Beruflich Dokumente
Kultur Dokumente
Review
Biodegradable
polymers for food
packaging: a review
Valentina Siracusaa,*, Pietro
Rocculib, Santina Romanib and
Marco Dalla Rosab
a
Introduction
The current global consumption of plastics is more than
200 million tonnes, with an annual grow of approximately
5%, which represents the largest field of application for crude
oil. It emphasises how dependent the plastic industry is on oil
and consequently how the increasing of crude oil and natural
gas price can have an economical influence on the plastic
market (www.european-bioplastics.org). It is becoming increasingly important to utilize alternative raw materials. Until now petrochemical-based plastics such as polyethylene
terephthalate (PET), polyvinylchloride (PVC), polyethylene
* Corresponding author.
0924-2244/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tifs.2008.07.003
Chemistry of degradation
The bioplastic aim is to imitate the life cycle of biomass,
which includes conservation of fossil resources, water and
CO2 production, as described in Scheme 1 (www.
european-bioplastic.org).
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636
Although hydrocarbons polymers make a positive contribution to environment because they can be mechanically recycled if clean, incinerated with energy recovery, with
a calorific value almost identical to the oil from which they
coming on, they are not compostable. According to the European standard norm UNI EN 13432 (2002), a product to be
defined compostable must be biodegradable and disintegrable in brief time, or rather it must be turned from the microorganisms into water, carbonic and fertile anhydride
compost. Finally, to be defined compostable, the manufactured article must result compatible with a process of composting, that means it must not release dangerous
substances and must not alter the quality of the produced
compost. The last Financial Law out as objective the dismissing 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 justified, 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 renewable (Kale, Auras, & Singh, 2006). While most of the
commercialized biopolymer materials are biodegradable,
these are not fully compostable in real composting conditions, 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 shelflife. The specific barrier requirement of the package system
is related to the product characteristics and the intended
end-use application. Generally plastics are relatively permeable to small molecules such as gases, water vapour, organic 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
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638
where DHc is the exothermic enthalpy of cold crystallization, DHm is the endothermic enthalpy of fusion, DHcm is
the endothermic heat of melting of purely crystalline polymer under study (for example: for PLA is 135 J g1, Kale
et al., 2006; for PET is 125.6 J g1, 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 (pH 6, acetic acid solution) and strong acid
(pH 2, hydrochloric acid solution) for a period of 0, 1,
3, 5 and 7 days.
The most important analysis for film used in food packaging application is the determination of the oxygen, carbon dioxide and water vapour transmission rate (OTR,
CO2TR and WVTR, respectively). These tests are performed 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,
Aliphaticearomatic copolymers
These materials are a combination of polyetilene terephthalate (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,
too high for a degradable material. The aliphatic monomer creates a weak spots in the aromatic polymeric chain which makes
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
639
Tg ( C)
Tm ( C)
DHcm (J g1)
Percent crystallinity (xc)
Oxygen transmission rate (OTR)
(cc m2 day)a
Oxygen permeability
rate (OPC) (kg m m2 s1 Pa1)b
Water vapour transmission
rate (WVTR) (g m2 day1)a
Water vapour permeability
rate (WVPC) (kg m m2 s1 Pa1)c
a
PLA
62.1 0.7
150.2 0.5
93
29.0 0.5
56.33 0.12
4.33E-18 1.00E-19
15.30 0.04
1.34E-14 3.61E-17
640
CH3
HO
O poly
n
CH3
CH3
H2O
CH3
O
O
HO
O
O
CH3
CH3
O
O
CH3
O poly
HO
n
OH
CH3
H
HO
n
O
CH3
CH3
O poly
OH CH
3
As reported from Kale et al. (2006), Pometto et al. in a previous research studied the banana field exposition of PLA
film in Costa Rica. They found that this film lost its mechanical properties faster than during exposure in simulated conditions 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 coming from the hydrolytic degradation phenomena of PLA
polymer films 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 system 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 performance of the oriented PLA polymer (OPLA) in food application, Auras, Singh & Singh (2006) made a comparison
with two of the commonly used materials used for fresh
food packaging application, which are polyethylene terephthalate (PET) and oriented polystyrene (OPS). The physical experimental data obtained on PLA samples are
reported in Table 1.
Concerning the physical data, OPLA presents the lowest
Tg and Tm 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
film for food like tomato and other breathable products where
the oxygen and carbon dioxide barrier requirements are specifically 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, carbon dioxide and ethylene). Usually the specific gas requirements are achieved by controlling the type of films 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
641
higher than those for PET and OPS. The modulus of elasticity
showed a similar trend with the best value for the OPLA polymer, while the elongation at break was similar at room temperature for the three polymers but was much higher for PET
at value below the room temperature. 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 performance because the containers had different shapes.
