ENGINEERING THERMOPLASTICS

Introduction
 Thermoplastics materials, which have the capacity to
withstand tensile pressure of more than 400 kg/cm2 and
temperature of more-than 100°C under specified fiber stress in
continuous use are considered as engineering plastics.
 They are capable of being formed or shaped to precise and
stable dimensions.
 The polymers like Polyamide 6, Polyamide 66, Polyethylene
Terephthalate (PET), Polybutylene Terephthalate (PBT),
Polycarbonate (PC), Polyphenylene Oxide (PPO), Polyacetal
(POM) etc. represent this group of plastics.
 Classification

 Amide based engineering plastics

For example Polyamide 6, Polyamide 66 belong to this category.

 Ester based engineering plastics
PET, PBT and PC belong to this class of materials.
 Acetal based engineering plastics
Polyoxymethylene (Polyacetal) material is classified to this
category.

Ether based engineering plastics

Poly Phenylene Oxide (PPO) fall in this category. Since its chemical name is
Poly (1,4 (2,6 di-methyle phenyl) ether)
 The engineering thermoplastics can be classified into two
categories, based on their crystallization characteristics.
Crystalline Amorphous
Polyamide 6 PC (Polycarbonate)
Polyamide 66
PET
PBT
POM
PPO
 Polyamide
Of the numerous methods of manufacturing polyamide,
three are of commercial importance.
Polycondensation of dicarboxylic acids and diamines via.
an AH salt in aqueous medium, eg. the salt of
hexamethylene diamine with adipic acid undergoes
condensation to PA 66.
Polycondensation or ω-amino acids.
Ring opening and polymerisation (or polyaddition) of cyclic
amide (eg. caprolactam) in the presence of water or in the
absence of water by anionic and cationic high-speed
polymerisation.
 The characteristics of polyamides are determined by the
–CO–NH group.
 There are two groups of polyamides differentiated
according to their structure.
 PA 6, PA 11 and PA 12 have molecular chains consisting
of one basic units and two basic units lead for example to
PA 6 6, PA 6 9 and PA 6 10.
Polyamide General Information
 Nylon66 or Polyamide 66

Introduction
Nylon 66 (Polyamide 66) was first produced by W.H.
Carothers & Julian Hill in 1935 by the condensation of
adipic acid and hexamethylene diamine.

Commercial production of this polymer for subsequent

conversion into fibres was commenced by the DuPont
company in December 1939, in Arlingcton, New Jersey.

The first commercial Nylon 66 (Polyamide 66) was

produced in a pilot plant in Seaford, Delaware in 1940 and
the first molding powder for the fabrication of engineering
plastics was made available to DuPont customers in 1941.
But the polymer became well known to customers in 1950.
Monomer prepration for Polyamide 66
Adipic Acid
The adipic acid and hexamethylene diamine are used for preparation of salt
(Hexamethyelene Diammonium adipate)

Hexamethylene Diamine

Hexamethylene diamine is conventionally prepared from

adipic acid via adiponitrile
 Synthesisof Polyamide 66

The Polyamide 66 is prepared from Polyamide salt, which is prepared by

reacting the hexamethylene diamine and adipic acid in boiling methanol.

A 60% aqueous solution of the salt is then run into a

stainless steel autoclave together with a trace of acetic acid
to limit the molecular weight.
 Manufacturing process of Polyamide 66

The polymerization of Polyamide 66 is carried out in several different

reactors connected in series

Figure: Flow Diagram of Continuos Process of Polyamide 66.

The starting material is an aqueous solution of polyamide salt (AH salt)
containing equivalent quantities of hexamethylene diamine and adipic acid

The solution with about 60% solid content is fed into the first horizontal
cylindrical reactor then divided into several components where the water is
drawn off as vapor and precondensate of low mol. wt. is formed.

This is pumped into the second reactor, which is a heated tube reactor with a
gradually increasing diameter.

The Polycondensation proceeds here and vapor forms at falling pressure.

The next step is the removal of water in a steam separator followed by feeding
the polymer melt by means of a screw conveyor into the last reactor, which
consists of a heated screw conveyor where water vapor is again withdrawn and
the final poly-condensation equilibrium is attained.
Relations of Structure and properties of Polyamide 66

The following structural variables affect the properties.

