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The interaction of llers and

lubricants in rigid PVC
compositions
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by the/an author.
Additional Information:

A Doctoral Thesis. Submitted in partial fullment of the requirements for

the award of Doctor of Philosophy of Loughborough University.

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https://dspace.lboro.ac.uk/2134/13708

c S.T. Pepper

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BLOS C rw:- Ox 7160<:' I

LOUGHBOROUGH
UNIVERSITY
OF.. TECHNOLOGY
. .
LIBRARY
\.

AUTHOR/FILING TITLE

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I
I

11IE INTERA.CTION OF FILLERS JIND

LUBRICANTS IN RIGID PVC COMPOSITIONS

by

STEPHEN THOMAS PEPPER

A DOCTORAL THESIS submitted

in partial fulfilment
of the requirements for the
award of Doctor of Philosophy of the
Loughborough University of Technology

1988

Supervisor: M.Gilbert,

PhD

Institute of Polymer Technology

and Materials Engineering
.

by S.T.Pepper,

-,

1988

'~

..

, I

if

of

~ unMlllily'
LlbraIy ,
T~o!ogy

DaI&

a.

J;

'to

~. ~oo IfS'01

I
I

CERTIFICATE OF ORIGINALITY
This is to certify that
for

the

that
as

work

that

submitted

the original
specified

in

work

in

this

thesis,

is my own except

acknowledgements,

and

neither the thesis nor the original

work contained herein has

to

am responsible

this

or

any

other

been submitted

institution

degree.

S.T.Pepper

for

ACKNOWLEDGEMENTS

am deeply indepted to my supervisor.

for

Gilbert.

invaluable

her

assistance

Dr Marianne
unceasing

and

encouragement.
I

wi sh

Research

to

Council

ac know1 edge

and

Cookson

the
Group

Science
plc

Engineering

for

the

joint

. financial support throughout this research project.

My thanks also go to:Dr Andrew Craig.

Cookson Industrial

Materials Ltd.

for enthusiastic support and discussions as my collaborative

supervisor.
Dr

Michae1

International

Ltd.

Hancock
for

and

advice

Dr

and

Robert

ECC

Higgs.

suggestions

during

number of joint meetings.

The technical staff at Cookson Research laboratories
for

the

genuine desire to help during my visits

to

their

laboratories.
The

technicians

and Mr Tony Davies.

I
assistance

at

IPTME.

Mr

Ray Owens

who never refused a request.

am especially grateful
and

especially

patience

during

thesis

-i-

to Miss G. A. Hunt
the

preparation

for her
of

this

ABSTRACT
The physical properties of rigid PVC products can be related
to

formulation,

preblending and processing characteristics.

A fuller

understanding between these interrelations involves investigation of a

complete

processing system from powder additives

knowledge

of

these

relationships

can

lead

to

to

end

product.

optimisation

A
of

formulation aspects and processing conditions.

Fillers and lubricants have often been incorporat ed into PVC
compounds on a empirical basis,
range

of

compositions

were

however in this investigation a wide

carefully chosen and

included

calcium

carbonate filler at levels upto 40 phr. These were dry blended and then
characterised

by

bulk

density

and

filler

content.

The

processed using an instrumented twin screw extruder,

'window'
in

premix

was

a wide processing

being chosen to provide a product range with large variat ions

fusion

level.

Further cOJllpounds were ext ruded,

incorporat ing

two

different impact modifiers.

The
di fferent ial

extrudates
thermal

was

assessed

analYSiS,

sol vent

for

degree

of

fusion

immersion and microscopy.

by
The

filler distribution, surface appearance and residual grain structure was

observed using a range of microscopy techniques and the results related
to operating conditions.

A measure of fusion level was obtained from

mast er curves of heat of fusion versus processing temperat ure'.

The

filler level did not influence the degree of fusion.

Various

mechanical

properties

of

the

pipe

were

Impact performance was measured using an instrumented falling

impact

tester and the subsequent

composition
reduced

at

and
a

fusion

critical

level.
filler

fracture
Impact

content

weight

behaviour depended on the

properties
and

assessed.

were

dramatically

ductile-brittle transition

temperatures were obtained for the extrudates by testing at low and high
temperatures.

Tensile

properties did not

follow the

trends

observed

during impact testing but indicated a progressive reduction in tensile

properties with increasing filler content.

-11-

LIST OF SYMBOLS

Endothermic area of A peak

Tensile specimen overall length
Cross sectional area

Time base setting

Tensile specimen width
Endothermic area of B peak

Average shear strain

Length of narrow portion of specimen

6H A

Energy of endotherm A

6H a

Energy of endotherm B

6H F

Heat of fusion

6Hp

Heat of fusion for polymer

6HMAX

Maximum heat of fusion

6P

Extrusion pressure
Pressure loss due to entrance effects
Viscous pressure loss

6q ..

Y axis sensitivity

Capillary diameter
Width of narrow portion of specimen
Elongation at break

Elongation at yield

Cell calibration constant

Small radius
Impact failure energy
Available impact energy
Total energy available

Large radius

Fa

Tensile force at break

Fy

Tensile force at yield

Acceleration due to gravity

Distance between reference lines

Test height

Distance between sample grips

Thickness <preferred)
Fracture toughness

-111-

le

Extension at break

10

Initial guage length

ly

Extension at yield

Capillary length

Sample mass
Impact mass
Extruder mass output
Velocity

Viscous loss term

Volume fraction of filler

Pressure

Pl

Metering zone pressure

P2

Adaptor pressure

P3

Pipe head pressure

Specific energy consumption

Capillary radius

ae

Ultimate tensile stress

GREL

Relative tensile stress

av

Yield stress

s. d

Sample standard deviation

Stress concentration function

S..

Recoverable shear strain

SS

Screw speed
Shear stress

Average shear stress

Te,

Glass transition temperature

TMl

Adaptor temperature

TM2

Pipe head temperature

TM3

Screw temperature

TQ

Measured torque

TQo

Torque under no load conditions

Predicted head pressure

yP

Multiple regreSSion value for pressure

-iv-

TABLE OF CONTmiTS

Page No
Acknowledgements

ii

Abstract
List of Symbols

11i

Table of Contents
CHAPTER 1
1. 1

LITERATURE REVIEW

INTRODUCTION

1. 1. 1 Poly<vinyl chloride>

1. 1. 2 Consumption and applications of PVC

1.1.3 Manufacture of PVC

1. 1. 3. 1 Vinyl chloride monomer

production

1.2

1. 1. 3. 2 Tox1cit Y of VCM

1. 1. 3. 3 Polymerisation of VCM

1. 1. 4 Classification of PVC

ADDITIVES FOR PVC

1. 2.1

Introduction

1.2.2

Stabilisers

1.2.3

Lubricants

1.2.3.1 Introduction

1.2.3.2 Lubrication mechanisms

1.2.3.3 Classification of lubricants

10

1.2.3.4 Multiple-component lubricant

systems
1.2.4 Fillers

12
13

1. 2. 4. 1 General requirements of a

PVC filler

13

1. 2. 4. 2 Calcium carbonate as a filler

for PVC

14

1. 2. 4. 3 Manufacture of calcium
carbonate fillers

15

1.2.4.4 Surface treated calcium

carbonate fillers

-y-

16

1.2.4.5 Properties of calcium

carbonate filled systems
1. 2. 5 Impact modifiers

16
18

1. 2. 5.1 Impact modifier

classification

19

1.2.5.2 Mechanisms of impact

modification
1.3

1.4

1.5

20

MORPHOLOGY AND MOLECULAR STRUCTURE OF PVC

23

1. 3. 1

Suspension polymerisat ion

23

1.3.2

PVC nomenclature

25

1.3.3

Molecular structure of PVC

26

1. 3. 3. 1 PVC crystallinity

28

FUSION OF PVC

30

1. 4. 1

Fusion mechanisms

31

1.4.2

Assessment of fusion

37

1. 4. 2. 1 Microscopy

38

1.4.2.2 Solvent testing

38

1.4.2.3 Torque rheometry

39

1.4.2.4 Capillary rheometry

40

1.4.2.5 Thermal analysis

42

1.4.2.6 Miscellaneous techniques

45

PROCESSING AND PROPERTIES OF UPVC

46

1. 5. 1

Dry blending

46

1.5.2

Extrusion of UPVC

46

1. 5. 2. 1 Single screw versus twin

screw extruders
1.5.2.2 Twin screw extruders
1.5.3

46
47

Interrelation between processing.

fusion and properties

48

1. 5. 3. 1 Int eract ion of addi t1 ves

52
53

1.6 PROJECT AIMS

-vi-

CHAPTER 2

EXPERIMENTAL PROCEDURE

2. 1

INTRODUCTION

56

2.2

PVC FORMULATION

56

2. 2. 1

PVC polymer

57

2. 2. 2

Filler

57

2.2.3

Composite stabiliser/lubricant
57

system
2.3

LUBRICANT/MODIFIER STUDY

58

2.4

DRY BLENDING

59

2.5

ASSESSMENT OF DRY BLENDS

60

2.5. 1

Ash content

60

2.5.2

Bulk (tap) density

61

2.6

TWIN SCREW EXTRUSION

61

2. 6. 1

Operat ion of ext ruder

63

2.6.2

Processing of lubricant/modifier
65

compositions
2.7

SURFACE APPEARANCE

66

2.8

ADDITIVE DISPERSION

66

2.9

ASSESSMENT OF FUSION

67

2.9. 1

Acetone shearing test

67

2.9.2

Differential thermal analysis

67

69

2. 10 MECHANICAL PROPERTIES
2.10.1 Tensile testing

69

2.10.2 Impact properties

71

2. 10. 2. 1 Experiment al procedure

for impact testing
CHAPTER 3
3. 1

PROCESSING RESUL TS

78

DRY BLENDING-

78

3.1.1

Dry blend characteristics

79

3. 1. 1. 1

Ash cont ent

79

3. 1. 1. 2

Bulk (tap) density

80

3. 1. 1.3

Scanning electron microscopy of powder blends

3.2

73

86

TWIN SCREW EXTRUSION

3.2. 1

Mechanical energy:

3. 2. 2

Extrusion pressures:

3.2.3

Extrusion results:
-vii-

82

Filler content
Filler content

Additive study

86
89
89

3. 3

3. 4

CHAPTER 4
4. 1

EXTRUDATE APPEARANCE

95

3.3.1

Appearance: Outer surface

95

3.3.2

Appearance:

96

Inner surface

METHYLENE CHLORIDE TEST

98

11IERMIIL AND MICROSCOPY RESUL TS

99

DIFFERENTIAL THERMAL ANALYSIS

99

onset t emperat ure

101

4. 1. 1

'B'

4.1.2

Processing of filled systems

103

4. 1. 3

Endothermic energy of peak' A'

105

4.2

THERMAL ANALYSIS OF ADDITIVE BLENDS

110

4. 3

MICROSCOPY OF FILLED EXTRUDATES

111

4.4

4. 3. 1

Opt ical microscopy

111

4.3.2

Acetone swelling test

121

4.3.3

Electron microscopy of pipe surface

122

MICROSCOPY OF ADDITIVE SERIES

CHAPTER 5

129

4. 4. 1

Opt ical microscopy

4.4.2

Acetone shearing test for additive

4.4.3

129

series

136

Micro-surface of additive series

136

RESULTS OF MECHANICAL PROPERTY TESTS

137

5. 1

TENSILE PROPERTIES OF FILLED EXTRUDATES

137

5. 2

TENSILE PROPERTIES OF ADDITIVE SERIES

143

5.3

IMPACT PROPERTIES OF HIGHLY FILLED SYSTEMS

144

5.3.1

Impact properties:

Influence of

test temperature

153,/

IMPACT PROPERTIES OF ADDITIVE SERIES

155/'

DISCUSSION OF RESUL TS

157

6. 1

INTRODUCTION

157

6. 2

DISCUSSION OF FILLED EXTRUDATES

157

5. 4
CHAPTER 6

6.2. 1
6.2.2

Dry blending and dry blend

characteristics

157

Processing of filled extrudates

160

6.2.2.1 Extrusions characteristics

160

6.2.2.2 Extrudate homogeneity

169

6.2.2.3 Assessment of the degree

of fusion
-v11i-

172 ,/

6.2.3

6.3

Mechanical properties

181

6.2.3.1 Tensile properties

181

6.2.3.2 Impact properties

185 ,/

DISCUSSION OF ADDITIVE SERIES

6.3. 1

192

Dry blending and processing of

additive series

192

6.3. 1. 1 Dry blending and dry blend

characteristics

192

6.3.1.2 Processing characteristics

193

6.3. 1. 3 Extrudate homogeneity

196

6. 3. 1. 4- Assessment of the degree

of fusion
6.3.2

6.4-

Mechanical properties

204-

6.3.2.1 Tensile properties

204-

6. 3. 2. 2 Impact properties

205/'"

INTERACTION OF FILLERS AND LUBRICANTS IN

209

RIGID PVC
CHAPTER 7

200

CONCLUSIONS AND SUGGESTIONS FOR FURTHER WORK 2 14-

7. 1

CONCLUSIONS

214-

7.2

SUGGESTIONS FOR FURTHER WORK

222

REFERENCES

224-

APPENDICES

236

-i)(/"\.

CHAPTER ONE

LITERA71JRE REVIEW

1. 1 INTRODUCTION
1. 1. 1 POLY <VINYL CHLORIDE)

Poly<vinyl
thermoplastic

<PVC)

chloride)

which

has

been

is

large

commercially

the beginning of the last war.

tonnage

available

since

Its wide acceptance has been

attributed to the scope of additives which enable a host of

compositions to be formulated and these additives have to a
large

extent

overcome

the

inherent

processing problems

of

PVC.

The versatility of this polymer can be highlighted by

its

range

of

material

properties

and

applications

result in both flexible and rigid products.

which

1.1.2 CONSUMPTION AND APPLICATIONS OF PVC

The

consumpt ion

of

PVC

has

dramat ically

increased

since the war with the notable exceptions of the oil crisis
in 1974 and the discovery that VCM is a major health hazard.
The current importance of PVC can be shown in the table 1.1
depicting the UK consumption of plastics.
The major application areas for PVC are vast and can
be

highlighted

considering

by

the

breakdown

of

PVC

consumption in Western Europe ( 2) as shown in table 1. 2.

Table
tonnage
ranges.
by

its

commodity

and

1.2

plastic

illustrate
with

that

wide

PVC is

number

of

large

product

The material has obtained an important market share

competitive

conversion
include

1. 1

costs

UPVC

pipe,

material

(3).
UPVC

The

cost,

future

windows,

versatility
expected

biaxially

and

growth
blown

low
areas

bottles,

rigid foams and crosslinked plasticised PVC (3,4).

Page

Introduction/l

TABLE 1. 1

UK consumption of plastics

[ll

(' OOOt)
Low density PEtLLDPE
High density PE
Polypropylene
PVC
Polystyrene
Expandable POlystyrene
Polyamides
ABS copolymer
Acetals
PET/PBT
Acrylics
Polyester film
Phenolic resins
Amino resins
Polyester resins
Epoxides
Urethanes
Others

1985
580
250
330
450
148
30
22
55
11
41
28
24
50
125
51
18
94
295

1986
610
275
370
484
156
33
23
58
12
45
29
24
49
131
53
19
100
265

TOTAL

2602

2736

TABLE 1. 2
PVC Market in Western Europe
MARKET

1986
(' OOOt)

Total

Rigid PVC

Bottles
Film and Sheet
Injection moulding
Pipe and Conduit
Profile Extrusion
Records
Miscell aneous
TOTAL RIGID

342
436
81
990
536
77
93
2555

83
105
20
239
129
1 9

22
617

Plasticised PVC

Coated Fabrics
Film and Sheet
Flooring
Tubing and profiles
Wire and Cable
Miscellaneous
TOTAL PLASTICISED

161
338
210
167
394
162
1432

40
95
39
346

Other applications
TOTAL CONSUMPTION

153
4140

37
1000

39
82
5 1

Page

Introduction/1

1. 1. 3 MANUFACTURE OF PVC
1.1.3.1 VINYL CHLORIDE MONOMER PRODUCTION
The
(VCM)

does

modern
not

productton

depend

upon

of

vinyl

acetylene

chloride

as

raw

monomer
material,

since the growth of the petrochemical industry has provided

a ready supply of ethene.

Ethene is converted to VCM via two

distinct processes (5].

A)

The

traditional

conversion

ethene

process

involves two main stages

Stage One:

Ferric Chloride

------30:50~C------~

CH 2 =CH 2 + Cl,
Ethene

+ Chlorine

CH,Cl-CH 2 Cl

Ethylene dichloride

Stage Two:

CH,Cl-CH 2 Cl
Ethylene dichloride

VCM

Hydrogen
chloride

8) A one stage conversion process has been recently

introduced using a balanced oxychlorination process.

Ethene + Hydrogen + oxygen

chloride
VCM is a sweet smelling gas
be

stored

as

liquid

under

VCM

(8. Pt

Water

-13C) which may

pressure

without

polymerisation inhibitor.
1.1.3.2 TOXICITY OF VCM
VCM was not
although

hazards

appreciated,
operators

until

originally considered a

of

fir.e,
the

contracted

explosion

mid
various

1960' s

and

when

diseases

health hazard,
narcosis

some

PVC

including

were
plant
acro-

Page

Introduction/1

osteolysis,

Raynaud's syndrome and scleroderma [63.

Further

work using animals to elucidate the causes and connection of

VCM to these diseases revealed a

rare fatal cancer of

liver named as angiosarcoma of the liver.

the

The indications of

this work [7) and many others suggested that VCM was a human
carcinogen
confirmed

and
with

these
the

preliminary

discovery

of

investigations
number

of

plant operators had contracted angiosarcoma.

of

VCM resulted in radical

operat ion
were

and

introduced

approximately
ppm.

removal
in

residual

in

ppm
EEC

plant

These improvements
VCM levels

million)

directive has

where

plant design,

VCM.

(parts per

cases

The new hazards

1974 and reduced plant

300

The present

of

changes

were

to less

stipulated a

from

than

technical

long term limit value (TLTLV) of less than 3 ppm.

1.1.3.3 POLYMERISATION OF VCM.
PVC is commercially polymerised by four techniques:i)
ii)
iii)
1v)

Suspension
Bulk or Mass
Emulsion
Solution

Suspension polymerisation predominates over bulk and

emulsion techniques in terms of tonnage,
o'f

world

nameplate

capacity

[8),

approximately 80%
while

solution

polymerisation is mainly used for copolymers and speciality

applications.

Suspension

characterised

by

diame'ter),

high

and

mass

their

coarse

bulk

density

polymers

particle
and

are

size

good

generally

(100-150
free

flm

flowing

properties while emulsion polymers are finer in size (0'1-2

flm diameter) and have good plasticiser absorption properties
[ 93.

The typical

product

applications for

the grades of

PVC produced via the differing polymerisation techniques are

highlighted in the following table.

Page

Introduction/1

TABLE 1.3

Ranges of application of PVC [101

pvc

rtgo-

processV19

K - values

I 5 I 8

150-

calendering

55} 57-55 755 70'00

Ihermol refined
7580
films

floor covering

PlC

pJasJlCIZed -

I 8

-valves

fss 7O

70

50-80 SO 10

xtruS/Of) cl ngi:J PlC

10 ~7-58 15 7-68

pressure ppes
profiles

sl'eets and 1101

lilm":.
blown fIlms

fss' 7O 55-57 57-{;8

~0.55 60

60

50 57-SO 60

ex !rusion of plo -

sticized - PVC
general

55-70 fIi -70 55-70

55-BD
70
10
55-00 5065
15 7 - 60 5868
15 5 - 60 156-50 - 55-70 55'60

coblerroferia's

mainly
blON rroukisng
injectIOn m:.ukJmg
pr')cesslf):} 01

pastes

10-8:. 708]

1. 1. 4 CLASSIFICATION OF PVC

The

requirements

of

nature of its application,

PVC

depend

upon the

exact ing

however an ASTM publication lists

the major criteria for the classification of PVC [111.

Molecular Weight
Molecular

can

weight

be

assessed

viscometry to yield a viscosity number

in

cyclohexanone

(Fikent scher 'K'

important

at

25"C>

value>,

bearing

high

upon

level

of

the

related

to

processability

mechanical

and easier process;lng

table,

table

generally used for

(0'5% solution of PVC

value

'K'

and

physical

in general a compromise is taken

value>

1. 3,

solution

The molecular weight of PVC has an

properties of the polymer,

between

or

via

<low' K'

demonstrated

that

performance
value>,
low

'K'

<high

'K'

The previous
values

were

int ensi ve processing ope rat ions such as

Page

Introduction/!

injection

moulding

applications,

while

in

such as pastes,

heavily

a high' K'

plasticised

value is advisable

in order to retain the level of physical properties.

The
assessed

molecular

by

gel

weight

permeation

distribution
chromatography

of

PVC

(OPC)

can
to

be

yield

important processing information.

Sieve Analysis
The
retained
present,

PVC

polymer

measured

to

may

be

ensure

sieved
that

and

no

the

large

percentage
grains

are

alternatively the particle size distribution may be

measured via a bank of sieves or other techniques such as a

Coulter counter,

microscopy etc.

The particle size,

particle

distribution and particle shape have a significant influence

upon processing techniques and bulk handling equipment.
Bulk Density
Bulk

density

is

measure

of

the

weight

per

unit

volume of PVC particles and can be related to the spherical

shape

and

particle size distribution

of

PVC.

A high

bulk

density indicates a high packing efficiency and is preferred

for maximum output from processing equipment.
PlastiCiser Absorption
The amount of plasticiser absorbed is a function of
particle size,
The

ability

plasticiser

surface area and porosity of the PVC grains.

of

particular

is

importaht

grade

in

of

PVC

assessing

characteristics of plasticised compositions.

PVC

grains

may

be

examined

by

techniques

to

the

absorb
dry

blend

The porosity of
such

as

light

microscopy and mercury intrusion porosimetry [12].

Dry Flow
The

ability

of

PVC

powder

restrictions and hoppers is important

to

flow

through

for many processes and

can be assessed by the flow of the powder through a standard

funnel.

Page

Introduction/l

Electrical Conductivity
The electrical properties of PVC can be considerably
reduced

by

thus

measure

impurities
of

such as surfactant

electrical

residues etc

conductivity can be

used

and
to

assess the purity of the PVC material.

Other tests which may be useful to characterise PVC include
percentage
(ungelled
course,

heat
PVC

loss,
in

heat

st abili t y,

milled

sheet),

fish-eyes'
transparency

cont ent
and,

of

processing studies.

1.2 ADDITIVES FOR PVC

1. 2. 1 INTRODUCTION

/PVC,
a

~un-l-i-ke-i-t.s-ma-i-n-compet.iJ_or:s,_

is unique in that

technology has been borne to overcome t he poor

processing

stability

of

the

polymer.

Thus

PVC

inherent

technology

usually involves the introduction of additives to facilitate

acceptable

processing,

extend

material

cost etc./Therange of additives is

reduce

v~st but in general the

main additives can be listed as follows

[1~)

Stabilisers

Fillers

Plasticisers

Pigments

Impact modifiers

Lubricants

Polymeric Processing Aids

Extenders

Miscellaneous
fire

properties,

additives

ret ardant s,

stabilisers,

include

antistatic

brighteners,

Blowing

agents,

agents,

dyes,

fungicides,

light

viscosity depressants etc.

The processing of PVC usually involves a temperature

and shear history and since PVC is notoriously susceptible
to

decomposition

under

these

condi t ions,

then

Page

the

Int roducti on/ 1

introduction of stabilisers is commonplace. /

The effects of degradation include :- colour change
due

to

gaseous

polyene

formation,

byproducts,

processing,
performance

streaks

dramatic
and

acidic
of

gas

degraded

reduction

attack

of

(HCl),

in

voids

due

material

to

during

mechanical/electrical

corrosive

gas

upon

processing

machinery and personnel.

The actual mechanisms of degradation and associated
theory

of

stabilisation

have

not

be

universally

agreed,

however the generally accepted requirements of an effective

'ideal'

stabiliser might be as follows [14,15,16):

i)

The reaction with hydrogen chloride.

ii)

The replacement of structural weaknesses with

more stable groups.

iii) The rendering of pro-degradent substances

innocuous.
iv)

The interruption of conjugated polyene

structures.

v)

The neutralisation or removal of resin

impurities or contaminates.

A PVC stabiliser may be expected to comply to one or

more

of

these

requirements

but

it

is

unlikely

that

stabiliser will be effective in all of these criteria.

stabilisers

may

be

categorised

into

three

main

a
PVC

classes

[12,16):
Primary Heat Stabilisers
Lead salts,

heavy metal salts and organotin compounds

Secondary Heat Stabilisers

Organic compounds,

organophosphites and epoxy compounds

Light Stabilisers

Cadmium compounds,tin

c~mpounds,

organophosphites etc.

Page

Introduction/1

Primary

stabilisers

can

be

combined

with

the

less

effective secondary stabilisers and in some circumstances a

synergistic

behaviour has been noted.

salts were exclusively used;

in general.

powerful.

salts

have

compounds

are:

applications).
cont ent

dual
toxic

ot herwise

and versatile and some lead

as

lubricant.

(rest rict i ve
stainin~

sulphur

lead

these primary stabilisers are.

low cost
purpose

In this project

voiding

However

legal isat ion

restricted

may

occur

in

by a

and

lead

cert ain

safe lead

lastly

PVC

compositions containing lead compounds are generally opaque

due to the tinctorial power of the stabiliser.
1. 2. 3 LUBRICANTS

1.2.3.1 INTRODUCTION
/Lubricants

are

primarily

facilitate easier processing.

shear

these

formulation

overfused.
have

of

possess

poor

lubricants

materials
lead

poor

aesthet ic
is

to

finish.

is

not

Unfortunately the
understood and

which are

propert ies

appearance.

The

complicated

to

lower heat and

well

products

physical

further

commercial range.
that

can

in PVC compounds

greater output.

history and better surface

interaction
poor

used

and

under

possibly

incorporat ion

by

the

or
of

available

contrasting literature and the requirement

lubricants should be tailored to speciic formulations

and processing machiner y . /

1.2.3.2 LUBRICATION MECHANISMS
Lubricants are generally classed into two differing
gr?ups:

internal and external.

EXTERiaL
These materials provide a lubricating layer between
,

polymer

efficiency

melt
in

and
this

hot

metal

manner

surface.

depends

upon

their

lubricating

low compatibility

Page

Introduction/l

especially
film.
in

at

operat ing

condi t ions

and

Poor formulation or excessive

'plate-out',

properties,

poor

fusion,

st rong

boundary

lubrication can result

possible

melt slippage and poor surface

reduction

in

finish.~

INTERNAL

These

addi t i ves

are

fundamentallY; different

to

external lubricants since lubrication occurs by a reduction

in

the

internal

temperature.

friction

of

the

melt

at

the

The characteristics of internal

processing

lubricants are

increased compatibility with PVC and little affinity for the

hot metal surface.

They reduce heat-build up of the melt and

lower melt viscosity.

While external lubricants are commonly

referred to as fusion retarders,

effect

upon

fusion

rates

or

these materials have little

deemed

are

mild

fusion

promoters/
1.2.3.3 CLASSIFICATION OF LUBRICANTS
The
lubricants
varied,

commercial
is

vast

and

range
their

of

additives

chemical

classed

formulation

as

equally

however luoricants can be considered as a member of

one of the following groups [171:

a) Straight chain carbon molecules:

paraffin and

hydrocarbon waxes.
b) Straight chain carbon molecules with polar end
groups:

fatty acids and fatty acid esters.

c) Polar centre molecules with long carbon chains

attached:
Although

the

metal stearates.
chemical

nature

of

can be classed into well defined groups,

more difficult

to generalise.

common

lubricants

their action is far

The efficiency and nature of

lubricants have been considered by an array of techniques:

Pase

10

Introduction/1

Chemical structure and polarity [18-20].

Torque rheometry [21-25].
Optical properties such as haze [20,23,26-27].
Capillary rheometry [28-29].
Glass transition temperature [19,27].
'Fluidity'

test [18,26].

Optical wetting and penetration [30].

Frictional forces through extrusion die [31].
Mechanical properties [18,26,32-34].
Processing studies [17,22,34-36].
Most studies have attempted to relate the action of
a

lubricant

with

measurable

property

such

as

torque

rheometry or have observed the relationship between the role

of

lubricant

Marshall

and

propert y,

haze,

PVC,

poor

and

its

Jacobsen

haze

chemical
[26,18]

structure.

For

example

identified

the

optical

as a measure of the lubricant's funct ion in

representing poor

compatibility and thus

more external nature.

[ 23]

Hartitz
rheometer as a
any

at

group

Brabender m

the

tool which could class a lubricant

torque
into two

the .first group had little or no effect upon fusion

groups;
time

considered

concentration

lubricants

of

('internal')

significantly

while

delayed

the

second

fusion

time

(' ext ernal' ).

King
using

and

[19]

No~l

differential

conducted

scanning

calorimetry

fundamental
to

detect

study
slight

Changes in the glass transition temperature (TG) of PVC when

blended with lubricants.

The level of TG reduction indicates

lubricant

and

compatibility

effectiveness

as

an

internal

lubricant.
A simplified overview of the publications concerning
single
straight

component
chain

lubricated

carbon

processing behaviour.

compositions

lubricants

are

mainly

suggest

that

external

Straight chain carbon molecules

in
with

polar end groups are possibly intermediate and lastly polar

groups with

long chain carbon molecules can be grouped as

Page

11

Introduction/1

lubricants.

internal

Formulation

studies

using

the

aforementioned techniques have led to contrasting views on a

number

of

number

well

of

stearate

known commercial

workers
behaves

processing

as

studies

stearate as a

[24,30]
an

lubricants,

have

suggested

external

[17,22,25,37]

for
that

lubricant,
have

example a
calcium

while

categorised

other

calcium

fusion promoter which thus should be classed

as an internal lubricant.
The

understanding

complicated

since

combinations

of

of

UPVC

many

differing

these systems is,

these

additives

composi t ions

lubricants;

in general,

the

is

further

incorporat e

composition

of

based upon empirical knowledge

rather than scientific appraisal.

1.2.3.4 MULTIPLE-COMPONENT LUBRICANT SYSTEMS
The

interaction

of

various

lubricant

have been assessed [23,25,27,29,32,36,38,39]

combinations

and a number of

these studies have revealed a synergistic influence between

commercial

combinations.

combination

of

Rabinovitch

calcium

stearate

[27]

with

assessed

paraffin

wax

the
and

reported a synergistic response at intermediate levels upon

toughness,

surface

finish

and extruder

power requirements.

An 'ideal'

model was proposed which was based upon a mobile

layer of calcium stearate adhering to PVC primary particles

and

the

hot

metal

surface,

calcium stearate film of

with

interlayer within

paraffin wax molecules.

Thus

the
the

interaction of these components at a specific ratio provides

a better boundary layer.
Hart i t z
lubricants

of

[23]
an

blended a

external

number

nature

and

of

met al soaps wi th

noted

a synergistic

delay in fusion time as measured on a Brabender plastograph.

Yu

et

a1

(38)

propounded a

certain combinations of

delay

in

fusion

behaviour

for

paraffin wax and calcium stearate;

this phenomenal delay could not be explained on the basis of

the work within the paper.

Page

12

Introduction/1

1. 2. 4 FILLERS

PVC has been filled,

at

some period of

almost every variety of filler available,

time,

with

and the extent of

the filler range can shown in the following figure [40,411:

FIGURE 1. 1
Fillers for PVC

ORGANIC

INORGANIC

'"

Fibrous

'\

Fibrous

Particulate

IWoodflourl Carbon black

Graphite

Particulate

Asbestos

Calcium carbonate

Glass Fibre

Clays
Calcined clays
Talcs
Silicates
Silica

Al though
commercial

the

filler

range
is

of

fillers

predominantly

obtained by natural

or synthetic

is incorporated

most

in

opaque

vast,

calcium

routes.
UPVC

is

the

main

carbonate

Calcium carbonate

formulations

and

far

outstrips all the other fillers in terms of application and

tonnage,

for

example

the

West ern

Europe

consumpt ion

of

calcium carbonate is approximately 100,000 tonnes per annum

[42] .
1.2.4.1 GENERAL REQUIREMENTS OF A PVC FILLER
The desirable characteristics of a PVC filler depend
to

large

extent

upon

the

intended

application,

however,

the basic criteria may be listed as follows [40,41,431:

Page

13

Introduction/l

i)

Maximum improvement or no deleterious effect

upon properties

ii)

Low moisture content

iii) Good wetting of polymer matrix

iv)

Freedom from impurities

v)

Appropriate specific gravity

vi)

Low cost and good availability

vii) Non-flammable
viii)Absence of odour and good colour
ix)

Chemical resistance and heat resistance

x)

Available in range of controlled particle size

and particle size distribution

xi)

Good processing and dispersion characteristics

xii) Low water solubility and low plasticiser uptake

It is unlikely that a filler candidate will be ideal
in each of the above performance criteria,
compromise is taken between amount,

type,

but generally a

characteristic

of

the filler and the properties of the filled compound.

