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 Composites: Part A 77 (2015) 1–25

Contents lists available at ScienceDirect

Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Review

A review of the recent developments in biocomposites based on natural

fibres and their application perspectives
T. Gurunathan, Smita Mohanty, Sanjay K. Nayak ⇑
Central Institute of Plastics Engineering & Technology, Guindy, Chennai 600032, India
Laboratory for Advanced Research in Polymeric Materials, R&D Wing of CIPET, Bhubaneswar 751024, India

a r t i c l e i n f o a b s t r a c t

Article history: The growing ecological and environmental consciousness has driven efforts for development of new
Received 2 June 2014 innovative materials for various end-use applications. Polymers synthesized from natural resources, have
Received in revised form 5 June 2015 gained considerable research interest in the recent years. This review paper is intended to provide a brief
Accepted 6 June 2015
outline of work that covers in the area of biocomposites, major class of biodegradable polymers, natural
Available online 14 June 2015
fibres, as well as their manufacturing techniques and properties has been highlighted. Various surface
modification methods were incorporated to improve the fibre–matrix adhesion resulting in the enhance-
Keywords:
ment of mechanical properties of the biocomposites. Moreover, an economical impact and future direc-
A. Polymer-matrix composites (PMCs)
A. Fibres
tion of these materials has been critically reviewed. This review concludes that the biocomposites form
B. Environmental degradation one of the emerging areas in polymer science that gain attention for use in various applications ranging
B. Mechanical properties from automobile to the building industries.
Ó 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Major classes of degradable polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Environmentally degradable polymeric materials from renewable resources. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1.1. Polysaccharides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1.2. Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.3. Natural material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2. Biodegradable synthetic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.1. Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Natural fibre for biocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1. Lignocellulosic natural fibre . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2. Surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2.1. Physical modification of natural fibre . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.2. Chemical modification of natural fibre . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3. Manufacturing/processing aspects of biocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4. Biocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.1. Starch-based composites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2. Poly(hydroxyalkanoate)-based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.3. Poly(lactic acid)-based composites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.4. Soy resin-based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.5. Wood–Plastic Composites (WPCs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
5. Environmental and economic impact of biocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
6. Future scope of biocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

⇑ Corresponding author at: Central Institute of Plastics Engineering & Technology, Guindy, Chennai 600032, India. Tel.: +91 044 22253040; fax: +91 044 22254787.
E-mail address: drsknayak@gmail.com (S.K. Nayak).

http://dx.doi.org/10.1016/j.compositesa.2015.06.007
1359-835X/Ó 2015 Elsevier Ltd. All rights reserved.
2 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
7. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1. Introduction
Due to the concerns about environment and sustainability
issues, this century has witnessed remarkable improvements in
green materials in the field of polymer science through the devel-
opment of biocomposites [1,2]. These biocomposites can be easily
disposed of or composted at the end of their life without harming
the environment, which is not possible with synthetic fibre based
polymer composites. The Municipal solid waste (MSW) landfills
represent the dominant option for waste disposal in many parts
of the countries, 70% of MSW in Australia has been shown to land-
fills without pretreatment in 2002 [3]. Fishbein [4] has stated that
construction and demolition debris account for 10–30% of waste
received at landfill sites around the world. From the publication,
it is understood this [5] that to use a number has reached 40% in
the United States (US). The production of materials from renewable
feedstocks is expected to increase from 5% in 2004 to 12% in 2010,
18% in 2020 and 25% in 2030 [6]. Expectations are that
two-thirds of the USD 1.5 trillion global industries can eventually
be based on renewable resources. Lignocellulosic fibre, such as flax,
hemp, kenaf, henequen, banana, oil palm, and jute have drawn
considerable attention as substitutes to the synthetic fibres, such
as glass and carbon fibres [7,8]. Natural fibre-reinforced biocom-
posites have been used for many applications, such as automobiles,
aerospace, packaging and building industries, where a high load
carrying capacity is not required [8]. In addition, it is reported that
the US Department of Agriculture (USDA) and the US Department
of Energy (DOE), have targeted the achievement of 10% of basic
chemical building blocks arising from renewable plant resources
by 2020, which is expected to rise to 50% by 2050, as hurdles to
their use are reduced [9,10]. The attractive features of natural fibre
over the traditional counterparts include relatively high specific
strength, free formability, low self-weight and substantial resis-
tance to corrosion and fatigue [11]. In contrast, natural fibre is
not a problem-free alternative, and they maintain some shortfall
characteristics that are the high moisture absorption and highly
anisotropic nature [12]. Many studies on mechanical properties
of natural fibres and incorporated into various thermoplastics
(PHA and PLA) and thermosets (polyester, epoxy, and phenol
formaldehyde) have been attempted [13–18]. All these studies
have emphasized that the adhesion between the fibre–matrix
plays a significant role in the final mechanical properties of the bio-
composites since the stress transfer between matrix and fibre
determines the reinforcement efficiency [19]. However, natural
fibres contain large amount of cellulose, hemicelluloses, lignin
and pectins, it tends to be active polar hydrophilic material while
polymer materials are a polar and exhibit significant hydrophobic-
ity [2,12,19]. The weak interfacial bonding between highly polar
natural fibre and non-polar organophilic matrix can lead to a loss
in final properties of the biocomposites and ultimately hinders
their industrial usage [14,16,18,20]. Different strategies have been
applied to eliminate this deficiency in compatibility and interfacial
bond strength, including the use of surface modification tech-
niques [21]. It is worth mentioning that the chemical treatment
of the fibre, and hence good understanding of what occurs struc-
turally is required [22].
Chemical treatment involves modification of hydroxyl (AOH)
and carbonyl (C@O) groups in the fibre introducing distinct inter-
acting groups that can efficiently interlock with the matrix at the
interface [23]. Nowadays, to improve the compatibility between
fibre–matrix, various greener methods, such as plasma treatment
and treatments using enzymes, fungi, and bacteria have been
explored. Physical methods have also been examined, and a com-
prehensive review was collected by Mukhopadhay and Fangueiro
[24]. Plasma treatment offers a new approach to the modification
of natural fibre surfaces. Plasma treatment improves the fibre–ma-
trix adhesion mainly by providing polar or excited groups or even a
different polymer layer that can make strong covalent bonds
between the fibre and the matrix [25]. It has also been reported
that plasma radiations create a rough surface topology in the fibre
that increases the mechanical interlocks between the fibre and the
matrix [26].
Among various composite materials, natural fibre-reinforced
biocomposites are primarily used as low-cost materials that have
functional structural properties. Indeed, the depletion of petro-
chemical based materials has paved the way to switch to renew-
able resources based materials [27]. One of the earlier
publications on the topic under discussion is the work of Faruk
et al. [28] where they proposed simultaneous incorporation of
materials selection, the part geometry and the constraint and char-
acteristics of the production processes in the development of bio-
composites components. By taking advantages of natural fibre
based composites, spatial distribution of the lignocellulosic fibre,
biological, physical and chemical treatments, are associated with
each manufacturing process. Although several reviews
[1,2,8,12,19,20,29] deal with lignocellulosic based composites,
including preparation methods, properties and interfacial adhesion
between fibre–matrix, work remains to be done on the collective
analysis of various applications of cellulose-based material. This
review article describes the recent research works related to vari-
ous aspects of natural fibre and their use in the realization of bio-
composites. The constituents in terms of fibre–matrix
reinforcement systems, a variety of surface modification of fibre,
mechanical properties, and performance characteristics are also
evaluated. At the conclusion of the article, the authors pointed
towards some further research trends in this field to the wide-
spread use of biocomposites and natural materials.
2. Major classes of degradable polymers
2.1. Environmentally degradable polymeric materials from renewable
resources
Depending on the sources, existing biodegradable polymers can
be listed on the basis of their properties, origin, or synthesis
methodology. Averous and Boquillon [30] suggested the classifica-
tion of biodegradable polymers depending on the synthesis as
shown in Fig. 1. According to this classification, biodegradable
polymers themselves can be classified depending on their origin
as agro-polymers (polysaccharides, proteins), microbial PHA,
chemically synthesized using bio-based monomers like PLA, and
chemically synthesized monomers.
2.1.1. Polysaccharides
Polysaccharides (glycans), otherwise known as carbohydrates,
are the most widespread polymers in nature playing essential roles
to sustain living organisms. Polysaccharides have a general formula
Cx(H2O)y, where y is, usually, a large number between 200 and
2500. Polysaccharides are made of many monosaccharides
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25 3

Fig. 1. Classifications of the different biodegradable polymers [30].

Fig. 2. Structure of amylase (A) and amylopectin (B) macromolecules.

