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Processing of UPVC in
single and twin screw
extruders
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• A Doctoral Thesis. Submitted in partial fullment of the requirements for

the award of Doctor of Philosophy of Loughborough University.

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Publisher: c J.A. Covas

Please cite the published version.

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. - §,J-Uf1990
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28 JUN 1996
27 JUN 1997
 PROCESSING OF UPVC

IN SINGLE AND T.vIN SCREW EXTRUDERS

by

, ,
~ JOSE ANTONIO COLA90 GOHESt,Q9VAS

A Doctoral Thesis submitted in partial fulfilment

of the requirements for the award of
Doctor of Philosophy of the
Loughborough University of Technology

1985

Supervisor: D E Harshall. PhD

Institute of Polymer Technology

©by J A Covas. 1985

To Cristina
 i

ACKNOWLEDGEMENTS

I would like to express my gratitude to the Comissao Permanente

INVOTAN and the Instituto Nacional de Investiga9ao Cient{fica,
Lisboa, Portugal, for the financial support throughout most of my
student leave in the United Kingdom.

I am also indepted to:

- Dr D E Marshall, my supervisor, whose constant assistance and

advise helped me throughout this work;
- Dr M Gilbert for her useful suggestions, specially in thermal
analysis, and supervision in the later stages of the project;
- Mr D A Hemsley for his guidance in optical microscopy;
- Mr R Buxton for his advice in the statistical analysis;
Mrs R West for her help in solving the problems related to
analogue/digital conversion;
- Mr R C Stephenson and Mr C Domn for the ICI facilities made
available whenever necessary;
- Mr C Lines who, with skill and patience, manufactured the
equipment specially designed for this project;
- Mr J Cook for his help in performing the twin screw extrusion
experiments;
- the staff and colleagues in IPT, whose friendship and
encouragement helped me to accomplish this work.

Finally my gratitude to my parents who have endured our long

separation with fortitude and to my wife for her constant
encouragement despite the periods of material hardship.
 /~
ii

ABSTRACT

The processing characteristics of PVC compounds play a major

role on the ability of the equipment to control the final properties
of the product. Therefore. information on the effect of processing
conditions on such characteristics. and its influence on the final
properties can lead to an optimization of the extrusion process.

In this work. a statistically based experimental design was

used in order to investigate the role of the operating conditions
on the extrusion of a simple lead based PVC formulation. Both a
single and a twin screw extruder were used - they were instrumented,
and data collected by computer. A die was designed for the
formulation used. with both shear and extensional flows being taken
into account. These experiments produced both core samples along
the screw(s) and final products with varying states of fusion.

The fusion mechanism on processing was monitored with the help

of electron and light microscopy techniques. thermal analysis and
density measurements. In both types of extruders the primary
particles were found to fuse well before the grains. but the overall
mechanism differs for each type of machine.

An experimental technique was developed for the study of the

ReSidence Time (RT) and Residence Tine Distribution (RTD) of the
material in the processing equipment. These functions were related
to the operating eondi tions and compared with the available models
for extrusion.

The degree of fusion of the processed products was assessed by

rheolOgy and thermal analysis. A range of mechanical properties,
relevant to the general end - use of rigid PVC formulations. was
analysed: flexural. tensile and impact properties were found to be
directly related with fusion level. Hardness, measured using a
newly developed apparatus. proved to be a potential technique for
the degree of gelation of PVC formulations.
 f~
I

iii

LIST OF SYMBOLS

et half angle of the taper

attenuation constant (eq. 2.13)
i3 blending efficiency
Y shear rate
YN average strain
MlA,MlB - energy of endotherms A, B
Ml
f
heat of fusion
6qs Y-axis sensitivity
e: extensional strain
tensile deformation rate
elongation at break
Hencky strain
elongation at yield
melt viscosity
normalized time
extensional viscosity
mel t densi ty
a standard deviation
tensile or flexural stress
T shear stress
A area
constant (eq. 5.6)
area of endothermic curve (eq. 4.1)
B time base setting
constant (eq.5.6)
BM bending moment
BO,B. ,B .. ,B .. - coefficients of regression pOlynomial
1 11 lJ
Bp circulation factor
c concentration of tracer
C average specific heat
Cv heat capacity at constant volume
d thickness of specimen
D barrel diameter
diameter of breaker plate holes (eq. 2.13)
maximum deflection (eq. 4.11)
 iv

DR die resistance
el ,e 2 ,e - elastic, delayed elastic and plastic deformation
3
E residence time distribution
cell calibration constant (eq. 4.1)
EEl electrical energy input to the motor
E EF I - extrusion efficiency index
F force
cumulative residence time distribution
modulus of springs in mechanical model
breaker plate thickness
H channel depth
thickness of die land (eq. 2.3)
dimensions of tapered flow channel (eqs. 2.7, 2.8)
heat losses by radiation/convection (eq. 5.1)
HEI heat energy input to the heaters
HL heat losses
I moment of inertia
lIE increase in internal energy of the polymer
k Mnstant
kl constant defined by eq. 2.19
L length of capillary
length of die land (eq. 2.4)
support span (eqs. 4.8 - 4.10)
L* imaginary breaker plate length, given by eq. 2.12
m number of thread starts, twin screw extruder
mass of sample (eq. 4.1)
slope of the flexural curve (eq. 4.9, 4.10)
ID mass flow rate
MEr mechanical energy input to the screw
n power law index
viscous loss term (eq. 1.19)
N rotation speed
P pressure
fraction of material with plug flow (eq. 5.9)
q electrical input to heaters
Q volumetric output
Qc,Qf,Qs,Qt - gaps in twin screw extruder geometry
r maximum strain in the outer fibres
 v

R radius of capillary
radius of breaker plate holes (eq. 2.11)
rate of flexural testing (eq. 4.7)
RT residence time
RTD residence time distribution
s shape factor
S screw speed
safety factor (eq. 2.13)
SR elastic deformation
t time
t mean residence time
T temperature profile
Tg glass transition temperature
vd veloci ty of material
V volume of a C-shaped chamber
velocity
Xi,X j - independent variables
Y response
Z mechanical power delivered to the screw
 vi

TABLE OF CONTENTS

Page No

Acknowledgements i
Abstract ii
List of Symbols i11
Table of Contents vi

CHAPTER 1 INTRODUCTION 1
1.1 GENERAL 1
1.1.1 PVC 1
1.1.2 Polymerization Processes 2
1.1.3 Formulation Ingredients 4
1.1.3.1 Stabilizers 4
1.1.3.2 Lubricants 5
1.1.3.3 Other Additives 5
1. 2 MORPHOLOGY AND MOLECULAR STRUCTURE OF PVC 6
1.2.1 Mechanism of Suspension Polymerization 6
1.2.2 Morphology 8
1.2.3 Molecular Structure and Crystallinity 9
1.3 THE RHEOLOGY OF PVC 12
1. 4 SINGLE AND TlITN SCREW EXTRUDERS 14
1.4.1 Comparison of Characteristics 14
1.4.1.1 Introduction 14
1.4.1.2 Single Screw Extruders 16
1.4.1.3 Twin Screw Extruders 22
1.4.1.4 l-lixing Characteristics 26
1.4.1.4.1 Residence Time and Residence
Time Distribution 26
1.4.1.4.2 Strain and Strain
Distribution 32
1.4.2 Processing of UPVC 35
1.4.2.1 Dry Blending 35
1.4.2.2 Single Screw Extrusion 35
1.4.2.2.1 Melting Mechanism 36
1.4.2.2.2 Mechanism of Gelation 38
 vii

Page No
1.4.2.3 Twin Screw Extrusion 40
1.4.2.3.1 Melting Hechanism 42
1.4.2.3.2 '4echanism of Gelation 43
1.4.2.4 Fusion Models 43
1.4.2.5 Influence of Processing
Conditions on Properties 46
1.4.2.5.1 Impact 47
1.4.2.5.2 Tensile 50
1.4.2.6 Reprocessing 52
1. 5 HETHODS OF ASSESSING THE STATE OF FUSION 53
1. 5.1 Sol vent Testing 53
1.5.2 Physical Properties 54
1.5.3 Microscopy 54
1.5.4 Capillary Rheometry 55
1. 5. 5 Thermal Analysis 56
1. 6 AII1S OF PROJECT 58

CHAPTER 2 DIE DESIGN 61

2.1 INTRODUCTION 61
2.2 ANALYSIS OF FLotl PEE!,;mIENA lITTHIN THE DIE 61
2.2.1 General 61
2.2.2 Determination of the Die Profile 64
2.2.2.1 Die L~~d 64
2.2.2.2 Adaptor 66
2.2.2.3 Breaker Plate 71
2.2.3 Method of Calculation 71
2.3 DATA REQUIRED 76
2.3.1 Measurement of Shear Flo;1 Properties 76
2.3.2 Measurement of Elongational Flow
Properties 78
2.3.3 Results and Discussion 82
2.4 PROFILE OF DIE 86

CHAPTER 3 PLANNING OF EXTRUSION EXPSIlIMENTS 92

3.1 EXPERIMENTAL DESIGN 92
3.1.1 Introduction and Aims 92
 viii

Page No

3.1.2 Choice of Experimental Design 93

3.1.3 Model Fitting and Assessment 95
3.1.4 Interpretation of the Fitted Model 97
3.2 INSTRUMENTATION OF THE EQUIPMENT 9B
3.2.1 Introduction and Aims 9B
3.2.2 Hardware 9B
3.2.3 Software 104

CHAPTER 4 EXPERIMENTAL PROCEWRE 107

4.1 PREPARATION OF FORMULATION 107
4.2 EXTRUSION lOB
4.2.1 Single Screw Extrusion lOB
4.2.2 Twin Screw Extrusion 112
4.3 COMPRESSION HOULDING 114
4.4 PRODUCTION OF PELLETS 115
4.5 DEVELOPMENT OF FUSION ALONG THE SCREl>l(S) 115
4.5.1 Optical Microscopy 115
4.5.1.1 Jamin-Lebedeff Interferometer 115
4.5.1.2 Fluorescence Hicroscopy 117
4.5.2 Scanning Electron Microscopy 117
4.5.3 Differential Scanning Calorimetry 11B
4.5.4 DenSity lIB
4.5.5 Solid Bed / Helt Pool Ratio 11B
4.6 RESIDENCE TIHE AND RESIDENCE TUIE DISTRIBUTION 11B
4.7 ASSESSMENT OF DEGREE OF FUSION 119
4.7.1 Differential Scanning Calorimetry 119
4.7.2 Capillary Rheometry 120
4.B PROPERTIES 120
4.B.1 Mechanical 120
4.B.1.1 Tensile Testing 120
4.B.1.2 F1exura1 Testing 122
4.B.1.3 Impact Testing 123
4.B.1.4 Hardness 125
4.B.2 DenSity ~leasurernents 137
 ix

Page No
CHAPTER 5 RESULTS AND DISCUSSION
SINGLE SCREW EXTRUSION 138
5.1 ENERGY EFFICIENCY OF THE PROCESS 138
5.1.1 Introduction 138
5.1.2 Calculations 139
5.1.3 Results and Discussion 141
5.1.3.1 Mass Output 141
5.1.3.2 Electrical Energy Input 141
5.1. 3.3 Heat Energy Input 144
5.1.3.4 Heat Losses 144
5.1.3.5 Increase in Internal Energy 144
5.1.3.6 Mechanical Energy Input 145
5.1.3.7 Extrusion Efficiency Index 146
5.2 MIXING CHARACTERISTICS 147
5.2.1 Calculations 147
5.2.2 Results and Discussion 148
5.3 MELTING MECHANIS:4 154
5.3.1 . Identification of the Melting
Mechanism 155
5.3.2 Growth of the Melt Pool along the
Screw Length 164
5.4 MECHANISM OF GELATION 170
5.4.1 Identification of the Mechanism of
Gelation 170
5.4.2 Progression of Gelation along the
Screw Length 177
5.4.2.1 Thermal Analysis 180

CHAPTER 6 RESULTS AND DISCUSSION

T".'IIN SCRE'II EXTRUSION 186
6.1 EVALUATION OF EXTRUSION CHARACTERISTICS 186
6.1.1 Mass Throughput 186
6.1.2 Torque 187
6.1. 3 Pressure 188
6.2 HIXING CHARACTERISTICS 190
6.3 HELTING HECHAiHSH 196
 x

Page No
6.4 MECHANISM OF GELATION 204
6.4.1 Identification of the Mechanism of
Gelation 204
6.4.2 Progression of Fusion along the Screw 207
6.5 COMPARISON OF TWIN AND SINGLE SCRE!'/ EXTRUSION 212

CHAPTER 7 RESULTS AND DISCUSSION,

PROPERTIES OF THE EXTRUDATES 216
7.1 DEGREE OF GELATION OF THE EXTRUDATES 216
7.1.1 Influence of Processing Conditions 218
7.1.2 Comparison of Techniques 220
7.2 MECHANICAL PROPERTIES 223
7.2.1 Tensile Testing 223
7.2.1.1 Yield Parameters 227
7.2.1.2 Post-Yield Parameters 228
7.2.2 Flexural Strength 237
7.2.3 Impact Strength 239
7.2.4 Hardness 244
7.3 DENSITY MEASUREMENTS 249
7.4 COMPARISON OF TWIN AND SINGLE SCREl'/ EXTRUSION 253
7.5 REPROCESSING EFFECTS 254

CHAPTER 8 CONCLUSIONS AND SUGGESTIONS FOR FURTHER ['10RK 256

8.1 GENERAL CONCLUSIONS 256
8.2 OPTIMIZATION OF PROCESSING CONDITIONS 265
8.3 SUGGESTIONS FOR FURTHER l'IORK 268

References 270

APPENDICES A Computer Program for Die Design 281

B Flowcharts of Calculations for Shear and
Extensional Flow Properties 288
C Drawings of Die 291
D Output of the GLIM Package 292
E Thermograms of Single Screw ExtruSion
Core Samples 293
 - 1 -

CHAPTER 1
INTRODUCTION

1.1 GENERAL

1.1.1 PVC

. 1
In spite of being one of the oldest plasti cs, poly (vinyl chloride)
- PVC - has not lost any of its technical and economic importance in
recent years. This is mainly due to its low cost and versatility:
prad:.ically every type of plastics processing technique can be applied
to PVC; sound formulation can lead to a wide range of final properties.

It is expected that by the end of 1984 3.7 million tonnes of this

product will have been consumed in Viestern Europe 2 ; 60% of these will
be of rigid PVC and this proportion is likely to increase in the
3·
future. A breakdown of the consumption in Western Europe is ~iven
in Table 1.1. From the analysis of the data, it is immediately
apparent that a high proportion of rigid applications are in the
building industry.

Processing I Application Market share (%)

Rigid PVC 61.5
Pipes and fittings 25.5
Proliles 12.0
Film and sheet 10.0
Blow mouldings 7.5
Records 2.0
Other 4.5"
Plastici:ed PVC 38.5
Film and sheet 9.0
Synthetic Ieath~r 4.5
Floor coverings 5.0
Tube and fittings 4.0
\vire and cable insulation 10.0
Other 6.0

Total 100

TABLE 1.1 Breakdown of the Western European PVC market by application

(1982)2
 - 2 -

The collapse of the business activity in 1973-5, together with

the environmental problems created by the discovery of the carcinogeniC
character of vinyl chloride (VCM), PVC's monomer precursor, changed
dramatically the growth pattern of the sixties, when 16% per annum
was recorded 4 • This created an excess of supply over demand, that
has been responsible for the drastic changes in the industry's
structure. Between 1976-79 the Western European consumption of PVC
increased by 4% annually, but the recession of 1980, when the building
sector was particularly hit, led once again to a reduction in demand 2 •
Presently, however, there are signs of economic recovery and, provided
the building industry experiences a revival and there are further cuts
in polymer capacity in order to establish a realistic supply/demand
balance, an annual growth rate of 2% can be expected throughout this
decade 4 •

Hence, despite the modest growth rate, PVC can be considered an

established commodity product, with good future prospects. Fundamental
new spheres of application~ no longer expected, but new developments
continue to occur5 Also, increased attention has been lately drawn
to the discussion on energy requirements, as means of effective
savings in materi'al costs. PVC has the lowest energy equivalent value
(53 MJ Kg-I) of any commercial thermoplastic5, 6, thus Challenging the
other thermoplastics and traditional materials, as far as cost is
concerned.

1.1.2 POLYMERIZATION PROCESSES

Presently, there are three main commercial processes for the

manufacturing of PVC: i) suspension, ii) emulsion and iii) bulk or
mass polymerization. PVC can also be obtained by iv) bulk gas phase
and v) solution/diluent polymerization; the first of these uses a
fluidised bed reactor, the process not having yet reached commercial
status; the second is used to produce vinyl acetate copolymers, for
speciality applications and is far less important than the three main
ones ..

Each of these manufacturing techniques produces raw materials

 - 3 -

w:i. th characteristic particle size, shape and porosi ty. Suspension

and mass PVC are a coarse powder of 100-150 ~m mean size, with free
flowing properties, good agglomeration ability and good feed behaviour
into screws. Therefore, they find wi-de application, ranging from
rigid formulations for extrusion of pipes and profiles to soft
footwear compounds. The emulsion process creates 'square- sided'
grains of 0.1-2 ~m in size. These particles absorb plasticizer very
well, making ita good material for plastisol production.

Apart from the polymer morphology, its molecular weight (K-value)

also affects both the processabili ty and physical properties: lower
K-value means lower melt viscosity at a given temperature and, in
general, easier processing, whilst a higher K-value is generally
associated with better mechanical properties. K-values that are a
compromise between processability and product properties, and types
of raw material can tp.erefore be associated with the various
processing techniques, as indicated in Table 1.2.

pvc
~
ftgd- plasticized - PVC
E I 5 I B E I 5 I B
processing K - valves K -values

calendering 160-
65) 7-6$ 7-6$ 70-80 6$-70 70
thermal refmed
films
75-81) - - - - -
floor covering - - - 60-81) 6O-1[)
~xtrusiQl1 d rigo P.C
pressure ppes 70 ~7-6B 7-68
profiles 6$-70 65-67 5~
sheets and flot
films 60-6$ 60 60
blown films 60 57-60 60
..
ex tfusion of plo -
sficized - PVC
general 6$-70 15-70 6S-7C
coblemaferiols - 65-81)
mainly - 70 70
blCIN moulding - ~7-60 58-68 6S-81) 60-65
injectIon rro.1fdmg - 55-60 156-60 - 65-70 55-60
processing 01
postes - - - 70-8: 70-/11

7
TABLE 1. 2 Ranges of appli ca tion of PVC
 - 4 -

1.1.3 FORl4ULATION INGREDIENTS

PVC is unique in the fact that not only it may contain additives
to enhance specific properties, it must contain additives. Its
susceptibility to decomposition under the influence of heat, light
and oxidants, requires the constant presence of a stabilizer; to
facilitate processing lubricants and processing aids are used, and
other additives like plastiCizers, impact modifiers, fillers or
pigments are commonly added.

1.1.3.1 STABILIZERS

PVC can be easily degraded by heat and/or light. Its degradation

is characterized by change in colour, deterioration of physical
properties and liberation of hydrogen chloride. VCB has also been
identified as a product of degradationB. Stabilizers are additives
used to inhibit these effects. There are different types available:
i) lead salts, ii) metallic soaps, iii) organotin compounds,
iV) organic compounds, v) organophosphites and vi) epoxies. The last
three are commonly known as 'secondary stabilizers' because, not
being powerful enough by themselves, they are usually used in
conjunction with the 'primary' ones.

Lead salts will be used in this project. They are widely applied
because of their effectiveness and low cost. However, they cannot be
used for clear compounds, turn black in presence of sulphur containing
atmospheres and are toxic, their use being limited by legislation in
some countries. Tribasic lead SUlphate (TBLS), dibasic lead stearate
(nBLS) - which is believed to work both as a stabilizer and a
lubricant - and normal lead stearate are the major types.

The types mentioned are primarily effective against heat,

although some of the metallic soaps and organotin compounds have some
light stabilizing action. Generally, however, to obtain optimum
results it is essential to include a specific light stabilizer (eg.
organophosphites).
 - 5 -

1.1.3.2 LUBRICANTS

Lubricants are used to control the frictional properties of the

compound at the various stages of the fabricating process; they might
affect the adhesion of the material to the walls of the equipment, or
reduce inter-particle and intermolecular friction thus decreasing mel t
viscosity and frictional heat build-up. They are classified as
'external' or 'internal', respectively. When feeding powder along
the screw the external lubricant must impart a lower external friction,
whereas in shearing the melt the internal friction must be controlled
to prevent heat build-up; when the melt flows in the die a low external
friction will allow wall slip and a good surface finish. Lubricants
must therefore have a wide range of mel ting temperatures.

The lubricants used for PVC are usually fatty acids, fatty
alcohols, oils and waxes, some of relati ve high melting points. Some
common compounds, in order of decreasing compatibility (thus changing
from internal to external types) are: ethyl palmitate, butyl stearate,
calcium stearate, po~thylene wax.

1.1.3.3 OTHER ADDITIVES

In addition to stabilizers and lubricants, a PVC compound may

al so contain:
- Processing aids: these materials are often polymeric (typically
polymethylmethacrylate); they fuse (or become tacky) more readily than
PVC, thus forming a nucleus of fused material that works as a good
heat transfer medium for PVC and helping to increase the rate of fusion.
- Plasticizers: they are high boiling point organic materials
which convert PVC from a hard product to a more or less flexible one,
depending on the amount added to the compound (usually from 15-50%).
The general aspect of plasticizers have been analysed in the
li terature 9 •10 and will not recei ve further attention here.
- Impact Modifiers: these polymers of elastomeric nature enhance
the impact strength when mixed wi th PVC; their mechanism of action is
still under debate.
- Fillers: are added to a formulation primarily to reduce the
 - 6 -

cost, or to enhance certain properties. Their aspects have also been

9
discussed in the 1i terature •

The inclusion and percentage of all the mentioned addi ti ves in

a formulation will have decisive effects on i) cost-effectiveness,
ii) processing characteristics of the compound and iiU final properties
of the product. Knowledge of the influence of the addi ti ves in
presence of others is far from complete, so the formulator usually has
to rely on deduction from previous work, making formulation one of the
most difficult stages in the general processing of PVC compounds (as
an example of the development of a formulation, Kieferl l studies a
composition for window/door applications).

1.2 MORPHOLOGY AND MOLECULAR STRUCTURE OF PVC

12
In 1967 Berens and Fol t presented evidence that PVC resin
particles can act as the flow units in melt deformation processes.
One would expect the size and shape of the particles to affect the
melt flow behaviour. The particle structure, in turn, is controlled
by the type of polymerization process.

1.2.1 MECHANISM OF SUSPENSION POLYMERIZATION

In suspension polymerization the monomer phase is converted into

droplets by vigorous agitation in the presence of an aqueous solution
of a protective colloid. The suspension is continuously agitated and
maintained at constant temperature. Both the level of agi tation and
temperature have a marked influence on the grain structure; the first
influences porosi ty and grain shape, the second the molecular weight
and al so porosl"ty13 ("lncrease ln
" tempera t ure 0 f po1 ymerlza
" t "10n
decreases the molecular weight).

The general mechanism of suspension polymerization has been

13 15
described in the 1i terature - and is schematically represented in
Figure 1.1.
 - 7 -

W/'Ien
INIT~TION Formed FlI'tally
R'. VCM ~ COiled Macro Radicals @' ~

1s1 AGGREGATION STEP ... - 50 er;

Micro OOIT.,.,n ® 100 -2ooA ?
,ind AGGfI~Q.~Tl0!j STEP ~ • 10 3

("';m~~::;"U'1 '$'
p,l!OWTH (INTRA - PRIMARY) ...

~;;~~O Q-6-Q-e,..m

3rd AQGREG.!TIOtL§J.£P .. 1Scale 4·'O~

A."om.,," ~
Q...8.Q'tITH t INTER· PRIMARY) II Scet.

~=@~
FIGURE 1.1 Schematic representation of the mechanism of VCM
13
polymerization

It is clear that the growth of PVC takes place through a series

of aggregation steps. In the early stages of polymerization a skin
or pericellular membrane is formed by graft polymerization of
poly(vinyl alcohol) and poly(vinyl chloride) from the interior of the
droplet. As polymerization continues, this membrane develops to a
15
thick wall (around 10-20 nm ) that completely covers the surface of
the granules. Because of the agitation the skin is unable to retain
the stabilizing chloride ions inside the droplet, hence allowing a
network formation to take place. From aggregation of coiled macro-
-radicals the first morphological unit - the microdomain (20 nm) is
produced. The domains are formed by large agglomerations (around
1000 units) of these, consti tUing primary particle nucleus. These
will grow, and in the range of 3-10% conversion will become unstable
and flocculate to form aggregates of 1-2 \lm in diameter. Further
 - 8 -

polymerization after this stage produces a gradual increase in size

to 2-10 !lm.

At high conversions, and because the material is more dense than

water, the particle collapses bringing all the beads into contact,
15
and giving rise to the irregular shape of the grains

1. 2. 2 MORPHOLOGY

~lhen describing the mechanism of suspension polymerization some

morpholOgical units were identified, namely agglomerates, primary
particles, domains and microdomains. The presence of a skin surrounding
the surface of the grains was also mentioned.

In the literature most investigators agree that PVC grains consist

13 27
of agglomerations of primary particles - , but the terminology used
to describe the morphology is varied and confusing. In an attempt to
28
obtain consistency, Gei1 published a table with proposed terminology.
This formed the basis of the nomenclature proposed by A1lsopp13 and
adopted here (Table 1.3).

TABLE 1.3
PVC :"omcndarure
--------------
Term Approxil1wf(' .f;:t' PI'('I"ic!II.~ f('rmil/')/O!!l"
Rang!' Arcragl' (with n:/('n'llt"l'.\)
film) fill")
--
Grain 5D-2S0 1)0 Visibh: con~iilUt'nlS ur free !l\)wmg. powders. made Granulc~
up of mor~ th.ln I nh'n\)mCr drllplcl. Cellular grain ,I
Suh-gr:lin 1])- 150 Pol) IllcriscJ mnnM:1cr Jrl"'lpkL Sub-granu!c:
CniccW
Agglom~ratc 2 10 5 Formed dUring ~.Irly st.lge \)1' rnl~mCflsatlon b~ Aggrcg;lte~
l'l1;!lc~ccncc
\11' primar~ particles (I 2/lffi). Gro\\s Cluster J
with COn\Cf~ll'n In :-.IIC ,ho\\o. ~1acro-glohulc.l

Pnm<lry Ot> 0& 0·; Gr0WS from d . ,main. Formed at Il'\\" comersi(ln \1~crogranul~ •
particle (lco;s than 1".,) h) cl';!I~scence of micro-d(1main: Primary parta.:k-
grows wilh cllilh'rsilltl to ~i7C ~h,.'~\n. Granule"
\1icro-glohulc 4
Domain 0·1· 0-2 o<:! Primary particle nlu:leu:-. Conlain~ ahout 10) micro- Primarv nt!c!eus~
(200 om) domains. Onl\' obscrved at low con\crsion (less Granufe J
(2000A) (If after m.:...:hanlcal ~H1r"ing. T.:rm only
U
than 2 ,,)

used to descrihe 1)·1 pm ~p'~'t.'ics: hc('"ome~ primary

panide as soon a~ !!Jowth starts.
l\.1icro-dClmain 0-01 0-02 ::::0·02 Sm,lllest ~pC(ies so f,IT idenlif:ed. Aggrcg.llc of Basic particle:
(20 om) polymer (bir.s--pr,'b~lhJ~ ahollt 50 in number. P..!rticlc-'
(200 Al
- - - - _.._-----_.
"'·ore'.f
1. The domain is not a feature of PVC morphology in high coO\crSll'll polymer s;\mpk~ since a growth of this ~pecies \\ ilh con\'crsion obliterates
ull memory of it. It may only bc 'regeneratcd' and obs/'ncd !tftcr subcqucnl proces~ing.
2. As soon <lsfl1rmation ofthcdomain is c0mplclc and growth is fI:gi~tcred it;~ preferahle toc,lll it It primary part;..:le. Therefore. the term domain
is often ignored in favour of primary particle even at the poin! of morphogenesis of the 0 2 Jlm primaries at low conversion.
3. The reason for a separate identity for the domain is th:n it may h<,'l-hown in future to contain ,10 atypical morphological or molecular feature,
e.g. higher le,e1 of crystallinity.
 - 9 -

13-22
From the reports of several authors an idealized model of
the PVC grain can be defined (Figure 1.2).

'·O}Jm
. PRIMARY PARTICLE
- ---... """ ," SUB··GRAIN 50ym
Y'
200 A
MICRO-DOMAIN
\

~\ I~::~,~~b~~;CLE
"

AGGLOMERATE [
5pm

"-
2000 A "MICROOOMAINS
0·2 pm DOMAIN
,/'" / 200A(10nm)
(PRIMARY PARTICLE
at 2". conversion)
---
13
FIGURE 1.2 Hodel of PVC grain morphology

A suspension polymerized resin consists of grains of 100-150 ]Jm

in size, surrounded by a protective colloidal skin. Each grain is
formed by agglomerates (5-10 ]Jm) of primary particles (1 ]Jm),
agglutinations of agglomerates being identified (sub-grains). The
primary particles are made of smaller structures, the domains (100 nm)
and the microdomains (10 nm). The grains can have a number of forms
and shapes, as described by Tregan and Bonnemayne 29 •

1. 2. 3 t10LECULAR STRUCTURE AND CRYSTALLINITY

If the morpholog".)' of Pile as described above can be considered to

enjoy a general consensus, PVC's microstructure is still the subject
of research. It is agreed that the microdomain structure is the site
for eventual cryst2-llini ty, but the relationship bet"een both is not
unde rs tood ye t.

PVC has a fundamental repeating unit - CH CHCl -. The chloride

2
atoms can be disposed in three different ways with respect to the
backbone, giving rise to configurational isomers termed as isotatic,
 - 10 -

syndio·tatic and atatic:

- CH -CH-CH -CH-CH -CH-CH

2 2 2 2
I I I
x x x

Isotatic

x x

- CH -CH-CH -CH-CH -CH-CH

2 2 2 2
I
X

Syndiota ti c

- CH -CH-CH -CH-CH -CH-CH

2 2 2 2
I I
x x
Atatic

The first two are regular. but the third is random. By

crystallini ty one generally means three-dimensional molecular level
structuralorder. The ability of the PVC macromolecules to pack in
an orderly crystalline array is determined by the regularity of the
polymer chain. Changes in the chain regularity can be due to
difference in tactici ty. in the degree of branching or in monomer
addition (head-to-head or head-ta-tail). It is believed that in PVC
crystallini ty is related to the presence of short syndiotatic
sequences22.36.37 .39. the degree of syndiotactici ty correlating well
wi th the degree of cry stallini ty39 The presence of syndiotactici ty
increases wi th decreasing temperature of polymerization. The degree
of chain branching of PVC is estimated to be about 0.2 to 2 branches
per 100 carbon atoms; it also decreases with decreasing polymerization
39
temperature
 - 11 -

The crystal structure of PVC was first investigated by Natta

30
and Corradini who concluded that the material crystallizes in the
orthorhombic form. This result was later confirmed by other
reports 31 ,39. However, Henil 2 found the crystals to grow in a
lame11alike fashion, clustering together in stacks of two crystals,
33
and Summers put forward a model where the crystals are of platelet
type (Figure 1.3), connected together by tie molecules having a 10 nm
spacing (Figure 1.4).

FIGURE 1. 3 Average crystal FIGURE 1.4 The microdomain

33 33
size of PVC structure of PVC

The degree of crystallinity of PVC made at normal polymerization

temperatures is usually reported to be between 5_10%22,25,34-37,39,40;
some authors were, nevertheless, unable to find any crystallinity at
38
al1 •

For conventional PVC, effects attributed to the mel ting of

crysta11i tes have led to estimated melting pOints from about 180-200
39
to 210_250 oC • Hi th the aim of explaining the anomalous flow
behaviour of PVC melts, some attempts have been made. to correlate
crystallinity with microstructure. This subject will be discussed in
later sections.
 - 12 -

1. 3 THE RHEOLOGY OF PVc.

In the early 1960's, despite treating PVC as a normal polymer

mel t, investigators had observed some peculiarities, namely
25 :

i) pecrease of' apparent viscosity with increasing particle size,

ii) extreme non-N.ewtonian character of' the flow curves,
iii) increasing die-swell with increasing temperature.

In 1967, twelve years after the postulation of 'supermolecular

41
flow uni ts' by Hooney and 1'101 stenholme ,Berens and Fol t
12
showed
that resin particles had maintained their identi ty and shape during
the melt flow; this led to postulating that mel t flow occurs largely
by rolling and slipping of the polymer particles past each other.
Berens and Fol t 12 ,17 also showed that the identi ty of the PVC particles
is largely lost when the melt is processed above 200°C: rapid molecular
interdiffusion of PVC across particle boundaries occurs, the
characteristic particle slippage flow process behaviour being obscured
by an increase in the homogeneity of the melt.

Further evidence for the presence of two distinct mechanisms of

flow was reported by Collins and Krier42 • The flow of a PVC dry-blend
was found to have two different activation energies in the range of
temperatures from 160 to 230°C, both at constant shear rate and shear
stress (Figure 1.5). The low temperature range was characterized by
the predominance of' particle flow and a low activation energy at
constant shear rate (10 Kcal/mole), whereas in the high temperature
region, where molecular flow becomes important, its values were of
20 Kcal/mole. The transition from one flow to another was attributed
to the melting of crystalli tes. Later, Collins and Hetzger
43 showed
that the dual value nature of the activation energy was also common
to suspension polymerization. Similar results were reported by
Park167 for elongational flows.

The works mentioned originated a new approach to the study of PVC

mel ts. Realizing that processing is made below the crystalline melting
poin t, thus in conditions under whi ch the supermolecular structure can
lead to peculiar rheological behaviour, some attempts have been made
 - 13 -

O.on R•• tn. 10lEP F24

·......
• 1.0 uc-l

·••
•"
of "
1$0

.l!
•

FIGURE 1.5 Viscosity vs reciprocal temperature at constant shear

42
rates

to explain the anomalies in terms of a network structure formed by

crystallites in the melt - this will be dealt with in section 1.4.

1Vi th commercial compounds additional complexities are introduced

by 'the presence of additives:

- Change of flow properties with time and thermal history. These

effects promote the breakdown of the grains, i.e. the fusion of the
resin. Heasurements are usually carried out in a Brabender
Plastograph 20 ,24,27, roll mill or extruder.

- Slip flow. Lubrication, as referred in section 1.1.3.2 prevents

the adhesion of the polymer to the walls; the re suI ting slippage
strongly decreases the extrusion pressure and enhances plug flow.

- Viscous Heat Generation. Given the high viscosi ty and the

marked non-Newtonian behaviour of PVC, the influence of viscous heat
generation should be taken into account even at relati vely low shear
 - 14 -

rates; this is however a difficult task unless both the axial and
radial temperature profiles of the melt flow are known.

Some revie1-ls cover to a greater extent the effects mentioned.

Collins 44 considers particulate flow, true melt flow and the flow of
PVC compounds; Pezzin 37 and Henges and Bernsten 45 identify the peculiar
aspects of PVC rheology; Hwo and Johnson 46 review the experimental
data on concentrated solutions and PVC compounds.

1.4 SINGLE AND T~:rN SCRIDl EXTRUDERS

1.4.1 COMPARISON OF CHARACTERISTICS

1.4.1.1 INTRODUCTION

'If your single screw extruder is doing an efficient, high quality

job for you, then continue to use it. Twin screw extruders are not
necessarily everyone's panacea '. 1vi th these words of advise, Prause 50
initiated one of the many reports published in the literature 47 - 61 ,137
of single vs twin screw extruders. Twin screw extruders are dominant
in Europe for the extrusion of PVC dry blends, whereas in the U.S.A.
single screw extruders - often with complex geometries - are common.
Thus, it is not surprising that much of the literature was published
in this country 47-52 , by . .
~ndustrlal workers
47-55 59 61
" , some of them
working in design of processing equipment50 - 52 ,61

It is very often claimed that twin screw extruders: i) can handle

47
slight variations in compounds better than singles , ii) have less
energy costs due to smaller drive units 47 ,50,55-58, iii) use cheaper
compounds because the material is processed at lower temperatures and
there is less shear heat bUild_up 47,50, iv) have higher outputs than
singles with a surge-free melt discharge 47 ,50, v) achieve a good
control of the melt temperature13 ,49,52.56,131, vi) have a self
cleaning action 50 ,51,55,61, vii) produce a very homogeneous product50 • 61
Single screw extruders are claimed: i) to be mechanically much simpler,
hence necessi ta ting less maintenance time 47,51,53,54, ii) to need lO1-ler
capital investments 47 ,54, iii) to have cheaper replacement costs for
 - 15 -

parts 47 •Some manufacturers also claim that both the compound and
. ·1 ar47 •
energy cos t s are Slml

It is universally agreed that the major difference between the

two types of machines is the conveying mechanism. In the single screw
extruder, this is based on frictional forces in the solids conveying
zone, and viscous forces in the melt conveying zone. Thus, the
process is highly dependent on the frictional and viscous properties
of the material, themselves dependent on the temperature and difficult
to compute because of the presence of the additives 55 • Twin screw
extruders (this discussion is limited to the intermeshing counter
rotating type) have the so called 'posi ti ve conveying characteristics'.
The flight of one screw fits into the channel of the opposite screw,
creating a compartment in which the material is trapped; as the screws
rotate, the material is prevented from rotating as well and passes to
the next compartment. The better the seal between the flight of one
screw and the channel of the other, the more positive will the
conveying characteristics be. The frictional and viscous properties
of the material will therefore have a minimal effect on the conveying
behaviour.

Single screw extruders are usually operated at high screw speeds

with the aim of putting enough work on the material, and so ensure
. 47 ' 49 , 55 • However, if this has the advantage of giving
adequate fUslon
higher outputs, it also generates frictional heat that has to be
controlled. Not only this is difficult to do, it makes it harder to
achieve steady-state conditions. "li th varying temperatures the
posi tion along the screw at which melting takes place is liable to
change, causing fluctuations in the output, unsteady intake of feed
stock and uncertain venting51 ,53,56,57 • Also, if processing UPVC,
prolonged exposure to high temperatures demands the use of larger
amounts of heat stabilizers and processing aids, thus sacrificing
physical properties to some extent. From the energy point of view,
high speeds mean more power to the drive unit, usually more expensive
than for barrel heaters, due to losses in the gear system and bearings;
fUrthermore, an important part of this energy is lost through the
cooling water, specially in the feed section55, 56.
 - 16 -

Twin screw extruders heat the melt mainly through controllable

external heaters because they do not generate excessive frictional
heat. However, if the gap between the screws is too small, the
material will be subjected to high shear force~. Hence, a minimum
gap is a must, but this implies loss of the self-cleaning action
and limited screw speed, ie. throughput50 ,52,53. Moreover, because
of the positive conveying action, overloading of the feeed section
is possible, unless mechanical devices are used 50 •

Prause's advice seems therefore relevant. Comparisons of capital

investments and energy costs cannot be made just in terms of the
geometry of the equipment, but 'only on output and final quality of the
extrudate. It must be also kept in mind that each machine requires
its own specially designed composition for optimum results. A more
detailed discussion on the general characteristics of each type of
machine follows.

1. 4.1. 2 SINGLE SCREl~ EXTRUDERS

Present day plastics extruder technology has developed from

knowhow from rubber extrusion (some good historical reviews are
available in the literature 62 ,143). It has always been the aim of
workers to develop models that could correctly describe the behaviour
of a processing machine in order to be able to optimize its
performance, determine its melting capacity, evaluate the overall
characteristics of the screw, predict eventual instabilities and
make scaling-up rules available.

In a conventional single screw extruder the solids usually flow

gravitationally in the hopper and into the screw channel; here they
are conveyed, compressed and melted, mixed and pressurized, finally
flowing through the die. These steps correspond roughly to the three
zones (feed, compression and metering) one can usually identify in a
screw.

The available mathematical models describing the whole process 63 ,64

were generally put together from work previously developed for each
one of the stages. These will therefore be analysed separately.
 - 17 -

Feed Hopper. - in a column of particulate solids contained in a

vertical bin, the pressure at the base will not be proportional to the
height of the column because of the friction between the solids and
the wall; instead, a complex stress distribution develops in the system,
which depends on the properties of the solids and loading method 64 •
\valker65 has derived equations for the pressure distribution in both
vertical and convergent bins, assuming stress equilibrium at the base
of the hopper.

Solids Conveying Zone. - the solids conveying mechanism is one of

drag-induced flow, ie. flow due to the frictional drag of the barrel
and screw surfaces on the solid polymer particles. Following the
original work of Darnell and Mol1 66 , some refinements were later
applied to their one-dimensional plug flow model 67-71 The models
allow, at least to some extent, to account for pressure and temperature
build up. Once the material's melting point is reached, the frictional
drag mechanism changes into a viscous one. The models require an
estimate of the inlet pressure under the hopper, thus connecting the
extruder to the loading stage. This is because under certain
condi tions, small variations in the solids height in the hopper
creates pressure surging near the die 64 • It is therefore safe to
operate with a good level of material in the hopper.

Melting Zone. - qualitative understanding of the melting mechanism

was first obtained by Maddock 72 and Street73 , who developed an
experimental technique still used today: after allowing the extruder
to operate at a steady state for some time, the rotation of the screw
is stopped, both the barrel and the screw are chilled, thus qUickly
solidifying the polymer in the screw channel; the screw is then
removed from the barrel, and the polymer uncoiled from it; sections
perpendicular to the flights are cut and examined. To help the
visualization of the process, often a small fraction of coloured
polymer is added as a tracer.

According to their observations, the unmelted polymer travelling

in the feed section reaches an axial position when the barrel is heated
above its melting point; a film of melt is thus created between the
surfaces of the solid mass and inner barrel; this film is intensi vely
 - 18 -

sheared, thus generating more heat, and increasing in thickness. Until

the melt film is thinner than the gap between the tip of the screw
flights and the barrel surface no other evolution seems to be
noticeable. After a few turns, however, the film thickens beyond the
clearance and the flights start to scrape the melt off the barrel,
forcing it to accumulate at the pushing flight, thus creating·a melt
pool (Figure 1.6). In this, a particle has a circulatory flow
al ternating between two positions; in the upper it moves towards the
pushing flight, whereas in the lower towards the solid bed. The solid
material flows continuously into the melt film interlayer, being
melted there. The melt accumulated at the pushing flight exerts a
pressure on the solids, which pushes it towards the melt film; thus,
the height of the solid bed remains constant, its width decreasing
until a limiting value is reached, when it collapses and 'dissolves'
in to the mel t.

olten film
borrE'1

.~~~¥~~:~~~~~k)~~{~·
."; solid bed ..,'.~~

~~%%.~\~.
'.
,", " ",", .screw.

FIGURE 1.6 Maddock melting mechanism

74 77
Based on this model, several iterative numerical - and
. 78-80
analyt2cal methods were developed; indeed, most of the published
mathematical treatments were made following the observations of
Maddock and Street.

81 84
Other mechanisms were, however, reported in the li terature - •
81
Menges and Klenk were the first to observe that PVC compounds (both
in granular and dry blend form) create the melt pool near the trailing
flight. Furthermore, they refer that the model of Maddock and Street
can only be applied to medium and low viscosity, wetting thermoplastics.
According to their observations (Figure 1.7), in the feed zone the
powder moves forward, while being heated by the internal barrel wall and
 - 19 -

sintered (zone 1, a). Depending on the gap between the barrel and
the flight of the screw, a certain amount of powder or sintered
material is pressed between the screw land and barrel, subjected to
intensive shear, and consequently melted and homogeneized (zone 2, a).
This material is brought to the gap by movement of the screw and
positive pressure build-up. Zone 2 will increase by deposition near
the trailing flight due to constant addition of sheared material.
While this process takes place, and due to both heat conduction and
frictional heating, the material near the screw also sinters (zone
1, b). lolhen reaching a certain temperature, this sintered material
is converted into a plastic state (zone 4, b, c). This sintering/
/plasticization process progresses to the channel centre (d). The
cooler powder will remain inside the channel, and because it still
contains air, this will·be trapped and carried along with the melt,
leading to voids in the final extrudate. Thus, in this process there
is material melted and homogeneized by shear (zone 2), plasticized
by conducted heat (zone 4), sintered (zone 1) and material only warm
(zone 3).

a .........~""""""""'
..
direction of melt flow

.. ,...'~ ...~.L...~)_'

~---

, ~i+~~~~:;@~:: . . ·./::~
. . '. 'trapped ~ir'
f0~#;A~'''''if:C;~

81
FIGURE 1.7 Melting mechanism for wall-slipping thermoplastics
 - 20 -

The authors conclude, therefore, that this mechanism cannot provide a

85
homogeneous extrudate, and in a second paper advise the use of
specially developed screws for PVC. This work was generally supported
by Gale 82 • No mathematical models for this mechanism are found in the
l i terature.

