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Nanocomposite Technology in Food Packaging

recent comprehensive literature review by my

ized by extremely high surface-to-volume ratio, as

student Caroline Morris and colleague Louise

much as 750 m2 /g, making them highly reactive in

Wicker in the University of Georgia’s Master

comparison to their macroscale counterparts and

in Food Technology program provides data to but-

thus presenting fundamentally different properties.

tress the belief that nanocomposites can improve

Polymer-Clay Nanocomposites

mechanical strength; reduce weight; increase

heat resistance; and improve barrier against

Polymer-clay nanocomposites are plastics

oxygen, carbon dioxide, ultraviolet radiation,

in which are homogenously dispersed a

moisture, and volatiles of food package materials.

small percentage of nanoclay particles. The

Nanotechnology is the control or

aspect ratio (diameter:thickness) of the

manipulation of matter at the atomic, molecular,

exfoliated sheets is in excess of 100.

or macromolecular level, in which one of the

Nanoclays exist as agglomerated bundles

in their natural state, composed of thousands

of platelets bound by Van der Waals forces

that arise from the molecular polarization of


dipoles. In nanoclay technology, the silicates

are layered to a thickness of approximately

one nanometer, forming stacks with interlayer

gaps, also known as the gallery. The interlayers

contain charged ions to facilitate penetration of

the gallery space through exfoliation or inter-

calation of the polymer, wherein dispersed clay

silicate is layered throughout the polymer.

Dispersion in the clay layers is affected by

the hydrophilicity/hydrophobicity of the polymer,

leading to the intercalated or exfoliated structure.

Surfactants may be added to compatibilize the

hydrophilic nanolayers with hydrophobic polymers.

When dispersed in a polymer matrix,

layered silicate clays form one of three

arrangements: non-intercalated or flocculated

microcomposites, intercalated nanocomposites,

or exfoliated nanocomposites. In non-intercalated

or flocculated versions, the polymers cannot

Montmorillonite nanoclay structure showing

components affects functional behavior. Fine

intercalate between silicate sheets constituting

parts of two clay sheets surrounding an

particulates (100 nm or less) are incorporated

the traditional class of polymer-filler composites.

exchangeable cation in the gallery, the area

into plastics to improve the properties over

In intercalated types, polymer chains are


between the sheets.

those of conventional counterparts.

present between the alternating silicate layers.

Illustrations by Jake Mulligan, University of Georgia

Polymer nanocomposites are thermoplastic

The chains assemble inside the well-ordered

polymers which have nanoscale inclusions, 2–8%

galleries of the layered host crystals sandwiched

by weight. Above 8%, exfoliation becomes difficult,

between the silicate layers. In exfoliated, or

creating conversion problems during processing.

delaminated forms, the clay platelets are separated

Nanoscale inclusions consist of nanoclays, carbon

into random arrangements and are more fully

nanoparticles, nanoscale metals and oxides, and

dispersed in the polymer matrix, because the

polymeric resins. Nanocomposites are character-

silicate layers are not close enough to interact

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with adjacent layers in their enlarged gallery

spacing. The nanoclay platelets at the outermost

region cleave off, exposing more platelets for

separation. This dispersed form is ideal because

it obtains the best gas barrier properties, but it

is difficult to achieve during synthesis and/or

processing, and so compatibilization is essential.

American Copak
Characteristics

Nanocomposites have three main components,

with a portion of each being necessary for a

synergistic effect at the polymer–nanopar-

ticle interface: the matrix, reinforcement, and

the interfacial regions. The matrix supports

the reinforcement and imparts physical and

mechanical properties to enhance the matrix.

1/2 ISL 4C

Silicate layers (reinforcement) within the

polymer matrix may be naturally occurring

(e.g., montmorillonite), or synthetic. The

interfacial region “communicates” between

the matrix and reinforcement with behavior

that controls the properties. The filler has

different properties than the matrix due to its

proximity to the reinforcement surface.

Montmorillonite is the current clay mineral of

choice because it is available and inexpensive,

and can be used in conjunction with high- and

low-density polyethylene (PE, LDPE, HDPE), nylon,

polyvinylidene chloride (PVdC), and biopolymers.

