Review

Biodegradable
polymers for food
packaging: a review
Valentina Siracusa
a,
*
, Pietro
Rocculi
b
, Santina Romani
b
and
Marco Dalla Rosa
b
a
Department of Physical and Chemical Methodology
for Engineering, Engineering Faculty, University of
Catania, Viale A. Doria 6, 95125 Catania, Italy
(Tel.: D39 095 7382755; fax: D39 095 333231;
e-mail: vsiracus@dmfci.unict.it)
b
Department of Food Science, Alma Mater Studiorum,
University of Bologna, Cesena (FC), Piazza Goidanich
60, c.a.p. 47023, Italy
For a long time polymers have supplied most of common pack-
aging materials because they present several desired features
like softness, lightness and transparency. However, increased
use of synthetic packaging lms has led to a serious ecological
problems due to their total non-biodegradability. Although their
complete replacement with eco-friendly packaging lms is just
impossible to achieve, at least for specic applications like food
packaging the use of bioplastics should be the future. The aimof
this reviewwas to offer a complete viewof the state of the art on
biodegradable polymer packages for food application.
Introduction
The current global consumption of plastics is more than
200 million tonnes, with an annual grow of approximately
5%, which represents the largest eld of application for crude
oil. It emphasises howdependent the plastic industry is on oil
and consequently how the increasing of crude oil and natural
gas price can have an economical inuence on the plastic
market (www.european-bioplastics.org). It is becoming in-
creasingly important to utilize alternative rawmaterials. Un-
til now petrochemical-based plastics such as polyethylene
terephthalate (PET), polyvinylchloride (PVC), polyethylene
(PE), polypropylene (PP), polystyrene (PS) and polyamide
(PA) have been increasingly used as packaging materials be-
cause their large availability at relatively low cost and be-
cause their good mechanical performance such as tensile
and tear strength, good barrier to oxygen, carbon dioxide, an-
hydride and aroma compound, heat sealability, and so on. But
nowadays their use has to be restricted because they are not
non-totally recyclable and/or biodegradable so they pose se-
rious ecological problems (www.european-bioplastics.org;
Sorrentino, Gorrasi, &Vittoria, 2007). Plastic packaging ma-
terials are also often contaminated by foodstuff and biologi-
cal substance, so recycling these material is impracticable
and most of the times economically not convenient. As a con-
sequence several thousands of tons of goods, made on plastic
materials, are landlled, increasing every year the problemof
municipal waste disposal (Kirwan & Strawbridge, 2003).
The growing environmental awareness imposes to packaging
lms and process both user-friendly and eco-friendly attri-
butes. As a consequence biodegradability is not only a func-
tional requirement but also an important environmental
attribute.
The compostability attribute is very important for bio-
polymer materials because while recycling is energy expen-
sive, composting allows disposal of the packages in the soil.
By biological degradation it produced only water, carbon
dioxide and inorganic compounds without toxic residues.
According to the European Bioplastics, biopolymers
made with manufactures renewable resources have to be
biodegradable and especially compostable, so they can
act as fertilizers and soil conditioners. Whereas plastics
based on renewable resources do not necessary have to be
biodegradable or compostable, the second ones, the bio-
plastic materials, do not necessary have to be based on re-
newable materials because the biodegradability is directly
correlated to the chemical structure of the materials rather
than the origin. In particular, the type of chemical bond de-
nes whether and in which time the microbes can biode-
grade the material. Several synthetic polymers are
biodegradable and compostable such as starch, cellulose,
lignin, which are naturally carbon-based polymers. Vice
versa, same bioplastics based on natural monomer, can
loose the biodegradability property through chemical mod-
ication like polymerization, such as for example Nylon 9
types polymers obtained from polymerization of oleic acid
monomer or Polyamid 11 obtained from the polymerization
of castor oil monomer. * Corresponding author.
0924-2244/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tifs.2008.07.003
Trends in Food Science & Technology 19 (2008) 634e643
Plastics are compounds based on polymers and several
other chemicals like additives, stabilizers, colourants, pro-
cessing aids, etc., which quantity and type change from
a polymer to another, because each nal products have to
be optimized with regard its processing and future applica-
tion (Guilbert, Cuq, & Gontard, 1997; Petersen et al.,
1999). For these reasons, manufacture a product using
a 100% renewable resources is neither impossible in the
early future and the tendency is to utilize the highest pro-
portion of renewable resources possible. Until now bioplas-
tics contain more than 50% weight of renewable resources
(www.european-bioplastics.org). Many bioplastics are
mixes or blends containing synthetic components, such as
polymers and additives, to improve the functional proper-
ties of the nished product and to expand the range of ap-
plication. If also additives and pigments can be based on
renewable resources, we can obtain a polymer with approx-
imately 100% weight of biodegradation compounds.
Bioplastics, like plastics, present a large spectrum of ap-
plication such as collection bags for compost, agricultural
foils, horticultures, nursery products, toys, bres, textiles,
etc. Other elds such as packaging and technical application
are gaining importance (www.european-bioplastics.org).
The performance expected from bioplastic materials
used in food packaging application is containing the food
and protecting it from the environment and maintaining
food quality (Arvanitoyannis, 1999). It is obvious that to
perform these functions is important to control and modify
their mechanical and barrier properties, that consequently
depend on the structure of the polymeric packaging mate-
rial. In addition, it is important to study the change that
can occur on the characteristics of the bioplastics during
the time of interaction with the food (Scott, 2000). As de-
scribed in Biodegradable polymers applications in food
packaging eld section, the study of the literature shows
up that only a limited amount of biopolymers are used
for food packaging application. Unlike the usual wrap,
lms, labels and laminates came from fossil fuel resources,
the use of biodegradable polymers represents a real step in
the right direction to preserve us from environmental pollu-
tion. Several University Research Center in the world (Italy,
Ireland, France, Greece, Brazil, USA and so on) and several
Industry like NatureWorks LLC, are focalizing their atten-
tion to the study of these bio-based materials.
From our point of view, it is important to understand not
only the physical and mechanical properties of such mate-
rials for the task but also the compatibility with the food,
which has been recognized as a potential source of loss
in food quality properties (Halek, 1988).
Chemistry of degradation
The bioplastic aim is to imitate the life cycle of biomass,
which includes conservation of fossil resources, water and
CO
2
production, as described in Scheme 1 (www.
european-bioplastic.org).
The speed of biodegradation depends on temperature
(50e70