83
A third melting model has been observed in large extruders ,84.
In contrast to the previous mechanisms, it was observed that the melt
accumulates in the melt film itself, thus it is difficult to identify
a 'melt pool' (Fi gure 1. 8).

mE'tt
3
( granules " J
4 10
t)·~~{ q
11

r
4
.. )
5 11
C.'..,;; !J
12

5 6 12 13
r
6
j
7
(:Y.,;C::;:;;.;,;"
13
t =51

14
~ =- ~
\0 /##§##%W44##i~'3t±5 '!/
7 8 M 15
\ '/1,Wv)'?w!t?mj/22h /4:<;1iJ
~ • ~ mett "
8 9
~€ )J
9
~o
~

84
FIGURE 1.8 Melting of polypropylene in 90mm single screw extruder

Lindt84 developed a mathematical model for this type of mechanism.

From the calculations, he concludes that the force (F ) acting upon
x
the solid bed and being responsible for the formation of a melt pool
depends on the character of the melt circulation rather than on the
clearance flow alone. His calculations suggest that F decreases with
x
increasing down-channel pressure gradient ap/az. This is due to
increasing rate of pressure flow through the clearance and to its
interaction with the rest of the cross-channel circulation. At small
(and negative) ap/az, F > 0, ie., the force generated pushes the
x
solid bed against the passi ve flight - Maddock and Street mechanism.
vii th rela ti vely small ap/az, and if the thickness of the upper film
is smaller than the one of the lOHer film, F is very small; in this
x83
si tuation the mechanism described by Dekker occurs. At large
 - 21 -

ap/az the cross-channel force is predicted to reverse its direction

(Fx < 0) and consequently force the solid bed against the pushing
flight; hence, Lindt confirms theoretically the mechanism found by
Menges and Klenk, for large down-channel pressure gradients.

lofetering Zone - this zone received quite early attention from

researchers; this was not only because a 'homogeneous' melt phase was
present, but mainly because it was recognized that it "as important -
given the operating conditions and the physical properties of the
fluid - to know the flow rate and the temperature at which the polymer
is discharged from the die, as well as the required power input to
" 60 74 86-88
pump ~t. Theoret~cal models were therefore developed ' ,

Three types of flow can be distinguished:

- drag flow, producing a forward component in the melt flow,

resulting from the velocity difference between barrel and screw
(Figure 1. 9) ;
- pressure flow, in the form of a return flow, as a result of
pressure generation at the die (Figure 1.9);
- leakage flow over the flights of the screw •

. -",''-' "

P,:> 0 ,
_::=t _ _
v "------tv
1.1 Ibl

FIGURE 1.9 8 drag flow and b pressure flow

For hydrodynamic purposes the latter can be considered as a

second order effect, hence the throughput can be expressed as the
difference between the drag and pressure flows.

The combined downstream and transverse velocity profile is

illustrated in Fig. 1.10. Tl1e effect of the superimposed downstream
flow is to cause the melt to move in a flattened helix along the screw
channel. The path of a fluid particle anywhere in the channel cross-
 - 22 -

-section can therefore be theoretically predicted. This is

fundamental for mixing studies (section 1.4.1.4).

FIGURE 1.10 left: circulation of a fluid element as it passes down

the screw channel; right: combined downstream and
transverse channel flows

1.4.1.3 TIiIN SCREW EXTRUDERS

The different types of twin screw mechanisms are shown in

Figure 1.11. It is immediately apparent that these devices are much
more complex than the single screw machine, and will behave very
differently from each other. Thus, it is not surprising that the
less extensive literature is spread over the various geometries. This
discussion will be limited to the case of the intermeshing counter
rotating twin screw extruders. These machines can have a parallel or
conical screw configuration, but the principles are similar.

The geometry of the screws .form C-shaped chambers (Figure 1.12)

that convey positively the material to the head of the extruder. The
profile of the screws is designed in order to define feed, compression,
degaseification and metering zones.

Feeding Zone. - in order to feed as much product as pos~ible, the

.-----.
screws turn outward on top. Due to the calendering effect. solids are
forced between the screws and crushed. As a result, the screw elements
 - 23 -

are forced apart in rul angle at the top. possibly c~eating severe wear.
This can be minimized by an increase of the gap and/or lower screw
speeds.

SCREW SYSTEII COUom:R-ROTATING CO-ROTATING

ENGAGEIIENT

~
LENGTHWISE AND THEORETICALLY
CROSSWISE CLOSED NOT POSSI6LE
i I 2
~~
.~§
LENGTltWISE OPEN TltEORETICALLY I
... '" AND
•r , ..... '-
~=
NOT POSSIBLE 4 ,-~
CROSSWISE CLOSED )
Cl

~
Z i LENGTltWISE AND
CROSSWISE OPEN
TltEORETICALLY POSSIBLE

5
BUT PRACTICALLY
HOT REAL[~ED li G =UID1--
SIa: LENGTHWISE OPElj
.-~.
THeORETICALlV
AND - .....
i ~-
...
~
~ CROSSWISE CLOSED 7
_.
~~
~

8
NOT POSSIB1.E

:'! .. ~-
.~:= ~
.....
I-lI
a: a: LENGTHWISE AND 9A -~- lOA " .
CROSSWISE OPEN
~ :h~-
1£~.
'.",J!.~~
·'· ....~~1-::d"1
_ ..... ~~."' ....
..
9B 'OB .~ .~.~-

"zor "zx
~ tHlB
1-'" I- •• LENGTHWISE AND
0!i
i la:
i
Za:
..
~
CROSSWISE OPEN

11 12

FIGURE 1.11 Types of twin screw mechanisms 89

Tr-"nspot"'ldU"Q;Cllo n
•

FIGURE 1.12 left: a C-shaped chamber; right: various leakage flows

in the extruder 58
 - 24 -

Desaseification Zone. - tbe solid bed is continuously interrupted

by the flights of one screw, and gases present can only escape through
the gaps; however, if the polymer is partially molten it can seal
these gaps and hinder gas flow, thus creating the need for a
degaseification zone.

Metering Zone. - Schenke1

60 derived the first equation for the
output of a multi-screw extruder (number of C-shaped chambers becoming
free per unit time multiplied by the volume of one chamber; for a twin
screw machine Q = 2mNV with m the number of thread starts, N the
th
rotation speed and V the volume of the chamber). In practice the
output is smaller than predicted because of the presence of leakage
flows within the extruder. These were identified by Janssen 58 ,wto
also produced the most complete available study of these machines. A
Newtonian flow behaviour was used in the analysis. Recently Lai-Fook
and Isherwood 90 extended Janssen' s work to the power law fluid case.

Four kinds of gaps, with the consequent flows, can be distinguished

(Figure 1.12).
- flight gap (Qf)' between the flights of the screws and the
barrel wall;
- calendar gap (Qc)' between the bottom of the channel of one
screw and the flight of the other;
- tetrahedron gap (Qt)' between the flanks of the flights of the
two screws;
- side gap (Qs)' between the flanks of the screws perpendicular
to the screw axis.

The main driving force is the posi ti ve displacement action by

rotation of the screws; the back flow consists of leakages through the
gaps mentioned; the drag and pressure flows are limi ted to each chamber
and only influence the output through the leakage flows. Hence, if
these are disregarded, the output is rroPortional to the screw speed.
Because the solid bed is broken by rotation of the screws, no pressure
transmission can occur, and the throughput is independent of the die
pressure.
 - 25 -

The melting mechanism in these machines was identified using the

.
experimental techn1que of Maddock and Street58 " 89 91 It was observed
that the melting length is very short, the complete melting sequence
can be found within one chamber. Screw speed does not affect the
mel ting length, but only the location of the melting zone. Die
pressure affects both length and location: with high die pressures,
pressure build-up may start before the melting process is complete;
this leads to higher leakage flows causing the polymer to stick
together, preventing the tumbling action that ensures good homogeneity,
causing a delayed melting of some solid material and thus a longer
58
mel ting length • The general mel ting mechanism is schematized in
Figure 1.13.

-
-
~TI
FIGURE 1.13 Mechanism of fusion within one C-shaped chamber when
working with polypropylene powder and left: low die
pressure, right: high die pressure 58

At low die pressures the prinCiple of the melting mechanism is

similar to the one of single screw extruders 58 ,89 i) development of a
melt film on the barrel wall, ii) scraping off the melt film by means
of a pushing side of the flank, iii) collection of the melt in front
of the pushing flank. At high die pressures, because the powder is
compressed into a strong solid bed, the melting process seems to start
 - 26 -

from the leakage through the gaps, and then penetrate in the chamber.

The reports on conical twin screw extruders seem to be almost

limited to the processing of PVC 48 ,49,91-93,132. I t is usually claimed
that compared to the parallel machines they offer some advantages:

- the wide spacing of the Screw axis at the feed end allows for
more room for thrust bearings;
- large diameters at the feed end facilitate the installation of
screw temperature control equipment;
- at the output end, the smaller diameter of the screws leads to
lower shearing speeds.

The manufacture of this type of geometry is, however, more

difficul t and expensive. Also, unlike the parallel configuration, it
is impossible to vary the screw(s) profile by interchanging of screw
elements.

1.4.1.4 MIXING CHARACTERISTICS

1.4.1.4.1 Residence Time and Residence Time Distribution

Residence time may be defined as the time a portion of material

being processed is exposed to a certain heat and shear load.
Particularly in the case of PVC where problems of sensi vi ty to heat
and need of good mixing with additives arises, the knowledge of the
Residence Time Distribution (RTD) is relevant: with this the flow
condi tions can be more easily understood, thus providing useful
information on the degree of mixing, life expectancy of particles in
94
the extruder and degree of degradation • The time needed for a
routine switch from one material to another can be calculated. Also,
when the velocity profiles in the machine are unknown, RTD can provide
information on the conveying mechanism of the machine 48.

Danckwerts's work on scale of segregation led to the development

of the RTD functions 95 - 97 • The most commonly used in the 'cumulative
residence time distribution', F. It represents the amount of flow at
the exit of the system that has spent a time t or less in the system.
It is obtained by integration of f(t)dt, the 'external RTD function',
 - 27 -

representing the fraction. of flow at exit that has spent a dwell time
in the system between t and ttdt.

(1.1)

Simi1ar1y,a 'residence time distribution' E(t) can be obtained

by integration of the 'internal RTD function', representing the
fraction of material in the system with a residence time between t and
ttdt.

The experimental residence time distribution is calculated using

the output concentration c of a tracer placed into the fluid system,
versus time t. If the distribution is only known at a number of
discrete points, it is defined as98-100:

i) Residence time distribution

C
i
E(t) = (1.2)
'"
I i lIti
C

i=O

ii) Cumulative distribution

i=O
F( t) = l: E(t).lIt = -00
-- (1. 3)
I i lI\
C

i=O

iii) Mean residence time

00

2 t. c. lit.
l. l. l.
i=O
t = 00
(1. 4)

I c. lit.
l. l.
i=O
 - 28 -

The variance, measure of the spread of the distribution around

the mean is 100

i=O
02 = =-"-----
co
(1. 5)

48 94 98-102
It is common " to plot the distribution functions in a
nonnalized fonn, against nonnalized time:

E( e) = t. E( t) (1.6)

F( e) = F(t) (1. 7)

o 2
P
e =0 (1. 8)
2 /

wi th e = tIt.

Two ideal systems are perfect mixing and plug flow (Figure 1.14)
defined respectively by the equations

F( e) = 1 - e -e (1.9)

F( e) = e e<1
(1.10 )
F( e) = 1 e >= 1

LAMINAR PIPE fLOW

PERfECT MIXER

PLUG fLOW

FIGURE 1.14 F-Curves for various models available

 - 29 -

In the first case some of the input material is immediately

present in the output; also, some original material will remain mixed
with the tracer for much longer than the mean residence time. The
plug flow model is the other extreme: here, the new material never
mixes with the original, emerging at a time exactly equal to the mean
residence time.

The conditions in both the single and the twin screw extruder are
neither that of perfect mixing or plug flow. They will fall in between
these two ideals, allowing' for a characterization of the degree of
mixing. For both types of extruders, combinations of these flows have
been suggested and theoretical models developed.

Pinto and Tadmor94 evaluated theoretically the RTD function for

melt fed single screw extruders, using a parallel plate model and
isothermal Newtonian flow. This model cannot predict the influence of
process parameters on RTD. Nevertheless, it was used by Ingen Housz103
in an attempt to compute the thermal load in the channel of the screw.
104
Bigg and Middleman extended Pinto and Tadmor's model to non-Newtonian
power law model fluids, also using screws of uniform channel geometry.
They concluded that the shape of the F curve depends on both the power
law index and processing conditions. The lower the power law index the
bigger the deviation of the F curve from the Newtonian. case, the curves
becoming broader. For a particular power law index, the F curve is
similar to the Newtonian· case at low values of back pressure; if this
increases the curves broaden, indicating more axial dispersion 96 •
Eventually, at some value of back pressure, the F curve develops an
inflection point and begins to approach the plug flow response
(Figure 1.15).
. 98
l~olf and lI'hi te measured experimentally RTD in both melt and
plasticating extruders. The results were compared to the model of
Pinto and Tadmor and other mixing uni t operations. It was observed
that the solids conveying zone is very close to plug flow; in the
liquid conveying process the RTD function can be properly represented
by the model of Pinto and Tadmor; the RTD for plasticating extrusion
showed little difference from the melt extrusion process, hence the
model of Pinto and Tadmor was found to be the best theoretical
 - 30 -

representation of all the models compared. For both melt and

plasticating extrusion, between 60 and 70% plug flow was obtained.
The effect of operating parameters was also studied: no significant
effect on RTD was found by changes in rotational speed of the screw,
only some increase in mixing was detected by cooling the screw.

I. Gz =3. 2 .s
~~~/.• S
.8

.6

FII)
.4

.2

o.L-__ JL~ ____ ~ ______ ~ ____ ~ ______ ~ ____- L__

.S 1.0 I.S 2.0
Ij f
8

FIGURE 1.15 F-Curves for a fluid with a power law index of 0.4 at
various dimensionless back pressures 96

Lidor and Tadmor105 computed theoretically the RTD for plasticating

extruders of constant channel depth and barrel temperature.
Considering a Newtonian flow, they divided the channel into small
increments and followed the path of fluid elements from hopper to die.
The effect of operating conditions and screw speed on RTD were studied
only by computer simulations.

The work of Zemblowski and Sek102 was experimental. Changes in

the resistance to flow through the die head, screw speed and channel
depth were found to cause RTD to vary between the ideal cases of plug
flow and perfect mixing.

vlhen observing the extrusion of wall-slipping UPVC, Mennigl 06

 - 31 -

recognized that RT is dependent on whether and how much the material

slips on the barrel walls. He observed experimentally that with PVC,
unlike PE whereRTs are not dependent on the operating conditions, the
values are similar at equal barrel temperatures, but shorter for
higher temperature profiles. These re suI ts were interpreted as
evidence of wall slippage at lower temperatures.

The literature on RTD of counter-rotating twin screw extruders is

scarcer, because of the difficulty in deriving theoretical models.
Janssen et al 58 ,lOl developed a computational model assuming that the
C chambers along the extruder contain well mixed material. Both the
RTD and the mean RT were found to be very stable and practically
independent of operating conditions (pressure, screw speed and
temperature), in accordance with the theory developed. Only the die
pressure was found to have some influence on the tail of the RTD: at
higher pressures the tendency of the tail is to become shorter.
However, when plotting the measurements on a log-linear scale the form
of the tail of the experimental curves does not agree with the model,
showing that the material in the chambers is not well mixed as assumed.

Todd107 measured RTDs experimentally and concluded that the use

of low helix angles decreases axial mixing, as shown by the narrow
RTDs. Rauwendaal 48 observed a dramatic increase in RT and widening
of RTD when the throughput is reduced to low values. At low
throughputs and high screw speeds the leakage flows have a relatively
large effect on the conveying characteristics of the extruder; at
high throughputs and low screw speeds that effect is reduced and short
RT and narrow RTD are found. Rauwendaal points out that this is one
reason why twin screw extruders are used at low speeds: advantage is
taken from the posi ti ve conveying characteristi cs with re suI ting
narrow RTD. He concludes by stating that the conveying characteristics
of the single screw machine compare favourably with the twin;
apparently, in the first there is a strongly posi ti ve influence of
the long solid bed on the overall conveying characteristics. This is
53
in contradiction with the results presented by Fems (based on the
work of Hermann108 ): twin a::rew extruders exhibit shorter RT tails,
which indicates good self~cleaning action.
 - 32 -

The results published in the literature for both types of

extruders do not always agree. Perhaps because some works were made
using a limited experimental field, the influence of processing _
condi tions is not clearly defined yet. It must be also emphazised
that the use of F curves for analysing laminar flow mixing can be
misleading in some situations. From the analysis of the F curve, it
could be concluded that mixing in a pipe (Figure 1.14) is midway
between a perfect mixer and a plug flow system. However, if the two
components are introduced side by side, as in Figure 1.16, no mixing
will occur. RTD curves fail, therefore, to completely characterize
mixing in laminar systems because they cannot predict whether elements
of fluid with the same RT can be considered well mixed.

FIGURE 1.16 Side-by-side flow of two viscous fluids in a pipe under

laminar flow conditions 96

1.4.1.4.2 Strain and Strain Distribution

When two components are mixed the interfacial area between them
increases. Spencer and Wileyl09 developed a theoretical relationship
to predict the variation of that area during laminar mixing. They
concluded that an increase in the interfacial area is directly
proportional to total strain, and proposed strain as a parameter to
quantify mixing. It can be predictable from knowledge of the flow
pattern, and may be related to mixer geometry and operating
conditions 68 • Ina continuous mixer - as extruders are - superimposed
on the different paths of the fluid particles there is also a different
RT for every fluid particle in the system, hence an average strain
 - 33 -

must be computed.

McKelvey87 developed a model for calculating the average strain

of the system in a single screw extruder for an isothermal Newtonian
od Th e average s t ra i n ~s
fl u~. ° de fO~ne d by48,87,97,1l0

(loll )

where y is the mean shear rate and t the bulk residence time. McKelvey
concluded that the strain becomes very large for long screws with
shallow channels. For a given screw it can be made large by operating
it with a high ratio of pressure to drag flow (ie. small outputs) or
using very small or very large helix angles (the pumping efficiency
becoming then very low). Finally, McKelvey recognized that the fluid
elements passing through the extruder are not strained to the same
extent, the strain being a function of the position of the. element (in
fact it is inversely proportional to channel depth). In order to take
this into account, Pinto and Tadmor94 introduced the concept of
'weighted average total strain' WATS. (calculated by integration of the
strain of particles with respect to the RTD), which is a measure of
the total deformation experienced in the extruder. A high WATS value
indicates a well mixed extrudate. Pinto and Tadmor reported similar
conclusions to McKelvey's. Bigg and Middleman104 extended the analysis
of Pinto and Tadmor to non-Newtonian fluids; they concluded that
because the strain distributions are flat and similar in shape, there
is little difference between average strain and WATS. Bigg97 presented
the results of other workers on the influence of design and operation
parameters in extrusion, supporting the conclusions of Bigg and
Middleman: both the strain functions increase exponentially with'
decreaSing dimensionless output rate, the curves being numerically
close. Bigg also mentiolBs that the effect of non-Newtonian behaviour
is small.

Because in extrusion different parti cles experience different

strain histories, Lidor and Tadmor105 defined a 'Strain Distribution
Function' SDF, similar in concept to the RTD function. SDF has to be
calculated from the velocity distribution in the system, and cannot
 - 34 -

be worked out from experimental RTD fUnctions. .The authors,

therefore, conclude that experimental techniques have to be developed
for measuring SDF, since in many mixers theoretical evaluation is a
formidable task.

For simplicity, the use of average strain seems appropriate for a

single screw extruder. In the metering zone of this machine, with a
barrel diameter D, a frequency of screw rotation N, a channel depth H
and a bulk residence time t, the average strain is given by97

'ITDN
Y = -- t (1.12)
N
H

Establishing the strain distributions for twin screw extruders is

much more difficult due to their complex geometry. Consequently, the
literature is very scarcel11-114, and the models developed employ a
number of simplifications. Investigators 97 have therefore attempted
to use RTD data to quantify mixing. One procedure is to determine the
area ~ on a RTD curve between a perfect mixer and the one being
investigated and compare it to the area 6A between a perfect mixer
2
and a plug flow system. The resulting term, 'blending efficiency' 13,
is defined as 96 ,97

13 =1 - (1.13)

For a perfect mixer i3 = 1, for plug flow 13 = O. Hence, if 13 is a

measure of the degree of mixing, its values should increase with
increasing strain. Bigg and Middleman104 showed that this does not
happen, 13 showing a maximum at relatively small values of strain. It
was therefore concluded 97 that, like RTD, 13 is a measure of dispersion
in the primary flow direction, thus does not provide information on
48 used 13 values
mixing in the transverse flow direction. Rauwendaal
to support his results with RTD curves.
 - 35 -

1.4.2 PROCESSING OF UPVC

1.4.2.1 DRY BLENDING

High speed mixers raise the temperature of the powder by conducted

heat and heat generated from the high shearing forces imposed. A
vortex in the powder ensures that the ingredients will eventually come
into contact with the chamber wall and pass through the gaps between
blades and chamber. Frequently batches are taken up to 120°C before
cooling in another mixing chamber; allowing a further increase in
temperature would require longer cooling cycles and increase the risk
. . 27 82
of degradatJ.on ' •

Because the characteristics of the dry blend will affect the

processing behaviour, some investigations have been undertaken on the
general dry blending behaviour of PVC compounds and groups of
additives1l5 ,1l6 and on eventual changes in morphology and distribution
of individual additives 27 ,1l7,118. One of the most comprehensive
128
studies was carried out by l1iadonye who analised the effect of
blending conditions (rotor speed, mixing time and charge weight) on
the distribution of additives and morphological changes with two types
of mixers (double and Single layer arrangement). It was found that
double layer arrangements produce dry-blends with better stabilizer
distribution and physical properties; also, an optimum operating
window could be defined for each type of machine.

1.4.2.2 SINGLE SCREW EXTRUSION

The processing of PVC in dry blend form and the tendency of the
material to degrade under exposure to heat, with the consequent need
for narrow RTDs,has created difficulties in the use of the Single
screw extruder. Some work was done on the search for better design
of equipment81 ,85,119,120 but, generally, these efforts had limited
success. Due to the peculiar rheological behaviour mentioned in
section 1.3, the optimization of the process needs knowledge of:

- the melting mechanism in the channel of the screw, ie., how

 - 36 -

and where the melt pool is ·formed and progresses; how the efficiency
and mixing characteristics of the process are dependent on this
mechanism; how additives, particle structure and eventual slippage
at the wall will influence the mechanism;

the mechanism of gelation of the material, ie., the way the

original morphology is destroyed and the role of crystallinity in the
process;

- the influence of processing conditions in both the melting and

gelation mechanisms and in the final properties of the extrudate. The
latter will be dealt with in section 1.4.2.5.

1.4.2.2.1 Melting Mechanism

Of the melting mechanisms described in section 1.4.1.2. both that

of Maddock and Street72 • 73 and Menges and Klenk 81 have been observed
with UPVC. Klenk120 analysed in detail the latter mechanism.
postulating that high viscosity wall slipping thermoplastics always
follow it. Unfortunately. its mixing efficiency is limited, both melt
and sintered material coexisting in the tip of the screw.

Gale82.130 found that on decreasing the lubricant compatibility

in a formulation particle friction is reduced, so· that fusion rate is
decreased. A transformation to the model of Menges and Klenk occurs.
Gale points out that if fusion is late then the material passes along
a substantial part of the channel in an unstabilized state (the
stabilizer being present as a particle surface coating) which causes
Sufficient degradation for the centre of the particles to become pink
in colour. The Menges and Klenk mechanism was also found by Kulas
and Thorshaug1~ for both bulk and suspension polymerized resins at
lower screw speeds (up to 50 rpm). At higher screw speeds some resins
Changed to the Maddock and Street model in the compression zone, due
to decrease in viscosity caused by rise in temperature. The core
samples produced by Allsopp13 showed ~~at the fused material was at
the front of the screw channel. the solid bed existing along the
entire length of the screw. The melt pool represented at least 50% of
the channel cross-section. In their studies of wall-slippage of PVC,
 - 37 -

Mennig and Hegler106 ,122,123 found the mechanism described by Menges

and Klenk for wall slipping conditions. This mechanism can therefore
be considered common when extruding UPVC.

Even though a better knowledge of the effects of wall slip is

necessary, information is scarce106 ,120,122-124,144. A maximum of
wall sticking is necessary if the mechanical energy reqUired to melt
and homogeneize the material by shear deformation is to be achieved123 •
However, a certain degree of sliding can indeed be desirable to prevent
any particular portion of the melt being near the barrel wall for too
long. Slip occurs after a critical shear rate has been exceeded
against the barrel wall, but not on the screw122 • Wall slippage has
been primari:l¥ attributed to lead stabilization81 ,120 ,123. Its effect
decreases with increasing temperature and decreasing wall shear
stresses, but is to be expected at normal processing temperatures
between 170 and 210 oC123 •

The Maddock and Street model was observed by Tadmor and Klein 74 ,
25 and Shinagawa19 The particles are often found to be
Fahei
elongated in the down channel direction, but elongation is mainly at
the boundary with the rolling melt.

The progress of the melting mechanism can be further assessed by

computing the ratio of area of fused material over total cross-sectional
. t th e screw 1 eng th82,121 ,125 • Ku1 as an d
area 0 f th e ch anne1 ,agal.ns
Thorshaui 21 found that the rate of progression of the mel t pool often
decreased in the compression zone. This was found to be dependent
upon shear rate, lubricant content and particle structure: the more
compact resin particles are, less heat can be generated internally,
hence fusion starts:h the outer regions of the particles; if fusion takes
place inside the particles, the grain boundaries are still visible and
computed as solid in the ratio of areas, thus accounting for the
decrease in rate of mel ting.

Bowerman and McKelvey126 used a laboratory extruder to evaluate

die-induced viscoelastic phenomena (melt fracture, sharkskin and die
swell) and nerve; the first two were found to decrease with increasing
temperature and decreasing shear rate; die swell, as expected,
 - 38 -

increases with increasing temperature. It was concluded that nerve

is caused by incomplete fusion of the compound in the screw, or
failure of the flow process to deliver material at uniform temperature.
Despite the fusion mechanism not being reported, one can suspect that
the model of Menges and Klenk was applicable.

1.4.2.2.2 Mechanism of Gelation

The way the transition from powder to melt takes place is far
from being established. Mechanisms similar to the one found in the
Brabender Plastograph 20 ,24 involving major changes in particle size
are often reported, but a model in which particle breakdown plays the
13
minor role has also been described. There are three possible
routes for fusion 24 ,25:

breakdown of the grains to the submicron particles, compaction

of these and densification to form a fused material;

- breakdown of the grains into the primary particles, compaction

and internal fusion of these and diffusion, to form the melt;

- no breakdown but compaction and, under temperature and time,

internal fusion of the particles and interdiffusion to form the fused
material.

In the opinion of Sieglaff25 a combination of all three takes

place in commercial processing, shear being an important component in
the breakdown of the resin. The reports found in the literature
usually fall into the three types.

Hattori et al14 and Shlnagawa

. 19
describe the me chani srn of gelation
as being the process of breaking the original granules down to the 1 ].lm
particles and then (around 190°C) to fine thread s - fibril s - 30 nm
thick. These are considered to exist in the original structure. At
higher temperatures the breakdown is complete, and no noticeable
morphological change occurs. Experiments in an oven14 led to the
I
conclusion that heat per se can be effective in breaking down the 1 ].lID
particles, but the potential for breakdown becomes more efficient when
heat is combined with shear.
 - 39 -

22
Menges et al report that up to 160°C the powder grains slide
against each other; above this temperature, and depending on the shear
rate, the grains break open, the primary particles forming the unit
of flow; above 190°C these structures melt, the additives dissolving
or precipitating. If the temperature is further increased degradation
occurs. The crystalline regions, being physical cross-linking points
could be the real cause for the high stability of the primary
particles. These results are supported by Summers et al16 , who report,
in opposition to Hattai et al14 that the effect of temperature on the
morphology of the extrudate is much more important than shear.
Uitenham and Gei1 23 found the hierarchy of the grains to be
progressively broken down during processing; the grains break down to
10 ~m agglomerates and these to 1 ~~ primary particles, the major flow
uni t for most processing conditions.

In the works mentioned above, although the screw was extracted

for observation of the gelation mechanism, the evolution of the
morphology of both the solid bed and melt pool was not reported.

Fahey125 observed no grain destruction in the solid bed, the

grains persisting even after extensive intergrain fusion had occurred.
The melt pool was found to be composed of clusters of primary
particles in the early screw flights, but did not show evidence of
particulate structures of this size in later flights.

A more complete analysis of the gelation mechanism was reported

. 13
by Allsopp • In opposition to the creamy white of the melt pool, the
solid bed was found to be brown127 ,128, which was attributed to poor
stabilizer distribution. The material in the melt pool appeared to be
well homogeneized; in the solid bed, as one progresses along the screw,
the grains are densified, internal fusion taking place121 ; when in
contact with the barrel, the grains are subjected to high shear and
become highly elongated, until a mel t is observed; simultaneously the
additives, previously concentrated around the grain boundaries,
dispe~se into the melt. This mechanism has become known as the CDFE
mechanism (because it involves compaction, densification, fusion and
elongation) •
 - 40 -

The mechanisms of gelation described are summarized in Figure 1.17.

{9J @ ~ r-Y-J
@: 'COFE'
MECHANIS.... c::::P -+ ~
~'"""'..
Porosity
1 130pmGRAINIS
COMMI~TION
Qj~

ill
X ~tes MECHANISM
AdditiYes
~q . .
~oo
·"'b"d I
t:;:7 q. _c:::> •
r,/<? $ •
'<J ~ po IFINAL
• MELT
• I ~ECTION
0° 1-·.:
!-:.·.i IOF
iSHEAR
I .. i- .-.:..-- 1
~.---' ...

FIGURE 1.17 Mechanism of gelation during processini 3

1.4.2.3 TWIN SCREW EXTRUSION

As with the single screw extruder, the literature on the twin

screw machinery for PVC is spread over studies for the improvement of
the mechanical design131,134,138, the meltini 3 ,91,130,133 and gelation
mechanisms13 ,i6,128,135 and the influence of additives and processing
, , 130 132 133
cond~ t~ons on these ' , • A better understanding of the
characteristics of the machine is however necessary to improve the
design of the equipment, and this was the subject of a number of
, t' t'
~nves ~ga ~ons
48,91,92,120,132,133,136 •

133
Menges and Klenk found melt temperatures to be higher than the
set values, due to shear. Beyond the breaker plate, with increasing
screw speeds the temperature field develops from one temperature
profile (with the highest temperature in the core) to two, each one
originated by one screw. Klenk120 supported these re suI ts, but
Stasiek134 found exactly the opposite. Menges and Klenk also reported
periodic flutuation of pressure, which they attributed to pulsations
in the screw feed. The periods were found to be dependent on the
speed. The output also showed pulsations, as successive chambers are
120
descharged. Klenk also observed these phenomena, reporting that
they are due to varying pressure within the chambers, are more serious
 - 41 -

in starved extruders and can be minimized by proper design of the

screws. Doboczky137 derived a equation for the amplitude of the
fluctuations.

The average material temperature is believed to be easily

maintained by this type of machine131 Only with increasing screw
speed the temperature difference between set and real temperature
increases.

It has been generally found that the output rate is independent

of the conditions at the die 92 ,133 and that it varies linearly with
screw speed120 ,133,138; pressure increases directly with the
92' 138 • Gale130 reported that the ou tpu t ra te ~. s depend en t on
ou tpu t
the dry-blend physical properties: if the bulk density increases, so
does the output; above a certain level, however, the feed zone
(smallest feed volume .per revolution) is overfed, the pressure build-
-up profile altering completely. It is therefore advisable to use a
feeding device 92 ,120,138.

Reber91 points out that the top half of the screws runs partially
empty, except in the feed and metering zones, due to the counterrotation
of the screws. Here there is a considerable leakage flow, varying
from 35% of the total throughput rate in the feed zone to 160% in the
metering zone; 88% of the total energy into the polymer came from
mechanical work, more than usually attributed to these machines. Also,
because at the die end the screws are completely full, the loading
rate does not seem to affect the fusion temperature132 •

Some authors 92 ,136 have described the use of laboratory twin

screw extruders to assess the processing properties of different
compositions. There are however limitations in scaling-up to
industrial machinery due to the relative gap size, surface to volume
ratio and relative contribution of shear and conductive heatinl 2 •

Harhenkel138 examined the influence of operating parameters on

the pressure build-up. This becomes only measurable in the last third
of the screw, then rising very rapidly. Stasiek134 advises small
clearances in the feed zone, avoiding solids sticking to the screws
 - 42 -

and diminishing the chamber volume, to improve the output. With

smaller chamber heights the energy input by viscous dissipation will
increase, and residence time will be shorter. To improve mixing,
kneading sections should be inserted in the fully filled zone.

1.4.2.3.1 Melting Mechanism

It is generally reported that most of the length is occupied in

compacting and heating the PVC powder, mel ting taking place, quite
rapidly, towards the end of the screw. t1enges and Klenk133 found
melting to occur in the last screw thread over a length of approximately
1 cm, but mel ting is usually reported to occur in the beginning of the
metering zone over one or a few turns of the screw. The material
fuses in the intermeshing clearance and at the hot metal surfaces 91 ,
some fusion taking place before the fusion point: a thin skin of melt
is formed on the ribbons of the material extruded through the
130
intermeshing gaps. Gale found the mixing action to be such that the
unmelted powder is dispersed in layers with the melted material.

The higher the barrel temperature, the nearer to the input zone
does the material begin to plasticize128 ,133. As with the single
screw extruder, colour changes in the material along the screw were
observed13 ,128. Miadonye128 found the number of screw channels between
powder compaction and first colour change to decrease with increasing
tempe ra tu re •

130
Unlike Gale who reported the melting rate to be relatively
insensitive to changing screw speeds, Menges and Klenk133 observed a
shift of start of plasticization to the end of the screw with higher
screw speeds, as a result of the conflicting effects of dwell time and
heat conversion of mechanical energy.

138
Supporting the earlier work of Marhenke1 , other
investigators91 ,133 have found pressure to rise sharply after the
transition solid/melt to a maximum value at the tip of the screws.
 - 43 -

1.4.2.3.2 Mechanism of Gelation

Even in the absence of a separate solid bed/melt pool, the

different gelation mechanisms reported for the single screw extruder
have also been observed with the twin screw extruder. Summers et al16
reports that the 2 ~m primary particles form the unit of flow below
190oC; at 190°C agglomeration and better adhesion between the primaries
occurs and,' above 190°C, a continuous melt can be observed. The CDFE
mechanism was observed by Allsopp13,135 and supported in the
128
literature ,139,140. Some residual grain memory could be found in
the extrudate, but - according to Allsopp - it was lower than the one
with single screw extrusion. Also, the progressive fading of
fluorescence observed in the breaker plate and die means that the melt
becomes increasingly more homogeneous. Miadonye128 reported similar
phenomenon, although a decrease in fluorescence from hopper to die was
observed.

1.4.2.4 FUSION MODELS

The function of an extruder is to pump an homogeneous polymer

melt through the die, so that the right shape of melt can be produced.
Unfortunately, as seen above, the two types of extruders used with PVC
are far from full filling this aim. In the single screw extruder the
mechanism first described by Menges and Klenk 81 is commonly encountered,
causing poor mixing characteristics and unmelted material at the die
exit. In the twin screw machine most of the length of the screws is
used in compacting and heating the powder, thus also making possible
the presence of unmelted material in the final extrudate. This will
surely affect the physical properties of the product. However, even
if an homogeneous melt was obtained at the tip of the screw(s), one
would expect different physical properties of the extrudate with
varying processing conditions. This is because of the crystallinity
of the material; therefore, a knowledge of the way PVC grains break
down to a melt and the role of crystallinity in the various stages is
fundamental.

As described in previous sections there are two main routes for

 - 44 -

the fusion process. One seems to be typical. of the Brabender

Plastograph 20 ,24 and invol vas breakdown of the original grains to
smaller structures, the other, the CnFE mechanism, proposed by
Allsopp13,135 Both are supported in the literature16 ,22,23 and
128,139, 140 respectively
. One limitation to Allsopp1s mechanism is
the lack of explanation of the role of crystallinity: once the melt is
obtained, no further hypotheses are advanced. This view was extended
140
by Gilbert et al , by postulating a melting and recrystallising
process leading to a network formation of molecules linked by small or
imperfect c~stallites formed during the cooling that follows extrusion.

Unlike Allsopp, Krzewki and Collins 24 observed the breakdown of

the resin particles to smaller structures. Interdiffusion of these,
wi th the formation of a molecular network across their boundaries
commences, and with further progress the boundaries between particles
will disappear;the particles therefore lose their identi ty, and a
three-dimensional network of polymer chains is formed. The degree of
interpenetration of particles is a measure of fusion achieved, and
the determining factor of the strength of the fused material. The
structures formed from the breakdown of the grains can be either
primary particles or domains, depending on the thermomechanical
energy introduced into the material. Also, it can eventually happen
that primaries will breakdown to domains. If the units of flow are
the primaries and no further breakdown takes place, they will then
begin to fuse in ternally, increasing their internal strength: the
weakest link in this case will therefore be the interface between
primaries.

In the model proposed by Portingel127 breakdown of the. primary

particles takes place. The microdomains initially contain molecular
chains held in localized networks by association with crystallites.
As temperature increases these begin to melt, the molecular chain
mobility increasing. Shear will cause the breakdown of the primary
particles, thus permitting diffusion of the chains across the old
boundaries and entanglement wi th chains from other domains; the rate
will increase with temperature and shear. Fusion, as described by
this model, is therefore characterized by increasing molecular
 - 45 -

mobili ty and entanglement. On cooling. crystalli tes are reformed.

wi th the re suI t of a newly formed network. the degree of fUsion being
the degree to which this network is formed. A similar model was put
141
forward by Benjamin

33
The model presented by Summers assumes that primary particles
are the uni t of flow. Figure 1.4- shows the microdomain structure of
PVC. At low temperatures (typically 160 - 170°C) there is poor
interaction between primary particles16.17.132. the material within
them being held together by a three-dimensional structure (Figure 1.18).
At higher temperatures - Figure 1.19. some of the crystalli tes mel t.
and despite the primary particles not being completely destroyed.
interaction increases. On cooling down (Figure 1.20) recrystallization
occurs linking the primary particles together by newly formed
cry s talli tes. This will produce a tougher product. ~li th this model.
Summers was able to explain the two different flow activation energies
observed by ColI in and Metzger (43 and section 1.3): at low melt
temperatures the structure schematized in Figure 1.18 is present.
gi ving low activation energies. At high temperatures the interaction
between primary p'l-rticles will create a large activation energy for
flow.

FIGURE 1.18 Primary particles FIGURE 1.19 Primary particles.

33
in a low temperature melt partially melted and interacting.
in a 177°C mel t 33
 - 46 -

FIGURE 1.20 Primary particles after cooling and recrystallization

33
from a 177°C melt

In their attempt to correlate morphology with mechanical properties

23
Uitenham and Gei1 also found the primary particle to be the unit of
flow for most processing conditions. If the microdomains are related
to the crystallites, as one approaches their fusion temperature the
primaries will merge or fuse, their inner structure fusing as well.
However, the microdomains will reform upon cooling, unlike the primary
particles. Hence, at low processing temperatures physical properties
will depend on the degree of cohesion between the primary particles,
wh~reas at high temperatures the microdomains will play the major role
in supporting stress.

It seems therefore a common idea to explain the behaviour of PVC

melts at processing temperatures by assuming that crystallites act as
· k
cross- 1 J.n S 'J.n a th ree- d'lmenSJ.ona
. 1 ne t werk 21 ,141,142,148 • It i S J.n
.
the preparatory steps that the models put. forward seem to differ.

1.4.2.5 INFLUENCE OF PROCESSING CONDITIONS ON PROPERTIES

Due to the structural changes during processing, one can expect

a dependence of the product properties on the operating conditions.
From the discussion above, an easier mechanical failure of a product
 - 47 -

with large volume~ of unfused material and improvement of properties

with increasing fusion seems likely. One question remains, however,
whether mechanical properties improve with fusion, or some optimum
level of fusion exists. Benjamin141 conjectured that the various
physical properties of a compound are affected differently by an
increase in fusion level; properties concerned with brittle-ductile
behaviour would show an optimum value, whereas properties concerned
with stiffness would show an increase over the whole fusion range
(Fi gure 1. 21) •

Stiffness
Strength

1
'"
.!

Ductility

Gelation level

FIGURE 1.21 Influence of the gelation level on the basic properties

of UPVC pipe 141

In order to assess the mechanical properties the two main tests

used by investigators are the impact and tensile tests. A third one,
internal pressure, is obviously limited to pipes, and will not be
discussed here.

1.4.2.5.1 Impact

Apart from few exceptions145 impact strength is usually found to

increase with fusion, but disagreement occurs on the possible
exi s tan ce 0 f a maximum. Compari son 0 f the re suI ts is di ffi cuI t
because of the existance of various types of tests and preparation of
specimens (unnotched specimens reflect the behaviour of the material
up to the point of initiation of cracks leading to failure, whereas
notched specimens, because of the severity of the triaxial stress field
 - 48 -

ahead of the notch, reflect the crack propagation). Gonze146 found

tensile impact strength to increase with increasing fUsion, a
levelling off at high fUsion levels taking place; similar results
were reported by Berens and Folt147 • Lamberty148 measured impact
energy with the Charpy test and found it very sensi ti ve to
heterogenaties of fUsion; for some machines, however, there was a
direct relationship between impact energy and degree of fUsion. Such
a steady increase was also observed by Gilbert and Ansari149 for both
notched and unnotched specimens. Using the dart drop impact test,
Uitenham and Gei1 23 observed increasing energy to failure with
increasing extrusion temperature. They explained these results by
increasing cohalescence of primary particles
-
with increasing extrusion
--~--

temperatures, the reg:bns of poor fUsion and adhesion to the addi ti ves
- acting as crack initiation sites - progressively disappearing.

Benjamin141 measured impact strength by tensile impact energy

and falling weight tests. Both produced a maximum in impact energy
at gelation values between 44 and 68%. It was therefore concluded
that after reaching optimum ductility, the material becomes increasingly
brittle. A maximum in impact strength was also observed by Parey and
Kruger 26 and Menges et al 22 , with impact modified samples (HI-PVC).
The location of this maximum was at 188°C extrusion temperature,
corresponding to the existence of a network structure throughout the
material; Menges et al put forward an explanatory model (Figure 1.22).
Below 188°C the primary particles are enveloped by the impact modifier.
In the event of deformation, crazes formed in the particles interfaces
perpendicular to the direction of stress will be stopped when reaching
a boundary interface across the direction of propagation; new crazes
will be initiated at other boundary interfaces. This mechanism
absorbs a high energy level. If the primaries are destroyed (above
l8S 0 C), the soft phase will form numerous and densely distributed
inclusions in the brittle PVC matrix, creating stress concentration
points that give rise to crazing. If a craze is found it will soon
encounter a neighbouring particle before it has attained a critical
length, and the growth is stopped. This mechanism is, however, able
to absorb less energy. Portingell 27 points out that despite this work
being limi ted to EVA modified PVC, it can explain why some workers
 - 49 -

find maxima in properties and others only an increase: most ingredients

can be expected to behave in a similar manner, ie •• coating particles
at first, then globules in a matrix after fUsion of the parti cles; if
they interfere with craze initiation and properties, a maximum will be
observed. Therefore, the formulation is a fUndamental parameter when
comparing results.

F F

t t

inihation at crazeos ot the ImtiatlOn of crazes

particle- borders

~ ..se
~
~ ~

limItation of
crazes
Inew crazes
'!'Iiliolion of IsmltotlOn of croze - Size

HI - PVC

FIGURE 1.22 Formation of crazes before and after the phase conversion 22

Marshall et al139 observed a maximum of impact strength for

samples in the 60-70% fUsion region for a number of different
formulations. From the analysis of force/time traces it was concluded
that samples with lower fUsion level have higher maximum forces during
impact and longer fracture times, hence they appear to be more ductile.
An increase in impact strength with increasing extrusion rate was
observed, which disagrees with the observations of Summers et al132
who reported that extrusion rate did not have any effect on the impact
properties. Also, in an earlier work16 impact failures at low
temperature were found to be brittle as opposed to the ones at higher
temperature. This was correlated with changes in morphology, ie., loss
 - 50 -

of primary parti cles and formation of a continuous melt. A maximum

in impact energy was, however, observed with increasing mel t
temperatures132 • Trying to account for this behaviour, it was
observed that wi th high temperatures melt fracture and lubricant
failure took place, with melt sticking to the metallic surfaces. To
confirm this, Summers et al press polished the samples at the
previous extrusion temperature to obtain a smooth surface and then
observed no loss of impact energy.

Terselius142 compared different impact tests; unlike tensile

impact which produced a levelling-off of impact energy at high gelation
levels, the other tests produced more or less distinctive maxima for
50-60% gelation level. In order to check the hypothesis of Summers et
al132 , the surfaces of the samples were machined in order to obtain a
smooth surface, but a maximum was again obtained. It was therefore
concluded that the maximum was a true bulk property of the material
and a consequence of the optimization of the degree of fusion. The
analysis of load traces showed that they could be superimposed for the
various processing temperatures, their length being the only variable
- the longest load trace corresponding to the maximum impact energy.
It was therefore concluded that the absorbtion of impact energy is
related to cold drawini 50 •

In summary, while it is widely recognized that impact strength is

affected by processing conditions, explanations of this influence are
contradictory. Comparison of the data presented is difficult, since
the nature of the test, test conditions, the geometry of the specimen
and formulation all play a part in the behaviour.

1.4.2.5.2 Tensile

In the literature, it is generally observed that elongation at

break (CB) increases with increasing processing temperature14 ,19,23,26,
142,150, 154, the destruction of primary particles and improved
homogenization often being the reason given for this behaviour. Stress
at break has the same trend 23 ,26,142 although not varying as much as
CB. The reports on yield parameters are much more contradictory.
 - 51 -

Gilbert and Ansari149 , studying compression moulded samples, found

yield stress to steadily increase with temperature until a levelling-
-off at high temperature took place. Uitenham and Gei1 23 and Pezzin
150
et al found both yield stress and strain to be independent of
degree of fusion. Uitenham and Geil suggested that these properties
develop in the late compression or early metering zone of the extruder,
thus becoming independent of later morphological changes; these
properties are affected by surface interaction between the primary
particles once the grains break down. Benjamin141 found tensile yield
strength to reach an optimum between 68 and 90% gelation level; also,
and unlike most works, there was a maximum in elongation at break at
44% gelation. Menges et al 22 also found a maximum for cB for the
processing conditions corresponding to the destruction of primary
particles, for both UPVC and HI-PVC.

Terselius142 carried out an extensive unaxial test programme on

test specimens cut from PVC pipes extruded at varying mass temperatures.
The tests were performed at different drawing rates and temperatures.
Like other workers 23 ,26 Terselius found yield parameters to be
insensi ti ve to gelation level at all testing conditions. Post-yield
deformation behaved differently, specially at elevated temperatures:
despi te following the same load-extrusion curve, specimens processed
at higher temperature had greater elongation at break. Therefore,
Terselius related strain at break (~) to resistance to disentanglement.

The effect of gelation level on ~ increased with increasing test

temperature up to 90°C; above this value the destruction of load
bearing crystalli tes favouring progressi ve disentanglement caused a
decrease in the total strain.

The morphological aspects of the fracture process have also been

investigated152 ,153. Comes and Haward152 observed that under the
influence of applied stresses crazes are produced, initiated ei ther
by extraneous particles inside the matrix or superficially. As
yielding takes place, they seem to pass through the neck almost
unchanged; with further elongation of the neck the crazes grow into
diamond-shaped cavities that will develop by tearing in the direction
 - 52 -

perpendicular to polymer orientation. Eventually, local stresses will

.. .... 153
cause rapid failure. Tormala et al described a similar mechanism,
except that no crazes were observed; instead, cavities seem to nucleate
from stress concentrations on the surface of the test piece immediately
after the beginning of the cold flow.

The results found in the literature for both yield and post-yield
parameters are therefore contradictory. The work presented by
Terselius on tensile tests at elevated temperatures produced
interesting results, providing a possible technique to assess the
degree of fUsion of extrudates.

1.4.2.6 REPROCESSING

Fusion as described in section 1.4.2.4, seems unlikely to be

reversible. Surprisingly however, the little work done on this subject
proved that this is not the case, with quite unexpected results
possible to be obtained. Lamberty148 showed the possibility of
reducing the degree of fUsion by reprocessing at lower temperatures
when monitoring changes in the reprocessed material. Portingel1 27
studied these effects in greater detail. He processed UPVC samples
in a Brabender Plasticoder up to IBOoC, and then reprocessed them to
135°C and IBOoC. Extrusion of the testing materials in a capillary
rheometer showed similar readings for the top temperatures but lower
entry pressure for the sample reprocessed to 135°C. Chain scission
had not occured because there were no significant changes in molecular
weight distribution. So, Portingell explained the lowering of fUsion
as a 'combing-out' effect on molecular network due to high shearing
forces; as the temperature of reprocessability increases, so does the
chain mobility combating the combing out effect, and the network
reforms. Portingell observed also that the sample processed to IBOoC
had lost any evidence of primary particle structure but, most
surprisingly, the one reprocessed to 135°C showed some evidence of
primary particles. No explanation of these observations was given.
Patel155 extended Portingell's study to plasticized PVC. Samples
previously mixed in a Banbury at temperatures between 150 and 200°C
were extruded~t 134°C. He found the state of fUsion of all samples
 - 53 -

to be reduced to the one expected for 134 DC after processing. As an

explanation, he proposed that the crystalline crosslink sites were
broken down at various points under the high shearing forces. DSC
traces showed that these forces had no effect on the annealed more
perfect crystallites. The reprocessed extrudates were smoother,
which agreed with previous work by Rudin156 also on plasticized PVC.
Like Portingell, patel observed microscopically that reprocessed
samples ressembled very clearly samples processed at low temperatures.
As it is difficul t to imagine primary particles to reappear on
subsequent processing, he postulated the creation of a new structure
by application of high shearing forces, of the order of the primary
particles. Finally, it was observed that the tensile properties of
the reprocessed samples showed no difference from the ones extruded
at similar temperature.

1.5 METHODS OF ASSESSING THE STATE OF FUSION

Throughout the earlier sections it has become clear that the

extent of fusion has profound influence on the characteristics of the
final product. Specially if a maximum in mechanical properties is
observed with increasing processing temperature, a definition of the
state of fusion is of particular importance. A number of methods have
been established and reviewed in the literature27.140.155, therefore
only an overview will be presented here.

1. 5.1 SOLVENT TESTING

Immersion of processed PVC samples in a solvent (eg. acetone or

methylene chloride) has been widely used to assess their fusion levels.
As it is known that tlB existance of a molecular network allows for the
swelling of the sample with little effect on its cohesion, it can be
expected that with increasing degree of fusion less desintegration of
the sample will take place. However. for high levels of fusion
(around 70%) it is difficult to distinguish between small differences
in fusion. It has been shown157.158 that the rate of solvent uptake,
 - 54 -

slope of the sorption curve and percentage of sol vent absorbed at

equilibrium depend on the thermal history and type of PVC.

1. 5.2 PHYSICAL PROPERTIES

As seen in section 1.4.2.5, both tensile and impact properties

are generally reported to increase with processing temperature to
reach either a peak or plateau. For a known compound, a measured
property can therefore be used to indicate fusion level. Tensile
142
tests at high temperatures, as reported by Terselius , seem to be
particularly interesting since great sensivity to gelation level can
apparently be obtained. However, a relatively large amount of sample
is required in a specified form, which makes these tests of limi ted
practical interest for quali ty control.

139
Marshall et al and Terselius142 have also reported a direct
relationShip between density and processing temperature. In both
cases density was found to decrease with increasing processing
,
temperature, a minimum being observed. Terselius attributes
this observation to the presence of residual grain inclusions.

1.5.3 MICROSCOPY

A logical way to establish the state of fusion is to observe it

wi th a microscope. Light microscopy methods have a resolution down to
0.5 urn, allowing ~~erefore fusion to be examined at both the grain and
primary particle levels of morphology. For improved resolutions the
ideal instrument is the Scanning Electron Microscope (SEM); it has,
however, some important disadvantages, namely i) difficulty in specimen
preparation, ii) limited area of specimen allowed for observation, and
iii) high price of the equipment.

If total fusion implies uniform density, ie., re fracti ve index

(RI), the degree of fusion can also be investigsted by the magnitude
and extent of RI fluctuations in the material. Differential
 - 55 -

Interference Contrast (DIC) and Jamin-Lebedeff Interferometer140.151

are two techniques very sensi ti ve for this purpose.

A further technique to assess the degree of fusion has been

suggested by Summers et al16 : samples of PVC are immersed in excess
of acetone; fragments of the swollen PVC are then sheared between a
microscope slide and coverslip and examined using a common light
microscope. The image contrast and visibili ty of the particles is
controlled by the RI difference between the swollen polymer and the
acetone.

1.5.4 CAPILLARY RHEOMETRY

The use of a rheological method to assess the degree of fusion of

PVC was first developed by Gonze146 and Lamberty148 and later reported
by a number of authors141.159.160. It is now widely used both for the
quantification of the state of fusion and the effects of addi ti ves on
progression of fusion139.142.161. In this method, by measuring the
entrance pressure losses in a short capillary at a temperature above
Tg (typically 130-150 0 C), one is able to get a measurement of the
elastic build-up in the processed PVC. It is therefore assumed that
i) changes in the particulate structure can be assessed by corresponding
changes in the elastic nature of the material; ii) with increasing
degree of interpenetration of the particulate domains the melt
elasti ci ty increases, and iii) changes in the melt elasticity can be
characterized by changes in the capillary entrance pressure loss. This
is mainly achieved by the use of a short capillary (small L/R value)
making P, the pressure required to force the sample through the
capillary, mainly a function of the elastic deformation. P is given by

(1.19 )

where Po - pressure loss due to entrance effects

Pvisc - viscous pressure loss
T - shear stress at the wall of the capillary
n - vi scous loss term
SR - elasti c deformation
L/R - length/radius of the capillary.
 - 56 -

If one plots pressure loss versus processing temperature, S-shaped

curves are obtained: an initial decrease in extrusion pressure is
usually attributed to grain breakdown; the subsequent increase is due
to the gradual formation of a continuous molecular network. It is
common to present the gelation levels as a percentage value, which
implies a standardization of the reference curva1 41 :

P - P .
Gelation level %= sample mln x 100 (1. 20)
Pmax-P'
mln

The main limitation of this test is the fact that one standard
curve has to be produced for every compound and processing eqUipment,
since the fUsion curve depends on both shear and heat history.

Parey and Zajchowski162 reported the use of the simpler 'melt

flow index system' instead of the capillary rheometer. The measuring
conditions are slightly different: instead of constant velocity,
constant stamping-load is applied; instead of pressure, the melt flow
is recorded. Flowability undergoes a pronounced reduction as processing
temperatures increase, and if standardization is applied, curves
similar to capillary rheometry are obtained.

1.5.5 THERMAL ANALYSIS

Gilbert and Vyvoda163 showed that Differential Thermal Analysis

(DTA) can be used to evaluate thermal history and level of fusion of
processed PVC samples. 10 mg samples were heated from room temperature
to 240°C at 20°C per minute, using a DuPont 990 Thermal Analyser fitted
with a DSC cell.

A DSC trace of rigid PVC powder (Figure 1.23) blend has an

endothermic baseline shift at T and a broad endothermic melting range
g
from approximately 155 to 195°C. If the sample is subjected to
processing (namely extrusion) T is largely unchanged, but lower
g
mel ting crystalli tes melt while higher melting crystallites are
annealed so that their melting temperature increases to produce a
smaller endotherm (denoted B) at a higher temperature. If the
 - 57 -

100 150 200

T~mptZrcture (OC)

FIGURE 1.23 DSC thermograms of compression moulded samples at

various temperatures163

processing temperature reaches or exceeds 160°C. there is enough melted

material to permit recrystallization on cooling and an additional
endotherm (denoted A). having a range from about 110°C to the onset of
B. appears. ~HA' the energy of this endotherm. increases with
processing temperature and. if plotted against processing temperature.
produces a S-shaped curve similar to the reference curve obtained by
capillary rheometry. Unlike A. and because of the melting of the less
perfect or smaller crystallites. peak B decreases while shifting to
higher temperatures (annealing of unmelted crystallites). Endothermal
peaks belOl, T have also been observed164-166 and attributed to
g
enthalpy relaxations. A peak near 100°C may also be observed; it
develops on room temperature storage of rigid PVC due to a slow
reduction in free vOlume164 •
 - 58 -

Gilbert et al140 reported that for most compounds analysed the

maximum value observed for ~HA is 10-12 Jg- l ; if this value is shown
to be widely applicable, it could be possible to evaluate fusion
wi thout the necessity of producing a standard fusion curve for each
compound and processing equipment (one exception seems to be the
Brabender at high rotor speeds, where exceptionally high ~HA values
were obtained; this could be due to different fusion mechanisms caused
by high shear - section 1.4.2.2). Also, from data gathered from a
large number of different compounds, it was concluded that the onset
temperature of the B endotherm corresponds to the processing
temperature of the compound. A further advantage of this method is
the small size of the sample. allowing for several measurements along
a thick section, for example; this can, however, also create problems
in obtaining a representative measurement for the processed product.

Gilbert et al140 found that a linear relationship can be obtained

between ~A and the pressure losses in the capillary rheometer, for
samples extruded at a particular rate.

1.6 AIMS OF PROJECT

This work forms part of a large programme being undertaken in the

Institute of Polymer Technology, aimed at studying the relationship
between PVC morphology, processing conditions, structure and properties
of the final products.

From the literature survey presented in this chapter it has been

concluded that: i) the mechanism of fusion inside the processing
machine is not fully understood, ii) the degree of fusion has a
profound influence on the mechanical and physical properties of the
extrudate, iii) the degree of fusion can be successfully assessed by
techniques such as capillary rheometry and DTA. vii th this in view,
the work undertaken concerns a comparison between single and twin screw
extruders, with the purpose of better understanding the ability of each
to control the properties of rigid PVC compositions (Figure 1.24).
 - 59 -

r DIE 1 SINGLE/1I1IN
t:>
~
'"~ t:>t/l
::t:~""
OBTAINING I RT & RTD I CORE SAMPLES
E-.>-<O
~~~
EXTRUDATES ALONG SCREW(S) t/ltls
~&li3
",,,-0