The properties which can characterise a filler
have

direct

bearing

upon

selection

criteria

and

can

be

reviewed as follows [15,40,43,44];

a) Particle shape,size and distribution
b) Surface area
c) Oil absorption
d) Bulk dens it y
e) Specific gravity
f) Refractive index, opacity and colour
g) Hygroscopicity and moisture content
h) Hardness and modulus
i) Surface treatment
j) Chemical composition and impurities

1.2.4.2 CALCIUM CARBONATE AS A FILLER FOR PVC

coated

calcium

throughout this program.

related

to

its

low

carbonate

filler

used

was

The popularity of the filler can be

cost,

abundance,

non-toxicity

Page

and

14

Introduction/1

versatility
technical

terms

in

advantages

of

particle

have

been

criteria.

proposed

for

number

the

of

prudent

incorporation of calcium carbonate fillers:

Advantages
Low cost
Non toxic,
White,

non irritating,

odourless

low refractive index and easily coloured

Softness <Mohs hardness of

~3)

Abundant raw material from natural minerals

Synthetic production from calcium salts
Wide range of particle size and distributions
Easily coated in dry form
Antiplate agent
Acid acceptor
Pigment
Reduction in shrinkage problems
Stability over wide temperature range
Disadvantages
Attacked by acids
At high temperatures,

calcium carbonate decomposes

Little/zero reinforcing of properties

Relative high moisture content
Processing of filled compounds may prove difficult
Low stiffness filler
Final specific gravity of compound increased
1.2.4.3 MANUFACTURE OF CALCIUM CARBONATE FILLERS
Calcium
techniques
dry

to

carbonate
produce:

processed

coarse

can

be

puri fied
calcium

obtained
ground

via three

main

calci urn carbonat e,

carbonate

and

precipitated

calcium carbonate [41,44-47J.

widely
produce

Dry

processed

used

since

coarse

the

calcium
dry

particle

carbonate

grinding
size

of

grades
nat ural

distribution

and

are

not

minerals
inherent

Page

15

Introduction/1

impurities which can lead to dark and inferior products in

terms of mechanical properties.
PreCipitated

calcium carbonate

fillers

high quality grades which are considered

combinat ion
produced

of

propert ies

synthetically

upon

by

PVC.

can

produce

to infer the best

These

recarbonation

grades

process

are
which

regenerates calcium carbonate by precipitation from calCium

hydroxide.
order,

The

mean

particle

for example 0'2-2'0

size

can

be

of

very

low

~m.

Purified calcium carbonate grades have gained recent

commercial interest and involve the wet grinding of purified
natural minerals such as chalk deposits.
is

The median particle

intermediate between the two other types,

1-10

approximately

~m.

1.2.4.4 SURFACE TREATED CALCIUM CARBONATE FILLERS

The possible advantages of coating calcium carbonate
fillers have been known for some time [45J
agents

coating
although

other

coatings

can

mixers.

be

are

stearic

coatings
applied

acid

have
by

and

been

dry

and the typical

calcium

tried

blending

stearate,

[48-49J.
in

high

The
speed

The main reasons for the coating of purified grades

of calcium carbonate are considered as follows [48, 50J:

a) Lower oil/plasticiser absorption
b) Less hydrophiliC nature
c) Increased thermal stability due to stabilising
effect of coating
d) Reduced problem of filler agglomeration
e) Processing aid
f) Better 'wetting'

of PVC matrix

1.2.4.5 PROPERTIES OF CALCIUM CARBONATE FILLED SYSTEMS

There are few pubi"ications concerning the properties

of

calcium carbonate

filled

systems,

especially at

levels

Page

16

Introduction/I

greater than 20% and the vast commercial range adds to the
ambiguity

of

highlight

the

the

situation.

The

importance

of

studies

have

dispersion

tended

and

to

particle

size/distribution.
The

'top cut'

of

filler

grade,

10% of

the particle size distribution,

effect

upon

surface

properties

appearance,

processing
calcium

resistance

[46, 51l.

carbonate

can have a dramatic

such as notched

tear

equipment

namely the upper

can

impact

and

machine

Similarly

produce

coarser

can

occurs

act

as

zones

whereby

Alternatively,

[50, 52J.

wear

on

grades

of

substantially

products since relatively large particles

~m)

resistance,

(in excess of

concentration
fine

inferior

of

particle size

10

stresses
calcium

carbonate fillers have been known to provide enhancement to

propert ies such as not ched impact
54J.

The

filler

fine

grades

surface

of

areas

resistance [34, 46, 51, 53-

calcium

and

thus

carbonate
many

interaction with the polymer matrix,

provide

bonding

large

sites

for

hence the retention and

possible enhancement of some mechanical properties [51J.

An important
is

dispersion;

feature in the use of filler additives

poorly

dispersed

filler

is.

similar

in

behaviour to the presence of oversized or large particles.

The effect

of

poor dispersion was unintentionally observed

by various workers [53,55J.

Chauffoureaux and fellow colleagues [53)

prepared a

joint report upon calcium carbonate filled PVC from a number

of companies.
fillers

(mean

loadings,
the

The investigative study considered two coated

particle

10 and 20%.

production

sizes:

sheets

respective samples

between

impact,

Impact

clearly

and

2'4

~m)

at

two

The first stage of the work involved

of

properties.

0'07

by

extrusion

'houses'

performance,

demonstrated

for
drop

that. the

and
a

testing

the

large number

ball
fine

and

of

tensile

particle

size

filled grades were significantly inferior when compared to

unfilled

and

coarse

filled

extrudates.

These

results

were

linked to poor dispersion as observed by scanning electron

microscopy.

The

micrographs

illustrated

the

gross

Page

17

Introduction/!

agglomeration of

the

finer

particle sized filler

and this

poor dispersion was accepted as the main contributory factor

for

the

poor

produced

impact

samples

of

behaviour.

The

the

formulations

same

second

milling and then compression pressing,

performance

of

the

by

of

work

two

roll

this mixing procedure

removed any agglomerates greater than 1

impact

stage

In this case the

~m.

samples

were

significantly

improved by the addition of 10-20% of the fine particle size

coated calci um carbonat e,

an improvement of approximat ely 2

and 6 fold respectively being observed.

The dispersion of
aided

by

the

coating

which

surrounding

lubricant

fine particle size filler may be

the

is

considered

filler

to

act

particles

as

to

prevent

tear,

fatigue

whi le

physical

agglomeration and aid mixing.

Specific
and

properties such as

low t emperat ure

criteria

are

including

toughness

(K t e

weathering

and

>,

generally

tensile

lowered,

creep

behaviour,

(tensile,

moduli

shrinkage

tensile,

are

fracture
flexural>,

Young's,

enhanced.

Impact

behaviour

depends upon filler specification and processing conditions.

Thus filler loading,

dispersion,

grade,

coating and

particle size characteristics have a important bearing upon

the properties of filled PVC products [51-53,561.
-7

1.2.5 IMPACT MODIFIERS

/

The impact performance of UPVC can be substantially

improved by the addition of mOdifier~ Although the fracture
behaviour
pattern

of

of

PVC

usage

is

not

demands

considered

more resilient

applications such as cladding,

products

the

general

products.

Outdoor

window profiles and rainwater

specify adequate impact retention even at sub-zero

temperatures.~~e
critically
and/or

brittle,

dependant

processing

provide a

impact performance of many PVC products is

upon

slight

conditions.

The

changes
use

of

in

formulation

modifiers

well balanced composition which does not

c-/

can

respond

dramatically to these minor alterations/

Page

18

Introductionll

1.2.5.1 IMPACT MODIFIER CLASSIFICATION

Modifiers are generally semi-compatible with PVC and
are

based

argued

upon

whether

rubbery-type
certain

calcium carbonate,
in a

materials,

fillers,

such

although
as

fine

should be considered as

separate class.

it

can

be

precipitated

impact modifiers

However the major additives which are

termed impact modifiers can be listed as follows:

Acrylonitrile/butadiene/styrene (ABS)
Methyl methacrylate/butadiene/styrene (MBS)
Acrylics;

All acrylics or modified acrylics (ACR)

Ethylene vinyl acetate (EVA)

Chlorinated polyethylene (CPE)
These additives can be melt
of

EVA

and

C?E,

grafted

to

PVC

blended or,
by

adding

in the case

the

preformed

modifier to the PVC prepolymerisation ingredients.

The level

of addition is typically between 5 and 15%.

MBS

and

applications

due

ABS
to

are'

poor

not

recommended

UV stability

butadiene segment o'f the terpolymer,

for

associated

out door
with

the

while the other generic

materials offer good weathering stability.

All acrylic

type

modifiers are widely used in United States of America while

Europe

has

traditionally

used

CPE

and

EVA

for

certain

applications.
This
modifiers,

project

namely a

investigated
CPE and

summary of the general

an all

two

different

acrylic

(ACR).

impact
A brief

attributes of each type is given in

table 1. 4 [57]:

Page

19

Introductionl1

TABLE 1. 4Performance of CPE and ACR impact modifiers

Advantages

Impact

Disadvantages

Modifier
1.

CPE

1.

Outdoor applications

processed

(esp in Europe)
2.

2.

Good low temperature

properties,

better
3.

at low temperatures
than acrylics

4-.

Poor hot strength

Good impact retention

5.

Higher specific
gravity than ACR

4.

Good melt elasticity

1.

Outdoor applications

2.

Wide processing

1.

Low heat deflection

t emperat ure

window

3.

Low heat deflection

temperature

and efficiency

ACRYLIC

Yellowing in
white products

ductility

3.

Can be over-

2.

Moderate low

Excellent colour,

temperature

impact efficiency

per f ormanc e

and retention
4-.

Low die swell

1.2.5.2 MECHANISMS OF IMPACT MODIFICATION

The
high

enhanced

strain

mechanisms;

rates
firstly

particles within a
modifier

forms

behaviour
can
the

be

of

modified

explained

modifier

is

by

PVC

under

two

dispersed as

very

distinct
d.iscrete
.'

continuous PVC network and secondly the

continuous

phase

which

encapsulates

PVC

primary particles.

Page

20

Introduction/1

Acrv1ic modiFiers
The

modi fier

in

blend

wi t h

particles within the PVC matrix;

PVC

forms

discrete

an improvement in impact is

visualised by deformation/cavitation of the rubber particles

during a high speed stress wave [58-59) and the lowering of
yield stress permitting cold drawing which can also act

as

an additional mechanism of energy absorption [59-60).

The

all-acrylic

system

is

based

upon

saturated

acrylic rubber which is not prone to weathering problems and

the extent

of

impact

dispersed

particles

improvement
i1>

is

related to:

particle-matrix

i)

evenly

adhesion

iii)

particle size distribution iv) viscoelastic nature of rubber

v)

rubber

content

and

lastly vi)

modifier

level

(61).

The

particle size distribution of the modifier is generally not

affected

by

processing

conditions,

since

the

crosslinked

discrete particles are determined during polymerisation and

thus acrylic modified grades are less susceptible to 'overprocessing'

(62).
CPE and EVA modifiers

These modifiers are considered to produce a 'honeytype

comb'

network

is

embedded.
blend's

of

structure

formed

The

in

[63-68),

which

improvement

where

primary

in impact

irreversible deformation

PVC

an

elastomeric

particles

are

can be relat ed t o t he

behaviour.

Siegmann

et

a1

[59) observed that in the case of unmodified PVC the failure

behaviour
crazing,
until

during

tensile

deformation

was

predominantly

followed by shear banding and then finally voiding

failure.

However

CPE modified

systems

differed

from

this sequence since shear banding followed by voiding were

seen as the mode of failure.

Although these conclusions can

not be directly linked to failure in an impact test,

they do

provide an insight to the possible mechanisms involved.

Page

21

Introduction/1

A number
importance
structure
impact

of

of

st udies

mechanicel

of

network

enhancement

is

[62, 65-68]

processing

systems.

The

observed

when

encapsulates

the

primary

temperatures

or

an

upon

the

optimum
a

particles.

increased

have ment ioned

shear

honey-comb

condition

elastomeric

In

the

the

case

history

for

network

of

the

higher
primary

particles are destroyed which also leads to the destruction

of

the

network,

resulting

in

the

formation

globules in a continuous PVC matrix.

inclusions

do

distribution
thus

not

inferior

to

for ,good

required
impact

original blend,

The resultant spherical

the

ideal

impact

size

particle

efficiency

when

performance,

discrete

[61]

and

to

the

compared

is observed.

Menges
PVC

conform

of

et 81 [67]

produced a

high

impact

grade of

<via copolymerisation with EVA) and examined compression

moulded and extruded samples by elect ron microscopy,

tensile

and

dramat ic

sorption

dependence

strength;

at

techniques.

of

The

processing

temperature

of

188'C

performance

was

observed.

At

higher

performance

was

associated
produce

with

discrete

introduced,

the

destruction

particles

of

revealed

temperat ure upon

progressively

study

impact,

the

of

the

optimum
and

impact

this

network

the' modifier.

as shown in figure 1. 2,

impact

temperatures

reduced

the

system

A model

which could account

the
was
to
was
for

the reduction in impact properties.

FIGURE 1.2
Influence of processing upon EVA modified PVC

!'
StQ~t
or (.rCI'" --t~~~fr~~2j
formatIon Ot _

r
SIQrt 01

a:o:z:e

ro~mat'on

boundary to ... r1Qces

(Al)

E""t,"g erOles
.100

new

(Bl)

LimitatIon 01 crQzt
tor-fruition

crazes form

(A2)

(B2)

Page

22

Introduction/l

Case A:

Modified PVC processed at low temperatures

In the early deformat ion of modi fied PVC (At),

small

crazes develop at

the primary particle interface which are

perpendicular

the

to

direction

of

applied

stress.

formation acts as a source of energy absorption,

Craze

the craze

continuing to propagate until it encounters a perpendicular

boundary interface where continued growth is prevented
and

further

crazes

are

initiated

at

other

(A2)

convenient

boundary interfaces.
Case B:
The

Modified PVC processed at high temperatures

situation

after

phase

destruction of network structure,

ie

t ransformat ion,

suggests that in the early

stages of deformation crazing occurs around these globules

of

modifier

(B1>.

Further

deformation

leads

to

propagat ion and int erconnect ion of crazes unt i1 a

craze

cri t ical

length is reached whereby growth is stopped (B2)'

Rabinovic
EVA,

CPE

and

[62J

all

impact

acrylic

tested milled
modifiers

UPVC blends of

and

confirmed

the

sensitivity of CPE and EVA to over-processing when compared

to the all acrylic modifier.
1.3 MORPHOLOGY AND MOLECULAR STRUCTURE OF PVC
The
earlier
[70J,

particulate

studies

nature

including

of

Berens

PVC
and

was

highlighted

Folt

[69J

and

by

Hori

and the influence of this unique morphology has wide

ranging

ramifications

properties.

upon

processing

and

subsequent

The origins of the particulate nature of PVC can

be related to the mechanism of polymerisation.

1.3.1 SUSPENSION POLYMERISATION
The conversion

pr~cess

which produces PVC from vinyl

chloride monomer involves suspending the monomer,

droplets,

in a

continuous water phase by a

as liquid

combination of
Page

23

Introduction/l

vigorous

agitation

colloid.

The

maint ained

and

batch

at

in

the

mixt ure

speci fic

presence

is

of

cont inually

polymerisat ion

agi t at ed

t emperat ure

75'C) until the required conversion is achieved,

resultant
then

slurry

finally

temperature
variables

coarse

[71 J.

particles

, stripped'

is

and

rate

level
in

residual

to

screened

The

involved

of

of

colloid

the

control

large

polymerisation

protection are
of

<"'50-

dried and

extraneous

remove

and

whereby the

VCM,

agitation,

of

protective

the

main

molecular weight

and

grain characteristics such as porosity and shape.

The
aggregation
[72]

conversion
steps

process

[71-73]

and

proceeds
an

by

schematic

series

of

representation

is shown in figure 1.3.

FIGURE 1. 3

Mechanism of suspension polymerisation

CONVERSION

R" + VCM - . . Coiled Macro Radicals ~

1st AGGREGATION STEP

Formed

Finally

100 -200"

.. 50

Micro- Domain

@:

~ 10'

2nd AGGREGATION STEP

'Prim~":;,eusl
GROWTH

SIZE

When-

ONInATrON

UNTRA-PRIMARY}

0,,- 0-2)Jfn

...

Prima'YO

G-e-O8)A"'1

Particle

3rd AGGREGATION STEP

15ea1e

4lOt

~._t.~
~

UNTER PRIMARY)

!i

1-2F

Scale

~<"'
Page

24

Introductionll

The polymerisation
reaction
occurs.
the

temperature
Also

mixture is quickly warmed to the

and

decomposition

of

the

initiator

a skin or pericellular membrane encapsulat ing

polymerising

droplet

occurs

at

very

low

rate

of

conversion [71]

and is formed by the graft copolymerisation

of

chloride)

poly<vinyl

protective
droplets

colloid.

on

to

Coalescence

can often occur at

the
of

poly<vinyl
a

number

acetate)

of

conversion levels of

monomer
5-15% to

produce particles which are termed grains.

Within the monomer droplet the growing polymer chain
soon precipitates out of the monomer since PVC is insoluble
in

VCM,

agglomerat ion

maximum)
namely
short

form

the

coagulate
primary
remain

and

to

nuclei

and

until

become

aggregate

of

species;

first
are

growth

<"1000
to

grow

and

step,

stable

only

stage,

microdomains

to

3-10%

flocculate

agglomerates.

<"50

aggregation

for

domains or

microdomains).

approximately

unstable

polymer chains

identified species:

continue

at

of

the

brief

form the next

stable

domains

number

Microdomains

after

part icle

particles

product

microdomains.
time

of

The

domains

produce

primary

conversion

to

form

Agglomerates

the

the
third

increase

in

size with increasing conversion rate due to further growth

of the primary particles to produce an agglomerate diameter
of approximately 2-10
The

final

attributed to
high

~m.

irregular

appearance

of

the reduction in internal

conversion

rat es

leading

to

PVC

grains

is

grain pressure at

part ial

collapse

of

the

grain.
1.3.2 PVC NOMENCLATURE
The particulate nature of PVC has been identified or
observed by a large number of workers [71-82],
[82]

summarised

Symposium

<Lyon

discussion

Villeurbanne,

held
1976)

at
upon

terminology for the morphology of PVC.

preferred

nomenclature,

origin

of

an
the

Table

species

however Geil
International
preferential
1.5 lists the

and approximate

Page

25

Introduction/1

size range.
the

Allsopp [72]

proposed

has applied this classification to

outlined
polymerisation as
mechanism of

previously.

TABLE 1. 5
PVC NOMENCLATURE
Term

Grain

Agglomerate

At-wage

(/Jm)

(pm)

50-250

130

10-150

40

2-10

Primary
particle

0-6-0-8

Domain

0+0-2

Micro-doffitlin

(wilh r(1ert'ncn)

Visible constituents of frc:e flowing powders. made

up of more than J mODamer droplet.

Granule 1
Cellular grain J

Polymerised mODamer droplet.

Sub.granule 2
UnicelP
Aggregale 2
Cluster)
Macroglobule 4

Formed during early stage of polymerisation by

coalescence of primary particles (1-2 pm}. Grows
with conversion to size shown.
.

0-7

Grows from domain. Formed at low conversion

(less than 2 'YJ by coalescence of micro-domain:
grows with conversion to size shown.

Microgranule
Primary particle l
Granule l
Micro-globule 4

Primary particle nucleus. Contains about 10] microdomains. Only observed at low conversion (less
than 2 'YJ or after mechanical working. Term only
used to describe 01 pm species; becomes primary
particle as soon as growth starts.

Primary nucleus 2
Granule l

Smallest species so far identified. Aggregate of

polymer chains-probably about 50 in number.

Basic particle l
Particle]

0-2
(200nm)
(2000 A)

0-01-0-02

previous lamin%gy

Origin ur dC'saiptiull

Approximate si=e

Range

~0-02

(20nm)
(200 A)

NOles
I. The domain is not a feature of PVC morphology in high conversion polymer samples since a growth of this species with conversion obliterates
all memory of it. It may only be 'regenerated' and observed after subsequent processing.
2. As soon as formation of the domain is complete and growth is registered it is preferable to call it a primary particle. Therefore. the term domain
is often ignored in favour of primary particle even at the point of morphogenesis of the 02 pm primaries at low conversion.
3. The reason for a separate identity for the domain is that it may be shown in future to contain an atypical morphological or molecular feature,
e.g. higher level of crystallinity.
.

The application

of

standard

terms

to describe

the

particulate structure observed by many investigators [70,7273,76,78,80]

provides a

has

lead to an overall

universal

approach to

the

idealised model

which
understanding of PVC

particulate structure.
1.3.3 MOLECULAR STRUCTURE OF PVC
The previous section considered the particulate
nature of PVC and a general idealistic model of PVC grain
morphology can be presented <figure 1.4).

Page

26

Introduction/1

FIGURE 1. 4-

PVC grain morphology

'O}lm
PRIMARY PARTICLE

-.......
........ ySUB-GRAIN SOl""

lat high conversion)

200 A
MICRO DOMAIN

AGGLOMERATE

"""

51""

"---~A-"-..A

2000 ;.
O'2pm DOMAIN
(PRIMARY PARTICLE
at 2'- conversion)

PRIMARY PARTICLE
l ... m (1000 nml

" MICROOOMAINS
200 A {lO nm)

However the molecular structure of PVC has also been

the subject of much debate and thus far a general agreement
has not been reached.
Vinyl pOlymers have a general repeat unit -CH 2 -CHX-,
where the substituent

X is a

chlorine atom in the case of

PVC.

of

substituent

consequence

configuration isomers can occur,

that

is

group

whereby the substituent can

be placed in a number of distinct positions with respect to

the backbone.
to

The dominat ion of a

large

degree
if

polymerisat ion,
favoured
Figure

then
1.5

upon
a

energetic

particular

stereoregular

depicts

part icular isomer depends

the

considerations

substituent
polymer

three

will

tactic

during

placement
be

is

produced.

placements

of

the

while

the

substituent chlorine atom for PVC [83J.

The
final

first

tactic
with

[60, 84.-85J.
by

the

placements

techniques
a

are

regular,

Commercial

irregular.

generally

syndiotactic

value

favour
of

syndiotactic

approximately

55%

The degree of syndiotacticity can be increased

use

of

effective

polymerisation temperatures.
dependant

is

placement

polymerisation
polymers

two

upon

tacticity,

chain

transfer

agents

or

low

The regularity of a polymer is

degree

of

branching

and

other

Page

27

Introduction! 1

structural defects such as head to head/tail to tail monomer

addition,

unsaturation,

peroxide/hydroperoxide groups etc.

FIGURE 1. 5

Tactic placements for PVC

Cl

Cl

-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2I

Cl

Cl

Syndiotactic (rrr)
-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2I

Cl

Cl

Cl

Cl

Isotactic

(mInm)

Cl

Cl
I

-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2I

Cl

Cl

Heterotactic (rmr)
1.3.3.1 PVC CRYSTALLINITY

The crystalline nature of PVC has been studied by a

wide

range

of

diffraction
density,

(WAXS/SAXS),

infra-red

scat t ering
that

(SANS).

crystallinity

syndiot act ic
of

and
The
is

sequences

syndiotacticity

[60,88].

techniques

including wide/small angle

differential
recently

small

implicat ions
related

to

of
the

[60, 67, 86-87]

produces

thermal

more

angle

analysis,
neutron

these st udies
presence

and

X-ray

of

are

short

increasing levels

crystalline

pOlymer

It is also suggested that the microdomains contain

cryst alline

nucleus

surrounded

by

const rained

amorphous

material [89-90].

Page

28

Introduction/l

The
Natta

and

crystalline

Corradini

nucleus

(91l,

cell,
the
like

5 1

planar

crystals

grow

structures

may

lamellae.

Summers

structure

<figure

together

by

tie

syndiotactic.
in

a
be

that

the

chains,

Wenig

(90)

lamella-like manner,
present

(92)
1.6)

investigated
the

unit

due

to

considered
in

molecules

which

the

<figure

1. 7)

two

5 4

per

unit

concluded

that

although

rod-

deformation
platelet
crystals
to

by

cell

b- and c- dimensions of 10' 6,

A respectively and that

were

first

who proposed

was orthorhombic with a-,

and

was

of

the

crystal
are

produce a

held
three

dimensional network.

FIGURE 1. 6

PVC Blatelet crystal

FIGURE 1. 7

The microdomain structure of PVC

Page

29

Introduction/l

The

level

polymerised

PVC

of

is

crystallinity

usually

reported

in

to

although Straff

[77,67,86-87,88,93-94];

be
et

commercially
between

81 [95]

5-10%

did not

obtain a SAXS peak for UPVC and thus stated that PVC is not
crystalline.
SAXS

peak

Similarly Singleton et B1 [96]

for

plast icised

UPVC

PVC.

but

were

These

able

examples

to

did not obtain a

observe a

highlight

peak

the

for

inherent

problems in ascertaining the crystallographic nature of PVC,

since low levels of crystallinity are

involved and results

are often complicated by large background scatter,

di ffract ogram of
applied a

PVC.

Ballard et

SANS technique to plasticised PVC

di-n-octylphthalate).
is

A recent st udy ,

more

of

WAXS

81 [97],

(10% deutoero-

The investigators suggest that i) SANS

sensitive

crystallinity

e. g.

technique

PVC

is

than

WAXS/SAXS,

ii)

the

and

iii)

the

apprOXimately

15%

technique could assess the melting characteristics of PVC.

There
suggest

that

development
chain

is

considerable

annealing

of a

or

evidence

drawing

of

[84,98-100]

PVC

results

in

to
the

two-dimensional order perpendicular to the

(nematic mesomorphic

phase).

One of

the observations

of this secondary crystallinity is a broad melting endotherm

which may be related to, a network of imperfect crystallites
[84] .

1.4 FUSION OF PVC

The fusion
and,

no

doubt,

research.
PVC

is

however

attained.
to

continue

to

be

the

source of

critically

dependent

further

the 'quality'

upon

the

level

the precise fusion mechanism is not

of
of

easily

Since the pioneering work of Berens and Folt [69],

workers

fUSion

will

PVC has been studied by many workers

is generally appreCiated that

products

fusion,
many

It

of

have

the

attempted

observed

to

relate

particulate

the

nature

development
of

PVC.

of
The

investigative tools include optical and electron microscopy,

torque

rheometry,

capillary rheometry,

differential

thermal

analysis and property measurements.

Page

30

Introduction! 1

1. 4. 1 FUSION MECHANISMS

Sieglaff

[771

and

separate publications

Krzewki

and

proposed that

Collins

fusion

[811

of PVC

in

could be

achieved by three different routes:

a)

PVC

grains

are

broken

down

into

particles which are then compacted.

sub-micron

These structures

interdiffuse to produce a fused material.

b)

Breakdown of

the grains produces

micro-particles

which are compacted and undergo internal fusion.

The

microparticles interdiffuse to complete fusion.

c)

The

grains

st ruct ures,
fusion

do

t he

not

rupture

grains

occurs.

Again

are

to

yield

compact ed

these

units

sub-grain

and

int ernal

interdiffuse

to

the

of

obtain a fused network.

These
mechanisms

general

rout es

observed

[67,75,79, 1011,

by

however

mechanisms.

number

experimental
for

Sieglaff

for

large

mechanisms were detailed

fusion

account

of

workers

evidence and

specific

better

[771

commercial processing techniques,

maj ori t y

understanding of

also

postulated

that

the
in

a' combination of all three

routes may be appropriate.

An
inner
in

st ruct ure

were
the

early st udy

methyl

of

between

ultramicrotomed

170C)
while
micron

microscope.

the
at

inner

mat erial.
processing

a1

The

observed

At

processing

low

[731

observed

the

which were embedded

ext rudat e

range

section

of

via

specimens

160-210C
a

seems

<160-

unaffected,

approximately

fim primary particle)

and

transmission

temperatures

structure

temperatures of

<"'1

et

specimens

particulate

extrudate

particles

Hat t ori

ext rudate

methacrylat e

obtained

electron

by

180'C the

are loosened and

form a continuous network .

A further increase in processing

temperature

to

0190'C)

leads

breakdown

of

this

network

Page

31

lntroductionll

and

the

Network

inclusion

of

fine

disintegration

threads

described

roll

milling.

by Vidyikina
A

fibrils

is complete at

morphology transitions were noted.

also

or

higher

A).

300

and no further

A fibrillar structure was

[102J

B1

et

200'C

(ca.

during a

screw speed resul t ed

in an

study of
increase

in processing temperature before the various phase changes

occurred.
that
by

t he

same

st udy,

Hat t ori

application

of

temperatures

heat
3

<ie.

alone

but

minutes

B1

et

this particle breakdown to fibrils

the

high

In

was

was

also

observed

still

possible

only

220C).

induced
Thus

at

they

concluded a fusion mechanism involving particle breakdown to

form fibrils and that a

shear regime had an additive effect

to processing temperature.
Faulkner
postulate
various

[103J,

[80J

applied

particle

features
figure

of

1. 8,

Brabender

breakdown
a

were

plasticorder~

mechanism

typical

for

PVC,

temperature-torque

associated

with

specific

to
the

trace

particle

transitions.

FIGURE 1. 8

Brabender temperature-torque trace

30

20

I!

100

120

140

160

180

200

220

240

Temperoture 'C

Page

32

Introduction/1

Faulkner conducted an extensive study by collecting

small
and

samples

at

assessing

the

transmission
following
figure

intervals
particle

inferences
peak

to

(a)

the

hierarchy

microscopy.

electron

1. 8;

throughout

the

was

rheometer

trace

scanning

and

attributed

the

via
He

characteristic

reported

to

peaks

shown

contain a

in

compacted

mixture of whole grains and ruptured grains.

At peak (b) the

micrographs

material

reveal

deformed

fibrillated

still retains a primary particle nature.

peak

<c)

and

t he

primary

mat erial

has

undergone

particles

are

not

structure might

be

present.

processing history
determining
[104]

its

Brabender

the

molecular

deformat ion

although

author

suggested

trace.

previous

study,

and

Also

the

by re-

Rabinovitch

rheometer

however

domain

that

compound could be assessed

temperature-torque

conditions

At the final torque

evident,

temperature-torque

conducted

confirmed

of

The

which

the

study

and

effect

of

upon

the

polymer .characteristics

position of the aforementioned peaks was emphasised.

An

overview

of

fusion

publications [80,105-106]
he
two

inferred

that

components.

the

based

upon

various

was presented by Portingell [107];

fusion

Firstly

progressive breakdown of

mechanism cal'l: 'be divided

supra-mole'cular component,
particulate

st,ructur~

into
where

occurs

from

stage III particles to a mixture of stage' 11 and III and of

stage 11 and I
stage

I's

primary

fe~

to a true melt with possibly a

<Stage

Ill,

particles

11

and

and

particles

domains

refer

that

even

in

the

to grains,

respectively).;,. The,' second

component involves a parallel molecular activity;

acknowledged

surviving

predominantly

here it is

particle

flow,

region there is a level of molecular deformation across the

surface

layer

of

the

particles

[105].

Thus

degree

of

interdiffusion and entanglement of chain segments across the

particle

boundaries

invokes

processing temperat ure

molecular

chain

boundaries and

increases

mobility

part icle breakdown is

to

level

fusion.

As

the

the cryst allit es

mel t

and

increases,
permit

of
while

molecular

promote chain entanglement.

the

effect

di ffusion

of

across

The greater the

Page

33

'

Introduction/!

particle

breakdown

and

processing

temperature

then

greater the molecular mobility and thus entanglement

degradation limit).
new network
upon

the

the

(upto a

On cooling the crystallites reform and a

is obtained.
degree

Thus

the

of

fusion

breakdown

particle

of

level

depends
with

coupled

Benjamin (108)

crystalline melting and molecular di f fusion.

suggested a similar scheme.

A pictorial model was presented by Summers [92,109110)

which involves a crystal structure,

1. 6,

and the assumption that

flow

units.

170C)

A low

yields

interaction,

the

primary particles are the main

processing

primary

particle

particles

as shown in figure

temperature
flow

with

(typically
poor

are being held

160-

particulate

together

by

the

three dimensional network structure shown in figure 1.9.

FIGURE 1. 9

Primary particles in a low temperature melt

At a higher processing temperature 0177C),

the

crystallites

particles

is

structure

is

melt

increased
not

thus

<figure

completely

recrystallisation takes
together

and

interaction
1. 10).

destroyed

The
and

between

crystallites cause a fibrillation

the

particulate
upon

place which can link the

by newly formed crystallites

some of

cooling
particles

(figure 1. 11>.

These

effect when the material

Page

34

Introduction/l

is acetone sheared between two glass plates (110J.

Summers

could therefore account for the anomalous flow behaviour of

PVC as described by Collins and Metzger (111J 1. e.

the two

activation energies for PVC flow behaviour could be assigned

to the different
The

low

interactions shown in figure 1. 9 and 1. 10.

activation

t emperat ure

energy

f low behaviour

discrete and a higher

value

when

is

the

due

primary

to

low

melt

part icles

are

flow activation energy is associated

with increased interparticle diffusion.

FIGURE 1. 10

Primary particles in a higher temperature melt

FIGURE 1. 11

Primary particles after cooling and recrystallisation

Page

35

Introduction/l

Lastly

Allsopp

[112J

conducted

which assessed the effect of different

upon the particulate nature of PVC.
breakdown

was

extrusion

not

and

the

normal

an

extensive

study

processing equipment

He revealed that

mechanism

in

for

previous

publ1cat ions

studies

generally

accounted

the

grain

case

of
by

\I

suggesting

that

PVC

preparation via high shear equipment

plasticorder~

and

laboratory

involved

sample

such as the Brabender

mixers.

Banbury~

Thus

two

'I

fusion routes were identified <figure 1. 12):

a) Comminut ion mechanismj

the grains are broken down

into finer structures such as primary particles.

b)

'CDFE'

mechanisffij

the less aggreSSive conditions

do not induce grain attrition but instead the grains

are

compacted,

appreciable
due

to a

densified,

shear

forces

are

high directional

fused

and

present,

and

shear stress

before
finally

the grains

are elongat ed.

FIGURE 1. 12

Fusion 'mechanisms during processing

@j:I@

~-

KEY:

res-.
~ "'""'os

Porosity

)(

'CDFE'
MECHANISM

~o
0

"
0~~()od

C? .... c::::>
1]"" G
D

~
0 ' .p
t

{{p.

Qj,.
I

1aoVm GRAINS

COMMINUTION
MECHANISM

Denotes
Additives

---+

o' ID
I

...

FINAL MELT

.. ...

+--

1oF

DIRECTION
SHEAR

Page

36

Introduction/l

This
number

of

laboratory

proposal

has

workers

[ 113-116].

and

received

processing

recent

support

Allsopp

ranked

equipment

in

an

from

common

attempt

to

predetermine the possible route of fusion (figure 1. 13).

