wt% (Gao et al. 2012). The use of
bio-based thermosets clearly represents an area of significant interest, since further
combination of environmental friendly high performance materials with cellulosic
nanostructures can surely give the opportunity of creating new high performance
hybrids.
134 D. Puglia et al.

2 Natural Fiber/Agrowaste Based Thermoplastic

Composites

2.1 Production of Natural Fiber Composites: Perspectives

and Difficulties

The manufacturing of natural fiber composites can represent a tough challenge due
to the inherent properties of natural fibers that differ significantly from those of
synthetic ones such as glass, aramid and carbon fibers. The key parameters for
successful processing of natural fiber composites are related to their hygroscopic
behavior and low resistance to high temperature that have so far limited the pos-
sibilities for selection of polymers to be effectively used as matrix in a composite
material. Also, the use of natural fibers would require, at least in principle, the
subsequent adoption of biopolymer matrices, in order to obtain a fully
biodegradable, if not compostable, composite material, so to yield substantial
environmental advantages, which are strongly desirable in some fields of applica-
tion. In addition, the suitability of traditional manufacturing techniques for natural
fiber reinforced polymer composites is still under evaluation due to the fact that
mechanical and thermal properties of both natural fibers and biodegradable poly-
mers are somehow different from those of synthetic fibers and petroleum-based
polymers (Ho et al. 2012). In practice, the way natural fibers are introduced as
reinforcing material in polymer composites has to be adjusted to the available
production techniques so as to make easier for industries their adoption in viable
industrial products. Composites manufacturing processes can be broadly divided
into two main manufacturing categories according to the nature of polymer matrix,
namely thermoset or thermoplastic but, in the case of natural fiber composites, the
processing parameters are usually dependent also on the type of natural fiber.
Manufacturing methods for processing thermoset composites offer the following
advantages (Mazumdar 2001):
• processing of thermoset composites is much easier because the initial resin
system is in the liquid state and fibers are easy to wet with thermosets, thus
voids and porosities are less;
• heat and pressure requirements are less in the processing of thermoset com-
posites than thermoplastic composites, thus offering energy savings;
• a simple low-cost tooling system can be used to process thermoset composites.
The disadvantages are related (i) to the lengthy cure time that results in lower
production rates than thermoplastics, (ii) to the impossibility of reform thermoset
composites once cured to obtain different shapes and (iii) to the difficulty in their
recycling at the end of service life.
Low viscosity thermosetting polymers that can be cured at room temperature are
considered a right choice as they can easily impregnate natural fibers without the
damage associated to their thermal degradation. Resin transfer molding (RTM),
vacuum assisted resin transfer molding (VARTM) and sheet molding compound
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 135

(SMC) represent some of the most ordinary techniques used for impregnating and
forming thermoset-based natural fiber composites (Francucci et al. 2012; Kong
et al. 2014; Richardson and Zhang 2000; Rodriguez et al. 2004; van Voorn et al.
2001).
The long cycle times and high cost (mainly due to post molding operations such
as trimming) in processing thermoset composites have shifted the attention to
natural fiber composites based on thermoplastic matrices. In the case of thermo-
plastic composites, the initial raw material is in solid state and needs to be melted to
obtain the final product. The advantages of processing thermoplastic composites
include:
• the process cycle time is usually very short because there is no chemical reaction
during processing, and therefore can be used for high-volume production
methods;
• thermoplastic composites can be reshaped and reformed with the application of
heat and pressure and are therefore easy to recycle.
Selection of the production technique depends on the production rate and the
product status (semi or finished). Injection molding requires prepared pellets of
composites whilst the pultrusion and extrusion processes can deal directly with
fibers to have a profile product. Moreover the production technique affects the fiber
aspect ratio and fiber orientation and hence the mechanical properties of the
resulting composites. For example, in pultrusion long and unidirectional fibers are
obtained within the produced profile, while more randomness in the fiber direction
is achieved in extrusion and injection molding. It is important to emphasize that
these processes involve heating of the material above the melting point of the
chosen matrix. Since the degradation temperature of most natural fibers lies in the
range of 150–220 °C, attention should be paid to minimize the exposure of natural
fibers to these high temperatures. The thermal decomposition of fibers generates
volatiles and the resulting composites are always characterized by low mechanical
properties (Gassan and Bledzki 2001; Kim et al. 2005; Ouajai and Shanks 2005).
For this reason, the polymers presently used as matrices are those with low to
moderate melting temperatures, that is to say polypropylene (PP), polyethylene
(PE), poly(vinyl chloride) (PVC) and polystyrene (PS) (Abdelmouleh et al. 2007;
Faruk et al. 2012; Khalil et al. 2013; Ku et al. 2011; Van den Oever et al. 2000;
Singha and Rana 2012; Zampaloni et al. 2007). Strictly related to the choice of
thermoplastic matrix is the poor compatibility between the mostly hydrophobic
thermoplastic polymers and the hydrophilic natural fibers that makes it necessary
the use of coupling agents and fiber surface treatments (Belgacem and Gandini
2005; Fuqua et al. 2012; Keener et al. 2004; Mohanty et al. 2001). Another concern
that can affect in a significant way the composites is related to moisture content of
natural fibers that is usually in the range of 6–12 wt% and should be reduced to less
than 3 wt% in order to enable the production of molded parts of good quality.
In the following subparagraphs special attention will be given to the manufac-
turing processes and issues related to agro green thermoplastic composites
136 D. Puglia et al.

reinforced with natural fibers both on a micro and nanoscale even though very often
the manufacturing route is only secondary to the mechanical and thermal properties
obtained.