MEASUREMENT OF FUSION 1
DTA, CAP. RHEOMETRY
T
FINAL PROPERTIES: DEVELOPMENT OF FUSION
ALONG SCREW(S):
* DENSITY MIXING
* MECHANICAL CHARACTERISTICS * MACRO MECHANISM
Impact Mel ting Mechanism
Tensile Mel t Pool along
Flexural Screw
Hardness
* MICRO MECHANISM
Mechanism of Fusion
along Screw(s)
Degree of Fusion
along Screw(s)

I CONCLUSIONS I

RELATIONSHIP BETWEEN FINAL PROPERTIES, FUSION MECHANISM AND

PROCESSING CONDITIONS

FIGURE 1.24 Layout of project

The objectives of this research are therefore as follows:

i) Identify the fusion mechanism of both twin and Single screw
extruders;
i1) Identify the influence of processing condi tions on the fusion
mechanism;
iii) Investigate the eventual relationship between degree of
fusion and relevant physical and mechanical properties;
iv) Analyse the relationship between degree of fusion and
processing conditions.
 - 60 -

If a direct relationship exists between degree of fusion and

final properties, the first will be the important parameter to control;
furthermore, with a direct relation between degree of fusion and
processing conditions, one can foresee the ideal situation where,
knowing the equipment geometry, the processing characteristics of the
material and defining the desired properties, one could choose the
processing conditions that would lead to a maximum output.

In this project the fusion mechanism will be identified by

analysis of core samples obtained with the use of the technique
developed by Maddock 72 and Street73 • The mechanical properties that
seem relevant to the general end-use of rigid PVC extrudates are
impact, tensile and flexural strengths and hardness. Mixing
characteristics will be detected via Residence Time and RTD.

In order to carry out the experimental work, the appropriate

die to be mounted on the head of each extruder must be produced. A
further aim of the project was therefore established:

v) Identify the procedure for the design of a slit die for PVC
processing.
 - 61 -

CHAPTER 2

DIE DESIGN

2.1 INTRODUCTION

PVC has been the material of choice for profile extrusion for
many years. Not only has the finished part an excellent balance of
properties, it is easier to make complex cross-sections and hold the
shape using PVC than any other common thermoplastic.

The general aim of a die designer is - given the dimensions and

required output rate - to calculate the dimensions of the die at exit
and to define an appropriate flow channel in the body of the die in
order to achieve an acceptable pressure drop (within the operating
range of the extruder), and to minimize the likelihood of flow defects.
For this, it is generally assumed that the extruder can produce a
continuous stream of molten polymer homogeneous in temperature,
composition and shear history at the required operating conditions.

2.2 ANALYSIS OF FLOvl PHENOMENA WITHIN THE DIE

2.2.1 GENERAL

The key factors in die design are the flow properties of the
polymer melt, and the way this behaves within the various geometrical.
configurations found during processing. The shear stress versus shear
rate curve, over the relevant ranges of temperature, as obtained by
capillary rheometry, is commonly used to describe the pseudoplastic
behaviour of the melt; mathematically it is frequently expressed in
terms of a power law, although other representations are possible168 •
This data is usually obtained relying on the following assumptions:
no slip at the wall, laminar (low Reynolds numbers) and isothermal
flow and an incompressible homogeneous melt with time-independent
properties. These assumptions have been discussed generally in the
li terature169 •
 - 62 -

As seen in chapter 1 (section 1.4.2.2.1) it is common to encounter

wall slippage of PVC in the barrel of an extruder. Therefore, it is
not surprising that a similar phenomenon has been observed in capillary
rheometry124,170,171. Worth et al124 presented a model for Newtonian
behaviour, requiring the measurement of wall slip data. They concluded
that after a limiting shear stress is reached, the onset of wall slip
occurs, with a decrease in output rate and power consumption. Brown171
developed an experimental technique for the measurement of velocity
profiles of melt within the capillary die. Above the crystalline melt
tell'jlerature the flow was found to obey the power law; below that
temperature the velocity profile is flatter and more like plug flow
than predicted by the power law; this was attributed to a high elastic
modulus due to crystallinity leading to slippage at the wall or melt·
fracture. Brown points out that slippage accounts for the advantage
of PVC in making complex profiles: especially at low temperatures, the
melt has very flat velocity profiles and, therefore, flows out of
different sections of a complex die with equal velOCity. He also
proposes a model concerning melt fracture and slippage at the wall.
If the shear stress at the wall is greater than the tensile strength
of the material at the processing conditions, melt fracture occurs;
if the shear stress is smaller than the tenSile strength but greater
than the onset of wall slip, slippage will occur without melt fracture.
Lubricants reduce the critical stress for slippage. Uhland170
discusses the possible causes of slip of polymer melts and studies
flow profiles with different boundary conditions: i) the polymer melt
sticks to the wall; ii) the polymer melt slips directly at the die
wall, iii) existance of a thin layer of low viscosity fluid between
polymer melt and die wall, acting as a lubricant. According to Uhland,
the latter is observed for UPVC compositions with external lubricant.
Hence, this observation implies a high viscous fluid flowing in a
central core surrounded by an annulus of low viscous fluid; no true
slippage occurs at the wall, but an apparent slip velocity can be
defined between the boundary of the two flows. From this sr.Jall
literature survey it can be inferred that the exact nature of the
velocity profile in capillary dies is not yet fully known, the simple
mathematical models already established being applicable only to the
circular geometry. Therefore, for the purposes of die design, the
 - 63 -

models assuming no slip were used.

In the flow of a viscous fluid a vast amount of mechanical energy

is converted irreversibly into heat owing to the fluid's internal
friction. This viscous heat disSipation not only leads to an overall
increase in the fluid bulk temperature, but also causes a noticeable
temperature variation to develop across the shear field. Because
properties like viscosi1y and den si ty vary directly with temperature,
a knowledge of the temperature field is a must for a fully correct
prediction of the flow characteristics. This involves the solution
of the governing equations of momentum, continuity and energy together
with the rheological equation of state (eg. the power law) and the
appropriate boundary conditions. For a three dimensional geometry
only with the help of numerical methods it is pOSSible to solve those
equations, the results for a limited number of geometries having been
.
reported in the l~terature172-175 • Because die design is not the

main aim of this project and the use of numerical methods is very
time consuming due to their complexity, viscous heat generation was
disregarded in the calculations; an isothermal wall and flow were,
therefore, considered.

If shear stresses are dominant every time there is a flow through

a channel of any given constant cross-section, in a tapered flow
channel extensional deformations play an important part: if the
tensile stress exceeds a critical value, rupture of the melt occurs
and the extrudate will show melt fracture 176 • Extensional flows are
also responsible for pressure drop. The experimental data is usually
obtained from constant stress or strain rate tensile rheometers, or
by studies of flow in converging dies177-178 in the capillary
rheometer.

The elastic behaviour of the melt manifests itself in the flow

in the form of swell of the extrudate immediately after the die
exit169 • The amount of die swell is dependant on the shear rate and
geometry. The latter creates the problem of relating the swell in
capillaries to the complex shapes of extrusion dies. Furthermore,
the cross-section of the extrudate will differ in shape from that of
 - 64 -

the die orifice, as with cessation of shearing action molecular

coiling is able to proceed.

The mentioned phenomena must therefore be taken into consideration

when designing a die. The aim here is to produce a rectangular
cross-section. The die will consist of a land to help streamlining
and achieving the desired cross-section; an adaptor, linking the die
land to the circular head of the extruder and, optionally, a breaker
plate. Die design aspects have been widely discussed in the
li terature179-184.

2.2.2 DETERMINATION OF THE DIE PROFILE

2.2.2.1 DIE LAND

The first step in computing the die profile is the definition of

the cross-sectional dimensions of the die lips. This requires that
the die-swell has to be taken into account, not only as a change in
area, but also in shape. Very little work185 ,186 has been done on the
latter subject, and the overall conclusion seems to be that an exact
prediction of the distortion of the profile can rarely be given;
furthermore, besides recoverable elastic strains, stretching, uneven
cooling and contact with sizing dies, guides or other drag points
along the drawing path can also lead to distortions of the profile.
As it is practically impossible to take all these factors into account,
the change in shape of the extrudate was disregarded, and a die with
rectangular cross-section was assumed.

So, design procedures must be found for predicting die swell from
a knowledge of the product dimensions, output rate and basic flow
data. The most common are tables of percentages by which to undersize
die dimensions relative to wanted profile dimensions to allow for the
typical swell to be expected187 • Another is to use the extrudate
swell data obtained from capillary dies for the sli t geometry, wi th
area swell as the common parameterl77 ,188 ,189 • ~ihil e Po~ell188
reports the swelling ratio in the thickness direction to be equal to
the square of that across the width, Brown et al189 observed that for
 - 65 -

PVC the amount of swell is inversely proportional to the width to

thickness ratio; the area swell ratio is found by squaring the diameter
swell ratio. Therefore, if s is the shape factor (width/thickness),

thickness swell = ___s___·x Area swell (2.1)

s+l

1
wid th swell = ------. x Area swell (2.2)
s+l

The area die swell data is often given versus the shear rate at
188
the die exit, y. For a slit

6 vd
Y= ----
H
(2.3)

where H is the thickness and vd is the speed of the material at exit,

given by Q/TH 2 , with Q the volumetric output and T the width. The
knowledge of the shear rate allows therefore a knowledge of the
188
swelling ratio. Powell proposes an iterative process for the
calculations, adopted here:

i) The dimensions of the product are taken as a first approximation;

ii) The shear rate is computed;
iii) The die-swell is calculated using the procedure described;
iv) Hi thin the new die exit dimensions, the calculations are
repeated;
v) If the new and the last die-swells are similar, the process is
completed; if not, new iteration is done until full convergence takes
place.

If draw-down exists, its effect must be subtracted from the die-

-swell. Drawdown was disregarded here.

The next step in the calculations is the definition of the die

land length187.190 It is usually reported49.179.182 that physical
properties improve with increasing die land length; the dwell time
in the die will increase. enabling the polymer to recover from eventual
non-linear patterns before and in the die entrance. However, for PVC
residence time (RT) must be kept to a minimum and small die land
 - 66 -

lengths have been advised181 It has also been reported49.181 that

the different processing histories of the material in single and twin
screw extruders require different die land lengths. In the twin screw
machine the melt temperature is more homogeneous. and the dwell time
can be longer - therefore ratios of length to thickness up to 30:1 are
possible; in the single screw extruder. due to its flow pattern. some
points have different processing histories. hence ratios of around
10:1 are advised180.181.184.188.191. As the same die will be used for
both extruders. a ratio of 10:1 was adopted.

The pressure drop in the die land can therefore be calculated.

Approximate methods usually consisting of a general equation with a
shape factor describing different geometries have been reported in the
literature168.183.187,190.192. The inhibiting action of the edge
zones on the flow field increases in importance as the square cross-
-section is approached. Schenkel193 produced a formula ~here the
influence of the edge zones was taken into account. but the model was
based on the Ostwald and de ~Iaele
law and lacks experimental
confirmation. According to Carlei 83 , rectangular cross-sections
wi th large width/thickness ratios have isovels parallel to each other
for most of the width of the rectangle. Practically speaking. this
case can be approximated to a simpler one-dimensional flow, ie •• flow
between parallel plates. Therefore169

tiP = 2LT/H

where T is the shear stress obtained from the flow curves.

2.2.2.2 ADAPTOR

Because the cross-section of the die land is very different from

the head of the extruder, an adaptor must be designed. The geometry
of this zone has obvious repercussions in the flow pattern; dead
spots, turbulent flows, melt fracture and sudden changes in the flow
speed have to be avoided. The angle of the taper and its profile are
the parameters to define.
 - 67 -

The angle of the taper describes the type of compression induced.

Its choice depends mainly on the tensile properties of the melt. The
tensile stress in the flow direction increases with a decrease in
cross-section, the maximum being reached at the narrower end of the
taper; if this maximum is beyond a critical value, melt rupture
occurs. From the relationship between average tensile deformation
rate E, and shear rate t, both at the narrow end of the taper, one
has176

3 E
tgo: = T (2.5)

where 0: is t.J,e half-angle of the taper. From the experimental data

E can be obtained; y is known from the die land calculations.
max
Therefore, 0: can be defined. Values of about 30° or less are
max
usually advised in the literature179 ,181 ,182,189.

The definition of the inclination of the taper is not sufficient

to ensure an extrudate with good quality: poorly designed prOfiles
can create sudden accelerations; because friction increases steadily
with speed, sudden acceleration can cause local burning. Sors187 ,
who analysed fluctuations of speed for different adaptor prOfiles,
concluded that tapers of even reducing dimensions have poor
characteristics and advised the use of trumpet-shaped designs for
constant acceleration flows.

Overeijnder194 finds some usefulness in the existence of an

adaptor. After passing through the holes of the breaker plate, the
PVC molecules have to be 'welded' again, in order to create an
homogeneous flow; this must be done in the short residence time (RT)
inside the die, and is greatly improved if a compression ratio is
used: the larger the compression ratio, the less RT will be needed.

For easier designing of the adaptor, it was decided to divide it

into two zones: i) a trumpet shaped profile changes the rectangle
into a square, ii) the square is changed to a circular cross-section,
a certain compression ratio being induced. Two complexities are
therefore created: the angle of the taper changes continuously, and
in both the thickness and width directions. Attempts have been made
 - 68 -

to predict theoretically pressure drops within tapered channels.

Plaje/ 95 , Rao168 and Wortberg et al175 divide the geometry in a
number of similar parallel elements using the models for constant
cross-sections. Lenk and Frenkel196 computed the pressure drops
developed by shear flow for tridimensional tapered channels.
176
Cogswell presented a more complete analysis in the sense that in
his model the total pressure drop derives from both shear and
extensional flows. These are assumed to be separable, and computed
as such. In addition it is assumed that bulk deformations are
neglected, the power law is valid over the relevant ranges of shear
stress and the viscosity under simple tension is independent of
stress. The model is one-dimensional, disregarding the influence of
the die width T. The three-dimensional geometry in study must
therefore be adopted to the model in terms of the pressure drop
calculations (Figure 2.1).

FIGURE 2.1 Adaptor's first zone composed geometry

The geometry of the first zone was divided into three elements:
i) and ii) two two-dimensional tapers, taking the melt from the square
cross-section to the die exit width (~) and thickness (<3); iii) a
constant gap «(1).
 - 69 -

The total pressure drop is given by

(2.6)

The equations for the tapers are176 (Figure 2.2 ) :

,,
I

,
L

H,
FIGURE 2.2 Dimensions of tapered flow channel

H
T r\ 1 - ( ...1 )2n
=
HO 1 (2.7)
M'shear
n (HO-HI)

!::,p
exten
=
1
2
0 ( I - ( HI
HO
)2 1 (2.8)

where T and 0 are the shear and tensile stresses respectively, and
n the power law index. In the calculations the composite geometry
was divided into small elements of constant taper length, each of
them treated as described.

In the second zone of the adaptor there is a transition from

square to circular cross-section. The geometry is more complex than
 ------ --------------

- 70 -

in the first zone, and very few attempts have been made to tackle it.
Masberg172 ,197 uses the finite element method (FEM) to treat this
problem. Nevertheless, the simplifications include disregard of
normal stress effects, and constant cross-section in the flow
direction. Cogswell's model was again applied here, which implied
an arrangement of two-dimensional tapers, as indicated in Figure 2.3.

FIGURE 2.3 Adaptor's second zone composed geometry

The total pressure drops are given by

l1P
ext =2 • lIPtaper (2.10)

The equations for LIP are the same as for the first zone; due to
the steady change in cross-section, it is not necessary to divide the
taper into elements. The angle of the taper is defined as in the
first zone; it must be noted, however, that three different angles
must be considered, namely the absolute inclination of the taper e,
and relative angles towards the adaptor's first section, e- (l and
e - y.
 - 71 -

2.2.2.3 BREAKER PLATE

If the pressure drop created by the die land plus adaptor is

less than the optimum for the material, the presence of a breaker
plate is useful. Hence, from the calculations point of view, this
element is used to keep the total pressure drop under control.

The determination of the pressure drop in breaker plates is

usually performed assuming that the melt flows in the holes of the
breaker plate evenly distributed; therefore, the total equals the
sum of the pressure drops in the several holes. It is also assumed
stationary flow and there is disregard for entrance effects. However,
these are obviously important169 and must be taken into account. A
simple method proposed by Masberg198 will be used here. The pressure
drop will be gi ven by

tiP = 2L*T/R (2.11 )

as in capillary rheometry, but L* is an imaginary length given by

L* = (L/RL + E) ~ (2.12)

with L the length of the breaker plate, RL its radius and E a constant
taking the value 6 for thermoplastics.

Before leaving this section it must be noted that any die

designed with the data and calculations presented here will have an
optimum performance with one specific material and one set of
processing conditions.

2.2.3 METHOD OF CALCULATION

The sequence of steps to design the die was developed into a

computer program. From rough trial dimensions prOvided (eg., given
from past experience), the program performs the calculations
appropriately correcting geometries if any flow defects are to be
expected and provides the possibility of optimizing the output for a
gi ven geometry,
 - 72 -

The dimensioning of the bolts linking the die to the head of the
extruder and the breaker plate thickness is also provided. The
. ~ven
1 a tt er ~s . by
198:

bP S )0.5
h = B D ( et 0perm (2.13)
p

where: B circulation factor, describing the various peripheral

P
clamping conditions of the breaker plate. For a rigidly
clamped plate, B ~ 0.4;
p
D - diameter of the breaker plate;
S - safety factor: 1.5 - 1.8;
et - attenuation constant, given by 1 - 2R/t, with R the radius
of each hole and t the distance between centre of holes;
aperm - maximum acceptable stress;"
/!.P - pressure drop in the breaker plate, given by
{Sp /!.PL + /!.P sz + /!.P s }, wi th Sp a safety factor index
accounting for short-term high pressure losses ahead of
the breaker plate (eg. starting up), assumed to be 2;

L the pressure drop in the breaker plate; /!.P sz and /!.P s

/!.P
the pressure drops if screen gauges become clogged and
screen pressure drop, respectively; since no screen
gauges were used, these values are obviously zero.

The flow chart of the program is given in Figure 2.4.

The computer program is presented in Appendix A, including the

list of data to be input. This can be divided into four major
classes:
- concerning the product: product width and thickness;
- concerning the processing conditions: output, melt temperature;
- concerning the equipment: type of extruder, number of holes
of the breaker plate, diameter of flow channel in the head of the
extruder;
- concerning the flow properties: maximum pressure drop, shear
rate and tensile deformation rate; shear stress versus shear rate and
tensile stress versus tensile strain rate relationships; die swell
data.
 - 73 -

LAST VALUES ARE ZERO

r - - - - -.---------.t:-====-=:::;----l ,
I
I
I
Dm = PRODUCT
'f~IICK~lESS
THICKl'ESS
DIS llIDTH = PRODUCT UIDTH
DECREASE
OUTPUT
,I
I
I
I
I
SI-lEAR RATE> S.R.;:AX.
,
I

I
I D.SlIELL = I
I
I DIE S,vELL I
L C~Qj~I~ I
- --
r-- ------- .
THIN SCREF EXTRUDER
r-----------~F~---------,
INGLE SCREl'I EXTRUDER I
I DIE LAND DIE LA:m
I
I I.ENGTH LE:~GTH
I
I I
I I
I I
I
IL- DI;;
__ LAND _

FIGURE 2.4 Flowchart of computer program for die design

 - 74 -
2 3 4
r - ------Q)----- - f'
---~.;:: F-';: F-
f1
I IINDICES OF PROFILE EQS. 1
I 1
ilAX. ALFA & GAllA
I
I -.
I

DO CYCLE INCREASE
I 1 ••• Nm1BER LENGTH
OF ELEMENTS
I
I
r COORDINATES X. Y & ALFA. GAHA
I
I RELATIVE ALFA & GAMAl
I ALFA REL. OR
~AMA REL. > MAX.
I
I PRESSURE DROPS: DECREASE
SHEAR & EXTENSIONAL OUTPUT
I _~RESSURE DROP UP TO NOH > MfX. tJ'
_ I
I
I r INCR:,ASE 1ST . ,-
/l'IJUTE/ INCREASE 1ST I
SECTION LENGTH SECTION LENGTH
t - I
I A~P!2R:..E. f!.J?SJ:... S~!E!' _ _ _ _ _ _ ____
'-
r --------~---
TETA LHUT ------ ---- -
-- .,
- 1---. I-J
':I.. LENGTH I
I ~ :~) > LINIT F LENGTH
,<y < NIN.
I
I
RELATIVE ANGLES FROM
INCREASE FIRST SECTION I
I DECREASE LENGTHj
LENGTH OF OF SECTION I
I SECTION
~EL. ANGL!': > LIl1TIf- I
I
I
I
INCLINATION
> MAX. TETA
¥
PRE' q';R:!: DROPS:
sm .t." EXTENSIONAL
I
I
I
I ADAPTOR'S
I /lIRITE/
I
I- - - -- - - - t - - - ------- - -
SECOND SECTION
f-o- .J
rPRESSURE DROP 1 DECREASEl
OUTPUT
IF t
1 4
 - 75 -