 The distance between the repeating –CONH- group

The number of methylene groups in the intermediates

The molecular weight

 Characteristics of Polyamide 66
The material is semicrystalline and having high water absorption capacity.
 It is milky white- yellow colour compound.

 It is identified by the smell of burnt horn when burned, yellow flame with a
blue tip, can be formed into a filament.

 Its melting point is 264°C

 Its short term and long term service temperature are respectively 140 -
170°C and 80 - 100°C.
 Characteristics of Polyamide 66

 The general characteristics of Polyamide 6 is

summarized below
 Hard and tough thermoplastic
 Good abrasion resistance
 low co-efficient of friction
 High tensile strength
 Good dimensional stability
 Smooth appearance of surface
 Average to high surface gloss
 Resistance to lubricants, engine fuels, grease etc.
 Characteristics of Polyamide 66

 Good resistance to coolants, refrigerants, paints,

solvent cements.
 Resistant to aqueous solution of many inorganic
chemicals.
 Posses high HDT
 Attacked by strong acids, phenols, cresol at elevated
temperature
 High temperature resistance
 Low co-efficient of linear thermal expansion
 High water absorption
 Properties of Polyamide 66

Properties Units Values

PA-66
Specific gravity ---- 1.14
Tensile strength MPa 90
Tensile modulus MPa 3400
Flexural modulus Mpa 2896
Elongation at break % 20
Impact strength izod, Notched, J/m 37
Hardness M90
Deflection temperature under load 0C 104
(1.82 Mpa)
Coefficient of linear expansion mm/mm/0C 81 x 10-6
Water absorption, 24hrs % 2.8
Dielectric strength KV/mm 108
Melting point 0C 255
Glass transition
Temperature 0C 60
Mould shrinkage % 1.0-2.5
 Additives of Polyamide 66

1. Functional Additives

2. Fillers

3. Reinforcements
 Additives of Polyamide 66

1. Anti oxidants

2. Heat stabilizers

3. UV stabilizers

4. Nucleating agents
 Fillers

1. Silicon dioxide - increase tear & tensile strength

2. Mica and talc improve stiffness, strength, hardness, heat

distortion characteristics, dimensional stability and surface finish

3. Metal powders (aluminium, bronze, steel, lead, zinc, copper,

nickel) improve heat distortion characteristics and particularly,
electrical conductivity.

4. MoS2 and graphite are used particularly in glass fiber

reinforced polyamides to improve slip and wear characteristics.
 Reinforcements

The main reinforcement for PA is glass fiber material.

It is used in proportions of up to 50% w/w in PA 6 and PA 66 and upto
30% w/w in PA 69, 61, 11 and 12. Tensile strength, stiffness, hardness,
heat distortion characteristics, chemical and hydrolysis resistance are all
improved.
Carbon fibers increase the elastic modulus significantly more than glass
fiber material and also improve slip properties, thermal and electrical
conductivity
 Grades of Polyamide 66

The Polyamide 6 is available in various grades

Injection molding grade

 Extrusion grade
 Rotational Molding grade
 Fluidized bed coating grade
 Applications of Polyamide 66

Areas of applications are very similar to Polyamide 6.

 Appliances
 Automotive
 Business equipment
 Consumer Products
 Electrical
 Hardware
 Machinery and packaging
 Applications of Polyamide 66

Elevators Grills Guide shoes Textile Shuttle

Hammer Handles
Spoons Television Tuner Parts

Trimming Sprocket & Gears

In Automotive Applications

Manifolds Wheel covers

Gears Bearings
 Blends of Polyamide 66/PE

 In compatible hydrocarbon polymers such as PE can be

melt with Polyamides to yield compositions that have
improved higher permeability and are processable film and
filaments and bottles.
 Improvement in moisture absorption, impact strength,
flexibility, moulding characteristics and structure uniformity
are claimed for blends made from Polyamide and ethylene
/ alkyl acrylate ester copolymers.

CORPORATE TRAINING AND PLANNING

 Blends of Polyamide 66/PPO

The alloys of polyamide (Polyamide 66, and PPO) are

used as a commercial products because higher HDT
and reduce sensitivity to moisture. Toughness are use
to reduce brittleness of these blends.