2.2 Starch Based Thermoplastic Composites

In the past decades there has been a renewed interest in the use of environmentally
friendly alternatives to petroleum based polymers that has triggered the develop-
ment of the biodegradable polymers, whose taxonomy is schematically summarized
in Fig. 4. Except the last family that is of fossil origin, most polymers are obtained
from renewable resources: in particular, this subsection will be devoted to the first
family that represents the so called agro polymers obtained from biomass by
fractionation and in particular on starchy materials.
Starch is a polysaccharide mostly produced by higher order plants as a means of
storing energy. It is stored intracellularly in the form of spherical granules
2–100 μm in diameter with multilevel structures from macro (native granules) to
molecular scales, i.e. starch granules, alternating amorphous and semicrystalline
shells (growth rings) (100–400 nm), crystalline and amorphous lamellae (period-
icity) (9–10 nm), and macromolecular chains (*nm) (Xie et al. 2012). Most
commercially available starches are isolated from grains such as corn, rice and
wheat, and from tubers such as potato and cassava (tapioca) (Wollerdorfer and

Fig. 4 Classification of biodegradable polymers

Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 137

Bader 1998) (Teixeira et al. 2012). Starch is a polysaccharide consisting of

D-glucose units with two major biomacromolecules that are amylose and amy-
lopectin. Amylose is a sparsely branched carbohydrate mainly based on α(1–4)
bonds whereas amylopectin is a highly multiple-branched polymer based on α(1–4)
(around 95 %) and α(1–6) (around 5 %) links, with constituting branching points
localized every 22–70 glucose units. Moreover, in starch granules are also found
very small amounts of proteins, lipids and phosphorus depending on the botanical
source (Xie et al. 2012). Depending on the source, amylose content of starch can lie
in the range from 1 to 70 % and most native starches are semicrystalline with a
crystallinity of about 20–45 % (Liu et al. 2009).
Processing these materials is much more complex than using traditional
polymers due to the multiple chemical and physical reactions that take place, e.g.
water diffusion, granule expansion, gelatinization, decomposition, melting and
crystallization.
Gelatinization is particularly important because it is the basis of the conversion
of starch to a thermoplastic and refers to the destruction of the crystalline structure
in starch granules. In fact, native starches are non-plastic due to the intra- and
inter-molecular hydrogen bonds between the hydroxyl groups in starch molecules,
which represent their crystallinity. Thermal processing is used to disrupt and
transform the semi-crystalline structure of starch granules to form a homogeneous
and amorphous material. This transformation is usually accomplished using small
amounts of molecular substances commonly known as gelatinization agents or
plasticizers (water, glycerol, glycol, citric acid, urea). The transformed material is
known as thermoplastic starch (TPS). Furthermore, since materials consisting
mainly of pure starch normally offer unfavorable final product properties such as
poor mechanical characteristics, limited long-term stability and high moisture
sensitivity, TPS is regularly blended with other polymers such as poly(lactic acid)
(PLA), polycaprolactone (PCL), poly(butylene succinate adipate) (PBSA), poly
(hydroxy ester ether) (PHEE) and polyvinyl alcohol (PVA) (Liu et al. 2009). In
addition to blending, another approach consists in the use of cellulose-based fillers.
Starch based materials can be processed with the same techniques used for con-
ventional polymers, such as extrusion, injection molding, compression moulding
and film casting even though the formulation and processing conditions have to be
carefully selected, optimized and controlled due to the singular phase transitions
that can occur. A detailed investigation of the thermal processing and the rheology
of these materials can be found in Liu et al. (2009) and Xie et al. (2012).

2.2.1 Biocomposites Based on TPS and Natural Fibers

Several types of fibers have been tested along with TPS: bleached leafwood fibres
(Averous and Boquillon 2004; Avérous et al. 2001a, b; Funke et al. 1998), fibres
from bleached eucalyptus urograndis pulp (Curvelo 2001), fibers from paper pulp
(Averous and Boquillon 2004), flax fibers (Wollerdorfer and Bader 1998), jute
fibers (Wollerdorfer and Bader 1998), ramie fibers (Wollerdorfer and Bader 1998),
138 D. Puglia et al.

hemp fibers (Gironès et al. 2012), oil palm fibers (Wollerdorfer and Bader 1998),
sisal fibres (Gironès et al. 2012; Leblanc and Saiter 2009), bagasse fibers Kaewtatip
and Thongmee (2014) and luffa fibers (Kaewtatip and Thongmee 2012). Averous
and Boquillon (2004) tested various formulations based on plasticized starch
matrix, varying matrix formulation (glycerol/starch ratios = 0.257 and 0.538),
fibers length (from 60 μm to 1 mm), filler content (up to 30 wt%) and fibers’ nature
(natural cellulose fibers from leafwood and paper pulp fibers). A wheat starch was
used in order to prepare two different TPS matrices characterized by a dissimilar
amount of glycerol as plasticizer, namely TPS1 (less amount of glycerol and
therefore brittle at room temperature) and TPS2 (higher amount of glycerol and
therefore soft at room temperature). After dry blending, native wheat starch and
glycerol were added to a turbo-mixer (2000 rpm). After dispersion in the mixer,
cellulose fibers were added and the final mixture was obtained at higher speed
(2500 rpm). The blend was then extruded in a single screw extruder and the pellets,
after a first granulation, were again extruded to allow a better dispersion. Final
pellets were then injection molded (100–130 °C, 1500 bar) to obtain the specimens
for the mechanical characterization. The authors found that both Young’s modulus
and tensile strength increased with the fiber length and content in comparison with
the neat matrix whereas the elongation at break decreased. These improvements are
consistent with a good compatibility at the filler/matrix interface as found in other
investigations (Avérous et al. 2001b; Funke et al. 1998). In particular, cellulosic
fibers showed a better interface adhesion compared to the lignocellulosic ones and a
higher amount of plasticizer was found detrimental to the properties of the com-
posites due to the formation of glycerol rich domains that affected in a negative way
the filler/matrix adhesion. The introduction of these agrofillers was found positive
also for the thermal resistance (Dufresne and Vignon 1998) of the biocomposites
with lignocellulosic fibers that caused higher degradation temperatures in the
resulting composites.
Similar positive results were found by Wollerdorfer and Bader (1998) who tested
several formulations of natural fibers and thermoplastics such as biodegradable
polyesters, polysaccharides and blends of thermoplastic starch. A wheat starch was
plasticized with glycerol and sorbitol using a co-rotating twin screw extruder at
115 °C and 50 rev/min. The extrudate was then pelletized and processed by
injection molding. Depending on the type of polymer matrix, a maximum fiber
content of 20–35 wt% was attained. The chemical similarity of polysaccharides and
plant fibers resulted in a fourfold increase of tensile strength of the reinforced
polymer compared to the neat TPS (Fig. 5). The Young’s modulus also increased in
a similar way to the tensile strength while the elongation at break was drastically
reduced (from 45 % up to 1.3–2.0 %).
In addition to injection molding, compression molding has been extensively
investigated for processing starch based polymers. In (Kaewtatip and Thongmee
2014) pregelatinized cassava starch, glycerol and NaOH treated bagasse fibers at
different contents (0–20 wt%) were mixed in polyethylene bags until a homoge-
neous dispersion was achieved. The mixture was then compressed at 160 °C for
10 mins under a pressure of 200 kg/cm2 and subsequently cooled down to room
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 139

