Journal of Polymers and the Environment, Vol. 12, No.

2, April 2004 ( 2004)

An Overview on the Mechanical Behaviour of Biodegradable

Agricultural Films
D. Briassoulis1

The mechanical behavior of various types of biodegradable materials depends, mainly, on their
chemical composition and the application conditions. Various additives are added into the
bioblends to improve their properties, which sometimes even reach the levels of the conventional
plastics. It is well known that the environmental conditions during production, storage, and usage
of these materials inuence their mechanical properties. Ageing during the useful lifetime also
causes great losses in the elongation. In the present paper, the overall mechanical behavior
of biodegradable lms, which may be considered suitable for agricultural applications, but also of
partially biodegradable lms, is reviewed and analyzed. Selected critical mechanical properties
of lms before their exposure to biodegradation are investigated and compared against those of
conventional agricultural lms.
KEY WORDS: Biodegradable materials; agricultural lms; plastic lms; mechanical properties.

INTRODUCTION

biodegradable lms [e.g., starch with poly(ethyleneco-acrylic acid)] have been produced in the USDA laboratories [1] and elsewhere. Polylactone and poly(vinyl
alcohol) lms are readily degraded by soil microorganisms, whereas the addition of iron or calcium accelerates
the breakdown of polyethylene. Commercially available
biodegradable soil mulching lms have already been
produced. Innovative biodegradable starch-PCL (poly(caprolactone) based mulching lms and lms for low
tunnels are under development in the course of a current
European project.2 The performance of these lms compared to the performance of the conventional polyethylene lms in the eld under real cultivation conditions (in
several locations in Europe), as well as in the laboratory,
is currently under investigation. In another case, carbon
blacklled, biodegradable copolyester mulch lm and
commercial carbon blacklled, high-density polyethylene (HDPE) mulch lm were exposed for 12 weeks to
commercial vegetable crop growing conditions in the
United States, the positive results are reported in [3]. The
efcient and protable use of biodegradable lms aiming
at reducing pollution through practicing environmentally

Recently, there is an increasing interest in the use

of mulching and low tunnels for protected cultivation
[1]. The market of plastics used for these purposes in
Europe involves hundreds of thousands of hectares and
thousands of tons of plastic lms per year [2]. A large
portion of these is left on the eld or burnt uncontrollably by farmers, releasing harmful substances with
the associated obvious negative consequences to the
environment. The reasons for these environmentally
dangerous practices are the lack of cost-efcient systematic disposal techniques available to the growers
and the high labor cost for the proper collection of the
plastic lms following the end of the cultivation. Thus
use of biodegradable materials appears as a challenging,
attractive alternative for enhancing sustainable and environmental friendly agricultural activities in mulching
and low-tunnels cultivation.
Several types of biodegradable agricultural lms
such as starch with poly(vinyl alcohol) but also partially

Agricultural University of Athens, Department of Agricultural

Engineering, Iera Odos 75, 11855, Athens, Greece. E-mail:
briassou@aua.gr

Bioplastics: Biodegradable plastics for environmentally friendly

mulching and low tunnel cultivation, QLK5-CT-200000044.

65
1566-2543/04/0400-0065/0 2004 Plenum Publishing Corporation

66
friendly, sustainable agriculture, involves several crucial
technological questions. Among them, a dominant question concerns their mechanical behavior.
The adequacy of various formulations of biodegradable agricultural lms depends primarily on their mechanical behavior with regard to the specic applications
under consideration and, of course, on their biodegradability behavior. Developing biodegradable lms with an
optimum combination of desirable mechanical properties
and biodegradation performance represents a rather
challenging multidisciplinary problem. A literature
review on the mechanical behavior of various types of
biodegradable materials reveals that their mechanical
properties depend, in general, on their chemical composition [4,5]; the production, storage, and application
conditions [6,7], and ageing.
In the present paper, a rather focused literature review on the mechanical behavior of biodegradable and
partially biodegradable materials, with special emphasis
placed on lms, is presented. It should be made clear
that this review does not concern biodegradable materials in general but only the mechanical behavior of
biodegradable lms. Even though the relevant published
research work in this specic eld is limited, the information collected is considered to represent a valuable
basis for understanding the mechanical behavior experienced by the biodegradable agricultural lms made by
materials already available on under development and
the mechanical behavior experienced by more generic
biodegradable lms, which may be used for agricultural
applications under certain conditions and possible modifications. The mechanical behavior of agricultural
biodegradable lms currently in use, or new formulations under development, can be better evaluated if
the critical issues pertaining to the overall mechanical
behavior of biodegradable materials are understood.
In addition, to enrich the limited information available in
the literature, some selected critical mechanical properties of the experimental (starch-PCL) fully biodegradable
agricultural lms are presented and compared against
those of conventional agricultural lms. Only the mechanical behavior of original materials is considered
herein. Ageing, biodegradation, and storage effects are
not considered in this work.

BIODEGRADABLE MATERIALS
Categories of Biodegradable Materials
Between the nonbiodegradable petroleum-based
plastics and the renewable sourcebased biodegradable
bioplastics, the chemical industry is also thinking in

Briassoulis
terms of aliphatic/aromatic ratio by using chemical
process engineering to achieve petroleum-based
biodegradable plastics [8]. According to Narayan [9],
biodegradable plastic technologies can be classified
under three broad categories and several subcategories:
1. Aliphatic polyester based (petrochemical feedstock;
agricultural feedstock; microbial synthesis)
2. Natural polymer based (starch and starch derivatives
[starch esters]; cellulose and cellulose esters; proteins,
other polysaccharides, and amino acids)
3. Blends, alloys, and graft copolymers of natural polymers and polyesters.
Following the comprehensive review of [1],
biodegradable materials may be grouped as follows:
1. Natural biodegradable polymers or biopolymers: Polymers formed in nature during the growth
cycles of all organisms. Included are:
a. Polysaccharides: The most important polysaccharides of concern to material applications are cellulose
and starch. Increasing attention is being given recently to
more complex carbohydrate polymers produced by bacteria and fungi, such as xanthan, curdlan, pullulan, and
hyaluronic acid [1].
Starch: Starch is a well-known polymer, naturally produced by plants in the form of granules (mainly from
potatoes, corn, and rice). Starch granules vary from
plant to plant but are in general composed of a linear
polymer, amylose (in most cases up about 20 wt%
of the granule), and a branched polymer, amylopectin
[1,7,9].
Cellulose: Cellulose is another widely known polysaccharide produced by plants. The molecular chain of
cellulose is very long, consisting of one repeating unit
(cellobiose), and occurs naturally in a crystalline state
[1,1012].
Chitin and chitosan: Chitin is a macromolecule found
in the shells of crabs, lobsters, shrimp, and insects. It
consists of 2-acetamide-2-deoxy-b-D-glucose through
the b-(14)-glycoside linkage [1,1315].
Alginic acid: Many polysaccharides in solution upon
the introduction of counterions, form gels. Alginates
are able to form gels in the presence of divalent
cations [1,1618].
b. Polypeptides of natural origin: The proteins that
have found applications as materials are, for the most part,
neither soluble nor fusible without degradation, so they
are used in the form in which they are found in nature [1].
c. Bacterial polyesters: This category includes natural polyesters, which are produced from renewable
resources by a wide variety of bacteria as intracellular

