1.

Polyethylene

Properties related to structure

Additives
General properties
Processing behaviour
Processing techniques
Grades available
Applications
1.5 Properties related to structure
-(CH2 – CH2 – CH2 – CH2) - n
The flexibility of carbon–carbon single bond would leads to
low values for the glass transition temperature.
In the absence of impurities the polymer would be an
excellent high frequency insulator because of its non-polar
nature.
The properties of polyethylene vary due to differences
raised from the following variables.
* Variation in the degree of long/short chain
branching.
* Variation in average molecular weight.
* Variation in molecular weight distribution.
* The presence of impurities or Polymerization
residues.
Differences in molecules of (a) LDPE, (b) LLDPE, (c) HDPE
 Types of Polyethylene

 Based on densities

 Low Density, (Between 0.916 to 0.930 gm/cc)

 Linear Low Density, (Between 0.916 to 0.930 gm/cc)

 Medium Density, (Between 0.930 to 0.940 gm/cc)

 High Density, (Above 0.940 gm/cc)

Differences in molecules of (a) LDPE, (b) LLDPE, (c) HDPE
 Basic Polymer Properties
• Melt Flow Index (MFI)(g/10min) : The number of gms of resin
which can be forced through 2.095 mm orifice when subjected
to 2.16 kg load in 10 mins. At 190oC. MFI is measured as per
ASTM D 1238
• Density(g/cc) : Ratio of mass per unit volume of the material &
is reported in g/cc at given temperature (usually 23oC or 27oC).
It is measured as per ASTM D 1505
• Molecular Weight Distribution (MWD): Ratio of weight
average molecular weight (Mw) to number average molecular
weight (Mn) MWD gives general picture of the ratio of large,
medium & small molecular chains in the polymer.
 1.6 Additives
- Carbon black has some reinforcing effect and is of use in
cross-linked polymers. It is also of some use in
introducing a measure of conductivity to the polymer.
- The principle requirements of a pigment are that it should have
a high covering power-cost ratio and that it should withstand
processing and service conditions (pigments based on Co,
Cd & Mn).
- Polyethylene burns readily and a number of materials have been
used as flame retarders (ex. Antimony trioxide & halogenated
material).
- Slip agents may be added to reduce the friction between layers
of film (fatty acid amides such as oleamide and erucamide are
used).
- Antistatic additives are widely used to reduce dust attraction
and also in films to improve handling behavior.
Material
Properties
Properties of Polyethylenes.
Unit LDPE LLDPE HDPE UHMHDPE

Specific gravity -- 0.915-0.925 0.915-0.935 0.941-0.967 0.93

Tensile Strength MPa 6.9-17.2 14-21 18.6-30.3 19.9-41.4
Tensile modulus MPa 138-310 137-186 420-1400 140-760
Flexural modulus MPa 55-410 248-365 689-1654 900-960
Elongation at break % 100-700 200-1200 100-1000 300
Impact Strength J/m No break 10.6 (0.6)No No break
(Izod) break
Hardness --- D45-60 D47-53 D60-70 D60-70
HDT (under 1.82 MPa °C 42 37 45 68-82
load).
Glass transition °C -126 -130 --- ---
temperature.
Melting point °C 106-112 125 135 135
Dielectric Strength KV/mm 18-40 20-35 15.7-23.6 17.7
 L D P E - Characteristics
OUTSTANDING PROPERTIES
• Products offer excellent processability
• Low motor loads
• Excellent bubble stability (films)
• Very low neck-in and excellent adhesion
• Very good optical properties
• Very good barrier to moisture
• Moderate product properties
• Mechanical properties
• Dart Impact strength and Tear strength
DRAWBACKS
• POOR Heat Sealing properties compare to LDPE .
 LLDPE -Characteristics
OUTSTANDING PROPERTIES
• GOOD TENSILE / ELONGATION
• EXCELLENT DOWNGAUGING
• SEAL THRO’CONTAMINATION
• EXCELLENT ESCR
• BLENDABILITY

DRAWBACKS
• POOR MELT STRENGTH
• HIGH MELT VISCOSITY (DIFFICULT PROCESSING)
 HDPE -Characteristics

• Highest density –Better orderliness / Crystallinity

• Very good melt strength –BM / FILM / PIPE Appln.
• Very good chemical resistance / UV stability.
• Very good stackability& rigidity
• High molecular weight (Low MFI -HM grades) possible
only in HDPE
• HM grades –Excellent impact strength and Flexural
modulus.
• Very good dart impact strength in films
• Caters entire application / processing range.
 1.7 General properties

1.7.1 Mechanical Properties

- Stiffness of the material increases with
increase in density because more density
means more crystallanity in which there is a close
packing of molecules causing the stiffness.
- Tensile Strength increases with increase in
density therefore strong intermolecular forces
are present causing the increase in tensile
strength.
- Impact Strength decreases with increase in
density therefore higher the crystallanity lower
the impact strength.
- Torsional strength increases with increase in
density.
1.7.2 Thermal Properties

- As density of the polymer increases there is great

increase in its softening point.
- As density increases, viscosity at melt temperature
increases.
1.7.3 Chemical Properties
- The chemical resistance of Polyethylene is just like
that of an alkane. Non-oxidizing acids, alkalis and many
aqueous solutions do not chemically attack on the polymer.
Nitric acid oxidizes the polymer leading to a rise in power
factor and to deterioration in mechanical properties.
- Polyethylene is a crystalline hydrocarbon polymer
incapable of specific interaction with any liquid and there are
no solvents at room temperature. Low density polymers will
dissolve in benzene at about 60°C but more crystalline high
density polymers only dissolves at temperatures some 20-30°C
higher.
1.7.4 Electrical Properties

Polyethylene is a non-polar material.

