Natural Sciences Tripos Part II

MATERIALS SCIENCE
C14: Polymer Processing

Dr J A Elliott
Easter Term 2011-12
II
Name......................... College............................
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C14 - POLYMER PROCESSING

COURSE CONTENT
(6 lectures + 1 Examples Class)

A. Introduction

Motivation, Basic classification of polymers, basic types of processing

B. Basics of polymer melt rheology

Viscosity, Reynolds number, non-Newtonian behaviour, flow through a pipe, flow curves,
slippage, Bagley correction.

C. Materials Behaviour during the Processing Stages

Overview

Melt flow: die entry (extension, melt fracture), viscoelastic effects (Deborah number), ie- exit
effects (die swell, sharkskin), flow front (fountain flow, weld lines), orientation retraction)

Melting: memory effects, degradation, conductivity

Cooling: heat transfer, Fourier equation, shrinkage, crystallization

Mixing: additives, types of mixing, forces and energy

D. Industrial Processing Methods

Mixing: blending, intensive mixing

Extrusion based processes: screw extruders, blow moulding, bubble blowing, calendering,
Stentor process

Moulding processes: compression moulding, injection moulding, machine, rotational
moulding, reaction injection moulding, push-pull moulding

Thermoforming: vacuum, pressure

E. Processing Design

General principles, gating, mould filling design

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Book List

1) W.A. Holmes-Walker: "Materials Processing [Unit 11]: Polymer Processing", Open
University 1981 (ABS6.7).

2) N.G. McCrum, CP. Buckley and CB. Bucknall, "Principles of Polymer Engineering",OUP,
1997 (AN6d.57a).

3) N.J. Mills, "Plastics", second edition, Edward Arnold, London 1993 (AN6c.126b).

4) J.A. Brydson: "Flow Properties of Polymer Melts", Butterworth, London, 1970 (AN6d.10).

5) D.H. Morton-Jones: "Polymer Processing", London, Chapman and Hall, 1989 (AN6d.56).

6) P. C. Powell and A.J. Ingen Housz: "Engineering with Polymers", 2
nd
ed. Stanley Thomas,
1998 (AN6d.29a).
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A. Introduction
1. Motivation
Polymer products are part of our everyday life as well as some of the most advanced applications.
Polymer Processing is about the efficient control of their manufacturing, the harnessing of the
intrinsic polymer properties to achieve the desired end product properties, and the design of
machinery suitable for handling them. Its ongoing importance stems from the need to control
existing processes, to make new shapes, use different materials, reduce wastage and energy costs,
make lighter products, improve properties, lower the price.

The main concern of this course is the behaviour of polymers during processing, and to a small
extent the engineering design of processing equipment.


2. Basic classification of polymers with respect to processing

Thermoplastics Thermosets

Examples:

Washing-up bowl Tyres









Characteristics














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2. Basic types of processing
- Shaping and moulding: Extrusion and injection moulding processes.
- Diagram of a screw extruder:



Diagram of an injection moulding set-up



Individual techniques are variations on the common theme and will be subject of a later section.

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B. Basic polymer melt rheology


1. Viscosity

- Recap: measure of fluidity, thickness, consistency
- Definition: stress/ strain rate








- e.g. simple shear:










- cf. modulus = stress/strain
- Viscosity of polymers: high in comparison with most other liquids:

Range of viscosities in fluids:
Water
- Zn(450 C)
Polymer:








- High has some important effects





- Reasons: Long chain, entanglements.

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The molecular weight has a strong effect on viscosity


Effect of shear strain on shear stress - non-Newtonian behaviour:























7
The definition of true viscosity ( ) and apparent viscosity ( ) in a pseudo plastic fluid.

- Shear thinning - what is the underlying molecular behaviour?



8
- Extensional flow: occurs in many processing situations

- Effects of extensional flow:






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2. Flow through a circular pipe
2.1 Shear stress
10
2.2 Throughput and shear rate
11
12
2.3 Flow curves

On the basis of equations (1) and (6) it is possible to determine both the shear stress and the shear
rate at the wall for different outputs and pressures. This yields material specific curves, known as 'flow
curves' .

Different types of flow curves are:

q t q t vs , vs , vs
a a
.



However, it is cumbersome to determine flow curves. Therefore the apparent shear rate at the wall
is often replaced by
,
4
3
R
Q
a w,
t
= (11)

the so-called apparent shear rate at the wall. The justification for this is that it can be shown (see
Ref 4, section 2.2.3) that for a time-independent liquid, the shear stress is a function of 4Q/R
3
only,
and that the difference to the true case is less than 15%, which in general is acceptable.