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

reserve materials. Bacterial polyesters are thermoplastic
biopolymers. The basic polymer with R CH3, poly-bhydroxybutyrate (PHB) is highly crystalline [1,1926].
2. Polymers with hydrolysable backbones:
Polymers with hydrolysable backbones have been found
to be susceptible to biodegradation. Among them aliphatic
polyesters, polycaprolactone, polyamides, polyurethanes
and polyureas, polyanhydrides and poly(amide-enamine)s
[1]:
a. Polyesters: Polyesters derived from diacids of
medium sized monomers (C6C12) [e.g., poly(glycolic
acid)] are more readily degraded by fungi (Aspergillus
niger and Aspergillus avus), than those derived from
longer or shorter monomers [27]. The reason for that, as
well as for the fact that exible aliphatic polyesters are
degradable, whereas rigid aromatic polyesters are not, is
that biodegradability by enzyme catalysts requires that
the synthetic polymer chain t into the enzymes active
site [1,28,29]. Poly(glycolic acid) (PGA) is the simplest
linear, aliphatic polyester.
b. Polycaprolactone: Poly(e-caprolactone) (PCL)
[3033] is generally prepared from the ring-opening
polymerization of e-caprolactone. PCL is biodegradated
by fungi and can be degraded enzymatically [1,34].
c. Polyamides: The strong interchain interactions of
polyamides and so their higher crystallinity results in low
rate of biodegradation. Low-molecular-weight oligomers
may be degraded by enzymes and microorganisms
[1,3537].
d. Polyurethanes and polyureas: Polyurethanes have
the structural characteristics of polyesters and polyamides,
whereas polyureas might be viewed as poly(diamide)s
[1]. If the prepolymer is a polyester, then polyurethanes
are readily biodegradable, whereas polyether-based
polyurethanes are resistant to biodegradation [38].
e. Polyanhydrides: Polyanhydrides are a group of
polymers with two sites in the repeating unit susceptible
to hydrolysis [1]. These are ber-forming polymers that
are very susceptible to hydrolysis [39].
f. Poly(amide-enamine)s: Poly(amide-enamine)s
have been found to be susceptible to hydrolysis and
biodegradation, both by fungi and enzymes [40].
3. Polymers with carbon backbones: These polymers (e.g., vinyl polymers) require an oxidation process
for biodegradation because they are not susceptible to
hydrolysis in general. Most of the biodegradable vinyl
polymers contain an easily oxidizable functional group
and catalysts are added to promote their oxidation or
photooxidation, or both [1].
a. Poly(vinyl alcohol) and poly(vinyl acetate):
Poly(vinyl alcohol) (PVA) is the most readily biodegradable of vinyl polymers [1] (microbial degradation as well

67

as enzymatic degradation by secondary alcohol peroxidases isolated from soil bacteria of the Pseudomonas
strain) [41,42].
b. Polyacrylates: Poly(alkyl acrylate)s and polycyanoacrylates generally resist biodegradation [1].
Weight loss in soil-burial tests has been reported for
copolymers of ethylene and propylene with acrylic acid,
acrylonitrile, and acrylamide [43].

Biodegradable Films
Not all of the biodegradable materials are suitable
for production of biodegradable lms. Even though there
are rapid developments in the manufacturing and marketing areas of biodegradable materials, at least three
major commercially available biobased degradable polymers groups from which biodegradable lms may be
produced can be identied within the above main categories (apart from cellulose-based lms): starch-based
polymers, polyhydroxybutyrate (PHB) polymers, and
polylactides (PLA). In the category of nonbiobased
biodegradable polyesters from petrochemical feedstock,
commercial lms have been developed from biocopolyesters (e.g., Eastar) or from starch-PCL blends [9]. Of
course, other biodegradable materials have also been
used for lm production (e.g., blends of soy protein and
biodegradable polyesters, etc.) [9]. Intensive ongoing
research efforts around the world aim at the development
of laboratory samples of innovative degradable polymers
or the improvement of available materials, some of
which could be used as biodegradable agricultural lms.
The basic characteristics of the most important categories of biodegradable materials from which biodegradable lms are produced are briey presented below.

Polyhydroxybutyrate (PHB)
A major type of commercially available biobased
polymer consists of polyhydroxybutyrate (PHB) and
polyhydroxyvalerate (PHV) polymers, which were initially produced by fermenting a sugar feedstock (glucose
is currently being used) with a naturally occurring microorganism [1926]. One of the commercially available
products, for example, is technically a family of linear
polyesters of three hydroxybutyric and three hydroxyvaleric acids produced in nature from the fermentation of
sugars by the bacterium Alcaligenes eutrophus. This
biodegradable product is stable when stored in air and is
quite stable when stored even in humid conditions.
Degradation to carbon dioxide and water will occur only
when they expose the polymer to microorganisms found

68
naturally in soil, sewage, river bottoms, and other similar environments. The rate of degradation is dependent
on the material thickness and the amount of bacteria
present. The fact that this material decomposes more
rapidly without oxygen present is signicant because
oxygen is not present in modern landlls. This kind of
PHB based resins can be converted into various types
of plastic products, depending on the physical properties
of the resin used. Major products are likely to be plastic
lms and coatings.

Starch-Based Polymers
There are several degradable polymers groups made
from starch [1,7,9]. For example, a fully biodegradable
starch-based polymer is manufactured primarily from
corn or potato starch, along with smaller amounts of
food-grade additives (not intended for human consumption). This resin is suitable for manufacturing injectionmolded pieces, lms, and a starched-based loose-ll
packaging material. This kind of resin degrades in an
active biological environment like polyactides. Another
starch-based commercial resin contains performanceenhancing additives, such as synthetic linear polymers,
plasticizers, and compounds that trigger or accelerate
degradability. These kinds of materials are intended to be
mixed with synthetic polymers to create plastic products,
making the products more degradable than traditional
synthetic plastics (i.e., these materials may be only
partially biodegradable). A typical product would contain about 43% starch, 50% synthetic polymer, and 7%
proprietary ingredients. Many biodegradable starchbased thermoplastic blends have been developed and
studied extensively, such as starch/polycarpolactone,
starch/cellulose acetate, and starch/ethylene-vinyl alcohol copolymer [4447].

Polylactides (PLA)
These biodegradable polymers are made from lactic
acid produced via starch fermentation. PLA polymers are
generally derived by fermenting carbohydrate crops such
as corn, wheat, barley, cassava, and sugar cane [1,9]. The
process involves the fermentation of sugars to produce
lactic acid, which is converted to PLA through low-cost,
high-yield catalytic polymerization. PLA-based polymers
are completely degradable under compost conditions.
Although PLA is not water-soluble, microbes in marine
environments can degrade it into water and carbon
dioxide. PLA-based resins can be modied to adapt to
many applications, from disposable food-service items,

Briassoulis
sheet extrusion, or coatings for paper. PLA is
a hard material, similar in hardness to acrylic plastic with
a hardness on the Rockwell H Scale of more than 60.
Because of the hardness, the PLA fractures along the
edges, creating a product that cannot be used. To overcome these limitations, PLA must be compounded with
materials to adjust the hardness (e.g., such a commercial
product has a hardness of 20.6 on the Rockwell H Scale).

THE MECHANICAL BEHAVIOR OF

BIODEGRADABLE MATERIALS: A BRIEF
LITERATURE REVIEW
The mechanical behavior of various biodegradable
materials reported in the literature concerns a variety of
critical properties and parameters. The most important
factors inuencing the mechanical behavior of biodegradable or partially biodegradable materials, are presented
herein, with the aim of underlining the critical issues with
respect to the evaluation of the mechanical properties of
these materials.

Polyhydroxybutyrate (PHB)
One of the main groups of biodegradable materials
studied with regard to their mechanical behavior is
the group of the bacterial thermoplastic polyesters poly(3hydroxyalkanoate), known as PHAs, produced by the
fermentation of renewable materials (e.g., sugars and molasses) [48]. The pure homopolymer PHB, produced in
large quantities, is a brittle material (elongation at break
br 10%, impact strength 3 kJ/mm2) with a large elastic modulus (E 1.7 GPa) and high fracture stress (u
35 MPa). The pure copolymer PHB/V is also brittle (br
15%, E 1.2 GPa, u 25 MPa). It should be noted
that a polymer is designated as brittle if br 20% [48].
Being brittle, PHB and PHB/V are not suitable for technological applications such as lms, etc. The brittleness
of PHB is attributed to [48]: (1) the secondary crystallization of the amorphous phase during storage time at
room temperature leading to rapid decrease of elongation
at break. As a result of secondary crystallization in the
amorphous region, density, crystallinity, stress and Emodulus increase while the material becomes brittle and
hard with much lower elongation at break; (2) the glass
temperature (Tg) being close to room temperature; (3) the
low nucleation density, which results in the development
of large spherulites exhibiting interspherulitic cracks.
Efforts to improve the poor mechanical behavior of
PHB and PHB/V by mixing them with other polymers
had limited success because of problems of chemical