C), humidity, number and type of microbes. The
degradation is fast only if all three requirements are present.
Generally at home or in a supermarket biodegradation occurs
very low in comparison to composting. In industrial com-
posting bioplastics are converted into biomass, water and
CO
2
in about 6e12 weeks (www.european-bioplastic.org).
Polymer-based products are required to biodegrade on
a controlled way: natural polymer (like rubber, lignin, hu-
mus) and synthetic polymer like polyolens biodegrade fol-
lowing an oxo-biodegradation mechanism (Arvanitoyannis,
1999) and consequently cannot satisfy the rapid mineraliza-
tion criteria requested for standard biodegradation. Also, at
ambient temperature, oxo-biodegradation is a slower pro-
cess than hydro-biodegradation as well described by Scott
and Wiles (2001). These authors explained that during the
oxo-degradation of carboxylic acid, molecules of alcohols,
aldehydes and ketones biodegradable with low molar mass
are produced by peroxidation, initiated by heat or light,
which are the primary cause of the loss of mechanical prop-
erties of hydrocarbon polymers. Than bacteria, fungi, en-
zymes start the bioassimilation giving rise to biomass and
CO
2
that nally form the humus. Generally synthetic poly-
mers contain antioxidants and stabilizers added to protect
the polymer against mechano-oxidation during the process-
ing operation and to provide the required shelf-life. So,
from one hand antioxidant is necessary to improve the per-
formance of these materials but, on the other hand, for the
biodegradation process it is better to not add these mole-
cules during polymer processing.
Hydro-biodegradation is the well-known process that
gives bioassimilable products from cellulose, starch, poly-
esters, etc. Aliphatic polyester is hydrolyzed and bioassimi-
lated rapidly in an aqueous environment in much the same
way as starch and cellulose (Scott & Wiles, 2001).
Polyolen were selected as a basis for the study of biode-
gradable polymer because theyhadalready achieveda central
position for packaging application, thanks to their combina-
tion of exibility, toughness, excellent barrier properties, all
at low cost because coming from low value oil fraction.
Synthetic and natural polymers stand at the opposite
ends of a spectrum of properties: polyolens are hydrocar-
bon hydrophobic polymers, resistant to peroxidation, bio-
degradation, highly resistant to hydrolysis, which is their
main attribute in packaging, and not biodegradable. To
make it biodegradable it is necessary to introduce pro-
oxidant additives which promote the oxo-biodegradation
by producing low molar mass oxidation compounds bioas-
similate from the microorganisms. Natural compounds, like
cellulose, starch and so on, are hydrophilic polymers, water
wettable or swellable and consequently biodegradable.
They are not technologically useful for food packaging
where water resistant is required. Between these two ex-
tremes are the hydro-biodegradable aliphatic polyesters
such as polylactic acid (PLA) and the poly(hydroxyacid)
(PHA) (Scott & Wiles, 2001).
635 V. Siracusa et al. / Trends in Food Science & Technology 19 (2008) 634e643
Although hydrocarbons polymers make a positive contri-
bution to environment because they can be mechanically re-
cycled if clean, incinerated with energy recovery, with
a caloric value almost identical to the oil from which they
coming on, they are not compostable. According to the Euro-
pean standard norm UNI EN 13432 (2002), a product to be
dened compostable must be biodegradable and disintegr-
able in brief time, or rather it must be turned from the micro-
organisms into water, carbonic and fertile anhydride
compost. Finally, to be dened compostable, the manufac-
tured article must result compatible with a process of com-
posting, that means it must not release dangerous
substances and must not alter the quality of the produced
compost. The last Financial Lawout as objective the dismiss-
ing of the mono-use pouches not biodegradable, for food staff
transportation, within the 2010 (Scott & Wiles, 2001).
The use of long-lasting polymers as packaging materials
for short application is not justied, also because physical
recycling of these materials is often impractical because
food contamination. So there is an increasing demand on
the use of biodegradable polymer which could be easily re-
newable (Kale, Auras, & Singh, 2006). While most of the
commercialized biopolymer materials are biodegradable,
these are not fully compostable in real composting condi-
tions, which vary with temperature and relative humidity.
Barrier properties
The determination of the barrier properties of a polymer
is crucial to estimate and predict the product-package shelf-
life. The specic barrier requirement of the package system
is related to the product characteristics and the intended
end-use application. Generally plastics are relatively per-
meable to small molecules such as gases, water vapour, or-
ganic vapours and liquids and they provide a broad range of
mass transfer characteristics, ranging from excellent to low
barrier value, which is important in the case of food
products. Water vapour and oxygen are two of the main
permeants studied in packaging applications, because they
may transfer from the internal or external environment
through the polymer package wall, resulting in a continuous
change in product quality and shelf-life (Germain, 1997).
Carbon dioxide is now important for the packaging in mod-
ied atmosphere (MAP technology) because it can poten-
tially reduce the problems associated with processed fresh