r---- ---0f~-. . :. .,.:- - - - -;- ---- ~

FIRST APPROXH1ATIm!
RADIUS

I B.P.LENGTH RESISTAHCE I
INCREASE BREAKER
I PRESSURE DROP I PLATE LENGTH

~'Y
PR. DROP > liP MAX. AT FIRST ITERATION
I,
PR. DROP > liP MAX. I~

....---.......
I KEEP
----, IDECREASE RADIUS I
LAST VALUES
I
RADIUS < MIN. RADIUS
~~~- - - - - - I r - - - . l - - - - - ,
L----;::T=O=T=AL=PR=E~SlSUR-E-DR-O-P""'1 (~O N~:~T~F A /
/ ~REAKER PLATd

/ IJRITE /

- - - - - - - - - - - - - -.1-1
r - -OUTPUT
- -OPTIMIZATION
---- - - - - - - - - ----h
~~l
I NOT DESIRED "I F I
I ~ LAST OUTPUT = ACTUAL OTP. I
I
I
Y
IINCREASE OUTPUT I
I
I
I I
I j\JRITE / I
I
I
~ENOUGH CALCULATIONS \1ERE fJOT HA DE I
I
L.. _ __
OUTPUT ____ _
OPTIj-iIZATION _______ -.1
------
,
/vJRITE DIl1ENSIONS /

BOLTS
,1ININUM DIAHETER

l END)
 - 76 -

Practical experience176 ,188,191 suggests that the observed

.
values of swell ratio are usually within 10 percent of predicted
values and pressure drops within 20 percent.

2.3 DATA REQUIRED

The product is a rectangle, the dimensions 60mm x 3.5mm having

been chosen to allow for the determination of flexural (D790M-Bl),
impact (D256-Bl) and tensile (D638-B2) properties of the material,
according to the ASTM standards.

Because the performance of the die has an optimum for just one
set of processing conditions, for the purposes of die design, a
compromise must be achieved for the operating range of single and
twin screw machines. After some experimental trials with the two
types of extruders and from the processing conditions reported in the
li terature for both types of machines14 ,22,23,92,121, a melt
temperature of 190°C was chosen together with an output of
2.0 x 10- 7 mSs- i •

The maximum pressure drop is usually dependent on the capacity

of the extruder; from the experiments performed and from the data
reported in the literature181 ,184,189 1.0 to 2.8 X 10 7 Nm- 2 was
considered to be the optimum range for UPVC processing. Bigher values
18l
can cause leakages in the die

The remaining data depends on the measurement of shear and

elongational flow properties.

2.3.1 MEASUREMENT OF SHEAR FLOl'i PROPERTIES

As mentioned above, information is needed concerning the shear

stress T versus shear rate y relationship. The composition was
assumed to follow the power law
 - 77 -

(where n is the power law index and k a constant) and the data was
obtained with the use of a capillary rheometer. The wall shear
69
stress Tw is given bi

where /:,p is the pressure difference between the ends of the capillary
of length L and radius R; the shear rate at the wall yw is given by
(simplification of the Rabinowi tsch equation169 )

Yw = (3n4n+ 1) (4Q)
~ (2.16)

where Q is the volumetric flow rate. In order to derive these

relationships it is assumed that: i) there is no slippage at the wal~
ii) the fluid is time-independent, iii) the flow is isothermal, iv) the
melt is incompressible and v) there is a constant flow pattern along
the tube. The last assumption is subject to some degree of error, as
the distance between the entrance and the point of fully developed
flow can be quite substantial. The longer the length, the smaller
the error will be. To take account of these effects, the use of dies
of zero land length (simplification of the Bagley method) is usually
adopted. Two dies, one with a significant L/R ratio (15.5 in the
experiments), another with a L/R ~ 0 are used. If 0 denotes the
latter, the true wall stress T is given by169
w

.R • (2.17)

For power law fluids it ca~ be shown169 that

10 g ( ~f) = n 10 g f ;~ 3) + 10 g k I (2.18)

where

(2.19)

Therefore, by plotting log (/:,p) versus log (Q), n can be

evaluated; a plot of T versus y is then possible. A computer program
 - 78 -

was developed to perform the calculations. a simplified flowchart

being presented in Appendix B. Besides the shear stress - shear
strain rate relationship. the apparent viscosity (Nsm- 2 ) versus
shear rate and apparent viscosity versus shear stress relationships
are also computed. Information on swelling ratio versus shear rate
and shear stress is also available. provided experimental data is
generated. The mathematical approach used was a polynomial evaluation.
Weighted least-square polynomial approximations to the sets of data
points were performed. the polynomial being represented by its
Chebyshev - series and power series form (NAG subroutines from the
FORTRAN library were used). Subroutines based on the GINOF and
GINOGRAF packages allowed for graphical representation.

A Davenport Extrusion Rheometer (described in greater detail in

chapter 4) was used; extrusion speeds varied from 2.5 up to
100 cm min- 1 • At this value melt rupture occurred. therefore the
maximum shear rate could be defined. To avoid any degradation. only
one reading was taken per movement of the ram; the barrel was then
emptied. cleaned. the steady state reached again. and a new run
begun. All the experiments were repeated once.

2.3.2 MEASUREMENT OF ELONGATIONAL FLml PROPERTIES

In spite of its importance. only a relatively small amount of

work has been done on the elongational flow behaviour of melts because
of' the difficulties in experimentation. Both the general flow
behaviour and relevant experimental techniques have been reviewed in
the literature169.199-202. The terminology used here is schematized
in Figure 2.5. It is generally reported that for highly viscous melts
the viSCOSity under tension (Trouton viscosity) is independent of
stress and equal to three times that under simple shear. The reports
on PVC are scarcer. Park and Riley203 attribute this to the
complexity of' the melt. whose characteristics are aff'ected by its
supermolecular structure. A literature survey on the work on PVC was
presented by Petrie 200 • Since 1972. the experimental work has been
carried out using a rheometer in a constant strain rate mode.
Vinogradov et al 204 obtained a maximum logarithmic strain of 2.7. but
 - 79 -

. ...... ..._......
"..
,-' F 1: = or,
0=-
f-----"( A 1

--- I
F
f
I I
extensional viscosity = A = Qt
I A
I t 11
Hencky strain ~ = J10 81L = In -1110
£ = Y.1 with V = d1/dt

FIGURE 2.5 Notation used for elongation of flows

his experiments were perfonned on highly oriented threads of 100 to

300 fibres formed by spinning;de Vries and Bonnebat 205 wor~ing with
CPVC obtained 1.8, and Kazama et al 206 observed strains up to 1.0.
Park and Riley203 used both constant stretching rate and constant
tensile stress modes. For strain rates between 0.003 and 0.1 s-1
the maximum hencky strain achieved was 1.3 (a maximum of 1.8 was
obtained for 3 s-I).

Extensional flows can be studied uSing specially built rheometers

or from the flow through th€1 die orifice of a capillary rheometer178 •
The validity of the latter analysis is still under serious debate 207 •
It was decided to use the facility available at IPT, namely, a
Rutherford Extensional Rheometer. This apparatus is able to work
either in constant stress or constant strain rate modes. The first
step is therefore the choice of the modus operandi. +n practical
polymer processing the melt is usually pushed through a certain
geometry at constant strain rate, not constant stress. Constant
stress measurements are relatively quick, the achievement of constant
stress being obtained mechanically. However, the tests are performed
using strain rates below those obtained under normal processing
conditions. The recent tendency is to use constant strain rate
measurements 200 ,203; the constant strain rate is achieved through
 - 80 -

electronic circuitry now easily available. Therefore, this mode was

chosen.

In the apparatus available at IPT a specially designed sample

consisting of an oval ring (Figure 2.6) is clamped between a fixed
and a moving carriage. The assemblage is immersed in silicone oil.

~
./
~
./ \
i
i i
---t-o ---'-i-'
.I I.
I

57.4

FIGURE 2.6 Sample for extensional rheometry. Dimensions in mm.

After reaching thermal equilibrium, the carriage begins its movement,

pulling the sample with increasing speed in order to maintain constant·
strain rate; the force, carriage speed and sample length are measured
and the readings electronically processed in order to ensure the
constant strain rate and provide the relevant output (stress and
sample length).

The samples were prepared by compression mOUlding. The operating

conditions that led to the most successful product were as follows:

- heating temperature 190 DC;

- pre-heating time 6 minutes;
- heating time (under pressure) 10 minutes;
- extraction of spe cimens ,,'hen 50 DC were reached;
- pressure 20 Tonnes;
- amount of material" 14 g (mOUld with capacity for 4 samples).
 - 81 -

l'lhen performing the experiments, the samples were left for 10

minutes in the silicone oil bath, before thermal equilibrium was
considered to have been achieved. Due to the low thermal expansion
of PVC (around 6 x 10- 5 m/m/OK) the increase in dimensions when
heating up the sample to 190°C was disregarded. The output of the
rheometer was in graphical form - stress and length with time (see
Figure 2.7). Each experiment was repeated twice, the results being
quite reproducible. Tests were performed at 0.001, 0.005, 0.01, 0.05
and 0.1 s-I, the latter being the maximum strain rate available. The
following data was also obtained:

- tensile stress versus tensile strain;

- extensional viscosity versus tensile strain;
- tensile stress versus tensile strain rate.

STRESS

LENGTH

TIME

FIGURE 2.7 Experimental results for (; = 0.01 s-I'

 - 82 -

The results were treated by computer. A polynomial fit was

made to each set of data pOints, and the several results 'added'
to produce one master curve for each strain rate. This was then
treated to generate the different relationships. Both stretching
ratio and Hencky strain were considered. The methodology is similar
to the one used for studying shear flow properties (a simplified
flowchart is presented in Appendix B).

2.3.3 RESULTS AND DISCUSSION

Selected results of the shear flow studies are presented in

Figures 2.8 to 2.10. They show a typical non-Newtonian behaviour,
with a power law index of 0.24. The shear stresses were of the order
of 10 5 Nm- 2 and the apparent viscosity around 10 4 Nsm- 2 , which
correlates well with the data published 37 ,42-44. As expected, the
die-swell was found to increase with both shear rate and shear stress.
A plateau was reached for shear rates of 40 s-l and shear stresses of
5 x 10 5 Nm- 2 , corresponding to the onset of melt fracture; beyond the
critical shear stress, die-swell would have decreased169 • Die-swell
values between 11 and 16% were measured, which agrees well with the
figures of 12 to 20% usually presented in the literature181 ,189.

Results from the extensional flow studies are presented in

Figures 2.11 to 2.13. The maximum Hencky strain varied between 0.82
and 1.2 for the various strain rates used, which falls directly in
the range reported in the literature (section 2.3.2). There was a
tendency for the strain at failure to increase with increasing
stretching rate (Park and Riley203 observed similar phenomenon). At
all strain rates, stress increases of two to three orders of magnitude
were observed during the stretch. This strain hardening effect has
been previously noted for PVC and other materials 203 ,208; it is
believed to be associated wi th the deformation of an entanglement
network structure possessing the same degree of extensibility between
the entanglement points. It has been shown 208 that this behaviour is
independent of polymer structure.

At all the strain rates studied, the stress only showed a slight
 L-OG13
POLYNOMIAL OF DEGREE 3
"7
,,",
r,
i-- -
<-J .---
I
L: --
Z
~

Ln
er;
I..LJ
CL:
f-
v)
6
=-
(Y.
.<
'LJ
T
en
>c
5
1-
/---r--I--+-t-I-I--+++---+--+-t---H-l-f-H

o
r TEM'" Jse) C I
r L. _________ l _____,--'_____ L_-'--'--'-.Lf-_ _ _-'-,_-'--'_--'--'---'I_-L--'---'-:!.
2
SheAR R.\ TL (S-I) L_OS 1 Cl

FIGURE 2.8 Shear stress versus shear strain rate

 APPROXIMATION BY CHEBYSHEV SERIES REPRESENTATION

LOG10 POLYNOMIAL OF DEGREE 3

" 6
N
I
I::
en
z
>-
I-
;;:; 5
o
u -
en
....... -x, v
> ~

CL
~
«: ~
4 f'x

TEMP. 190 C
3
5 6
SHEAR STRESS (NM_~9G10

FIGURE 2.9 Apparent viscosity versus shear stress

 APPROXIMATION BY CHEBYSHEV SERIES REPRESENTATION
X10- 2
POLYNOMIAL OF DEGREE 3
1 1'7

1 16 x
x X
0
1 15 :
X
~

1-1 1 4
<
(Y.
1 13 -
t')

~ 112
_I x
00
u:l111-
::;: x \J<

(/)110:

109 -
108 :

197-

106 -_
: TEMP. 190 C
105
0 2

SHEAR RATE (S-l )LOG19

FIGURE 2.10 Swelling ratio versus shear strain rate

 - 86 -

trend to level off at high values of strain. This indicates possible

inability to determine the Trouton viscosity of the material and is
consistent with the observations of shear flow, as it indicates non-
-Newtonian flow behaviour169 ,203. It also means that one of the
assumptions of the analysis of tapers by Cogswell176 carries
considerable degree of error.

2.4 PROFILE OF DIE

After input of the relevant data, the program for die design was
run, and the profile established. The mechanical details of the design
can be appreciated in the drawings of Appendix C. The die is basically
divided into two elements, the die land and the body. A breaker plate
can be coupled to the latter. Both the die and the body are sectioned
in two halves to facilitate the machining operations. These halves
are tightly clamped together to avoid any possible leakage. The die
is fixed to the head of the extruder via a clamping ring and the
appropriate adaptor, a special one having been designed for each of
the extruders used.

Apart from the definition of the best profile for the die and
,dimensions of the breaker plate and fixing bolts, the output of the
program also provides the pressure build-up profile along the length
of the die, the shear and extensional pressure drops being presented
separa tely •

\fuile the shear pressure drops were of the order of 10 7 Nm- 2 , the
values for the extensional pressure drops were around 10 5 Nm- 2 , showing
that the main effect of extensional flows is not the pressure drop
created, but the eventual onset of melt rupture defects when a tensile
stress limi t is surpassed.

A number of experiments was performed to check the accuracy of

the values computed. The compound was extruded in a single screw
extruder whose die temperature was set to 190 DC (for details of the
composition and eqUipment see chapter 4). Samples of the extrudate
were taken without any cooling or haul-off and the values of pressure
 APP~OXIMATION BY CHEBYSHEV St~IES REPRESENTATION
POLYNOMIAL OF DEGREE 4
LOG10
7 _ _ _ __

'"'
Cl.
~

(f)
(f)
w
CY.
f-
(f)

W
-' 00
(f) -J
Z
W
I-

HE~CKY STRAIN LOG(L/LO)

FIGURE 2.11 Tensile stress versus Hencky strain

 APP~OXIMATI0N BY CHEBYSHEV SERIES REPRESENTATION
LOG10
POLYNOMIAL OF DEGREE 3

Vl
<
CL
~

>-
0-
Vl
Cl
U
Vl
>
-'
<
z
Cl
~.
00
(j) 00
z
W
0-
X
W

8 9 10 11 12
X10- 1
HENCKY STRAIN LOG(L/LO)

FIGURE 2.12 Extensiona1 viscosity versus Hencky strain

 LOG10
7
- ...
nl Y\if n~ r.:~

_. ..
,
6 .
»
.
. ))
V)
(/)
UJ
V
'"
l-
V)

UJ / 0.0 1 L ( ) )
-'
(/) / V Ii
:z
UJ
I- 5 . / / ---I , ,,
I

- .
..

. ...
I
-. / --j-
I
.

11 , i

1
TM Pc I I Ii
2 3 1 5
LOG10
EXTENSIONAl STRAIN RATE (5-1) X 10E5
FIGURE 2.13 Tensile stress versus extensional strain rate
 - 90 -

and temperature of the die monitored.

The observed values of swell ratio were within 8 percent of the

predicted values; however, the extrudate was never rectangular, and
with increasing speeds the width of the extrudate decreased. The
pressure drops measured fell within 25 percent of the values predicted.

Figure 2.14 assesses the homogeneity of the extrudate. Samples

along the width were extruded in a capillary rheometer at constant
speed, the pressure being monitored. The experimental procedure is
described in chapter 4. The smaller the pressure differences along
the width, the more homogeneous is the extrudate. The pressure
differences being quite small, one can conclude that the homogeneity
of the profile is good, therefore the die seems to be appropriately
designed, not creating big differences in the velocity profile. It
also seems that the presence of the breaker plate does not improve the
degree of homogeneity significantly. The assumption of isothermal
flow was also tested. Despite measuring the temperature field only at
one point of the cross-section, it can be seen (Figure 2.15) that the
assumption carries a progressively bigger error with increasing screw
speed.
 - 91 -
[PSI]

",0
_.-E>-._._. _.~
1
~. ~.~.

e- 0
-----e-·-2
4000 .... 3
~4
.........,"'7
.,.'"
.......
~.
<:::jl....... "'"....
.. ... ~ / " /

'.... ..... ..........

~.......
.....
-- ----*--- _.. .",.""

J'''''
,
.;
"
.. -.. A-
.... ~ ..-.--.-
left Tig.1t
3500~~--------~----------~--------~~--'

EXTRUDATE WIDTH

FIGURE 2.14 Jegree of gelation along the extrudate >lidth. Curves

1 and 3 obtained at 5 rpm. curves 2 and 4 obtained at
10 rpm; single screw extrusion

[OC]

191-
190-------, .A~~======:-====
189-

3 5 10 15
RPM
FIGURE 2.15 Temperature of extrudate for varying screw speeds
 - 92 -

CHAPTER 3

PLANNING OF EXTRUSION EXPERI:1ENTS

3.1 EXPERIMENTAL DESIGN

3.1.1 INTRODUCTION AND AIMS

In planning and evaluating experiments one starts by considering

the selection of the most suitable amongst the available designs, and
by analysing the possibli ty of representing the process by a
mathematical model. In the latter case, after performing the
experimental work the accuracy of the predicted results is tested.

In a conventional experiment each variable is inspected

indi vidually by holding the other stationary, and then varying each
one in turn. This type of experiment can be very inefficient since
it can only provide limited amount of information for a maximum of
time and experimental material. Statisticians have provided researchers
wi th numerous methods for the planning of experiments; by choosing the
appropriate design one can:

- make more use of the experimental material;

- do exploratory work with the aim of quickly determine the
effects of each factor;
- investigate interactions between the separate factors
(interaction between two effects exists when the effect of one of
them depends on the particular level of the other);
- evaluate the range of validity of the conclusions.

In the literature there exist relatively few works which tackle

the problems of PVC processing by statistical methods 74 ,145,209-211.
This fact led Barth 211 to review experimental planning, from the
defini tion of the problem to the choice of models for planning the
experiments for PVC profile extrusion. In this work, the statistical
design approach was also used.
 - 93 -

3.1.2 , CHOICE OF EXPEHmENTAL DESIGN

The choice of an experimental design consists of the selection

of the points in the control space at which experimentation is to be
carried out, and the specification of the number of runs to be carried
out at each point. vlhen selecting the experimental points one is
restricted to the areas of the control space in which experimentation
is feasible, ie., the operability region. Prior to selecting the
factors and their levels a knowledge of the important variables (and
acceptable levels) is useful; the fewer the number of variables the
Simpler the experimental design. For both single and twin screw
extruders the screw(s) speed, barrel temperature profile and die
resistance are obvious independent variables; their acceptable levels
can only be determined by preliminary exploratory work.

A variety of deSigns, ranging from a full factorial to a number

of speCial purpose designs211-213 exists. The choice depends on a
multitude of parameters, namely necessary accuracy, reliability of
resul ts, continuity of the result field and importance of interactions.
Because it is impossible to ensure complete adequacy of a model, it
is usually advisable to compromise with an experimental design
capable of indicating model adequacy to some extent, even at the
expense of a slight loss of precision in the parameter estimates.
Therefore a design, the Rotatable Centre Composite Factorial Design
(RCCFD), was selected from a set of standard ones; it consists of a
complete two level, three variable factorial experiment.

The Rotatable Centre Composite Factorial Design is built up by

adding further treatments to those obtained from a complete two
level factorial (in this case 2 3 ) . The 2n factorial enables an
estimation of the first-order effects and all the interactions. The
further treatments - consisting of a further (2n + 1) combination -
allow an estimation of the quadratic effects and the experimental
error. The total is therefore 2n + 2n + 1 = 15 runs for n = 3. The
2n extra points - known as star points are located in pairs along
the coordinate axes at ±~,±a 2 ••• ±an • The remaining point is
located at the centre. Replicating runs at the centre point 'provides
an estimation of the experimental error and of the adequacy of the
 - 94 -

model. The values of a's can be chosen so that there is more

information on variations along the control space or more assurance
of the values at the extremes, or to minimize the bias it can create
if the true form of the response is not quadratic.

The design matrix used in this project is summarized in Table 3.1

for the arrangement shown in Figure 3.1. Each independent variable
was treated at three levels, where 0 is the midpoint. The absolute
values of these levels was predetermined for each independent variable
by trial experiments with the two different types of extruder. They
are indicated in chapter 4. In order to prevent systematic errors,
the order of the fifteen runs was chosen at random (this procedure
being particularly time consuming in the case of temperature profile
changes) •

+ •,

+-=
Cl)
.-
Cl)
QJ
t...
-.
•
QJ
.-
"C
I

+
•
temp.

o factorial ;;oi nts

... star pOints

~ centre point

FIGURE 3.1 Central Composite Design

 - 95 -

RUN SCREVI TEMPERATURE DIE

NUMBER SPEED PROFILE RESISTANCE

1 -1 -1 -1
2 -1 -1 +l
3 -1 +l -1
FACTORIAL 4 -1 +l +l
POINTS 5 +l -1 -1
6 +l -1 +l
7 +l +l -1
8 +l +l +l

9 -1 0 0
10 +l 0 0
STAR 11 0 -1 0
POINTS 12 0 +l 0
13 0 0 -1
14 0 0 +l

CENTRE POINT 15 0 0 0

TABLE 3.1 Central Composite Design for a 2 3 factorial

3.1.3 HODEL FITTING AND ASSESSMENT

The statistical approach to experimentation centers on the

representation of a process by a mathematical model. This can be
derived in a mechanistic way by trying to infer the structure of
the model from a scientific understanding of the problem; it can
also be derived empirically. by choosing a model that is sufficiently
flexible to describe a wide range of different types of behaviour.
if the theoretical understanding of the process is insufficient to
enable an identification of the structure for the relationship
between factors and response. This seemed to be the situation at
the start of this project. The main limitation of empirical
modelling is the di ffi cuI ty in generalizing the results to new
 - 96 -

situations; it is also hazardous to use the model to predict the

level of a response corresponding to values of the control variables
outside the range of the experimental data. 11i th this in mind, a
polynomial model allowing for interactions and curvature in the
relationship between controls and response was chosen. It has the
general form:

k k k k
L L
i=l
L LBi·X.X.
i<j J 1J
(3.1 )
i=l

where: Y - response
X.X. - independent variables
1 J
Bo' Bi , Bii , Bij - coefficients of the polynomial (independent,
linear, quadratic and interaction coefficient,
re spe cti vely ) •

For three variables the equation becomes:

(3.2)

The criteria used in fitting the model to the set of experimental

data was the least squares method, particularly indicated for linear
type models; it has also the advantage of having well established
computer packages. One of the best currently available (although of
difficul t command structure) is the GLIM program 214 , on the PRIME
computer at L.U.T. The experimental results are input in the form
of a data file which is processed by the computer package, each
response being treated seperately.

The program (a sample of the output is given in Appendix D):

- performs the regression analysis and fits a curvilinear model

which relates the individual responses to the three independent
variables, together with their quadratics and cross multiplier terms.
A Normal distribution is assumed;
- lists the coefficients of the polynomial, their standard
deviation and labels them;
 - 97 -

- prints a table of the experimental and predicted values and

the residuals (difference between the two);
- plots the residuals versus the predicted points, allowing for
the assessment of the adequacy of the mathematical model; if the
points in this plot are randomly scattered the model is adequate; if
it looks organized in any way this means that other alternative
distributions must be tried (Poisson, Binomial and Gamma are
available) ;
- displays the deviance of the model for each response and the
degree of freedom. The standard deviation is given by

Deviance
02 = --------- (3.3)
Degrees of freedom

and is due to experimental error and/or poor fit of the polynomial

model.

3.1.4 INTERPRETATION OF THE FITTED MODEL

Once the coefficients of the polynomials for the various

responses are determined and the accuracy of the model assessed (and
considered appropriate) the interpretation of the re suI ts can take
place by analysis of the polynomials. However, this can be difficult
in situations where the effect of interactions is important, or
minima/maxima exist in the control space. In these instances suitable
graphical representation can assist the understanding of the results.
From the three main types of t"lO-dimensional representations -
contour plots, isometric projections and shading diagrams - the first
was considered appropriate.

A contour plot is a graph in which two control variables are

represented on rectangular axes, and contours, or lines joining
points where the response is constant, are plotted against these
axes. If a diagram shows one response against two control variables,
for a complete study of a response nine contour plots will be
necessary. A computer program was developed to plot all the contours
for each individual response and, if desired, to superimpose several
responses. The algorithm for producing the contours is contained in
 - 98 -

the GINOSURF library. Some other. subroutines used in the program

belong to the GINO F or GINOGRAF library. The program:

- reads the coefficients of each polynomial from a data file;

- sets one of the independent variables to the different code
values (from -1 to +1), and produces a new polynomial expression
(relating the individual response to the other remaining variables)
with six coefficients. This procedure will be repeated for the
other independent variables;
- evaluates the new polynomial between -1 and +1, producing a
10 x 10 matrix; this is then used for the production of the contour
plots.

Some plots thus produced are presented in Figure 3.2.

3.2 INSTRUJ.lENTATION OF THE EQUIPMENT

3.2.1 INTRODUCTION AND AIMS

The implementation of measuring device~ in an extruder can

provide useful information on the overall process. The shear and
heat history of the polymer inside the machine can be followed; the
existance of a steady state can be more easily assured. The two
extruders available for this study have different levels of
instrumentation. i>Jhereas the twin screw extruder has temperature
probes and pressure transducers strategically located along the
profile of the screws, the single screw machine has only one of these
devices before the die. It was therefore decided to instrument this
machine, ie., to provide it with temperature and pressure measuring
devices along the screw. The number and location of these is
obviously limited by the size of the gaps between the band heaters
on the barrel.

3.2.2 HARDWARE

The difficulty in instrumenting a machine is not implementing

the measuring devices, but ensuring a fast, reliable and efficient
 ROTATABLE CENTRE COMPOSITE FACTORIAL DESIGN
THREE YAR!18LE "ACTOR!IL

FIGURE 3.2 Contour plots

CO~TOUR HEIGHT: aUT PUT 2S

p IS I(fDT "T LE'VEL-I P !S I(EPT ~T LEVEL 0 P IS I(fPT "r LFYEL I

'"'"
1.0

L:~
! I I I I I I

\' TI'\ I
I
~
- I
N 1 ! I
N u
I

.5
\

.,'JJ
"'--
w
'"2
~
Q'
., r ",
1
" \!
\ r-

\'-
w
~

'"
"\~ "r
~
-.2 -.2
-J -r
\
\\
I
'" N N N
"
\.r
\\ r
-.6 -.6 -.E
\'-
~
-1.0
-1.0 -.6 -.2 .2 .6 Le
"1.0
I
-1.0 -.6 -.2 .2 ,5 i.0
-1.0
I
\
-i .0 -.6 -.2 .2 .b ; .~
 ~OTATABLE CENTRE COMPOSITE FACTORIAL DESIG~
THREE V~RI~BLE HCTORI~L

CONTOUR HEIGHT: OUTPUT 25

T t~ I(Epr A.T LEVEL-\ T IS KEPT ~T LEvEL 0 T IS KEPT ~T LEVEL I

1.0 I I I I I I I I I

-
! 1 1 ~
1
1 11 1 11 r
1.0 1
I I I
~
1
~ ~
I
~
I ~
I
~

-
.6;- I- .G;-
- r - I
~
~
=>
.2 .2:-
[ ,- ,
,
1
~
~ - -
~
~
o. ,j
- ,-
-I
-.2 -.2:-
-.2
- ~ ~ ~ ~ ~
- - - - ~ ~ N ... ~
- - - - ~
~ ~ ~ ~ ~
-

If!
-.6 -.6;- -

-1.0
I j -1.0
-
r 11 r
-.6;-

-;'0
-
I
/i
1

11
1 I I I 1 I 1 I I I I I I I
-1.0 -.6 -.2 .2 .G 1.0 -1.0 -.6 I I I I
-.2 .2 .G 1.0 -1.0 -.6 -.2 .2 .6 , .?
 ~OTATABlE CENTRE COMPOSITE FACTORIAL DESIGN
THREE VARI~BLE FACTORI~L

CONTOUR HEIGHT: OUTPUT 25

S IS ~EPT ~T LEVEL-I S IS KEPT H LE~EL 0 S IS ~EPT H LEVEL I

I.B-t.r-rh-+-rh-+-.,.....,~r-+-7--'--t- f-'
I.B'-l--,-+--r'-r-'-r---;f-+-,.l--f--'7-'-+!3

.6
.G

.2
.2 ~
-.2
-.2

-.6
-.6

-I.B -.G
-I.B'-+I-'-r-r'"-.-"-r-'f--r-r"'-r-.--r-
-.2 .2 .G I.B -1.0 -.6 -.2 .2 .6 1.0
CONTOUR HEIGHT "0- 3 CONTOUR HEIGHT "B-3 CONTOUR HEIGHT "B-3

TEMPFRATURE
 - 102 -

way of collecting the data. The use of a chart recorder for each
device is unpractical and very expensive. Hicrocomputers, very
efficient and with the advantage of not only collecting but also
processing data, seemed a much more attractive solution.

The scheme shown in Figure 3.3 was therefore used:

fibre optics

DIE EXTRUDER rotational

potentiom.
digital pressure
termom. transduce

power
supply I-------~

printer APPLE lIe disc

COMPUTER drive

FIGURE 3.3 Layout of instrumentation

- Four j·1heatstone bridge Dynisco pressure transducers were

located along the screw length and head of the extruder. For an
input of 6 volt (power supply in the diagram) they produce a voltage
output in the range 0 - 10 mV linearly proportional to the pressure.
 - 103 -

- A digital thermometer (DIGITRON 2751-K) connected to a type K

thermocouple protruding into the melt stream at the head of the
extruder allowed an immediate reading of the tenperature, and easier
monitoring of the system. This thermometer also provides an output
of 1 mY/cC.
- A Infrared Thermal Honitor (VANZETTI TM-2) was also used for
measuring temperatures. This system makes Use of infrared radiation
which is received from the target; its response time is 100 mSec; it
consists of an optical fibre bundle and an head assembly containing
an infrared detector and a pre-amplifier, connected via a cable to
an electronic chassis with controls, digital display and connectors.
The output can be temperature or vOltage in ~~e range 0 - 10 V.
- The pressure and .:temperature readings can be related to the
location in the channel of the scre\~ by use of a rotary potentiometer.
This device produces an output voltage linearly proportional to the
angle of its rotor. If the device is mounted on the screw in such a
way that a certain voltage output corresponds to a known coordinate
in the channel of the screw, the direct relation can be established.
A Penny & Giles 3081 rotary precision potentiometer was used; for a
6v input, an output in the range 0 - 10 V is produced.
- The Analogue/Digital Converter converts the continuous varying
electric voltage of the measuring devices into the digital form the
computer can cope with. The device used - CIL PCI 1001 - had 16
channels available for scanning; these were specially prepared for
inputs in the 0 - 100 mV, 0 - 1 V and 0 - 10 V ranges. The output
of the device consists of two bytes (bw eight bit words) of data
that are deposited into two locations of the computer memory for
peeking into the program. l1i th all the inputs shortcircui ted the
outputs read 0 ± 1 digit; when each input is connected to a vOltage
source equal to full scale, the output is 4000 ± 1 digit. This
device, being one of the first of its generation, is only capable of
a small number of scans per second (approximately 20).
- The computer available for this study l<as an Apple ne
Personal Computer \u th 64K RAN, together wi th Disk Drive and an
Apple Sylentype Printer. For the purposes of this project the
computer was also provided with a 80 column text and additional 64K
RAN memory card and a IEEE-488 interface bus and card. This device
 - 104 -

is dire ctly conne cted to the A/D and its circuits perform the function
of translating the program instructions into commands understood by
the A/D.

3.2.3 SOFTI'lARE

The aim of the system is the fast reading, processing and storing
of information. By developing the software as a combination of
independent specially-built subroutines, one is also able to use parts
of the system for other research work (chapter 4).

First, a fast transfer routine in machine language was developed.

It starts by defining the general control values, and sets the chip
of the IEEE-488 card (THS 9914) into the desired state; the receiving
of data from the talker is then defined. Once the transfer routine
was ready, the software (in Applesoft BASIC) could be developed.
Figure 3.4 presents a scheme of the software created for the extrusion
experiments.

The software can be divided into three groups:

- calibration of the measuring devices: programs were developed

for the calibration of pressure transducers, digital thermometer and
fibre optics. Basically, they consist of linear or polynomial
regression of a set of output voltage versus measured pressure/
/temperature points. The pressure was measured using a Budenberg
Standard Testing Gauge, the temperature using mercury thermometers
near the temperature probe;
- warming-up of equipment: the software provides two ways of
monitoring the warming-up of equipment and achievement of steady
state: a) table of values of pressure and temperature updated every
two seconds; b) graphical displays, created by takihg advantage of
the scrolling-up of the print-out in the monitor;
- collecting and processing of data: once the steady state is
achieved, sampling of data can take place; this operation was
automatized, so that full attention can be paid to operating the
equipment. The data collecting routine scans all the measuring
devices in turn, each together with the rotary potentiometer. After
 - 105 -

IMENUI
t
WARMING-UP
I
SAMPLING
t
CALIBRATION
I
1 ~

p',~P
. scan []7B •

~,RP scan
~-----l

DUMPING IN DISC
J
~ I
I
,
I

TREATMENT OF DATA
I
I I
FAST SCANS SLOW SCANS
~
•
average of
each run
graphs, print out, ~
average cycle average of
experiment

FlGU'!E 3.4 Flowchart of soft·.,are

 - 106 -

scanning each sensor. a general scan of all channels is made. in

order to ensure that the steady state is maintained throughout the
experiment. After concluding the experiment. the dumping of data
into disk is undertaken: each scan is stored in its own file for
later treatment. This is also schematized in Figure 3.4: the routine
prepared for the individual scans presents the values graphically
and is also able to identify and isolate an average cycle per
rotation of the screw; the overall scans are averaged. per scan and
for the experiment.
 - 107 -

CHAPTER 4

EXPERIMENTAL PROCEDURE

4.1 PREPAR~TIO!~ OF FORHULATION

An extrusion type suspension resin supplied by BP Chemicals Ltd

was used throughout this project. Its technical data is given in
Table 4.1.

Viscosity no. (ISO method IS 174:1974) 111

K-value (0.5% so1ution of cyclohexane) 66
Bulk density (Kg m- 3 ) 550
Particle size (%) less than 250 \.Im 99.5
less than 75 \.Irn 2.0

TABLE 4.1 Technical data for Breon SllO/ll

A simple formulation, chosen by BP Chemicals, Barry, and referred

to as the 'standard formulation', was considered to be a good
compromise of workability with both types of extruders used in this
work:
p.h. r.
S-PVC Breon SllO/ll 100
Diabasic Lead Stearate 2.5
Calcium Stearate 0.4
O.S. 2411P wax 0.3

DBLS - 2PbO.Pb (C02.C17.H35)2 - is a white powder, with a specific

gravity of 2.0, a 55.6% lead content and a melting temperature of
95°C, as determined by DSC. Calcium stearate - Ca (C02.C17.H35)2 -
melts at 120°C. The external lubricant - O.S. 2411P - is a low
molecular weight compound with a melting range between 84 - 101°C.

The ingredients were mixed in a 8 li t.re T.K. Fielder Internal

 - 108 -

Mixer. The general principles of this machine are discussed in

chapter 1. A 2 Kg batch of the blend was placed in the upper chamber,
preheated by steam to 75°C. The rotors were made to rotate at 3600
rpm until the blend reaches 120°C (which takes approximately 20
minutes); the blend was then discharged through a pneumatic valve
into a lower speed coder mixer. The chamber of this mixer was cooled
by running water, its large blade rotating at 1500 rpm. After 2
minutes the blend was discharged into a container. These operating
condi tions were determined by previous research work128 Both the
blender and cycle are shown schematically in Figure 4.1. Several
hundred kilograms of formulation were prepared in this way.

2K?
charge
JACKET TEMP. 75'C

U
3600 rpm JS;:s;;::~ ~;::s::::s:::s:::::q~
JACKET COOLED
WITH WATER

\J
1500 rpm
FIGURE 4.1 Mixer and blending cycle

4.2 EXTRUSION

4.2.1 SINGLE SCRE':1 EXTRUSION

The dry blend was fed into the hopper of a 1.5 inch Bone Craven
Single Screw extruder, and pI~cessed into a rectangular strip as
 - 109 -

produced by the die designed in chapter 2. The dimensions of the

screw are shown in Figure 4.2.

The extruder is driven via belt, by a 22 KI'/ thyristor controlled

DC motor; instruments for measuring motor supply and voltage and
screw speed are available. The facility of cooling the barrel
heaters by running water was implemented. Also, a pneumatic jack
was fitted at the end of the screw to make possible its fast
extraction. This is only possible after removing both the die and
adaptor from the head. The barrel, adaptor and die temperatures
were controlled via on/off Eurotherm temperature controllers connected
to thermocouple sensors. This type of heaters allowed the measurement
of the heat input, by recording the 'on' and 'off' time periods in
an event recorder attached to the controllers.

The experimental matrix and independent variables having been

defined in chapter 3, the absolute values were found from trial
experiments. They are indicated in Table 4.2.

CODE VALUE
VARIABLE
-1 0 +l

SCREl1 SPEED 20 50 80

REAR BARREL 170 182 194

I1ED. BARREL 170 182 194
---
TEXPERATURE FRCNT BARREL 170 182 194

PROFILE REAR ADAPTOR 174 186 198

FRONT ADAPTOR 174 186 198

DIE 178 190 202

NO :.!EDIUf1 HIGH
DIE RESISTANCE BREAKER RESISTANCE RESISTANCE
PLATE B. PLATE B. PLATE

TABLE 4.2 Absolute values of independent variables - single screw

extrusion
 P ..'1

o1
I
I
I
i

1~.~_____ L_2______ -+~____ t~ap~e_r_f_ro_m_6_._35

._3_81___ __W
__2._2_86____ 4.+I~.___________
L1__________ .~1 ~
D = 38.1 h1 = 6.35 = 152.4
L1 t = 3.988
P = 38.1 h2 = 2.286 L2 = 228.6 o = 0.0762
$ = 17.65 b = 32.512
Uniform taper over 381 mm
Dimensions in millimetres Number of turns = 20 Not to scale

FIGURE 4.2 Dimensions of screw

 - 111 -

At the start of each run the temperature controls were mu tched

on and set to the required levels. A zero voltage output from the
rotary potentiometer was made to ccrrespond tc a particular position
of the screw; for this, the screw flight could be observed through
one of the pressure transducers mounting holes. Enough time was
allowed for thermal equilibrium to be reached. This could be checked
ei ther by observing the output of the warming-up routine in the
computer, or by monitoring the regularity of the 'on' and 'off'
swi tChings.

The hopper was supplied with powder, the level of material being
kept constant to avoid surging (chapter 1). The extruded strip was
fed into a cooling bath with a calibrating die, and a caterpillar
haul-off. After steadying the extrusion line, the screw speed was
adjusted to the required level. The steady state was reached after
10 to 15 minutes.

The experiment was initiated. The event recorder was switched

on, the voltage and current input to the motor recorded; the mass
output was measured by monitoring the amount of extrudate produced
after an elapsed time of operation. The computer program was set in
data-collecting mode. Enough extrudate was produced for later
analysis.

Once these operations were concluded, core samples were obtained:

the barrel heaters and motor were switched off and the production
line interrupted. Cooling water was made to flow inside the heaters.
Simultaneously, the rotary potentiometer was disconnected from the
screw end and the extracting jack mounted. The die was dismantled,
followed by the adaptor. The material inside was removed and coded.
The jack was operated, and the screw began to move slowly; its speed
increased as more length ceased to be in contact with the barrel.
Once the screw was fully out, the material in the flights was numbered
from the tip to the powder end. If the operation was quick enough,
the material would not be completely rigid, so could be uncoiled from
the screw. However, it was also noticed that if the screw was not
removed quickly, the material would degrade extenSively. This happened
very often with material in the adaptor and die, where no cooling
 - 112 -

facilities could be provided. Usually - depending on the processing

condi tions - it was not possible to recover material from flights 16
onwards, because it was still in powdered form. The entire stripping
process took, on average, 10 minutes. An example of the core samples
obtained is shown in Figure 4.3.

FIGURE 4.3 Helix of core material from the single screw extruder

4.2.2 TI:IIN SCREI, EXTRUSION

The twin screw extruder available for this project, a laboratory

fully intermeshing conical counter-rotating Krauss Maffei KMD-L25,
has been already described in the literature 92 • The profile of the
screws is divided into four zones, feed, compression, degasing and
metering. The screws are 400mm long, with diameter of 25 and 50mm
at the tip and in the powder end, respectively. The instrumentation
of the machine includes melt temperatures (before venting and die),
pressures (end of feeding zone, beginning of metering zone and
adaptor), screw temperature, torque and screw speed measuring devices.
During the experiments a horizontal dosing screw with variable speed
was used; its speed was kept constant for each operating speed,
regardless of the other independent variables. As with the single
 - 113 -

screw extruder, the absolute values of the controls were determined

from preliminary experimental work, their values being shown in
Table 4.3.

CODE VALUE
VARIABLE
-1 0 +1

SCRE'/l SPEED 18 32 46

SCRE'.·JS 165 175 185

TEMPERATURE REAR BARREL 170 180 190
PROFILE FRONT BARREL 185 195 205
DIE 190 200 210
NO MEDIUM HIGH
DIE RESISTANCE BREAKER RESISTANCE RESISTANCE
PLATE B. PLATE B. PLATE

TABLE 4.3 Absolute values of independent variables - twin screw

extrusion

The experimental procedure was identical to that for the single

screw extruder,.except that the temperature controllers were of the
proportional type, thus not allowing measurement of heat input. The
technique for obtaining core samples was also different; after having
obtained enough extrudate and monitored pressures, torque and output,
the screws were stopped and the oil heaters switched to 140°C. The
die and adaptor were removed, and the core samples collected; the oil
pipes for heating the screws were removed, and the screws disconnected
from their shafts; the entire unit (barrel plus screws) was than free
to rotate on an axis perpendicular to the screw length and the screws
could be pulled out from the inside of the barrel. The material in
each screw turn was numbered from the tips to the powder end. Because
towards the latter the material was still in powder form, it was not
possible to collect samples from the feeding zone. A sample of the
core material thus obtained is shown in Figure 4.4.
 - 114 -

FIGURE 4.4 Core material from twin screw extruder

The process took on average 15 minutes; except in the die, where

the material could be kept at high temperatures for some time, no
problems with degradation were found.

4.3 COMPRESSION MOULDING

\'Ii th the aim of obtaining material with limited shear history,

sheets were produced by compression moulding at various temperatures,
from 145 to 205°C. The cavity of the mould had the dimensions 190 x
x 120 x 2.2 mm, and the press was 40 Tonnes manually operated with
electric heating and water cooling system. The operating conditions
were as follows:

quantity of material (g) 85

pre-heating time (min.) 7
pressure during pre-heating time (Ton.) 5
heating time (min.) 6
moulding pressure (Ton.) 20
 - 115 -

4.4 PRODUCTION OF PELLETS

A 1 inch Betol single screw extruder, fi tted with a screw for

PVC with L:D = 20, coupled to a die of circular cross-section, was
used to produce rod. ,This was later fed into a specially prepared
Kopp Lace Cutter, in order to obtain pellets of average dimensions
3.7mm (diameter) x 2.7mm (length). The screw rotated at 20 rpm,
and two temperature profiles were used, with temperature settings
at the die of 179°C and 192°C. Lower or higher temperatures would
create too high back pressures and degradation of material,
re spe cti vely •

4.5 DEVELOPHENT OF FUSION ALONG THE SCREvl( S)

4.5.1 OPTICAL MICROSCOPY

4.5.1.1 JAmN-LEBEDEFF INTERFEROHETER

In the Jamin-Lebedeff Interferometer (Figure 4.5) there is a

complete separation of the image field into reference and measurement
regions, by use of polarised light and doubly refractive optical
140 151 .
components' The 11ght from the source is plane polarised by
the polariser. On passing through the doubly refracting beam
spli tting prism Rl in the 45° position, this light is divided into
two rays; the ordinary ray passes through the prism without change
of direction,but the extraordinary ray is displaced laterally.
This second ray will pass through the specimen, the first through a
reference region; both will then enter the recombination prism R ,
2
identical in nature to~. A specimen with a zero Optical Path
Difference (OPD)(*) with respect to the reference region will produce
a dark view, a non-zero value of OPD will lead to light passing by
the analyser, producing a bright image. Variable OPDs will produce
a sequence of different image colours, making this technique very
sensitive.

(*) OPD is the phase difference between two light waves, given by
t(ri -ri ), where t is the section thickness and ri and ri the
l 2 l 2
refractive indices of specimen and reference region, respectively.
 - 116 -

E
E ro
E
re
QJ
QJ
Ll
ro Ll
QJ
-0
.D QJ C
...., en
ro
0
u
QJ
~ E Vl

ANALYSER

OBJECTIVE LENS

~V
V Rz PRISM
1/1/
REFERENC E SPE CIMEN

"A/2 HALF WAVE PLATE

1/ V R, PRISM

CONDENSER LENS

POLARISER

LIGHT SOURCE
FIGURE 4.5 Principle of Jarnin-Lebedeff system

In this work a Jamin-Lebedeff system (Pol-Int I 10/0.22 and

Pol-Int II 40/0.65) was attached to a Zeiss Universal Microscope.
Thin sections (2um thickness) were cut from the specimens using a
Lei tz 1400 microtone with a 'D' profile blade. The sections were
mounted between a standard slide and COver slip using tricresyil
phosphate as the mounting fluid. The sections had the shape of
small strips to avoid overlapping the reference area.
 - 117 -

4. 5.1. 2 FLUORESCENCE MI CROSCOPY

Certain materials, when exposed to electromagnetic radiation (in

the u.v. region) absorb part of it and re-emit it with a larger
wavelength (within the visible spectrum). It is then said that these
materials fluoresce. It is known that when PVC degrades, if exposed
to u.v. radiation it will fluoresce in the visible region129 In
this "ork fluorescence microscopy was used to assess the degree of
degradation, which is related to the processing history of the polymer.
An incident light system was used, with the specimen both irradiated
and viewed from above, through the objective lens. A Zeiss Universal
Hicroscope, with a Zeiss III RS fluorescence attachment and a Plan
Neofluar xI6/0.50 objective was used. The light source was a 50 watt
HEO high pressure mercury vapour lamp. The fluorescence attachment
contained a G365 exciter filter (peaking the radiation from the lamp
to the optimum wavelength for maximum visible light emission from PVC)
and. a barrier filter LP420 (removing the u. v. radiation and
transmitting all the visible spectrum).

The measurements of fluorescence intensity were made using a

Lei tz .1PV Compact Microscope Photometer wi th a 600 volt setting and
xl sensivity, using a square zone of constant size. \'Jhen a section
was brought under the measuring square, a recording button was pressed
and the measured value of relative fluorescence intensity displayed.
Ten measurements were made for each specimen, and their average
determined.

The specimens were prepared on a Leitz 1400 microtome and held

on the slide by plasticine.

4. 5.2 SCANlIDIG ELECTRON MI CROSCOPY

The samples were fractured after immersion in liquid nitrogen,

sputter coated with gold, and mounted on aluminium stubs. Their
examination was carried out on a Scanning Electron Microscope
Cambridge Stereos can 2A.
 - 118 -

4.5.3 DIFFERENTIAL SCANNING CHORIMETRY

For instrument details and experimental conditions see section

4.7.1.

4.5.4 DENSITY

A density gradient column was used. See section 4.8.2 for

details of preparation of column.

4.5.5 SOLID BED/1!ELT POOL RATIO

The helix of material unwrapped from the screw was sectioned

along a plane perpendicular to the channel length. Two distinct
phases could be observed, one light yellow of melted material, another
brown of partly melted material or compressed powder. A sharp
boundary was found between the two. The ratio of melted material
over the channel cross-sectional area was obtained by photographying
the whole area, and weighing the enlarged prints correspondent to the
two zones. This procedure was repeated for the various screw turns
and factOrial runs.

4.6 RESIDENCE TIME AND RESIDENCE TIHE DISTRIBUTION

The experimental procedure for the det.ermination of the RTD

involves the presence of a tracer t.hat is placed into t.he fluid st.ream.
After both extruders had reached a steady state, and before carrying
out the experimental runs, a sample (5g) of tracer was added very
quickly into the hopper when the screws were nearly starving (the
injection time was considered instantaneous: at time t=O the tracer
was fed into the system). The exit concentration was then monitored
as a function of time until a new steady state condition was reached.
This procedure was repeated for the fifteen runs of the factorial
experiment.

Later, cross-sections of the extrudate were cut, polished and

 - 119 -

observed under a Zeiss Universal Light l1icroscope in reflectance mode

coupled to a Lei tz MPV Compact Microscope Photometer (previously
described). Using a 25X magnification, each cross-section
corresponding to a certain elapsed time from the pulse was scanned; a
number corresponding to its 'clarity' obtained. This is directly
proportional to the presence of tracer in the extrudate, so a
'concentration' versus time curve was plotted.

Two tracers were used, one for each type of machine. For t.he
single screw Extruder, 'vulcan C' (ISO N293, type CF) carbon black
was chosen, as its agglomerate size is similar to the PVC grains,
therefore minimizing the effect on the conveying characteristics.
In t.he case of the twin screw machine, t.he use of a 'cleaner' tracer
could be afforded: titanium dioxide was used.

4.7 ASSESSMENT OF DEGREE OF FUSION

4.7.1 DIFFERENTIAL SCANNING CALORIlIETRY

A DuPont 990 Thermal Analyser fitted with a DSC cell was used.
The cell is made of a constantan disc enclosed in silver heating
block and lid. The sample and an inhert reference are closed in
pans which sit on marked locations on t.he disc. Heat is transferred
through the disc into the sample and reference (air) via the pans.
Their temperatures are monitored by chromel-constantan thermocouples
formed by the junction of the constantan disc with a chromel wire at
each pan location. The signal difference between the two thermocouples
is amplified and monitored on a recorder against the sample temperature.

In this work samples of 10-12 mg of mat.erial were scanned from

room temperature to 240°C, Et a heating rate of 20°C min- 1 and a
Eensi vi ty of 1 mV cm -1. The areas of the endot.hermi c curves were
measured with a planimeter and converted into heat of fusion via the
equation:
A
= - - (60BElIq)
m s
 - 120 -

where l\.ljf - heat of fusion (Jg- 1 )

A - area of endothermic curve (cm 2 )
m - mass of sample (g)
B - time base setting (= 0.5 min cm-I)
E - cell calibration constant, evaluated from endotherm
areas of standard samples. The value taken was
0.254 ml1 mV-!
~q - Y-axis sensivity (mV cm-I)
s

4.7.2 CAPILLARY RHEONETRY

The Davenport capillary rheometer used in this study consists

mainly of a barrel that can be kept at the required temperature,
through which a ram moves up or downwards at variable controllable
speed. At the bottom end of the barrel a capillary die can be
located; a lateral hole was provided at a height correspondent to the
die entrance, so that a pressure transducer could be attached. In
this work the latter was connected to the Apple lIe I AID converter
ensemble, the average pressure in the experiment being computed. The
mac.hine panel includes course and fine temperature controls, and
control and display ef t.he ra.m speed. The temperature in the ca.rrel
can be checked with a thermoe.ouple and Comark.

An effectively zero length die (LID = 0.08) with a diameter of

2mm was used. The barrel was preheated to 130°C and the 30g of
sample were loaded and heated for 10 minutes. The pressure was
measured as the piston moved at 2cm min-!. All the runs were carried
out in duplicate.

4.8 PROPERTIES

4.8.1 MECHANICAL

4.8.1.1 TENSILE TESTING

Uniaxial tensile testing was carried out using Instron and JJ

Uni versal Testing 1-Iachines, the latter for tests at high temperatures.
 - 121 -

The test specimens were cut out in both parallel and perpendicular
to the extrusion direction and machined to conform wi th the type V
profile (Figure 4.6) of the ASTl1 D638-82 standard. At room
temperature the tests were carried out at the rates of 5, 20 and 200
mm min- 1 , each test being repeated four times. For the tests at
high temperature, a SPRI environmental chamber coupled to the JJ
machine was used. An accuracy of ± 2°C could be achieved. The
testing bars were preconditioned at the testing temperature in an
oven for 20 minutes, and then qui ckly t.ransferred to the chamber for
a further 10 minutes. The clamping of the specimens was critical,
specially at temperatures above T , to avoid their fracture at the
g
clamps. The tests were performed at 20 mm min- 1 at 60, 90, 120 and
150°C. The initial gauge length ,!as 25.4 mm. The reproducibility
of the results was found to be excellent, therefore each test was
repeated only twice.

I+~
Fl=t=l =1 LO
~~T

T - thickness 4 or under
U - width of narrow section 3.18 ± 0.5
NO - width overall 9.53 ± 6
1 - length of narrow section 9.53 ± 0.5
10 - length overall 63.5 no rnax
G - gage length 7.62 ± 0.25
D dist~~ce between grips 25.4 ± 5
R - radius of fillet 12.7 ±1

FIGURE 4.6 Test specimen dimensions (type V) for ASTH D638-82, mm

From the force - cross-head displacement curve, the following

parameters were derived:

- ultimate tensile stress

 - 122 -

- yield stress o
y
= F
y
lA (4.3)

- Young's modulus E = oh (4.4)

- elongation at yield £ = (.R.y-.R. ) 100%/.R.0 (4.5)

y o
- elongation at break £B = (.R.:t 20) 100%120 (4.6)

where FB - force at break un

A - eross-sectional a.rea of dumbell bar (m 2 )
F - force at yield point (N)
y
o - stress measured Id thin the proportional limi t of the
material (Nm - 2)
E - strain corresponding to 0

.R. - displacement at yield point (m)

y
.R.O - initial gauge length (m)
.R.B - displacement at break (m)

Above T , because the material behaved like a rubber, there was

g ' .
no yield point; also, there was no true proportional behaviour,
therefore the modulus was calculated for a specific elongation, 10%.

4.8.1. 2 FLEXURAL TESTING

The flexural tests were carried out on a JJ Testing Machine

T5002, following - Id th slight modifications - the directions of the
method I of the AST~1 D790M-81 standard. According to this. for
specimens with thickness greater than 1.6mm the support span of the
three point bending test must be 16 times the value of the specimen
thickness. However, because the accessory available did not allow a
continuous variation of the span, a constant value (38mm) was
maintained throughout the experiment. The samples Here rectangular.
with dimensions 130 x 12.7 mm and a thickness around 2~m. They were
obtained by removing t.he skin of the ext.I'udate and er.sure a good
surface fini sh.

The rate of t.he test, as defined by the standard, is

 - 123 -

where Z is the rate of straining of the outer fibre (0.01 min- 1 ), L

the support span (mm) and d the thickness of the beam (mm). :. R =
= 1.27 mm min- 1 • As the minimum stable value achievable with the JJ
is 2 mm min- 1 , this value was adopted.

j"lhen performing the test, a force - displacement curve was

produced. The parameters monitored were:

BM 3FL
- flexural stress 0 =- 1l. (Nm - 2) (4.8)
I 2 = 2bh 2

L3 m
- tangent flexural modulus Et = (Nm - 2) (4.9)
4bd 3
L 3m* (Nm- 2 )
- secant flexural modulus "s = (4.10)
4bd 3
~

where BM - bending moment (Nm)

I - moment of inertia (m 4 )
b - width of profile (m)
h - height of profile (m)
L - support span (m)
m - slope of tangent to the curve within the proportional
limit of the material (Nm- 1 )
m* - slope of straight line from the origin to a constant
point of the curve (Nm- 1 )

The above equations are only valid for small deflections, the
maximum deflection being given by the formula

D = rL 2 /6d (mm)

where r is the maximum strain in the outer fibres (0.05 mm min- 1 );

D is 6.33 mm. In this work, the post-yield point measured for each
curve was obtained from equation 4.11 with r = 0.015 mm min- 1 •

4.8.1.3 IMPACT TESTING

It is well known that the impact strength of a polymer depends

both on the geometry of the specimen and test method. Despite the
 - 124 -

difficul ty of correlating the re sul ts obtained from different met.hods,

a large number of tests have been devised. In this work the Advanced
Ceast Fractoscope, model AFS/HK2 was used in the Izod mode. The
equipment consists of two independent units, the digital pendulum
and the fractoscope. The first includes the basic frame, an
electromagnetic system for release with double push buttons, and a
digital display of break energy expressed in Joules. The fractoscope
unit stores in memory the force-time values during impact and
processes and presents them in both digital and graphical form; the
maximum load and failure energy are displayed, and plots of force
and energy versus time are possible. The values of the pendulum and
fractoscope de net. always agree due to internal friction, vibratione
and elastic energy stored by the machine. An analogue pendulum,
making use of the same hammer and support for the specimen \;as also
used.

The preparation of samples was carefully carried out: each

extrudate was machined in order to remove the skin formed upon
processing/cooling and obtain a good surface finish. Rectangular
strips with the dimensions required by the ASTI1 D256 standard ",ere
cut, and the sides polished. The thickness of the specimens was
approximately constant but smaller than the standard (average 2.2mm).
Preliminary tests showed that unnotched bars were unbreakable with
the hammer available, thus all specimens were notched as prescribed
in the standard. The dimensions of the specimens used are shown in
Figure 4.7.

The tests ",ere carried out at room temperature, after enough

warming-up time of the electric circuitry, and calibration of the
force display. The following conditions were used:

Pendulum mass 1.25 Kg

Pendulum energy 7.5 J
Impact speed 3.46 ms- 1
Force range 95.5 daN
Time scale 0-4 ms
 - 125 -

1--r======:::-.t----, ~'---t-----,- DIRECTION OF

IMPACTED END I o w
COMPRESSION

IJ.ot====_B__--_-_~_, -J T 7:,,~,O,'::'
SPECIMEN

ntln
1\ 11I.lhl 0,0<; q~t")! '"om2
It ,12.20 I :!hO
:tl,:'>o 1,240
(" 6.l:'1l 2.500
('OJO 2..'15
!) O.:!:'iR ± O.IIS lI.tlloR .t 1I,fM):!
L 1:!.70±fJ.lS 1I.:'\01).:! u.r~)(,

FIGURE 4.7 Di~ensions of Izod impact specimens

.The impact strength of each sample is given by

-2) ____~i~m~p~a~c~t~e~n~e~r~gy~~a~t~~f~a~i=l~u~r~e~--~~
I.S. ( Jm = cross-sectional area behind the notch

4.8.1.4 HARDNESS

The mechanical tests above mentioned being of destructive

nature, it was decided to monitor hardness.

Hardness is essentially resistance to indentation 215 ,219 and

can therefore be considered a surface property. It has been related
to properties of the material such as tensile yield stress, modulus
and viscoelasticity215,216 and can therefore be expected to vary
with gelation level.

The experimental procedure for the test most commonly used -

Rockwell hardness - is specified in ASTM D785, derived directly for
 - 126 -

metals: since plastics are generally considered to be softer than

metals a lighter load and a larger indentor are used; because
polymers are viscoelastic, a rigid time cycle is applied. The
indentor is initially forced into the material under a minor load
of 10 Kg for 10 seconds, the major load of 60 to 150 Kg being then
applied for 15 seconds; the measurements are taken 'on the run',
ie., while the indicator is still moving, often quite rapidly, 15
seconds after removal of the major load. This procedure can result in
innaccuracy, since it depends on the skill of the operator; also,
it has been shown 215 ,216 that in practice different polymers have
different relaxation times, hence the inaccuracy of the data can be
substantial.

There has been limited work into hardness testing as a function

of time and on developing methods for its analysis using traditional
viscoelastic theory. Philips et al 215 showed that a hardness test
is a compressional version of a tensile creep and recovery test, but
the dependence of the relaxation time on the loading time made its
mathematical modelling very difficult. Narisawa 217 extended this
work to PVC. Most of the other reports have been limited to
developing testing machinery, often capable of performing runs at
varying temperature 218-221

A testing machine was developed for this work, so that the

potential of hardness testing as a technique for the assessment of
degree of fusion could be investigated. The layout of the equipment
is shown in Figure 4.8.

In this instrument the indentor is attached to a cylindrical

housing, itself coupled to a linear displacement transducer. When
a load is applied at the other end of the device, it will be
multiplied by the mUlti-lever system, and cause the indentor to
penetrate the sample, and the transducer to produce an electrical
signal. The latter, a Penny &Giles LVDT 1355 Displacement
transducer, capable of measuring displacements between 2 ~m and
10 mm, was connected to an Apple lIe Computer via a AID Converter.
The software developed allowed monitOring of the depth of penetration
wi th time, with graphical representation and data processing.
 - 127 -

FIGURE 4.8 Hardness testing instrument

The sample is placed on a variable height table (which allows

the testing of different sample geometries). This, together wi th
the indentor, is enclosed on a sealed environmental chamber with a
solid glass front door. It is possible to move the table accurately
from outside, in order to carry out a number of measurements without
opening the door. The chamber is heated by a resistance heater, its
temperature being controlled by a thermocouple and a on-off RS
temperature controller. An accuracy of ±50C was achieved. Near
the specimen the temperature is monitored with a Comark.

The sample in the form of a 30 mm square was located on the

table, its centrepoint below the indentor. The test was coded in
the computer and the total time defined. After applying the minor
load for a determined time (achieved by rotating the micrometer
laterally), the data collecting subroutine was initiated: the
indentation so far was zeroed and, as the major load was applied
(manually), the depth of penetration with time was displayed both
graphically and numerically in the monitor. When reaching the
loading time the major load was removed and the recovery monitored;
 - 128 -

the test was stopped automatically after the total time pre-defined
for the experiment had elapsed. A new·specimen was used for each
experiment, a total of 5 being used for each condition.

For tests above room temperature the samples were preheated in

an oven for 20 minutes and left for an extra 10 minutes in the
chamber of the tester.

In order to establish the best operating conditions for the

hardness test, the effect of the minor load, loading time, geometry
of the indentor and test temperature on the final hardness was
investigated.

When a stress 00 is applied to the material (Figure 4.9), an

elastic deformation e l takes place instantly upon application of
the stress and will recover immediately and completely upon its
removal. If the stress is large enough and maintained long enough,
delayed elastic deformation (e 2 ) and viscous flow (e ) will occur.
3

2a:

2(e 1+ ~) Il t
2e.
e1+e,
2e t

r~'
2e,
e, et
2e)

FIGURE 4.9 left Schematic representation of the hardness experiment

right correspondent Maxwell - Voigt mechanical model

\Vhile elastic deformation results in the bending of the bond angles

of the polymer chain, delayed elastic deformation and plastic flow
correspond to the chain un coiling mechanism and chain-chain
 - 129 -

slipping219 If the deformation takes place by the chain uncoiling

mechanism, upon removal of the stress the deformation, although
time dependent, will be recoverable. If the chain-chain slipping
mechanism is present, viscous flow will take place: while the stress
is applied the deformation will continue and upon removal of the
load none of the deformation will recover.

The behaviour deSCribed above is usually represented by a

corresponding mechanical model, with Haxwell and Voigt elements in
series. G corresponds to the elastic deformation, G and 1)2 in
l 2
parallel represent the chain un coiling mechanism and 1)3 represents
the chain-chain slipping mechanism. As Philips et al 215 have
shown, this model is an over-simplification since in reality the
delayed elastic deformation should be represented by a series of
elements with different viscous and elastic constants.

vllien performing the test follOwing the guidance provided by the

ASTH, the measurement of the indentation is made with most·of the
delayed elastic recovery still taking place. By moni toring the
ratio between maximum indentation (occuring just before release of
the load) and indentation after a recovery time T longer than
required by the standard, one is able to define the minimum operating
time capable of producing data with little error. Also, the use of
the above ratio will provide more information on the viscoelastic
nature of the material than the hardness number alone.

Using the same operating conditions (indentor with a diameter

of 3.18 mm, major load of 50 Kg and a loading time of 30 sec) various
minor loads were used, producing the results shown in Figure 4.10.

Increasing minor loads decrease the amount of elastic recovery;

this is obviously expected, since with increasing load the element
1)3 of the mechanical model will flow at increasing rate. It is also
apparent that the rate of recovery of indentation is practically
independent on the value of the minor load; it was therefore decided
to use the value of 10 Kg defined in the standard.

The effects of varying the major load and loading time can be
established from the analysis of Figures 4.11 and 4.12.
 - 130 -

2.4 1 KG

1--2.2
w
z ~
0 ......
.....

: : :
I--
u2.0
I--
3 KG
~ UJ
Z 0::
w
0 I-- 6 KG
Z
...... «
L 0
z 1.8 9 'G 9 9 8 KG
~
~ ......
L
.....
~
;:::: : : : :
X
« ~1.6
L
10 KG
o·
z
......
13 KG

1.4

1 2 3 4- 5 6
RECOVERY TIME T
LOADING TIME
FIGURE 4.10 Influence of minor load on the recovery of indentation

As wi th increasing minor loads, increasing major loads cause

higher indentations and smaller recoveries. With increasing loading
time the viscous element can deform fUrther and, upon removal of the
load, there will be more delayed elastic recovery and more permanent
deformation. As a result, the ratio maximum indentation / indentation
at recovery time T decreases with increasing loading time (Figure
4.12).

According to the mechanical model presented (Figure 4.9), the

recovery curves should be superimposable over each other for the same
loading time and indentor. The results obtained are presented in
 - 131 -

INDENTATION [MM]
1.0~---------------'

30 KG

0.5
163060 120 240 sec
it l l ~
o.01.L--....-.....----.---.--..------.--....----.----l
1.0
40 KG

0.5 240 sec

120
63060
/1

0.0
1.0
50 KG

120 240 sec

0.5 n6 3060
/'
\.

0.0 480
120 240 360
TIME [SEC]
FIGURE 4.11 Indentation and recovery curves for various loads and
loading times. Small indentor
 - 132 -

2.5

-------_. ._._._._._._.-
Zw
oL
t-

>-< >-<
t-t-
«.
.--- ---'
~-.-.-.-.-.-.-.-.-
~~~.~.~.~~~~~====~~::=====
"-'-'-