The viscosity determined by
a w,
w
f a,

= q

(12)

is called the false apparent viscosity.

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2.4 Power law fluids

Can we find an analytical expression describing the flow curve?



- Flow profiles:
Note tendency towards plug-flow for shear-thinning liquids.




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2.5 Slippage

Equation (2) contains the velocity at the wall, previously set to zero. If we assume Poiseulle flow
(equation (5)), and replace the pressure drop by the wall stress (equation (1)), we get:

















-> lubrication approximation:.
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2.6 The Bagley correction

Streamlines indicating the flow pattern at the entry point to a tube. Note the significant axial
acceleration before the start of the tube.



This leads to some pre-tube pressure drop, shown in the following Figure.




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Bagley (1957) introduced a correction for P
entry
, treated as increasing the effective tube length:



















A typical Bagley plot is shown in the Figure below.


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C. Polymer behaviour during the processing stages

1. Overview of processing stages and their main features
Mixing








Melting



Meltflow



Cooling and solidification






Crosslinking





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2. Melt flow
2.1 Introduction

Many polymer processing methods involve a polymer melt being driven through channels of
various dimensions (extrusion dies, injection moulding runners, gates, and moulds). Here we study
some basic aspects of such processes.

2.2 Effects of viscoelasticity
Recap: Maxwell element.


A measure of the extent to which elastic processes can be expected is given by the Deborah Number:










Example of process memory:



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- Die swell: As the polymer leaves the die, the extrudate diameter increases. This is also a
viscoelastic effect, largely due to the highly shear-oriented polymer molecules close to the wall.




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2.3 Die entry effects

Convergent flow at the die entry leads to extensional flow.






If the resulting tensile stress exceeds the tensile strength of the melt (ca 10
6
Nm
-2
), the result is so-
called melt fracture, leading to poor products:





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2.4 Die-exit effects

As the melt leaves the tube (die), the material close to the wall has to accelerate. This generates a
tensile stress which leads to surface orientations. If the stress exceeds the melt strength surface
ruptures appear, described as sharkskin: . If the conditions become worse, one gets 'orange peel', and
eventually 'bambooing'.





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2.5 The flow front

Fountain flow:



Weld lines: form where two melt fronts meet and join together.



Effects: Weakness, surface blemishes, crack-like defects

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3. Melting











4. Cooling


4.1 Heat flow

- Consider polymer surface in contact with cold surface (of metal, water or air), such that heat
transfer away from the surface is fast. Rate limiting process then is the internal heat transfer by
conduction within the polymer. This is quantified by the Biot number Bi = hL/k , where h is the
surface heat transfer coefficient. Typically, h =1000 Wm
-2
K
-1
, L =1mm, hence Bi 1. This
means that the temperature difference at the surface T- T
e
is small compared to the through
thickness variation.



Consider a polymer product as a series of flat elements:

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The flow of heat can be described by a 1-dim heat conduction equation:




More simply, assuming k to be temperature independent, we get the important parameter a, known
as thermal diffusivity:





Since Bil, we can also approximate T at surface = T
e
. Then the main term in the solution of the pde
yields:

( ) 4 exp
2
/ Fo T T
e ave
t


2
t/L Fo o = with .

Hence cooling is exponential, and the time taken to reach a certain degree of cooling is L
2
/ a.
With a typically 10
-7
m
2
s
-1
, and L = 1mm, times are 10-100 sec. Want to keep wall thickness as
small as possible to reduce cooling time!

4.2 Effects of freezing

Solidification starting from the quenched wall: Neumann-Stefan Problem

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Progress of crystallization into semi-infinite space



Inhomogeneities in structure: skin-core texture, transcrystallization:





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- Frozen-in orientation Reheating of product allows relaxation of stretched molecules: retraction..
This leads to shrinkage in parts of the product, warping etc. But put to use in shrink-wrapping.



- Effects of core freezing last: Shown in Figure 31 is the internal stress distribution across the
thickness of a sheet of polycarbonate. The surface regions are in compression, the centre is in
tension. Fig 32: Residual stresses, sink marks and voids.





