2.1.

1 Types of Wood for Paper Making

Paper is defined as a substance made from wood pulp, rags, straw, or other
fibrous material, usually in thin sheets, used for writing or printing, for wrapping
things, etc.

Wood pulp is the fibrous raw material for the production of paper, paperboard and
corrugated board. Many fibers have been used for the manufacture of paper such as
wood fibers from trees, bamboo, various leaves, and other grasses and kenaf. At
present, about 75% of the world’s paper and board is made from the wood pulp and
about 85% of the wood pulp used is from spruces, firs and pines trees.

Woods can be divided into two categories which are softwoods and hardwoods.

1. Softwoods

The cell wall of softwoods is preferred for most pulp products. Softwood can be
obtained from evergreen, cone-bearing tree species such as spruces, firs, and
pines. It is a long-fibered wood generally between 2 to 4 mm, therefore the longer
the fiber, the stronger the paper. Softwood could provide paper strength and good
runability in the paper machines. It is best used for grocery bags or paperboard such
as boxes which requires strength.

2. Hardwoods

Hardwood can be obtained from leaf-falling tree species such as oak, hickory, and
birch. It consists of short-fibered wood with less than 1.5 mm. Hardwood
could produce finer and smoother paper sheet but it is less strong. It also
provides good printability in the form of optical properties such as brightness and
smoothness.

Table 2.1 Average composition of softwoods and hardwoods

Composition Softwood Hardwood

Cellulose 42 ± 2% 45 ± 2%
Hemicellulose 27 ± 2% 30 ± 5%
Lignin 28 ± 3% 20 ± 4%
Extractives 3 ± 2% 5 ± 3%

Advantages of paper

 Paper provides superior printability as it offers a wide variety of designs such

as offset printing, flexographic printing, and typographic printing.
  The production of paper is an easy process with a simple fabrication process,
enables mass production.
 Product packed using paper gives an appropriate stiffness to keep the
packaging intact and to protect product contents.
 Paper is a lightweight material, thus it is easy to be transported as it can be
compacted, foldable and collapsible.
 Paper is cheap compared to other types of containers.
 Paper provides good mechanical strength – enough strength to support product
weight.
 Paper is a biodegradable material and it provides a good environmental image.

Disadvantages of paper

 Paper exhibits naturally poor properties such as porous, opaque, low barrier to
moisture and gasses as well as not resistance to oil or grease.
 Paper does not prevent loss of flavour components or volatiles from foods.
 Paper cannot be heat-sealed.
 Paper cannot be co-extruded to produce laminate and must use adhesives.
 Paper is easily torn.

2.1.3 Paper Manufacturing

There are two main stages involved in paper manufacturing. The first stage is pulp
processing which relates to the conversion from the pulp of log woods to the
bleaching process while the second stage paper making process involved beating
and refining, paper making and converting process. Figure 2.53 shows the overall
process of paper manufacturing.

Stage 1: process of pulping is which wood/ other fibrous raw materials are reduced to fibrous mass through
softening & dissolving the intracellular substances to release individual fibers

Wood logs/wood chips Purpose to separate the fibers without

damaging them so that they can then
be reformed into a paper sheet in the
Accomplished by either
papermaking process
mechanical, thermal,
pulping
chemical or combination of
these treatments
Objectives:
1) to produce a well-cooked pulp, free
from non-cellulosic portions
Digestive
2) to ensure a constant supply of pulp
Process consists of treating of the correct quality
wood in pressurised vessel
under controlled conditions of
Bleaching
temperature, time & liquor
Chemical process applied to the pulps
concentration
in order to increase their brightness &
improves pulp cleanliness by removing
lignin & other contaminant
 Stage 2: process of papermaking involves depositing very dilute aqueous fibers suspension(>99% water) on to fine
woven wire screen in which >95% water is then removed. The fiber sheet formed will then undergo pressing,
drying & converting to turn it into various types of paper
Stock pulp
Dried stock pulp Purpose:
Are dispersed in water in process
1)To improve strength & other physical
known as slushing or repulping
properties of the finished sheet
Beating&refining 2)To influence the behaviour of the
Quality and characteristics of system during the sheet forming &
finished paper depend on drying steps
beating & refining treatments
Sheet forming Conducted using fourdrinier machine where
Wood logs/wood chips fiber suspension (0.4-1.2% concentration)
Unbeaten pulp has low density delivered to moving screen in which water is
rather soft & weak drained
Beaten pulp produce paper that is Pressuring&Drying
denser, hard & strong Wood logs/wood chips Sheet formed (75-90% water) will pass
Extremely beaten pulp produce through several presses & dryers for further
very dense, translucent & glyssine water removal until the final moist (4-10%)
type paper Converting depend on type of paper

Process where further treatments

Various types of paper additional additives, fillers, coating, sizing

Figure 2.53 Flow-chart of the paper manufacturing process

2.1.4 Types of Paper, properties and uses

There are many different types of paper used as food packaging. These papers have
their own special properties that make them suitable for certain food products.

1. Kraft Paper

Kraft paper is typically coarse and heavy-duty paper made on the Fourdrinier machine.
It is sometimes made with no calendering and the rough surface will prevent these
papers from sliding over one another when stacked on pallets. Kraft paper often used
to produce bags, multi-wall sacks, and liners for corrugated board.
2. Bleached Paper

Bleached paper (Figure 2.55) is manufactured from pulps that are relatively white,
bright and soft and receptive to the special chemicals necessary to develop many
functional properties. it is more expensive and weaker than the unbleached paper.

3. Greaseproof Paper

Greaseproof paper is a translucent machine-finished paper that has been hydrated to

give oil and grease resistance. The performance of greaseproof paper depends on the
extent to which the pores have been closed. The formation of a few interconnecting
pores between the fibers will cause the difficulties of liquids to pass through.
Greaseproof papers are not strictly 'greeseproof' since oils and fats will penetrate them
after a certain time. Despite this, it is commonly used for packaging butter, baked
goods, and similar fatty foods.

4. Glassine Paper

Glassine paper is characterised by a glassy, smooth surface, high density, and

transparency. It is produced by further treating greaseproof paper at the calendaring
process. The transparency varies widely depending on the degree of hydration of the
pulp and the basis weight of paper. The addition of titanium dioxide makes the paper
opaque and frequently plasticised to increase its toughness.

5. Vegetable Parchment

Parchment paper has excellent wet strength, free of lint, odor, and taste and resistant
to grease and oils. However, it is not a good barrier to gasses. Due to its grease
resistance and wet strength, it strips away easily from food material without defibering,
thus it has been used as interleaver between slices of food such as meat or pastry.
Besides, labels and inserts in products with high oil or grease content are frequently
made from parchment. it also can be treated with mould inhibitors and used to wrap
foods such as cheese.
6. Waxed Paper

Waxed paper provides a barrier against the penetration of liquids and vapors. The
function of the wax is to provide a moisture barrier and a heat-sealable laminant. The
3 types are wet-waxed, dry-waxed and wax-laminated. Wax-waxed papers have
continuous surface film on one or both sides and high degree of gloss on the coated
surface. Dry-waxed papers are produced using heated rollers and do not have a
continuous film on the surfaces. Wax-laminated paper is bonded with a continuous
film of wax that acts as an adhesive.

2.1.5 Paperboard products

Paperboard is generally termed when its grammage exceeds 224 gm-2.

Boards can be produced using a single Fourdrinier wire, a single cylinder former, on
a series of formers of the same type or a combination of types. Multiply boards are
produced by the consolidation of one or more web plies into a single sheet of
paperboard and manufactured into rigid boxes, folding cartons, beverage cartons or
similar products.

