Sie sind auf Seite 1von 73

Food Packaging

Packaging is the technology


 enclosing or protecting products for distribution, storage, sale, and
use. and sells.[1] In many countries it is fully integrated into
government, business, institutional, industrial, and personal use.
 Package labeling is any written, electronic, or graphic
communication on the package or on a separate but associated label.
Packaging Materials
 wooden boxes, pottery vases, wooden barrels, woven bags
glass and bronze vessels.
 Metal container, Glass, leather
 Paper, wood
 Polymeric Material
Purpose of Packaging
• Physical protection - The food enclosed in the package may require protection
from, among other things, shock, vibration, compression, temperature, etc.
• Barrier protection - A barrier from oxygen, water vapor, dust, etc., is often
required. Permeation is a critical factor in design.
• Containment or agglomeration - Small items are typically grouped together in
one package for reasons of efficiency. powders, and granular materials need
containment.
• Information transmission - Packages and labels communicate how to use,
transport, recycle, or dispose of the package or product. Some types of
information are required by governments.
• Marketing - The labels on package can be used by marketers to encourage
potential buyers to purchase the product.
• Marketing communications and graphic design are applied to the surface of
the package and (in many cases) the point of sale display.
Purpose of Packaging
• Security - Packages may include authentication seals to help indicate that
the package and contents are not counterfeit. Packages also can include
anti-theft devices, such as dye-packs, RFID tags, or electronic article
surveillance tags, that can be activated or detected by devices at exit
points and require specialized tools to deactivate. Using packaging in this
way is a means of retail loss prevention.

• Convenience - Packages can have features which add convenience in


distribution, handling, stacking, display, sale, opening, reclosing, use, and
reuse.

• Portion control - Single serving packaging has a precise amount of


contents to control usage. Bulk commodities (such as salt) can be divided
into packages that are a more suitable size for individual households. It
also aids the control of inventory: selling sealed one-liter-bottles of milk,
rather than having people bring their own bottles to fill themselves.
Types of packaging materials : traditional
materials
 Wood
Wooden containers protect foods against crushing, have good stacking
characteristics and a good weight-to-strength ratio. Wooden boxes, trays and crates
have traditionally been used as shipping containers for a wide variety of solid foods
including fruits, vegetables and bakery products. Small wooden boxes are used to
pack tea or spices for tourist markets in some countries. Wooden barrels have been
traditionally used as shipping containers for a wide range of liquid foods, including
cooking oils, wine, beer and juices. They continue to be used for some wines and
spirits because flavour compounds from the wood improve the quality of the products,
but in other applications have been replaced by aluminium, coated steel or plastic
barrels.
 Leather
Leather containers made from camel, pig or kid goat hides have traditionally been
used as flexible, lightweight, non-breakable containers for water, milk and wine.
Manioc flour and solidified sugar were also packed in leather cases and pouches,
but the use of leather has now ceased for most commercial food applications.
Industrial materials
• These materials have been developed over the last 200-300 years and are the main types
of packaging used by small-scale food processors. The availability of glass, metal or plastic
containers varies considerably in different countries, and this, together with the relative
cost of different materials, determines their uptake by local processing industries. Where
these materials have to be imported, large minimum order sizes can be a significant
constraint on the development of a processing sector.
• Metal containers
There are two basic types of metal cans: those that are sealed using a ‘double seam’ and
are used to make canned foods and those that have push-on lids or screw-caps that are
used to pack dried foods (e.g. milk or coffee powder, dried yeast) or cooking oils
respectively. Double-seamed cans are made from tin plated steel or aluminium and are
lined with specific lacquers for different types of food. Cans have a number of advantages
over other types of container: when sealed with a double-seam they provide total
protection of the contents; they are tamper proof; and they can be made in a wide range of
shapes and sizes. However, the high cost of metal and the high manufacturing costs make
cans expensive compared to other containers. They are heavier than plastic containers and
therefore have higher transport costs. There are few can-making factories in developing
countries and small-scale food processors generally do not use metal cans because of these
disadvantages and/or lack of availability. Larger (200 litre) metal drums are widely used as
shipping containers for oils, juices and other liquid foods, although cheaper plastic drums
are steadily replacing them.
Other types of metal containers include aluminium foil cups and trays, laminated foil
pouches as alternatives to cans or jars, collapsible aluminium tubes for pastes, and
aluminium barrels. The advantages of aluminium are that it is impermeable to moisture,
odours, light and micro-organisms, and is an excellent barrier to gases. It as a good weight-
strength ratio and a high quality surface for decorating or printing.
Glass
Glass bottles and jars have some of the advantages of metal cans: they are impervious to
micro-organisms, pests, moisture, oxygen and odours; they do not react foods or have chemicals
that migrate into foods; they can be heat processed; they are recyclable, and (with new lids) they
are re-useable; they are rigid, to allow stacking without damage; and unlike metal cans,
they are transparent to display the contents. The main disadvantages of glass are: the higher
weight than most other types of packaging, which incurs higher transport costs; containers are
easily broken, especially when transported over rough roads; they have more variable dimensions
than metal or plastic containers; and there are potentially serious hazards from glass splinters
or fragments that can contaminate foods . Glass containers are still widely used for foods such as
juices, wines, beers, pickles/chutneys and jams , especially in countries that have a glass-making
factory, but their disadvantages and the high cost for imported containers in other places mean
that they are steadily being replaced by plastic containers.

Paper and cardboard


Paper and boards are made from wood pulp and additives are mixed into the pulp to
give particular properties to the packaging, including:
Fillers such as china clay, to increase the brightness of paper and improve surface
smoothness and printability.
Binders, including starches, vegetable gums, and synthetic resins to improve
the strength.
Resin or wax sizing agents to reduce penetration by water or printing inks.
Pigments to colour the paper and other chemicals to assist in the manufacturing
process.
Different types of paper are used to wrap foods: 'sulphate' paper is strong and
used for single- or multi-walled paper sacks for flour, sugar, fruits and vegetables;
'Sulphite' paper is lighter and weaker and is used for grocery bags and sweet wrappers,
as an inner liner for plastic biscuit wrappers and laminated with plastic films.
Greaseproof paper is sulphite paper made resistant to oils and fats, and used to wrap
meat and dairy products. ‘Glassine’ is a greaseproof sulphite paper that is given a high
gloss to make it resistant to water when dry, but it loses its resistance once it becomes
wet. Tissue paper is a soft paper used for example to protect fruits against dust and
bruising. Papers are also treated with wax to provide a moisture barrier and allow the
paper to be heat sealed. Wax coatings are easily damaged and the wax is therefore
laminated between layers of paper and/or polyethylene when used for bread wrappers
and inner liners for cereal cartons.

‘Paperboard’ is a term that includes boxboard, chipboard and corrugated or solid


fibreboards. Typically, paperboard has the following structure:
1. A top layer of white material to give surface strength and printability.
2. Middle layers of grey/brown lower grade material.
3. An under-layer of white material to stop the colour of the middle layer showing
through.
4. A back layer if strength or printability are required.
All layers are glued together with adhesive.
White board is suitable for contact with foods and is often coated with wax or laminated with plastic
to make it heat sealable. It is used for ice cream, chocolate and frozen food cartons. Chipboard is
made from recycled paper and is used for example as the outer cartons for tea or cereals but not
in contact with foods. It may be lined with white board to improve the appearance and strength.
Other types include moulded paperboard trays for eggs, fruit, meat or fish or for egg cartons.
Small paperboard tubs or cans are used for snackfoods, confectionery, nuts, salt, cocoa powder
and spices. Larger drums are used as a cheaper alternative to metal drums for powders
and other dry foods and, when lined with polyethylene, for cooking fats. They are lightweight,
resist compression and may be made water resistant for outside storage. Other products that
are handled in lined drums include fruit and vegetable products, peanut butter and sauces.
Corrugated board resists impact, abrasion and compression damage, and is
therefore used for shipping containers. Smaller more numerous corrugations give
rigidity, whereas larger corrugations or double- and triple-wall corrugated material
provides cushioning and resists impact damage. Corrugated cartons are used as
shipping containers for bottled, canned or plastic-packaged foods. Wet foods may be
packed by lining the corrugated board with polyethylene or a laminate of wax-coated
greaseproof paper and polyethylene, and used for chilled bulk meat, dairy products
and frozen foods.
Flexible plastic films

In general, flexible plastic films have relatively low cost and good barrier properties
Against moisture and gases; they are heat sealable to prevent leakage of contents;
they add little weight to the product and they fit closely to the shape of the food,
thereby wasting little space during storage and distribution; they have wet and dry
strength, and they are easy to handle and convenient for the manufacturer, retailer
and consumer. The main disadvantages are that (except cellulose) they are produced
from non-renewable oil reserves and are not biodegradable.
Concern over the environmental effects of non-biodegradable oil-based plastic
packaging materials has increased research into the development of ‘bioplastics’
that are derived from renewable sources, and are biodegradable. However, these
materials are not yet available commercially in developing countries.