4 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
Table 1
Composition and characteristics of different starches [36].
Starch Amylose contenta Amylopectin contenta
(%) (%)
Wheat 26–27 72–73
Maize 26–28 71–73
Waxy starch <1 99
Amylomaize 50–80 20–50
Potato 20–25 79–74
a
Determined on a dry basis.
b
Determined after equilibrium at 65% RH, 20 °C, N.S.: Not Specified.
(hydroxy aldehydes or ketones), which are composed primarily of
carbon, oxygen, and hydrogen. The most common types of
monosaccharide units contain either five-(furanose) or six (pyre-
nees) carbon atoms. Due to the presence of many hydroxyl
(AOH) groups within the monosaccharide structure, hydrogen
bonds are formed between polymer chains [31]. Polysaccharides
are natural based materials possessing a unique combination of
functional properties and environment-friendly features. They are
non-toxic, biodegradable and renewable materials. Common
names for well-known polysaccharides are retained, such as starch,
proteins, cellulose, chitin, xanthan gum, dextrin, and carrageenan.
2.1.1.1. Starch. Among the natural polymers, starch has been con-
sidered as one of the most promising materials because of its
attractive combination of availability, low price (0.25–
0.6 USD/kg) and thermoplastic behaviour, besides the fact that
they are biodegradable, recyclable and renewable [32].
Unfortunately, these materials still have poor mechanical proper-
ties, remarkable sensitivity to moisture, difficulty of processing
and brittleness, which make it unsatisfactory in some industrial
purposes [33]. Starch is a natural polysaccharide that can be found
in several plant resources, such as roots (sweet potatoes, tapioca),
tubers (potatoes), stems (sago palm), cereal grains (corn, rice,
wheat, barley, oats, sorghum), and legume seeds (peas and beans)
[34]. In 2013, annual world corn (Zea mays L.) production was
about 964 million t that generated about 67 million t of cornhusk
[23]. Based on the fibre production as reported by Reddy and
Yang [35], at least 9 million t of cornhusk fibre can be produced
with a production cost competitive with cotton (Gossypium hirsu-
tum L.). Cornhusk is also one of the major food processing
by-products in Thailand. The economic feasibility of developing
cornhusk as an alternative to natural fibre is promising compared
to the availability and production cost of other natural fibre.
Starch granules have dimensions from 0.5 to 175 lm and can
appear in a wide variety of shapes. The starch is a polysaccharide
consisting only of homoglucan or a-D-glucopyranosyl repeating
units which can be organized to form two different molecules,
amylose and amylopectin [36]. Fig. 2 shows the typical structure
of amylose and amylopectin macromolecules. This biodegradable
polymer mainly consists of about 70–80% amylopectin
(poly-a-1,4-D-glucopyranoside and a-1,6-D-glycopyranoside), a
highly branched with a weight-average molecular weight (Mw) of
107–109 g mol 1 [36], and 20–30% amylase (poly-a-1,4-
D-glycopyranoside), a linear polymer with molecular weight of
105–106 g mol 1 and can have a degree of polymerization (DP) as
high as 600 [36,37]. The different molecular weights and degrees
of branching of both molecules are responsible for the quite differ-
ent properties of starch isolated from sources with diverse amy-
lose/amylopectin relative ratios [36]. The density of dry starch
varies from 1.514 to 1.520 g cm 3 whereas the density of equilib-
rium moisture content varies from 1.468 to 1.485 g cm 3.
Physically, most native starches are semi-crystalline, and their
crystallinity has been reported to be between 20% and 45%.
Amylose and amylopectin are arranged in granules in complex
Lipid contenta Protein contenta Moisture contentb Granule diameter Crystallinity
(%) (%) (%) (l) (%)
0.63 0.30 13 25 36
0.63 0.30 12–13 15 39
0.23 0.10 N.S. 15 39
1.11 0.50 N.S. 10 19
0.03 0.05 18–19 40–100 25
structures consisting of crystalline and amorphous regions [38].
The crystalline regions are formed as a consequence of the partic-
ular arrangement of the branches in the amylopectin chain [39].
The short branches are supposed to form double helices, which
to a great extent are organized into crystallites. The amorphous
and crystalline parts are arranged in alternate layers within the
starch granules [40].
Table 1 shows the starch composition, granule diameter and
degree of crystallinity of starches from different sources. As can
be seen, starch contain the least amount of amylopectin, in this
case, the amylomaize shows lower percentages of crystallinity.
Among the other starches, all those with a higher number of amy-
lopectin, wheat, maize and waxy starch, showed the percentage of
crystalline between 36% and 39%, whereas potato, is 25% [38,40].
The starch molecule has two primary functional groups, the
hydroxyl (AOH) group that is susceptible to substitution reactions
and the acetal (CAOAC) group that is susceptible to chain break-
age. The hydroxyl (AOH) group of glucose has a nucleophilic char-
acter. By reaction of its hydroxyl (AOH) group, modification of
various properties can be obtained, leading to materials with dif-
ferent properties [36]. Different strategies have been widely stud-
ied in order to improve starch mechanical and barrier performance
and reduce its hydrophilic nature, like adding crosslinking agents,
such as graft copolymerization [41], blending with thermoplastic
polymers [42], chemical modification [43], and development of
multilayer structures [44]. Among these techniques, many authors
have proposed blending of starch physically with other degradable
polymers, to enhance microstructures, such as co-continuous
structure can be formed by melt blending. The polymers used to
blend with thermoplastic starch (TPS) included cellulose nanopar-
ticles [45], and most often biodegradable polymers, such as chitin/-
chitosan [46], castor oil-based polyurethane (PU) [47], and
synthetic-derived polyester, such as poly(e-caprolactone) (PCL)
[48]. Some starch-based blends are nowadays marketed on a com-
mercial scale, with trademarks as Mater-BiÒ (Novamont, Italy),
BioplastÒ (Biotech, Germany), Novon™ (produced by Chisso in
Japan and Warner-Lambert in USA), BioparÒ (Biop Biopolymer
Technologies AG, Germany), GaialeneÒ (Roquette, France), and
SolanylÒ (Rodenburg Biopolymers, Netherlands).
In 2003, the market for starch-based bioplastics accounted for
about 25,000 t [49]. The market share of these products accounted
for about 70% of the global market for bioplastics. The global con-
sumption of starch-based biodegradable polymers increased up to
114,000 t in 2007. However, the production capacity according to
Fig. 3. Sturcture of amide bond linking amino acid.
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
the latest data reported by the University of Utrecht [49] shows as
projected increase to 810,000 t for 2020. The current production
capacity of Novamont is 8000 t. The physical–mechanical proper-
ties of Mater-BiÒ are similar to those of conventional plastics, such
as poly(ethylene) (PE), poly(propylene) (PP), and poly(styrene)
(PS). The amount of Mater-BiÒ which ranges at present from 1.92
to 45.12 USD/kg, compared to prices of between 3.84 and
6.4 USD/kg in 2003 [49]. However, this is still at highest price com-
pared to commodity plastics, such as PE, PP, PS, poly(ethylene
terephthalate) (PET) and poly(vinyl chloride) (PVC) (1.28–
1.79 USD/kg), which limits the use of starch-based plastics in some
applications.
With the concern for the industrial applications, starch-based
plastics represent a great potential because of their biodegradabil-
ity, their combustibility and renewable. The packaging industry
has been using some clever techniques to make use of starch and
more recently some novel manufacturing applications have been
shown in Lescher et al. [50]. Moreover, the foam derived from
starch has insulating properties similar to those of PS foam that
has been industrially produced by an extrusion process [51].
According to Guan and Hanna [52], starch foams can be employed
to substitute PS products, especially for loose-fill packaging appli-
cation. Loose-fill packaging materials provide protection, stabiliza-
tion, and cushioning of articles packaged and has to present
enough resilience, low density, and compressibility [53]. TPS foams
have promising characteristics but are susceptible to moisture
when they are stored in high relative humidity. Water molecules
attack the hydrogen bonds of starch, weakening them and decreas-
ing the functional properties of the materials. Some studies have
shown that the TPS blends with hydrophobic polymers are already
used commercially as oxygen barriers and easily foamed without
water [54]. In addition, blends incorporating water-free TPS with
hydrophobic polymers (PE) in the production of multilayered
materials to improve moisture sensitivity have been reported as
having good results [50]. They observed that the rotomoulded
samples, a high-amylose starch choice gave excellent stability over
time, but injection-moulded samples did not swell substantially
regardless of material choice. Lescher et al. [55] demonstrate
unique blends of water-free rotomouldable TPS/PE blend has been
produced in a single-step extrusion. The X-ray diffraction demon-
strates complete plasticization of the starch phase to be contingent
on high glycerol content.
2.1.2. Proteins
Proteins are one of the three essential macromolecules in bio-
logical systems and can easily be isolated from natural resources.
Proteins consist of natural chains of alpha-amino acids and are
extended through the formation of the amide linkages shown in
Fig. 3, which are readily degraded by protease enzyme. Proteins
can be classified into proteins from plant origin (wheat, corn,
soy, pea, and potato) and proteins from animal origin (casein,
whey, keratin, collagen, and gelatin). Plant proteins are complex
macromolecules that include a number of chemically linked amino
acid monomers, which collectively make polypeptide chains [56].
Table 2
Typical compositions of marketed soy proteins [36].
Soy material Component (%)
Moisture Protein Fat Fibre Ash
Full Fat Soy Four 3.40 41.00 22.50 1.70 5.10
Defatted Soy Flour 6.50 53.00 5.100 3.00 6.00
Soy Concentrate 9.00 65.30 0.300 2.90 4.70
Soy Isolate 4.80 92.00 – 0.25 4.00
a
Note: Protein Efficiency Ratio (PER) is a measurement of the efficient utilization
of the proteins in the body.
5
These proteins often have high molecular weights, in the range
of 1.66  10 19 g mol 1 which make them suitable for polymers.
Their decomposition temperature is considerably lower than that
of other natural polymers and hence finds limited usage in blends.
2.1.2.1. Soy protein. Soy protein, the major component of soybeans,
is readily available from renewable resources and by-products of
agricultural processing. Soybeans contain about 18% oil, 38% pro-
tein, 30% saccharides (15% soluble saccharides and 15% starch)
and 14% moisture and ash [56]. Typical compositions of soy protein
varieties are tabulated in Table 2. The attractive features of soy
protein are that it is biodegradable, environmental friendly, abun-
dant in renewable resource and has functional properties desired
for industrial applications [56]. Soybeans have been cultivated
for more than 3000 years in China and other Asian countries, such
as Japan and Korea. Some trials to cultivate soybeans have been
known in France and England during the 18th century, but have
not been developed further. According to the report of Nishinari
et al. [56] USDA developed the cultivation process and now USA
has the largest production capacity in the world [USA, 7  107 t;
Brazil, 5.8  107 t; Argentina, 5.8  107 t; China, 1.7  107 t; India
1.0  107 t]. Jane and Wang [57] have patented the processes to
provide a thermoplastic material made from soy protein into
moulded, solid plastic articles by extrusion and injection moulding.
They stated that the soy protein used may be in the form of soy-
bean meal or defatted soy flour (DSF) with 40–50% protein (includ-
ing 8.5% N), soy protein concentrate (SPC) with P70% protein
(11.5% N), and soy protein isolate (SPI) with P90% protein (13.7%
N). These products have different functional properties. Alkali
extraction of DSF provides SPC and SPI followed with acid prepara-
tion. Consequently, using soy protein in the form of DSF as much as
possible rather than SPI or SPC indicate more benefit in terms of
cost. Soy protein polymers are macromolecules that contain a
number of acidic amino acids (glutamic and aspartic acids) amides,
basic amino acids (lysine and arginine), nonpolar amino acids (ala-
nine, valine, and leucine), and an uncharged polar amino acid (gly-
cine) which have functional groups, such as acid (ACOOH), amine
(ANH2), and hydroxyl (AOH) [58]. These active functional groups
of soy protein can interact with natural fibre.
Soy protein can be processed using existing plastic processing
technologies: from the physicochemical or film casting method
[59] to thermoplastic/mechanical method (extrusion or compres-
sion moulding) [60]. However, common processing technique,
such as injection moulding has not been found to be useful for
the processing of protein-based bioplastic applications [60]. The
possible use of protein-based polymer to create various kinds of
shaped products entails new arguments in support of considering
these biopolymer materials as alternative to synthetic plastics for
different applications.
Soy proteins are globular, reactive and often water soluble.
Biocomposites from soy protein shows potential applications for
rigid packaging, coatings, and printing inks, lubricants, plastics,
automobile parts, transportation, housing and other special prod-
ucts [56]. However, the potential application of the soy protein
plastics is limited because of its low strength and high-moisture
absorption. Numerous studies have been reported and reviewed
by Song et al. [61] and Lam and Nickerson [62]. Considering differ-
ent alternatives to improve the mechanical properties and to
decrease the water sensibility of soy proteins based materials thus
PERa extending their usefulness. It can be blended with another
2.10
biodegradable polymer through physical–chemical or enzymatic
2.30 treatments or proteins and film forming dispersions. In 1940,
2.30 Henry Ford presented a car body made from soybean-based mate-
1.1–2.6 rials. Liang et al. [63] studied the suitability of soy proteins for
manufacturing moulded specimens. They noted that both SPI and
SPC resins represented rigid and brittle polymer properties after
6 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
curing, with tensile stress values similar to that of PS. Chabba and
Netravali [64] modified the SPC with glutaraldehyde and polyvinyl
alcohol (PVA) and formed composites with flax yarns and fabrics
exhibited an excellent properties. The main commercialization of
soy protein plastics is done in the USA (Heartland, Resource
Technologies, Iowa, Urethane Soy System Company, Illinois; and
Dow Chemical with SoyOilÒ and BioBalanceÒ).
2.1.2.2. Casein. Casein is a phosphoprotein obtained from skimmed
milk, which is about 80% of the total protein content of the milk.
Casein micelles are composed of several thousand molecules,
bonded via calcium phosphate nanoclusters [65]. Owing to its
excellent mechanical and barrier properties, casein finds the appli-
cation in food and non-food industrial sectors. In addition to this,
casein bears excellent emulsifying ability, high nutritional value
and solubility in water. The major fraction of milk proteins belongs
to the casein group which consists of as1-, as2-, b-, and j-casein
and their portions are nearly 38%, 10%, 36% and 12%, respectively,
with the respective molecular weights of 23,164, 25,388, 23,983
and 19,038 Da [66]. The chemistry of caseins concerns either side
phenomena of their isolation or techniques used to improve their
properties. Some essential chemical groups are present in the
casein molecule and 55% of the amino acid residues contain polar
groups, such as carboxylic (25.8%; CH2COOH, CH2CH2COOH),
amino (15.1%; (CH2)4NH2, (CH2)3NHC(@NH)NH2), and hydroxyl
(14.6%; CH2OH, (CH2)7OH, CH(CH3)OH) [67]. The primary reactions
described in the literature are dephosphorylation, glycosylation,
deamidation, acylation, enzyme-catalysed reactions, grafting,
crosslinking, and temperature effects. Casein can be distinguished
from other milk components by precipitating near their isoelectric
pH (4.6 at 20 °C). Deamidation of proteins involves the acid- or
base-catalysed hydrolysis of asparagines (Asp) or glutamine (Glu)
amide groups [68]. Zhang et al. [69] showed that the deamidation
rate is more dependent on the protein nature and its amide content
under basic conditions than under acidic conditions; this allows
the differentiation of proteins. Darewicz et al. [70] carried out
in-depth studies on the structure and properties of glycated casein.
They showed that the glycated protein contains up to six glucose
moieties and forms emulsions with smaller droplets of the
non-modified casein.
2.1.2.3. Other proteins. Gelatin is a commonly used natural polymer
that is derived from collagen. The principal raw materials used in
gelatin production are cattle bones, cattle hides, and pork skins.
Collagen is distinctive among proteins because it contains an
unusually high level of two cyclic amino acids, hydroxyproline
and proline. It consists of three helical polypeptide chains would
around each other and connected by intermolecular crosslinks.
This is particularly important in pharmaceutical and medical appli-
cations because of its biodegradability [71] and biocompatibility
[72] in physiological environments. This structure acts as a rigid
rod, which becomes the major stress-bearing element of the verte-
brate connective tissues. The collagen molecule has a molecular
weight of 65,000–300,000 g mol 1, diameter of 1.5 nm, and length
of 2800 nm [72]. The most important characteristic feature of gela-
tin (arising from its amino acid content) is that it is very rich in free
amino (ANH2) and carboxyl (ACOOH) groups. In addition to the
intra- and intermolecular condensation reactions, crosslinking
with bifunctional reagents involving these free functional groups
is possible [73]. Gelatin readily forms thermally reversible gels
over a wide range of pH with a variety of solutes. Gels are also
formed by covalent crosslinking of organic reagents with amino
and carboxyl functions and by individual multivalent metal ions
that form complexes with various amino acid side groups.
Anhydrous gelatin has a density of 1.64 g cm 3; if it is heat-dried
Fig. 4. General structure of poly(hydroxyalkanoate). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of
this article.)
below 1% moisture, it tends to crosslink covalently and becomes
insoluble [74].
Gluten is the main storage protein in wheat and corn. It is a
complex mixture of hundreds of related but distinct proteins,
mainly gliadin and glutenin. The mechanical treatment of gluten
leads to the formation of a disulphide bridge which is responsible
for the creation of strong, viscoelastic and voluminous dough [75].
The protein based materials, such as wheat gluten (WG) films exhi-
bit humidity dependent gas (O2 and CO2) permeabilities and water
vapour permeability (WVP); allowing optimal gas composition for
food preservation [76]. Corn gluten meal (CGM) and corn gluten
feed (CGF) containing protein fractions are by-products in the
wet milling process. Non-gluten proteins include a-amylase/
trypsin inhibitors and have recently been suggested to induce
intestinal inflammation [77].
Silk fibrous protein belongs to the group of secretion-type ani-
mal fibre. They possess high stiffness, high strength along with
outstanding elongation at break. Silks are produced mostly by spi-
ders and insects, especially by silkworms [78]. Although both
fibroin and sericin consist of proteins, they strongly differ in the
related building blocks. It is worth noting that all proteins are built
up of twenty naturally occurring amino acids. The silkworm fibroin
is a single protein that follows the pattern -Gly-Ala-Gly- [79], while
sericin is a mixture of proteins containing various amino acids. The
molecular conformation with the crystalline modification (a- and
b-forms) is still a topic of some discussion. An numerous
H-bonds (˜C@O


HAN—) form between the chains within the crys-
talline unit. The degree of crystallinity of silks produced by various
domestic and wild silkworms varies between 39.0–47.2% and
39.5–446.4%, respectively. The related densities are in the ranges
of 1.244–1.371 and 1.271–1.345 g cm 3. The average density value
of silk is usually reported to be 1.3 g cm 3. The length of
non-broken silk fibre is changes between 300 and 1500 m [80].
2.1.3. Natural material
2.1.3.1. Poly(hydroxyalkanoate) (PHA). Poly(hydroxyalkanoate)
(PHA) are also capable of being delivered from a wide variety of
substrates, such as renewable sources (sucrose, starch, cellulose,
triacylglycerols), fossil resources (methane, mineral oil, lignite,
hard coal), chemicals (propionic acid, 4-hydroxybutyric acid),
byproducts (molasses, whey, glycerol), and carbon dioxide [81].
PHA’s are polyesters of hydroxy alkanoate (HA) which have the
repeat structure and unit as shown in Fig. 4. In PHA polymer, the
carboxyl group of one monomer produces an ester bond with the
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25 7

