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Carbohydrate Polymers 71 (2008) 343–364

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Review

Biofibres and biocomposites

Maya Jacob John, Sabu Thomas *

School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills P.O., Kottayam, Kerala 686 560, India

Received 14 February 2007; received in revised form 22 May 2007; accepted 24 May 2007
Available online 10 June 2007

Abstract

This review deals with a recent study of the literature on the various aspects of cellulosic fibres and biocomposites. Cellulosic fibre
reinforced polymeric composites are finding applications in many fields ranging from construction industry to automotive industry.
The pros and cons of using these fibres are enumerated in this review. The classification of composites into green composites, hybrid
biocomposites and textile biocomposites are discussed. New developments dealing with cellulose based nanocomposites and electrospin-
ning of nanofibres have also been presented. Recent studies pertaining to the above topics have also been cited. Finally, the applications
of cellulosic fibre reinforced polymeric composites have been highlighted.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Biocomposite; Biofiber; Green composite; Textile; Hybrid

1. Lignocellulosic fibres/natural fibres main components of natural fibres are cellulose (a-cellu-
lose), hemicellulose, lignin, pectins, and waxes.
Natural fibres are subdivided based on their origins, Cellulose is a natural polymer consisting of D-anhydro-
coming from plants, animals or minerals. All plant fibres glucose (C6H11O5) repeating units joined by 1,4-b-D-glyco-
are composed of cellulose while animal fibres consist of sidic linkages at C1 and C4 position (Nevell & Zeronian,
proteins (hair, silk, and wool). Plant fibres include bast 1985). The degree of polymerization (DP) is around
(or stem or soft sclerenchyma) fibres, leaf or hard fibres, 10,000. Each repeating unit contains three hydroxyl
seed, fruit, wood, cereal straw, and other grass fibres. Over groups. These hydroxyl groups and their ability to hydro-
the last few years, a number of researchers have been gen bond play a major role in directing the crystalline pack-
involved in investigating the exploitation of natural fibres ing and also govern the physical properties of cellulose.
as load bearing constituents in composite materials. The Solid cellulose forms a microcrystalline structure with
use of such materials in composites has increased due to regions of high order i.e. crystalline regions and regions
their relative cheapness, their ability to recycle and for of low order i.e. amorphous regions. Cellulose is also
the fact that they can compete well in terms of strength formed of slender rod like crystalline microfibrils. The crys-
per weight of material. Natural fibres can be considered tal nature (monoclinic sphenodic) of naturally occurring
as naturally occurring composites consisting mainly of cel- cellulose is known as cellulose I. Cellulose is resistant to
lulose fibrils embedded in lignin matrix. The cellulose fibrils strong alkali (17.5 wt%) but is easily hydrolyzed by acid
are aligned along the length of the fibre, which render max- to water-soluble sugars. Cellulose is relatively resistant to
imum tensile and flexural strengths, in addition to provid- oxidizing agents.
ing rigidity. The reinforcing efficiency of natural fibre is Hemicellulose is not a form of cellulose and the name is
related to the nature of cellulose and its crystallinity. The a misnomer. They comprise a group of polysaccharides
composed of a combination of 5- and 6-carbon ring sugars.
*
Corresponding author. Tel.: +91 481 2730003; fax: +91 481 2561190.
Hemicellulose differs from cellulose in three aspects.
E-mail addresses: [email protected], [email protected] (S. Firstly, they contain several different sugar units whereas
Thomas). cellulose contains only 1,4–b-D-glucopyranose units.

0144-8617/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2007.05.040
344 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

Secondly, they exhibit a considerable degree of chain helically wound cellular microfibrils formed from long
branching containing pendant side groups giving rise to chain cellulose molecules: the angle between the fibre axis
its non crystalline nature, whereas cellulose is a linear poly- and the microfibrils is called the microfibrillar angle. The
mer. Thirdly, the degree of polymerization of native cellu- characteristic value for this parameter varies from one fibre
lose is 10–100 times higher than that of hemicellulose. The to another.
degree of polymerization (DP) of hemicellulose is around Such microfibrils have typically a diameter of about 10–
50–300. Hemicelluloses form the supportive matrix for cel- 30 nm and are made up of 30–100 cellulose molecules in
lulose microfibrils. Hemicellulose is very hydrophilic, solu- extended chain conformation and provide mechanical
ble in alkali and easily hydrolyzed in acids. strength to the fibre. The amorphous matrix phase in a cell
Lignin is a complex hydrocarbon polymer with both ali- wall is very complex and consists of hemicellulose, lignin,
phatic and aromatic constituents. They are totally insolu- and in some cases pectin. The hemicellulose molecules are
ble in most solvents and cannot be broken down to hydrogen bonded to cellulose and act as cementing matrix
monomeric units. Lignin is totally amorphous and hydro- between the cellulose microfibrils, forming the cellulose–
phobic in nature. It is the compound that gives rigidity to hemicellulose network, which is thought to be the main
the plants. It is thought to be a complex, three-dimensional structural component of the fibre cell. The hydrophobic lig-
copolymer of aliphatic and aromatic constituents with very nin network affects the properties of other network in a
high molecular weight. Hydroxyl, methoxyl and carbonyl way that it acts as a coupling agent and increases the stiff-
groups have been identified. Lignin has been found to con- ness of the cellulose/hemicellulose composite.
tain five hydroxyl and five methoxyl groups per building The structure, microfibrillar angle, cell dimen-
unit. It is believed that the structural units of lignin mole- sions,defects, and the chemical composition of fibres are
cule are derivatives of 4-hydroxy-3-methoxy phenylpro- the most important variables that determine the overall
pane. The main difficulty in lignin chemistry is that no properties of the fibres (Satyanarayana et al., 1986). Gener-
method has been established by which it is possible to iso- ally, tensile strength and Young’s modulus of fibres
late lignin in its native state from the fibre. Lignin is consid- increases with increasing cellulose content. The microfibril-
ered to be a thermoplastic polymer exhibiting a glass lar angle determines the stiffness of the fibres. Plant fibres
transition temperature of around 90 C and melting tem- are more ductile if the microfibrils have a spiral orientation
perature of around 170 C (Olesen & Plackett, 1999). It is to the fibre axis. If the microfibrils are oriented parallel to
not hydrolyzed by acids, but soluble in hot alkali, readily the fibre axis, the fibres will be rigid, inflexible and have
oxidized, and easily condensable with phenol (Bismarck, high tensile strength. Some of the important biofibres are
Mishra, & Lampke, 2005). listed in Table 1.
Pectins are a collective name for heteropolysaccarides.
They give plants flexibility. Waxes make up the last part 1.1. Cellulosic fibres: advantages and disadvantages
of fibres and they consist of different types of alcohols.
Biofibres can be considered to be composites of hollow The growing interest in lignocellulosic fibres is mainly
cellulose fibrils held together by a lignin and hemicellulose due to their economical production with few requirements
matrix (Jayaraman, 2003). The cell wall in a fibre is not a for equipment and low specific weight, which results in a
homogenous membrane (Fig. 1). Each fibril has a complex, higher specific strength and stiffness when compared to
layered structure consisting of a thin primary wall that is glass reinforced composites. They also present safer han-
the first layer deposited during cell growth encircling a sec- dling and working conditions compared to synthetic rein-
ondary wall. The secondary wall is made up of three layers forcements. Biofibres are nonabrasive to mixing and
and the thick middle layer determines the mechanical prop- molding equipment, which can contribute to significant
erties of the fibre. The middle layer consists of a series of cost reductions. The most interesting aspect about natural
fibres is their positive environmental impact. Biofibres are a
renewable resource with production requiring little energy.
They are carbon dioxide neutral i.e. they do not return
excess carbon dioxide into the atmosphere when they are
composted or combusted. The processing atmosphere is
friendly with better working conditions and therefore there
will be reduced dermal and respiratory irritation. Biofibres
possess high electrical resistance. Thermal recycling is also
possible. The hollow cellular structure provides good
acoustic insulating properties. The worldwide availability
is an additional factor.
The inherent polar and hydrophilic nature of lignocellu-
losic fibres and the non-polar characteristics of most ther-
moplastics results in compounding difficulties leading to
Fig. 1. Structure of biofibre. non-uniform dispersion of fibres within the matrix which
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 345