- Power factor and dielectric constant are independent of
temperature and frequency.
- Reduction in density leads to small reduction of dielectric
constant.
 1.8 Processing behaviour

- The low water absorption of the polymer avoids the

necessity of predrying before processing except where
hygroscopic additives are present.
- Although processing temperatures are low compared
with many plastics the specific heat, which varies with
temperature is high.
- Flow properties are dependent on molecular weight and
amount of branching but usual moulding grades may be
as easy flow.
 1.9 Processing techniques
1.9. 1 Injection Molding

- Injection molding produces a very large number

of products. In this process the polymer is melted and
injected into a mould that is at a temperature below the
freezing point of the polymer. Melt temperatures are of the
order of 160-190°C for LDPE and up to 50°C higher with
high-density materials. Because of the tendency of the
material to crystallize, high shrinkage values are observed
ranging from 0.015-0.050 cm/cm with low density
materials to 0.025–0.060 cm/cm with high density
polymers.
1.9.2 Extrusion Process

- Extrusion process consists of metering polymer

into a heated barrel in which a screw is rotating. The
rotation of the screw causes the granules to move up the
barrel where they are compacted and plasticized. The
resultant melt is then forced under pressure through an
orifice to give a product of constant cross-section. Although
the polymer may be processed on variety of different
machines, the screws usually have a length–diameter (L/D)
ratio in excess of 16:1 and compression ratio between 2.5:1
and 4:1.
1.9.3 Compression molding

- This process is occasionally used with

polyethylene. In this process the polymer is heated in a
mould at about 150°C, compressed to shape and cooled.
The process is slow since heating and cooling of the mould
must be carried out in each cycle and it is employed only for
the manufacturing of large blocks and sheets and for
relatively strain-free objects such as test pieces.
1.9.4 Blow Molding

- Many articles like bottles and containers in

particular are made by blow molding technique. A hollow
tube is extruded vertically downwards on to a spigot. Two
mould halves close on to the parison and air is blown
through the spigot to inflate the parison so that it takes up
the shape of the mould. Recommended melt temperatures
are in the order of 165°C for LDPE and 210°C for HDPE
materials.
1.9.5 Powder Coating

- In fluidized-bed coating, a metal object that is to be

coated is heated to about 160–250°C and then suspended in
a fluidized bed of powdered polymer. Blowing air through a
porous base in the powder container so that in effect the
individual particles are lubricated with a thin film of air
brings about fluidization. Particles coming into contact with
the hot metal fuse and adhere to the metal part. The metal
object together with the adhering particles is then transferred
to a second oven where the particles fuse together to give an
even coating.
1.9.6 Rotational Molding

- In rotational molding, the required amount of

powder is added to the mould that is completely closed and
then rotated in an oven about two axes. The powder melts
and is distributed over the walls of the mould. The mould is
then cooled while the moulds are rotating.
1.10 Grades Available

- Molding Grade
- UV Stabilized grade
- Anti oxidant grade
- Film Grade
 1.11 Applications

Rotational Moulding Flexible Packaging (LLDPE, LDPE)

Blow Moulded containers (HDPE) PIPE (HDPE)

 1.11 Applications

CABLE SHEATING (LDPE) GREEN HOUSE FILMS (LDPE)

2. POYPROPYLENE
Properties related to structure
Tacticity
Properties of PP (isotactic form)
General properties
Additives for isotactic PP
Processing behaviour
Processing techniques
Grades of PP
Applications
Copolymers of Polyolefins
 Properties related to structure
-CH2 – CH –
|
CH3

- PP is a linear polymer with little or no unsaturation.

- Methyl group in the chain leads to increase in
melting point and chain stiffening.
- The tertiary carbon atom provides a site for
oxidation so that the polymer is less stable than PE
in the presence of oxygen.
- Methyl group leads to products of different tacticity.
- Commercial polymers are usually about 90-95%
isotactic.
- The isotactic polymer is stiff, highly crystalline and
with a high melting point, whereas the atactic
polymer is an amorphous somewhat rubbery
material.
 Tacticity
Isotactic
- CH2 - CH - CH2 - CH - CH2 - CH - CH2 - CH -

CH3 CH3 CH3 CH3

Syndiotactic
CH3 CH3
| |
-CH2 - CH - CH2 - CH-CH2 - CH - CH2 - CH-
| |
CH3 CH3

Atactic
CH3 CH3 CH3
| | |
-CH2 -CH - CH2 - CH- CH2 - CH - CH2 - CH-
|
CH3
 Properties of PP (Isotactic form)

- It has lower density (0.90 gm / cc).

- It has a higher softening point and hence a
higher maximum service temperature. Articles
can withstand boiling water and can be
subjected to steam sterilizing operations.
- It has a higher brittle point.
- It is more susceptible to oxidation.
 Properties of Polypropylene
Name Value Unit
Specific gravity 0.90 --
Tensile Strength 35.5 MPa
Tensile modulus 1380 MPa
Flexural modulus 1690 MPa
Elongation at break 35-350 %
Impact Strength (Izod ) 37 J/m
Hardness R100 ---
HDT (under 1.82 MPa load.) 55 °C
Glass transition temperature 5 °C
Melting point 164 °C
Dielectric Strength 24-28 KV/mm
 General Properties

Chemical properties

- No solvent affects PP at room temperature.