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3. Mixing
3.1 Purposes of mixing
3.2 Types of mixing
Different processes/additives/polymers require different types of mixing. In principle, distinguish
two types:
(a) distributive mixing (extensive mixing, blending)


(b) dispersive mixing (intensive mixing, compounding)



They are conflicting processes:






3.3 Forces in mixing
Forces are transmitted by fluid mechanical stress in the mixer! Calculate the energy per unit volume
necessary to exert a certain stress. We have






Hence less energy is needed under high viscosity conditions to achieve good dispersion. 'Baker
prefers kneading a stiff dough to beating a thin batter'.



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3.4 Types of additives

Affecting physical properties:
Plasticizers



- Active fillers: reinforcing, toughening, improved abrasion resistance, conductivity,



- Short fibres:
- Rubber:
- Polymer: (blends)
- Pigments:
- modified clay (nanocomposite):
- inert fillers:






Affecting chemical properties:
- Cross linking agents -
- Foaming Agents -



- Protective additives:
- Antistatic agents -
- UV absorbers:
- Flame retardants:





Affecting processing properties:
Lubricants

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D. Industrial Processing Methods
1. Mixing


31
2. Extrusion
2.1 Screw Extruder





32


33








34
35



36


37



38
39


40


41


42







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Examples Class

1. Define what is meant by a power law fluid and indicate the form of its flow curve. The figure
below shows flow curves for polypropylene (melting point about 165 C).



Show how the behaviour at 180 C can be described in terms of two power law fluids.
Determine the corresponding exponents. Convince yourself that the curve could be well
described by the Ellis model which is expressed as:

1
0
+ =
q
q a
k
Account for the different behaviour shown at 170 C, and hence suggest why the flow curve
at 180 C can be fitted to power law functions rather more successfully than would generally
be the case.

2. The material for which the flow curve is given in the handout on page 12 is to be extruded
through a slit die at 210 C, and hauled off without tension at a speed of 1 cm s
1
. The
dimensions of the die are length L = 200 mm, width w = 20 mm, and height h = 2 mm.
Assuming w h, derive the expression for the shear stress as a function of position in the die,
and the apparent strain rate. (Follow the methodology used in lectures for the cylindrical pipe
geometry). Calculate the maximum apparent shear rate in the die. Use the flow curve to
estimate the pressure drop in the die, assuming that the apparent viscosities given are actually
false apparent viscosities. As a comparison, discuss the cases of a power law fluid and a
Newtonian fluid.

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3. Why is the die swell across the width of a sheet less than across the thickness?
You want to extrude bars with the cross sections shown below from a polymeric material.
Roughly what shapes would the respective dies have to be?



4. Each half of a standard audio tape cassette has the form sketched below. Consider production
from polystyrene by injection molding through a gate as indicated. Using a melt temperature
of 180 C and a mould temperature of 20 C, many mouldings are found to have cracks.
Where would the crack most likely appear? As a remedy you consider increasing the melt
temperature to 230 C, or increasing the mould temperature to 40 C. Why are these steps
likely to help? Also suggest and explain a more radical solution.


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Question Sheet

1. Explain, by using a processing equation, two ways by which your body may control blood
pressure. Which is likely to be more efficient and why?

2. The flow behaviour of polypropylene was investigated on a capillary rheometer. A die of
length L = 14 mm, and diameter D = 2 mm were used. The polymer was forced through the
die from a barrel reservoir of diameter d = 10 mm by a moving piston. The pressures required
to achieve certain piston velocities were recorded on a chart writer, which was calibrated as
giving 1.192 MPa mm
1
. From the measurements shown below, determine the shear stresses,
apparent shear rates at the wall and false apparent viscosities, and draw the viscosity-stress
flow curve. Can you estimate the difference between the apparent and the actual
(Rabinowitsch) wall shear rate?


V [mm/sec] P [mm]
0.333 12.7
0.625 15.9
0.833 17.9
1.667 23.2
2.50 27.2


3. As explained in the lectures, melt fracture may be caused by an excessive stress exerted on the
polymer melt in the die entry region. Discuss the factors involved in causing this stress and
suggest possible remedies. Which is likely to be the most effective?

4. Injection moulded articles generally show an oriented microstructure. (a) Describe an
advantageous and a disadvantageous effect of the orientation. (b) Which two ways may be
used to reduce the degree of orientation, and why?

5. What is the processing method of choice for (i) the cylinder of a bicycle pump, (ii) the
handle?

6. Give some differences between polymer melt processing and metal casting and discuss their
implications for processing and product properties.