Fig. 5 Tensile strength of

TPS reinforced composites

temperature. The authors found that there was a good adhesion between the treated
fibers and the TPS matrix as a result of the fiber’s surface roughening caused by the
NaOH treatment (Cao et al. 2006) and of the chemical similarity of fibers and starch
that makes it easy the formation of hydrogen bonds in the structure (Kaewtatip and
Thongmee 2012). The water absorption of the TPS reinforced composites was
lower compared to the neat TPS due to fiber-matrix interactions and to the higher
hydrophobic character of the cellulose that is related to its high crystallinity
(Curvelo 2001; Dufresne et al. 2000; Dufresne and Vignon 1998). In addition,
maximum weight loss of TPS reinforced composites was measured at a higher
temperature compared to that measured for the neat matrix: the difference was by
about 12 °C for 20 wt% of treated bagasse fibers, which also inhibited the ret-
rogradation of the starch, The beneficial effects of introducing natural fibers into
TPS matrices can be further confirmed by the results obtained on sisal fiber rein-
forced TPS composites obtained through a combination of extrusion and com-
pression molding (Fig. 6) (Leblanc and Saiter 2009).

2.2.2 Starch-Based Nano-biocomposites

Several types of nanofillers have been used with plasticized starch that can be
broadly subdivided in organoclays (montmorillonite, hectorite, sepiolite and so
forth), polysaccharide nanofillers (nanowhiskers/nanoparticles from cellulose,
starch, chitin, and chitosan) and carbonaceous nanofillers (carbon nanotubes, gra-
phite oxide, and carbon black). In this section only the use of polysaccharide
nanofillers from cellulose will be addressed. A detailed review of the state of the art
in the field of starch-based nanocomposites can be found in Xie et al. (2013). There
is a wide range of cellulose particle types currently under investigation for various
commercial applications. The diversity of cellulose particle types depends on cel-
lulose source and extraction processes. There are basically two families of nano-
sized cellulosic particles, the former consisting of cellulose nanocrystals (CNC) or
140 D. Puglia et al.

Fig. 6 Tensile strength and Young’s modulus of TPS reinforced composites as a function of sisal
content

nanowhiskers (CNW), whilst the latter is microfibrillated cellulose (MFC) (Brinchi

et al. 2013; Lu et al. 2008). CNC has been isolated from a variety of cellulosic
sources, including plants, animals (tunicates), bacteria and algae and in principle
can be extracted from almost any cellulosic material. The isolation of CNC from
cellulose source materials occurs in two stages, where the first one is a pre-treatment
of the source material that for wood and plants involves the complete or partial
removal of matrix materials—hemicelluloses, lignin, etc.—and isolation of the
cellulosic fibers. The second one is a controlled chemical treatment, generally
hydrolysis with a concentrated mineral acid (usually sulphuric acid), in order to
remove the amorphous regions of the cellulose polymer and obtain a highly crys-
talline structure. Usually the manufacturing process of choice is the solution casting
(Cao et al. 2008; Lu et al. 2006) even though also melt blending techniques have
been explored (Teixeira et al. 2009). According to the literature, the mechanical
properties (tensile strength and Young’s modulus), thermal property (Tg), and
moisture resistance generally show improvement with addition of CNWs to
starch-based materials (Cao et al. 2008; Chang et al. 2010; Kvien et al. 2007). This
can be related to both the good nanofiller dispersion in the matrix, resulting from
the chemical similarity, and the strong nanofiller–matrix adhesion by hydrogen
bonding interactions (Cao et al. 2008; Lu et al. 2006). In particular, the increase in
mechanical properties can be assisted by the formation of a rigid network of the
CNWs, the mutual entanglement between the nanofiller and the matrix, the efficient
stress transfer from the matrix to the nanofiller along with an increase in the overall
crystallinity of the system stemming from the nucleating effect of the CNWs. The
increase in Tg is due to the restriction of mobility of the amorphous starch chains by
the contact with the CNW surface or by the increased crystallinity, and to the
relocation of the plasticizers (including water) from the starch matrix to the CNW
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 141

surfaces that can decrease the overall plasticization effect on the amorphous regions.
As for cellulose-based microfibers, moisture resistance improves and this behavior
can be explained by the less hydrophilic nature of cellulose and the geometrical
hindrance created by the CNWs, by the constraint of the starch swelling due to the
presence of the rigid CNW network, and by a decrease in the mobility of the starch
chains, resulting from an increase in the Tg or the crystallinity as previously dis-
cussed (Xie et al. 2013).