Table 1 fabrication. In addition, cellulose possesses a flattened oval

List of important biofibres cross section that enhances stress transfer by presenting an
Fibre source Species Origin effectively higher aspect ratio.
Abaca Musa textilis Leaf Researchers (Kozlowski, Muzyczek, & Mieleniak, 2004)
Bagasse – Grass at the Institute of Natural Fibres, Poland have developed
Bamboo (>1250 species) Grass fire resistant upholstery using fire-retarded flax nonwoven
Banana Musa indica Leaf
Broom root Muhlenbergia macroura Root
(LinFR) FT. The non-woven used in the composites plays
Cantala Agave cantala Leaf the role of fire barrier that reduces the vulnerability of fill-
Caroa Neoglaziovia variegata Leaf ing material to the development and spread of fire. The
China jute Abutilon theophrasti Stem softness of the upholstery system is also enhanced. In
Coir Cocos nucifera Fruit another interesting study, researchers (Zimniewska, Koz-
Cotton Gossypium sp. Seed
Curaua Ananas erectifolius Leaf
lowski, & Rawluk, 2004) investigated the influence of nat-
Date palm Phoenix Dactylifera Leaf ural and synthetic fibres which covered the forearm
Flax Linum usitatissimum Stem muscles on the activity of motor units in these muscles.
Hemp Cannabis sativa Stem The electrophysiological parameters of motor units were
Henequen Agave fourcroydes Leaf measured with electromyographical methods. The results
Isora Helicteres isora Stem
Istle Samuela carnerosana Leaf
indicated that temporary covering of examined muscles in
Jute Corchorus capsularis Stem the forearm with the synthetic clothing changed the pattern
Kapok Ceiba pentranda Fruit of motor units activity of muscles. Clothing made of natu-
Kenaf Hibiscus cannabinus Stem ral fibre did not evoke this kind of effect.
Kudzu Pueraria thunbergiana Stem Recently, natural cellulose fibres having properties
Mauritius hemp Furcraea gigantea Leaf
Nettle Urtica dioica Stem
between cotton and linen and suitable for various indus-
Oil palm Elaeis guineensis Fruit trial applications were extracted from cornhusks (Reddy
Piassava Attalea funifera Leaf & Yang, 2005a). High quality cellulosic fibres from corn-
Pineapple Ananus comosus Leaf husks mean food, clothing and other major industrial
Phormium Phormium tenas Leaf products from the same source without the need for any
Roselle Hibiscus sabdariffa Stem
Ramie Boehmeria nivea Stem
additional natural resources. Using cornhusks for fibrous
Sansevieria (Bowstring hemp) Sansevieria Leaf applications would save the land and other natural
Sisal Agave sisilana Leaf resources required to grow fibre crops and will conserve
Sponge gourd Luffa cylinderica Fruit the non-renewable petroleum sources required to produce
Straw (Cereal) – Stalk synthetic fibres. More than 9 million tons of natural cellu-
Sun hemp Crorolaria juncea Stem
Cadillo/urena Urena lobata Stem
lose fibres with a potential sale value of $19 billion and
Wood (>10,000 species) Stem with a value addition of at least $12 billion could be pro-
duced from the cornhusks available every year. Utilizing
cornhusks as a source for natural cellulose fibres will signif-
impairs the efficiency of the composite. This is a major dis- icantly benefit the agriculture, fibre, food and energy needs
advantage of natural fibre reinforced composites. Another of the future and will also benefit the environment. The
problem is that the processing temperature of composites is structure and composition of the natural cellulose fibres
restricted to 200 C as vegetable fibres undergo degrada- obtained from cornstalks were found to be different from
tion at higher temperatures; this restricts the choice of that of the common bast fibres such as flax and kenaf.
matrix material. Another setback is the high moisture Cornstalk fibres were found to have relatively lower per-
absorption of natural fibres leading to swelling and pres- centage of crystallinity but similar microfibrillar angle as
ence of voids at the interface, which results in poor that of the common bast fibres (Reddy & Yang, 2005a,
mechanical properties and reduces dimensional stability 2005b). Another study reported on the production and
of composites. Another restriction to the successful exploi- characteristics of natural cellulose fibers obtained from
tation of biofibres for durable composite application is low the leaves and stems of switchgrass. The composition,
microbial resistance and susceptibility to rotting. These structure and properties of fibers obtained from the leaves
properties pose serious problems during shipping, storage and stem of switchgrass were studied in comparison to the
and composite processing. The non-uniformity and varia- common natural cellulose cotton, linen and kenaf. The
tion of dimensions and of their mechanical properties (even leaves and stems of switchgrass were found to have tensile
between individual plants in the same cultivation) poses properties intriguingly similar to that of linen and cotton,
another serious problem. respectively. Fibers obtained from switchgrass leaves pos-
It is quite clear that the advantages outweigh the disad- sessed crystallinity of 51%, breaking tenacity of 5.5 g per
vantages and most of the shortcomings have remedial mea- denier (715 MPa) and breaking elongation of 2.2% whereas
sures in the form of chemical treatments. The the corresponding values for fibers obtained from switch-
lignocellulosic fibres have an advantage over synthetic ones grass stems were 46%, 2.7 g per denier and 6.8%, respec-
since they buckle rather than break during processing and tively (Reddy & Yang, 2005a, 2005b). Shih (2007) studied
346 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

the fiber obtained from the water bamboo husks by CP/ polymers have also attracted the attention of researchers
MAS C13 NMR, elemental analysis, and adiabatic calo- due to their high degree of unsaturation. Fish oil based
rimeter. The pyrolysis behavior of the fiber was also stud- polymers also possess unique good damping and shape
ied by TGA, TGA–GC–MS and Py–GC–MS. The fiber memory properties (Technology International Exchange,
obtained from the water bamboo husks was found to be 1996).
cellulose I. The history of fibre reinforced plastics began in 1908
with cellulose fibre in phenolics, later extending to urea
2. Cellulosic fibre composites and melamine and reaching commodity status with glass
fibre reinforced plastics. The fibre-reinforced composites
The history of mankind has witnessed several surges in market is now a multibillion-dollar business (Material
the field of research and development. The rampant use Thoughts, 2002) (Fig. 2). Though hailed as a miraculous
of petroleum products has created a twin dilemma; deple- discovery long back, plastic products now enjoy an
tion of petroleum resources and entrapment of plastics in ambiguous reputation. Scientists at the BioComposites
the food chain and environment. The increasing pollution Centre at the University of Wales, Bangor are developing
caused by the use of plastics and emissions during inciner- high-quality packaging of goods, using starch from corn
ation is affecting the food we eat, water we drink, air we and potatoes to tackle the problem of high cost waste dis-
breathe and threatening the greatest right of human beings, posal (Material Thoughts, 2005a, 2005b). Researchers
the right to live. The exhaustive use of petroleum based (Material Thoughts, 2005a, 2005b) are also exploring
resources has initiated the efforts to develop biodegradable the aspects of producing plastics from limonene which is
plastics. This is based on renewable biobased plant and extracted from citrus. After decades of obscurity, biofibre
agricultural products that can compete in the markets cur- reinforced composites are being touted as the material of
rently dominated by petroleum based products. The pro- the millennium.
duction of 100% biobased materials as substitute for
petroleum based products is not an economical solution. 2.1. Classification of composites
A more viable solution would be to combine petroleum
and biobased resources to develop a cost-effective product 2.1.1. Green composites
having immense applications. Biopolymers or synthetic Research efforts are currently being harnessed in devel-
polymers reinforced with natural or bio fibres (termed as oping a new class of fully biodegradable ‘green’ composites
biocomposites) are a viable alternative to glass fibre com- by combining (natural/bio) fibres with biodegradable resins
posites. Scientists are looking at the various possibilities (Netravali & Chabba, 2003). The major attractions about
of combining biofibres such as sisal, flax, hemp, jute, green composites are that they are environmentally-
banana, wood and various grasses with polymer matrices friendly, fully degradable and sustainable, i.e. they are truly
from non-renewable and renewable resources to form com- ‘green’ in every way. At the end of their life they can be eas-
posite materials to make the biocomposite revolution a ily disposed of or composted without harming the
reality (Mohanty, Drzal, & Misra, 2002). environment.
Broadly defined, biocomposites are composite materials Fig. 3 shows a classification of biodegradable polymers
made from natural/bio fibre and petroleum derived non- in four families (Averous & Boquillon, 2004). Except the
biodegradable polymers (PP, PE) or biodegradable poly- fourth family, which is of fossil origin, most polymers
mers (PLA, PHA). The latter category i.e. biocomposites (family 1–3) are obtained from renewable resources (bio-
derived from plant derived fibre (natural/biofibre) and mass). The first family is agro-polymers (e.g. polysaccha-
crop/bioderived plastic (biopolymer/bioplastic) are likely rides) obtained from biomass by fractionation. The
to be more eco-friendly and such composites are termed second and third families are polyesters, obtained, respec-
as green composites. tively by fermentation from biomass or from genetically
The best known renewable resources capable of making modified plants (e.g. PHA, polyhydroxyalkanoate) and
biodegradable plastics are starch and cellulose (Wilkinson,
2001). Starch is one of the least expensive biodegradable
materials available in the world market today. It is a versa-
tile polymer with immense potential for use in non-food
industries. Cellulose from trees and cotton plants is a sub-
stitute for petroleum feedstocks to make cellulose plastics.
Another aspect that has gained global attention is the
development of biodegradable plastics from vegetable oils
like soybean oil, peanut oil, walnut oil, sesame oil and sun-
flower oil. Green composites from soy protein based bio-
plastics and natural fibres show potential for rigid
packing and housing and transportation applications
(Tummala, Mohanty, Misra, & Drzal, 2003). Fish oil based Fig. 2. Fibre reinforced plastic composites used in 2002.
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 347

Fig. 3. Classification of biodegradable polymers.