product, leading a signicantly longer shelf-life. For exam-
ple, for fresh product respiration rate is of a great impor-
tance in MAP design so identify the best packaging is
a crucial factor. The most important barrier properties of
polymer lms used in packaging application are described.
Oxygen transmission rate (OTR)
The oxygen barrier property of a food packaging container
for fresh product (e.g. fruits, salad, ready-to-eat meals) plays
an important role on its preservation. The oxygen barrier is
quantiedbytheoxygenpermeabilitycoefcients (OPC) which
indicate the amount of oxygen that permeates per unit of area
and time in a packaging materials [kg mm
2
s
1
Pa
1
]. So,
when a polymer lmpackaging has a lowoxygen permeability
coefcients, the oxygen pressure inside the container drops to
the point where the oxidation is retarded, extending the shelf-
life of the product. Generally the biodegradable polymers pres-
ent a value one or more order of magnitude belowthe synthetic
polymer used in the same eld like PET and OPS. Several
authors reported in literature the oxygen permeability coef-
cients of one of the most commercialized biodegradable poly-
mer like the PLA (Auras, Harte, & Selke, 2004; Auras, Singh,
& Singh, 2006; Auras, Singh, & Singh, 2005; Lehermeier,
Dorgan, & Way, 2001; Oliveira et al., 2004).
Together with the permeability coefcient the oxygen
transmission rate (OTR), expressed in cc m
2
s
1
is given.
The OPC is correlated to the OTR by the following
equation:
Scheme 1. Life cycle www.european-bioplastics.org.
636 V. Siracusa et al. / Trends in Food Science & Technology 19 (2008) 634e643
OPC OTRl=DP 1
where l is the thickness of the lm (m), DP is the difference
between oxygen partial pressure across the lm [Pa].
DP p
1
p
2
, where p
1
is the oxygen partial pressure at
the temperature test on the test side and p
2
is equal to
zero on the detector side.
Water vapour transmission rate (WVTR)
The water vapour barrier properties for the packaged
product whose physical or chemical deterioration is related
to its equilibrium moisture content, are of great importance
for maintaining or extending its shelf-life. The water va-
pour barrier is quantied by the water vapour permeability
coefcients (WVPC) which indicate the amount of water
vapour that permeates per unit of area and time in a packag-
ing materials [kg mm
2
s
1
Pa
1
]. For fresh food products
it is important to avoid dehydration while for bakery or del-
icatessen is important to avoid water permeation. The
WVPC of the PLA biodegradable polymer is reported in
the literature (Auras, Harte, Selke, & Hernandez, 2003;
Auras et al., 2005, 2006).
Together with the permeability coefcient is given the
water vapour transmission rate (WVTR), expressed in
cc m
2
s
1
(or g m
2
day
1
). The WVPC is correlated to
the WVTR as described up in Eq. (1) for the oxygen
parameter.
Carbon dioxide transmission rate (CO
2
TR)
Like the oxygen and water vapour barrier properties,
also the carbon dioxide barrier property is of particular im-
portance on food packaging application. The carbon diox-
ide barrier is quantied by the carbon dioxide
permeability coefcients (CO
2
PC) which indicates the
amount of carbon dioxide that permeates per unit of area
and time in a packaging materials [kg m m
2
s
1
Pa
1
]. To-
gether with the permeability coefcient is given the carbon
dioxide transmission rate (CO
2
TR), expressed in cc m
2
s
1
(or g m
2
day
1
). The CO
2
PC is correlated to the
CO
2
TR as described up in Eq. (1).
Mechanical properties
It is well-known that the polymer architecture plays an
important role on the mechanical properties, and conse-
quently on the process utilized to modelling the nal prod-
uct (injection moulding, sheet extrusion, blow moulding,
thermoforming, lm forming). In addition, many packaging
containers are commercially used below room temperature,
so it is important to assess the mechanical performance un-
der these conditions (Auras et al., 2005).
Tensile test analyses are made to determine the tensile
strength (MPa), the percent elongation at yield (%), the per-
cent elongation at break (%) and the elastic modulus (GPa)
of the food polymer packaging material. These values are
important to get mechanical information of the biopolymer
materials to be compared with the commercial
nonbiodegradable ones (ASTM D882-02, Standard Test
Method for Tensile Properties of Thin Plastic Sheeting).
Impact properties test is a method utilized to determine
the energy that causes the plastic to fail under specic im-
pact conditions, conducted following the ASTM D1709-03,
Standard Test Methods for Impact Resistance of Plastic
Film by the Free-Falling Dart Method.
The compression test is normally conducted on thermo-
formed sample, according to the ASTM D642, Standard
Test Method for Determining Compressive Resistance of
Shipping Containers, Components, and Unit Loads. Natu-
rally the compression strength is function of the material
and of design (shape and size).
Chemical resistance properties
Products that could be packaged in this kind of con-
tainers may have weak or strong acid characteristics; so it
is necessary to assess the performance and the suitability
of biopolymers stored with common food packaging solu-
tion as a function of time. The interaction and absorption
between chemical compounds and polymer may affect the
nal mechanical properties of a polymer (Auras et al.,
2005). Normally the chemical resistance is tested measur-
ing the tensile stress, elongation at break and modulus of
elasticity of sample submerged in weak and strong acid so-
lutions as a function of time, simulating real conditions, at
ambient temperature (23

