EGE UNIVERSITY

Chemical Engineering Department

Che 438: PROCESSES IN POLYMER TECHNOLOGY

Polyolefin Based Film

Manufacturing Processes and
Biodegradable Films
Prepared by;
Merve AYVAZ
İsmail Bahadır KARA
CONTENT OF PRESENTATION
 Properties of polypropylene
 Polymerization reactions
 Usage areas
 Film manufacturing methods
 Corona Treatment
 Biodegradable films
 Recycling
General Information about PP?

 PP is a strong, lightweight thermoplastic polymer.

 First discovered in Italy by Cullio Natta in 1957.
 A methyl group is attached to the carbon atom in
structure.

The chemical structure of monomer

 Similar to polyethylene, polypropylene belongs to the

group of polyolefin's.
 A polyolefin is a polymer produced from an alkene with
the general formula CnH2n as a monomer.
Differences Between PP and PE?
• Because of PE and PP are in polyolefin group, they
have similarities in their properties such as:
-in solution behavior and
-in their electrical properties.
• Exhibition of CH3 group in PP change the chemical
properties of polymer in some ways such as:
- Increase in the crystalline melting point. Melting point of
most regular PP is some 50 oC higher than regular PE .
-PP is less stable than PE to the influence of oxygen
because tertiary carbon in PP provides a site for
oxidation. It results with degradation from UV radiation.
What is Isotactic Polymer?
 Most significant effect of CH3 group is making different
tacticity.
 Most commercial polypropylene is isotactic form. Since all
CH3 groups are gathered on one side of the molecule.
CH3 CH3 CH3 CH3 CH3

Isotactic form of PP

 Greater the amount of isotactic material, the

greater:
-crystallinity -greater the softening point
-stiffness, modulus -tensile strength, hardness
Types of Polypropylene
 There are two general types of polypropylene:
-Homopolymer
-Block Copolymer
 Homopolymer: A polymer is a large molecule composed of
repeating structural units typically connected by covalent
bonds.
 Block copolymer: A polymer derived from two (or more)
monomeric species, as opposed to a homopolymer
where only one monomer is used.
-Copolymerization is the method that is used to
chemically synthesize a copolymer.
-The comonomer used is typically ethylene.
 Types of PP
 Addition of ethylene as comonomer increases
homopolymers low temperature impact strength.
 Hence comonomer decreases the polymer
crystallinity and makes the polymer more
transparent. Which it is preferred in film
manufacturing.

PP PE
monomer monomer

Two or more homopolymer subunits linked by covalent bonds

Characteristics of Polypropylene
 Low density: 0.9 g/cm3
 Good mechanical stability
 High rigidity and hardness
 Good heat forming stability
 Very good chemical stability
 Good hot water stability (hydrolysis resistance)
 Low moisture absorption
 Very good dielectric insulating behavior
 Non-toxic, Inflammable and Inexpensive

Properties creates disadvantages:

 Damage from stress corrosion in outdoor applications
 Inadequate impact resistance at temperatures below 0ºC
 PP is unsuitable for sliding functions
Additives used for PP
1) Fillers: Talk and Calcium carbonate for stiffness,
impact strength, thermal resistance, brighter color.
2) Rubbers: Butyl rubber for reducing the brittleness.
3) Pigments: Higher processing temperature and less
resistance to oxidation, pigment selection is
important.
4) Carbon black and ultra-violet absorbers:
Hindered amine and nickel to improve resistance to
ultra violet
5) Antioxidants: They are normally added to prevent
polymer degradation
6) Nucleating agents
USAGE AREAS
Such usage areas are ;

 Films for packaging,

 Textiles (e.g. ropes, thermal underwear and carpets),
 Stationery*
 Plastic parts and reusable containers of various types,
 Laboratory equipment,
 Automotive components

*Stationery=kırtasiye malzemesi
Polymerization Reaction
Polymerization of propylene takes place either in
-Gas phase; fluidized bed
-Liquid phase; slurry
In the fluidized-bed process
•The monomer flows through perforated distribution
plate at the reactor bottom.
•Rapid gas circulation ensures fluidization and heat
removal.
•Unreacted polymer is separated from the polymer
particles at the top of the reactor and recycled.
•A modification uses a second reactor connected in series to
perform copolymerization.
Polymerization Reaction
In slurry process
• Process run in loop reactors with two stirred tank reactors
in
series
• The reaction is carried out in hexane/heptane heavy
diluents.
• Polymerization reaction takes place in boiling solvent.
• At last step the slurry is flashed and volatiles are recycled
to the process.
• The polymer is purged and dried before pelletization.
• A gas phase reactor can be added for block copolymer
production.
Primary Gas Phase Reactor Copolymer Gas Phase Reactor