Table 3
Comparison of mechanical properties of biodegradable polymers with polyolefins [7,2,36].
3
Type of polymer Tg (°C) Tm (°C) Density (g cm ) T.S. (MPa) T.M. (GPa) Strain at break (%)
PLA 45–60 150–162 1.21–1.25 21–60 0.35–3.5 2.5–6
L-PLA 55 170 1.24 15.5 2.7 3
DL-PLA 50 – 1.25 27.6 1 2
PGA 35–40 220–233 1.5 60–99.7 6–7 1.5–20
PCL 60 to 65 58–65 1.11–1.146 20.7–42 0.21–0.44 300–1000
P(3HB) 5–15 168–182 1.18–1.262 25–40 3.5 5–8
P(4HB) 48 53 – 104 149 1000
Starch – 110–115 1–1.39 35–80 0.125 31
DL-PLA/PGA50/50 40–50 – 1.30–1.40 41.4–55.2 1–4.34 2–10
DL-PLA/PGA75/25 50–55 – 1.3 41.4–55.2 0.21–0.44 2.5–10
P(3HB-co-20%3HV) 1 145 1.25 20 1.2 50
P(3HB-co-16%4HB) 7 150 – 26 – 444
P(3HB-co-10%4HHx) 1 127 1.07–1.25 21 – 400
PP 10 to 23 160–176 0.899–0.920 26–41.4 0.95–1.776 15–700
PS 100 110–135 1.04–1.09 30–60 4–5 1–2.5

Tg: glass transition temperature; Tm: melting point; T.S.: tensile strength; T.M.: tensile modulus.

hydroxyl group of the adjacent monomer (Fig. 4). In Fig. 4, the ‘R’
refers to the side chain, whereas ‘X’ refers to the number of ‘CH2’
groups. Both ‘R’ and ‘X’ determine the HA unit is constituting the
polymer chain. PHA exists as discrete inclusions that are typically
0.2 ± 0.5 mm in diameter localized in the cell cytoplasm. The
molecular weight of PHA ranges from 2  105 to 3  106 g mol 1
[83].
Many works have been reported on the production of bacterial
PHA’s at an industrial scale, but results showed that these poly-
mers were much more expensive to produce than conventional
petrochemical-based plastics [82]. Over 150 different types of
hydroxyalkanoate (HA) monomers have been identified, and there
is an enormous variation possible in the length and composition of
the side chains [83]. PHA varies in their physical and chemical
characteristics owing to their varied monomer content. Factors
affecting the monomer content include microorganisms
(gram-negative or gram-positive), modes of fermentation (batch,
fed-batch, continuous), media ingredients, fermentation condi-
tions, and recovery [81]. Bacterial PHA can be broadly divided into
three main types depending on the number of carbon atoms in the
monomers. This category includes short chain length (scl) poly-
mers consisting of 3–5 carbon atoms containing monomers, syn-
thesized by various bacteria, including Alcaligenes latus and
Cupriavidus necator. The other group is a medium chain length
(mcl) polymer, consisting of 6–14 carbon atom containing mono-
mers, also synthesized by bacteria including Pseudomonas putida
and Pseudomonas mendocina. Furthermore, copolymers of PHA
are found among the scl-PHA, e.g. poly(3-hydroxybutyrate-co-3-hy
droxyvalerate (PHBV) and mcl-PHA, e.g. poly(3-hydroxyhexanoa
te-co-3-hydroxyoctanoate) P(3HHx-co-3HO); as well as copoly-
mers of scl and mcl PHA containing the scl and mcl monomers
(long chain length PHA (lcl-PHA, ˜C14) [84]. These materials have
mechanical properties that are comparable to those of PP and PS is
shown in Table 3.
PHA have received extensive attention due to their inherent
biocompatibility and biodegradability. Microorganisms in nature
are able to degrade PHA by non-enzymatic and enzymatic hydrol-
ysis in animal tissue [85]. However, many factors affect the
biodegradability and biocompatibility of PHA, such as stereoregu-
larity, molecular mass, monomeric composition, crystallinity, and
its surface area of the polymer. In addition, environmental condi-
tions including temperature, moisture level and pH affect the rate
of degradation. Studies carried out by Tokiwa et al. [86] showed
that biodegradation of PHA is influenced by its chemical structure,
such as the presence of functional group in the polymer chain, the
hydrophilicity/hydrophobicity balance, crystallinity and
morphological properties. As a result, mcl-PHA with low crys-
tallinity and low Tm are more degradable than scl-PHA that have
comparatively higher crystallinity and higher Tm. Moreover, blend-
ing with gelatin created a more porous polymer surface, which was
exposed to hydrolytic attack, as observed by scanning electron
microscopy (SEM) analysis [86]. Wang et al. [87] blended gelatin
with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx)
and they found that blending of gelatin accelerated the degrada-
tion of PHBHHx. They concluded that the weight loss is seen first
due to a reduction in the crystallinity of the blended polymer as
confirmed by the weakening of its crystalline peak from X-ray
diffraction (XRD) analysis.
In recent years, poly(3-hydroxybutyrate) (PHB) has been pro-
duced commercially in many different forms; some plasticized
and others copolymerized. Biomer P226, studied herein, is PHB
plasticized by a proprietary citrate plasticizer and produced in
Germany. The tensile properties of Biomer P226 were measured
by Taha and Ziegmann [88] as 22.7 MPa, 3.7 GPa, and 6.62% for ten-
sile strength, modulus, and elongation, respectively. PHB industrial
SA (Brazil) produces PHBV (HV = 12%) 45% crystalline from sugar-
cane molasses. The BiocycleÒ production was planned to be
4000 t in 2008 and then to be extended to 14,000 t. In 2004,
Procter & Gamble (US) and Kaneka Corporation (Japan) directed
efforts to the development and commercialization of a variety of
PHA copolymers under the name Nodax. The NodaxÒ family of
copolymers is poly(3-hydroxybutyrate-co-3-hydroxyalkanoate)
(PHBHx, PHBO, PHBOd) with a copolymer content varying from 3
to 15 mol% and chain length from C7 up to C19 [89]. The major
manufacturers of PHA including BiogreenÒ (Mitsubishi Gas
Chemical Company Inc, Japan), Mirel™ (Telles (ADM/Metabolix),
USA), BiomerÒ (Biomer Inc, Denver), ENMAT™ (Tianan Biologic,
Ningbo china), GreenBioÒ (Tianjin Green Bio-Science Co.,
China/DSM, Netherlands), BIOPOLÒ (Metabolix Inc., USA),
TephaFLEXÒ (Tepha Inc., USA), VersaMer PHA (PolyFerm Canada,
Canada), and Procter & Gramble (USA).
2.2. Biodegradable synthetic polymers
2.2.1. Polyesters
2.2.1.1. Poly(lactic acid) (PLA). Poly(lactic acid) or polylactide [PLA:
(ACH(CH3)ACOAOA)n] is the most extensively researched and uti-
lized biodegradable thermoplastic polyester, having potential to
replace conventional fossil fuel based polymers [90]. To determine
if PLA is environmentally sustainable, life cycle assessment (LCA)
studies are carried out by many researchers. Vink et al. [91] have
reported the energy input for a NatureWorks™ PLA in comparison
8 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25

Fig. 5. Synthesis route of poly(lactic acid).

Fig. 6. Classification of natural and synthetic fibres. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
Fig. 7. Structural organization of the major constituents in the fibre cell wall. (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
to petrochemical-based polymers. They found a gross fossil energy
requirement of 54 MJ/kg for production. This represents an energy
conservation of 25–55% compared to petrochemical-based poly-
mers like Nylon 66 and PP. The authors pointed out that an
improved production process developed by Cargill Dow led to
the fossil energy reduction of more than 90%. PLA is a renewable
(derived from potato, corn, and beet sugar), recyclable, com-
postable and bioabsorbable polyester that exhibits excellent pro-
cessability [92]. PLA has many industrial applications, such as the
packaging, textiles, biomedical, fibre, consumer goods and automo-
tive industries because of its unique properties [92].
Many studies have investigated have studied the biodegradabil-
ity of PLA, and it has been concluded that it mainly depends on the
molecular weight [91]. Based on the above backdrop, it appears
that a holistic approach should be undertaken for the synthesis
of PLA. However, there are serious limitations, notably inherent
brittleness and poor toughness (less than 10% elongation at break),
9
slow degradation rate (hydrolysis of backbone ester groups), which
impede its extensive application [93]. PLA degradation is depen-
dent on time, temperature, impurities and residual catalyst con-
centration [94]. Catalysts and oligomers reduce the degradation
temperature and increase the degradation rate of PLA. PLA is syn-
thesized either through ring-opening polymerization of lactide
(LA) or polycondensation of lactic acid (2-hydroxy propionic acid)
as illustrated in Fig. 5 [95].
The synthesis of PLA through polycondensation of the lactic acid
monomer provided, an average molecular weight less than
1.6  104 g mol 1 whereas ring opening polymerization of lactides
gave average molecular weights ranging from 2  104 to
6.8  104 g mol 1 [95]. The monomer, lactic acid, can be produced
on a mass scale by the microbial fermentation of agricultural
by-products mainly the carbohydrate-rich substances. Lactic acid
is one of the simplest chiral molecules and exists in three stereo-
chemical forms: poly(D-lactic acid) (PDLA) and poly(L-lactic acid)
10 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25

Table 4
Chemical composition and structural parameters of common lignocellulosic fibre.

Fibre Cellulose (wt%) Hemicellulose (wt%) Lignin (wt%) Pectin (wt%) Water soluble (wt%) Wax (wt%) Microfibrillar angle (deg) Ref.
Bark/Stem fibre
Flax 71–78 18.6–20.6 2.2 2.3 3.9–10.5 1.7 5–10 [2,7,113]
Hemp 70.2–74.4 17.9–22.4 3.7–5.7 0.9 2.10 0.8 2–6.2 [7,28,113]
Jute 61–71.5 13.6–20.4 12–13 0.2 1.2 0.5 8 [2,7]
Kenaf 45–57 21.5 8–13 3–5 N.S. N.S. N.S. [7,113,22]
Ramie 68.6–76.2 13.1–16.7 0.6–0.7 1.9 6.1 0.3 7.5 [7,113]
Banana 63–64 10 5 N.S. N.S. N.S. 11 [12,113]
Nettle 86 4.0 5.4 0.6 2.1 3.1 N.S. [113]
Leaf fibre
Sisal 67–78 10–14 8–11 10 1.3 2 10–22 [2,7]
Curaua 73.6 9.9 7.5 N.S. N.S. N.S. N.S. [28]
Pineapple 80–83 15–20 8–12 2–4 1–3 4–7 8–15 [28,113]
Abaca 56–63 21.7 12–13 1.0 1.6 0.2 N.S. [28,113,22]
Henequen 77.6 4–8 13.1 N.S. N.S. N.S. N.S. [22]
Fruit/Seed fibre
Cotton 85–90 5.70 0.7–1.6 0–1 1.0 0.6 20–30 [2,7]
Coir 36–43 0.15–0.25 41–45 3–4 5.2–16.0 N.S. 30–49 [2,7]
Oil palm 65 0–22 19 N.S. N.S. N.S. 46 [25]
Wood
Hardwood 43–47 25–35 16–24 N.S. N.S. N.S. N.S. [12]
Softwood 40–44 25–29 25–31 N.S. N.S. N.S. N.S. [12]

N.S.: Not Specified.

