2. 2
Polyamide
• PA is considered the first engineering thermoplastic
• PA is one of many heterochain thermoplastics, which has
atoms other than C in the chain.
• PA was created when a condensation reaction occurred
between amino acids, dibasic acids, and diamines.
• Nylons are described by a numbering system which indicates
the number of carbon atoms in the monomer chains
– Amino acid polymers are designated by a single number,
as nylon 6
– Diamines and dibasic acids are designated with 2
numbers, the first representing the diamine and the second
indicating the adipic acid, as in nylon 6,6 or nylon 6,10
with sebacic acid.
3. Preparation of Nylon 66
+ COOH(CH2)4COOH
Adipic Acid
NH2(CH2)6NH2
hexamethylene diamine
(heat)
n[NH2(CH2)6NH . CO (CH2)4COOH ]
nylon salt
[NH2(CH2)6NH . CO (CH2)4CO ]n + nH2O
Nylon 6,6 polymer chain byroduct
3
4. 4
Polyamides are heat sensitive materials.
ThePolyamide 66 is processed in the
temperature range of 260-320°C.
The material has to be predried at 80°C for 2 - 4 hours
The annealing temperature of Polyamide 66 part is 149
– 177°C.
Injection moulding, Extrusion techniques,
Compression moulding, Foam moulding and
Rotomoulding techniques are used for processing the
materials.
Processing considerations for PA 66
5. 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.
Preparation of Nylon 66
5
6. 6
Characteristics of Polyamide 6 & 6,6 (For
identification)
• It is semicrystalline & highwater absorption capacity.
It is milky white - yellow colour
It is identified by the smell of burnt horn when
burned, flame with a blue halo, can be formed into a
filament.
Its melting point is 215°C (PA6) & 264°C(PA66)
Its short term and long term service temperature are
respectively 140 - 160°C(For PA6,6 10°C more) and 80
- 100°C.
9. 9
Relations of Structure and properties of Polyamide 6
The structural variables that affect polymer
properties.
1. The distance between the repeating – CONH-
group
2. The number of methylene groups in the
intermediates
3. The molecular weight
4. N- substitution
5. Co-polymerization
10. 10
• The Polyamide 6 is available in various grades
Injection molding grade
Extrusion grade
Rotational Molding grade
Fluidized bed coating grade
Grades of Polyamide 6
11. 11
Processing considerations for PA 6
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 or size
Minimizing drooling by nozzle of reverse tapper type.
Shrinkage of the part
Annealing at 130° to 149°C for 10 - 20 hrs.
13. Applications
Machinery
Agricultural
Mining and oil drilling
Food processing
Printing
Textile processing
Engine parts
Pumps/valves/meters/filters Air
blowers
Material handling equipment
Standard components
Gears Cams Sprockets
Bearings
Gaskets Pulleys Brushes
13
14. Applications for Polyamides
14
• Fiber applications
– 50% into tire cords (nylon 6 and nylon 6,6)
– rope, thread, cord, belts, and filter cloths.
– Monofilaments- brushes, sports equipment, and bristles (nylon 6,10)
• Plastics applications
– bearings, gears, cams
– rollers, slides, door latches, thread guides
– clothing, light tents, shower curtains, umbrellas
– electrical wire jackets (nylon 11)
• Adhesive applications
– hot melt or solution type
– thermoset reacting with epoxy or phenolic resins
– flexible adhesives for bread wrappers, dried soup packets, bookbinding
15. 15
Comparison between different polyamides
Polyamide 6 Polyamide 66
processing easy easy
Strength good better
Abrasion resistance Low High
Toughness Low higher
Water absorption high high
cost less Little High
17. Chemistry Name of linear polyamides
• Nylon 6, 10 - polyhexamethylenesebacamide
[NH2(CH2)6NH . CO (CH2)8CO]n
• Nylon 11 - Poly(11-amino-undecanoic-amide
[NH(CH2)10CO ]n
• Nylon 12 - Poly(11-amino-undecanoic-amide
[NH(CH2)11CO ]n
• Other Nylons (Nylon 8, 9, 46, and copolymers
from other diamines and acids)
17
18. Nylon 11 or Polyamide 11
• It is a bioplastic and is an odd nylon.
