Nanotech packaging

Nanotechnology
in packaging:
a revolution in waiting
Back in 2000 the food industry was gripped by excitement
about nanotechnology and what it might mean for
future development and growth. Many of the larger food
manufacturers enthusiastically embraced the new field
and researchers in the academic sector took advantage
of generous funding opportunities and collaborations to
begin ambitious new programs that would herald a
much-hyped revolution in food technology. Eight years
later, much of the steam has gone out of nanotechnology
in the food sector, and most proposed nanofoods are still
a long way from the market. The one sector that has not
developed cold feet to quite the same extent is packaging.
Despite lingering concerns over safety, consumer resistance,
costs and regulation, the potential of the technology may
be about to be realised.
The US National Nanotechnology Initiative
defines nanotechnology as the understanding and control of matter at dimensions of
Food Engineering & Ingredients

roughly 1 to 100 nanometres, where unique

phenomena enable novel applications. It is
that last part of the definition that is really

important. Materials do not necessarily

behave in the same way at the nano-scale as
they do at a macro-scale. Take titanium dioxide for example. At the macro-scale it is a
brilliant white pigment used in a wide range
of applications, but nanoparticles of titanium
dioxide are transparent, though still resistant
to ultraviolet radiation and thus suitable for
a whole range of new applications. Many
materials have been found to have entirely
different physical, chemical and biological
properties at the nano-scale.
The food industry is a latecomer to the
nanotechnology field, and hasnt yet been
able to exploit its potential. There have
been plenty of ideas from products
containing nanoparticles of functional
ingredients and nanocapsules for delivering
flavours, to biofilm-resistant nanocoatings
for food processing equipment and even
futuristic notions of using nanotechnology
to create foods at a molecular level but
very few marketable products. Today, nanotechnology is barely mentioned by most
big food manufacturers. There are several
September 2008 Volume 33 Issue 3

possible reasons for this. One is undoubtedly cost many applications are significantly more expensive to make than existing
products. Another is uncertainty about
regulation of nanofoods. For example, the
European Food Safety Authority (EFSA)
Scientific Committee has been conducting
a risk assessment of the technology for the
European Commission and was due to publish an opinion on its deliberations in July,
although at the time of writing, this had
still not appeared. But probably the biggest
reason is the fear of a consumer backlash
like the one that greeted the introduction of
GM products.

Packaging sector leads the way

with nanocomposites
Food packaging is the one sector of the
industry where nanotechnology applications
are beginning to live up to their promise.
This is partly because packaging developers
have been able to come up with some costeffective nanotechnology applications that
have real benefits for food manufacturers,
consumers and the environment. Furthermore, recent consumer surveys have tended
to show much less concern over the use of
nanotechnology in packaging than its direct
application in foods. Crucially also, the
regulatory position for nanopackaging in
the EU is clearer than for nanofoods. This
is mainly a consequence of Regulation (EC)
1935/2004, which includes special requirements for active and intelligent packaging.
The main limitation on active and intelligent packaging over traditional materials
is that it should not cause changes, or give
information, that might mislead consumers as to the freshness and condition of
the food. This has allowed a more flexible
approach to new packaging technologies
than was previously the case. However,
there may still be issues over whether nanoparticles in packaging materials behave in
the same way as larger particles in terms of
migration into food, and testing to determine this may be crucial to the success of
some applications.

is embedded a filler material made up

of nanoparticles. These fillers may be
nanoscale particles of a metal or oxide,
nanotubes or fibres, or nanoclays, and
their function is to modify the physical
properties of the resin matrix. Most food
packaging applications developed to date
have incorporated metal or oxide particles, or more commonly nanoclays. It is
these nanoclay-based composites that have
found commercial applications and have
come on to the market.
Nanoclays are usually produced from
naturally occurring clays, such as montmorillonite (also sometimes known as
bentonite). The clay has to be purified and
then chemically treated to ensure that the
normally hydrophilic clay particles will
disperse properly in the resin matrix. The
clay filler is then mixed with the resin,
either during polymerisation or by a melt
compounding process. This is the most
difficult step in clay-based nanocomposite
production, since the particles need to
be evenly dispersed at the correct density. The process must also cause the clay
filler to exfoliate separate into single
plate-shaped particles about 1 nanometre
thick and 100 or more nanometres in
diameter and the plates must disperse so
that they sit parallel to the surface of the
resulting nanocomposite. This is the secret
of their functionality. The effect of evenly
dispersed nanoclay particles in a plastic is
to greatly increase its barrier properties,

especially for gases. This is because the

layers of clay platelets lying parallel to the
surface greatly increase the distance that
the gas has to travel before it can penetrate
the film, thus slowing gas transmission.
In effect, the clay filler does the same job
as a much thicker resin layer. These claybased nanocomposites also have UV-light
barrier properties, yet remain transparent,
and show greater strength than
non-composite resins.
Several companies have already mastered
the art of nanocomposite production and
currently offer products to packaging
developers. Honeywell has developed three
products for different applications making
up the Aegis range of nanoclay-based barrier nylon resins. Aegis OX is an oxygenscavenging nylon resin designed for use
as a barrier layer in PET containers where
high oxygen barrier properties are needed,
such as beer bottles. It is also resistant to
carbon dioxide transmission and delamination. PET bottles incorporating Aegis
OX are claimed to compare favourably
with glass bottles in terms of performance
and cost. Aegis HFX is also an oxygenscavenging nylon film with high barrier
properties, but is used in bottles for juices,
teas and condiments. It is also claimed to
stand up well to hot filling processes without delaminating. Finally, Aegis CSDE is
a non-scavenging resin with high carbon
dioxide retention properties, designed for
carbonated soft drinks and water.