(PLLA), respectively. PLA has a crystallinity of around 37%, a glass
transition temperature (Tg) between 50–65 °C, a melt temperature
(Tm) of 173–178 °C and a tensile modulus 2.7–16 GPa [96]. The
properties of the PLA are presented in Table 3.
Applications of PLA are expected to increase so that the produc-
tion cost of PLA is likely to decrease in the near future. In 2002,
Cargill-Dow LLC was producing PLA to the tune of 140 t in Blair,
Nebraska, USA. Cargill Dow LLC introduced PLA fibre Ingeo™ spun
from the NatureWorks™ polymer in 2003 [96]. Dow sold its share
to Cargill in 2005, which renamed their PLA business NatureWorks
LLC. Currently, there are other manufactures, such as LOOPLAÒ
(Galactic, Belgium), EcolojuÒ (Mitsubishi Plastics, Inc. Japan),
Zhejiang Hisun Biomaterial (Zhejiang, China), PalgreenÒ (Mitsui
Chemicals Tohcello, Japan), Pyramid Bioplastics Guben GmBH
(Germany), PURALACTÒ (Purac, Netherland), BIOFRONTÒ (Teijin,
Japan), Shanghai Tongjieliang BioMaterial (Shanghai, China),
VYLOECOLÒ (Toyobo, Japan) and LactyÒ (Shimadzu Corp. Japan),
have been known to produce PLA.
3. Natural fibre for biocomposites
3.1. Lignocellulosic natural fibre
Natural fibre is subdivided, based on their origins, viz. plants,
animals, or minerals. All plant fibres are composed of cellulose
while animal fibres consist of proteins (hair, silk and wool). Plant
fibres includes bast (or stem or soft sclerenchyma) fibre, leaf or
hard fibre, seed, fruit, wood, cereal straw and other grass fibres.
A diagram with a classification of the various fibres is shows in
Fig. 6. Over the last few years, a number of researchers have been
involved in studying the exploitation of natural fibre as composite
materials [97].
Lignocellulosic fibres have three primary chemical constituents,
namely cellulose (a-cellulose), hemicelluloses and lignin. In addi-
tion, lignocellulosic fibres also contains minor as amount of pectin,
waxes, and water-soluble substances [29]. The general chemical
structures of cellulose, hemicelluloses, lignin and pectin are shown
in Fig. 7. Table 4 lists the chemical composition of several lignocel-
lulosic fibres. Lignocellulose fibres compositions and structures
vary greatly, depending on plant species, age, climate, and soil con-
ditions. The information on the chemical composition of
lignocellulosic fillers and fibres is important because it determines
their properties and thus their applications.
An essential part of all lignocellulosic fibres is cellulose.
Cellulose itself is a linear macromolecule consisting of
b-D-glucose units, linked together by b-1,4-glycosidic linkages at
C1 and C4 position to generate a linear polymer chain [29].
Cellulose is a polysaccharide (C6H12O5)n which can be degraded
to yield glucose (C6H12O6). The shortest repeat unit is cellobiose
(C6H11O5)2O developed by the condensation of two glucose units
and hence is also known as anhydrocellobiose as shown in
Fig. 7a. Each repeat unit contains six hydroxyl groups, which form
intermolecular and intramolecular hydrogen bonds with the
macromolecule itself and also with other cellulose macro-
molecules or polar molecules [2]. Therefore, all lignocellulosic
fibres are hydrophilic in nature. The degree of polymerization of
cellulose varies according to the plant species (7000–15,000).
Cellulose macromolecules exist in tightly packed; slender
rod-like crystalline structures called microfibrils. The remaining
portion that has a lower packing density is referred to as amor-
phous cellulose [98]. The cellulose chains agglomerate to 3–
5 nm thick (microfibrils) with crystalline and non-crystalline
regions. It is water insoluble but recalcitrant to hydrolysis because
of its densely packed highly crystalline structure with straight,
stable supra-molecular fibre of high tensile strength and its low
accessibility [2,20]. The hydroxyl groups of the glucose residues
from one chain form hydrogen bonds with the oxygen molecules
on the same or a neighbour chain, thereby holding the chains
firmly together and forming microfibrils that make the recalcitrant
compact structure [20,98].
Hemicellulose the second most abundant organic material on
earth after cellulose, it was assumed that the moisture of the hemi-
cellulose is 2.6 times higher than lignin [29]. Hemicellulose is
structurally more complex than cellulose, which contains only
1,4-b-D-glucopyranose linkages (Fig. 7b) [97]. It is bound to the
cellulose and lignin component by covalent and non-covalent
bonds in the cell wall, the interactions between these components
increase the rigidity and flexibility of fibre cell wall. Hemicelluloses
are a group of homo- and heteropolymers consisting mainly of
anhydro-b-(1-4)-D-xylopyranose, glucopyranose, mannopyranose,
and galactopyranose main chains with a number of substituent
[97]. In addition, the degree of polymerization of native cellulose
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25 11

Table 5
Physical and mechanical properties of commercially important lignocellulosic fibre and of E-glass fibre [2,7,8,21,28,29,113,232,248].
1
Fibre Density Length Diameter Strain at Tensile Young’s Specific Specific Moisture Price (kg )
(g cm 3) (mm) (lm) break (%) strength (MPa) modulus (GPa) strength (MPa) modulus (GPa) content (%) (USD)
Cotton 1.21 15–56 12–35 2–10 287–597 6–10 194–452 4–6.5 33–34 $1.5–$2.2
Jute 1.23 0.8–6 5–25 1.5–3.1 187–773 20–55 140–320 14–39 12 $0.926
Flax 1.38 10–65 5–38 1.2–3 343–1035 50–70 345–620 34–48 7 $3.11
Sisal 1.20 0.8–8 7–47 1.9–3 507–855 9–22 55–580 6–15 11 $0.65
Ramie 1.44 40–250 18–80 2–4 400–938 61.4–128 590 29 12–17 $2
Hemp 1.35 5–55 10–51 1.6–4.5 580–1110 30–60 210–510 20–41 8 $1.55
Coir 1.2 0.3–3.0 7–30 15–25 175 6 92–152 5.2 10 $0.2–$0.4
Kenaf 1.2 1.4–11 12–36 2.7–6.9 295–930 22–60 246–993 18–50 6.2–12 $0.378
Banana 1.35 0.9–0.4 12–30 5–6 529–914 27–32 392–677 20–24 10–11 N.S.
Pineapple 1.5 3–8 8–41 1–3 170–1627 60–82 287–1130 42–57 10–13 $0.40–
$0.55
Abaca 1.5 4.6–5.2 10–30 2.9 430–813 31.1–33.6 N.S. N.S. 14 $0.345
Bamboo 0.6–1.1 1.5–4 88–25 1.3–8 140–441 11–36 383 18 N.S. $0.5
Nettle 1.51 5.5 20–80 1.7 650 38 N.S. N.S. 11–17 N.S.
Hardwood 0.3–0.88 3.3 16 N.S. 51–120.7 5.2–15.6 N.S. N.S. N.S. $0.44–
$0.55
Softwood 0.30.59 1.0 30 4.4 45.5–11.7 3.6–14.3 N.S. N.S. N.S. $0.44–
$0.55
E-glass 2.5 N.S. 15–25 2.5 2000–3500 70–73 800–1400 29 N.S. $2
S-glass 2.5 N.S. N.S. 2.8 3–3.5 63–67 1.8 34.4 N.S. $2

N.S.: Not Specified.

is about 10–100 times greater than that of hemicellulose. Although partly esterified with methanol or have no or negligible amounts
the chemical bonds between cellulose and hemicellulose are not of methyl esters [29]. Pectins typically represent a complex group
covalent, they are still very strong and difficult to separate. The of heteropolysaccharides called glycosaminoglycans, which also
major hemicellulose components in softwood are mannan-based vary in methyl ester content. The simplest pectin is homogalactur-
and those in hardwood xylan-based. Hemicelluloses constitute onan (HG), an unbranched polymer of a-(1 ? 4) linked
on average about 26% of hardwood, 22% of softwood, and 30% of D-galacturonic acid as shown in Fig. 7d. The predominant galactur-
various agricultural residues [19,97]. onan backbone of pectin is, however, modified by the insertion, at
Lignin is defined as polymeric natural products arising from an intervals, of a-L-rhamnopyranose units [101]. Rhamnogalacturonan I
enzyme-initiated dehydrogenative polymerization of three pri- (RGI) is a complex pectic polysaccharide with a backbone com-
mary precursors: trans-coniferyl, trans-sinapyl, and trans- posed of alternating a-(1 ? 2) linked L-rhamnose-a-(1 ? 4) linked
p-coumaryl shown in Fig. 7c [19]. The only difference between
D-galacturonic acid. Rhamnogalacturonan II (RGII) is a highly
the precursors is the number of methoxyl groups (AOCH3) present
branched pectic polysaccharide with a backbone made of (1 ? 4)
on the aromatic ring. Lignin fills the spaces in the cell wall between
linked galacturonic acid residues. RGI has been suggested to func-
pectin, hemicellulose, and cellulose. Lignin is a three-dimensional
tion as a scaffold to which other pectins, such as RGII and HG, are
(highly branched) polymer composed of aromatic units with strong
covalently attached [101].
intramolecular bonding [19]. Lignin is encrusted in the cell wall
Waxes are also important in terms of technological parameters.
and partially covalently bonded with hemicellulose. In addition,
They determine soft touch, low friction and thus the case of mov-
chemical substituents of the backbone of the hemicellulose, such
ing the fibre [2,19]. In flax fibre, waxes are present mainly in the
as arabinose, galactose, and 4-O-methylglucronic acid, are cova-
outer part of the stem, in the epidermis, and in smaller amounts
lently linked with lignin. Due to its insolubility in water, amor-
in fibre cells. Waxes contain different types of alcohols that are sol-
phous, hydrophobic binding capacity, and cannot be broken
uble in water as well as in acids, such as phenolic, oleaginous and
down into monomeric units. The hydrophobic lignin system affects
stearic acid.
the properties of another network, in a way, that it acts as a cou-
The low density and particular microstructure of natural fibre
pling agent and improves the stiffness of the cellulose/hemicellu-
are known to be mainly responsible for their relatively good speci-
lose in the plant [99,100]. It has been shown that lignin
fic mechanical and physical properties, where as sometimes higher
possesses a softening temperature of about 90 °C and a Tm of
than those of glass fibre as indicated from available data from sev-
170 °C.
eral authors (Table 5). Globally, the specific tensile strength of
Pectin plays an important role in the natural fibres as a compo-
plant fibre is between 1600 and 2950 MPa, during their specific
nent that binds the fibres into bundles and also determines the lus-
strength modulus varies from 10 to 130 GPa. The Young’s modulus
ter and touch of the fibres. Pectins are present in plant tissue to
of cellulose is about 140 GPa while that of hemicelluloses has been
varying degrees, being found predominantly in fruit peel and gums
estimated at 8 GPa [100], both varying according to the relative
[19]. Unretted flax contains between 3% and 4% pectins [29]. In
humidity. It is also well known that lignin increases the stiffness
flax, pectins are to be found in the cells surrounding fibre bundles,
of the fibre structure by acting as a compatibilizer between cellu-
especially those separating from core tissue of plant. The high con-
lose and hemicellulose [28,2].
centration of pectins occurs in the primary cell wall and middle
lamella of fibre. Here, in conjunction with hemicelluloses, their
function is that of a cementing material. Because of their impor- 3.2. Surface modification
tance as a binding material, removal of pectins during the retting
process is particularly important in the production of technical Considering that fibre usually does not have good adhesion with
fibre. Pectins are a family of compounds that in turn make up a lar- polymer matrices due to their hydrophilic nature. In order to over-
ger family of pectic substances including pectins, pectic acids, and come this issue, a number of surface modification methodologies
pectinic acids. Pectin is both a dietary fibre and functional fibre. have been attempted. Such modifications not only improve their
Pectinic acids represent polygalacturonic acids that either are wettability with the polymer matrices, but also reduce the
12 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25

Scheme 1. Possible chemical interaction between plasma-treated PPDO fibre and PLA matrix [26].

Scheme 2. Shown in schematic presentations of some of these surface modifications of natural fibre.