FIGURE 1. 13

Comminution/densification mechanisms of fusion

,
I

,I , n

>

~
x

>

~
~

~
~

0
c

--

I ~,

x
w

"0'

,;I

~I

0'

El

a
z

.,
~'

\ "in
Z

si

OENSIFtCATION 100%

COMMINUTION

Gilbert

c
"
1 ~l
~i
< i
w,
w
c

100"-

"z

2z
"c Z~
51

I,~I~i

>

~,

u'

~I
w

I~I

i
I
.1

et

a1

[114]

confirmed

CDFE

route

for

extrusion and further extended the mechanism by postulating

a

primary

crystalline

melting

mechanism

which

on

recrystallisation leads to a network formation consisting of

secondary crystallites.
1.4.2 ASSESSMENT OF FUSION

It
and

is

subsequent

evident
fusion

upon the type of

Thus

in order

relate

fusion

assessment

is

that

the

complex particle

mechanism

are

processing equipment

to evaluate these
levels
required.

to

critically

hierarchy
dependant

and conditions used,

processing effects and to

properties

There are

method

number

of

fusion

of established

'

techniques available which have been extensively reviewed in

Page

37

Introduction/l

the

literature

this

[107,114, 117l,

section to discuss,

is

it

therefore intended

in detail,

in

those techniques which

are relevant to this project.

1. 4. 2. 1 MICROSCOPY

Particle breakdown can be qualitatively evaluated by

microscopy techniques.
nature

of

particles,
much

and

the

units.

The

publications

of

possible

possible

breakdown

previous

which

have

electron

microscopes

fusion

mechanisms

However as a

section,

used
to

the

is

sample
which

cited

resolution

conclusions

upon

[73,77,80,81,108, 116, 118l.

technique for quantifying the level of fusion,

not

easily

preparation
is

primary

1. 4. I,

high

yield

these instruments are problematic since:

level

into

while more powerful electron microscopes can view

smaller

various
power

PVC

Light microscopy can detect the grain

deemed

obtained,

is

value for fusion

careful

essential,

and

small

to be representative

of

reproducible

area

is

viewed

the speCimen,

and

lastly the equipment is not recommended as a quality control

test because of high capital cost and operator expertise.
is

therefore

common

to

use

these

microscopes

to

It

confirm

observations from other fusion tests.

Other microscopy techniques can distinguish between
fUSion

levels,

contrast

(DIC)

[114, 119l;

for
and

these

example,

use

of

techniques

differential
Jamin-Lebedeff

can

detect

interference
interferometer

refractive

index

fluctuations with thermal history.

1.4.2.2 SOLVENT TESTING
Solvent

tests are convenient

and are widely used as

a quick appraisal of fusion.

Solvent attack

methylene

chloride)

depends

upon

molecular

network;

areas where a

poorly

the

fused

(e. g.

extent

of

specimen

acetone or
a

will

cohesive
contain

fusion network exists and also particles that

are not restrained by the molecular network.

The swelling of

Page

38

Introduction/l

these

particles

could

lead

to

partial

thus severe visual attack (1071.

visualised
'free'

as

network

of

disintegration

and

A well fused product can be

high

integrity

and

thus

particles which could lead to gross solvent

few

attack.

Poorly fused articles can show quite dramatic failure during

these

tests,

but

discrimination

between quite highly

specimens is more subjective (1141.

have

been

Solvent
of

introduced

for

this

fused

International standards

type

of

test

(120-1211.

uptake has also been related to the thermal history

PVC

(113,116,1221

although

the

application

of

this

phenomenon has yet to be fully evaluated.

Summers

B1 (109-1101 measured the acetone uptake

et

in PVC and concluded that

enters

the

destroyed

amorphous

and

thus

shearing of

swollen

microscopy,

could

acetone at

phase,

the

continue
acetone

to

crystal lites

act

samples,

differentiate

room temperature only

as

are

not

crosslinks.

The

as

viewed

by

optical

between

levels

of

fusion.

Poorly fused products diSintegrated into discrete particles,

while more highly fused specimens lead to a
by fibrils.

This solvent

network

linked

again provides a qualitative

test

result and the discriminating power between moderately fused

specimens is limiting.
1.4.2.3 TORQUE RHEOMETRY
A

used

to

temperature-programmable
assess

Faulkner (801

the

processing history

from

processed
a

dry

illustrates

rheometer

of

PVC

can

be

compound,

developed a testing procedure which compared a

torque/temperature curve
the

torque

<figure 1.8)

composition
blend

the

of

the

with

that

same

relationship

fused compound using this test.

for a

ground crumb of

of

reference

composition.

between

well

Figure
and

curve
1. 14

poorly

The results can be difficult

to interpret and again provide a comparative analysis.

Page

39

Introduction/l

FI GURE 1. 14-

Temperature programmed Brabender curves

DRY BLEND

UNDER FUSED ?ELLET

60

EX TRUDATE
40

E
z

.30
~

20

10

100

120

140
160
180
Temperature C

200

220

240

1. 4. 2. 4 CAPILLARY RHEOMETRY
Gonze [103] and Lamberty [123) published a method of
determining

the

level

composition.

The

rheological

pressure

loss

in

of

short

130-150'C) .

(typically

[81,108,124-126]

can

of

fusion
method

measures

capillary

The

provide

at

widely
a

the

low

particulate

the

corresponding

changes

material;

melt

b)

network interaction;
indicative

of

me1t

structure
in

the

elasticity

technique

reported

measurable
can

be

elastic

fusion
a)

value
changes

assessed

behaviour

increases

elastic

temperatures

providing the following assumptions apply [77]:

in

PVC

processed

with

of

by
the

increasing

c) capillary entrance pressure loss is

elasticity.

The

technique measures

pressure necessary to extrude the material

capillary (small length/diameter ratio),

the

through a short

6P is defined as:

4L
6P = or (2n + S .. ) + or _

(1. 1)

Where

6P
or
n

S ..
L

Extrusion pressure
Shear stress at capillary wall
Viscous loss term
Recoverable ~hear strain
Capillary length
Capillary diameter
Page

40

Introduction/l

The

first

term of

the above

the entrance pressure loss,

viscous behaviour,
6P

1. e.

equation accounts

and the second term represents

6P can be rewritten;

6P ENT + 6P vxsc

Where

for

(1. 2)

Pressure loss due to entrance effects

Viscous pressure loss
Lamberty demonstrated that if a low L/R capillary is

used

(' Zero-length'

term,
loss

capillary)

The

predominates.
can

components.

be

further

Han [127]

then

divided

the

total

into

has shown that

entrance

pressure

entrance

pressure

viscous

and

elastic

the viscous component

is only 10% of the total pressure drop and so for practical

purposes,

ent rance

pressure

losses

are

measure

of

mel t

elasticity.

plot

of

capillary

temperature can produce a'S'

pressure

versus

processing

shaped curve (figure 1. 15).

FIGURE 1. 15

Capillary fusion curve [103J

140

150

160

170

Stoc;" TemperatureC

180

190

200

Page

41

Introduction/l

The initial decrease in entry pressure is related to

grain

breakdown,

molecular

followed

network

by

format ion.

the

The

gradual

product ion

increase
of

in

st andard

reference curve then enables further results to be quoted as

a percentage [108];

.-

Gelation level

The
the

main

t est

PSAMPLE

P MAX

provides

limitation

reference

seems

for

curve

PM'IN

x 100

<1.3)

P"'IN

quantifiable

result,

to

production

every

be

the

and

composition

al though
of

processing

technique.
1.4.2.5 THERMAL ANALYSIS
Thermal
scanning
thermal

analysis

calorimet ry,
t ransi t ions

techniques,

can
such

provide
as:

analysis

of

PVC

has

trace than might

useful

and

been shown to

differential

information

upon

transition temperature

glass

crystalline melting point

(TG),

i. e.

so

forth.

produce

The

thermal

more

complex

be expected from an essentially amorphous

material [69,94,128-129].

Gilbert and Vyvoda [128J

accounted

for the complex pattern and suggested a relationship between

observed

endothermal

1. 16 depicts

(value

peaks

and

processing

history.

Figure

the effect of compression moulding temperature

quoted

on

right-hand

side

of

trace)

upon

DSC

thermograms for the processed samples.

A DSC trace of virgin PVC and dry blends of limited
heat

hist ory

melting
about

show a

endotherm
155

processed

to
then

TG

for

195"C.
TG

of

approximat ely 80" C and

primary

crystallinity

If

dry

remains

the

blend

unchanged,

is

broad

ranging

from

subsequently

however

the

broad

endothermic peak is replaced by two endothermic peaks ('A'

'B')

as

shown

t emperat ure

in

the

endotherm

above
' B'

figure.
represents

The

sharper

the

&

higher

mel t ing

crystallites of various sizes and degrees of perfection.

increase in processing temperature leads to the melting of

of
An

Introduction/1

FIGURE 1. 16
DSC thermograms of processed PVC

Moulding

iemperc1U"'eS

,60-C

,70C
0
x
w

1
I,
~

160C

0
0

192"C

2OOC

2,OC

220C

200

050

'00

(Temperature C)

lower

temperature crystallites and. the annealing of higher

temperature crystallites.
at

higher

to

temperature
produces a

higher

exceeds

appears,

peak

attributed

crystallites
against
produced
capillary

decreases in size while

second

increase

observed

If

the

processing

endotherm

peak,

processing

in

A',

temperature

larger and broader peak range from approximately

the

If

endotherm,

temperature.

"'160C

further

110C to

order.

t h e ' B'

processing temperatures,

shifting

is

Thus

onset
to

the

to

energy

'B'

the

produce

processing
which

of

of

recrystallisation
secondary
this

temperature,

resembles

endotherm.

rheometry studies.

This endothermic
of

the

crystallites

endotherm

reference

'S'

of

(6H A >

is

shaped

primary
plotted

curve

curve obtained

Therefore Gilbert

et

lower

al

is
from

[128]

proposed a potential method for determining the fusion level

Page

43

Int roductionll

of processed PVC.

It was also concluded that

temperature corresponds to the mass

the'S'

onset

processing temperature

and is analogous to the effect of annealing temperature upon

the position of the'S'

endothermic peak [94,129).

The above

method has been used to assess samples produced via a number

of

processing techniques and the results suggest

technique

differentiates

between

equipment

that

the

and

may

types

elucidate the fusion mechanism involved.

A recent study by Terselius et 81 [116) has provided
support for the application of differential thermal analysis
to measure fusion levels of processed PVC samples.

The study

produced samples by roll milling and extrusion and assessed

t he

process

rheometry

of

fusion

and

via

thermal

analysis,

elect ron

transmission

capill ary

microscopy.

correlation of breakdown of primary particles and formation

of secondary cooling crystallites was observed, the onset of
breakdown

occurs

<166-174C)

as

at

lower

opposed

temperature

to

for

extrusion

roll

milling

<190-194C).

The

findings provided further evidence to support the concept of

a thermomechanical mechanism of fusion.
Patel

et

81

(130)

produced a

'master curve'

which

related capillary rheometer pressures to endothermic energy

(6H,,)

values.

The

master

curve

types of processing equipment

measure

of

fusion

can

be

combined

and it

quoted

results

of

three

was suggested that

for

an

unknown

sample

irrespective of its thermomechanical history.

Covas
progression
ext ruders.

[1311
of

The

used

fusion

thermal
within

technique was

study since only a

analysis
single

to measure

and

particularly

provided

for

this

small sample is needed and information

upon primary and secondary crystallinity is

results

screw

twin

useful

the

complementary

evidence

avail abl e.
to

support

The
an

extended version of the fusion mechanism proposed by Allsopp

[112],
Although thermal analysis is a relatively new method
for

the assessment

small

test

of

specimen,

fusion
less

the suggested
dependence

advantages are:

upon

composition,

Page

44.

Introduction/l

'internal'

estimate

of

processing

gradients can be investigated.

present

problems

when

temperature

The small

representative

and

fusion

test specimen can

value

is

required

relationship

between

from a bulk product.

1.4.2.6 MISCELLANEOUS TECHNIQUES

Physical
physical

properties: -

properties

and

the

The
level

of

established and the literature will

section,

1. 5. 3.

Physical

assessing fusion
test

specimens

may

is

be

testing

required

and

is

far

be reviewed in a

as

difficult

fusion

an

indirect

since a

the

test

from
later

method

of

large number

of

shape

may

not

be

easily obtained from the physical form of the product.

Melt

flow

out modified MFI

index

(MFI): -

KrUger

and

Menges

carried

tests upon PVC samples at different stages

of processing and concluded that the MFI is a measure of the

ratio of

fused

quantitative

to non-fused primary particles.

measure

of

processing

can

easily be

with a simple and readily available MFI unit

Extrudate

appearance: -

An

Therefore a

increase

obtained

r 132].
in fusion

level

leads to an increase in melt elasticity which can result in

a decrease in the quality of the extrudate appearance due to
'melt

fracture'

appearance
'zero

r 107,124,133-134].

under

length'

extreme

die,

shear

can provide a

Therefore

the

conditions,

for

extrudate
example;

qualitative assessment

of

fusion.
Viscoelastic

r 134]
to

methods:-

Elongational

and dynamic oscillatory testing

observe

response:
difficult

the

effect

however
to

the

interpret

of

fusion

techniques
so do

not

r 106]

level
are
lend

flow

rheology

have been used

upon

viscoelastic

sophisticated
themselves. to

and
quick

and easy measurements.

Page

45

Introduction/l

1.5 PROCESSING AND PROPERTIES OF UPVC

1. 5. 1 DRY BLENDING

Powder

feedstock

is

commonly

speed blending unit consisting of a

linked to a larger,

prepared

via

high

high speed heater mixer

jacketed cooler mixer.

The additives are

distributed in the heater mixer by a centrifugal action of a

high

speed

forces
until

impellor

inv'oke a
a

blend

to form a

significant

temperature

fluid

vortex.

increase

of

about

High

in charge temperature
120C

is reached,

the premix is discharged to the cooling mixer.

consequences
additives,

of

high

speed

densification

mixing

of

PVC

and liquids/low melting point

shearing

include:

grains,

The possible
dispersion

grain

additives

when
of

comminution,

'adsorbed onto PVC

grains [136]. "

The continual widespread use of powder feedstock as
a precursor to UPVC processing <particularly pipe extrusion)
has

lead

to

number

[42,107,119,136-139].
of
as

flowing

dry

upon premix

adsorpt ion/absorpt ion,

behaviour,

blending

studies

The studies have monitored the effects

dry blending variables

addi t i ve

of

addi t i ve

characteristics such
bulk

dispersion

densi t y,

and

free

processing

stability.
Miadonye
variables,
to

the

,[ 139]

correlated

such as rot or speed,

aforementioned

premix

high

speed

mixer

mix time and charge weight,

charact erist ics.

It

was

therefore proposed that an optimum operating window could be

ascertained for a particular type of high speed mixer.
1.5.2 EXTRUSION OF UPVC
1.5.2.1 SINGLE VERSUS TWIN SCREW EXTRUDERS
Single
process

UPVC;

principles.

and

twin

however

screw

the

extruders

ext ruders

are

operat e

both
via

used

to

di fferent

The single screw generates high shear and high

Page

46

Introduction/1

temperatures
efficiency
heating,

with

of

single

backflow

within

the

amount

screw

low shear,

residence

extrusion

time.

depends

screw

upon

mixing

Alternatively,

design.

mechanism

of

possible

and,

screw

ext ruder is a
mixing

minimum

the

The
shear

sections

twin

screw

high volume posi t i 'le pump and its

depends

upon

rolling,

kneading

action

with heat input via induction [140].

Twin screw ext ruders
for

the

extrusion of

UPVC

dominat e

dry

t he market

blends,

in Europe

while single screws

are still widely used in the U.S.A.

A conical
ext ruder

was

counter

used

in

rotating intermeshing twin screw

this

proj ect

and

therefore

further

discussion bears this configuration in mind.

1.5.2.2 TWIN SCREW EXTRUDERS
These
conveying
forward

extruders

are

characteristics,

motion

by

the

designed

the

to

material

action

of

have

being forced

intermeshing

produce discrete chambers of material

positive

(' C'

in

screws

a
to

shaped packets).

The output from such machines are not significantly affected

by the extruder temperature profile [141-142],
increases

linearly

with

increasing

screw

Also the characteristics of

the powder

to

rate

influence

138];

the

extrusion

of

while output

speed

[142-143],

feedstock
twin

are known

screw [36, 137-

high bulk density results in increased mass output.

Over-feeding can result in excessive screw torque and 'melt'

pressures and thus feeding mechanisms are recommended [142144] .
The
extruders

mel t ing

has

been

mechanism
reported

[112,131,141,145-146].
majority
heating
place,
(melting
molten

of
of

the

number

of

length

powder,

while

rapidly,

during

the

is

in

in

the

film

UPVC

screw

twin

publications

A generalised view suggests that

barrel

complete

of

over

the

last

several

produced

at

involves
melting
section
turns,

the

compact ion
process
of

the

possibly

barrel

wall

the
and

takes
screws

one).
which

Page

'A
is

47

Introduction! 1

introduced to a compacted solid bed of powder,

violent

tumbling action

produced.
heat

melt

pool

of

distorted shape

Further melting quickly develops,

transfer,

Processing
upon

the

at

and due to a

due to shear and

the solid bed/melted material

conditions

are

reported

melting mechanism [131l

to

is

have

although

interface.

little

the

effect

position

of

melt formation may alter [139,141],

1.5.3 INTERRELATION BETWEEN PROCESSING. FUSION AND PROPERTIES
There

are

few

reported

studies

which

attempt

to

correlate the relationships between the processing of a UPVC

composition,

measured

fusion

value,

and

the consequences

of a processing history upon physical properties.

Benjamin
controlled
fusion

[108)

conditions

level

was

rheometer

method

reference

curve

and
The

and
that

resisted

attack

were affected.
const ant
while

the

series

by

four
a

of

gelation

'zero

results

by

milling

solvent

attack,

water

samples
the

pressure.

with

poorly

tensile,
high

fused

under

levels.

length'

pressure
roll

pipes

capillary

related

to

(32,44,68,90%

pipes were subjected to a

while

wide range

impact,

Solvent

levels
pipes

testing

of

(32

crack
fusion

and

44%)

Tensile results (stress at yield) suggested a

maximum value

ductility

strain at break,
opt imum

the

hydrostatic

revealed

provide

prepared

tests including:

formation

to

determined

gelation levels).
of

extruded

val ue

at

tests,

higher

such

as

gelat ion

tensile

level

impact,

resistance to crack formation,

at

approximat ely

44-68%

of

68%,

tensile

produced an

gel at ion

level.

Bejamin concluded that a gelation level of approximately 6070%

would

particular
confirmed

provide

the

pipe

and

his

pipe extrusion
8,1

[67)

also

earlier

best

composition
hypothesis

(figure 1. 17).
observed

balance

of

properties

chosen.

based

upon

Berndtsen [147)

maximum in

ultimate

for

The

the

results

experience

in

and Menges et
strain

at

an

Page

48

appropriate processing lev~l.

Introduction/1

FIGURE 1. 17

Pipe properties versus gelation level

Stiffness

Ductile
brittle
behaviour

;;
>
o

Fusion

Marshall
gelat ion

levels

et

81

than

range from 170-227C.

Level

[113J

produced

Benj amin

with

die

wider
set

range

of

t emperat ure

The strip extrudates were assessed for

fusion level by a range of techniques;

differential

thermal analysis

(DTA)

capillary rheometry.

and solvent absorption.

Capillary rheometry and DTA results provided broad agreement

with a maximum in test value at approximately 215C.

Solvent

absorption was also shown to produce a standard fusion curve

and

thus was established as a

quantitative method

assessment of fusion in a processed sample.

also

studied

pressure

and

values

temperatures.

An

its
was

effect
negligible

instrumented

used to assess Izod impact

after removal

upon
pendulum

the

Screw speed was

capillary

except

for

at
impact

rheometer

low

profile

tester

was

specimens of the extruded strip

of the extrudate surface.

The impact

results

Page

49

Introduction/l

generally

support

ductility

at

strength

Benjamin's

mid

at

fusion

levels,

approximately

explanation for

1. e.

fusion

60%

this impact

of

short

maximum

in

hypothesis

level.

term
impact

possible

behaviour was discussed as the

processing condition whereby grain structure is destroyed in

favour of a inhomogeneous 'melt'.
Summers
considered

et

the

in

81

effect

upon

series

of

papers [109,148-149)

impact

performance by

plotting

dropped dart impact strength versus extrusion temperature.

distinct

peak

at

an

was obtained for

approximate melt
low output

temperature

rate,

of

190C

while a higher output

rate resulted in lower overall impact

strength with a

peak

at

The

were

higher

assessed

temperature

for

4. 2. 2)

fusion

(aI95C).

level

by

the

extrudates

acetone

test

confirmed

steady

increasing

processing

and

the

progression

in

fusion

temperature.

An explanation for these results was postulated

(1.

micrographs

shearing

level

with

as a consequence of melt fracture or

leading

to

poor

surface

finish

'lubrication'

and

thus

failure,

poor

impact

retention.

A higher processing temperature tends to promote

this

phenomenon

melt

similarly,
of

melt

due

to

higher

melt

elasticity

and,

a high extrusion rate would induce the likelihood

fracture

impact properties.

and

consequently

overall

decrease

In order to confirm this postulation,

in
the

product surface was press polished at the original extrusion

melt
did

and
not

then
yield

impact
a

tested.

maximum,

The

press poli shed specimens

instead

monotonic

'S'

shaped

curve which did not differentiate between extrusion rate was

observed.

Therefore

the

presence

concent rat ors produced during mel t

of

surface

stress

fract ure waS proposed as

the possible cause for reduced impact performance at higher

processing temperatures.
Terselius
[116,125,150-152)

pipe

series.

extrusion

et

81

published

number

of

papers

which discussed the physical properties of

The

pipe series

temperatures

ranging

corresponding fusion range of

was

extruded at

from

180-204C

10-7570

different
and

had

(measured by capillary

Page

50

Int roduction/ 1

rheometry).

A initial

study

[125]

maximum in a falling weight

3127),
and

illustrated
test

impact

however other impact tests,

tensile

impact,

produced

processing temperature
temperature
cited

region.

similar

modified grades
study [150]

until

The

(1.

monotonic

2.5.2:

conclusion

to

the

at
of

behaviour

notch
with

the upper
this
of

CPE and EVA modifiers).

work

impact
A later

reaffirmed a maximum during falling weight tests

for both instrumented and 850 type tests.

Also,

in

not

contrast

to

disappearance
polished.

ISO/DIS

increase

levelling off

initial

mechanism

(850 test:

such as double 'V'

distinct

Summers

of

It

et

maximum

was

[149J

81

when

concluded

did

the

that

samples
the

this study
observe
were

most

the

press

efficient

resistance to crack initiation is found in pipes of moderate

gelation level and that

this may be attributed to enhanced

post-yield deformation [60J.

Terselius
aforementioned

et

[151],

81

pipes

for

also,

tensile

evaluated

propert i es.

the
Yield

properties were concluded to be insensitive to a change in

gelation level,
suggested
Further

as

discriminating

post-yield

temperatures
PVC.

while post-yield deformation behaviour

tensile

revealed

for

tests

at

maximum at

gelation

levels.

different

the approximate

test
for

Te,

The yield results were explained by considering that a

'yield flow unit'

is a small entity which is unaffected by

the network formation.

were

test

was

related

to

an

Alternatively,

increase

in

cold

dependence on the development of a

entanglements
supported,

in

and

crystallites.

whole

or

part,

post-yield parameters
drawing and

thus

load bearing network of

These
by

tensile results

number

of

are

workers

[75, 105, 153J.

Covas
processing,

[131]

provides

recent

structure and properties.

correlation

between

This processing study

considered both a single and a twin screw extruders,

and a

mechanism of

'CDFE'

fusion

was

proposed by Allsopp [112J.

conjectured

based

upon the

Tensile properties were evaluated

by producing families of stress-strain curves with different

Page

51

Introduction/l

levels

gelation

temperatures.
unaffected

Yield

by

different

at

properties

fusion

level

and

maximum

break

value

again,

were

seen

test
to

attributed

between

be

to

however elongation at

were dependant

occurred

and

rates

were,

molecular relaxation mechanism,

and st ress at

test

break

upon gelat ion level.

fusion

levels

40-65%

A
as

observed by Benjamin [108].

This fusion range corresponds to

of

processing

tensile

temperature

properties

were

193-203'C

related

to

and

the

the

optimum

existence

of

network morphology with possible residual primary particles.

Testing above TG showed that increasing gelation level leads
to increased post-yield parameters which may be accounted by
a

continuing

development

performance

using

of

an

network

notched

coherence.

Izod

specimen

Impact
on

an

instrumented pendulum impact tester produced another maximum

when impact strength is plotted against gelation level.

The

occurrence of this broad peak was reported at a fusion range

of

40-50%,

similar

ductility tests;

to

results

obtained

for

post-yield

this result was related to the introduction

of a network with residual primary particles.

1.5.3.1 INTERACTION OF ADDITIVES
The
fillers
terms

interaction

and
of

impact

the

preparation,

of

modifiers,

complete
have

is

extrusion

extrusion and,

Lubricants

additives,

finally,

been

not

such

as

well

lubricants,

understood

process

i.e.

in

add i t ive

product performance.

thoroughly

investigated

by

laboratory tests such as the Brabenderm rheometer and roll

mill in order to evaluate the behaviour of the lubricant in
terms of lubricant
mixed

(1. 2. 3. 3).

external

type

effective melt

mechanism,
Processing

lubricants

1. e.

external

studies

delay

fusion

have

or internal or
suggested

while

viscosity [22,33-34,36,142,154],

that

lowering

the

however the

effect upon specific fusion levels and properties is rarely

discussed.

Marshall

et

a1 [113]

showed that a

higher level

of external lubricant produced a delay in fusion as measured

Page

52

Introductionll

by capillary rheometry studies,

in

delay

in

the delay in fusion resulted

attaining maximum impact

overall lowering of impact properties.

empirical

an

which

approach

introduction of lubricants.
studies

whereby

properties

and

an

Ditto [155J discussed

can

be

applied

to

the

The paper cites a series of case

extrusion

problems

are

overcome

by

the

addition of selective ingredients determined by experience.

The

overall

conclusion

suggests

that

the

balance

between

gelation promoters and gelation retarders can be adjusted to

solve melt quality problems.
The
fillers

introduction of

have

although

been

little

consequences

of

appreciable amounts of

evaluated

work

has

to

some

processing

conditions

(1.2.4.5)

extent

published

been

as

and/or

mineral
to

the

formulation

aspects.
Finally
impact

the

performance

effect
of

of

impact

processing
modified

conditions

grades

upon

have

been

assessed by a number of publications (1.2.5. 2).

1. 6 PROJECT AIMS
A considerable amount

in the

of work has been carried out

area of structure,

gener~l

processing and properties

of PVC compounds at the Institute of Polymer Technology,

this

project

aims

to

continue

this

theme,

albeit,

and
in

different direction.
The overall objective of this project is to provide
a

fuller

blending,
properties

understanding
formulat ion,
for

filled

these relationships can,

of

the

extrusion
UP VC

relat ionships
conditions

compositions.

hopefully,

and

between
product

knowledge

of

lead to a optimisation

of formulation aspects and processing conditions.

The literature review presented in this chapter has
identified a number of relevant conclusions:
a)

The mechanism of

fusion

for

a gi ven processing

machine is still not fully understood.

Page

53

Introduction/l

b) The level of fusion can have a significant effect

upon properties,

however poor agreement

is observed

bet ween workers.

c)

A number

established

of

experimental

which

can

techniques

provide

have

been

quantitative

assessment of fusion levels for processed PVC.

d)

Little

work

incorporation

is

published

upon

part icularly,

and,

the

filler

effect

of

processing filled grades upon fusion characteristics

and propert ies.
e)

Formulation

studies

have

attempted

not

to

overview a complete extrusion process from additive

incorporation to product testing.
f)

The

introduction

economically
process,

of

desirable

low

since

such as extrusion,

cost

additives

is

material

costs

accounts for

in

70% [156)

of the product costs.

The objectives of this project were therefore sub-divided as
follows:
i)

Incorporate

filler

into

appreciable
base

amounts

composition

of

and

mineral

monitor

any

effects upon processing parameters.

ii)

Process

processing

the

window

filled
in

within

broad

establish

fuller

grades

order

to

understanding of processing filled systems.

iii)

Evaluate

fusion,

the

filler

pipe

extrudate

dispersion,

for

surface

degree

appearance

of
and

relevant mechanical properties.

Iv)

Analyse

possible

relationships

between

properties and processing conditions with particular

reference to filler addition.
v)

Alter

addition

the
of

balance
specific

of

the

lubricant

lubricants

and

system

observe

by
the

effects upon processing and properties.

vi)

Consider

t he effect

of

int roduct ion of

impact

modifiers into unfilled and filled compositions.

Page

54-

Introduction/l

Figure

1.

18

presents

schematic

layout

of

the

project objectives and experimental techniques applied.

FIGURE 1. 18

Schematic layout of pro1ect

BASE COMPOSITION
+
FILLER

BASE COMPOSITION
+
FILLER
+
IMPACT MODIFIERS

BASE COMPOSITION
+
FILLER
+
DIFFERENT LUBRICANTS

I DRY BLENDING I
DRY BLEND CHARACTERISATION
Bulk density
Ash content

INSTRUMENTED TWIN SCREW EXTRUDER

Wide processing window;
Head temperature 165~200C

I PIPE

EXTRUDATES

I
MECHANICAL
PROPERTIES
-Tensile
-Instrumented
impact

I
SURFACE
APPEARANCE
-Visual
-SEM

I
FUSION
ASSESSMENT
-DTA
-Solvent
-Microscopy

I
FILLER
DISPERSION
-Microscopy
-SEM

I CONCLUSIONS I
RELATIONSHIPS BETWEEN BLENDING, FORMULATION,
EXTRUSION, FUSION AND PRODUCT PROPERTIES

Page

55

CHAPTER 710/0

EXPERIMENTAL PROCEDURE

2. 1 INTRODUCTION
The
interest:

project

i)

effect

properties and ii)

and

impact

Therefore

objectives
of

effect
were

upon

unfilled

prepared

two

main

processing,

of additives,

upon

modifiers,

samples

filler

defined

for

areas

fusion

of
and

such as lubricants
and

filled

subsequent

systems.

test ing

in

two stages.
2.2 PVC FORMULATION
A general purpose UPVC pipe formulation,
Cookson group plc,

supplied by

was used as the- basis for processing and

formulation studies (table 2.1).

TABLE 2. 1
PVC formulation
phr _
Polymer 'Corvic' S68/173

100

Filler Polcarb S

0=50

Stabiliser/lubricant system
Tribasic lead sulphate

20

Normal lead stearate

12

Calcium stearate

04

Primary lubricant:
t

These

Sasol H1

01-

Increments of 10 phr

compositions

were

used

exclusively

in

the

first stage of this project and were coded 0=5 inclusive.

Page

56

Experiment 01/2

2.2.1 PVC POLYMER

A

suspension

PVC

polymer,

rigid PVC twin screw extrusion,

particularly

suited

was produced by ICI plc.

to
The

technical specification for this grade can be listed in the

following table [157J:
TABLE 2. 2
Technical speci ficat ion for 'Corvic'

568/173

Grade

568/173

Viscosity No <ISO R174: 1974)

116

'K' Value (from Visc No)

68

Apparent density (g/ml)

056

Relative density

1'40

Particle size (%)

less than 250 flm

)99

less than

<
<

75 flm

Volat iles cont ent

(%)

5
O' 3

2.2.2 FILLER
A

stearate

coated

fine

carbonate

calcium

manufactured and supplied by E.C.C international was used as

a

representative

material

and

the

technical

specification

for this common filler can be listed as shown in table 2.3

[ 158J .
2.2.3 COMPOSITE STABILISERILUBRICANT SYSTEM
The main heat stabiliser in this system was tribasic
lead

sulphate

and

versatile

<TBL5:

3PbO. PbSO . H.O),

stabiliser,

commonly

which
used

is
in

powerful

twin

screw

extrusion.
Normal

lead

st earat e

(NL5t:

Pb (CH, (CH.)

16

COO.

is

generally used in conjunction with other lead salts and its

Page

57

Experimental/2

intended application is as a moderate external lubricant in

a well balanced lead stabilised system.
Calcium stearate

(CaSt:

Ca(CH 3 (CH 2 ),.C00 2

is

not

very effective as a heat stabiliser but is primarily used as

a 'internal'
The

lubricant.
last

component

of

this

combined

lubricant system was' a primary lubricant.

The lubricant for

this section of the study was Sasolwaks H1,

melting

point,
and

C SO H'02)

crystalline,
is

paraffin wax

predominantly

stabiliser/

which is a high
(average

classed

as

an

formula:
external

lubricant.
Detailed technical data on the above ingredients is
provided in Appendix A.
TABLE 2.3
Technical data forPolcarb S
85

Bright ness <ISO)

10

Particle size (%)

greater than 53 flm

001

(max)

greater than 10 flm

05

(max)

less than

860 3

2 flm

Surface area (m 2 g-' )

70

011 absorption (g/100g)

18
(max)

02

Moisture (%)
Chemical anal)lsis (%)

970

calcium carbonate
acidic residues

l' 8

stearate addition

l' 0

2.3 LUBRICANT/MODIFIER STUDY

The
effect

of

processing

second

stage

lubricants
and

of

study

impact

and

properties

this

of

an

investigated

modifiers

unfilled

and

upon
a

the
the

heavily

Page

56

Experimental/2

filled UPVC pipe.

The base composition,

shown in table 2. I,

was altered by the replacement of the primary lubricant with

a

series of other lubricants and,

impact

modifiers.

Table

2.4

secondly,

lists

the

the addition of

type

and

level

of

addi t i ves used.

TABLE 2.4
Description of lubricants and modifiers
Addit ive
reference

Description

phr

Lubricant
Sasol HI
Oletec 6009
Oletec 6009
Loxiol 012
Loxiol 015
PE 520
Pristerene 4903

High M. pt paraffin wax

Low M.pt paraffin wax
Low ~pt paraffin wax
Fatty acid ester of glycerine
Hydrogenated castor oil
Polyethylene wax
Stearic acid

O' 1
0'2
l' 0
l' 0
l' 0
0'2
l' 0

Modifier
Dow 3615
KM 323B

Chlorinated polyethylene
All-Acrylic

Sample
code

A
B
C
D
E

10' 0
100

Further information is provided in Appendix A.!, 2.