CORPORATE TRAINING AND PLANNING

List of Manufacturers /Suppliers of Polyamide 66
 Polyamide 6

The Polyamide 6 (MP. 226° C) was first introduced by Paul

Schlack in 1938 by the alkaline catalyzed polymerization of a
cyclic compound called ε caprolactam.
Monomer Ingredients for polyamide 6

Cyclohexanone is normally prepared either from phenol or

from cyclohexane.
Preparation of Polyamide 6

Polyamide 6 is prepared from  caprolactam in the presence of water

(which acts as a catalysts) and acetic acid as a molecular weight regulator.

The typical combination is charged into the vessel and reacted under a
nitrogen blanket at 250°C for about 12 hours.
 Manufacturing of Process
The schematic diagrams of the continuous polymerization of  caprolactam to
produce Polyamide 6

Flow diagram of continuous production of Polyamide 6

 Manufacturing of Polyamide 6
The so-called VK tube is used in the polyamide process.
Reactive end groups are formed by hydrolyzing the caprolactam to - amino caproic
acid.
A lactam melt with a relatively high water content (~15%) is fed to the top of
the VK tube equipped with a stirrer and heating coil.
The water vaporizes at the top, when viscosity is still low, to give a residue of the
desired composition.
In the lower part of the tube, the equilibrium degree or polymerization is reached with an
increasing viscosity of the melt.
The polymer is drawn off at the bottom and granulated. Its equilibrium content of
caprolactam and oligomers is about 10% at a final temperature of 270°C.
The monomer and oligomers are extracted from the chips with hot water, and the
polymer is subsequently dried with hot gas in a ventricle cylinder hot dryer.
Intensive drying can produce a further reaction in the solid state and according to the
polycondensation equilibrium a higher degree of polymerization reached.
Relations of Structure and properties of Polyamide 6

The following structural variables affect the properties.

The distance between the repeating –CONH- group

The number of methylene groups in the intermediates

The molecular weight


 Characteristics

 The general characteristics of Polyamide 6 is

 summarized below

Hard and though thermoplastic

Good abrasion resistance
Low co-efficient of friction
High tensile strength
Good dimensional stability
Smooth appearance of surface
Average to high surface gloss
Resistance to lubricants, engine fuels, grease etc.
Characteristics of Polyamide 6
Good resistance to coolants, refrigerants, paints, solvent
cements.

Resistant to aqueous solution of many inorganic chemicals.

Posses high HDT

Attached by strong acids, phenols, cresol at devoted

temperature

High temperature resistance

Low co-efficient of linear thermal expansion

High water absorption

CORPORATE TRAINING AND PLANNING

 Properties of Polyamide 6
Properties Units Values
PA-6
Specific gravity 1.13
Tensile strength MPa 80
Tensile modulus MPa 3000
Flexural modulus Mpa 2414
Elongation at break % 50-100
Impact strength izod, Notched, J/m 53
Hardness M86
Deflection temperature under load 0C 55-75
(1.82 Mpa)
Coefficient of linear expansion mm/mm/0C 81 x 10-6
Water absorption, 24hrs % 3.0
Dielectric strength KV/mm 100
Melting point 0C 215
Glass transition
Temperature 0C 50
Mould shrinkage % 0.7-1.5

CORPORATE TRAINING AND PLANNING

 Additives of Polyamide 6

1. Functional Additives

2. Fillers

3. Reinforcements

CORPORATE TRAINING AND PLANNING

 Functional Additives

1. Anti oxidants

2. Heat stabilizers

3. UV stabilizers

4. Nucleating agents

CORPORATE TRAINING AND PLANNING

 Fillers
1. Silicon dioxide - increase tear strength

2. Mica and talc improve stiffness, strength, hardness, heat distortion

characteristics, dimensional stability and surface finish

3. Metal powders (aluminium, bronze, steel, lead, zinc, copper, nickel)

improve heat distortion characteristics and particularly, electrical
conductivity

4. MoS2 and graphite are used particularly in glass fiber reinforced

polyamides to improve slip and wear characteristics.