Catalyts

Dispatch

Monomer Comonomer Ethylene

Film Production Processes
1.Blown Film Process

2.Flat Film Process

Blown Film Process
The first blown film was patented in 1938 in the United States
The first successful plastics film was based on regenerated
cellulose.
 Lower melt temperature (air cooling)
 Film thickness variations are kept at 10%
 The film widths are in the range of 100 mm to 7 m
according to die and extruder widths and the film thickness
is in the range of 6 μm to 250 μm
 Slow cooling cause less gloss more clear film
 The capital investment and output are less
 Materials: LDPE, LLDPE, HDPE, Modified PE, PVC, Nylon
EXTRUDER

 Film can be compose

of number of layers.
Each layer is
produced by
different extruders.
So number of layers
is equal to number
of extruders in the
process.
Screw Design
 Single screw extruders supplied a flow of molten polymer
to the die which extrudes a thin walled tube.

 L/D ratios of the screws are in the range of 15-25 to 1.

 Screws has feed, compression and metering zone.

 The dept of the metering zone depended on the shear

sensitivity of the polymer.

 More shear sensitive polymers are processed with deeper

metering zone and lower screw speeds.
Breaker Plate and Screen Pack
 Made of stainless steel
 Placed between the extruder and die in order to
generate back pressure and hence to improve mixing
in the screw.
 It will also out put impurities in the melt before they
reach die
 They may cause punctures in the blowing stage.
Breaker Plate and Screen Pack
 The screen pack surprisingly does not eliminate gels of
lightly crosslinked or very high molecular weight polymer.
This cause faults in film which calls as fish eyes.
 The life of screen pack depends on the polymer used. The
life of screen pack is several weeks for LDPE and 12 hours
for PVC which is thermally unstable.
 This process often involves stopping the line and separating
die from extruder in order to remove screen pack. Systems
are available which do not necessitate extruder shut down.
Blown Film Dies
Blown Film Dies
 Dies are usually heated with electrical resistance to
prevent heat lost. Temperature of the each layer are
kept in the die.

 The aim in the die temperature control is to maintain

the die uniformly at a temperature close to the
temperature of the melt.

 Sometimes outer layer is heated in the die to

improve surface finishing by further softening of the
outer layer.
Cooling Rings
 Cooling increased by directing a flow of air from the
cooling ring on the out side of the bubble. This is
called external cooling.
 The ring sits on the top of the film die with a thermal
insulation layer between it and hot die.
 Non-uniform air flow gives rise to variations in the film
thickness.
 Inlets should direct air into the ring either in radial or
perpendicular direction to the plane of the ring. Air
flows over baffles in the ring.
Bubble Guides and Collapsing
Frame
 Between cooling ring and the top
nip, bubble guide may be placed to
reduce sideways movement of the
bubble. These are often horizontal
metal bars and easily to
accommodate different diameter
bubbles.
 Collapsing frame is fitted to guide
the bubble from its cylindrical
shape to layflat sheet at nips.
Film Thickness Measurement for
Bubble

 Film thickness is measured

by electronic control
system and data is send to
the control room.
Web Transport
 Film is transport from nip-roll to winding by series of
freely rotating flat metal rolls. Speed of the rolls are
adjusted according to the seed in winding unit. The
film thickness and tension is controlled by
automatic systems along this transportation.
Winding
 Finally film is wounded
in real form on a
cardbore. Then it is
going to part in slices in
different lengths.
Flat Film Process
 Higher melt temperature (water cooling)
 Fast cooling forms outstanding optical clarity and
gloss
 High capital investment and high output
 Film thickness variations are kept at 5%
 Materials: Polypropylene, polyester, nylon
 Biaxially oriented (BOPP) and uniaxially oriented
(CPP) films are produced by this method.
 BOPP film could not be streched at the end of the
production, but CPP could be streched.
PP is preferred in Flat Process
 Melt temperature of PP ranges between 215-230 oC

 In Flat Process, PP is rapidly cooled from the melt to

give low level of crystallinity. Consequently, clear
and glossy film is formed.

 To use PP in Blown Process water should be used

instead of air for cooling of extruded melt.
Biaxially Oriented Polypropylene
Film
Film compose of three layers.
corona

Copolymer + Antiblock masterbatch 1 , satellite 1

18 
Homopolymer
Antistatic / Slip Masterbatch

Terpolymer + Antiblock masterbatch 1 , satellite 1

Heat Sealing Property With
Terpolymer
 Heat sealing property is ability to stick of edges of
packing films to each other.

