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plastics
organic macromolecular compounds
PLASTICS obtained by polymerisation,
polycondensation, polyaddition or any
similar process from molecules with a
lower molecular weight or by chemical
PRO alteration of natural macromolecular
compounds

(reference 2001/62/EC)

Why is widely used? Definition of Terms

flowable and mouldable under certain
conditions, to make sheets, shapes and
structures
generally chemically inert, though not
necessarily impermeable
cost effective in meeting market needs
lightweight
provide choices in respect of transparency,
colour, heat sealing, heat resistance and barrier.
mer a unit, e.g. a basic unit in a chemical
structure
polymer many units
Plastic deforms, can be shaped by a shear
force in excess of a plastic yield minimum.
thermoplastic shaped by reducing the yield
stress by heat softening (they can be repeatedly
softened and melted when heated)
thermosetting initially shaped by heat, but
shape is then set permanently (can be moulded
once by heat and pressure. They cannot be
resoftened, as reheating causes the material to
degrade)

Types of plastic in food

Definition of Terms packaging

crystalline regular, periodic shape

amorphous opposite to crystalline, random
shape
isotactic possessing a preferred
orientation of molecules (same feel)
atactic molecules in structure are
randomly oriented (no feel)

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Construction of Rigid
Plastics
1. Blow Moulding
a process for producing hollow parts in one operation,
primarily used to make plastic bottles.

A hot plastic tube (a parison)
inflated against a cold

mould.
Final shape
thin neck
The parison is produced by extruding the plastic at high
T & P.
Variations
- coextrusion blow moulding, - injection
blow moulding, & - injection stretch moulding.
Labeling can also be done in the mould.

2. Injection Moulding
direct injection of molten plastic into a shaped
space between two moulds.
The moulds separate after the plastic cools to
allow the final shape to fall out.
for making solid plastic objects (e.g.: cups,
closures, plastic toys).

3. Thermoforming
heating plastic sheet until it softens,
then shaping by stamping it between two cooled
moulds.

A growing requirement of moulded plastics:

microwaveable (the softening point is well > 100C)
shelf-stable.
Plastics are generally slow to degrade under
ambient conditions, but may
dis-colour or become brittle.

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Construction of Plastic
Sheet & Film

Films are manufactured using an extruder.

The plastic resin granules & other ingredients
are fed into the extruder,
& compressed & heated until the plastic flows
out of the die.
Two main die shapes: - slit circular & - slit
rectangular.

The extruded plastic may then be

stretched while still hot and flexible:
monoaxially
the die is designed to give a wide sheet of
plastic film.
can be stretched in the machine direction, by up
to 80x its original length,
effect
thinning the sheet & orienting the
molecular structure.
Result: the plastic can be stretched easily in one
direction after cooling, but not in the other.

The properties of plastic films

biaxially and sheets are dependent on
(1) Tenter process
jaws & rollers stretch the film apart in
both directions at once.
molten film
onto a casting wheel
through a series the plastic(s) used and
of rollers => stretch the film in the machine direction.

through the Tenter section oven (the jaws grip the the method of film manufacture together with
softened plastic & pull it apart in the transverse direction) any coating or lamination.
Result: stiff plastic.

In film and sheet manufacture, there are two

(2) The bubble method
the plastic is extruded as a continuous cylinder,
distinct methods of processing the molten plastic
& a bubble of air is blown up the centre of the cylinder, which is extruded from the extruder die.
forcing bi-axial expansion.
As the plastic heat-sets it will shrink slightly

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In the blown, or tubular, film

In the cast film process, process,
the molten plastic is extruded through a straight the molten plastic is continuously
slot die onto a cooled cylinder, known as the chill extruded through a die in the
roll. form of a circular annulus, so
that it emerges as a tube.
The tube is prevented from
collapsing by maintaining air
pressure inside the tube or
bubble.
In both the processes, the
molten polymer is quickly
chilled and solidified to
produce a film

metallised plastic
The plastic passes quickly through an evacuated
chamber in which Aluminum is vapourised.
This deposits a metal layer several molecules
thick (about 200 angstroms), giving a metallised
appearance.
often to replace foils
is cheaper, but does not
have the same barrier properties as foil
(although there will be some improvement over
untreated film).

Properties of Plastics
POLYOLEFINS
I. Polyethylene (polythene) PE
polymerisation of ethylene gas
(C2H4)n.
invented in 1930's.
two main manufacturing processes:
(1) Low Density Polyethylene (LDPE)
(2) High Density PE (HDPE).