by synthesis from monomers obtained from biomass (e.g. Table 2

PLA, polylactic acid). The fourth family are polyesters, Natural and biodegradable matrices
totally synthesized by the petrochemical process (e.g. Biodegradable polymer matrices
PCL, polycaprolactone; PEA, polyesteramide; aliphatic Natural Synthetic
or aromatic copolyesters). A large number of these biode- 1. Polysaccharides 1. Poly(amides)
gradable polymers (biopolymers) are commercially avail- Starch 2. Poly(anhydrides)
able. They show a large range of properties and they can Cellulose 3. Poly(amide-enamines)
compete with non-biodegradable polymers in different Chitin 4. Poly(vinyl alcohol)
2. Proteins 5. Poly(vinyl acetate)
industrial fields (e.g. packaging).
Collagen/gelatin 6. Polyesters
Another important biocomposites category is based on Casein, albumin, fibrogen, Silks 6.1 Poly(glycolic acid)
agro-polymers matrixes, mainly focussed on starchy mate- 3. Polyesters 6.2 Poly(lactic acid)
rials. Plasticized starch, the so-called ‘thermoplastic Polyhydroxyalkanoates 6.3 Poly(caprolactone)
starch’ (TPS) is obtained after disruption and plasticiza- 4. Other polymers 6.4 Poly(orthoesters)
Lignin 7. Poly(ethylene oxides)
tion of native starch, with water and plasticizer (e.g. pol-
Lipids 8. Poly(phosphazines)
yol) by applying thermomechanical energy in a Shellac
continuous extrusion process. Unfortunately, TPS shows Natural rubber
some drawbacks such as a strong hydrophilic character
(water sensitive), rather poor mechanical properties com-
pared to conventional polymers and an important post- 2.1.1.1. Biofiber–plastic composites. Poly(a-hydroxy acid)
processing variation of the properties. TPS properties such as poly(glycolic acid), PGA, or poly(lactic acid),
reach equilibrium only after several weeks. To improve PLA, are crystalline polymers with relatively high melting
these material weaknesses, TPS is usually associated with point. Recently PLA has been highlighted because of its
other compounds. availability from renewable resources like corn. PLA is a
The design and life cycle assessment of green composites hydrophobic polymer because of the incorporation of the
have been exclusively dealt with by Baillie (2005). Green CH3 side groups when compared to PGA. Poly(b-hydrox-
composites have been used effectively in many applications yalkanoate)s (PHAs), which are synthesized biochemically
such as mass produced consumer products with short life by microbial fermentation and which may be produced in
cycles or products intended for one time or short time the future by transgenic plants, represent natural polyes-
use before disposal. Green composites may also be used ters. Bacteria came first and are still the only real source
for indoor applications with a useful life of several years. of these polyesters; it will still require some more years’
The reinforcement of biofibres in green composites has research until transgenic plants will be available for pro-
been highlighted by Bismarck et al. (2005). duction. Poly(b-hydroxybutyrate) (PHB) (commercial
A number of natural and biodegradable matrices that name Biopol) is a biotechnologically produced polyester
are available for use in such green composites (Stevens, that constitutes a carbon reserve in a wide variety of bacte-
2002) are listed in Table 2. The classification of green com- ria and has attracted much attention as a biodegradable
posites based upon the different types of biodegradable thermoplastic polyester. It can be degraded to water and
matrices is given below. carbon dioxide under environmental conditions by a vari-
348 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

ety of bacteria and has much potential for applications of The thermal stability of biodegradable composite films
environmentally degradable plastics (Mohanty, Misra, & prepared from blends of poly(vinyl alcohol), cornstarch,
Hinrichsen, 2000). and lignocellulosic fibre was investigated by Imam, Cinelli,
In an interesting research Plackett, Andersen, Peder- Gordon, and Chiellini (2005). Thermogravimetric analysis
sen, and Nielsen (2003) used commercial L-polylactide (TGA) indicated the suitability of formulations for melt
which was first converted to film and then used in com- processing, and for application as mulch films in fields at
bination with jute fibre mats to generate biodegradable much higher temperatures. The study also revealed that
composites by a film stacking technique. Degradation both starch and lignocellulosic fibre degraded much more
of the polylactide during the process was investigated rapidly than PVA. The addition of fibre to the formula-
using size exclusion chromatography. The tensile proper- tions was found to enhance the PVA degradation. In
ties of composites produced at temperatures in the 180– another interesting study, the thermal behavior of green
220 C range were significantly higher than those of composites fabricated from bagasse fibre and polyvinyl
polylactide alone. Examination of composite fracture alcohol was investigated by Fernandes, Cinelli, and Chiel-
surfaces using electron microscopy showed voids occur- lini (2004). They observed an increase of thermal stability
ring between the jute fibre bundles and the polylactide upon incorporation of bagasse fibre.
matrix in some cases. Size exclusion chromatography In another study biocomposites (Mehta, Mohanty, Mis-
revealed that only minor changes in the molecular ra, & Drzal, 2004) were fabricated using a non-woven fibre
weight distribution of the polylactide occurred during mat (90% hemp fibre with 10% thermoplastic polyester bin-
the process. der) as reinforcement, and unsaturated polyester (UPE)
In an innovative study, novel biodegradable films were resin as well as blends of UPE and functionalized vegetable
fabricated from chitosan and poly(lactic acid) by Sébastien, oils as the polymer matrix. All composites were made with
Stéphane, Copinet, and Coma (2006). It was found that 30% volume fraction of fibre, which was optimized earlier.
composite films offered a great advantage in preventing The structure–property relationships of this system as well
the surface growth of mycotoxinogen strains because of as the thermo-mechanical properties of these composites
their antifungal activity. However, the physico-chemical were measured. The notched Izod impact strength of bio-
properties of such heterogeneous films, dramatically limit composites from biobased resin blends of UPE and func-
their further usage as packaging materials. tionalized vegetable oil and industrial hemp fibre mat
Lee and Wang (2006) investigated the effects of lysine- were enhanced by 90% as compared to that of the pure
based diisocyanate (LDI) as a coupling agent on the prop- UPE-industrial hemp fibre mat composites. The tests also
erties of biocomposites from poly(lactic acid) (PLA), showed an improvement in the tensile properties of the
poly(butylene succinate) (PBS) and bamboo fiber (BF). composite as a result of the incorporation of the deriva-
They observed that the tensile properties, water resistance, tized vegetable oil.
and interfacial adhesion of both PLA/BF and PBS/BF Researchers have also developed green composites from
composites were improved by the addition of LDI, but jute fabric and Biopol composites (Mohanty, Khan,
thermal flow (Ohkita & Lee, 2006) was hindered due to Sahoo, & Hinrichsen, 2000). Chemical modification of
cross-linking between polymer matrix and BF. Enzymatic the fabric was carried out to improve interfacial properties.
biodegradability of PLA/BF and PBS/BF composites was A significant amount of research has been done at the Ger-
investigated by Proteinase K and Lipase PS, respectively. man Aerospace Centre (DLR) in Braunschweg on biode-
It was seen that the composites could be quickly decom- gradable plastics and composites (Peijs, 2002). Starch and
posed by enzyme and the addition of LDI delayed the deg- modified resins have also been used as matrix to form green
radation. Fig. 4 shows the SEM micrographs of PLA or composites (Goda, 2002).
PBS/BF (70/30) composites with LDI degraded for differ- Biodegradable composites were developed from
ent degradation time. It can be clearly seen that the matrix poly(propylene carbonate) (PPC) reinforced with granular
of both composites became reduced as enzymatic degrada- cornstarch by Ma, Yu, and Zhao (2006). The authors also
tion proceeded. investigated the effects of succinic anhydride (SA) on the
Green composites composed of regenerated cellulose morphology, thermal properties, as well as mechanical
(lyocell) fabric and biodegradable polyesters [poly(3- properties of the composites. The authors are of the opin-
hydroxybutyrate-co-3-hydroxyvarelate) (PHBV), poly- ion that SA enhances the properties of PPC/starch com-
(butylene succinate) (PBS), and poly(lactic acid) (PLA)] posites, which was ascribed to the improvement of the
were prepared by Shibata, Oyamada, Kobayashi, and Yag- interaction between PPC and granular.
inuma (2004) and properties studied. The tensile moduli In another study (Ge, Xu, Meng, & Li, 2005) involving
and strength of all the biodegradable polyester/lyocell com- poly(propylene carbonate) (PPC), starch–g-poly(methyl
posites were found to increase with increasing fiber con- acrylate) (S–g-PMA) copolymer was used to reinforce
tent. The biodegradation test revealed that the lyocell PPC. Starch–g-poly(methyl acrylate) (S–g-PMA) copoly-
fabric in PLA/lyocell composite degraded, as shown in mer was prepared by ceric ammonium nitrate-initiated
Fig. 5. Pure PLA film was found to be almost unchanged polymerization of methyl acrylate onto corn starch (CS).
after 120 days. Tensile tests showed that the S–g-PMA incorporation
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 349

Fig. 4. SEM micrographs of PLA or PBS/BF composites with LDL (NCO content, 0.65%) after different enzymatic degradation time. (a) Control of
PLA/BF composite, (b) after 7 days, (c) 9 days, (d) control of PBS/BF composite, (e) after 2 days, (f) 4 days.