CORPORATE TRAINING AND PLANNING

 Reinforcements
The main reinforcement for PA is glass fiber material.
It is used in proportions of up to 50% w/w in PA 6 and PA 66 and
upto 30% w/w in PA 69, 61, 11 and 12. Tensile strength, stiffness,
hardness, heat distortion characteristics, tracking resistance,
chemical and hydrolysis resistance are all improved.
Carbon fibers increase the elastic modulus significantly more than
glass fiber material and also improve slip properties, thermal and
electrical conductivity

CORPORATE TRAINING AND PLANNING

 Grades of Polyamide 6

The Polyamide 6 is available in various grades

 Injection molding grade

 Extrusion grade

 Rotational Molding grade

CORPORATE TRAINING AND PLANNING

 Processing considerations
The tendency of the material to absorb water
The high melting point of the homopolymer
The low melt viscosity of the homopolymers
The tendency of the material to oxidise at high temperature
where oxygen is present
The crystallinity of the solid polymer and hence the
extensive shrinkage during cooling.

CORPORATE TRAINING AND PLANNING

 Processing considerations
The material has to be predried at 80°C for 2 - 4 hours
While molding Polyamide attention on the following points
is essential.

High Injection speed of the molding machine

Control of shot size
Minimizing drooling by nozzle of reverse tapper type.
Shrinkage of the part
Annealing at 130° to 149°C for 10 - 20 hrs.
 Polyamide 6 – By casting Technique

 Cast Polyamide 6 : This is made by activated anionic

polymerization of monomeric caprolactam in molds. Properties
are similar to PA 6. Cast Polyamide 6 is normally of very high
molecular weight. Depending on the polymerization condition, its
properties can be varied between tough and elastic to tough and
hard.

Thick walled mouldings, high weight mouldings (upto 1000

Kg), embedding of components (Roller cores)
Large mouldings of all kinds eg. heating oil tanks upto 10000
liters capacity

CORPORATE TRAINING AND PLANNING

Applications of Polyamide 6(Areas of Applications)

 Appliances
 Automotive
 Business equipment
 Consumer products
 Electrical
 Hardware
 Machinery
 Packaging

CORPORATE TRAINING AND PLANNING

Appliances

 Laundry equipment
 Cooking equipment
 Dishwashers and disposers
 Cooling equipment
 Consumer electronics
 Housecleaning equipment
 Small kitchen appliances
 Sewing machine
 Personal care and grooming

CORPORATE TRAINING AND PLANNING

Automotive
Business equipment
 Chassis parts
 Power plant  Business machines
 Decorative body parts  Vending machines
 Functional body parts  Office equipment
 Electrical parts
 Fuel system
 Instrumentation
 Heating, ventilating, air-conditioning
 Accessories

CORPORATE TRAINING AND PLANNING

Electrical
Industrial controls
Wiring and associated devices
Industrial connectors
Batteries
Telephone parts
Switches

Hardware

Furniture fittings
Door and window fittings
Tools
Lawn and garden implements
Boat fittings

CORPORATE TRAINING AND PLANNING

Machinery Standard
Agricultural components
Mining and oil drilling
Gears
Food processing Sprockets
Caster Wheels
Printing Bearings
Textile processing Gaskets
Pulleys
Engine parts Brushes
Pumps, valves, meters, filters
Spur and Pinion gears
Air blowers

Material handling equipment

Bushing and Bearing

CORPORATE TRAINING AND PLANNING

Consumer products
Kitchen utensils

Toys

Sporting goods
Football face guards are made of Nylon 6
because of its great toughness
Apparel fitments

Personal accessories

Photographic equipment
Tennis racquet
Musical instruments

Brush bristles

Packaging

Film for cooking Polyamide 6 film for meat packaging

List of Manufacturers/ Suppliers of Polyamide 6
 Nylon 6,10
Introduction:
Nylons are some of the most important fibres produced commercially. A lot of
the nylon produced ends up as clothing.

But nylon can be more than just fibres.

It also ends up as other everyday things like rope, tents, and toothbrush
bristles.

Sometimes nylon is used to make the belts that reinforce tires. Most passenger
car tires have steel belts, but reinforcement for tires for aircraft, trucks and off-
road vehicles are often made of nylon.

Nylon-clay composites are used to make automobile parts.

Nylon is used for self-lubricating gears and bearings.
 Nylon 6,10
This polymer is referred to as Nylon 6—10 because six carbon atoms are from
the 1,6—Hexanediamine and ten carbon atoms are from the Sebacyl Chloride.

Nylon 6,10 is formed at the interface between the two solutions. The polymer
produced is referred to as Nylon 6,10 because six carbon atoms are from the
1,6-diaminohexane and ten carbon atoms are from the sebacoyl chloride.
Properties
Nylon-6,10 (PA610) is semicrystalline polyamide commonly used
in monofilament form in applications such as
bristles
brushes.
Due to its low moisture absorption compared to other nylons, it
retains its properties better when wet.