Polypropylene will dissolve in Decaline at
130°C.
- Aromatic and chlorinated solvents often swell
polymer at elevated temperature.
- Strong oxidizing acids slowly attacks the resin
(fuming HNO3).
 Electrical properties

- PP is an excellent insulator due to non-

polarity. It is used in many molded products,
as well as in winding coils and transformers.
 Flammability

- PP burns slowly and can be identified by an

odour of crude oil. Flame–retardant grades
are available for specific electrical
applications.
 Mechanical properties

- Commercial grades of PP is tough and having good

impact resistance. PP becomes more brittle than
many other thermoplastics at zero temperature.
 Weathering properties

- Standard grades have shorter life when exposed to

the outdoor. Discoloration, colour fade and
crazing occur in products not stabilized with anti
oxidants or carbon black.
 Additives for Isotactic PP

Fillers
- About 3% of PP compounds are filled with talc The
improved stiffness and heat deformation resistance
has led to the use of such compounds for the
manufacturing of heater housings, car mounting
components and several domestic appliances. Talc
filled PP sheet is used as an alternative to carton
board.
- In comparison to the talc – filled grades the CaCo 3
filled grades claimed to have higher impact strength,
brighter colour, higher thermal stability, improved
fatigue strength but lower stiffness and tensile
strength is markedly reduced with both fillers.
 Rubbers

- Particularly butyl rubber is used to reduce the

brittleness of PP.
- Rubbers are used because of their reasonable
price, structure, good weathering properties,
negligible toxicity and easy processability and
re- processability.
 Pigments

- The selection of pigments for PP follows the

same considerations as for PE because of the higher
processing temperature and lesser resistance
to oxidation, selection does require more care.
 Carbon black

- To improve the resistance to UV light, carbon

black is use as a light screen.
 Antioxidants

- Antioxidants are necessary for prevention

from adversity of oxidation.
- For optimum processing stability a single
antioxidant of the phenol alkane type, for
e.g., 1,1,3 – tris (4 hydroxy - 2
methyl, 5 – t – butyl phenyl) butane, tends to give
the best results.
 Processing behaviour

- Processing of Polypropylene is similar to

Polyethylene, particularly high-density
polyethylene. The differences are in the lower
specific heat and the greater sensitivity of flow
properties to temperature and shear rate. Flow
properties depend on molecular weight and
additives present. Unfilled grades generally
considered as easy flow. Flow Path: wall
thickness ratios of 175:1 are possible on 1mm
wall thickness sections. With easy flow grades
the ratio may be as high as 350:1.
 Processing techniques

Injection Molding

- Recommended processing temperatures

ranges from 210 to 275°C and injection
pressures are of 150 to 180 MPa depending
on the grade of the material. Thermal
stability is quite good in the absence of
oxygen so that there is no need to purge
with another material when shutting down.
Because of crystallanity there is high
molding shrinkage and is reasonably
uniform in all directions.
 Blow Moulding

- Blow molding of polypropylene is carried out

on conventional extrusion blow and injection blow
systems. Nonoriented containers are made by
conventional process by using low melt flow rate
homopolymers. Random copolymers overcome low
melt strength limitations and also improve low
temperature impact resistance and clarity. In
typical extrusion process, the die temperature
should be about 20 – 25°C below maximum barrel
temperature.
- Stretch blow molding, which is generally
limited to homopolymers, produces light weight
containers with good clarity and stiffness that can
compete with PVC and HDPE for household chemical
and detergent uses.
 Pipe Extrusion
- Pipes are manufactured by extrusion
process, which continuously extrude the
molten plastic horizontally through an
annular opening into one of the several
devices for cooling it and fixing its
dimensions. The heart of the extrusion
process is the “screw” which plasticate the
compound and conveys it through a pipe
die head. PP-R has less heat conductivity
compare to PE, therefore needs longer time
to melt. This requires longer L/D ratio 30:1.
The melt temperature is recommended to
be 220-230°C.
 Manufacturing Process of BOPP
Film

- BOPP film is manufactured with the blown

method. Molten resin is extruded from a circular die
to form a thick tube. The tube is stretched with air
pressure at controlled temperature to achieve
transverse orientation and simultaneously pulled by
take off nips to achieve machine direction
orientation.
 Calendaring

- The calendaring process consists essentially

of rolling out a mass of fluxed plastic between
pairs of large rolls to form a homogeneous
and accurately sized sheet.
Most plastic calendars have been four roles
arranged in an inverted ‘L’ configuration, with
three roles in a vertical stack and the fourth
roll horizontally to the side of top roll of the
stack.
 Grades of Polypropylene

- Low melt flow grade.

- High melt flow grade.
- Flame retardant grade.
- Impact resistance grade.
- UV resistance grade.
 Applications

Multilayer PP coating for Offshore applications

Car Dashboard and Bumper

Coffee Maker and Toaster PP furniture

 Copolymers of Polyolefin
1 Ethylene–Vinyl acetate
(EVA) copolymer.
- Both filled and unfilled EVA copolymers have
good low temperature flexibility and toughness.
- EVA with 15-20 mol % Vinyl acetate content
are rubbery copolymers with about 28% Vinyl
acetate content are used as hot–melt
adhesives.
- EVA films are used for liquid packaging,
frozen foods, meat wrap, ice bags, drum liner.
Molded and extruded EVA resins are use in
flexible toys, bumper pads, hose,gasketing.
 Ethylene–acrylate copolymers
- Ethylene – ethyl acrylate (EEA) and ethylene –
methyl acrylate (EMA) copolymers with up to 20%
weight EA, MA content respectively are commercially
available.
- EEA resins have higher thermal stability and can
withstand higher processing temperatures than EVA
- EMA resins yield blow film with rubber like
limpness and extremely high dart-drop impact strength.
They find useful applications in extrusion coating, co-
extrusion and laminating applications
Ethylene– acrylic / methacrylic acid
copolymers
- Copolymers up to 6.5% acrylic acid and
15% by weight of methacrylic acid are used
for melt processing applications.
- The acid group promotes excellent
adhesion to various substrates and increases
abrasion resistance and stress cracking
resistance
- These resins are extrusion coating onto
aluminium foil for pouches, for composite
tooth- paste tubes, wire and cable applications,
blown or extruded films for packaging of food
and other products and various lamination
applications.
 Ethylene–Propylene Copolymers
- Two main types of ethylene (E) propylene (P)
resins are EPM and a terpolymer (EPDM) which
includes a third monomer, a non-conjugated diene.
The rubberiness of EP copolymer depends on the
extent to which the copolymer is random as well
as on the ethylene/propylene ratio (E/P).
- Rubbers which are rich in either ethylene or
propylene have higher tensile strength and
elongation at break (%) in the unvulcanized state
than those rubbers which contain equal amounts of
E and P.
- EPM rubbers can be vulcanized only by
peroxides or high energy radiation. This limitation is
overcome in EPDM rubbers where the third monomer
has two double bonds; one enters the
polymerization process and the other C=C bond
remains as a side chain available for vulcanization
with sulphur/accelerator systems.
 3. POLYSTYRENE

