Polymer Processing, Properties and Applications

There are two basic types of polymeric

materials, (excluding rubbers). These are:

 Thermoplastic polymers are solid at room

temperature but become a viscous liquid at
elevated temperature. This is a reversible
process through cooling and heating without a
significant change to the material.

Examples: polyethylene (PE)

polypropylene (PP)
polyamide or nylon (PA)
poly (vinyl chloride) (PVC)

 Thermosetting polymers when initially heated

soften and flow for moulding but also undergo
a chemical reaction (cross-linking) which
hardens the material into a solid. Reheating of
the material causes degradation and char.
This process is irreversible

Examples: epoxy
polyester (thermoset)
phenolic
 Polymer Processing, Properties and Applications

Polymer Processing

Heat Pressure
reduce viscosity

Flow and
shape

Cool and
hold shape

Flow and heat transfer

 Polymer Processing, Properties and Applications
Characterisation of Flow
Shear
stress
Newtonian flow
(ideal)

Shear rate

Shear
stress

Non-Newtonian
flow
(shear thinning)

Shear Shear rate

stress

Yield followed by
Newtonian flow

Shear rate
 Polymer Processing, Properties and Applications
Polymer Characterisation -- Capillary Rheometry
Force F

Velocity Piston - area A

v

Heaters
Molten
polymer

Barrel
diameter
d
Capillary
Capillary length
length Capillary
LLcc diameter
dcc
Die swell

Extrudate

Shear stress  = P/(4A. (Lc/dc)) -- [Nm-2]

Shear rate  = 2/15 (d2.v/dc3) -- [s-1]

 Polymer Processing, Properties and Applications
Apparent
Viscosity
a Decreasing molecular
(log scale) weight
(Nsm-2)

Eg pp MFR 0.5 g/min

Eg pp MFR 3.5 g/min

Eg pp MFR 9.0 g/min

Shear rate s

(log scale)

Variation of apparent viscosity with shear rate

for a typical polymer for different grades (chain length)

Apparent
Viscosity
a Different chain architectures
(log scale)
(Nsm-2) Eg polycarbonate

Eg polyamide

Eg polypropylene

Shear rate s

(log scale)

Variation of apparent viscosity with shear rate for

different polymers (chain architectures)
Polymer Processing, Properties and Applications

Apparent
Viscosity
a
(log scale)
(Nsm-2)
Normal molecular
weight distribution

Narrow molecular
weight distribution

Shear rate s

(log scale)

Variation of apparent viscosity with shear rate for a typical

polymer with different (molecular weight distributions))

Apparent
Viscosity
a
(log scale)
(Nsm-2) Virigin PP polymer

PP plus 2% brown
pigment

Shear rate s

(log scale)

Variation of apparent viscosity with shear rate for a typical

polymer with different (molecular weight distributions))
 Polymer Processing, Properties and Applications

Apparent
Viscosity
Decreasing
a
temperature
(log scale)
(Nsm-2)
pp barrel temperature 190 oC

pp barrel temperature 230 oC

pp barrel temperature 260 oC

Shear rate s

(log scale)

Variation of apparent viscosity with shear rate

for a typical polymer at different temperatures
 Polymer Processing, Properties and Applications
Polymer melt characterisation
Brabender Plasticorder

Torque
meter

Set up extrusion conditions, temperature profile and

screw speed and measure the screw torque.