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

incompatibility (i.e., poor mixture). In an effort to produce biodegradable blends with improved mechanical
properties, aiming at desirable values such as fracture
stress of 1827 MPa, elongation at break 400%660%,
improved impact strength, and long-time stability (comparable to those of PE), PHB and PHB/V (possibly also
including some other polymers; e.g., 4%20% wt PVAc)
are mixed with various additives, all of which are
biodegradable materials. The mechanical properties of
the PHB/V copolymer can also be tailored by varying the
HV content to produce different grades with exibilities
and tensile strengths comparable to those of polyethylene
and polypropylene [49]. Possible modications of PHB
and PHB/V to improve their mechanical properties
include the addition of the following [48]:
Nucleating agents: Nucleation agents and crystallization conditions inuence the average size of the
spherulites [48]. In the case of PHB, large spherulites
are developed with cracks and splitting around the
center, which are responsible for the poor mechanical
behavior of the material [48]. In the case of blends
produced by the addition of nucleating agents (small
crystalline particles; e.g., 0.5% wt saccharin), numerous small, ne imperfect, spherulites are developed
while the crystallization rate is increased. Note that
during fast cooling from the melt, the degree of
crystallinity is lower and small crystallines are formed
[48]. Concerning the impact strength, impact depends
on the number and size of the crystalline structures
and the degree of crystallinity (samples with high
crystallinity 40% are brittle, and samples with 30%
crystallinity are ductile; note: crystallinity of PHB
is 60%, PHB/V is 45%). For the same crystallinity,
material with big spherulites is more brittle than
material with ne spherulites.
Plasticisers: High elongation at break and high degree
of exibility require that glass temperature must be
lower than testing temperature. In general, elongation
and impact strength depend on glass temperature
and morphology [48]. By adding plasticisers (e.g.,
9.5% wt glycerol, 7.5% wt triacetin, 5.5% wt tributyrin [48]), the rigidity of PHB and the fracture stress
are reduced (E 743250 MPa; u 1826 MPa)
as a result of enhanced molecular motion and lower
glass temperature, while the elongation and the impact
resistance are increased (br 150660%, impact
strength above 20 kJ/mm2) [48]. The plasticisers may
also affect the adhesion at the ller/matrix interface
[49].
Lubricant in processing: Addition of lubricant in
processing (e.g., 2% wt glycerolmonostearate, 2% wt

69

glyceroltristearate) results in reduced degradation of

chains and so decrease in molecular weight and melt
viscosity [48].
Apart from using additives, it has also been reported
that feeding the bacteria with a variety of carbon sources
led to the production of different copolymers, and a material was obtained with better mechanical properties
than PHB [1,2426].
Another class of PHB-based biodegradable materials can be designed by blending the basic biodegradable
material with other biodegradable (or environmental
benign) polymers, llers and plasticizers, for specic applications (e.g., blends with cellulose esters, starch, and
polylactic acid). Thus the inclusion of granular starch
(25%) and CaCo3 (10%) in the PHBV matrix (8% HV,
5% plasticiser) results in a drop of the tensile strength to
16 MPa, an increase of the exural modulus to 2.0 GPa,
and a signicant reduction in the cost [49]. In such a
case, PHBV composites with cornstarch [50] had poor
mechanical behavior as a result of poor adhesion
between the starch granules and the PHBV matrix (e.g.,
u 10 MPa). The large-size spherical starch granules
(15 m) are responsible for development of stress
concentrations and crack growth [50]. Using PEO (polyethylene oxide; molecular weight 20000; partially compatible with PHBV; note that pure PEO is softer and
more exible than pure PHBV) as the interfacial layer
resulted in improved adhesion of the starch to the PEO
(probably by hydrogen bonding) and/or resistance to
crack growth, with a signicant improvement in the mechanical properties of the composite. In fact, a signicant
improvement was obtained in the mechanical properties
of the composite (50/50 blend of PEO-coated starch and
PHBV:tensile strength 19 MPa, elongation at break
23%) [50]. No effect on the crystallinity of PHBV was
detected by the addition of PEO [50]. However, questions arise on the lower degree of biodegradability of the
so-produced material.
The effect of blending starch on the physical
properties of PHB was studied in the work of [51], by
adopting a lm casting from a common solvent approach. The blend lms had a single glass transition
temperature for all proportions of PHB-starch, and they
all were found to be crystalline. The tensile strength of
the blend lm with the ratio of 0.7:0.3 PHB/starch
was maximum (31.45 MPa) compared to virgin PHB
(18.29 MPa). In another case of blending with starch,
poly(butylene succinate adipate) (PBSA), an aliphatic
thermoplastic biodegradable polyester available commercially, however, of high cost, was blended with granular corn starch [52]. Pure PBSA lm has been studied

70
for various applications, including agricultural film
applications. It was shown that the PBSA/starch
biodegradable system (up to a starch content of 30%) has
mechanical properties useful for blown lm applications.
Both elongation at break and tensile strength were shown
to decrease with increasing starch content (from 780% to
500% and from 32 MPa to 20 MPa, respectively).
Very-high-strength lms may be developed by uniaxial orientation. Thus uniaxially oriented lms with high
mechanical properties were processed from ultra-highmolecular-weight poly(R)-3-hydroxybutyrate (P(3HB))
by two-step drawing procedure [53]. Maximum growth
rate of spherulites was observed in one-step hot-drawn
lms along with orientation of molecular chains and a
nger-joint structure of lamellar crystals with tensile
strength up to 277 MPa and elongation at break 84%.
The tensile strength of two-step drawing process reached
400 MPa and remained unchanged for 2 months as a result of planar zigzag conformation and a highly ordered
structure with nger-joint structure of lamellar crystals,
avoiding in this way secondary crystallization [53].

Starch-Based Polymers
The main motivations for developing starch-based
polymers include several advantages [54]: exibility in
adjusting the material properties to the needs of the
particular application by modifying appropriately the composition, low-cost blending process as opposed to innovative synthetic material development, and biodegradability.

Starch
As far as starch is concerned, starch granules are
hydrophilic and so the water content of starch changes
with relative humidity changes [55] (e.g., corn starch
contains 6% moisture at 0% RH and 20% moisture at
80% RH). Starch contains crystalline areas within the
branched amylopectin component (and so retains its
structure when immersed in water), whereas the linear
amylose is mostly amorphous. Granules are ruptured
(gelatinized) in water at 130C and at lower temperatures
in alkaline solutions. In general, granular starch may be
used in two ways in biodegradable plastics. (1) It may be
compounded into plastics in the form of biodegradable
ller [55]. Gelatinized starch may also be used as small
size ller in plastics (if dried during processing). (2) It
may be plasticized with water (5%20%) [55] and compatibilized with other polymers to become part of
the plastic matrix. The extruded starch remains in the
amorphous state when stored at room temperatures and

