Progress in Polymer Science 34 (2009) 982–1021

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Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Biodegradable composites based on lignocellulosic fibers—An overview

Kestur G. Satyanarayana ∗ , Gregorio G.C. Arizaga, Fernando Wypych
Department of Chemistry, Federal University of Paraná, P.O. Box 19081, Jardim das Américas, 81531-980 Curitiba, PR, Brazil

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

Article history: The development of commercially viable “green products” based on natural resources for
Received 4 June 2008 both matrices and reinforcements for a wide range of applications is on the rise. This effort
Received in revised form
includes new pathways to produce natural polymers with better mechanical properties and
25 November 2008
thermal stability using nanotechnology and use of natural polymers to make biodegradable
Accepted 2 December 2008
Available online 12 January 2009 plastics and their composites with lignocellulosic fibers. This paper presents an overview
of the developments made in the area of biodegradable composites, in terms of market,
Keywords: processing methods, matrix–reinforcement systems, morphology, properties and product
Lignocellulosic fibers development. Some critical issues and suggestions for future work are discussed, under-
Biopolymers scoring the roles of materials scientists and textile engineers for the future of these new
Mechanical properties “green” materials through value addition to enhance their use.
Biodegradability © 2009 Elsevier Ltd. All rights reserved.
Composite processing
Societal applications

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 983
2. Biodegradable materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 986
2.1. Bio-based matrix materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 986
2.1.1. Starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 989
2.1.2. Poly(hydroxyalkanoate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 992
2.1.3. Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
2.2. Bio-based reinforcement/filler materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 995
2.3. Surface treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 997
2.4. Processing aspects of biodegradable composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 999
2.4.1. Starch-based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
2.4.2. Poly(hydroxyalkanoate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002
2.4.3. Other natural resins including rubber based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
2.4.4. Other biodegradable composites with lignocellulosic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
2.4.5. Hybrid biodegradable composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1004
3. Properties of biodegradable composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1004
3.1. Starch-based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005
3.2. Poly(hydroxyalkanoates)-based composites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1007
3.3. Triglyceride-based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1009

∗ Corresponding author. Tel.: +55 41 3361 3473; fax: +55 41 3361 3186.
E-mail address: kgs satya@yahoo.co.in (K.G. Satyanarayana).

0079-6700/$ – see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2008.12.002
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021 983

3.4. Other matrices/properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1009

3.4.1. Biodegradability of various composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1011
3.5. Nanocomposites with nanometric fillers in biodegradable matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1011
4. Products/applications/market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1012
5. Critical issues and suggestions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013
5.1. Raw materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013
5.1.1. Reinforcements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013
5.1.2. Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013
5.2. Interface between the reinforcement and matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1014
5.3. Processing aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1014
5.4. Design and performance aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1014
5.5. Other aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1015
6. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1015
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1015
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1015

1. Introduction or sometimes burned in the fields as means of disposal,

are utilized as fillers/reinforcements in polymer or cement
There has been an expanding search for new materi- to develop new materials (composites) for the construc-
als with high performance at affordable costs in recent tion industry. Yet another example is the use of sugar cane
years. With growing environmental awareness, this search in Brazil for the production of poly(hydroxyalkanoates),
has particularly focused on eco-friendly materials, with explored for medical applications [74]. In Brazil, pineapple,
terms such as “renewable”, “recyclable”, “sustainable” one of the contributors for agricultural economic activity of
and “triggered biodegradable” becoming buzzwords. This the country, has the potential to produce about 19,600 tons
underscores the emergence of a new type of materials—a of fibers from about 1011 leaves produced on 58,794 ha,
change from non-renewable, but difficult to degrade or with collection and extraction of fibers being done in the
non-degradable, to renewable and easily degradable mate- rural sector, thus providing jobs and improving the living
rials. The development or selection of a material to meet the conditions of the rural population [56]. These examples
desired structural and design requirements calls for a com- underline not only the development of new materials based
promise between conflicting objectives. This can be over- on renewable materials, but also the possible generation
come by resorting to multi-objective optimization in mate- of additional employment through the collection, trans-
rial design and selection. Composite materials, which are portation and development of new materials. It is reported
prepared using natural or synthetic reinforcements and a that increasing use of renewable materials would create or
variety of matrix materials, are included in this philosophy. secure employment in rural areas, the distribution of which
The development of such materials has not only been a would be in agriculture, forestry, industry, etc. [75]. It is also
great motivating factor for materials scientists, but also an reported that estimated production of heat, electricity and
important provider of opportunities to improve the stan- fuels could be increased by 90 million metric tons of oil-
dard of living of people around the world. This is true, equivalent corresponding to 14 million hectares of land by
since many of the renewable materials are based on agri- 2010 from 40 million metric ton in 1995 by the agro based
cultural products as a source of raw materials, particularly renewable materials.
to plastic industries, and these could generate a non-food Biodegradable type composites are not new to mankind.
source of economic development for farming and rural Their use dates to antiquity, such as the Great Wall of China
areas in developing countries. This can provide a poten- whose construction started initially in 121 B.C. as earth
tial for economic improvement based on these materials works were connected and made strong by clay bricks made
even though major thrust for their use has been driven by of local materials initially using red willow reeds and twigs
the needs in industrialized countries. For example, ligno- with gravel during the Han dynasty (209 B.C.), and later
cellulosic fibers such as jute, sisal, pineapple, curauá, etc., with clay, stone, willow branches, reeds and sand during
whose extraction is an important process that determines the Qin dynasty (221–206 B.C.) [76–78]. Other examples
the properties of the fibers, can generate rural jobs since include, bows made with adhesively bonded laminates of
these fibers have established their potential as reinforc- animal horns and tendons, wood or silk used by the Mongo-
ing fillers in many polymers, and products based on these lians in 1200 A.D. Composite materials have gone through
have found increasing use on a commercial scale in recent significant developments in terms of use of different raw
years [1–72]. Another example for the generation of jobs materials, processes and even applications. Similarly, use
by agro-based materials is provided by the use of rice husk, of natural polymers is not new, since paper, silk, etc., have
which constitutes more than 10% of a world rice production been used from historical times.
[73]. A variety of inorganic materials such as silica, zeo- The use of natural polymers was superseded in the 20th
lites, solar grade silicon, building and thermal insulating century as a wide-range of synthetic polymers were devel-
materials, polymer composites, etc., can be produced using oped based on raw materials from low cost petroleum.
this most promising agro-waste [1]. Similarly, straws of rice However, since the 1990s, increased attention has been
and sugarcane (bagasse), often used as fuels in households paid to the use of natural polymers and lignocellulosic
984 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
fibers. The reasons for this include: (i) growing interest in
reducing the environmental impact of polymers or com-
posites due to increased awareness to eco-friendliness; (ii)
finite petroleum resources, decreasing pressures for the
dependence on petroleum products with increasing inter-
est in maximizing the use of renewable materials; and (iii)
the availability of improved data on the properties and
morphologies of natural materials such as lignocellulosic
fibers, through modern instruments at different levels, and
hence better understanding of their structure–property
correlations. These factors have greatly increased the
understanding and development of new materials such as
biocomposites.
Synthetic polymer-based composite materials are now
well established all over the world for a wide variety
of applications because of their high specific strength
and modulus compared to conventional materials such
as metals and alloys, along with their long durability
[1,8,9,13,16,23,25–27,31–40]. However, the use of large
volumes of polymer-based synthetic fiber composites in
different sectors despite their high cost has led to disposal
problems. In fact, the European Union has already approved
laws for the reduction of such environmentally abusive
materials, triggering greater efforts to find materials based
on natural resources in view of the latter’s eco-friendly
attributes. Agro-based materials such as plant fibers and
natural polymers are some examples. These are abundantly
available in nature, but more often than not lead to the
generation of “wastes” as shown in Table 1.
Such agro wastes being organic in nature are also a
source for carbon and a host of other useful materials and
chemicals, particularly for the production of “green” mate-
rials. Further, such wastes may generate additional jobs, if
with an integrated approach these materials can be uti-
lized in other areas as useful materials. Several developing
countries such as India, Malaysia, Indonesia, Philippines,
Brazil and some of the African countries have national
projects for the utilization of several of their agro wastes
such as coconut based materials, wastes from rubber and
palm oil industries, rice husk, etc., while International
Center for Science and High Technology of UNIDO in
Trieste-Italy and TNO Center of Applied Physics, Eindhoven,
The Netherlands, Appropriate Technology International,
and The Swedish Cement & Concrete Institute are some
of the organizations in the forefront of developing and
transfer of technologies particularly for housing based
on such waste materials ([24], http://www.ist-world.org/
Org Unit Details, http://www.ics.trieste.it./Portal/Default.
Table 1
List of some agro wastes, their availability and potential uses (India) adopted from reference [1].
Waste Industry
Bagasse Sugar mills
Corn cobs and stalks Agricultural farms
Coconut husk and byproducts Coconut based
Jute sticks and bark Jute mills
Rice husk Rice mills
Peanut husk Agricultural farms and peanut oil mills
Straws of rice and wheat Agricultural farms
aspx). These materials thus form inexpensive “new or sec-
ondary resources”, which could make them more valuable
for wider utilization. When such materials are used in
composites, developing countries, which produce these,
become part of global composite industry as developer and
manufacturer leading to increasing revenues and the cre-
ation of jobs [33].
Lignocellulosic fibers have some unique attributes, such
as being less abrasive to tooling and not causing as many
respiratory problems for workers [9,13,25,27,32,45,71].
Furthermore, because they are inexpensive and have load-
bearing potential, the use of natural fiber based composites
has spread to various sectors, including aircraft, construc-
tion, grain and fruit storage and footwear.
In addition, some European countries, where greater
environmental consciousness exists, have already estab-
lished the use of Lignocellulosic Fiber Incorporated
Polymer Composites (LCFIPC) in automotive applications
[13,25,31–36,39,40,43,57]. In view of this, a good amount
of LCFIPC products have been exported to the U.S. and other
countries [25,34,35] despite these materials being only par-
tially biodegradable. Although these composites exhibit
the attractive attributes mentioned above, they are limited
to non-degradable polymeric matrices, such as polyester,
poly(propylene) (PP), epoxy and phenol formaldehyde (PF),
which may not be fully biodegradable, while the fibers
are fully biodegradable. Fortunately, traditional engineer-
ing thermoplastics (ETP) markets, such as those for exterior
auto components, noise shields and door panels, or as
“wood ceramic” for electromagnetic shielding, have been
effectively taken over by the new commodity polymers and
their composites due to their improved performance. In
addition, many of lignocellulosic materials, such as rice and
wheat straw, sugarcane bagasse and rice and coffee husks,
which were either used as household fuels or sometimes
burnt in situ in the fields as a means of disposal, have also
been tried as fillers/reinforcements in polymer or cement
to develop new materials for the construction industry [1].
These successful attempts have opened up a large range of
raw materials for the development of biodegradable mate-
rials. Besides this, the increasing focus on eco-friendliness,
such as the European Union’s directive that all new vehi-
cles must use 95% recyclable materials to achieve the “end
of life” required by 2015 has led to greater impetus for the
development of commercially viable biodegradable com-
posites. Under this directive, about 85% of these materials
recoverable through reuse or mechanical recycling and
about 10% through energy recovery or thermal recycling
Annual production Potential uses
(mt) in 2000
5.0 Insulation boards
14.0 Building boards
3.0 Roofing, composites and brick
5.0 Roofings and composites
25.0 Particle boards, cement, pozzalona, chemicals
and condensed silica fume
2.5 Composites/insulation boards
90.0 and 33.0 Composites/fiber boards
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
[35,37]. It is therefore not surprising to note that many lead-
ing plastics companies in U.S. and other western countries
are in the forefront in developing biodegradable materials
from natural materials, including “secondary resources”, to
mitigate environmental impacts. Also, it is reported that by
2020, about 10% of the basic chemical building blocks will
come from renewable plant resources, expected to rise to
50% by 2050 as hurdles to their use are reduced [27,32].
Textile engineering and modeling aspects have been
used in composite fabrication with a view to increase the
use of these materials [79,80]. In this context, textile engi-
neering has provided an opportunity for producing hybrid
composites as evident from studies on the effect of fiber
content, fiber orientation and roving texture of hybrid fab-
rics on the mechanical properties of polymer composites.
Also, it has provided different but commonly used weave
styles, such as plain (each warp fiber passing alternately
over and under the weft fiber), twill (repeated weaving of
one or more warp fibers under or over the weft fibers), satin
(twill weave but have fewer intersections of the weft and
warp), leno (weave pattern to improve stability of fabrics
having lower fiber content), etc., to prepare the required
form of reinforcements. In a reinforced woven fabric, the
fibers are interlocked up to a certain degree depending on
the weave pattern, such that they deform into or drape
in a stable, predictable and reversible manner, leading to
desirable use properties [15]. While hybridization effect of
lignocellulosic fibers with synthetic fibers on various prop-
erties has been extensively studied, very limited studies
with hybrids of lignocellulosic fibers mainly with non-
degradable matrices have been reported [59]. Hence, more
studies in lignocellulosic fiber based hybrids are required,
which not only could increase the amount of fibers used,
but also open new applications for these materials.
While discussing the textile engineering aspects in the
development of composites, two recent exciting examples
are of interest. The first is the weaving of super-tough
carbon nanotubes to develop polymer nanocomposite
(570 J g−1 , compared to 33 J g−1 for Kevlar fiber and 12 J g−1
for graphite fiber) [81,82], with a special spinning method
being adopted [82] to obtain about 100 m of solid nanotube
composite of 50 nm diameter containing 60% single-walled
nanotubes. The resulting textiles are reported to have
potential for making electronic devices such as sensors,
connectors, antennas, etc. The second example is electro-
spinning of polymeric fibers [71], one of the most efficient
methods to produce nano-polymer fibers, which exhibit
large surface area useful for various applications, including
composites.
The growing importance of these new biodegrad-
able materials is evident from the increasing number of
publications during the last decade, including reviews
and patents (Fig. 1), particularly from groups at Michi-
gan State University, the University of Delaware, Cornell
University in the U.S. and the Materials and Packag-
ing Research Center CERME (ESIEC) in France, presently
at the University of Louis Pasteur, Strasbourg, France,
which are in the forefront as shown by their publications
[10–14,16–22,26–30,42,44,46–49,52–55,62–64,83–85].
These references are from publications found in the
ISI Web of Knowledge database by entering the words
985
Fig. 1. Number of publications and patents on biodegradable lignocellu-
losic fiber based Composites (1995–2007) (found in the ISI database by
entering the words “biodegradable, polymer, fiber”).
BIODEGRADABLE POLYMER and FIBER as topics in all doc-
ument types. A literature survey also indicates that work
on biodegradable composites started nearly three decades
ago. Other relevant publications on completely biodegrad-
able polymers and their composites can be found, includ-
ing periodic reviews and overviews [4–7,11–14,16–23,
26–31,34,35,38,41,44,46–49,52–56,62–71,83–92]. Many of
these deal either with different types of biodegrad-
able matrices or their composites, mentioning different
processing techniques and their effect on properties of
biopolymer blends [18,19,21,83–86,88–92]; the sources of
lignocellulosic fibers, their extraction, production, cost,
chemical composition, physical and mechanical properties
and degradability [13,17,20,23,29,30,47,71]; and the trends
and challenges of biodegradable polymers [22,25].
A review by Avella et al. [18] discusses the blending of
poly(hydroxybutyrate) (PHB) and poly(hydroxybutyrate-
co-valerate) (PHBV) through miscibility, mechanical behav-
ior and morphology, while Van de Velde and Kiekens [88] in
their overview of biopolymers, highlights the importance
of such reviews for researchers to get a comprehen-
sive view of the available data on the properties of four
basic polymers: poly(lactic acid) (PLA), poly(glycolic acid)
(PGA), poly(␧-caprolactone) (PCL) and PHB, along with two
copolymers and two optically active polymer forms, sin-
gling out clearly suitable biopolymers for composites based
on his critical assessment of their important properties.
It may be noted that despite the considerable research
carried out on PLA and its composites mentioned later
in this paper, its biodegradability is still being discussed.
On the other hand, Klemchuk [89] examines starch-based
plastics, and reviews by Wool et al. [16,17,21,48] from the
University of Delaware discuss mainly soy oil based com-
posites.
This paper gives an overview of recent literature cover-
ing all aspects of biodegradable composites. These include
some of the recent developments made in the area of
biopolymers and “biodegradable composites”, their pro-
cessing methods, a variety of biological, physical and
chemical pretreatments of lignocellulosic materials, their
986 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021

morphology and properties and some product develop- Table 2

Time to degrade for various materials and polymer-LC fiber composites.
ments. Also, we present some critical issues including the
Adopted from references ].
role of textile and design engineers for the future of this
new material to highlight the future growth in this area. Material Time to degrade in the environment
While passing, nano-biodegradable composites with lig- Cotton 1–5 months
nocellulosic materials are also mentioned. We hope that PCL-g-MAH/starch 2 months
commercially viable development of these environmen- PCL-starch 2 months
PCL-g-MAH/starch 2 months
tally acceptable materials from natural resources and the
WG/PVA 1 month
suggestions made for value addition to enhance their uti- WG/SCB 1 month
lization will lead to their sustainable development, while Conventional copy paper 1 month
opening up a new area for materials scientists, textile and PHB–PHB/starch 1 month
design engineers and technologists. WG 1 month
WG/PVA 1 month
WG/SCB 1 month
2. Biodegradable materials WG/WG/SCB film 1 month
Wool stocking 1 year
Bamboo stick 1–3 years
Commodity polymers constitute 80% of the poly- Chewing gum 5 years
mer market. Most of them are based on non-renewable Painted wood 13 years
petroleum, whose price is increasing and unstable, as is the Plastic 450 years
case with other materials, including lignocellulosics, and Glasses and tyres Uncertain time
are non-biodegradable. Furthermore, it is pointed out [91] PCL, Poly(caprolactone); MAH, maleic anhydride; WG, waste gelatin; PVA,
that producing fossil-based materials such as petroleum poly(vinyl alcohol); SCB, sugar cane bagasse; g, grafting; * p. 281–92; ** p.
from biomass takes 106 years, compared to 1–10 years for 51–6.

the conversion of many chemical into CO2 (Fig. 2). In order

to produce fully renewable and biodegradable composites,
both the polymeric matrix and the reinforcement must be
derived from renewable resources, normally produced by
plants in a period of less than one year [91].
Hence, the use of fossil-based products is not sustain-
able. Accordingly, to overcome the dependence on such
fossil sources of polymers, attempts have been made to
produce “new polymers”, including sustainable polymers,
using renewable natural resources, where the rate of CO2
fixation equals its consumption rate. An ASTM test method
is being developed, along with a definition for bio-based
content [91]. Also, the use of natural polymers, which are
normally biodegradable, is an important design parameter
for opening up new market opportunities for development
of value-added products from natural polymer feed stocks,
keeping in view the design approach for new products
based on sustainable ecology and “green chemistry” with
the holistic approach of life cycle assessment [25,34,35].
Besides this, the problem of the solid waste gener-
ated by plastic materials after their final use increases
the importance of biodegradable polymers/composites.
Indeed, this is one of the most common arguments
put forth to develop biodegradable polymers or biopoly-
mers [4,5,41,89,93–99]. Accordingly, many definitions have
been proposed for biodegradable polymers/composites
[7,19,93,100]. One well accepted definitions reads that
“materials obtained from nature or by synthetic route, whose
chemical bonds are cleaved at least in one step by enzymes
from the biosphere”, to which one can add, ‘with appropriate
pH and temperature conditions and total processing time
for completion’. The suitability for a specific application of
such materials will be dictated by their mechanical proper-
ties as well as their degradation. Typical degradation times
for various materials and some biocomposites are shown
in Table 2 [101,102].
It can be seen that most biodegradable materials, includ-
ing composites, degrade rapidly (2 weeks to 6 months).
Accordingly, as summarized in Section 2.1, many attempts
have been made to develop such matrix materials. Also,
attempts have been made to form networks and centers
of know-how within such networks to develop biodegrad-
able materials. Some examples are Bio Fiber Net, a forum for
industry and academy, and the International Biodegradable
Polymers Association & Working Groups in Europe (IBAW),
an organization networking in the field of bio-based mate-
rials, especially biodegradable polymers. It may now be
possible to expand the utilization of lignocellulosic fibers
for sustainable manufacture of industrial products through
such networks [75]. Attempts to replace even wood/GRP
have increased in recent years [8,45].