There is a very wide choice of plastic films made from different types of plastic
polymer. Each can have ranges of mechanical, optical, thermal and moisture/gas
barrier properties. These are produced by variations in film thickness and the
amount and type of additives that are used in their production. Some films (e.g.
polyester, polyethylene, polypropylene) can be ‘oriented’ by stretching the material
to align the molecules in either one direction (uniaxial orientation) or two (biaxial
orientation) to increase their strength, clarity, flexibility and moisture/gas barrier
properties. There are thus a very large number of plastic films and small-scale processors should obtain
professional advice when selecting a material to ensure that it is suitable for the intended product and shelf life.
Typically, the information required includes: type of plastic polymer(s) required; thickness/strength; moisture
and gas permeability; heat seal temperature; printability on one or both sides; and suitability for use on the
intended filling machinery (see also Technical Brief: Filling and Sealing Packaged Foods).
A summary of the main different types of flexible plastic films is as follows:

Cellulose
Plain cellulose is a glossy transparent film that is odourless, tasteless and biodegradable
(within approximately 100 days). It is tough and puncture resistant, although it tears easily. It has
dead-folding properties that make it suitable for twist-wrapping (e.g. sugar confectionery). However,
it is not heat sealable and the dimensions and permeability of the film vary with changes in humidity. It is
used for foods that do not require a complete moisture or gas barrier, including fresh bread and some
types of sugar confectionery. Cellulose acetate is a clear, glossy transparent, sparkling film that is permeable
to water vapour, odours and gases and is mainly used as a window material for paperboard cartons.

Polypropylene
Polypropylene is a clear glossy film with a high strength and puncture resistance. It has a moderate barrier
to moisture, gases and odours, which is not affected by changes in humidity. It stretches, although less
than polyethylene. It is used in similar applications to LDPE. Oriented polypropylene is a clear glossy film
with good optical properties and a high tensile strength and puncture resistance. It has moderate
permeability to gases and odours and a higher barrier to water vapour, which is not affected by changes
in humidity. It is widely used to pack biscuits, snackfoods and dried foods.
Polyethylene (or polythene)
Low-density polyethylene (LDPE) is heat sealable, inert, odour free and shrinks when heated.
It is a good moisture barrier but is relatively permeable to oxygen and is a poor odour barrier.
It is less expensive than most films and is therefore widely used for bags, for coating papers or
boards and as a component in laminates.
Polyethylene is a thermoplastic polymer consisting of long hydrocarbon chains. Depending on the
crystallinity and molecular weight, a melting point and glass transition may or may not be observable.
The temperature at which these occur varies strongly with the type of polyethylene. For common
commercial grades of medium and high-density polyethylene the melting point is typically in the
range 120 to 180 °C (248 to 356 °F). The melting point for average, commercial, low-density polyethylene
is typically 105 to 115 °C (221 to 239 °F).

Chemical properties
Most LDPE, MDPE and HDPE grades have excellent chemical resistance, meaning that it is not attacked by
strong acids or strong bases. It is also resistant to gentle oxidants and reducing agents. Polyethylene burns
slowly with a blue flame having a yellow tip and gives off an odour of paraffin.
Classification of polyethylene

Low-density polyethylene (LDPE)


High-density polyethylene (HDPE)
Linear low-density polyethylene (LLDPE)

LDPE is also used for shrink- or stretch-wrapping. Stretch-wrapping uses thinner LDPE
(25 – 38 µm) than shrink-wrapping (45 - 75µm), or alternatively, linear low-density polyethylene I
s used at thicknesses of 17 - 24 µm. The cling properties of both films are adjusted to increase
adhesion between layers of the film and to reduce adhesion between adjacent packages.
HDPE is defined by a density of greater or equal to 0.941 g/cm3. HDPE has a low
degree of branching and thus low intermolecular forces and tensile strength. The
lack of branching is ensured by an appropriate choice of catalyst and reaction
conditions. HDPE is used in products and packaging such as milk jugs, detergent
bottles, butter tubs, garbage containers and water pipes. High-density polyethylene
(HDPE) is stronger, thicker, less flexible and more brittle than LDPE and a better
barrier to gases and moisture Sacks made from HDPE have high tear and puncture
resistance and have good seal strength. They are water proof and chemically
resistant and are increasingly used instead of paper or sisal sacks. They are mainly
used in oil packaging.

Linear Low density Polyethylene(LLDPE) LLDPE is defined by a density range of


0.915–0.925 g/cm3. LLDPE is a substantially linear polymer with significant
numbers of short branches, commonly made by copolymerization of ethylene with
short-chain alpha-olefins (for example,1-butene, 1-hexene and 1-octene). LLDPE
has higher tensile strength than LDPE, it exhibits higher impact and puncture
resistance than LDPE. Lower thickness (gauge) films can be blown, compared with
LDPE, with better environmental stress cracking resistance but is not as easy to
process. This is mainly used for high speed filling machine. It offers very
good sealing properties. They are popular for high clarity, high elongation,
softness.
Polypropylene

Polypropylene is a clear glossy film with a high strength and puncture resistance. It has a
moderate barrier to moisture, gases and odours, which is not affected by changes in humidity.
It stretches, although less than polyethylene. It is used in similar applications to LDPE.
Oriented polypropylene is a clear glossy film with good optical properties and a high tensile
strength and puncture resistance. It has moderate permeability to gases and odours and a
higher barrier to water vapour, which is not affected by changes in humidity. It is widely used
to pack biscuits, snackfoods and dried foods.

Cellulose
Plain cellulose is a glossy transparent film that is odourless, tasteless and
biodegradable (within approximately 100 days). It is tough and puncture resistant,
although it tears easily. It has dead-folding properties that make it suitable for
twist-wrapping (e.g. sugar confectionery).
However, it is not heat sealable and the dimensions and permeability of the film
vary with changes in humidity. It is used for foods that do
\ not require a complete moisture or gas barrier, including fresh bread
and some types of sugar confectionery. Cellulose acetate is a clear,
glossy transparent, sparkling film that is permeable to water vapour,
odours and gases and is mainly used as a window material for paperboard cartons.
Polymers used in packaging

Polyethylene terephthalate
Commonly used for bottles, trays, and as thin flexible film in ouches and flow wrap
applications. PET possesses excellent high‐temperature properties, high strength and
clarity, and has high oxygen and carbon dioxide barrier properties. Often used for
medical application pouches, boil‐in‐bag applications, meat, snack, and baked goods,
PET is an important player in the field of flexible packaging.
Types of plastic in packaging
• PE – Polyethylene
• Polyethylene later progressed to become three variations of itself—high density polyethylene (HDPE), low
density polyethylene (LDPE), and linear low density polyethylene (LLDPE). HDPE, LDPE, and LLDPE are
used in flexible packaging applications due to their flexibility, good low‐temperature performance,
durability, high moisture‐ barrier, and ability to seal to itself without any coating.PP – Polypropylene

LLDPE

LDPE

HDPE
Polypropylene(PP)
PP is commonly used in bottles, trays, and as a thin flexible film in pouches and flow wrap applications.
It is used commonly for meat trays and for bottles. There are a number of types of PP including OPP,
BOPP.

PS – Polystyrene
Is commonly used for pots, particularly yoghurt pots and some vegetable punnets. PS is not commonly
recycled in the UK and again can come in a number of formats including EPS.
PVC – Polyvinyl Chloride
Is still used in some applications such as trays and pots. However the UK has generally been moving
away from the use of PVC.
PA – (Polyamide or nylon)
Used as parts within trigger sprays and as a flexible film for barrier properties. Not currently recycled.
Also found in other formats such as OPA and BOPA.

Nylon 6,6
PROTECTION-BARRIER

• Oxygen Barrier PET, for example, provides a good


• ....PET barrier to oxygen, while HDPE fares much
• -Moisture Barrier worse. On the other hand, HDPE offers a
• ....BOPP, CPP, HDPE significantly better barrier against water vapor
• -High Gas & Moisture Barrier (Opaque) than PET. HDPE is used for packaging milk in
• .....Foil, Metallised Films bags and bottles.
• -High Gas & Moisture Barrier (transparent) LDPE is used for making plastic bags and
• ……PVDC coated films
containers for general purposes. PP has
excellent chemical resistance, is strong and
• High Gas Barrier(transparent)
has the lowest density of the plastics used. It
• ….Nylon,EVOH
has a high melting point,
• 􀂾 Medium light barrier
making it ideal for filling with hot liquids.
• …..White opaque films PET is a clear, strong and has good barrier
• 􀂾 High light Barrier properties to gases and moisture. The use of
• …..Foil and Metallised films PET to make plastic bottles for carbonated
• 􀂾 Physical Barrier(puncture resistance) drinks is increasing. It has good resistance to
• ……Nylon and Polyester heat, mineral oils, solvents and acids.
Frequently used as packaging film (mainly
made of PE, PP and PVC), containers (bottles,
cans, etc.) usually are made of PVC, PET and
PE, a polymer foam as a protective packaging .
LAMINATE STRUCTURES….
􀂾 PET/Foil/Poly...Light, Moisture and Gas Barrier
Example…Coffee Powder
􀂾 PET/MetPET/Poly.... Light, Moisture and Gas Barrier
Example…..Milk Powder , Biscuits
􀂾 BOPP and PET are interchangeable as printing layers
Biscuits
􀂾 BOPP / BOPP hs
􀂾 BOPP / Met BOPP hs
􀂾 BOPP / Met PE
􀂾 PET / Met PET / PE
Snack Food
Gas Flushed
􀂾 PET / Met PET / PE
TEA
PET / PE
BOPP / Paper / PE
COFFEE
PET/Foil/PE
PET/Met PET/PE
Ketch-up/Jams
􀂾 PET / Foil / PET / PE
􀂾 PET / Met PET / PE
􀂾 PET / PE / Foil / PE
Other films

Polyvinylidene chloride is very strong and is therefore used in thin films.