Available grades
Properties related to structure
General properties
Processing behaviour
Processing techniques
Applications
High Impact Polystyrene (HIPS)
General properties
Properties of HIPS
Applications
Acrylonitrile Butadiene Styrene (ABS)
Preparation of ABS
Properties of ABS
Processing behaviour
Processing techniques
Applications
Styrene Acrylonitile (SAN)
General properties
Properties of SAN
Applications
 POLYSTYRENE
Available grades
General purpose polystyrene (GPPS)
Good balance is maintained to have good heat
resistance, reasonably high setting-up temperature,
good flow properties, and moderate impact strength.

High molecular weight polystyrene (HMPS)

HMPS gives strength without the loss of clarity.

Heat resistant grade

By reducing monomer from 5% to 0%, softening
point may be raised from 700C to 1000C.

Easy flow grade

It can be obtained by using low molecular
material, by using internal lubricant, by using external
lubricant and by controlling size and shape of granules.
Properties related to structure
-CH2-CH-
C6 H 5

- PS is linear hydrocarbon polymer being thermoplastic in

nature.
- Specific gravity of polystyrene is 1.054.
- Due to benzene ring causing stiffening effect, the Tg. of
commercial polymer is 90° to 110°C. Consequence of
this Tg value and amorphous nature of material make it
hard and transparent at room temperature.
- Solubility Parameter of PS is 18.6 M Pa ½ hence it is
soluble in benzene, styrene, toluene. The presence of
benzene ring results in polystyrene having greater
reactivity than polyethylene.
- Due to phenyl group, polystyrene undergoes chlorination,
nitration, hydrogenation and halogenations etc.
- PS has extremely good electrical insulation properties.
 General properties
- Polystyrene is hard, rigid and
transparent thermoplastic. Because of its low
cost, good mouldability, low water absorption,
good dimensional stability, good electrical
insulation properties, colourability and
reasonable chemical resistance it is widely
used as an injection moulding and vacuum
forming material. Due to low thermal
conductivity of polystyrene foam, it is used for
thermal insulation. The limitations of the
polymer are its brittleness, inability to
withstand the temperature of boiling water and
its mediocre oil resistance.
 Properties of Polystyrene
Name Value Unit
Specific gravity 1.05 --
Tensile Strength 32.4-56.5 MPa
Tensile modulus 3103-3276 MPa
Flexural modulus 3103-3448 MPa
Elongation at break 1.2-3.6 %
Impact Strength (Izod ) 13.3-24 J/m
Hardness M 60-84 ---
HDT (under 1.82 MPa load.) 76-108 °C
Melting point --- °C
Glass transition temperature 74-110 °C
Dielectric Strength 19.7 KV/mm
 Processing behaviour

- The negligible water absorption avoids

the need for predrying granules.
- Specific heat of PS is less, therefore
higher plasticizing capacity machines should
be used.
- The strong dependence of apparent
viscosity or shear rate. This necessities
particular care in the design of complex
extrusion dies.
- Due to amorphous in nature, polymer gives
low mould shrinkage.
 Processing Techniques
Injection Moulding

- Polystyrene melts are of medium viscosity

but highly pseudo plastic. Typical flow path : wall
thickness ratio is 150:1 for GPPS and 130:1 for
HIPS. Melts have good stability at processing
temperatures. Plastic temperature in the process
range from 200° C to 250°C for GPPS and 180° to
250°C for HIPS grades. Injection pressures are of
30 to 275 MPa depends on the grade of the
material. Low viscosity materials required lower
pressures and lower temperatures. High
viscosity and fiber – reinforced and mineral-filled
resins require higher pressure and temperatures.
 Extrusion

- High impact polystyrene is widely

extruded to make sheets used in
thermoforming. An extruder having screw L/D
ratio 25:1 to 30:1 and compression ratio 2:1 to
3:1 are recommended to ensure that a uniform
melt temperature. Recommended process
temperature is around 150°C to 220°C
 Thermoforming

- HIPS is one of the major thermoforming

materials. Solid sheet of HIPS is extruded and
shaped by a variety of forming methods; the
most common method is in-line vacuum
forming. In this process, vacuum is drawn
between sheet and mold or pressure is applied
to the mold plug while air is drawn out from the
space the sheet and mold. Typical forming
temperature range is around 130° to 180°C
and temperature at which forming may be
removed from the mould is at 85°C.
 Applications

PS Room Partitioner PS Bathroom cell

PS Door fittings CD cover

 High Impact Polystyrene (HIPS)

- HIPS are manufactured by

dissolving unsaturated rubber in
styrene monomer and polymerizing
the monomer in a solution or mass-
suspension process. The rubber is
generally polybutadiene. In this process
the resultant blend will contain not only
rubber and polystyrene but also a
graft polymer where short styrene side
chains have been attached to the
rubber molecules and this enhances the
impact strength. The rubber content
in solution polymerization can go up
to 14% by weight. HIPS obtained by this
process are having impact strength 7 times
greater than GPPS.
 General Properties