These additives were incorporated in the formulation
containing

30

phr

of

Polcarb

and

also

in

an

unfilled

composi t ion.
2.4 DRY BLENDING
Two high speed mixers were initially investigated:
8

litre

T. K. Fielder

study [168l

and

40

litre

Henschel.

previous

reported severe problems

of filler

segregation

during the dry blending of highly filled calcium carbonate

compositions,
necessary
premix.

in

All

int ensi ve

and
an
the

mixer

t emperat ure,

therefore

attempt
main

to attain a

blending

was

rotor

further

var.ied
speed

significant improvement

experimentation
representative

parameters
(1.

and

e.

bat ch

batch

for

was

filled

the

Fielder

weight,

jacket

sequence)

and

no

in filler distribution was obtained.

Page

59

Experimental/ 2

Thus the geometry and size of the mixer was not considered
appropriate to provide highly filled dry blends.
The operating conditions of the Henschel mixer were
also studied,

and the optimum conditions determined.

case an increase in batch weight

In this

<increase in fill

factor)

aided the production of highly filled compositions.

Figure

2.1

illustrates

blending process [107]:

the

basic

layout

of

dry

a batch weight of 18 kg was premixed

by hand and then placed in a pre-warmed heater mixer <45C),

the

heater

mixer

is

preset at 1500 rpn

where

the

started

and

the

impellor

speed

was

The dry ingredients were mixed to 120C,

to

the

stationary cooler mixer by a pneumatic discharge valve

<the

cooler

material

was

mixer was started after hot

minimise filler loss).

impellor
quickly

<low
of

the

30-40C.

55 secs for

batches

was

heating)

dryblend

discharged and reweighed.

:!:

dumped

material

was dumped to

The lower speed of the cooler mixer

frictional

cooled

temperature
mins

automatically

the

carefully

The

<3-5

and

the

mins)

cooled

cooled
to

premix

jacket

handling
was

then

The blending time varied between 9

blends and the cycle time between
controlled

at

mins

to

ensure

consistent heater mixer temperature before mixing <45-50C).

2.5 ASSESSMENT OF DRY BLENDS
2.5.1 ASH CONTENT
A small amount of dry blend <6
accurately weighed,
a

:!:

0'2 g) was sampled,

and then ashed in a furnace at 900C for

period of one hour.

The remaining ash was reweighed and

the percentage ash retained calculated,

this value was then

related to a calibration graph,

as shown in Appendix B,

yield

The

filler

content

<phr).

calibration

graph

to
was

prepared by ashing filled blends which had been accurately

weighed

and

hand

mixed.

An

average

of

three results

were

taken and an accuracy of better than 1 phr was achieved in

all cases.

Page

60

Experimental/2

FIGURE 2. 1
Dry blending process

BATCH WEIGHT
18KG
HEATER MIXER

DISCHARGE @ 120C

COOLER MIXER

DISCHARGE @ 30-40C

2.5.2 BULK (TAP) DENSITY

Approximately 100 g of the dry blend was poured into
a

tall

graduated

volumeter~

cylinder

and

vibrated

using

Tap-pack

at a rate of one drop per second until the volume

equilibrated.

The tap density was reported as the ratio of

powder weight

to final

and

an

accuracy

of

volume.

1 cm'

was

Two measurements were taken

noted,

equivalent

to

tap

density of 0'01-0'02 g/cm'.

2.6 TWIN SCREW EXTRUSION

A

Krauss

Maffei

KMDL-25

twin

screw

extruder

at

Cookson group central laboratories was used to produce pipe

specimens from the Henschel blends.

The intermeshing conical

counter-rotating

fully

machine

literature [131,142,154];

has

been

described

in

the

a standard head was fitted with an

Page

61

Ezperimental/2

approximate overall diameter of 32 mm and an annulus gap of

18 mm.

Table 2.5 lists the salient technical specifications

for this extruder [154J:

TABLE 2.5
Machine details of KMDL-25
Screw diameter

25

tip

50 mm

. feed

The

mm

Screw length

400 mm

Screw speed

5 05-50' 5 rpm

Screw torque (max)

5'19 Nm

Dc motor rat ing

O 265-2' 65 kW

Output capacity (max)

"'lS kg/hr

screw

configuration

is

shown

in

figure

2.2

[ 169J .

FIGURE 2.2
KMDL-25 Screw design

~'

A . '

'

..

.. - .

A-B

The laboratory extruder was instrumented to provide

information

at

all

stages

within

the

extrusion

process.

Figure 2.3 illustrates the KMDL-25 and the positions where

temperature and

pre~sure

probes are located [142J:

Page

62

Experimenta1l2

FIGURE 2.3
Instrumentation of KMDL-25

P3/TM2
P1

P2ITM1

HOPPER
FEED

TM3

Die

Barrel

Where:

Screw

TMl = Adaptor temperature

("C)

TM2 = Pipe Head temperature

("C)

TM3 = Screw temperature

("C)

Pl

= Metering zone pressure

(Bar)

P2

= Adaptor pressure

(Bar)

P3

= Pipe head pressure

(Bar)

The pipe head has an electrical heater band around

the body and tip while the screw and barrel is heated by oil
jacket s;

bot h

proportional
hardware

systems

controllers

provides

measurements

and,

a
in

carefully

are
and

thermocouples.

continuous
addition,

hardcopy

monitored
The
of

indicates torque

maximum torque) and screw speed (SS:

by

attached

the

above

(TQ:

% of

premixes

were

rpm).

2.S. 1 OPERATION OF EXTRUDER

The

conditions

under

which

the

processed were determined by an extensive trial study,

conditions were chosen to allow a

the

wide processing 'window'

of vastly different compos.itions.

Page

63

Experimenta1l2

TABLE 2.6
Extrusion conditions
EXTRUDER PROFILE CODE
VARIABLE

At

Bt

G*

Screw speed

(rpm)

25

25

25

25

25

25

25

Volumetric feeder

(rpm)

38

38

38

38

38

38

38

Zone 1 temperature

( '0

165

165

165

180

180

200

210

Zone 2 temperature

("C)

165

165

165

180

180

200

210

Screw temperature

( 'C)

150

150

150

150

150

150

150

Head temperature

( 'C)

165

170

180

180

190

200

210

Die tip temperature ( '0

165

170

180

180

190

200

210

t Unable to produce 'acceptable' pipe

streaks; included for 0 phr as reference only

* Degradation
The
and

above

each

table

ext ruder

increment.

indicates

profile

wide

used

was

processing
for

range

each

filler

The pipe specimens were key coded with respect to

filler content and extruder conditions;

the filler code 0,,5

(increments

of

followed

of

representing

phr

10

by the extruder profile

code

Polcarb

shown above.

was

S)

Thus

pipe code of 3E represents a 30 phr composition extruded at

condi t ions E.
The experimental procedure was largely influenced by
the

incorporat ion

low

extrusion

since

flood

of

temperatures.

feeding

quantities of

filler

and

The

extruder

starve

fed

the

machine

limit

for

substant ial
tripped

was
torque

higher levels of filler and a relatively low screw speed was

also necessary.

The

feeding

of heavily filled compositions

led to severe handling problems;

the
thus,

hopper

and

adhere

ultimately,

lead

to

the

to

the

material would bridge

volumetric

surging.

largely overcome by ensuring that

screw

These

feeder

problems

and
were

the screw feeder remained

as cool as possible and implementing a multi-pronged stirrer

in the feed hopper.
was

also aided

The feeding of

these problem materials

by al ternat ing the ext ruder runs

bet ween

Page

64-

Experlmental/2

heavily

filled

dry

blend

and

progression

dry

filled;

The occurrence of surging or reduction in output was

head

pressure;

reduction

in

the

st eady

feed

rate.

graphical

reduct ion
However,

filled

out put
in

of

torque

after

to

blend

than

by

lightly

filled

rather

carefully moni t ored

of

lightly

heavily

torque and
indicat ed

applying

the

above

remedies,

a steady state situation was quickly obtained (15-

20 mins)

and pipe samples were taken when the instrumented

values levelled off.

and

wat er

trough

eccentricity.
length

per

subj ect ed

uni t

The
unit

to

Pipe section was produced via a sizing

and

pipe
time

t he

sect ion

output
and

methylene

was

moni t ored

for

measured

as

mass

and

length

of

pipe

was

small

chloride

was

test

(MCT:

15

minut es

immersion at room temperature).

Pipe specimens could not

be obtained for

extrusion

profiles A and B due to poor melt

extensibility and at

the

highest

G,

degradation/' burn

up'

and thus this profile was only used for 0

phr

profile

was evident,
as

an

code

indicator

considered,

of

the

maximum

processing

temperature

possible for the composition used.

2.6.2 PROCESSING OF LUBRICANT/MODIFIER COMPOSITIONS
The processing of these compositions was similar to
the experimental procedure noted above,
extrusion

condition,

profile provided a
(0

code

or 30
E

and

phr

was

chosen

since

this

The resultant pi pes were labelled 0 or

Polcarb S:

then

E,

pipe with acceptable processability and

ext rudate appearance.

3

profile

except that only one

lastly

!l2.3)
a

followed

by the extrusion

lubricant/modifier

code

as

described in table 2. 4.

Page

65

Experimental/2

2.7 SURFACE APPEARANCE

The

surface

appearance

of

pipes

was

qualitatively

assessed by:
i)

Visual

observation:

the

pipes

were

ranked

in

order of roughness.
ii)

Scanning electron microscopy:

the pipe,

small

samples of

representative of the complete pipe,

mounted onto aluminum specimen stubs,

were

sputter coated

with gold and viewed under a Cambridge Stereoscan 2A

electron

microscope.

The

surface

appearance

was

photographed at various levels of magnification.

2.8 ADDITIVE DISPERSION
Additive
microscopy:

3-5

dispersion
sections

~m

1400 microtome with a

'D'

was

observed

by

were microtomed using

profile steel blade.

optical
a

Leitz

The section

was mounted between a glass slide and glass cover slip using
cedarwood

oil

as

suitable

mounting

fluid.

The

were viewed using a Zeiss universal transmission

sections

microscope

with various objectives <Zeiss 63/0'16 & 1610'35) in common

light,

phase contrast and dark field modes.

Sections were taken in the direction of extrusion as

well as transverse to the machine direction.

A number
also

observed

degraded then
lead

to

of

via
the

the thin sections prepared above were

UV

fluorescence

formation

primary

of

microscopy.

If

PVC

an conjugated species

fluorescence

in

the

visible

is

will

region.

Similarly poor distribution of stabilising additives could

lead to regions of fluorescence [112, 170] during processing.
Thus

this

history,

t echn:i.que

provides

an

indicat ion

of

processing

additive dispersion and residual grain content.

The

Zeiss microscope was fitted with a Zeiss III RS fluorescence

attachment incorporating a 50 watt HBO high pressure mercury

Page

66

Experimenta1l2

vapour

lamp.

filter

for

barrier

The

also

maximum visible light

fil t er,

spect rum

attachment
for

[170].

only

photographed

420,

LP

using

365

emission at

sect ions

special

0365

t ransmiss10n

The

housed

UV

of

nm and a

the

were

exciter
visi bl e

focussed

objective;

and

Plan-Neufluor

16/0' 50.
2.9 ASSESSMENT OF FUSION
2.9.1 ACETONE SHEARING TEST
Summers

et

[109]

81

described

optical microscopy

technique using sheared acetone swelled samples to provide a

better

discriminating

immersion tests.
mm

cube)

glass

were
were

common

light

then

traditional

Therefore small specimens

cut

stoppered

samples

power

from

tubes

sheared

the

of

pipe

between

microscopy

(approximately 2

samples

acetone for
glass

and

immersed

hours.

slides

(Zeiss

solvent
in

The treated

and

universal

viewed

via

microscope:

63/0'16) under dark field illumination.

2.9.2 DIFFERENTIAL THERMAL ANALYSIS
The application
measuring

fusion

levels

discussed in l.4.2.5.
Thermal

Analyser

sample pan and a

respective

of

thermal

of

processed

PVC

as

tool

for

has already

been

The instrument used was a Du Pont 990

with

Du

Pont

reference pan

positions

analysis

on

DSC

(empty)

constantan

cell.

An

aluminium

are placed on their

disc.

The

disc

is

embedded within a silver heating block and a silver lid caps

the complete unit;

the

block is heated at

and heat

is efficiently transferred

disc

the

to

separate

pans.

The

through

chromel-constantan

the pan location.

recorded

on

This

x-y

constant

thermocouples

rate

the constantan

differential

between the sample pan and empty reference

by

heat

flow

pan is measured

positioned

underneath

signal response can be amplified and

plotter

versus

sample

temperature.

Page

The

67

Experimenta1l2

cell was accurately calibrated by thermal analysis scans of

known
have

mat erials,
sharp

values,

such

melting

and

thus

as

t in

pOints

the

cell

and

with

indi umj
precise

can

be

measurements of unknown materials.

these

mat erial s

heat

of

fusion

calibrated

for

energy

A purge gas (nitrogen) is

used to maintain the cell and prevent

corrosion by noxious

gases.
Figure 2.4 illustrates a typical DSC thermogram of a
'moderately'

processed UPVC pipe with the salient

features

noted.
Small

samples

of

pipe

(10-12

mg)

are scanned

from

room temperature to 240'C at a heating rate of 20'C/min and

an Y axis sensitivity of

1 and 2 mY/cm.

minimum of three

samples were taken each pipe specimen and no skin effects

was observed for the thin pipe section.
gas was pumped throughout

The nitrogen purge

the scanning period at

a rate of

60 cc/min.

FIGURE 2.4
Typical DSC thermogram
Signal

EXO

tl
~

ENDO

. . ,.

128

,.

14..

\_

Temperature (oC)

..
Page

68

Experimenta1l2

The area of peaks 'A'

planimeter

and

converted

and 'B'

into

can be determined by a

heats

of

fusion

by

the

following relationship:

Where

loHF

A
m

(2. 1)

(60 B E logs)

= Heat of fusion

(Jig)

= Endothermic area (cm2)

= Sample mass

= Time base setting (0'5 min/cm)

(g)

logs = Y axis sensitivity (1 & 2 mV/cm)

E

(025 & 022 mW/mV)

= Cell calibration constant

2. 10 MECHANICAL PROPERTIES
2. 10. 1 TENSILE TESTING
Tensile
samples
J. J

and

specimens

uniaxial

Lloyd universal

infra-red
prepared
with

tensile

cutting,

press

die

The
the

(T5002)

dumb-bell

parallel

and

from

the

properties evaluated

the

to

using

pieces

extrusion

were

direction,

conformed

Part A2

pipe

fitted with an

test

pieces

test

dimensions of type 1 of BS 903 :

[171]

prepared

testing machine

extensometer.
by

were

(1971)

to

the

standard

(figure 2.5).
FIGURE 2.5
Tensile specimen:

Type 1

P,)SltlOn
tines

of reference

Page

69

Experimenta1l2

Where

A
B

C
D
E
F
G

=
=
=
=
=
=
=
=
=

Overall length (minimum)

75

Width at ends

125

:!:

Length of narrow portion

25

:!:

Width of narrow portion

4'0

:!:

0'1

Small radius

80

:!:

05

Large radius

12'5

:!:

10

Distance between reference lines

20

Distance between sample grips

40

Thickness (preferred)

:!:

2'0

All dimensions are in millimetres

Five test pieces were tested at a crosshead speed of
50

mm/min

and

at

room

temperature

conditions.

An

initial

gauge length of 20 mm was marked with graphite tape and the

infra-red extensometer positioned to follow these markers.
The

resultant

force-extension

graphs

were

used

to

determine the following tensile parameters:

Ultimate tensile stress

Yield stress

= (Ta =
= (Tv

Fe
(2. 3)

A
Fv
(2.4)
A

Elongation at yield

= v =

(I v-la)
-------

x100%

(2. 5)

------- x 100%

(2. 6)

10

(le-la)
Elongation at break

= a =

10

Where

Fe
A

=
=

Force at break
Cross-sectional
dumb-bell

Fv
Iv

10
le

=
=
=
=

(N)

area

of

waisted portion

of

(mm 2 )

Force at yield point

(N)

Extension at yield point

(mm)

Initial gauge length

(mm)

Extension at break

(mm)

Page

70

Experimental/2

2.10.2 IMPACT PROPERTIES

Impact testing is a widely used property measure for
UPVC products and is covered by a large number of standards.

Traditionally,
Gardner

type

failure

rate

impact

evaluation
tests
is

tests

information
reduce

has

where an

upon

been

failure

More

recently,

used

failure

the number

of

which

mechanisms,

t est

Charpy,

impact

determined.

have

included

pieces.

Izod

energy

and

or

50%

instrumented

can

provide

product

more

testing

The correlat ion

and

bet ween

processing and impact properties is not well understood,

conclusions

differ

from

the

presence

of

maximum

and
to

monotonic increase with increasing fusion level (1.5.3).

A Rosand instrumented falling

weight

impact

(type 5A) was used to evaluate impact properties.

layout

tester

The basic

of the falling weight column is shown in figure 2.6

[ 172J.
A
impactor
this

Kistler~

probe

and

arrangement,

transducer

is

the

impact

weight;

impactor

probe

the

gravity,

towards the sample holder.

trigger

optic

begin

data

fracture

which

collection

event

may

(typically <10 ms),

be

activates
of

the

only a

however

positioned
on

between

drop release

accelerates,

of
to

The probe assembly flags

a

force

transient
signal

recorder

with

time.

few thousandths of

the

due

the

12

bit

transient

to
The

second

recorder

can obtain 2000 data points during this period to provide an

accurate account of the fracture behaviour.
(modified BBC model B)

receives the digitised force signal

and provides data handling,

facilities.
behavio~r

The
as

A microcomputer

storage,

microcomputer

force-time

or

can

analysis and print-out

represent

force-deflection

the

graphs

analysis of the trace yields detailed information,

gradient,

force or energy,

at any gi ven point.

fracture
and

such as

Energy val ues

are obtained by integration of the trace upto the force/time

co-ordinates.

The salient features of the force-deformation

trace are shown in figure 2.7 [174J.