It has a high barrier to gas and water vapour and is heat shrinkable and heat sealable.
It has a brown tint which limits its use in some applications.

Polyamides (or Nylons) are clear, strong films over a wide temperature range (from – 60 to 200°C)
High barrier properties nand low permeability to gases and are grease proof.
The films are expensive to produce, require high temperatures to heat seal, and the permeability changes at different storage
humidities.

They are used with other polymers to make them heat sealable at lower temperatures and to improve the barrier properties, and
are used to pack meats and cheeses.

Coated films
Films are coated with other polymers or aluminium to improve their barrier properties or to
impart heat sealability. For example a nitrocellulose coating on both sides of cellulose film
improves the barrier to oxygen, moisture and odours, and enables the film to be heat sealed
when broad seals are used. Packs made from cellulose that has a coating of vinyl acetate are
tough, stretchable and permeable to air, smoke and moisture. They are used for packaging
meats before smoking and cooking. A thin coating of aluminium (termed ‘metallisation’)
produces a very good barrier to oils, gases, moisture, odours and light. This metallised film is
less expensive and more flexible than plastic/aluminium foil laminates.
Coextruded films
Coextrusion is the simultaneous extrusion of two or more layers of different polymers to
make a film. Coextruded films have three main advantages over other types of film: they
have very high barrier properties, similar to laminates but produced at a lower cost; they
are thinner than laminates and are therefore easier to use on filling equipment; and the
layers do not separate.
There are three main groups of polymers that are coextruded:
* Low-density and high-density polyethylene, and polypropylene.
* Polystyrene and acrylonitrile-butadiene-styrene.
* Polyvinyl chloride.

Typically, a three-layer coextrusion has an outside layer that has a high gloss and
printability, a middle bulk layer which provides stiffness and strength, and an inner layer
which is suitable for heat sealing. They are used, for example, for confectionery, snack-
foods, cereals and dried foods. Thicker coextrusions (75 - 3000 m) are formed into pots,
tubs or trays.
Oxygen transmission rate (OTR in cm3 m-2 d-1 atm-1 at 23°C, 50% RH)
and water vapor transmission rate
(WVTR in g m-2 d-1 at 23°C, 75% RH) of composite films based on 12 μm PET
films.
Film OTR WVTR Specification
(µm)
FiFilm OTR WVTR Specification (μm)
PET 110 15 12
PET/PE 0.93–1.24 0.248–0.372
12/50
PET/PVDC/PE 0.33 0.132
12/4/50
PET/PVAL/PE 0.13 0.26–0.39
12/3/50
PET/EVOH/PE 0.06 0.134–0.268
12/5/50
PET/Al-met/PE 0.06–0.12 0.006–0.03
12/–/50
PET/Al-foil/PE 0 0
12/9/50
PE = polyethylene low density; PET = polyethylene terephthalate; PVDC = polyvinylidene chloride;
PVAL = polyvinyl alcohol; EVOH = ethylene vinyl alcohol; Al-met = aluminum metallization;
SiOx = silicon oxide; Al-foil = aluminum foil.
Rigid and semi-rigid plastic containers
There is a wide range of plastic bottles, pots, jars, trays and tubs made from single or coextruded
plastics that are increasingly used for processed foods, when they are available in developing countries.

Advantages:
* Lower weight, resulting in savings of up to 40% in transport and distribution costs.
Cups, tubs and trays are tapered (a wider rim than base) for more compact stacking for transport and storage.
* Lower production costs using less energy.
* Tough, unbreakable and easy to seal.
* Very good barrier properties.
* Precisely moulded into a wider range of shapes than glass or metal containers.
* Can be colored for consumer appeal and to give UV-light protection to foods.

Disadvantages

Not biodegradable and re-usable,


Less rigid than glass or metal for stacking and cannot be heated to the same high temperatures as glass and metal.

Applications:
* Cups or tubs for margarine, processed meats, cheese, spreads, yoghurt, peanut butter, dried foods or ice
cream and desserts (high-nitrile resin copolymers or high-impact polystyrene and acrylonitrile butadiene styrene).
* Trays for meat products and chocolates, tubs for margarine or jams, and (polyvinyl chloride) - good oil resistance
and low gas permeability.
* Bottles and jars for fruit juices, squashes and juice concentrates, vinegar, cooking oil, milk, wine, syrup and, and as drums
for salt and bulk fruit juices (HDPE, polyvinyl chloride).
* Bottles for carbonated drinks (polyethylene terephthalate (PET) - PET is a very strong transparent glossy
film that is a good moisture and gas barrier. It is biaxially oriented to develop the strength for use in carbonated drinks bottles.
* Squeezable bottles and pots for mustard, mayonnaise, jams, tomato ketchup and other sauces .
(polypropylene coextruded with ethylene vinyl alcohol).
* Trays for chocolates, eggs, or soft fruit.
* Foam cartons or trays for eggs, fresh fruits and takeaway meals (polystyrene).
Controlling Volatile Flavors and Aromas
The loss of volatile flavors and aromas is a packaging issue that stems from the mass transfer of
components between and within food and its packaging. For example, direct contact between
the food and its packaging results in the migration of packaging components into food.
 The unintended absorption of volatile food flavors by package materials is known as flavor
scalping. Most incidences of migration occur in plastic packaging systems. Polyethylene
materials are responsible for most of the flavor scalping in food.
Both migration and flavor scalping are unfavorable because they deteriorate food quality and
reduce consumer confidence in packaged food items.
The solution to these issues is packaging components that incorporate absorption and barrier
controls. Flavor and odor absorbers usurp unwanted gaseous molecules such as volatile package
ingredients, chemical and microbial metabolites, respiration products, or rancid flavors and odors.
Flavor and odor utilize the same transfer mechanism as flavor scalping to remove unintended
Characteristics in the forms of sulfurous compounds, amines from protein degradation, aldehydes
and ketones, and bitter taste compounds. High-barrier packaging reduces absorption, desorption,
diffusion of gases and liquids to maintain food quality. It also assists in preventing oxygen and
water vapor from penetrating packages. Polymer blending, lamination and metallization are all
ways to enhance the barrier properties of packaging materials. Other innovative tools for
the barrier property of packaging material include transparent vacuum-deposited or
plasma-deposited coating of silica oxide PET films and composites of plastics
with nanoparticles.
Green Packages
One of the key trends within food packaging is sustainable packaging.
The Sustainable Packaging Coalition—an international consortium of
more than 200 industry members characterizes packaging as sustainable
if it meets the following criteria:
•It is beneficial, safe, and healthy for individuals and communities
throughout its life cycle;
• It meets market criteria for performance and cost;
• It is sourced, manufactured, transported, and recycled using renewable
energy;
• It maximizes the use of renewable or recycled source materials;
• It is manufactured using clean production technologies and best
practices;
• It is made from materials healthy in all probable end-of-life scenarios;
• It is designed to optimize materials and energy;
• It is recovered effectively and used in biological and/or industrial cradle
to-cradle cycles
Active and Intelligent Food Packaging
Active and intelligent food packages use more dynamic techniques to contain and preserve food.

Two common issues in maintaining the quality of packaged food are oxygen and moisture
control.

Oxygen in packages aids the growth of aerobic microbes and molds


Unintended odors and flavors and changes in color or nutritional quality.

Moisture in food packages may cause


 Powdered products to form lumps or crisp products to soften
 Supporting the growth of microbes.

Oxygen scavengers remove oxygen from food packages, thereby impeding the growth of microbes
and preserving the intended flavor and odor of foods.
Carbon dioxide emitters suppress microbial growth in products such as meat, poultry, and cheese.

Moisture-control agents suppress water activity, serving to remove fluids from meat products, prevent
condensation from fresh produce and curb the rate of lipid oxidation.
Maintaining humidity in packages is accomplished by humidity controllers, which can either diminish the
loss of moisture from foods or reduce excess moisture in the interstices of package closures.

Other tools in the array of active packaging components include antimicrobials and ethylene absorbers.
While active packaging incorporates robust ways to control oxidation, microbial growth, and moisture,
intelligent packaging designs facilitate the monitoring of food quality .
Time temperature indicators (TTIs), ripeness indicators, biosensors and radio
frequency identification (RFID) are all examples of intelligent packaging components.
Most of these smart devices have not had widespread commercial application, but two
are gaining more notoriety: TTIs and radio frequency identification. TTIs can play a
critical role in indicating the freshness and safety of a product. They monitor and
communicate which food products are safe to eat, which becomes extremely
important when food is stored in less than optimal conditions such as extreme heat or
freezing. In the case of foods that should not be frozen, a TTI would indicate whether
the food had been improperly exposed to cold temperatures. Conversely, a TTI could
specify whether foods sensitive to heat had been exposed to unnaturally high
temperatures and the duration of exposure.

Radio frequency Identification provides wireless monitoring of food packages through


tags, readers and computer systems. It increases the efficiency of supply chains. But
perhaps the ultimate benefits of RFID in food packaging are that it speeds stock
rotation and improves tracking.
Nano method may enhance food packaging
Nanotechnology is a method of controlling matter at near-atomic scales to produce unique or
enhanced materials, products and devices. With a different nanostructure, the gas and water
vapour permeability of plastics can be engineered to preserve fruit, vegetables, beverages,
wine and other food.