Fig. 5. Photographs of PLA (top) artd PLA/lyocell composite (bottom) after the soil burial test: (a) before test, (b) at 60 days, and (c) at 120 days.

improved the stiffness and tensile strength of composites of PLLA/KF composites were investigated. It was found
significantly. TG results indicated that the S–g-PMA addi- that the incorporation of KF significantly improves the
tion led to an improvement in the thermal stability of crystallization rate and tensile and storage modulus. The
resulting composites. crystallization of PLLA can be completed during the cool-
Bio-based polymer composite was from plant-derived ing process from the melt at 5 C/min with the addition of
kenaf fiber (KF) and biodegradable polyester, poly(L-lac- 10 wt% KF. It was also observed that the nucleation den-
tide) (PLLA), by melt-mixing technique, by Pan et al. sity increases dramatically and the spherulite size drops
(2007). The effect of the KF weight contents (0, 10, 20, greatly in the isothermal crystallization with the presence
and 30 wt%) on crystallization behavior, composite mor- of KF. In addition, with the incorporation of 30 wt%
phology, mechanical, and dynamic mechanical properties KF, the half times of isothermal crystallization at 120
350 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

and 140 C were reduced to 46.5% and 28.1% of the pure The presence of resin on some fibre surfaces for the SPI
PLLA, respectively. Moreover, the tensile and storage and MSPI resins clearly indicates good interfacial interac-
modulus of the composite are improved by 30% and tion between the fibre and the resins.
28%, respectively, by the reinforcement with 30% KF. In an interesting study, researchers (Chabba, Mathews,
Scanning electron microscopy observation also showed & Netravali, 2005) modified soy flour (SF) by cross-linking
that the crystallization rate and mechanical properties it with glutaraldehyde (GA). The cross-linked soy flour
could be further improved by optimizing the interfacial (CSF) polymer was characterized for its tensile and thermal
interaction and compatibility between the KF and PLLA properties. The effect of glycerol on the mechanical proper-
matrix. ties of the soy flour was also characterized and optimized.
The morphology, mechanical and thermal properties of CSF polymer showed improved tensile properties and ther-
composites of poly(L-lactide) with hemp fibers was investi- mal stability, compared to unmodified SF resin, for use as a
gated by Masirek, Kulinski, Chionna, Piorkowska, and resin to fabricate composites. Unidirectional green com-
Pracella (2007). The thermogravimetric analysis of the posites using flax yarn and CSF resin were fabricated and
composites, carried out in both nitrogen and air, showed characterized for their tensile and flexural properties. The
that the degradation process of fiber-filled systems started composite specimens exhibited fracture stress and Young’s
earlier than that of plain PLA, independently of the pres- modulus of 259.5 MPa and 3.71 GPa, respectively, and
ence of the plasticizer. Mechanical tests showed that the flexural strength of 174 MPa, in the longitudinal direction.
modulus of elasticity of the composites markedly increased Recently green composites were fabricated using pineap-
with the hemp content, reaching 5.2 GPa in the case of ple leaf fibre and soy based plastic (Liu, Misra, Askeland,
crystallized PLA reinforced with 20 wt% hemp, whereas Drzal, & Mohanty, 2005). The addition of compatabilizer
the elongation and stress at break decreased with an (polyester amide grafted glycidyl methacrylate (PEA-g-
increasing amount of fiber for all examined systems. GMA)) was seen to increase the mechanical properties of
composites. In another interesting study involving biocom-
2.1.1.2. Biofiber–soy based composites. In US, soybeans posites, the effect of alkali treatment on the thermal prop-
provide over 60% of the fats and oils used for food and erties of Indian grass fibre reinforced soy protein green
the majority of the feed protein. Soybeans typically contain composites was studied by the same group (Liu, Mohanty,
about 20% oil and 40% protein. Protein levels as high as Askeland, Drzal, & Misra, 2004).
55% have been observed in soybeans. Soybeans consist of The characterization of Phytagel modified soy protein
discrete groups of proteins (polypeptides) that span a isolate (SPI) resin and unidirectional flax yarn reinforced
broad range of molecular sizes and are comprised of green composites was undertaken by Lodha and Netravali
approximately 38% of non-polar, non-reactive amino acid (2005). The incorporation of Phytagel in SPI resin led to
residues, while 58% are polar and reactive. Modifications an overall 10-fold increase in the tensile fracture stress and
that take advantage of water solubility and reactivity are a 9-fold increase in the Young’s moduli of the SPI resin
exploited in improving soy protein for use in plastics and along with a 7-fold decrease in fracture strain. The dynamic
other biomaterials (Thames, 1994). Soy protein plastics mechanical properties such as storage and loss modulus of
of different compositions have been prepared by injection the modified resin increased and the glass transition tem-
moulding (Jane, 1996). Compression moulding is also used perature also increased by about 56 C.
for soy plastic processing. Dried soy plastics display an
extremely high modulus, 50% higher than that of currently 2.1.1.3. Biofiber–natural rubber composites. The primary
used epoxy engineering plastics (Wang, Sue, & Jane, 1994). effects of bio-fibre reinforcement on the mechanical proper-
So with proper moisture-barrier, soy protein is a potential ties of natural rubber composites include increased modu-
starting material for engineering plastics. lus, increased strength with good bonding at high fibre
Researchers recently investigated the effect of stearic concentrations, decreased elongation at failure, greatly
acid on tensile and thermal properties of ramie fibre rein- improved creep resistance over particulate-filled rubber,
forced soy protein isolate (SPI) resin green composites increased hardness and a substantial improvement in cut,
(Lodha & Netravali, 2005). It was observed that part of tear and puncture resistance. Biodegradation of vulcanized
the stearic acid crystallized in SPI resin and that the crys- rubber material is possible, although it is difficult due to the
tallizability was affected by the addition of glycerol as a interlinkages of the poly(cis-1,4-isoprene) chains, which
plasticizer. The fabricated green composite was found to result in reduced water absorption and gas permeability
have enormous potential for certain indoor applications. of the material (Seal & Morton, 1996). Certain Streptomy-
The interfacial adhesion in the composites was apparent ces strains were seen to degrade rubber samples after 12
from SEM photomicrographs of the fracture tensile sur- months of incubation.
faces of the ramie/SPI and ramie/modified soy protein iso- The reinforcement of coir fibre in natural rubber has
late (MSPI) composites tested in the axial direction is been extensively studied (Geethamma, Joseph, & Thomas,
shown in Fig. 6a and b, respectively. Some of the fibres 1995). Researchers have also investigated the reinforcement
at the fracture surface do not show any resin, where as a effects of a leaf fibre – sisal fibre – in natural rubber (Var-
few other fibres clearly show resin sticking on the surface. ghese, Kuriakose, Thomas, & Koshy, 1994).
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 351

Fig. 6. (a, b) SEM photomicrographs of the fracture tensile surfaces of untreated and treated composites.

Attempts to incorporate oil palm fibre in rubber matrix

have also been successful. The effect of fibre concentration
on the mechanical properties of oil palm reinforced natural
rubber composites was investigated by Ismail, Rosnah, and
Ishiaku (1997). They observed the general trend of reduc-
tion in tensile and tear strength with increasing fibre
concentration.
An interesting report on the reinforcement effect of grass
fibre – bagasse – in natural rubber was presented by Nas-
sar, Ashour, and Washid (1996). Aging experiments
revealed tensile strength retention of 97%. Scientists have
also developed composites comprising of kenaf fibre and
natural rubber (El Sabbagh et al., 2000). An increase in
rheometric and mechanical properties was observed. Pine-
apple (Bhattacharya, Biswas, Chaterjee, & Pramanick, Fig. 7. Variation of tensile strength with chemical modification.
1986) and jute fibre (Arumugam, Tamareselvy, Venkata
Rao, & Rajalingam, 1989) have also found their way as a
potential reinforcement in natural rubber. In an innovative study, a unique combination of sisal
In an interesting study, researchers have used a novel and oil palm fibres in natural rubber has been utilized to
fibre – isora fibre – in natural rubber (Mathew, Joseph, & design hybrid biocomposites. It was seen that the incorpo-
Joseph, 2004). Isora fibres are present in the bark of the ration of fibers resulted in increased modulus (Jacob,
Helicteres isora plant and are separated by retting process. Varughese, & Thomas, 2004a, 2004b). Chemical modifica-
Isora fibre resembles jute in appearance but surpasses it in tion of both sisal and oil palm fibres was imperative for
strength, durability and lustre. The effects of different increased interfacial adhesion and resulted in enhanced
chemical treatments, including mercerisation, acetylation, properties (Jacob et al., 2004a, 2004b). The viscoelastic
benzoylation and treatment with toluene diisocyanate (Jacob, Francis, Varughese, & Thomas, 2006), water sorp-
and silane coupling agents, on isora fibre properties and tion (Jacob, Varughese, & Thomas, 2005), dielectric
mechanical properties were analyzed. Isora fibre was seen (Jacob, Varughese, & Thomas, 2006a, 2006b) and stress
to have immense potential as reinforcement in natural rub- relaxation (Jacob et al., 2006a, Jacob, Varughese, & Tho-
ber. The variation of tensile strength with chemical modifi- mas, 2006b) characteristics were also studied.
cation is given in Fig. 7. A major hurdle to the commercialization of green com-
Researchers have also designed novel rubber biocom- posites is the high cost of biodegradable matrices. Most of
posites by using a combination of leaf and fruit fibre in nat- the biodegradable resins cost significantly more than the
ural rubber (Haseena & Unnikrishnan, 2005). The commonly used resins. Inexpensive production of oils for
incorporation of sisal and coir fibre in NR was seen to resins through biotechnology would certainly be of help
increase the dielectric constant of the composites. These in expediting their commercialization. The manufacturing
hybrid biocomposites were found to have enormous appli- costs can also be reduced by faster, better and more effi-
cations as antistatic agents. In another interesting study, cient processing.
the preparation of composites comprising of waste paper Efforts are on the anvil for the development of
in natural rubber along with boron carbide and paraffin ‘‘advanced green composites’’ made out of high strength
wax, for radiation shielding applications, was investigated protein fibres (spider silk) and biodegradable matrices. Bio-
(Madani, Basta, Abdo, & El-Saied, 2004). technology is being used to increase the yield of specific tri-
352 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