Page

71

Exper1menta1l2

FIGURE 2.6
Instrumented impact tester

COLUMN

Catcher/Release

Fa16ngWeighl
Trigger Switch Unit
t"O;:llo-S .... 'IC.tn

Camp Release

Stripper

8ar-:----7~-Jll,..f!~~~~:__~~:::::::;;;;;~::::.--'\\0amp, FuB Presstr"e

'Safety-Rod~ Unit

Safely-Rod position
adjuster

1i'r'~"r<::-+-7"e::...._-----t-

MagnelicSwiICh
(Safely i'lIer~

~~~---------------t-Door~D

SAMPLE AREA

Page

72

Experimentall2

FIGURE 2.7
Force-deformation trace

Force (KN)

Slope

Peak
force

-----j-

Distance
. (mm)

Deformation
at
peak force

Deformation at
failure

The type of fracture behaviour can be generalised as

shown in figure 2.8.
with

failure

Ductile failure produces a broad peak

occurring

beyond

yield.

Brittle/ductile

behaviour is suggested when failure occurs at a sharp yield

peak

and

lastly

deformation

brittle

values

with

fracture
difficulty

produces
in

low

force

discerning

initiation and propagation characteristics.

and

between

These terms are

applied to pipe fracture and a number of intermediates are

envisaged depending upon conditions.
2.10.2.1 EXPERIMENTAL PROCEDURE FOR IMPACT TESTING
IMPACT RIG

Pipe specimens are commonly tested using a

block

which

supports

an

unclamped

length of

pipe.

'V'

45'

However

the geometry and ductility of a proportion of the pipes to

be

tested

surface(s);

did

not

instead,

allow

complete

fracture

of

the

pipe

pipe collapse and deformation yielded a

complicated trace which could not discriminate between the

Page

73

Ezper1mental/2

FIGURE 2.8
Typical Pipe fracture
Force (N)
.........
...

:':
i!

..--'~

, '

.,I

: ~
/
I
~
~.
,
'
,f
:;'
~-;

!
:
.
:.
,

/ if

/ ./
.:

I ,r"
i !
I

,.'-

. . .::~,
" ,
,

,!

....

..

/ ,/

BritUe
--_. Brittle/Ductile
....... Ductile

,
,,

Defonnation (mm)

pipe

walls.

Thus

further

work

geometries and finally an impact

considered

number

of

rig was designed and used

throughout the program (Appendix C).

A minimum of ten split

pipe samples were measured for pipe wall thickness,

clamped

in the rig and then tested,

IMPACT VELOCITY

The test speed is determined by the drop height:

=

J(2gh)

(2.7)

Page

74

Experimental/2

Where

\)

Velocity (m/s)

Acceleration due to gravity

(981 m/s 2

Test height

and

the chosen speed was

proposal [173J.

1. e.

(m)

00 5 m) did not greatly affect test

The drop height

results

suggested

by a

draft

BSI

1 metre drop height corresponding to an

impact velocity of 4'4 m/s.

The

available

impact

energy

can

be

determined

at

this height by the simple relationship in equation 2.8:

Where

(2.8)

Eo

mgh

Eo

Available impact energy

Impact mass

Acceleration due to gravity

(25'35 kg)

(981 m/s 2

Test height

impact

energy

is

impact

energy;

since

It

must

large
a

in

force-deformation

maximum

permitted

satisfy

this

trace.
and
can

test

of

the available

comparison

the

absorbed

impact

velocity

large reduction

[173J

criterion

energy at

be ensured that

due to energy absorption can affect

the

(m)

Therefore the available impact

one metre is 249 J.

(J)

with
in

the characteristics of

reduction

the

impact

be .estimated

of

mass
by

20%

is

required

the

the
to

following

equat ion.

3 x

Where

m
EToT

(2.9)

g.h

Impact mass (kg)

Total energy available

Acceleration due to gravity

(9' 81 m/s 2

Test height

(J)

(m)

Page

75

Experimental/2

In

all

cases

the

reduction

in

impact

velocity

was

estimated to be less than 5% of original impact velocity.

FILTERING
The force

signal

of

inst rument ed

invariably filtered to some degree by a

an attempt

impact

test ers

is

low pass filter

in

to reduce adventitious vibration

brittle materials>.

However excessive filtering can hide the

true

characteristics

of

peak

values

peak

such

as

the

filter

digital

filter

which

fracture

force.

incorporates non-resonant
digital

<especially for

The

behaviour
Rosand

materials such as

can

'post-filter'

allows an optimum filter

reduce

impact

tester

titanium and a

the
to

or

Signal;

this

be chosen after

tes,ting and thus reduces the likelihood of spurious results.

The maximum reduction in peak force observed for the filters
chosen

<1'5-~

kHz> was <3%.

BRITTLE-DUCTILE TRANSITIONS
The

majority

temperature.
F

of

testing

was

performed

at

room

In addition the pipe series extruded at profile

<2. 6.1) was subjected to low and high temperature impact

testing.
~1,

60,

were
for

The temperatures involved were -20,

80 and

100'C

conditioned

in

C.

cold

-10,

0,

10,

20,

The cold temperature samples

finger

bath of

ethylene glycol

8 hours while the high temperature samples were placed

in a

hot

during

air oven for

removal

of

minimum of 8

sample

from

the

hours.

medium

Heat

transfer

to the

specimen

holder was considered insignificant

since the complete test

cycle

and

was

approximately

seconds

the

impact

rig

was

also conditioned at the prescribed test temperature.

Page

76

Experimenta1l2

SUMMARY OF TEST CONDITIONS

Impactor tip

10 mm hemispherical (ISO)

Impact speed

~. ~

Impact height

1'0 m

Impact mass

25'35 kg

Number of specimens

10 (minimum)

Sweep time

5, 10 and 20 ms

Low pass fll t er

1'5, 2'0,

Test temperature

All pipes at room temperature

m/s

3'0 and

~O

kHz

Pipes processed at profile F:

-20, -10, 0,10,20,41,60,80, 100'C

EXTRUDER PROFILES:

&

Pipes manufactured at these low temperature profiles

did not

produce a regular shaped pipe and thus could not be

tested

in

the

longitudinally

above
split

compression press at

manner,

and

125'C,

These

extrudates
a

hot

were

placed

in

upstroking

after a

period of 10 minutes a

pressure of 5000 kg was applied and held for 5 minutes.

The

pressed samples were then cooled by Circulating cold water

throughout
tested

the

using a

pI at ens.
DIN anvil

The

result ant

sheet s

(60 mm 00/40 mm ID)

were

impact

with a

ring

clamp pressure of 3000 N.

Page

77

CHAPTER 771REE

PROCESSING RESUL TS

3. 1 DRY BLENDING

The dry

blending of highly filled

compositions can

lead to a severe problem of filler segregation.

conditions
results
weight

were

determined,

suggested
and

that

blending

compositions

as described

careful

control

sequence

containing

were

The optimum

in 2.4,
on

overall

necessary

representative

and

amounts

the

batch

to

obtain

of

filler.

Blending time was unaffected by an increase in filler level

except for blends 4 and 5 <representing filler levels of 40
and

50

phr

respectively).

The

higher

levels

of

filler

produced a delay in mixing time as shown in table 3. 1.

TABLE 3. 1

High speed blending time

Blend
code

Filler
level
<phr)

Discharge
time
<min)

8'5"

10

8'10"

20

8'5"

30

8'10"

40

8'45"

50

9'45"

All

the

blends

<O,3E-

to

O,3EH)

produced

for

the

additive study yielded a discharge time of approximat.ely 8 min

10 S

and

thus

the additives did not

affect

the blending

time.

Page

78

Processing/3

3. 1. 1 DRY BLEND CHARACTERISTICS

3. 1. 1. 1 ASH CONTENT

The filler contents of the blends were determined by

ashing a small quantity of the dry blend and comparing the
percentage ash retained with a reference graph (2. 5.1>.

The

results can be tabulated as follows:

TABLE 3.2
ASH CONTENT

Ash
content
(phr)

Volume
fraction
(% VoU

00

0'0

85

0046

181

O' 1208

27'1

0'163

35'6

O 2228

400

O' 2569

Blend
code

A good
filler

loading

agreement
and

is

ash

obtained

content

upto

loadings of

40 and 50

result

proportion of the filler

t he

in a

mixer

chamber,

phr.

1. e.

between the
the

expected

higher

filler

The highly filled compositions

mixer

being retained within

foul ing.

These resul t s

are

supported by the blending results since high filler loadings

and

possible

filler

loss

leads

to

reduction

in

the

effective mixing charge involved in the vortex type mixing

action and thus a longer mix time.
The blends produced for the additive study were also
assessed

and

yielded

i. e.

phr

compositions

30

similar

results

indicated

to
a

the above
filler

table,

content

of

between 27-28 phr.

Page

79

Processing/3

(TAP) DENSITY

3. 1. 1. 2 BULK

Tap density
pack

efficiently

indicates

and

the ability

possibly

the

effect

for

of

the

powder

to

particle

size distribution involved.

All

the

blends were tested and the results can be

listed in table 3.3 and figures 3.1 and 3.2.

TABLE 3.3
Tag density of gowder blends

a) Varying filler content:

Blend
code

Tap (Bulk)
density
(g/cm' )

Filler
content
(phr)

00

073

8'5

075

18' 1

O' 78

27'3

O' 79

356

086

40'9

096

b) Varying addi t i ve type:

BLEND CODE

Filler
code

Tap density (g/cm')

074 0'73 075 074 0'71 072 0'74073073

079 079 0780'81 0'78 079 0'82 082 082

Figure
increase

in

approxi~tely

observed.

3. 1

tap
30

illustrates
densi t y

phr,

where

upt 0
a

Figure 3.2 suggests that

an
a

approximate
filler

exponential

linear

content

of

increase

is

additive type has little

effect upon tap density of the base composition and that the
effect of filler is more prominent.
Page

80

Processing/3

FIGURE 3.1
Top density versus Filler contem
Tap density (g/cm3)
1.05 , . . . . - - - - - - - - - - - - - - - - - ,

:"

0.95

0.85

0.75
. :

10

20
30
filler content (phr)

::

40

FIGURE 3.2
Top density for Additive blends
Top density (g/cm.3)
0.95,....---------------...,

0.90

0.85

Additive code

Page

81

Process1ng/3

3. 1. 1. 3 SCANNING ELECTRON MICROSCOPY OF POWDER BLENDS

Scanning

electron

micrographs

of

the

dry

blended

powders were taken and a selection is shown in figures 3.3-

3.B

inclusive.

unfilled

dry

Figure
blend

3.3
(0)

and

3.4

illustrate

resembles

suspension'polymer and the distinct

that

of

that

the

the

virgin

irregular surface formed

by the agglomeration of sub-grains can clearly be seen.

micrographs
that

the

of

the

filler

lightly

is

located

(figures 3.5 and 3.6)

The

presence

can

be

and

element

map

as

by

the

filler

coating
grain

of

in

level,

surface

to

figure

in

the

1B'1

phr

phr,

1B'1

and

large

is . coated.

of

the

produce

3.7.

The

fold

however it

of

grain

filler
calcium

map

is

the

the filler

the

particle

The blend containing a

reveals

much

proportion of

loading leads to a slight

the filler,

folds

figure 3.6 and infers that

situated

filler

suggest

(1),

calcium carbonate

rather than on the grain extremities.

higher

blend,

the

analysis

illustrated

preferentially

within

of

X-ray

same field of view as

is

dry

to form a more spherical shaped grain.

position

detected

filled

The

further

more

the

increase

even

available
in

filler

increase in the covering power of

is evident

that

the grain surface is almost

at a

filler level of

completely covered

by

filler.
The

micrographs

explain

the

difficulty

blends

and

the

of

the

observed

results

characterist ics.
surface

presented

moderate

PVC

grains

onto the

in

level
and

is

polymer

of filler will continue to coat

surface is completely covered;

for
of

some

to

blending

obtained

possibly adsorbed

can,

representative

the
filler

therefore
surface.

ext en t ,

dry

blend

coats

the

at t ached

A higher

level

the grain surface until

at

or

the

this level there is 'free'

or loosely attached filler particles and it can be envisaged

that

this free

system.

If

the

filler
above

can be removed quite easily from the

results

are

considered

then

the

dry

blending procedure becomes more difficult at higher levels

of filler. (blerids4--&'5Y'andTtie'-ash content indicates_'that.
a higher proportion of filler is lost as

fo~ling

of the
Page

82

Processing/3

FIGURE 3.3:

Micrograph of powder blend 0

("lOO)

280 flm
1----------1

FIGURE 3.4:

Micrograph of powder blend 0 ("1000)

28 flm
1----------1

Page

83

Processing/3

FIGURE 3.5:

MicrograEh of powder blend 1 (xlOO)

--

---~

280 flm
1----------1

FIGURE 3.6:

M1crograEh of powder blend 1 (xlOOO)

28 flm
1----------1

Page

84-

Processing/3

FIGURE 3.7: Ca micrograph of powder blend 1 (xlOOO)

28 flm
1----------1

FIGURE 3.8:

Micrograph of powder blend 2 (xlOOO)

28 flm
1----------1

______________ J

Page

85

Processing/3

mixer i.e.

a filler rich layer within mixer chamber).

Bulk density suggests a steady increase is observed

due

to

the higher

specific gravity

modal

particle

filler

level of 30 phr is reached.

density

size

of

until

distribution,

increases -dramatically

the

At

filler
an

the

bi-

approximate

this value,

since

and

'free'

the tap
filler

attempts to fill the interstices between the pOlymer grains

and thus produce a more efficiently packed powder.
3.2 TWIN SCREW EXTRUSION
The instrumented KMDL-25 provides a large amount of
data

for

each

extruder

profile

and

composition

chosen,

however some of this data is used to monitor the operating

condi t ions

of

the

ext ruder

and

characteristics of the material.

jacket
that

temperatures,

the

processing

These results,

such as oil

are given in- Appendix D.l and suggest

the oil jackets provide good,

reproducible temperature

control for a given extruder profile.

adapt or

t emperat ure val ues indicat e

extruder at

that

not

specific

point

Similarly the head and

the t emperat ure of the

rather than the' melt'

or

material temperature.

Thus it is difficult to assign a true

melt

temperature

to

particular- profile/composition

run

since the material temperature will not be wholly dependant

upon

the

temperature

inability

to

of

accurately

the

surrounding

calibrate

metal

the

and

the

thermocouple/

transducer probes used in the Krauss Maffei.

The

results

which

can

be

used

to

assess

the

processability of a material are listed into two main areas:

Mechanical/processing energy
Extrusion pressures
3. 2. 1 MECHANICAL ENERGY:
The

FILLER CONTENT

instrumented

screw torque as a

extruder

percentage of

the

continuously

monitors

permitted maximum and

Page

86

Processing/3

also

torque

can

be

related

to

the

measured output

by

the

following relationship [142, 175];

2ft . SS .

(TQ-TQo)

(3. 1)

III

Where

Specific energy consumption (rev. %/g)

SS

Screw speed

TQ

Measured torque (%)

Torque under no load conditions (20' 5%)

TQo =

Extruder

III

(20 rpm)

Specific

(g/min)

throughput

mB.SS

energy consumption gives a

measure of

the

mechanical energy supplied to the material per unit mass of

material.
Appendix
compositions

D.2

presents

extruded

at

the

data

profiles

A-F

for

the

filled

inclusive,

while

figures 3.9 and 3. 10 represents the data graphically.

It
curves

can

are

be

seen

produced

from

the

as

might

and

figures
be

that

expected

decrease in mechanical energy requirement

F

and,

an

generally,

increasing filler content.

increase

in

family
there

is

of
a

from profile A to

torque

and

with

Both figures are similar and the

quadratic curves clearly differentiate between the profiles

unt il

dist inct

deviat ion

is

observed

filler level of 30 phr for profiles D,

at

approximat e

E and Fi

a levelling

off is observed instead of a sharp upward turn as seen for

the other profiles.
obtained
fully

in

the

true

extrusion

characterise the effect

process.
final

from

Since a

'melt'

data

then

of

filler

temperature is not
it

is difficult

to

upon the extrusion

An indirect method was therefore used to obtain the

processing temperature,

1. 4. 2. 5)

and

the

(the DSC

interrelations

technique

will

be

described

discussed

in

Page

87

!14. 1. 1.

Processlng/3

FIGURE 3.9
Torque versus Filler content
Torque (r.)
.20

...

..

c
D

...

E
F

"f::::---.~----

.L-______

______

______

________

...

~ontennph~

filler

~~

FIGURE 3.10
~ech an icol

energy versus Filler content

(rev.To/g)
ft

..

~--------------------------------~

A
B

..
..

..

~---

D
E
F

I.

______

______

________L-______

__--'

Page

88

Processing/3

3.2.2 EXTRUSION PRESSURES:

The

extrusion

FILLER CONTENT

pressures

within

the

Krauss

Maffei

KMDL-25 are recorded via force transducers positioned in the

pipe head and adaptor piece.
and

inlet

3. 11

3. 12

respect i vely.
PI,

adapt or

head

pressures are given in Appendix D.3 and figures

and

zone,

The results for the PI,

illustrate

The

is
and

pressure

particular blend,

and

the

st art

at

insignificant
head

head

zones

unless
are

inlet
of

the

the

the

discharge

pressures

relat i vely

indicating that

pressures

high

length of

in

the

for

the

the solidi

melted material has increased to the start of the discharge

zone

and

thus

illustrates
appearance

to

producing
series
the

of

torque

response
quadratic

and

at

PI.

Figure

3. 11

curves

similar

in

measurements;

clearly

the

curves show the dependence of the set head temperature upon

head pressure.

For instance profiles C and D differ in terms

of barrel temperature and not the set head temperature;

resultant
indicating

pressure curves for C and D are almost

the

significant

influence

of

head

the

identical

temperature

upon head pressure.

filler
each

Figure

3.12

content

and

profile.

The

represents
a

linear

lines

are

the

inlet

relationship
not

parallel

pressure

versus

is observed
and

again

for
the

influence of the set head temperature can be seen.

3.2.3 EXTRUSION RESULTS:

ADDITIVE STUDY

The second stage of the

processing work considered

the interaction of lubricants and impact modifiers in filled

and unfilled UPVC;

the processing characterist ics of

these

compositions can be monitored within the instrumented twin

screw extruder.
these

values

inclusive.

The results are listed in Appendix D. 4 and

can

be

represented

in

figures

3. 13-3. 16

It can be seen from the results that although the

main extrusion parameters remained constant the experimental

values are significantly different from the original series

Page

89

Processing/3

of

extrudates

and

wide

which

filler

attributed

to

incorporated

range.

the

extruder

stage of processing;
additive series

These

wide

apparent

being

processing

window

differences

rebuilt

after

can

the

be

first

similarly the output rates for the two

(0 phr and 30 phr)

are not

identical which

again can be related to a slight modification of the rebuilt

extruder between the two additive trials.
of

data

also

are

the

reproducible

value

throughput,

of

is

within

which

Q,

similar

each

accounts

for

the

However the sets

distinct
for

series

differing

processing

of

and
mass

identical

blends (OE- and 3E-) during each individual extrusion trial.

Pressure at
not

noted for

the start of the discharge zone,

P1,

is

the majority of the unfilled blends with the

exception of OEE and OEH.

No response was obtained for

the

filled blends.
Figures
effect

of

3.13

small

and

an

reveal

unfilled
the

produce

change of

upon the

formulation.

trend

similar

invest igat ed.

Is

pipe

same

demonstrate

concentration

additive type can have

of

3.14

Q,

i. e.

ranking

first

then

the

significant

an additive and

processing characteristics
The

bar

head
order

chart s

and
for

pipe- codes

general 1 y

inlet

pressure
additives

the

If the influence of lubricant

considered

the

amount and type

can be

ranked

in

terms of mechanical energy and head pressure as follows:

LOW ------ value -------

HIGH

OEB

OEF

OEA

OEC

OE-

OED

OEE

Head pressure

OEB

OEF

OEA

OE-

OEC

OED

OEE

It
explanation

is,
for

of

course,
the

t emperat ure and level

trend

difficult
without

to

provide

details

of fusion which are not

full

upon

melt

present ed at

this stage.

Page

90

Processing/3

FIGURE 3.11
Head pressure versus Filler conlenl
Head pressure (Bar)
~

r---------------------------------,
A
B

o
E

..

~----_L_

______'--___

18

28

_1._ _ _ ___+--...J
38

filler content (phr)

FIGURE 3.12
Inlet pressure \/emus Filler contenl
Inlet pressure .(8ar)

...

A
B
C

o
E
F

'"
.oL...._____..J...._ _ _ _

le

filler

_ _ _ __1._ _ _ _....._ _ '

~ontent

(phr)

....

Page

91

Processing/3

However it is interesting to note that a relatively

high level

of a

low melting point

paraffin wax

produce a

low Q and head pressure result;

high

polyethylene

m. pt

wax

<OEE)

pressure

characteristics

when

paraff in

wax

equal

used

in

(OEC)

and

castor

oil

(OED)

high torque

compared

to

proport ions

and

low

m.pt

<OEA).

The

lubricants such as GMS

resulted

pressure than a comparable level of,

does

alternatively a

yielded

incorporation of suggested 'internal'

(OEB)

in

say,

higher

head

a paraffin wax.

The effect of incorporating a impact modifier (OEG &

OEH) upon a unfilled composition (OE-) suggests that the CPE
additive

(OEG)

does

not

affect

the

processing

characteristics dramatically while the application of an all

acrylic modifier leads to higher melt pressure values.
Figures

3.15

and

3.16

illustrate

results for the filled composition (30 phr)

the

processing

using the array

of additives discussed for the 0 phr series.

It can be seen

from the bar charts that the processing characteristics are

again dependant upon the additive and the lubricant systems
can be ranked as follows:
LOW

------ value -------

HIGH

3EB

3EF

3ED

3E-

3EC

3EE

3EA

Head pressure

3EF

3EB

3EE

3E-

3EC

3ED

3EA

In
dramatic

this
as

exceptions of

series

for

the

3EB and

the

effect

unfilled
3EF,

of

lubricant

compositions

is

not

with

as
the

these lubricants again yielded

low torque and head pressure results.

The effect of impact modifier addition differed from
the unfilled system in that torque and Q values were largely
unaffected,

although a

sizable reduction in head and inlet

pressures (especially for 3EG) were noted.

This
will

be

brief

expanded

introduction
in

fundamental results,

later

to

chapters

the

extrusion

when

such as fusion level,

results

discussion

upon

is presented.

Page

92

Process1ng/3

FIGURE 3.13
Torque and Q for Additive blend.

Torque (%). 0 (rev.%/g)

70r-----------------------------~

Ophr

60

1"""'lTorque
I!!!!!!!I Q

50

40
30

:,
:'

20

10

Additi\le code

FIGURE 3.14
Extrusion pressure for Additive blends
Heodjinlet pressure (Bar)

240r---------------------------,

Ophr
200

l!lZ!JHeod

IiiiliIiIiilnlet
160

A B

Additi\le code

Page

93

Processing/3

FIGURE 3.15
Torque and Q for Additive blend.
Torque (7.). Q (rev.7.I9)
70~----------------------------'

27-28 phr

1"""'lTorque
50

==Q

40

30

20

10

Additive code

FIGURE 3.16
Extrusion pressure for Additive blends
Heod/inlet pressure (Bar)

24Or--------------------------.
27-28 phr

200

1,,,IHeod
EiilIliIlnlet

160

120

80

40

Additive code

Page

94

Processing/3

3.3 EXTRUDATE APPEARANCE

The

aesthetic

important

parameter

arbitrary

assessment

commonplace.
surface

All

finish;

appearance
in

an

extrudate

extrusion

the

based

of

upon

is

an

and

an

examinat ion

is

process

visual

the extrudates were visually assessed for

both

the

outer

and

inner

surfaces

examined and ranked in ascending surface quality.

the

arbitrary

nature

difficulties,

of

however

such

the

an

assessment

pipes

were

were

Obviously

can

relatively

present
easily

segregated in groups of similar surface texture and gloss.

3.3.1 APPEARANCE:

OUTER SURFACE

The introduction of an appreciable amount of filler

(20 phr)

leads to a darker product

1. e.

brown tint

the impurities associated with the. filler.

of

the

pipe series containing a

wide

due to

The outer surface

filler range

can

be

ranked as shown in table 3.4:

TABLE 3.4

Outer surface of pipe series 0-5

GROUP

II

III

IV

VI

5A,B
4A,B

5C-F

3A-D

3F

2F

4C-F

2A,B

3E
2C,D

IF

lA,B
OA,B

lC,D
OC,D

2E
lE
OE

Where I

= poor

The above table

temperature of the

surface finish and VI

indicates

extrud~r

that

profile

an

(A~F)

OF

= best
increase

in

the

leads to a better

surface finish and the extrudate quality deteriorates beyond

a

filler

level

of

approximately

30

phr.

The texture
Page

and
95

ProcessingJ3

gloss of the heavily filled systems remain poor even at

the

higher temperature profiles.

The

ext rudat e

appearance

can

also

be

ranked

in

similar manner for the additive series <table 3.5):

TABLE 3.5
Outer surface of additive series

GROUP
V

IV

VI

OEA

OE-

OEF
3E3EE,F

OEB-E

3EH
OEH

OEG
3EA-D
3EG

Where groups as per table 3.4

The additive variations seems to have little effect

upon

the

impact

surface

finish

modifier;

in

with

this

the exception

case

clear

of the acrylic
improvement

is

observed.
3.3.2 APPEARANCE:
The

INNER SURFACE

inner

surface

is

often

evaluation of the processability of a

the

extrudates

for

this

study

can

considered

in

the

composition and again

be

ordered in

terms

of

quality.
The

inner

surface did not

discriminate between the

processing and

composi t ion range

more difficult

to arrange into discrete groups.

can be observed that

that

is,

part icularly well

the reverse of

and are

However it

table 3.5 is obtained,

a high filler content/low temperature profile gave

a better surface finish.

Page

96

Processing/3

TABl.E 3.6

Inner surface of pipe series 0-5

GROUP

IV

III

Il

OB-F

lC,O

OA

lE,F

20,E

lA,B

4C

2A-C

4E,F

2F

5C-F

3A-F
4A.B
40
5A,B

Table

3.7

presents the

approximate

ranking

of

the

inner surface for the additive series:

TABl.E 3.7

Inner surface of additive series

GROUP t

Il

III

IV

VI

OEG

OEA-F

3EO

3E-

OEH

3EG

3EA

3EB,C

3EH

3EE

3EF

t Where groups as per table 3.6

The additive series requires extra groups since the

inner surface quality has been extended upto group VI which
is very smooth and glossy.

It

is

interesting to note that

the filled grades generally give a better finish.

Page

97

Processing/3

3.4 METHYLENE CHLORIDE TEST

All

the

extrudates

passed

the

methylene

chloride

test after 15 minutes immersion at room temperature with the

exception of extrudates processed at profiles A and B.
ext rudates

processed

using

low t emperat ure

profile

Other
showed

signs of attack and swelling but in the context of the test

did

not

fail.

The

pipes

extruded

at

low

processing

temperature CA & B) showed excessive swelling and splitting.

Page

98

CHAPTER FOUR

71fERMAL AND MICROSCOPY RESUL TS

4. 1 DIFFERENTIAL THERMAL ANALYSIS

The technique of
1.4.2.5 and 2.9.2,
the

thermal

analysis,

has recently been applied to ascertain

processing history of PVC products.

discussed

in

parameters:
onset

2. 6. 1

were

assessed

All
for

heat of fusion of peak' A'

of peak'S'

as described in
the extrudates
the

(6HA>,

following

heat of fusion

(6H B > and the onset temperature of peak'S'

temperature>.

(' S'

The values obtained for 6H A can then be

related to a percentage fusion by the following expression.

% Fusion

Where

6H MAX -

=
=
=

6H A
6Hp
6HMAX

(4. 1 >

100

6Hp

Experimental value for heat of fusion

Heat of fusion for polymer (0 28 Jig>
Maximum heat of fusion

(1053 Jig>

The area of the respective peaks can be related to a

heat of fusion by the expression given in 2. 1.
value

was

obtained

for

the

virgin

included in the above expression (4.

maximum heat

of

polymer

1)

this

was

for completeness.

The

fusion was obtained for

3F and is used to represent

A negligible

100% fusion.

and

the pipe extrudate

The heat of fusion

values were calculated as an energy value per gram of PVC;

therefore

the

were corrected,

values

obtained

for

the

filled

using the measured ash content,

compositions
on a weight

basis to provide a comparable energy value.

Table 4.1

lists the results obtained for the filled

compositions processed within a large processing window.

Page

99

Fusion and MicroBcopy/4

TABLE 4. 1
Thermal Analysis of filled compositions

Pipe
code

' S' Onset

temperature
( C)

b.H A

b.He

fusion
(J Ig)

(J Ig)

OA
OS
OC
00
OE
OF

1703
172- 7
175-2
178-6
167-2
197-5

0'43
1'11
255
3'25
537
763

193
180
166
l' 13
049
O' 12

l' 4
8- 1
22- 1
29-0
49-6
71' 7

lA
IB
lC
10
lE
IF

1757
1740
1840
166'6
193'2
2035

369
l' 69
5'91
5'96
757
937

1 25
1'06
074
063
O' 13
O' 10

33-3
13-7
54-9
55'4
71' 1
88-7

2A
2B
2C
20
2E
2F

1757
1765
185'6
186'7
195'3
203-2

l' 68
304
5-27
521
6-41
992

l' 35
1 24
075
072
027
004

13-7
26'9
487
48' 1
79-3
94' 1

3A
3B
3C
3D
3E
3F

1742
178-0
186-2
190-2
1952
207-3

2- 13
2-87
5-69
622
8- 16
11- 18

l' 29
0'99
0'77
0'34
028
0'00

18'0
253
528
58'0
769
106'4

4A
4B
4C
40
4E
4F

175'8
1800
192'8
1933
194 8
203'5

1- 97
2-34
7'63
7' 13
7'96
931

l' 42
1 15
0'42
0'42
036
000

16'4
20- 1
71- 7
66-9
74-9
68-2

5A
5B
5C
50
5E
5F

1797
177-7
1882
1922
195-8
204'5

3 15
282
5-92
7 12
7-35
9' 45

1 41

1'14
O 51
038
025
0-00

26-0
24'8
55 1
668
690
895

Page 100

Fusion and

4.1.1 'B'

ONSET TEMPERATURE

The

onset

compared with
via

temperature

the

indicated

of

shown in figure 4.1.

line relationship

for

temperature.

'B'

peak

can

temperature

arrangement

be

recorded

(table

D.

as

1)

It can be seen that generally an upward

straight

series

the

extrusion

thermocouple/transducer

the

Microscopy/~

are

is

observed,

shifted

to

The head temperature,

however the values

higher

recorded

head

as indicated in 3.2,

is

a measure of the local extruder temperature rather than the

material

temperature at

calibrate

the

that

transducer

or

point.
the

Also

the inability

recording

device

to

suggests

that the recorded head temperature value does not provide an

accurate means to assess the processing regime.
of

calibration

extrudates;
different

can

these

trial

be

observed

extrudates

for

were

the

The problem
series

processed

of

during

to the filled systems and the recorded head

temperatures indicate a significantly higher value than the

'B'

onset

for

peak 'A'

at

their

measurement

were in fact

respective

suggested,

in

t emperat ure

although

is

case,

best

energy

values

obtained

lower than the filled extrudates

profile

t his

the

temperatures.

t hat

an

indicat ed

It

est imat e

by t he

is
of

therefore
processing

indirect

method

of

thermal analysis.
Figure
profiles

illustrates

4.2

chosen

for

this

processing temperature

('B'

the

study
onset).

effect
upon

of the
the

extruder
estimated

The unfilled extrudates

differed from their filled counterparts and this observation

can be related to the setting of the extruder rather than a
material

consideration.

Little

profiles A & Band C & D.

barrel

t emperat ures

temperature
effective
to C,
'B'

is

and

the

difference

temperature,

in

thus

major

it

would

variable

an

seem that
in

Changing

to F resulted in a
fact

seen

between

These profiles differ in terms of

processing temperature.

D to E and E

is

increase

the

head

controlling

the

profiles

from B

dist inct increase in

of

10C

is

observed

which can be related to the 10C difference in set head

Page 101

Fusion and Microscopy/4

FIGURE 4.1
'S' Onset versu. Head temperoture

...

'S' Onset (oC)

- DATA
Grodienl =1
... - 0 Series

...

- ---

a
a

-9D

aa

a
lee

Cl

Cl

B_

?a

.~

&-______-L______

...

178

________L_______

lee

198

______

2'.

28Q

Head Temperature (oC)

FIGURE 4.2
'B' Onset versus Extrusion profile
'B' Onset (oC)
2

:zoo
I

...

I
I
I
I

...
?a

L-____~----=-----~----~~----=_----_=---J

Extru.ion Profile

Page 102

Fusion and Microscopy/4

temperature.
to

The effect

marginal

of

increasing filler content

increase.

in

'B'

onset

leads

temperature

at

intermediate profile temperatures which could be related to

the higher viscosity of

filled systems.

The higher profile

temperatures do not differentiate between the filler levels

since the proportion of mechanical energy is reduced due to
the higher temperatures of the extruder.
4. 1. 2 PROCESSING OF FILLED SYSTEMS
Figures 4.3 and 4.4 represent the extrusion results
presente'd

in 3. 2. 1-3.2.2

versus

'B'

onset

temperature.

family of curves are produced which are similar and clearly

distinguish between filler levels.
decrease

in

ext rusion

value

The figures show a strong

(head pressure

or

Q)

wi than

increase in processing temperature (especially at the lower

end of the processing window).
further,
combine

linear
the

multiple

components

temperature with a
4.2

depicts

the

linear

correlation

the

In order to evaluate the data

regression
of

filler

analysis was
content

measured extrusion

relationship

regression
suggests

an

analysis,

processing

property.

Expression

these
the

of

expression 4.3,

yields a more accurate model.

and

coefficient

of

regression

= 721523 + 3'982(XF) -

Correlation (r)
SD of errors
Where

components

acceptable. model,
multiple

=
=

to

and

transformation

YP

the

between

used

however

further

analysis,

3'416(xs)

via

(4.2)

097
14' 73

yp

= multiple regression value for pressure

XF

= filler content

Xs

=' B' onset temperature CC)

(Bar)

(phr)

Page 103

Fusion and

M1croscopy/~

FIGURE 4,3
Head pressure versus 'B' Onset
Head pressure (8a r)

179

1~

lee

1~

198

1"

288

210

2m

'B' Onset temperature (oC)

FIGURE 4.4
Q versus'S' Onset

(rev.To/g)

,_ r-------------------------------------,

..
..
.
..
..

40

38

35.6
27.1
18.1

211

,Q

8.5
178

17S

198

1SS

198

195

2IiI8

28:S

211J

'8' Onset temperature (DC)

Page

10~

Fusion and Microscopy/4

Where

73869 + 000299<yp)2

Correlation <r)

SO of errors

= 11 39

=
=

y
yp

<4.3)

0982

predicted Head pressure <Bar)

multi-regression value

Figure

4.5

depicts

the

<Bar)

relationship

between

the

actual head pressure results and the predicted head pressure

values using this type of analysis.
Thus

from

the

dependence

on

temperature,

which can

and 4.3,
can

be

above

both

analysis

filler

there

content

be accounted

for

is

and

strong

processing

in expression 4.2

thus the significance of these dependant variables

determined

and

combined

to

predict

head

pressure.

Therefore the expression given in 4. 2 condenses the family

of

curves

shown

in

figure

4.3

to

single

mathematical

relat ionship.
4.1.3 ENOOTHERMIC ENERGY OF PEAK 'A'
The area of a
can

be

converted

to

peak obtained from a

an

energy

value

by

UPVC thermogram
the relationship

given in equation 2.1.

Endothermic energies were calculated

for

as shown in table 4.1;

peaks 'A'

and 'B'

are plotted against 'B'

in figure 4.6.

these values

onset temperature and are presented

The graph illustrates that an increase in 'A'

peak is obtained with increasing processing temperature and

that

the pOints occur as groups according to the extrusion

profiles chosen.

A curve can be fitted to the scatter pOints

which describes the observations well:

6H A = -11589 + 1018<' B') - 000197<' B')2

<4.4)

Correlation <r) = 09874

SO of errors
Where

'B'

= 'B'

= O 4592

onset temperature <C)

Page 105

Fusion and Microscopy"

FIGURE 4.5
Pnolysis of Heod pressure

Head Pressure (Bar)

~

r----------------------------------,

... r... -

",.

,
Data
_._. Gradient=1

..

...;

,
,..
,

.(.

.r'

., .;

,~

...

".,. .
.,.
,
"

... -

..

,,' .
,.'
..

I
50

lea

158

28Q:

lOO

Predicted Head Pressure (Bar

A very low energy value is measured for extrudates

processed

at

profiles

A &

S,

and the

rapidly with increasing'S'

onset

increase

diminish

in

AH~

temperature of
can

be

seen

begins

185'C

from

to

peak

area

temperature.
above

increases

The rate of

an

approximate

leading to the observed curvature.

the

error

bar

<standard

deviation

It
of

errors) that a low degree of scatter is obtained considering

the wide processing window and filler loading. Since all the
data

points

fit

single curve

then

the effect

of

filler

loading upon AHA appears negligible.

Page 106

Fusion and Microscopy/4

FIGURE 4.6
Master Fusion Curve
Energy (Jjg)
14
I-

12 IIl-

la

l-

'/

, .

.-...

'A'

/,

l-

. .
. ....
/

8 '-

.~,,,

.
:....
.
.

'-

". ,"

6 -

.
.
.
.
. . ..'
..
.-. .- .
,/

lll2 I-

.
..

.
:

~
.' .
(
1713

I
175

.,/.

'.

..
I
180

'8'

.,
I
185

r
1910

..

I
195 2130 2135 210

'S' Onset temperature (oC)

Page 107

Fusion and Microscopy/4

In the case of t.H B,

with

increasing
t.H~

manner to

'B'

a decrease in value is observed

onset

temperature

and

in

similar

the trend can be characterised by a polynomial

curve:
t.HB

43'954 - 0'409('B') + 0'00095('B')2

(4.5)

Correlation (r) = 0'9633

SO of errors
The
content
202 C,

t rend

and

the

= 0'149

again
value

although

the

shows

no

decreases

ability

dependence

to

to

zero

at

measure

filler

approximately

the

processing temperatures is more difficult

upon
at

t.HB

high

due to the small

peak area and baseline definition.

A maximum of 10'53 Jig is obtained from the best fit
curve
code

of
3F.

level

t.HA

from the

experimental

This value was

from

which

value

taken as an

other

t.HA

values

provided

by

pipe

arbitrary 100% fusion

can

be

compared

as

percentage (equation 4.1 and table 4.1).

If the calculated t.HA values are plotted against the
extruder

profile,

4.2

onset

(' B'

then

similar

trends

are

noted

to

figure

temperature versus' extrusion profile)

which

reaffirms the relationship seen in figure 4. 6.

Figure 4.7
the

filled

window.
the

is,

of
t.H~

depicting

extrudate with a
can

fusion

compositions processed within a

The graph

figure

illustrates the master

level of

be characterised

by a

course,
and

similar
can

fusion.

be

curve

for

wide processing
in appearance

used

to

label

to
a

Again the scatter points

single curve with the following

attributes:
% Fusion = -1080,09

+ 9.4122(' S') - 001795(' S')2

(4. 6)

Correlation (r) = 09842

SO of errors

= 506

Page 108

Fusion and Microscopy/4