2.1. Bio-based matrix materials

It is well known that renewable resources such as

Fig. 2. Global carbon cycle-sustainability driver. Reproduced with the kind
permission of Author/Publisher [91].
plants (e.g., cellulose or chitin, vegetable oils, etc.), bac-
teria [6,103] as well as non-renewable petroleum (e.g.,
aliphatic/aliphatic–aromatic co-polyester) are sources of
a variety of polymeric materials [103–108]. Accordingly,
biodegradable polymeric materials have been classified
as natural or synthetic depending on their origin. Also,
biodegradable polymers themselves can be classified
depending their origin such as agro polymers (starch
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
Fig. 3. Classification of biopolymers and their nomenclature.
or cellulose), microbial (poly(hydroxyalkanoate)), chem-
ically synthesized from agro based resource monomers
(poly(lactic acid)) and chemically synthesized from con-
ventionally synthesized monomers. The classification of
these polymers and their nomenclature is shown in Fig. 3,
while Table 3 [88,109,110] presents some of their proper-
ties. These include density, glass transition temperature
Tg and melt temperature Tm , water absorption, degrada-
tion time and mechanical properties. While the density
values are important to predict the weight of the compos-
ite to be produced, particularly with lignocellulosic fibers,
the degradation time is also important. The low strength
properties of these polymers would suggest appropriate
fibers to choose to prepare the composite with the selected
polymer. Finally, the characteristic temperatures give indi-
cations of the thermal stability of the resulting composites,
which may also have some bearing on the mechanical prop-
erties [88,110,111].
Products made using such polymers are shown in
Fig. 4(a–e) [112]. These include a drinking cup (Fig. 4a)
similar to a polystyrene disposable cup both in appearance
and characteristics, but starch based using environmentally
friendly water steam foaming and pressing process; lawn
cutting and leaf bags (Fig. 4b) made of corn starch by blow
molding with the red symbol printed near the top of the bag
indicating the Danish mark for ecological products; “green-
pens” (Fig. 4c) based on starch based Mater-Bi® , developed
by Novamont, produced by injection molding (except the
ink refill); razors (Fig. 4d) manufactured using PHA by injec-
tion molding (handle) and insert molding (razor head) by
Table 3
Physical properties of polymers. Adopted from references [88,110,111].
Property Type of biopolymer
PLA l-PLA dl-PLA
Density (kg/m3 ) 1210 1240 1250
T.S. (MPa) 21 15.5 27.6
Y.M. (GPa) 0.35 2.7 1 6
Elongation (%) 2.5 3 2
Tg (◦ C) 45 55 50
Tm (◦ C) 150 170 am
T.S.: Tensile strength; Y.M.: Young’s modulus; Tg : glass transition temperature; Tm : melting point, am: amorphous and thus no melt point.
987
the Kay Razor Company and foamed trays (Fig. 4e) made of
thermoplastic starch by BIOTEC, Germany. While the bag
shown in Fig. 4b is reported to create rich organic humus,
which can be used as soil nutrients, the foamed trays shown
in Fig. 4e are reported to possess a very good permeability
for water vapor along with excellent gas (oxygen and car-
bon dioxide) barrier properties. There are other examples,
such as dinnerware based on potato starch and limestone
marketed by the EarthShell® , packing products for general
purposes made with potato/corn starch designed by Pro-
terra BV, International Centre for Agro-based Materials and
shampoo bottles formerly made of PHBV by the Monsanto
Company using injection molding (cap) and blow molding
(bottle) [112]. All these can be composted after use. There
is also a patent for manufacturing biodegradable starch-
based products [83,112].
Combinations of both synthetic and renewable sub-
stances, such as Sorone (polyurethane prepared from
castor oil) or epoxy/polyesters or blends (thermoplastic
starch—TPS) afford other possibilities. These two mate-
rials blend well when the polyurethane content is less
than 15 wt%. The resulting biodegradable blend is reported
to have improved tensile properties (Young’s modulus:
40–75 MPa; tensile strength: 3.4–5.1 MPa and elongation at
break: 116–176%) [113]. Such materials have proved to be
fully biodegradable [7]. In the case of PHB co-polymerized
with urethane, the mineralization of samples with 50% PHB
occurs at value similar to that for PHB alone [114].
Another example is the use of acrylated epoxidized soy-
bean oil blended with polystyrene whose storage modulus
PGA PCL PHB Starch
1500 1110 1180
60 20.7 40 5.0
0.21 3.5 0.125
1.5 300 5 31
35 −60 5
220 58 168
988 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021

Fig. 4. Biopolymer products: (a) disposable cup; (b) compostable bag; (c) writing “green” pens; (d) shaving razor heads; (e) foamed trays (reproduced with
kind permission from T. Lenau and www.designinsite.dk [112]).

is improved more than five times by adding recycled tions, belongs to the family of poly(hydroxyalkanoates)
paper, a cheap source of cellulose [64]. Many of these have (PHAs). This material can be made to exhibit very
been well reported in reviews, in textbooks, as well as interesting properties such as thermo-plasticity with high
at many international conferences [13,63,115–117]. These crystallinity and large spherulitic structures. Similarly, with
biopolymers are presently available in the market through plasticizers, starch behaves as a normal synthetic thermo-
manufacturing companies such as Mitsui Chemicals, Nova- plastic polymer for extrusion, injection and blow molding,
mont, Dupont, Bayer, etc., while plant-derived biodegrad- even into thin films. Also, it can be converted into enhanced
able polymers are commercially available in Japan and biodegradable thermoplastics by graft co-polymerization
Brazil. The market has been growing fast for these biopoly- (say, with vinyl monomers), blending with more hydropho-
mers, with sales increasing by 20–30% a year in 2000 [14]. bic and biodegradable thermoplastic polymers and by
In North America alone, it was projected to increase from chemical modification. The following structures show
about 9090 metric tons (20 million lbs.) in 2000 to about
17,500 metric tons (35 million lbs.) by 2005 [42]. This was
expected to lead to increased sales from around US$ 150
million in 2000 to US$ 1.4 billion by 2005. The perspective
for world wide manufacturing capacity of bioplastics from
both renewable and non-renewable petrochemical materi-
als till 2010 is illustrated in Fig. 5 [118], which underlines
the growing dependence on the renewable materials. Also,
a growing market for biodegradable plastics from almost
zero tons per annum in nineties to 600,000 tons per annum
to date, has been reported, the majority of which are based
on renewable materials [87]. This estimated to the con-
sumption of biopolymers in Europe alone to expand to
roughly 10 million metric tons/year by 2020 [118].
Although PLA and thermoplastic starch are com-
mercially successful bio-based polymers, the most
extensively studied biodegradable polymers are starch and
poly(hydroxybutyrate) (PHB), particularly for composites,
since the main sources for both are renewable resources.
For instance, corn, potatoes and wheat are the sources of
Fig. 5. World wide manufacturing capacity of bioplastics [118].
starch, while PHB, which is synthesized in the interior of Reproduced with the kind permission from http://www.european-
a determined lineage of bacterial cells for biological func- bioplastics.org/media/files/docs/en-pub/capacity.pdf.
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021 989

Scheme 1. Silylation of Starch with bulky thexyldimethylchlorosilane (TDSCl) in N-methylpyrrolidone (NMP)/ammonia (adopted from reference [119]).

Scheme 2. Preparation of a starch-graft-poly(1,4-dioxan-2-one). The diisocyanate (NCO) group links the poly 1,4-dioxan-2-one (PPDO) to the starch chains
(adopted from reference [120]).

functionalized starch with organic moieties with silane,
cyanate and carboxylate groups [119–121].
Most natural polymers are water sensitive, in that they
absorb water, and may even be water soluble, causing their
properties to deteriorate (Schemes 1–3). This is normally
overcome by blending them with polymers or plasticizers
to enhance their performance (and value). These can lead to
“new polymers” with attractive properties. To take advan-
tage of this and their cost as well as the properties of “old
polymers”, several low-cost monomers are used. Thus, a
change in the paradigm in polymers has been occurring
during the last few decades to obtain functional polymers,
including structural polymers. The details of some biopoly-
mers are given below.
2.1.1. Starches
These are natural hydrophilic polymers processed by
conventional methods. Native starch occurs in the form of
discrete and partially crystalline microscopic granules that
are held together by an extended micellar network of asso-
ciated molecules. The crystallinity of the starch granules
is attributed mainly to the amylopectin and not to amy-
lase, which although linear, presents a conformation that
hinders its regular association with other chains. Starches

Scheme 3. The OH groups of the starch (St) are reacted with lactic acid and then the polymerization is started by adding Sn(Oct)2 as catalyst (adopted from
reference [121]).
990 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
exhibit poor melt processability and are highly water solu-
ble, difficult to process and brittle due to anarchical growth
of one their constituents, and hence need a plasticizer
[90,122] to make them suitable for engineering applica-
tions.
Plasticizers such as water or glycols make starches flow
and suitable for thermoplastic processing [122]. In this pro-
cess, the glass transition temperature Tg and melting point
of starch decrease due to the mechanical and heat energy.
Also, by using the blends of some of these polymers, it is
possible to tailor the mechanical properties of such ther-
moplastics to suit structural applications, depending on the
source and processing conditions, or by using fillers, includ-
ing cellulose micro/nanofibrils and natural “macro” fibers
[5,122,123].
Modifications of starches, including blending them with
other polymers, have been the subject matter of many
studies. For example, blends of wheat starch with PLA
or low density polyethylene (LDPE) have been prepared
economically using twin-screw extruders [86,124], with-
out affecting their biodegradability, by incorporating dry
starch granules into the poly(lactic acid) (PLA) or LDPE,
where the starch granules act as a filler resulting in an
increased modulus, but also in further loss of ductility
with increasing starch content. In both the cases, glyc-
erol and water were used as plasticizers for the starch.
This is an important result since such plasticized starch
can lead to a wide range of properties, including vari-
able biodegradation, depending on the plasticizer content
(glycerol and water) and its dispersion in the PLA. This com-
bination (PLA or LDPE + wheat starch + plasticizers) can be
processed using the twin-screw compounding technique
by adjusting the composition of its constituents. The tensile
strength (TS) and Young’s modulus (YM) of these mate-
rials (PLA–starch containing 30 and 36 wt% of glycerol)
increased with increasing PLA content (TS: 16–22 MPa,
YM: 1.8–2.4 GPa for 40 wt% PLA to TS: 52–56 MPa and YM:
3.6–4 GPa for 100 wt% PLA), but remained constant at these
values even after 10 weeks of aging at room tempera-
ture giving a stable material during that period, indicating
the protection of plasticized starch by PLA from potential
changes in glycerol and water (plasticizer) content of the
starch. The viscosity of starch was affected by the glyc-
erol and residual water content. For example, with shear
rates increasing from 1 to 75 s −1 the viscosity decreased
from 0.2 × 105 to 0.2 × 103 Pa s and ∼104 to 0.5 × 102 Pa s,
for materials with 30 and 36 wt% glycerol, respectively. On
the other hand, the viscosity of PLA remained constant (∼
0.6 × 103 Pa s) remained constant over a wide range of shear
rates (10−2 to <101 s −1 ), before it decreased to 0.2 × 103 Pa S
at shear rates above 10 s −1 [86].
The thermal stability of potato starch with and with-
out plasticizer (glycerin) and blended with PHB using the
solvent casting method [125] revealed (Table 4) that the
melting point of PHB was not much affected by blending.
On the other hand, Tg increased slightly, but it increased
markedly when thermoplastic was used. The thermal sta-
bility was also found to be higher for the TS blend.
Insert Table 4 [125]. Similarly, the effect of poly(vinyl
alcohol) (PVA) content on the mechanical properties of
starch blends has been studied [126] using a single-screw
Table 4
Composition of starch blend, melting point, glass transition temperature
and thermal stability (adopted from reference [125]).
Starcha PHB/starch Melting point Tg (◦ C) Thermal
ratio (w/w) (◦ C) stability (◦ C)
– 1.0/0.0 168.1 63.1 223.3
Starch 0.5/0.5 167.9 75.9 219.7
TS 0.5/0.5 165.4 145 259.9
Starch 0.7/0.3 167.0 71.3 217
TS 0.7/0.3 165.5 147.4 260.3
a
TS: Thermoplastic starch.
extruder. PVA content below 65 g in 300 g of starch gave an
inhomogeneous surface morphology, but it became homo-
geneous above this. Thermogravimetric analysis showed
three decomposition stages for the blend, the first one
between 273 and 373 K (100–300 ◦ C) due to the loss of
water and glycerol.
Similarly, the effect of poly(vinyl alcohol) (PVA) content
(65, 75, 85 and 95 g) on the mechanical and thermal prop-
erties of starch (cassava) blends with water or citric acid
or adipic acid or glycerol as plasticizers has been studied
[126] using a single-screw extruder. PVA content below
65 g in 300 g of starch gave an inhomogeneous surface
morphology, but it became homogeneous above this. Ther-
mogravimetric analysis carried out under air showed three
decomposition stages for the blends, the first one between
273 and 373 K (100–300 ◦ C) due to the loss of water and
glycerol, the second between 573 and 673 K (300–400 ◦ C)
and the third between 723 and 773 K (450–500 ◦ C) due
to mainly the oxidative decomposition, respectively, of
both PVA and starch, and finally the residual part of these
(a blend containing PVA and starch chains), indicating
improvement in the apparent thermal stability of PVA and
starch blends over that of primitive PVA and starch. This is
attributed to both the crystalline PVA and mixed “macro-
molecule” formed due to the good interaction between the
PVA and starch. Stress–strain curves of the blends revealed
an increase in breaking strength with increasing PVA con-
tent up to 85 g, which then decreased around 95 g of PVA.
On the other hand, elongation at break was 320%. Similarly,
biodegradability of the blend determined by weight loss
(85–90%) on burying in soil for 4 weeks and microstructure
observance showed consumption of plasticizers followed
by faster degradation of starch and PVA. The foregoing
results hold promise for the wide spread use of such poly-
mers.
Stress–strain curves of the blends revealed an increase
in breaking strength with increasing PVA content up
to 85 g, which then decreased around 95 g of PVA. On
the other hand, elongation at break was 320%. Similarly,
biodegradability of the blend determined by weight loss
(85–90%) on burying in soil for 4 weeks and microstructure
observance showed consumption of plasticizers followed
by faster degradation of starch and PVA. The foregoing
results hold promise for the wide spread use of such poly-
mers.
On the other hand, the effect of plasticizer and plasma
treatment on the physical and mechanical properties of
PVA/starch blends prepared as mentioned above revealed
plate-like starch formation with poor interface between
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021 991

Fig. 6. AFM photographs of cornstarch matrix films (bars indicate—400 nm). (a) uncoated; (b) C:H coated and (c) Similar to (b) and SF6 treated (condition:
100 V for 60 s); Z-scale for these are 127, 190 and 250 nm respectively. Reproduced with kind permission of the Publishers/author [128].