 Terpolymer layers have heat sealing property at

130C. To achieve this property some additives are
used.

 Copolymer does not have heat sealing property so it

does not stick on each other.
Protection of Ink By Upper Layer
 Ink is applied on the middle layer. The upper layer
protects the ink from destruction and maintain high
gloss on the printed surface.
corona

Copolymer + Antiblock masterbatch 1 , satellite 1

18 
Homopolymer
Antistatic / Slip Masterbatch

Terpolymer + Antiblock masterbatch 1 , satellite 1

Steps of the Production Process
http://www.polinas.com/page.php?pageID=4&langID=tr
This is a continuous process as one line,

 Weighting and Mixing

 Extrusion
 Molding and Chill Roll
 Orientation
 Corona
 Winding
Weighting and Mixing
 Raw materials pass through the metal detector to
grab the possible metal particles. Then they sent to
the raw material weighing hopper.
 Weighing hopper is small 0.2m3 tank. After the
weighing, the material is sent to the mixing hopper.
 Mixing hopper is a conical device with a rotating
large diameter screw. This agitating system makes
the chip like raw material smooth
 Automatic control system sends them to the
extrusion step regularly.
Extrusion
 There are three extruders in the system; one main
(for middle layer) and two satellite extruders.

 The screw speed & torque are very important

parameters to control. If the screw speed is more
than determined by control system the film
thickness increases.

 Also the temperature profile along the length of the

screw and the metering rate are controlled.

 All these parameters are adjusted by the

computerized control with the set values.
Extrusion

 The melting is achieved at temperature of 230C.

That is supplied by electrical heaters on extruder
body.

 The main extruder is water cooled.

 There’s an air cooling system for the other two

satellite extruders.
Film Die
 The homogenised melt extracted from the extruder
is filtered.
 The melt coming from the extruders are fed in the
die just above the die.
 Die, has three holes in it
where homopolymer from
the main extruder enters
into the middle and
satellite layers into the
other two holes. So they
flow into the die as three
layers of melt.
Chill Roll
 It is a wide, horizontal,
cylindrical device which
cools the film by cooling
water inside of the roll.
 Film that comes from
the die flows onto the
chill roll continuously to
maintain homogeneous
cooling.
Air used to take the dirt from
 The speed of the whole
the outer surface of film. System blows system is adjusted
according to the CR
high pressurized air so that the film
speed.
sticks to the surface of chill roll
homogeneously without any bubble
forming.

Rapid cooling increases the gloss of film

Orientation Process-MDO
 At MDO the film is stretched up to the 5-6 times of its
original length in machine direction. The stretching is
provided by the rolls which are turning in different
speeds.
 The pre-heating rolls are heated up to 104-112 C by oil
flowing in the channels, which flows in the rotating rolls.
After the film is heated, it is stretched in the machine
direction.
Orientation Process-TDO
 TDO is basically a large oven in which the film is heated
up to 150-160 C. At the entrance of TDO the film is
gripped from its edges by the clips, which are perfectly
synchronized. The film is stretched in transverse
direction up to 9-12 times of its original width as the clips
are travelling along a diverging rail system. This step is
applied just for BOPP.
Corona Treatment
 Most plastics, such as PE and PP,
have low surface tension which
causing them to be non-receptive
to bonding with printing inks,
coatings, and adhesives.
 Although results are invisible to
the naked eye, surface treating
modifies surfaces to improve
adhesion.
 Corona treatment is also suitable
for the treatment of injection and
blow molded parts.
Corona Application
 Corona discharge equipment consists of a high-
frequency power generator, a high-voltage
transformer, a stationary electrode, and a treater
ground roll.
 Standard utility electrical power is converted into
higher frequency power. The treater station applies
this power through ceramic or metal electrodes over
an air gap onto the material’s surface.
 The effects of corona treatment diminish over time.
Therefore many surfaces will require a second corona
treatment at the time they are printed.
Atmospheric Plasma
 Atmospheric plasma is very similar to corona but there
are a few differences between them.
 Both systems use one or more high voltage electrodes
which positively charge the surrounding air ion particles.
 However in atmospheric plasma systems, the bonding
rate of oxygen molecules to a polymer 100 times more.
That cause higher ion bombardment and higher surface
quality.
Flame Plasma
 Flame plasma treaters generate more heat than other
treating processes.

 Materials treated through this method tend to have a

longer shelf-life.