Clays can be added as coatings on flexible

or paperboard packaging or added in aqueous

solutions. Polymer-clay nanocomposites

become hydrophobic due to ionic exchange

of the sodium interlayer cation with an

onium cation from the polymer matrix.


The advantages of nano-engineered hybrid

plastics over conventional include improved

mechanical properties (strength-to-weight ratio

and dimensional stability); moisture retention

and decreased permeability to gases and water;

improved clarity; and better thermal stability.

Processing Methods

Polymer nanocomposites can be prepared by

solution, or template synthesis; solvent, or

mesophase-mediated processing; interlamellar

(in-situ) polymerization; or melt processing.

The thermal behavior and crystallization of

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[PACKAGING]

Nanocomposite Technology continued...

with the nanoparticle surface, e.g.,

enhanced, in part, by the attractive

layered silicates or chemically bound

forces between the molecule’s

small molecules. Hydrophilic layered

interchain forces, which are

silicates can be rendered more

stronger than those of conventional

organophilic as the hydrated cations

molecules, and exhibit higher tensile

of the interlayer are exchanged with

strength and melting points. Affec-

cationic surfactants. Compatibil-


tive polymeric properties include the

izers maximize the enhancement

degree of polymerization, or number

properties of layered silicates

of structural units in a polymer chain;

dispersed in a polymer matrix.

molecular mass; distribution of the

A surface treatment is added

polymer fraction; crystallinity; glass

to the clay because some clays are

transition temperature; and melting

Illustration of transmission

montmorillonite nanocomposite

hydrophilic and must be chemically

point. Thermal conductivity is also

of oxygen (orange spheres)

is influenced more by the type of

modified with compatibilizers to

enhanced to maintain processability

through polymer films filled

dispersion than by the clay content.

make the surface more receptive

during extrusion and molding.

with clay nanoparticles

• In the solution method,

to dispersion with mostly hydro-

The combination of barrier and

(dark sheets shown imbed-


ded in the polymer film).

the polymer is dissolved in a

phobic polymers. Once treated,

mechanical properties of polymer

solvent and the polymer molecules

the clays are dispersed into the

clay nanocomposites might make

move between silicate layers of

polymer matrix by polymeriza-

multilayer plastic engineering

the added filler. The solvent is

tion or melt compounding.

currently employed in food and

evaporated and the layers obtain

beverage packaging antiquated.

Properties

an intercalated or exfoliated form.

• Clarity. Nanoclay polymers

• In mesophase-mediated

Polymer-layered silicate nanocom-

do not interfere with clarity or

processing, a solvent is employed

posites share one common feature, a

transparency of packaging materials

in a double-phase reaction medium.

layer of interphase polymer near the

because their nanometer length

In the first phase, silicate layers


inorganic surface. The composite

scale minimizes the light scattering.

are suspended in the aqueous

properties of the interphase layer

• Recyclability. Used in

phase. In the second phase,

are more than the sum of the bulk

conjunction with recyclable

polymerization of a monomer

properties. The behavior of the

polymers, nanocomposites can

occurs within the suspension.

nanocomposite depends on the size

decrease environmental waste.

• In interlamellar polymerization,

of the clay platelets. The thinner and

Natural bio-based polymers, such as

the layered silicates swell via

smaller the platelets, the greater

polylactic acid (PLA), are mediocre-

absorption of a liquid monomer

the available surface area to

barrier degradable alternatives

which then migrates into the

interact with the polymer matrix.

to petroleum-based packaging.

galleries of layered silicates. Polym-

• Barrier Properties. In
Biodegradable nanocomposite

erization initiated by heat, radiation,

nylon-6 nanocomposites, the

films show good intercalation of the

or diffusion of an initiator that occurs

increase in degree and type of

polymeric phase into clay interlayer

between the intercalated sheets.

crystallinity, together with the

galleries paired with increased

• In melt processing, polymer

tortuous path development due

mechanical and barrier properties.

chains diffuse into the galleries

to exfoliated dispersion, are

Barrier Plastics

between the silicate layers. Clay

primary reasons for improvement

fillers intercalate in the molten

in gas barrier properties.

Nycoa, Bayer, Honeywell, and

state of the polymer, forming the

• Mechanical Properties.