/~...:- ---------
t-w
Zw
wo::
0t-
/':;", .... -----
" ,... .....
.

~« 1/" --
~_-:-";;'.;;.".--:-..:::.=-'7'=":-_._._'-'-'-'-'-
Lz2.0
:::>8 I ...... ::;.
--- --

T-
~~.
Lt- ?;.7"., -
X~ MAJOR LOAD [KG) LOADING TIME
«z
~w
o 30 40 50
z
.....
t _.- 16 SEC
30 SEC
----- 60 SEC
_..- 120 SEC
240 SEC
1.5;.1.----.-1--.....2---.3---4.------.-5 ---6---
RECOVERY TIME T
LOADING TIME
FIGURE 4.12 Recovery curves for various loads and loading times.
Small indentor.

Table 4.4, the large indentor having a diameter of 6.35 mm. Although
further work is necessary to confirm this, it seems that if the
ratio maximum indentation / indentation at recovery time T is used,
the results can effectively be considered independent on the value
of the maj or load.

Figure 4.11 shows that for loading times of 30 seconds and

beyond, the slope of the indentation curve suffers little change;
Figure 4.12 shows that for recovery times of at least 3 times the
value of the loading time no significant evolution occurs in the
 - 133 -

recovery curves. Therefore, these two operating conditions were

used for the tes1B at room temperature.

MAJOR LOAD (KG)

INDENTOR LOADING AVERAGE
TIt1E (SEC)
30 40 50

16 2.52 2.29 2.26 2.36 ± 0.14

30 2.23 2.31 2.04 2.19 ± 0.14
SMALL 60 2.34 2.04 2.13 2.17 ± 0.15
120 2.19 1.97 2.01 2.06 ± 0.12
240 2.13 1.89 1.81 1.94 ± 0.17
16 3.98 3.84 3.86 3.89 ± 0.08
30 3.88 3.89 3.42 3.73 ± 0.27
LARGE 60 3.68 3.63 2.96 3.42 ± 0.40
120 3.22 3.51 3.23 3.32 ± 0.16
240 3.12 3.12 2.90 3.05 ± 0.13

TABLE 4.4 Ratio maximum indentation / indentation at recovery time T

for different test conditions

The effect of varying test temperature on the values of

hardness was investigated carrying out experiments at 60, 90, 105
and 120°C. Tests beyond the latter value were abandoned, since an
indentation would also appear on the suface opposite to the one
being tested.

The indentation and recovery curves typically obtained are

illustrated in Figure 4.13, Figures 4.14 and 4.15 presenting the
indentation and recovery curves in more detail.

Both the maximum and after recovery indentations (the latter

corresponding to the hardness number) increase almost linearly with
test temperature; as T is approached the rate increases and beyond
g
T a small increase in the test temperature causes a substantial
g
development in indentation. The results below T are supported by
g
the work of Stern and Berlot 220 who also worked in a specially
------------------------ -

- 134 -

INDENTATION [MM]

2 o
120 C

90 •C
•
rt=p~~60 C.
23 C
100 200 300 400 500
TIME [SEC]

FIGURE 4.13 Indentation and recovery curves typically obtained

when testing at different test temperatures

designed hardness instrument.

At room temperature the viscosity of the dashpots ~2 and ~3

(Figure 4.9) is high, the material responding in a relatively rapid
elastic manner defined by the modulus of spring G • As the
l
temperature increases, the viscosity of the dashpots decreases
allowing more rapid chain uncoiling and recoiling, but simultaneously
more chain-chain slipping to take place. The effect of increasing
 - 135 -

test temperature loading time

23 • C 0 16 sec
f-
UJ ---- 60 • C IJ 60 sec
L
..... _._.- 90· C 0 120 sec
f-

>
0
---- 105· C
u
UJ
120· C
crz.5
~
z
.....
0

~
f-
z
UJ
0
z
,... "' ..... --
-
.....
52.0
.....
f-
/.""'
.....
....
II'
~ //
I
Z
UJ I
0 I
z
.....

--- ---
'" ... -- ----
,

.. ---"" T"'";

-- ... -
~---.-.-.-e-. :-;;11'-....-::..... -.~ - - - - -
- - -- - - - -
,..,-

/
/
_----.-8--
#I'

.,. ....
... -:. ......... -
,. ... e ___ - ..0- -
....... - -

. --.. ~"".
,,/I ,.'"
~,... .

I,.,.....-
' -~--­

t l

1 234 5 6 7
RECOVERY TIME T I LOADING TIME
FIGURE 4.14 Recovery curves of various loading times and test temperatures
 - 136 -

[MM]
MAXIMUM
5 2.0
INDENTATION

-
1.5
zOW
......
I- ..-.
~

«I-.
I-
z>
Wo INDENTATION
Clw
Zw
...... 0:: T =240 sec
~I-
~ « 3 1.0
...... z
Xo
«-
~~
I-
Z
W
Cl
Z
......

2 0.5

40 60 80 100 120 140

TEST TEMPERATURE [OC]

FIGURE 4.15 Indentation and recovery curves for varying test

temperatures
 - 137 -

temperatures depends therefore on the interactions between these

two mechanisms. For temperatures below T , the modulus of spring
g .
G decreases, the delayed elastic response becoming less effective
2
and allowing the stress to be transmitted to the dashpot D • As
3
a result, more non-recoverable deformation occurs. Above T ,
g
despite the further decrease in both n and D3' causing higher
2
increases in maximum indentation and indentation after recovery
time, the existance of an entanglement network prevents the
molecules from slipping past each other, and upon release of the
load they recoil causing an increase in the ratio of indentation
recovery.

The performance of hardness testing at low and high temperatures

involves different deformation mechanisms. At low temperatures the
values of indentation are comparatively small, with a high
proportion of elastic recovery; at high temperatures the recovery
is also significant, but the sharp increase in indentation can
create practical difficulties in the execution of the test.
Consequently, the correlation between hardness and degree of
gelation was mainly investigated with experiments at room
temperature.

4.8.2 DENSITY MEASUREMENTS

Because the densities of the extruded samples were expected to

differ only slightly, accurate measurement was needed. A density
gradient column was used. The mixing of varying proportions of a
denser and a lighter solution of calcium nitrate created a linear
increase of denSity from top to the bottom of the column. The two
extreme densities were defined by the initial solutions, and were
never more than 0.02 g cm- 3 apart. The column was kept at 23 DC.
The denSity of any sample in the column could be determined by
entering its height on a height versus density chart, obtained by
reading the position in the column of calibrated floats (usually
4-5 floats were used).
 - 138 -

CHAPTER 5
RESULTS hVD DISCUSSION
SINGLE SCRBI EXTRUSION

5.1 ENERGY EFFICIENCY OF THE PROCESS

5.1.1 INTRODUCTION

A better understanding of the extrusion process can lead tc more

efficient production and better quality products. As energy costs
continue tc rise, it becomes increasingly important to minimize energy
consumption during production. The energy balance approach has been
examined in the ll.. terature 222-224 as a way of determining the overall
energy efficiency of the extrusion process and highlighting areas of
potential energy savings.

The energy balance for the entire extruder can be written as 223

Z +q = CQ~T + Q~P +H (5.1 )

where Z - mechanical power delivered to the screw;

q - electrical power to heaters;
C - average specific heat of the polymer;
Q - volumetric extrusion rate;
~T - temperature rise in the polymer;
~P - pressure rise in the polymer;
H - heat losses by radiation and/or convection.

The pressure energy term, Q~P, is the power required for forming
the material through the die, and is usually less than 5% of the
tota1222, 224. I t will t..'1erefore be disregarded.

If the extruder could be operated in such a manner that the heat

loss H was balanced exactly by the power input to the heaters q, and
no heat was transferred either t.o or from the plastic, an adiatGtic
state would exist, with all the heat and pressure energy in the
 - 139 -

plastic arising from ~echanical work~ng

. 222 • Mennig and Subramanian144
have shown that for polyethylene the shaft work is completely
converted into useful energy, albeit an additional net thermal energy
is required. For PVC, however, a high amount of shaft work was
necessary, indicating the presence of a mat.erial with high viscosi ty
throughout the length of the screw and poor efficiency in the increase
of t.he material's enthalpy. Also. high heat losses were observed.
meaning that most of the conversion of mechanical energy into heat
took place near the barrel wall and not within the material itself.
These observations were shown to be caused by the wall-slipping
characteristics of the material at low temperatures, leading to the
mel ting me chani srn reported by Klenk120 •

The purpose of the following sections is the computation of the

terms of equation 5.1. and establishing the range of processing
conditions that allow more energy efficiency.

5.1.2 CALCULATIONS

The energy balance equation 5.1 can be re-written as

MEI + HEI = lIE + HL

where MEI is the mechanical energy input to the screw, measured

experimentally from the t.orque; t.his is usually determined
by set.ting a brake on a shaft. placed in the empty machine
instead of the screw. Because such a device was unavailable.
NEI was obtained by manipulating equation 5.2.
HEI is the heat energy input to the heaters. It is calculated
after analysis of the 'on' and 'off' time intervals recorded
by the event recorder. The full power of the heaters
attached to the barrel was determined from measurements of
their electrical resistance. The power was calculated from
V2 /R, with V the voltage across the terminals and R the
overall resistance of the heaters. The results are
indicated in Table 5.1. together with the nominal values
quoted by the manufacturers.
 - 140 -

ZONE R POl'iER :IOMIll AL POloJER

(0) on (IV)

1 79 2917 3000
2 79 2917 3000
3 79 2917 3000
4 27 2133 2200
103 559 650
5
200 228 350

TABLE 5.1 Full po\;er of barrel heaters

lIE is the increase in the internal energy of the polymer, given

by
nE = ID C bT (5.3)
v
with ID - mass flow rate (g/s)
Cv - heat capacity at constant volume = 1.05 J/g OK64
bT- (Melt Temperature - Room Temperature) (OK)

HL are the heat losses; they equal the heat energy input by the
heaters "hen the extruder runs empty, since after the steady
state is reached any additional energy input is necessary to
balance the heat losses. HL was calculated as HEI, with the
machine running empty.

The electrical energy input to the motor (EEl) can be calculated

by multiplying the supplied voltage by the supplied current (and
subtracting the EEl values for the machine running empty).

The efficiency of the process was evaluated by an 'extrusion

efficiency index' (E EF 1)226, defined as the ratio of the volumetric
input divided by the total energy input to the system:

Q
E EF I = (5.4)
EEl + HEI

where
Q = rli/p (5. 5)
m
wi th Pm the melt density of the polymer.
 - 141 -

The quantities measured during the extrusion experiments (section

4.2.1) and computed are shown in Table 5.2. The density of the
polymer was determined in a density gradient column, following the
procedure described in section 4.8.2. The individual responses were
stored in a computer file and treated separately by the GLIM progra~

(section 3.1.3), the coefficients of the polynomial being obtained.

Contour plots (section 3.1.4) were produced to make the analysis of
the polynomials easier. The coefficients are displayed in Table 5.3.

5.1.3 RESULTS AND DISCUSSION

5.1.3.1 MASS OUTPUT

The re suI ts suggest that there are no interactions bet"een the

independent variables. The mass output increases steadily with
increasing screw speed, and decreasing barrel temperatures and die
resistance, although the effect of these is small. The results can
be explained by the well known equation for the output Q of a single
screw extruder:
BM'
Q = AN - (5.6)
T)

where N is the screw speed, ~p the pressure gradient, T) the melt

viscosity and A and B constants based on the geometry of the extruder.
An increase in die resistance will cause higher back pressures and
therefore a decrease in the output. vii th increasing temperature both
M' and T) decrease; the overall effect could lead to a decrease in the
output. This decrease could also be due to a decrease of melt density
wi th increasing temperature. Maximum outputs can be obtained at low
die resistances and high screw speeds, the temperature profile has
l i ttle significance.

5.1.3.2 ELECTRICAL E:IERGY INPUT

The value of EEl decreases with increasing temperature. This is

logical, since the temperature profile determines the viscosity of the
polymer mel t and therefore the torque required by the screw. \'Ii th
 machine empty wi th material T3 •
m EEl HEl IIE HL HEl Q E EF I
RUN* (OC) g/s (w) (w) (w) (w) (W) (cm 3 s- 1 ) x10-'cm 3 J- 1
A V A V

1 4.2 72 25.0 78 190.9 2.62 1648 1899 1216 1915 1232 1.87 5.272
2 4.5 78 22.0 82 186.5 2.42 1453 1813 1112 2216 1514 1.72 5.281
3 4.2 72 18.0 73 210.0 1.99 1012 2671 963 2653 945 1.42 3.855
4 4.6 83 18.4 79 208.0 1.67 1072 2628 805 2459 636 1.19 3.222
5 7.5 248 28.0 253 190.9 7.62 5115 1582 3536 2193 4147 5.44 8.123
6 7.1 275 30.0 273 189.3 6.41 6237 1637 2964 2075 3401 4.58 5.816
7 7.3 248 28.6 253 209.2 7.55 5425 1983 3648 2714 4379 5.38 7.263
8 7.1 251 29.0 272 210.2 6.62 6102 1816 3205 2644 4034 4.74 5.987
9 4.5 73 20.8 76 197.9 2.05 1252 2324 966 2438 1080 1.46 4.082
10 7.6 248 23.2 250 199.6 4.20 3915 1376 1988 2525 3136 3.00 5.670
11 6.2 170 28.4 156 190.3 4.41 3376 1449 2044 2471 3036 3.14 6.507
12 5.8 154 18.2 155 211.2 2.93 1928 2390 1422 2651 1682 2.09 4.847
13 5.8 150 22.3 158 198.7 3.62 2653 1865 1700 2217 2052 2.58 5.710
14 6.5 166 33.0 166 198.7 2.94 4399 1828 1388 2366 1926 2.10 3.372
15 5.8 150 23.6 155 198.9 3.47 2788 1862 1639 2310 2087 2.47 5.312

* according to Table 3.1

TABLE 5.2 Values for energy efficiency calculations
 COEFFICIENTS
RESPONSE
S T P SS TT PP ST SP PT
• {g/s}
m 2.945 2.165 0.272 -0.334 0.312 0.857 0.467 0.19 -0.202 0.02

EEl {l~} 2673 2036 -229.0 341.0 -61.2 7.33 881.3 149.0 241.8 -23.7
HEI {N} 1823 -294.3 310.7 -27.8 37.4 107.1 33.9 -125.9 2.2 -22.6
lIE {W} 1388 1028 -82.8 -158.9 151.2 407.1 218.8 114.2 -94.0 9.45
IlL {w} 2437 46.97 225.1 6.8 13.4 93.1 -176.6 13.5 -36.8 -55.7
MEI (vI) 2002 1369 -168.4 -124.3 127.2 393.1 8.2 253.6 -133.0 -23.6
E EF I {xl0- 4 cm 3 J- 1 } 4.909 1.115 -0.582 -0.654 0.067 0.868 -0.268 0.348 -0.369 0.049

TABLE 5.3 Polynomial Coefficients of the responses of the energy balance

 - 144 -

increasing die resistance the value of EEl should increase, since

back pressure increases; however, so does the amount of shear leading
to a decrease in viscosity. The balance of the tl<O effects is
responsible for a decrease in EEl at medium die resistances; at
higher values of die resistance the effect of shear can no longer
match the increase in back pressure and E~I increases.

ScreH speed, as expected, is the dominating variable, EEl

increasing steadily with it. The minimum values of EEl occur therefore
at 101< screH speeds, medium die resist~~ces and high temperature
profiles.

5.1. 3. 3 HEAT ENERGY INPUT

The amount of conducted heat is decreased by increasing screH

speed and die resistance, probably because both contribute to more
mechanical Horking. There is a strong dependence of HEI on the
temperature profile, HEI increasing with higher temperature profiles.
Therefore, the minimum HEI occurs at low temperature profiles, and
high screw speeds and die resistance.

5.1.3.4 HEAT LOSSES

The heat losses increase steadily with increasing temperature,

therefore more conducted heat (HEI) is required to maintain the set
temperature. The effects of die resistance and screw speed are not
statistically significant; as HEI decreases Hi th increasing screw
speed, it can be concluded that increasing rate of production allows
more efficient conversion of mechanical energy.

5.1. 3.5 INCREASE IN INTERNAL ENERGY

The increase in the internal energy of the polymer, ie., the

power required for melt preparation, produced unexpected results.
h~ereas one would expect temperature to be the dominant variable,
no significant influence could be detected. These results can only
be explained by the significant increase in the melt temperatures
 - 145 -

specially at low temperature profiles due to high level of shearing,

and by the observed decrease in output with increasing temperature
profile.

Because the energy supplied by the heaters (HEI) is mainly used

to overcome the heat losses, an increase in screw speed allows more
mechanical energy to be converted into heat - the increase of lIE
with increasing screw speed was expected. A slight decrease of lIE
with increasing die resistance was observed.

Maximum lIEs can be obtained at high screw speeds and low die
resistance.

5.1. 3. 6 MECHANICAL ENERGY INPUT

The values of MEI were obtained by manipulation of equation 5.2.

222
It has been shown that the mechanical pOlo/er delivered to the screw
is proportional to the product of the volumetric flow rate Q,
viscosity of the material n and rate of shear y:

HEI 0: Q nY (5.7)

Therefore, MEI should increase ,;1 th increasing extrusion rate

and decreasing temperature profile. This was observed. Additionally,
MEI decreased wi th increasing die resistance; equation 5.7 can
account for this behaviour, as increasing die resistance causes Q
and n to decrease.

At this point it is interesting to compare the results obtained

with those reported by Mennig and Subrar.Ianian144 These authors
indicate that high heat losses and amount of shaft work are
characteristics of a wall-slipping material, thus indicating poor
efficiency(lf), with most of the conversion of mechanical energy into
heat taking place near the barrel wall. Although the value of the

(*)
Efficiency is defined as the ratio of increase in internal
energy over the total power input.
 - 146 -

heat losses and amount of shaft work were also appreciable in this
work, the energy efficiency was greater than that reported by Hennig
and Sub ram ani an , although far from the values typical of
144
polyethylene • Also, while Mennig and Subramanian report that for
wall-slipping materials MEI decreases with increasing screw speed,
the behaviour for wall-sticking plastics was observed here. One
could therefore conclude that the composition being studied either:

i) behaves generally like a wall-slipping material, but the

processing conditions used are close to the onset of wall sticking;
a mechanism of fusion similar to the one described by Klenk120 but
presenting more wall-sticking characteristics and energy efficiency
could be expected;
ii) behaves like a wall-sticking material, but with very poor
energy efficiency. This could be due to the use of a poorly designed
screw.

5.1.3.7 EXTRUSION EFFICIENCY INDEX

This index describes what volume of material the machine is

capable of producing per unit energy input to the system. The
evaluation of its dependence on the operating conditions enables the
definition of an optimum processing window from the energy consumption
point of view.

EEFI decreases with increasing temperature and die resistance,

mainly because an increase in temperature means more HEI demand and
an increase in die resistance less output (although a decrease in
HEI). As expected, E EF I increases steadily with screw speed, as
HEI decreases and the throughput increases.

Despite some effect of the interactions (ST and SP), the maximum
of E EF I takes place at high screw speeds and low temperature
profiles and die resistance; the minimum at high die resistances and
temperature profiles and low screw speeds.
 - 147 -

5.2 HIXING CHARACTERISTICS

The m~x~ng characteristics of the process were assessed by

monitoring the Residence Time Distribution (RTD) and Average Strain
Distribution (ASD) and how they are affected by changes in processing
condi tions.

5.2.1 CALCULATIONS

Curves of relative concentration vs time were obtained by

analysing the coloured extrudates obtained as described in section
4.6. Typical curves are shown in Figure 5.1.

90
14
~70
..-
~
er
f-
:z:
UJ
u
50
z
0
u

~ 30
0-0
f-
«
-'
UJ
0:: 10
-~
•

\
1 2 3 5
TIME [MINJ
FIGURE 5.1 Relative concentration vs time curves for selected
factorial experiments, single screw extrusion

Using equations 1.2 to 1.5, which were normalized (equations 1.6

to 1.8), the mean residence time, residence time distribution and
 - 148 -

standard deviation were obtained. The F curves were compared to the

theoretical and experimental models available. In addition to
perfect mixing, plug flow (equations 1.9 and 1.10, respectively) and
Pinto and Tadmor94 models, two other situations were also considered:
i) laminar flow in pipe, where the extruder is assumed as a channel
through which material flows:

F( e) =1 - (21e r e >= 0.5 (5.8)

(a non-Newtonian flow analysis has been recently published 227 );

ii) combination of perfect mixing and plug flow
228

F( e) = 1 _ e
_[...L)
I-P
(e-p)
e >= P
(5.9)
F( e) = 0 o< e<P
where P is the fraction of material with plug flow.

The ASD in the extruder was computed from equation 1.12.

As farasRTD is concerned, because the response is a function, the

use of the GLIH system is not efficient. Instead, the influence of
the control variables - screw speed, temperature profile and die
resistance - was analysed separately, by comparing the curves for
the experimental runs (Table 3.1) 9, 10 and 15, 11, 12 and 15 and
13, 14 and 15 respectively.

5.2.2 RESULTS AND DISCUSSION

The influence of processing conditions on the F curve is shown

in Figures 5.2 to 5.4. No effect on RTD could be detected by changes
in die resistance; this is unexpected, since higher values of back
pressure enable more leakage flows, hence axial dispersion. The
curves present an inflection point, as observed previously by Biggs
and Hiddleman104 for non-Newtonian fluids and high values of back
pressure (section 1.4.1.4.1). This inflection is likely to increase
wi th increasing die resistance. It is therefore possible that the
 - 149 -

.9
fOIE RESISTANCE

F( e)

.7

.5

.3

1.0 1.4 18
8

FIGURE 5.2 Influence of die resistance on the F curve

processing conditions compared in Figure 5.2 are in the range "here

the inflection point develops and the behaviour begins to approach
the plug flo" response. Further analysis is sho1<n in Figure 5.5,
"here runs 1 and 2 and 7 and 8 (Table 3.1) are compared, since they
also reflect the influence of die resistance. It is no" apparent
that by increasing the level of the control variable axial mixing
increases, until the inflection point develops. From then on"ards,
and "i thin the experimental field, no further evolution could be
identified. It may also be noticed that the gro"th of the inflection
seems to depend on a combination of the control variables ( the back
pressure of experiment 8 is smaller than the one of experiment 1).

The influence of barrel temperature and scre" speed on the

F-curve is apparent from Figures 5.3 and 5.4 (and also Figure 5.5).
The higher the temperature the broader the RTD, hence the better the
axial dispersion. This is caused by a drop in viscosity and more
 - 150 -

.9
-----. t TEMPERATURE
F( e)

.7

/
."
.5
/, " .
/"
."
./"
'"
.3 ./"
/" "
."
/"
."
, /1
/
/ I
.1 , I,
/ /
I

.6 1.0 e 1.4 1.B

FIGURE 5.3 Influence of temperature profile on the F curve

.9
-.:-- fSCREW SPEED

F( e)

.7

.5

.3

.1

.6 1.0 1.4 1.8

e
FIGURE 5.4 Influence of sc:-e" s;:lOed on the F curve
 - 151 -

significant leakage flows. Unlike other workers 98 ,105, it was

possible to detect a slight influence of screw speed on the F curve:
with increasing screw speeds, despite the trend of the F curves
being similar, the tail of the distribution tends to increase. This
could again be due to more leakage flows and decrease in viscosity,
a consequence of high shear.

It can be concluded that processing conditions influence the

axial mixing of PVC in the machine. Apart from a few exceptions102 ,
little influence has been reported in the literature 94 ,98,105. This
could be due to the use of more limited experimental field, and/or
polymers having a more Newtonian behaviour.-

Two extreme experimental curves were compared to the models

available, Figure 5.6. Although the trend is similar, the experimental
results present shorter tails than the models. There are two possible
reasons for this behaviour. First, because the material is extremely
non-Newtonian (section 2.3.3) with a high viscosity, more plug flow
96 104
behaviour can be expected' • Secondly, and as concluded in
section 5.1.3.6, the material could present wall-slipping
characteristics. It has been reported144 that in this case the
efficiency of mixing decreases, therefore one would expect F curves
wi th shorter tails. ~/i th increasing barrel temperatures, the wall-
-slipping behaviour is discouraged and the curves broaden.

The model combining plug flow and perfect mixing seems to provide
the best fit, for plug flow percentages of 60-70%. These figures
agree well with the values found by v/olf and White 98 using
polyethylene, who, however, reported that the model of Pinto and
Tadmor94 prOvided the best approximation.

The minimum residence time -(time until first output of tracer

from the die lips) t . , mean residence time t and standard deviation
ml.n
o produced the following quadratic polynomials:

tmin = 1.327 - 0.9275S + 0.2265T + 0.069P + 0.3958SS +

+ 0.0608TT + 0.0508PP + 0.0181ST - 0.0787SP -
- 0.0212PT (5.10)
 - 152 -

.9
=~=~~tDIE
I RESISTANCE

F( 6)

.7

.5 ,
~/
.3
7 .'
el ,/
.1
,;;' ,
,7 /

,,
."It'
.6 1.0 1ft. 1.8
e
FIGURE 5.5 Influence of die resistance on the F curve for runs
1, 2, 7 and 8

•
_--::::
..

.9 •
I
I

.7
- EXPERIMENTAL CURVES
-f- PLUG FLOW
.5 -- PERFECT MIXING
........ PINTO & TADMOR
LAMINAR FLOW IN PIPE
.3 COMBINATION OF PLUG
AND PERFECT MIXING

.1

.6 1.0
e 1.4 1.8
FIGURE 5.6 Comparison of experimental F curves with published models
 - 153 -

t = 3.047 - 1.8478 + 0.5977T + 0.4460P + 0.432688

- 0.0079TT + 0.0647PP - 0.19888T - 0.38848P -
- 0.1785PT (5.n)

o = 1.951 - 1.0233 + 0.4411T + O.4293P + 0.058633 -

- 0.147TT + 0.1009PP - 0.23723T - O.34003P -
- 0.1956PT

The main influence of the control variables is shown in

Table 5.4:

tmin t 0

(min) (min) (min)

-1 1.8 5.6 3.2

3 0 1.3 2.7 1.5
+l 0.7 1.6 1.1

-1 1.1 2.4 1.2

T 0 1.3 2.6 1.6

+l 1.7 4.0 2.6

-1 1.3 2.9 1.9

DR 0 1.3 2.6 1.6

+l 1.5 3.6 2.5

TABLE 5.4 Influence of processing conditions on minimum and mean

residence times and standard deviation

The minimum residence time decreases steadily wi th increasing

screw speed and slightly wi th decreasing temperature profile; no
significant effect of the die resistance could be found. The mean
residence time also decreases with increasing screw speed, decreasing
temperature and decreasing die resistance. These results are as
105
expected ,since high temperatures and die resistance will cause
more leakage and back flo,JS, whereas screw speed has a posi ti ve
 - 154 -

eff'ect on the drag flOl;. The interaction of these effects causes a

minimum at low die resistances and temperature profiles and high
screw speeds, and a maximum at the opposite processing conditions.
The standard deviation behaves in a manner similar to the mean
residence time.

The degree of mixing can be further assessed by monitoring the

average strain distribution. The response is

YN = 7869 + 702.5S + l3l5T + 680P - l878SS + l16TT +

+ 306pp + 339ST - 283SP - 254PT (5.13)

The degree of mixing improves with increasing barrel temperature

and die resistance, although temperature is the main effect. This is
not surprising, both variables cause a decrease .in the output and an
increase in the bulk residence time. The effect of screw speed is
more complex: keeping temperature and die resistance constant, at low
screw speeds Y is small because of' the low level of shear; with
N
increasing screw speeds the level of shear increases, and the degree
of mixing improves. A further increase in speed creates even more
shear, but decreases significantly the bulk residence time, the
overall effect reducing strain.

The maximum degree of mixing occurs therefore at high temperature

profiles and die resistance, and average screw speeds. The minimum
occurs at low levels of the independent variables.

5.3 MELTING MECHANISM

Ili th the purpose of' identifying the melting mechanism of the

material within the extruder, the core samples obtained as described
in section 4.2.1 were analysed visually and under the microscope.
The description of the tests used is given in section 4.5. Also,
because the extruder was instrumented (see chapter 3), the variations
of pressure and temperature per revolution of the screw were known,
providing complementary information.
 - 155 -

Simple visual observation distinguished between the solid bed

and melt pool. The colour of the first progresses from white near
the hopper to dark brown towards the screw tip. The melt pool was
practically transparent in the first turns of the compression zone,
becoming light yellow towards the metering section. These changes
have previously been reported 31 ,81,82 and explained as follows:
first, a non-uniform distribution of the additives in the solid bed
allows a visualization of the degradation. Also, degradation takes
place more easily; in the melt pool there is better stabilizer
distribution, the degradation being 'masked' and progressing more
slowly13 • Second, the spectrum of degraded PVC shows discrete band
structures in the ultraviolet region and in the visible spectrum to
about 450 nm. This is due to the presence of sequences of conjugated
double bonds. As degradation increases, the sequence length
increases, moving the peaks to longer wavelengths. 1'li th continuing
degradation cross-linking takes place, this effectively reducing the
sequence lengths and moving the peaks back to the ultraviolet
wavelengths127 ,128.

For most of the samples observed, the material seemed to be

fully melted when reaching the screw tip. It was also noticed that
the melt pool was deposited near the trailing flight; as discussed
in section 1.4.2.2.1, this can be considered common when extruding
UPVC, although unusual for other thermoplastics. Only for some
experiments (factorial runs numbers 4, 7, 12 and 14), the high
values of one or more of the control variables were responsible for
a decrease in viscosity that created, in addition to the melt pool
at the front, a smaller melt pool in the rear of the channel.

5.3.1 IDENTIFICATION OF THE !1ELTING HECHANISM

The core helices (like the one pictured in Figure 4.3) were cut
along planes perpendicular to the channel length at locations
corresponding to a screw revolution. Selected re suI ts for tIVO
different runs (13 and 14) are presented in Figure 5.7.

It is apparent that: i) the melt pool develops on the trailing

 - 156 -

FIGURE 5.7 Cross-sections of core helices for runs 13 (left) and

14 (right). Trailing flight on the right. Top to
bottom, screw turns numbers 1, 3, 5, 7, 10, 13 and 15.

flight; ii) this pool seems to have been linked to the chamber ahead
by a thin film of melt; iii) in some sections, apart from solid and
mel ted material, there is also some material sintered to different
extents; iv) the shape of the melt pool suggests that some material
also fuses mainly due to heat conduction. These observations
indicate similarity with the model of Menges and Klenk (Figure 1.7).

Visualization of cross-sections under the microscope provides

additional information. It has been mentioned (section 4.5.1.2)
that when PVC degrades, if exposed to ultra-violet radiation it will
fluoresce in the visible region. This is due to the increase in
molecular insaturation with the formation of double bonds and
conjugated double bonds, largely as a result of the
 - 157 -

dehydrochlorination of the saturated polymer chains129 Therefore,

fluorescence microscopy can assess the degree of degradation of the
material, itself related to its processing history. Using the
quantitative method described in section 4.5.1.2, the fluorescence
intensity of the core samples was measured for various experimental
runs, Figure 5.8 and 5.9. The raw powder and the solid material
with poor cohesion were embedded in a Polaron kit.

_ _ _ _ _ _ _ ...0--
~ --~- ---.----- ..
-- --
_ _ 0- .

pa __ e---
100 ,
I , . . . - . - '-'-'-1'"'-
I 13
,, ./.;/ i
I

I
r- 80
t-
......
,I
I
I
I,
,,
V1
Z
lJ.J
t- I raw material: 55.6
I
z 60
...... d
I I
lJ.J
!E
lJ.J !
U
V1
lJ.J
11"_------- .-----
_ ----·--t--4-----~
'_0_.0...... 0

a:: ,'f~,...:;:::.-.-.-.--.-t.-.-.
0
::>
100 , .
--I
U- " . ! 14
/ I
80 ," -MELT POOL i.
" - - -. SOLID BED (GRAINS) !
" _.- INTERFACE SOLID BED I!
60 , BARREL WALL !
15 13 11 9 7 5 3 I

TURN OF SCREW I

FIGURE 5.8 Fluorescence intensity along the length of the screw

for runs 13 and 14

For both experiments the fluorescence intensity of the melt pool

is always smaller than that of the solid bed, and the one of the
interface of the solid bed / barrel wall even smaller. All the readings
 - 158 -

100 um

FIGURE 5.9 Fluorescence microphotograph of the interface melt pool/

/solid bed at turn of scre,/ number 5 of factorial
experiment 13.

increase tm/ards the screw tip, the rate being higher in the
compression zone (turns numbers 16 to 6). The higher fluorescence
of the solid bed can be explained by the non-uniform distribution of
the additives around the grains, thus allowing more degradation to
occur; the loss of fluorescence intensity in the melt pool is due to
random dispersion of the stabilizer particles. The fluorescence of
both solid bed and melt pool increases along the length of the screw,
as the material is subjected to heat and heat and shear, respectively.
In the interface of the solid bed/melt pool the material has just
fused, hence its fluorescence intensity is minimal; the melt is then
pushed towards the melt pool, and immediately replaced by newly fused
material, again with low fluorescence intensity. The fluorescence
intensi ty of this zone depends on that of the solid bed, therefore
it is not surprising that both cUrves are relatively parallel.
 - 159 -

It may also be observed that the overall fluorescence intensity

increases with increasing die resistance. A similar phenomenon was
observed with increasing temperature profiles.