• It is produced by the polymerization of 11-
aminoundecanoic acid. It is produced from
castor beans by Arkema under the trade
name Rilsan.
18
19. 19
Advantages
• Low water absorbing nylon
• Good chemical resistance
• Ability to accept high loading of fillers
Limitations
• High cost relative to other nylons
• Minimal heat resistance
Nylon 11 or Polyamide 11
20. • It is made from ring opening polymerization.
of laurolactam at 260-300˚C.
• Melting point: 178 to 180 °C (352 to 356 °F; 451 ...
• Density: 1.01 g/mL
Nylon 12 or Polyamide 12
20
21. 21
Advantages
• Low water absorbing nylon
• Good chemical resistance
• Ability to accept high loading of fillers
Limitations
• High cost relative to other nylons
• Minimal heat resistance
Nylon 12 or Polyamide 12
23. 23
Physical Properties of Polyamide
Nylon 6 Nylon 6,6 Nylon 6,10 Nylon 6,12
Optical Translucent to
opaque
Translucent
to opaque
Translucent
to opaque
Translucent
to opaque
Tm 210C -220 C 255C – 265C 220 C 195 -219 C
Moisture
Absorption
1.3-1.9% (24h)
8.5-10 (Max)
1.0-2.8% (24h)
8.5% (Max)
1.4% (24h)
3.3% (Max)
0.4 – 1.0%
(24h)
2.5 –3 %
(Max)
Oxidation
Resistance
good good good good
UV
Resistance
Poor Poor Poor Poor
Solvent
Resistance
Dissolved by
phenol &
formic acid
Dissolved by
phenol &
formic acid
Dissolved by
phenol &
formic acid
Dissolved by
phenol &
formic acid
Alkaline
Resistance
Resistant Resistant Resistant Resistant
Acid
Resistance
Poor Poor Poor Poor
Cost $/lb $1.30 $1.30 $3.00 $3.10
24. 24
Advantages of Polyamide
Tough, strong, impact resistant
Low coefficient of friction
Abrasion resistance
High temperature resistance
Processable by thermopalstic methods
Good solvent resistance
Resistant to bases
25. 25
Disadvantages of Polyamide
– High moisture absorption with
dimensional instability
– Subject to attack by strong acids and oxidizing
agents
– Requires UV stabilization
– High shrinkage in molded sections
– Electrical and mechanical properties
influenced by moisture content
– Dissolved by phenols
27. Synthesis of PET and PBT
O
•Thermoplastic polyesters have ester(-C-O) repeating
link
•Polyester (linear) PET , PBT & PC
27
28. 28
PET Properties
• The flexible, but short, (CH2)2 groups tend to leave the
chains relatively stiff.
• PET is known for its very slow crystallization. If cooled
rapidly from the melt to a Temp below Tg, PET solidifies
in amorphous form.
• If PET is reheated above Tg, crystallizaiton takes place to
up to 30%.
• In many applications PET is first pre-shaped in amorphous
state and then given a uniaxial (fibers or tapes) or biaxial
(film or containers) crystalline orientation.
• In Injection Molding PET can yield amorphous transparent
objects (Cold mold) or crystalline opaque objects (hot
mold).
35. Processing of PET
PET can be processed by following techniques:-
1. Injection molding
2. Stretch molding
3. Thermoforming
4. Extrusion
Processing Behaviour:-
1. Since PET is hygroscopic, perdrying is essential,
and DehumidifierHoppers are recommended.
2. Because of free flow of nature of material,
restricted Nozzels are recommended.
3. A back flow valve fitted to screw are used.
36. Processing Behaviour
4. Cylinder temp is 260 deg C, and mold temp about 140
deg C to promote proper crystallization.
5. Mold temp also effects cycle time, warpage, shrinkage,
surface gloss, colour .