Food packaging is the one sector of the industry

where nanotechnology applications are
beginning to live up to their promise.

At the forefront of nanotechnology in food

packaging is the rapidly growing field of
nanocomposites. These materials consist
of a resin matrix, such as nylon, in which
Food Engineering & Ingredients

September 2008 Volume 33 Issue 3

Nanotech packaging

US-based nanoclay producer Nanocor has

also developed its own range of high-barrier
nanocomposite nylon resins, called Imperm,
working in an alliance with the Mitsubishi
Gas Chemical Company. Imperm grade 103
is designed for use in multiplayer PET bottles for the beverage industry, whereas grade
105 is designed as a non-contact barrier layer
for multilayer films and sheets in combination with polyethylene, polypropylene and
other resins. Imperm 105 has good gas barrier properties and is said to help extend shelf
life in oxygen-sensitive food products, such
as cheese, snack products and cooked meats.
Researchers at Bayer Polymers also developed a nanoclay-based nanocomposite
called Durethan KU 2-2601, which is now
supplied by Lanxess AG. This material uses
polyamide resin and nanoclay filler from
Nanocor to produce a nanocomposite film
with much improved gas barrier properties
over plain polyamide. The film is also said
to have an enhanced gloss a result of the
clay particles beneficial influence on the
crystallisation of the plastic. Dr Ralph Ulrich
of Bayer Polymers research department saw
Durethan film as suitable for applications
in which conventional polyamides are too
permeable and EVOH is too expensive. A
particularly promising application is said to
be as a low-cost coating film for paperboard
cartons containing oxygen-sensitive products
like fruit juices.
Australian bioplastics producer Plantic Technologies has also been looking at nanocomposites in collaboration with the Cooperative Research Centre for Polymers and has
successfully tested the incorporation of
substantially exfoliated hydrophobic clays in
their Plantic R1 sheet. Plantic is a biodegradable plastic made from corn starch and the
addition of nanoclays improves its gas barrier
performance, clarity and strength. The result
is a material that can be used for rigid and
flexible food packaging and also has strong
green credentials. Nanocomposite technology
may have a key future role in improving the
performance of bioplastics, such as PLA.
Nanocomposites are the nanotechnology
products that have made by far the most
progress towards commercialisation. A 2004
Food Engineering & Ingredients

Bakery goods could benefit from packaging

materials which incorporate antimicrobials on
the inner surface of the package.

report predicted that consumption of these materials in the food

and drink industry could reach
around 50,000 tonnes by 2011,
with carbonated soft drinks and
beer producers being the biggest
customers. But there is no shortage of other ideas and potential
applications for nanotechnology in food packaging. Many of
these can be classified as active
or intelligent packaging applications. Proposals already being
investigated include nanosensors for temperature, time and
moisture monitoring, fluorescent
nanoparticles with attached
antibodies that can detect the
presence of food poisoning
bacteria, nanosensors that can
detect chemicals associated with
spoilage, nano-scale systems that
release preservatives into the
food in response to spoilage, and
even self repairing plastic films.
For example, researchers at the
University of Pisa in Italy have
developed a biodegradable plastic film that
can indicate when it has been exposed to
stretching and raised temperatures. The
polyester film contains nanoparticles of a
stilbene dye that normally forms aggregates
in the film, which look green under UV
light. Stretching and raised temperatures
pull these aggregates apart, causing the
film to appear blue. While some of these
ideas are very much at the research stage,
and may never be suitable for commercial
exploitation, one area that shows promise
for the emergence of practical products is
antimicrobial films.

Nanotechnology could
provide a boost for
antimicrobial packaging
Packaging materials incorporating antimicrobials were one of the first active packaging ideas to be investigated some years ago.
The idea was to use antimicrobials already
approved as food additives and apply
them to the inner surface of packaging to
improve product safety and reduce microbial spoilage. This could be particularly
useful for products vulnerable to surface

spoilage, like cheese, bakery goods and

sliced meat products, and which could be
vacuum packed or film wrapped so that
most of the product surface is in contact
with the packaging.
A number of antimicrobial compounds
have been investigated by researchers for
active packaging applications. For example,
traditional antifungal preservatives, such
as potassium sorbate, have been shown
to inhibit mould growth on pre-packed
cheeses when applied to the inner surface
of packaging. Elsewhere, a so-called natural
preservative, the bacteriocin nisin, has
been applied to the inner surface of LDPE
films, using methyl cellulose as a carrier,
to help control the growth of Listeria on
the surface of vacuum-packed hot dogs. A
number of these developments have proved
to be quite successful at a research level,
giving longer shelf life and better control of
pathogens. Although some products based
on these ideas have been launched in Japan,
it appears that only one type of antimicrobial packaging has made it to commercial
production in Europe.
September 2008 Volume 33 Issue 3