Torque
N.m

Time s

Torque trace --- mean torque

 Polymer Processing, Properties and Applications
Polymer Characterisation -- Melt flow indexer

Piston

Heaters
Molten
polymer

 Cut extrudate
Die swell

Extrudate

Melt flow rate MFR = 600 x average weight of cut-off (g)

time interval between cut-offs

[g/min.]
Polymer Processing, Properties and Applications

Polymer extrusion

Essential features of a single screw extruder

 Polymer Processing, Properties and Applications

Heat Transfer

Conduction -- extruder or injection moulding barrels,

cooling tanks, mould walls etc

Convection -- forced convection in air cooling, quenching,

forced convection in screws

Radiation -- in stretching ovens, or in relaxation ovens

Melting and homogenisation

conduction from the barrel wall

convection flow patterns between the screw flights

to provide uniform temperature of melt

Excessive temperature, reduced viscosity -- poor quality

 Polymer Processing, Properties and Applications

Degradation -- temperature - time dependent

polyvinyl chloride (PVC) extremely heat sensitive

Degradation Tertiary C atom

H R H R H R H

C C C C C C C

H H H H H H H
Chain scission energy
Iso-tactic polyolefin

H R H R H R H R

C C C C O O C C C C

H H H H H H H H

Chain scission
reduction in molecular length
reduced viscosity
 Polymer Processing, Properties and Applications

Degradation

chain scission, reduced melt viscosity,

more easily processed, excessive flash,

poor mechanical properties.

Heat Removal -- cooling rate

Crystalline structure

Slow cooling -- highly developed structure,

low molecular orientation
low frozen-in strains
low shrinkage
low through-put

Fast cooling -- poorly developed structure

high molecular orientation
frozen-in strains
high shrinkage
high through-put
 Polymer Processing, Properties and Applications
Thermal Analysis

Heat flow and temperature are very important for processing

polymers.

High temperature reduces viscosity - lower pressure for same flow,

but
:
1. the temperature of the molten material has a direct influence of
both the structure and crystallinity of the finished product.

2. if temperature is too high, degradation, ie molecular breakdown

will occur making processing difficult with poor mechanical
properties.

Methods of determining thermal properties (including decomposition)

utilise three general techniques:

1. measurement of weight loss as a function of temperature

(thermogravimetric analysis TGA)

2. differential scanning calorimetry (DSC) using an energy

balance method and differential thermal analysis using a
temperature difference method (DTA).

3. thermo-mechanical analysis measuring changes in

expansion contraction or penetration of polymer samples.
 Polymer Processing, Properties and Applications

Thermal Analysis

Properties, which can be determined by thermal methods

include:

 Structural changes: glass transitions, melting

(boiling) point, transitions and phase changes in
general.

 Mechanical changes: hardness, expansion,

contraction

 Thermal constants: specific heats, melting points

 Chemical reactivity: solid-solid and solid-gas

reactions, dehydration and curing reactions
 Polymer Processing, Properties and Applications
Thermo-gravimetric analysis TGA

Moisture loss decomposition

400
100
Weight
Temperature
loss o
C
%

100
0
time

Determination of moisture content and thermal

breakdown
decomposition

Additional anti-oxidant
100

Temperature
Weight
loss o
C
%
isothermal

Increased
dwell time

0
time

Determination of dwell time before thermal degradation

during processing
 Polymer Processing, Properties and Applications

Differential Scanning Calorimetry DSC)

Energy Melting Temperature

input peak o
C
Processing
window
temperature
On-set of
degradation

time
Processing window
dwell time
Determination of the processing window using DSC

Polymer plus

Temperature
Energy
input additive

polymer
o
C

On-set of
degradation

time
Determination of the thermal stability of an additive
 Polymer Processing, Properties and Applications

Thermo-mechanical Analysis TMA

Solid
Softening point
Temperature
o
C
Melting point

Liquid

Penetration of sample using a sharp probe

Expansion Shrinkage at low

temperature mould
Temperature
o
C
Shrinkage for high
temperature mould

Contraction

Expansion of sample with frozen-in strains

Polymer Processing, Properties and Applications

To gain the most comprehensive understanding of the

raw material, the following should be assessed:

(i) flow characterisation under simulated

processing conditions.

(ii) thermal response i.e. melting and degradation

temperatures.

(iii) granule size variation

(iv) residue content, e.g. by ashing

Note that the cost implications of this can be quite

significant.