Briassoulis
humidities up to 80% (Tg is at or above room temperature room at 15%25% water content and is lowered by
moisture absorption). At 15% water content, extruded
starch has poor mechanical properties, not adequate for
lm applications (initial tensile strength 2030 MPa and
elongation at break 10%15%). These properties are
very much affected by changes in the relative humidity
and so by the corresponding changes in Tg [55]. It has
been shown that the fracture mechanism of starch extrudes turns from brittle to plastic for water content
above 15% [56]. Ageing of extruded starch at constant
temperature and moisture (only in a few hours at 20%
moisture levels) leads to further reduction of elongation
at break. Mechanical properties, moisture resistance, and
temperature stability of starch granules can be improved
in several ways [55]: by increasing the crystallinity to
improve mechanical properties, reduce ageing effects
and water sensitivity; by adding nonvolatile plasticizers
to get a more exible product and lower Tg below room
temperature, so that ageing is eliminated; by blending
with other polymers (e.g., blending gelatinized starch
with poly(ethylene-co-acrylic acid) copolymer (EAA) to
improve all properties. However, it should be taken into
account that EAA is non biodegradable
Especially concerning lms made of starch only,
they have high tensile strength, but they are brittle and
exhibit almost no elongation [50]. It has been suggested
that lms containing starch as a biodegradable component should meet the following minimum target values:
tensile strength 27.6 MPa, elongation at break 100%, tear
strength 78N/mm, impact resistance 4.2 kJ/m2[57].
Usually only the tensile strength value is met.
Among other techniques, modied starch has been
used to improve the mechanical properties of starch.
Acetylation of starch, for example, is a well-known
reaction leading to starch with a high content (70%) of
linear amylose [58] and is a relatively easy derivative to
synthesize [59]. The resulting high-amylose starch acetate is considerably more hydrophobic than starch, has
been shown to have better retention of tensile properties
in aqueous environments, has improved solubility compared to starch, and is easily cast into lms from simple
solvents. High-amylose starch also exists naturally.
Thus, for example, in some varieties of peas, amylose up
to 50% was measured, out of which a part was found to
be complexed by native lipids [60]. In another work, in
eld peas, starch content was shown to have reached the
maximum (44% in DM) 26 days after owering, with
45% amylose in total starch [61]. In garden peas, 25 days
after owering, starch content had only reached half of
its maximum (32% in DM), with an extremely high amylose proportion (88%). Differences have also been found

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

in the morphology of the spherulites [62]; spherulites are
easily formed in mung bean and potato starch, whereas
ordinary maize starch yields less numerous, not well developed coarse spherulites. Acid-modied maize starch
yields a large number of very round spherulites, whereas
wheat and tapioca starches form very poorly developed
spherulites. No spherulitic morphology was observed in
oat, rice, sorghum, amaranth, and yellow pea starches.
Starch crystallinity has been investigated extensively. Crystallinity of amylose and amylopectin thin
lms with 0, 10%, and 30% of glycerol and stored at RH
0, 54%, and 91%, prepared of water cast dilute solutions,
was studied in [63]. Each fresh amylose lm showed Btype crystalline structures, and depending on the glycerol
and water contents, the amount of crystallinity varied
from 6% to 32%, whereas the fresh amylopectin lms
were completely amorphous. The crystal formation in
the highly plasticized amylopectin lm was suggested to
be due to its rubbery state under the storage conditions.
Amylose lms were stable in water, unlike amylopectin
lms, which dispersed quickly in water. About 35% of
the amylose lms were resistant to -amylase, whereas
amylopectin films were hydrolyzed wholly. It was
concluded that even if part of the amylose lms were
amorphous, these amorphous regions were more resistant to hydrolysis than the amorphous amylopectin
structures.
Cross-linking has been related to crystallinity and
the mechanical properties of starch lms. Thus, for example, mechanical tensile properties, water vapor transmission rate (WVTR), and oxygen permeability coefcients of cast high amylose starch lms were determined
as a function of cross-linking degree and percentage of
free humidity [64]. The effect of using increased amounts
of cross-linking agents, was an increased cross-linking
degree that tends to reduce the degree of crystallinity,
thus modulating mechanical properties, water vapor permeability, and oxygen permeability coefcients. Maximal
values of yield strength, tensile strength at break, and
WVTR versus cross-linking degree were reached for
moderate cross-linking degree. Optimal crystalline/
amorphous ratio in the lms may induce interactions
and balanced effects, which would be responsible for
the nonlinear behavior of some of the investigated properties [64]. By cross-linking with epichlorohydrin in
the range of 110 g cross-linker/100 g polymer, the
mechanical properties of the lms were found to be
still related to water content while water vapor permeability remains high compared to that of some synthetic
polymeric materials.
Natural ber reinforcement also has been used to
improve the mechanical behavior of starch lms. In such

71

a case, native corn starch and hydroxypropylated starch

(HPS) based plastic lms were prepared using the short
pulp ber as the reinforcement and the glycerol as the
elasticizer [65]. The crystallinity of lms increased with
pulp content, but decreased with glycerol content and degree of substitution by hydroxypropylation. The results
of tensile test showed that the strain and stress at break
and elastic modulus increased with pulp content [66].
With glycerol content, the strain at break increased considerably, but the breaking stress and elastic modulus
decreased. The brittleness problem of the lms was overcome by the pulp, glycerol, and water content. The hydroxypropyl starch lms showed results similar to those
of the native starch lms. The exibility of the lms was
found to be improved by the hydroxypropylation.
Aimed at meeting the needs of specic applications,
multilayer starch-polyesters lms have also been developed. Multilayer lms based on plasticized wheat starch
(PWS) and various biodegradable aliphatic polyesters
have been prepared through at lm coextrusion and
compression molding [67]. Poly(lactic acid) (PLA), polyesteramide (PEA), poly(epsilon-caprolactone) (PCL),
poly(butylene succinate adipate) (PBSA), and poly(hydroxybutyrate-co-valerate) (PHBV) were chosen as the
outer layers of the stratied polyester/PWS/polyester
lm structure. The multilayer lms may be suitable for
applications in food packaging or disposable articles.
To improve the overall mechanical performance of
starch-based lms, intensive research work has also been
devoted to developing starch blends with synthetic readily biodegradable polymers such as PVA (poly(vinyl
alcohol) [57]. Starch blends with nonbiodegradable polymers such as EAA (poly (ethylene-co-acrylic acid) or
LDPE have also been developed and studied extensively.
However, polyethylene/starch blends or any other blends
of starch with nonbiodegradable polymers are not
considered to be biodegradable materials but possibly
only partially biodegradable (synergism of biological
degradation of starch component (when above 30%) and
chemistry of ageing; the question on possible successive
biodegradation of PE, over a long time, remains a controversial issue [1,54,68]). Therefore these blends may not
be considered (or labeled) as biodegradable or used as
such in agricultural lm applications but may be considered only as biodisintegradable. The analysis of their mechanical behavior is, however, of more general interest,
applicable as a reference in several aspects to other really
biodegradable starch-based polymers, and it is therefore
included in the present literature review. This is combined
with the fact that the relevant information in the technical
literature on the mechanical behavior of starched-based,
fully biodegradable polymers is rather limited.

72
EAA, PVA/Starch Blends (EAA/Starch Blends: Possibly
Only Partially Biodegradable)
Hydrophobic synthetic polymers are incompatible
with starch [55]. Increasing starch component in starchEAA lms results in decrease of elongation at break
(from 260% at 10% starch to 92% at 40%) without any
major change in tensile strength. In particular, addition
of EAA was shown to increase viscosity of starch solutions by complexing with more than one starch molecule.
As a result, starch-EAA mixtures containing 40% starch
could be processed to produce good-quality (not fully
biodegradable though) lms by extrusion blowing [57].
Replacement of EAA with LDPE (also nonbiodegradable) for reducing cost, results in decrease of both
elongation at break and tensile strength. Thus, at 40%
starch, there is a decrease in the elongation at break from
92% (starch blends with no PE) to 34% (starch blends
with ratios per hundred: 20 EAA:40 PE) and in tensile
strength from 26.7 MPa to 20.1 MPa, respectively.
Replacing part of EAA by PVA results in increase of
tensile strength and decrease of elongation at break [55].
EAA forms a helical inclusion complex with starch, but
also it can form complexes with PVA; thus a single
EAA molecule could be used to bind together starch and
PVA in a starch-EAA-PVA complex.
In the work of Lawton and Fanta [57], glycerol was
used as plastcizer. An increase in the glycerol content,
used as plastcizer, was shown to result in a decrease of the
tensile strength [57], as happens with plasticizers used
with synthetic polymers in general, whereas no signicant
effect from PVA or EAA was detected on tensile strength
in this case. On the contrary, elongation at break was
shown to increase with glycerol, EAA, and PVA content
(i.e., with less starch content). A three-way interaction between the three variables was established. In particular, it
was shown that the addition of small amounts of EAA
improves elongation of cast lms containing starch, glycerol, and PVA (too much EAA leads to brittle lms
because of complexes with starch, too little EAA leads to
phase separation between PVA and starch) [57].
Concerning glycerol plasticized lms prepared from
starch-PVA mixtures with starch over 50%, it was found
that a mixture of 55.6% starch, 2.8% EAA, 28.3% PVA,
and 13.3% glycerol produced lms with elongation at
break at least 100% and tensile strength of 25 MPa [57].
In another case, starch-PVA lms (with a small
amount of EAA added to the lm formulation; 41%
starch, 41% PVA, 3% EAA, and 15% glycerol on a dry
basis) were investigated after storage in different temperatures for 7 days [7]. It was observed that elongation
increases as %RH increases. This effect is attributed to