3 Conclusions

As a whole, the production of natural fiber/agrowaste based thermoplastic com-

posites represents a promising possibility in the way to produce a biodegradable
material, aimed at applications such as packaging and automotive, with additional
benefits for the environmental impact of the whole process. Some difficulties persist
nonetheless, in particular: it is not obvious to ensure a good compatibility between
the biopolymer matrix and the vegetable fiber if they have not been obtained using
waste from the same agricultural crop. In other words, polysaccharides extracted
from agrowaste show a non negligible influence deriving from the botanical species
they were obtained, which in turn affects a number of properties in the final
composite, such as interaction with water and bacteria, crystallinity, glass transition
temperature, etc. To enhance crystallinity, the fabrication of nanocomposites could
be recommended, which needs in turn a further degree of chemical complexity that
may not always be desirable, especially when the final properties of the filler are not
outstanding, an outcome that may be attributed to the diversity of dimensions and
characteristics of cellulose particles.
In the future, it is suggested that study over possible agrowaste sources will be
expanded, with the aim both to lead to a sound characterization of their respective
properties and merits and to come to a suitable selection of plant-derived materials
based on their inherent characteristics rather than simply on their local availability
and limited cost.

References

Abdelmouleh M, Boufi S, Belgacem M, Dufresne A (2007) Short natural-fibre reinforced

polyethylene and natural rubber composites: effect of silane coupling agents and fibres loading.
Compos Sci Technol 67(7–8):1627–1639. doi:10.1016/j.compscitech.2006.07.003
Adekunle K, Akesson D, Skrifvars M (2010) Biobased composites prepared by compression
molding with a novel thermoset resin from soybean oil and a natural-fiber reinforcement.
J Appl Polym Sci. doi:10.1002/app.31634
Andjelkovic DD, Larock RC (2006) Novel rubbers from cationic copolymerization of soybean oils
and dicyclopentadiene. 1. Synthesis and characterization. Biomacromolecules 7(3):927–936.
doi:10.1021/bm050787r
142 D. Puglia et al.

Averous L, Boquillon N (2004) Biocomposites based on plasticized starch: thermal and

mechanical behaviours. Carbohydr Polym 56(2):111–122. doi:10.1016/j.carbpol.2003.11.015
Avérous L, Fringant C, Moro L (2001a) Plasticized starch–cellulose interactions in polysaccharide
composites. Polymer 42(15):6565–6572. doi:10.1016/S0032-3861(01)00125-2
Avérous L, Fringant C, Moro L (2001b) Starch-based biodegradable materials suitable for
thermoforming packaging. Starch—Stärke 53(8):368. doi:10.1002/1521-379X(200108)53:
8<368:AID-STAR368>3.0.CO;2-W
Aziz SH, Ansell MP (2004) The effect of alkalization and fibre alignment on the mechanical and
thermal properties of kenaf and hemp bast fibre composites: Part 1—polyester resin matrix.
Compos Sci Technol 64(9):1219–1230. doi:10.1016/j.compscitech.2003.10.001
Barbosa V, Ramires EC, Razera IAT, Frollini E (2010) Biobased composites from tannin–phenolic
polymers reinforced with coir fibers. Ind Crops Prod 32(3):305–312. doi:10.1016/j.indcrop.
2010.05.007
Barreto ACH, Esmeraldo MA, Rosa DS, Fechine PBA, Mazzetto SE (2010) Cardanol
biocomposites reinforced with jute fiber: microstructure, biodegradability, and mechanical
properties. Polym Compos 31(11):1928–1937. doi:10.1002/pc.20990
Barreto ACH, Rosa DS, Fechine PBA, Mazzetto SE (2011) Properties of sisal fibers treated by
alkali solution and their application into cardanol-based biocomposites. Compos A Appl Sci
Manuf 42(5):492–500. doi:10.1016/j.compositesa.2011.01.008
Barreto ACH, Junior AEC, Freitas JEB, Rosa DS, Barcellos WM, Freire FNA et al (2012)
Biocomposites from dwarf-green Brazilian coconut impregnated with cashew nut shell liquid
resin. J Compos Mater. doi:10.1177/0021998312441041
Belgacem MN, Gandini A (2005) The surface modification of cellulose fibres for use as
reinforcing elements in composite materials. Compos Interfaces 12(1–2):41–75. doi:10.1163/
1568554053542188
Biermann U, Friedt W, Lang S, Lühs W, Machmüller G, Metzger J et al (2000) New syntheses
with oils and fats as renewable raw materials for the chemical industry. Angew Chem
(International ed. in English) 39(13):2206–2224
Bisanda ET, Ogola W, Tesha J (2003) Characterisation of tannin resin blends for particle board
applications. Cem Concr Compos 25(6):593–598. doi:10.1016/S0958-9465(02)00072-0
Boquillon N (2006) Use of an epoxidized oil-based resin as matrix in vegetable fibers-reinforced
composites. J Appl Polym Sci 101(6):4037–4043. doi:10.1002/app.23133
Brinchi L, Cotana F, Fortunati E, Kenny JM (2013) Production of nanocrystalline cellulose from
lignocellulosic biomass: technology and applications. Carbohydr Polym 94(1):154–169.
doi:10.1016/j.carbpol.2013.01.033
Campaner P, D’Amico D, Ferri P, Longo L, Maffezzoli A, Stifani C, Tarzia A (2010) Cardanol
based matrix for jute reinforced pipes. Macromol Symp 296(1):526–530. doi:10.1002/masy.
201051069
Cao Y, Shibata S, Fukumoto I (2006) Mechanical properties of biodegradable composites
reinforced with bagasse fibre before and after alkali treatments. Compos A Appl Sci Manuf 37
(3):423–429. doi:10.1016/j.compositesa.2005.05.045
Cao X, Chen Y, Chang PR, Muir AD, Falk G (2008) Starch-based nanocomposites reinforced with
flax cellulose nanocrystals. Express Polym Lett 2(7):502–510. doi:10.3144/expresspolymlett.
2008.60
Chang PR, Jian R, Zheng P, Yu J, Ma X (2010) Preparation and properties of glycerol
plasticized-starch (GPS)/cellulose nanoparticle (CN) composites. Carbohydr Polym 79(2):
301–305. doi:10.1016/j.carbpol.2009.08.007
Chen Y, Zhang L, Deng R, Liang H (2006) Toughened composites prepared from castor oil based
polyurethane and soy dreg by a one-step reactive extrusion process. J Appl Polym Sci 101
(2):953–960. doi:10.1002/app.24023
Curvelo A (2001) Thermoplastic starch–cellulosic fibers composites: preliminary results.
Carbohydr Polym 45(2):183–188. doi:10.1016/S0144-8617(00)00314-3
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 143