6. Selection of mold temp. is related to wall thickness.
7. As the Tg of PET is 80 deg C so, if we keep mold temp
below Tg, ie below 50 deg C, we get an amorphous and
transparent product.
8. Crystalline, Opaque moldings are produced by using a
mold temp of about 130 deg C.
9. Biaxial stretching of PET is possible so, Biaxially
oriented films and Biaxially oriented bottles are made.
37. PET Grades Available
PET is available in following grades:-
1. Glass filled grade
2. Injection molding
3. Extrusion Grade
4. Stretch Blow molding Grade
41. 41
PBT Properties
• It is a Semi Crystalline material.
• The longer, more flexible (CH2)4 groups allow for
more rapid crystallization than PET.
• PBT is not as conveniently oriented as PET and is
normally injection molded.
• PBT has a sharp melting transition of 220 deg C,
with a rather low melt viscosity.
• PBT has rapid crystallization and high degree of
crystallization causing warpage concerns
42.
43. Processing of PBT:-
PBT can be processed by following techniques:-
1. Injection molding
2. Extrusion
3. Blow molding
Grades of PBT:-
1. Unmodified grade.
2. Glass reinforced grade.
3. Mineral filled grade.
4. Flame retardant grade.
5. Impact modified grade.
45. 45
PET PBT
Optical Transparent to
Opaque
Opaque
Tmelt
245C -265 C 220C – 267C
Tg 73C - 80C
H20 Absorption 0.1 - 0.2% (24h) 0.085% (24h)
0.45% (Max)
Oxidation Resistance good good
UV Resistance Poor Poor
Solvent Resistance halogen
hydrocarbons
good
Alkaline Resistance Poor Poor
Acid Resistance Poor Poor
Difference in PET & PBT
46. 46
Advantages of Polyesters
– Tough and rigid
– Processed by thermoplastic operations
– Recycled into useful products as basis for
resins in such applications as sailboats,
shower units, and floor tiles
– PET flakes from PET bottles are in great
demand for fiberfill for pillows and sleeping
bags, carpet fiber, geo-textiles, and regrind
for injection and sheet molding
– PBT has low moisture absorption
47. 47
Disadvantages of Polyesters
–Subject to attack by acids and
bases
–Low thermal resistance
–Poor solvent resistance
–Must be adequately dried in
dehumidifier prior to processing to
prevent hydrolytic degradation.
52. 52
Advantages
– High impact strength, excellent creep resistance,
– Very good dimensional stability
– continuous temp over 120 C
Disadvantages
– High processing temp,UV degradation
– Poor resistance to alkalines
– subject to solvent cracking
55. 55
PPO/PPE
• Poly(p-phenylene oxide) or poly(p-phenylene
ether) (PPE) is a high-temperature thermoplastic.
• It is an amorphous high-performance plastic.
• It is rarely used in its pure form due to difficulties in
processing and mainly used as blend with PS, HIPS or
PA.
• It can be used in applications upto 110 C temperature
intermittently.
68. 68
Polyoxymethylene POM
• Polyoxymethylene (POM), also known
as acetal,[2] polyacetal, and polyformaldehyde.
• It is an engineering thermoplastic used in precision
parts requiring
– high stiffness,
– low friction,
– and excellent dimensional stability.
70. Relations of Structure and Properties of POM
Due to structural similarity properties of acetal polymers are compared
with those of polyethylene.
Both polymers are linear with a flexible chain backbone and are thus
both thermoplastic.
Both the structures are regular and since there is no question of tacticity
arising both polymers are capable of crystallization.
In the case of both materials polymerization conditions may lead to
structures which slightly impede crystallization; with the polyethylene, this
is due to a branching mechanism, whilst with the polyacetals this may be
due to co-polymerization.
The acetal polymer molecules have a shorter backbone (-C-O-) bond
and they pack more closely together than those of polyethylene. The
resultant polymer is thus harder and has a higher melting point.