The advantages of multiply forming is the ability to utilise inexpensive and bulky low
grade waste materials such as old newspaper or other post-consumer waste papers
in the inner plies of the board. Nevertheless, multiply boards manufactured from post-
consumer waste paper are not used for food contact purposes.

The three types of multiply boards manufactured and extensively used as packaging
materials.

A. Folding cartons

Folding cartons are containers made from sheets of paperboard with thickness ranged
between 300 -1100 um, cut and scored for bending into desired shapes. The boards
used for cartons have a ply structure and many different structures ranging from
recycled fibres to duplex boards made from bleached chemical pulp. There are several
types of paperboards used to make folding carton such as:

 Coated solid bleached board (SBB)/ Solid Bleached sulfate (SBS) – made from
pure bleached chemical pulp
 Coated Solid Unbleached Board (SUB)/ Solid Unbleached Sulfate (SUS) –
100% virgin, unbleached, chemical furnish
 Folding Box Board (FBB) – made from middle layers of mechanical pulp
sandwiched between two layers of chemical pulp
 White Lined Chipboard (WLC) – made using predominantly recovered fibres.

Coating and laminating are carried out when special barrier properties are required:
  wax lamination provides moisture barrier
 lining with glassine provides grease resistance
 Lamination or extrusion with plastic materials provides heat sealing properties

Coating of the outer board applied during the board making operation or subsequently
improves the external appearance and printing quality. The used of foil-lined boards
could improve reheability of the contents.

Figure 2 Folding carton

B. Beverage carton

Beverage carton normally consists of SBB layers and SUB coated internally and
externally with LDPE that impermeable to liquids and heat sealing.

The design of Gable top retains the basic geometry of beverage cartons. Refinements
such as plastic screw caps and reclosable spouts are added together. Incorporation
of an aluminium foil layer permits longer shelf life of chilled premium juice product.
Besides, this foil is sometimes replaced with barrier polymer such as EVOH or SIOx
coated PET.

Brick-shaped cartons is a liquid tight and hermetically sealed carton that has been
used widely in aseptic packaging for products such as milk, juices, soups and wines.
This commercially sterile technique could retain the shelf life of product between 6 to
9 months.

Retortable square-shaped paperboard cartons has been used for soups, ready meals,
vegetables and pet food to replace the metal can. The used of PP replacing LDPE
improve the shelf life of products up to 18 months when store at ambient conditions

C. Moulded pulp containers

Moulded pulp is used to describe 3D packaging and food service articles. it is

manufactured from aqueous slurry of cellulosic fibers by forming into discrete products
on screened molds. The raw materials consists of virgin mechanical, chemical wood
pulp and waste paper pulps. In manufacturing this container, two molding processes
are used. During the first stage, a pressure injection process which involved the used
of air under pressure at temperature of 480oC was introduced to produce a mixture of
pulp and water in a mould. then, the process continues with a suction moulding
process where a partial vacuum is applied to one side of the mould screen after the
pulp mixture has been placed in the mould.

Common uses of pressure moulded containers include the packaging of bottled spirits
where a pulp sleeve moulded to the profile of the bottles and enables them to be
packed head to tail in a carton. Besides, other well known forms of moulded pulp are
egg cartons, food trays and many other forms of tray shaped articles. PET can be
used to laminate the surface of moulded pulp as to enable the function of dual
ovenability container for frozen diners. Example is Egg Tray

2.2.1 Composition and Structure of Glass

Glass is a highly viscous liquid but exists in a glassy state in which molecular units
have a disordered arrangement with sufficient cohesion that gives mechanical
rigidity exhibiting solid material characteristics.

Chemically, glass has a random atomic structure meaning that the atoms are capable
of arranging themselves in different orders. The basic structural unit of glass is silicon
(Si) surrounded by four oxygen (O) atoms in tetrahedron shape as shown in Figure
2.1 below.

Glass is defined by the American Society for Testing and Materials (ASTM) as "an
amorphous, inorganic product of fusion that has been cooled to a rigid
condition without crystallising".

The main raw material used in glass production is silica derived from sand, quartz or
flint. Other ingredients added include alkali fluxes, lead, alumina, boron etc. in various
proportions.

The addition of alkali fluxes have important functions in the glassmaking

process. Sodium and potassium carbonates lower the fusion temperature and
viscosity of silica. While calcium and magnesium carbonates act as stabilisers which
prevent the glass from dissolving in water.

The functions of other ingredients are to enhance certain physical properties of glass.
For example, lead gives clarity and brilliance but reduces the strength of
glass. Alumina increases the hardness and durability of glass. Boron is added to form
borosilicate glass (commonly used in laboratory glass apparatus) reduces the leaching
of sodium from glass structure.
Glass Corrosion

Although it may seem that glass is more resistant and inert compared to metal, glass
is still subjected to corrosion. Under certain conditions, the glass will corrode and even
dissolve (Figure 2.2).

Figure 2.2 Glass surface dissolving

Aggressive chemicals such as hydrofluoric acid, concentrated phosphoric acid, hot

concentrated alkali solutions, and superheated water are among the chemicals that
can attack the glass. However, acids and alkali solutions attack glass in different ways.
Alkalis attack the silica directly while acids attack the alkali in the glass. Glass
corrosion can be divided into three types which are etching, leaching, and
weathering.

a) Etching

This type of corrosion is due to the alkaline attack, which slowly destroys the silica
network of glass and releasing other glass components. Consequently, the glass
surface will simply dissolve.The alkaline corrosion process proceeds at a uniform rate
as long as the supply of alkali is sufficient therefore the etching process will
continuously expose a fresh surface layer of glass which in turn, will also dissolve.
Compared with acid attacks, glass is highly susceptible to attack by alkaline materials,
especially a concentration of (-OH) ions with a pH greater than 9.0.

b) Leaching

This corrosion is characterised by an acid attack in which hydrogen ions exchange for
alkali or other positively charged mobile ions in the glass.
By dissolving the alkali in the glass composition, a porous surface is left, which
consists of the silica network with holes where the alkali has been removed by the
acid. This porous surface slows the rate of attack since the acid must penetrate this
surface layer to find alkali to dissolve. This makes the remaining glass (mostly Si)
retain its normal integrity.
c) Weathering

This type of corrosion occurs at a very slow rate and may take centuries before
it becomes apparent. Surface bloom is a mild form of weathering corrosion.

Figure 2.4 Example of weathering corrosion

2.2.2 Glass Advantages & Disadvantages

Advantages of glass

 Glass is made from silica sand which is an abundant and easily obtainable raw
material.
 Glass has a distinctive environmental friendly image being reusable and 100%
recyclable and can be recycled endlessly without loss in quality. An estimated
80% of recovered glass containers are made into new glass bottles.
 Glass is inert, there are no chemical interactions between glass packaging and
products to affect the taste, aroma and flavour of food and beverages.
Therefore, it is regarded as the safest packaging material. There is no flavour
scalping issue for glass container since it does not impart any odour unlike
plastic or metal packaging materials.
 Glass is impermeable and non-porous to moisture, gases and vapours, so it
maintains product freshness for a long period of time without impairing taste or
flavour.
 Glass is able to withstand high processing temperatures which makes glass
suitable for heat sterilization of both low-acid and high-acid foods.
 Glass is rigid, strong and able to resist certain amount of internal pressure
which makes it easier to handle on the production filling line, and glass retain
its shape during all phases of marketing.
 The transparency of glass allows consumers to see the product. For light
sensitive products, variations in glass colour helped in protecting the content.
Disadvantages of glass

 Glass is fragile and has poor shock resistance. Protection is needed against
shock by the bottles knocking each other during production process and
transportation. In other words, glass is susceptible to breakage from physical
and mechanical abuse.
 Glass is also affected by sudden change in temperature known as thermal
shock.
 Glass is heavy in weight; therefore, it adds to transportation cost.
 Since glass is rigid, it is also a disadvantage as an inflexible material.
 Broken glass may become a hazard to consumer if splinters are dropped inside
the product.