Several composites have been developed by adding reinforcing compounds to polymers to


enhance their thermal, mechanical and barrier properties.

Polymer composites are mixtures of polymers with inorganic or organic fillers with certain
geometries (fibers, flakes, spheres, particulates). The use of fillers which have at least one
dimension in the nanometric range (nanoparticles) produces polymer nanocomposites.

Depending on many dimensions, three types of fillers, are in the nanometric range can be
distinguished
Isodimensional nanoparticles, such as spherical silica nanoparticles or semiconductor
nanoclusters, have three nanometric dimensions.
Nanotubes or whiskers are elongated structures in which two dimensions are in the
nanometer scale and the third is larger.
When only one dimension is in the nanometer range, the composites are known as
polymer-layered crystal nanocomposites, almost exclusively obtained by the intercalation
of the polymer (or a monomer subsequently polymerized) inside the galleries of layered
host crystals.
A uniform dispersion of nanoparticles leads to a very large matrix/filler interfacial
area, which changes the molecular mobility, the relaxation behavior and the
consequent thermal and mechanical properties of the material.

Fillers with a high aspect ratio is important due to their high specific surface area,
providing better reinforcing effects . In addition to the effects of the
nanoreinforcements themselves, an interphase region of altered mobility
surrounding each nanoparticle is induced by well dispersed nanoparticles, resulting
in a percolating interphase network in the composite and playing an important role
in improving the nanocomposite properties.
For a constant filler content, a reduction in particle size increases the number of
filler particles, bringing them closer to one another; thus, the interface layers from
adjacent particles overlap, altering the bulk properties significantly. Besides
reinforcing nanoparticles, whose main role is to improve mechanical and barrier
properties of the packaging materials, there are several types of nanostructures
responsible for other functions, sometimes providing active or “smart”
properties to the packaging system such as antimicrobial activity, enzyme
immobilization, biosensing etc.

Some particles can have multiple applications, and sometimes the applications
of type 1 can overlap with type 2, such as some immobilized enzymes which can act
as antimicrobial components, oxygen scavengers and/or biosensors.
nanocomposites, almost exclusively obtained by the intercalation of the polymer
(or a monomer subsequently polymerized) inside the galleries of layered host crystals.
Polymer nano composities
 Nanostructures can be classified according to the number of dimensions
at the nanometer level.
 Nanospheres or nanoparticles have the three dimensions in the
nanoscale. Both nanowhiskers (nanorods) and nanotubes have two
nanometric dimensions, with the difference that nanotubes are hollow,
while nanowhiskers are solid.
 Nanosheets or nanoplatelets have only one nano-sized dimension .
 Some types of nanostructures can have multiple applications, and
sometimes applications can overlap, such as some immobilized enzymes
which can act as antimicrobial components, oxygen scavengers and/or
nanosensors.
 Uniform dispersion of the filler in the polymer matrix results in a very
large interfacial area matrix/filler, which reduces the mechanical
movement of the matrix and improves the mechanical, thermal
(particularly the glass transition temperature, Tg) and barrier properties
Polymer-Clay nano composities

Nanotechnology is a method of controlling matter at near-atomic scales to produce


unique or enhanced materials, products and devices. With a different nanostructure,
the gas and water vapour permeability of plastics can be engineered to preserve
fruit, vegetables, beverages, wine and other food.
Several composites have been developed by adding reinforcing compounds to
polymers to enhance their thermal, mechanical and barrier properties. Most of
these reinforced materials present poor interactions at the interface of both
components. Macroscopic reinforcing components usually contain defects, which
become less important as the particles of the reinforcing component are smaller.
Although several nanoparticles have been recognized as possible additives to
enhance polymer performance, the packaging industry has focused its attention
mainly on layered inorganic solids like clays and silicates, due to their availability,
low cost, significant enhancements and relative simple processability.
Toyota was the first company to commercialize nanocomposite materials, using
nano-sized montmorillonite clay to increase mechanical and thermal properties of
nylon . In food packaging, montmorillonite clay is being explored as the nano-
component in a variety of polymers: polyethylene, polyester, nylon, and starch.
Nanocomposite plastic films block oxygen, carbon dioxide, and moisture from
reaching food, so when used as packaging, the material extends the shelf life of
food.
Nanocomposite food packages are also light, strong, and heat resistant.
Nanocomposites hold promise in food packaging through improved barrier
properties, another type of nanomaterial shows great potential in managing
microbial growth
Carbon nanotubes exert powerful antimicrobial effects: Direct contact with
aggregates of carbon nanotubes proves to be fatal for Escherichia coli. The theory
is that the long, thin nanotubes puncture E. coli cells, causing cellular damage.
Nanosensors, when integrated with food packaging, can detect chemicals,
pathogens, and toxins in food. For example, biosensors have been developed that
detect Staphylococcus enterotoxin B, E.coli, Salmonella spp., and Listeria
moncytogenes. Nanosensors can also detect allergen proteins to prevent adverse
reactions to foods such as peanuts, tree nuts, and gluten .
1.Structure and properties of layered silicate

The commonly used layered silicates for the preparation of PLS nanocomposites belong to
the same general family of 2:1 layered or phyllosilicates. Their crystal structure consists of
layers made up of two tetrahedrally coordinated silicon atoms fused to an edge-shared octahedral
sheet of either aluminum or magnesium hydroxide. The layer thickness is around 1 nm, and the
lateral dimensions of these layers may vary from 30 nm to several microns or larger, depending
on the particular layered silicate. Stacking of the layers leads to a regular van der waals gap
between the layers called the interlayer or gallery.

Isomorphic substitution within the layers (for example, Al3+ replaced by Mg2+ or Fe 2+,
or Mg2+ replaced by Li+) generates negative charges that are counterbalanced by alkali
and alkaline earth cations situated inside the galleries.

This type of layered silicate is characterized by a moderate surface charge known as the cation
exchange capacity (CEC), and generally expressed as mequiv/100 gm. This charge is not locally
constant, but varies from layer to layer, and must be considered as an average value
over the whole crystal.
MMT, hectorite, and saponite are the most commonly used layered silicates
1.2. Structure and properties of organically modified layered
silicate (OMLS)

The physical mixture of a polymer and layered silicate may not form a nanocomposite.
In immiscible systems, the poor physical interaction between the organic and the
inorganic components leads to poor mechanical and thermal properties. In contrast,
strong interactions between the polymer and the layered silicate in PLS
nanocomposites lead to the organic and inorganic phases being dispersed at the
nanometer level. Pristine layered silicates usually contain hydrated N+ aþ or K+ ions .
Obviously, in this pristine state, layered silicates are only miscible with hydrophilic
polymers, such as poly(ethylene oxide) (PEO), or poly(vinyl alcohol) (PVA) . To
render layered silicates miscible with other polymer matrices, one must convert the
normally hydrophilic silicate surface to an organophilic one, making the intercalation
of many engineering polymers possible. Generally, this can be done by ion-exchange
reactions with cationic surfactants including primary, secondary, tertiary,
Preparation of Nanocomposites
• The nanocomposites are generally prepared by i) solution method, ii) insitu/
interlamellar polymerisation technique and iii) melt processing.

• i) In the solution method, the organoclay is swollen in a solvent. The polymer,


separately dissolved in that solvent is added to it so that the polymer molecules
can crawl between the silicate layers of the filler. The solvent is then evaporated to
obtain intercalated/exfoliated nanocomposite forms.

• ii) The in-situ method, also known as interlamellar polymerisation, involves


swelling of the layered silicates by absorption of a liquid monomer, or a monomer
solution. The monomer migrates into the galleries of the layered silicate, so that
polymerisation can occur within the intercalated sheets. Polymerisation can be
initiated either by heat or radiation, by diffusion of a suitable initiator, or by an
organic initiator.

• iii) The melt intercalation method involves incorporation of clay filler in the molten
state of the polymer to form the nanocomposite material. The last method is
widely accepted in nanocomposite research due to its solvent-free process.

and quaternary alkylammonium or alkylphosphonium cations. Alkylammonium
or alkylphosphonium cations in the organosilicates lower the surface energy of
the inorganic host and improve the wetting characteristics of the polymer
matrix, and result in a larger interlayer spacing. Additionally, the
alkylammonium or alkylphosphonium cations can provide functional groups
that can react with the polymer matrix, or in some cases initiate the
polymerization of monomers to improve the strength of the interface between
the inorganic and the polymer matrix.
Improving compatibility of clays with polymers