Da Silva Santos R, de Souza AA, De Paoli M-A, de Souza CML (2010) Cardanol–formaldehyde
thermoset composites reinforced with buriti fibers: preparation and characterization. Compos A
Appl Sci Manuf 41(9):1123–1129. doi:10.1016/j.compositesa.2010.04.010
De Teixeira EM, Pasquini D, Curvelo AAS, Corradini E, Belgacem MN, Dufresne A (2009)
Cassava bagasse cellulose nanofibrils reinforced thermoplastic cassava starch. Carbohydr
Polym 78(3):422–431. doi:10.1016/j.carbpol.2009.04.034
De Teixeira EM, Curvelo AAS, Corrêa AC, Marconcini JM, Glenn GM, Mattoso LHC (2012)
Properties of thermoplastic starch from cassava bagasse and cassava starch and their blends
with poly (lactic acid). Ind Crops Prod 37(1):61–68. doi:10.1016/j.indcrop.2011.11.036
Derksen JTP, Cuperus FP, Kolster P (1996) Renewable resources in coatings technology: a
review. Prog Org Coat 27(1–4):45–53. doi:10.1016/0300-9440(95)00518-8
Dufresne A, Vignon MR (1998) Improvement of starch film performances using cellulose
microfibrils. Macromolecules 31(8):2693–2696. doi:10.1021/ma971532b
Dufresne A, Dupeyre D, Vignon MR (2000) Cellulose microfibrils from potato tuber cells:
processing and characterization of starch-cellulose microfibril composites. J Appl Polym Sci
76(14):2080–2092. doi:10.1002/(SICI)1097-4628(20000628)76:14<2080:AID-APP12>3.0.
CO;2-U
Dutta S, Karak N, Baruah S (2010) Jute-fiber-reinforced polyurethane green composites based on
Mesua ferrea L. seed oil. J Appl Polym Sci 115(2):843–850. doi:10.1002/app.30357
Dweib MA, Hu B, Shenton HW, Wool RP (2006) Bio-based composite roof structure:
manufacturing and processing issues. Compos Struct 74(4):379–388. doi:10.1016/j.
compstruct.2005.04.018
Faruk O, Bledzki AK, Fink H-P, Sain M (2012) Biocomposites reinforced with natural fibers:
2000–2010. Prog Polym Sci 37(11):1552–1596. doi:10.1016/j.progpolymsci.2012.04.003
Faulstich de Paiva JM, Frollini E (2006) Unmodified and modified surface sisal fibers as
reinforcement of phenolic and lignophenolic matrices composites: thermal analyses of fibers
and composites. Macromol Mater Eng 291(4):405–417. doi:10.1002/mame.200500334
Francucci G, Vázquez A, Ruiz E, Rodríguez ES (2012) Capillary effects in vacuum-assisted resin
transfer molding with natural fibers. Polym Compos 33(9):1593–1602. doi:10.1002/pc.22290
Frollini E, Oliveira FB, Ramires EC, Barbosa V Jr (2008) Composites based on tannins:
production, process and uses
Funke U, Bergthaller W, Lindhauer MG (1998) Processing and characterization of biodegradable
products based on starch. Polym Degrad Stab 59(1–3):293–296. doi:10.1016/S0141-3910(97)
00163-8
Fuqua MA, Huo S, Ulven CA (2012) Natural fiber reinforced composites. Polym Rev
52(3–4):259–320. doi:10.1080/15583724.2012.705409
Gao Z, Peng J, Zhong T, Sun J, Wang X, Yue C (2012) Biocompatible elastomer of waterborne
polyurethane based on castor oil and polyethylene glycol with cellulose nanocrystals.
Carbohydr Polym 87(3):2068–2075. doi:10.1016/j.carbpol.2011.10.027
Gassan J, Bledzki AK (2001) Thermal degradation of flax and jute fibers. J Appl Polym Sci 82
(6):1417–1422. doi:10.1002/app.1979
Ghassemi H, Schiraldi DA (2014) Thermoplastic elastomers derived from bio-based monomers.
J Appl Polym Sci 131(3). doi:10.1002/app.39815
Gironès J, López JP, Mutjé P, Carvalho AJF, Curvelo AAS, Vilaseca F (2012) Natural
fiber-reinforced thermoplastic starch composites obtained by melt processing. Compos Sci
Technol 72(7):858–863. doi:10.1016/j.compscitech.2012.02.019
Gopalakrishnan S, Linda FT (2011) Bio-based thermosetting tough polyurethanes. Der Chem Sin
2(5):54–64
Haq M, Burgueño R, Mohanty AK, Misra M (2008) Hybrid bio-based composites from blends of
unsaturated polyester and soybean oil reinforced with nanoclay and natural fibers. Compos Sci
Technol 68(15–16):3344–3351. doi:10.1016/j.compscitech.2008.09.007
Herrmann AS, Nickel J, Riedel U (1998) Construction materials based upon biologically
renewable resources—from components to finished parts. Polym Degrad Stab 59(1–3):
251–261. doi:10.1016/S0141-3910(97)00169-9
144 D. Puglia et al.