moisture absorption, sometimes impart unique properties and
ease of processing. Surface modification typically involves one of
four methods, chemical (mercerization, acetylation, silane treat-
ment, etc.), physic-chemical (solvent extraction), physical (use of
different rays or plasma, steam explosion) and mechanical meth-
ods (rolling, swaging) attempted by many researchers.
3.2.1. Physical modification of natural fibre
Physical methods involve treatment by corona-discharge treat-
ment [102], physic-chemical ones, such as steam explosion treat-
ment [103], high energy ray radiation processing [104] and
autoclave treatment [105]. All these techniques aim to improve
the fibre–matrix adhesion by reducing the difference between
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
hydrophilic/hydrophobic characters of fibre and the matrix [102].
It is noteworthy that physical treatments appear as the most
eco-friendly ones. Plasma treatment offers a unique approach to
modifying the chemical and physical structures of both fibre and
polymeric surfaces without altering the bulk structures and char-
acteristics of resulting materials [106]. Plasma treatment is mainly
applied for the cleaning, sterilization and surface etching of the
films in food packaging application. In fact, surface hydrophilicity
and adhesion ability of the films increase dramatically after plasma
treatment because polar groups are formed on film surfaces.
Therefore, further modification is possible through assembling
hydrophilic substances with antimicrobial abilities onto the sur-
face of the treated films. On the other hand, steam explosion
results in improved properties of lignocellulosic materials, which
include reduced stiffness, smoother surface, improved bending
properties, and better distribution [107,108]. Steam explosion pro-
cess, a high-pressure steaming involves heating of lignocellulosic
materials at high temperatures and pressures followed by mechan-
ical disruption of the pretreated material by violent discharge
(explosion) into a collecting tank. This process has been applied
to many lignocellulosic materials to enhance dispersibility and
adhesion with the polymer matrix [108].
In an innovative study, interfacial properties and microfailure
degradation mechanisms of the oxygen plasma treated biodegrad-
able poly(p-dioxanone) (PPDO) fibre/PLA composites have been
reported by Park et al. [26]. The interfacial shear strength (IFSS)
between plasma-treated PPDO fibre and PLA was improved by
induced polar functional group and showed twice the improve-
ment with respect to the untreated case. Scheme 1 shows the pos-
sible chemical interaction between plasma-treated PPDO fibre and
PLA matrix. Oxygen-based functional groups were produced on the
surface of PPDO fibre by oxygen plasma treatment. Primary cova-
lent and secondary hydrogen bondings enhancing interfacial adhe-
sion could occur between hydroxyl and carboxyl groups on the
surface of PPDO fibre and hydrogen in PLA matrix. Yuan et al.
[109] investigated the effect of air plasma and argon treatment
on IFSS between sisal fibre and PP by means of single fibre
pull-out test. They found that optimum treatment parameters
were shortest plasma treatment time, medium power level, and
medium chamber pressure. Under these conditions, the IFSS of
air plasma treated sisal fibre were found to be higher than argon
plasma treated fibre. Sinha and Panigrahi [110] have studied a
low-pressure argon plasma treated jute fibres. The fibres were
treated in argon plasma for 5 min, 10 min and 15 min, respectively.
With longer plasma treatment, the fibre became rougher, and the
formation of pits on the fibre surface was observed when the fibre
were plasma treated for 15 min. Ragoubi et al. [102] have applied a
corona discharge on miscanthus fibre and they have observed a
chemical oxidation as well as physical etching inducing an increase
of mechanical properties of miscanthus/PLA and miscanthus/PP
composites.
3.2.2. Chemical modification of natural fibre
Chemical modifications were applied to natural fibre in order to
improve the matrix–fibre adhesion. Some chemical modification
could lead to reduced moisture absorption of natural fibres and
their composites. Most of the chemical modifications of natural
fibre involve silanization, alkalization (mercerization), acetylation,
cyanoethylation, benzoylation, isocyanates treatment, dewaxing,
esterification, etherification, and graft copolymerization. Other
modifications of natural fibres include crosslinking with formalde-
hyde, p-phenylenediamine and phthalic anhydride; nitration; dini-
trophenylation and transesterification [112,113]. Their chemical
composition allows them to react with the fibre surface, which
forms a bridge of chemical bonds between the fibre and matrix.
Schematic presentations of some of these surface chemical
13
modifications of natural fibre are shown in Scheme 2. Some of
the most effective chemical modification strategies are briefly
described as follows.
Alkaline treatment or mercerization is one of the oldest, cost
effective and most used chemical methods for natural fibre when
they used to reinforce thermoplastics and thermosets. Its efficiency
depends on the type and concentration of the alkaline solution,
time of treatment, and the temperature used for modification
[112]. If the alkali concentration is higher than the optimum con-
dition, the excess delignification of the fibre can take place, which
results in weakening or damaging the fibre. This treatment
removes lignin, hemicellulose, wax and oils covering the surface
of the fibre. Addition of aqueous sodium hydroxide (NaOH) to nat-
ural fibre promotes the ionization of the hydroxyl group to the
alkoxide natural fibres (fibre–cell–O–Na) [22]. The chemical reac-
tion of the fibre–cell and NaOH is represented in Scheme 2.
The development of a rough surface and the enhanced aspect
ratio result in a better mechanical interlocking that induces as
improved the fibre–matrix interfacial adhesion in the resulting
composites. Several studies conducted on alkali treatment of natu-
ral fibres and they reported that the mercerization led to an
increase in the amount of amorphous cellulose while reduce the
hydrogen bonding intensity [22]. Ali et al. [114] have studied the
effect of fibre treatment on the tensile properties of Mater-BiÒ Y
and Mater-BiÒ Z with 20% of short sisal fibre. They have showed
that the alkaline treatment favored an increase fibre aspect ratio
and improved mechanical properties of the Mater-BiÒ Z and
Mater-BiÒ Y/sisal fibre biocomposites. The effects of alkali treat-
ment of pineapple leaf fibre on the performance of pineapple leaf
fibre/PLA biocomposites have been shown by Huda et al. [21]. It
was found that the alkali-treated fibre reinforced biocomposites
offered superior mechanical properties compared to untreated
fibre biocomposites. This study also suggested that the appropriate
modification of natural fibre surface significantly contributes to
improving the interfacial properties of the resulting biocomposites.
Cao et al. [115] investigated the effect of NaOH treatment of
bagasse fibre on the mechanical properties of bagasse fibre rein-
forced polyester biocomposites. Among, the various concentration
of NaOH used, superior properties were obtained for the biocom-
posites made from 1% NaOH treated bagasse fibre. Mishra et al.
[116] employed sisal fibre with 5% and 10% NaOH, cyanoethylated
and acetylated fibre surface treatment for fabricating of hybrid
glass-sisal composite and the result showed that the 5% NaOH
solution treated sisal fibres has the best effects on the interface
bonding of composite because of higher alkali concentration.
Silane is a multifunctional molecule which is used as a coupling
agent to modify fibre surfaces. Silane was found to be the most
effective among many coupling agents for the natural fibre surface
treatment. The uptake of silane is very much dependent on a num-
ber of factors including hydrolysis time, organofunctionalized of
silane, temperature, and pH. It undergoes several stages of hydrol-
ysis, condensation and bond formation during the treatment pro-
cess of the natural fibre. After hydrolysis, one end of silanol
reacts with the cellulose hydroxyl groups (Si–O–cell–fibre) and
the other end reacts (bond formation) with the matrix (Si–matrix)
functional groups [15]. After silane modification, hydrocarbon
chains allow the fibre to absorb more water, which means that
its chemical affinity to the polymer matrix is improved [118].
The chemical reaction is given in Scheme 2.
Goriparthi et al. [119] also studied jute fibre to reinforced PLA
composites, but their focus was to improve the adhesion between
the fibre–matrix by surface modification of jute fibre in the pres-
ence of alkali, permanganate, peroxide and silane treatments.
Combination of the special prepreg fabrication method along with
surface treatment on their composite sample exhibits enhance-
ment at least 45% on the tensile and flexural modulus. Other
14 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25

authors investigated the effect of silane treatments on non-woven
kenaf/PLA composites [120] and the effect of a combined alkali and
silane treatment on ramie fibre/PLA composites [121]. They found
a significant improvement of the overall mechanical properties, the
alkali and combined alkali/silane treatments showed the best
results.
Acetylation treatment is known as esterification methods for
plasticizing of natural fibre. Acetyl group (ACH3COO) reacts with
the hydrophilic hydroxyl groups of the fibre and takes out the
existed moisture. As a result, hydrophilic nature of the fibre is
reduced while improves the dimensional stability as well as dis-
persion of fibre into polymeric matrices. After acetylation, the
moisture regains considerably reduced as the fibre became more
hydrophobic due to the substitution of hydroxyl groups with acetyl
groups [122]. Natural fibres are acetylated with and without an
acid catalyst to graft acetyl groups onto the cellulose structure.
In general, acetic acid and acetic anhydride individually do not
react sufficiently with the natural fibre. To accelerate the reaction,
the natural fibre is initially soaked in acetic acid followed by trea-
ted with acetic anhydride between the time periods of 1–3 h with
higher temperature.
In benzoylation of natural fibres, benzoyl chloride is used for
fibre treatment. The benzoyl (C6H5CO) group interacts with the
hydroxyl group of natural fibre and thus decreases the hydrophilic
nature of the fibre. The introduced benzoyl groups of the natural
fibres improve the interfacial adhesion between the fibre–matrix,
thereby increasing the performance of the composites.
Manikandan et al. [124] reported that the benzoylation of the short
sisal fibre improved fibre–PS adhesion, thereby, considerably
increasing the strength of the composite.
Among several strategies based on the preparation of effective
coupling agents, the additions of a maleic anhydride (MHA) grafted
coupling agent provide efficient interaction with the functional
surface of the fibre–matrix. The maleic units induce the formation
of covalent bonds (via condensation reactions) and physical inter-
actions (via hydrogen bonds) with hydroxyl groups of natural fibre
surface. According to Scheme 2, thus acting as a linkage phase and
providing a stronger interconnection and a better wettability
between components. These interactions allow both the reduction
of the hydrophilic nature of fibre and the improvement of fibre–
polymer compatibility. There are numerous published studies in
which the effect of MAH grafting on the mechanical properties of
natural fibre has been investigated, and it is impossible to list all
of them here. Hence, only a few representative studies are dis-
cussed here. Mohanty et al. [125] used MAPP as coupling agent
for the surface modification of sisal fibres. It has been found that
a 30% fibre loading with 1% MAPP concentration in toluene and
5 min impregnation time with 6 mm average fibre lengths gave
the best results. The composite a significant increase in flexural
and impact strength was observed with the treated composites.
In recent publications, it was revealed that anhydride grafting onto
PHB-HV can be achieved by reactive blending and is an effective
coupling agent in natural fibre biocomposites [126].
An alternative to chemical and physical methods is represented
by the rapidly expanding use of biological agents, such as fungi
[127] and enzymes [128]. Biological modifications offer several
advantages over chemical and physical methods. They can selec-
tively remove hydrophilic pectin and the hemicellulosic material
while requires less energy input. Kardas et al. [129] investigated
the effect of four type of enzyme treatments (Lipase A, Lipase AK,
Lipozyme, and Esterase) on the micro-topography of polyester fab-
ric. They found that the esterase preparation was the most effec-
tive method for producing a more uniform and homogeneous
texture of the fabric material. Li and Pickering [130] used chelators
and enzymes to separate hemp fibre into individual bundles. They
found that the crystallinity and thermal properties improved after
separating the bundles. In another study, Pietak et al. [131] inves-
tigated the surface wettability of natural fibre using atomic force

Table 6
Recent works on surface treated lignocellulosic fibre reinforced biocomposites.

Fibre matrix composites Treatment methods Measurements Results Ref.