The homogeneous dispersion of most clays in organic polymers is not easy due to the
hydrophilicity of its surface. Organoclays, products from interactions between clay
minerals and organic compounds, have found an important application in polymer
nanocomposites. A proper organophilization is a key step for successful exfoliation of
clay particles in most polymeric matrices. The organophilization reduces the energy of
the clay and improves its compatibility with organic polymers. Organoclays are
cheaper than most other nanomaterials, since they come from readily available
natural sources, and are produced in existing, full-scale production facilities.
Organomontmorillonite (oMMT) have been produced, for example, by exchanging
inorganic cations of MMT with organic ammonium ions, improving compatibility of
MMT with organic polymers, leading to a more regular organization of the layers in
the 3 structures, and decreasing the water uptake by the nanocomposite.
Improving compatibility of clays with polymers
The homogeneous dispersion of most clays in organic polymers is not easy due
to the hydrophilicity of its surface . Organoclays, products from interactions
between clay minerals and organic compounds, have found an important application
in polymer nanocomposites. A proper organophilization is a key step for successful
exfoliation of clay particles in most polymeric matrices. The organophilization
reduces the energy of the clay and improves its compatibility with organic
polymers.
Organoclays are cheaper than most other nanomaterials, since they come from
readily available natural sources, and are produced in existing, full-scale production
facilities.
Organomontmorillonite (oMMT) have been produced, for example, by exchanging
inorganic cations of MMT with organic ammonium ions, improving compatibility
of MMT with organic polymers, leading to a more regular organization of the layers
in the 3 structures, and decreasing the water uptake by the nanocomposite .
CATION EXCHANGE REACTION
Bentonite Organic Compound Organoclay
ORGANOPHILIZATION PROCESS
Clay Organo Clay

in water
Bentonite suspension Cation exchange

Filtration/ Drying
Washing Milling

OPTIMIZATION OF
ORGANOPHILIZATION PROCESS

1. Type of bentonite
2. Purification process
3. Reaction time
4. Type of amine & Amine additional level
5. Type of reaction
6. Washing/filtration
7 Milling/Particle size
ORGANOCLAY CHARACTERIZATION
(1)CATION EXCHANGE CAPACITY (CEC)
􀂾 Silver – Thiouria Method
The organophilization percent (%) is calculated:
(Organophilization percent) % = [(CEC)orig. - (CEC)fin.]*100/ (CEC)orig.
(2) XRD

(3) SWELLING INDEX IN ORGANIC SOLVENTS


ADVANTAGES OF POLYMER NANO COMPOSITES

• Improved mechanical and thermal properties


• Reduced gas permeability
• Reduced flammability
• Increased biodegradability
Improving compatibility of clays with polymers
The homogeneous dispersion of most clays in organic polymers is not easy due to
the hydrophilicity of its surface . Organoclays have found an important application
in polymer nanocomposites. A proper organophilization is a key step for
successful exfoliation of clay particles in most polymeric matrices. The
organophilization reduces the energy of the clay and improves its compatibility
with organic polymers. Organoclays are cheaper than most other nanomaterials,
since they come from readily available natural sources, and are produced in
existing, full-scale production facilities. Organomontmorillonite (oMMT) have
been produced, for example, by exchanging inorganic cations of MMT with
organic ammonium ions, improving compatibility of MMT with organic polymers,
leading to a more regular organization of the layers in the 3 structures, and
decreasing the water uptake by the nanocomposite.
Surfactants can also be used to improve the dispersibility of the clay. Amphiphilic
block and random polyethylene copolymers can be used as surfactants to improve
dispersion of oMMT in a polyethylene (PE) matrix; the surfactants were able to
increase spacing between clay layers (d-spacing) to different extents, depending
on the number of polar units in the copolymer molecules. Maleic anhydride
grafted cellulose acetate butyrate (CAB-g-MA) is also used as compatibilizer for
cellulose acetate nanocomposites with an oMMT. Nanocomposites with
compatibilizer showed better exfoliated structure and better mechanical properties
than the counterpart without compatibilizer.
a) exchangeable nanocomposites that forms by penetration of the polymer chains in
the interlayer region of clay, producing a multi-layer furnished structure with
alternating polymer/inorganic layers and b) stratified (exfoliated) nanocomposites
that involve penetration of extensive polymer with clay layers delaminated and
randomly dispersed in a polymer matrix. Exfoliated nanocomposites show the best
performance for optimal interaction of clay-polymer.

Cellulose filler are interesting materials for the preparation of low-cost, lightweight
and very strong
Types of nanocomposities
In general, layered silicates have layer thickness on the order of 1 nm and a very
high aspect ratio(e.g. 10–1000). A few weight percent of layered silicates that
are properly dispersed throughout the polymer matrix thus create much higher
surface area for polymer/filler interaction as compared to conventional
composites. Depending on the strength of interfacial interactions between the
polymer matrix and layered silicate (modified or not), three different
types of PLS nanocomposites are thermodynamically achievable .

Intercalated nanocomposites: In intercalated nanocomposites, the insertion of a


polymer matrix into the layered silicate structure occurs in a crystallographically
regular fashion, regardless of the clay to polymer ratio. Intercalated
nanocomposites are normally interlayer by a few molecular layers of polymer.
Properties of the composites typically resemble those of ceramic materials. The
intercalated nanocomposites result from the penetration of polymers chains
into the interlayer region of the clay, resulting in an ordered multilayer
structure with alternating polymer/inorganic layers at a repeated distance of a
few nanometers .
Typically clay for nanocomposites are usualy two dimensional plate, a very thin (typically
about 1 nm) and several micrometers in length.
The most studied clay is montmorillonite (MMT) which has a general chemical
formula (Na,Ca)0.33(Al,Mg)2(Si4O10)(OH)2·nH2O, a soft 2:1 layered phyllosilicate clay
comprised of highly anisotropic platelets separated by thin layers of water ).
The platelets have an average thickness of about 1 nm and average lateral dimensions
ranging between a few tens of nm to several μm.
Each platelet contains a layer of aluminum or magnesiumhydroxide octahedra sandwiched
between two layers of silicon oxide tetrahedra.
Montmorillonite is a 2:1 layered phyllosilicates, whose boards have double-layer sheets of
tetrahedral silica filled with a central octahedral sheet of aluminum. This type of clay has a
moderately negative charge on the surface of which is important for defining
Flocculated nanocomposites: Conceptually this is same as intercalated nanocomposites. However, silicate
layers are some times flocculated due to hydroxylated edge–edge interaction of the silicate layers.

Exfoliated nanocomposites: In an exfoliated nanocomposite, the individual clay layers are separated in a
continuous polymer matrix by an average distances that depends on clay loading. Usually, the clay
content of an exfoliated nanocomposite is much lower than that of an intercalated nanocomposite.
Exfoliated nanocomposites have been reported to exhibit the best properties due to the optimal interaction
between clay and polymer.

Polyolefins such as polypropylene (PP) , polyethylene (PE) , polyethylene oligomers,


copolymers such as poly(ethylene-covinyl acetate) (EVA), ethylene propylene diene
methylene linkage rubber (EPDM) and poly (1-butene) have been used. Biodegradable
polymers for the preparation of nanocomposites such as polylactide ( PLA) is also used.
Techniques used for the characterization of nanocomposites

The structure of nanocomposites has been established using WAXD analysis and
transmission electron micrographic (TEM) observation. Due to its easiness and
availability WAXD is most commonly used to probe the nanocomposite structure
and occasionally to study the kinetics of the polymer melt intercalation. By
monitoring the position, shape, and intensity of the basal reflections from the
distributed silicate layers, the nanocomposite structure (intercalated or exfoliated)
may be identified. For example, in an exfoliated nanocomposite, the extensive layer
separation associated with the delamination of the original silicate layers in the
polymer matrix results in the eventual disappearance of any coherent X-ray
diffraction from the distributed silicate layers. On the other hand, for intercalated
nanocomposites, the finite layer expansion associated with the polymer intercalation
results in the appearance of a new basal reflection corresponding to the larger
gallery height. Although WAXD offers a convenient method to determine the
interlayer spacing of the silicate layers in the original layered silicates and in the
intercalated nanocomposites (within 1–4 nm), little can be said about the spatial
distribution of the silicate layers or any structural non-homogeneities in
nanocomposites. Additionally, some layered silicates initially do not exhibit well-
defined basal reflections. Thus, peak broadening and intensity decreases are very
difficult to study systematically. Therefore, conclusions concerning the mechanism of
nanocomposites formation and their structure based solely on WAXD patterns are
only tentative.
On the other hand, TEM allows a qualitative understanding of the internal structure,
spatial distribution of the various phases, and views of
the defect structure through direct visualization. The WAXD patterns and
corresponding TEM images of three different types of nanocomposites are presented
in Fig.
PROPERTIES OF NANOCOMPOSITES
Several properties e.g., mechanical strength, thermal properties, flammability and barrier properties of PCN materials are
claimed to be improved when compared to neat polymer counterparts. The extent of the enhancement is dependent on the
type of polymer and nanoclay used as well as the extent of dispersion of the nano-particle in the polymer matrix.

Mechanical Properties
The modified organoclays have the potential to improve the mechanical properties of the matrix polymer
substantially even with a low level of filler loading, usually 1-5 wt%. At such a low filler loading, polymers
such as Nylon-6 show significant improvement in mechanical properties e.g., an increase in Young’s modulus of 103%,
and in tensile strength of 49% . It is found that 100% increase in Young's Modulus of low-density polyethylene (LDPE)
could be achieved using chemically treated nanoclay fillers.