PVA and starch, but good compatibility between them
[127]. Plasma treatment marginally improved both the
ultimate stress and strain, but treatment of the blends
with water and citric acid showed marked improvement
(10–45%) of strain by the latter, indicating the effectiveness
of both treatments.
In an effort to overcome the hydrophilicity of corn
starch, a new coating of amorphous carbon by chemi-
cal vapor deposition (CVD) using plasma of methane and
subsequently with sulfur hexafluoride (SF6 ) was studied
[128]. By contact angle measurements it was found that
methane/SF6 plasma treatment yielded very high surface
hydrophobicity. The coating was observed by atomic force
microscopy (AFM) images as shown in Fig. 6 and revealed
to be homogeneous. This change in contact angle is related
to the observed rearrangement of surface polymer chains,
as seen in Fig. 6c, and to the chemical modifications of the
surface mentioned earlier. With the blending of corn starch
with polymer, the biodegradability of starch–polyethylene
composites evaluated by weight loss, CO2 production and
mechanical properties revealed up to 84% of the degradable
materials became biodegradable, along with an increase in
CO2 content after about 300 days [129].
All the results with corn starch reported above suggest
better and wider utilization of these in composite technol-
ogy [128].
Recently, potato starch has been processed by injection
molding in the presence of water. A study of its rheolog-
ical, thermal and molecular changes [130] revealed that
the stress–strain curves of this material exhibit a typical
glassy thermoplastic behavior, yielding a YM value (1.5 GPa)
similar to that of poly(propylene) (PP) and high density
poly(ethylene) (HDPE). Differential scanning calorimetric
(DSC) study showed two endothermic peaks at 348 and
423 K (75 and 150 ◦ C), with 42% and 12% water content,
respectively. These indicate characteristic gelatinization of
conventional starch processing at lower temperatures due
to swelling and destruction of starch granules and melt for-
mation at higher temperatures due to thermal and aqueous
destruction of crystallites and molecular order. Rheological
studies indicated that this starch could be processed like
poly(ethylene) (PE).
Yet another source of starch is wheat proteins. Starches
based on these are also used with appropriate plasticiz-
ers, whereby strong inter and intramolecular interactions
among proteins are reduced. This results in more flexibility
and extensibility. Attempts have been made to chemically
modify this starch using glycol, leading to the development
of cross-linked networks, which improved processing and
doubled the mechanical properties (tensile strength from 8
to 15 MPa, 130–140% in elongation), lowering Tg (from 308
to 288 K or 35 to 15 ◦ C) [131] at low humidity (55% relative
992 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
humidity—RH). The limited work on this and other types of
starches such as cassava starch has hindered expansion of
their utilization in composites.
2.1.2. Poly(hydroxyalkanoate)
Poly(hydroxyalkanoate)s (PHAs) are a family of natural
polyesters produced by a wide variety of microorganisms,
which use it for internal carbon and energy storage for
their survival [132]. Hence, it has been gaining increasing
attention for more than one decade [133]. PHAs hav-
ing a structure with the same three carbon backbones
and differing alkyl group at the ␤, or 3, position [134].
They may be obtained from recycling materials, renewable
agricultural sources or through the action of microor-
ganisms to get biodegradable materials. Such materials
become more attractive when their mechanical proper-
ties compare with those of commercial polymers. This is
attracting attention due to both economic and ecological
considerations, since they are obtained through biosynthe-
sis, while their biodegradability enhances environmental
safety.
Poly(3-hydroxide butyrate) (PHB), was first mentioned
in 1901, but described in detail only in 1920s, by Lemogine
[134] in a series of remarkable papers during 1923–1927 (he
produced PHB using B. megaterium bacteria). PHB belongs
to the PHA family and research on this material proceeded
slowly after its discovery.
Synthetic PHB biodegrades into CO2 and H2 O through
natural microbiological mineralization [135]. It is produced
by bacterial fermentation in integrated sugarcane mills in
Brazil, and has been commercially available since 2000,
at a rate of 50 metric tons/year and cost of US$ 3–5/kg
(commercial name: Biocycle) [136]. The cost is expected to
decrease with the increased output the company intends
to inaugurate by 2010, an industrial plant with annual
capacity of production of 10 thousand tons. Since this
is still more expensive than synthetic polymers, differ-
ent strategies including the use of better bacterial strains
and low-cost renewable resources have been attempted to
improve its physical properties and to bring down its cost
[4,125,137,138].
The optimum processing procedure for PHB using an
internal mixer was determined from DSC, FTIR and optical
microscopy analysis, which evaluated parameters such as
temperature, time and rotor speed of the rotor used [139].
It was found that changes in temperature (443–453 K or
170–180 ◦ C) and rotor speed (20–70 rpm) lead to minimum
thermal degradation, as evident from the insignificant
change in melting point and increased crystallinity (from
17.3 to 21.9%) and enthalpies of fusion (from 25.2 to 32 J/g).
On the other hand, spherulite size increased with increas-
ing processing temperature, while rotor speed decreased
without significant molecular changes as observed in the
Fourier transform infrared spectroscopy (FTIR) spectra.
Considerable effort has been made to improve the
properties of PHB. For example, because PHB is brit-
tle, co-polymerization of ␤-hydroxybutyrate with ␤-
hydroxyvalerate has been attempted, resulting in a polymer
called poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV),
first marketed about the same time as research started on
PHB [88].
A test was conducted with Co60 -␥-radiation to deter-
mine the effects on the chemical, mechanical and thermal
properties of PHBV. Predominant reactions in chain scission
and bond cleavages were observed using FTIR-ATR (atten-
uated total reflectance) and nuclear magnetic resonance
(NMR) spectra) [10]. Besides this, the molecular weight
(evaluated from the intrinsic viscosity), melting temper-
ature, tensile strength and fracture strain were found to
decrease due to radiation. The results of tensile properties
indicated enhanced brittleness, confirmed by the observed
brittle fracture morphology, along with some voids in the
scanning electron micrographs.
Recently, we have studied the effect of pressure and
incorporation of sugarcane bagasse fibers on the physi-
cal and thermal properties and structure of PHB [140]. A
shift in the X-ray diffraction peaks was observed with the
application of a load from 2 to 10 metric tons force on
a 12 cm × 12 cm area sample (i.e., 1 metric ton force pro-
duces a pressure of 6.94 kgf/cm2 ) (Fig. 7). Also, a decrease
in the unit volume with increasing applied force up to
6 metric tons was observed, after which the trend was
different. The crystallinity of PHB decreased in the same
way in both DSC and powder X-ray diffraction (XRD)
measurements. Based also on optical microscopy stud-
ies, we concluded that 6 tons is the optimal pressure for
the maximum packing of the PHB unit cell with polymer
helical chains being packed in an orthorhombic cell clas-
sified in the space group P212121 . Furthermore, possible
use of these curves and lattice parameters for modeling
of nanoscale/macroscale simulation was suggested, with
some correlation coefficients, whereby it may be possible to
predict mechanical properties using continuum equations
[140].
Surface characterization and chemical composition of
PHB subjected to biodegradation experiments (30 days
in simulated soils) and having mechanical properties
similar to those of conventional plastics, particularly to
poly(propylene) (PP), was carried out using scanning elec-
tron microscopy (SEM), DSC and X-ray photoelectron
spectroscopy (XPS) techniques [141–143]. In the SEM anal-
ysis, the non-degraded samples showed homogeneous
surfaces, while a heterogeneous surface was observed in
the degraded ones [143]. Also, a decrease in crystallinity
and carbon/oxygen ratio was observed with increasing
degradation time (from 55 to 49%) in DSC analysis and
XPS study, respectively. The DSC curves before and after
degradation are shown in Fig. 8(a) [140,141].
The dynamic mechanical analysis (DMA) curve of PHB
in Fig. 8(b) shows a peak at tan ı (about 25.7 ◦ C), an onset
of Tg at −3 ◦ C, in agreement with Tg of PHB by DSC study,
and high values of E (storage modulus) at low tempera-
tures (about 123 K or −150 ◦ C) due to the high molecular
weight, linearity and isotacticity of PHB, the latter of which
favors amorphous packing, and consequently low loss fac-
tor (tan ı) [140]. This very low loss factor indicates that the
behavior is nearer to an elastic solid (spring), without loss
of energy inside the system, due to the few degrees of free-
dom the molecules have at the temperature and frequency
of the measurement, as a consequence of the low free vol-
ume, which limits the internal structural movements under
these conditions [144].
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
Fig. 7. (a) X-ray diffraction patterns of PHB at different applied pressure; (b) comparison of crystallinity values at different applied load (12 cm × 12 cm
sample) determined by X-ray and DSC techniques [140]. [Courtesy: Carlos Eduardo da Silva Pinto].
One of the problems with PHB is its processability due
to its high stiffness and brittle nature. When PHBs are
processed in an internal mixer under different tempera-
ture and rotor speeds, they will be rendered crystalline
as evident from increased crystallinity with increasing
rotor speed [122,139]. To improve the processability of this
highly crystalline but less rigid PHB, plasticizers such as
PVA and stearic acid are used, as with starch. For exam-
ple, a mixture of PHB and PVA or stearic acid processed
by injection molding revealed [143] that the later was a
more effective plasticizer than the former based on the
melt flow index. However, decreases of about 10.8% in ten-
sile strength (20 MPa for PHB), 3.6% in flexural strength
(29.5 MPa value obtained for PHB), 26.5% in impact strength
(18 J/m for PHB), 1.3% in hardness (80 Shore D for PHB) and
4.7% increase in thermal distortion temperature (123 ◦ C for
PHB) were observed for the stearic acid–PHB, compared
to decreases of 13.8% in tensile strength, 6.9% in flexu-
ral strength, 48.4% impact strength, 5% in hardness and
an increase of 7.8% in thermal distortion temperature for
PVC–PHB. These values suggest more effective plasticizing
by PVA due to its greater molecular size and concentration.
Besides this, the thermal degradation of PHB with both the
plasticizers decreased at 10% poly(vinyl chloride)—PVC and
2% stearic acid, suggesting that use of the latter is more
suitable in composite applications.
Furthermore, to lower the cost of this useful biopoly-
mer, blending with other biodegradable polymers has
been attempted, including starch [125]. Reported prop-
erties of these biopolymers reveal an increase in tensile
strength (TS) from 17.08 to 31.45 MPa, Young’s modulus
(YM) from 18.29 to 33.43 MPa and elongation from 3.2 to
6.7%. Thermal stability increased from 496 to 532.6 K and
Tg from 336 K for pure PHB to 410.4 K for PHB–starch blend.
Besides, successful grafting and cross-linking of polysac-
charides (cellulosics and chitosan) have been achieved to
get biopolymers and fibers for composites [132]. Blends of
993
PHB with starch derived copolymer showed an increase
of about 105% in percentage of elongation with decreas-
ing starch content [145]. Blending of PHB with amorphous
polymers such as PE glycol resulted in a translucent and
flexible product exhibiting a wide range of loss modu-
lus (108 –1010 ) and tan ı values associated with broad Tg
(223–323 K or −50 to 50 ◦ C). But, the storage modulus value
decreased with an increasing amount of polyglycol.
Blends of PHB with PHBV processed by injection mold-
ing with increasing PHBV content from 20 to 100% showed
a reduction in hardness (1.8–4.83%), decrease in tensile
strength (5.6–14%), decrease in Young’s modulus (15.9 and
34.4%) for 50% and 20% PHBV content, indicating increased
flexibility (increased ductility) in the blend [146].
Additionally, highly biodegradable PHB is blended with
commonly used inexpensive poly(ethylene) to enhance the
biodegradability of the latter. The thermal properties and
biodegradability of this blend with and without a copoly-
mer (PE-g-GMA) have been evaluated with aging up to 8
months in soil [147]. With increasing PHB content, there
was an increase in biodegradation after 3 months due to
the heterogeneous morphology of the blends, while the
highest water retention was observed for raw PHB, which
decreased with decreasing PHB content in the blend. The
lower interaction between the constituents of the blends
with or without copolymer was evident from the similar
melting temperature, which was similar to that of pure
polymers, suggesting the inefficiency of the copolymer for
this blend.
Homogeneous and heterogeneous bioblends of chitin
derivatives, a biopolymer with poly(ethylene) oxide (PEO)
and PVA, for applications as membranes and paper addi-
tives to improve strength are also reported [148]. Foregoing
suggests the attempts mentioned above will certainly
expand the utilization of this brittle polymer particularly
for composites while motivating researchers to carry for-
ward their studies.
994 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
Fig. 8. Characterization of PHB. (a) DSC curves of PHB sample before (top) and after (bottom) biodegradation [141]; (b) DMA curves [140] [reproduced (a)
with the kind permission of Publisher and (b) by the courtesy C.E.S. Pinto].
2.1.3. Others
Poly(lactic acid) PLA, one of the oldest and most promis-
ing biodegradable polymers (aliphatic polyester), obtained
from agricultural products such as corn, sugarcane, etc., is
at the forefront of emerging biodegradable polymer indus-
tries through improved manufacturing practices that lower
its production cost [90]. Its crystallinity and hydrophilicity
can be controlled so that the overall degradation rate can
be decreased.
Natural triglycerides are another source to bio-resins.
Studies have been in progress since 1996 on chemical
routes to convert natural triglyceride oils into polymers/
composites. Three these routes are: (i) introduction of poly-
merizable groups; (ii) reduction of triglycerides into mono-
glycerides through glycerol sis-reactions; and (iii) fraction-
alization of the unsaturated sites [26]. More detail on these
can be found in references [13,16,17,21,26,27,47,54].
Studies on soy-based resins used as matrices for
biodegradable composites for large structures (housing,
truck and automotive parts) showed comparable properties
to those of structural woods and hence their suitability for
structural applications [26]. In this case, the resin is cured
at high temperature, but a vacuum assisted resin transfer
molding process has made a room temperature cure possi-
ble, thus reducing the cost, while diminishing the ecological
risks. Such studies should facilitate the use of untapped
renewable sources as materials for composite technology.
Another method successfully attempted to obtain nat-
ural polymers such as carboxymethylcellulose and lignins
is by self-assembly technique [149–151]. This is a low-cost
technique normally used to prepare different architecture
in ultra-thin films of organic materials through alternate
spontaneous absorption of oppositely charged polyions in
relatively short times. It can be applied to both ionic and
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
Table 5a
Comparison of some specific properties and cost of lignocellulosic fibers and synthetic fibers.
Fiber Specific gravity Specific tensile strength (GPa)
Plant fiber 0.6–1.2 1.60–2.95
Glass 2.6 1.35
Kevlar 1.4 2.71
Carbon 1.8 1.71
non-ionic hydrogen bonding polymers, with the former
taking place through electrostatic interactions [152–154].
This type of research will help in developing low cost
biopolymers.
Cashew resin is a biopolymer that has been extensively
studied for its processing, modifications and characteri-
zation [155], but scarcely used to prepare biodegradable
composites [156–159]. Cashew nut shell liquid, a byprod-
uct of the cashew nut processing industry, has anacardic
acid, cardanol and castrol as major components [155], with
other minor components including polymeric materials.
The presence of hydroxyl and carboxyl groups and valu-
able aliphatic unsaturation in side chains make chemical
reactions possible. With the addition of curing agents such
as hexamethylenetetramine and sodium hydroxide as cat-
alysts, the properties of cashew nut shell liquid resin can
be changed to allow its use in composites. Details of these
can be seen in the sources mentioned above.
Polyesters have also been prepared by condensation
polymerization of monoglycerides obtained by alcoholy-
sis of rubber seed oil, another renewable material. Three
polyesters were synthesized with the modified monoglyc-
erides prepared from rubber seed oil (RSO). Properties such
as acid value, saponification value, iodine value, volatile
content, etc. were determined. Of the three polyesters, the
one modified with maleic anhydride was found to be supe-
rior in chemical resistance compared to those from pure
(neat) RSO [160].
Natural rubber is an extensively used natural polymeric
matrix, whose structure and properties are available in
many standard textbooks on polymers and materials sci-
ence and hence not covered here. However, biodegradable
composites with rubber will be discussed below. Similarly,
kraft lignin is used as a matrix to prepare biodegrad-
able boards [161]. The foregoing suggests the possibility
to expand the availability and potential of various natural
resources for the development of useful new biopolymeric
materials.
2.2. Bio-based reinforcement/filler materials
It is well known that bio-based lignocellulosic (LC)
materials have been used in the preparation of compos-
ites since historical times, with one of their particular
applications in aircraft as early as the 1940s [162–166].
However, for various reasons, such as the superior proper-
ties of synthetic fibers and unavailability of complete data
on different lignocellulosic fibers, the use of LCs in compos-
ites decreased until the 1980s. Since then, there has been
increased motivation for the use of LC fibers, principally for
the reasons mentioned earlier, along with those given in
the following:
995
Specific tensile modulus (GPa) Cost (US$/tons) Energy content (GJ/tons)
10–130 200–1000 4
30 1200–1800 30
90 7500 25
130 12500 130
(i) the existence of sources throughout the world, with
some of them being abundant in the tropics (one
estimate gives their primary production in 2000 as
2 × 1011 metric tons compared to 1.5 × 108 metric tons
of synthetic polymers [165], while another estimate
puts the fibrous raw materials from agricultural crops
to be about 2.5 × 109 metric tons [72,166] with the
share of natural fibers including cotton is 44.3% of the
total 54.2 million metric tons of the world inventory of
fibers;
(ii) increasing ecological concerns, leading to greater
focus on plant derived fiber and crop derived plas-
tics as materials for the 21st century, due to their
attractive aspects, such as CO2 sequestration, reduced
dependence on petroleum products and value added
opportunities for agricultural industries, and
(iii) the availability of complete data concerning their
structure and properties, which depend on the source
from which they are extracted, the method of extrac-
tion, the age of their source, processing, etc. [166].
Other reasons for their increased use may be seen in
Tables 5a and 5b. The former shows a comparison of spe-
cific properties, energy to produce and the cost of these
fibers with those of synthetic fibers. The latter lists several
merits of these biodegradable fibers in composite technol-
ogy, highlighting the reasons for the choice of these raw
materials often quoted fielding the literature. In addition,
these materials have a steadily growing market, with the
North American market projected to grow from US$ 155
million in 2000 to US$ 1.38 billion by 2025 [167]. All these
also underline the importance of economic and technolog-
ical aspects of lignocellulosic fibers leading to sustainable
Table 5b
Merit list for the use of Lignocellulosic fibers incorporated composites.
Non-brittle fracture on impact
Same performance for lower weight
Stronger (25–30%) for the same weight
Low cost—less than the base resin
Fully and easily recyclable
Reduced molding cycle time—up to 30%
Non-abrasive to machinery
Natural appearance
Low thermal expansion coefficient
Good sound abatement capability
Better energy management characteristics
More shatter resistant
Low mold shrinkage
Easily colored
High flex modulus—up to 5× base resin
High tensile modulus—up to 5× base resin
High notched impact—up to 2× base resin
Lower processing energy requirements
Meets minimum recycle content requirements
996 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021

Fig. 9. Lignocellulosic reinforcements. (a) Banana; (b) sugarcane bagasse; (c) curauá; (d) flax; (e) hemp; (f) jute; (g) sisal; (h) kenaf. Typical pattern of
reinforcements used in the hybrid LC based biodegradable composite synthesis. (i) Jute fabric; (j) ramie–cotton fabric. (k) jute–cotton fabric. (j—reproduced
with the kind permission of the Editor [169]).

development, since these fibers may lead to the produc-
tion of consumer products with high durability that can
be more easily recycled as well [168]. Also, because these
fibers are hollow and lignocellulosic in nature, they are
better thermal and acoustic insulators. Also, they possess
fewer health and environmental hazards than synthetic
fibers. Fig. 9 [169] shows some of the main fibers used in dif-
ferent forms in biodegradable polymer composites, while
Table 6 lists their major chemical constituents and typical
physical and mechanical properties of various biodegrad-
able fillers/reinforcements. It is clear from Tables 5a and 5b
that their specific strength properties will certainly be
attractive for their use as replacements for synthetic fibers
particularly in composites for certain applications. Similar

Table 6
Physical/chemical and tensile properties of some lignocellulosic fibers used for biocomposites. Adopted from reference [166].