The analysis of pressures and temperatures collected by the

computer allow a clearer understanding of ~~e fusion mechanism. The
results for factorial run 9 are presented in Figure 5.10, the lower
level of screw speed in this experiment allowing more data points
per revolution of the screw. In each graph the top curves represent
either pressure (p) or temperature (T), and the bottom ones the
signal from the rotary potentiometer (see Figure 3.3); the second
allows the identification of each revolution of the screw, which the
computer identifies with a solid vertical line. Trailing and pushing
flights are identified by a d (die side) and f (feed sIde),
respectively. The horizontal line in each graph corresponds to the
average value of the measured variable. PI and Tl were measured at
turn number ID, P2 and T2 at turn number 6 and P3 at turn number 2
(see also Figure 5.12).

Although a steady state had been assumed (the following

conditions being present: i) constant screw speed, ii) equilibrium
shown by warming-up subroutine, barrel heaters and event recorder,
iii) constant temperature before the die) in practice the readings
varied randomly. The possible consequences have been mentioned in
section 1.4.1.1. The causes of this phenomenon include too low
compression ratio of the screw, meaning that the conveying capacity
of the metering zone is higher than the one of the feed section, and
causing instabilities in the conveying mechanism. It is believed
that this was not the case, since high pressures were measured and
both melt pool and solid bed were well defined and continuous. The
non-steady state must be caused by fluctuations in the temperature
of the barrel heating zone, and reflected also on the pressure
profile 57 The inertia of the on/off system and the difficulty in
efficient dissipation of heat through the barrel wall must be
responsible for the variations; as they are inherent to the extruder
no further steps were taken 57 •

At the beginning of the compression zone, when most of the

material is solid, the pressure profile (PI) is practically
 --- - - - - l
- 160 -

t----hl--H---I:+--+-lf-++~_h______l 1614 PSI

d f d

f-----tt-JL--+-f--l~-I-----,l-4-_+_4_-~ 1699 PSI

d f d

1----N-+-D-l-J-I-+--I+-I--H-+4+--l----I 2813 PS I

d f d

Top:P1 CENTRE: P2 BOTTOM: P3

(Figure 5.10)
 - 161 -

167.4 ·C

f d

187.8 ·C

d f d

Top:T1 BOTTOM: T2
FIGURE 5.10 Data collected by the computer on experiment 9. Top
of each graph, pressures or temperatures; bottom,
rotary potentiometer. d - trailing flight; f - pushing
flight

symmetrical along the channel width, the material moving in a plug

flow manner. At the end of the compression zone (P2) the pressure
is higher near the trailing flight, then decreasing towards the
pushing flight. A similar phenomenon is observed in the metering
zone (P3). This suggests that the melted material passed along the
 - 162 -

gap between the flight of the scre'l and barrel and, depositing
near the trailing flight, forced the solid bed backwards. As the
pressure is absorbed and transmitted along the channel, the presence
of sintered material is to be expected near the trailing flight,
immediately after the melt pool. The readings of temperature confirm
this interpretation, as its values are definitely higher near the
trailing flight at both locations, decreasing as one scans backwards
through the channel width.

The amplitude of the variations of pressures and temperatures

'Iith varying processing conditions is shown in Table 5.5.

(PSI) (QC)

Pl P2 P3 Tl T2

-1 145 359 96 0.38 0.58

S
+l 182 286 101 0.56 1.66

-1 268 302 108 0.80 4.32

T
+l 209 178 57 0.13 1.57

-1 181 211 63 0.34 1.71

DR
+l 151 261 103 0.38 4.32

TABLE 5.5 Pressure and temperature variations per revolution of the

screw

Both pressure and temperature differences become larger with

increasing values of the control variables, the exception being
barrel temperature profile. The results for increasing screw speeds
correlate well 'Iith the values found by Janssen et a1 225

From the results obtained and taking into account earlier

81 120 a model for the melting mechanism can be defined
reports'
(Figure 5.11): as the material travels in a plug-flow like manner
along the channel of the screl", it reaches a point where the
temperature of the barrel is high enough to promote fusion (A).
Despite the high viscosity and the low friction characteristics of
 - 163 -

(;~l [1])]J]]]HJ])],IJ,' et ~t [111.1.1 J.[[[I'] 1] I1 [(W

(@ A

11 ! B

o
•
_ melt . . sintered material :tm powder

FIGURE 5.11 Melting mechanism in the single screw extruder

the melt. the melted film will move backwards; if the gap between
the flight of the screw and the barrel is high enough. the melt will
cross it. and finding material compacted in the other chamber will
deposit in the trailing flight. pushing the solid bed towards the
pushing flight (B). as predicted by Lindt B4 • As the melt pool grows.
the solid bed will become more compact and able to transmit pressure
and temperature more efficiently. Eventually. the solid material
nearer to the melt pool will sinter and. because the additive
distribution is poor. will become brown (C). The material nearer to
the melt pool is subjected to shear and will join it. Simultaneously.
the zone of sintered material progresses to the center of the channel
where the cooler material is. Towards the end of the screw the melt
pool encompasses most of the channel's cross section (D). Eventually.
the remaining solid bed/sintered material bed will be broken and
quickly diSSipate into the melt. If the control values cause high
levels of temperature. the viscosity of the melt will decrease and
its friction characteristics will change. wall-slipping decreasing.
 - 164 -

In this case, together with the main melting mechanism, an additional

melt pool may form near the pushing flight.

Menges and Klenk 81 and Allsopp13 report that the so12d

. bed can

be observed throughout the length of the screw, resulting in the

presence of unmel ted material in the final extrudate. It was
therefore concluded 81 that the me chanism observed could not provide
an homogeneous extrudate. In this work, for almost all the
processing conditions, the solid bed dissipated qUickly into the
growing melt pool before the material left the screw. If the level
of shear and residence time in the die and adaptor are high enough,
an homogeneous extrudate can be obtained. It must be noted, however,
that the extrusion of PVC in a single screw extruder makes the
efficiency of the heaters controls an important parameter; they must
be able to react quickly to variations in temperature, and the
barrel should be able to dissipate heat efficiently. Otherwise,
variations in temperature will cause pulsations in the output and
could lead to different conveying and melting characteristics.

5.3.2 GROl~TH OF THE MELT POOL ALONG THE SCREW LENGTH

The development of the melt pool along the screw was monitored
using the procedure described in section 4.5.5; the results are
presented in Figure 5.12, together with the pressure profiles.

As expected, increasing barrel temperatures promote the earlier

creation of the melt pool and its quick growth along the compression
zone. Nhereas for high temperature profiles the material in the
metering zone is practically all melted, at low temperatures the
amount of solid material is still important. Increasing die
resistance has a similar effect, although not so significant: higher
die resistances create higher back pressure, promoting shear and
heat transfer. It is apparent that the effect of die resistance is
mainly felt in the metering zone. Increasing screw speeds create
two opposite effects: the average residence time is reduced, but
the level of shear is increased. The overall effect is a balance of
the two parameters: increasing screw speed delays the growth of the
melt pool in the compression zone; in the metering section, however,
 .. 165 ..
compression zone metering zone
100~------~------------------r.~--~,~~'-=;r-~-~~
.1 / . -
t
== TEMP~RATURE If
I I

Y 3000

.I
;!
•
/ .
50 --------;
+ - ' - ' - ' -...~--t--

-I
.

...--''/
,",' I. I
7

W
Z
z /'.,.,.'- X' 000
et
::I: ~
,........-; 0 0
I
'I
• I •
U 10 •..-' / 1 .....
u... Vl
o ~ --~ Q.

et ,
w
~Oo I
-
-I
o
oQ.
-..:-- f SCREW SPEED
!
.1
" ~/
-,,,,,,,,,-'j
/ .
!
4000

w
I , I
" 'I ~.--.r -~
~- •
Cl::
::>
~
w I /'1 ,1.. ..,:-- Vl
Vl
w
~ , /' I
...J/' f Cl::

+-,_.-. _,-' " e.

Q.

50 ,
. . ... ' ,,1II
2000
, . . . '1 I '
I
.,. .... ". .... "" . /d I
~---- j/ /
. .
----0"
..I>------ _ .
-""..

./ 1000
..//~/ ! /-'
10
,"""~-:-,~- .-.-,-~--,<,~.

15 10 6 1
TURN OF SCREW
(Figure 5,12)
 - 166 -

100
0~

....J
t DIE RESISTANCE
UJ
Z
z
<! , W
:r: ,, 0:
w :::J
u.. Vl
0 Vl
w
<! 50 0:
UJ 0..
0:

-
<!

....J
0
0 1000
0..
I-
....J
UJ
:E 10

15 10 6 1
TURN OF SCREW
FIGURE 5.12 Development of melt pool and pressure profile along
the screw. Influence of processing conditions

due to the higher level of shear, the rate of melt growing increases,
so that near the screw tip practically all the material is fused.

Despite their differences, the shape of the curves presents

similari ties: after the birth and ini tia1 growth of the me1 t pool,
the rate of building-up of the melted material decreases towards the
end of the compression zone; in the metering section the rate
increases again, until the material is completely me1 ted. Ku1as and
Thorshaug121 , observing similar phenomenon, interpreted it as
evidence of intraparticu1ar fusion along wi th interparticu1ar fusion:
in the compression zone the melt pool develops, and with increasing
compactation of the granules intraparticu1ar fusion takes place.
However, when computing the ratio of areas of solid bed/melted
 - 167 -

material, whenever the grains are visible, regardless of their

internal status, they will be computed as solid. In the metering
zone the higher temperature of the solid bed and its improving
mixing with melted polymer result in a sharp increase in the rate
of growth of the melt pool.

Figure 5.13 shows the development of temperature along the

screw for the experiments of Figure 5.12. This data was obtained
from DSC traces of 10 - 12 mg samples of material from the solid bed
and melt pool at different screw locations. Both the equipment and
the experimental procedure have been described in section 4.7.1. As
mentioned in section 1.5.5, two endothermic peaks A and Bare
developed, Gilbert et al 140 having reported that the onset of the B
endotherm corresponds to the processing temperature of the compound.
This temperature was therefore plotted against the screw length. An
increase in the control variables produces an overall increase in
the average temperature. The temperature of the melt pool is several
degrees higher than the one of the solid bed. This is also apparent
from Figure 5.10, but the measurements there were made near the
barrel wall, where the maximum temperature difference does not
necessarily occur. This may also account for the differences
between the readings of the fibre optics and the data gathered from
the DSC traces. Anyway, these differences are never greater than
8°C, confirming the ability of the onset of the B endotherm to provide
information on the maximum temperature of the material140 • The
slopes of the temperature profiles are more uniform than the ones of
the development of the melt pool (Figure 5.12), supporting the
conclusions of Kulas and Thorshaui 21 , ie., apart from the
interparticular fusion responsible for the differentiation between
melt pool and solid bed, interparticular fusion also takes place.

Figure 5.14 compares the temperatures of the extrudates with

the values set in the barrel heaters, the temperatures being
determined again from DSC traces. The values measured are always
higher than the set ones, suggesting the presence of a material of
high viscosity and a high level of shear. For the same set
temperature (level a), an increase in die resistance induces an
increase in the temperature of the extrudate, since heat transfer is
 - 168 -

=== t SCREW SPEED

190

170
• - MELT POOL
-- - SOLID BED
LJ
• •• AV. TEMPERAT.• F. OPTICS

LLJ150
0::
::::I

~
~
:L2.10
LLJ
=== t TEMPERATURE
t-

190
".-
,. +
" .
, ..
. ,-' • / "
" " "

, ,," + ;3- - - - - ___ 13'

.-
.
/
/
fI ,-
170
,-
,- "
,-
"
15 11 7 4 1
TURN OF SCREW
(Figure 5.13)
 - 169 -

~
w
0...
== t DIE RESISTANCE

~
W
I-

190

170

150

15 11 7 4 1
TURN OF SCREW
FIGUR~ 5.13 Temperature profile of melt pool and solid bed along the
screw. Data obtained from DSC traces

[OC 1
+1
S __ -_210 /,.-8
9" 0
/'0 0 o /ODR-
+1-cf~
o - - - - -200
-rl~ ----
T o
-1
0- - - - - - - 190 - - - - - - - - --

FIGURZ 5.14 Temperature of the extrudate vs die setting. Influence

of processing conditions
 - 170 -

improved and the level of shear increased. The effect of increasing

screw speed is balanced beb"een increasing level of shear and shorter
residence times. At 10" speeds the second seems to be dominant but
at high revolutions the increase in level of shear cannot compensate
the decrease in d"ell time. Kulas and Thorshaug121 observed a
continuous increase in extrudate temperature "ith increasing screw
speeds, but temperature differences reaching 40-50 oC at 80 rpm "ere
reported.

5.4 MECHANISM OF GELATION

5.4.1 IDENTIFICATION OF THE MECHANISl1 OF GELATION

To identify the mechanism of gelation of the material within

the extruder core samples in the longitudinal and transverse
directions of the screw channel "ere analysed under the microscope.
A Jamin-Lebedeff Interferometer and Fluorescence Microscopy "ere used
(sections 4.5.1.1 and 4.5.1.2); also, samples fractured after
immersion in liquid nitrogen were observed with a Scanning Electron
Microscope (SEH) (section 4.5.2). The results are presented in
Figures 5.15 to 5.21, Figures 5.19 to 5.21 having been obtained with
the SEN.

The mechanism of gelation is the 'process through which the

ini tial powder (Figure 5.15) "ill be converted, through application
of heat and shear, into a more or less homogeneous extrudate (Figure
5.21 C).

As Allsopp13 reported, little morphological evolution in the

melt could be followed with light microscopy. The mechanism of
gelation was therefore monitored in the solid bed and in the interface
solid bed/barrel ",all where, according to the mechanism of fusion
put fOr>lard (section 5.3.1), the material is subjected to shear.

In the first turns of the compression zone, turn number 15, the
grains are still free, the inner structure being easily observed
(Figure 5.16). They will then be compacted, both pressure and
 - 171 -

20 ].Jm

FIGURE 5.15 Microphotograph of raw material

20 ].Jm
!
FIGURE 5.16 Microphotograph of material in turn 15. sho,ling internal
structure still present
 - 172 -

temperature being therefore more easily transmitted. Towards the

end of the compression zone - turn number 7 - the grains are highly
compacted (Figure 5.17). It is also apparent that: i) the additives
are deposited in pockets around the surface of the grains, ii) the
inner structure of the grains seems to have disappeared, while their
contours are clearly visible. These observations correlate well with
the results of Allsopp13 and Kulas and Thorshaug121

The interface solid bed/melt pool is shown in Figure 5.19. The

grains are clearly evident, the melting pool showing no evidence of
particle structure. The destruction of the grains must therefore
take place in the interface solid bed/inner barrel wall, where they
are subjected to high shear. This region is shown in Figure 5.lB;
clearly, the grains are highly elongated in the direction of shear,
eventually being destroyed and forming a melt into which the additives
will quickly disperse. The CnFE mechanism13 seems therefore
recognized, as compaction, densification, internal fusion and
elongation are confirmed. Further evidence can be gained i'rom Figures
5.19 and 5.20 and Figures 5.24 and 5.25, where the compaction,
densii'ication and degree oi' fusion in the solid bed is evident.

Eventually, towards the screw tip the melt encompasses most oi'
the cross-section oi' the channel. The grains surviving fusion
will be surrounded by melt, elongated due to shear and dissipate into
the melt. If an appreciable amount of solid bed is still present at
the screw tip and the residence time of the melt in the adaptor and
die is not suffi cient for its fusion, some unmel ted material can be
present in the extrudate. In this case, quite oi'ten voids can also
be found; they are probably formed by hydrogen chloride evolution at
points where the residual grains cause poor stabilizer distribution.

Despite having observed the CDFE mechanism in this work, one

feels that the reports oi' many workers14 ' 19 , 22 , 23 on the role oi'
particle breakdown are difficult to disregard completely. Figure
5.21 shows the morphology of the melt pool at the beginning of the
compression zone and beginning and end of metering zone, respectively,
for run number 13. ~lhereas in Figure 5.21 a) primary particles are
clearly distinguishable, in Figure 5.21 c) an homogeneous melt with
 - 173 -

20 urn
I

FIGURE 5.17 Microphotograph of solid bed, turn of screw number 7

...
' '",
".. ·.1 ..

100 urn

FIGURE 5.18 Interface solid bed I inner barrel wall at turn of screl,
number 3
 - 174 -

50 um
I I
FIGURE 5.19 SEM microphotograph of interface solid bed / melt pool
at turn of screw number 15

~~
~

FIGURE 5.20 SEM microphotograph of solid bed, turn of screw number 8

 - 175 -

5 IJm
I

10 IJm
I

2 IJm

FIGURE 5.21 SEM microphotograph of melt pool along the screw length
a) turn number 15; b) turn number 4; c) turn number 1
 - 176 -

well dispersed stabilizer is observed. Figure 5.21 b) seems to show

an intermediate stage. The melt pool of Figure 5.21 a) was formed
from grains showing the morphology displayed in Figure 5.16, ie.,
when their inner structure still remains; the applicatio!l of shear
will cause the grains to break open, the primary particles forming
the unit of flow. Subsequent shear and heat will cause them to melt.

Therefore, the two mechanisms of gelation reported in the

13
literature ,22,23 and summarized in Figure 1.17 can in fact coexist
in the same process. Kulas and Thorsaug121 showed that resin
particle structure influences the degree of intra- and interparticular
fusion. Therefore, if extruding a compound with little tendency for
intraparticular fusion, with a screw with a low compression ratio,
at low temperature and screw speed, the breakdown mechanism could
predominate over Allsopp's13 , and a final melt containing primary
particles could be obtained.

The mechanism of gelation observed for various processing

conditions with the extruder and compound used in this work can
therefore be summarized as follows (Figure 5.22):

MELT POOL .. • •:...-~~

.~~

• • "',j
.
-Il"...
e"
.

~.II'''''-,'''''
;.~~~'.·:.:A,
_;\:a
'" .
.. - . . -~B

I
<-
IV
<U
..c
(/)

SOLID BED
- --M
CV
x additives melted material

FIGURE 5.22 :1echanism of gelation in a single screw extruder

 - 177 -

As the po,.der moves :in till feed zone it is increasingly heated

up, so that in the beginning of ,the compression zone fusion can take
place. In this section the powder is progressively compacted
together: heat transfer between the solid grains is therefore more
efficient, and intraparticular fusion develops to a significant
degree. Eventually, at the beginning of the metering zone the inner
grain structure is lost. Throughout this process the additives
remain deposited in pockets around the surface of the grains.

Simul taneous with the powder conveying mechanism, the layer of

material near to the barrel wall is subjected to a high degree of
shear and subsequently deposited in a melt pool; when the grains are
subjected to shear they become highly elongated until they eventually
break open and a melt is formed, with the additives quickly
dispersing into it. However, the morphology of this melt depends on
the structure of the solid bed; if the inner morphology of the grains
is still present, when they break open primary particles will become
the unit of flow - and through the continuous application of shear
and heat will eventually melt; if the grains are internally fused,
when they are destroyed due to shear a homogeneous melt is
immediately formed.

If at the end of the screw a solid bed still remains - albeit

without inner structure - it can only melt by shear and heat transfer
with the melt. If the dwell time for this is not enough, grains may
be present in the extrudate; also, their presence means poor
stabilizer distribution, allowing the formation of microvoids due to
production of hydrogen chloride.

5.4. 2 FROG RES SI ON OF GELATION ALONG THE SCREVl LENGTH

The measurement of the degree of gelation of the melt pool and

solid bed at strategic locations along the screw is conditioned by
the small size of the samples. The DSC technique seems ideally suited
for this purpose; therefore, samples of 10 - 12 mg of material were
tested as described in section 4.7.1. As mentioned in section 1.5.5
the energy of endotherm A - corresponding to the growth of low order
 - 178 -

crystallites formed upon cooling - increases with processing

temperatures163 • In Figure 5.23 that energy was plotted as relative
percentage against the screw length for the factorial experiments
allOwing an identification of the effect of varying processing
condi tions.

The degree of gelation of the melt pool is always higher than

the one of the solid bed, but they become progressively Similar
along the metering zone. Here, the rate of increasing degree of
gelation raises, as an homogeneous melt leaves the scre" and is
subjected to shear and high temperatures in the adaptor and die.

Increasing barrel temperature and die resistance increase the

average degree of gelation: high back pressures create more shear in
the melt pool and better heat trasfer in the solid bed. IncreaSing
screw speed allows less residence time for fusion in the screw, but
the higher level of shear in the adaptor and die creates a higher
degree of gelation of the final product.

The progression of gelation in both the solid bed and melt pool
can also be followed by monitOring the denSity changes along the
screw length. Figures 5.24 and 5.25 show the effect of die resistance
and screw speed on the denSity (the effect of barrel temperature
being very similar to the one of the die reSistance).

The grains in the solid bed are highly compacted in the

compression zone, their density still increasing until all the
material is melted. The compaction and densification of the solid
bed mentioned in the previous section is therefore confirmed. The
behaviour of the melt pool is different: along most of the screw
length no trend could be identified but, from the metering zone
towards the die lips ,the density decreases. Also, the higher the
degree of gelation, the lower the denSity. Similar results have been
reported139 ,142. It must therefore be concluded that the
crystallini ty of the material decreases with increasing processing
temperature: "hen extruding PVC, the crystalline mel t point is never
reached (section 1.2.3), only some of the low order crystallites
being destroyed, hence accounting for the decrease in size of peak B
 - 179 -

% GELATION
100
== t SCREW SPEED

70
- melt pool
- - - solid bed

40

10 -
100
== t TEMPERATURE

70

40 ......
..... ....
. ~..
.. /
~

, //

,,
/
/
, /

10
,
~ , - -+- - - --- - -
~---- -- ~

15 11 7 4 1
TURN OF SCREW
 - 180 -

% GELATION

100
== t DIE RESISTANCE

70

40

10 ,
... '
- - ---""-----... ----- ---~
--- --
---~
15 11 7 4 1
TURN OF SCREW
FIGURE 5.23 Development of gelation along the length of the screw.
Influence of processing condi tions

of the DSC trace (section 1.5.5). The higher the processing

temperature the more of those crystallites are melted. Secondary
crystallinity formed upon cooling - peak A - is less ordered, so that
the overall effect is a decrease in crystallinity, responsible for
lower density.

Al though dealing again wi th this subject in chapter 7, it seems

relevant to speculate here on the evolution of peaks A, B and AtB
wi th increasing processing temperature.

5.4.2.1 THERMAL ANALYSIS

The endothermic energy of peaks A, Band A+B versus processing

temperature for the core samples of runs 9 and 13 (Table 3.1) is
 - 131 -

DENSITY

----- 8 __ ; .... e.c--=.

1.400 -+-
.-- .,.---
... ... --
.Ir- - - - - -
r
/

... - ... .".

--
/ ...(]'
/
...-'-
Ij!I'I'
1/
I'
/1
/1
f/
/ /
1380 I I
1 / ,
"
/'

I 1
,I
/1
/ =1 DIE RESISTANCE

, 1
/ 1
/ I
/ I
, 1
I '
1.350
, :
, I I
/

/ I
I ,
I I
/ 1
/ 1
I 1
, 1
It! , I
/
,1
I
/ melt pool
I
1
1
solid bed
/
,
, 1

1
,
I

1.300 1
I
1
I
.,./
15 11 7 4 1
TURN OF SCREW
FIGU:tE 5.24 Influence of Die Resistance on the progression of densi ty
along the screH length
 - 182 -

DENSITY

~~)C:::::::::::;:;r;II~:!II::::~&~==--·--~,,~-*"
- ~ >~
1.400
~ '" " ' ,, '
"
'" '" '" ," "
.,.-- ... -
_ ...... - - - - - ¥ '" --' Ji!!!'
--
--- - Ia"--
, t"
I ,
,,
, I
, ,

,,,
1.380
,,I f/1
,
,, ,,
I ,

,,,
,,
I

,,
,,
,

=1 SCREW SPEED

,,, ,,,
I ,

,
1350
,, ,,,
I

,,
I ,,,
,,
I
,
, ,,,
,,,
I

I
, ,
I

,,, ,,,
I
melt pool
I
,
, solid bed
,, ,,
I

,, I
, ,, I

, ,
,
I

1.300 , ,
I

, ,
, I
I
I

15 11 7 4 1
TURN OF SCREW
FIGURE 5.25 Influence of Scre;) Speed on the progression of densi ty
a1 on g the screw 1 en gth
 - lS3 -

shown in Figure 5.26. The processing temperatures were determined

from the onset of peak B.

As expected, the energy of peak A increases with processing

temperature, ie., the degree of fusion increases with processing
temperature. Also, the energy of peak B decreases steadily with
increasing temperature, as more crystallites are destroyed. As a
result, the energy of A+B shows a minimum between ISO and 190°C,
increasing thereafter. Similar behaviour was obtained with compressed
moulded samples (obtained as described in section 4.3), in the
absence of shear.

Up to ISO-190°C the destruction of primary crystallinity seems

to be predominant over the formation of crystals A: in the solid bed
the inner structure of the grains still remains,the primary particles
are the unit of flow in the melt pool. Above these temperatures the
internal fusion of the grains and the existance of progressively less
primary particles in the melt pool produces more cross-linking pOints,
favouring secondary crystallinity. This is particularly apparent in
Figure 5.27, where it is shown that the rate of growth of peak A
increases drammatically after 190°C. This also indicates that despite
the lower order of crystallinity of peak A, the observed overall
increase in endothermic energy could be responsible for a smaller
decrease in density at high temperatures than the one expected in the
previous section.

The validity of the onset of peak B indicating the processing

temperature of the material has already been mentioned (section 5.3.2)
and is further assessed in Figure 5.2S. Here the onset of the B peak
of the compressed moulded samples was plotted against the set
temperature; the results of samples heated at 10oC/min in the DSC up
to various temperatures and then scanned in the usual way (section
4.5.3) are also included.

A good correlation was obtained, specially in the range 175 to

210°C; below this temperature the onset of the B peak is usually
placed below the processing temperature; above 210°C, the peak A can
eventually spread above the set temperature. Also, with the eventual
disappearance of the peak B it is extremely difficult to determine
the processing temperature.
 - 184 -

ENDOTHERMIC ENERGY [JIG]

13 7
3 -...
"" -A
""'tJ 5
\
2 \ •
\
\
\ 3
1 q,.~~ --___ ..a-
0 .... __ ....0 -- melt pool
....
- - - solid bed 1

9
4

.-- --
6
B - 13
'!l,
9
4
"- ... ...
... ...
...
2
•
150 160 170 180 190 rC 1TEMP. ONSET B
FIGUR:;; 5.26 3n1othermic energy of peaks .'1, 3 and A+3 versus prooessing.
temperature for runs 9 and 13
 - 185 -
A/B
----A/B ----B ---A -A+B

-
~8
l!:l
-.

~6
w
ifi
w
~4
0:::
W
:c
b
Cl
~2

160 170 180 190 TEMP_ ONSET B[OC)

FIGURE 5.27 Zndothermic energy of peaks A, Band AtB versus
processing temperature for compression moulued samples

220 --- 45 •
- exp_ curve
~

«w200
0.. [oC)
(C

u..
o
I- 180
w o compression mould_
Vl
Z
o • heated powder
160
160 180 200 220
STOCK TEMPERATURE

FIGU:lE 5.28 Stock temperature versus onset of B peak for compression

moulded samples
 - 186 -

CHAPTER 6

RESULTS AND DISCUSSION

TWIN SCRm" EXTRUSION

6.1 EVALUATION OF EXTRUSION CHARACTERISTICS

As mentioned in section 4.2.2, the fully intermeshing conical

counter-rotating twin screw extruder available for this project used
proportional heat controllers for the barrel and screws. Therefore,
the energy balance approach used for single screw extrusion was not
possible, the extrusion characteristics being evaluated from torque,
pressure and temperature measurements, as well as mass throughput.
The latter was obtained by weighing extrudates processed for a
determined time.

Following the procedure described in section 4.2.2, extrudates

were obtained for different combinations of the independent variables.
It was then possible to monitor the influence of the processing
conditions on the extrusion characteristics. The use of the GLIM
package provided the knowledge of the quadratiC polynomials
describing each response; contour plots were also obtained.

6.1.1 MASS THROUGHPUT

It has been mentioned (section 1.4.1.3) that intermeshing screws

imply the presence of C-shaped chambers that will posi ti vely convey
material to the die. Unlike "d th the single screw extruder, slip at
the wall becomes irrelevant since the intermeshing part of one screw
prevents the material in the other screw from rotating freely58. It
has been shown (section 1.4.1.3) that the output is theoretically
proportional to the screw speed; in reality, however, the presence
of leakage flows and the degree of filling of the C-shaped chambers
will cause a decrease in the theoreti cal output. The flow through a
particular leakage gap is determined by the drag of the moving
surfaces and the pressure difference between the two relevant
chambers. The latter involves the contribution of the die and the
pressure gradient in each chamber, developed in a similar Hay to the
 - 187 -

single screw extruder case. Therefore, a decrease in output with

increasing die resistance would be expected. Increasing the barrel
temperature profile will cause a decrease in the viscosity of the
melt, specially towards the die. As a consequence, despite the
leakage flow becoming easier, the back pressures are smaller, and a
very small change in output with increasing temperature profile
would be expected.

The mass output (g/s) is defined by the polynomial:

m= 1.863 + 1.1318 + 0.1184T - 0.0712P + 0.136788 0.0753TT -

- 0.0033PP + 0.08778T - 0.04978P + 0.0632PT (6.1 )

whose graphic representation is given in Figure 3.2.

The results were as expected: mass output increases steadily

with increasing screw speed, although at progressively slower rates,
and slightly with increasing temperature profile. The output
decreases with increasing die resistance. Although the interactions
are not very significant, a maximum mass output can be obtained at
high screw and temperature profile values, and small die resistance;
a minimum will occur at the opposite operating conditions.

The decrease in rate of pumping capacity with increaSing screw

speed was also expected: due to the small size of the laboratory
extruder, the gaps between the screws become significant 92 •

It can be generally concluded that under most operating

conditions the output is practically independent of the conditions
at the die end of the extruder. This is also reported in the
l i terature 92 ,133. The output rate can be controlled by the rate at
which the material is introduced into the feed port.

6.1.2 TORQUE

The values of torque used in the regression analysis were

corrected for the background torque, estimated by running the extruder
empty for the set of experimental runs. The quadratiC polynomial for
 - 188 -

the response obtained is (see Table 6.1):

TORQUE (%) = 23.10 + 5.74S - 6.60T + 4.06p - 2.25SS +

+ 1.00TT - 2.25PP + 0.14ST + 0.88SP - 0.26PT (6.2)

S T. DR
-1 0 +l -1 0 +l -1 0 +l

TO 21.0 26.5 30.0 25.5 26.5 26.0 26.5 26.5 26.5

(%) Texpo 36.0 48.0 57.5 54.0 48.0 43.5 43.5 48.0 52.0
T 15.0 21. 5 27.5 28.5 21. 5 17.5 17.0 21. 5 25.5

TABLE 6.1 Values of torque with varying processing conditions

Torque values provide information on the mechanical energy

supplied to the material; because the rear part of the screw usually
runs partially filled with material, most of the torque must occur
in the metering zone, where the fusion mechanism is usually reported
to take place 58 ,92. The sensivity of the torque readings to varying
processing conditions must therefore reflect variations in the
rheological behaviour and pattern of gelation of the material.

Torque increases with increasing screw speed and die resistance,

and decreases with increasing temperature profile. These results
were expected, as increasing screw speed and die resistance increase
the amount of work induced in the material and increasing temperature
reduces its viscosity. The minimum values of torque will be obtained
when running the extruder at low speeds and high temperature
,. profiles
and with low die resistances.

6.1. 3 PRESSURE

The pressure build-up in processing UPVC in the twin screw

extruder has been discussed in the literature133 ,138; it is usually
reported that it becomes measurable in the last third of the screw,
 - 189 -

then increases rapidly. These results are confirmed in Table 6.2,

where the values of the pressures before the compression zone PI,
before the metering zone P2 and adaptor P3 are shown. (It must be
noted that due to practical impossibility of calibrating the pressure
transducers, the values have only comparative significance).

PRESSURE (psI)
PI P2 P3
-1 189 644 1372
S 0 199 1073 1594
+l 210 1225 1720
-1 182 1400 1923
T 0 199 1073 1594
+l 178 595 1543
-1 213 737 1497
DR 0 199 1073 1594
+l 232 1199 3042

TABLE 6.2 Pressure build-up along the screws. Influence of

processing conditions. PI - before compression zone;
P2 - before metering zone; P3 - adaptor

The values of PI are practically irrelevant, demonstrating that the

feed zone can be regarded as a pOl<der- conveying section. It is in
the metering section that the values of pressure become significant.
Because of the die resistance this zone is full of material so that
pressure is transmitted backwards through the leakage flows. If
the values of P2 are above a limit, material is then forced through
the vent.

As expected, the values of both P2 and P3 increase with

increasing screw speed and die resistance and decrease with
 - 190 -

increasing temperature profile. Stephenson 92 found a direct

relationship between P3 and mass output at constant melt temperatures.
Therefore, because the adaptor pressure depends on the output rate
and the rheological properties of the material and P2 must depend on
the length of the gelled material, like torque, pressure values can
be readily used to characterize the formulation and/or the processing
characteristics.

6.2 MIXING CHARACTERISTICS.

The mixing characteristics of the process were assessed by

monitoring the residence time distribution and its variation with
different processing conditions. Due to the complexity of twin screw
extrusion, the average strain could not be computed (section
1.4.1.4.2).

The calculations performed have been described in section 5.2.1:

from relative concentration versus time curves (Figure 6.1) F curves
were derived and normalized and later compared to the theoretical
and experimental models available.

The influence of varying processing conditions on the F curves

is shown in Figures 6.2 to 6.4 (factorial runs 9 to 15, Table 3.1).
It is apparent that the curves are very similar for the whole range
of processing conditions used. Similar results have been reported
by Janssen et aliOi • No influence of varying barrel temperature
could be detected, but increasing screw speed and die resistance
seemed to decrease the tail of the distribution. The effect of die
resistance was also reported by Janssen et al iOi , no explanation
having been put forward. Because residence time distribution is a
measure of axial dispersion (section 1.4.1.4), shorter tails are a
result of less leakage flows. An increase in die resistance will
cause a decrease in viscosity and an increase in back pressure, hence
an increase in leakage flow. Shorter distribution tails must
therefore be explained by a decrease in the number of fully filled
chambers. An increase in temperature profile will also cause a
 - 191 -

z40
o
.....
~
0::
I-
z~
UJ
w
Z
o
w

TIME [MIN]
FIGUR~ 6.1 Relative concentration versus time curves for selected
experiments. T,,,in Scre'd Extrusion

.9
----- t SCREW SPEED
,-
,- '" '"
'I "
F( e) r'
~
I
.5
if"
"
,7l'

'/"
I'
.3 ,/
I,
,'I
1/"
.1 ,I
/'
l'

.6 to 8 1.4 1.8
FIGURE 6.2 Influence of scre,., speed in the F curve
 - 192 -

.9
=--- t TEMPERATURE
F( e)
.7

.5
7
/
I
,I
.3
W
, I

,//
'/
,/1
.1 '1
,/1
, I

.6 1.0 1.4 1.8

e
FIGURE 6.3 Influence of temperature profile on t'le F curve

.9
== tOIE RESISTANCE

F (e)

.7
l,1
,.,I
.5
,I"
,1"
"
.3
l ¥
/!
I
.1 'I
1
I

.6 1.0 1.4 1.8

e
FIGURE 6.4 Influence of die resistance on the F curve
 - 193 -

decrease in viscosity but, as seen in the previous section, this does

not necessarely create more leakage flows due to a decrease in back
pressure.

The experimental curves are compared to the models available in

Figure 6.5; they are more plug flow like than those found by Janssen
101
et al ,leakage flows taking a minor role in the process; as \~i th

single screw extrusion, the model combining plug flow and perfect
mixing provides the best fit, specially for plug flow percentages of
85%. This is higher than the 70% found by Janssen et al 101 •

.9
F(e)

.7
-'
,/ " ..........
...-'; EXPERIMENTAL CURVE
// I -+- PLUG FLOW
.5
"."."
"."."f""
.I + PERFECT MIXING
/'
/ ' ,/ / rI
/ ... JANSSEN'S EXP. CURVE
'I I LAMINAR FLOW IN PIPE
.3
'
I
" I
I

1
/
A./ I + .. COMBINATION OF PLUG
AND PERFECT MIXING
f
I
f
i'
'/
; /

•
.I
iI , /
.1
"
I
f

.,. . /.7 /85

I
I ......, ,

.6 to t4 1.8
e

FIGURE 6.5 Comparison of experimental F curves with published models

 - 194 -

In contrast with the observations of Janssen et al 101 and

48
Rauwendaal , a comparison of figures 6.5 and 5.6 provides the
conclusion that the conveying characteristics of the twin screw
extruder compare favorably with those of the single screw extruder.
Despite the presence of a long solid bed with a plug flow like
conveying mechanism and the high viscosity of the material accounting
for the good conveying characteristics of the single screw extruder
reported by those workers, the positive conveying mechanism of the
twin screw machine and the small significance of the leakage flows
seem to provide even better characteristics.

There are two reasons supporting the results found in this work.
First, in the twin scre", extruder the back pressure is only felt in
the last third of the extruder, where the material presents high
viscosity characteristics and the level of shear is smaller due to
the reduced diameter of the screws. The leakage flows are therefore
never encouraged. Second, in the single screw extruder, despite the
existence of a long solid bed with good positive conveying
characteristics, the wall-slipping behaviour of the material is
responsible for a melting mechanism where leakage flow plays an
important part (section 5.3.1) in widening the residence time
distribution.

These conclusions should not be generalized to other materials

or types of machine, since the geometry of the equipment and the flow
. 96 107
propert~es of the compound/polymer play a major role ' •

The minimum and mean residence times and the standard deviation
produced the following polynomials:

t. m~n
= 2.259 + 1.679S - 0.226T + 0.144P + 0.545SS +
+ 0.332TT + 0.170PP + 0.132ST - 0.076sp - 0.137PT (6.3)

t = 3.299 - 2.28S - 0.209T + 0.261P + 0.934SS + 0.155TT

- 0.130PP + 0.128ST - 0.176SP + 0.012 PT (6.4)

a = 1.024 - 0.903S + 0.273T - 0.131P + 0.48SS + 0.006TT

- 0.140PP - 0.326ST + 0.208SP - 0.283 PT (6.5)
 - 195 -

The influence of the processing conditions can be identified

from Table 6.3.

(min)

t lun
. t 0

-1 4.0 6.5 2.6

s 0 2.5 3.2 1.0

+l 1.5 2.0 0.7

-1 2.8 3.8 1.1

T 0 2.5 3.2 1.0

+l 2.3 3.1 1.0

-1 2.3 3.0 1.0

DR 0 2.5 3.2 1.0

+l 2.4 3.3 0.8

TABLE 6.3 Influence of processing conditions on minimum and mean

residence times and standard deviation

48
As reported in the literature screw speed was found to be the
dominant variable: increasing screw speeds lead to smaller minimum
residence times. Variations in temperature profile and die resistance
do not significantly affect the values of the response, although there
is a tendency for it to increase with increasing die resistance and
decreasing temperature profile. This is expected due to the influence
of the control variables upon the output. The combination of the
different effects leads to a minimum value of the response for high
screw speeds and temperature profiles and low die resistances.

The behaviour of the mean residence time is qualitatively similar

to t •
min
A steady decrease in the standard deviation is observed with
increasing screw speeds. This is consistent with the F curves, where
 - 196 -

a shorter tail was obtained for increasing screw speeds. Identically,

the response decreases with increasing die resistance. a was found
to increase very slightly with increasing barrel temperature: an
increase in the latter will cause a decrease in the material's
viscosity, thus allOwing for increasing leakage flowS; this effect
must be very small, since no change could be detected in the F curves.

6.3 MELTING MECHANISM

To identify the melting mechanism within the twin screw machine,

core samples were obtained as described in section 4.2.2 (Figure 4.4).
The mechanism was characterized as in single screw extrusion, by
visual analyses, fluorescence microscopy, thermal analysis and
pressure and temperature measurements.

Disctinction between the solid bed and melt pool was always
possible; the colour of the solid material progressed from white
near the hopper to more or less dark brown towards the metering zone,
depending on the processing conditions used. The melt seemed to be
always light yellow, the colour being practically independent of the
operating variables and position along the length of the screws. The
changes in colour have been accounted for in section 5.3.

For the range of processing conditions observed fusion took

place quite suddenly, within one C-shaped chamber at the beginning
of the metering zone (Figure 4.4). This agrees well with the
observations reported in the literature 92 ,58,128,133 although the
mechanism observed here was less dependent on processing conditions
than usually reported. Hence, the values of pressure P2 seem to
provide information on the characteristics of the melting mechanism
rather than on its length (section 6.1).

The C-shaped chambers where melting took place were cut in five
different locations along planes perpendicular to the channel length.
The results obtained with varying temperature profile (factorial runs
numbers 11, 15 and 12, Table 3.1) are shown diagrammatically in
Figure 6.6.
 - 197 -

3
direction

A) B)

FIGURE 6.6 A) Locations of transversal cuts along the C-shaped

chamber;
B) Channel of C-shaped chamber unwrapped. Low temperature
profile;

Increasing the temperature profile seems to increase the length

for the development of a fUlly melted channel cross-section. Since
high temperatures allow better heat transfer, the result must be
explained by the higher back pressures at low temperature profiles
(section 6.1.3).

58
Janssen reports that increasing back pressure creates more
leakage flow of melt, causing ~1e still particulate polymer to stick
together, with a decrease on the efficiency of the tumbling action
that normally ensures uniform temperature distribution (Figure 1.13).
In this work, probably because the leakage flows seem to play a
relatively minor role, it was observed that the tumbling action was
in fact more violent at higher back pressures. the flow patterns
being clearly discernible in the sample (Figure 6.6 B)).

The melting mechanism observed seems to present characteristics

common to the ones reported by Janssen 58 for low and high back
pressures, Figure 1.13. and is quite different from the mechanism
found in the single screw extruder.
-QI

"-
o
Allllllf1 AIIIII 1f1 .fA
t-
Cl..

0...
E
Allllllth JJllllth 41. _
QI
4-

~
·
Allllllth Alllth _[1 1&
1 2 3 4 5
DIRECTION OF TRANSPORT
•

11111111 fll solid melt

G)

FIGL~E 6.6 G) Gross-sections of G-shaped channels for different barrel temperature profiles
 - 199 -

In the beginning of the C-shaped chamber the powder is

compressed into a strong solid bed, its colour qUickly changing.
Like Janssen's model for low back pressures, melting starts at the
heated barrel "all (with shear and backwards flo", as in the single
screw extruder). However, the local high back pressures will cause
. a violent tumbling action, with melt developing in the solid bed/
/melted material interface. The melt pool will now present a
distorted shape, similar to the one reported by Janssen for high
back pressures. l~ben the area of the melt pool is significant, the
process will accelerate, with fusion taking place both due to shear
and heat transfer.

As for the single screw extruder, the analysis of the cross-

-sections under the fluorescence microscope provides additional
information on the process; using the quantitative method described
in section 4.5.1.2, the fluorescence intensity of the core samples
along the screw length and in the C-shaped chamber where melting
takes place was measured for various experimental runs; the results
are presented in Figure 6.7. Material with poor cohesion was
embedded in Polaron.

A different profile from the one for the single screw extrusion
experiments (Figure 5.8) is obtained; whereas in the latter machine
the fluorescence intensity (FI) increased always from the hopper to
the die, in the twin screw extruder the FI of the solid material
increases towards the metering zone, reaching a maximum just prior
to melting taking place; then, as in the single screw extruder, there
is a loss in FI due to better additive dispersion. Along the
metering zone the fluorescence intensity decreases, which can be
attributed to progressively better additive dispersion, and more
efficient stabilizer action. Allsopp13 observed development of
fluorescence of the polymer until the end of the screws, where it
reached a maximum, decreasing thereafter. This behaviour also
accounted for an increased homogeneity with respect to additive
dispersion. Miadonye128 , reporting that the melting mechanism took
place in the metering zone, observed a decrease in fluorescence
intensity from hopper to die. This result seems difficult to account
for, speCially since the changes in colour observed in this work
 - 200 -

T +1

)-40
I-
~

VJ
e ~ ~

Z
w
~20
~
0 solid
w
u
z
• melt
w
~60
w T 0
0::
0
:::>
-I
u..
40
• •
20
raw material: 8.9
14 12 10 B 6 4 2
TURN OF SCREWS

FIGURE 6.7 Fluorescence intensity along the length of the screws.