Barrier properties

Barrier properties against oxygen, carbon dioxide, ultraviolet, moisture and volatiles are perhaps the most important
properties that a nanocmposite food packaging can offer. Significant improvement in the gas barrier properties of Nylon-6 is
observed in which ultra-thin, nanoscale silicate platelets of high aspect ratio. The improvement in the barrier properties by
incorporation of nanoclay fillers in the polymer matrix can be explained by considering the layered clay sheets as
impermeable obstacles in the path of the diffusion process. In a well exfoliated and dispersed state, individual clay platelets
are believed to increase the barrier properties by creating a maze or ‘tortuous path’ that retards the progress of gas and
vapour molecules through the polymer matrix.The effective diffusivity through PCN depends on clay sheet orientation,
volume fraction, polymer-clay interaction and aspect ratio.
Figure Tortuous path of a permeant in a clay nanocomposite
Since clay layers constitute a barrier to gases and water, forcing them to follow a tortuous path, the introduction of
nanoclays into polymer structures has been shown to greatly improve barrier properties. The most widely known theories
to explain the improved barrier properties of polymer-clay nanocomposites are based on a theory developed by Nielsen
(1967), which focuses on a tortuous path around the clay plates, forcing the gas permeate to travel a longer path to diffuse
through the film. The increase in path length is a function of the high aspect ratio of the clay filler and the volume % of
the filler in the composite. Nielsen's model predicts permeability of systems at clay loading rates of less than 1%, but
experimental data deviates significantly from predicted values at higher loading rates and more extensively in certain
polymers. According to Bharadwaj (2001), increased length of silicate sheets enhance the barrier properties, because of
the increased tortuosity. Many deviations can be explained by factors such as poor clay orientation or less than complete
exfoliation. However, even those factors cannot explain much lower permeability than predicted proposed a new model to
predict permeability of polymer nanocomposites, focused on the polymer-clay interface as the governing factor in
addition to the tortuous path.
This model provides a correction factor applicable to Nielsen’s model.
It defines three 3 regions around clay plates: the surface modifier region, the constrained polymer
region, and the unconstrained polymer region. The surface modifier region (1-2 nm) binds the
clay with the polymer; it is assumed to be small enough to have little effect on the permeability
of the composite. The unconstrained polymer region is not affected significantly by the clay, its
properties being that of the bulk polymer. The constrained polymer region, less well defined and
indirectly confirmed, is in direct contact with the surface modifier and may extend 50-100 nm
from the clay surface as a function of polymer interaction parameters; it is assumed to have a
lower free volume and therefore a lower diffusion coefficient than that of the bulk polymer.
Since the main effect of the constrained region is to lower free volume, and this effect is not
significant in crystalline regions, the constrained region of semicrystalline polymers does not
significantly affect permeability unless the crystallinity is decreased. Indeed, most of the large
deviations from the simple tortuous path model involve amorphous polymers.

The oxygen barrier properties of nylons is further enhanced by a novel active barrier approach
where proprietary polymeric oxygen scavengers were melt blended into nanoscale dispersions
of high oxygen scavenging efficiency.
Nylons (Aegis) were developed for use in multilayer packaging structures, particularly in
multilayer, co-injection stretch blow moulded of EVOH nanocomposites for multi-layer
papolyethylene terephthalate (PET) bottles for extended shelf-life packaging of oxygen sensitive
foods and beverages. Ethylenevinyl alcohol copolymer (EVOH) nanocomposite has achieved the
oxygen barrier requirement for the MRE. However, these properties are dependent on
temperature and humidity. These EVOH nanocomposite layers are being sandwiched between
LDPE using a new in-house co-extrusion line to make multilayer films.
These applications are likely to utilize a co-injected multi-layer preform with the nanocomposite
barrier layer on the inside. Nanocor claimed significant progress in joint development ckaging.
Nanocor introduced a new nanoclay, Nanomer , designed for compounding with EVOH. Within
the range of 50-80% relative humidity, it reduces oxygen permeability of EVOH by 66-80%.
It has been found that moisture absorption and diffusion is dependent on the type of
organoclay. The moisture permeability of octadecylamine-modified MMT is lower than that of
quaternary alkylaminemodified MMT (KH-MT), due to the larger interlayer distance that
extends the water molecules’ diffusion path in the nanocomposites. Mixing with an epoxy resin
followed by curing resulted in intercalation of clay with an interlayer distance of 3.3 nm. The
enhanced gas/vapour barrier properties of nanocomposites make them attractive and useful in
food packaging applications, both flexible and rigid. Specific examples include packaging for
processed meats, cheese, confectionery, cereals and boiling the-bag foods, also extrusion-
coating applications in association with paperboard for fruit juice and dairy products, together
with co-extrusion processes for the manufacture of beer and carbonated drinks bottles. The use
of nanocomposite formulations is expected to considerably enhance the shelf life of many types
of food. It provides gas barriers to carbon dioxide and oxygen resulting in a shelf life up to 3-6
months for beers and fruit juices and up to one year for carbonated soft drink
Thermal stability
The thermoplastic poly(vinyl chloride) (PVC) together with polyethylenes, is nowadays used in
a wide range of food packaging. Although PVC provides excellent mechanical properties,
high compatibility with additives, processability and low cost, the evolution of hydrogen
chloride gas, extensive discolouration and lowering of physical and mechanical properties
are still serious thermal degradation problems The thermal decomposition behaviour and
linear dimensional changes of recycled PVC (RPVC) could be improved by the incorporation
of organically modified clays. In the case of RPVC/clay nanocomposites the degree of
improvement of the above properties was proportional to the clay content.
The thermal expansion (CTE) of RPVC/clay nanocomposites decreased with increasing
clay content. For example, CTE of RPVC was decreased by about 3.5 times by incorporating
only 5% of organically modified clay.
Flammability reduction
It has been reported that this novel class of clay fillers can also be useful to reduce flammability.
Under fire-like conditions nanocomposites form char with a multilayered carbonaceous silicate
structure which helps in improving flammability properties regardless of exfoliation or
intercalation of clay lamellae. This multilayered carbonaceous silicate char formed on the
surface during burning insulates the underlying material and reduces volatile products’ escape
rate during decomposition. This property can be estimated by measuring the heat release rate
(HRR) of the nanocomposites. Improved flammability reduction of polystyrene, Nylon 6 and
maleic anhydride grafted polypropylene nanocomposites are evident from 50 to 75% lower
HRR during combustion. As minor disadvantages of nanoclays on polymers, have described
decreased transparency.
Layer-by-layer (LbL) assembly involving clays
Layer-by-layer (LbL) self-assembly is a method by which a multilayer coating/film of
nanometer-thick layers can be made by sequential adsorption of oppositely charged
polyelectrolytes on a solid support . This multilayer film can be made by depositing
intercalating layers of anionic sodium MMT and cationic polyacrylamide on a PET
substrate. Oxygen transmission rate (OTR) decreased as a function of number of
bilayers deposited, until a negligible value - below 0.005 cm3/(m2.day.atm) has been
achieved with a 30-bilayer film, which is attributed to a brick wall nanostructure
comprised of completely exfoliated clay. The resulting thin film, potentially
microwaveable and with a good optical transparency (higher than 90%), is presented
as a good candidate for aluminum foil replacement in food packaging. The LbL
assemblies swelled when exposed to high environmental humidity, which can be
explained by decreasing the volume concentration of clay platelets and increasing
distance between them.
Examples of polymer nanocomposites with montmorillonite with improved barrier
properties are made of polymer matrix: polyamide, polystyrene, polyolefins, polyethylene
terephthalate, epoxy resins, polyurethanes. Examples of these polymer composites are:
- Imperm® (Color Matrix Europe) - used in multilayer PET bottles and sheets for food and
beverage packaging to minimise permeation of O2 and loss of CO2 from beverages.
- Duretham ® KU 2-2601 (LANXESS Deutschl and GmbH) - nanocomposite films based on
polyamides with improved properties when required better barrier properties in
packaging juices.
- Aegis® OX (Honeywell Polymers) a polymerised nanocomposite film contains a blend of
active and passive nylon that incorporate active O2 scavengers and passive
nanocomposite clay particles to enhance barrier properties.
BIODEGRADABLE POLYMER CLAY NANOCOMPOSITES
This special class of polymer follows microbially induced chain scission (i.e. the
enzymatic action of living organisms such as bacteria, yeasts and fungi) leading to
mineralisation, often called biodegradation, under a few specific conditions such as pH,
humidity, oxygenation and the presence of some metals.
 Biodegradable polymers such as starch, polylactic acid (PLA) and polycaprolactone (PCL)
have attracted considerable attention in the packaging industry. Owing to its
biodegradability, wide availability and low cost, starch-based material has received
enormous interest for food packaging applications.
Limitation of starch
Poor film forming Properties
Starch is commonly pretreated with a plasticiser to make it thermoplastic thus enabling
melt-processing as thermoplastic starch (TPS) .
Poor barrier properties : the use of starch films such as high water, gas and solute
permeability and uptake.
These problems of starch and starch products can be decreased by homogeneous
incorporation of sheet-like non-permeable barrier elements such as clay minerals by mix-
melting. The nanoclays are the potential ingredient in this application as they are
environmentally acceptable, naturally abundant minerals that are toxin-free and can be
used as one of the components for food packaging.