FIGURE 4.7
Master Fusion Curve

% Fusion
1213.----------------------------------------,

11313

813

613

413

213

13L---L.J...LLU..l.J...J...LLU..l..l..LUL.l..l..l..l..LULU..l.J...LLLLl...LJ...l..l.l..L1__- l
1713 175 1813 185 1513 195 21313 2135 2113

'8' Onset temperature (oC)

Page 109

Fusion and Microscopy/4

4.2 THERMAL ANALYSIS OF ADDITIVE BLENDS

In a

similar manner to the filled compositions the

extrudates incorporating a
via thermal analysis.

range of additives were assessed

Table 4.2 presents the data obtained:

TABLE 4.2

Thermal Analysis of additive blends

Pipe
code

' B' Onset

temperature
( 'C)

l>Hs

"HA

Predicted

fusion
(J Ig)

(J Ig)

fusion

OEOEA
OEB
OEC
OED
OEE
OEF
OEG
OEH

1887
1890
1880
186'0
1875
1853
186'8
190'8
1920

527
556
581
583
5'46
6' 19
738
6'45
869

l' 19
028
052
120
O 19
037
O 18
O' 19
020

486
51' 5
539
54 1
505
577
69'3
602
82'1

569
576
550
496
537
477
51' 7
623
65'4

3E3EA
3EB
3EC
3ED
3EE
3EF
3EG
3EH

1908
189 8
1930
192'7
189'0
190'7
190'0
190'8
1957

750
624
9'43
7 12
8 11
6'94
6'60
529
8'44

0'45
l' 14
O' 17
0'32'
048
0'38
0'34
050
0'22

70'4
58'1
892
66'8
76'4
650
61' 7
48'9
797

623
59'7
67'9
67'1
57'6
620
60'2
62'3
74'4

Figure
graph;

4.8

presents

the

'B'

the variation within the 0

onset

do

exceptions that

not

reveal

any

as

bar

phr series is relatively

low with the notable exception of OEH.

compositions

data

large

Similarly the filled

differences

with

the

the overall values are slightly higher than

for the zero series and 3EH yields a slightly higher result.
It may not be acceptable to directly compare the two sets of
data

since

(3. 2. 3).

the

extrusion

conditions

are

not

identical

However it is evident that the twin screw extruder

Page 110

Fusion and Microscopy/4

accurately

controls

the

bUild-up

temperature

for

the

different compositions.
The second figure (4.9) demonstrates that the degree
of

fusion

differs

between

additive

processing temperature is similar

observed variation must
explanation.
fusion

the

equation given

the

blends

for

be accounted for

measured

for

'B'

onset

since

the

then

the

by an alternative

variation
this

type/amount

in

'B'

value

and

onset
%

of additive has a

size of the' A'

temperature

the filled compositions

The predicted fusion level accounts,

between

and

The last column in table 4.2 is the predicted %

using

slight

types

peak.

(equation

to some extent,

temperature

and

significant

the
4.8).

for the

comparison

indicates

fusion

in

that

the

bearing upon the

These results will considered in full

when compared with complementary evidence (6.3.1. 4).

4.3 MICROSCOPY OF FILLED EXTRUDATES
4. 3. 1 OPTICAL MICROSCOPY

Microscopy slides of extrudates containing 0_40 phr

of

filler were prepared as discussed in 2.8.

were

taken

extrusion;

parallel

transverse

to

the

direction

of

however little variation was observed between the

direction of
sections

and

The sections

sampling.

can

be

The results of

summarised

into

the

the

large number of

following

relevant

points:
The extrudates containing a relatively low level of
filler

(0

st ruct ure;

&

8 5

phr)

distinct

residual

bright speckled matrix.

may be attributed

additives

grain

t he grain inclusions were clearly ident i fied as

dark spheres within a

effect

revealed

and

since

to the

additives

The speckled

dispersion of particulate
are

not

dispersed

within

residual grains the outline of the grain can be observed.

Page 111

Fusion and Microscopy/4

FIGURE 4.B
'B' Onsel for Additive blend.
'S' Onset (cC)
200r----------------------------,

1','10 phr
1!!m27 phr

195

190

185

180

BeD

Additive code

FIGURE 4.9
% Fusion for Additive blends

fusion (r.)

100r----------------------------,

90

80

70

60

50

40

A BeD

G H

Additive code

Page 112

Fusion and Microscopy/4

A dark

field

illuminated

background

was

used

for

these sections so that the grains are seen as dark entities

as opposed to near transparent spheres in an ordinary light
background.
Figures 4. 10-4. 12 are shown to represent
OA-OF and lA-IF;

the first

ext rudat es

figure is an section of OA which

indicates a few residual grains and is similar in appearance

to the section of
indicates

that

processed

at

lA.

the

Figure 4.11

residual

profile

ls

grain

was

far

a section of OB

content
lower

of

extrudates

than

extrudates

produced at the higher process temperature B.

are spherically shaped and generally a
was observed
. the higher

for

the 8.5

profile

phr filler

temperatures).

representative of pipes;

OB-C and

The inclusions

higher grain content

series

The

and

(especially at

micrograph

of

OB

is

IB-C where the spherical

nature of the grains remains intact and distinct.

An increase in profile temperature did not result in
the

complete

destruction

of

the

grains

but

progressive

elongation of the grains in the direction of extrusion with

increasing profile temperature.

Figure 4.12

illustrates the

elongation of the grains in section OE which ultimately can

be observed as streaks.

The elongation of grains are clearly

seen in sections OD-F and ID-F with the increased likelihood

of

'streaking'

in the high profile temperatures of OF and

IF.
It
of

the

is difficult

original

to accurately measure the diameter

grains

since

size

distribution

is

envisaged and also the problems of sectioning a sphere must

be appreciated,
can

be

however an approximate diameter of 50-100

suggested

from

the

large

number

of

~m

micrographs

observed.

Page 113

Fusion and

FIGURE 4. 10:

Microscopy/~

Microphotograph of section OA

Dark Field
Illumination
380 flm
1----------1

Section

11

The

second

series

of

figures

~.

influence of a higher loading of filler

profile

temperature

dispersed

blends

sections

(e. g ..

figure

lightly filled extrudates,

of

residual

grains.

<If

A,

(18' 1 phr);

&

Higher

intermediate
agglomeration

can

finally

distinct

quite

be

of

residual

grains

dispersion

seen

(section

areas

of

are

higher

profile

unlike

the

D,

where
2D

detected
& F

result

traces

of

in figure

of

and

shown

patches.

and

in

filler

4.14)

agglomeration as

temperatures

then

the low temperature

section 2E in figure 4.15 as white spherical

the

well

do not contain significant traces

profile temperatures

stages

the

the low

indicate

which,

4.13)

the grains are highly elongated even at

profiles).

depict

13-4. 15

in

Thus

yielded

extrudates with poorer filler dispersion.

Page

11~

Fusion and Microscopy/4

FIGURE 4. 11:

Microphotograph of sect ion OB

I Dark

Field

1 Illumination

1
11

--=~~-~~--I

I
III

FIGURE 4. 12:

Section

Microphotograph of section OE

Dark Field
Illumination

380

~m

1----------1

11 Section

Page 115

Fusion and Microscopyl4

FIGURE

4.. '13: Microphot ograph of sect ion 2A

--

-----~-------------

~-----

Dark Field
Illumination
380 )-lm
1----------1

....
11 Section

L--_ _ _ _ _ _ _ _ _ _ _ _ _ _ ~_~ _ _ _

further

increase

in

filler

loading

results

in

extrudates which differ depending upon the extent of filler

dispersion.
seen
all

in

The increases in filler

the

micrographs,

these highly filled

however

loading can be clearly

the

extrudates

dominant

(27,1,

3S'6 and 40

-appears to be the level of filler dispersion.

mixing

is

evident

at

low temperature

feature

profiles

(A &

4. 17)

and

finally

obtained for samples produced at

very

poor

B)

as

however

poor dispersion can be seen at intermediate profiles

figure

phr)

Some degree of

shown by the micrograph of section SA (figure 4.16),

ego

for

(C & D

dispersion

is

the high extruder profiles

(E & F) as illustrated by section SF.

Poor

dispersion of

filler

produces

agglomerates

of

approximately 30-40 )-lm in diameter which on sectioning can

lead to filler drop-out,
seen

as

dark

voids

grain content
where
high

is not

residual
filler

as

grains

content

the effect of filler drop-out being

shown

in

significant

micrograph

Resi dual

(with the exception of 3A

were detected),
which

4. 18.

prevents

or

is

masked

identification

by

the

in

the

field of view.

Page 116

Fusion and Microscopy/(

FIGURE 4. 14:

Micro~hotogra~h

of section 20

Dark Field
Illumination
380 flm
1----------1

. !-.

11 Section

~'"

~'-4

....."..

FIGURE 4.15:

Ill'

...

J'

...".

..

Microphotogra~h

of section 2E

I
I

Dark Field
Illumination
380 flm
1----------1

1 Section

Page 117

Fusion and Microscopy/4

FIGURE 4.16:

Microphotograph of section 5A

Dark Field
Illumination
380 I-'m
1----------1

FIGURE 4.17:

Section

Microphotograph of section 5e

Dark Field
Illumination
380 I-'m
1----------1

Section

Page 118

Fusion and Microscopy/4

FIGURE 4.18:

Microphotograph of section 5F

".

., .

Dark Field

...

Illumination

380 flm
1----------1

1 Section

The presence of residual grains was also verified by

0.;

the

UV

fluorescence

technique

described

in

2.8.

Here

the

grains are identified as bright areas of fluorescence within

a additive-rich matrix exhibiting little or no fluorescence.
Figure

illustrates

4-.19

the

presence

elongated grains in a extrudate,

high

extrusion

t emperat ures.

inferences gained
however

the

The

from the dark

level

temperatures

1F,

does

of
not

technique
field

easy

few

highly

processed at relatively

fluorescence
allow

of

complement s

the

microscopy

sections,

at

extrusion

lower

identification

of

the

residual grains and therefore limits the application of UV

fluorescence in this case.
Figure
fluorescence
The

filler

4-.20

illustrates

technique

for

fluoresces

and

thus

highly

section
filled

enables

distribution of the filler to be examined.

confirm

the

dark

field

microscopy

the

using

the

UV

extrudate,

5A.

presence

and

The results again

technique

as

an

appropriate method to examine filler distribution.

Page 119

Fusion and

FIGURE

~.

19:

Microscopy/~

Microphotograph of section 1F

Fluorescence
150 fJ.m
1----------1

1 Section

FIGURE 4.20:

Microphotograph of section 5A

Fluorescence
150 fJ.m
1----------1

" Section

Page 120

Fusion and

Microscopy/~

4.3.2 ACETONE SWELLING TEST

The

swelling

of

PVC

in

acet one,

shearing

bet ween

glass slides and observation under' a common light microscope

has been reported in a number of publications [109-110,130).
This

simple

to

provide

information upon the fusion level of processed PVC.

In this

project,

small

micrographs
4.23

and

provide

convenient
samples

taken

of

examples

of

the

test
the

is
pipes

sheared

of

the

applied
were

fragments.

results

for

assessed
Figures

all

the

blends

produced.

Extrudate samples processed at

and

under

acetone

down

to

between
cohesion

the

primary
the

shearing

test

were

and

4.21filled

profiles A

easily

broken

particles with little discernible cohesion

particles.

strength

and

Figure
can

be

4.21

demonstrates

considered

to

this

represent

poor
all

blends with a filler range 0-40 phr.

FIGURE 4.21:

Acetone shearing of OA

Dark Field
Illumination

380 I-'m
1----------1

Page 121

Fusion and

Higher
particulate

profile

temperatures,

breakdown

clearly shows that

and

the

and

micrograph,

Microscopy/~

0,

resisted

figure

4.22,

primary particles existed albeit

degree of cohesion;

with a

the agglomerates can still be disrupted

into smaller units via shearing.

The
the

last

filled

beyond D,

microphotograph,

blends

1. e.

processed

E and F;

figure

at

the

4.23,

represents

profile

temperatures

here the primary particles are not

readily observed and the breakdown of the swollen fragments

is prevented.

The cohesion strength within the specimen is

significantly

greater

which

results

in

fibrillar

tearing

during acetone shearing.

Although
approach

to

the

technique

quickly

qualitative method

assess

does not

does

the

provide

quality

quantify

of

useful

fusion,

the extent

of

the

fusion

nor is it able to distinguish between relatively large steps

in

the

degree

of

fusion.

Thus

the

t est

does not

provide

significant information of the consequences upon fusion when

large

amounts

of

complementary

filler

are

evidence

added,

to

the

but

it

thermal

does

provide
data

analysis

discussed earlier in this chapter.

4.3.3 ELECTRON MICROSCOPY OF PIPE SURFACE
The
microscopy

surface
(2. 7)

of
and

the

pipe

was

the

results,

viewed
in

via

electron

general,

provide

complementary evidence to the visual examination of the pipe

surface.

The

electron

technique

to

thus

pipes

the

surface

observe
can

quality.

micrographs

the
be

Table

detail

easily
4.3

surface quality and is almost

of

provide
the

grouped

lists

the

convenient

outer surface
according

to

pipes

terms

in

and

their
of

comparable with the previous

classification given in table 3.4;

also an example of each

group is given in the electron micrograph figures 4.24-4.29.

'.

Page 122

Fusion and

FIGURE 4.22:

----

----

M1croscopy/~

Acetone shearing of OD

----

Dark Field
Illumination
380 )lm

1----------1

FIGURE 4.23:

Acetone shearing of OF

Dark Field
Illumination
380 )lm

1----------1

Page 123

Fusion and Microscopy/4

TABLE 4.3

Micro-surface of pipe series 0-5

Il

GROUP
III

5A,B

5C-E
4C-E

3A-D
2A-C

4A,B

IV

VI

3F
2E
lE

IF

IA,B

3E
2D
IC

OA, B

OC

OE

5F

2F

4F

OD

OF

ID
t

Where I

poor surface finish and VI = best

Reformatted pipes are highlighted in bold text
~

FIGURE 4.24:

Micro-surface of pipe 48

28 J.1m
1----------1

Group I

-------- -------

-----

--

.-

-------

Page 124

Fusion and Microscopy/4

FIGURE 4.25:

Micro-surface of pipe 4E

28 J-lm
1----------1

Group 11

FIGURE 4.26:

Micro-surface of pipe 3C

28 J-lm
1----------1

Group III

Page 125

Fusion and Microscopy/4

FIGURE 4.27:

Micro-surface of Eipe 3E

28 ).Im
1----------1

Group IV

FIGURE 4.28:

Micro-surface of pipe lE

------- ------

28 ).Im
1----------1

Group V

Page 126

Fusion and Microscopy/4

FIGURE 4.29:

Micro-surface of pipe OF

o
o

""

28 flm
1----------1

=
o
o

Group VI

o
o
o

o 0

An

increase

in

filler

content

not

only leads to a

general deterioration in the surface quality of the pipe as

discussed

in

amount

deposited

of

63.3. 1

but

also

filler

leads

on the

to

an

surface.

increase

the

These deposits

can be qualitatively assessed by mapping calcium,

via x-ray analysis,

in

wi thin the elect ron microscope;

detected
figures

4.30-4.32 demonstrates the increase in detected calcium with

increasing filler loading.

Page 127

Fusion and Microscopy/4

FIGURE 4.30:

Micro-surface of pipe 1F

28 Ilm
1----------1

Calcium map

FIGURE 4.31:

Micro surface of pipe 2F

28 Ilm
1----------1

Calcium map

Page 128

Fusion and Microscopy/4

FIGURE 4.32:

Micro-surface of pipe 5F

28 )lm

1----------1

Calcium map

4.4 MICROSCOPY OF ADDITIVE SERIES

4. 4. 1 OPTICAL MICROSCOPY

The

blends

cont aining

the

range

of

addi t i ves

discussed in 2.3 were also sectioned and viewed via light

microscopy.

The

micrographs

significant

differences

additive series;
manner

to

the

the

and

an

these

between

the

unfilled

extrudate

of

filled

series

and

OA"OF

yielded
unfilled
similar

revealed

The occurrence of these grains was

upon the type and level of

order

extrudates

unfilled additive series in a

residual grain structure.

dependent

of

decreasing

residual

additive incorporated
grain

cont ent

can

be

presented as follows:
POOR
OEG

----- grain content ----OEB

OEF'

OE-

OEC

OEA

OED

OEE

GOOD
OEH

Page 129

Fusion and

M1croscopy/~

Figures 4.33-4.37 present a number of micrographs to

ill ust rat e
Again

the gross di fferences

no subt le

differences

in residual

were

observed

grain cont ent.

between sect ions

taken parallel or transverse to the direction of extrusion

Figure
grains.
this

OEG

4.33

being

series.

shows

clearly

Extrudates

high

distribution of

t he

worst

OEB

and

of

all

OEF

residual

ext rudat es

show

in

marked

improvement in terms of residual grain content and similarly

extrudates OE- and OEA are next in the series with few grain
inclusions.
suggest
fewer

an

Pipes
almost

inclusions

extrudate

OEC,

in

OED

and

homogenous
than

terms

were observed with

of

its

OEE

are

section;

similar

homogeneity

very

OEE

similar

reveals

slightly

counterparts.
was

the additives well

OEH;

few

and

The

best

inclusions

dispersed to

yield a

homogeneous section.

FIGURE 4.33:

Microphotograph of section OEG

Dark Field
Illumination

380

~m

1----------1

1 Section

----------~-

--

----.-

Page 130

Fusion and

FIGURE

~.3~:

Microscopy/~

Microphotograph of section OEB

Dark Field
Illumination
380 flm
1----------1

1 Section

-------

FIGURE 4.35:

--------

Microphotograph of section OE--~----I

I
Dark Field
Illumination
380 flm
1----------1

1 Section

Page 131

Fusion and Microscopy/4

FIGURE 4.36:

Microphotograph of section OEE

Dark Field
Illumination

380 ",m
1----------1

" Section

FIGURE 4.37:

Microphotograph of section OEH

Dark Field
Illumination

380 ).1m
1----------1

1 Section

Page 132

Fusion and Microscopy/4

The additive series containing approximately 27 phr

of

Polcarb

distribution

filler
was

differed

not

in

that

prominent

residual

feature.

grain

here

the

dispersion of the filler was the significant factor and the

distribution
level

of

of

the

additive.

increasing

filler

filler
The

was

series

dispersion.

which quite large agglomerates

homogeneous
separation.

section

which

affected
can

be

from a
(20-30
does

by

the

ranked in
poor
~m)

not

type

and

terms

of

distribution

in

can be seen to a
indicate

filler

Figures 4.38-4.42 illustrate the trend shown in

the list below:

POOR
3EA

--- filler dispersion --3EE

3E-

3EC

3EB

3ED
FIGURE 4.38:

3EF

GOOD
3EH

3EG
Micro~hotogra~h

of section 3EA

Dark Field
Illumination
380 ~m
1----------1

11 Section

-_____J

Page 133

Fusion and Microscopy/4

FIGURE 4.39:

Microphotograph of section 3EC

-------..........---- ---- - -

Dark Field
Illumination
380 /lm
1----------1

1 Section

FIGURE 4.40:

Microphotograph of section 3EB

Dark Field
Illumination
380 /lm
1----------1

" Section

Page 134

Fusion and Microscopy'(

FIGURE 4.41:

Microphotograph of section 3EF

Dark Field
Illumination
380 f.Lm
1----------1

11 Section

FIGURE 4.42:

Microphotograph of section 3EH

Dark Field
Illumination
380 f.Lm
1----------1

11 Section

----~-----

--

-~--

Page 135

Fusion and

Microscopy/~

4. 4. 2 ACETONE SHEARING TEST FOR ADDITIVE SERIES

The extrudates incorporating the range of additives
were also subject to the acetone shearing test in a similar
manner to 4. 3. 2.

In this case,

few discernible differences

were observed between the pipe specimens,

did

not

identify

discriminating

poorly

power

extrudates

were

pipes

were

extruded at

gross

changes

indeed,

the

of

of

in

between
acetone

fusion

level

and

the

test

was

equal
profile
not

shearing

test

did

The original

that

(E)

limited
all

the

level.

The

and

be

the test

the

fusion

might

therefore

expected

not

and,

distinguish

series processed at

revealed an approximat e correlat ion

obtained via thermal analysis and the

test.

additive series were,

and

suggested

level

range

shearing

test

the same

fusion

solvent

t emperat ure

the

specimens

approximately

between the extrudates.

wide

fused

that is,

However

at least,

unable

to

the

extrudates

moderately fused
provide

further

for

the

(table 4.2)
evidence

to

indicate or measure the degree of fusion involved.

4.4.3 MICRO-SURFACE OF ADDITIVE SERIES
Scanning electron microscopy of the surface of these
extrudates provided evidence to support the trends observed
via

visual

increasing

examinat ion
surface

1. e.

table

quality

3.5.

was

The

same

suggested

order
by

of
the

photomicrographs obtained via this technique.

Page 136

CHAPTER FIVE

RESUL TS OF MECHJlNICAL PROPERTY TESTS

5. 1 TENSILE PROPERTIES OF FILLED EXTRUDATES

The pipes containing 0=40 phr of the mineral filler,
Polcarb

S,

were

subject

described in 2. 10. 1.
did

not

produce

to

uniaxial

pipes

testing

as

The low temperature extruder profiles

regular

pipe

section

preparation of tensile specimens;

for

tensile

processed

at

which

prevented

thus results are presented

extruder

profiles

D,

C,

and

F.

These resul ts can be summarised in table 5. 1:

It
the

can

measure

of

particularly
does

5.1

and

5.2

the

of

was

consider

failure

not

the

quite

and

where

However

the

which can highlight

fusion
of

tensile properties;

high,

values

evident.

trends

influence

in general,

is

break

always

loading

that,

(s. d)

at

number of

filler

results

scatter

elongation

identify

infl uence

from

experimental

failure

the

yield and

seen

for

reproducible
test

be

level.

Figures

filler content
a

upon

steady decrease in

yield stress is observed with increasing filler content with

some

deviation

filler

between

loadings

i. e.

profile

temperatures

extrudates

at

containing

the

35'6

higher
phr

of

filler processed at E and F profiles resulted in a lower av

value then profiles C and D.
The

influence

of

filler

loading

charact erist ics can be seen in figure 5. 2;

in

ultimate

content,

stress

is

observed

with

upon

failure

again a decrease
increasing

filler

however the results differentiate between extruder

temperature

profiles.

Profiles C

and

produce similar

aB

values while profiles E and F illustrate that an increase in

processing
stress

temperature

values.

processing

It

was

t emperat ure

leads

to

observed

in

det ermined

profiles C and D were similar,

reduction
64. 1

by

that

thermal

in

ultimate

the estimated
analysis

for

while an approximate 10C

Page 137

Properties/S

TABLE 5. 1
Tensile properties of filled extrudates

Pipe
code

Yield
stress
ay

s.dt

Ultimate
stress
(MN/m' )
s.d
aB

OC
OD
OE
OF

52'1
51' 8
52'7
523

0'7
03
02
0'4

41' 2
41' 9
40'3
38'6

lC
ID
lE
IF

488
47'1
468
482

1'0
05
0'4
0'3

41 2
4!-7
38'5
362

2C
2D
2E
2F

433
44'1
435
438

3C
3D
3E
3F

(MN/m')

Yield
elongation

Ult imate
elongation

(%)

(%)

Ey

s.d

lOB

05
0'4
07
0'4

10 7
10'0
11'0
170

05
0'0
0'8
0'8

90
124
114
61

21
4
24
23

1 4
06
09
0'4

108
11' 7
143
150

08
05
05
00

128
135
133
67

7
4
7
12

0'3
0'1
03
0'2

402 1 6
40' 1 2'0
37'3 08
360 02

10'0
11'0
16'0
150

0'0
00
0'8
I' 3

121
140
136
60

8
6
6
4

423
41' 4
398
37'5

05
l' 2
0'2
0'8

37' I
36'3
34'3
336

0'6
1 2
O' 1
02

4'7
40
107
133

0'9
00
0'9
05

41
29
33
27

4
1
4
2

4C
4D
4E
4F

373
375
36'4
35'0

09
l' 2
06
l' 0

350
34'7
34'7
32'4

02
09
0'1
02

103
8'7
8'0
103

l' 2
05
0'0
0'5

20
26
15
23

3
4
3
3

5C
5D
5E
5F

35'7
37'4
37'1
35'0

10
02
05
0'2

345
35'1
348
330

07
0'4
03
03

10'0
9'0
103
93

0'0
0'8
05
09

26
29
23
14

3
15
3
0

t s. d

s.d

Sample standard deviation

Page 138

Properties/5

FIGURE 5.1
Yield stress versus Filler content

Stress (MN/m2)

W,----------------------------,
55 -

45 -

40---- F profile
....... E profile
_._. D profile
- - C profile

35f--

~~I--~I--_~I~I--~I~

10

20
30
Filler content (phr)

40

FIGURE 5.2
Ultimate stress versus Filler content

Stress (MN(m2)
~,----------------------------,

.... -._,_.

40 -

35f-

..... .

---- F profile

....... E profile

_._. D profile
- - C profile

~~I--_~I~I--_~I~I~

10

20

Filler content (phr)

30

40

Page 139

Properties/5

increase

in

profiles D

measured

approximate

values

processing

if

and

(Jy

can

was

be

measured

replotted

temperature

5.3 and 5.4.

shown in figures

obtained

temperature

between

& E and E & F.

The
as

processing

were

(JB

(' B'

onset

Similar

plotted

against

the

temperature)

figures would

against

fusion

be

level

because of the strong relationship obtained in 4. 1. 3.

Figure 5.3 presents the yield values as a family of
curves

which

filler

are

dependant

loading

results

in

substantially

lower

than

however

yield

val ues

the

upon
a

filler

loading;

series

the

of

higher

which

filler

const ant,

with increasing 'B'

different base levels,

data

preceding

remain

loading,

albei t

at

onset temperature

until a filler level of approximately 27 phr is reached.

this

filler

loading

produces

observed

for

filled

and

decrease
the

in

data

extrudates

beyond

an

collected

and

increase in

yi eld st ress.
the

results

35'6

the

of

5C

(0

and

At

onset

'B'

Little difference

upon

is

40

symbol)

is
phr

seem

unreliable.
The second figure

(5.4) again provides sets of data

which distinguish between filler

yield values,
the filler

are
for

temperatures,
observed

not
the

and

between

filled grades
a

increase in B'

an

onset

although,

unlike

temperature for

all

loadings leads to a decrease in ultimate stress.

The results
especially

loadings,

as

precise as

testing of
this

the

fact

(85 and

account

yield stresses,

processed at
for the

extrudates

181 phr).

relatively large amount

the

extrudates

may

unfilled

for

and

low

crOSsover

the

lightly

The extrudates containing

of filler

(356 and 40 phr)

were

very similar with a spurious result noted for 5C as seen for

the yield values.
If the values measured for Ey and Ea are considered,
then it can be seen that
wi th

perhaps

temperature
elongation

small

for

the

at

yield

yield elongation differs slightly

increase
lightly

with

increasing

filled

measurements

for

processing

extrudates;
the

heavily

whereas
filled

pipes seem unaffected by the processing temperature.

Page 140

Properties/5

FIGURE 5.3
Yield stress versus 'B' Onsel
Stress (MN/m2)
~

..
.

r------------------------------------,
.

6.5

..

G
""

t'"

t..

185

198

18.1

27.1

~
1"

28e

'B' Onset temperature (cC)

35.6

40

....

"0

FIGURE 5.4
Ultimate stress versus '8' Onset
Slress (MN/m2)

.
8.5
18.1

27.1

~35.6
40

S7'!!

lee

Ul5

198

1"

28e

'B' Onset temperature (cC)

28!5

218

Page 141

Properties/S

Tensile

extension

at

failure

was

dependent

upon

filler content and processing temperature as shown in figure

5.5.

The

scatter

consideration
trends
phr

and

may

observed.

filler

and

processing

of

results
account

values

aB

above

temperature

contrast,

the

extension

value

at

low

extrudates

into
in

the

containing 27 1

independent

at

processing

taken

variation

extrudates

remain

filled

be

some

relatively

and

lightly

for

for

seem

should

low

of

the

value.

In

achieved

temperatures

high

but

this

value sharply diminished at the highest temperature profile,

F.

The

elongation

at

break

measurements

observed for ultimate stress and it

ultimate
filled

elongation
extrudates

values
(8 5

were

and

mimic

the

trends

is interesting to note

higher

18 1

for

phr)

at

the

lightly

intermediate

extrusion temperatures than the unfilled series.

FIGURE 5.5
Ye"'''''

Ullimale elongation

.
,..

'B' Onsel

Elongation (%)

..

.
.

8.5
18.1

1~

"le

185

198

195

____
288

'B' Onset temperature (oC)

27.1

4()
__

2SS

__

__

__

____

__

~~----_

~
....
_.-:.
:..:::.-:<:::::::..~' 35.6
~

"
28

..

218

Page 142

Properties/5

5.2 TENSILE PROPERTIES OF ADDITIVE SERIES

(~27

The unfilled and filled

phr)

pipes containing

the wide range of additives were also assessed for

properties and

summary

of

results

is presented

tensile
in

table

5.2:
TABLE 5.2
Tensile properties of additive series

Pipe
code

Yield
stress

Ultimate
stress

(MN/m' )
ay s. dt

Ultimate
elongation

Yield
elongation

(MN/m' )
aB
s. d

(%)
10

(%)

s. d

lOB

s. d

OEOEA
OEB
OEC
OED
OEE
OEF
OEG
OEH

534
518
522
539
547
544
53'8
42'4
49'3

03
0'5
0'9
0'5
0'9
0'4
0'6
0'5
0'7

469
44' 4
43 0
42 1
41'7
441
42'7
44 5
515

2'4
l' 9
l' 8
l' 2
1'0
2'0
07
l' 7
2'1

60
48
58
100
8'0
80
9'0
100
100

0'0
08
04
00
0'0
00
1'0
0'0
0'0

165
179
157
158
83
169
148
191
206

18
14
9
22

3E3EA
3EB
3EC
3ED
3EE
3EF
3EG
3EH

45 4
45'3
449
44 4
44'8
447
447
429
41 1

O' 4
0'3
0'4
1 0
O' 4
0'9
0'9
0'5
O' 8

415
41'0
443
42'1
40'5
39'9
422
47'9
45'5

19
08
12
08
0'7
13
23
1'4
2'1

100
117
103
11'1
9'2
97
9'0
110
100

0'0
07
13
18
10
07
1'0
00
00

154
148
180
149
122
145
162
194
196

9
9
12
7
18
10
16
12
7

12
18
8
17

t s.d = Sample standard deviation

Figure 5.6 illustrates yield stress for the additive
blends and it can be seen that the type or concentration of
additive
except ion

has

little

of

impact

effect

modi fier

yield stress

is

modifier

the extent

and

type and whether

lowered ?y
the

upon

of

yield

properties with

addi t ion.

In

this

the

incorporation of

the

reduction

material

is

filled.

depends

Case
an

the
the

impact

upon the

The CPE modifier

Page 143

Properties/5

(additive
reduces

code

G)

yield

(additive
filled

in

an

while

stress

code

H)

has

system the

unfilled

the

all

moderate

roles

system

significantly

acrylic

modifier

lowering effect.

are reversed

in

that

In

the

the

acrylic

modifier has a greater lowering effect.

The
figure
and

5.7

ultimate
and

ultimate

drawing,

tensile

are

depicted

relationship between elongation at

stress

is

indicate

observed

i. e.

large

dependence

upon

the

by

break

amount

produces a higher tensile stress.

in general,

results

properties

of
The

type

and

concentration of the additive and the consequences of these

results

will

be

discussed

fully

in

6. 3. 2.1

when

complementary evidence is also considered.

5. 3 IMPACT PROPERTIES OF HIGHLY FILLED SYSTEMS

The
determined

impact
via

of

propert ies

an

instrumented

the

extrudates

falling

impact

were

tester

as

descri bed in 2. 10. 2.

The
profiles

extrudates

produced

at

the

lowest

temperature

(A and B) were not a regular shaped pipe and thus

presented problems of sampling as a split pipe,

however for

the purpose of impact testing these samples were hot pressed

to produce flat plaques (2. 10.2.1).

The flattened specimens

were supported and clamped onto a DIN ring anvil and tested
using
pipe.

the

same

test

variables

as

described for

the

split

The geometry of the test piece is a well known testing

variable in impact testing and this must be considered when

comparing with results for the split pipe.
The
ext ruder
value

thickness

runs

and

in

the

results

individual

results

Differences

in

disproportionate

of

the

order
were

by

pipe
to

provide

the

even

test

dividing

the

of

thickness

between

comparable

by

thickness

results

slightly

, normalised'

specimen
impact

varied

the

specimen.

can

produce

after

normalising,

however the thickness variation in this study was relatively

Page 144

Properties/5

FIGURE 5.6
Yield stress fo r Additive se ries

Stress

(~N/m2)

Wr----------------------------,
1,"""10 phr
1i55l27 phr

55
,

50

;~

45

.'

40

35
A

Additive code

FIGURE 5.7
Ultimate stress tor Additive series

Stress (~N/m2)
55r----------------------------,

50

45

40

35

8
Additive code

Page 145

Properties/5

low and an extensive trial study indicated that

normalised

values were constant for a given pipe.

Another test
high

strain

rate

feature which should be considered in

tests

is

the

application

of

filters.

Filtering is normally required to yield practicable

and overcome excessive' noise to signal'
for

testing

fitted

with

signal

with

filtering
figures

of

brittle

digital

number

shown

in

filter

of

brittle

materials.

The

which

available

material
Appendix

spikes,

be

The

is
the

effect

illustrated

Figure

E.

tester

post-filter

filters.

can

especially

impact

can

results

in

of
the

effectively

E. 1

demonstrates the unfiltered brittle failure of a split pipe

in the rig described in Appendix C;
to

analyse

and

complicated

opposing case of

by

the trace is difficult

signal

extreme filtering,

artefacts.

figure

In

the

E.2 illustrates

the same impact data of E.l but with a high powered filter.
Over-filtering can lead

to a reduction in peak response and

therefore is a source of variability.

indicates

the

eliminates

application of

the spikes of a

an

The final trace,

intermediate filter

for

the

sensible

application

of

The criterion
a

filter

maximum deviation in peak value of less than 3%.

trials for each set

which

noisy signal while retaining a

true representation of the fracture behaviour.

suggested

E.3,

is

A series of

of extrudates provided the appropriate

post-filter value.
The

salient

fract ure

charact erist ics

as

shown

in

figure 2.7 for the filled extrudates are summarised in table

5.3:

The

results

indicate

strong

between the major characteristics of

is,

the

force,

general

deflection

gradient

(maximum

trends
and

are

similar

energies.

value

of

The

slope

in

interrelationship

impact
for

fracture;

the

exception
a

that

measures
is

of

maximum

force-deformation

trace)

which

remains

series

(C=F)

and increases slightly with increasing filler

loading.

relatively insensitive

within

pipe

The ability to measure the slope is complicated by

Page 146

Properties/5

TABLE 5.3

Impact properties of filled extrudates

Pipe
code

Peak
Peak
Force Deflection
(N/mm)
(mm)

Peak
Energy
(J Imm)

Failure
Deflection
(mm)

Failure
Energy
(J Imm)

Er

Type
of
Failure

s_dt

OA
OB
OC
OD
OE
OF
OG

24-0
165
1223
124.6
1192
1261
1216

3-4-1
2-5414--00
15-07
14--68
14--90
14--35

0-40-2
6-3
9-6
8-6
9-9
8-6

7-51
5-62
15-4-0
16-4-1
20-31
20-6419-83

0-7
0-49-0
10-5
11-0
12-5
10-9

0-40- 1
0-5
1- 1
0-7
0-7
0-5

lA
lB
lC
ID
lE
IF

964822
1263
134-3
1258
1293

7-51
6-65
12-90
14--66
14- - 19
15-4-6

3- 1
2-3
8-3
9-5
8-7
10-4-

8-88
7-75
14--4-0
15-78
15-4-8
17-89

3-6
2-6
8-9
10 - 1
9-412 - 1

1- 5
1- 2
1- 2
1- 0
0-8
0-7

2A
2B
2C
2D
2E
2F

174117
219
295
262
1034-

2-4-7
1- 946-36
5-98
7- 17
11 -84-

0-2
0-1
0-9
1-0
1- 2
5-8

8-28
7-69
10-98
7-70
10- 13
13-05

0-7
0-6
1- 5
1- 2
1- 6
6-3

0-1
0-1
0-3
0-3
0-2
0-7

3A
3B
3C
3D
3E
3F

103
66
185
256
180
198

1 -91
1- 62
5-07
4--99
4--4-3
5-39

0- 1 .
0-1
0-8
0-9
0-6
0-7

9-65
7-85
9-548-68
7-18
7-75

0-6
0-5
1- 2
1 -40-9
1- 0

0-3
0- 1
02
0-2
0- 1
0-2

4-A
4-B
4-C
4D
4E
4F

9491
184191
194180

2-242-39
4--20
5-21
6-50
5-71

0- 1
0- 1
0-5
0-7
1- 1
0-8

8-69
10- 31
9-647-71
7-76
8-03

0-7
0-8
1- 2
1- 0
1- 1
1- 1

0-2
0-3
0-2
0-2
0-2
0- 1

5A
5B
5C
5D
5E
5F

91
89
203
178
212
184-

2'4-42-33
6-22
5-85
5 - 15
6- 15

0- 1
0- 1
1-0
0-6
0-8
0-9

11-11
8-348-4-2
8-12
778
-9-00

0-8
0-5
1- 3
1- 1
1- 2
1- 2

0-3
0- 1
0-2
0-4
0- 1
0-3

B = Brittle_ BID = Brittle/Ductile_ D

. t Sod = Sample standard deviation

Maximum
Gradient
(KNmm/m)

123
114
116
119
113

130
142
123
125

B
B
BID
BID
D
D
D
BID
BID
BID

BID
BID
D
B
B

126
108
131
116

204
211
158
137

B
B
B

BID
B
B
B
B
B
B
B
B

150
149
168
166

B
B
B
B
B
B

167
166
198
155

B
B
B
B

= Ductile
Page 147

Propert1es/5

the differing

impact

might be expected.
the

maximum

because

of

provide

traces encountered and

It was not possible to accurately measure

gradient
the

some variation

for

small

the

flat

deflection

sufficient

number

hot

at

of

pressed

peak,

pOints

specimens

which

for

the

did

not

automatic

calculation of slope.
It

is

also

characteristics
plaques
split

di fferent
flat

obtained

(profiles

pipe

A &

impact

between

the

can

to

two

deformation

are considered.

seem

values for

The

the
for

flat

than

the

by

the

deforming

pipe.

However

reasonably

techniques,

impact

lower

when

hemispherical

sampling

of

accounted

invol ved

characteristics

peak

testing

be

behaviour

compared

failure

the

the

are considerably

This

deformat ion

that

from

B)

specimens.

specimen

failure

evident

especially
for

the

comparable
if

the moderately filled

results obtained

profiles

the
pipes

A and

with a filler content of 0 and 8.5 phr are vastly different

from their counterparts;

however it

values

impact

are

possible

related

specimen

to

geometry

brittle

or

performance

factor

transition is observed 1. e.

is suggested that
since

rather

these

than

brittle-ductile

failure mechanism changes

ductile/brittle

to

ductile

on

from

increasing

processing temperature.
Since
analysis
energy

of

can

f iller

the

results

the

force-deformation

be

used

loading

performance.
indicated

and

represent
processing

similar

trends

traces,

the

then

relationships

condi t ions

and

for

the

failure
between
impact

The measure of scatter (s.d) within the data is

and

type of test;

to

indicate

can
a

extrudates which

be

considered

quite

acceptable

larger degree of variation

fail

in a

for

this

is observed for

brittle manner and some samples

which exhibit a brittle/ductile behaviour.

The criterion for

classifying the mechanism of failure is described in 2.10.2

and shown in
data for
the

main

figure

5.8,

which superimposes representative

three different

extrudates and clearly identifies

modes

of

fracture:

ductile,

brittle/ductile

and

brittle.

Page 148

Praperties/5

FIGURE 5.B
Typical failure mechanisms
Force (N)
,~

r-------------------------------------,

,-

OB: BritiJe

---- oc:

...
,...

BrittJe/Ductile

....... OF: Ductile

....

...
...
...

Brittle
running a

1~

19

20

Defannation (mm)

fracture

is

visually

observed

as

crack

considerable length parallel to the direction of

extrusion or an area of the pipe wall which is sheared out.

A

crack

running

'capped'

at

in

the

direction

in

approximat e

wall being 'pushed out';

the

size

of

may

be

The length of the crack can vary

but can be in the order of 100 mm.

resul t s

extrusion

either end by further cracks transverse to the

original propagated crack.

out

of

the

Brittle/ductile

circular

sect ions

of

the

pipe

the area of the holes are at least