Influence of processing temperature

were also reported by Miadonye.

From Figure 6.7 it is also apparent that, as for the single

screw extruder, an increase in the barrel temperature profile causes
an overall increase in the fluorescence intensity of the samples.

Unlike with the single screw extruder and because of the limited
location of the melting zone, the analysis of pressures and
temperatures collected by the computer does not provide significant
information on the melting mechanism. The values of pressures PI,
P2 and P3 (see section 6.1.3) for the factorial experiment number 11
are presented in Figure 6.8, together with the output of the
 - 201 -

182 PSI

r I--

~ '-- ~ "-
- 1923 PSI

1\
\ 1\ f\ 1\
TOP: P1 CENTRE: P2 BOTTOM: P3
FIGUR~ 6.8 Data collected by computer on factorial experiment 11.
Top of each graph: pressure; bottom: rotary potentiometer
 - 202 -

rotational potentiometer (allowing an identification of each rotation

of the screws).

The steady state is here clearly achieved. It is evident that

the pressure profiles vary cyclically as the screws rotate. PI is
small and reflects the posi ti ve conveying mechanism of the first
section; the profile P2 is more complex; here. a balance between
posi ti ve conveying characteris.t i cs and leakage flow of melt due to
back pressure is measured. This profile seems therefore to indicate
that melting does not take place far from the first turns of the
metering zone.

The increase in material temperature along the screws for the

experiments analysed in Figure 6.6 is shown in Figure 6.9. The data
was obtained as in Figure 5.13. ie •• from the onset temperature of
the B peak from DSC traces of the core samples.

---- f TEMPERATURE
200

w
-190
•
UJ
0::
~ -*"-_ - - ,---x
I-
«
.... - -
--- I
I

ffi180
~ c.-----~ , )t- -- -~
-~ -~
,
"
, I
'X
I
I
I

UJ X
I-

170 ~-~
--- ~ -- ¥:'

14 12 10 8 6 4 2
TURN OF SCREWS
FIGURE 6.9 Temperature profile of the material alon'g the screws.
Data obtained from DSC traces
 - 203 -

As expected, the average temperature of the material within the

extruder increases with increasing barrel temperature profile. The
temperature of the solid material increases'along the length of the
screw until the C-shaped chamber where melting takes place. Here,
the temperature rises quickly due to efficient heat transfer and
high level of shear; after all the polymer is fused the temperature
increases less drammatically towards the die. Because no barrel
heater could be provided between the tip of the screws and the die,
the temperature in that zone ca~ eventually drop. Thereafter, the
high level of shear created by the breaker plate will cause a fast
increase in the melt temperature, so that the final extrudate is
hotter than the material at the screw tip.

Figure 6.10 compares the temperatures of the extrudates with

the values set in the die, the data having again been determined
from DSC traces. The figure is directly comparable with Figure 5.14.

.
[ [1
'

+1-- - - - - - - - - - 210 --------------

+1
T 0- - - - - - - ~
- - - -?OO -
.-8"."-
-.--9--
0
s- e--
o
-
0
- --f:j--
0 o w·- 0
o DR-
-1-- - - - - - - - - - 190 --
-1

FIGURE 6.10 Temperature of extrudates versus die settings.

Influence of processing condi tions

Unlike with single screw extrusion, the values measured are

always lower that the set ones, meaning that the overall level of
shear is smaller than in that machine. This also means that in the
twin screw machine the melt temperature is mainly controllable
 - 204 -

through the external heaters. with the advantages described in

section 1.4.1.1. However. shear also plays a significant part. as
can be seen from the influence of increasing screw speed and die
resistance at constant set temperature: the temperature of the
extrudate increases with increasing level of the three variables.
due to high back pressures and increase in the level of shear. The
effect of die resistance seems to be more important than the one of
screw speed. since the latter is a balance between an increase in
the level of shear and a decrease of the resistance time of the
material within the extruder.

6.4 MECHANISM OF GELATION

6.4.1 IDENTIFICATION OF THE MECHANISM OF GELATION

The mechanism of gelation was identified by analysing core

samples from along the length of the extruder under the microscope.
The Jamin-Lebedeff Interferometer. Fluorescence Microscopy and
Scanning Electron Microscopy (Sro1) were used (see chapter 4 for
details of experimental procedure). The results are presented in
Figures 6.11 to 6.14. Figures 6.12 to 6.14 having been obtained
wi th the SEM.

As with the single screw extrusion process. the raw material

(Figure 5.15) is converted into an homogeneous melt (Figure 6.14)
by application of heat and shear. The morphological evolutions
observed correlate well with the CDFE mechanism (section 1.4.2.3.2)
proposed by Allsopp13 and supported by other workers128 •139 : ~n
. the

compression zone the grains begin to be compacted together. their

internal porosity being progressively eliminated. Heat transfer
will be increasingly more effi cient and because the local pressure
will be able to be transmitted. a compact mass of hot powder is
formed. This results in a significant development of inter- and
intragrain fusion. As the material advances in the extruder. the
presence of a compact mass will soon create high local pressure
gradients and fusion develops qUickly; in a single C-shaped chamber
some grains near the barrel wall will be subjected to shear and
 - 205 -

100 )lm
I

FIGURE 6.11 l1icrophotograph of solid bed in C-shaped chamber

, "lhere
mel ting takes place

100 )lm
I

FIGURE 6.12 S~~ microphotograph of material in chamber number 12

 - 206 -

5 urn
I

FIGURE 6.13 S~1 microphotograph of melted material in chamber number 9

2 urn
I

FIGURE 6.14 SEM microphotograph of material in chamber number 1

 - 207 -

elongated. and will eventually break open. the additives dispersing

into it. This will form a nucleus of melted material that. due to
shear and heat transfer. will grow along the chamber length.

The process can be followed in Figures 6.11 to 6.13. Figure

6.12 was obtained in chamber number 12. before the metering zone;
the grains are still free. no significant degree of compression
being apparent. Figure 6.11 shows the degree to which compaction
of the grains has developed and how the internal grain structure
has disappeared at the beginning of the C-shaped chamber where
melting will take place. The features discernible inside the grains
are the re sul t 0 f swellin g due to penetration of the mounting
liquid - tricresyl phosphate. It is also apparent that the
additives are deposited in pockets around the grain contours.
Figure 6.13 was obtained a little further along the chamber; unlike
wi th single screw extrusion. even in the first melt pool no evidence
of the presence of primary particles could be detected.

Despite the hydrodynamics of the process in the single screw

machine and in the twin screw extruder being quite different. the
morphological changes in the material seem to be parallel. with the
grains being initially compacted and densified. internally fused and
then elongated in the direction of shear and forming a melt. In the
case of the twin screw extruder. the melt will be progressively more
homogeneous. as the results of fluorescence microscopy seem to show
(section 6.3). The mechanism of gelation for this machine is
schematized in Figure 6.15.

6.4.2 PROGRESSION OF FUSION ALONG THE SCRDI

The DSC technique was again used to measure the degree of

gelation as it progresses along the screw. In Figure 6.16 the
endothermic energy of peak A was plotted as relative percentage of
gelation against the screw length for the factorial experiments
concerned with the influence of varying temperature profile.
 heat
•
heat
A
- 00x -~,,--
shear in:t!:l'1: shear
+ + -melt front j(
pressure pressure
-barrel welll ,,,o
continuing
Raw Melterial '"
shear

;:.o:~ internal structure of grains

x additives
,r-~ melted material
Homogeneous
Mel t
FIGU:lE 6.15 :4echanism of gelation in a t"in scre>l extruder
 - 209 -

% GELATION

100
-t TEMPERATURE

...... ~
f'
I
I
/
X
/
------)(------y
i t:====::::::'-.a1o )("'">t-
-- --
10
~-------~
14 12 10 8 6 4 2 EXIT
TURN OF SCREWS
FIGURE 6.16 Development of gelation along the length of the screw.
Influence of temperature profile

As expected, the average degree of gelation of the material

increases with increasing temperature profile. For each experiment
the degree of gelation increases slightly along the screw until
chamber number 9, where the fusion mechanism takes place (section
6.3). Here the degree of gelation increases rapidly, as the solid
bed disappears and a fully melted material is formed. From then
onwards the degree of gelation should increase towards the die.
Unexpectedly however, as indicated by the analysis of the temperature
profile (Figure 6.10), the absence of barrel heaters in the extruder
seems to cause a slight decrease in the degree of fusion; in the die,
due to the high set temperatures and level of shear, the degree of
gelation will increase again.
 - 210 -

The fact that the degree of gelation of the material near the
screw tips is lower than the previous one means that the amount of
secondary crystallinity formed upon cooling, after having reached a
maximum in the metering zone, has been reduced. Similar data has
been reported in the literature on reprocessing studies155 , the
results having been interpreted as evidence of crystalline cross-
-linking sites being broken down at various points under the high
shearing forces at lower temperatures. It is di ffi cuI t to accept
this explanation here, since one is in presence of an homogeneous
melt and a continuous process with similar shear characteristics;
the sensivi ty of the DSC trace to changes in processing conditions
seems therefore di ffi cuI t to account for.

Patel155 also reported that while the endothermic energy of

peak A is reduced with reprocessing at lower temperatures, the onset
of the B peak is unaffected. Clearly, this was not observed here
(as Figure 6.10 shows), the onset temperature of the B peak
decreasing for lower degrees of gelation.

If the endothermic energy of peaks A and B for the samples

along the screw is plotted against the B onset temperature for the
three processing conditions being monitored, the curves shown in
Figure 6.17 are obtained. Not surprisingly, the shape of the curves
is similar to the ones found for single screw extrusion (Figure 5.26)
and compression moulding (Figure 5.27). The initial decrease in
endothermic energy is due to a steady decrease in the B endothermic
energy, when secondary crystallinity is still insignificant; the
increase of total energy at high temperatures is caused by a sharp
increase in the energy of the A peak, the B peak being now
practically non-existent.

An increase in the barrel temperature profile will cause an

increase in the total degree of gelation, and an increase in the
temperature of the material. However, the graph also shows that
for the same processing temperature, samples produced under lower
temperature profiles will show a higher degree of gelation, which
can only be due to the higher levels of shear present. Both in
their early resul t i 63 and in a later report140 , Gilbert et al have
 - 211 -

7
-:- I TEMPERATURE
01
I
1•
i
f

6 I

I
I I
•
I .I
5 ID I
, .i
I

I
I
A+B- / xi
I
I I
•
>-
l!J I Ix
ffi3
z
0,0 i
/
LU
/ /
I~X ,IX
W
-'
~2
LU
::J:
l-
" ho
\
\
'.
o '. ~ .y
-
........
o f/ x
a
\ v
Cl
Z
LU
I
7 ix
I ~.
6 01
A- I
5 I /
•
I
ID I
.
4
I
, J .
3 I.
/0
/
9 /
2
'::/..-
A~x?
.;.>'.
x
W_·-l(·
1
-B
170 180 190 200 210
(C 1 TEMP. ONSET B
FIGURE 6.17 Endothermic energy of peaks A. 13 and A+B versus
pro~essing temperature
 - 212 -

observed similar phenomena for different processing techniques and/or

compounds; Figure 6.17 shows that the same happens within one process.
Identical results were obtained for the single screw extrusion
experiments under different processing conditions. Also, Figure 5.26
shows (specially for factorial experiment number 13) that, because
the level of shear in the melt pool is higher than the one in the
solid bed, for the same B onset temperature its degree of gelation
is higher than the one of the solid bed.

A further conclusion to be taken from Figure 6.17 is that the

temperature at which the minimum endothermic energy occurs increases
with increasing temperature profile. This is again due to lower
energy of the A peak for high temperature profiles for the same
processing conditions.

One can therefore extrapolate these observations and expect that

different processing conditions leading to the same melt temperature
will in effect produce materials with various degrees of gelation.
Hence, if degree of gelation is plotted against stock or processing
temperature for a range of processing conditions where the shear
level varies greatly, one would expect an. S-shaped curve with a
significant scatter of results.

The change in density of the material along the length of screw

is as expected (Figure 6.18), providing similar conclusions to the
single screw extruder case (section 5.4.2). The grains in the solid
bed are highly compacted in the compression zone and in the C-shaped
chamber where fusion takes place, causing a large density increase
with a decrease thereafter, as the temperature increases. Also,
wi th increasing temperature profile the overall density decreases,
further supporting the conclusions of section 5.4.2.

6.5 cm1PARISON OF TWIN AND SINGLE SCREI-I EXTRUSION

From the experiments performed throughout the present and the

previous chapter it has become apparent that the differences in the
development of the pressure profile along the screw (sections 5;3.2
 - 213 -
DENSITY

t---- __ -----iE--__ --~--.,.\ ~

,,
x

1.400
I
I
I
I
I
I
I
=-=-= t TEMPERATURE
I
I
1.395 I
I
I
I
I
I
I
I
I
I
I
I
1.390

1.385

12 10 8 6 4 2
TURN OF SCREWS

FIGURE 6.18 Influence of barrel temperature profile on the progression

of densi ty along the length of the screws
 - 214 -

and 6.1.3), m~x~ng characteristics (sections 5.2 and 6.2) and

melting mechanism (sections 5.3 and 6.3) reflect substantial
differences in the mechanism of transportation of single and twin
screw extruders.

As far as the processing of PVC is concerned, the melting

mechanism of the twin screw extruder is more efficient than the one
of the single screw machine: at the beginning of the metering zone,
where the temperature increases - and so does the danger of
degradation - the material is quickly fused, the dispersion of the
additives improving throughout the remaining of the extruder, as
shown by the fluorescence intensity results (section 6.3). In the
single screw machine there is a long solid bed of material throughout
most of the length of the screw. without proper additive protection,
the material being only fully melted near the screw tips. As a
result, the fluorescence intensity of the melt pool was found to
increase continuously along the length of the screw (section 5.3).
Also, as discussed in section 6.2, the conveying characteristics of
the twin screw extruder compare favourably with those of the single
screw machine. This is important for PVC, since it means that all
the material spends a similar residence time inside the extruder,
the risks of degradation being smaller.

Despite the different characteristics, both machines induce

parallel morphological changes in the material, the CDFE mechanism13
being generally observed (sections 5.4 and 6.4), and both are
capable of producing a melt where the additives seem to be well
dispersed, as shown by SEM microscopy. Furthermore, from the DSC
results it is concluded that in this melt there is a progressive
destruction of primary crystallinity as the processing temperatures
are increased towards the die lips, so that the final product will
contain a network of entanglements and secondary imperfect
crystallites formed upon cooling.

The morphological characteristics of the extrudate being

similar, it is in the ease of operation that the advantages of twin
screw extrusion become more apparent. Unlike single screw extrusion,
the temperature of the extrudates is always lower than the values
 - 215 -

set (sections 5.3.2 and 6.3), therefore more easily controllable.

This is due to the lower level of shear induced by these machines
which, in the case of conical extruders, is helped by the progressive
reduction in diameter of the screws along the metering zone. Also,
the steady state can be clearly achieved, unlike with single screw
extrusion (section 5.3.1). In the latter, this can cause changes in
the melting mechanism with consequent fluctuations in the output and
unsteady intake of feedstock (section 1.4.1.1). A further advantage
derives from the fact that the output in twin screw extrusion is
independent of the conditions at the die end (section 6.1.1), whereas
in single screw extrusion it decreases with increasing die resistance
(section 5.1.3.1).
 - 216 -

CHAPTER 7

RESULTS AND DISCUSSION

PROPERTIES OF THE EXTRUDATES

7.1 DEGREE OF GELATION OF THE EXTRUDATES

The degree of gelation of the material obtained by single and

twin screw extrusion was determined using the capillary rheometry
and thermal analysis techniques, previously described (sections
4.7.1 and 4.7.2, respectively).

It is common to present the degree of gelation as a percentage

value 141 , as defined by equation 1.20, versus stock temperature.
Although this equation was defined for capillary rheometry, it can
also be used for DSC if the pressure at the entrance of the capillary
P is substituted by the endothermic energy of peak A, ~A.

The advantages of the use of a statistical experimental design

throughout this work have been discussed in chapter 3. Its use,
however, may also limit the broadness of the experimental field, due
to special combinations of values of the independent variables in
some ·.experimental runs. For example, from Table 3.1 it is apparent
that the determination of the temperature profile was conditioned
by the pressure drops created in experiments 2, 5 and 6. Because
of these runs, the lowest temperature profile is in fact relatively
high (Table 4.2). The attribution of 0% gelation level to the
minimum degree of gelation measured has little real significance.
To avoid this, when standardizing the gelation curves, the zero
gelation level was taken as the value measured experimentally with
raw powder. It is thought that this definition provides a more
realistic measurement, as all values of gelation defined are
relative to a real 0% gelation.

The use of a statistical design also meant that, for the same
temperature profile setting, the degree of shear induced by
variations in the other two independent variables caused changes
 - 217 -

in the melt temperature. Instead of set temperature (chapters 5

and 6), the degree of gelation was plotted against the more real
B onset temperature.

The results for the single and twin screw extrusion experiments
are shown in Figures 7.1 and 7.2, the Capillary Rheometry and DSC
gelation curves behaving similarly for the two types of extruders.
As expected, the degree of gelation increases with increasing
processing temperature, the curves presenting two regions of
different behaviour; between 185 and 200°C small changes in the
melt temperature produce a substantial increase in the degree of
gelation; beyond 200°C, relatively large changes in temperature
produce little changes in the degree of gelation. Similar results
have been reported139 ,140 and a number of authors12 ,17,42,43,167
have showed that the transition is due to a change in the nature of
the flow units in the melt. As shown in section 5.4.2.1, up to
190°C the presence of primary particles produces few cross-linking
si tes, the increase in the degree of gelation being only SlO1~.

100

...J
UJ
G:; 60
...J
Z
o
.....
~40
...J
UJ - - -- Cap. Rheom.
l!J
-DSC
20

190 200 210

B ONSET TEMP. [OC]
FIGURE 7.1 Gelation curves for single screw extrusion
 -. 218 -

With increasing temperature the loss of primary particles becomes

more important22 ,25,33 and more secondary crystallites form upon
cooling. Above 200 - 205°C no primary particles remain, therefore
little further change can take place and the curves tend to level-
-off.

100 ~,-Q"-
;;:DJ"' Cl Cl
/'" D --
.-
~80
o~ "" /
~
/ ~P'
...J I Cl I
UJ I
~60 I
...J
z
o.....
~40
...J
UJ Cap. Rheom.
l!J

DSC
20

180 190 200 210

B ONSET TEMP. [OC]

FIGURE 7.2 Gelation curves for twin screw extrusion

7.1.1 INFLUENCE OF PROCESSING CONDITIONS

For all the curves, 100% gelation was obtained with run number
8 (Table 3.1), where the three independent variables are at their
maximum. The minimum degree of gelation was obtained for run
number 5 (single screw extrusion) and run number 1 (twin screw
extrusion), where the temperature profile and die resistance are at
their minimum and screw speed at its highest and lowest levels,
respecti vely. The general influence of the processing conditions
on the gelation level is indicated in Table 7.1 and by the
 - 219 -

polynomials obtained by regression analysis of the data.

%Gel CR SINGLE = 90.67 + 2.40S + 4.93T + 5.l7P + 0.37SS +

+ 0.52TT - 3.BBPP + 0.60ST + 3.30SP -
- 1.92PT (7.1 )

% Gel CR TlHN = 94.77 + 2.96S + 10.17T + 2.41P - 0.67SS -

- B.52TT - 1.22PP - 0.85ST + 3.00SP -
- 1.87PT (7.2)

% Gel DSC SINGLE= 77.06 + 4.11S + 21.26T + 10.07P + 6.05SS -

- 10.00TT + 2.65PP - 3.37ST + 5.72SP -
- 7.35PT (7.3)

% Gel DSC T~IIN = 67.70 + 7. 96S + 13.64T + 6.39P - 3.08SS +

+ 1.42TT + 4.l7PP - 0.4lST + 3.56Sp -
- 4.8IPT (7.4)

DEGREE OF GELATION (%)

SINGLE S. EXTRUSION TI'iIN S. EXTRUSION
CR DSC CR DSC
-1 86.1 39.3 74.5 57.1
S 0 89.2 84.9 93.2 74.0
+1 97.0 90.9 98.8 78.0
-1 88.3 69.2 92.5 48.5
T 0 89.2 84.9 93.2 74.0
+1 94.5 93.1 96.5 77.6
-1 80.9 68.5 93.2 59.1
DR 0 89.2 84.9 93.2 74.0
+1 93.4 87.0 94.7 81.4

TABLE 7.1 Influence of processing conditions on the gelation level

of the extrudates
 - 220 -

An increase in the level of the independent variables causes

an increase in the gelation level. As the breakdown of the primary
particles can be obtained by the sole application of heat14 ,
increasing temperature profile will speed up the process. But,
because the application of shear increases the efficiency of the
process14 , increasing die resistances and screw speeds will also
cause a significant increase in the degree of gelation. The effect
of the latter is also dictated by the residence time of the material
inside the extruder, and is clearly shown for the single screw
extrusion process, where the minimum degree of gelation was obtained
at maximum screw speed (experiment no. 5).

From Table 7.1 it is also apparent that a variation in the

screw speed and die resistance can cause changes of the same order
of magnitude for both single and twin screw extrusion. Since the
average level of shear in the latter is lower (section 6.5), these
changes must be mainly accounted for the shear conditions in the
adaptor and die.

7.1.2 COMPARISON OF TECHNIQUES

The·curves produced by capillary rheometry and thermal analysis

cannot be superimposed for either single or twin screw extrusion.
This result is supported in the literature139 and is expected, since
the two techniques measure different phenomena: while capillary
rheometry quantifies the elastic bUild-up in the material due to
increasing interpenetration of the partlculate domains (section
1.5.4), thermal analysis measures the heat of fUsion of secondary
crystallinity formed upon cooling by recrystallization of more
perfect primary crystallites (section 1.5.5).

The latter technique seems to provide a better discrimination

between similar degrees of gelation, but this is opposed by a
greater scatter of results caused by the small size of the test
specimens, as compared to the width of the extrudates. The scatter
of results is also due, as discussed in section 6.4.2, to the
different combinations of the independent variables producing, for
the same processing temperatures, material with varying degrees of
 - 221 -

gelation.

Different relationships between the two techniques have already

been reported. Gilbert et al140 compared the measurements for
compression moulded and extruded samples of both rigid and
plasticized formulations at a particular rate. A linear correlation
was obtained, the relationship depending on the extrusion rate.
155
Patel obtained a limit value in capillary pressure as the heat
of fusion was increased, but his work was limited to plasticized
formulations. In this work - Figure 7.3 - a linear relationship
was observed, but the correlation is different for each extruder.

[J
11 [J

0
X
9
.....
-
l!J
-.
~

7
X

-
z
0
VI
:=I
u.
u. S
0
I-
X . S
«
w single twin
:J:
3
• [J
• -1

••
X 0
0 +1
1

18 20 22 24 26 28
CAP. EXTRUSION PRESSURE [MN/M')
FIGURE 7.3 Correlation between capillary rheometry and thermal
analysis for single and twin screw extrusion

•
 - 222 -

By plotting heat of fusion against the 'B' onset temperature for

the two machines (Figure 7.4) it can be concluded that the shift
in the straight lines seems to have been created by the capillary
rheometry results, whereas the DSC values cause the variation in
the slope of the lines. No significant influence of extrusion rate
could be detected, but this could well be masked by the variations
of the other two independent variables.

11 c9
00 0
<0
-
~
0
l!J
0
-.
~
9
z
0
......
Vl
:::>
•
00

o. •
Il... 7
Il...
0 • ••
I-
~
UJ
:c 5
0.·
•
•• ee
0
3
• • 0

•
single
twin

1~~--~~----~~--~~---.-
190, , 200 210 220
B ONSET TEMP. ["Cl
FIGURE 7.4 Correlation between heat of fusion and processing
temperature for single and twin scre,,, extrusion

Figure 7.3 also shows that the maximum value observed for ~HA
was 11 Jg-1 for single screw extrusion, compared with 8 Jg -1 for
twin screw extrusion. This correlates well with the maximum range
 - 223 -

of 10 - 12 Jg- 1 reported by Gilbert et al140 and shows that the

single screw extrusion process, despite the lower temperature
settings used (Table 4.2), can produce well fused material due to
the high level of shear induced. Identically, the maximum extrusion
pressure for single screw extrusion was 27 HN m- 2 compared with
24 HN m- 2 for twin screw extrusion, which leads to the same overall
conclusion that both processes can produce material with a high
gelation level.

7.2 I1ECHANICAL PROPERTIES

The mechanical properties of the extrudates were assessed by

monitoring their tensile, flexural and impact strength, and how
these are affected by changes in the degree of gelation. The
measurement of these properties, together with capillary rheometry
and thermal analysis, can be used to determine the degree of
gelation of UPVC samples. Capillary rheometry and thermal analysis
do not need special and time consuming techniques for the
preparation of test specimens and DSC in particular, due to the
small size of the samples used, can be considered a non-destructive
technique. Hardness testing will fall most certainly in the latter
category of tests, with the advantage of lower cost of equipment
and no need for a skilled operator. The potential of hardness
testing as a technique for the assessment of the degree of gelation
of PVC samples was therefore investigated.

7.2.1 TENSILE TESTING

Despite tensile properties having been investigated quite often

in the literature (section 1.4.2.5.2), the way they are affected by
changes in the gelation level is far from established.

Yield parameters have been reported to be independent of degree

of gelation 23 ,142,150, but some authors141 ,149 have found other
relationships. Also, elongation and stress at break are reported to
either increase with increaSing gelation leve1 23 ,142 or to reach a
 - 224 -

maximum 22 ,141. Information on the relationship between these

parameters with gelation level for tests performed at high
142
temperature is much scarcer , with some indication that for test
temperatures around 90°C post-yield deformation is very sensitive
to varying degree of gelation.

vii th the aim of establishing the relationship between the

tensile parameters and gelation level for the composition and
processing techniques used, an experimental programme including
tests at room temperature at different rates and at 60, 90, 120 and
150°C was .defined. Specimens were cut both parallel and perpendicular
to· the extrusion direction. The details of the experimental
procedure and method of obtaining the tensile parameters were
presented in section 4.8.1.1.

The family of stress-strain curves obtained for samples with

different gelation levels and at various test temperatures is
presented in Figures 7.5 and 7.6.

A typical stress-strain curve at test temperatures below T

g
presents an instantaneous elastic response, followed by a vis coelasti c
one due to molecular relaxation. As extension proceeds, the delayed
elastic and plastic deformations increase in magnitude and the curve
becomes increasingly non-linear. Simultaneously, extraneous
particles cause regions of stress concentrations that, upon
achievement of a critical strain, will grow into crazes or
microcavities152 ,153 near the surface of the specimen. At the yield
point the stress reaches a maximum and a neck is formed, the VOiding
during crazing and the formation of bands of sheared material causing
stress whitening to occur. The crazes pass almost unchanged through
the neck152 ,153. Terselius142 suggests that with sufficient
thinning the neck becomes orientation hardened and stabilized by
cold drawing; the adjacent parts deform at the shoulders of the
speCimen, travelling along the neck. 1'li th increasing strain the
crazes grow into cavities that develop by tearing in the direction
perpendicular to the polymer orientation152 • Eventually, the local
stresses will cause failure of the specimen.
 - 225 -

50

40

""--;:;-"'11 2

V')
V')
w
Cl::
l-
V')

20

11, 2, 10, 3, 8
•
incr. gelation
10
90°C
--.----------- -"-~
------
--
.
-- . .--" --- . .--.----

.
/
./'

01~-1~0----3~0~~5~0--~~70~~~90~~~11~0~~1~30~~
STRAIN [% 1
FIGURE 7.5 Stress-strain Curves of twin screw extrusion speci~ens for
tests at different temperatures and material wi t!1 varying gelation level
 - 226 -

12
11
10
11, 2, 10, 3, 8
9
incr. gelation
8
7
6
5
4
3
2
1

FIGURE 7.6 Stress-strain curves of twin screw extrusion specimens

for tests at different temperatures and material with
varying gelation level - scale magnified

The curves above T reflect the behaviour of the material in the

g
rubbery state. The influence of characteristics like entanglement
and crystallinity are more evident here, and will be discussed later.

For test temperatures above T the stress-strain curves of

g
specimens with different gelation levels were superimposed, the only
difference being the point where failure took place. Below T ,
g
however, the post-yield behaviour was different for each gelation
level.
 - 227 -

7.2.1.1 YIELD PARAMETERS

The analysis of Figures 7.7 and 7.8 shows that the yield
parameters are insensitive to variations in the degree of gelation
for both twin and single screw extrudates. Yield strain increases
with increasing test temperature, yield stress with increasing
crosshead speed.

The magnitude of the values observed as well as the insensivity

to variations in gelation level agree well with the results presented
by many authors 23 ,142,150. As yield is independent of the relative
coherence of the entanglement network and number of crystalline
junctions, it must be related to molecular relaxation processes.

60

50
~

'"L
"-
z
~40
V)
V)
UJ
0::
:;;3 _Si---- -- --iT-
Cl .~ y----.. -.. .
- - - - __ ...JI....
_ . - ...... __________ -./'i-----
A A
______-• -__
0 t..
.... - _________
A At\...
... -~~-v"'""-. . . . . . . L~_
..
-I
.....
UJ

~20
single twin
23 'C, 20 mm/min
23'C, 5 mm/min
10 60'C, 20mm/min

O~----~~~----~----~----------~------~
40 50 60 70 80 90 100
GELATION LEVEL (DSC) [%]
FIGURE 7.7 Variation of Yield Stress with gelation level for single
and twin scre,1 extrusion specimens and different test
condi tions
 - 228 -

~6
Twin
0
~

0
04
-I 0 DEI 0
0
B 0 r:Pq, U E!I
LLI
)::2
)( )( xx )( )E >i' X Ill( xx X l(

~
«
:z -60·C 23·C Single
~6
0::
~
Vl4

2 ~ ~ 8 ~ ~ g$2~2 ;~

40 50 60 70
80 90 100
GELATION LEVEL (DSC) [%)
FIGURE 7.8 Variation of Strain at Yield with gelation level for
single and twin screw extrusion specimens and different
te st conditions

This is also supported in the literature142 ,150, Terselius142

suggesting that yield involves molecular re arrangements between
entanglement and network junctions, the 'flow units' of PVC at yield
being domains of the order of 100 monomer units - the entanglement
spacing of PVC. As a result, strain at yield is similar for both
single and twin screw test specimens. As far as the yield stress is
concerned, the values obtained for the twin screw extrudates are
slightly higher than those for Single screw extrusion (52.5 MN m- 2
and 51.0 MN m- 2 respectively, for tests at room temperature and at a
rate of 20 mm min- l ).

7.2.1.2 POST-YIELD PARAMETERS

Unlike the yield parameters,both elongation (EB) and stress at

break were found to be sensi ti ve to variations in gelation level.
The results are presented in Figures 7.9 to 7.12, for the twin and
 - 229 -

300
x
x
x
250

200

FIGURE 7.9 Influence of varying gela ticJn level on the elongation

at break (EEl - THin Scre,·! Extrusion
 - 230 -

x
300
x

250

200

150
0
120°C
0
100 60°C

:- ~ 150 °C

~
[J [J

:
I
50
:. •
r •

23°C
01L---~4~O----5~O--~6~O--~7~O----8~O~--~9~O--~10~O~-­
GELATION LEVEL (DSC) [%]

FIGURE 7.10 Influence of varying gelation level on the elongation

at break (E ) - Single S~,'e,·; Extrusion
B
 - 231 -

•
•
•
• •

40

10

GELATION LEVEL (DSC) [0/01

FIGURE 7.ll Influence of varying gelation leve1 on t:1e stress at
break - THin Sere" Extrusi on
 - 232 -

••
50 •
•

40

_-+__o 0
o

~
«
UJ
a:
al
I-
«
Vl
~20
a:
I-
Vl

0 tfi I oOO~ oe .1Q 2O •c•

• e 0
150 C
0
40 50 60 70 80 90 100 I

GELATION LEVEL (DSC) [%]

FIGURE 7.12 Influence of varying gelation level on the stress at
break - Single Scre'. Extrusion
 - 233 -

single screw extruded specimens. The error bars represent the

average deviation from the mean value for each experiment. Again,
the results are very similar for both extruders.

For test temperatures below T , both elongation and stress at

g
break reached a maximum for gelation levels between 65 and 85%.
This maximum is supported in the literature 22 ,141 and corresponds
to processing temperatures in the range 193 - 203°C (Figures 7.1
and 7.2). As discussed in section 7.1, the primary particle
structure is progressively destroyed in this temperature range.
For temperatures above 205°C, where no primary particle structure
remains, a drop in both stress and elongation at break is observed.
Therefore, the maximum in £B can be attributed to the existence of
a network morphology. Similar results were reported by Menges et
al 22 , who observed a maximum in £B at 185°C, with destruction of the
primary particle structure around 190°C.

For tests carried out above T a continuous increase in

g
elongation and stress at break with increasing gelation level was
observed. Also, as mentioned above, the stress-strain curves were
superimposed, the only difference being the point where rupture
occured. Since an increase in the degree of gelation causes an
increase in the density of entanglements and crystalline junctions,
these results would be expected, increasing gelation level
determining more resistance to disentanglement.

Figures 7.9 and 7.10 also show that the elongation at break
reached a maximum for test temperatures around 90°C, decreasing
thereafter; this fact is more eaSily apparent from Figures 7.13 and
7.14, where strain at break was plotted against test temperature
for several samples having different gelation levels.

Elongation at break increases with increasing test temperature

below T. For test temperatures above, low melting primary
g
crystallites begin to be destroyed and disentanglement favoured,
resulting in a decrease of elongation at break. This process will
grow with increasing test temperature, therefore a continuous drop
in the maximum elongation with increasing test temperature is
142
observed. These results are generally supported by Terselius' work
 - 234 -

STRAIN AT BREAK [%1

350

300 /I ~'~,
\'
"
\\
1
I;
'\'"
i' ,Q. \ ,\\
250 ., I'
\'
~ "
" ,,
/, I

" ,\ \' \

,/1 ' \\'

'.11
h ~,
: . \\
200
,: ,: '\\\\
Ih '
, : .1\
\,\
.' ,
IJ, I \' ,
" I •\ \
150 ~/,'
• I I
\"\ \
I , ., ,
. I , \\<Sl,
'J ' , " ,
li~ ,t' \' ,
" r ,IS\ "
I/,• ,I I, " "
....._-&_
.' "
100 '/,'
0"
" ,.. ' - , '....
''''
,J I'" ".......
. , I ~ ....
~ / , '-. '---0.
';9
./'
, ,
, "~~.A -'
.....-
~.., ,
-, , /" ,"
50 ,'" ,iI"
,"
~'

0L-~-4~0----6~0--~8~0--~1-0-0~--12~0~--14~0~-'­

TEST TEMPERATURE [ °C 1

expo runs nos -11 - 2

gelation level
-'-10 ----3
.. ----8

FIGURE 7.13 Influence of test temperature on tbe strain at break -

Twin Scre>1 Extrusion
 - 235 -

STRAIN AT BREAK [%1

300

250

200

150

0
40 60 80 100
120 140
TEST TEMPERATURE [" C1

expo runs nos -5 -9

gelation level
--6
.. ----8

FIGURE 7.14 Influence of test temperature on the strain at break -

Single Screw Extrusion
 - 236 -

As reported by this author, the sensivity of elongation at break to

variations in the gelation level reached a maximum at the, test
temperature of 90°C, confirming tensile testing at elevated
temperatures as a potential method for the assessment of the
gelation level of UPVC samples.

Stress at break (Figures 7.11 and 7.12) was found to vary with
gelation level in a similar way to strain at break. Below T these
g
variations were more significant, as beyond the yield point the
stress-strain curves were dependent on the gelation level. Above T •
g
however, the curves were coincident and stress at break increased
only slightly with increasing gelation level.

At all test conditions the values of the tensile parameters

obtained with samples cut along and in the perpendicular to the
direction of extrusion were similar, showing no orientation effects
within the extrudate. This could be due to the slippage of the
material at the die wall, with the velocity profile approaching plug
flow.

As mentioned in the begining of this section, the results for

the twin and single screw extrudates were very similar, both
qualitative and quantitatively, as shown in Table 7.2.

EB (%) (MN m- 2 )
TEST <1l
EB GELATION LEVEL OR GELATION LEVEL
TEMP.
(OC)
SINGLE. TWIN SINGLE TlVIN SINGLE TI'/IN SINGLE TIVIN

23 58 62 75-88 60-70 52.9 53.2 75-78 55-65

60 125 148 75-88 65-75 35.4 34.5 75-78 55-65
90 302 325 75-88 80-85 14.2 11.8 75-85 70-80
120 131 134 100 100 3.0 2.5 90-100 100
150 86 89 100 100 1.0 0.7 100 100

TABLE 7.2 Comparison of post-yield parameters for single and twin

screw extrudates
 - 237 -

Elongation at break (EB) was always higher for the twin screw
extrudates, whereas the single screw extrudates showed bigger stress
at break (OR).

The eventual maximum in either EB or OR was usually reached at

60-70 and 75-88% of gelation level, for twin and single screw
extrusion, respectively. These differences are possibly due to the
definition of gelation level used (section 7.1).

7.2.2 FLEXURAL STRENGTH

In the design of plastic components flexural stresses are

frequently the major criterion used. When a bar is subjected to a
bending moment (Figure 7.15 a) a stress field is developed (Figure
7.15 b) with the stress reaching a maximum at the surface given by
equation 4.8.

F
x '-_._.-. ._._.-.-. a)
h
L
z

) '\. f -I

r--.-.-.~~v:: bl
(+l'\. x

FIGURE 7.15 a) Bar subjected to a bending load

b) Stress due to bending

For the purposes of design, this stress must not exceed the
proportional limit of the material. Figure 7.15 b) also shows that
when the material is subjected to the bending moment the various
 - 238 -

cross-sections along the longitudinal axis are under either

compression or tension, depending on their relative position above
or below the neutral surface. If the maximum flexural stresses are
related to the degree of gelation, correlations similar to those
obtained with tensile testing would be expected, ie., post-yield
flexural stresses shoUld be sensitive to variations in gelation
level, a maximum between 65 and 85% (section 7.2.1.3) being expected.

The flexural strength of the UPVC samples was determined

following the ASTM D790M-81 as described in section 4.8.1.2. As
mentioned in that section, the equations for the modulus and stress
were only valid for small deflections, so the tests were discontinued
when the deflection reached 6mm, the flexural parametemthen being
computed.

The results obtained are presented in Figures 7.16 to 7.18.

The stress at maximum deflection (Omd) reached a maximum for gelation
levels in the range 60-70% (as defined by thermal analysis) for both
the single and twin screw extrudates; these values correlate well
with those found for tensile testing at room temperature, confirming
the appearance of a maximum elongation at bre~~ for tests at low
temperature.

As the yield point was difficult to determine, only the flexural

moduli were computed. Their values seem to be insensitive to
variations in gelation level, again in agreement with the results
for tensile testing (Figure 7.5).

As with tensile testing, the twin screw test specimens showed

slightly better characteristics than the single screw extrudates
with a maximum flexural stress of 68 MN rn- 2 • compared with 65 MN m- 2
for the latter. Identically, the moduli were higher for the first
machine, the tangent modulus reaching 255 MN m-2 ,compared with
236 MN m- 2 for the second.
 - 239 -

''''GII
68
"
,
,

,
66 I
I
I " ,
,
,

I
I
,,
I
I
,,
64
,,
, 0

I 0
10
'0' o
62
I
I
0',
I \
0 III 01

,,
I 0 0.
60 0 o \
\

I!J \
I \
\
\
58 \
DSC \
\
Cap. Rheom. ,
56

4:0 50 60 . 70 80 90 100
GELATION LEVEL [Oh]

FIGURE 7.16 Influence of varying gelation level on the flexural

stresses - Twin Screw Extrusion

7.2.3 IMPACT STRENGTH

Like tensile testing, numerous reports can be found in the

literature on the behaviour of the impact strength of UPVC with
varying gelation levels.
 - 240 -

65
o p''''-a,
/ \
/ \

~
63
o
I" 0 \
I \

61
P
I
0\0
\
\
\ 0
\
\0 0
\
\
59 \
\
\
I
DSC
57 o 0
Cap. Rheom.

55

40 50 60 70 80 90 100
GELATION LEVEL [%]·
FIGURE 7.17 Influence of varying gelation level on the flexural
stresses - Single Screw Extrusion

Al though comparing re suI ts is difficult due to the variety of

types of tests and preparation of specimens, impact strength is
usually found to increase with increasing fusion, but disagreement
occurs on the possible existence of a maximum (a review of the
literature has been made in.section 1.4.2.5.1).

In this work extrudates were tested for impact strength using

the Izod test with notched specimens, as defined by the ASTH D256-81.
 - 241 -

~~ SINGLE SCREW EXTRUDER

300
~~ TWIN SCREW EXTRUDER Et
o

~220
~ ~~~
....I
::J
o
7/?YT~
o
~
....1180
«
a::
::J
xUJ
i:C140
0»>7f»)znkM
100
40 50 60 70 80 90 100
GELA nON LEVEL (OS Cl [ %]

FIGURE 7.18 Influence of varying gelation level on the flexural

modulus. Et - tangent modulus; Es - secant modulus

Both the equipment and experimental procedure have been described

in section 4.8.1.3.

A typical trace provided by the Ceast Fractoscope is shown in

Figure 7.19. The energy per unit area absorbed by the specimen
during the fracture process is obtained by integration of the force
displacement curve.

The first peak in the load trace represents the first impact
of the hammer with the sample and is possibly caused by stored
------------_.---

- 242 -

[J)

>- 0.2641

~ ----~~~~-----------------------

[daN)
32.0
UJ
u
0:
o
u..

2 msec
TIME

FIGURE 7.19 Typical load/energy traces obtained during the experiments

elastic energy. Because the presence of the notch decreases the

ability of the material to deform in a ductile way by introducing a
triaxial stress field ahead of the notch tip, this impact will
either: i) cause the development of a plastically deformed zone
along most of the cross-section ahead of the notch tip, ii) cause
the propagation of readily initiated cracks leading to an almost
immediate fracture of the sample. In the first case the propagation
of the cracks will create more than one peak, the number depending
on the ductility of the sample. Marshall et al139 observed that
increasing levels of fusion up to 60% were accompanied by a longer
fracture period, thus increasing the total energy at failure; samples
beyond this level were more brittle, with fracture taking place in
shorter times.

The results obtained in this work are shown in Figure 7.20 for
the single and twin screw extrusion test specimens. Both curves
presented a maximum in impact strength, this taking place for
gelation levels in the range 70-85 and 60-70%, respectively. This
agrees well with the works of Menges et al 22 ,Parey and Kruger 26 ,
 - 243 -

'"~5
"""
::.:::
~
0
:c
I-
l!J
Z
UJ
0::
l-
V)

I-
u
(E4 0
~
0-4

single screw extrusion

twin screw extrusion
3

30 40 50 60 70 80 90 100
GELATION LEVEL (DSC) [%]

FIGURE 7.20 Variation of impact strength wi th increasing level of

fusion
 - 244 -

Marshall et al139 , Benjamin141 and Terselius142 • The values of the

impact strength were very similar for the two types of specimens,
although slightly higher for single screw extrusion (6.1 KJ m- z ,
compared with 5.9 KJ m- z for the twin screw extrudates).

The impact strength being defined by the ductility of the

specimen, the results obtained should be qualitatively similar to
those observed in tensile testing for elongation at break (CB).
Effectively, in those tests CB reached a maximum of gelation levels
in the range 65 to 85% (section 7.2.1.3) compared with 65-80%
observed here. The maximum in impact strength can therefore be
again attributed to the existence of a network morphology, with a
coherent entanglement network existing between the primary particles
(as indicated by Summers mode1 33 f~r a 177°C melt - Figure 1.19).
The impact energy will be dissipated into plastic deformation, the
'particle surface reducing stress concentrations and the well
dispersed additives avoiding the formation of microvoids that grow
into crazes. \'1i th the disappearance of the primary particles, a
drop in impact strength is observed.

This conclusion is widely supported in the literature:

Terselius142 attributes maximum impact strength to an'interparticular
coherent entanglement network'; Marshall et al139 linked maximum
impact performance to the reduction of the PVC grain structure in
favour of an 'inhomogeneous melt'; Menges et a1 22 related the maximum
in impact strength to the existence of a network structure
throughout the material and put forward (Figure 1.22) a model in
which the additives surround 'globules' of material (section
1.4.2.5.1).

7.2.4 HARDNESS

As discussed in section 4.8.1.4, the experimental procedure for

the test most commonly used - Rochlell hardness - can result in poor
accuracy of the data gathered. As different polymers have different
relaxation times, when performing the test following the guidance
provided by the ASTM D785, the measurement of the indentation is
made with most of the delayed elastic recovery still taking place.
 - 245 -

To avoid this, a modified experimental procedure l;as established

in that section and followed here. The details of the equipment used
are also provided in section 4.8.1.4.