glycerides and oils in beans for producing resins. These res- a matrix. Hybridization with glass fibre provides a method
ins will be inexpensive compared to those available today to improve the mechanical properties of natural fibre com-
and if suitably modified, could be biodegradable. Research posites and its effect in different modes of stress depends on
is also being conducted to develop new pathways to synthe- the design and construction of the composites. The effect of
size inexpensive biodegradable resins (Allen, Moore, Lob- hybridization of glass fibre in thermoset biocomposites has
kovsky, & Coates, 2002) with better mechanical been discussed in detail (Ray & Rout, 2005).
properties and thermal stability using nanotechnology The tensile and impact behavior of oil palm fibre-glass
(Maiti & Giannelis, 2002). fibre-reinforced epoxy resin was investigated by Bakar,
Hariharan, and Abdul Khalil (2005). The hybridization of
2.1.2. Hybrid composites oil palm fibres with glass fibres increased the tensile strength,
The incorporation of several different types of fibres into Young’s modulus, and elongation at break of the hybrid
a single matrix has led to the development of hybrid bio- composites. A negative hybrid effect was observed for the
composites. The behavior of hybrid composites is a tensile strength and Young’s modulus while a positive
weighed sum of the individual components in which there hybrid effect was observed for the elongation at break of
is a more favorable balance between the inherent advanta- the hybrid composites. The impact strength of the hybrid
ges and disadvantages. Also, using a hybrid composite that composites increased with the addition of glass fibres.
contains two or more types of fibre, the advantages of one Cellular biocomposite cores fabricated from industrial
type of fibre could complement with what are lacking in the hemp or flax fibres with unsaturated polyester were hybrid-
other. As a consequence, a balance in cost and perfor- ized with woven jute, chopped glass, and unidirectional
mance could be achieved through proper material design carbon fabrics (Burgue~ no et al., 2005). Material character-
(Thwe & Liao, 2003). The properties of a hybrid composite ization showed improved stiffness, strength, and moisture-
mainly depend upon the fibre content, length of individual absorption stability, while flexural tests on laboratory-scale
fibres, orientation, extent of intermingling of fibres, fibre to plates demonstrated enhanced structural behavior. These
matrix bonding and arrangement of both the fibres. The hybrid cellular biofibre-based composites were found to
strength of the hybrid composite is also dependent on the provide an economic and environmentally friendlier alter-
failure strain of individual fibres. Maximum hybrid results native to entry-level synthetic composites.
are obtained when the fibres are highly strain compatible Hybridization also has a profound effect on the water
(Sreekala, George, Kumaran, & Thomas, 2002). absorption property of composites. An attempt to study
The properties of the hybrid system consisting of two the moisture uptake characteristics of hybrid systems was
components can be predicted by the rule of mixtures. performed by Mishra et al. (2003). The composite systems
chosen were sisal/glass and pineapple/glass fibre reinforced
P H ¼ P 1V 1 þ P 2V 2; ð1:1:1Þ
polyester composites. Composites were prepared by vary-
where PH is the property to be investigated, P1 the corre- ing the concentration of glass fibre and by subjecting the
sponding property of the first system and P2 the corre- bio-fibres to different chemical treatments. The authors
sponding property of the second system. V1 and V2 are observed that water uptake of hybrid composites were less
the relative hybrid volume fractions of the first and second than that of unhybridized composites.
system and A comparative study of the water absorption of the glass
fibre (7 wt%)/natural biofibre (13 wt%) with that of non-
V 1 þ V 2 ¼ 1: ð1:1:2Þ
hybrid composites is given in Table 3 where a lowering in
A positive or negative hybrid effect is defined as a positive water absorption is evident (Rout, Mishra, Tripathy,
or negative deviation of a certain mechanical property Nayak, & Mohanty, 2001).
from the rule of hybrid mixture. The novel development of a photofabrication process of
The term hybrid effect has been used to describe the phe- biofibre composites, based on oil palm empty fruit bunch
nomenon of an apparent synergistic improvement in the fibres was recently reported (Kumar, Hee, & Rozman,
properties of a composite containing two or more types
of fibre. The selection of the components that make up
Table 3
the hybrid composite is determined by the purpose of Comparative study of the water absorption of the glass fibre/natural
hybridization, requirements imposed on the material or biofibre with that of non-hybrid composites
the construction being designed. The problem of selecting Sample Water absorption (%)
the type of compatible fibres and the level of their proper-
Nonhybrid (coir–polyester Hybrid [coir/glass–
ties is of prime importance when designing and producing composite) (20 wt%) polyester composite]
hybrid composites. The successful use of hybrid composites
Untreated 8.53 5.186
is determined by the chemical, mechanical and physical sta- Alkali- treated (5%) 4.994 3.147
bility of the fibre/matrix system. PMMA grafted (5%) 3.98 2.663
Hybrid biocomposites can be designed by the combina- PAN grafted (10%) 4.119 2.997
tion of a synthetic fibre and natural fibre (biofibre) in a Cyanoethylated 3.6 3.138
Bleached 5.8 3.718
matrix and a combination of two natural fibre/biofibre in
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 353

2005). The process consisted of the following steps: (1) the unhybridized samples. Thermal properties and resistance
preparation of nonwoven mat of biofibre, either alone or in to water absorption properties of the hemp fiber compos-
combination with glass and nylon; (2) drying the mat; (3) ites were improved by hybridization with glass fibers.
preparation of photocurable resin matrix, consisting of The ballistic properties of flax, hemp, and jute fabric–
vinyl ester and photoinitiator; (4) impregnation of the steel hybrid polypropylene composites processed by hot
mat by photocurable resin; and (5) irradiation of the compression moulding were investigated by Wambua,
impregnated mat by UV radiation to effect the cure of Vangrimde, Lomov, and Verpoest (2007). The composites’
the composite. Oil palm fibre, glass, and nylon fibres were ballistic limit (V50) was determined by subjecting the mate-
mixed in different proportions. A ‘‘mixture experimental rial to ballistic impact loading by fragment simulating pro-
design’’ was used to generate experimental compositions jectiles (FSPs) using a block manometric cannon
of the reinforcing fibres and to model dependency of the interchangeable (BMCI) gun. Flax composites exhibited
response variables on the components through mathemat- better energy absorption than hemp and jute composites.
ical relationships. The composites failed by shear cut-out, delamination and
The flexural behaviour of hybrid laminated composites fibre fracture. It was found that the ballistic properties of
(LC) with a hemp fibre/polypropylene core and two glass the hemp composites increased significantly when a mild
fibres/polypropylene surface layers at each side of the spec- steel plate was used as facing and backing.
imen were investigated by Reis, Ferreira, Antunes, and The mechanical and thermal properties of hybrid bio-
Costa (2007). When compared with full glass fibres rein- composites from oil palm empty fruit bunch (EFB) fibers
forced polypropylene laminates, the hybrid composites were and kaolinite in polyurethane was studied by Amin and
found to have economical, ecological and recycling advan- Badri (2007). The occurrence of chemical interactions
tages and also specific fatigue strength benefits. Static and between the hydroxyl terminals in both fillers and the PU
fatigue tests were performed in three point bending for both system was determined via FTIR spectroscopy. Hybrid
laminates to evaluate flexural strength properties and fati- bio-composites showed improved stiffness, strength, and
gue behaviour. The major findings were that laminated com- better water resistance with the addition of kaolinite to
posites (LC) exhibited an ultimate strength about 4% higher an extent. At 15% of kaolinite loading, maximum flexural
than the hybrid laminated composites (HLC) associated to and impact strengths were observed. The interaction
changes in failure mechanisms, while the stiffness’ modulus between kaolinite with PU matrix and EFB fibers enhanced
was also about 3.8% higher. Fatigue strength of hybrid lam- the mechanical properties of the bio-composites.
inated composites was also about 20% lower than the lami- The effect of the various layering patterns on the water
nated composites as consequence of the change of the failure absorption of the banana-glass hybrid composites was stud-
mechanisms and of the different static strengths. ied by Pothan, Cherian, Anandakutty, and Thomas (2007).
Scientists (Morye & Wool, 2005) at the Affordable Com- It was found that water diffusion occurs in the composite
posites from Renewable Resources (ACRES) program at depending on the layering pattern as well as the tempera-
the University of Delaware investigated the mechanical ture. In all the experiments, it was found that composites
properties of glass/flax hybrid composites based on a novel with an intimate mixture of glass and banana show the max-
modified soybean oil matrix material. Composites with dif- imum water uptake except for temperature of 90 C. At
ferent glass/flax ratios and different fibre arrangements 90 C the maximum water uptake is found to be for compos-
were made using a modified soybean oil matrix material. ites where there is one layer of banana and another layer of
The fibre arrangement was varied to make symmetric and glass. The water uptake follows the same trend as that in all
unsymmetric composites. The latter were tested in different other temperatures till a time span of 4900 min is reached.
modes in flexural tests and drop weight impact tests. The The kinetics of diffusion was found to be Fickian in nature.
mechanical properties of the composites were found to Another innovative approach to hybrid composites is
depend upon the glass/flax ratio and the arrangement of the incorporation of two natural fibres/biofibre in a matrix
fibres in the composite. On proper selection of the arrange- system. Recently, the mechanical performance of short ran-
ment of fibres in the composite, the glass fibres and flax domly oriented banana and sisal hybrid fibre reinforced
fibres were found to act synergistically resulting in an polyester composites was investigated with reference to
improved flexural and impact performance. the relative volume fraction of the two fibres at a constant
The mechanical, water absorption, and thermal proper- total fibre loading of 0.40 volume fraction (Vf), keeping
ties of injection-molded short hemp fiber/glass fiber-rein- banana as the skin material and sisal as the core material.
forced polypropylene hybrid composites was investigated A positive hybrid effect was observed in the flexural
by Panthapulakkal and Sain (2007). The authors observed strength (Fig. 8) and flexural modulus of the hybrid com-
that hybridization with glass fiber enhanced the perfor- posites. The tensile strength of the composites showed a
mance properties. A value of 101 MPa for flexural strength positive hybrid effect when the relative volume fraction of
and 5.5 GPa for the flexural modulus is achieved from the two fibres was varied, and maximum tensile strength
hybrid composite containing 25 wt% of hemp and 15 wt% was found to be in the hybrid composite having a ratio
of glass. Notched Izod impact strength of the hybrid com- of banana and sisal 4:1 (Idicula, Neelakantan, Oommen,
posites exhibited great enhancement (34%) compared to Joseph, & Thomas, 2005).
354 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