C) and at 18

C, 23

C and
29

C. The weak acid solution is prepared with acetic
acid while the strong acid solution is prepared with hydro-
chloric acid (Auras et al., 2005).
Some important production consideration
Currently, there are several types of bio-based polymers
on the market: same coming from petrochemical monomer,
like certain types of polyester, polyester amides and polyvi-
nyl alcohol, produced by different manufacturer, used prin-
cipally as lms or moulding. Four other bio-based polymers
are starch materials, cellulose materials, polylactic acid
(Polyester, PLA), polyhydroxy acid (polyester, PHA). Until
now, the PHA polymer is a very expensive polymer because
it is commercially available in very limited quantities. PLA
is becoming a growing alternative as a green food packag-
ing materials because it was found that in many situations it
performs better than synthetic ones, like oriented polysty-
rene (OPS) and PET materials (Auras et al., 2005).
Different types of materials can be combined to form
blend or compounds or seminished products such as lms.
The degradation of the materials is normally studied under
real compost conditions and under ambient exposure by dif-
ferent techniques. The polymer degradation rate is deter-
mined by the nature of the functional groups and the
polymer reactivity with water and catalysts. Any factor which
affects the reactivity such as particle size and shape, temper-
ature, moisture, crystallinity, isomer percentage, residual
monomer concentration, molecular weight, molecular weight
distribution, water diffusion, metal impurities from the
637 V. Siracusa et al. / Trends in Food Science & Technology 19 (2008) 634e643
catalyst, will affect the polymer degradation rate (Kale et al.,
2006). In general high temperature and humidity will degrade
more rapidly the polymer. By visual inspection the packages
are observed for colour, texture, shape and change in dimen-
sion. Generally a digital camera is used to take the pictures.
The thickness of the packages is determined by a thick-
ness gauge according to the ASTM norm D4166-
99(2004)e1, Standard Test Method for Measurement of
Thickness of Nonmagnetic Materials by Means of a Digital
Magnetic Intensity Instrument, or by micrometer according
to ASTM D 374-99, Standard Test Methods for Thickness
of Solid Electrical Insulation.
By gel permeation chromatography it is possible to de-
termine the molecular weight of samples dissolved in the
appropriate solvent. Molecular weight variations are an
indication of the degradation rate of the polymers and
give information about when the main fragmentation oc-
curs in a polymer.
By differential scanning calorimetry (DSC) it is possible
to determine the glass transition temperature (T
g
), melting
temperature (T
m
) and crystallinity of the polymer sample
(ASTM D3418, Standard Test Method for Transition Tem-
peratures and Enthalpies of Fusion and Crystallization of
Polymers by Differential Scanning Calorimetry). The crys-
tallinity is determined according to ASTM D3417-97 and
using the following equation, well-known in the literature,
x
c
% 100 DH
c
DH
m
=DH
c
m
2
where DH
c
is the exothermic enthalpy of cold crystalliza-
tion, DH
m
is the endothermic enthalpy of fusion, DH
c
m
is
the endothermic heat of melting of purely crystalline poly-
mer under study (for example: for PLA is 135 J g
1
, Kale
et al., 2006; for PET is 125.6 J g
1
, Auras et al., 2003).
By thermo-gravimetric analysis (TGA) it is possible to
obtain the decomposition temperature, according to the
ASTM E1131-03, Standard Test Method for Compositional
Analysis by Thermogravimetry.
The determination of the pH of the sample surrounding
is one of the most important factors of hydrolytic polymer
degradation since pH variations can change hydrolysis
rates by few order of magnitude. The chemical resistance
is normally determined exposing the materials to weak
acid (pH6, acetic acid solution) and strong acid
(pH2, hydrochloric acid solution) for a period of 0, 1,
3, 5 and 7 days.
The most important analysis for lm used in food pack-
aging application is the determination of the oxygen, car-
bon dioxide and water vapour transmission rate (OTR,
CO
2
TR and WVTR, respectively). These tests are per-
formed according to the ASTM norm described before.
Concerning the mechanical properties, the samples
could be analysed by Impact tests, Tensile properties and
Compression Test of Thermoformed Containers. Generally
these parameters are studies at ambient temperature (22

C)
and at frozen food storage temperatures of 18

C,
23

C and 29

C, since fresh produce packaging and
deli containers are generally used commercially at this
conditions.
Biodegradable polymers applications in food
packaging eld
The eld of application of biodegradable polymer in
food-contact articles includes disposable cutlery, drinking
cups, salad cups, plates, overwrap and lamination lm,
straws, stirrers, lids and cups, plates and containers for
food dispensed at delicatessen and fast-food establish-
ments. These articles will be in contact with aqueous,
acidic and fatty foods that are dispensed or maintained at
or below room temperature, or dispensed at temperatures
as high as 60

C and then allowed to cool to room temper-
ature or below (Conn et al., 1995).
In the last few years, polymers that can be obtained from
renewable resources and that can be recycled and com-
posted, have garnered increasing attention. Also their opti-
cal, physical and mechanical properties can be tailored
through polymer architecture so as a consequence, biode-
gradable polymers can be compared to the other synthetic
polymers used in fresh food packaging eld, like the
most common oriented polystyrene (OPS) and polyethylene
terephthalate (PET).
Depending on the production process and on the source,
biopolymers can have properties similar to traditional ones.
They are generally divided into three groups: polyesters;
starch-based polymer; and others.
Polyesters
These materials can be:
i. Polymers directly extracted from biomass like pro-
teins, lipids, polysaccharides, etc.
ii. Polymeric materials synthesized by a classical poly-
merization procedure such as aliphaticearomatic
copolymers, aliphatic polyesters, polylactide aliphatic
copolymer (CPLA), using renewable bio-based mono-
mers such as poly(lactic acid) and oil-based mono-
mers like polycaprolactones.
iii. Polymeric materials produced by microorganisms and
bacteria like polyhydroxyalkanoates.
Aliphaticearomatic copolymers
These materials are a combination of polyetilene tere-
phthalate (PET), resistant to microbial attack, with three or
more biodegradable aliphatic polyesters. It is soft, pliable
with a good touch but with a melting point of around 200