Fiber Dimensions L (mm)/ ␣-Cellulose Lignin (%) Young’s Ultimate tensile Elongation at
D (␮m) (%) modulus (GPa) strength (MPa) break (%)

Sugarcane bagasse 10–300/10–34 32–44 19–24 17.9a –27.1 222 1.1

Banana 300–900/12–30 60–65 5–10 27–32 700–800 2.5–3.7
Jute 120/25–30 59–71 11.8–12.9 10–30 400–800 1.5–1.8
Ramie 900–1200/20–80 80–85 0.5 44 500–870 1.2
Flax 750–900/50–150 62–72 2–5 60–80 780–1500 1.2–2.4
Pineapple 900–1500 80–83 12– 82 180 3.2

Curauá wet 35/7–10 70.7–73.6 7.5–11.1 30–80b 1250–3000b 4.5–6b

10.5 439–495 (MOR)c 1.3

Curauá dry 27.1 117 (MOR)c /495 1.3–3.2

34–96d 87–310 d 4–4.9d

Sisal 900/8–50 60–67 8–12 17–22 530–630 3.64–5.12

Cotton 35/10–45 90 <2 12 400
Coir 20–150/10–50 43.77 45 6 220 23.9–51.4
Luffa-cylíndrica, Brazil 25–60 (Diameter) 62 11.2 – – –
a
Calculated.
b
Diameter: 30–60m; test length: 20 mm and strain rate: 5 mm/min.
c
MOR: Modulus of rupture.
d
Diameter range 26–64 ␮m.
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
properties as well as the morphology and fracture behavior
of most of these lignocellulosic fibers are available else-
where [2,10,20,25,39,59,72,166,170,171] and accordingly,
the properties of individual fibers are not dealt with here
as is done with biodegradable matrix materials [166,169].
The microfibrills in lignocellulosic fibers are arranged
into a mesh within the cell walls of fibers and can also be
produced by bacteria. The stiffness and tensile strength of
these microfibrills have been reported to be 130–140 GPa
and 7 GPa, respectively, comparable with 180 and 3–4 GPa
for synthetic Kevlar fibers [172–174]. A recent review
presents the details of preparation of cellulosic whiskers,
their suspensions, properties and their use in the prepara-
tion of polymer nanocomposites along with mathematical
modeling to understand the reinforcing effect of cellu-
lose whiskers [175]. The stiffness and tensile strength for
whole phloem fiber cells of flax fibers are reported to be
80 and 2 GPa respectively [172]. Attempts have been made
to exploit these microfibrills (or nanofibrils) by appropri-
ate extraction [176] for their use in composite technology,
where the mechanical properties of nanofibrils exceed the
majority of the commonly used reinforcements. For exam-
ple, composites produced from Swede root (non-fibrous)
reinforced polymer composite with PVA resin have exhib-
ited tensile strength of 70 GPa and Young’s modulus of
5–4 GPa [172]. Studies have also been reported on the tex-
tile aspects of some LC fibers (jute, hemp, etc.) such as
(i) a variety of non-woven products and different produc-
tion methods; (ii) homogeneous blending for yarns and
non-wovens (opening, cleaning and blending, processing
by Lin-line method), and in different forms (fabrics, non-
wovens) through spinning/hybridization with interlayer
barrier effect, etc. These are used in polymer matrices to
produce composites for a variety of applications [175].
The proper method of yarn spinning to obtain the appro-
priate density for a wide range of textiles is available
whereby blended yarns with different natural fibers can
be obtained. Chemical–mechanical processing of cut fibers
and cording of fibers on the machine have been attempted.
Preparation methods of fibers for spinning/blending have
also been studied, and attempts have been made to weave
other fibers, as in the case of cotton. It has been observed
that the fiber size (thickness) determines the fiber content
in blending [177].
For hybrid biodegradable composites, initially plant
fibers were used mostly as short fibers and later as woven
or non-woven mats/fabrics. The latter were normally
obtained based on textile engineering concepts. Woven fab-
rics of jute–cotton and wood flour–sisal waste or short
fibers have also been used. Blankets/mats of sisal fabric
have been produced by compression using glue [178], while
blankets of luffa cylindrica fibers available in nature have
been successfully tried with advantages in the prepara-
tion of molded composites by compression or resin transfer
molding (RTM) [179]. Fabrics of LC fibers are generally
produced by hand weaving with one of the fibers in the
warp direction (as yarns) and the other in weft direction,
observing the specific number of counts in the weft/warp
directions to get suitable yarn width and count. Fig. 9(i–k)
shows a typical pattern of reinforcements used in hybrid
LC-based biodegradable composite synthesis. Such rein-
997
forcement materials available readily in nature, as in the
case of luffa cylindrica or materials prepared by textile engi-
neering concepts will go a long way in the preparation
of composites. Furthermore, while many lignocellulosic
materials are a source for cellulose, the surface of this
cellulose has potential for significant surface modifica-
tion through carbohydrate chemistry, resulting in potential
nanoparticle properties. This has led to several researchers
to use such renewable and abundantly available lignocellu-
losic materials to synthesize nanosized materials and their
composites similar to the well-known polymer composites
containing clays [180].
Permeability studies of lignocellulosic reinforcements
indicate the amount of reinforcement (volume fraction)
that can be used based on their compactness and per-
meability values. Thus, recycled paper, having lower
permeability (3.60 × 10−13 m2 ), is found to be more com-
pact and hence a higher volume fraction (42.3%) can be used
compared to cellulose 200, which has the highest perme-
ability value (6 × 10−10 m2 ) and hence the lowest content
(18.3 vol%) [26]. Various merits for using lignocellulosic
fibers in composites have already been given in Tables 5a
and 5b.
From the foregoing, knowledge is available on various
lignocellulosic fibers, their size, chemical composition and
tensile properties, available forms and merits for their use
in developing composites.
2.3. Surface treatments
The synthesis of polymer composites containing lig-
nocellulosic fibers will often result in fibers physically
dispersed in the polymeric matrix. In the majority of cases,
poor adhesion and consequently poor mechanical prop-
erties result. Hence, surface treatment of the fibers is
essential. Generally surface modification of LC fibers is
not necessary to improve the bonding for the prepara-
tion of biodegradable composites, in view of the similar
chemical nature of both the fiber and matrix, which have
a hydrophilic nature, unlike the situation with synthetic
polymers, which tend to be hydrophobic. However, surface
modification can be useful even in the case of biodegrad-
able composites to improve many specific aspects, such as
providing greater adhesion and reduced moisture sensitiv-
ity. Although better adhesion between the natural matrix
and reinforcements is imparted by the similar polarities of
the two materials, water absorption increases in the com-
posite. Hence, it becomes all the more important to have
suitable surface modifications of these fibers.
Surface modification typically involves one of four
methods, namely chemical, physical, physical–chemical
and mechanical. Chemical methods involve treatment with
silanes or other chemicals through chemical functionaliza-
tion reactions and leaching of the surface through alkali or
bleaching. Physical methods involve treatment by plasma,
corona, laser or ␥-ray and subjected to steam explosion.
Plasma and laser treatments of lignocellulosic fibers have
been reported to improve the surface of lignocellulosic
fibers [101,102]. On the other hand, steam explosion results
in improved properties of LC materials, which include
smoother surfaces, reduced stiffness, improved bending
998 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021

properties, better fineness distribution, higher fineness and
more concentrated distribution [181–186]. Steam explo-
sion process, a high pressure steaming, involves heating
of lignocellulosic materials at high temperatures and pres-
sures followed by mechanical disruption of the pretreated
material by violent discharge (explosion) into a collect-
ing tank [184]. This process has been applied to many
lignocellulosic materials to enhance dispersability in and
adhesion with polymeric matrices [185]. Mechanical meth-
ods involve rolling or swaging may damage the fibers.
Finally, physical–chemical methods involve solvent extrac-
tion of surface gums and other soluble components of the
fibers. As an alternative to the methods described above,
drying LC fibers can be an effective surface modification,
both in cost and to improve properties [187].
It should be noted that all the above mentioned treat-
ments of lignocellulosic fibers have helped to improve their
bonding with the matrix materials, increasing adhesion
of fibers with the matrix through surface roughness of
fiber, leading to increased strength or other properties of
composites through higher fiber incorporation (60–85%)
and possibly providing greater durability of the compos-
ites. More details on surface modification of lignocellulosic
fibers may be seen in many references (for example:
[9,13,16,20,28,50,60,61,71,72,166]). Some researchers have
modeled [188–190] the moisture absorption in lignocel-
lulosic fibers as a capillary flow and as a mass transfer
process, and hence chemical–physical methods, such as
treatments with NaOH, latex coating, ␥-radiation, etc., have
been attempted [191]. It has also been observed [192]
that the biodegradation process of the reinforcement in
biodegradable composites can be delayed by the chemical
modification of the fibers.
For example, both (untreated) sisal fibers and their
self-reinforced composites (plasticized sisal fiber acting
as matrix and unplasticized cores—continuous or discon-

Fig. 10. SEM photographs of sisal-composite. (a) Untreated fiber; (b) untreated, but enzymolyzed fiber for 192 h; (c) surface of self reinforced sisal composite;
(d) same as (c), but enzymolyzed for 192 h. Reproduced with the kind permission of Publisher [192].
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021 999

tinuous fiber, as reinforcement) have been subjected to by conventional methods, such as compression molding
degradation tests by aging in water or “enzymolyzed” by and extrusion with injection molding used for other poly-
aging in an enzyme solutions (a process called “enzy- mer composites. However, attempts should be made with
molysis”) and burial in soil. Untreated sisal fibers were regard to some important aspects, such as preservation of
compared with sisal fiber treated in benzyl chloride solu- mechanical properties of the LC fibers by minimizing attri-
tion, in which the benzylation diminished the uptake of tion and mixing degradation, attaining a high degree of
water and reduced the degradation of the fiber [192]. This fiber dispersion and ensuring good wettability, whereby
was reflected in the flexural and impact properties of their incorporation of a higher volume fraction of fibers with
self-reinforced composites, which decreased, dependent control of fiber orientation can be achieved. Some of the
on the benzylation time. The SEM photographs in Fig. 10 techniques used for this purpose are shown in Fig. 11
show, morphologies of (a) the untreated sisal fiber, (b) the
untreated sisal fiber enzymolyzed for 192 h, (c) the surface
of self-reinforced sisal fiber composite and (d) surface of
the self-reinforced composite enzymolyzed for 192 h. The
authors observed splits and cavities on the cell walls of the
fibers due to the attack of cellulase, along with a skele-
ton of cells still existing due to the hindrance of lignin. On
the other hand, they observed a number of cracks on the
surface of their composites due to enzymolsis, suggesting
initiation of biodegradation at the surface of the composite
samples, which then occurred inside with the cellulase dif-
fusion indicating the major role played by the enzymolysis
of plasticized skin layers of the fiber. Further, soil burial of
these composites for 6 months showed overall degradation
of both the matrix and the reinforcing fibers as evidenced by
the presence of both cracks and an eroded fiber-like struc-
ture on the surface of the composite (see reference [192]
for the SEM photograph).
It is important to say here that natural fiber is degradable
by fungicidal action as well as by bacteria, as demonstrated
by the soil burial test of jute–polyesteramide composite
[32], which is considered to be environmentally benign.
More studies on surface modification aspects for fibers and
possible modification of matrices may help in arriving at
composites with better performance in different type of
environments with adequate durability. Also such studies
may result in some cost effective surface treatment meth-
ods [192].

2.4. Processing aspects of biodegradable composites

The factors that are necessary for the development

of biodegradable composites include proper mixing of
LC fibers, selection of appropriate biopolymer matrix,
suitable surface treatments if required, along with low-
cost but high-speed fabrication techniques [167]. Some of
the attractions in the processing of LC-based biodegrad-
able composites are less abrasiveness for tooling unlike
glass fiber composites, and the absence of airborne par-
ticles, reducing respiratory problems for workers. Some
of the other merits of using lignocellulosic fibers in com-
posite technology are mentioned in Table 5b. Also, the
availability of reinforcements in suitable form will add
to the advantages. For example, three preforming tech-
niques have been developed for reinforcements [193].
They are filtration forming, solvent impregnation and co-
mingling of fibers. The pulp fiber reinforced cellulose
diacetate preforms prepared by these techniques elimi-
Fig. 11. Processing techniques for biodegradable composites. (a) and (c)
nated the fiber degradation in the final processing. Because
Reproduced with the kind permission of Prof. L.T. Drzal, Michigan State
of these factors, attempts have been made to develop University (unpublished private communication); (b) with the kind per-
biopolymer-based composites using renewable resources mission of the authors and the publishers [167].
1000 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021

[167], include (i) dry processing (Fig. 11a), where com-
posite sheets for compression molding were obtained; (ii)
wet processing (Fig. 11b), where a sheet-molding prod-
uct was obtained; and (iii) powder impregnation (Fig. 11c).
The latter method is reported to have many advantages,
such as no need to use organic solvents, the absence of
voids, ease of mixing and dispersion of multiphase com-
ponents, low energy consumption and the possibility of
recycling of powders. However, this method also has some
disadvantage, such as use of the requirement that the rein-
forcements are in a powder form, inhibiting use of their
potential strength properties. In general, press molding
seems to be the most preferred technique for the pro-
duction of composites with lignocellulosic fibers due to
the advantages it offers over the others to be mentioned
later.

Table 7a
Matrix–reinforcement–processing and characteristics of biodegradable composites. Starch-based composites.

Matrix system Reinforcement Processing Characteristics References

Corn starch 35%, corn gluten 35%,
glycerol 20%, water 10%
Thermoplastic starch, corn
starch–glycerol (30–50 wt%)
Corn starch
Blended acetylated starch acetate
Wheat starch (amylose 26%,
amylopectin 74%)
Thermoplastic starch
Non-extracted cassava bagasse
(63.1% starch + 36.9%
fiber) + cellulose acetate
Commercial starch-cellulose
acetate
Thermoplastic starch (MaterBi-Y® )
Potato starch + glycerol (0–30%)
10 wt% coir, jute or sisal
eucalyptus pulp 16% (w/w)
1–15 wt% cellulose fibers
Cellulose fiber (2–45 wt%)
NaOH treated corn stalks
(fiber 2–14%)
10–18% leafwood cellulose;
0–30% both leaf wood
fibers and paper pulp
Flax
Long fibrous Kraft paper
(10%)
Pine wood flour
(20–50 w/w)
Short sisal fibers (7.2 mm
long and 5–15 wt%)
0–40 wt% microfibrills of
potato pulp (cellulose)
Mixing followed by hot Increase of 100% in tensile strength and [195,123]
pressing 130 ◦ C, hot more than 50% in modulus respect to
pressing 170 ◦ C starch matrix
Intensive batch mixer Characterization by HP size exclusion [196]
at 100–150 ◦ C chromatography; glycerol content
reduces starch degradation while
increased fiber content increased
degradation. Lower polydispersity
index for matrix than that of native
starch due to shear induced
fragmentation of selective breakage of
large amylopectin molecules
Heating the mixture Composite foams formed; tensile [197]
inside a closed mold strength increased with increasing
fiber content up to 15 wt% fiber, then
up to 30 wt% fiber no significant
change observed; lower strength for
still higher fiber content due to
non-uniform distribution of fiber
Extrusion at 150 ◦ C in a Foams produced with good [198]
co-rotating twin-screw compatibility. Physical properties
extruder with 12–18% (expansion, density and shear
ethanol and 5 wt% talc strength) increased up to 10% fiber
content, but decreased above it
Extrusion followed by Fibers are well embedded in the starch [199,200]
injection molding and increase the storage modulus;
consistent and better static mechanical
behavior, and improved thermal
stability (by 30–38 ◦ C) but low weight
loss
Hot press molding with Fiber content and its lay-up dictated its [201]
film stacking of tensile properties and fracture mode
unidirectional and with tensile strength increasing by 3
cross-ply times and Young’s modulus by several
orders due to the fiber incorporation
Hot press molding Variation of tensile strength in rupture [202]
and elongation with lower water
absorption compared to
un-impregnated
Extrusion followed by Mechanical properties dependent on [203]
injection molding fiber orientation with transverse
properties being slightly higher than
those in radial direction
Press Marginal increase in flexural modulus [94–96]
molding/injection (1.94–2.3 GPa) with increasing fiber
molded content, but its significant loss
(33–50%) with increasing immersion
temperature (5–60 ◦ C); higher YM and
TS in the longitudinal direction
compared to transverse direction
Casting in Teflon mold Better thermal stability even with [122]
5–10% fibers (no change in storage
modulus with filler content below Tg )
but above this significant increase,
exhibited glass rubber transition and
decreased water absorption (20–30%
compared to 55% for un-plasticized
starch) with increased fiber content
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021 1001

Table 7b
Matrix-reinforcement-processing and characteristics of biodegradable composites. PHA (poly(hydroxyalkanoates)) and poly-acids-based composites.