2.2.3 Glass Manufacturing

Raw materials for glass production

The major raw materials for making glass are silica (65 to 75%) which derived from
sand, flint or quartz; and cullet (15 to 50%) which is recycled glass. Other raw
materials include alkali fluxes(Na2CO3 and K2CO3) which are added to lower the
viscosity of silica and melting temperature; limestone and dolomite (CaCO3and
MgCO3) are added to stabilise and prevent the glass from dissolving in water.

Other ingredients are added in smaller amounts but have significant effects on the
physical properties of glass. Addition of lead provides clarity and brilliance; however,
it softens the glass structure. Alumina (Al2O3) increases hardness and durability,
while boron is added to reduce the leaching of sodium and form a borosilicate glass.

Colour of glass results from two factors which are the oxidation state of glass and the
dyes used. Mineral oxides are normally added to obtain coloured glass, for example,
chromium oxide gives blue-green colour, a mixture of chromium oxide with iron oxide
give dark green colour, and blue glass is obtained by addition of cobalt to low-iron
glass. Amber in a coloured glass is caused by the degree of oxidation and by addition
of iron chromite.
Glass Manufacturing Process

a) Batch mixing

Prior to mixing with other ingredients, sand (SiO2) is washed and sifted to remove
shells, stones and exceptionally large grains of sand. Manufacturing of glass starts
with a mixing process where the required ingredients are mixed in a rotary mixer to
ensure uniformity before feeding it into a furnace.

b) Melting

In the furnace, the mixture is heated to ~1500oC for 12-48 hours, where all the
ingredients are melted. Several chemical reactions take place during melting in which
CO2 and SO3 gases are evolved. When all the gases have evolved, the bubble-free
molten glass is moved through a heated channel called forehearth, where it is slowly
cooled to temperature ~1100oC to increase its viscosity. After that, the red-hot glass
is sheared or cut-off into gob (weighed cylindrical molten glass) which is then
channelled to a forming machine to be moulded into the desired shape.

c) Moulding glass containers

There are three types of moulding process: Blow and Blow (B&B) to produce long neck
bottle, Press and Blow (P&B) to form jars or wide opening bottle and Narrow-neck
P&B for lightweight bottle with shallow neck
d) Annealing

The newly formed glass will be transferred to an annealing lehr (special oven), where
the bottles are reheated to 600oC and then slowly cooled to remove stress points and
to prevent the glass from becoming brittle.

e) Protective coating

The surface treatment is applied to the bottle in two stages namely hot end and cold
end treatments to modify mechanical properties.

Hot end treatment is carried out while the bottle is still hot (550oC), where tin or titanium
vapour is sprayed, forming a thin molecular layer of metal oxide. This prevents surface
damage and improves adhesion of the subsequent cold end coating. Cold end
treatment is conducted at less than 100oC where waxes, stearates, silicones, oleic
acid, polyesters waxes or polyethylene is sprayed. This increases lubricity of a glass
container by providing a low coefficient friction surface which aids flow through a high-
speed filling line.
2.2.4 Glass Defects

Glass Defects

In glass manufacturing, defects are divided into three categories: critical, major and
minor defects.

a) Critical defects are those that may injure an operator in the plant or a customer,
or alternatively they may be so serious that they may cause the food to become
unsafe. In other words, glass with critical defects is hazardous to the user. Glass with
this type of defect is completely unusable.

Table 2.1 Examples of glass critical defects

b) Major defects are those that make a package unsuitable for use in the process or
result in a serious loss of money for a business (wasted product, legal action etc). This
type of defect reduces the usability of the container or its content. Examples of major
defects are glass weight below minimum and height or diameter outside tolerances.

c) Minor defects are the majority of faults that occur in glass container fabrication.
This type of defects do not affect the usability of the container but lower the
attractiveness, appearance or user acceptability. For example, uneven outer surface,
slightly off-colour glass and rough mould lines.
thermal, optical and mechanical properties of a glass container in respect to its
function as a food packaging material.

a) Thermal Properties

Compared to other food packaging materials, glass is the least resistant to

temperature change. Thermal shock or sudden cooling or heating will cause glass to
break. This is due to the uneven tensile stresses created on either the internal surface
or outer surface of the glass

When a glass is suddenly cooled (for example, on removal from hot oven to cold
storage), the inner surface of the glass has to compensate for the stresses that occur
on the outer surface of the glass. Conversely, when the glass is subjected to sudden
heating (for example, hot water is poured in a cold glass), surface compression (on
the outer surface) and internal tension occur.

Normally, the stresses due to both sudden cooling and heating are temporary and will
disappear once the equilibrium temperature is reached. However, if the tension of
stresses are too great, fracture will happen.

Notably, sudden cooling is much more damaging compared to sudden heating. This
is because the amount of tension produced on the outer surface of a bottle by suddenly
chilling it is twice the amount of tension produced by sudden heating, assuming the
same temperature change in both cases (Moody, 1977). In order to withstand thermal
shock, factors such as the type of glass used and ingredients added during its
manufacturing, the design shape of the glass and the thickness of the glass container
play important roles.

In food processing or in food service, thermal shock occurs in operations such as

washing, pasteurisation or hot-filling processes, during transfer from a warmer to a
colder condition or vice versa. Resistance to breaking towards such operations is
determined by transferring glass containers which have been totally immersed in a hot
water bath (typically at 63°C) for 5 min to a cold water bath (typically at 21°C), and
observing the number of breakages (ASTM 2014: C149-14).

b) Mechanical Properties

Any small imperfections such as flaws, cracks, scratches or checks which are
normally found at the surface of glass will become a stress concentrator that
induces glass to shatter when high enough tensile stress is applied, as shown
by the formula: Tensile Stress + Stress Concentrator = Fracture

In term of mechanical properties of a glass container, the following aspects are

important:
i) Internal pressure resistance

In food processing, the glass containers are likely to be processed in boiling water or
sterilised in pressurised hot water, which creates an internal pressure. This pressure
produces bending stresses at various points on the outer surface of the container, as
shown in Figure 2.14.

ii) Vertical load strength

The load strength of glass depends on the design of the shoulder which is important
to minimise breakage during high-speed filling and sealing operations.

iii) Resistance to impact

There are two forms of impact: (1) when a moving bottle come into contact with a
stationary object, for example when a bottle is dropped; and (2) when a moving object
contacting a stationary bottle, for example at the filling line. Impact of forces on sidewall
of a glass container. Surface treatments and the design features of the glass container
help to strengthen the contact points at the sidewall to lessen the fragility of glass.

iv) Resistance to scratches and abrasions

As mentioned earlier, presence of surface damage such as scratches, abrasions or

microcracks (as stress concentrator) will greatly affect the overall strength of a glass
container. Surface treatments involving tin compounds provide the scuff resistance
capability, including careful handling during and after forming, and annealing will help
to make glass more break resistant.

c) Optical Properties

The optical properties of glass is determined by the absorption of light within the glass
and reflection of light on the glass surface. In other words, it relates to the degree of
spectral transmission of light as a function of wavelength. This transmission can be
controlled by addition of colouring agents such as metallic oxides, sulfides or selenides
and other compounds as listed in Table 2.2. The three most common colours of glass
containers are flint or clear, amber or brown and green.