Poor mechanical Properties:


Poor Thermal Properties:
•Starch-polymer clay nanocomposite
•The relative water vapour diffusion coefficient of TPS was decreased to
about 65% of the value without montmorillonite
•The temperature at which the composite lost 50% weight was increased
from 305 to 3360C.
•A noticeable improvement in the O2 gas permeability of PLA clay
nanocomposites made using a melt intercalation technique. They found
systematic improvement in the above property with increasing clay content.
Even at 4% clay loading, the permeability of the nanocomposite was reduced
by about 40 %, which further reduced to about half of the PLA permeability
value at 6% clay loading. This phenomenon might be explained by the
increase in the lengths of the tortuous paths in nanocomposites in the
presence of high clay content.
The nanocomposite materials from starch and clay (PS/C) have higher
Young’s modulus and stress at peak values indicating the highest tensile
strength at all relative humidity storage conditions, compared with the
material without nanoclay
Bio-nanofibers such as chitosan, cellulose and collagen have high specific surface area per unit
of weight and 1000-times relative to the microfibers, excellent mechanical properties and are
lightweight. The fibers may in some cases have superior properties compared to traditional
polymers and can be used in both cases, either as a packaging material or as an additive to be
injected into the polymer matrix in order to achieve additional functional properties
Cellulose-based nanoreinforcements
Structure and obtainment
Cellulose, the building material of long fibrous cells, is a highly strong natural polymer.
Cellulose nanofibers are inherently a low cost and widely available material.

They are environmentally friendly and easy of recycling by combustion, and require
low energy consumption in manufacturing. All of this makes cellulose nanofibers an
attractive class of nanomaterials for elaboration of low cost, lightweight, and high-
strength nanocomposites

Basically two types of nano reinforcements can be obtained from cellulose - microfibrils
and whiskers. In plants or animals the cellulose chains are synthesized to form
microfibrils (or nanofibers), which are bundles of molecules that are elongated and
stabilized through hydrogen bonding. The microfibrils have nanosized diameters (2-
20 nm, depending on the origin), and lengths in the micrometer range. Each microfibril
is formed by aggregation of elementary fibrils, which are made up of crystalline and
amorphous parts. The crystalline parts, which can be isolated by several treatments, are
the whiskers, also known as nanocrystals, nanorods, or rodlike cellulose microcrystals,
with lengths ranging from 500 nm up to 1-2 μm, and about 8-20 nm or less in diameter
, resulting in high aspect ratios. Each microfibril can be considered a string of whiskers,
linked along it by amorphous domains (which act as structural defects), and having a
modulus close to that of a crystal of native cellulose (about 150 GPa) and a strength of
about 10 GPa values which are only about seven times lower than those of single-
walled carbon nanotubes
The main method used to obtain cellulose whiskers has been acid hydrolysis,
consisting basically in removing the amorphous regions present in the fibrils
leaving the crystalline regions intact; the dimensions of the whiskers after
hydrolysis depend on the percentage of amorphous regions in the bulk fibrils,
which varies for each organism. Cellulose whiskers are not yet commercially
available, instead microcrystalline cellulose (MCC), a closely related item, is
available. MCC is formed by particles of hydrolyzed cellulose consisting of a very
large amount of cellulose microcrystals together with amorphous areas . MCC is
prepared by removing part of the amorphous regions by acid degradation having
the less accessible crystalline regions as fine crystals of typically 200-400 nm in
length and an aspect ratio of about 10. Degree of polymerization (DP) is 6 about
140-400, depending on the cellulose source and treatment procedure .
Internal structure of a cellulose microfibril: (A) a cellulose chain; (B) an elementary fibril
containing bundles of cellulose chains; © parallel elementary fibrils; (D) four microfibrils
held together by hemicellulose and lignin
Factors affecting performance of cellulose nanoreinforcements
The resulting properties of nanocomposites with cellulose fibers depend
 dimensions
 aspect ratio of the fibers
 geometric and mechanical percolation effects
 orientation of cellulose fibers
 Percolation theory predicts a maximum improvement in composite properties when
there are just enough fillers to form a continuous structure, since they are properly
dispersed within the matrix , which means that modulus and strength are expected to be
improved if each fiber is in contact with two more others, on average . It has been reported a
2.5-fold increase in modulus of PVOH when 5% fibers were added, but further increases in
fiber contents were not helpful. So, the higher the aspect ratio of the fibers, the better the
film performance, even at low fiber contents.

On application of a magnetic field to a nanocomposite of polyvinyl alcohol (PVOH)


with cellulose whiskers to orient the whiskers; the modulus of the resulting nanocomposite
was greatly increased by orientation.
Aspect ratios are related to :
 origin of the cellulose
 whisker preparation conditions. ACC
.
ACCESCRIPT
Applications and effects on polymers matrices

Cellulose nanoreinforcements have been reported to have a great effect in improving


modulus of polymer matrices .

Poly(styrene-co-butyl acrylate) latex film containing 30 wt% of straw cellulose whiskers


presented a modulus more than a thousand times higher than that of the bulk matrix.
It is assumed that a great effect is ascribed not only to the geometry and stiffness of the
whiskers, but also to the formation of a fibril network within the polymer matrix, the
cellulose fibers being probably linked through hydrogen bonds.

It is reported that fibril contents of up to 5% resulted in no strength or stiffness


improvement of PVOH composites, and it ia assumed that probably a minimum fibril content
is required to induce intense interactions between fibrils and thus the formation of
networks. Moreover, cellulose fibers have been effective to improve strength and modulus
of polymers, especially at 4 temperatures above the glass transition temperature (Tg) of the
matrix polymer.
Percolation theory predicts a maximum improvement in composite properties when
there are just enough fillers to form a continuous structure, since they are properly
dispersed within the matrix , which means that modulus and strength are expected to
be improved if each fiber is in contact with two more others, on average . It has been
reported that a 2.5-fold increase in modulus of PVOH when 5% fibers were added, but
further increases in fiber contents were not helpful. So, the higher the aspect ratio of the
fibers, the better the film performance, even at low fiber contents.

Starch-based materials have been extensively investigated as a choice product to


improve biodegradability of a variety of plastics. However, the brittleness of starch
requires the use of plasticizers such as polyols, which improve starch flexibility but, on
the other hand, decreases its thermomechanical properties. The addition of whiskers to
starch systems enhances their thermomechanical properties, reduces the water
sensitivity, and keeps their biodegradability properties , Tg increasing effect of cellulose
nanofibers on starch. this reinforcing effect depends strongly on the formation of a
cellulose microfibrils network within the matrix, resulting from hydrogen bonds which
can be formed during the evaporation step. The water uptake by starch films decreases
linearly with increasing cellulose whisker content. A reduction in starch brittleness by
introduction of cellulose whiskers is due to the transcrystallization phenomenon, i.e.,
orientation of crystals of a semicrystalline matrix perpendicularly to the cellulose
microfibrils, as described . Moisture barrier of polymer films has been observed to be
improved by cellulose . The presence of crystalline fibers is thought to increase the
tortuosity in the materials leading to slower diffusion processes and, hence, to lower
permeability .
Nanosized cellulose fibrils have been also reported to improve thermal properties
of polymers. The thermal stability of polymers in nanocomposites with cellulose
whiskers was reported to be improved when compared to those of the
corresponding bulk polymers On the other hand, their effects on Tg of
polymers have been controversial. The presence of cellulose nanofibrils results
in a smaller portion of the matrix participating in the glass transition rather
than a consistent increase in Tg. Two proposed another mechanism, according
to which the presence of whiskers could influence Tg values in two opposite
ways. First, the solid surface of cellulose whiskers could restrict mobility of
polymer chains in the vicinity of the interfacial area, which would result in a
global shift of Tg toward higher temperatures. In an opposite way, the cross-
linking density of the polymeric matrix was decreased in the presence of
whiskers, which would indirectly decrease Tg.
Due to the hydrophilic surface of cellulose, interaction between cellulose nanofiller and
hydrophilic matrices are generally satisfactory On the other hand, the incorporation of
cellulosic nanofiller in the hydrophobic matrix usually results in a weakinteractions filler-
matrix and filler aggregate by hydrogen bonds . Another disadvantage of the hydrophilic
nature of cellulosic nanofiller is a high absorption capacity of water, which is undesirable
in most applications.
Such problems can be minimized by various modifications (hydrophobization) on the
surface of the cellulose by several reactions with hydroxyl groups such as esterification
and acylation with a fatty acid. The nanoparticles of silica improve tension properties of
polypropylene, starch, starch/polyvinyl alcohol, except that the starch reduces the water
absorption and improves the barrier to oxygen for polypropylene.
Other nanomaterials
Carbon nanotubes
Carbon nanotubes (CNTs) may consist of an one-atom thick single-wall nanotube (SWNT), or a number of
concentric tubes called multiwalled nanotubes 4 (MWNT), having extraordinarily high aspect ratios and
elastic modulus. Theoretical elastic modulus and tensile strength values as high as 1 TPa and 200 7 GPa,
respectively. CNT is modified by introducing carboxylic acid groups on their surfaces in order to enhance
their intermolecular interactions with the poly(ethylene-2,6-naphtalene) (PEN) matrix. CNTs, even in
concentrations as low as 0.1 wt%, greatly improved thermal stability as well as tensile strength and
modulus of PEN. Other polymers have been found to have their tensile strength/modulus improved by
addition of CNTs, such as PVOH , polypropylene and polyamide

Silica (SiO2)
Silica nanoparticles (nSiO2) have been reported to improve mechanical and/or barrier properties of
several polymer matrices. With the increase in SiO2 content, the tensile properties and water resistance
of the films were improved. There was also an increase in the intermolecular hydrogen bonds, as well as
formation of C-O-Si groups, between nSiO2 and starch, or nSiO2 and PVOH, which improved the
miscibility and compatibility between film components.

• Other np used in packaging are TiO2, Starch nano crystal, Chitosan nanoparticles etc.