Matrix system Reinforcement Processing Characteristics References

(i) Poly(3-hydroxy butyrate) (PHB), (ii) Flax Heating and No degradation of fiber. The [67,206]
poly(butylene succianate) (PBS), (iii) compressing a stack of evolution of the tensile properties
poly(butylene adipate-co-terephtalate) (PBAT) polymer films and fiber of the composites as the fiber
mats volume fraction increases
(i) Poly(␧-caprolactone) (PCL), (ii) poly(3-hydroxy Abaca fibers Hot pressing at: 80 ◦ C Weight loss in degradation burial [207]
butyrate-co-3-hydroxyvalerate) (PHBV), (iii) for PCL, 160 ◦ C for test was PCL > PHBV > PBS > PLA.
poly(butylene succinate) (PBS) PHBV; 170 ◦ C for PBS PCL losses ca. 45% after 180 days
and PLA and PLA ca. 10% in 60 days
Bionelle/PLA Flax Compression molding Tensile modulus and strength [208]
increase. Highest tensile strength
of p-PLLA is reached when
polyethyleneglycol-grafted flax is
added
PHB/copolymer PHV Flax – Adhesion between the fibers and [209]
the polyesters was better than for
analogous polypropylene
composites. Bending modulus was
increased. Storage modulus as
4 GPa at 25 ◦ C
PLA Flax 30–40% Twin extruder 180 ◦ C Strength is about 50% better [210]
compared to similar PP/flax fiber
composites. Stiffness of PLA is
increased from 3.4 to 8.4 GPa in the
composite. PLA was not degraded
by the compounding process
Polyester amide Hemp Twin extruder The extent of fiber determines the [211,212]
rate of degradation. More the fiber,
faster the degradation
PHB [hydroxyvalerate copolymer] Steam exploded Twin-screw extruded Tensile strength of the ductile [168]
Hemp material was almost doubled by
the reinforcement with 27% of
fibers to 30 MPa, the E-modulus
was quadrupled to 3.5 GPa
Biodegradable polyester Hemp 25% Twin-screw extruded Maximal reinforcement was not [212]
and injection molding achieved, because of a too weak
fiber matrix adhesion in
combination with an insufficient
fiber length caused by fiber
damage in the extrusion and
injection molding process
Biopol® (biopolyester) Jute yarn Hot press molding Composite enhances 194% the [13]
(180 ◦ C) tensile strength, 79% the bending
strength, 166% the impact strength
and 162% the bending-E-modulus
comparing with the matrix
PHB-co-PHV Recycled Impregnation in Tensile strength of the composite [6]
cellulosic fibers fluidization chamber parallel to the fiber direction was
(10%) and hot pressing 128 ± 12 MPa (10 vol% fiber) up to
278 ± 48 MPa (26.5 vol% fiber),
compared to 20 MPa for the PHB/V
matrix. Young’s modulus was
5.8 ± 0.5 GPa (10 vol% fiber) and
reached 11.4 ± 0.14 GPa (26.5 vol%
fiber), versus 1 GPa for the matrix

Tables 7a–7d lists the matrix–reinforcement–processing
combination of some of the biodegradable composite sys-
tems studied so far, along with their characteristics. Brief
discussions follow below [4,6,7,93–95,110,111,122,123,194–
222,167].
2.4.1. Starch-based composites
A number of biocomposite systems prepared by differ-
ent techniques based on starch as the matrix are listed in
Table 7a. It may be seen that the most common fabrica-
tion methods seem to be hot-press/compression molding
and extrusion followed by injection molding. These give
composites with adequate properties for some applica-
tions.
Although a supramolecular structure and crystallinity
were observed in the homogeneous matrix during process-
ing of thermoplastic starch (TPS) (plasticized by glycerol),
the mechanical properties of the TPS decreased and hence
fiber incorporation became necessary to improve the
properties. There are many studies with starch as a matrix
[4,6,7,93–95,110,111,122,123,194–203,223], including the
preparation of biodegradable chitin–starch composite,
using chitin (one of the most abundant polysaccharides)
in the form of flakes, with granular starch [194]. Using
1002 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021

Table 7c
Matrix–reinforcement–processing and characteristics of biodegradable composites. Other natural resins including rubber-based composites.

Matrix system Reinforcement Processing Characteristics References

Natural rubber
Cardanol 40%, cardanol
heated with
formaldehyde at 80 ◦ C
Soy flour (52% protein)/
polyester amide
Soy flour
Cellulose acetate
plasticized with 30% of
citrate plasticizer
Acrylated epoxydized
soybean oil
Soybean oil-based resin
Poly(butylenes adipatic-co-
terephthalate)
Poly(butylenes adipatic-co-
terephthalate)
Biopolymer-Bionelle-3020
Films of polyester amide
(BAK 1095)
Cotton fiber. Surface modified
with polyaniline
Both short and continuous
fibers of ramie, flax or hemp.
Up to 73%
Pineapple leaf
Indian grass
Hemp 30%
Flax, cellulose, pulp, recycled
paper, chicken feather
Hemp 20% (w/w)
Wheat straw
Wheat straw + lignin content
(14–30%)
Vacuum-dried waste flours of
spruce and paper (both of size:
150 ␮m) and olive husk
(125 ␮m) with and without
surface treatments
Sandwiched layers of sisal or
pineapple leaf fiber (PALF) fiber
non-woven mats with and
without several chemical
treatments
Hot pressing
Cured resin and hot pressing
Twin-screw extrusion and
injection molding, 130 ◦ C
Twin-screw extrusion and
injection molding
(1) Powder impregnation and
compression molding. (2)
Extrusion and injection
molding (compression
molding—210 ◦ C, 1000 psi)
Vacuum assisted resin transfer
molding
– Tensile strength of 35 MPa and
Injection molded
Extruded and injection molded
Mixed using rotor
Hot pressing
Storage modulus (E ) four times [216]
higher than the matrix. Tg
matrix = −67 ◦ C, Tg
composite–49 ◦ C
Tensile modulus, tensile [156]
strength and elongation at
break are near to the same
fibers loaded in polyester
matrix
Impact strength, tensile and [53]
flexural modulus significantly
improved
Improve tensile, flexural [54]
properties and heat deflection
temperature. Impact strength
did not change
Poor adhesion. Lack of fiber [46,217]
dispersion. Superior strength.
150% storages modulus over
the matrix
Composite beams made from [62]
recycled paper have strengths
and stiffness that make them
suitable for use in structural
applications where wood
members would normally be
used
[26]
a tensile modulus of 4.4 GPa.
The flexural modulus was
similar to 2.6 GPa and the
flexural strength was in the
range 35.7–51.3 MPa
Low intermolecular bonds [219]
between the constituents in
conformity with surface
tension results and SEM
No improvement of properties [219]
with several compatibilizing
agents. Increased stiffness and
Tg
Lower tensile strength and % [220]
elongation of the three
composites for both treated
and untreated flours than the
matrix
Higher tensile strength with [30]
increasing fiber content up to
50% fiber content; increase by
about 139.6% and 18.4% for
sisal and PALF composites,
respectively, over that of the
matrix