C,
toohighfor a degradable material. The aliphatic monomer cre-
ates a weakspots inthe aromatic polymeric chain whichmakes
them susceptible to degradation through hydrolysis.
Also if it is totally biodegradable, coming from fossil
fuels such as oil, coal and natural gas, PET production
638 V. Siracusa et al. / Trends in Food Science & Technology 19 (2008) 634e643
causes a consume of non-renewable and nite resources
and with an heavy impact on global waste disposal. If prop-
erly disposed it degrades in 8 weeks but if it is trash without
any control in the environment, the degradation process can
take 50 years to breakdown the structure. The long polymer
molecules are cleaved by moisture into smaller ones, which
are naturally consumed by microbes and converted to car-
bon dioxide and water. This material is commonly used
for eating utensils (like fork, knife, spoon, dishes and so
on) and bottles but it costs twice as much than commercial
ones (Salt, 2002). DuPont (Tennessee) produce the PET/hy-
dro-biodegradable polyester under the trade name of Bio-
max, exported in all over the world.
Aliphatic polyesters
These materials have properties similar to PE and PP
polymers, they are biodegradable but with lack in thermal
and mechanical properties. These materials come from
polycondensation reaction of glycol and aliphatic dicarbox-
ylic acid, both obtained from renewable resources. They are
odourless and can be used for beverage bottles and they
biodegrade in soil and in water giving carbon dioxide and
water, in a period of 2 months (e.g. for a 0.04 mm thick
lm) (www.designinsite.dk).
A commercially available aliphatic copolyester is pro-
duced by Procter and Gamble Co. (P&G, Cincinnati, OH)
with the trade name of Nodax and it can degrade in aerobic
and anaerobic environmental conditions. The other one
is the Eastar bIo, produced from the Eastam Chemical
Company (Hartlepool, UK).
Polylactide aliphatic copolymer (CPLA)
This material is a mixture between renewable resources
as lactide and aliphatic polyesters like dicarboxylic acid or
glycol, with hard (like PS) and soft exible (like PP) prop-
erties, depending on the amount of aliphatic polyester pres-
ent in the mixture. It is easy to process and thermally stable
up to 200

C. The heating value and the quantity of carbon
dioxide generated during combustion are about the half of
that generated from commercial polymer like PE and PP,
and incineration does not produce toxic substances. In nat-
ural environment it starts to degrade in 5e6 months, with
a complete decomposition after 12 months. If composted
with food garbage, it begins to decompose after 2 weeks.
Polycaprolactone (PCL)
It is a fully biodegradable polymer coming from the po-
lymerization of not renewable raw material, like crude oil.
It is a thermoplastic polymer with good chemical resistance
to water, oil, solvent and chlorine, with a melting point of
58e60

C, low viscosity, easy to process and with a very
short degradation time. It is not used for food application
but if mixed with starch it is possible to obtain a good bio-
degradable material at a low price, used for trash bags.
Poly(lactic acid) (PLA)
One of the most promising biopolymer is the poly(lactic
acid) (PLA) obtained from the controlled depolymerization
of the lactic acid monomer obtained from the fermentation
of sugar feedstock, corn, etc., which are renewable resources
readily biodegradable (Cabedo, Feijoo, Villanueva, Lagaron,
& Gimenez, 2006). It is a versatile polymer, recyclable and
compostable, with high transparency, high molecular weight,
good processability and water solubility resistance. In gen-
eral commercial PLA is a copolymer between poly(L-lactic
acid) and poly(D-lactic acid). Depending on the L-lactide/D-
lactide enantiomers ratio, the PLA properties can vary con-
siderably from semicrystalline to amorphous ones. Re-
searches carried out to improve the performance quality of
this material are made on PLA with D-lactide content less
than 6%, which is the semicrystalline polymer. However
the amorphous one, containing 12% of D-lactide enantiomer,
is easy to process by thermoforming, which is the actual tech-
nology in the food packaging sector, and it shows properties
like polystyrene. This material is commercialized by differ-
ent companies with different commercial names, like for ex-
ample the NatureworksPLA produced by Natureworks
LLC(Blair, NB). Currently it is used in food packaging appli-
cation only for short shelf-life products.
In Table 1 physical characteristics of PLA obtained from
Auras et al. (2006) are reported.
Kale et al. (2006) studied the compostability of three
commercially available biodegradable packages made of
PLA, in particular water bottles, trays and deli containers,
to composting and to ambient exposure. They investigate
the properties breakdown of these packages exposed to
compost conditions by several experimental procedure in-
volving gel permeation chromatography (GPC), differential
scanning calorimetry (DSC), thermal gravimetric analysis
(TGA) and visual inspection. The compost pile was pre-
pared with cow manure, wood shaving and waste feed, at
Table 1. Physical experimental data for PLA (Auras et al., 2006)
Experimental data PLA
T
g
(

C) 62.1 0.7
T
m
(

C) 150.2 0.5
DH
c
m
(J g
1
) 93
Percent crystallinity (x
c
) 29.0 0.5
Oxygen transmission rate (OTR)
(cc m
2
day)
a
56.33 0.12
Oxygen permeability
rate (OPC) (kg mm
2
s
1
Pa
1
)
b
4.33E-18 1.00E-19
Water vapour transmission
rate (WVTR) (g m
2
day
1
)
a
15.30 0.04
Water vapour permeability
rate (WVPC) (kg mm
2
s
1
Pa
1
)
c
1.34E-14 3.61E-17
a
Thickness of 20.0 0.2.
b
OPCOTR l/DP, with l is the thickness in m and DP is the
difference in oxygen partial pressure across the lm.
c
WVPCWVTR l/DP, with l is the thickness in m and DP is
the difference in water vapour partial pressure across the lm.
639 V. Siracusa et al. / Trends in Food Science & Technology 19 (2008) 634e643
a temperature above 60