impactor

greater (upto 3x).

Brittle failure via shear

probe

failure

is

and

can

be

considerably

generally characterised

by a complete shattering of the specimen which is associated

Page 149

Properties/5

with crack propagation in many directions.

Ductile failure is observed as gross deformation of
the pipe,

local yielding at point of impact with attributed

st ress whi t ening,

of

drawn

cont inued deformat ion and finally tearing

yield area.

Therefore a

puncture hole of

similar

dimensions to the impact or probe is seen which can lead to a

continued

force

signal,

due

to

further

penetration of

the

probe through a restricted puncture.

The effects of
can

be

seen

in

filler

figure

loading and extruder profile

5.9;

the

impact

sensitive to processing conditions at

Here

higher

higher
impact

profiles
general
values
the

profile

resistance.

and

trend
than

temperature,

are

in

that

moderat ely

and
A

Profile F

processed

slightly higher impact

low

profile

profile B.

in

The values

very

produce equally poor impact

produces a

obtained for
are

extruder

reversed

to

nominally
D

(C,

and

the

higher
from

wi t h

E)

filler levels greater and

including 18. 1 phr then all profiles,

F,

general,

is clearly distinct

At

is

low filler content;

yields

ext rudat es

energy.

performance

with the exception of

resistance.

Profile F at

an

intermediate filler loading of 18'1 phr retains a modicum of

resistance but

is approximately halved when compared to the

unfilled grade.
Figure
levels

for

level

the

extrudates

A similar

(4.1).

presents

5. 10

graph

failure

axis

was

replaced

temperature

(' B'

onset

via

implied

would

be

by

energy

thermal

observed

the

versus

al.o

analysis

the

if

estimated

temperature)

fusion
fusion

processing

derived

from

thermal analysis.
If

the

highly

considered first;

filled

then fusion level has no

poor impact resistance obtained.

the

extrudates

dramatic
most

containing

increase in

fused

(~27'

extrudates

member;

impact
the

specimens failing in a

18'1

effect

phr)

are

upon the

A similar trend is seen for

phr

of

filler

until

resistance is observed for

improvement

is

dramatic

with

a
the
the

brittle/ductile manner as opposed to

a brittle mode.

Page 150

Properties/S

FIGURE 5.9
Failure ene".lY versus Filler canlent
Foilure energy (J/mm)

.e

..

.L.....-J--=-..J.....--J"-......I._....L._..L..._J...........J._-1..--.J
10
1!5
28
15
3Q

Filler content \phr)

FIGURE 5.10
Failure energy versus Fusion level
Foilure energy (J/mm)

B
.6 BID

12

8.5

,.

20

.. .

Fusion level

(r.)

.ee

.20

Page 1Sl

Properties/5

The

unfilled

and

lightly

filled

extrudates

<0

and

85 phr) illustrate a transition from poor brittle behaviour

to

'high'

impact,

ductile

The

characteristics

lightly

fused

with

increasing

fusion

level.

series

(extrudates

impact,

although lA and 1B do exhibit some impact resistance

processed

at

extrudates

of

A and

indicate

B)

these

two
poor

which might be associated with their higher level of fusion

(c. f.

low fusion levels of OA and OB).

It is interesting to

note that figure 5.9 demonstrated that impact properties for

lA and

1B were reversed in terms of

extruder profile;

while

fusion levels for these two extrudates are also reversed and
thus

might

fusion

account

levels

for

the impact

result

values

obtained.

considerably

in

Higher
impact

higher

properties until a levelling off or maximum is obtained;

lightly

filled

indicating
obtain

the

the

level

the

of

(8.5

requirement

same

resistance
sharp

series

transition

increases

until

levelling

off

o
at

shifted

higher

after

approximate
failure

actual

to

decrease

is

is

right

level
The

passing

fusion

mode

the

fusion

performance.

series,

phr

ductile
or

of

is

impact

of

an

phr)

the
to

impact

through

level

reached

observed.

of

20%,

where
The

a
a

last

member of this series (joined via a dotted line) is pipe OG,

which is included to demonstrate the possible existence of a
maximum

in

profile

impact

temperatures

degradation
equipment;
(' B'

energy.

due

to

OG

is

(2.6.1)

hot

spots

pipe

which

extruded
has

within

at

high

traces

the

of

processing

thermal analysis indicates a fusion level of 80%

onset

temperature

and

201. 2'C)

impact

testing

suggests ductile failure but with a reduced impact energy.

Therefore

impact

testing

of

the

filled

extrudate

series illustrated the poor impact properties of the highly

filled

pipes

and

the

transition

from

poor

to

maximum

impact value with increasing fusion level.

Page 152

Properties/5

5.3.1 IMPACT PROPERTIES:

The

INFLUENCE OF TEST TEMPERATURE

influence

of

environmental

temperature

upon

impact performance was assessed for the unfilled and filled

extrudates

processed

(2. 10.2. 1).

at

extruder

profile

temperature

The samples were carefully conditioned at

F
the

appropriate test temperature and then quickly transferred to

the pre-conditioned impact rig for testing.

The results are

presented in table F. 1 of Appendix F.

Failure
illustrate

impact

impact

characteristics

energy
an

be

although

performance,

show

again

can

increase

with

used

to

deflection

increasing

test

temperature and is not strictly related to failure energy as

in the above case.
of

It should be appreciated in the analysis

these results that

levels.

Figure

5.11

the extrudates have different

illustrates

the

dependence

of

fusion
impact

energy upon test temperature.

FIGURE 5.11
Failure energy versus Tes! temperature

failure energy (J/mm)

BID

D.

-20

Test temperature

(oC)

...
Page 153

ProperUes/5

The highly filled specimens,

unaffected

by

test

temperature

of

80C

35 5 and 40 0 phr,

temperature
and

until

conditioning

respectively,

100C

are

where

the

specimen undergoes a hot tearing mechanism which can be seen

as a small brittle/ductile impact trace.
The testing of 3F produces a

broad brittle-ductile

transition that begins at 40C and ends with a ductile trace

at

Although

100C.

ductile

fracture

is

obtained,

the

impact value is relatively small.

The
broad

moderately

filled

brittle-ductile

transition

levelling off at 50C.

failure

is

increase

in

again

2F,

beginning

produces

at

and

10C

The impact value obtained for ductile

substantially
test

pipe,

higher

t emperat ure

than

did

not

3F

and

improve

further

t he

energy

value.
The
similar

unfilled

failure

and

energies

lightly
with

filled

the

onset

pipes

produced

of

narrower

brittle-ductile transition beginning at -lOC for

OC

for OF and

finally

The

better

temperature

low

ending in ductile
properties

lF versus

failure at

of

lF

are

20C.

probably

related to the substantially higher level of fusion compared

to

OF

(c.

f.

88'7%

versus

71' 7%)

and

the

consequences

of

fusion upon ductility will be discussed in chapter six.

The

val ues

the

obtained

for

impact

energy are

qui t e high

but

level appears to decrease beyond 40C.

Therefore

the

influence

distinguishs between filler levels,

ductile
property

transitions,
with

indicates

increasing

of

test

temperature

determines any brittlelevelling

temperature

and

off

of

impact

suggests

that

fusion level can cause a shift to ductile behaviour.

Page 154

Properties/5

5. 4 IMPACT PROPERTIES OF ADDITIVE SERIES

The

pipes

containing

the

range

of

additives

were

tested in a similar manner and the properties can be listed

as given in table 5. 4:
TABLE 5.4.
ImBact BroBerties of additive blends

Pipe
code

Peak
Deflection

Peak
Force

(mm)

(N/mm)

Failure
Deflection

Peak
Energy

(mm)

(J Imm)

Failure
Energy

Maximum
Gradient

(J Imm)

(KNmm/m)

EF
OEOEA
OEB
OEC
OED
OEE
OEF
OEG
OEH

1124
1067
929
1094
1211
1175
1052
1108
1279

12'05
1264
1157
14 48
15 21
1504
12 56
16'11
1674

3E3EA
3EB
3EC
3ED
3EE
3EF
3EG
3EH

848
615
1064
915
676
753
1062
1079
1065

10'47
853
13'36
11' 28
9' 13
9'80
13' 14
15 17
14 57

BID

6' 1

62
48
78
9'2
8'8
6' 1

8'6
10'8
3'9
23
4'6
28
33
6'3
7'5
7'0

s.dt

13'29
1453
1339
2217
21'33
22'24
14'26
21' 47
21' 20

67
69
53
102
11'4
11'2
6'7
10'3
12'4

1'3
07
06
06
0'8
0'4
1'3
0'5
0'7

124
117
107

BID
BID
BID

115
116
118

D
D
D

118

D
D

11' 76

4'4
2'7
7'3

0'6
0'2
07

5'1

O' 5

3'2
3'7
7'0
83
77

0'4
07
0'6
0'4
1'0

100
99
100
104
99
103
104
102
102

BID
BID
BID
BID
BID
BID
BID
BID
BID

9'76
1465
1253
10'46
11' 05
14'44
16'94
15'84

6'6

Type
of
Failure

BID

111
98

= Brittle/Ductile.

t s. d

= Sample
The

figure

D = Ductile
standard deviation

values

5.12;

it

for

failure

should

be

energy
noted

are
that

illustrated
the

in

extrusion

conditions between the two additive series are not strictly

comparable

(2. 6. 2)

and

within each series.

sizeable
with a

It

differences

thus

comparisons

is evident

can

be

from

obtained

in

should

the

pipes OEA and OEB,

bar graph

impact

small change in type of additive or,

be

made
that

properties

in the case of

an increase in the concentration of the

Page 155

Properties/5

same

lubricant

(2.3).

In fact

two fold

increase can be

obtained with an accompanying change in fracture mode from

brittle/ductile to ductile behaviour.
will

Possible explanations

be discussed when factors such as ease of processing.

fusion

level

and

microscopy

results

are

presented

(6. 3. 2. 2>'

Figure 5.12
Foilure energy for Additive series

Failure energy (J/mm)

14r-----------------------------,
12
':

.,
10

'l

':

8
6

2
0

C
D E
Additive code

Page 156

CHAPTER SIX

DISCUSSION OF RESUL TS

6. 1 INTRODUCTION
The

preceding

chapt ers,

3-5

inclusive,

presented the results obtained from dry blending,

and

the

subsequent

tests

as

series

of

have

extrusion

brief

discrete

sections.

It is intended in this chapter to discuss the data

in detail

and compile the results to evaluate the possible

interactions.
In order
chapter
pipes
will

is

divided

processed
be

subtle

to simplify
into

over

considered.
differences

three

wide

following
parts;

range

Secondly
in

the

the

formulation

discussion,

firstly

of

the

ext rusion

extrudates
for

an

filled

condi t ions

incorporating

unfilled

relatively highly filled grade will be reviewed.

general

the

and

Lastly the

inferences gained from the above two sections will

be presented to provide a general

overview of the complete

process from powder additives to finished pipe.

6.2 DISCUSSION OF FILLED EXTRUDATES
6.2.1 DRY BLENDING AND DRY BLEND CHARACTERISTICS
The dry blending
that

dry

until

blending

the

time

addition

of

results outlined in 3. 1 revealed

was

unaffected

high

loadings

by

of

filler

filler

filler loading of 40 and 50 phr respectively).

filler

loadings

longer

blending

times

were

loading
<original

At these high
observed

which

can be attributed to filler loss as seen in the heater mixer

as

mixer

material

fouling;
available

filler
to

loss,

generate

in

effect,

frictional

reduces

heating

the

between

the particles and the high speed rotor and also between the
particles

themselves.

Thus

longer

time

was

required

to

achieve the required discharge temperature [138, 1~7l.

Page 157

DiscussioniS

The

filler

resultant

loss

is

also

shown

quantitatively by the estimated ash content,

which shows a

significant

variation

actual

content

original

for

between
filler

expected

contents

and

of 40

filler

and 50 phr.

In

fact an original loading of 50 phr yielded only 40 phr after

dry

blending,

even

though

the

dry

blending operation

carefully optimised to prevent excessive filler loss

was

(2.4).

The relatively high filler loss appears to be related to the

surface
grains

adhesion
filler

filler

is

is not

since

involved

preferentially

to

m'/g)

(70

m'/g)

(1

filler

It

(3. 1. 1. 3).

area of
grain

of

of

unlikely

surface,

at

the

polymer

possible to relate the surface

is

the

located

surface

directly to that

it

at

the

the

of

that

filler

polymer

the polymer
monolayer

is shown

folds,

and

of

to

be

only

portion of the filler surface is involved in its attachment

to

the grain surface.

appear

saturate

to

possibly

produce

adheres

to

the

polymer

filler

filler

surface

either

the

unassociated

High
a

loadings

of

the

layer

grain

pOlymer
filler

surface

or

Since

fine

particles.

subjected to higher frictional

of

(blends

forces

&

grains

tendency of

mixer

fouling by

and

which

weakly

yields

'free'

powders

are

than coarse particles

and are more likely to stick to metal surfaces [178],

the

5)

"free'

or

then

easily removed

filler particles can be explained.

The SEM micrographs (figures 3.5,3.6 & 3.8) indicate
that

the

mineral

filler

adheres

to

the

polymer

surface

initially by electrostatic and possibly chemisorption forces

[42]

and that the filler is also preferentially situated in

the

folds

of

the

irregular

shaped

polymer

grains

described in similar dry blending studies [136,176].

[42],

using

the same grade of

temperatures,

illustrated

filler

micrographs

partial adsorption of the filler;

micrographs
the

grain

which

Hancock
blending

indicated

the

however in this study the

(figures 3.6 and 3.8) provide little support to

this suggestion,
to

and similar

as

and instead the filler

surface

in

similar

is shown to adhere

manner

to other

solid,

high melting point additives [176,180].

Page 158

Discussion/6

The

level

of

adhesion

is

probably

related

to

the

filler particle size/surface area and the surface treatment

of the filler (42,51, 177J.
The

micrographs

introduction of filler,
8' 5 phr,
1. e.

illustrate

also

particularly at

that

the

levels greater than

produces polymer grains which appear more rounded,

attrition of the non-rounded fragments associated with

the original PVC grains and the preferential filling of the

folds

with

diamet er

can

compared.
report
(42],

filler.
be

A slight

observed

decrease

if

in the average grain

micrographs

3. 3 and

3. 5

are

Similar observations have been made by an interim

from TNO (176]

and a more recent report from Hancock

where the dry blending of filled grades produced more

spherical

shaped

grains

and

slightly

lower

average

particle size.
Bulk
increasing
obtain

density

blend

maximum

values

temperature
values

blending (136,177],

generally

increase

with

(137,139,168,176-177,180]

after

relatively

short

and

periods

of

although the rate of heat generation and

increase in bulk density depends to a

large extent

type and operation of the high speed mixer.

on the

In this study,

the discharge temperature remained constant and increases in

bulk density measurements were dependent
filler

content

<figure 3.1).

expected

due

to

gravity

material

efficiently 1. e.
filled

grades

increases.

the

Higher tap densities might

incorporation

of

particles

which

and

upon increases in

they are more spherical,

<blends

& 5)

higher

can

be

specific

pack

more

however the highly

yielded

disproportionate

At these high loadings the filler particles which

are unattached or loosely associated with the grain surfaces

can fill the interstices between the polymer grains to yield
exceptionally

high

tap

density

values

as

seen in

the

bar

graph of figure 3. 1.
The implications of the dry blending results suggest
that

in

order

representative
powder

to
of

produce
the

characteristics,

filled

original
then

dry

blends

formulation
the

filler

and

which

are

have. good

should

ideally

Page 159

Discussion/6

adhere

to

the

large

polymer grains.

The

problem of

filler

segregation for highly filled blends may be less significant

in a commercial dry blending process since the mixer is not
cleaned

out

after

each

batch

and

thus

steady

state

situation might occur where filler loss is minimalised.

content
level

provides an accurate means to

whereas

composition,

bulk
1. e.

density can

Ash

determine the filler

provide a

quick check

tap density is commonly

used for

upon

quality

control measurements on site.

6.2.2 PROCESSING OF FILLED EXTRUDATES
6.2.2.1 EXTRUSION CHARACTERISTICS
The instrumented twin screw extruder,
KMDL-25,

enabled the important ext rusion charact erist ics to

be monitored,

1. e.

powder flow properties,

mechanical processing energy,

temperatures.

The

presents

problems

many

when

extrusion

to a

full

down

product ion

proven

in

for

twin

attempting

screw
to

or even attempt
from a

scale production model.

useful

machines,

of

characteristics
model

mass throughput,

ext rusion pressures and 'mel t'

complexity

from one machine to 'another,

likely

Krauss Maffei

use

predicting

in

'The

extruders

relate

results

to predict the

laboratory machine
KMDL-25 is a

the

laboratory

extrusion

behaviour

scaled
and

on

has

larger

on which trials would be economically prohibitive,

and for the evaluation of formulation and processing aspects

[131, 142, 154, 179].

Hopper flow properties

The

introduction

of

substantial

amounts

can lead to various material handling problems,

of

extruder

filler
high

[177],

poor

segregation [42]
extruder

torque

powder

flow

and high bulk

values

[177].

of

i.e.

properties

filler
surging

[168,177],

densities leading to
These

problems

were

originally observed during preliminary extruder trials with

Page 160

Discussion/6

filled

blends

blends

(3,4

containing more

& 5)

than

properties

ultimately resulting in bridging of the extruder.

During the

runs

minimalised
the

hopper

by

these

the

poor

these

dry-flow

experimental

exhibited

18' 1 phr filler;

problems

fitting

of

horizontal

controlled

or

multi-pronged agitator

which gently agitates

characterist ics to a

were

the

dryblend to aid

screw dosing unit

The dosing unit accurately metered the dry blend

to

flow

(2. 6. 1).
to prevent

surging and excessive torque values.

throughput

Mass

It
that
speed

is

generally

reported

an increase in output
[131,141,142, 179l

for

twin

screw extruders

is obtained by increasing screw

and

higher

bulk

densities

138,138,154,177l.

However

since

the

screw

constant

machine starve

fed,

then

was

and

the

controlled

by

the

rate

introduced [142, 179, 181, 183l.

opposed to flood
densities)

and

was dependant

the

extruder
ext ruder

constant,

densi t y.

The values obtained

table

D.2)

processing

was

kept

the output

rate

the

material

was

The machine was starve fed as

loadings

temperature
(2. 6.

(high bulk

profiles

induced

Therefore t he out put

1).

upon the rate of the dosing feed unit,

was kept
D:

which

fed since high filler

low

ove.rloading of

at

speed

[136-

which

and thus seen to be independent of bulk

were

also

conditions

for

mass

independent

indicating

throughput
of

the

the

(Appendix

wide

positive

array

of

conveying

behaviour of the extruder and the design of the screw zones

[131,141-142,179l.

'Melt' temperature
Processing temperature was
a

thermocouple

indirect

situated

method

relationship

was

of

in

the

thermal

observed

measured by two methods;

die

head

analysis

between

the

and secondly

(1. 4. 2.5).
two

methods

the

linear
(figure

4.1) as also shown in a number of reports [114,131,179,182l,

Page 161

Discussion/6

the

however,

to

inability

accurately

the

calibrate

thermocouple resulted in the measurements being offset when

compared

to

the

thermocouple

reading

calibration.
estimated

thermal
high

Therefore it
processing

analysis produced a

analysis
or

low

measurements,

depending

1. e.

upon

day's

was suggested in 4. 1. 1 that

obtained

temperature

better measure of melt

via

the

thermal

temperature and

thus further mention of extrusion melt temperature refers to

this method of determination.
It

was

shown

that

'B'

onset

temperature

increased

with increasing set head temperature (figure 4.1),

in fact a

10'C rise in set head temperature resulted in an approximate

10'C

increase

in

'B'

onset

temperature.

Profiles

which

involved an increase in barrel temperatures and not further

increases
onset
'B'

in

die

head

temperature
onset

temperatures

did

(A & Band C & D),

indicates

the

effective

not

increase

'B'

thus suggesting that

processing

temperature

which is dominated by the die head conditions [131).

The

infl uence

t emperat ure
increase

in

profiles

(C

was

almost

value

at
,with

D)

&

temperature profiles
suggested
extruder

that
set

difference

of

the

filler

negligible

unfilled
the

blend

and

'B'

temperature

even

was

figure

onset

series and the rest of the blends.

processing

at

A slight

temperature

higher

or

(E & F and A & B respectively).

temperatures

between

extruder

effect

processing

4.2).

(figure

intermediate
little

upon

addition

extruded

4.4

lower
4.1. 1

at

lower

illustrated

temperatures

for

the
this

The good control over the

when

significant

amounts

of

filler are added can be attributed to low mass throughput,

low screw speed,
extruder

low shear rates for

[131,181)

and

controllers (Appendix D:

accurate
table D.

this type of

proportional

conical

temperature

1).

Extrusion pressures

The

twin

screw

extruder

was

fitted

with

pressure

transducers which measured the extrusion pressure at

positions within the extruder;

beginning of

three

discharge zone
Page 162

Discussion/6

(Pl>,

adaptor zone (P2) and die head (P3).

could not

These transducers

be calibrated in situ and thus gave comparative

results.
Extrusion pressures at P1 were only measured in such
where

cases

present

high

adaptor

head

by high die

resistances

temperature profiles

(A & B)

increasing filler content.

were

also

induced

by low extrusion

and the value increased with

A value is also obtained for 5C

indicating

the

resistance.

The high die resistance (high back pressure) for

these

conditions

(numbers of
the

effect

pressures

A measurable response was

table D. 3).

(Appendix D:

obtained

and

response

was

high

increased

chambers

position

of

of

full

the

the

filler
length

content
of

the 'gel

column'

and

thus

[131, 142J.

Although

under

certain

pressure value was measured by P1

it

possible

predict

within

extruder.

Covas

the

[131J

position

conducted

of
an

melting

to

measurable

conditions a
to

die

of solid or melted material)

transducer

obtained

upon

extensive

was not
the

processing

study on the same machine and concluded that the position of

melting (within one 'C'

shaped chamber) remained constant at

the beginning of the discharge zone under a wide variety of

conditions.

However

his

study

used

flood

feeding

pressure response was always registered at

full

P 1 indicat ing a

chamber of compacted unmelted material.

In this study,

due to the starve feed conditions,

always

is questionable whether

the

obtained at

melting

and thus it

P1

mechanism

position for

all

the

composition

range

would

blends

chosen.

have
under

full

and

occurred

with

Therefore

the

increasing melt
extrusion
pressure

P1

barrel

pressures
of

temperatures)

viscosity

the

bUild-up

are

screw

and

and

it

is

same

usually
the

(increases

content).

reported

becomes measurable in

transducer

increases

(increasing filler
generally

the

and the value is

upon the extruder temperature profile

decreasing

section

in

the wide processing and

provides information upon the 'Gel column'

dependant

chamber was not

in

with
Low

the

feed

suggested

that

last

third of

the screw [131,141, 143J.

Page 163

Discussion/6

Adaptor/inlet
blends

is

pressure

illustrated

in

response

figure

6.1

for

the

filled

3.2.2).

(from

The

values increase linearly with increasing filler content and

depend

upon

[ 14-2 J

the

extruder

evaluated

suggested
rate,

that

the

KMDL-25

adapt or
of

geometry

temperature

pressure

flow

in

t emperat ure and

rheological

concluded

at

that

temperature,
melt

the

constant

and

control

it

the
is

in the barrel

adaptor

transducer

properties
increase

of
in

head

flow geometry
suggested
to

material
content

ratio

filler,

and

out put

die,

out put

in

'genuine'

throughput

the pipe

that

the

(3.2).

provides

rate

die

was

temperature

Therefore the

the

point

He

adaptor

indicate

that

such as

upon

constant

indicate

at

tool

the material.

and

zones was good

filler

and

In this study,

increase in P2 which suggests that

low aspect

dependant

output

seems

the

was

pressure would

also

Stephenson

processing

properties of

viscosity differences.
constant,

the

constant

adaptor

remained

as

profile.

rheological

[131,1421.
roughly

An

linear

the loading of an inert

Polcarb

effect upon melt viscosity [184, 185J.

5,

has

linear

The effect of extruder

temperature profile is more difficult to establish since the

transducer does not

provide a

point

for

and

without

sampling

material

thermal

temperature at

analysis

is

not

possible

stripping the pipe head and adaptor assembly;

inlet /adaptor

pressure

could

not

be

plott ed

that
thus

against

t emperat ure.
The last
and resultant
filler
Head

transducer was positioned in the pipe die

head pressure was shown to be dependant

content

and

pressure

extruder

increased

with increasing set

with

head

temperature
filler

profile

content

and

temperature as might

upon

(3. 2. 2).
decreased

be expected.

In section 4.1.2 multiple regression analysts was applied to

predict

head

processing
filler
which

pressure

temperature

content.
clearly

response
(measured

mathematical

shows

due

that

the

by

to

the

thermal

components
analysis)

relationship
two

components

was

of
and

obtained

control

the

pressure response and figure 6.2 illustrates the acceptable

Page 164

Discussion/6

FIGURE 6.1
Inlet pressure Ye"'U' Filler conlen!
Inlet pressure (8ar)

...
...

c
o
E
F

,oo

.~

______

,.

______

______

..

________

Filler ""
content (phr)
"'"

~--J

FIGURE 6.2
Analysis of Head pressure
Head Pressure (8ar)
~

r----------------------------------,

..., Data
.... -

_._. Gradient=1

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

. . , ..

2110-

,,;.

:~

."
,..
,

,oa r,oo

r-

.., --.

"

.. ~I--~I~I--~I--~I~I~
lee

1~

2ee

2Sl...

Predicted Head Pressure (Bar)

Page 165

Discussion/6

straight

line

analysis

relationship

(equations

4.2

composition containing
a

wide

range

of

obtained

and

from

4.3).

the

Thus

regression

for

the

base

phr of Polcarb 5 processed over

0~40

processing

conditions,

the

transducer

response in the head could be well defined.

Torque

The final .extrusion characteristic monitored by the

twin screw extruder is motor torque (T'1);

this value can be

related to output by the expression given in equation 3.1 to

give specific energy consumption
method

of

evaluating

the

('1).

'1 is perhaps a better

mechanical

work

involved

in

extrusion since '1 is a measure of mechanical energy per unit

mass.

In

this

constant,

case,

where

the

mass

throughput

is

almost

the figures 3.9 and 3.10 which depict torque and '1

data respectively are very similar.

Thus it

is intended to

refer to Q data for further discussion and these values are

replotted in figure 6. 3 for ease of reference.
Specific energy consumpti'on
metering

zone,

in

similar

('1)

manner

is dominated by the

to

pressure

build-up,

since resistance to flow is generated late relative to the

screw length.
number

of

Also the value of '1'is dependant

paramet ers;

properties

of

[131]

extent

and

material

remains constant.
upon

the

melting

melting

zone.

extruders

set

[131,142],

of

[142J,

length

back pressure

to

be

rheological

of

'Gel

column'

assuming

that

output

behaviour

concluded

of

[181l

that

the

material

evaluated

Q was

an

two

'measure

of

the

total

within
twin

important

parameter for the analysis of such extruders.

large

Thus the value of '1 provides information

Rauwendaal

and

temperat ures

on a

the

screw
process

He considered

deformation

that

the

material is exposed to during the extrusion process and the

stress that is required to bring about this deformation'.
1. e.

'1

ex

;:

(6. 1)

Page 166

Discussion/6

Where

Average shear stress

Average shear strain

Also average shear strain can be considered as the

product of average shear strain rate and residence time.
These components are virtually impossible to compute
[1311

but have a significant effect upon mixing properties;

shear

stress

dispersive
parameter
also

is

reported

mixing

[186]

in
in

that

be

and

distributive

demonstrated

increase

to

important parameter

shear

mixing

under

specific

an

strain
[187].

certain

energy

is an

important

Rauwendaal

conditions

consumption

in

[181]

large

involved

significant increase in minimum residence time.

The extrusion data does not include melt temperature
within the discharge zone and thus Q can not be related to
melt

zone

temperature.

temperature
As

might

(' B'

be

temperature

However

onset

temperature)

Q falls

expected
and

the

the

influence

effect

processing

is shown in figure 4.4.

with
of

of

increasing

filler

is

extrusion

to

produce

series of curves depending upon the level of filler content

(4. 1. 2)

1. e.

family

of

curves

with

the

highest

filler

content producing the largest torque.

Figure 6. 3 presents the influence of filler content
upon Q;

as suggested in 3. 2. 1,

filler

content

differentiate
requiring

and

the

between

Q increases with increasing

temperature

the curves

substantially

less

profiles

with

the

mechanical

energy

for

exceptionally

high values

and

profiles

input.

The

namely profiles A &

figure highlights a number of anomalies,

B yield

higher

clearly

secondly a

tendency

the curves to level off when highly filled blends are

extruded at high profile temperatures.

associated

with

profiles

& B

The large value of Q

might

significant increase in residence time,

be
1. e.

related

to

long residence

time invokes a large value for specific energy consumption

[1811.
since a

The pressure data for P1 complements this suggestion

substantial

residence

time)

was

increase
noted

in

'Gel

whereby

column' (increase in
response

at

P1

was

Page 167

Discussion/6

obtained.

levelling

The

commensurate

with

poor

off

tendency

dispersion.

appeared

Poor

to

dispersion

be
was

obtained for extrudates containing 356 and 40 phr of filler

at

extruder

profile

temperatures

D,

and

(4. 3.1).

Figures 4.17 and 4.18 illustrate the dispersion of Polcarb 5

for

the

extrudates

5C

and

5F

respectively

(40

phr);

the

microphotographs indicate a degree of mixing for 5C while 5F

has poor filler dispersion resulting in filler dropout

An explanation for the levelling off of the Q

microtoming.
curve

(figure

6.3)

dispersion might
profiles

D,

(equation

upon

be that

E and
6.1)

and
F

the

increased

likelihood

of

poor

the high extrusion temperatures of

reduce

the

substantially

component

of shear

resulting

in

stress

lower

than

expected Q values and reduced dispersive mixing efficiency.

FIGURE 6.3
Mechanical energy ve",us Filler contenl
Q

(rf'N.'x.fg)

" r-----------------------------------,

.
.
..

.. +---~

___-<:::::::::s

E
F

28

!-_--......~

I.

~----

__~______~______i _____--+_--J

le

20

38

filler content (phr)

...

Page 168

Discussion/6

6.2.2.2 EXTRUDATE HOMOGENEITY

Optical microscopy of the filled extrudates revealed

two

main

features;

unfilled

contained residual grains,

and

lightly

filled

extrudates

and secondly moderate to highly

filled grades differed in terms of filler dispersion.

Grain content

Residual

grains

cont aining 0 and 8 5

were

phr of

detected

fill er

in

extrudates

(4. 3. 1);

the

presence

and consequences of residual grain content has been noted in

the

literature

grains

present

were

Residual

[112,116,137,142,170,188-1891.

extrudates

in

at

processed

low

processing temperatures as spherical entities, approximately

the same diameter as the original polymer grains,
flow

band

(figure

However

4. 11).

when

the

temperature was increased the grain content

the

grains

became

highly

elongated

within a
processing

was reduced and

(figure

The

4.12).

existence and shape of the grains were therefore

dependant

upon

a1

the

processing

observed a

temperature.

Terselius

et

(116)

similar behaviour and extended this approach by

quantifying the grain content of a"pipe cross-section via a

series

of

micrographs.

approximately

30%

for

processing

temperature

decreased

to

processing

virtually
shown

obtained

poorly

processed
while

(176C),

t emperat ure

microphotograph

They

negligible
was

in

4.11

value

pipe

the

at

grain

amounts

increased

figure

to

low

content

when
205 C.

reveals a

of

the
The

relatively

high level of residual grain content attributed to the low

processing temperature

(1727C)

but the total content does

not approach a value of 30% mentioned above i.e.

the machine

type and/or composition plays an important role in the level

of

mixing.

mixing

was

Stephenson
dependant

(142)

upon

suggested
leakage

gelling wi thin the ext ruder i. e.

that

flows

and

the

level

of

position

of

backpressure det ermined by

the processing conditions and composition.

Page 169

Discussion/6

Backpressure accounts for the lower residual content

of

OA

and

lA

(!!4-. 3.1>'

pipes

Little

when compared

difference

in

to OB and

processing

measured between the respective profiles

the

higher

via

profile

lower

pressures

B.

supports
type

content

presence

(CDFE)
of

pipes

(A and B),

than

and

with

was

however

shape

appreciably

of

residual

densification,

4-.1>.

(1.

an

extrudates processed

mechanism proposed

machine

[179]

yielded

, compact ion,

the

elongation'
Obande

grain

The

temperature

developed by the extrudates processed

(3. 2. 2)

residual

profile

this

1B extrudates

Similarly

conduct ing more fundament al

grains

fusion

by Allsopp
Covas

and

[112]

for

[131]

and

upon

this

st udies

particular extruder also suggested the 'CDFE'

at

mechanism.

Filler dispersion
Extrudates

~18'

containing

phr

did

not

contain

significant amounts of residual grains and those present are

highly

elongated

compositions
ensure

(figure

invoke

almost

4-.14-),

sufficient

complete

the

finished

breakdown

conditions

extrudate

(114-.3.1>.

The

suggests

extruder

these blends did show different

in

which
of

that

the

back pressures

the

grains.

to

However

levels of filler dispersion

depending

lightly

upon

filled

the

processing

grade

of

8'5

phr

presented no problems of dispersion but the slightly higher

level

of

higher

18 1 phr
processing

agglomerates
were

contained agglomerates

quite

were
well

temperatures
approximately

distributed.

characterised

by

temperatures

180'C),

temperatures
high
poor
high

(upto

processing
dispersion
processing

approximately

degree

of

with

t emperat ures
jim

10-20

Higher

at

4.15).

jim

in

filler

These

diameter
loadings

dispersion at

the
and
were

low processing

at

intermediate

and then very poor dispersion at

temperatures

30-4-0

(figure

deterioration

~190'C)

obtained

of filler

in

()195C).
the

The

highly

produced

diameter

which

exceptionally

filled

blends

agglomerat es
lead

dropout upon microtome sectioning (figure 4.18).

to

at
of

filler

Thus filler

Page 170

Discussion/6

dispersion
general,

is dependent

an

increase

deterioration
high

in

upon

in

the

processing conditions and,

processing temperature leads

quality

of

processing temperatures

noted

in

the

discussed
upon

the

discussion

in 6. 2. 2.1.
amount

of

upon

upon

Thus

dispersion.

to

effect

a
of

highly filled blends was

torque

filler

mechanical

The

in

characteristics

dispersion is

energy

input

and

as

dependent
the

filler

level.

Surface appearance
The aesthetic appearance of the pipe's outer surface
was

assessed

scanning

by

visual

electron

assessments

examination

(4. 3. 3).

microscopy

reveal

similar

(3. 3.1)

results

as

and

Both

shown

also

via

arbitrary

in

table

4.3;

any differences between the two examinations are highlighted

in

bold text.

viewing

area

differences
apart

The SEM micrographs produced a more detailed

(cf.

than
were

visual
noted

examination,

which

were

no

however
more

only

than

one

few

group

table 3.4 with table 4.3),

The results possibly confirm what might be expected,

t hat

is,

high

processing

contents produce the best

contents

and

low

quality surface,

temperat ures

and

low

filler

surface finish while high filler

processing

temperatures

produce

poor

the quality of the surface being a function

of the ability for the material in the die head/tip to flow

and

reproduce

4.3

(4. 3. 3)

the dimensions
separates

the

of

the

pipe die [148].

extrudates

into

4 & 5.

poor

The highly filled blends

surface

finish

t emperat ures
temperatures
surface

(upt 0
was

other

two groups

group

(2

&

'"

3)

surface finish

at

at

195C).

only

qUite
The

(",Group
the

equivalent
III:

lowest

equivalent

table

main
2 & 3

(4 & 5) produced very

high

processing

highest

improved the finish

("'2040

quality

even

three

i.e. 0 & 1,

groupings according to the filler loading,

and

Table

to
4.3).

of the
the

ext ruder
pipes but

worst

The next

processing temperature

to the more highly filled

of

the

filler
had

blends