Ho M, Wang H, Lee J-H, Ho C, Lau K, Leng J, Hui D (2012) Critical factors on manufacturing
processes of natural fibre composites. Compos B Eng 43(8):3549–3562. doi:10.1016/j.
compositesb.2011.10.001
Hu B, Dweib M, Wool RP, Shenton HW (2007) Bio-based composite roof for residential
construction. J Archit Eng 13(3):136–143. doi:10.1061/(ASCE)1076-0431(2007)13:3(136)
Jenck JF, Agterberg F, Droescher MJ (2004) Products and processes for a sustainable chemical
industry: a review of achievements and prospects. Green Chem 6(11):544. doi:10.1039/
b406854h
John J, Bhattacharya M, Turner RB (2002) Characterization of polyurethane foams from soybean
oil. J Appl Polym Sci 86(12):3097–3107. doi:10.1002/app.11322
Kaewtatip K, Thongmee J (2012) Studies on the structure and properties of thermoplastic
starch/luffa fiber composites. Mater Des 40:314–318. doi:10.1016/j.matdes.2012.03.053
Kaewtatip K, Thongmee J (2014) Preparation of thermoplastic starch/treated bagasse fiber
composites. Starch—Stärke 66(7–8):724–728. doi:10.1002/star.201400005
Kaplan DL (ed) (1998) Biopolymers from renewable resources. Springer, New York
Keener T, Stuart R, Brown T (2004) Maleated coupling agents for natural fibre composites.
Compos A Appl Sci Manuf 35(3):357–362. doi:10.1016/j.compositesa.2003.09.014
Khalil HA, Tehrani M, Davoudpour Y, Bhat A, Jawaid M, Hassan A (2013) Natural fiber
reinforced poly(vinyl chloride) composites: a review. J Reinf Plast Compos 32(5):330–356.
doi:10.1177/0731684412458553
Kim H-S, Yang H-S, Kim H-J, Lee B-J, Hwang T-S (2005) Thermal properties of agro-flour-filled
biodegradable polymer bio-composites. J Therm Anal Calorim 81(2):299–306. doi:10.1007/
s10973-005-0782-7
Kong C, Park H, Lee J (2014) Study on structural design and analysis of flax natural fiber
composite tank manufactured by vacuum assisted resin transfer molding. Mater Lett 130:21–
25. doi:10.1016/j.matlet.2014.05.042
Kouisni L, Fang Y, Paleologou M, Ahvazi B, Hawari J, Zhang Y, Wang XM (2011) Kraft lignin
recovery and its use in the preparation of lignin-based phenol formaldehyde resins for
plywood. Cellul Chem Technol 45(7–8):515–520
Kozak N, Lobko E (2012) Bottom-up nanostructured segmented polyurethanes with immobilized
in situ transition and rare-earth metal chelate compounds—polymer topology—structure and
properties relationship, polyurethane, Dr. Fahmina Zafar (ed). InTech. doi:10.5772/48002,
ISBN 978-953-51-0726-2
Ku H, Wang H, Pattarachaiyakoop N, Trada M (2011) A review on the tensile properties of natural
fiber reinforced polymer composites. Compos B 42(4):856–873
Kvien I, Sugiyama J, Votrubec M, Oksman K (2007) Characterization of starch based
nanocomposites. J Mater Sci 42(19):8163–8171. doi:10.1007/s10853-007-1699-2
Laurichesse S, Avérous L (2014) Chemical modification of lignins: towards biobased polymers.
Prog Polym Sci 39(7):1266–1290. doi:10.1016/j.progpolymsci.2013.11.004
Leblanc N, Saiter JM (2009) Characterization of bulk agro-green composites: sisal fiber reinforced
wheat flour thermoplastics. Polym Compos. doi:10.1002/pc.20877
Lee K-Y, Wong LLC, Blaker JJ, Hodgkinson JM, Bismarck A (2011) Bio-based macroporous
polymer nanocomposites made by mechanical frothing of acrylated epoxidised soybean oil.
Green Chem 13(11):3117. doi:10.1039/c1gc15655a
Lin S, Huang J, Chang PR, Wei S, Xu Y, Zhang Q (2013) Structure and mechanical properties of
new biomass-based nanocomposite: castor oil-based polyurethane reinforced with acetylated
cellulose nanocrystal. Carbohydr Polym 95(1):91–99. doi:10.1016/j.carbpol.2013.02.023
Liu Z, Erhan SZ (2008) “Green” composites and nanocomposites from soybean oil. Mater Sci
Eng A 483–484:708–711. doi:10.1016/j.msea.2006.12.186
Liu Z, Erhan SZ, Akin DE, Barton FE (2006) “Green” composites from renewable resources:
preparation of epoxidized soybean oil and flax fiber composites. J Agric Food Chem 54
(6):2134–2137. doi:10.1021/jf0526745
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 145