A light-resistant glass is defined as one which passes no more than 10% of incident
radiation at any wavelength between 290 and 450 nm through the average sidewall
2.2.6 Nomenclature of Glass Container

Glass container comes in various designs, sizes, and shapes according to the nature
of the product, specific end uses, aesthetic appeal and customer requirements.
However, the term used in the design of a glass container has similar basic
nomenclature as shown in Figure 2.17 below.

Figure 2.17 Glass container

Finish: The part of the container that holds the cap or closure (i.e., the glass
surrounding the opening in the container). It must be compatible with the cap or closure
and can be broadly classified by size (i.e., diameter), sealing method (e.g., twist cap,
cork, etc.) and special features (e.g., snap cap, pour-out, etc.). The finish has several
specific areas including the sealing surface, thread and neck ring.

Neck: The design of the neck depends on the type of bottle (long neck or short neck
for bottle, jar has no neck). It is important in determining the filling capability, air
displacement and dispensing performance of a bottle.

Shoulder: This part is very important for efficient production and for good design. The
most vulnerable portion where fractures normally occur during handling and shipping.

Body: Most generalised area of the bottle where the label is attached.

Base: Area on which the bottle rests which should be as large as possible for good
stability.
2.2.7 Closures for Glass Container

Closures are required in order to provide effective seal to prevent product (liquid,
solid or gases) from spilling out from the container. The design of the closure should
also provide easy opening and/or reclosing as well as evidence of tampering to
avoid violation of the product. Closures for glass bottle can be made either from metal
or plastic.

Metal closures can take four forms: screw cap, crown, lug cap, and spin-on/roll-on
closures. These closures are stamped out of tinplated steel (ETP), tinfree steel
(ECCS) or aluminium sheets (thickness ~0.25 mm) which are usually coated with
enamel to prevent metal from reacting with food contained in the bottle.

Plastic closures are made using compression or injection moulded with plastic resins
or thermoplastic polymers such as polystyrene (PS), low density polyethylene (LDPE),
high density polyethylene (HDPE), polypropylene (PP) and PVC.

To form an effective seal, a sealing component of either a gasket or liner are

required. Liner, also known as wad, is generally made from coated paper or
paperboard while gasket is made from rubber or plastisol. Development of
thermoplastic resins are able to make ‘linerless’ closures, which rely on sealing rings
to create hermetic seal.
2.2.8 Glass Reuse & Recycling

Benefits of glass recycling

Glass has a good environmental image as it can be reused and recycled. In general,
a glass bottle can be reused for about 12 trips per bottle on average. With the decline
of doorstep delivery and limited numbers of drinks manufacturers that operate
returnable systems, glass reuse by manufacturer becomes obsolete. This, however,
has caused glass recycling to become a significant process. Furthermore, there are
many recycling bins and collection systems in place which makes glass recycling
easier.
Glass is one of the easiest materials to recycle. It can be crushed, melted and reformed
an infinite number of times with no deterioration of the structure. It is the only
packaging material that retains all its quality characteristics when it is recycled.

Using recycled glass or cullet to manufacture new glass containers has few
advantages such as (a) reducing the need to quarry and transport raw materials, (b)
reducing the energy required to melt and process glass and consequently decreases
gas emissions and (c) reducing the amount of solid waste going into the landfill.

The most important thing to note is that only food-based glass containers can be
recycled.

Glass recycling process

The first step in the glass recycling process is sorting of the glass bottles based on
colour. Clear bottles are separated from the coloured ones, followed by thorough
washing and cleaning to remove adhering product left-over. During this process,
closures either a plastic cap or a metal cap are removed from the glass container. Any
paper or plastics labels were also removed during the cleaning process. After that, the
glasses are crushed into small pieces of broken glass known as cullet.

When adding cullet in glassmaking, the presence of other contaminants such as metal,
gravels, dirt or non-container type of glass will become a risk to the manufacturer. It
will damage the machinery, slow down the production and produce defective glass.
Therefore, it is important that the first stage of sorting and cleaning were done properly.
Figure 2.25 below shows the process flowchart of glass recycling.

Figure 2.25 Glass recycling

2.3.1 Advantages and Disadvantages of Metal

Advantages of metal packaging

 Food products in metal can have very long shelf life (2 to 5 years) compared to
those in other types of container.
 Metal can is rigid and stackable, which makes it easier for retail shelves display
and storage.
 Metal can is tamper proof, it does not require additional tamper proof material
unlike glass or plastic container.
 Metal is recyclable and considered as environmental friendly, specifically
aluminium (Al) cans..
 Metal can provides total protection of its content; preserves colour and taste of
products, protects against insects and rodents, provides a barrier from gas,
moisture and light.
 Metal has superior mechanical strength compared to other packaging
materials.
 Metal has good thermal conductivity and resistance to relatively high
temperature which make metal packages particularly suitable for in-package
thermal processing.

Disadvantages of metal packaging

 Compared to paper, more space and higher cost are needed to transport newly
fabricated cans since they cannot be supplied in flattened condition to food
manufacturers.
 Metal can is not suitable for high acid or high alkali foods and needs special
coating to contain such products. Aluminium has low resistance to brine
solution.
 Metal is heavier than other materials, except glass, and therefore have higher
transportation costs.
 The high energy requirement for Al production makes Al the most expensive
material used in food packaging.

Food product that is filled in metal container can be divided into two types based on
the processing method.

 Thermally processed foods such as fruit pulp/juices, vegetables, tomato

puree, meat and fish, ready-to-eat foods and pet foods.
 Non-thermally processed foods such as condensed milk, baby food, milk
powder, ghee and instant beverages in powder form.
2.3.2 Manufacturing of steel-based plate

Manufacturing of steel-based metal into a food metal container involves four major
processes which are:

1. Ironmaking process

The source of iron comes from iron ores in the form of hematite (Fe2O3) and magnetite
(Fe3O4) obtained from rocks. Solid fuel (coke) and fluxes (limestone and dolomite)
are mixed together with the iron ores in blast furnace at ~1800oC to reduce iron oxides
into metallic iron. The molten iron is poured into a mould and left to solidify (pig iron).
The by-product of this process (slag) is removed and used to build road, turn into
cements or fertilisers.

2. Steelmaking process

The pig iron contains 3.5 to 5% carbon and other elements such as manganese,
sulfur, phosphorus and silicon which makes it hard and brittle. To produce steel, the
carbon must be reduced to 0.5 – 1.5% and this is done by melting pig iron in Basic
Oxygen furnace (BOF) or Electric Arc furnace (EAF). From the furnace, the steel is
cast into ingots, which are then rolled into slab of ~250 mm thick and further hot
rolled to 2 mm thickness. During this process, oxide layers or scale are formed which
is removed through pickling process using dilute sulfuric acid (10 to 15%) solution
near its boiling point. The clean steel is then coated with oil to prevent from rust and
act as lubricant in subsequent steps.