Antimicrobial nanocomposites
• The incorporation of antimicrobial compounds into food packaging materials has received considerable attention. Films with antimicrobial
activity could help control the growth of pathogenic and spoilage microorganisms. An antimicrobial nanocomposite film is particularly desirable
due to its acceptable structural integrity and barrier properties imparted by the nanocomposite matrix, and the antimicrobial properties
contributed by the natural antimicrobial agents impregnated within. Materials in the nanoscale range have a higher surface-to-volume ratio
when compared with their microscale counterparts. This allows nanomaterials to be able to attach more copies of biological molecules, which
confers greater efficiency .

• The most common nanocomposites used as antimicrobial films for food packaging are based on silver, which is well known for its strong
toxicity to a wide range of microorganisms , with high temperature stability and low volatility. Some mechanisms have been proposed for the
antimicrobial property of silver nanoparticles (Ag-NPs): adhesion to the cell surface, degrading lipopolysaccharides and forming ‘‘pits’’ in the
membranes, largely increasing permeability ; penetration inside bacterial cell, damaging DNA (; and releasing antimicrobial Ag+ ions by Ag-NPs
dissolution. The activity of silver-based polymers depends on releasing of Ag+, which binds to electron donor groups in biological molecules
containing sulphur, oxygen or nitrogen.

• Chemical reduction is the most common method for preparation of Ag-NPs as stable, colloidal dispersions. The reduction of Ag+ in aqueous
solution produces colloidal silver with particle diameters of several nanometers . Initially, the reduction leads to the formation of silver atoms
(Ag0) and their subsequent aggregation into oligomeric clusters, which leads to the formation of Ag particles. The synthesis is often performed
in the presence of stabilizers in order to avoid undesirable agglomeration of colloids. studied the influence of surfactants and polymers on
aggregation stability and antibacterial activity of Ag-NPs, and reported that modified Ag-NPs had improved bactericidal effect. A correlation
was found between the aggregation stability and antibacterial activity. Ag-NPs has been successfully tested as an antimicrobial material .
Smaller Ag-NPs, having larger surface area available for interaction with microbial cells, result in better bactericidal effect than larger Ag
particles .

• TiO2 powder-coated packaging film is verified its ability to reduce E. coli contamination on food surfaces, suggesting that the film could be
used for fresh-cut products. Metal doping improves visible light absorbance of TiO2 and increases its photocatalytic activity under UV
irradiation . It has been demonstrated that doping TiO2 with silver greatly improved photocatalytic bacterial inactivation. This combination is
used for antibacterial properties from TiO2/Ag+ nanoparticles in a nanocomposite with PVC. The antibacterial activity of nano-scale chitosan is
also reported. One possible antimicrobial mechanism proposed by those authors involves interactions between positively charged chitosan and
negatively charged cell membranes, increasing membrane permeability and eventually causing rupture.
• and leakage of intracellular material. This is consistent with the observation that both raw chitosan and engineered nanoparticles are ineffective
at pH values above 6, which would be due to the absence of protonated amino groups . Another two antimicrobial mechanisms are proposed:
chelation of trace metals by chitosan, inhibiting enzyme activities; and, in fungal cells, penetration through the cell wall and membranes to
bind DNA and inhibit RNA synthesis. CNTs have been also reported to have antibacterial properties. Direct contact with aggregates of CNTs is
demonstrated to be fatal for E. coli, possibly because the long and thin CNTs puncture microbial cells, causing reversible damages . On the other
hand, there are studies suggesting that CNTs are cytotoxic to human cells, at least when in contact to skin and lungs, which would affect
people working directly with CNTs in processing stages rather than consumers. Nevertheless, it is mandatory to know eventual health effects
of CNTs when ingested, since the risk of ingestion of particles incorporated to a food packaging material must be taken into account because of
the possibility of migration to food.

• Improving compatibility between cellulose nanofibers and hydrophobic matrices

• Chemical compatibility between the filler and the matrix plays a critical role in the filler dispersion within the matrix and in
the adhesion between both phases. Because of their hydrophilic surface, interactions between cellulose fibrils and
hydrophilic matrices are usually satisfactory . “All-cellulose composites” (in which both the reinforcing fiber and the matrix
are cellulose based) is an especially interesting group of composites, since it has the advantage of the excellent interaction
between the fiber and the matrix which is critical for good mixing characteristics and for the mechanical performance of
the composites . On the other hand, the use of cellulose whiskers in nanocomposites with hydrophobic matrices results
frequently in weak filler-matrix interactions . When added to non-polar matrices, the highly polar surface of cellulose fibers
results in some problems: low interfacial compatibility with the matrices, low moisture resistance/barrier, and inter-fiber
aggregation by hydrogen bonding . Another limitation to the application of cellulose fibrils, also related to its hydrophilic
surface, is their high water absorption capacity, which is undesirable in many potential applications . PVOH can be used to
improve dispersion of cellulose whiskers in a PLA matrix. However, PLA and PVOH formed two immiscible phases with a
continuous PLA phase and a discontinuous PVOH phase, most whiskers having located in the PVOH phase. As a result, the
thermal stability and the mechanical properties of the nanocomposites were not improved compared to its unreinforced
counterpart . A variety of surface modifications on cellulose nanoreinforcements can greatly improve their miscibility within
hydrophobic matrices. Cellulosic surfaces can be derivatized by several reactions involving the hydroxyl groups, such as
esterifications, so as to improve their compatibility with less polar polymers .cellulose fibers by acylation with fatty acids in
order to prepare them for composites with polyethylene (PE). The surface chemical modification of the cellulose fibers
resulted in improved interfacial adhesion between the fibers and the matrix, which was evidenced by enhanced mechanical
properties and thermal stability.
• Moreover, the water uptake capacity of the material was decreased. Surfactant addition can also improve the compatibility
between cellulose and hydrophobic matrices. The hydrophilic head group of the surfactant adsorbs on the cellulose surface
whereas its hydrophobic tail solves in the matrix, avoiding aggregation of cellulose fillers via steric stabilization; the
improved performance of the nanocomposite would be explained not only by a better wettability and adhesion between
phases, but also by a more uniform distribution of the fillers within the matrix.

Grafting between a hydrophobic matrix and hydrophilic fibers can also improve
• their otherwise poor adhesion. 1% dicumyl peroxide (DCP), a crosslinking agent which can be used to induce grafting
between a PE matrix and cellulose fibers from sisal,
• presented much improved strength than composite with untreated fibers
Oxygen scavenging films
ACCOxygen (O2) is responsible for the deterioration of many foods either directly or indirectly. Direct oxidation reactions
result in browning of fruits and rancidity of vegetable oils, to name a few examples. Food deterioration by indirect action of O2
includes food spoilage by aerobic microorganisms. The incorporation of O 2 scavengers into food package can maintain very low
O2 levels, which is useful for several applications. Attention has particularly focused on the photocatalytic activity of
nanocrystalline titania (TiO2) under ultraviolet radiation. Oxygen scavenger films are successfully developed by adding titania
nanoparticles to different polymers. The authors suggested their use for packaging a wide variety of oxygen-sensitive products.
Since TiO2 act by a photocatalytic mechanism, its major drawback is the requirement of UVA light.
Nano-based sensors
Nanoparticles can be applied as reactive particles in packaging materials. The so-called nanosensors are able to respond to
environmental changes (e.g.,temperature or humidity in storage rooms, levels of oxygen exposure), degradation products or
microbial contamination. The food expiration date is estimated by industries by considering distribution and storage conditions
(especially temperature) to which the food product is predicted to be exposed. However, it is not unknown that such 1 conditions
are not always the real ones, and foods are frequently exposed to temperature abuse; this is especially worrying for products
which require a cold chain. Moreover, micropores or sealing defects in packaging systems can lead food products to an
unexpected high exposure to oxygen, which can result in undesirable changes.

When integrated into food packaging, nanosensors can detect certain chemical compounds, pathogens, and toxins in food,
being then useful to eliminate the need for inaccurate expiration dates, providing real-time status of food freshness
According to Hongda Chen (USDA, Washington, DC), nano-based sensors to detect pathogens, spoilage, chemical
contaminants, or product tampering, or to track ingredients or products through the processing chain are already under
development or have been commercialized (Nachay, 2007). Mahadevan Iyer (Georgia Tech Packaging Research Center,
Atlanta, GA) pointed out several advantages of these sensors, based on CNT, over the expensive and time
consuming conventional detection methods such as HPLC. He mentioned the rapid and high-throughput detection; the
simplicity and cost effectiveness; the reduced power requirements and easier recycling; and the unnecessity of
exogenous molecules or labels. Iyers have been working on develop
Time-temperature integrators Time- temperature indicators or integrators (TTIs)
are designed to monitor, record and translate whether a certain food product is safe to be
consumed, in terms of its temperature history. This is particularly important when food is
stored in conditions other than the optimal ones. For instance, if a product is
supposed to be frozen, a TTI can indicate whether it had been inadequately exposed to
higher temperatures and the time of exposure. The communication is usually manifested by
a color development (related to a temperature dependent migration of a dye through a
porous material) or a color change (using a temperature dependent chemical reaction or
physical change) (Fig. 2) Timestrip® has developed a system (iStrip) for chilled foods, based
on gold nanoparticles, which is red at temperatures above freezing. Accidental
freezing leads to irreversible agglomeration of the gold nanoparticles resulting in loss of the
red color.

Intelligent inks that change color with the


temperature