Liu W, Drzal LT, Mohanty AK, Misra M (2007) Influence of processing methods and fiber length
on physical properties of kenaf fiber reinforced soy based biocomposites. Compos B Eng 38
(3):352–359. doi:10.1016/j.compositesb.2006.05.003
Liu H, Xie F, Yu L, Chen L, Li L (2009) Thermal processing of starch-based polymers. Prog
Polym Sci 34(12):1348–1368. doi:10.1016/j.progpolymsci.2009.07.001
Lligadas G, Ronda JC, Galià M, Cádiz V (2010) Plant oils as platform chemicals for polyurethane
synthesis: current state-of-the-art. Biomacromolecules 11(11):2825–2835. doi:10.1021/
bm100839x
Lochab B, Shukla S, Varma IK (2014) Naturally occurring phenolic sources: monomers and
polymers. RSC Adv 4:21712
Lu Y, Weng L, Cao X (2006) Morphological, thermal and mechanical properties of ramie
crystallites—reinforced plasticized starch biocomposites. Carbohydr Polym 63(2):198–204.
doi:10.1016/j.carbpol.2005.08.027
Lu J, Askeland P, Drzal LT (2008) Surface modification of microfibrillated cellulose for epoxy
composite applications. Polymer 49(5):1285–1296. doi:10.1016/j.polymer.2008.01.028
Lubi MC, Thachil ET (2007) Particleboard from cashew nut shell liquid. Polym Polym Compos
15:75–82
Maffezzoli A, Calò E, Zurlo S, Mele G, Tarzia A, Stifani C (2004) Cardanol based matrix
biocomposites reinforced with natural fibres. Compos Sci Technol 64(6):839–845. doi:10.
1016/j.compscitech.2003.09.010
Mahendran AR, Wuzella G, Aust N, Muller U, Kandelbauer A (2013) Processing and
characterization of natural fibre reinforced composites using lignin phenolic binder. Polym
Polym Compos 21(4):199–205
Mansouri NEEl, Yuan Q, Huang F (2011) Synthesis and characterization of kraft lignin-based
epoxy resins. BioResources. doi:10.15376/biores.6.3.2492-2503
Masoodi R, Pillai KM (2012) A study on moisture absorption and swelling in bio-based
jute-epoxy composites. J Reinf Plast Compos 31(5):285–294. doi:10.1177/0731684411434654
Masoodi R, El-Hajjar RF, Pillai KM, Sabo R (2012) Mechanical characterization of cellulose
nanofiber and bio-based epoxy composite. Mater Des 36:570–576. doi:10.1016/j.matdes.2011.
11.042
Matyjaszewski K, Möller M (eds) (2012) Polymer science: a comprehensive reference. Elsevier B.
V, Amsterdam
Mazumdar S (2001) Composites manufacturing: materials, product, and process engineering. CRC
Press, Boca Raton
Meier MAR, Metzger JO, Schubert US (2007) Plant oil renewable resources as green alternatives
in polymer science. Chem Soc Rev 36(11):1788. doi:10.1039/b703294c
Merlini C, Soldi V, Barra GMO (2011) Influence of fiber surface treatment and length on
physico-chemical properties of short random banana fiber-reinforced castor oil polyurethane
composites. Polym Test 30(8):833–840. doi:10.1016/j.polymertesting.2011.08.008
Mohanty AK, Misra M, Drzal LT (2001) Surface modifications of natural fibers and performance
of the resulting biocomposites: an overview. Compos Interfaces 8(5):313–343. doi:10.1163/
156855401753255422
Mosiewicki MA, Casado U, Marcovich NE, Aranguren MI (2008) Vegetable oil based-polymers
reinforced with wood flour. Mol Cryst Liquid Cryst 484(1):143/[509]–150/[516]. doi:10.1080/
15421400801904344
Müssig J (2008) Cotton fibre-reinforced thermosets versus ramie composites: a comparative study
using petrochemical- and agro-based resins. J Polym Environ 16(2):94–102. doi:10.1007/
s10924-008-0089-4
Ofem MI, Umar M, Ovat FA (2012) Mechanical properties of rice husk filed cashew nut shell
liquid resin composites. J Mater Sci Res 1(4):p89. doi:10.5539/jmsr.v1n4p89
Ouajai S, Shanks RA (2005) Composition, structure and thermal degradation of hemp cellulose
after chemical treatments. Polym Degrad Stab 89(2):327–335. doi:10.1016/j.polymdegradstab.
2005.01.016
146 D. Puglia et al.