compression molding, we have been studying the prepa-
ration of starch-based (corn base and castor oil cake base)
composites incorporating different amounts of Brazilian
fibers of banana, sugarcane bagasse and luffa cylindrica.
Two patents have been obtained on these [204,205].
These composites have been evaluated for their tensile
properties and morphologies including fracture behavior.
These results will be published shortly.
2.4.2. Poly(hydroxyalkanoate)
Table 7b lists some of the biocomposite systems
based on poly(hydroxyalkanoate) (PHA) matrices pre-
pared by different processing techniques [5,12,18,19,
22,50,55,68,71,135,140,206–213]. Similar to starch-based
composites, the most promising techniques seem to
be hot-press/compression molding and extrusion fol-
lowed by injection molding. Apart from the reinforce-
ments mentioned in the table, others used include
wood flour. This biocomposite was prepared by injec-
tion molding using biodegradable PHB (thermoplastic
polyester) and wood flour [135]. Another study reports
a PHB–starch blend incorporated individually with 30%
each of wood flour, rice husk and sugarcane bagasse
[50].
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
Table 7d
Matrix–reinforcement–processing and characteristics of biodegradable nanocomposites.
Matrix system Reinforcement
Starch Potato cellulose microfibrills
10%
PLA Bentonite and microcrystalline
cellulose (MCC)
PVA Cellulose nano-whiskers
On the other hand, compression molding and press
forming have been used by some authors [214,215] to pro-
cess biodegradable composites of 20 wt% bagasse fibers
incorporated in a biodegradable aliphatic polyester, while
Kobayashi et al. [213] prepared PHB–sugarcane bagasse
(20–40 wt%) composites, first mixing them by twin screw
extrusion followed by injection molding.
We have used compression molding to prepare
biodegradable composites of PHB–sugarcane bagasse fibers
with and without steam explosion surface modification
[140]. The matrix, an industrial PHB called “Biocy-
cle”, is a white powder of high purity (>99.5%) with
molecular weight of 600,000 g/mol (by size exclusion
chromatography—GPC), density of 1220 kg m−3 and mois-
ture below 0.3%.
Apart from randomly distributed fiber/wood flour com-
posites, biocomposites have also been prepared with
20–30 wt% pineapple leaf fiber (PALF) placed in different
orientations by sandwiching between the films of PHBV
matrix and hot pressing [11]. All the studies reported
on PHA-based composites suggest that these polymers,
though basically exhibit lower strength properties, can
be strengthened by incorporating appropriate lignocellu-
losic fibers whereby very useful biodegradable composites
could be developed through different processing tech-
niques.
2.4.3. Other natural resins including rubber based
composites
As mentioned in Section 2.1, in addition to starch
and poly(alkanoate)s, other natural resins have been used
to prepare biocomposites. These are listed in Table 7c
[26,46,47,53,54,62,156,216–220]. Of these, soybean oil
based resin and natural rubber seems to be the most
promising and hence more attention has been focused on
them. More detail on these may be found in references
[16,17,21,26,48,49,62,71]. Processing of biodegradable com-
posite systems with other matrices, such as cashew nut
shell liquid (CNSL) and cellulose acetate have also been
reported using either hot pressing or powder impregnation
followed by compression molding and extrusion followed
by injection molding methods [71,156,217].
A novel processing method of photo-fabrication of photo
curable vinyl ester-oil palm fruit fibers biodegradable com-
posite has also been reported recently [71].
Most extensively used methods for processing of these
composites seems to be extrusion followed by injection
1003
Processing Characteristics References
Casting with gelatinized starch Thermal stabilization and [122]
(water/glycerol) and fibers decreasing of water uptake
suspension
Solution casting (chloroform, Bentonite improves tensile [221]
50 ◦ C) modulus and yield strength. MCC
reduces elongation to break
greatly. Storage modulus is higher
in both cases
Solution casting, evaporation Oriented nano-whiskers, [222]
and application of magnetic directional properties exhibited
field
molding, or compression/hot press molding techniques,
due to the advantages these processing techniques offer
and the resulting properties of the composites. For exam-
ple, hot pressed natural rubber–cotton fiber with and
without surface modification of the reinforcing fiber with
poly(aniline) showed [216] four times higher storage mod-
ulus E than that of the matrix alone (3 GPa), while Tg
changed to −49 ◦ C, compared with −67 ◦ C for the matrix.
These improved properties observed are explained as due
to efficient transfer of load at the matrix/fiber interface
produced by the processing technique. It is also reported
[71] that soy-based dried plastics produced by compres-
sion molding exhibit about 50% higher modulus than that
of epoxy engineering plastics suggesting soy protein could
be potential starting material for engineering plastics pro-
vided moisture is avoided.
2.4.4. Other biodegradable composites with
lignocellulosic materials
Attempts have been made to prepare biodegradable
composites using other forms of various lignocellulosic
materials. One important and almost unexplored field is
the use of nanosized reinforcements, either inorganic or
organic and synthetic or of natural origin. From natu-
ral origin, one of the promising materials that can be
cited is nanofibrous cellulose, which when reinforced in
a biopolymer results in biodegradable nanocomposites.
Though nanocomposites are beyond the scope of this paper,
processing and properties of some nano-biodegradable
composites based on lignocellulosic materials is mentioned
here with a view to underline the tremendous enhance-
ment of properties (strong reinforcement effects) obtained
even at low volume fraction (1–5%) of nanosized reinforce-
ments, unlike larger amounts in macrocomposites, keeping
in mind (i) the intense interest from both the industrial and
academic research sectors to develop and apply such com-
posites and (ii) the very limited studies reported on them
[70,71,221,222]. For example, it is reported that nanofibers
of cellulose can yield incredible mechanical properties,
with the Young’s modulus even exceeding that of many
steels and close to that for very expensive carbon nanotubes
[71,175]. More detail on these composites may be seen in
references [71,72].
In view of the outstanding properties that can be
developed, cellulose nanocomposites are becoming a hot
topic and there is no doubt that nanocomposite materials
will soon occupy an important position in science and
1004 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
industrial applications. Some examples of such composites
are mentioned in the following.
Attempts have been made to process nanocomposites
based on starch and PLA by solution casting. Improved
properties of the composites have been observed irrespec-
tive of the matrix used in these systems. One example is
the nanocomposites prepared using 2–10 wt% of cellulose
microfibrils (obtained by acid hydrolysis of cellulose fibers
from soft wood dissolving pulp and cotton) as reinforce-
ment and wheat starch as the matrix using deionized water
and glycerol as plasticizers by twin extrusion [180]. Other
composites studied include starch blended with 30% glyc-
erin and 16% wood pulp as fillers indicating wood pulp
as more efficient filler in improving mechanical proper-
ties [110]. More details of such composites may be seen
elsewhere [71,122,175,221,222].
A composite of the nitrile butadiene rubber (BR) matrix
with rice husk ash (2.3 ␮m size) with silane as a cou-
pling agent, was processed by blending and compression
molding. The resulting material exhibited increasing ten-
sile properties and hardness [92] with increasing amounts
of rice husk ash. Some of these are listed in Table 7d.
To conclude this discussion on the processing aspects of
biodegradable composites, it can be said that with selec-
tion of an appropriate processing technique, optimization
of processing conditions along with the proper reinforce-
ment form including lay-up of these, it would be possible
to further improve the properties (tensile, flexural, etc.) of
these composites for any of the matrices mentioned above.
This may open the possibility for these composites to be
used even in structural applications [35].
2.4.5. Hybrid biodegradable composites
In the case of partially biodegradable hybrid composites
involving lignocellulosic fibers with non-degradable poly-
mers, conventional manufacturing methods have mostly
been used, with compression molding being favored. The
same procedures may be used for biodegradable compos-
ites. Also, extrusion followed by injection molding and
other techniques are used in a limited way. Reinforcements
have been incorporated either by: (i) intermingling of two
types of short fibers thoroughly before incorporating them
into the polymer in a mixer or added alternately into the
polymer with or without modification [224–238]; (ii) sand-
wiching of fibers or their mats or fabrics [27,238]; or (iii)
using woven or non-woven fabrics of both types of rein-
forcements, as in the case of glass fiber-LC fiber composite
systems [27,238,239]. In the first case, the mixture of fibers
and the matrix may be subjected to rolling or injection
molding. When LC fabrics are used, appropriately mea-
sured fabrics are arranged in the mold for impregnating
with the polymer, as is done with natural fiberglass sys-
tems [27,233,238]. Another method used is film stacking
of the polymer matrix, such as PLA, which diminishes the
degradation of the polymer [67]. In this method, stacks of
the matrix are interlaced with flax fibers and then pressed
under heating.
The laminates need to be cured at suitable pressure
and temperature for a given time depending on the system
under study. Normally, the curing can be at room tempera-
ture because the reaction is exothermic. Studies have been
conducted to evaluate the strength and other properties of
these composites as a function of the fibers used and their
content and orientation, fiber and/or matrix modification,
characteristics of processing, and finally aging of compos-
ites. Very few studies on biodegradable hybrid composites
have been reported [239].
3. Properties of biodegradable composites
Characterization of any material, particularly newly
developed ones, is important from various standpoints,
such as its utility and value addition, which may open up
new areas for further development to assess the effective-
ness of its processing, the effect of different environments
on its properties and to find suitable areas of application.
For example, for urethane pre-polymer with jute compos-
ite, the elongation at break test was a relevant parameter,
which revealed that jute cloth can be stretched to about
double its original length as a composite, and this value is
useful in the design of sacks, bags, tents, etc. [46].
Chemical changes such as oxidation and degradation,
as well as glass transition temperatures in LC fibers-
based composites, are studied through thermal analysis
(thermogravimetry (TGA), differential thermal analysis
(DTA), differential scanning calorimetry (DSC) and dynamic
mechanical analysis (DMA)). One has to judiciously use rel-
evant technique for each property determination.
For example, it been noted that DSC is the most-
cited technique to determine characteristic temperatures,
i.e., glass transition (Tg ) and melting temperature (Tm )
[88]. Also, in many scientific publications involving natu-
ral fibers, little interest is shown in their thermal behavior,
since these studies mainly refer to degradation of the
products of the main components, such as cellulose, hemi-
cellulose and lignin, in addition to the determination of
humidity and/or volatile components like essential oils
and inorganic matter in the form of ashes. However, such
studies are important in the case of biodegradable com-
posites for their use in various application sectors. Also, a
few studies on the rheological behavior of composite melts
and other mechanical properties such as creep behavior
have also been reported [94–96]. These analyses can com-
pliment other evaluations by X-ray diffraction, absorption
spectroscopy in the infrared region, microscopic techniques
(scanning electron microscopy (SEM) and transmission
electron microscopy (TEM)), etc.
Some of the mechanical properties of biopolymers
determined include the following: ultimate tensile
strength—UTS (the maximum engineering stress in ten-
sion that may be sustained without fracture, often termed
also as tensile strength); flexural strength—FS (stress at
fracture from a bend or flexure test); flexural modulus—FM
(an indication of material’s stiffness when flexed and it is
the ratio, within the elastic limit, of the applied stress on
a test specimen in flexure, to the corresponding strain in
the outermost fibers of the specimen; impact strength—IS
(the degree of resistance of any material to impact load-
ing with or without notch in it) and interlaminar shear
strength—ILSS (a measure of the in situ shear strength of
the matrix layer between the plies. Since no exact method
for its determination is available, several indirect methods
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
such as short-beam three beam bending, double-notch
shear test, etc. are used to determine this property).
Some of the qualitative characteristics of biodegradable
composites have already been mentioned in Tables 7a–7d.
In general, biodegradable composites, particularly those
with flax, hemp and ramie fibers (the most frequently used
reinforcements), exhibit comparable mechanical proper-
ties to those of glass fiber reinforced polymer composites,
indicating the suitability of the former for structural
applications [13]. In the following pages, some reported
quantified details are discussed, mainly on mechanical
properties, thermal analysis results and other properties
of various biodegradable composite systems studied so far.
3.1. Starch-based composites
The tensile properties of starch-based biodegradable
composites vary depending on the type of fiber, its orien-
tation (random or unidirectional), content and form (fiber
or fabric) and type of blending/plasticizer used. For exam-
ple, reinforced unidirectional hemp fiber and yarns made of
ramie fiber and starch-based polymer composites exhibit
tensile strengths in the range of 200–250 MPa, compa-
rable to that of steel, while attempts are being made to
develop high strength “Bio Steel” fibers based on pro-
teins such as spider silk [35]. On the other hand, a jute
fabric–biopol composite showed [219] about 130–150%
increase in tensile strength (TS), impact strength (IS) and
Young’s modulus (YM), and 33% elongation and 50–81%
in bending strength over the matrix properties, while,
starch—30% glycerine—16% eucalyptus urograss pulp fiber
(l/d = 60, l = 1 mm) composite laminate of 2–4 mm thickness
exhibited 156% and 120% increase in YM and TS, respec-
tively, over the matrix, while the elongation and water
absorption decreased by 33% and 40%, respectively [123].
The reason proposed for these properties was the good
adhesion, as revealed by the fractographs of these compos-
ites. Another study with kenaf fiber based biodegradable
composites with corn starch revealed some features of frac-
ture modes of the composites, highlighting the poor and
good bonding between the fibers and the matrix as well as
the interfacial reactions, respectively [215].
The rheological properties of composites provide impor-
tant information on processing parameters, such as the
viscosity and possible effects of deformation on the
microstructure, including the extent to which the reinforce-
ment has been distributed in the matrix. A composite of
cellulose and starch (MaterBiY), mixed with 5–15 wt% sisal
fibers by injection molding showed [94] that the shear rate
was most important in the processing of the composite.
Higher shear stresses along with efficient mixing of the
composite melts resulted in opening of the fiber bundles,
leading not only to higher aspect ratio of the fibers but
also higher average viscosity of the composite melt for both
untreated and treated fibers. Short-term flexural creep tests
of the same composite carried out [95] to study the effects
of both the fiber content and temperature revealed that the
incorporation of fibers indeed has a positive influence on
the creep resistance of the composite.
The effect of processing parameters can be seen in
corn starch–glycerol (30–50 wt%)-1–15 wt% cellulose fiber
1005
composites processed by an intensive batch mixer at
100–150 ◦ C, through characterization by high performance
size exclusion chromatography (HPSEC). The glycerol con-
tent was found to reduce starch degradation, while
increased fiber content increased degradation. Also, a lower
polydispersity index for the matrix than that of native
starch was observed due to selective breakage of large
amylopectin molecules, caused by the shear induced frag-
mentation [223].
The effect of processing parameters on the properties
corn starch-based foams containing 2–45 wt% cellulose
fiber, developed to replace expanded polystyrene foam
trays, showed increased tensile strength with increasing
fiber content up to 15 wt%, no significant change in tensile
strength between 15 and 30 wt% fiber, while higher fiber
content showed lower strength due to a non-uniform dis-
tribution of fiber [197]. On the other hand, foams produced
from blended acetylated starch acetate with 2–14 wt%
NaOH treated corn stalks, using extrusion at 150 ◦ C in
a co-rotating twin screw extruder with 12–18% ethanol
and 5 wt% talc, showed good compatibility with increased
physical properties, such as expansion, density and shear
strength, up to 10% fiber content, but all of them decreased
above this point [198].
Recently, it was observed [195] that the Young’s modu-
lus of composites of 35% each of corn starch (28% amylose)
and corn gluten (70.3% proteins, 16.3% starch, 5.7% lipids,
3.09% fibers and 0.8% ash), 20% glycerol and with one of
three lignocellulosic fibers (coir, jute and sisal) at 10 wt%
of total weight of starch and corn gluten increased by
about 100, 189, 286% over the matrix (161 MPa) for the
untreated coir, jute and sisal fibers, respectively. These val-
ues improved further with mercerization treatment of the
fibers, by 52.2, 15.5 and 53.7% over their untreated counter-
parts. Similarly, ultimate tensile strength (UTS) values also
showed improvement by 76, 86 and 90%, respectively, over
the matrix for the three fibers respectively. With mercer-
ization, the improvement in these properties was 8.3 and
3.8% for coir and jute respectively, while they decreased
by 21% in the case of sisal. On the other hand, elonga-
tion decreased significantly (33–67%) in all the cases for
untreated fibers relative to that for the matrix, while it
showed marginal increases over these values for mercer-
ized jute and sisal fibers and about 35% for a coir fiber
composite. These observed values were related to the adhe-
sion between the fibers and matrix, as seen by SEM studies.
Our preliminary results (Guimarães et al., paper under
preparation) of tensile testing of composites of starch with
commercial glycerol and recovered glycerol (byproduct of
biodiesel) as matrices and different amounts of banana
(20–35 wt%) and 25 wt% bagasse fibers have shown trends
as given below.
Young’s modulus showed an initial increase by about
2.5 and 3.8 times for 20 and 25 wt% banana fiber content
respectively and then it decreased (3.5 times); ulti-
mate tensile strength (UTS) remained almost constant
with increasing banana fiber content; yield strength (YS)
increased by nearly 2 times for 20% fiber, 2.8 times for 25%
fiber and 3.2 times for 35% fiber, while elongation decreased
with increasing fiber content, about 5 times for 20%, 6
times for 25% fiber and 7 times for 35% fiber. This indicates
1006 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
Fig. 12. SEM photographs of tensile tested banana fiber-corn starch composite showing (a) fiber distribution and fracture and some pull outs; (b) fiber
fracture and pull outs; c: fiber fracture in corn starch–sugarcane bagasse (Courtesy: Guimarães, JL. Unpublished).
that banana fiber acts as reinforcement with yield strength
and Young’s modulus showing increases although the ulti-
mate tensile strength remained almost constant. Also, not
being very stiff, banana fiber did not contribute to mod-
ulus enhancement above 25% suggesting that 25% might
be the maximum amount to give stiffness to the matrix
and thereafter it might not have any effect. Nevertheless,
the elongation decreased with fiber addition was expected
because the matrix was more ductile (75.57%) than the
fibers (2.5–3.7%) [72].
The tensile properties are dictated by the reinforcing
fiber used for the composite. Accordingly, the observed
trend in tensile properties indicated starch-bagasse com-
posites showing higher tensile properties than those of
starch–banana system even with lower amount of fiber
content (25 wt%) compared to banana fiber (30 wt%). The
Young’s modulus of bagasse fiber containing composite was
almost 2.5 times higher than that of banana fiber composite
and 8 times over the matrix with commercial glycerol; The
UTS was about 1.7 times higher than that of banana fiber,
but about 1.4 times lower than the matrix with commercial
glycerol; YS was about 3 times higher than that of both the
banana fiber, and the matrix with commercial glycerol. All
these have been explained in terms of structural aspects of
the fibers and the fractographic studies. SEM fractographs
of banana biocomposites revealed (Fig. 12a and b) uniform
distribution of fibers, good wetting of the fibers with the
matrix and fracture of fibers themselves. On the other hand,
SEM of bagasse biocomposites showed more uniform dis-
tribution of fibers (see Fig. 12c), moderate wetting of the
fibers with the matrix and pull out of fibers, sometimes
with fracture of the fibers.
A study of the fiber content and lay-up on the properties
of hot-press molded thermoplastic starch matrix film stack-
ing of unidirectional and cross-ply composites with flax,
revealed that the tensile properties and fracture mode, with
tensile strength increasing by 3 times and Young’s modulus
by several orders due to the fiber incorporation [201].
The effect of the starch source is illustrated in the
following comparison of a plasticized corn starch–chitin
(polysaccharide)—system I [194] and a wheat starch with
leaf wood cellulose fibers—system II [199,200]. Studies
on I (prepared by extrusion) exhibited increased modu-
lus and elongation (36–55% with increasing chitin content
(0.1–1%), while the tensile strength did not change much
(2.5–3.6 MPa). By contrast, both the strength properties and
water content of the composite II decreased compared to
that of the starch matrix I, which was much better than the
composite of the same fibers with a poly(ethylene) matrix.
On the other hand, a composite made by aqueous cast-
ing of gelatinized non-extracted cassava starch (bagasse)
and long fibrous kraft paper and impregnated in starch
acetate exhibited [202] no effect on mechanical properties
was observed (variation of tensile strength at rupture being
9–17% and those coefficients for elongation at rupture being
6.2–12.6%). Also, this impregnated composite showed
almost one-fourth the water absorption compared to un-
impregnated composite (cassava bagasse + kraft paper) and
similar characteristics as molded packaging material based
on recycled paper.
Regarding the thermal behavior of some of the starch
based biocomposites, a DSC study of a starch—30%
glycerine—16% eucalyptus urograss pulp fiber composite
showed an increase of glass transition temperature and
two transition peaks in the DSC curve [123]. The higher
transition occurred at 17 ◦ C for the composite showed an
increase of glass transition temperature and two transi-
tion peaks in the DSC curve [123]. The higher transition
occurred at 17 ◦ C for the composite and 2 ◦ C for the ther-
moplastic starch, with the lower transition at −45 and
−55 ◦ C for these, respectively. The ‘higher transition tem-
perature’ was determined as the temperature for one-half
of the change in the heat capacity during the higher tem-
perature transition. Fiber interaction with the plasticizer
was attributed to this difference in the ‘higher transition
temperature’ for the two materials. Water sorption of the
composite at two humidity values (43 and 100%) showed
a dramatic reduction due to absorption of glycerin by the
fiber, making the matrix less hydrophilic. Similarly, TGA
studies of a commercial blend composed of cellulose and
starch (MaterBiY), mixed with 5–15 wt% sisal fibers by
injection molding [240] showed two activation peaks, the
first at 107–108 ◦ C was not affected by the addition of fibers,
but the second depending on the amount of the fibers
loaded in the sequences 453, 449 and 445 K for 5, 10 and
15% of sisal fiber, respectively. On the other hand, study
of moisture diffusion by microscopic mass balance equa-
tions for diffusion in solids of the same composite prepared
by press molding showed increasing diffusion coefficients
with increasing test temperature, indicating that water acts
as a plasticizer. Also, a marginal increase in flexural mod-
ulus (1.94–2.3 GPa) with increasing fiber content, but a
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
significant loss (33–50%) with increasing immersion tem-
perature 278–333 K (5–60 ◦ C) have also been observed [94].
The effect of moisture content on the tensile properties
of injection-molded composite containing 5–15 wt% sisal
fibers showed higher YM and TS in the longitudinal direc-
tion compared to the transverse direction.
On the other hand, extruded and injection-molded
composite of leaf wood fibers with plasticized wheat
starch showed strong evolution of the main reflection
temperature in its DMA, confirming interaction among
the constituents due to possible decrease in starch chain
mobility. This was supported by the static mechanical
behavior and SEM [241]. Similar results in extruded-
injection molded starch + lignocellulosic fibers (0–30% both
leaf wood fibers and pulp from broad-leaved species)
showed consistently better static mechanical behavior
and improved thermal stability (by 30–38 ◦ C), but low
weight loss (5–7 times over the matrix) for lignocellulosic
fibers with change of filler type, fiber length (60 ␮m to
1 mm) and amount (up to 30 wt%), and glycerol/starch ratio
(0.257–0.538) than cellulose [111].
The thermal degradation in a biocomposite of a
biodegradable polyester amide (known by the BAK, com-
mercial name given by Bayer) and jute fiber studied
through its differential thermogravimetry (DTG) profile
[29] showed the major decomposition related to thermal
stability for the fiber occurred at 307 ◦ C (63.4% mass loss)
and for the polymer it was at 385 ◦ C (88.88% mass loss). The
thermal stability of the composite between these temper-
atures was found to be 339 ◦ C (64.24% mass loss).
DMA studies of plasticized wheat starch [241] showed a
decrease of the storage modulus E due to glass relaxation of
the matrix, but an increase before and after ␣ transition and
after the fibers were incorporated. On the other hand, two
peaks were observed in the evolution of tan ı, the first main
relaxation at 31 ◦ C was associated with the large tan ı peak,
while the second (at about −50 ◦ C) was associated with
the glass transition of glycerol. With the introduction of
leaf wood fibers, the main relaxation shifted by 28 ◦ C with
fiber content up to 10 wt% and then by another 4 ◦ C when
the fiber content increased to 18 wt%, due to the strong
interaction between the two carbohydrate products. A sim-
ilar result was observed with another plasticized starch
(potato). This decreased the starch chain mobility, leading
to increased glass transition of the matrix. The length of
the fiber (short to medium to long) also affected the tran-
sitions, changing by about 9 ◦ C from 51 ◦ C. The shifting of
the storage modulus towards a higher value indicates the
fiber’s reinforcing effect. Similarly, composites of potato
starch containing up to 40 wt% microfibrills of potato pulp
(cellulose) materials and up to 30% glycerol processed by
casting in a Teflon mold, even in small amounts (5–10%),
showed no change in storage modulus with filler content
below Tg, but above that it increased significantly. Also,
the composite exhibited increased glass–rubber transition,
with the relaxed modulus remaining constant at 380 K, all
these results suggesting better thermal stability of the com-
posite. Decreased water absorption (20–30% compared to
55% for unplasticized starch) with increased fiber content
was also observed for this composite [122]. From the fore-
going it becomes evident that properties of starch based
1007
biodegradable composites depend on the processing tech-
nique used.
3.2. Poly(hydroxyalkanoates)-based composites
One of the interesting points to note is the excellent
dispersability of fibers achieved in this system com-
pared with synthetic polymers [133]. Tensile properties of
alkanoate-based composites also depend on the type of
poly(alkanoate)-based resins (PHB, PHBV, etc.), type and
form of fiber and its content and plasticizer used. These are
discussed below.
For example, composites of 20 wt% bagasse fibers
incorporated in biodegradable aliphatic polyester exhib-
ited tensile strength of 16.52 MPa, flexural strength of
31.19 MPa, flexural modulus of 1.14 GPa and impact strength
of 4.12 kJ/m2 without treatment to the fibers [136]. These
properties increased by 12, 10, 16 and 47%, respectively,
with alkali treatments, while they increased by about 42,
41, 101 and 114% when the fiber content increased to 65%.
On the other hand, PHB/wood floor biocomposite
showed constant density [1200 kg m−3 ] between the
matrix and its composite, while it showed an increase in YM
(3.26–5.32 GPa) and Shore D hardness (from 79.5 to 81.1),
a decrease in TS (from 27.8 to 24.2 MPa) and elongation
(1.88–0.67%), with increasing wood flour content from 10
to 40 wt% [135]. These properties did not show any change
on surface modification of the reinforcement by either
NaOH or corona (electric discharge, which changes sur-
face energy of fibers) of wood flour. However, PHB/starch
blends that incorporated 30% of wood flour, rice husk
or sugarcane bagasse revealed that tensile strength elon-
gation increased in the order of PHB/starch blend < PHB/
starch blend + rice husk and PHB/starch blend + bagasse <
PHB/starch blend + wood flour [50]. On the other hand, the
Young’s modulus of these increased in the order of PHB/
starch blend < PHB/starch blend + rice husk or bagasse <
PHB/starch blend + wood flour and impact strength in the
order of PHB/starch blend + bagasse > PHB/starch blend >
PHB/starch blend + wood flour > PHB/starch blend + rice
husk. Also, crystallinity as measured by DSC decreased in
the order PHB/starch blend < PHB/starch blend and PHB/
starch blend + wood flour < PHB/starch blend + bagasse <
PHB/starch blend + rice husk without any variation of the
melting temperature for any combination. These results
indicate that the natural fibers can at least be used as fillers
in this matrix, with all of them improving only stiffness and
bagasse increasing the impact strength also. In an investi-
gation of the various effects of different types of matrix and
fiber on the tensile properties, PHB containing recycled cel-
lulose fibers showed high tensile strength [5], while wood
flour and its pulp in PHB showed low values (24.20 and
11 MPa, respectively) [135].
In contrast, composites of PHB + 5–12% PHV with flax
showed better adhesion than composites of PP with
flax fibers. In this case, both fibers and coupling agents
increased nucleation, bending modulus, storage modulus,
melting point and Tg (maximum of loss modulus in the
curves), but the value of the loss modulus showed low
values [209]. Silane coupling agents increased only the
mechanical properties. Also, composites of PHB with flax
1008 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
fibers with plasticizers exhibited lower adhesion of fibers,
while movement of plasticizers from fiber to the matrix
changed Tg , crystallization and crystallinity of the matrix
[206].
Another study on injection-molded biodegradable
poly(butylene adipatic-co-terephthalate) composite with
wheat straw showed [200] a reinforcing effect in both
tensile and impact strength measurements, but without
any brittleness, unlike similar composites with poly-
olefin matrix. However, no improvement of properties was
observed with several compatibilization agents used. In
a recent study [218] the mechanical behavior (increased
stiffness) and thermal behavior (increased Tg ) of these com-
posites revealed to be useful in non-packaging applications,
such as in agriculture, sports, etc.
The effect of surface treatment of fibers on the
properties of biodegradable composites has revealed
enhanced dispersibility of lignocellulosic fibers, giving
them greater potential as reinforcing agents. For exam-
ple, composites of degummed hemp fibers (separated into
single cells) with two different polymers, namely brittle
poly(3-hydroxybutyrate-co-hydroxyvalerate) and ductile
co-polyester amide matrix processed by a co-rotating twin
screw extruder, showed [211] that both the fiber content
(up to 42 vol%) in the composites and the tensile prop-
erties increased due to steam explosion. The increase in
the tensile strength of the co-polyester matrix was almost
doubled (30 MPa) by the reinforcement with 27% of fibers,
while the Young’s modulus was quadrupled (3.5 GPa). No
such improvements with PHB were observed except for its
Young’s modulus (6 GPa) and the accompanying reduction
in impact strength.
The effect of another fiber surface treatment, such as
steam explosion, on the strength properties of biocompos-
ites has been studied for some systems. For example, for
PHBV + steam treated 10–30 wt% wheat straw (rich in cel-
lulose and more reactive), the crystallization rate increased
without affecting crystallinity and there was a higher
increase in Tg (nearly 6 times over the matrix and 10% filler
content), lower failure stress (8–11 MPa) and failure strain
(0.4–1.4%) compared to those of the matrix (10–19 MPa and
1–2.4% respectively), while no change in the biodegradabil-
ity rate of composites both in soil burying or in a liquid
environment was observed, except for fiber content >10%
[19]. These observations were confirmed by scanning elec-
tron microscopy (SEM).
Another effect of surface treatment of reinforcements
is illustrated in vacuum-dried waste flours of spruce and
paper and olive husks with and without surface treatments,
blended in biopolymer-Bionelle-3020 [220]. In this case,
the matrix was also modified using maleic anhydride, while
doing grafting reaction in a rheomixer. In general, tensile
strength and elongation of the three composites for both
treated and untreated flours showed lower values than
the matrix, except those with compatibilized paper. The
decrease in tensile strength was 45.6% for husks, followed
by 37.5% for spruce and 29.1% for paper. The decrease of
percentage of elongation ranged from 520% for the matrix
to 3.5% for the composites. These were attributed to poor
interfacial adhesion between the constituents of the com-
posites. On the other hand, Young’s modulus of all the three
composites increased in both treated and untreated flours,
ranging from 2 times for olive husks to 4–4.5 times for the
other two composites. The water sorption and biodegrad-
ability of the composites also improved.
A study on the tensile properties of PHB and PHB
containing different amounts of sugarcane bagasse fibers
with and without steam explosion [140] showed more or
less similar stress–strain curves for both the matrix and
its composites, though they differed in their slopes and
strain at failure. This suggested a change in the behav-
ior of PHB with the incorporation of sugarcane bagasse
fibers, attributed to the debonding with the matrix, lead-
ing to the beginning of the fracture of the composite as
observed in fractographs. The values of Young’s modu-
lus YM, tensile strength TS, yield strength YS and strain
at break obtained from these curves showed comparable
values to those reported for wood flour–PHB composites
[50,143], but higher than that reported for biodegrad-
able aliphatic polyester–bagasse fiber [214]. Further, the
composites with the fiber subjected to steam explo-
sion (5 and 30 wt%) showed a significant increase in the
maximum stress, while the modulus remained almost
constant for the composites and modulus increased to
1.9 GPa compared to 1.4 GPa for PHB matrix. The ran-
domly distributed raw bagasse fiber lead to higher values
(2.1 GPa). Also, the crystallinity obtained from both DSC
and X-ray diffraction techniques were almost identical.
The observed strength properties of composites were
explained as due to surface defects in the fiber, lack of
bonding between the untreated bagasse fibers and PHB,
presence of some air bubbles leading to defects in the
samples, as observed in the SEM photographs (Fig. 13a
and b), and also to the lowering of PHB crystallinity
under pressure. These studies clearly suggest that sur-
face treatment of reinforcements play an important role
in enhancing the properties of biodegradable composites
[140].
Directional variation in properties has also been
observed in biodegradable composites. For example, the
tensile and flexural properties of PHBV–pineapple fiber
unidirectional composites were found [12] to increase in
the transverse direction while they decreased in the trans-
verse direction, respectively, over those of matrix values
with increasing fiber content. These properties, which
were lower than those predicted by the models used,
were explained using the SEM photographs. The non-
unidirectional nature, fiber pullout, interfacial failure and
fibrillar nature of the fiber were evident from these frac-
tographs.
The tensile and flexural properties of pineapple leaf fiber
(PALF) composites placed in different orientations by sand-
wiching between films of PHBV matrix and hot pressing
[11] were found to be lower in the grain direction com-
pared with the perpendicular direction (0/90/0 direction),
both of which were higher than those of the matrix. For
example, the tensile strength increased by 1.75 and almost
2 times for 20 and 30% fiber composites respectively over
the matrix, and almost the same increases were observed
for Young’s modulus, while the strain at break decreased
by about 1/3 for both the composites. On the other hand,
the flexural strength increased by 1/3 to 1.5 times, flexural
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
Fig. 13. SEM photographs of tensile tested sugarcane bagasse–PHB composite. (a) Composite containing fiber without treatment showing fiber fracture
and some pull out; (b) composite containing steam exploded fiber with homogeneous distribution [140] [Courtesy: C.E.S. Pinto].
modulus by 1/2 to nearly 2 times and there was a marginal
decrease in the strain at break.
Regarding the thermal behavior of these composites,
a DSC study of the PHBV–pineapple fiber unidirectional
composites [12] revealed that the non-isothermal crystal-
lization kinetics, crystallinity and thermal decomposition
of the matrix resin were unaffected by the incorporation of
fibers.
DMA studies of biodegradable PHB composites con-
taining different amounts of sugarcane bagasse fibers
with and without steam explosion treatment showed
[140] tan ı values of the composites very close to those
of the fibers at temperatures ca. 50 ◦ C, indicating load
transfer from matrix to fiber. This was supplemented
by an abrupt decrease in the loss modulus E . On
other hand, injection-molded biodegradable poly(butylene
adipatic-co-terephthalate) composite containing wheat
straw showed thermal characteristics of low intermolec-
ular bonds between the constituents, in conformity with
surface tension results and SEM [216].
3.3. Triglyceride-based composites
Both the origin of the triglycerides and the type of
reinforcement with its form dictate the properties of this
system. For example, biocomposites of 40 wt% flax fiber
with triglyceride-based resins exhibited TS of 20–30 MPa,
FS of 45–65 MPa [21], while that with the same amount of
hemp fiber showed TS of 35 MPa, FS of 35.7–51.3 MPa, FM
of 2.6 GPa and YM of 4.4 GPa. Another study on a hemp-
triglyceride composite reported similar result [212]. On
the other hand, a jute fabric–biopol composite showed an
80–150% increase in TS, more than 33% in elongation, 150%
in YM, 130–150% in IS and 50–80% in bending strength
compared to TS of 20 MPa and YM of 1 GPa for the matrix
[14,22].
Acrylated epoxidized soybean oil (AESO) based com-
posites containing 34 and 20% flax fiber exhibited UTS
30 and 35 MPa respectively, while YM for the latter was
4.4 GPa [16]. SEM photographs of hemp–AESO composites
showed fracture surfaces with large number of pull outs
than those observed in flax–AESO composites [17]. Also,
some of the fibers were found to have the resin adhered
1009
to their surfaces. Improvements in the properties in other
reinforcements, such as hemp, can be seen in Table 7c.
Thermal behavior of AESO composites containing 14
different types of cellulose (flax/hemp/cellulose/news
paper/pulp) cured composites were studied by DMA in the
temperature range of 35–150 ◦ C [48]. The results revealed
increase in the storage modulus E by almost 5 times with
50 wt% reinforcement, the highest value being for cellu-
lose derived from recycled paper (cheaper in cost). On the
other hand, the loss modulus E was observed at two dif-
ferent temperatures, one at 310 K and the second at the
temperature where the modulus was found to be maxi-
mum Tmax . This also increased with the incorporation of the
fibers by almost 2.3 times over the matrix value of 190 MPa.
The ratio of these two moduli, which is represented by
tan ı (damping factor) at the two temperatures (310 K and
Tmax ), was maximum (0.3) for cellulose containing compos-
ite, followed by values of 0.25–0.27 for flax/cellulose/hemp
containing composites, with the lowest being 0.1 for news-
paper containing composite. This indicates that all the
cellulose-based AESO composites can be good candidates
for structural applications requiring good damping, such as
automotive uses.
3.4. Other matrices/properties
The strength properties of various biodegradable com-
posite systems with other matrices are given in Table 7d.
Some of these are discussed further here. For example, nat-
ural rubber–cotton fiber, both with and without surface
modification with polyaniline, prepared by hot pressing
exhibited [216] a storage modulus E four times higher than
that of the matrix (3 GPa), while Tg changed by 224 K com-
pared to 206 K for the matrix.
Fiber boards made with Miscanthus Sinensis wood with
steam-exploded kraft lignin showed improvements in var-
ious properties (18.8% in Young’s modulus, 13% in modulus
of rupture, 20.6% in internal bond strength, 71% decrease
in water swelling, 24% in water absorption) in compari-
son with those made without that treatment [161]. This
was due to the elimination of low molecular weight sub-
stances during steam explosion, which also helped improve
the mixing with cellulosic fibers.
1010 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021