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(1) LDPE
formed at high P (1000-3000 atm).
results in long branched chains, weakly linked to each
other by van der Waal forces (but strong overall force
due to length).
The branching is random, so LDPE is an atactic polymer.
Neighbouring chains can slip past each other, allowing
the material to bend easily (flexible).
So, poor printability.
Low density
as the long chains exhibit branching

the molecules are not able to fit closely together
irregularity in structure also results in a lower melting
point & less crystalline (ordered chain) structure.
(2) HDPE
produced at low T & P (about 10 atm).

ordered molecular structure
an isotactic polymer.
Karl Ziegler (1940) - Ziegler process
stiffer, harder, less flexible, waxy
higher T required to produce thermoplasticity (melt point
134 C)
used for making containers, e.g. crates, bottles, bags,
tubs, plastic knives & forks, etc.
can be steam-sterilised (LDPE cannot).
HDPE bottles are opaque
specific examples: used for detergent and milk bottles
resists fats and oils (better than LDPE)
does not seal easily.
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tough, semi-transparent (poor clarity), flexible,
waxy feel.
resists most chemicals < 60 C; melt point 105
C
resists water moderately but not gases (poor O2
barrier).
used as thin sheets, or laminated to other
packaging materials.
Used for bag manufacture (bread, nappies), for
low temperature storage (due to its low barrier
properties), & still used for rice.
Poor printability plastics
Available PE's include
low, medium, and high density PE,
linear low (LLDPE) and medium densities
Copolymers of PE's,
copolymers with vinyl acetate (EVA) & ionomer film
(surlyn), may be coextruded with nylon, saran & EVOH
sandwiched inside PE.
Such films have:
high strength, flexibility, clarity & barrier properties,
used for bag-in-the-box, pouches, cup and lids, etc.
Usually the form of PE used will be a trade-off between
barrier properties required & cost
II. Polypropylene PP
monomer formula CH2=CH-CH3.
Prof. Guilio Natta (1954)
forms a regular polymer at low P in the presence of
certain catalysts
highly ordered
isotactic PP
high crystallinity (high clarity & gloss), hard, heat
resistant (higher softening point, 150 C),
good memory, flex crack resistance, puncture resistance
& stiffness.
chemical resistant (except aromatic & chlorinated
hydrocarbons)
excellent moisture & average gas barrier properties
can be printed on, ideal for reverse or surface printing.
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coated with saran or acrylic for a better barrier &

Cast PP (CPP) has excellent heat sealability
used for injection moulded containers and blister packs,
laminations, carton overwraps, snack food bags,
confectionery bags
PP may be coated (for example with PVDC or acrylic), &
may have additives
poor heat stability, so precise heat control is required in
the packaging equipment
the film may be stretched during production
giving oriented (OPP) or bi-axially-oriented film (BOPP)
of high clarity, strength & resistance to water vapour &
gases (e.g. for wrapping snack foods),
heat sealability
causes contact transparency ("show through")
may be pearlised (CaCO3 + heat generates CO2
bubbles, resulting in reduced barrier properties
& strength, but no show through)
or white (pigmented, better print density, saves
undercoat, reduced show-through),
used for confectionery, especially chocolate
may be coextruded with PE for heat sealability.

III. Polyvinyl Chloride (PVC)

monomer formula CH2=CH-Cl.
vinyl means that a halogen has been substituted for a
H atom.
low crystallinity (good transparency when pure),
higher inter-chain bonding than PE due to the Cl-
halogen, so is harder and stiffer.

plasticisers may be added during manufacture.
for ex. vitafilm (for meat) with particular O2 diffusion
characteristics.
good feel and printability. Highly inert.
glossy, excellent resistance to moisture,
fats & gases.

great variety of compositions, for ex. stabilisers,

impact aids, lubricants & other additives.
+ stabiliser ?
because the decomposition
point for PVC is close to the melting point.
For food products, the extraction of the stabiliser
from the PVC must be less than 1 ppm of the
stabiliser.
used in bi-axial-stressed form, e.g. shrink-
wrapping of cheese & meat.
used for thermoformed containers, e.g.
chocolates.
used for plastic pipes & toys.