- Good dimensional stability even at low

temperature and high impact strength than the
general purpose polystyrene, good toughness,
ease of processing, higher resistance to stress
cracking, high elongation at break, less
resistance to ageing than GPPS, lower hardness
and rigidity than GPPS and dissolved by alcohols,
ketones, ethers etc.
 Properties of HIPS
Name Value Unit
Specific gravity 1.05 --
Tensile Strength 16.0-41.3 Mpa
Tensile modulus 1653- Mpa
2549
Flexural modulus 1791- Mpa
2687
Elongation at break 1.0-1.5 %
Impact Strength (Izod ) 48.1-219 J/m
Hardness M 63-88 ---
HDT (under 1.82 MPa load.) 69-76 °C
Melting point --- °C
Glass transition 93-105 °C
temperature
Dielectric Strength 11.8-19.7 KV/mm
 Applications

HIPS Instrument body HIPS Solid shape

HIPS Television Cabinet HIPS Floppy Storage

 Acrylonitrile Butadiene Styrene
(ABS) Copolymer

- These materials are complex blends and

copolymers of Acrylonitrile, butadiene and styrene.
In most types, Acrylonitrile and styrene are
grafted onto a polybutadiene backbone. The
product also contain unreacted polybutadiene and
some acrylo nitrile styrene copolymer. The
reasons for its widespread acceptance are
high impact resistance, good stiffness,
excellent surface quality, high dimensional
stability at elevated temperatures
 ABS Preparation
- Styrene and Acrylonitrile are added to
polybutadienelatex and the mixture warmed to about
50°C to allow absorption of the monomers.
- Water soluble initiator is added to polymerize
the styrene and Acrylonitrile. The resultant
materials will be a mixture of polybutadiene,
polybutadiene grafted with Acrylonitrile and
styrene, and styrene-Acrylonitrile copolymer.
Properties of Acrylonitrile Butadiene
Styrene (ABS)
Properties Value Unit
Specific gravity 1.03-1.06 --
Tensile Strength 30-52 MPa
Tensile modulus 2070-2760 MPa
Flexural modulus 2200-3030 MPa
Elongation at break 2.3-3.5 %
Impact Strength (Izod ) 134-320 J/m
Hardness R 105-112 ---
HDT (under 1.82 MPa load.) 93-104 °C
Melting point --- °C
Glass transition temperature 105-115 °C
Dielectric Strength 16-31 KV/
mm
 Processing Behaviour

- May absorb upto 0.3% moisture and

therefore must be stored under dry condition.
- Greater tendency to degradation than PS
during processing so important not to overheat.
Avoid too high screw speed and back pressure
during moulding
- Generally less free flowing than PS
particularly with heat resistance grades.
- Being an amorphous, the materials have a
low moulding shrinkage.
 Processing Techniques

Injection Moulding

- ABS grades can be injection molded

using reciprocating screw or plunger
machines, the former is preferred
because of it provides a more uniform
melt and higher available pressure.
Processing temperatures range from 177
to 280°C, depending on the specific grade.
Injection pressures of 69 to 138 MPa and a
clamp pressure of 280 to 420 kg/cm²
compression ratio of 2:1 to 3 : 1 and an
L/D ratio of 20: 1 are recommended.
Extrusion
- An extruder having a min. L/D ratio of
24:1 is recommended to ensure that a
uniform melt temperature is delivered
to the die two stage screws are
preferred to aids in devolatalization. A
single lead, full-flighted, constant pitch
screw with a progressively increasing root
diameter and a compression ratio of
2:1 to 2.5:1 is suitable for most ABS
grades.
Thermoforming

- ABS can be thermoformed over a

temperature range of 130 to 190°C with the
optimum conditions depend on material
grade, part design, draw ratio, sheet
thickness and forming technique.
Acceptable techniques include drape
forming, plug asset, snap back, pressure
forming or a combination of these. The
depth of draw in simple forming is usually
limited to the width of the part.
Electroplating

- ABS polymer is treated by an acid

etching process which dissolves out
some of the rubber particles at or near the
polymer surface. After sensitization and
activation electroless metal deposition
processes are carried out . The peel-
strength between the ABS and the
plating depends on the type of mechanical
press.
 Applications

ABS Car Dashboard ABS car interiors

ABS Car bumper ABS meter box

 Styrene Acrylonitrile Copolymer
(SAN)
- SAN is a copolymer of styrene and
acrylonitrite.
- Because of the polar nature of Acrylonitrile
molecule these copolymers have better
resistance to hydrocarbons, oils and greases
than polystyrene.
- SAN is produced by three different
polymerization techniques viz. emulsion,
suspension and continuous mass
polymerization.
 Properties

- It has excellent dimensional stability, very

good tensile and flexural strength.
- Good abrasion resistance, good impact
strength.
- It has high chemical resistance, better
resistance to stress cracking and crazing. It
does not react with bleaches and resistance
to water, acid and alkalis water absorption is
greater than PS.
 Available grades
- Standard grade
- UV stabilized grade
- Antistatic grade
- Glass reinforced grade
 Properties of SAN
Name Value Unit
Specific gravity 1.07 --
Tensile Strength 57-75 Mpa
Tensile modulus 3420-3720 Mpa
Flexural modulus 3080-3560 Mpa
Elongation at break 2.0-3.5 %
Impact Strength (Izod ) 13-24 J/m
Hardness M 80-83 ---
HDT (under 1.82 MPa 99-109 °C
load.)
Melting point --- °C
Glass transition 115 °C
temperature
Dielectric Strength 12-16 KV/mm
 Applications

SAN cassette casing SAN speedometer cover

 POLYVINYL CHLORIDE

Properties related to structure

Characterization of commercial polymer
Processing behaviour
Processing techniques
Compounding and Ingredients
Formulations
Properties of PVC compound
Applications
 Properties Related to Structure