Composites of pine wood flour (20–50 w/w)– On the other hand, short hemp fiber composites
commercial starch–cellulose acetate composites [203] behaved differently with regard to toughness, untreated
prepared by extrusion followed by injection molding fiber composite showing higher toughness than that with
showed decreasing viscosity with shear rate, but above treated fibers. In the case of kenaf fiber composite [157],
40% flour, they showed quasi Newtonian flow behavior. the variation of the tan ı peak was similar to that of hemp
The mechanical properties of these composites were found fiber composite, while not much change was observed
to be dependent on fiber orientation, with transverse in E values for both the composites containing treated
properties being slightly higher than those in the radial and untreated fibers. Correspondingly, the loss modulus
direction. For example, the tensile strength values for the E = E /tan ı differed for the two composites, with both
transverse and radial directions for 50% flour were 28 the composites showing broader loss modulus peaks on
and 22 MPa, and Young’s modulus for these composites addition of fibers. For example, treated hemp fiber com-
was about 5.5 and 4.8 GPa, respectively. Also, the increase posites showed higher peak temperature compared to the
in these properties only occurred up to 50 wt%, where untreated fiber composites, while treated kenaf fiber com-
after they decreased. But the toughness almost remained posites showed only a slightly higher value compared
constant between 0.8 and 0.1 MPa when the flour content to untreated fiber composites. These results underline
increased from 0 to 50 wt%. Though the composites showed improved adhesion and greater interfacial bond between
increased properties, they were difficult to process. Use of the matrix and the fibers, and thus higher interfacial
15% glycerol improved the processing without affecting strength of these composites.
the properties, due to destruction of hydrogen bonds by A comparative study was reported [94–96] on the ther-
glycerin, leading to decreased viscosity. SEM of fractured mal behavior of cellulose acetate (CA), cellulose derivative
composites showed coating of flours by matrix, suggesting blend with starch (CDS) and their composites with 5–15%
good fiber–matrix adhesion. sisal fibers by TGA/DTG technique in the temperature range
On the other hand, composites of non-woven mats of of 298–1273 K under N2 atmosphere (20 ml min−1 ). TGA
sandwiched layers of sisal or pineapple leaf fiber (PALF) and DTG curves obtained in this study are shown in Fig. 14. It
with and without several chemical treatments and films may be seen that the blend exhibits a two-step degradation
of polyester amide (BAK 1095) prepared by hot pressing
exhibited higher tensile strength with increasing fiber
content up to 50% fiber, with sisal composites showing an
increase of about 139.6% and PALF composites only 18.4%
over the that of the matrix [30]. Surface treatments on sisal
showed improvement in tensile and flexural strengths
with 20 and 14% over the untreated fiber composites.
Thermal behavior of cashew nut shell liquid (CNSL)–
hemp and CNSL–kenaf fiber biocomposites have been stud-
ied by DSC [157]. One wide endothermic peak was observed
for the former (CNSL–hemp fiber composite), while with
the later (CNSL–kenaf fiber composite) exhibited one
endothermic peak and two exothermic peaks in their ther-
mal analysis curves. The wide endothermic peak observed
for both the composites was between 40 and 150 ◦ C in the
first run, indicating the presence of adsorbed water in the
composites. The first exothermic peak, which was small in
the case of kenaf fiber containing composite was at 174.7 ◦ C,
indicating incomplete resin curing, while the second at
275 ◦ C was associated with the fiber. The endothermic
peaks were observed for both the composites, with a flat
baseline in the second run, suggesting that the water was
completely removed. Both the composites were well cured.
On the other hand, in the same study [157], DMA results
of both hemp and kenaf–CNSL composites showed vary-
ing behavior. The hemp fiber composite, containing treated
fibers, showed higher storage modulus E compared to
that with untreated fibers, indicating higher dynamic stiff-
ness in the treated fiber containing composite. The hemp
fiber–CNSL composite containing treated long hemp fibers,
exhibited higher storage modulus (E ∼ 8.05 ± 0.08) over
that with long untreated hemp fibers (E ∼ 7.05 ± 0.08),
both decreasing with increasing temperature contrary
to the unsubstantiated earlier report in a study of jute
Fig. 14. (a) TGA and (b) DTG curves for starch, cellulose derivative, sisal
fiber–polyester composites by dynamic mechanical anal- fiber and their composites. Reproduced from [94] with the kind permis-
ysis [242]. sion of Elsevier Publishers.
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
Table 8
Results of DSC study of cellulose acetate (CA), cellulose derivative blend
with starch (CDS) and their composites with sisal fibers (adopted from
references [94–96]).
Sample Temperature at maximum decomposition
rate (K)
Starch 563–604
CA + starch blend 580–618
Blend + sisal fiber 583–587/625–629 (first peak)
635–665/635–660 (second peak)
processes depending on the temperature range, with mass
loss taking place at each step with associated activation
energy. The apparent activation energy of these decompo-
sition processes for both the peaks calculated by different
methods was found to be 105.8–108.3 kJ. mol−1 for the first
peaks and 175.4–182.3 kJ. mol−1 second peaks, irrespective
of the method used. These results were attributed to cleav-
age of linkages with similar bond energies. The observed
constancy of activation energies suggests that fiber incor-
poration does not change the decomposition mechanism.
With increasing fiber content, no change in the degra-
dation process was observed during the first step, while
higher temperature and activation energy in the first peak
and lower temperature and lower activation energy were
observed in the second peak. In addition, only one decom-
position peak at 365 ◦ C was observed for CA, while there
were two for sisal fibers, with the first at 300 ◦ C due to
hemicellulose and glucosidic link polymerization and the
second at 360 ◦ C due to thermal degradation of ␣-cellulose.
Also, a broad peak was observed at all temperatures due
to lignin decomposition. On the other hand, two decom-
position peaks were observed for the CDS blend, the first
at 314 ◦ C due to decomposition of starch and the second at
354 ◦ C due to decomposition of the blend itself. Also, partial
overlapping of the decomposition curves was observed for
both the blend and the fiber. The heating rate (5–25 ◦ C/min)
and temperature at maximum degradation rate shifted to
higher values with increasing heating rates for both the
matrix and its composites. This was attributed to heat
transfer between the sample and the instrument. However,
the fiber content did not show any effect on these in both
the decomposition peaks, as shown in Table 8 [94–96].
3.4.1. Biodegradability of various composites
Generally, the biodegradability of composites is deter-
mined by their weight loss in soil burial. Some of
the standards for the determination of biodegradability
reported include ASTM D6400-99, which includes D-
6002-96, D5338-98 and D6340-98; European standards
(CEN/TC 261/SC 4N 99 and ISO 14855); DIN-Standard
draft 54,900 and ISO/CD-standard 15986.2. In the standard
for burial test, the compostability of biodegradable poly-
meric materials is evaluated. According to these standards
[243], chemical examination and ultimate degradation of
polymer (mineralization) and disintegration under real
conditions in a composting plant or lab conditions are to be
followed. The procedure prescribes biological degradation
by aerobic living microorganisms in a liquid system. The
test sample is mixed with microbial activated soil, packed
in glass columns and incubated under continuous aeration.
1011
The degradation rate is calculated according to the organic
carbon in the sample. Measure of released CO2 indicates
the degradation rate.
Very limited studies are reported on this aspect. For
example, the behavior of biodegradable jute composite
with urethane pre-polymer with aliphatic chains for the
textile industry was evaluated for biodegradability by the
weight loss method in soil burial (ca. 3% water), clay with
22 and 33% water and only water [89]. Degradation of the
composite was observed in clay environment, but not in
soil or water environments. Simulated weathering condi-
tions by alternating sunshine and condensation showed
degradation of the composite. The tensile strength of Hes-
sian cloth (burlap) was found to be enhanced by coating
it with formulated solutions of an oligomer (50–60 w/w),
N-vinylpyrrolidone (24 and 48 w/w), 2-ethyl hexy acetate
(12–48 w/w), two plasticizers (12 w/w) and an initiator (2
w/w) followed by irradiation with ultraviolet light (UV).
This increase in strength depended on the number of treat-
ments given to the reinforcement.
Another study reported decrease in flexural strength
of hot-pressed composites of non-woven mats of sisal or
pineapple leaf fiber (PALF) with and without several chem-
ical treatments incorporated in films of polyester amide
(BAK 1095), when the composites were buried in soil for
60 days. The decrease with PALF composite was 48.8%
that of sisal composite, with weight loss of about 9.2%
and 8.2% for the PALF and sisal composites, respectively
[30].
3.5. Nanocomposites with nanometric fillers in
biodegradable matrices
Very limited studies have reported on the properties
of biodegradable nanocomposites containing lignocellu-
losic and other natural materials [70,71], book of references
[72,222,244–248]. It is to be noted that in a biodegrad-
able LC-nanocomposites the disperse phase formed by
the LC fibers should have one dimension in the order of
nanometers [244]. Rodriguez et al. [245] have reported sig-
nificant mechanical integrity at high temperatures (well
above Tg ) in PVA composites containing sisal fiber based
nano-whiskers (1–10 wt%, 250 nm long and 4 nm in diam-
eter) produced in film form. This indicates higher thermal
stability of the nano-biocomposite. Tg seemed to decrease
with increasing humidity (0–98%RH) due to the stabiliz-
ing effect of the whisker network, while the tan ı peak
decreased with increasing whisker content (1–10 wt%) and
increasing test temperature (−50 to +150 ◦ C). The storage
modulus E remained constant until room temperature,
then decreasing for temperatures up to 100 ◦ C for all the
composites.
High strength properties are reported in nanocompos-
ites of an acrylic matrix containing purified plant cell wall
fragments of Swede root [246]. Similarly, a compressed
nanosize modified plant structure of pine veneer–phenol
formaldehyde nanocomposite showed improved proper-
ties [247]. The modification of plant structure included
partial removal of lignin and hemicellulose in the pine
veneer, with a view to increase the volume fraction of
microfibrillar cellulose.
1012 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021