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IV. Polyvinylidene Chloride (PVDC)
= PVC, except that there is a double chlorine
substitution, giving CH2=CCl2.
PVDC has a more ordered structure, with high
crystallinity & softness.
excellent barrier properties (especially to O2),
commonly used as a co-polymer with PVC.
reasonable clarity, good feel, good printability &
strength.
It is difficult to cut as it lacks stiffness
hard to
machine by itself,
too expensive for use as a pure monofilm
PS is usually co-polymerised, especially with
butadiene, to give high impact polystyrene
(HIPS), which has a less brittle structure (the
melting point of HIPS is 100 C).
Ex. yogurt and ice-cream tubs. Margarine tubs
may be made from ABS (acrylo-nitrile
butastyrene).
PS is also used for disposable plates and cups.
good barrier to gases; permeable to water
vapour.
resists grease, acids, alcohols & alkalis
(chemically stable)
oriented PS is heat shrinkable.
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resists chemicals, low water, gas, aroma and flavour
permeability (due to Chlorine ions), high strength.
High chemical stability. Hygrophobic.
used with PVC as a copolymer to coat other packaging
materials to provide good barrier properties.
used in laminates; important shrink film; excellent cling
properties.
cannot be reprocessed because it degrades (melt point
162 C).
co-extrusion lamination is difficult; can still be used in
coating from solution.
When used in co-extrusion it must be co-polymerised
first (for example with vinyl chloride) to give better
temperature stability.
VI. Polystyrene (PS)
results when an ethylene hydrogen is replaced
by a phenyl radical (CH2=CH-C6H5).
This is a synthetic rubber, which does not
degrade over time.
amorphous (random packing), low in density &
brittle.
In the pure form it has good clarity & printability.
for loose bulk packaging, especially for packing
fragile materials.
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OTHER
THERMOPLASTICS
Some examples of non-ethylene derived thermoplastics:
I. Polyesters (e.g. PET, PEN)
formed by the polymerisation of esters.
have reasonable clarity, poor feel & printability; strong,
versatile & have good heat resistance.
useful for boil-in-the-bag type applications (the plastic
must sustain temperatures of 100 C without deforming
or softening).
When metallised they are also used for snack & coffee
pouches.
ethylene glycol & terephthalic acid gives
polyethylene terephthalate (PET).
PET has high strength & chemical stability.
used for blow-moulded bottles & some films,
for thermoformed trays, & for boil-in-the-bag
products.
has excellent clarity, comparable to glass.
can be printed, metallised & laminated.
has high barrier properties for a plastic film.
a cheap plastic (due to efficient recycling).

commonly used as the outer layer of a

laminate structure due to its gloss &
temperature stability (melt point 254 C).
used for microwave pie wraps (micro-
perforated).
forms of PET:
-APET (atactic PET), -CPET (crystalline
PET), -OPET (oriented PET), -PETG
(copolymer PET/cyclohexane dimethanol,
melt point 265 C).

polyethylene naphthalene (PEN)

low permeability to gases.

II. Cellulose

made from viscose cellulose.

still widely used today, due to the addition of coatings
the first transparent film to be used (invented by that have given cellophane great adaptability.
Du Pont) in packaging; widely used until the
advent of PP. Ex. of coatings: nitrocellulose (making cellophane
flexible & durable), PVC, PE & PVDC (O2 barrier
biodegradable. properties).
= Cellophane, a TM name of British Cellophane can be laminated to foil, paper & some plastic films.
Ltd. retains folds (dead fold)
ideal for individual sweet
clear, stiff, printable, glossy, but has poor feel & wrapping.
moisture resistance. tearable.
good heat dimensional tolerance. used for biscuits, confectionery, crumpets & pastries, in
not heat sealable. situations where vapours may need to breathe to
naturally antistatic; good for powders prevent surface moulding.
(e.g. milk powder). available in weights of 22-60 g/m2.

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IV. Polyamides (nylons)

made from condensation of a diacid (e.g. adipic

acid) & a diamine (e.g. hexamethylene diamine).
have high crystallinity, strength, impact strength,
puncture & stress-crack resistance, flexibility,
melting (255 C) & softening points.
have good chemical resistance.
used for boil-in-the-bag type products, frozen
foods, fish, meat, vegetables, processed meat
and cheese, always in laminations.
low water barrier, high gas permeability.

Polyvinylidene-coated or metallised nylon
the

price 2x of pure nylon film.
available as cast nylon (18-100 m) & bi-axially-
oriented (BON) nylon (12, 15 and 20 m).
can be metallised or PVDC-coated for better
barrier properties & is usually laminated.
must be bi-axially oriented to give printing and
machining stability.