Hemp non-woven mat 0.16% NaOH for 48 h Mechanical Tensile strength was increased by 30% and doubled the shear strength properties [112]
with euphorbia resin property, SEM was found compared to the untreated fibre composites
(EURE)
Flax-organic resin 0.5–2 bars autoclave Mechanical, 2 bar autoclave-treatment positively impacted the water resistance in the core of [123]
treatment water sorption, fibre by reducing Henry’s absorption rate
SEM
Bagasse-aliphatic 1%, 3%, 5% NaOH for 2 h Mechanical 1% NaOH treatment an average improvement of 13%, 14% in tensile, flexural [115]
polyester property strength and 30% in impact strength
Miscanthus fibre-PLA Corona discharge Mechanical, Highly enhanced the interfacial adhesion compared to the untreated fibres [102]
treatment DMA, SEM, XPS
Sisal-PP Mercerization, Thermal, Tensile, flexural and impact strengths of the composites are significantly improved [125]
cyanoethylation, MAPP mechanical by the addition of MAPP in compare to other treatments
treatment property
Flax and hemp fibre Enzymatic treatment Mechanical, Hemicelluloses, pectinase and oxidoreductase treatments rendered the surface [117]
SEM and XPS topography of both fibre free of contaminants and exposed the individual fibre
bundles
Jute-epoxy Mercerization Mechanical 4% NaOH increased transverse composite strength up to 30% [22]
property
Flax-epoxy Mercerization Mechanical 30% increased in tensile strength and modulus with the removal of pectin. [134]
property
Sisal-polyester 2%,4%,10% NaOH Mechanical 4% alkali treatment reported maximum tensile strength properties. [22]
property
Flax-PLA 10% organosilane, 5% Physico- Increased the hydrophobicity of the fibre and moderate improvement in the [128]
NaOH chemical and mechanical properties of the biocomposites
mechanical
Hemp-PLA 5% NaOH, 0.5% silane Mechanical and 5% NaOH, 0.5% silane, increased adhesion force by 100% and 45%. [225]
POM
Banana-PU 10% NaOH Physico- Interfacial adhesion increased by 93% [111]
chemical study
Banana-epoxy 0.5–20% NaOH Mechanical and 1% NaOH treated fibre reinforced composites behaves superiorly than other [14]
SEM untreated fibre composites
Wood-PP Argon and air-plasma Mechanical, Tensile strength and tensile modulus of the composite sheet improved to some [16]
(60W, 30s) SEM and XPS extent after the plasma treatment
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
microscopy and contact angle measurements. They measured an
increase in adhesion force for treated samples because enzymatic
and chemical treatments (steam explosion) removed the primary
cell wall exposing the secondary wall. The same study provides a
clear evidence of the hemicellulose removal from hemp fibre after
enzymatic treatment. A recent study conducted on bamboo fibre
treatment using a number of enzymes (xylanase, cellulose, pectin
lyase and laccase) and it revealed that the different systems were
effective in improving fibre fineness, presumably as a result of
the removal of the more polar hemicellulose fraction [132].
Enzymatic treatments were shown to remove surface impurities
of surface the fibre and to improve the division of fibre bundles
and increase the fineness as shown by Saleem et al. [133] on hemp.
A brief review of the recent works regarding treated natural fibre
reinforced biocomposites is given in Table 6.
3.3. Manufacturing/processing aspects of biocomposites
The manufacturing of natural fibre reinforced biocomposites is
based, in general, on the technologies used for conventional syn-
thetic fibre composites. Typical processing techniques include
extrusion, injection moulding, compression moulding, pultrusion
and filament winding, direct long-fibre thermoplastic (D-LFT) is
suitable and investigated for natural fibre reinforced thermoplastic
biocomposites [28,135]. On the other side, resin transfer moulding
(RTM) and sheet moulding compound (SMC) are implemented
with thermosets matrices. Processing methods and suitable pro-
cessing conditions have significant influence on the parameters
(moderate temperatures (below 200 °C), dispersion, orientation
and aspect ratio) that determine the mechanical properties of a
natural fibre reinforced biocomposites [136]. Therefore to choose
a suitable process to fabricate natural fibre reinforced biocompos-
ites, design, and manufacturing engineers would mainly focus on a
number of criteria including desired properties, size, and shape of
resultant composites, the production rate, processing qualities of
raw materials and the manufacturing cost [137]. Drying of the fibre
before processing is necessary because moisture on the fibre sur-
face acts as a debonding agent at the fibre–matrix interface.
Additionally, because of water evaporation during the reaction,
voids appear in the matrix (thermosets have a reaction tempera-
ture above 100 °C). Both the aspects lead to a decrease in the
mechanical properties of biocomposites.
Many studies have been conducted on the potential of using
natural fibre as reinforcement for renewable polymers to make
biocomposites through injection moulding [138,139]. It is possible
to produce complex geometric components with functional ele-
ments fast and also in great numbers by injection moulding.
There are a number of advantages (minimal warping and shrink-
age, economics of scale, high function integration) as compared
to compression moulding [139]. The influence of injection mould-
ing process on the mechanical properties of the hemp fibre rein-
forced PP composites was investigated [139]. Their investigations
included fibre treatments and modifications, model predictions of
micro-mechanics and strengths, the optimization of hemp fibre
quality. Compression moulding is used to produce components at
high production volume, and it is suitable to produce automotive
components [140]. Thermoset bulk moulding compound (BMC)
and SMC are two moulding materials traditionally used in com-
pression moulding [121]. For thermoplastic materials, glass mat
thermoplastic is normally a typical moulding compound for com-
pression moulding. High strength Manila hemp fibre reinforced
starch based biodegradable resin composites have been produced
with a hot pressing technique [113]. These preliminary composites
were put in a metal mould and heated to 130 °C for 5 min with a
flexible heater shaped to fit around the metallic mould and hot
pressed at 10 MPa for 10 min. The volume fraction of Manila hemp
15
fibre in the specimens was varied from 30% to 70% during the pro-
cessing [141].
The fibre attrition is significant in most extrusion and com-
pounding processes, which often precede injection moulding. The
degree of fibre attrition is dependent on initial fibre length, fibre
volume fraction and several process variables including screw
design, shear rate and melt viscosity. In order to optimize fibre dis-
persion, there is often some form of mixing required before the
final processing of specimens. However, the lack of compatibility
between natural fibre and matrix often has more to do with differ-
ences in the polarity [137]. Some methods of processing natural
fibre biocomposites result in significant fibre attrition. In particu-
lar, specimens that undergo mixing followed by a granulation step
before being injection moulded shows a significant fibre length
reductions [142]. Gatenholm et al. [143] found that in processing
PHB with cellulose, the fibre size reduction of cellulose was related
to the reduction in molecular weight of the PHB. They proposed
that chain scission of PHB was occurring during processing; this
resulted in the formation of crotonic acid, which hydrolysed the
cellulose. The result was significant fibre attrition, but also
improved fibre dispersion. Karmaker and Youngquist [144] have
noted fibre attrition during high shear mixing, such as
thermo-kinetic processes used by extrusion and injection mould-
ing. Furthermore, true fibre can have orientations and the ability
to overlap and interlock, giving better mechanical properties.
However, these factors significantly affect the formability of the
composite sheets and cannot be addressed by examining wood-
flour reinforced thermoplastic composites. In addition to this work,
Bhattacharyya et al. [145] have developed thermoforming of
woodfibre and PP composite sheets produced without any modifi-
cation of the fibre or the polymer, the emphasis being on their
formability and the associated issues. The authors investigated
four thermoforming processes, such as V-bending, die-match
forming, air pressure forming and deep drawing, to examine both
single-curvature and double-curvature deformation conditions.
They also used the technique of grid strain analysis (GSA) which
has been applied to quantify the difference in strain distributions
during sheet deformation. It was concluded that the properties of
woodfibre–PP composite sheets possessed better mechanical, and
stiffness properties compared to those of the unreinforced PP.
Liquid composite moulding (LCM) is a generic name for similar
processes where a liquid resin is transferred into a closed mould cav-
ity filled with dry reinforcement. LCM processes encompass RTM,
vacuum assisted resin transfer moulding (VARTM), structural reac-
tion injection moulding (S-RIM), resin infusion under flexible tooling
(RIFT) and other subsets where the basic approach is to separately
inject the liquid resin into a bed of stationary performs [146]. The
successful implementation of RTM involves optimization of numer-
ous parameters. Of these, the mould filling process is related to the
perform architecture and permeability, resin viscosity and tempera-
ture, gate location and configuration, vent control, and perform
placement techniques [147]. The RTM process has become a popular
composite manufacturing process due to its capability for high vol-
ume production and cost effectiveness. RTM and RIFT are often
reported as the manufacturing route for natural fibre reinforced bio-
composites [148]. The hemp fibre-unsaturated polyester composites
manufactured with RTM process were found to have a uniformity
with no noticeable defects [149]. The tensile, flexural and impact
properties of these materials were found to increase linearly with
increasing fibre content. It was observed that the optimum proper-
ties were not reached in this study and that fibre content higher than
35 vol% should yield better mechanical properties. O’Donnell et al.
[150] showed how VARTM was able to cure large-volume natural
fibre/soybean oil composites at room temperature.
Pultrusion is a popular manufacturing method for synthetic
fibre and, while it has only recently become a more popular area
16 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
Table 7
Manufacturing conditions in different processing technologies [155].
Semiproducts/raw materials/Equipment Injection moulding
IM
Average fibre length in the component (mm) 0.1–1
Fibre content (wt%) <40
Fibre orientation 3-D
Anisotropy Medium
Possible complexity of the resulting part High
Type Arburg
Screw diameter (mm) 60
Length-to-diameter ratio 16.5
Compatibilizers added as Powder
Actual, tested fibre length in the composite (mm) 1.14
of exploration for use with natural fibre, it has high potential for
use with natural fibre and biodegradable polymers [151].
Angelov et al. [152], and Linganiso et al. [153] reported recently
on the pultrusion of natural fibre and different matrices.
Depending on the natural fibre used, the profiles exhibited specific
properties equivalent to those of glass fibre reinforced composites.
This makes natural fibre reinforced biocomposites appropriate
candidates for potential applications in the automotive industry
[154].
D-LFT processes essentially combine compounding and mould-
ing into an integrated process. In D-LFT systems the moulder can
introduce a resin, reinforcement and additives at moulding prior
to feeding, directly, to injection or compression moulding for part
processing [28]. D-LFT is relatively capital intensive and less com-
mon than pre-compounded long fibre granules (LFG). The most
common approach of compounded LFGs is polyolefin and polya-
mide plastics reinforced with long glass (primarily) or carbon (or
other) fibre [155,156].
A more elegant method involves spinning of the fibre with the
compatibilizer. This avoids metering and handling problems for
the mat or composite manufacturer [157]. In addition, MAH graft-
ing onto polypropylene chains (MAH-PP) is the possible way to
increase the adhesion between fibre–matrix and later in the com-
posite and, it probably results in completely bonded MAH. The pro-
cessing of natural long fibre granules by injection moulding
(LFG/LFG-IM) results in an easier increase of the fibre–matrix adhe-
sion since compatibilizers can simply be added to the granules. At
the same time, the MAH-PP products could be spun into the PP
fibre to produce granules that already contain the bonding agent.
When natural long fibre granules are used in injection moulding
and extrusion–compression moulding (ECM) processes, the fibre
length is set by the granule and will decrease in the screw equip-
ment [158]. The degree of the fibre length drop depends on the
processing conditions and the screw design. The same is valid for
the D-LFT extrusion–compression moulding (D-LFT-ECM). Table 7
shows the processing conditions and the respective fibre lengths
resulting from the LFG-IM, LFG-ECM, D-LFT, and CM processes.
Injection moulded and plasticized made with natural LFGs hardly
differ in their tensile properties. The direct process results in lower
tensile parameters. The highest tensile and stiffness values are
found in composites manufactured by compression moulding of
non-wovens or mats. As referred to above, fibre length in a rein-
forced polymer matrix influences the final performance of a part
in terms of stiffness, strength and impact strength [28].
4. Biocomposites
4.1. Starch-based composites
Various reinforcing natural fibre, such as caraua [159], hard-
wood (HW) and softwood (SW) [160], silk protein [161], pehuen
Extrusion–compression moulding Compression moulding
LFG D-LFT-ECM CM
1–25 1–25 >10
<40 <40 >40
2-D 2-D 2-D
High Very high Low
Medium Medium Low
Kannegiesser single-screw Dieffenbacher double-screw Schwabenthan
80 75
26 14
Powder Powder Compatibilizer containing sheet
8.31 3.79 32.6
cellulosic husk [162], date palm and flax [163], and newspaper
fibre [164] are mixed with starch-based polymers to increase the
modulus or impact toughness and reduced water uptake of the
thermoplastic composites. Such composites are completely
biodegradable and compostable and therefore considered ‘‘envi-
ronmental friendly’’ since, at the end of their useful life, they can
be discarded without causing any damage to the environment
[165,166]. The improvement of the tensile properties of
starch-based biocomposites varies depending on the type and nat-
ure of the fibre, its orientation (random or unidirectional), content
and form (fibre or fabric) and type of blending/plasticizer used
(Critical factors on manufacturing processes of natural fibre com-
posites). Teixeira et al. [167] used plasticized cassava starch as a
matrix and combined it with cassava bagasse cellulose nanofibrils
as reinforcing materials. Expansion of corn starch based biocom-
posites reinforced with graft copolymers of Saccharum spontaneum
L. (Ss) fibre was achieved by Kaith et al. [168]. Recently, Vallejos
et al. [169] applied corn and cassava starches plasticized with
30% glycerin as biometrics and using a fibrous material obtained
from ethanol–water fractionation of bagasse as reinforcement.
Another relevant research based on starch materials was carried
out by Duanmu et al. [170]. They determined moisture absorption,
dimensional stability, and mechanical properties of wood fibre
reinforced allyl glycidyl ether modified (AGE)–potato starch com-
posites. However, no study has been carried out to evaluate the
potential use of sugar palm starch (SPS) as a matrix.
Raw woody hemp core (WHC) was recently used in a thermo-
plastic composite as a reinforcement agent for a starch based
biopolymer [171]. The mechanical properties reported for WHC
previously may fulfil some technical requirements. A final illustra-
tion of the applications of WHC in composites is the
styrene-butadiene rubber composites presented by Wang et al.
[172]. The authors stated that the mechanical properties of the
composite improved with an increasing content of WHC powder,
and interestingly, the short WHC fibre has a positive effect on
the elongation at break compared with results obtained for long
fibre.
Sahari et al. [173] demonstrates the effect of fibre content on
mechanical properties, water absorption behaviour and thermal
properties of sugar palm fibre reinforced plasticized sugar palm
starch (SPF/SPS) biocomposites. The biocomposites were made
with various amounts of fibre (10%, 20% and 30% by weight per-
cent) by utilizing glycerol as plasticizer for the starch. It was
declared that the mechanical properties of plasticized SPS
enhanced with the inclusion of SPF fibre. The tensile strength
and modulus of SPF/SPS biocomposites showed increasing trend
with increasing SPF while the addition of the SPF made the elonga-
tion fall from 8.03% to 3.32%. This was due to the remarkable
intrinsic adhesion of the fibre–matrix interface caused by the
chemical similarity of starch (SPS) and the cellulose fibre. Water
uptake and moisture content of SPF/SPS composites decreased
with the characters of fibre, which is due to better interfacial
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25 17

Table 8
Mechanical properties of natural fibre-starch, soy resin, PLA, PHA biocomposites.

Composites Tensile properties Strain at break (%) Processing method Ref.

Strength (MPa) Modulus (GPa)
TPS/cellulose nanoparticles (5%) 10.5(+250%) N.S. 3( 73%) Solution casting [45]
Starch/30% jute 26.3 ± 0.55 2.5 ± 0.23 2 ± 0.3 Thermoplastic injection moulding [174]
Cornstarch/curaua (70 vol.%)/10% NaOH treated 216 13 1.53 Direct [159]
275 29 1.24 Preforming
327 36 1.16 Prepreg sheet
PLA-soyprotein/3% cornhusk/5% silane 17.09 ± 0.10 0.72 ± 21.1 N.S. Single-screw extruder [23]
Soy flour and BAK 1095/30% PALF 30 3.75 1.18 Extrusion + injection moulding [200]
Acrylated epoxidized soy oil/35% flax 30 4 N.S. Resin transfer moulding [195]
Acrylated epoxidized soy oil/Hemp (20%) 35 4.4 N.S.
PhytagelÒ modified (20%) SPI/45% flax yarn 220.2 ± 28.5 4.11 ± 0.1 7.5 ± 0.7 Compression moulding [203]
PLA/30% flax 53 ± 3.1 8.3 ± 0.6 1 ± 0.2 Twin-screw extruder [185]
PLA/1% microfibrillated cellulose 45.9 ± 4.1 4.6 ± 0.27 3 roll mill + injection moulding [184]
PLA/30% ramie 66.8 ± 1.7 N.S. 4.8 ± 0.2 Hot pressing-sheet moulding [121]
PLA/20% flax 64.4 6.197 6.21 Extrusion + injection moulding [88]
PLA/62.1% lyocell 100.5 5.55 6.4 Compression moulding [187]
PHBV/63.2% lyocell 108.8 2.46 10.6
PLA/30% ramie/5MA 61.7 ± 0.9 4.5 ± 0.1 4.3 ± 0.1 Twin-screw extruder [18]
PLA/40% wood flour 60.24 ± 1.70 7.40 ± 0.42 1.06 ± 0.08 Injection moulding [186]
PLA/bamboo fabric laminate direction 77.58(6.83) 1.75(0.19) 14.59(1.62) Film stacking [249]
PLA/5% silk fibre 70.6 ± 1.1 4.08 ± 0.05 3.8 ± 0.5 Injection moulding [248]
PLA/cuphea oilseed 62.6(3.3) 1.43(0.03) 7.8(0.8) Extrusion + injection moulding [191]
PLA/bamboo fabric (warp direction) 80.6 5.92 N.S. Compression moulding [174]
PLA/bamboo fabric (weft direction) 61.9 5.17 N.S.
PHBV (Zeneca)/30% pineapple 55.8 2.25 3.0 Film stacking + hot pressing [175]
Biopol™ D400GN/18% Wood 23 2.9 N.S. Hot pressing mats and granulate [180]