The results for chemical resistance tests showed that exposure 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 increase 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 elongation at break, it becomes more brittle with an increase in
the modulus of elasticity which is an indication of the brittleness 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. However, same properties such as flexural properties, gas permeability, 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 polymer 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 utilized 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 conventional polymer extrusion process. By SEM analysis
they found that this blend is immiscible across the composition range studied, but is was observed a plasticization effect
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of the blend compared to the PLA matrix (by Dynamicmechanical analysis, DMA) and a slight increase in its thermal stability (by Thermo-gravimetric analysis, TGA) with an
increment of this effect with the PCL amount increment. The
gas barrier properties showed a significant decrease proportional 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 PLA products must be performed to determine the range of compatibility of this polymer and to determine 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 application. He found that PLA is more energy efficient than PP
polymer because PLA consumes no feedstock energy. However, when it is taken in consideration the uncertainty of the
estimation, the difference between the two polymers becomes marginalized. He found also that the PLA and PP
greenhouse gas emission are equivalent.
Fang et al. (2005) studied the possibility to make a multilayer film with PLA and a natural material like modified starch
to have equal or better performance characteristics to those of
existing product not biodegradable like polyethylene/polyvinylidenchloride/polystyrene (PE/PVDC/PS) multilayer films.
Starch is a totally biodegradable polymer coming from agriculture; it is abundant, renewable, safe and economics but as
a component of biodegradable laminate film, it shows no plastic behaviour, no adequate mechanical properties and it thermally degrades at around 260 C. When it is extruded in
combination with plasticizers it becomes thermoplastic,
mouldable and an amorphous material with an excellent oxygen barrier characteristic, but it is extremely sensitivity to the
environmental humidity giving rapid biodegradation.
Polyhydroxyalkanoates (PHA)
These polymers are produced in nature by bacterial fermentation 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 plastic or starch give excellent packaging films (Tharanathan,
2003). The most common type is the polyhydroxybutyrate
(PHB), coming from the polymerization of 3-hydroxybutyrate 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 very high but it degrades in 5e6 weeks in a microbiology active environments, giving carbon dioxide and water 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 PHA polymers with different physical and mechanical properties, like
flexibility, tensile strength, melting viscosity. The use of
food waste is a good way to reduce the cost of bioplastics production, 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 oilbased 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 (colouring additives, flame retardant additives) the properties of
these materials can be varied a lot, becoming stable to unstable for example in hot/cold water.
Starch, consumed by microbial action, accelerates the
disintegration or fragmentation of polymer chain by producing pores in the materials which weaken them. This process 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 controlled 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 using water steam, replacing the polystyrene foam as 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 National Starch & Chemical) and Envirofill (from Norel).
Others biomaterials not used in food application
Another natural plastic material, the casein formaldehyde, can be generated from a natural protein obtained
from milk, horn, soy bean, wheat, etc. It looks like celluloid, ivory or artificial horn and it is insoluble in water, inflammable 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 thermoplastic obtained by introducing the acetyl radical of acetic acid into cellulose (cotton or wood). To decrease its
inflammability it is used with additives, with self-extinguishing properties. Cellulose acetate is an insulator material with a little tendency to electrostatic chargin, brittle
under freezing point. Horn is an organic thermoplastic material containing 80% of keratin; it can be pressed in various objects and laminas, like buttons, combs, pens, etc.
(www.designinsite.dk).
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, England, Netherland and Italy but other countries like Belgium, Austria, Spain and Switzerland are going to utilize
it in individual applications. The principal field regards
the use of films packaging for food products, loose film
used for transport packaging, service packaging like carry
bags, cups, plates and cutlery, biowaste bags, in agri- and
horticultural fields like bags and compostable articles.
Their development costs are high and yet they do not have
the benefit 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 consumption of approximately 200 million tons, with approximately
a 5% average growth per annum. However, plastics and bioplastics cover an abundance of types, each with its own individual profile, so they present an enormous diversity which
makes them so successful in numerous applications.
It was shown that polyolefins present the same oxo-biodegradability 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 applications in medicine field, where cost is much less important
than function. It seems very unlikely that biodegradable oilbased polymers will be displaced from their current role in
packaging application, where cost is more important for the
consumer market than environmental acceptability.
Biopolymers fulfill 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
field) 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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