- (CH2 – CH)n -
|
Cl
- PVC is polar in nature due to presence of C-Cl
dipole.
- PVC is resistant to non- polar solvents which
are having solubility parameter less than 19.4
MPa½ .
- PVC is flame retardant and self extinguishing.
- Presence of chlorine atom causes an increase
in inter chain attraction and increase hardness
and stiffness of polymer.
 Properties of Poly Vinyl Chloride
Name Value Unit
Specific gravity 1.18-1.70 --
Tensile Strength 5.5-26.2 MPa
Tensile modulus 4.8-12.4 MPa
Flexural modulus 30 MPa
Elongation at break 150-450 %
Impact Strength (Izod ) ----- J/m
Hardness A85 ---
HDT (under 1.82 MPa ---- °C
load.)
Glass transition --- °C
temperature
Melting point --- °C
Dielectric Strength 9.9-15.8 KV/mm
 Characterization of Commercial
Polymers
- Commercial PVC polymers are largely
amorphous, slightly branched molecules with the
monomer residues arranged in a head to tail
sequence. Individual grades of material do
however differ in average molecular weight,
molecular weight distribution, particle shape and
size, size distribution and in the presence of
impurities.
- For commercial purposes, the molecular
weight is usually characterized from
measurements of the viscosity of dilute solutions.
The value of ‘k’ is calculated by the relationship

Log10 ηrel = 75 k2 x 10-6 +

(k x 10-3) C
1+ 1.5 kc x 10 -3

ηrel = relative viscosity = η/ ηo

k = k-value
C= concentration in gm/ml.

From K-value one will be know the grade of PVC material

 Processing Behaviour

- Polymer doesn’t absorb water but some

plasticizers may do so.
- uPVC melts are viscous and typical flow path
ratio is in the order of 60 : 1 viscosity of
plasticized PVC depends on plasticizer level.
- Polymer lacks thermal stability and
degradation is rapid during processing
evolves hydrochloric acid. All the metal surfaces
that come in contact with the melt should be
resistant to this acid. Good ventilation of the
working area is also essential.
- Polymer is amorphous in nature so that
shrinkage is low.
 Processing Techniques
Injection Moulding

- Inline screw preplasticizing machines are

used for the injection moulding of UPVC. The main
points to bear in mind are the high melt viscosity,
the need to avoid overheating and steel corrosion
by hydrochloric acid evolved during processing.
This demands good control of operating
conditions, short runners, reasonably generous
gates and mould cavities which preferably are
either chrome or gold plated. Recommended
processing temperatures are in the range of 180–
200°C for uPVC and 150–190°C for PPVC and
injection pressures are 100–175 MPa for uPVC and
80–120 MPa for PPVC respectively. Very good
temperature control is necessary.
 Extrusion

- Twin screw extruder now dominates the

extrusion field due to their positive pumping action
which is so important with PVC in powder form. An
extruder having screw L/D ratio 14: 1 to 17: 1 and
compression ratio 2:1 are recommended for UPVC.
Dies must be designed so that there is no chance
of polymer stagnation in all flow path cross
sections. Accurate temperature control is very
important. Recommended process temperatures
are in the order of 150 to 180°C for UPVC and 140
– 175 °C for PPVC respectively.
 Blow molding

- Extrusion blow moulding of bottles has

been successfully accomplished . it is to be noted
that UPVC has a much lower average specific heat
between the processing temperature and room
temperature than polyethylene and no latent heat
of fusion. This leads to much less heat needing to
be removed on cooling of mouldings and very
short cycle times are possible. Blow molding is
confined to UPVC using general conditions given
under extrusion.
 Calendaring

- Calendaring is an important process for

making UPVC film or sheet. High molecular
weight PVC is compounded and partly
agglomerated in an extruder mixer. The heated
mix is then fed to an L- type calendar mixer. The
hot calendar rolls simply partly consolidate the
granules so that the resulting film or sheet is
strong enough to be drawn over a train of heated
drums which are well above the fluxing
temperature of the compound. The PVC is
therefore subjected to only a very short but
intense heating process. The resulting films with
the high mechanical properties are used for
magnetic tapes and for packaging applications.
 Compounding and Ingredients

A PVC compound may contain the following

ingredients.
- Polymer
- Stabilizers
- Plasticizers
- Polymeric Processing Aids
- Impact Modifiers
- Fillers
- Pigments
Some other miscellaneous materials include
flame (fire) retardants, optical bleaches and
blowing agents.
 Stabilizers

- Heating of PVC at temperature above 70°C

has a number of adverse effects on the properties
of the polymers. Sufficient degradation may take
place during standard processing operations (150-
200°C) to make the product useless.Therefore to
avoid degradation ‘stabilizers’ are found useful.
- The compounds of Cd, Ba, Ca and Zn are
prominent as PVC stabilizers.
 Plasticizers

Plasticizers are used

- For reducing processing temperature of
polymer below the decomposition
temperature.
- To modify the properties of finished
products such as flexibility or extensibility
etc.
- To modify processing properties.
All PVC plasticizers have a solubility parameter to
that of PVC.
Di-iso-octyl phthalate (DIOP) and di – ethyl
hexylphthalate (DEHP) are most important
plasticizers used in PVC.
 Extenders

- Sometimes plasticizers are not found

useful in PVC because of their limited
compatibility with the polymer. But when mixed
with ‘true plasticizer’ (commercially called
extenders), a reasonable compatibility is
acquired. They were also cheaper than
‘plasticizers’. Therefore plasticizers can often
be replaced by ‘Extenders’ without any adverse
effects on the properties of compound.
Commonly used extenders in PVC are
- Chlorinated paraffin waxes
- Chlorinated liquid paraffin fraction
- Oil extracts
 Lubricants

- In plasticized PVC the main function of a

lubricant is to prevent sticking of the compound
to the processing equipment. This is brought
about by selecting a material of limited
compatibility with PVC which will bleed out
from melt during processing to form a film
between the bulk of the compound and the
metal surface of the processing equipment. The
additives used for this purpose are known as
‘external lubricants’.
- Calcium stearate, normal lead stearate,
dibasic lead stearate, graphite are employed to
improve flow properties.
 Fillers