Next, the steel goes to cold rolling process to further reduce its thickness from 2 mm
to 0.2 mm. This process will increase the strength and hardness of steel but reduces
its ductility. Annealing is conducted by heating steel (600 to 700oC), causing
recrystallization of uneven metal crystals into finer grain structure. This process
increases ductility but affects the strength of steel. After annealing, a light cold rolling
is done to reduce possibility of fluting, paneling or creasing and to impart the desired
surface finish and also to increase the tensile or springiness of the steel.

3. Tin-plating/Chromium-plating process

Prior to electroplating, the steel-based plate is degreased, cleaned by light pickling

and thoroughly washed to prepare the surface. The electroplating process where tin
is coated on the surface of steel produces electrolytic tinplate (ETP) and where
chromium is coated on steel, as known as electrolytic chromium-coated steel (ECCS)
or tin-free steel (TFS). For producing ETP, there are two principal methods of coating
steel with tin which are Ferrostan process and halogen process.

After the plating stage, the tin-plated steel goes to a flow melting and passivation
processes. Flow melting process consists of heating the tin-plated steel at 260 to
270oC followed by rapid quenching in water. Passivation process is done using
electrolytic treatment in sodium dichromate electrolyte. These process make the ETP
surface more stable and resistant to the atmosphere conditions.
The production of ECCS or TFS is similar with ETP but without flow melting and
passivation treatments. Electroplating was done using dilute chromium oxide (CrO 3)
and sulfuric acid as electrolytes at temperature 50 to 70oC.

Figure 2.27 shows the steps for making tin-plated steel known as ETP (electrolytic
tinplate) and ECCS or TFS which are electrolytic chromium-coated steel and tin-free
steel respectively.

The advantages and limitations of ECCS compared to ETP is as follow:

 ECCS plate is much thinner than the lowest grade of ETP plate
 base layer of Cr on ECCS acts as corrosion barrier whereby the
superimposed layer of Cr oxide prevents rusting and iron taste pick up
 ECCS is easier to fabricate (simpler process than ETP)
 ECCS has good chemical and thermal resistance and resistance to greater
internal pressure
 Compared to ETP, ECCS is less resistant to corrosion thus has to be
enameled on both sides
 ECCS plate cannot be soldered by welding or using organic adhesives
 ECCS container cannot be used for acid products

Prior to shipment to can manufacturer, the finished ETP and ECCS plates are oiled
with permissible oil for food packaging such as dioctyl sebacate and acetyltributyl
citrate to help preserve the coating layers and assist flows in subsequent can making
operations. Finally, the sheets are sheared into strips or coiled and then packed for
shipment to can manufacturers.

2.3.3 Manufacturing of aluminium

The Earth crust contains ~8.8% of aluminium (Al) in the form of aluminium oxide
(Al2O3), diaspore (Al2O3.H2O), gibbsite (Al2O3.3H2O) and most commonly, bauxite (an
impure form of gibbsite). These are the raw material for the production of aluminium.

Aluminium is manufactured in two stages:

1. Bayer process – refining the bauxite ore to obtain alumina (Al oxide).
2. Hall-Heroult process – reduction of alumina to release pure Al.

In the Bayer process, firstly, bauxite ore in the form of rocks is mechanically crushed
and ground, mixed with caustic soda to produce a slurry that is pumped into a digester
(110-270oC, pressure 340 kPa) for several hours. The hot slurry of sodium aluminate
obtained is channeled to a series of flash tanks, filters and washers to separate
alumina and caustic soda (reuse). The filtered liquid containing alumina is pumped
into a precipitation tank where crystal alumina hydrate seed is added. Crystal
precipitate obtained is heated (1100oC) to form anhydrous alumina crystals which then
will be purified in the Hall-Heroult process.

Hall-Heroult is a high energy electrolytic process that releases the bonds between Al
and oxygen atoms, producing molten Al with 99.8% purity. This process is the only
method of extracting aluminium currently in use commercially. The process starts with
the dissolution of the alumina in an electrolyte solution (cryolite) in carbon-lined steel
vat which functions as a cathode. A set of carbon electrode rods (anode) is lowered
and an electric current of 50 to 150 MA is passed through the mixture. This results in
the release of oxygen from alumina molecules which is then attracted to the carbon
rods to form CO2 gas. Free Al atoms settle at the bottom of the vat as molten Al (99.8%
purity) is then cast into ingots or billets

Prior to fabrication as a food container, ingots are melted, mixed with alloying agents
to improve its mechanical properties and subjected to a series of rolling. The thickness
of the Al plate or sheet formed depends on the desired applications.

Today, about 50% of beverage containers are made from Al and ~80% of steel-based
beverage cans have Al end with pull tab. For food applications, Al with a purity of
99.5% is normally required.

As a food packaging material, Al is found in two forms, (i) Al can which is commonly
used for soft drink beverages, and (ii) Al foil, commonly used as a wrapper for grilling
or laminates. The highest purity of Al, being the most ductile, is used for the
manufacture of foil and carbonated beverage containers.

Advantages of aluminium

 Basic raw material (bauxite) is available in abundance in nature.

 A lightweight material compares to steel, this gives an economic advantage
during transportation.
 Al can be easily and economically recycled.
 Al is more ductile than the steel-based plate, provides ease for fabrication.
 Most easy open-ends and apertures are prepared from Al.

Disadvantages of aluminium

 Production of Al uses high electricity which eventually requiring a high cost.

 Al cannot be sealed easily by the seaming machine and cannot be soldered.
Producing 3-piece cans requires welding.
 Softer than steel-based cans so it must be handled with care during packing
and transportation.
 Has a greater tendency to bleach some highly-pigmented food products.
 Aluminum foil
Aluminum foil is a thin-rolled sheet of alloyed aluminium (Al) used for wrapping candy
bars, chocolate, and chewing gums. It is also laminated on paperboard for folding
cartons, formed and semirigid containers, foil lids, caps and cap liners, composite cans
and canisters.

The thickness of Al foil varies from 4 to 150 μm and this determines the permeability
of the foil to light, moisture and gases. Al foil with thicknesses lower than 15 μm is
permeable due to the presence of pinholes but becomes impermeable if it is greater
than 15 μm in thickness.

Al foil is produced by continuous casting with a series of hot and cold rolling until the
desired thickness is obtained followed by annealing to improve its mechanical
properties.

2.3.4 Fabrication of metal container

There are two methods of metal can fabrication used which are three-piece can and
two-piece can making processes.

A 3-piece can consist of three parts (bottom, body and lid) and usually made out of
ETP or ECCS materials. A 2-piece can have only two parts (body and lid) and mostly
made out of aluminium since Al is more malleable. The 2-piece can do not have side
seam to attach the body together since the body and bottom are combined through a
process called Drawn and Redrawn (DRD) or Drawn and Ironed (D&I).

Three-piece can formation process

The stages in the formation of 3-piece welded can are illustrated in Figure 2.30. The
process starts with the cutting of ETP or ECCS blank into a rectangular shape to form
a can body (body blank). It is then rolled to a cylindrical shape with the edges of both
ends overlapping each other. The edge is either welded or soldered together as a side
seam. Next, the bottom rim of the can body is flanged outward where a can end is
positioned, crimped and then double seamed to seal the bottom of the can.

Two-piece can formation process

Unlike the 3-piece can, the two-piece can have no side seam and has only one double
seam to attach the can end after the product has been filled. The absence of side
seam at the lap juncture makes the fabrication process much easier to be done and
to control. It also saves material in solder and makes the can lighter in weight. The
smooth body of a 2-piece can make for a more aesthetic appearance and increases
the effectiveness of printing area which permits for all-round decoration on the outside
of the can.
a) Drawn and Ironed (D&I)
The sequential stages in the production of D&I can are shown in Figure 2.31. The
process begins with a rectangular cut body blank (1), punched into a shallow cup (2),
the sidewall of the body is drawn and redrawn (3), followed by repeated ironing
process (4), (5) and base formation (6), finally the finished can is trimmed to required
height (7).