C. After 3 weeks the pile was put
on asphalt pad. The initial pile temperature, relative humid-
ity and pH was 65 5

C, 63 5% and 8.5 0.5, respec-
tively. The packages were subjected to composting for 1,
2, 4, 6, 9, 15 and 30 days and packages exposed to ambient
conditions were also studied. This is because it is well-
known that PLA absorb water, resulting in the hydrolysis
and cleavage of the ester linkages, autocatalyzed by the car-
boxylic acid end groups (Scheme 2).
They found that the degradation rate changes with the ini-
tial crystallinity and L-lactide content of the packages, with
lower degradation for the polymer with the highest content
of L-lactide (96 versus 94%) due to the higher crystallinity,
which makes more difcult the degradation of the whole
structure. During the hydrolysis process the sample decreased
in size (reduction of the thickness) and became tough (in-
crease in fragility) with a trend that depend to the shape.
The dimension of the containers before and after composting
was calculated by measuring the variation on width, length,
height andthickness. Duringthe rst periodof the ambient ex-
posure (within the rst 15 days) the molecular weight of the
sample M
w
showed a small increase probably due to UVor
gamma radiation which produces chain cleavage and subse-
quent recombination, which can result in crosslinking and
hence an increase in the M
w
. The increase in molecular weight
produced an increase in the glass transition temperature T
g
and leading to slower degradation since glassy polymers de-
grade more slowly than rubbery ones. The same trend was ob-
served for the sample exposed to the compost pile; the M
w
increase could be attributed to crosslinking or recombination
reactions. Subsequently, during exposure, the degradation
produced a molecular weight decrease that followed a rst or-
der kinetic associated to a rst order hydrolysis process af-
fected by the initial crystallinity, thickness and shape of the
sample (Tsuji & Ikada, 1998). Since the hydrolysis occurs
randomly, longer PLA chain is more susceptible to cleavage
than the shorter ones. The fragmentation process, which pro-
duces decomposition of the macromolecules into shorter olig-
omer chains and monomers, took place giving an initial rise of
the polydispersity index (PDI). Afterwards, polymer frag-
mentation took place with a decrease in PDI until 1.00 value,
when only oligomers of the PLA chains are present.
After the rst 4 days where an increase of T
g
was ob-
served correlated to a short increments of M
w
, the value
showed a reduction which was obviously associated to
the molecular weight reduction, starting from about 62