- Fillers are commonly employed in order

to reduce cost. They may also be incorporated
for technical reasons such as to increase the
hardness of a flooring compound, to reduce
tackiness of highly plasticized compounds, to
improve electrical insulation properties and to
improve the hot deformation resistance of
cables.
- For electrical insulation, china clay is
commonly employed while various carbonates
are used for general purpose work.
 Pigments

To add a pigment, firstly the following facts are

to be considered
- Will it decompose, fade or plate out?
- Will the pigment adversely affect the
functioning of stabilizer and lubricant.
- Will it fade, bleached out or will it bleed.
- Will the pigment adversely affect
properties that are relevant to the end
usage (because many pigments will reduce
the volume resistivity of a compound).
 Polymeric Impact Modifiers &
Processing Aids

- Unplasticized PVC has a high melt

viscosity leading to some difficulties in
processing. The finished product is also too
brittle for some applications. In order to
overcome these problems it has become
common practice to add certain polymeric
additives to the PVC. The ‘impact modifiers’
generally are semi-compatible and often
somewhat rubbery in nature.
- Chlorinated Polyethylene is being widely
used as an ‘impact modifier’ particularly where
good aging properties are required.
 Formulations

The formulation given below is intended as a

general guide but not for a specific application.
Suspension polymer ( K- 65) 100
DIOP 40
Trixylyl Phosphate 20
China clay 20
Tribasic lead sulphate 7
Staeric Acid 0.5
Pigment 2
 Properties of PVC compounds
- Unplasticized PVC is a rigid
material whilst the plasticized material is
flexible and even rubber at high plasticizer
loadings.
- PVC has a good resistance to
hydrocarbons but some plasticizers, particularly
the less polar ones such as dibutyl sebacate are
extracted by materials such as iso-octane. The
polymer is also resistant to most aqueous
solutions including those of alkalis and dilute
mineral acids.
- Below the second order transition
temperature, PVC compounds are reasonably
good electrical insulators over a wide range of
frequencies but above the second order
transition temperature their values as an
insulator is limited to low frequency
 Applications of PVC

Vinyl records PVC flexible blood bag

PVC Automobile interiors PVC wire and cable

 4.12.2 Polymerization

- Vinylidene Chloride can be

polymerized by bulk, emulsion and
suspension techniques but suspension
technique is very common in industries. In
suspension process, glass-lined reactor with
a water jacket for temperature control is
used. In this process, comonomers, water, a
methocel cellulose and free radical initiator
(Benzoyl peroxide or louryl peroxide) are
loaded and heated in a sealed reactor. The
polymer precipitates and crystallizes giving a
hard, porous bead.
 Poly Vinylidene Chloride (PVDC)
Properties related to structure
Cl
(—CH2—C—)n
Cl
- Molecules of PVDC are extremely regular,
thus capable in crystallization.
- Close packing of molecules results in higher
specific gravity, hence it will have low
permeability of vapour and gases.
- Its solubility parameter is 20.4 MPa½. It is
having no cohesive solvent at room temperature.
- Due to presence of chlorine atom, it is self
extinguishing.
- Copolymerization with vinyl chloride will
reduce regularity and increase
molecular flexibility. Vinylidene dichloride - vinyl
chloride copolymer is self extinguishing in
 Processing behaviour

- Vinylidene Chloride copolymers are thermally

sensitive. Overheating during processing evolves
HCl. Hence processing of Vinylidene Chloride
copolymers require careful control of the melt
temperature and minimum melt residence time. To
prevent degradation during melt processing, resins
are formulated with thermal stabilizers like inorganic
or organic salts, organic phosphates or phenolic
antioxidants are also used. In the processing of VDC
copolymers, materials’ feeding is accomplished by
air venting or by gravity feed. Mold Shrinkage is
0.005 – 0.025 in/in.
 Applications

- Copolymers may be used in the

manufacturing of extruded pipe and moulded
fittings and in chemical plants.
- Copolymers are used in the manufacture of
filament which may be extruded from
steam heated extruders with L/D ratio 10:1 and
compression ratio 5:1 into a quench bath. These
filaments are used for deck chair fabrics, car
upholstery, decorative radio grills, dolls hair, filter
brushes.
- Biaxially oriented film is used in packaging
for exceptional clarity, brilliance, toughness,
and water gas impermeability.
 ACRYLIC PLASTICS
Properties related to structure
- Commercial PMMA is hard, transparent,
amorphous material. Microscopic and X- Ray analysis
shows that material is amorphous.
- α-Carbon atom restricts chain flexibility leading
to higher Tg than PE i.e104°C.
- As polymer is polar in nature, it does not have
electrical insulation properties comparable with
polyethylene.
- Its solubility parameter is 18.8 MPa ½, hence
soluble in MMA, toluene, trichloro ethylene,
chloroform and ethyl acetate. It is unbranched
polymer.
Properties of Polymethyl methacrylate
 General Properties

- It is hard, rigid and amorphous transparent

material.
- It is having good weathering resistance.
- As it is polar thermoplastic material, it’s
mechanical, electrical and other properties
are strongly dependent on temperature,
testing rate and humidity.
- It is somewhat tougher than Polystyrene
but less tougher than Cellulose Acetate and
Acrylonitrile Butadiene Styrene Copolymer.
 Additives
- In general Di butyl phthalate is used as a
plasticizer in the quantity of 5% which will
improve melt flow with some what decrease in
mechanical properties. In order to improve light
stability, phenyl sallicilate, 2–4–di hydroxy–
benzo–phenone and methyl sallicilate are used.
 Processing behaviour
- The polymer absorbs moisture upto 0.3%,
hence pre drying is required before processing
and care must be taken with reground.
- Melt viscosity is higher than polystyrene,
polyethylene,polyvinyl chloride during processing.
Hence the equipment used must be robust
and capable of generating high extrusion and
injection pressure.
- The material is amorphous and the
moulding shrinkage is low and normally less
than 0.08 cm/cm.
 Processing Techniques
Injection Moulding