Figure 2.31 Fabrication flow of 2-piece can using D&I method [Gordon, 2013)

b) Drawn and Redrawn (DRD)

The fabrication stages of a DRD can is shown in Figure 2.32. Similar with D&I, the
process begins with a rectangular cut body blank (1), which is punched into a shallow
cup (2), followed by a first, second stage of redrawing process (3), (4) and finally, the
finished can is trimmed to its required height.

Figure 2.32 Fabrication flow of 2-piece can using DRD method (Gordon, 2013)

Double Seam
The process of double seam formation involves interlocking of flanges of the can body
to the can end mechanically.

Can End Manufacture

The lid of a can or can end is specifically designed for optimum deformation behaviour,
which is an important characteristic. The can end must be able to deform while not
becoming permanently distorted under internal and external pressure. In other words,
can end acts as a diaphragm, expanding during thermal processing and returning to
a concave profile upon cooling. The design is also dependent on the plate thickness,
contour of the expansion rings and the depth of countersink

The process of forming a can end starts with the cutting out of a blank tinplate sheet into a round
shape, which is then stamped using power press to form a ‘start’ curl straight. After that, the ends go
to another press with a curling tool to form the outside curl and diameter. A lining or sealing
compound is then applied into the seaming panel. The type of sealing compound used is either
natural-based or synthetic rubber which is dissolved in water or solvent. The main function of the
sealant is to assist the formation of a hermetic seal by providing a gasket between adjacent layers of
metal. Other functions include filling the void at the end of body hook, filling the end hook wrinkles,
and preventing any seam areas from metal to metal contact which will increase chances for corrosion.

2.3.5 Corrosion of metal can

Corrosion is the deterioration of materials by chemical interaction with their

surrounding environment. For food packed in a metal can, interaction between the
food and the internal surface of the can may cause an internal corrosion. Oxygen and
moisture surrounding the can interact with the outer surface of the can causing an
external corrosion.

Tin-plated can is resistant to corrosion towards the common acids found in foods, but
all other metals must be lacquered or enameled. However, tin-plated can must be
lacquered when particularly aggressive products are packed such as tomato puree, or
when there is a potential of pitting corrosion or surface staining to occur such as in
meat products packaging.

Factors that affect corrosion of foods in a metal container can be divided into two
groups:
 corrosion caused by the food itself, and,
 corrosion due to the processing and storage conditions of the canned food.

These factors are also interrelated and may combine in a synergistic manner to
accelerate corrosion of a metal can.

Corrosiveness of foods
Food products are an extremely complex chemical system with a mixture of various
ingredients that can act as corrosion inhibitors or accelerators.

From a corrosiveness point of view, foods can be divided into five classes (Robertson,
2013):
1. Highly corrosive such as apple and grape juices, berries, cherries, prunes,
pickles and sauerkraut
2. Moderately corrosive such as apples, peaches, pears, citrus fruits and tomato
juice
3. Mildly corrosive such as peas, corn, meat and fish
4. Strong detinners such as green beans, spinach, asparagus and tomato
products
5. Beverages
the corrosion contributing factors of food products in detail.

1. Acidity

Generally, acid is known to affect metal and has great tendency to form a complex
with dissolved tin which affects the polarity of tin and steel, and therefore influencing
the degree of corrosion. However, for food products, no direct proportionality exists
between acidity of a product with the degree of corrosion of tin-coated metal can. This
means that two products of the same acidity will not necessarily be equally corrosive.
Similarly, a pure solution of organic acids is less corrosive than the fruit juices. In other
words, fruit juices contain other compounds as depolariser that enhance its corrosive
action compared to pure organic acid alone.

2. pH

Similarly, pH shows no direct proportionality with the degree of corrosion of tin-plated

can. This is probably because when a metal is dissolved, the reaction product is not
always in the form of an ionic species but commonly as solid oxide or hydroxide. The
pH of the system also determines the relative cathodic protection given to steel.
Generally, corrosion rate is fairly independent of pH within the range of 4 to 10, but
increases rapidly when the pH falls below 4.

3. Sulfur Compounds

Sources of sulfur and sulfur compounds in canned foods may come from the spray
residues of agricultural chemicals and residues from sulfur-containing preservatives,
or sulfur-containing compounds such as proteins in meat, fish and certain vegetables.
Derivatives of thio- and dithiocarbamic acid fungicides are examples of sulfur
compounds from agricultural chemicals that lead to accelerated corrosion and failure
of plain tin-plated cans containing acid foods. Methionine and cysteine are the
common sulfur-containing amino acids in protein. During heat processing, proteins are
degraded thus releasing free sulfide or hydrosulfide ions and evolving hydrogen sulfide
gas into the headspace. Sulfur dioxide (SO2) may be directly reduced on the tin surface
to sulfide or even to sulfur, with tin passing into solution and causing unpleasant
odours and flavours. Residual SO2 accelerates corrosion through its action as a
depolariser. Trace amounts of SO2 as low as 1 mg/kg are sufficient to accelerate
corrosion.

There are two types of sulfide staining namely iron sulfide and tin sulfides. Both types
of staining do not constitute a health hazard or lead to failure of the can but lowers the
aesthetic aspect of the canned foods.
i) Iron sulfide stain: This type of stain is characteristically black in colour, and occurs
mainly in the headspace region during or immediately after heat processing. The
staining effect may be prevented by using enamel-coated cans.

ii) Tin sulfide stain: This type of stain is blue-black or sometimes brown in colour. It is
usually seen throughout the can and occurs during or immediately after heat
processing and will not increase during storage. The staining may be prevented by
using sulfur-resistant enamels containing added Zn or Al compounds. However, this
approach is not suitable for acid products since acids may attack the coating to
produce metals salt, which could be harmful to health.

4. Nitrates

Nitrates are an efficient cathode depolarisers which are capable of being reduced to
ammonia. They have been responsible for serious economic and toxicological
problems in some canned foods, notably in tomato products. Nitrates content in fruits
and vegetables comes from heavily fertilised soils, and may also occur in water
supplies as a result of pollution by fertilisers. In processed meats, nitrates and nitrites
are intentionally added as additives. This poses no problem because meat products
are above the critical pH of 5.5 for detinning to occur via the nitrate–tin reduction
system. Nitrate does not immediately affect the corrosion rate, but begins to act after
tin and iron ions have passed into solution. Ways to overcome this problem include
restricting the use of nitrate fertilisers and avoiding the use of waters with high nitrate
content for canning operations, but the most practical solution is to use enameled can.

5. Phosphates

The presence of phosphates in canned foods leads to the increase in discolouration

due to iron phosphate and sulfide formation. In processed meat products,
polyphosphates are intentionally added to help reduce the loss of water during
processing. Phosphates may also be naturally present in meat. To counter the effect
of polyphosphate in cans of processed meats, an Al sacrificial anode can be used to
protect the tin surface. However, this technique is not always completely successful,
and parchment liners may be used in addition or as an alternative.