C
to 30

C. The T
g
reduction of the PLA packages exposed
to compost conditions followed a linear trend, with a reduc-
tion in

C for day which depend on the shape of the con-
tainers (Kale et al., 2006). The T
m
variation as a function
of time did not follow a linear relationship, with a slight in-
crease of T
m
for the samples submitted to compost condi-
tions at the beginning of the composting process.
The decomposition temperature T
D
, determined by
thermo-gravimetric analysis (TGA), associated to depoly-
merization (rapid reduction of polymer mass with a slow
reduction in molecular weight) and random degradation
(slow loss of polymer mass with an exponential decrease
in molecular weight) was determined for PLA samples ex-
posed to ambient and composting conditions. No variation
of T
D
as a function of time was observed for the sample ex-
posed to ambient condition while for the other ones a reduc-
tion of T
D
was observed, with a linear variation.
PLA packages will compost in municipal or industrial
facilities but the PLA degradation is driven by hydrolysis
which needs higher temperatures to take place, so a com-
pletely compost will be difcult. Further studies will be
necessary to nd method and techniques that can assess
the degradability of the biodegradable food packaging un-
der real composting conditions.
n
HO
O
O
O
Opoly
O
O O
O CH
3
CH
3
CH
3
CH
3
H
2
O
HO
O
O
O
Opoly
poly
O
O
O CH
3
CH
3
CH
3
CH
3
OH OH
n
HO
O
O
O
H
O O
O CH
3
CH
3
CH
3
n
+
O
O
CH
3
HO
Scheme 2. PLA hydrolysis and molecular cleavage.
640 V. Siracusa et al. / Trends in Food Science & Technology 19 (2008) 634e643
As reported fromKale et al. (2006), Pometto et al. in a pre-
vious research studied the banana eld exposition of PLA
lm in Costa Rica. They found that this lm lost its mechan-
ical properties faster than during exposure in simulated con-
ditions in the laboratory, with a degradation enhanced by an
increase in temperature and relative humidity. This data not
concern complete packages degradation.
Concerning the PLA toxicology for human safety, Conn
et al. (1995) studied the migration of small molecules com-
ing from the hydrolytic degradation phenomena of PLA
polymer lms of food-contact articles, which are lactic
acid (a safe food substance), the monomer lactide and the
linear dimer of lactic acid which is lactoyllactic acid. In
any case dimers and oligomers hydrolyse in aqueous sys-
tem to lactic acid, which is a common food ingredient
that has been shown to be safe in food at levels far in excess
of any small amount that might result from the intended
uses of PLA. They studied the PLA components migration
by extraction tests in which samples of the polymer were
exposed to food-simulating solvents under conditions that
reproduce the most severe temperature/time conditions to
which food would be exposed while in contact with PLA.
The examined contact was with aqueous, acidic and fatty
foods. It was found that in any case migrants from PLA
other that lactic acid (dimers, trimers, etc.) represented
very small and safe amounts. Migrating quantities of these
species hydrolyse to lactic acid in the aqueous and acidic
media commonly found in food and in the stomach. Lactide
has demonstrated low intrinsic toxicity in testing while the
lactoyllactic acid is normally present in commercially
available lactic acid that is an evidence of its safety.
Concerning the optical, physical and mechanical perfor-
mance of the oriented PLA polymer (OPLA) in food appli-
cation, Auras, Singh & Singh (2006) made a comparison
with two of the commonly used materials used for fresh
food packaging application, which are polyethylene tere-
phthalate (PET) and oriented polystyrene (OPS). The phys-
ical experimental data obtained on PLA samples are
reported in Table 1.
Concerning the physical data, OPLA presents the lowest
T
g
and T
m
data respect the PET and OPS polymers, while
the crystallinity is very similar to that of PET (OPS is atactic
and does not crystallize so it is highly transparent). About the
oxygen transmission rate it was found that OPLA is a good
lmfor food like tomato and other breathable products where
the oxygen and carbon dioxide barrier requirements are spe-
cically matched to the respiration rate of the fresh produce.
In order to maintain the freshness property and shelf-life of
fruit and vegetable, it is necessary to control their storage
conditions, like humidity and quantity of gases (oxygen, car-
bon dioxide and ethylene). Usually the specic gas require-
ments are achieved by controlling the type of lms used as
packaging materials for different atmospheric conditions.
As far as mechanical properties are concerned, it was found
that at room temperature the three polymers showed similar
tensile strength while at temperature besides that, were
higher than those for PETand OPS. The modulus of elasticity
showed a similar trend with the best value for the OPLApoly-
mer, while the elongation at break was similar at room tem-
perature for the three polymers but was much higher for PET
at value belowthe roomtemperature. The compression test of
thermoformed containers had point out that OPLA and OPS
have similar compression strength while the PET containers
showed the best value but in this case it was not possible to
give an conclusive information about the overall perfor-
mance because the containers had different shapes.
The results for chemical resistance tests showed that expo-
sure to acid and vegetable oil resulted in a minimal strength
degradation PLA (and also for the other two polymer PET
and OPS). PLA studied in these conditions has showed that
when it is submerged to weak acid solution there is an in-
crease of tensile strength, it becomes more ductile and there
is a reduction in the modulus of elasticity as a function of
time. For sample submerged in strong acid solution there
was an increase of tensile stress, no variation in the elonga-
tion at break, it becomes more brittle with an increase in
the modulus of elasticity which is an indication of the brittle-
ness of the sample as a function of time.
The same mechanical properties were measured when
PLA sample containers were exposed to vegetable oil and
it was found that there was a decrease of the tensile stress,
a reduction of the elongation at break and an increase of the
modulus of elasticity.
Based on the experimental researches made until now it
has been found that PLA is safe and generally recognized
as safe for its use in food-contact articles. It has the advantage
of easily tailoring their physical properties by changing the
chemical composition (amount of L- and D-isomer) and the
processing conditions. PLA packages perform, as well as
other containers made on synthetic polymer like PET, PS,
etc., at room and low temperature, suggesting that PLA
would also be suitable for the same food application. How-
ever, same properties such as exural properties, gas perme-
ability, impact strength, processability, etc., are often not
good enough for this application. This material shows good
barrier to aroma but the most important limitation on the
use of PLA for food application packaging is the medium
barrier to gases and vapours and the brittleness properties.
A possible strategy to decrease the brittleness is to make
a blend between PLA and others polymer. Cabedo et al.
(2006) studied the blend of PLA with polycaprolactone
(PCL), which is also a biodegradable semicrystalline poly-
mer obtained from the polymerization of 3-caprolactone. It
showed low tensile strength, high elongation at break, and
processing temperature similar to the PLA and it can be uti-
lized like plasticizer to increase the gas permeability of the
PLA as a consequence of the poor gas barrier properties of
PCL. In this research to the PLA/PCL blend they added
also kaolinite nanocomposites by melt mixing using a con-
ventional polymer extrusion process. By SEM analysis
they found that this blend is immiscible across the composi-
tion range studied, but is was observed a plasticization effect
641 V. Siracusa et al. / Trends in Food Science & Technology 19 (2008) 634e643
of the blend compared to the PLA matrix (by Dynamic-
mechanical analysis, DMA) and a slight increase in its ther-
mal stability (by Thermo-gravimetric analysis, TGA) with an
increment of this effect with the PCL amount increment. The
gas barrier properties showed a signicant decrease propor-
tional to the amount of PCL added to the blend, which was
compensated in the sample containing kaolinite which shows
an increase in the gas barrier properties. Anyway, these
changes were clearly discernible but small. The effect of
the nanocomposites is currently under study but it is clear
that these compounds could be a valid route to decrease the
inherent rigidity of some biopolymers and to enhance their
applications.
Further studies on PLAproducts must be performed to de-
termine the range of compatibility of this polymer and to de-
termine the performance in real shelf-life studies. A study of
the Life-Cycle Assessment (LCA) for the PLA polymer was
just made by Bohlmann (2004), who made a comparison
with the most used polypropylene (PP) in food packaging ap-
plication. He found that PLAis more energy efcient than PP
polymer because PLA consumes no feedstock energy. How-
ever, when it is taken in consideration the uncertainty of the
estimation, the difference between the two polymers be-
comes marginalized. He found also that the PLA and PP
greenhouse gas emission are equivalent.
Fang et al. (2005) studied the possibility to make a multi-
layer lmwith PLAand a natural material like modied starch
to have equal or better performance characteristics to those of
existing product not biodegradable like polyethylene/polyvi-
nylidenchloride/polystyrene (PE/PVDC/PS) multilayer lms.
Starch is a totally biodegradable polymer coming from agri-
culture; it is abundant, renewable, safe and economics but as
a component of biodegradable laminate lm, it shows no plas-
tic behaviour, no adequate mechanical properties and it ther-
mally degrades at around 260