Briassoulis
the fact that starch is hygroscopic so the lm will gain or
lose water to be in equilibrium with the air. In addition,
because water acts as plasticizer, changing the water
content in the lm will change the properties of the
lms. In general, increasing plasticizer levels increases
the value of elongation. Of course, lms with good
properties should not change with humidity.
On the other hand, tensile stress of the same
starch/PVA cast lms appears to decrease with the increase of the relative humidity, which is consistent for
polymers containing increasing amounts of plasticizers.
For tear resistance, the behavior of this particular material was different [7]. Tear resistance was decreased at
low and high relative humidity. High RH means lower
strength in general as a result of the effect of the water
acting as plasticizer. Films stored at 51% and 76% did not
tear at all, because they were above their Tg. For low RH,
materials in the lm are below their Tg and so the lms
do not have much motion in their chains to absorb the
stress of being torn [7]. As far as the starch type is concerned, it was shown that all lms except for those containing high-amylose cornstarch, experienced a decrease
in elongation at break with ageing in 168 days; however,
the elongation at break did not drop below 100%. Films
made from waxy corn starch had lower impact strength
and experienced the greatest loss in elongation at break
with ageing (from 144% in 7 days to 34% in 168 days)
and a decrease in tensile strength with ageing. Films
made of high-amylose corn starch had the most consistent properties over the entire range of test condition [7].
The effect of the starch ratio on PVA/starch blends
was studied [69]. In particular, Poly(vinyl alcohol)
(PVA) starch (ST) blends (1/1, 1/3, and 1/5) were
prepared by gelation/crystallization from semidilute
solutions in dimethyl sulfoxide (Me2SO) and water mixtures and elongated up to eight times. The elongation up
to eight times could be done for the 1/1 blend, but any
elongation was impossible for blends whose ST content
was beyond 50%. To avoid phenomena of solubility for
blends whose the ST content was beyond 50%, crosslinking of PVA chains was carried out by formalization
under formaldehyde vapor. For the 1/1 blend, the amount
of ST dissolved in water at 23C was less than 3% for the
undrawn state and 25% for the drawn lm. The Youngs
modulus of the drawn lms with a draw ratio of eight
times was 2 GPa at 20C.
LDPE/Starch Blends (Possibly Only Partially
Biodegradable)
The mechanical properties of LDPE/granular starch
composites [4] have been extensively investigated as

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

functions of the starch volume fraction , granular size,
and presence of compatibilizers. A strong negative
dependence on of elongation at break ( 1/3) and
tensile strength ( ~ 2/3) has been conrmed. In fact,
several models have been presented for determining
the composite mechanical properties, taking also into
account the particle size distribution etc [56]. The elastic
modulus, on the other hand, increases with because of
the stiffening effect of the granule (note: several models
have been proposed for describing the composite modulus of a material with two crystalline and two amorphous
microphases [56]. It has also been reported [4] that the
reduction in tensile strength and elongation at break increases with the granule size. Starch granule size varies
from source to source (e.g., average diameters [4]: rice:
3 m, potato: 35 m, corn 10 m). As a result of the
starch volume fraction effect, most of the LDPE/starch
blends have shown lower tensile strength and percentage
elongation compared to LDPE [70]. It appears that in
binary LDPE/starch blends, the binding of starch granules to the LDPE matrix is not so strong because of the
relatively smooth surface of starch particles resulting in
premature fracture [70].
It has been established that during straining the
amorphous phase is rst deformed, followed by a high
orientation of both phases and the activation of crystallographic mechanisms [56]. Yielding of LDPE starts
from the activation of skeletal bonds motions, occurring
at temperature much lower that the one of the testing
conditions [56]. The fracture energy of LDPE/starch
blends is due to crack development, debonding of the
particles-matrix interface, yielding of LDPE bridges
and so the formation of microlaments during the elastic
deformation of LDPE. For LDPE/starch blends with
starch content less than 20%, it is the LDPE matrix that
dominates the plastic deformation because of small
number of starch particles resulting in fewer crazes [56].
However, even in such cases, in the zones near starch
particles, stress concentrations appear as a result of mist of the two phases. Concerning debonding phenomena,
it has been conrmed that when a particulate-lled polymer is subjected to stress, debonding between the ller
particles and the matrix occurs when the stress exceeds a
critical value [49], and so adhesion between the two
phases is lost. Then, as the matrix remains the sole loadbearing phase, the effective cross section is reduced and
so the tensile strength is reduced. The ller decreases the
elongation at break because the polymer matrix elongation is much greater than the macroscopic elongation of
the composite [49]. In some cases, rigid llers increase
the elongation at break by acting as inhibitors for crack
growth [4].

73

For a given composition of LDPE/starch blend, the

mechanical behavior was shown to depend also on the
conditioning of the sample over certain relative humidities. As the water content increases, under specic
relative humidity conditioning, the tensile strength and
the modulus of elasticity of a given composition of
LDPE/starch blend decrease signicantly, while the
elongation at break increases dramatically. This plasticization of LDPE/starch blends may be due to penetration of water and lling of the voids [56], with the water
acting as elasticizer. Tensile stress appears to decrease
with the increase of the relative humidity, which is
consistent for polymers containing increasing amounts of
plasticizers [7]. However, a case has been reported in
which no signicant effect from RH on the mechanical
properties of LDPE/granular starch composites was
observed [4].
It has been observed that starch/polyolen blends,
being incompatible, result in larger phase domains
which, in turn give rise to larger nondegradable residues
and subsequently to secondary pollution and to diminished mechanical properties of the blends [70]. To cope
with this problem, various techniques have been introduced to ensure homogeneity in blends at microscopic
level and reduce the interfacial tension and so improve
or retain the characteristics of the blend components.
One approach consists of the development of
starch/PE blends by using EAA as a compatibilizer (e.g.,
composite lms have been developed using starch and
copolymer of ethylene and EAA). The addition of a
compatibilizer (e.g., EAA) in LDPE/granular starch
composites does not signicantly affect the elongation or
tensile strength, but signicantly increases the composite
tensile modulus because of the improved adhesion
between the starch and the matrix [4]. In another case,
however, it has been suggested that adhesion has greater
effect on the tensile strength than granules size [4]. In
fact, dry starch/PE lms are brittle and tear easily [6].
A weak tear resistance of PE/starch composites was attributed to bad dispersion of two phases (starch/PE) with
different viscosity. It has been shown [6] that the EAA
level improves mainly tear resistance (the improved tear
resistance still remains low though). Susceptibility of
starch-EAA-PE lms to tear propagation, because of
line-wise propagation without any branching, renders
these lms inadequate for many applications (tear resistance 4 N/mm at 40% starch content).
Another proposed approach consists of the modication of starch by grafting of various monomers onto
starch (e.g., acrylamide, acrylonitrile, etc.), thus obtaining small domain size in blends [70]. In that way, a
variety of starch esters such as starch acetate and some