- PMMA granules tend to pick up

moisture and care should be taken in storage.
Polymer has limited thermal stability and may
depolymerize during prolonged exposure to
high processing temperatures. Screws with
decompression zones may be used to help
remove volatile monomer produced during
processing. Recommended processing
temperatures ranges between 200 to 240°C
and injection pressures in the range of 150 to
175 MPa. The higher temperatures are
required for large, thin walled parts molded
from stiff grades of PMMA. A cold mould could
produce hazy and stress parts. Recommended
mould temperatures are in the range of 21 to
 Extrusion

- PMMA can be processed on single

screw or multiple screw extruders. Sheets,
rods, tubes and sections are commonly
produced. Twin-screw extruders offer
improved feeding and degassing
characteristics. Proper screw design is
necessary for trouble free-operation and the
best results are achieved with longer barrels
(30:1 to 40:1 L/D ratio). A metering type screw
with a gradual compression (compression ratio
3:1) and constant pitch is preferred. The
processing temperature should be between
227 to 249°C for flat sheet and 210 to 230°C
for profiles.
 Thermoforming

- PMMA can be formed by vacuum forming

when it is heated above the Tg of the
polymer .
- The formed shape will recover about 90%
of the deformation.
- Typical forming temperatures are in the
range of 150 to 190°C.
- Parts should be cooled to at least 66°C
before they are removed from the mold.
 Applications

Vegetable tray Sign boards

Dental application
 6. CELLULOSE PLASTICS
6.1 Introduction
6.1.1 Polymerization
6.2 Cellulose Esters
6.2.1 Cellulose Acetate (CA)
6.2.2 Properties
6.2.3 Applications
6.3 Cellulose acetate butyrate (CAB)
6.3.1 Properties
6.3.2 Applications
6.3.3 Cellulose acetate propionate
6.3.4 Properties
6.4 Cellulose Ether
6.4.1 Ethyl cellulose
6.4.2 Properties
6.4.3 Processing
6.4.4 Applications
When A is and B is Plastic is
H H Cellulose
—C—CH3 —C—CH3 Cellulose acetate
|| ||
O O

—C—CH3 —C—CH2—CH3 Cellulose acetate propionate

|| ||
O O

—C—CH3 —C—CH2—CH2—CH3 Cellulose acetate butyrate

|| ||
O O

—C—CH2—CH3 —C—CH2—CH3 Cellulose propionate

|| ||
O O

—CH2—CH3 —CH2—CH3 Ethyl cellulose

—NO2 —NO2 Cellulose Nitrate

 Cellulose Acetate
Properties

-High water absorption

- Poor electrical insulation
characteristics
- Limited aging resistance
- Limited heat resistance
- Dissolved by wide variety of reagents
 Properties of Cellulose acetate
Name Value Unit
Specific gravity 1.28 --
Tensile Strength 40 MPa
Tensile modulus 2174 MPa
Flexural modulus 1794 MPa
Elongation at break 38 %
Impact Strength (Izod ) 160 J/m
Hardness R62 ---
HDT (under 1.82 MPa 61 °C
load.)
Melting point 240-260 °C
Glass transition 157 °C
temperature
Dielectric Strength 13.4 KV/mm
 Applications

CA Different applications Spectacles

Tool handles
- CAB has been prepared for a
number of years in United States.In the
manufacturing in commercial scale
bleached wood pulp or cotton linters are
pretreated for 12 hours with 40-50 %
sulphuric acid and then after drying with
acetic acid. After these etherification of
treated cellulose with mixture of butyric
acid and acetic anhydride with sulphuric
acid as a catalyst. Cellulose acetate
butyrate varies from the ratio of acetate /
butyrate.
 Cellulose Acetate Butyrate (CAB)

Properties
-Good toughness
- Excellent appearance
- Giving good coating with hard glossy surface
- Lower water absorption
- Better flow properties
- Lower density
 Applications

-Toys, tools handles, tabular keys, telephone

housing, pipes for conveying water, outdoor
display signs, vacuum formed products and
protective coating for metals.
Properties of Cellulose Acetate Butyrate
Name Value Unit
Specific gravity 1.19 --
Tensile Strength 34.5 MPa
Tensile modulus 1725 MPa
Flexural modulus 1449 MPa
Elongation at break 50 %
Impact Strength (Izod ) 187 J/m
Hardness R75 ---
HDT (under 1.82 MPa load.) 65 °C
Melting point --- °C
Glass transition temperature --- °C
Dielectric Strength 13.4 KV/mm
 Cellulose Acetate Propionate

- Cellulose Acetate Propionate having

shorter side chain and it is harder stiffer, and
poses higher tensile strength than Cellulose
Acetate Butyrate. Like cellulose acetate
butyrate, they are easy to vacuum form and
also tend to be used for applications like tool
handles, safety lockers, steering wheels, etc.
 Properties

- Cellulose Acetate Propionate have shorter

side chain and it is harder, stiffer and possess
higher tensile strength than Cellulose Acetate
Butyrate. Like cellulose acetate butyrate, this is
easy to vacuum form and also tends to be used for
applications like tool handles, safety lockers,
steering wheels, etc.
- Cellulose Nitrate is manufactured by the
reaction between cellulose, nitric acid and
sulphuric acid. It is possible to vary degree
of etherification according to the root
hydroxyl group which is replaced by nitrate
group. Fully nitrated cellulose, cellulose tri-
nitriate is an explosive. Cellulose nitrate is
precipiticised with camphor in order to make it
easy processable.
 Cellulose Nitrate

Properties
-It has good rigidity, water white transparency,
poor chemical resistance, reasonable toughness,
capable of forming highly attractive multi
coloured sheeting, highly inflammable.
 Applications

- The one time important application

was in photographic film. Today the
principal outlet are knife handles, table
tennis ball and spectacle frames.