71. Characteristics of POM
Good appearance
Homopolymer is resistant to mid acids and bases
Good electrical properties but affected by moisture
Stiff and rigid
Good toughness
Notch sensitive
Excellent fatigue resistance under repeated load
Excellent creep resistance under continuous load
Low coefficient of friction
Good abrasion resistance
Maintains the mechanical, chemical and
electrical properties over broad temperature range
and time
72. Characteristics of POM
High resistance to thermal and oxidative degradation
Very good resistance to stress relaxation
Excellent dimensional stability
Good processability
Copolymers have better thermal stability
Burn slowly without smoke generation
Susceptible to UV degradation
Attacked by phenol and aniline
Difficult to electroplate
Degradation at high processing temperature and
liberate formaldehyde
It is identified by the strong smell of formaldehyde, when burned,
faint color flame, melt and drips
Its melting point is 165-175°C
76. Properties of Polyacetal
Properties Values
Homopolymer Copolymer
Units
Specific gravity ---- 1.42 1.41
Tensile strength MPa 69 61
Tensile modulus MPa 3100 2829
Flexural modulus Mpa 2620-2960 2588
Elongation at break % 27-75 40-75
Impact strength izod, Notched, J/m 69-123 53-80
M92-94
136
M78-80
110
Hardness
Deflection temperature under load
(1.82 Mpa)
Vicat softening temperature
Coefficient of linear expansion
0
C
0
C
mm/mm/0
C
185
10-15 x 10-5
167
8.5 x 10-5
Water absorption, 24hrs % 0.25-0.32 0.22
Dielectric strength KV/mm 20 20
Dielectric constant 10-6
Hz 3.7 3.7
Power factor 0.005 0.006
Volume resistivity Ohm.m 10-13
- 10-14
-
Melting point 0
C 175 165
77. Grades of POM
The polyacetals are available in the following grades.
Injection grade
Extrusion grade
Extrusion blow grade
rotational grade
In addition to
that the
available,
following special grades are
Improved processability grade.
Low friction grade.
Glass filled grade
Mineral filled grade
UV-Stabilized grade
78. Processing considerations of
Polyacetals
While processing polyacetal following precautions to be taken.
1. Stepwise thermal or based catalyzed hydrolytic
depolymerization initiated from the hemiformal chain end with
the evolution of formaldehyde.
Oxidative attack at random
along the chain
leading to chain
scission and subsequent depolymerization.
Acid catalysed cleavage of the acteal linkages.
Thermal depolymerization through scission of C-O bonds can
occur catastrophically above 270°C and care must be taken not
to exceed this temperature during processing.
2.
3.
4.
The homopolymer is moulded at melt temperature of 200-210°C while the
copolymer would be moulded at melt temperature of 190-205°C.
Therefore end capping is done during polymerization and antioxidants and
acid
acceptors are added
80. Appliances: Housing for business machine,
gears, cams, friction pads, rollers, pulleys, nuts,
chain links and shelf support brackets, detergent
pumps, refrigerator clips, brackets, bearing, wear
strips and instrument housing in washers and
dryers, spray nozzies and soap dispensers in
dishwares , bowls, mixing blades and bearings in
counter-top appliance bodies, tops and cups in
water boilers.
Agriculture & Irrigation: Pop-up sprinklers
(nozzles arms, gears, housing and water ways),
pumps(housing, impellers, pistons) metering
valves, tractor components (shift lever housing,
hydraulic connectors, seed applicators, bearings
and gears)
Applications of Polyacetal
81. Automotive: Fuel level indicators, pump
components, gas caps, cooling fans, trip clips,
colour co-ordinated bucket housings, window
cranks, shift lever handles, knobs, lever and
mounting brackets, instrumental cluster gears,
bearings, housing and dials, exterior door pulls,
mirror housing and brackets
Industrial: Valves, springs, bearings, cams,
material handling components such as
conveyors, chain links gears, pumps and hose
connectors
Applications of Polyacetal
82. Applications of Polyacetal
Electrical: Key tops pluggers, switches, buttons,
cassette tape rollers and hubs, base plates in computer
keyboards, springs in telephones and connectors in
modular components.
Laser mark part HV
AC Control