posites that have superior mechanical properties, as contin-

uous orientation of fibres is not restricted at any point.
In applications where more than one fibre orientation is
required, a fabric combining 0 and 90 fibre orientations is
useful. Woven fabrics are produced by the interlacing of
warp (0) fibres and weft (90) fibres in a regular pattern
or weave style. The fabric’s integrity is maintained by the
mechanical interlocking of the fibres. Drape (the ability
of a fabric to conform to a complex surface), surface
smoothness and stability of a fabric are controlled primar-
ily by the weave style.

2.1.4. Common weave architectures

The following is a description of some of the more com-
Fig. 8. Variation of flexural strength with volume fraction of fibre.
monly found weave styles:
Plain
As a continuation to the above study the dynamic and Each warp fibre passes alternately under and over each
static mechanical properties of randomly oriented inti- weft fibre. The fabric is symmetrical, with good stability
mately mixed banana and sisal hybrid fibre reinforced and reasonable porosity. However, it is the most difficult
polyester composites were reported. Maximum stress trans- of the weaves to drape, and the high level of fibre crimp
fer between the fibre and matrix was obtained in compos- imparts relatively low mechanical properties compared
ites having volume ratio of banana and sisal as 3:1. The with the other weave styles. With large fibres (high tex) this
storage modulus was found to increase with fibre volume weave style gives excessive crimp and therefore it is not
fraction above the glass transition temperature of the com- generally used for very heavy fabrics.
posites (Idicula, Malhotra, Joseph, & Thomas, 2005).
Idicula et al. (2006) investigated the thermophysical
properties of banana-sisal hybrid reinforced composites as
a function of chemical modification. Sisal and banana fibers
were subjected to mercerization and polystyrene maleic
anhydride treatments. The authors observed that chemical
modification resulted in an increase of 43% in thermal con-
ductivity when compared to untreated composites.
The tensile properties of wood flour/kenaf fiber polypro-
pylene hybrid composites were investigated by Mirbagheri,
Tajvidi, Hermanson, and Ghasemi (2007). The hybrid
effect on the elastic modulus of the composites was also
investigated using the rule of hybrid mixtures and Hal-
pin–Tsai equations. The relationship between experimental Twill
and predicted values was evaluated and accuracy estima- One or more warp fibres alternately weave over and
tion of the models was performed. The results indicated under two or more weft fibres in a regular repeated manner.
that while nonhybrid composites of kenaf fiber and wood This produces the visual effect of a straight or broken diag-
flour exhibited the highest and lowest modulus values onal ‘rib’ to the fabric. Superior wet out and drape is seen in
respectively, the moduli of hybrid composites were closely the twill weave over the plain weave with only a small reduc-
related to the fiber to particle ratio of the reinforcements. tion in stability. With reduced crimp, the fabric also has a
Rule of hybrid mixtures equation was able to predict the smoother surface and slightly higher mechanical properties.
elastic modulus of the composites better than Halpin–Tsai
equation.
Researchers have also explored the incorporation of a
fruit and leaf fibre in natural rubber (Haseena, Dasan,
Namitha, Unnikrishnan, & Thomas, 2005). The addition
of sisal and coir fibres offered good reinforcement and
resulted in improvement of properties.

2.1.3. Textile composites

The development of textile technologies such as weaving,
knitting and braiding has resulted in the formation of com-
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 355

Satin which adjacent warp fibres are twisted around consecutive

Satin weaves are fundamentally twill weaves modified to weft fibres to form a spiral pair, effectively ‘locking’ each
produce fewer intersections of warp and weft. The ‘harness’ weft in place. Fabrics in leno weave are normally used in
number used in the designation (typically 4, 5, and 8) is the con-junction with other weave styles because if used alone
total number of fibres crossed and passed under, before the their openness could not produce an effective composite
fibre repeats the pattern. A ‘crowsfoot’ weave is a form of component.
satin weave with a different stagger in the repeat pattern.
Satin weaves are very flat, have good wet out and a high
degree of drape. The low crimp gives good mechanical
properties. Satin weaves allow fibres to be woven in the
closest proximity and can produce fabrics with a close
‘tight’ weave. However, the style’s low stability and asym-
metry needs to be considered. The asymmetry causes one
face of the fabric to have fibre running predominantly in
the warp direction while the other face has fibres running
predominantly in the weft direction.

Mock leno
A version of plain weave in which occasional warp
fibres, at regular intervals but usually several fibres apart,
deviate from the alternate under-over interlacing and
instead interlace every two or more fibres. This happens
with similar frequency in the weft direction, and the overall
effect is a fabric with increased thickness, rougher surface,
and additional porosity.

Basket
Basket weave is fundamentally the same as plain weave
except that two or more warp fibres alternately interlace
with two or more weft fibres. An arrangement of two warps
crossing two wefts is designated 2·2 basket, but the
arrangement of fibre need not be symmetrical. Therefore
it is possible to have 8·2, 5·4, etc. Basket weave is flatter,
and, though less crimp, stronger than a plain weave, but
less stable. It must be used on heavy weight fabrics made
with thick (high tex) fibres to avoid excessive crimping.

Researchers have looked into tensile strength of ramie-

cotton hybrid fibre reinforced polyester composites
(Junior, Carvalho, Fonseca, Monteiro, & Almeida, 2004).
They observed that tensile behaviour was dominated by
volume fraction of ramie fibres aligned in the test direction.
The fabric and diameter of the thread did not play any role
in tensile characteristics. Cotton fabric was found to have
minor reinforcement effect due to weak cotton/polyester
interface. Similar studies were performed by Mwaikambo
and Bisanda (1999) on kapok-cotton fibre reinforced poly-
ester composites.
Pothen, Thomas, Li, and Mai (2002) conducted tensile
Leno and impact studies of woven sisal fabric reinforced polyes-
Leno weave improves the stability in ‘open’ fabrics ter composites prepared by RTM technique. It was found
which have a low fibre count. A form of plain weave in that the weave architecture was a crucial factor in deter-
356 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