The relationship between hardness and degree of gelation for

different processing techniques and formulations is shown in Figures
7.21 to 7.23. The results for single screl; extrusion and compression
moulding are presented in Figure 7.21, the number of points for the
latter technique being limited by the poor cohesion of the test
specimens at low temperatures; Figure 7.22 presents the results for
the twin screw extrusion samples, and Figure 7.23 shows the results
obtained with a composition with a modified stabilizer system
(denominated 'blend 8' in the work of l'1arshall et al139 ).

The indentation after recovery was generally found to increase

with increasing processing temperature, ie., hardness decreased with
increasing gelation level, a minimum or, plateau being eventually
observed (Figures 7.21 and 7.23). As the material undergoes plastiC
flow under the compressive stress applied, the decrease in hardness
must relate directly with an increase in the ductility of the
material; the existence of a peak or plateau correlates well with
the increasing brittleness observed at high degrees of gelation for
both tensile and impact testing experiments (sections 7.2.1.2 and
7.2.3, respectively).

The maximum indentation was found to decrease with increasing

gelation level, again a minimum being eventually detected (Figures
7.21 and 7.22); because an increase in gelation level increases the
coherence of the entanglement network (and number of crystalline
junctions), less chain-chain slipping is likely to occur.

The behaviour of the two parameters discussed above led to a

significant decrease in the ratio maximum indentation / indentation
after recovery time T with increasing gelation level. Although
more research work is necessary to support these observations, the
experiments performed here seem to confirm that there is potential
in the use of hardness testing as a, quick, cheap and simple way of
assessing the degree of gelation of UPVC samples.
 \~
- 246 -

[MM]
- MAX. INDENT. I INDENT. REC. TIME
3.5 2.0
- MAXIMUM INDENTA nON
- - INDENTATION AT T = 150 sec

o
~O~---------Ir-ee-- -

3.0 1.5

- compression mould.
- single screw extr.

2.5 to

2.0 0.5

--
Cl

1.5,J--.....,......-1...,..70~,......--1~8-0-.-~19-:-0---20'-0-"'~2¥-10--~ 0.0
, ,
B ONSET TEMPERATURE [OC]
FIGURE 7.21 Indentation and recovery curves wi th varying processing
temperature for single screw extrusion and compression moulded samples
 - 247 -

[MM]

3.5 2.0

3.0 1.5
120
23 • (

2. 1.0
-t.......r---.,.
__••L --
~

2.0 0.5

--
1.5L...--'--=1:r.:--"''''''--:1:-:!''
ao ::O-'--1::-!:9':'''"0--.--2=:!0:-:-0--.-----=21r.:-0----T~10.0
70
, ,
B ONSET TEMPERATURE ['C]
FIGURE 7.22 Indentation and recovery curves with varying processing
temperature for twin screw extrusion samples. For code of symbols
see Fi gure 7. 21
 - 248 -

[MM]
- MAX. INDENT. I INDENT. REC. TIME
3.5 . 2.0
- MAXIMUM INDENTATION
-~ INDENTATION AT T = 150 sec

3.0 1.5

2.5 to

x
2.0 0.5
- 0

-
0
0
IQ 0
s

El n c I B 8 -- g

1. ~--"--1,...,.o-----:'18=o----.---:1~90,............----,2=00".--.---2::-:1-=-0--.-----lO.o
, ,
B ONSET TEMPERATURE [·C]
FIGURE 7.23 Indentation and recovery curves with varying processing
temperature for twin screw extrusion samples of blend 8 (see text)
 - 249 -

7.3 DENSITY MEASUREMENTS,

While determining the progression of gelation along the screw

length for single screw extrusion (section 5.4.2), it was observed
that the density of the material decreased with increasing
processing temperatures. It was therefore concluded that the
crystallinity of the material decreased with increasing processing
temperature. However, the analysis of the evolution of the
endothermic energy of peaks A and B (llH and llH , respectively)
A B
with increasing degree of gelation showed that the total heat of
fusion could be higher at elevated temperatures. The question is
whether the density is mainly dictated by the energy of peak B, or
high llHAs can lead to a 'recovery' of density values at high
temperatures.

Figure 7.24 helps to clarify the situation. For both single

and twin screw extrudates a good correlation was obtained between
llHB and the corresponding density measurement. It can therefore
be concluded that the density is a measure of primary crystallinity;
increasing processing temperatures should lead to lower densities,
regardless of the significance of secondary crystallinity.

Figure 7.25 shows the effect of increasing processing

temperatures on the density of extruded and compression moulded
samples. All curves show an increase in density at low temperatures,
followed by a decrease thereafter. At high temperatures, the
compression moulded samples showed a recovery in the value of
denSity. Curves similar to the latter have been reported in the
li terature139 ,142, Terselius142 attributing the high values of
densi ty at low temperatures to the presence of residual grain
inclusions of higher crystallinity.

The increase in density of the final extrudates at low

processing temperatures is a consequence of the mechanism of fusion
of both extruders (sections 5.3 and 6.3, respectively); at low
temperature profiles the final melt contained remnants of highly
compressed - and densified - grains and primary particles that were
not destroyed by shear. As a result, the density is lower than
that of the melted material (Figures 5.24, 5.25 and 6.18). As the
 - 250 -

DENSITY [G I CM 3 ]
1.404

1.400

o
o single screw extrusion
o twin screw extrusion
1.396

0.1 0.2 0.3 0.4 0.5 0.6 0.7

, ,
B ENDOTHERMIC ENERGY [JIG)

FIGURE 7.24 Density of extrudates versus heat of fusion of the B

peak

fusion mechanisms become more effective, less of this material will

be present within the extrudate, as it is subjected to high levels
of shear; the rate of destruction of the primary crystallinity
increases, with the consequent drop in density.

If density of single and twin screw extrudates is plotted

against degree of gelation (Figures 7.26 and 7.27) a maximum is
obtained for gelation levels in the range 60-70%, as given by thermal
analysis, which corresponds to an optimum in 'most mechanical
properties (section 7.2); the maximum value in density reflects
therefore the existence of a particulate network in the final
extrudate, with significant amount of primary crystallinity still
remaining.
 1.405

x
~
~

-
~
LJ

I !J
~

-
>-
I-
VJ
Z
UJ
0
1.400
compression moulding

7 single screw extrusion

:s.-: twin screw extrusi on

150 160 170 180 190 200 210 220

, ,
B ONSET TEMPERATURE [ °C]
FIGURE 7.25 Effect of processing temperature on the density of extruded and compression moulded samples
of the same compound
 - 252 -

1.404

>- 1.401
.....
I-
1Il
z:
~ - single screw extr.

1. 398 -- - twin screw extr.

70 80 90 100
GELAnON LEVEL (CR) [% I
FIGURE 7.26 Density versus gelation level of the extrudates, as
given by capillary rheometry

1.405

1.4:00

- single screw extruder

--- twin screw extruder

1.395 30 40 50 60 70 80 90 100
GELATION LEVEL (DSC) [%1
FIGURE 7.27 Density versus gelation level of the extrudates, as
gi ven by thermal analysis
 - 253 -

7.4 COI1PARISON OF Tl'IIN AND SINGLE SCREW EXTRUSION

The assessment of the mechanical properties of the twin and

single screw extrudates carried out in this chapter shows sharp
similarities between the values obtained: tensile and flexural
strength were 4% higher for the twin screw test specimens, whereas
impact strength was 3% better for the single screw extrudates.
Indeed, it is possible that these differences are only due to
experimental error.

This fact strengthens the conclusion drawn in section 6.5 that

both extruders are capable of producing melts with similar
characteristics. Therefore, as concluded in the same section, the
advantage in the use of twin screw over single screw extrusion lies
mainly in the easier control of the operating conditions.

It should be emphazised that the comparison of the behaviour of

the two types of machine throughout this work was based solely on
the results obtained with one compound, assumed to behave efficiently
in both extruders. The use of a different composition could well
lead to alterations in the conveying characteristics of the machines
(specially in single screw extrusion), with consequent changes in the
properties of the extrudates. Therefore, it is possible that the
use of other compounds may: i) alter the advantages of one extruder
over the other; ii) possibly lead to higher values for the
mechanical properties measured.

Finally, it should be noted that the lack of correlation between

the range of gelation levels at which the properties are at their
best, with the values reported in the literature, is a result of the
type of definition of the degree of gelation adopted here. The
conventional use of equation 1.20 would obviously lead to a decrease
in that range. In addition, the differences between single and
twin screw extrusion, as far as gelation level is concerned, are
due to the existance of different gelation curves for each process.
 - 254 -

7.5 REPROCESSING EFFECTS

As the observations reported in section 6.4.2 on the decrease

of the endothermic energy of peak A and onset temperature of the B
peak with decreasing processing temperature were difficult to
explain, some reprocessing studies were carried out with the aim of
clari fying/ confirming those results.

As described in section 4.4, pellets processed under two

different temperature profiles were fed into the hopper .of the twin
screw extruder and processed at three different processing conditions,
corresponding to runs 11, 12 and 15 of Table 3.1.

Despite the conveying mechanism of the twin screw extruder

being almost independent of the physical properties of the polymer
to be processed (section 1.4.1.3), it was generally found that when
extruding pellets the mean residence time (section 1.4.1.4.1) was
decreased by 20%, and the output increased similarly, specially at
low temperature profiles. This must be due to a change in the degree
of filling of the early C-shaped chambers of the screws.

The extrudates obtained were subjected to DSC analysis, density

measurements and tensile testing. The results obtained are presented
in Table 7.3.

The B onset temperature, corresponding to the maximum processing

temperature of the material, is affected by reprocessing at
temperatures either above or below the first processing. This
confirms the results presented in 6.4.2 and indicates that the high
shearing forces present at lower processing temperatures can affect
the more perfect crystallites, which is difficult to explain.

The values for the endothermic energy of peak A of the

reprocessed samples are, within the experimental error, similar to
those corresponding to the processing of powder. This either
corresponds to a reduction (pellets obtained at high temperature
profiles) or an increase. In the first case, the differences
between the values corresponding to processing and reprocessing of
 - 255 -

Tensile Testing
MATERIAL I 'B'ONSET DJI
A
DENSITY elongation at break (%)
EXPERIMENT TEMP.(Oe) (Jg- 1 ) (g cm- 3 )
90°C 120°C
L 180 3.76 1.4001 - -
PELLETS
H 201 8.05 1. 3995 - -
11 188 2.71 1.4031 240 74
15 198 5.94 1.4021 305 96
12 205 6.20 1.4013 313 109
L 190 ·4;12 1.4013 236 89
11
.
H 188 ·3;33 1.4012 248 77

L 198 5.69 . 1.4011 295 95

15
H 197 5.83 ·1.4011 280 102
L 205 6.49 ·1.4007 305 111
12
H 206 6.27 1.4010 315 111

TABLE 7.3 Results obtained on reprocessing studies. L - low

temperature profile; H - high temperature profile·

mat.erial seem to increase with increasing difference in processing

t.emperat.ures. This was also obtained by Pate1155 • The tensile
properties also show a sign of reversibility, t.he values for
processed and reprocessed samples mat.ching well.

27 155 and seem

These results correlate well wit.h those reported'
t.o confirm Pate1' s155 suggestion that a new structure has been
produced under the high shearing forces at lower processing
tempe ra ture.
 - 256 -

CHAPTER 8

CONCLUSIONS AND SUGGESTIONS

FOR FURTHER ~!ORK

8.1 GENERAL CONCLUSIO~;S

The experiments and calculations performed with the aim of

designing a slit die provided the following conclusions:

- The composition studied. based on a suspension polymerized

resin. showed a typical non-Newtonian behaviour. at 190°C. with a
power law index of 0.24. shear stresses of 10 5 Nm- 2 • apparent
viscosities of 10' Nsm- 2 and die-swell values bet,;een 11 and 16%.
At the same temperature the melt presented tensile stresses of
10' - 10 6 Nm- 2 and Hencky strains between 0.8 and 1.2. for
extensional strain rates in the range 0.001 - 0.1 s-l;

- The effect of ex tensional flows on the properties of the melt

was not significant in causing pressure drops. but could induce the
eventual creation of flow defects whenever a tensile stress limit
was surpassed.

Extrusion Characteristics

From the energy balance calculations for single screw extrusion

it was concluded that:

The mass output increases steadily "i th increasing screw

speed and decreasing temperature profile and die resistance. the
effect of these being s::lall;

- The extrusion efficiency index. defined as the ratio of the

volumetric output divided by the total energy input to the system.
reached a maximum at high screw speed and low temperature profile
and die resistance;

- The compound behaves generally as a wall-slipping material.

 - 257 -

the range of processing conditions possibly being close to the onset

of wall sticking. A melting mechanism similar to the one found for
I~all-slipping materials was proposed.

In the twin screw extruder it was observed that:

- The mass throughput increases steadily with increasing screw

speed, although at a progressively lower rate, and with increasing
temperature profile. It decreases only slightly with increasing
die resistance; for practical purposes output is independent of the
conditions at the die end;

- The torque readings increase with increasing screw speed and

die resistance, decreasing with increasing temperature profile;

- The values of pressure become significant only in the metering

zone of the extruder, increasing with increasing screw speed and die
resistance and decreasing with increasing temperature profile.

In the single screw extruder:

- The steady state was never reached, both pressures and

temp~ratures varying significantly. This is due to the inertia of
the on/off system and difficulty in· the efficient dissipation of
heat created by shear, through the barrel wall;

- The temperature of the extrudates was always higher than the

values set; for a constant temperature, an increase in die resistance
and screw speed increased the temperature of the extrudates, although
at high revolutions the te:nperature decreass:l slightly due to the
sharp decrease in the dwell time.

In the twin screw extruder:

- The steady state could be easily achieved;

- The temperature of the extrudates was always lower than the

values set, meaning that the overall level of shear is smaller than
in single screw extrusion. However, for the same set temperature,
 - 258 -

an increase in screw speed and die resistance also caused an increased

extrudate temperature.

Mixing Characteristics

The mixing characteristics of each extruder were studied by

monitoring the residence time (RT) and residence time distribution
(RTD) of a tracer input into the system.

For the single screw machine it was observed that:

- The RTD, ie., the degree of axial dispersion, is influenced

by changes in processing conditions •. ~1e tail of the curves increased
with increasing temperature profile and screw speed, indicating
better axial dispersion. In addition, increasing die resistances
increased the tail of the distribution but, as an inflection in the
curves was developed, no further increase was detected;

- Despite having a similar trend, the RTD curves presented

shorter tails than the experimental and theoretical models available.
Plug flow percentages of 60-70% were found. This behaviour accounted
for the marked non-Newtonian behaviour, high viscosity and wall-
-slipping characteristics of the material;

- The mean residence time decreases with increasing screw speed,

and increases with increasing temperature profile and die resistance;

- The average strain of the material in the extruder, ie., its

degree of transversal mixing, improves with increasing temperature
profile and die resistance. The effect of screw speed is balanced
by bulk residence time and level of shear: with increasing screw
speed the average strain increases but, above a limiting value, the
strain is reduced.

In the t,dn screw extruder:

- The RTD curves are very similar for the whole range of
processing conditions; nevertheless, a tendency for a decrease in
 - 259 -

the tail of the distribution with increasing screw speed and die
resistance could be detected;

- The experimental RTD curves were more plug-flow like than

reported in the literature, plug flow percentages of 85% being
observed. This behaviour was accounted by the wall-slipping
characteristics of the material in the adaptor and die;

- Both the mean residence time and the standard deviation

decrease with increasing screw speed and die resistance and
decreasing temperature profile.

The conveying characteristics of the twin screw extruder are

better than those of the single screw machine. Despite the presence
of a long solid bed with a plug flow like conveying !!Iechanism in the
latter machine, the positive conveying mechanism, the small effect
of leakage flows due to back pressures only felt in the last third
of the extruder, and the low level of shear due to the reduced
diameter of the screws in the metering zone seem to provide the best
conveying characteristics.

Mel ting Hechanism

In the single screw extruder:

- There is a melt pool and a solid bed throughout most of the

length of the cO!!lpression and metering zones, the material being
generally fully melted on reaching the tip of the screws;

- The !!Ielt pool "as deposited near to the trailing flight of

the channel, indicating similarity with the melting mechanism
observed with wall-slipping materials; if the value of the control
variables was high enough, as well as the main melting mechanism
an additional melt pool was formed near the pushing flight;

- Increasing die resistance and temperature profile promotes

the quicker growth of the melt pool along the compression zone.
Increasing screw speeds delay the growth in its early stages, but
 - 260 -

the high level of shear increases the rate of development in the

metering section;

- In the late compression / early metering zone the increasing

compaction of the grains in the solid bed promotes intraparticular
fusion;

- The fluorescence intensity of the melt pool is always smaller

than that of the solid bed and ·that of the interface of·the solid
bed / inner barrel wall is even smaller, all the values increasing
towards the screw tip.

In the twin screw extruder:.

- The solid powder progresses from white near the hopper to more
or less dark brown towards the metering zone; fusion takes place
quite suddenly, within one C-shaped chamber at the beginning of the
latter zone, regardless of the processing conditions;

- The melting mechanism presents characteristics common to those

reported for other thermoplastics for low and high back pressures;
mel ting starts near the heated barrel wall, but the violent tumbling
action soon causes a melt pool of distorted shape, melting developing
in the solid bed / melted material interface;

- Increasing temperature profiles increase the length for the

development of a fUlly melted channel cross-section, due to the
higher local back pressures at low temperature profiles;

The fluorescence intensity (FI) of the melted material is

always smaller than the one of the solid bed. FI increases along the
length of the screws, up to the C-shaped chamber where melting takes
place; here, there is a loss in FI due to better additive dispersion,
which continues throughout the remaining length of the extruder.

The melting mechanism in the twin screw extruder seems to be

more efficient than the one in the single screw machine: despite
the material having to cross most of the length of the screws with
 - 261 -

poor additive distributio~ towards the die, where the temperature

increases - and so does the danger of degradation - all the material
is quickly fused, the dispersion of· the additives improving. In
the single screw extruder the melting mechanism is more gradual,
beginning at the early compression zone, but it is only near the
screw tips that most of the polymer is fused; hence, some material
has a long residence time tu thin the extruder without proper
additive protection, making degradation more likely.

Gelation Mechanism

In the single screw extruder:

- The mechanism of gelation shows evidence of the CDFE mechanism,

but the breakdown of grains into primary particles can be also
observed in the early stages of the melt pool, when intraparticular
fusion of the grains is not yet fully developed. After the grains
are internally fused, their destruction - due to shear - leads to
a melt,. the additives quickly dispersing into it;

- The degree of gelation of the melt pool (as measured by DSC)

is always higher than the one of the solid bed, but becomes
progressively similar during the metering zone, where gelation
develops at an increasing rate;

- Increasing temperature profile and die resistance increases

the average degree of gelation of the core samples. ,Ii th increasing
screw speed the gelation level of the material in the screw is
smaller, but the high level of shear induced in the adaptor and die
causes a higher degree of gelation of the final product;

- .The density of the solid bed increased along the length of

the screw, although more sharply in the compression zone. The
density of the melt decreased towards the die lips and, generally,
with increasing processing temperatures.

In the twin screw extruder:

- The CDFE mechanism was observed, with material being

 - 262 -

compressed and densified in the compression zone. inter- and

intra grain fusion developing significantly. The grains near the
barrel wall and in the interface solid bed / melt pool were elongated.
eventually breaking open. the additives dispersing into the melt.
The homogeneity of the latter improves throughout the remainder of
the extruder;

- The degree of gelation of the core samples increases slightly

along the screw. up to the C-shaped chamber where melting takes
place; here. it increases significantly. but the rate decreases
thereafter; in the die. due to the high set temperatures. the
gelation level increases sharply again;

- Increasing temperature profiles increase the average degree

of gelation of the core samples;

- The density of the solid bed increased sharply until melting

took place; the density of the melt decreased towards the die lips
and. generally. with increasing processing temperature.

Despite the hydrodynamics of the processes in the two types

of extruders being quite different. the morphological changes in
the material seem to be parallel. the CDFE mechanism being generally
observed.

Thermal Analysis

The study of the core samples obtained from single and twin
screw extrusion (and also compression molding) provided the
following conclusions:

- The amount of secondary crystallinity formed upon cooling

increaseswi th increasing processing temperature; the amount of
primary crystallinity decreases with increasing processing
temperature;

The total heat of fusion decreases with increasing processing

temperature to a minimum for temperatures between 180 and 1900C
 - 263 -

increasing thereafter, eventually to values higher than the initial

ones;

- The 'B' onset temperature indicates accurately the maximum

temperature reached by the material, specially in the range 175 _
- 2l0oC;

- An increase in the temperature profile will cause an increase

in the degree of gelation and an increase in the temperature of the
final extrudate. For the same processing temperature, samples
produced under lower temperature profiles (but with different values
of the other two independent variables) .wi11 show a higher degree
of gelation, due to increased levels of shear. Also, for the same
'B' onset temperature, the degree of gelation of the melt pool is
higher than that of the solid bed;

- Processing conditions inducing various levels of shear but

leading to the same maximum processing temperature will cause
different degrees of gelation •

Degree of Gelation of the Extrudates

- The degree of gelation of the extrudates, as determined by

Capillary Rheometry and The~mal Analysis, increases with increasing
level of the processing variables;

- The two techniques produce similar results, although DSC

seems to discriminate better between similar degrees of fusion;
however, the scatter of results is higher than with Capillary
Rheometry, due to the small size of the test specimens;

- The correlation between the two techniques produced a

straight line;

- Single screw extrusion produced extrudates with ~As up to

11 Jg- 1 , compared with 8 Jg- 1 for tuin scre" extrusion.
 - 264 -

Hechanical Properties

The mechanical properties of single and t,;in screw extrudates

were similar.

From tensile testing single and twin screw extrusion test

specimens it was concluded that:

- Yield parameters are insensi ti ve to variations in the gelation

level;

- Post-yield parameters are sensitive to those variations, but

behave differently for tests below and above T ; below T , a maximum
g g
in elongation and stress at break was obtained for gelation levels
in the range 65-85%, this being attributed to the presence of a
particulate network morphology; above T both elongation and stress
g
at break increased with increasing gelation level, as the latter
causeS more resistance to disentanglement;

- The values of elongation at break (eB) increased with

increasing test temperatures up to 90°C; beyond this value the
melting of crystallites favours disentanglement and £B decreases;

- Tensile testing at 90°C provides an alternative method for

the assessment of the gelation level of UPVC products.

The flexural post-yield stress showed a maximum for gelation

levels in the range 60-70%, correlating "ell with the results for
tensile testing belo" T •
g

Impact strength of Izod notched specimens I,as found to reach a

maximum for gelation levels in the range 65 to 85%. Since impact
strength ',;as defined by the ductility of the test specimens, the
re suI ts correlated "ell with those found for tensile testing below
T. The maximum was attributed to the existence of a network
g
morphology, a coherent entanglement net<lork existing between the
primary particles.

The hardness of single and t"in screw extrusion test specimens

decreases with increasing gelation level, a peak or plateau being
 - 265 -

reached. This behaviour was attributed to plastic flow under the

compression stresses applied.

Hardness is proposed as an alternative test for the assessment

of the gelation level of UPVC samples.

Densi ty Heasurements

Density was found to correlate directly with the endothermic

energy of the B peak, ie., with the amount of the more perfect
primary crystallinity;

The density of the extrudates reaches a maximum for gelation

levels in the range 60-70%, corresponding to the existence of an
optimum in most mechanical properties. At lower gelation levels
non-fused material is present Id thin the extrudate, and beyond 70%
there is a sharp decrease in &qB due to the progressive destruction
of primary particles.

8.2 OPTIMIZATIOlI OF PROCESSING CONDITIONS

Having determined the variation of gelation level, degree of

mixing, extrusion characteristics, mechanical and physical
properties with processing conditions, an optimum operating window
can in principle be established, by determining the processing
condi tions that lead to the best values of these properties.

Figures 8.1 and 8.2 shot; the optimum operating windot;s for
single and twin scret; extrusion, determined in this way.

For single screw extrusion (Figure 8.1), the processing of the

compound at low ~ie resitance, high screw speed and medium to high
temperature profiles leads to gelation levels where the mechanical
properties, the mass output and the efficiency in energy consumption
are near their maximum, and the degree of mixing is quite significant.
110reover, the dwell time is small.

Although the absolute values of the independent variables are

 - 266 -

DIE RES. IS KEPT AT LEVEL -1

UJ
et:: 0.2
=>
I-
<C
et::
UJ
a. -0.2
:l:
UJ
I-

-0,6

-1-.0·~~~ ~~~~~:?46+-
-to -0.6 -0.2 0.2 0.6 to
SCREW SPEED

CONTOUR HEIGHT:

GELATION LEVEL (DSC)

MASS OUTPUT
EXTRUSION EF~ INDEX
- - - -- AVERAGE STRAIN x10

<~~~i~ OPTIMUM OPERATING WINDOW

FIGURE S.1 Optimum Operating Window - Single Screw Extrusion

 - 267 -

DIE RES. IS KEPT AT LEVEL -1

0.6

~ 0.2
::::>
.....
«0::
l.LJ
a..
~
-02
.
~

-0.6

-1. 0-4--LI,--'-..,....u;--.-.......,~~-,O---A\=o-+---+----I1-
-1.0 -0.6 -0.2 0.2 0.6 to
SCREW SPEED

CONTOUR HEIGHT;

GELATION LEVEL (DSC)

- - - - RESID. TIME STD. DEVIATION
MASS OUTPUT

OPTIMUM OPERATING WINDOW

FIGURE 8.2 Optimum Operating Window - Twin Screw

Extrusion
 - 268 -

different, the optimum operating window for twin screw extrusion

(Figure 8.2) is coincident, as the mechanical properties and the
mass output are also at their maximum. The degree of axial
dispersion is small, ie., full advantage is ~aken of the positive
conveying characteristics.

8.3 SUGGESTIONS FOR FURTHER 110RK

1. Since the wall-slipping characteristics of the material were

found to have a profound influence on the melting mechanism
for single screw extrusion, it seems important to determine:
i) the influence of the additives and of the gap between screw
flights and inner barrel wall on the melting mechanism;
ii) the degree of mixing (determined by the average strain)
achieved by a wall-slipping composition as compared to the one
produced by a wall-sticking material; iii) the influence of
processing conditions and additives on the onset of wall-
-slipping behaviour.

2. The degree of gelation cf the extrudates, as determined by DSC,

is derived from the heat of fusion of secondary crystallinity
formed upon cooling by re crystallization of more perfect
crystallites (section 1.5.5). Therefore, the influence of the
rate of cooling should be investigated, for example by analysing
the extrudates obtained at constant processing conditions, but
varying temperatures of the cooling bath.

3. Preliminary work (section 7.2.4) suggested a direct relationship

between hardness and degree of fusion; it is suggested that more
work is carried out to support these results; also, a portable
instrument should be developed, so that measurements on the
production line are possible.

4. The sensivity of the 'B' onset temperature to variations in the

gelation level, as observed in sections 6.4.2 and 7.4, being
difficult to account for, it is suggested that more work is
 - 269 -

done on the subject, if possible supported by microscopy

observations.

5. A study of the dependence of the product quality on the blending

conditions and blend properties still seems relevant: the
variations in properties of the blends from batch to batch
should also be determined.
 - 270 -

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214 BAKER, R J, NELDER, J A, 'The GLIM System - Release 3 Manual',

:lumerical A1gori thms Group and Royal Statistical Society,
London (1977)

215 PHILIPS, P J, RAMAKRISHllAN, :l R, OXLADE, P L S, Po1ym. Eng.

Sci., 18, 11, 869-874 (1978)

216 NARISAVlA, I, OGAHA, H, Rep. Prog. Po1ym. Phys. Jap., 23,

315-316 (1980)
 - 280 -

217· NARISAWA, I, Rep. Prog. Po1ym. Phys. Jap., ~, 263-266 (1981)

218 GRODZINSKI, P, Plastics, 312-314 (1953)
219 MAXl'IELL, B, Mod. P1ast., 22, 8, 125-136 (1955)
220 STERN, J C, BERLDT, R, P1ast. Mod. et Elastom., 19, 7, 147-153
(1967)

221 HARENDZA, H B, Kunstst., 68, 7, 421-425 (1978)

222 HADDOCK, B H, SPE-ANTEC, 157-176 (1959)
223 McKELVEY, J H, BERNHARDT, E C, SPE J., 10, 22-31 (1954)
224 KRUDER. G A, NUNN. R E, SPE-ANTEC, 648-652 (1981)
225 JANSSEN, L P B H, NDDHEN, G H. SMITH, J M, P1ast. & Po1ym.,
43. 135-140 (1975)
226 FREAKLEY, P, Private Communication
227 SAh'INSKY, J, SII1ANDI, B, Trans. 1. Cher.!. E., 60, 188-190 (1982)
228 liDLF, D, RESNICK, .1, Ind. Eng. Chem. Fundam .. ,g, 287-293 (1963)
 APPEHDIX A Computer Program for Die Design
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10098: 961 REHD< 5. 'f,')NEXT 00142 f
,10099" REAU(5, ,t.) (E.l(TS( J ). [;1. NE,\'P 01.:"1143 (.
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'0106 :
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963 CON T I N(lf titU.!11 .
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th:tl5;,:~ :
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[llltl:
till1 :
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tltl154 .
0(l155:
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N"'I1E'~, 7.';tI)SRLlI1.. SH"HTf. UUTPUT
750 FO~'NHT(·2it,\'.' DIE-SWELL CH(f/.lLHTI(lN~ "'/20,'(. "SNERI? RIH£
I
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20F DIE-SlolELL liNO RliOlPING NELT F'Ul-'rtlk....F ",''2~lX,' 11 IS ARtJ TO COR~FC l-lt1158 : GO TO 60tlO
"115 : JT THE OUTPUT fIN(I Tl-lf 1.1. . 'EPRLL Lfl.I(j1"H. "/20X.' (!ET~P""NF.~· TkE ({lRPFI.'T t1t1158 : 100 COh 1J "'liE
0116: 4LENGTH ANO HOLES (IIAMETEP Of: THf Ri:·FHIrJ:1? PI.ATE'/) 0l-t16tl:
011?- 00 jOt' 1=1 .. N
WRITE":. 61) 0(.-1161 : IF(SHRftJE LE fl( [)} OSPD:::f{ci+1)
0118: 61 FOPf'rAT<2t1X. "RND IN{llCATfS THE RO'- 7"5 MINIMUM ~7~-CT!I)~ ,', // ....../) tl(rl62 :
0119 : /F<I. f<J N) D~PO=B(".l
URITE(I( .• 100}/,JPPOO. TF'RI..1P. OUTPUT. 1FHf-1 , NHlil. Oti1ti3 . }OO CON TI,",UE
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;.1121' 1 F I (.•..,/-'J). 1:.'1';. OS-F·liA.) 00 TO 4#:10
1/20.11. "PRN)(ICT THICkNf55 =", f8 J. "M /2':I.V.· P/-SIf..'Et! Olll':'UT :,', f"8 00165'
J122: D55L / T=( f 1 +OSPO/1 HO. ) ·1'*2 -1 ) *1 Oft.
23" '1111'1-1 '/2ft.\·. 'EXTROSION TH'F'F~\H7IJ~'f ~ .. I-..'i 1. "f '/;':'1'.1.'. 'NUNR 00166' 5HFR=NO/f.\ r.... TDlfXT
:1123: lER OF BRfA'fR PLATf NOLfS' .1]. /) 00le.? .
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1129' IFUT/P. E,' 1.) "RI TE'K. 111) l:1til 73:
113tl: IFUTIP m. 2) ',"'I TUk, 112) Ot1174 . 25" FORMRT'2tlX.. • ME-SWELL CRLCULATIONS ::·/.'OX.. " THE ITERATH'f
PIIOCfSS 1/
lH1: 111 FllRIlAT(<'OX.' SINGLE SCRfW fJiTtlUI>H" ....·//) tJti1 75' 4(1,11RS NOT CONCLUD£I> RFTU rHE ". /],' ITERATIONS' /.')
COli TI NOt
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. 0017.9 .
IF([TIP fO 1) OLL. =1 '.l <TMf"XT
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tltid·2.';I· lGIlHGFN, S/tiH,. SlaE2, ITS. CONS 1.. ~N,. C$j. CS2, C51, C54, CSO" CS6" EPSLON, EXT
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01:1182 VP5VL=2 'VLL*Ttl(VTVlEXI f.W.::'':;;'b· 25, eEl. CE;? CB .• CH, CEo. CE6. ITE. COII<:10. RN2.//Exn
l:Jl:J.183 C 0022/' IFI/g. W v fflUPEC=IRUH
",1184 C 002 ;"t\ : fRE .... I=IIlU.'FC
RORPrOR GEOI1H''Y IlIIl> F'RES>URE DROP5
00185:C tfOic:'~ : frEPSH1= TffUE'r'·*1o.1L-f;( 1. -( 'r'NO r /VJ·f;·'I'(2.·RN) )/( RN-"'O·-~'Non.>
1. FIRSI 5EC1'JlW
tltl2j~tJ . DEPEX1=SJ(jE~'*( 1. -( I,'Nor /\0-·.> .. ·..·2. '>/2.
",'186'C
(l0.18?: 12L:Jtl RLFfllIl=,l t;02J1 . OEPIi·fC=2. <"to If'EC 1/1.0 I..-.vl
00188: GfiI1Il1/1=t! 00272: ftfPSk;';'=1 RUfZ*I·!L*(l, -(Z/ZNOT '>1f.·Jf'(2:4:F'N) )/(RN!f<<"ZNOT-Z})
00189 . VLP5H=O,
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lIl'190: VLPEX=lI, 002J4 : OfPSH=OfP"EC+OEPSH2-0fPSH1
0"191 : RLII1=FWA I (Lllt) 00215: IF(Wl>IExl. 61. D/IlI1E) DEPfX=OEPEX,t-DEPfX2
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00193: 1F (1401 EX r. L T ('t I finE,) EN1 :RLtlG1tHfIB.o;' ( U'R£.lEXT.SOI? T('2. .> -14(1 JFX r ) /i;.'. »/R
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VEL Of1 =ou rPT 1/( ,.'firE,," T* 1[1 I EX r*J601:1 *~()R T(2 )-'
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Oll199 : C1=], ,"Rt I1V5"Jll/ 0(1243 : RLFIlGR=lS", "RLFA/PI
80208: RLF 1I1:RTil//( (1) Ot1244 : GRt1R6R=lStl ,"'Wt",RIPJ
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t1tl2t12 : GR(lfL U,=R rHN( l'2' t1~1246:' oH"'';>fL=1~:I.l .1·GRf'lI.'EN/P 1
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:;'0204 : aLl v: 1 fa! *GflMLl It/f' l 0f.1248 : GA( J ;()=f;HI'1AliR
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VO 10!l" 1.'<=1, { 111. L
~1l12t16 .- X=FL OR T (I Xl/j!"'t1 tl025lt· aR~Il( IX ):GIlI1RfL
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RL =FLOR T(L )/1 "'''i
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013251:
tW25,;;"
OP1 <l X l =Pff'Sfll
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~.ft121t1 : 1-EXP(-X»/(1. -E>-;P<-RLII1/10llt-l .1)}.>fr2 00254' OP4(}X'=Pf-':';FX2
.:10211: 1F{I,JDlE.,\(7. Lt. MRl'lf.» z=oJP1f:·xr./;? +,\''''''fNl ).>1:2 00255' V/-'5 (' 1.>( ) =0£:",..,51-1
Jt1212 : R\O-'( I ,\')=1,'*500 00256: N'''( IX)=OfF'[x
:ltl213 : RZ( IX )=2-""5nfl O'J'>:'S7: [IP7( J .\"'>'=VL PSH
J02t4 : IF<J>i. E,l, 1) ;'NlH=1I>IFXT f.~(l258: OP$< lX)=l)L;"EX
,0215: IFUX EP J) ZIIOT=WI>1EXT 00259: DP!:l(IX}=Of)O
;10216: CflN5T1=<Y-\O-'Non/(2 :',Io'L) 00260: IlLFtlIIf=HU/1
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;10292: ourpT4=ourpUT/(~' .1SIlRT<2 )-.1 ) 081J6·C
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ftlc:'91: l7RLL SHEfW< ITS. rHU1. Sit·AT}1. t.:ON"T. RN. C~f.. CS;? f:SJ;. CS4, C.':i.~. C~:i~) ""341 . 0(1 TPU T=OU TPUT ~Il/JUT
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'0299: TEI?EL2=RB5 ( TEPEl ) t1tl~(4]· 55UO
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l'0161.- IF,P/lO/lBP GE. P{lR("'R> GO TO 90'ltl tf tl"'06 . 1"·//2"X.'·TkE INDICES OF THE PilRflS ..... IC 91i1PF OfSIONIlRf ·'/25>1.• 'N1
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l1ll198 16TH :", f8. ].,' ,.,., /20)<. ..• PRE55UJ.;'f PROP r"., t8. 3. ," N!1-2'- ,'//) D2=fiSHE2+-l1 EX T2
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OM01 1N'//2tlX.' THE INDEX OF THE PRRR80UC SHflPE OESI';N IS', lX. F5 y<'Og.' 00446 20X .. "LENGTH =" .. 13) " (1/'1'"///)
('0482 211RXII'1UI'1 IlLFR ='. F5 2.' PEOREfS··,'2,·IX. 'MRXIM/iM GRI'1Il =,', FS 2 . ' [)EIJRfE 0l:144?
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00456: IF<IBPL EO t1) ,,"'rTUI:.5200) t1t1500: 1PN2. NEXT>
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t1tl458:C l
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t10459:C BOL TS DIANErf~ CIILClI1I1T'T,m l~05t13 . EIJ(I
00460.' C Ot151J4 'C
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10485: C 00529: IFUIE~l 1:"0 ::-.1 (,/) 10 ~?3:
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10487." C 005]1 . IF(Nf:.-,'O til 4.1 !-:n.11-'
IlN88 : OII1ENSION EXTS< 5), efl (5),. eF2( ~:P.' CF]( 5).. tE4 (.5). CES( 5). ("E6< 5-' 00532: 9;::'1 IF(E"'~S. G£ f:)(TSl.1» 1=1
'0489: V~'='Ol/( RE*Y T*J6tltl -1<5(JR 1'(2 » l.:tt1513 : IF(EPPS L 1 f..xrS(1» l::~"
'0490: VZ=t12/( TO£'1<2Z*.?61.:l!1. .> l.10534 : t]0 ro 9?5
'0491 : SEY=6 'V\,,·'YT 00535: 9?2 U-(EPP5 /lE fXrS'(1» 1=1
"'492: SEZ=6, *V2/22 1105J6' IF(EPP.':;, UE I:X'1"S(2») 1=2
'049] : GRLL SHEHk'( I rs, TE~'" SE.,.'.. CONST. 1i'N. CS1. C,0;2.. CS?. CS4. C~S. CS,;} 00537: IF(EPP5_ L1" E~TS{"2n 1=):
'0494: CALL SNEA,;>( 1 TS. TEZ. SFZ, CONST. ~'N. 1~51. esp, (<;'?, (''';4. CS.'i. c~-:-~) t105J8: GO TO 9.'"
00539 9?J IHEP;:"5.IJf tXr~'(.1.}) 1=1
08540: 1F(EPP$, GE £X1'5('2» 1=2
11854L IFrEPPS GE EX/Sd!.) 1=]
Ol~542 : IF(EPPS. L 1. EXTSr J >.> 1=4
0054]: GO TO 975
tll~544 : 974 IF<EPPS LIE £}.;'I'5Ci» J:::1
00545: IF<EPP'5. Gt:, fXrS(i:;''» 1;2
00546: 1F(EPPS.OE EXrSCO) J=_"<
,1,154? : IFrEPPS. GF EXTS( 4» 1=4
0,1548: IF(EPPS. U. EXIS(4» 1=5
MS49: 9?5 CON r 1 NUE
,10550: IF(lTE. Ea. j ) SIlii'lll=Cf1 <I HC£2( n*TRAlF
0,1551· [FarE EO 2> S}G"'R=1.~f.·j (1 >+-CE2{ 1 )."'·TPHTE+CF".7:( 1 )*TP'H1E.f::f."2
1l0552: 1F( I rE EO 3) SI GNt-l=fEt (' J .> +-Cf2( f )* rPR rE +CF.?( f)·"" riNil {."-t"*2+CF 4 ( [ ) .".. n~1-lr
0055]: 1£**3
I.lIJ554 : IF(,]TE. Ea. 4) SIGMR:tE1( J )+Cf2( I >:f.:i'RRTf+CE.?:U )*1'RIHE**2+CE4( I )*1'(?Rr
00555: l.E*,"'J"'CE,,(' [).f: TRRTE**4
ll0556: IF([ rE. EO 5> SIGI'1A=CE1 (I )+CE2(J ):H"f?ATE+CF](J )*HNHF""*2+CF4( J ,).1'TRAT
).:10557: lE**3+CE5 ( 1.>·'Ie [RR T£**4 +eEe. ( [ .> ,""TRH TF..**5
J0558: 970 COltTINOf
,10559: RETURN
;10560: ENI>
 - 288 -

APPENDIX B Flowchart of Calculations for Extens, Flow Properties

AVERAGE CGEFFICI:2:TS.
1. E.. ONLY ONE CURVE

EVALUATIOK OF POLYNOMIAL

J < ilSR

POLY;'iC;.:rAL FIT AND

EVALUATIon

J < ~JSR

GEr':ERATIO~,~
OF ?OIXTS
TErSILE STR.:6SS vs
n:'iSIL:: STP-AI:: "AT::

POL1-:;C"IAL FT:' A"n

::VAL:5ATIOl!

J < ~iS!t

(conI, p, 290)
 - 289 -

Flowchart of Calculations for ~ Shear~ ,_, Flow Properties

,
( START)

I 11
I =
f
IREAD DATAl I = I+11

I La gtJ', LogQ J (ze ro and non-zero

! dies)
STRAIGHT LINE, n EVALUATION I
I,1\ I <2

IAVERAGE OF 12 I
•,
SHEAR STRESS AT WALL I 1

I SHEAR RATE AT ,fALL I y

I
t-
MATHEHATICAL HODELLING Relationships
OF THE SET OF EXPERIMENTAL
POINTS
1 vs y
T) vs y
T) vs 1
GRAPH PLOTS
(EXPERIME~TAL POINTS
AND REGRESSION)

I READ DIE Sl.'ELL DATA I

L
f
i1ATHEMATICAL MOSELLING
!)S vs

I GRAPE PLOTS] DS vs y

(END)
 - 290 -

1
A. NO PLOTS DESIRED
Y,
ITYPE OF GRAPH TO BE DRAI"IN I

I DIALOGUE \!ITH USER I

GRAPH
PLOTTING

4f'f!ORE
'/
THAN 1 DEGREE DESTRED

OTHER TYPE OF GRAPH DESIRED

F

(,,1:D J

H - number of trials for each strain rate

NSR - number of strain rates

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f RIW& FO'( CLAt1PING (£xrR. SIPE) 15 700L $T€EL fOR WIN SCUw ExTR.UDtft..
r NUT 14 11'

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A DESIGNATION N MATERIAL NOTES
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 - 292 -

APPENDIX D Output of the GLIM Package

5~~AL ;,'.~.~=ClPT.?
'. ;~;SE :'UN
:"(Lf c>n'I"";"=
1.. 8. 52,!SE"-t~.!

~"'FV!~AIC=: ',:1 '5~~! ':~-t'! t"co :' 5 .

:ST I!,ffHE 5 E. PilP.fmeTfP.
1 1.. 802. ,) 549!~-t1! ;:6'1
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101
t1 J:?:tl£--tl! r" .
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5 1:1 1367 ,~ ~J7t1f-t11 55
f" -I=t 7~]JF-t;1 t1 ~~17f':-t11. rr
- -t' J]'~7t-tl~' 1:1 ~.~?tlE-t'! pp \
'2 j~ 877'~~-t"1;' t; 7.5:!.2£-t'! 5f
? -I~ 49(,5F-f'1 t1 J.tii2£-Bf SP
!.e n 6"J2~F-t1! 1:1 J~~! 2F-B! Pr
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UN! ~ L1~:=,;,q:0 f:! rTF-D ReS !CI(lilL
:1. J. ZJ~1 'J. 2etl 0. 3e08£-t11
2 J 2:t:J ? ?is -0 8SJ.2E'-tl.f
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9 . .~6;(~ ", f?45 fJ 9248£-tli
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1j 1.5ft1 i 569 -0. filM
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 - 293 -

APPENDIX E Thermograms of Single Screw Extrusion Core Samples

A
o
X MELT POOL
UJ

flight no.
13

I-
<l

10

o
o
Z
LW

, , ,
100 120 140 160 180 200 220
TEMPERATURE [ ·C ]
/