bonding between the matrix and fibre as well as the consumption
to absorption caused by the fibre. On the other hand, fractographic
studies through scanning electron microscopy (SEM) showed
homogeneous distribution of fibre in the matrix with excellent
adhesion that play a significant role in improving the mechanical
properties of biocomposites. Lopez et al. [164] investigated fully
biodegradable composites which were obtained by melt blending
of TPS and was blended with PBAT and/or reinforced with cellu-
losic fibre obtained from recovered newspaper up to 30%. Fibre
from recovered newspaper acted as a reinforcing agent, increasing
the tensile strength and the Young’s modulus of TPS up to 260%. By
opposite, although it helped reducing the water uptake of compos-
ites and increased the rigidity of the materials, the incorporation of
the highly hydrophobic biodegradable PBAT to the biocomposite
formulations caused a sharp decrease in the water uptake of the
biocomposites. Nevertheless, even though PBAT has a higher ten-
sile strength than TPS, its incorporation failed to recover the mate-
rials. Prachayawarakorn and Hwansanoet [161] have explored the
thermoplastic rice starch (TPRS) reinforcing it with natural silk
protein fibre. The effect of silk contents and lengths of properties
of the TPRS/silk composites were examined. Internal mixer and
compression moulding machine were applied to process and
shaped the TPRS/silk composites. It was determined that stress at
maximum load and Young’s modulus of the TPRS/silk biocompos-
ites significantly increased with the incorporation of silk fibre.
Furthermore, mechanical and thermal properties including water
absorption of the TPRS/silk and TPRS/cotton composites were
comparable.
4.2. Poly(hydroxyalkanoate)-based composites
A variety of fibre materials has been explored to make biocom-
posites with PHB. It has been shown that the addition of natural
fibre increased modulus, Tg, and heat distortion temperature
(HDT) of PHB (or PHBV) composites. Nevertheless, the improve-
ments in tensile strength and toughness were found to be difficult
and to depend on many factors, such as fibre length and aspect
ratio, interfacial bonding, fibre sources, fibre treatments, and fibre
forms (single fibre/fabrics). Various co-polymers of PHB have been
combined with PALF [175], recycled wood fibre (RWF) [176],
empty fruit bunch (EFB) [177], and cellulose nanowhisker (CNW)
[178] to prepare biocomposites. These studies have shown that
the natural fibre can be embedded in the PHBV matrix as an excel-
lent reinforcer to improve mechanical properties. Table 8 gathers
the reported tensile, mechanical properties of PHA based biocom-
posites. One of the main advantages of PHA for biocomposite appli-
cations is their polar character since PHA show better adhesion to
lingo–cellulose fibre compared to conventional polyolefins [27].
Taha and Ziegmann [88] prepared randomly oriented
hemp/Biomer P226 composite specimens by extrusion and tested
them in tension and flexure. The highest material properties were
measured at 20% volume fraction. The tensile modulus, strength,
and elongation were 2.4 GPa, 21.4 MPa, and 4.20%, respectively.
The addition of hemp fibre increased the modulus but lowered
the strength and elongation relative to the pure polymer. At 20%
volume fraction, the flexural modulus and strength were 3.7 GPa
and 45.8 MPa, respectively.
Wong et al. [179] investigated the use of plasticizers in flax–
PHB composites. A weighed amount of flax fibre was added to neat
plasticizer followed by heating to 120 °C for eight hours. After
heating, excess plasticizer was removed by washing the fibre with
acetone and the residual solvent was removed under vacuum.
Flax–PHB composites with 1:1 fibre/polymer volume ratios were
then made by dissolving PHB in chloroform and mixing
plasticizer-modified fibre into the solution. Sample bars were
annealed at 70 °C for three hours to allow PHB to crystallise and
interact with the fibre. As a control material, PHB containing 4%
v/v plasticizer without added flax was prepared and subjected to
the same treatment as the PHB–flax composites. The mechanical
properties biodegradability of wood fibre reinforced Biopol™ com-
posites were investigated by Peterson et al. [180]. A significant
finding was that the wood fibre-Biopol composites were highly
biodegradable, often degrading faster than pure Biopol specimens.
Statistical analysis of composite tensile results showed which con-
ditions of pressure, temperature, heating time and time of pressing
gave the best strength and modulus results. Process temperature
18 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
had the greatest influence on composite tensile strength with val-
ues varying from 23 MPa at 219 °C to 17 MPa at 240 °C. The tensile
modulus varied from 2.9 GPa to 2.15 GPa over the same tempera-
ture range.
Javadi et al. [176] incorporated recycled wood fibre (RWF) and
synthetic filler like nanoclay into the PHBV/PBAT blend to provide
hybrid biocomposites with excellent material properties. To
provide good interfacial adhesion between hydrophilic wood fibre
and hydrophobic PHBV, the RWF were pre-treated with
silane. Salim et al. [177] evaluated properties of biocomposites
from oil palm empty fruit bunch (EFB) fibre blended with
poly(3-hydroxybutyrate-co-38 mol%-3-hydroxyvalerate) [P(3HB-
co-38 mol%-3HV)]. The authors used maleic anhydride (MAH),
and benzoyl peroxide (DBPO) to enhance the miscibility between
PHBV and EFB fibre. On the basis of this study, the possibility of uti-
lizing biodegradable PHBV/EFB blends showed fewer chemicals
leached compared to commercial packaging. Wu and Liao [17]
investigated the mechanical and biological properties of composite
materials produced from chestnut shell fibre (CSF) and PHA, as
well as CSF and glycidyl methacrylate grafted PHA (PHA-g-GMA).
Biocomposites developed from PHA-g-GMA/CSF were found to
have noticeable features of mechanical properties compared with
those of PHA/CSF. CSF could be homogeneously dispersed in the
PHA-g-GMA matrix as a result of condensation reactions.
Moreover, the PHA/CSF and PHA-g-GMA/CSF biocomposites were
more biodegradable than pure PHA. Ten et al. [178] successfully
demonstrated for the successful orientation cellulose nanowhisker
(CNW) in the PHBV matrix using an electric field. PHBV films with
1.5–7% of CNWs were produced using solution casting. A high
degree of fibre orientation was found under the electric field of
2 kV/cm and above. The authors observed that restrains were
attributed to CNW/CNW and CNW/polymer interactions.
Rheological results confirmed the enhance restraints. In another
study by the same authors, the reason was attributed to the
PHBV/CNW network structure in the rheological tests which were
formed without physical touching and geometrical overlapping
between nanotubes [181].
4.3. Poly(lactic acid)-based composites
Several researches have been performed to examine the possi-
bility of realizing PLA-based composites reinforced with natural
fibre with enhanced final properties. The fillers used include cotton
linters maple hardwood fibre [182], sweet sorghum fibre [183],
bamboo fibre [184], ramie fibre [18], and lyocell fibre [187]. Most
of these studies show that it is possible to achieve various degrees
of improvement in tensile and flexural strength and significant
increases in modulus with the creation of the respective compos-
ites. A number of biocomposites systems prepared by different
techniques based on PLA as the matrix are listed in Table 8. It
has been reported that tensile and flexural properties improved
by increasing the content of cellulose fibre reinforcements in
PLA-based composites. More recently, Liu et al. [188] proved that
the basalt fibre with the adequate sizing can significantly increase
tensile, bending and impact strength of PLA. By using 20% of basalt
fibre and 20% of ethylene-acrylate-glycidyl methacrylate copoly-
mer (EAGMA) it was possible to further increase the unnotched
impact strength of PLA from 19 kJ/m2 to 34 kJ/m2. Finally, it was
stated that there is a strong connection between the phases, due
to the absence of gaps at the fibre–matrix interface; however, the
surface of the fibre was still poorly wetted by the matrix.
Kurniawan et al. [189] treated the surface of the basalt fibre by
using atmospheric pressure glow discharge plasma polymerization
and analysed the adhesion between the basalt fibre/PLA in hot
pressed composites. It was demonstrated that by increasing the
plasma polymerization time above 3 min it was possible to
increase the tensile strength of the composites above the own
strength of PLA. The plasma polymerized fibre was well wetted
by the PLA on the electron microscopic micrographs.
Our previous study by Jandas et al. [190] examined that the
PLA/banana fibre (BF) biocomposites by melt mixing and compres-
sion moulding. Preliminary results showed that the properties of
PLA and BF fibre composites are promising. Before composites
fabrication, the BF fibre was chemically modified using acetic
anhydride, (3-aminopropyl)triethoxysilane (APS), bis-(3-triethoxy-
silylpropyl)tetrasulfide (Si-69), and mercerized using NaOH
solution to improve the compatibility with the PLA matrix. This
study concluded that the morphological analysis highlighted a very
significant enhancement of the surface wetting as well as on the
adhesion level.
Song et al. [192] focused on the physical behaviour of hemp/PLA
composites, particularly the thermal properties and viscoelastic
behaviour. They used twill and plain woven hemp fabrics as rein-
forcements by stacking film method. The impact and tensile prop-
erties of PLA resin reinforced with twill structure fabric were found
15% and 10% higher than the plain woven respectively. Increment
of fibre volume fraction from 6% to 20% was the reason why the
coefficient of thermal expansion of the fabricated hemp fabric
composites decreased considerably (from 70  10 6 m/°C to
10  10 6 m/°C), which indicates that the composites have great
potential for parts experiencing a wide range of temperatures, such
as automobile and aerospace applications. Goriparthi et al. [119]
developed a biodegradable composite using jute fibre and PLA,
but their focus was to improve the adhesion of jute fibre by surface
modification using alkali, permanganate, peroxide and silane treat-
ments. Combination of the special prepreg fabrication method
along with surface treatment on their composite sample exhibits
some enhancement at least 45% on the mechanical properties.
Ma and Joo [193] also studied the effect under different fabrication
conditions, such as fibre content (5%, 10% and 15%), processing
temperatures (200, 210, and 220 °C) and alkali treatment (6%, 8%,
10%, and 12%) on the mechanical properties and structure of jute
fibre with PLA using film stacking method. In the designed exper-
iment, the optimum mechanical properties of composites
(improvements up to 76%) can be obtained by using 15% of jute
fibre treated with 12% of NaOH for 8 h with a processing tempera-
ture of 2010 °C. The modified rule of mixture equation was also
developed and confirmed. It is more suitable to predict the tensile
modulus of jute fibre reinforced biocomposites. Huda et al. [194]
have studied PLA/recycled cellulose composites prepared by extru-
sion and injection moulding, finding that the filler (up to 30%) sig-
nificantly improved the rigidity without affecting the crystallinity
degree and thermal stability.
4.4. Soy resin-based composites
The soy-based biocomposites reinforced with natural fibre were
found to have better properties than PP composites with natural
fibre [201]. Liu et al. [196] reported the kenaf fibre reinforced
soy-based biocomposites were fabricated by extrusion/injection
moulding and compression moulding. The compression-moulded
samples showed high thermal and mechanical properties, and
the modulus, impact strength, and heat deflection temperature
values of the biocomposites increased as the fibre length, fibre con-
tent, and fibre orientation increased. Researchers recently investi-
gated the effect of stearic acid on tensile, and thermal properties of
ramie fibre reinforced SPI resin green composites [197]. It was
noted that part of the stearic acid crystallized in SPI resin and that
the crystallizability was transformed by the addition of glycerol as
a plasticizer. The fabricated green composite was found to have
enormous potential for certain indoor applications.
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
Jute fabric was used by Huang and Netravali [198] to reinforce
concentrated soy protein (SPC) modified with glutaraldehyde and
nanoclay. During composite fabrication, they used metal frame to
wind the hemp yarns and applied small tension to minimize the
yarn shrinkage and misalignment during the drying of the resin.
The unidirectional flax yarn strengthened SPC composites proved
longitudinal tensile failure stress of 298 MPa and Young’s modulus
of 4.3 GPa. The flexural stress was 117 MPa, and the flexural mod-
ulus was 7.6 GPa. All those results show that the flax yarn rein-
forced SPC has the potential to replace non-biodegradable
materials in many fields. Unlike reference [172], Behera et al.
[199] used woven and a non-woven jute in the different weight
percentage (40–80%) to reinforce soy resin (soy milk) based resin.
They found that both woven and non-woven jute composites, com-
posite having 60% jute felt showed highest mechanical properties.
Tensile strength and tensile modulus were recorded 35.6 MPa and
0.972 GPa for woven, 37.1 MPa and 1.04 GPa for the non-woven
jute composites respectively. Flexural strength and modulus were
documented 33.5 MPa and 1.02 GPa for woven, 38.4 MPa and
1.12 GPa for the non-woven jute composites respectively.
Furthermore, both kinds of fabric are different in structure, and
their comparison cannot be justified.
Reddy and Yang [201] fabricated environment-friendly biocom-
posites, used jute fibre to reinforce soy protein resin using water
without any chemical as plasticizer. Their composite was fabri-
cated using the prepreg method and they found that biocomposites
have excellent flexural strength, tensile strength and modulus in
comparison to jute/PP composite. Hydrogen bonding interaction
is often insufficient to ensure adequate mixing of lignin with pro-
tein. Huang et al. [202] blended kraft lignin with soy protein using
methylene diphenyl diisocyanate (MDI) as a compatibilizer. The
compatibilization occurred through MDI and hydroxyl groups of
lignin and protein molecules. Only a slight reduction in water
absorption was observed, but the addition of 2% MDI caused a
simultaneous enhancement of tensile strength, modulus, and elon-
gation at break of the polymer blends, which was attributed to
graft copolymerization and crosslinking.
The characterization of PhytagelÒ modified SPI resin and unidi-
rectional flax yarn reinforced biocomposites was undertaken by
Lodha and Netravali [203]. The incorporation of PhytagelÒ in SPI
resin led to an overall ten-fold increase in the tensile fracture stress
and a ninefold increase in Young’s modulus of the soy protein resin
along with a seven-7-fold decrease in fracture strain. The dynamic
mechanical properties, such as loss and storage modulus of the
modified resin increased and the Tg also increased by about
56 °C. Table 8 shows the mechanical properties of soy oil based
natural fibre composites manufactured using different processing
techniques.
4.5. Wood–Plastic Composites (WPCs)
In recent years, wood fibre/flour (WF) reinforced biocomposites,
named WPCs, play a vital role in the social, economic and environ-
mental growth of human history [204]. The WPCs show character-
istics, such as moderate strength, high durability, and light weight.
Besides, they are inexpensive and sustainable, which give them
attraction for innovative design [205]. WPCs refer to materials or
products consisting of one or more lignocellulosic fibre/flours
and one or a mixture of polymers. Various wood and natural fibre
have been used in the processing of WPCs, for example, hemp
[206], cellulosic fibre [207] and flax [208]. Recently, there has been
a commercial interest in the use of thermo-mechanical pulp (TMP)
fibre for manufacturing of WPCs [209]. According to Ashori [210],
WPCs are based on plant fibre (wood and non-wood) and ther-
mosets (epoxy and phenolic resins) or thermoplastics, such as PE,
PP, PS, PVC, and PLA [211,212]. Additionally, additives, such as
19
coupling agents, colorants, stabilizers, blowing agents, reinforced
agents, and lubricants could be applied to improve properties
[213]. The characteristics of wood fibre depend primarily on their
source. The average lengths of soft and hard wood fibre are 3.3
and 1.0 mm, diameters 33 and 20 lm, and strength 100–170 and
90–180 MPa, respectively [214]. The main applications of WPCs