mining the response of the composites. Researchers have (2006a, 2006b). The mechanical properties of the textile
studied the micromechanics of moisture diffusion in woven composites were found to decrease after chemical modifica-
composites (Tang, Whitcomb, Li, & Sue, 2005). The weave tion which was contrary to the behaviour in short fiber
pattern of the fabric was found to have a profound effect composites. The solvent sorption (Jacob et al., 2006a,
on the water uptake of the composites. They observed that 2006b) characteristics of the composites were also
woven composites exhibited quicker diffusion than that of investigated.
a unidirectional laminate with the same overall fibre vol-
ume fraction. The plain weave with a lenticular tow and 2.1.5. Applications of biocomposites
large waviness was seen to exhibit the quickest diffusion The use of biofibre reinforced composites has extended
process. to almost all fields. Recently three-layer particleboards
The mechanical performance of isothalic polyester- were produced from a mixture of sunflower stalks and
based untreated woven jute-fabric composites was investi- poplar wood at certain ratios utilizing urea-formaldehyde
gated by Ahmed and Vijayarangan (2007). It was found (UF) adhesives. Panels with a density of 0.7 g/cm3 were
that the tensile strength and tensile modulus of jute-fabric manufactured with the ratios of 25, 50, and 75 percent
composite are 83.96% and 118.97% greater than the ten- particles from sunflower stalks or poplar. Panels were
sile strength and modulus of unreinforced resin, subjected to various tests for physical properties. Results
respectively. show that all the panels provide properties required by
Novolac type phenolic composites reinforced with jute/ the normal standards for general purpose-use particle-
cotton hybrid woven fabrics were fabricated and its prop- boards (Bektas, Guler, Kalaycioǧlu, Mengeloglu, &
erties were investigated as a function of fibre orientation Nacar, 2005).
and roving/fabric characteristics (De Medeiros, Agnelli, Bio-based composite roof structures were successfully
De Carvalho, & Mattoso, 2004). Results showed that the fabricated from soy oil-based resin and cellulose fibres
composite properties were strongly influenced by test direc- in the form of paper sheets made from recycled card-
tion and rovings/fabric characteristics. The anisotropy board boxes. This recycled paper was previously tested
degree was shown to increase with test angle and to in composite sheets and structural unit beams and was
strongly depend on the type of architecture of fabric used, found to give the required stiffness and strength required
i.e. jute rovings diameter, relative fibre content, etc. The for roof construction (Dweib, Hu, Shenton, & Wool,
best overall mechanical properties were obtained for the 2006).
composites tested along the jute rovings direction. Com- In a study encompassing many applications, the flame
posites tested at 45 and 90 with respect to the jute roving retardancy of biodegradable polymers and biocomposites
direction exhibited a controlled brittle failure combined was investigated (Matkó et al., 2005). For the comparison,
with a successive fibre pullout, while those tested in the lon- flame retarded lignocellulosic filler reinforced biocompos-
gitudinal direction (0) exhibited a catastrophic failure ites were prepared using polypropylene (PP), polyurethane
mode. The researchers are of the opinion that jute fibre (PUR) and fully biodegradable starch matrices. The com-
promotes a higher reinforcing effect and cotton fibre avoids patibility of wood flake with PP was improved by applica-
catastrophic failure. Therefore, this combination of natural tion of an alkoxy silane based reactive surfactant. The
fibres is suitable to produce composites for lightweight silylation improved not only the compatibility but also
structural applications. the thermal stability of the wood flake according to TG
The thermal diffusivity, thermal conductivity and spe- measurements. Raman spectroscopic analysis of the silylat-
cific heat of jute/cotton, sisal/cotton and ramie/cotton ed product showed that the improved thermal stability is
hybrid fabric-reinforced unsaturated polyester composites the result of reduced ratio of the amorphous phase of cel-
were investigated by Alsina, Carvalho, Filho, and Almeida lulose. The phosphorus additives in flame retarded PUR
(2005). These properties were measured both parallel and biocomposites, comprising waste bio fillers and recycled
perpendicular to the plane of the fabrics. The results polyol, proved to be very effective because both the matrix
obtained show that higher values were obtained parallel and the filler components participate in mechanism of
to the plane of the fibres. Sisal/cotton composites showed flame retardancy.
a particular behavior, with thermal properties very close Researchers (Hong & Wool, 2004) developed a new
to those of the resin matrix. The thermal properties of low dielectric constant material suited to electronic mate-
the fabrics, i.e. without any resin, were also evaluated rials applications using hollow keratin fibres and chemi-
and were used to predict the properties of the composites cally modified soybean oil. The unusual low value of
from the theoretical series and parallel model equations. dielectric constant was due to the air present in the hollow
The effect of fabric pre-drying on the thermal properties microcrystalline keratin fibres and the triglyceride mole-
of the composites was also evaluated. The results showed cules. The authors are of the opinion that the low cost
that the drying procedure used did not bring any relevant composite made from avian sources and plant oil has
change in the properties evaluated. the potential to replace the dielectrics in microchips and
Textile biocomposites comprising of woven sisal fabric circuit boards in the ever growing electronics materials
and natural rubber were fabricated by Jacob et al. field. In an extension of the above study the authors have
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 357

also observed that the coefficient of thermal expansion case, coconut fibres were used in the commercial vehicles
(CTE) of the composite was low enough for electronic over a 9 year period. Mercedes also used jute-based door
applications and similar to the value of silicon materials panels in its E-class vehicles in 1996. In September 2000,
or polyimides used in printed circuit boards (Hong & Daimler Chrysler began using natural fibres for their vehi-
Wool, 2005). cle production. The bast fibres are primarily used in auto-
Plastic/wood fibre composites are being used in a large motive applications because they exhibit greatest strength.
number of applications in decks, docks, window frames The other advantages of using bast fibres in the automo-
and molded panel components (Li & Matuana, 2003). It tive industry include weight savings of between 10% and
has been reported that 460 million pounds of plastic/ 30% and corresponding cost savings. Recent studies have
wood fibre composites were produced in 1999. Statistics also indicated that hemp-based natural fibre mat thermo-
show that the production of these composites in 2001 plastics are promising candidates in automotive applica-
has increased to 700 million pounds. Over the last three tions where high specific stiffness is required (Pervaiz &
decades considerable research has been committed to find- Sain, 2003).
ing an alternative fibre to replace asbestos in fibre cement Virtually all the major car manufacturers in Germany
products. Australian research was centred on natural (Daimler Chrysler, Mercedes, Volkswagen, Audi Group,
fibres and ultimately it was a natural fibre, wood pulp BMW, Ford and Opel) now use biocomposites in various
fibre, which was responsible for the greatest replacement applications. Interior trim components such as dashboards
of asbestos in the beleaguered global fibre cement industry and door panels using polypropylene and natural fibres are
(Coutts, 2005). As these fibres are cheap and readily avail- produced by Johnson Controls, Inc. for Daimler Chrysler.
able the energy required for the processing of these com- In 2000 Audi launched the A2 midrange car in which door
posites is low; also the incorporation of random vegetable trim panels were made of polyurethane reinforced with
fibres in cement matrices requires only a small number of mixed flax/sisal mat. DaimlerChrysler has now increased
trained personnel in the construction industry. Recently, its research and development in flax reinforced polyester
researchers (Ghavami, 2005) have explored the use of composites for exterior applications (Automotive Indus-
bamboo fibre as reinforcement in structural concrete ele- tries, 2000).
ments. Pulp from eucalyptus waste and residual sisal Recent reports by Bledzki, Faruk, and Sperber (2006)
and coir fibres have also been studied as a replacement point out the importance of biofibers and biocomposites
for asbestos in roofing components (Agopyan, Savastano, in the automotive industry (Fig. 9a and b). The end of life
John, & Cincotto, 2005). The use of cactus pulp as a sta- vehicle (ELV) directive in Europe states that by 2015, vehi-
bilising agent to improve the behaviour of the sisal fibre cles must be constructed of 95% recyclable materials, with
reinforced soil has been studied (Mattone, 2005). 85% recoverable through reuse or mechanical recycling and
Chopped barley straw has also been used as a suitable 10% through energy recovery or thermal recycling (Peijs,
reinforcement for composite soil (Bouhicha, Aouissi, & 2003). This will definitely lead to an increased use of biofi-
Kenai, 2005). bres. The diverse range of products utilizing biofibres and
Biocomposites also offer immense opportunities for an biobased resins derived from soy beans is giving life to a
increasing role as alternate material, especially as wood new generation of composites for a number of applications
substitutes in the furniture market. Yet biofibre as con- like hurricane-resistant housing and structures (Wool,
struction material for buildings were known long before. 2002).
For centuries, mixtures of straw and loam, dried in the
sun, were employed as construction composite in Egypt. 2.2. Designing biocomposites
Pipes, pultruded profiles and panels with polyester matrices
are also quite popular. Large projects have been promoted Although biofibre reinforced polymer composites are
where jute-reinforced polyester resins are used for build- gaining interest, the challenge is to replace conventional
ings, e.g. the Madras House and grain elevators. Today, glass reinforced plastics with biocomposites that exhibit
a renaissance in the use of natural fibres as reinforcement structural and functional stability during storage and use
in technical applications is taking place, mainly in the auto- and yet are susceptible to environmental degradation upon
mobile and packaging industries (e.g., egg boxes) (Singh & disposal. An interesting approach in fabricating biocom-
Gupta, 2005). posites of superior and desired properties include efficient
In the automotive industry (Suddell & Evans, 2005), and cost effective chemical modification of fibre, matrix
cotton fibres embedded in polyester matrix was used in modification by functionalizing and blending and efficient
the body of the East German ‘‘Trabant’’ car. The use processing techniques. (Fig. 10)
of flax fibres in car disk brakes to replace asbestos fibres Another interesting concept is that of ‘‘engineered natu-
is also another example. Daimler–Benz has been exploring ral fibres’’ to obtain superior strength biocomposites
the idea of replacing glass fibres with natural fibres in (Mohanty et al., 2002). This concept explores the suitable
automotive components since 1991. A subsidiary of the blending of bast (stem) and leaf fibres. The judicious selec-
company, Mercedes Benz pioneered this concept with tion of blends of biofibres is based on the fact that the cor-
the ‘‘Beleem project’’ based in Sao Paolo, Brazil. In this rect blend achieves optimum balance in mechanical
358 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

Fig. 9. (a) Under floor protection trim of Mercedes A class made from banana fibre reinforced composites. (b) Newest Mercedes S class automotive
components made from different bio fibre reinforced composites.