Park S-J, Jin F-L, Lee J-R (2004) Synthesis and thermal properties of epoxidized vegetable oil.
Macromol Rapid Commun 25(6):724–727. doi:10.1002/marc.200300191
Pfister DP, Larock RC (2012) Cationically cured natural oil-based green composites: effect of the
natural oil and the agricultural fiber. J Appl Polym Sci 123(3):1392–1400. doi:10.1002/app.
33636
Phillips S, Kuo P-K, Demaria C, Lessarda L, Yan N, Hubert P, Sain M (2013) Development of
multi-scale biocomposites from flax, nanocellulose and epoxy by resin infusion. In: NIPMMP
Conference. Montreal, Quebec
Pranger L, Tannenbaum R (2008) Biobased nanocomposites prepared by in situ polymerization of
furfuryl alcohol with cellulose whiskers or montmorillonite clay. Macromolecules 41
(22):8682–8687. doi:10.1021/ma8020213
Quirino RL, Garrison TF, Kessler MR (2014) Matrices from vegetable oils, cashew nut shell
liquid, and other relevant systems for biocomposite applications. Green Chem 16(4):1700.
doi:10.1039/c3gc41811a
Ramires EC, Frollini E (2012) Tannin–phenolic resins: synthesis, characterization, and application
as matrix in biobased composites reinforced with sisal fibers Composites: Part B 43:2851–2860
Raquez J-M, Deléglise M, Lacrampe M-F, Krawczak P (2010) Thermosetting (bio)materials
derived from renewable resources: a critical review. Prog Polym Sci 35(4):487–509. doi:10.
1016/j.progpolymsci.2010.01.001
Raston C (2005) Renewables and green chemistry. Green Chem 7(2):57
Richardson MO, Zhang Z (2000) Experimental investigation and flow visualisation of the resin
transfer mould filling process for non-woven hemp reinforced phenolic composites. Compos A
Appl Sci Manuf 31(12):1303–1310. doi:10.1016/S1359-835X(00)00008-7
Rodriguez E, Giacomelli F, Vazquez A (2004) Permeability-porosity relationship in RTM for
different fiberglass and natural reinforcements. J Compos Mater 38(3):259–268. doi:10.1177/
0021998304039269
Rösch J, Mülhaupt R (1993) Polymers from renewable resources: polyester resins and blends
based upon anhydride-cured epoxidized soybean oil. Polym Bull 31(6):679–685
Sarkar S, Adhikari B (2001) Jute felt composite from lignin modified phenolic resin. Polym
Compos 22(4):518–527. doi:10.1002/pc.10556
Sharma V, Kundu PP (2006) Addition polymers from natural oils—a review. Prog Polym Sci 31
(11):983–1008. doi:10.1016/j.progpolymsci.2006.09.003
Shibata M, Nakai K (2010) Preparation and properties of biocomposites composed of bio-based
epoxy resin, tannic acid, and microfibrillated cellulose. J Polym Sci Part B Polym Phys 48
(4):425–433. doi:10.1002/polb.21903
Singha AS, Rana RK (2012) Natural fiber reinforced polystyrene composites: effect of fiber
loading, fiber dimensions and surface modification on mechanical properties. Mater Des
41:289–297. doi:10.1016/j.matdes.2012.05.001
Spontón M, Casis N, Mazo P, Raud B, Simonetta A, Ríos L, Estenoz D (2013) Biodegradation
study by Pseudomonas sp. of flexible polyurethane foams derived from castor oil. Int
Biodeterior Biodegradation 85:85–94
Stewart D (2008a) Lignin as a base material for materials applications: chemistry, application and
economics. Ind Crops Prod 27(2):202–207. doi:10.1016/j.indcrop.2007.07.008
Stewart R (2008b) Going green: eco-friendly materials and recycling on growth paths. Plast Eng
64(1):16–23
Sun G, Sun H, Liu Y, Zhao B, Zhu N, Hu K (2007) Comparative study on the curing kinetics and
mechanism of a lignin-based-epoxy/anhydride resin system. Polymer 48(1):330–337. doi:10.
1016/j.polymer.2006.10.047
Tang D, Macosko CW, Hillmyer MA (2014) Thermoplastic polyurethane elastomers from
bio-based poly(δ-decalactone) diols. Polym Chem 5(9):3231. doi:10.1039/c3py01120h
Tiamiyu AO, Ibitoye SA (2012) Effect of clay addition on service properties of a developed OPF–
CNSL–formaldehyde roofing material. Constr Build Mater 36:358–364. doi:10.1016/j.
conbuildmat.2012.04.130
Manufacturing of Natural Fiber/Agrowaste Based Polymer Composites 147

Van den Oever MJA, Bos HL, van Kemenade MJJM (2000) Influence of the physical structure of
flax fibres on the mechanical properties of flax fibre reinforced polypropylene composites. Appl
Compos Mater 7(5–6):387–402. doi:10.1023/A:1026594324947
Van Voorn B, Smit HH, Sinke R, de Klerk B (2001) Natural fibre reinforced sheet moulding
compound. Compos A Appl Sci Manuf 32(9):1271–1279. doi:10.1016/S1359-835X(01)
00085-9
Visakh PM, Thomas S, Chandra AK, Mathew AP (eds) (2013) Advances in elastomers II, vol 12.
Springer, Berlin. doi:10.1007/978-3-642-20928-4
Voirin C, Caillol S, Sadavarte NV, Tawade BV, Boutevin B, Wadgaonkar PP (2014)
Functionalization of cardanol: towards biobased polymers and additives. Polym Chem 5
(9):3142. doi:10.1039/c3py01194a
Wang R, Schuman TP (2013) Vegetable oil-derived epoxy monomers and polymer blends: a
comparative study with review. Express Polym Lett 7(3):272–292
Wang R, Ma J, Zhou X, Wang Z, Kang H, Zhang L et al (2012) Design and preparation of a novel
cross-linkable, high molecular weight, and bio-based elastomer by emulsion polymerization.
Macromolecules 45(17):6830–6839. doi:10.1021/ma301183k
Wik VM, Aranguren MI, Mosiewicki MA (2011) Castor oil-based polyurethanes containing
cellulose nanocrystals. Polym Eng Sci 51(7):1389–1396. doi:10.1002/pen.21939
Williams GI, Wool RP (2000) Composites from natural fibers and soy oil resins. Appl Compos
Mater 7:421–432
Wollerdorfer M, Bader H (1998) Influence of natural fibres on the mechanical properties of
biodegradable polymers. Ind Crops Prod 8(2):105–112. doi:10.1016/S0926-6690(97)10015-2
Xie F, Halley PJ, Avérous L (2012) Rheology to understand and optimize processibility, structures
and properties of starch polymeric materials. Prog Polym Sci 37(4):595–623. doi:10.1016/j.
progpolymsci.2011.07.002
Xie F, Pollet E, Halley PJ, Avérous L (2013) Starch-based nano-biocomposites. Prog Polym Sci
38(10–11):1590–1628. doi:10.1016/j.progpolymsci.2013.05.002
Yeganeh H, Mehdizadeh MR (2004) Synthesis and properties of isocyanate curable millable
polyurethane elastomers based on castor oil as a renewable resource polyol. Eur Polym J 40
(6):1233–1238. doi:10.1016/j.eurpolymj.2003.12.013
Yin Q, Yang W, Sun C, Di M (2012) Preparation and properties of lignin epoxy resin composite.
BioResources. doi:10.15376/biores.7.4.5737-5748
Zampaloni M, Pourboghrat F, Yankovich SA, Rodgers BN, Moore J, Drzal LT et al (2007) Kenaf
natural fiber reinforced polypropylene composites: a discussion on manufacturing problems
and solutions. Compos Part A Appl Sci Manuf 38(6):1569–1580. doi:10.1016/j.compositesa.
2007.01.001
Zhu L, Wool RP (2006) Nanoclay reinforced bio-based elastomers: synthesis and characterization.
Polymer 47(24):8106–8115. doi:10.1016/j.polymer.2006.07.076