Nanocor have combined silicates

nanocomposite. Clays are mixed

Mechanical property improvement

in nylon 6, which is fluid and easily

at temperatures that exceed the


of polymer-organoclay matrices is

penetrates small spaces between

polymer’s softening point, whereby

achieved at low filler loading, usually

layered silicates. Once mixed,

the polymer melt intercalates. Melt

1–5% (wt%). Nanocomposites

the layered silicate stacks are

processing is preferred because

exhibit improved tensile and bend

uniformly distributed throughout the

it does not require a solvent.

strength; increased stiffness

polyamide. When extruded, such as

Critical to any of the preparation

without loss of fracture tough-

a film, platelets orient themselves

methods is the engineering of the

ness; and improved interlaminar

parallel to the surface, allowing

polymer–nanoparticle interface.

strength. The addition of just 5%

for improved barrier properties.

Also, compatibilizers (surfactants)

nanoclay can increase thermal

Nylon 6 films and bottles exhibit

are commonly used to facilitate the

stability by as much as 350%.


enhanced properties, including

interface process. They include

The physical and chemical

oxygen, carbon dioxide, and water

small molecules ionically associated

properties of nanocomposites are

vapor barrier, UV radiation, clarity,

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stiffness, and thermal stability.

exhibits low aroma permeation,

premium beer bottle. Honeywell

reactive, they may interact with

Nanocor melt-compounds

a critical factor in flavor scalp-

also produces films that offer

other materials during disposal

its nanoclay additives with

ing. Imperm allows the reduced

excellent barrier properties

and recycling. Others fear that

MXD6 nylon to be used in films

oxygen permeation over a

against oxygen, aroma, and

nanomaterials may cause new

and polyester (PET) bottles.

broader relative humidity range

flavors; strength, toughness,


allergens, new toxic strains, and

Nanocor’s Imperm is a MXD6

than do nylon MXD6 and EVOH.

puncture, and tear resistance;

increased rates of nanoparticle

nylon/clay nanocomposite

Bayer offers a hybrid system

and gas and fat penetration

absorption by the environment.

plastic used as an oxygen barrier

of cast-film nylon 6 nanocompos-

resistance. Applications for

The dispersion of nanoclay

in beer and carbonated beverage

ites to be used where EVOH is

these films include fresh

into the polymer matrix requires

bottles and in packaging of

too expensive and conventional

red meat and poultry, fish,

a custom solution for each

processed cheese and meats,

polyamides are too permeable,

processed meat, cheese, chilled

polymer, thus requiring intensive

confections, and cereals, and in

such as a plastic coating for

fruit juices, and dried foods.


research and development

extrusion-coating of paperboard

paperboard juice containers.

capital, meaning that the costs

Issues

packaging for juice and dairy

Combinations of active/pas-

might be more than for plastic

products. Loading 5% Imperm

sive oxygen barrier systems

Interest groups are trying to

macromolecules.

in PET beer bottles is claimed

have been developed by Honey-

assess whether nanostructures

Nanotechnologies will cer-

to have a shelf life of six months

well for polyamide-6 materials.

or their manipulation change

tainly influence food packaging

and less than 10% carbon

Nanoclay particles are incorpo-

the toxicological profile.

in the coming decades. Caroline

dioxide loss, at a 10% cost

rated by melt processing with

Concerns have arisen regarding

Morris’s review clearly maps


premium over that of PET alone.

an oxygen scavenger, creating a

the effects of nano-sized

this challenging terrain. Request

a copy from me by e-mail. FT

MXD6 nylon, when combined

synergistic system. Honeywell’s

particles on the human body

with nanoclay, exhibits barrier

Aegis CSD reportedly extends

and the environment. The high

properties fi ve times those of

shelf life of 0.5-L beer bottles

surface-to-volume ratio of

Aaron L. Brody, Ph.D.,

Contributing Editor, President

water-vapor sensitive ethylene

from 9 to 16 weeks. Aegis OX is

nanomaterials makes them more

and CEO, Packaging/Brody, Inc.,

vinyl alcohol (EVOH); halves

used in the core layer for Anchor

reactive and potentially more

Duluth, Ga. • aaronbrody@aol.com

water vapor transmission; and

Brewing’s three-layer PET 12-oz

toxic. Because they are more