3. Electrospinning (ELSP)

Electrospinning has been recognised as one of the most

efficient techniques for the fabrication of nanopolymer
fibres. When the diameter of polymer fibre is shrunk from
micrometer to nanometre range, amazing new properties
are exhibited in the nanopolymer fibres. The large surface
area of the fibres contributes to various applications rang-
ing from medical prosthesis to composite preparation. In
addition, the electrospun fibres find applications in various
other fields such as tissue template, protective clothing, cos-
metics, drug delivery, conducting nanofibres, sensors, and
optical shutters etc.
Electrospinning has recently drawn strong attention in
biomedical engineering (Yoshimoto, Shin, Terai, & Vacan-
ti, 2003), providing a basis for the fabrication of unique
matrices and scaffolds for tissue engineering. ELSP is a
Fig. 10. Tricorner approach in designing of high performance spinning method that can produce polymer fibres with
biocomposites. diameters ranging from several micros to 100 nm or less
under a high-voltage electrostatic field operated between
properties for e.g., the combination of bast and leaf fibre is a metallic nozzle of a syringe and a metallic collector in
expected to provide a stiffness–toughness balance in the air. The fibres are typically deposited in the form of a
resulting biocomposites. non-woven fabric onto a target metallic collector through
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 359

Fig. 11. Proposed electrospinning techniques (a) electrospinning (b) multilayer spinning.

a random projected jet of polymer solution, the so-called degradable nanofibrous non-woven mats via multi jet elec-
cone or instable jet. The accumulated charges on the poly- tro spinning (Ding, Kimura, Sato, Fujita, & Shiratori,
mer solution ejected from the nozzle induce the radial 2004).
charge repulsion in the electric field, which induces the Another interesting study was the electrospinning of
instable jet. If the random deposition process of fibres in chitosan nanofibres from aqueous chitosan solution using
the instability jet is appropriately controlled on the meso- concentrated acetic acid solution as a solvent. A uniform
scopic scale, the higher-ordered spatial placement of the nanofibrous mat of average fibre diameter of 130 nm was
nano- and microfibres in the ELSP fabrics will be realized. obtained from 7% chitosan solution in aqueous 90% acetic
In addition, the high-speed movement of the collector or acid solution in an electric field of 4 kV/cm. An aqueous
nozzle may produce oriented meshes and more higher- acetic acid concentration higher than 30% was prerequisite
ordered macroscopic devices. for chitosan nanofibre formation, because more concen-
Researchers recently developed two novel ELSP tech- trated acetic acid in water progressively decreased surface
niques: multilayering ELSP and (multicomponent) mixing tension of the chitosan solution and concomitantly
ELSP, both of which are composed of different nano- increased charge density of jet without significant effect
and microfibres (Kidoaki, Kwon, & Matsuda, 2005). In on solution viscosity (Geng, Kwon, & Jang, 2005).
the multilayering ELSP, after electrospinning the first poly- The fabrication and characterization of poly(vinyl alco-
mer, the second polymer is sequentially electrospun on the hol)/chitosan blend nanofibers by electrospinning method
same target collector (See Fig. 11). Such a sequential spin- was investigated by Yong-Tang et al. (2007). The results
ning process can produce a multilayered fibre mesh, in showed that showed that the morphology and diameter
which a hierarchically ordered structure composed of dif- of the nanofibers were mainly affected by concentration
ferent kinds of polymer mesh could be obtained. For the of the blend solution, weight ratio of the blend, respec-
mixing ELSP, two different polymers are simultaneously tively. It was also observed that that there were strong
electrospun from different syringes under special condi- intermolecular hydrogen bonds between the molecules of
tions. The produced polymer fibres are mixed on the same chitosan and poly(vinyl alcohol).
target collector, resulting in the formation of a mixed fibre Recently researchers reported on the electrospinning
mesh. and crosslinking of zein nanofibre mats (Yao, Li, & Song,
Tremendous amount of studies are being undertaken in 2007). Zein is a protein found in corn. The authors
the field of electrospinning. The effect of molecular weight observed that crosslinked zein exhibited higher tensile
on fibrous PVA prepared by electrospinning has been properties than uncrosslinked zein.
reported by Koski, Yim, and Shivkumar (2004). Zarkoob
et al. (2004) have reported on the structure and property 4. Cellulose based nanocomposites
of electrospun silk fibres. In the above work, fibres with
diameter 50–200 nm could be obtained. The concept of nanostructured materials design is gain-
Recently scientists (Theron, Zussmann, & Yarin, 2004) ing widespread importance among the scientific commu-
have looked into the governing parameters in the electros- nity (Berglund, 2005). The strong reinforcement effects
pinning of polymer fibres. Researchers have studied the at low volume fraction resulted in a tremendous interest
mechanical characterisation of electrospun gelatin nanofi- from the industry and research circles. With this as an
bres (Huang, Zhang, Ramakrishna, & Lim, 2004). Another inspiration, the potential of nanoscale cellulose structures
innovative approach has been the preparation of blend bio- as reinforcement in novel composite materials was extre-
360 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364

lulose fibres without disrupting the hierarchical network

structures of individual cellulose fibres by means of poly-
merization-induced adsorption (Fig. 13).
High performance composites from low-cost plant pri-
mary cell walls were developed by Bruce, Hobson, Farrent,
and Hepworth (2005). Purified cell wall fragments and cel-
lulose microfibrils were developed from Swede root to form
novel composite materials. The composites fabricated from
purified cell wall fragments and acrylic matrix gave the best
tensile properties. Researchers (Bokobza & Chauvin, 2005)
have also reinforced natural rubber with nanofibres of sepi-
olite. The composites also contained silica particles gener-
ated in situ by the sol-gel process. The level of
reinforcement was assessed from mechanical and orienta-
tion behaviour.
Algae are also a potential source of cellulose for use in
composite materials. Researchers have concentrated on
the morphology of cellulose powder from Caldophora spat-
za algae from the Baltic sea. The effective stiffness of the
algae MFC (which is the combined effect of the microfibril
modulus and its aspect ratio) was found to be higher than
Fig. 12. Model of the cellulose microfibril structure. for the wheat straw cellulose. Bacterial or microbial cellu-
lose (BC) have also found their way as reinforcement in
mely interesting. The concept of cellulose nanocomposites composites. Cellulose can be produced from some bacteria
for load bearing applications is fairly new. Property such as Acetobacter xylinum, vinegar or acetic acid. Bacte-
enhancements are expected due to higher Young’s modu- rial cellulose is an extracellular product which is excreted
lus of pure cellulose reinforcement and finely distributed into the culture medium. Acetic acid bacteria are not pho-
reinforcing microfibrils. A major problem in the commer- tosynthetic but can convert glucose, sugar, glycerol to pure
cial use of cellulose microfibrils in structural materials is cellulose. Bacterial cellulose has been frequently studied to
the disintegration of cellulose from plant cell wall at rea- clarify the mechanism for biosynthesis (Tokoh, Takabe,
sonable cost and without severe degradation. Another Sugiyama, & Fujitha, 2002). Researchers have looked into
major problem is dispersion of cellulose microfibrils in a the development of cellulose nanocomposites based on bac-
polymer matrix. terial cellulose and cellulose acetate butyrate (Grunert &
A simple model of the cellulose microfibril structure is Winter, 2002). Though BC composites have evoked wide-
presented in Fig. 12. Cellulose nanocomposites are usually spread interest, the industrial use of BC composites
fabricated by utilizing these microfibrils of 10–50 nm on requires the development of efficient large-scale fermenta-
width as reinforcement in a polymer matrix. Although tion technology.
many studies provide detailed knowledge regarding the Nanoscale-modifed plant structures such as paper or
morphology and crystallography of different types of cellu- bast fibres also present a different approach to preparation
lose, the Young’s modulus of microfibrils from different of nanocomposite structures. An interesting study concen-
sources and subjected to different types of hydrolysis is sel- trated on the preserving the microfibril organization of
dom discussed. wood veneer in composites (Yano, Hirose, Collins, & Yaz-
The research group at CERMAV-CNRS has presented aki, 2001). Pine veneer was used as the starting material.
numerous studies based on cellulose whiskers reinforced
nanocomposites. The whiskers were disintegrated from an
edible tunicate, a sea animal. Another area of interest is
that of microfibrillated cellulose (MFC) nanocomposites.
MFC based on parenchyma cells (i.e. sugar beet, potato
tuber) tend to show small microfibril diameter and the
fibrillar structures resemble swirled mats of connected,
microfibrils rather than discrete rods (Dufresne, Cavaille,
& Vignon, 1997). A review of the recent research into cel-
lulosic whiskers, their properties and their application in
nanocomposite field has been presented by the same group
(Samir, Alloin, & Dufresne, 2005).
Recently scientists (Huang, Ichinose, & Kunitake, 2005)
achieved uniform polypyrrole nanocoating on natural cel- Fig. 13. Scanning electron micrographs of nanocoated cellulose fibres.
 M.J. John, S. Thomas / Carbohydrate Polymers 71 (2008) 343–364 361

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