74
fatty acid esters have been used for biodegradable
blends. In a specic case, partially biodegradable blends
of LDPE and esteried starch were developed (starch
phthalate, stath, a hydrophobic derivative obtained by
phthalation of starch). It was observed that most of the
blends had lower tensile strength and elongation at break
than LDPE (9.92 MPa and 92.5%, respectively) and that
the tensile strength and elongation at break increased,
while the modulus decreased as the starch was substituted by stath [70]. Morphology of binary LDPE/stath
blends showed improved adhesion, leading to enhanced
mechanical properties compared to LDPE/starch blends
[70]. The roughness of the stath particles brings about
increased adhesion as a result of the improved state of interface, so that fracture occurs only after much higher
elongation has taken place. LDPE/starch blends have
shown higher modulus than pure LDPE and binary
blends of LDPE/stath [70], attributed to the decreased
hydrogen bonding in stath as a result of substitution,
despite the fact that stath is more crystalline than
starch. The increasing modulus with increasing incorporation of starch in LDPE can be explained by the
crystallinity, hydrogen bonding, and stiffening effect of
the starch granules [1] (the estimation of the modulus
of granular starch of 15 GPa in [70], is considerably
greater than most unlled synthetic polymers of commercial importance, but signicantly lower than the
modulus of cellulose; it is also greater than another
reported value of 2.7 GPa for starch). Hydrogen bonding
dominates over crystallinity in these LDPE/starch
blends [70]. Concerning impact resistance, all blends
containing stath had higher impact resistance than
binary LDPE/starch blends, suggesting smaller particle
size in stath blends, but lower impact resistance than
LDPE.
In some cases, blends of LDPE/starch/PCL have
been developed. Thus, low-density polyethylene/plasticized starch/polycaprolactone blends were processed by
conventional extrusion, injection molding, and film
blowing techniques in the work of [71]. The ne dispersion of polycaprolactone phase in the polyethylene/starch
matrix of lms resulted in mechanical property increase,
whereas in injection specimens there was property
decrease as a result of phase coalescence. In another
work [72], a ner starch phase dispersion was achieved
in injection-molded products than in lms, probably because of the development of higher shear rates at injection molding. Starch incorporation in polycaprolactone
resulted in a material with decreased strength and elongation at, both yield and break, whereas the modulus increased. At high starch content, particle coalescence was
associated with a further mechanical property decrease.

Briassoulis
Modied PE/Starch Blends (Possibly Partially
Biodegradable)
Graft copolymerization of thermoplastic polymers
onto starch provides another method for preparing
starchpolymer composites [1]. Graft copolymerization
allows starch and synthetic polymers to be held together
by chemical bonding rather than as simple physical
mixtures. As a result, separation of the two polymer
phases is less likely to occur. Among several starch
graft copolymers of special interest proved to be the
starch- g-poly(methyl acrylate) (S-g-PMA). In particular,
S-g-PMA copolymers having grafted side chains with
molecular weights of less than 500,000 can be easily extruded into a lm that shows excellent initial tensile
strengths and elongations. This material may have an
application as a fully biodegradable plastic mulch [1].
Reactive blending represents another economical
and commercially viable approach in which graft or
block copolymers are formed in situ during the blend
preparation by using polymers containing reactive functional groups [1]. Reactive blending is known to improve
the compatibility and interfacial adhesion of two immiscible polymers. According to this method, synthetic polymers having functional groups such as carboxylic acid,
anhydride, epoxy urethane, or oxazoline, can react with
hydroxyl or carboxyl groups (in modied starch) to form
a blend with stable morphology. In such an application
[1] starch was used with oxidized polyethylene, and
LDPE to produce lms. The addition of high-molecularweight oxidized PE (OPE) in ratios OPE/starch 0.30.5
improved the tensile strength and elongation as a result
of hydrogen bonding between carboxyl groups in OPE
and hydroxyl groups on the starch surface. Once again, it
was reported that as the percentage of starch in the blend
is increased, the tensile strength and the percentage elongation decrease. In an alternative approach starch is
blended with polymers containing polar functional
groups that can interact with starch. In that way, blends
of starch and copolymers of an olen and, optionally, a
poly(mono)olen or poly(mixed)olen were developed
that were then injection molded or lm blown into
commercial articles [1]. Nevertheless, it was again conrmed that an increase in the starch percentage adversely
affected the physical properties of the blends.
In some cases, it was shown that the anhydride
compounds improve the properties of composites made
from cellulosic llers. However, analogous results for
reactive blending of starch with anhydride functional
polymers are limited [1]. Thus, for example, it has been
shown that maleated high-density polyethylene (HDPE)
improved the tensile strength of composites containing

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

wood our with increasing concentration of ller. Blends
of corn starch (50%80% wt) and synthetic polymers
containing anhydride groups (styrene maleic anhydride
copolymer [EPMA], and the corresponding nonfunctional polystyrene and ethylene propylene copolymers)
have been investigated. Blends containing EPMA absorbed less water than SMA blends containing the same
weight fraction of starch. The tensile strengths of blends
containing functional groups were superior compared to
the blends made from nonfunctional polymers. When the
starch contents increased from 60% to 70%, the tensile
strength remained unchanged for the SMA blend but
increased for the EPMA blend. All samples supported
the growth of microorganisms, which increased with
increasing starch content.
Starch-Based Blends for Films (Possibly Partially
Biodegradable)
In cases of partially biodegradable lms for food
packaging applications [56], made from LDPE, wheat
starch, and soluble starch, it was shown that the presence
of starch at contents higher than 30% had an adverse
effect on the mechanical properties of the blends (lower
tensile strength and modulus; note that the modulus of
wheat starch is rather low, 40.3 MPa). In another case,
mechanical properties such as tensile strength and
elongation at break of composites made from sago starch
(SS) and LLDPE were shown to decrease with increasing starch content, whereas the modulus increased [73].
The incorporation of sago starch into LLDPE led to an
increase in the modulus of the composites because the
starch granules are stiffer than the LLDPE matrix in
which they are dispersed. On the other hand, the yield
stress can be increased by the addition of llers and
reduced by the addition of plasticizers. The increase in
yield strength with increase in ller content is assumed
to be due to the ller carrying higher loads than the matrix. Because the polymer matrix is subjected to a larger
strain than the macroscopic strain (the ller particles do
not elongate), the material yields at a lower macroscopic
strain than the unlled material. The optimum ller content was found to be 15%, above which a sharp drop
in the mechanical properties occurred. It has been suggested [73] that this is a useful range for trash bags and
agricultural mulch, in which mechanical properties such
as tensile strength and elongation at break are not very
critical. Urea and polyols were also added to starch-EAA
formulations to facilitate the preparation and to improve
the economics and quality of the starch-based lms [1]
by improving the gelatinization of starch at low levels of
water, thus allowing direct extrusion of a uniform lm

75

from a semidry blend (16% water content). Initial tensile

strengths of urea-containing starch-EAA based lm were
generally lower than those made by the premix method,
but after water soaking to remove the urea, the tensile
strengths were nearly equal to those made without urea.
On the contrary, glycerol and starch-derived polyols can
be added to starch-EAA systems to increase the percentage of the biodegradable component without adversely
affecting the physical properties of the lms.
Starch/PE copolymer EAA composites for blown
lms were examined with regard to various compositions
of starch and EAA content, and water, ammonia, and
urea contents as percentage of starch [6]. The best lms,
containing 20% starch, were almost equivalent to PE
lms (tensile strength 20% lower than that of PE). The
second inuential variable affecting the lm performance was the water content, because it is considered
necessary for gelatinizing and plasticizing starch to make
it exible enough for the process of lm blowing
(best content 0.15 g water per gram of starch in the formulations examined in ref [6]; urea allows for complete
gelatinization).
Starch PCL-Based Blends for Films (Fully
Biodegradable)
Poly(e-caprolactone) (PCL), produced by the ring
opening polymerization of e-caprolactone, belongs to
the category of polyesters derived from petrochemical
feedstocks. This material is fully biodegradable. Film
extrusion of PCL has been reported, however, with a
poor impact and tear strength behavior [9]. To overcome
this problem, blends, alloys, and graft copolymers of
PCL with starch have been reported, including commercial lms based on starch-PCL [9]. In one approach,
plasticized starch instead of granular starch is used,
resulting in reduced mactrascopic dimensions (i.e., lm
thickness), smaller domain size, and improved strength
and processing characteristics. The properties of the
so-produced lms are comparable to LDPE lms and
better than PCL lms. The mechanical behavior of some
experimental PCL-starch lms is presented in a later
section.
In another case, investigation of the mechanical
behavior of two types of PCL/sago starch composites
(dried granulated sago starch and undried thermoplastic
sago starch) [74] has shown that in both types all major
mechanical properties, tensile strength, modulus of elasticity, and yield stress decrease as sago starch concentration increases. This is also attributed to the hydrophobic
nature of PCL leading to poor interfacial interaction
and so adhesion on sago starch granules on the fracture