The effect of orientation of nanosized reinforcements
on properties is reported [222] in a solution cast cellulose
whiskers reinforced poly(vinyl alcohol) (PVA) nanocom-
posite. With the application of a magnetic field of 7 Tesla
to orient the whiskers while the water was evaporated
after the casting of the composite, an increased dynamic
modulus of about 2 GPa was observed in the orientation
direction over that in the transverse direction. Similarly,
significant increases in Young’s modulus (674.5 times) and
tensile strength (3.5 times) were obtained by increasing
reinforcement content from 0 to 30 wt% in a nanocom-
posite of nanocrystals of flax cellulose reinforcement in
water borne polyurethane [248]. Observed increases are
attributed to the uniform distribution of nanocrystals and
improved morphology showing separation of soft and hard
segments of matrix.
More studies on this topic may be worth pursuing con-
sidering the advantages nanocomposites would offer in
general. It is worth mentioning here that the concept of
nanocomposites for load bearing applications being new,
challenges will be high for the commercialization of nanos-
tructured reinforcements such as cellulose microfibrils due
to their disintegration while extracting them from plant
cell walls and in also in polymer matrices, while high cost
involved in the former [71].
4. Products/applications/market
Unlike many biopolymer products being developed
and marketed, very few biodegradable composites have
been developed, with most of their technologies still
in the research and development stages. This is despite
the fact that the environmentally friendly composites,
where biodegradability is important, provide designers
new alternatives to meet challenging requirements. These
include aquatic and terrestrial environments, municipal
solid waste management and compostable packaging,
while those for automobiles include for parcel shelves,
door panels, instrument panels, armrests, headrests and
seat shells. Accordingly, a wide range of biodegradable
products have been produced using LC fibers and biopoly-
mers for different applications, ranging from automotive
vehicles including trucks, construction (hurricane resis-
tant housing and structures, especially in the USA) and

Fig. 15. Biodegradable Composites. (a–c) Building components [251]; (d) furniture [251]; (e) beam of chicken–soybean oil resin based composite [48];
(f) beam of paper–soybean oil resin based composite [49]; (g) cosmetic packing [251]; (h) house wares [251]. Reproduced (a–d and g and h) from
http://www.teel-grt.com/construction.php [251] with kind permission from Brynna Smith of Teel Plastics, 1060 Teel Ct. Baraboo, WI 53913 and e–f with
kind permission from the Publishers [48,49].
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
insulation panels, to special textiles (geotextiles and non-
woven textiles) [249,250]. The hurricane resistant housing,
structures and a variety of products developed using soy
oil with lignocellulosic fibers could be the forerunner for
diverse range of applications for the biodegradable com-
posites. Other identified uses for these materials include
bathtubs, archery bows, golf clubs and boat hulls. Fig. 15
shows some of the biodegradable products made by vari-
ous researchers [48,49,251]. These include patented roofing
panels, considered as revolutionary for being maintenance-
free, and longer-lasting and better-looking lightweight
components, such as cosmetic packages, tableware and
furniture. With reported estimate of about 100,000 met-
ric tons per annum of lignocellulosic fibers by 2010
for composites in the European automotive sector alone
[31,40], the development of a variety of products partic-
ularly for indoor applications in automotive and building
industry sectors is anticipated. This is further underlined
with the estimated global market of about 900,000 met-
ric tones of wood plastics and natural fiber composites
as per Steven Van Kourteren, Consultant, Principia Part-
ners [8]. Hence the market for biodegradable composites
can be expected to grow in the future. This is based
on continued technical innovations, identification of new
applications, persistent political and environmental pres-
sures, and investments mostly by governments in new
methods for fiber harvesting and processing of natural
fibers [250,48,49,251].
5. Critical issues and suggestions
Since bioplastics are considered “marginal” structural
materials, the addition of lignocellulosic fibers to improve
their chemical, physical and mechanical properties, includ-
ing their durability, is seen as necessary. Even with the
limited experience so far, they are expected to be useful for
a wide range of applications in mass-produced consumer
products for short-time uses (e.g. packaging), as well as
for long-term indoor applications (e.g. furniture), leading
to an exciting and promising future for these new genera-
tions of composites [27,32,35]. One of the major hurdles for
commercialization of lignocellulosic fiber composites until
recently is reported to be non-recognition of research and
development in developing countries, where these fibers
are abundantly available. This has been overcome with
many of the industrialized countries particularly in Europe
taking the lead in this area in recent years [32]. But these
materials also pose challenges to material scientists par-
ticularly with the acceptance criteria for these composites
being their performance and cost, despite the renewabil-
ity and recyclability of the matrix and the reinforcements
used. Accordingly, some of the critical issues/developments
required and the hurdles to be overcome are mentioned
below.
5.1. Raw materials
5.1.1. Reinforcements
(a) One of the prominent barriers for the large-scale man-
ufacture of lignocellulosic-based composites has been
1013
their widely dispersed resources and variable proper-
ties. The possibility of producing quality fibers suitable
for different applications through better cultivation
including the use of genetic engineering and treatment
methods to produce uniform properties is one such
step. Another important aspect is quality assurance and
the development of optimized fibers for specific sec-
tors, such as the automotive sector [250]. Limitation to
fibers with minimum range of properties will continue
to be the real challenge.
(b) The selection of cost effective and suitable fibers for
particular applications is another critical area to be con-
sidered. This may require consideration of other less
used, but potential fibers, such as curaua, or the devel-
opment of other reinforcement sources, as recently
reported [71,252,253].
(c) Since synergism of properties is observed in biodegrad-
able polymer–lignocellulosic fiber composite, the
development of component-dependent and non-
dependent blending system is another area in need of
development.
(d) The development of an appropriate reinforcement is
essential to obtain optimum balance in mechanical
properties. This is particularly relevant in the fabri-
cation of hybrid biocomposites using lignocellulosic
fibers, either as fibers or in other forms, with a view
to manipulate the biodegradable composite properties.
For example, one must determine the type of fibers
for use as warp and weft using textile engineering
concepts. This may be approached by the use of an inter-
esting concept of “engineered natural fibers”, in which
the proper blend of bast and leaf fibers are reported
to provide the proper balance of stiffness–toughness in
the composites [28]. Also, for balanced bi-directional
properties, the ratio of warp to weft should be deter-
mined based on the type of fibers used. For example,
in jute–cotton fabric, 60/40 warp/weft gives better
properties, while 70/30 of the same is better in uni-
directional composites. [15].
5.1.2. Matrix
(a) Consistent properties of biodegradable composites
along with affordable cost, their stability during stor-
age and shipment and recyclability are all of primary
concern for their large scale use in many application
sectors. These call for future critical areas of devel-
opments of suitable inexpensive biopolymers (mostly
thermoplastics since lower priced synthetic plastics
constitute about 70% of thermoplastics consumed by
the plastics industry [45]) to use lower processing
temperature to avoid degradation and/or volatile emis-
sions, which may affect the final properties of the
composite.
(b) Similarly, the processing and design of new polymers
with mechanical properties and thermal stability much
improved than those reported so far and appropriate
barrier properties and heat resistance characteristics
will be another area for future development. The fail-
ure to improve these properties will limit applications
of their composites such as packaging and structural
1014 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
components. This may call for new pathways for pro-
ducing natural polymers even using nanotechnology to
make biodegradable plastics by matrix hybridization or
blending with suitable natural polymers.
5.2. Interface between the reinforcement and matrix
(a) As in the case of synthetic polymers based composites,
the possibility of very high filler/reinforcement loading
(perhaps above 60 wt%) should be achieved to reduce
the final cost of the product. This requires development
of improved compounding technology and new cou-
pling agents [45] as critical areas of future research. This
can have a tremendous impact in lowering the usage of
petroleum-based plastics as well beneficial effects in
terms of the environment and also in socio-economic
sectors.
(b) Of course, some of the limitations for the use of
lignocellulosic fibers in composites such as low process-
ing temperatures (<170 ◦ C) and moisture absorption
have to be seriously considered, while developing
applications for these composites, particularly in the
automotive, building, and appliance sectors, which
have in fact, dramatically increased in recent times
[31,32,39,40,45,60,62,72,171].
(c) Since it is difficult to completely eliminate moisture
absorption of the lignocellulosic fibers, it is necessary
to develop suitable low cost coating or encapsulation
methods to minimize moisture absorption by the fibers,
which normally results in fiber swelling, leading to the
dimensional instability. One method suggested to pre-
vent this effect is the acetylation of some of the hydroxyl
groups present in the fiber [9,20,27,35,45,71]. This may
decrease the rate and amount of water absorbed by the
composite and may provide good matrix–matrix bond-
ing, but also may increase the cost of the fiber.
(d) In addition to reducing the moisture absorption, the
surface modification of fibers may also increase tensile
properties. Even mechanical loading during chemical
modification of fibers has been found to improve the
tensile properties significantly due to the structural
changes (change in microfibrillar angle) produced by
the loading [254]. This could be another area for future
development to increase the strength properties of
biodegradable composites, keeping in mind the com-
position and structure of lignocellulosic fibers.
(e) It is well known that fiber related parameters such as
their dispersion and length, any fiber orientation and
the adhesion of fiber and matrix determine composite
properties, with short fibers. In aggregate, these provide
various reasons for the lower properties of compos-
ites compared to the potential of the reinforcing agents
[255]. In the case of lignocellulosic fiber–biopolymer
composites, though some of these can be overcome,
such as adhesion between the fibers and matrix and dis-
persion of fibers due to both of them being hydrophilic
and breakage being the least for cellulose fibers [45],
clumping (mostly with long fibers leading to either
fiber-rich or the matrix-rich regions) and agglomera-
tion of fibers may still have to be overcome. To minimize
these or to obtain improved fiber dispersion with-
out agglomeration, development and/or selection of
suitable surface modifiers or dispersion aids/coupling
agents for the fibers is another critical area for future
development.
5.3. Processing aspects
(a) The limitation of low processing temperatures suggests
the importance of appropriate processing technique as
another critical area of development. It is well known
that high processing temperatures, to reduce melt
viscosity and facilitate good mixing, cannot be used
(except for short periods) [45], and hence other routes
are needed to facilitate mixing of the fibers and matrix
to produce these composites.
(b) Further, to achieve efficient stress transfer from the
matrix to the fiber along while retaining the maximum
length of fiber, improvement of interaction and adhe-
sion between the fiber and matrix should be maximized
[256]. It is also known that the stress transfer effi-
ciency of the composite is dependent on the properties
of the interphase zone, which includes the physical or
chemical interactions between two different interfaces
[45]. The selection of a suitable processing technique to
take care of these parameters, including matrix attri-
tion (breaking down of the long chain polymers to
shorter chain lengths) thus becomes relevant despite
the availability of several types of batch and continu-
ous compounding equipment for blending of fibers and
matrices [257]. This underlines the process dependence
of the properties of lignocelluloic fiber based com-
posites, particularly with thermoplastics. For example,
it has been reported that the level of fiber attrition
depended on the screw configuration and the process-
ing temperature during the blending of wood fibers
with high density poly(ethylene) (HDPE) in a twin-
screw extruder [258].
5.4. Design and performance aspects
(a) The development of an appropriate design for a com-
posite, which is dictated by the application, with a
high degree of variability, must be considered. Similarly,
there is need for product standards to support product
performance.
(b) In addition to conceptual developments, exploring
manufacturing, short-term experimental and analysis
of characterization of innovative designs incorporating
lab-scale concepts and some-long term performance
and durability under indoor and outdoor environments
are all critical areas of development for increased appli-
cation of these special composites.
(c) More studies are required on product development
and performance evaluation, including the effect of
environmental aging on the relationship between the
damage caused in the thermal–mechanical–chemical
processes of biodegradable composites, including their
hybrids.
(d) The development of degradation models for natural
fibers similar to those developed for glass fibers [80]
is another critical area for future work.
 K.G. Satyanarayana et al. / Progress in Polymer Science 34 (2009) 982–1021
(e) Understanding the aging of these composites exposed
to different environments, such as hygrothermal ageing
and loading as well as prediction of effects on the life-
times of these composites through modeling as recently
done for glass fibers [259] are other areas of interest for
development to enhance possibility of their utilization
in structural applications.
(f) Despite increasing interest in research and devel-
opment of lignocellulosic fiber based composites as
seen from increasing publications, a greater challenge
lies in making them structurally and functionally sta-
ble during storage and use, but easily degradable
on disposal. This calls for paradigm shift in design
such as the ‘tricorner approach’ [71] in designing
such high performance biodegradable composites. This
approach involves crucial steps as mentioned earlier,
such as efficient and cost effective modification of both
the reinforcements and the matrix materials through
proper functionalizing and blending, followed by effi-
cient processing technique for a variety of product
development.
5.5. Other aspects
(a) Many obstacles in terms of low strength, production
costs, product quality and supplier–user relations may
have to improved to increase the use of biodegradable
composites, and hence their market. It is also worth-
while to point out that until such time that development
of high strength in these composites is achieved they
may be used for non-critical, but large volume applica-
tions where moderate strength is desirable.
(b) Continuous research and development in biodegrad-
able composites in terms of the various aspects
mentioned above should be carried out as has been
done in the case of non-biodegradable composites,
whose performance is improved along with increasing
their demand and utilization, resulting in their low cost
and hence enlarging the market [13].
(c) The application of nanoscience in biodegradable com-
posites may reduce product cost through more efficient
production, with the added advantages of producing
less waste and the use of less energy. But, one has to
be careful while using nano-filler materials, particularly
if their products are used in food packaging, since it
involves legal and ethical aspects in view of their effect
on human health and the environment. Hence, regula-
tions for their use are needed.
6. Concluding remarks
Research on biodegradable polymer composites con-
taining lignocellulosic fibers is generating increasing
attention due to the dwindling petroleum resources, low
cost of lignocellulosic reinforcements with a variety of
properties and increasing ecological considerations. Differ-
ent types of biopolymers, both natural and synthetic, are
available and their structure properties are well studied.
Processing techniques for biocomposites are well docu-
mented and many of their properties have been studied.
However, only very limited attempts have been made so
1015
far regarding processing and characterization of hybrid
biodegradable composites based on lignocellulosic fibers.
This needs to be rectified in view of the opportunities
they offer for new applications with value addition. In
general, the use of lignocellulosic fibers in biodegradable
composites can help to generate jobs in both rural and
urban areas, in addition to helping reduce waste, thus
contributing to a healthier environment. However, more
studies are required on product development and perfor-
mance evaluation, including the effect of environmental
aging on the relationship between the damage caused in
the thermo-mechanico-chemical processes of biodegrad-
able composites, including their hybrids. With projected
global annual growth rate of 10–15% in new materials based
on lignocellulosics, it has been reported that the use of
renewable materials particularly those based lignocellu-
losic fibers [43,56,57], and research and development on
biodegradable composites will lead to use of suitable local
materials with possible local manufacturing of products
through local technological capabilities meeting not only
local but global demand in line with the “trinity essence of
design philosophy” enunciated earlier [33,260].
Acknowledgements
The authors are grateful to all the publishers (e.g.
Elsevier Publishers, Macromolecules-American Chemical
Society Brynna Smith of Teel Plastics, Editors) and authors
who have permitted to use figures and tables from their
publications. Special thanks are due to Prof. Lawrence T.
Drzal, Distinguished Professor, Chemical Engineering &
Materials Science, College of Engineering, Michigan State
University, USA, for providing high quality figures and their
use in this paper. The authors would like to thank CNPq
and CAPES, for financial assistance during the period of
this work. G.G.C.A. thanks the PEC/PG of CAPES/CNPq–IEL
Nacional–Brasil for awarding a doctoral grant. They also
acknowledge Prof. Cyro Ketzer Saul, Department of Physics,
Federal University of Parana, Curitiba, Brasil for his help in
producing high quality figures used in this paper. One of the
authors (KGS) wishes to thank Anand Sanadi, Research Sci-
entist, University of Copenhagen, Frederiksberg (Denmark)
for his reading the manuscript and suggestions to improve
the manuscript.
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