C. When it is extruded in
combination with plasticizers it becomes thermoplastic,
mouldable and an amorphous material with an excellent oxy-
gen barrier characteristic, but it is extremely sensitivity to the
environmental humidity giving rapid biodegradation.
Polyhydroxyalkanoates (PHA)
These polymers are produced in nature by bacterial fer-
mentation of sugar and lipids. They can be thermoplastic or
elastomeric materials, with a melting point between 40

C
and 180

C, depending on the monomer used in the synthesis.
These polymers, alone or in combination with synthetic plas-
tic or starch give excellent packaging lms (Tharanathan,
2003). The most common type is the polyhydroxybutyrate
(PHB), coming from the polymerization of 3-hydroxybuty-
rate monomer, with properties similar to PP but more stiffer
and brittle. The copolymer polyhydroxybutyrate-valerate
(PHBV), used as packaging material, is less stiff and tougher.
The price is veryhighbut it degrades in5e6weeks ina micro-
biology active environments, giving carbon dioxide and wa-
ter in aerobic condition. In anaerobic environment the
degradation is faster, with production of methane.
Yu, Chua, Huang, Lo, and Chen (1998) used different types
of food wastes as carbon source to produce several PHApoly-
mers with different physical and mechanical properties, like
exibility, tensile strength, melting viscosity. The use of
food waste is a good way to reduce the cost of bioplastics pro-
duction, but until now it is only an experimental procedure
without any possibility to have a commercial application.
Starch-based polymer
Commercial polymer coming from the synthesis of oil-
based monomer can be mixed with different percentage
(10, 50 and 90%) of starch used as additive. Depending
on starch percentage and other materials like additives (col-
ouring additives, ame retardant additives) the properties of
these materials can be varied a lot, becoming stable to un-
stable for example in hot/cold water.
Starch, consumed by microbial action, accelerates the
disintegration or fragmentation of polymer chain by pro-
ducing pores in the materials which weaken them. This pro-
cess is quite slow, it can be accelerated only if the starch
added to the mixture exceed 60%. Depending on the type
of the thermoplastic starch materials, they can degrade in
5 days in aqueous aerobic environment, in 45 days in con-
trolled compost and in water.
In 1993 LDPE-starch blend were commercialized under
the trade name Ecostar

. Other commercial trade names

are Bioplast

(from Biotec GmbH) and NOVON

(from
NOVON International) (www.designinsite.dk).
Starch can be transformed also into a foamed material us-
ing water steam, replacing the polystyrene foamas packaging
material. It can be pressed into trays or disposable dishes and
dissolves in water leaving a non-toxic solution, consumed by
microbic environment in about 10 days giving only water and
carbon dioxide as by-products. The commercial trade names
are Biopur

(from Biotec GmbH), Eco-Foam

(from Na-
tional Starch & Chemical) and Enviroll(from Norel).
Others biomaterials not used in food application
Another natural plastic material, the casein formalde-
hyde, can be generated from a natural protein obtained
from milk, horn, soy bean, wheat, etc. It looks like cellu-
loid, ivory or articial horn and it is insoluble in water, in-
ammable and odourless. This material is used to make
buttons, pins, cigarette-cases, umbrella handles and so on
but not in food application.
The cellulose acetate (CA) is an amorphous tough ther-
moplastic obtained by introducing the acetyl radical of ace-
tic acid into cellulose (cotton or wood). To decrease its
inammability it is used with additives, with self-extin-
guishing properties. Cellulose acetate is an insulator mate-
rial with a little tendency to electrostatic chargin, brittle
under freezing point. Horn is an organic thermoplastic ma-
terial containing 80% of keratin; it can be pressed in vari-
ous objects and laminas, like buttons, combs, pens, etc.
(www.designinsite.dk).
642 V. Siracusa et al. / Trends in Food Science & Technology 19 (2008) 634e643
Conclusions
Bioplastics development is just beginning; until now it
cover approximately 5e10% of the current plastic market,
about 50,000 t in Europe. The European countries with the
highest utilization of bioplastics are France, Germany, En-
gland, Netherland and Italy but other countries like Bel-
gium, Austria, Spain and Switzerland are going to utilize
it in individual applications. The principal eld regards
the use of lms packaging for food products, loose lm
used for transport packaging, service packaging like carry
bags, cups, plates and cutlery, biowaste bags, in agri- and
horticultural elds like bags and compostable articles.
Their development costs are high and yet they do not have
the benet of economic scale. The increased utilization of
biomass as energy source and raw materials is necessary in
the long term due to the fact that the crude oil and natural
gas resources are limited, but it is to be keep in mind that these
materials have to be found place in a very strong international
market of synthetic ones, with an annual plastics consump-
tion of approximately 200 million tons, with approximately
a 5% average growth per annum. However, plastics and bio-
plastics cover an abundance of types, each with its own indi-
vidual prole, so they present an enormous diversity which
makes them so successful in numerous applications.
It was shown that polyolens present the same oxo-bio-
degradability of biopolymers, but they are more economical
and effecting during use, so certain they will remain the
materials of choice for packaging application.
Bio-based polymers have already found important appli-
cations in medicine eld, where cost is much less important
than function. It seems very unlikely that biodegradable oil-
based polymers will be displaced from their current role in
packaging application, where cost is more important for the
consumer market than environmental acceptability.
Biopolymers fulll the environmental concerns but they
show some limitations in terms of performance like thermal
resistance, barrier and mechanical properties, associated
with the costs. Then, this kind of packaging materials needs
more research, more added value like the introduction of
smart and intelligent molecules (which is the nanotechnology
eld) able to give information about the properties of the food
inside the package (quality, shelf-life, microbiological safety)
and nutritional values. It is necessary to make researches on
this kind of material to enhance barrier properties, to ensure
food properties integrity, to incorporate intelligent labelling,
to give to the consumer the possibility to have more detailed
product information than the current system.
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