76
surfaces. The dried granulated sago starch acts better as
ller in terms of mechanical properties and the easy of
biodegradation, whereas the second type was shown to
impart better yield stress to the composites [74]. In
another study, starch blends with PCL as well as with
ethylene, vinyl alcohol, cellulose acetate were chemically modied by cross-linking [75]. The blends obtained had reduced water-uptake and stiffness (secant
modulus), especially for the case starch-PCL.
The behavior of some PCL-modied starch blends
has been investigated [76]. Seventy-micron lms were
prepared from modied starch and poly-CL (100%
polycaprolactone; 50% modified starch and 50%
polycaprolactone blend; 50% nonmodied starch and
50% polycaprolactone blends). It was observed that with
the addition of starch the Youngs modulus of polycaprolactone was increased and became less ductile,
whereas tensile strength and elongation at break values
decreased. The modulus of the nonmodied starch-PCL
blend was 273.0 MPa, which was signicantly higher
than that of the pure PCL, which was 167.6 MPa. Note
that using modied starch instead of native starch did
not change the elastic modulus signicantly, probably
because of the more compatible interface between modied starch particles. The decrease in tensile strength was
about 50%, which is similar to the values reported by
other investigators in the literature [77,78]. Decrease in
the elongation at break was about 40%.

Polylactides (PLA)
Poly-L-lactic acid (PLLA) is formed by a chemical
condensation reaction of the lactic acid monomer and has
a tensile strength at break of 4570 MPa and an elongation of 85%105%. Concerning the mechanical properties of representative commercial products, some typical
values are glass transition temperature 63.8C, tensile
strength 32.22 MPa, tensile stress at break 21.87 MPa,
elongation at break 30.72%). In a particular case [79], the
behavior of PLLA, PCL (polycaprolactone) and three
different copolymers based on PLLA and polyglycolic
acid (PLLA-co-PGA) and their composites with hydroxyapatite obtained from bovine bone (ossein: a biological
hydroxyapatite) were investigated. The addition of 5%
ossein did not affect signicantly the mechanical properties. It was conrmed, as in many other cases, that the
rigid llers increase the modulus and decreases the tensile strength and elongation at break for both polymers.
The yield stress also decreased, except for PCL, in which
it increased. The size of ossein particles was found to be
critical for the improvement of the mechanical properties.

Briassoulis
The mechanical properties of blends of PLA and
starch using conventional processes are rather poor because of incompatibility (below one half of the values of
the original PLA materials; elongation below 5%) [80].
Plastizers (with hydrophilichydrophobic structure) are
used to increase elongation (br above 75%) and obtain
biodegradable material that can be used for lm blowing.
Also, PLA and starch were blended with a reactive agent
during the extrusion process by adding a catalytic
amount of some reactants (peroxides, anhydrides). The
mechanical properties of the so-obtained reactive blends
improved signicantly because of the good compatibility
and the cross-linking or coupling reactions between
multicomponents [80].
Other kinds of PLA blends have been investigated
as well. Poly(L-lactic acid) (PLLA) was melt-blended
with a small amount of poly(aspartic acid-co-lactide)
(PAL) or poly(sodium aspartate-co-lactide) (PALNa)
and processed into homogeneous press lms in the work
of [81]. The mechanical properties and transparency of
such blends were found to be comparable to that of the
nonblended PLA lm. It was found that PAL and
PALNa are effective additives for accelerating the
hydrolysis of PLA. The nonenzymatic hydrolysis rates of
poly(butylene succinate) (PBS) and polycaprolactone
(PCL) were also enhanced by the presence of PAL in the
blend.
Graft polymerization has also been applied to PLA.
Cellulose diacetate-graft-poly(lactic acid)s (CDA-gPLAs) were synthesized successfully over a wide range
of composition in a combination of different ways of
graft polymerization: a copolycondensation of lactic
acid; a ring-opening copolymerization of L-lactide in
dimethyl sulfoxide; and a copolymerization similar to the
second, but in bulk, each initiated at residual hydroxyl
positions on CDA [82]. All the copolymer products
gave a single Tg. During tensile measurements conducted at 80100C for lm sheets of melt-quenched
CDA-g-PLAs, it was observed that their drawability increased drastically with increasing PLA content and, at a
certain w(PLA) of MS greater than or equal to 14, the
elongation at rupture reached a maximum of 2000%.

PolysaccharidesProteins Composite Films

Preparation of composite lms through combined
use of compatible polysaccharides and proteins to improve properties of biopolymers has been reported in the
literature [83]. Such complexes in many cases can display better functionality than proteins or polysaccharides
alone. For example, the use of xylan together with a

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

protein like wheat gluten may result in lms having quite
unexpected and useful properties, depending on the
numerous possible interactions and bonding with gluten
[83]. The possibility of using xylan as an agricultural
by-product for production of composite lms in combinations with wheat gluten was investigated [83]. Films
were obtained with added xylan without decreasing lmforming quality. Wheat gluten/xylan composite lms
having different characteristics can be produced depending on xylan type, composition, and process conditions.
Films made only of proteins exhibit several
problems. Soy protein lms, for example, without other
secondary components besides proteins do not have good
mechanical and barrier properties. However, adding
cystein and gluten allows the production of lms with
increased tensile strength and better barrier properties
(8.24 MPa without and 8.68 MPa with cysteine addition
[84]). Still, such values are rather low for agricultural applications. In another case [85], homogeneous lms were
obtained by dissolution of isolate of sunower proteins
in alkaline water (pH 12), addition of a plasticizer, casting, and drying. The use of ionic bases (LiOH, NaOH)
capable of interfering with the interproteic noncovalent
bonds resulted in the greatest tensile strength (3.9 MPa)
and elongation at break (215%251%). Plasticizers
conferred diverse tensile properties to the lms; the
use of 1,3-propanediol resulted in the highest (tensile
strength (27.1 MPa), and glycerol resulted in the greatest
elongation at break (251%). Different mechanical
properties were obtained by using mixtures of these
plasticizers.
In a study on the effect of chemical, physical, and
ageing treatments on the mechanical properties of wheat
gluten lms [86] it was shown that ageing of 360 h led
to a 75% and 314% increase in tensile strength (initial
value 1.7 MPa) and Youngs modulus, respectively, and
a 36% decrease in elongation (initial value 500%).
Severe thermal (above 110C, 15 min) and formaldehyde
treatments highly improved the mechanical resistance of
the lms (up to 376% and 654% increase in tensile
strength and Youngs modulus and up to 66% decrease
in elongation). However, in all these cases the maximum
tensile strength of the lms still remains rather low for
agricultural applications.
Edible lms were formulated [87] using various
proteins (casein, gelatin, albumin) in combination with
starch and nonthermal as well as intense thermal
blending. Nonthermal blended lm showed a double Tg,
indicating poor miscibility of the components and,
hence, a poor lm-forming property. However, all the
lms based on intense thermal blending showed a single
Tg, indicating complete molecular miscibility of the

77

components. Casein-based lm gave better lm properties with a lower water-vapor transmission rate, water
gain at different relative humidity conditions, and higher
tensile strength compared to counterparts containing
gelatin and albumin.