That exception is a range of materials

developed in Spain by researchers at the
University of Zaragoza, led by Professor
Cristina Nerin. Working with manufacturer
Artibal SA, the Zaragoza researchers have
been looking at essential oils from herbs
and spices, including cinnamon, oregano
and cloves, as the active components of
packaging. These essential oils have been
known to have a natural preservative effect
for many years and have been investigated
as preservatives for direct addition to foods.
So far, the collaboration has produced a
semi-rigid PET material with an added
antimicrobial and a flexible film coated
with a cinnamon extract that is claimed to
significantly increase the shelf life of bakery
products. They have also developed packaging incorporating natural antioxidants, such
as an extract of rosemary. Artibal says that
the packaging does not need to be in full
contact with the surface of the food, since
the antimicrobial and antioxidant effects
can occur in the vapour phase within the
pack. The technology can also be adapted
to all kinds of packaging materials.

silver nanoparticles behave differently from

larger pieces of the metal. Possibly because
silver in this form has a much larger surface
area, silver nanoparticles are far more effective at destroying bacteria and fungi. The
technology has been used effectively in
the medical field for some time to protect
medical devices from biofilm formation and
to make antimicrobial dressings, and antibacterial fabrics have also been developed
using nano-silver. By coating materials with
nanoscale silver particles, or bonding silver
cations into nanocomposites, it should be
possible to create effective and safe antimicrobial packaging. Some silver compounds
have already been evaluated successfully by
EFSA as antimicrobial additives for packaging
materials, although the assessments did not

Other researchers have developed similar

approaches based on essential oils. For
example, a group of scientists working for
the USDA Agricultural Research Service
have successfully tested edible films made
from apple puree and oregano oil as antimicrobial coatings for fresh produce that
can kill food poisoning bacteria, such as E.
coli O157. But all this research effort has
not led to the development of many commercial products. This may be because of
fears of consumer resistance and the danger
of expensive litigation in the event of any
failure of the technology. Despite this, some
experts believe that the potential offered
by applying a nanotechnology approach to
antimicrobial packaging could change that
concern in the future.

consider the implications of nanoparticles

of silver. In fact, the technology is already
in use in some parts of the world, such as
South Korea, China and the USA, to produce food storage containers, though not
food packaging as yet.

Leading the field of contenders for the

nanoscale approach to antimicrobial
packaging is nano-silver. Silver is one of
the oldest known antimicrobials and has
been used in the treatment of wounds for
centuries. Unfortunately it isnt very soluble
and its applications have been quite limited
until recently. But, like other materials,
Food Engineering & Ingredients

Another exciting idea is the development

of packaging films that actively generate a
biocide and release it into the pack. Based
on nanoscale controlled release technology,
Microsphre and Microlite are being developed by the Microactive Corporation in the
USA. The technology is designed to create
something that the company calls a Microatmosphre environment within the pack
by the sustained release of chlorine dioxide.
This is said to inhibit the growth of microorganisms and neutralise undesirable odours.
There is no need for direct contact between
food and packaging with this system, since it
produces a vapour in the pack. The Microatmosphre can be maintained for extended
periods and can also be switched on by UV
light or raised moisture levels.

Leading the field of contenders for

the nanoscale approach to anti-microbial
packaging is nano-silver.

One of the problems with nano-silver is

its cost, which may prove prohibitive for
disposable single-use packaging. Some
researchers have therefore looked at alternatives. A project at the University of Leeds in
the UK has been looking at the possibility
of using nanoparticles of zinc, calcium and
magnesium oxides and titanium dioxide in
antimicrobial packaging. Initial results have
been promising, and since these materials are
much cheaper to produce than silver, they
could be strong candidates for future antimicrobial packaging applications. It may also be
fruitful to look at other antimicrobials that
have already been investigated as packaging
additives on a macro scale, but not yet at the
nanoscale. For example, the performance of
natural preservatives, such as nisin and plant
essential oils might be enhanced if they were
applied to packaging as nanoparticles.

There is clearly a great deal going on at a

research level to develop effective nanotechnology-based antimicrobial packaging, but
there are also some big obstacles to overcome
before it can be successfully marketed. Safety
will have to be assured and uncertainties
over how nanoscale food contact-materials
will be regulated will have to be resolved to
make significant progress. Most importantly,
the consumer will have to be won over and
convinced of the benefits. The current industry approach to nanotechnology in general
appears to be not to talk about it, but the
wisdom of this as a long-term strategy must
be in doubt. An open debate is surely
a better option.

Comments on
this article?
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or simply questions
regarding the above article,
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September 2008 Volume 33 Issue 3