Glass transition temperature: 50oC.

Melting temperature: 215oC.
Suppliers
BASF
RTP
Nylon 12
A semi-crystalline engineering plastic with very high toughness
and good chemical resistance
for varied applications.
The main characteristics of Nylon 12 are as follows:
• Extremely tough
• Good sliding properties
• Abrasion resistant
• Good chemical resistance to many oils, greases, diesel, petrol
and cleaning fluids
• Light
• Low water absorption
• Good electrical insulation
• Easily machined
• Dimensionally accurate
• Easily welded and bonded
Advantages
Very flexible, good abrasion resistance, good-notched izod impact
strength and better elongation at break compared with
unmodified polyamide 12.
Disadvantages
Reduced heat distortion temperature, increased coefficient of
linear expansion and poor electrical characteristics compared with
unmodified polyamide 12.
Property Value
Density (g/cm3) 1.03
Surface Hardness RR80
Tensile Strength (MPa) 25
Flexural Modulus (GPa) 0.4
Notched Izod (kJ/m) 0.07
Linear Expansion (/°C x 10-5) 12
Elongation at Break (%) 300
Strain at Yield (%) 37.5
Max. Operating Temp. (°C) 70
Water Absorption (%) 0.2
HDT @ 0.45 MPa (°C) 135
HDT @ 1.80 MPa (°C) 50
Material. Drying hrs @ (°C) 2 @ 90
Melting Temp. Range (°C) 190 - 200
Mould Shrinkage (%) 1.4
Mould Temp. Range (°C) 40 - 60
Nylon 12 is commonly used in transport and conveyor technology, food
technology, textile, packing and paper processing machinery, printing and drinks
dispensing machinery, electrical engineering and the automotive industry.
Typical applications of Nylon 12 include:
• Conveyor screw sleeves
• Friction strips
• Gear wheels
• Fan impellors
• Castors
• Impact plates
• Cutting pads
• Friction bearings
• Housing parts
• Switch parts
• plug parts
• Damping plates
PA11 - Polyamide 11
Polyamide 11 or nylon 11 is a semi-crystalline aliphatic polyamide
with a very high chemical resistance. It has relatively little amide
groups in the chain compared to the most common nylons
( PA6 and PA66), therefore, the moisture absorption is low. This
means that the mechanical properties and dimensions are not
influenced much by the environment it is used in.
PA11 is produced from a renewable resource: castor oil.
It can be used at a wide temperature range, and remains ductile
down to very low temperatures (-40 °C or even lower). Due to the
relatively high price PA11 is mainly used in applications where the
excellent chemical resistance to hydrocarbons and low
permeability, and/or the low temperature ductility are vital, such as
in the oil and gas industry and in the automotive industry.
Specific properties
Density: 1.03 g/cm3.
Mechanical properties: Relatively low stiffness but very high
toughness/ductility, even at low temperatures. Due to low
moisture absorption the mechanical properties do not decrease
much when conditioned.
Fiber filled grades for higher Young's Modulus are available,
and plasticized grades for a elastomer-like are also available.
Thermal properties: Tg around 45 °C
Tm 180-189 °C. Stable at long term high temperature applications
(125 °C).
Chemical resistance: very good resistance against oil, fuels and
hydraulic fluids. More resistant to diluted acids and bases than
other polyamides.
 Property Min Max Unit
Hardness 106 106 Rockwell
Melting 190 190 C
temperature
Glass 46 46 C
temperature
Service -70 80 C
temperature
Density 1040 1050 kg/m3
Friction 0.32 0.38
coefficient
Refraction 1.52 1.52
index
Water 1.2 1.8 %
absorption (at
50% hum.)
Applications
Industrial: pneumatic hoses, hydraulic hoses, filters (fibers).
Oil and gas: flexible flow lines, flexible liners, cables, pipes,
fittings, valves.
Aerospace: cable sheathing, hydraulic and air-conditioning
hoses, oil tanks.
Electronics/communication: Optical and copper cable
sheathing, connectors, housings, clips.
Medical: catheters, solution bags, food and beverage tubes,
medical equipment.
Sports: components for rackets, shoe soles