6. Plant Pigments

Natural pigment such as anthocyanins are corrosion accelerators as cathodic

depolarisers since they are easily reduced. They also act as anodic depolarisers
through their ability to form complexes with cations. The molecular structure of the
anthocyanin compound also determines its corrosion ability. For example, raspberries
contain cyanidin glucosides with ortho-dihydroxy groups involved in the formation of
blue-tinted complexes with tin. However, the pigment of strawberries, pelargonidin-3-
glucoside, does not form blue colour complexes with tin salts.
Formation of a complex between tannins present in fruit and tin salts causes
discolouration in canned cranberry and darkening of canned maraschino cherries has
been attributed to the high tannin content.

7. Synthetic Colourings

In certain food products, synthetic colourings are used to enhance the colour of the
product. Addition of azo dyes, such as amaranth in soft drink, combine with presence
of residual O2 in the can. They are both corrosion accelerators and hence, pose as an
active corrosive agent. Dissolution of tin may adversely affect the colour of some
products while iron dissolution may lead to perforation and flavour defects. For such
products, a full and perfect enamel coating are an utmost importance.

8. Copper

Copper accelerates the corrosion of steel because it catalyses the reduction of O2.
The source of copper in food may come from copper-bearing utensils or equipment
used, from certain fungicides or from water supplies used in canning process.
Dissolved copper in canned food, especially in acidic products, can lead to accelerated
corrosion. Most food processing equipment today are made of stainless steel;
therefore, the effects of corrosion by copper are reduced.

Corrosion effects of processing and storage

1. Oxygen
An increase in oxygen concentration usually relates to the increase in corrosion rate.
Oxygen acts as a depolariser which accelerates corrosion by reacting with hydrogen
gas that is formed in can through a cathodic reaction. The source of oxygen in canned
foods may come from either fruit and vegetable cells or trapped and dissolved oxygen
in food products prior to can seaming. One of the procedures in canning is to remove
as much as possible the oxygen content which is done through exhausting, vacuum
and hot filling, closure under vacuum, steam flow closure and vacuum syruping. The
headspace volume of the can also must be control as larger headspace are likely to
have more residual oxygen.

2. Thermal Processing
High temperature processing such as in sterilisation process will not cause metal to
dissolve due to the short heating time used. However, degradation products formed
during thermal processing can become involved in corrosion (e.g., non-enzymic
browning intermediates and sugar derivatives). In canning operation, proper cooling
after heat treatment is an important process. If the cans are not cooled to a target
temperature of 40oC immediately after retort, it can lead to corrosion since the center
of the can takes slower time (may be several days) to reach ambient temperature. On
the other hand, if cooling progresses to a much lower temperature, external corrosion
may occur since moisture on can surface cannot fully evaporate for a complete drying.

3. Storage Temperature
It is a general rule that the rate of a chemical reaction increases by double for each
10°C increase in temperature. Therefore, to minimise undesirable reactions such as
non-enzymic browning in canned foods, it is preferable that storage temperatures are
kept as low as practicable.

2.4 Plastic Packaging Materials

The properties of plastics are determined by the chemical and physical nature of the
polymers used in their manufacture. These properties are determined by their
molecular structure, molecular weight, degree of crystallinity and chemical
composition. These factors affects the polymer density and temperature of
physical transitions.

A. Molecular Structure

i) Classification of Polymers

In terms of chemical composition, there are two broad types of polymers which are
homopolymers and heteropolymers. Homopolymer composed of only one (same)
repeating building-block unit throughout their molecules while heteropolymer
composed of two or more (different) building-block unit regular or irregularly distributed
throughout their molecules. Heteropolymers are referred as copolymer when of 2
different monomers are polymerised together while terpolymer consists of 3 different
monomers polymerised together.

Linear polymers consists of a backbone of carbon atoms and a number of side groups
which differ from polymer to polymer and is a straight chain molecules that extend in
one dimension. Linear copolymer may exhibit any three combinational forms

i) Alternating copolymer - two or more different repeating units occur alternately along
the chain

ii) Random copolymer - the units are arranged randomly along the length of the chain.

iii) Block copolymer - combination of the previous two which composed of alternating
lengths of homopolymer along the molecular chains.
Branched polymer or cross-linked polymer indicates by long chains that are connected
together and have links between the chains.

Plastic polymers can be divided into two broad categories which are linear polymer
and cross-linked polymers. Linear polymers are thermoplastic that is gradually soften
with increasing temperature and finally melt because the molecular chains can move
independently. These polymers may be readily moulded or extruded because of the
absence of cross-links. Increased in temperature will make this polymer become very
flexible and can be moulded into new shape even at temperature below their melting
point. Example of linear polymers are polyethylene, polypropylene, polyesters,
polyamides, PVC and PS.

Compared to linear polymer, cross-linked polymers belong to thermosetting

categories. These polymers become set into a given network when manufactured and
cannot be subsequently remoulded to a new shape. If temperature is raised to the
point where cross-links are broken, irreversible chemical processes or degradation
occur and thus destroy the useful properties of plastics. Thermosetting plastics do not
melt on heating but finally blister and char. Examples of thermosetting plastics are
epoxy resins, unsaturated polyester, polyurethanes and phenolic resins.

ii) Polymerisation Processes

Thermoplastics can be made by joining a sequence of monomers under suitable

conditions of temperature and pressure with the presence of a catalyst called
initiator. The formation of thermoplastics can be divided into two types of
polymerisation; addition and condensation polymerisation.

a. Addition Polymerisation

The polyaddition process involves the joining of monomers to form polymers which
have the same atoms as the monomers in their repeating units. A low molecular weight
molecule is induced to break the double bond and the resulting free valences are able
to join other similar molecules. This reactions occurs in the form of chain addition
process with initiation, propagation and termination steps. Examples of polymers
made by condensation process are polyethylene, polypropylene and polyvinylchloride.

b. Condensation Polymerisation

This polymerisation process involves two active sites joining together to form a
chemical bond with the loss of a smaller molecules, usually water, alcohol, acid or
ammonia. With an appropriate catalyst, a monomer loses H while the other loses OH
and later combine to form H2O. The remaining electrons form a covalent bond, and
the reaction repeats to form long chain of polymers. Examples of polymers made by
condensation process are polyamides and polyesters.

c) Ring-Opening Polymerisation

The mechanism of ring-opening polymerisation involves the cleaving of cyclic

compound followed by polymerisation in the presence of catalyst.

B. Molecular Weight (MW)

The average number of repeating units in a single molecule of polymer is known as

the degree of polymerisation (DP). The molecular weight (MW) of polymers can be
calculated based on atomic mass of the repeating unit and the DP. The molecular
chains that are produced vary considerably in dimensions. Thus, a polymer system
has to be characterised in terms of average molecular weight and broadness or
molecular weight distribution (MWD).

Two average molecular weights commonly employed are the number average
molecular weight (Mn) and the weight average molecular weight (Mw). Most
thermodynamic properties are related to the number of particle present and dependent
on Mn. Mn values are independent of molecular size and are highly sensitive to small
molecules present in the mixture. Compared to many bulk properties such as viscosity
and toughness which depend on the size of the molecules, Mw was used as
appropriate function which is more dependent on the number of heavier molecules
than Mn

Processing of plastic containers can be divided into 3 stages:

Stage 1: Production of monomer: Monomer is derived from the cracking

process used in petroleum oil refining and natural gas production. It is a chemical
process that produces hydrocarbon monomers such as ethylene, propylene, styrene,
vinyl chloride, acrylonitrile etc.

Stage 2: Polymerisation of monomer into polymer: This process is conducted

through polymerisation reactions such as condensation, addition and ring-opening.
Polymer produce in the form of pellets, beads or powder.