MECHANICAL BEHAVIOR OF THIN FULLY

BIODEGRADABLE AGRICULTURAL FILMS
Biodegradable Agricultural Films
The signicant interest in the use of mulching and
low tunnels for protected cultivation, aimed at elimination of weeds, conservation of water and fertilization,
and providing a better microenvironment for the plants
and protection against adverse climatic conditions, has
led to a rapid increase of the market of agricultural
plastic lms used for these purposes in Europe and
worldwide involving hundreds of thousands of hectares
and thousands of tons of plastic lms per year [2]. The
conventional agricultural plastic lms used today are
low-density polyethylenes (in some cases HDLE),
poly(vinyl chloride), polybutylene, or copolymers of ethylene with vinyl acetate. A side effect arising from the
use of these materials, however, concerns the problem of
handling tons of accumulated agricultural plastic wastes.
In an effort to cope with this severe and continuously
growing problem, polymer types (mainly polyethylene
with special light-sensitizing prooxidation additives)
have been designed for controlled degradation [88, 89].
Among the special additivation systems proposed are
a mixture of ferric and nickel dibutyldithiocarbamates,
the ratio of which is adjusted to provide protection
for specic growing periods before a rapid photodegradation starts and a combination of substituted benzophenones and titanium or zirconium chelates [1]. Also, it
has been reported that the addition of iron or calcium
accelerates the breakdown of polyethylene [1]. However,
there is a signicant controversy over the possible rate
of real biodegradation and/or accumulation of the
fragments of the rapidly photodegraded remains of
these agricultural polyethylene lms, along with questions about possible irreversible contamination of the
agricultural soils.
In parallel, really biodegradable agricultural lms
have been already produced specically designed for
mulching [90]. Among them [1], biodegradable lms
based on starch with poly(vinyl alcohol) [91] and
poly(vinyl chloride) [92] have been developed in the
USDA laboratories. Also acylated starch-plastic mulch
lm was developed and evaluated without any adverse
effects on soil microora [93]. In another case a variety

78
of starch-based polymers were blended with highperformance biodegradable polyester polymers to determine the applicability of lms to be processed on a lm
blowing line and to perform well in mulch lm eld
trials (thickness 3040 m, tensile strength 27 Mpa,
elongation at break 300%) [94]. Poly-lactone and
poly(vinyl alcohol) lms are readily degraded by soil
microorganisms.
Biodegradation agricultural lms should meet a set
of minimum design requirements, including adequate
strength and elongation at break for mechanical installation, good mechanical properties with regard to ageing
during the useful lifetime of the lm and 100% biodegradation in the soil, preferably before the next cultivation
season. In addition, depending on the geographical
region, the cultivation, and the season, special additives
may be required to adjust the physical properties of these
films. Specifically for low-tunnel films, the design
requirements also include an adequate mechanical
behavior of these lms to resist various loads and load
combinations (wind, hail, snow loads, etc).
A question is raised subsequently: have these design
requirements been established? The recent European
Standard on plastics: mulching thermoplastic lms for
use in agriculture and horticulture[95] and the Standard
Covering thermoplastic lms for use in agriculture and
horticulture[96] require that agricultural lms should
meet specic minimum values of selected mechanical
properties, without, however, relating those predetermined values with the conditions to which the lms will
be exposed and the installation and support systems.
Aiming at dening design requirements for biodegradable agricultural low-tunnel lms a systematic analytical
and experimental research work is in progress and the
rst results will be published soon [97].3

Mechanical Behavior of Agricultural Films

In the case of carbon blacklled, biodegradable,
copolyester agricultural mulch lm and commercial carbon blackfilled, high-density polyethylene (HDPE)
mulch lm, reported in the work of [3], the biodegradable
EA mulch lm exhibited higher tensile and elongation at
break than the presently used HDPE mulch lm. It was
shown that the mechanical properties, including the tensile strength of both the EA and HDPE, were sufciently
preserved from planting to harvest. The changes in the
elongation at break of the EA lm proved that it possesses
3

Bioplastics: Biodegradable plastics for environmentally friendly

mulching and low tunnel cultivation, QLK5-CT-200000044.

Briassoulis
the properties needed for the agricultural application and
could be installed using the same techniques currently
used for traditional HDPE plastic mulch lm.
In another case, PCL-starch biodegradable lms
have been developed for mulching and low-tunnel applications in the framework of a project in progress.2 Some
preliminary results obtained from the investigation of
these fully biodegradable experimental thin agricultural
lms are presented in this section to offer an overview of
the mechanical performance of these lms (before use)
compared to the corresponding behavior of the conventional synthetic lms. Two sets of biodegradable and
conventional agricultural plastic thin lms were examined: a set of thin biodegradable lms suitable for covering low tunnels (denoted by L; thickness 6080 )
and another set of very thin biodegradable lms (denoted
by M; thickness 2560 ), which may be used as
mulching lms. The conventional lms tested were
LDPE (denoted by L0b) and three-layer LLDPE-EVA
lms (denoted by L0a). The tensile properties, constituting a major category of mechanical properties of thin
lms, were determined in the Laboratory of Strength of
Materials of the Agricultural University of Athens in the
machine (P; parallel) and in the transverse (T) direction
according to the procedure described in [97].
The behavior of the thin L biodegradable lms
shown in Fig. 1 suggests a rather good mechanical behavior comparable to the one experienced by the corresponding conventional low-tunnel lms. Elongation at
break is higher in the transverse direction while strain
hardening in the parallel direction is characterized by a
higher tangent modulus. These curves tend to follow the
corresponding curves of greenhouse LDPE lms except
that the elongation at break values are about 80% of the
greenhouse thick LDPE lm values [98].
The behavior of the very thin M biodegradable
lms shown in Fig. 2 is probably different from the behavior of the low-tunnel lms. It is comparable to the one
experienced by the corresponding PE mulching lms in
the parallel direction, whereas in the transverse direction
the elongation at break is lower. The elongation at break
is again higher in the transverse direction, but this property
was found to be rather sensitive. Of course, the specic
application of mulching is not very demanding in terms of
the mechanical behavior of the thin lms. Another characteristic here is the higher stress at yield values obtained
with the biodegradable lms, especially in the transverse
direction along with insignicant strain-hardening effects.
Finally, the initial tear resistance results, shown in
Fig. 3 for four thin biodegradable low tunnel lms and in
Fig. 4 for four thin biodegradable mulching lms indicate a satisfactory behavior, comparable to that of the

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

79

Fig. 1. Typical tensile stress-strain curves for thin biodegradable agricultural lm in parallel (5-cm specimens) (a) and transverse (b) (5-cm
specimens) direction (two-digit numbers: thickness in ).

Fig. 2. Typical tensile stress-strain curves for very thin biodegradable mulching lm in parallel (a) and transverse (b) direction (10-cm specimens)
(two-digit numbers: thickness in ).

Fig. 3. Typical initial tear resistance curves for thin biodegradable low-tunnel lms in parallel (a) and transverse (b) direction (two-digit numbers:
thickness in ).

corresponding conventional PE lms. It should be noted

that values of the tear resistance normalized with respect
to thickness (N/mm) are comparable only for lms of the
same thickness (i.e., the tear resistance is not linearly
dependent on the lm thickness).

CONCLUSIONS
The mechanical behavior of various types of
biodegradable and partially (starch-based) biodegradable
materials used for lms is shown to depend, mainly, on

80

Briassoulis

Fig. 4. Typical initial tear resistance curves for thin biodegradable mulching lms in parallel (a) and transverse (b) direction (two-digit numbers:
thickness in ).

their chemical composition and the environmental

conditions during production, but also on storage and
usage conditions not considered in this work. Reported
information in the technical literature concerning on the
overall mechanical behavior of biodegradable lms,
which may be used for agricultural applications, but also
of partially biodegradable lms, is rather limited.
Investigation of selected critical mechanical properties describing the mechanical behavior of thin readily
biodegradable starchPCL experimental lms, which may
be used for low tunnels and soil mulching, conrm a rather
good mechanical behavior comparable to those of conventional agricultural lms. Additional aspects, such as other
mechanical properties, for example, impact and creep,
degradation effects, and application conditions, describing
the mechanical behavior of thin agricultural biodegradable
lms from other points of view and also their evolution
with time, are currently under investigation.
Both, biodegradable and conventional agricultural
lms are used in a rather empirical way, whereas the relevant standards do not cover adequately the complexity of
the various conditions to which these lms are exposed.
The open questions concerning the design requirements
of biodegradable agricultural lms are currently under
investigation in the framework of a European project.4

ACKNOWLEDGMENT
This work has been carried out in the framework of
the European research project Bioplastics: Biodegradable
plastics for environmentally friendly mulching and low
tunnel cultivation, QLK5-CT-200000044, funded by
the EU.
4

Bioplastics: Biodegradable plastics for environmentally friendly

mulching and low tunnel cultivation, QLK5-CT-200000044.

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