 Flame plasma occurs when flammable gas and surrounding

air are combusted together into an intense blue flame.

 Objects’ surfaces are polarized from the flame plasma

affecting the distribution of the surface’s electrons in an
oxidation form.
 AFM topographic images for (a)
untreated,
(b) 2s and corona treated PP films.

(a) Rough surface with granular

structures and presents some orientation,
which results from manufacturing process.
Contact angle is 90° between water and
film .

(b) Remarkable changes in the

morphology as small droplets. Atomic
oxygen formed in corona discharge, in air,
reacts with PP chains and forms oxidized
polar groups on the surface. Contact angle
is 54° between water and film .
Results of Corona Treatment
 Corona discharge treatment of PP films leads to the
incorporation of various chemical groups containing
oxygen, mainly C=O, into the films.

 As a result, the surface wettability by water (polar

liquid) increases (contact angle decreases), which is
the reason for the improvement of adhesion
performance of polymer.
Winding and Slitting
 The film is wounded after
corona treatment in the
original length. Then it
would be sliced in the length
and width of costumer
desired.
Metallized Film
 BOPP film durability is increased against the water vapor
and sun light by using metalizing process.
 Process takes place in vacuum chamber. Under high
vacuum, an aluminum wire is firstly vaporized in a boat.
 Aliminium vapor condensed on film
as extremely thin layer
 The film passes through several rollers
to adjust tension and cool
Preparation of Printing Films
 Packaging is the science, art and technology of
enclosing or protecting products for distribution,
storage, sale, and use.
 For printing of package film; most suitable and
chosen method is flexography.
 Flexography is also used at a wide range in food
packaging.
 After the flexographic printing operation, printed
product must be endurance by lamination process.
 Methods that combine two or more webs by bonding
them together are called as lamination process.
Process of Flexographic Film Printer
Process of Flexographic Film Printer
 Flexographic plates: Created by analog and digital plate
making processes
Ink Roller: Transfer ink to the anilox roll

Anilox Roller: Gives uniform thickness

to ink on plate cylinder

 Plate Cylinder: It keeps the flexo plates. Transfer ink to film

 Impression Cylinder: Apply pressure to film between plate
cylinder and impression cylinder.
 After the film has been printed, it is fed through overhead
tunnel dryer to remove solvents or water.
 The finished product is then rewound onto a roll or is fed
through the cutter.
Biodegradable Films
 Biodegradation is degradation caused by biological
activity, particularly by enzyme action leading to
significant changes in the material’s chemical
structure.

 Currently available degradable plastic materials can

be broken down into two main groups:
1. Polyester Polymers
2. Synergistic and Hybrid Polymers
Biodegradable Polyester Polymers
 Biodegradable polyesters which do not contain six-
carbon rings are known as aliphatic polyesters.
 They react with moisture at elevated temperatures.
 This process, called chemical hydrolysis, reduces
higher molecular weight polymer to much smaller
hydrocarbon compounds.
 The resulting molecules can then be absorbed by
microorganisms and metabolized for energy.
 Aliphatic polyesters however have poor physical and
mechanical properties like strength, flexibility, heat
resistance.
Biodegradable Polyester Polymers
 Some common biodegradable polyester polymers in
commercial use include examples of; Poly(caprolactone)
(PCL),
Poly(glycolic acid) (PGA) and Poly(lactic acid) (PLA).

PCL PGA
Biodegradable Polyester
Polymers
Raw material used in film making is: Poly(lactic acid) (PLA)
PLA:
-Made from fermented sugars extracted primarily from
food
crops such as corn or sugarcane.
-Then resulting monomer polymerized in the presence of
metal
catalyst to form high molecular weight.
Synergistic and Hybrid Polymers

 Mixtures of oil-based and naturally occurring polymers

 When mixed, there is intimate contact between the

two polymer chains so as to create a homogenous
single phase. In other words, once mixed they could
not be mechanically separated.

 A good example of a commercial, synergistic,

biodegradable material is Thermoplastic Starch (TPS).
RECYCLE
 Resin identification code:

 Manufacturers of PP based films, use the waste

films in production.
 The edge trims and the films are blended and
melted with extruder and finally converted to the
polypropylene granules again after
 According to the film type produced, these recycled
PP granules are used less than 15 % of the original
raw materials
CONTENT OF PRESENTATION
 Properties of polypropylene
 Polymerization reactions
 Usage areas
 Film manufacturing methods
 Corona Treatment
 Biodegradable films
 Recycling
 thanks
for your
attention