Stage 3: Conversion into products: Further processing of polymer with addition

of additives such as plasticisers and other types of modifiers is conducted to convert
polymer into food container such as bottles, trays and films. The methods used either
by extrusion moulding, injection moulding, blow moulding or thermoforming.
In this course, we will focus on the conversion process of polymer into a food container
(Stage 3) only.

There are several methods in which the polymer pellets, beads or powder are
converted into the final plastic products such as plastic bags, plastic bottles or plastic
containers.

1. Blow Moulding

The step-by-step process of an extrusion blow moulding for production of plastic bottle.
The operation of the process involves; Step 1: formation of hollow tube called
parison from molten polymer (extrusion process) ; Step 2 and 3: parison
is entrap between two halves of a mould of designated shape; Step 4 and 5: blowing
air or nitrogen gas (~100 psi) into the soft parison, expanding it against the contours
of cold mould cavity; Step 6: final shape solidifies upon coolingand then ejected from
the mould, and finally; Step 7: the finished bottle.

2. Injection Moulding

The extruder used for injection moulding consist of two main components: injection
unit and clamp unit. The operation involves heating of polymer pellets or powder until
it melts and able to flow under pressure, and then injecting the molten material into the
mould followed by a holding period in which the plastic melt filled up the space within
the cold mould until it solidifies, finally the solidified plastic is ejected from the
machine.

3. Thermoforming

Thermoforming process is use for forming moderately complex shaped containers that
cannot be injection moulded due to either the container is very large or it has a very
thin walls. This process is applied to almost all thermoplastics eg. ABS, PP, PS, PVC,
polyesters, acrylics, PC, cellulosic and nitrile resins. Examples of plastic packaging
products made using this method are egg cartons, fast-food disposables, boxes, cups,
meat packaging trays etc.

There are three techniques of thermoforming which are vacuum, mechanical and air-
blowing process. In general, the process consist of two stages, i) temperature
elevation of a thermoplastics sheet material until it is soft and pliable, followed by ii)
moulding or forming the material into the desired container shape.
a) Vacuum thermoforming process

The operations consist of firstly, clamping of heated plastic sheet mechanically onto
the top of the mould, and then vacuum is applied beneath the hot elastic sheet causing
the sheet to contour down onto the mould due to the vacuum pressure, finally, the
cooled container formed according to the mould shape is ejected out of the mould.

b) Mechanical thermoforming process

The steps in mechanical forming process involves are (i) the hot plastics sheet is
stretch and clamp over a female mould or draped over the mould force (male mould),
and then (ii) the two mould are close together therefore forcing the sheet onto the
mould gap forming the shape of the container (mould), finally (iii) the formed container
is remove from the mould.

c) Air-blowing thermoforming process

The first step (A) involves sealing of a heated plastic sheet across the cavity of the
bottom mould, and then (B) air at controlled pressure is blown into the mould cavity
causing the sheet to move upward forming an evenly stretched bubble, (C) a plug (top
mould) is then descend onto the sheet until it reaches the lowest position of the bottom
mould. In some cases, the plug can only reach a certain lowest possible position,
therefore, (D) vacuum is applied to complete the formation of the container required.
2.4.3 . Properties of Plastic and Applications

Table 2.3 shows examples of different types of plastic according to their recycling code
numbering. Their general properties and applications are stated as well in the Table.

Table 2.3 Types of plastics according to the recycling code

2.4.4 Plastic Migration

In food, migration is defined as a submicroscopic food-package interactioninvolving

the movement of chemical compounds which is controlled by molecular diffusion,
dissolution or dispersion, and the direction of migration is from the package to the food

While, the term reverse migration is use to describe migration of chemical

compounds from food to package. Another similar term to migration is leaching, it is
use to describe migration of liquid or moist foods from the direction of packaging to
food. An example of reverse migration is flavour scalping which causes the loss of
desirable flavours of the food which has good direct contact with the package.

2.5 Laminates

Laminate is any combination of distinctly different plastic film materials or plastic

plus non-plastics materials (typically paper and Al.foil), where each major
web/layer is generally thicker than 6 µm regardless of the method of manufacture.

There is no maximum limit of the number of webs used but two is minimum and one
of these web must be thermoplastic polymer material. Currently, laminate with 7 or 9
layers are used for food packaging applications

The subsections are:

 Definition and Importance of laminate

 Lamination process
 Lamination applications

Figure 2.5 Example of a 9-layers laminate package

2.5.2 Lamination Process

There are three techniques used in manufacturing a laminate which are adhesive
lamination, thermal lamination and coating lamination.

a) Adhesive lamination

In this lamination process, adhesive solution is used either using organic solvent or
aqueous. The solution is applied on the surface of the web and then pass through an
oven for drying or curing process. After that, another layer of packaging material is
combine to the adhesive applied layer, pass through a roller that apply certain heat
and pressure to combine both materials together. Flowchart below shows a simplified
procedure of adhesive lamination process.

For adhesive lamination, it is important to select the right combination of laminates,

suitable adhesive application and the drying conditions have to be accurately
controlled. Otherwise, lamination defect such as blocking (not unwinding
smoothly), curling (edges of the roll curl up), and delaminating (layers separating) will
occur.

b) Thermal lamination

The process of thermal lamination is conducted by joining two webs together

either with adhesive or without adhesive. The joined web is pass through a heated
roller that provide force and heat required to establish contact for bonding. Most
common adhesive used in thermal lamination are polyolefins (PE, EVA) polymer

There are three methods of lamination namely i) wet bonding ; ii) dry bonding, and iii)
solventless lamination.

i) Wet bond lamination uses solvent or aqueous-based adhesives and this method
can only be used when one or more of web is/are permeable to water or solvent. It
is generally not successful when laminating plastic material with paper. The adhesives
used include casein, sodium silicate, starch, PVA, latex, rubber and dextrin (Gordon,
2013).

ii) Dry bond lamination uses either aqueous, solvent-based or hot-melt adhesives
and then dried or cured by heat prior to laminating. Adequate drying of adhesives is
important in this method because excess solvent is the major cause of
delamination defect and there is potential for solvents (volatile organic compounds)
to permeate into package thus effect the food. The common adhesives used in this
method are epoxies, polyurethanes and urea-formaldehyde.

iii) Solventless lamination is conducted by bonding two webs together by curing in

absence of solvents. In order to cure the solventless adhesive, a reactive chemical
system is used such as urethane and polyester isocyanate.

c) Extrusion lamination

Another method of lamination using thermal is extrusion lamination. It is a process in

which two or more polymers are extruded and joined together in a die to form a single
structure with multiple layers. A co-extrusion lamination involves molecular bonding
process without the use of adhesives. The joining of layers is accomplished at high
pressure and temperatures in a sealed environment where no moisture or air can be
entrapped which will compromise the molecular bonding. The major advantage of this
method is that the co-extruded layers are difficult to separate therefore no
delamination defect will occur.

Advantages of coextrusion:

 Multiple barrier layers structure decreases the potential loss of barrier due to
flaws (eg. pinholes or negligible probability of two adjacent holes in separate
barrier layers)
 Less tendency towards delamination and greatly reduce cost
 Greater flexibility in obtaining a wide range of properties
 Simplified process where no adhesive or solvent is used
 Capable of producing a thinner layer compared to other lamination process

Disadvantages of coextrusion:

 Some polymers will not adhere well to other polymers therefore a tie layer to
promote proper adhesion is needed
 Scraps produced during the extrusion process are difficult to recycle
2.5.3 Lamination Application

Here are some examples of lamination applications.