are initially used for construction applications (decking, docks,
landscaping timbers, fencing) and non-structural applications,
but now they have been widely used for a broader range of appli-
cations, including automotive, gardening and outdoor products
[215]. According to the study by Markarian [216], the WPCs mar-
ket, including thermoplastics and thermosets, has been estimated
globally at 900,000 t, in which, 70% of this volume was consumed
by North America, 20% in Europe, and 10% from Asia. In Europe, the
market showed growth rates averaging 23% per year from 2003 to
2007 and predicted to continue at 26% per year from 2012.
Properties of WPCs depend on many factors like, interaction
between wood filler and matrix, including matrix characteristics,
chemical and physical characteristics of the wood filler and pro-
cessing conditions. On the other hand, the components of WPCs,
contain cellulose, hemicellulose and lignin, in which the hydroxyl
groups build plenty of hydrogen bonds between the macro-
molecules of the wood polymers [217]. The hydroxyl groups could
form new hydrogen bonds with water molecules, which induce the
water absorption, creation of micro-cracks in the sample, resulting
in reduced mechanical property because stress could not be trans-
ferred efficiently from the matrix to the fibre [217,218].
In order to overcome this disadvantage, different methods are
used for the enhancement of mechanical properties and water
resistance of WPCs. Some of them are focused on processing the
WF, such as MAH grafted copolymer of the matrix polymer [219],
silane treatment [217,220], heat treatment [217,218], and treat-
ment with sodium hydroxide [221]. Besides, the inclusion of
nanoparticles as reinforcing filler is another technique for improv-
ing the overall characteristics of lignocellulosic–thermoplastic
composites, such as silica nanopowder [222] and montmorillonite
clay [223]. However, these methods have their weaknesses, such as
complicated processing processes and easy aggregation of
nanoparticles that caused poor dispersion in the polymer matrix
and a limited increase in overall properties of composites.
The reinforcement capability of wood fibre in various matrix
polymers has been studied earlier. Maldas et al. [224] investigated
the effect of different wood species on mechanical properties of PS
composites. They concluded that the softwood pulps provided bet-
ter reinforcement for the polymer than hardwood pulps, which is
due to the difference in morphology, density and aspect ratios of
the wood fibre types. Bhattacharyya et al. [145] showed that wood
fibre with PP composites is indeed formable. The sheets they man-
ufactured used pinus radiate fibre along with PP powder, for a total
through thickness of 1.3 mm. Two types of composites were pro-
duced, layered and homogeneous with PP and wood fibre mixed
during formation. Results exposed a tensile modulus increase of
up to 250% with a 25–30% fibre volume fraction. This study found
that the ability to form these composites into not only
two-dimensional shapes, but also simple three-dimensional
shapes [225]. However, the impact performance of PLA-based
WPCs is not sufficient due to the inherent brittleness of PLA.
After being toughened with PHA [226] the impact strength of the
resulting PLA-based WPCs is significantly improved. However,
environmental impacts of the PLA-based WPCs must be evaluated
before they are used as engineering materials in the near future.
Bolin and Smith [227] found that the environmental impacts from
lumber treated with alkaline copper quaternary (ACQ) were 14
times less for fossil fuel use, potential smog emissions, almost 3
times less for greenhouse gas emissions, and water use, 4 times
less for acidification, and since half for ecological toxicity
20 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
compared with those from WPCs decking. For eutrophication, the
environmental impacts were approximately equal. Stark and
Rowlands [228] used TMP fibre in their investigations, however,
without varying the processing conditions during refining. Wood
chips were processed in a laboratory-scale of 300 mm single-disk
Sprout-Bauer pressurized refiner with incoming steam pressure
of 414 kPa and constant plate gap wide of 0.127 mm. As a result,
mechanical properties of the composites were well developed
when using wood fibre instead of wood flour.
Migneault et al. [229] compared injection moulding (IM) and
extruded WPCs made with different fibre length-to-diameter
(L/D) ratio of chemo-thermo-mechanical pulp (CTMP) with a
high-density polyethylene (HDPE) matrix. The IM process
appeared in greater composite physical and mechanical properties
than the extrusion process, but higher density was achieved with
the extrusion process. This study provides a good understanding
of the connections between processing method, fibre characteris-
tics, and composite performance. In the same manner, the author
also investigated the effect of white birch pulp fibre with different
aspect ratios (length-to-diameter), HDPE, and using two standard
processes: extrusion or injection moulding [230].
5. Environmental and economic impact of biocomposites
In broader public awareness, due to depletion and climatic
change there is an escalating demand for sustainable products
based on renewable sources. The objective is to replacement of
petroleum-based product with bio-based materials from renew-
able sources. The focus is to reduce the economy and the burden
on the ecology. Diversified use of agricultural products and many
other renewable resources for new industrial uses [231]. This rev-
olutionary application of biocomposites produced from natural
fibre and polymers, such as PE, PP, soy protein, PLA, and PHA have
contributed the activities in renowned research centres along with
their industrial partners for development of innovative biocompos-
ites end products. Application of natural fibre composites to niche
markets is in momentum during the last 10 years, especially in the
automotive sector [29,232]. The primary production of plant fibre
was estimated to 2  1011 t in 2000 compared to 1.5  108 t syn-
thetic polymers [233], while the estimated fibrous raw materials
from agricultural crops are about 2.5  109 t [234]. The North
American market for natural fibre is projected to grow from USD
155 million in 2000 to USD 1.38 billion by 2025 [2]. The report also
suggested that growing use of natural fibre composites in automo-
tive applications is driving the market. Indeed, automotive is
expected to remain the biggest market through 2016 [2].
Consequently, this report is compared with economic benefits,
such as low production costs and low resin consumption [235].
As a result, the requirements for natural fibre reinforced biocom-
posites have improved drastically over the past several years, for
various industrial applications in the manufacturing sector.
The uses of biocomposites in the automotive sector are not only
environment-friendly, but also they reduce weight by replacing the
high-density glass fibre to low-density natural fibre. Lightweight
vehicles reduce the cost in terms of price as well as fuel; this ulti-
mately reduces the emission of CO2. As per one study 25% reduc-
tion in weight of a vehicle equivalent to 250 million barrels of
crude oil and a reduction in CO2 emission to 220 billion pounds
per annum [236]. Japan is similarly strict, requiring 88% of the
vehicles to be recovered in 2005 (recovery grants for incineration
of some components), rising to 95% by 2015 [237]. In Brazil, car
manufacturers, such as Volkswagen, Ford, Honda and General
Motors already apply natural fibre in car seats, dashboard cover-
ings, roofs and trunk lids [238].
Recent work on biocomposites reveals that in the most cases
the specific mechanical properties of biocomposites are
comparable to widely used glass fibre reinforced plastic. In order
to be competitive, eco-friendly composites must have the same
desirable properties as obtained in conventional plastics especially
in the automotive sector. Alves et al. [140] substituted glass fibre
by jute fibre to produce structural frontal bonnets for a type of
off-road vehicle (‘‘buggy’’). The natural fibre reinforced the bonnet
improved the environmental performance of the whole vehicle,
mainly due to its lower weight compared to usual solutions.
Witik et al. [239] evaluated the potential advantages of some com-
posites (light polymer composites compared to magnesium and
steel) in automotive applications. They concluded that the weight
reduction does not always lead to better environmental perfor-
mance. Luz et al. [240] analyze the advantages of replacing talc
by sugarcane bagasse fibre as reinforcement in PP composites that
constitute automotive components. The detected beneficial aspects
of the sugarcane composites are: bagasse carbon absorption during
cultivation, which reduces global warming, cleaner production
processes, less weight, and bagasse-PP economic recovery (50%
incineration + 50% recycling scenario) at the end-of-life. Kvavadze
et al. [241] have recently reported that twisted wild flax fibre were
used by prehistoric hunter-gatherers for making cords for hafting
stone tools, sewing garments, or weaving baskets, around
Dzudzuana Cave (Georgia) 30,000 years before.
Recently, Bombyx mori silk fibre has been introduced as rein-
forcement in different polymeric matrix for automotive applica-
tions. Oshkovr et al. [242], investigated on the crashworthiness
characteristics of reinforced B. mori silk composite. Square tubes
energy absorbers of varied lengths were fashioned out of B. mori
silk natural silk/epoxy composite and compared for crashworthi-
ness. Parameters measured for this were the crash force efficiency
(CFE) and the total absorbed energy (E-total). Under axial compres-
sion tests, all the samples showed catastrophic failure. Samples
failed with mid-length buckling, which was a failure originated
from the mid of the tubes that then progress to other areas.
Indeed, the use of green materials is not only useful for the envi-
ronment and weight reduction but also to sustainable develop-
ment. However, affordable solution needs to be addressed to
particular areas discussed above. Similarly, current technology
and industry status is to produce car parts out of recycled plastics
and rubber. The future vision to manufacture ‘‘a car out of waste’’
by 2015 is the new trend in research [236].
In order to be able to expand into other markets, such as com-
mercial construction and consumer goods, serviceability, compos-
ites need to achieve high-quality performance, durability, and
reliability standards. Natural fibre biocomposites offer vast oppor-
tunities for an increasing role as alternate materials, especially
wood substitutes in the construction market [243].Various natural
fibre based composites products, such as laminates, panels, parti-
tions, door frames, shutters, and roofing have been produced as
an alternative to existing wood materials [243]. For mechanical
representation of Agave lechuguilla, natural fibre in Portland
cement composites exposed to harsh environment conditions
was reported by Juarez et al. [244]. In another study, window
frame fabrication by injection moulding process was carried out
by Rahman et al. [245]. Rice husk filled high-density polyethylene
was used as a natural material. Solid and hollow designs were cre-
ated to examine the pros and cons of each model. The studies were
carried out on packing, flowing, cooling and costing of injection
moulded window frame. From the analysis, they concluded that
the window frame with a hollow design is preferable since hollow
design has the advantage of filling, packing, and cooling properties.
The hollow design also costs less than reliable design of the win-
dow frame. Still, high injection pressure and clamping tonnage
are unfavourable for hollow design.
Natural fibre possesses a distinctive characteristic, which makes
them excellent materials for soil conservation. Originally produced
 T. Gurunathan et al. / Composites: Part A 77 (2015) 1–25
in the Netherlands for the construction of dykes, geotextile nets
made from hard natural fibre stimulate earthworks and encourage
the growth of plants and trees, which provide further reinforce-
ment. Utilization of palm-leaf geotextile mats to conserve loamy
sand soil in the United Kingdom was reported by Bhattacharyya
et al. [246]. The studies recommended covering palm-mat geotex-
tiles as buffer strips for soil and water conservation on erodible
moderate slopes. Mwasha [247] has stated the use of environmen-
tal friendly geotextiles for soil reinforcement. The studies demon-
strated the potential for the use of sustainable, biodegradable
vegetable fibre over man-made polymeric materials in ground
improvement.
6. Future scope of biocomposites
So far, we have taken a look at the applications to automotive
and construction sectors, which are the leading markets for bio-
composites. Although biocomposites are gaining in interest these
days, the challenge remains in replacing conventional composites
with those that exhibit comparable structural and functional sta-
bility during storage, use, and environmental degradation on dis-
posal [2]. For this reason, the market and commercialization of
biocomposites are anticipated to expand in the future owing to
social, environmental awareness among consumers and producers,
identification of new applications and development of efficient
processing technology. It is reported that one of the major hurdles
for commercialization of natural fibre reinforced biocomposites
until recently is the non-recognition of research and development
in developing countries, where these fibre are abundantly avail-
able. This hurdle has been overcome by many industrialized coun-
tries, particularly in Europe, which are now taking the lead in this
area in recent years [28]. However, materials scientists are sup-
posed to deal with challenges regarding the acceptance criteria
for these biocomposites being their performance and cost, despite
the renewability and recyclability of the matrix and reinforce-
ments are attractive. Furthermore, there is a need for product stan-
dards to support the performance of the products.
Biocomposites designed for a structural purpose should meet
regulations regarding the management of huge volumes of waste.
Also, new generations of biocomposites are expected to be used
in a wide range of applications in mass-produced consumer prod-
ucts for short-term uses, as well as for long-term indoor applica-
tions [9,197]. In addition, biocomposites are sustainable and
could be fully recyclable, but could be more expensive if fully nat-
ural based and biodegradable and they are extremely sensitive to
moisture and temperature. If a proper matrix is used, biocompos-
ites could be 100% biodegradable, but their biodegradation will
be difficult to control. Biocomposites exhibit good specific proper-
ties, but there is high variability in their properties. Their weakness
can and will be overcome with the development of more advanced
processing of natural fibre and their composites.
7. Conclusions
The exploitation of biocomposites in various applications has
opened up new avenues for both academicians as well as indus-
tries to manufacture a sustainable module for future application
of biocomposites. Different types of natural fibre and their proper-
ties have been studied as a potential replacement of synthetic fibre
like glass and carbon fibre. Furthermore, the effects of different
processing conditions and different surface modification tech-
niques on the fibre as well their biocomposites have been dis-
cussed in detail. The primary motivation for developing
biocomposites has been and still is to build a new generation of
fibre reinforced composites, but which are environmentally
21
compatible in terms of production, use, and removal. Therefore,
natural fibre reinforced biocomposites can be considered to be a
valid alternative or even superior to synthetic fibre composites.
Because of their compostability, they can serve as an efficient solu-
tion to the waste disposal problem of polymer-based materials.
Key activities to reach the goal will be the identification of raw
material extraction, sustainable crop growth, implementation of
biocomposites interfacial properties, material processing and pro-
duct manufacture, safe service life in the intended application,
and product design. Their individual properties should be a solid
base to generate new applications and opportunities for biocom-
posites in the 21st century ‘‘green’’ materials environment.
Acknowledgments
The authors are thankful to Department of Chemicals and
Petrochemicals (DCPC), Ministry of Chemicals and Fertilizers,
Government of India (GOI) for sponsoring the Project.
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