Page 171

Discussion/6

at

their

maximum

moderately
produced
Lastly

filled
pipe

the

yielded

temperatures
group

blends

of

temperatures,

higher

lightly

acceptable

finish

OD,OE,ID

temperatures
VI)

produced

containing

(2E,2F

filled
at

and

while

the

extrusion temperatures

appearance

and

(i. e.

(Group

at

acceptable

unfilled

an

extrusion

processing

IF)
a

and

3F).

(0

& 1)

blend
lower

and

at

separate

extrudates

processing
the

highest

classification
having

good

signs

of

melt

aesthetic appearance (OF and IF).

None
fracture

nor

surface.
amount

of

the

micrographs

evidence

of

exhibited

filler

agglomeration

on

the

An increase in filler loading does yield a greater

of

filler

4.30-4.32),

particles

on

the

pipe

surface

(figures

however the filler particles are not present as

agglomerat es.
The
examined

inner

(3. 3. 2)

surface

finish

and,

this

in

between samples was observed.

for

those

extrudates

of

the

case,

pipes

less

was

also

discrimination

A better finish was obtained

containing

substantial

amounts

filler and/or processed at low extrusion temperatures.

Table

3.6 ranked the unfilled extrudates processed within a

t emperat ure range

(0. 173-197"0

204C) as having the worst inner surface.

surface

which

is

extrusion

is

probably related

reduced

by

the

processing at

wide

and also t he light ly filled

extrudates processed at high processing temperatures

inner

of

(0.193-

The quality of the

to molecular

introduction

of

low temperatures

relaxation

filler

and/or

thus maintaining

the finish of the inner core pin of the die.

6.2.2.3 ASSESSMENT OF THE DEGREE OF FUSION
Fusion has been studied,

as discussed in

1.

4. 2,

by

a number of workers who have applied a range of techniques

in an attempt
articles.
solvent

to quantify the level of fusion in processed

Common
testing

techniques
and

more

include

recently

application of capillary rheometry

capillary
thermal

(1.

rheometry,

analysis.

The

4. 2. 4) relies on the

Page 172

DiscussionIS

measurement of elastic pressure losses in a short capillary

[103,108,123-126, 181J.
gelation curve'

However

effect

of

upon

the
the

extrudates

which
the

is

elastic

entrance

carbonate filler
for

technique

fillers

illustrates

higher

, standard

resul tant

has been shown to be sensitive to changes in

formulation/processing
introduction

the

more

reported

to

response

[ 124J .

pressure

contain
[190J;

[113,124-125, 179J

results

increasing

higher resistance to flow.

filled

for

amounts

the entrance

highly

have

and

the

diluting

Figure
a

6.4

series

of

pressure is

of

calcium
initially

compositions due

to

the

However the increase in entrance

pressure with increasing processing temperature indicates a

distinct

levelling

increasing

off

filler

pressure response

with

content
and

higher
appears

therefore

filler
to

reduces

contents.

mask

the

Thus

elastic

the discriminating

power of the technique.

FIGURE 6.4
Enl:rance pressure versus '8' Onset

Entrance

pressure

Davenport Rheometer
1400C : 20mm/min

{]

.oo

1&4

1Q:Q

Increasing filler
content

t 92

~,

'B' Onset-temperature (OC)

Page 173

Discussion/6

The techniques applied in this study to indicate the

extent

of

(3.4),

fusion

acetone

included

swelling

the

test

methylene
(4.3.2)

chloride

and

test

differential

thermal analysis (4.1>.

Methylene chloride test

The

methylene

control type test

chloride

test

provided

indicating a pass or fail

quality

result.

All the

extrudates after immersion in methylene chloride passed with

the

exception

of

those

extrusion temperatures,
excessive

swelling,

pipes

processed

profiles A & B,

(1.

splitting and surface

at
e.

the

lowest

"<180C) where

delamination

was

observed.
Thermal analysis
The application of
technique

for

the measure

thermal
of

analysis as

fusion

has

potential

been discussed

in

1.4. 2.5 and a typical thermogram for a moderately processed

pipe

is

redrawn

features

are

in

figure

similar

in

6.5

(figure

appearance

and

2.3:

2. 9. 2).

location

to

The
other

thermal analysis studies [115,128,131,179];

a)

An
the

endothermic
glass

baseline

transition

shift

corresponding

temperature

(TG )

of

to
the

mat eria!.
b)

A small endothermic peak at approximately 100C

due to a reduction in free volume during storage
[ 128, 129].

c)

The onset

of

indicator of

the 'B'

endotherm provides a

good

the maximum processing temperature

(6. 2. 2.1>.

Page 174.

Discussion/6

FIGURE 6.5
DSC The nnogrom of 1C
Signal

EXO

U
~

ENDO

eo

,eo

1-48
148
\Ge
Temperature (oC)

129

2..

""0

:HO

FIGURE 6.6
DSC Thenn"9roms
Signal

EXO

Polymer

ENDO

.. .

,ee

128

148

168

\98

...

228

Temperolure (cC)

Page 175

Discussion/6

d)

'B'

endotherm

crystallites

of

representing
various

perfection [128].
figure

6.6

endotherm
shifts

the

virgin

progressively
a

of

melting

of

and

degrees

of

A broad endotherm is shown in

for

to

melting

sizes

the

higher
low

polymer

decreases

in

this

size

and

to

the

crystallites

and

temperature

temperature

and

due

annealing of high temperature crystallites.

A

e)

broad

endotherm

processing

'A'

peak

temperatures

develops

at

attributed

low

to

the

recrystallisation of the primary crystallites to

provide secondary crystallites of a lower order.
Figure
temperature

6.6

upon

illustrates the

these

features

for

lightly filled extrudate series

value

is

also

noticed

exhibits

measured
(4. 1:

even

for

the

broad

at

low

Table

4.

and

increasing

processing

dist inct i ve

at

few

5 phr).

(028

of

Jig)

the

which

for

t emperat ures,

6H A

1. e.

'B'

The

temperat ures

but

wi t h

peak
at

is

higher

temperatures the peak becomes more difficult to detect

almost
6H B

disappears

becomes

[116]

in

this

more
study

4-.6).

Although the

difficult
allowed

to

concluded

in

values

thermal

analysis

to determine and

because

of

excessive

and

value of

measure,

the

identification

and

of this peak where appropriate.

peak was difficult

6HB

figure

increasing

thermograms
measurement

<IF:

is

'" 1 70C

progressi vely

temperature.

processing

members

A value

increases

processing

A negligible 6H A

polymer

endotherm.

processing

1),

low

(8'

virgin

'B'

influence of

Terselius

study that

et 81

the

'B'

refrained from quoting

scatter.

The

thermal

analysis data for the large number of extrudates considered

and the major peaks identified generally agree with previous
results [113,115,116,128,131,179],
Potente

et

the major

a1

[182]

peaks;

the endothermic

it

provided a
was

However a recent study by

different

concluded

peaks depended

upon

that
the

interpretation of
the development

of

particulate nature

Page 176

Discussion/6

of the material and whether the material had been processed

above a

'critical gelation temperature'.

and'S',
peaks

were

and

to

as

related

to

the

were

structure,
nei t her

referred

if

the

the

or'S'

'A'

gelation
was

was observed.

not

peak,

'S' ,

was

observed;

of

endotherm was

while

'S'

onset

temperature

associated

with

interpretation
similar
high

measured

yields

processing
No

development
important

of

well

these

is

peaks

structure.

The area of
from the

'A'

220'C>,

to

terms

'B'

of

until

at

for
peak

peak
This

24-5C>.

value

(ca.
offered

this

an endothermic

developed

this

above

baseline

(ca.

in

In

energy

temperatures

the

peak

the existence
of

project,

molecular
a

number

or
or
.of

differences from the above publication are noted;

the existence of a'S'

for

to

explanation

of

crystallinity

the onset
large

then

then a single

& 'S'.

'A'

by drawing

grain

compounded

processing

decomposition

proportions

disappears.

to

the

In t he case of compounded

temperature split this peak into two,

'S'

'A'

post-gelation

below the' critical gelation temperature'

PVC

6.6

and

destruction

blend

PVC

The two peaks,

the

and thus it
st ruct ure.

virgin
is not

endotherm is clearly shown in figure

polymer,

albeit

broad

and ill

defined,

related to the destruction of the grain

Secondly the measurement of 'S'

specimens differs since the baseline

for the processed

is drawn from the'S'

onset temperature to a second inflection in the trace at ca.

205-220C.

This

peak

is

related

to

the melting of

primary

crystallites and complete melting is envisaged at these high

t emperat ures.
The introduction of

filler

did not

characteristics of the thermograms and

by

the

filler

interaction

level

(191).

(53)

which

However

the

affect

the main

TG seemed unaffected

suggests

little

introduction

molecular
of

filler

obviously reduced the size of the endotherms proportional to

the level of filler;

if this effect is taken into account by

appropriate normalising (4.1),

then the size of 'A'

and'S'

are not dependant upon filler content.

Page 177

Discussion/6

Master

fusion

curves

are shown

in

figures

4.6

4.7 and these can be described mathematically as in 4.

These

normalised

extrudates,
6.7

and

6.8.

It

can
an

be

seen

inert

the level of

level

curves

which

both filled and unfilled,

introduction of
affect

fusion

fusion.

these

filler

Any slight

with increasing filler

1.

all

3.

the

are redrawn in figures

from

mineral

describe

and

content

graphs

did

that

not

the

appear

to

increases in fusion

(table

4.1)

were also

associated with increases in processing temperature and thus

these data points continued to fit
maximum value of
6H"

from

the

approximately

best

fit

temperature of 207Cj

curve

the polynomial

10.53 Jig was estimated

at

an

approximate

range

levels

of

values.
data

of

fusion

fusion,

The
points

levels

1. e.

fusion

A
for

processing

this value agrees well with a maximum

range of 10-12 Jig suggested by Gilbert

broad

curve.

OA

curves

were

obtained

043 Jig

comprised

according

to

et 81 [114],

the

from

(1'4%),

of

very

to

discrete

extruder

Thus a
low

high 6H"
groups

of

profilelhead

temperature (6. 2.2.1) and although the curves are beginning

to level off,

further

increase in 6H A may be obtained at

higher processing temperatures.

Therefore
provided

the

convenient

application
and

of

apparently

thermal

analysis

accurate

method

determine the fusion level of the pipe specimens,

the

composition

was

significantly

to

even when

altered

by

the

4.2.2) does not

yield

incorporation of large amounts of an inert filler.

Acetone

The acetone shearing test

quantitative
assessment

information

of

the

network.

The

(4. 3. 2)

according

temperatures
content

in

test
and
a

but

level

of

similar

provides

the

the

appeared

(1.

cohesion

divided
to

test

shearin~

to

manner

within

extrudates

original
be
to

qualitative
the

polymer

into

groups

extruder

independent
thermal

of

profile
filler

analysis.

similarity was observed between the groups obtained by this

Page 178

DiscussioniS

FIGURE 6,7
Mo.ter Fusion CUfYe:- Energy
Energy (Jig)

,.
'2

,.

,"

'A'

,,.. ,...

198
195
IN
1"
lB'!.
'B' Onset temperature \oC)

2'.

28!5

FIGURE 6,8
Master Fusion Curve:- % Fusion
10 Fusion

,a

..
.
.

..
a

,,. ,...

lee

185

198

19!!II

'B' Onset temperature \oC)

28S

2'.

Page 179

Discussion/6

assessment
6.8).

and

those

Extrudates

revealed

processed

at

fusion levels less than =30%

optical

microscopy

indicat ed
easy

very

of

poor

agglomerates
extruder

(figure

approximately
acetone

30-65%

shearing

acetone
of

the

primary

tast

and

(figure

swelled
network

yielded

(figure

or

in

part icle

at

moderate

fusion

level

of

breakdown

during

the

resisted

specimens

resulting

processed

indicated
and

analysis

part icles

Pipes

4.21>.

temperatures

profiles

the

to

thermal

(via thermal analysis) and the

cohesion

fragmentation

by

the

Lastly

4.22).

group

comprising of the extrudates processed at profiles E and F,

1. e.

)65% fusion,

resisted

breakdown

fibrillar
4.23).

produced a
and

ligaments

strong cohesive network which

under

sufficient

between

The subjective test

large

did not

an

approximate

(table 4.1>.
of
and

10C

difference

resulted

in

(figure

agglomerates

distinguish between the

(E and F),

higher extrusion temperatures

is

shear

in

even though there

'melt'

temperature

However the test does provide easy examination

poorly fused

specimens and complements thermal

the methylene chloride test

analysis

in establishing the extent

of fusion of processed products.

At

low

processing

temperatures

particles are clearly evident,

190C),

primary

via" the acetone test,

which

confirms the relationship between primary particle loss and

the

development

of

the

these low fusion levels

the

network

chloride test.

offers

'A'

peak

[116,131];

secondary

at

35%) the poor cohesive strength of

little

resistance

to

the

methylene

At higher processing temperatures the loss of

primary particles is evident [67,77,92)

of

similarly

crystallites

well

and the development

defined.

At

the

processing temperatures no primary crystallisation

highest
(6H B )

is

detected together with fewer primary particles (figure 4.23)

and also the 6H A /% fusion curve begins to level off.

Page 180

Discussion/6

6.2.3.1 TENSILE PROPERTIES

The

tensile

properties of

the unfilled

extrudates with varying degrees of

5.1;

and

filled

fusion are described in

the results can be discussed with reference to yield

and post-yield deformation.

Yield parameters
Yield properties are listed in table 5.1 and it can
be

seen

from

this

table

that

elongation

at

yield

(Ey)

appears independent of extrusion profile and filler content.

However yield stress
figure

6.9

illustrates

yield

(similar to figure 5.3).

phr),

remains

cry

is dependent

(cry)

At

upon filler content;

stress

versus

fusion

low filler contents

independent

of

fusion

level

(upto 18 1

level although the

load bearing characteristics at yield are clearly dependent

on

the

with

level

of

increasing

filler.
fusion

At

higher

level;

the

loadings,

cry

reduction is

decreases
concurrent

with poor dispersion obtained at higher filler loadings and

higher

processing

resulted

in

analogous
filler

temperat ures

large

to

filler

larger

(4. 3.

agglomerates

particle

Poor

1).

size

(4. 3.

dispersion

1)

filler;

which

is

increasing

particle size has been shown to have a detrimental

effect upon properties [52, 193J.

Thus yield parameters appear relatively insensitive
to

changes. in

workers

fusion

level

as

The

[75,131,151, 153l.

suggested
negligible

by

number

response

to

of
the

level of secondary crystallites and number of entanglements

suggest that
smaller

yield properties are dependant on 'flow units'

than

the

spacing

of

entanglement

couplings

[131,151l.

The influence of
illustrated in
with

figure

increasing

resulting

1n

filler content

6.10;

volume

dilution

fraction

decrease

reduction is almost

a
in

on yield stress is
effect

(similar

yield

to

stress

is observed
figure
[52,53l.

5.

1)

The

linear although deviations are observed

Page 181

Discussion/6

due to poor dispersion in extrudates containing substantial

amounts of
for

the

filler.

Nielsen [192]

stress-strain

presented a simple theory

properties

of

filled

polymers;

the

theory accounted for the consequences of perfect adhesion of

the

filler

to

the

polymer

matrix

and

alternatively

the

situation where all the load must be carried by the pOlymer.

In

the

no

adhesion

case

the

predicted

relative

tensile

stress can be estimated by the following relationship:

(6. 2)

(jREL

Where

(jREL

Relative tensile stress

Volume fraction of filler

Stress concentration function (=1)

Figure 6. 10
that

the no adhesion model

the relative tensile stress at

follow a
not

illustrates

similar

accurately

value for

yield values generally

relationship [52].

predict

the

actual

and

The simple model

observations

the stress concentration function

does

since

the

is unlikely to

be one and may differ according to the level of dispersion.

Post-Yield parameters
The

preceding

parameters

were

section

insensitive

to

suggested
the

level

that

yield

of fusion

while

yield stress was strongly influenced by the level of filler.

Post-yield values,
ability

of

the

however,

test

were strongly dependant upon the

specimen to neck

and

then cold

High extensions produced higher breaking stresses

(aB)

draw.
while

rupture during the necking mechanism resulted in low values.

This

relat ionship bet ween elongat ion

at

break

(e: B)

can be seen if

figures 5.4 and 5.5 are compared

high

scatter

degree

of

was

observed

for

these

and

(5.1>.

aB

post-yield

parameters (table 5.1) due to the instability of the necking

mechanism.

The transition between the formation of a stable

neck (cold drawing) and necking rupture has been examined in

Page 182

DiscussionIS

FIGURE 6.9
Yield stres. versus Fusion level

..
..

Stress (MN/m2)

..

..

o phr

8.5 phr

18.1 phr

35.5 phr

40 phr

.a
7e
fusion level

sa

er. J

ge

100

118

FIGURE 6.10
Yield stress versus Volume fraction
Relative tensile yield

---.......
_._.
--

I."

Profile
Profile
Profile
Profile

0
F
C

e.'

....
..,.

....
.... ....

No adhesion

8.t8

8.28

Volume fraction of filler

'.30

Page 183

Discussion/6

number

of

occurrence

previous

related

reports

to

tensile

aspects of the test

specimen,

characteristics.

would

instability

It

gave

&

test

to

rate,

and

its

geometrical

temperature and material

from table 5.1

poor

that

reproducibility

thus high standard deviation

neck

in

the

values

for

OB'

Figure 6.11 illustrates

technique)
with

strain

appear

raise

drawing region and

[151,194--197)

and

figures

divides

5.4- and

the

according

similar

tensile

to

the

trends

5.5.

ext rudat es

exhibited

responses.

The

low

are

The

into

of

low

val ues

observed

influence of

response

level

versus fusion level

OB

two

filler.
values

might

be

when

compared

filler

content

groups

The
and

(DTA

of

highly

filled

similarly

relat ed

to

data

low

OB

dil ut ion

effect

upon the load bearing characteristics of the polymer

being

replaced

by

consequence of
also

reported

an

inert

particulate

poor dispersion
the

reduction

(4-. 3. 1).

of

filler

increasing

filler

content and in one case of poor dispersion the value for

was severely reduced.
low

levels

of

relationship

The second set

filler

between

reveal
and

OB

Chauffoureaux [53]

with

OB

and/or

OB

of data incorporating

similar

filler

values

levels

and

is

the

not

as

straightforward as in the case for yield behaviour.

The influence of
ascertain;

figure

fusion

level

suggests

6.11

that

is more difficult
decreases

OB

to

with

increasing fusion level with a possible broad maximum at low

fusion

levels

observed
1.

5. 3.

feature
true
Covas

by

(cf.

figure 5.5).

various

workers

However

since

then

is

it

influence of
(131)

neck

perhaps

fusion

conducted

A maximum has indeed

[67,108,131)

as

instability

was

inappropriate

level.

Terselius

tensile

tests

demonstrated that the extent of cold drawing

been

discussed
a

in

prevalent

to consider

the

et a1 [151)

and

above

and

(e)

To,

provides a

good indication of the influence of fusion level.

Page 184

DiscussionIS

FIGURE 6.11
Ultimate stre"" versus Fusion level
Stre!:S (MN/m2)

r---------------------------------------,

.
27.3

,.

se

6.Q

7e

Fusion level (%)

100

He

6.2.3.2 IMPACT PROPERTIES

The

impact

interrelation
numerous

performance

with

reports

fusion

(1. 5. 3).

of

UPVC

level

has

However

ext rudat es
been

and

its

examined

in

meaningful

comparisons

are complicated since impact testing is critically dependent

on

the

method

unnotched,
holder,
an

of

test

testing,

temperature,

specimen thickness,

instrumented

(2. 10.2);

1. e.

falling

type

of

test,

notched

specimen preparation,
filtering etc.

weight

impact

or

specimen

In this project,
tester

was

used

the design of the test procedure was discussed in

2. 10. 2 and 5. 3.

Page 185

Discussion/6

Three types of failure were observed

arbitrarily defined as brittle,
according to
trace
and

visual

(figure
energy

fracture
produced

5.3).

the

Brittle

resulted

with

similar
in

failure

fracture

peak

instrumented

tester

and

characteristics

low force.

over

ductile

but

fract ure

produce

energy

produced

an

as

failures

(slope of force-deformation trace),

to

such

short
and

behaviour

in

in

fract ure

force

yield

di fferences

resultant

occurring

Brittle/ductile

deflection gradient
varied

brittle/ductile and ductile

examinat ion and

values

periods.

(5.3) and were

considerable

val ues.

Although

accurate

fracture

the
trace

which could be analysed to yield relevant information on the

main features discussed in 2. 10.2;
to

be

the

extrudates.
summarised

best

method

of

failure energy was found

distinguishing

between

the

The influence of filler and extent of fusion is

in figure 5.10 and is reproduced

in figure 6.12

for ease of reference.

The influence of fusion level can be seen to have a
dramatic

effect

upon

performance

dependent upon filler content.

a

and

is

critically

The unfilled series exhibited

sharp transition from brittle failure

poorly fused pipes to a

also

(.

symbol)

brittle/ductile fracture

of very

(a symbol)

of pipes wi t h a fusion level of approximatel y 20-30%.

performance continued to improve,
mode of failure
approximat e

(. symbol),

fusion

level

passing through a

Impact
ductile

and a maximum was obtained at an

of

70-75%

(' B'

onset

t emperat ure

"'193-196C).

A further

increase in fusion level indicated a

signi ficant

drop

impact

approximate

location

in

is

energy.

well

supported

publications [67,108,113,115,150, 179,198l,

maximum
by

and

its

number

of

however the exact

position and breadth of peak is not well defined.

Obande

[179l

observed

testing using different

screw

ext ruders;

maximum

depended

network,

which,

he
in

maximum

compositions

concl uded

upon

the

turn

that

existence

was

related

in

notched

processed on two
t he

development

of

an

to

the shear

Izod
twin
of

inhomogeneous
regime

during processing and the nature of the composition.

Page 186

DiscussionIS

FIGURE 6.12
Failure energy Yersus Fusion level

Failure energy (J/mm)

o phr

B
B/O

~e 8.5 phr

eO

12

I
I
I
I

f'

I
I
I

..

.,.",
~

..

..

..

4~_

..

,ee

!\"

fusion level (r.)

network'

network

optimised

27-4() phr

-~-~::---- -~
;;;::'J"
------.-

refer to an 'interparticulate

Terselius et B1 [150J
entanglement

18.1 phr

theory

produces

which,

maximum

unnotched falling weight tests;

in

the

case

of

performance

on the other hand,

an
in

they did

not obtain a maximum for the Charpy testing of notched pipe

Similarly Menges et B1 [67J

specimens.
whereby

particulate

network

proposed a mechanism

system

could

enhance

performance <figure 1.2).

Summers
peak

with

et B1 [149J

falling

weight

polishing the reduction

a~

also observed a maximum impact

impact

tests;

but

on

press

high processing temperatures was

eliminated to yield a monotonic increase in performance with

increasing

extrusion

temperature.

It

was

concluded

that

Page 187

Discussion/6

surface

stress

processing
work,

concentrators

temperatures

due

to

melt

resulted

in

fracture

at

high

impact.

In

this

poor

no evidence of melt fracture was observed from the SEM

micrographs
surface

(4. 3. 3)

and

roughness

was

thus

neither

melt

fracture

responsible

considered

nor

for

the

decrease observed for OG.

series

It

is

suggested

is

attributed

that

to

impact

the

development

particle

entanglement

with

structure

strength

of

of

the

coherent

low fusion levels retained a

particulate network structure;

primary

behaviour

(4.3.2)

little

cohesive

or

resulting in poor resistance

to failure,

also,

the proportionally high level of residual

grains

may

have

levels

increased

thus

impact

primary
absence
impact
a

the

residual

energies.

strong

The

while

final

strong coherent

of

effect.

Increasing

cohesive strength of

performance,

particles.

produced a

detrimental

fusion

the network

retaining

some

processing regime

and

residual

(T M "'201'C)

structure but with the possible

primary

particles

leading

to

reduced

The presence of a few primary particles in

network

provides

well

distributed,

discrete

weak

regions whereby energy dispersive mechanisms are invoked by

localised
discrete

yielding
rubbery

and

voiding

additives;

(cf.

UPVC

figure

1. 2).

modified
It

is

by
also

interesting to note that the value for primary crystallinity

(6Ha) measured by thermal analysis is virtually zero at this
processing temperature
residual

grains

(4.1),

with

and the progressive

increasing

processing

results in virtually no residual grains at

loss

of

temperature

this temperature

(114. 3. 1).

The

introduction

upon

failure energy

than

27 3

impact

phr

of

filler

(figure 6.12);

00.163

volume

had

filler

dramatic

effect

contents greater

fraction)

exhibited

poor

resistance with the failure energy value reduced to

approximately

10% of

This

reduction was also observed by Zolotor [521;

level

of

the

maximum

for

the

unfilled

series.

who concluded that samples 'containing 0'34 % volume fraction

of

filler,

irrespective

of

filler

particle

size,

had

an

Page 188

DiscussionIS

impact

resistance

poor

resistance

dispersion

of

concentration
propagat ion.
the

of

only

can

be

an unfilled grade.

The

the

and

attributed

the

filler;
loci

5-15% of

offers

to

number

easy

and

crack

level

size

of

initiation

stress

and

crack

The infl uence of fusion has li t t le effect

consequences

of

the

test

due

to

the

extent

upon

of

the

cri t ical flaws.

The moderately filled series containing 18'1
Polcarb

was

similar

in

behaviour

to

the

phr of

highly

filled

members until a brittle/ductile failure was obtained for the

highest
is

fused

still

member.

The failure energy of

considerably

lower

than

for

this

the

pipe

<2F)

brittle/ductile

failures of the unfilled or lightly filled extrudates which

might

be

filler.

expected
However

developed

at

detrimental
observed

due

it

high

effect

that

the

would

dilution

appear

extrusion
of

the

to

that

of

dispersion

inert

network

overcomes

concentrators.

of

an

stronger

temperatures

stress

level

effect

It

at

the

was

the

also

highest

processing temperature was considerably better than the more

highly

filled

series

<4. 3.

which

1)

suggests

that

poor

dispersion behaves in a similar manner to oversize particles

<1. e.

increases st ress concent rat ors effect)

The

similar

lightly

manner

to

observed

from

poor

improved

failure

than

unfilled).
failed

the

unfilled

impact

Further
in

ductile

the

unfilled

appears

to

be

shifted

brittle/ductile

low

filler

is

failures

mode.

level s

to

50%

fusion

to

level

higher

more

likely

since

the

fusion
to

values

the
were

curve

levels.

incur

filler

much

of

complete

the

was

resulted

the final member

and

The

brittle or

stiffens

matrix and thus reduces the critical flaw size [199],

brittle/ductile

failure

manner

than

the

value was slightly lower

unfilled

as might

series

the

Indeed

the lightly filled grades had a greater tendency to fail

a

<20% higher

The measured

series

in

transition

fusion

in

behaved

approximately

behaviour until

to

of

at

phr)

pipes;

increases

similar

introduction

series <85

energies at

in improved impact
series

filled

[53],

and

in
the

be expected from

Page 189

Discussion/6

the

incorporation

(' dilution

of

effect').

an

The

inert

85

phr

particulate
series

did

additive

not

show

tendency to peak at high extrusion temperatures which might

be

explained

by

the

fusion levels (i.e.

temperature),
for

high

shift

of

the

curve

to

higher

maximum not reached at highest extrusion

or if a particulate network is a prerequisite

failure

dispersed

general

small

energy
amount

then
of

the

introduction

mineral

filler

of

well

satisfies

this

cri t erion.
Thus the impact performance of the pipes was seen to
be

highly

dependent

upon

filler

level/dispersion

and

the

level of fusion.
The
considered

influence

(from figure

mode

of

failure

test

temperature

was

also

and the results are replott ed in figure

(5. 3. 1)

6.13

of

The test

5.11).

and

temperature affects

also the measured impact value.

the

Table

summarises the range of brittle to ductile transitions

6.1

observed for all the pipes.

It can be seen that
in

broader

beginning

at

transition
higher

increasing filler level results

with

test

the onset

of

temperatures.

the

The

transition

most

highly

filled pipes (35'6 and 40 phr) did not exhibit a transition

but

slight

improvement

in

fa1"lure

characteristics

temperatures corresponding to the TG of UPVC.

filled pipes

(18'1

and 273 phr)

at

The moderately

revealed broad transitions

with the final ductile failure energy commensurate with the

level of inert filler added.
The unfilled and lightly filled pipes were similar
in their response to test temperature;
occurring
[195l.

the

close

O'C

and

involving

range

of

30-40'C

A maximum in failure energy occurs at 41'C whereupon

values

polymer

to

the transition range

decretlse

(t able

F. 1).

slightly
The

due

to

slight ly

the

softening

lower

onset

of
of

the
the

brittle-ductile transition observed for the pipe containing

85 phr (IF) may be accounted
by the higher level of fusion
,
measured for this pipe versus the unfilled pipe <887%
versus 717%).

Page 190

Discussion/6

TABLE 6. 1

Brittle-ductile transitions

Filler
level
(phr)

Brittle-ductile
transition
( 'C)

Maximum impact
value
(J Imm)

-10 ... 20

14'

8'5

-20 ... 20

13' 6~ 41 'C

1~

41'C

18' 1

0 ... 60

10

273

20 ... 100

6'

35'6

60 ... >100

N/A

40

80 ... >100

N/A

1~

60'C

1~100'C

FIGURE 6.13
Failure ene'9Y versus Test temperature

Failure energy (J(mm)

BID

eO

B.5 phr

.B

,"e----.--'"
4

18.1 phr

,,

,,,
,,

27.3 phr

-20

28

"8

Tes! temperature (cC)

BB

'BB

Page 191

Discussion/6

Thus

figure

brittle-ductile
increases

and

6. 13

illustrates

transitions.
broadens

the

Filler
transition

the

presence

addition
to

of

generally

ductile

failure,

reduces impact energy even when ductile failure is observed,

and

above

critical

dispersion;

impact

filler

levels

performance

and/or

is

not

cases

improved

of
by

poor
higher

test temperatures.
6.3 DISCUSSION OF ADDITIVE SERIES
The

previous

section

containing a

wide range of

the

of

results

composition

an

filler

unfilled

containing

discussed

and

range

the

levels;
a

of

extrudates

in this section,

filled

phr)

(~27

primary

base

lubricents

and

impact modifiers will be considered (2.3).

The

base

composition

(2.2)

contains two additives

which are considered to have a lubricating function;

lead
of

stearate and calcium stearate.

a

primary

system'
this

lubricant

affects

normal

Therefore the addition

the

overall

'lubricant

and should not be viewed in a singular manner.

point

in

mind,

it

should

also

be

noted

that

With
the

concentrations used for the component lubrication system may

not

necessarily

the

achieve

experimentation may reveal

optimum

system;

better combination or

the exist ence of synergist ic int errelat ionships.

and levels of the primary lubricant

further
perhaps

The choice

was based on practical

experience where the base lubrication package is tailored by

the choice of the third component
design or

to overcome speci fic

melt fracture,

to suit

machine/die head

processing problems such as

weld lines etc.

6.3.1 DRY BLENDING AND PROCESSING OF ADDITIVE SERIES

6.3.1.1 DRY BLENDING AND DRY BLEND CHARACTERISTICS
,

The dry blending of these compositions was described

in 3. 1 and it

can be seen that

no significant

differences

Page 192

DiscussioniS

in dry blending times were observed.

Similarly,
density

and

the

ash

dry

content,

blend

characteristics,

remained

insensitive

to

tap

varying

additive type and the values were comparable to the original

series

(0-5).

content

of

The

"'27-28

ashing
phr

technique

for

suggested

filler

the 3E-=>3EH series which agrees

well with the original blend containing an estimated

of filler
and

the

(3).

30 phr

Tap density values depended on filler content

values

differed

slightly

with

variation

in

filler

content.
Thus the dry blending results of these compositions
confirm

the

trends

observed

for

the

original

series;

no

difference in dry blending time upto moderate filler levels,

filler
moderate
filler

content

agrees

filler

levels

level

blending

(6.2.1>.

behaviour

size/design

well

of

to

the

with

expected

and

tap

density

The

apparent

composition

high

speed

is

values

dependant

insensitivity

can

be

mixer

upto

related

which

upon

of

dry

to

the

ensures

good

distribution and uniform heat generation to produce similar

mix

times

and

similar

bulk

densities

per

given

filler

loading.
6.3.1.2 PROCESSING CHARACTERISTICS
The processing results for
presented in 3. 2. 3 and,
measured

processing

pressures)

have

say,

pressure

head

values

for

extruder

was

observed

between

extrudates
higher

is

the

blends

it can be seen that the

that

commensurate
The
good

(torque,

trends,

torque.

(3E-=>3EH)

temperatures.

parameters

considered

processing

modi fied

in general,

similar

Q and

the additive series are

extrudates

extrusion

is,

an

increase

in,

with

an

increase

in

temperature
since

and

control

little

except

of

the

difference

was

that

the

filled

were generally processed at a slightly

temperature
resulted

in

(4.2)

and

marginally

also the
higher

acrylic

processing

The dry flow properties of the blends did not

present any problems in the feeding of the extruder even at

Page 193

Discussion/6

30 phr filler
filled

levels.

series

signi ficant

The results for the unfilled and the

can

not

be

di fferences

in

compared

mass

directly

out put

and

due

screw

to

design

(3. 2. 3),

The

unfilled

differences
lubricant
first

five

called

processibility

members
results

internal

observed
m. pt.

are

and

indicated

when

the

different

considered

clearly
OE-

base

primary

(OE-=>OED),

OEA

If

the

then

the

the

so-

between

lubricants.

and

dramatic

lubricant.

differentiate

external

between

paraffin wax
low

series

was substituted by a

extrusion
was

in

additive

Little difference

where

the

high

m. pt.

was substituted by a higher level of a

(~95C)

paraffin

wax

These

(~60C).

lubricants

are

generally classed as external [19,27,37-38,200J and thus the

overall

lubricant

package

was

more

external

in

nature

producing low Q and extrusion pressure values.

When the level of the low m.pt.
10

phr

(OES),

component

the external

system was

wax was increased to

lubrication

enhanced further

efficiency

leading to

of

the

very

low

torque and pressure values.

Conversely

the

introduction

of

internal

lubricants

(OEC & OED) such as GMS (fatty acid ester of glycerine) and
hydrogenated
increase

in

castor

oil

ext rusion

[19,27, 146J

lead

characterist ics;

the

these compatible lubricants required a

in

mechanical

energy

input

proportions of a non-polar,
The
<"'105-110),

next
low

this

is

and

pressures

lubricant

were

might
due

an

to

efficiency.
substitution

final
was

OEF,

significant
compared

polyethylene
type
An

to

high m. pt.

low

significant

introduct ion of

incorporated

external

related

its

sufficiently
The

(OEE)

observed.

be

increase

to

similar

non-compatible lubricant.

concentration

considered

behaviour
being

member

when

to

to

member
where

have

the

which
l' 0

phr

high

wax.

additive,
late
the

this

of

addition

the
level

lubrication

involved
of

torque

for

action

external

m. pt.

Although

high

explanation

and/or
low

st earic

lubricant
acid

was

Page 194

Discussion/6

introduced.
that

of

The processing behaviour of this blend resembled

the highly lubricated blend containing

the low m. pt.

not
1. e.

appear
Q

was

stearic

efficient

low

but

in

not

pressures

containing

low

acid

compatible

phr of

paraffin wax except that the stearic acid did

as

head/inlet

1 0

as

low

were

levels
is

terms of

of

as

paraffin

is

not

mechanical energy input as,

OEB

while

comparable

predominantly

material

external lubrication,

wax

say,

to.

<OE-

external

as

values

of

ext rudat es

&

OEA).

Thus

but

the

more

efficient

in

reducing

the non-polar paraffin wax

at equivalent proportions.
(OED & OEH) in

The introduction of impact modifiers

conjunction with

the

melt

[146, 201J

viscosities

values

(cf.

modifier

OED

(ACR)

lubricant

OEH

&

and

with

system

system of
thus

respect

resulting

OE- yielded high

high

and

to OE-),

in

pressure

the

acrylic

substantially

higher

torques than the chlorinated polyethylene (CPE) system.

the

instrumented

twin

screw

extruder

provides

Thus

useful

comparative information upon the efficiency of lubricants to

reduce melt viscosity and mechanical energy input,
enVisaged

that

further

experimentation

and it is

would

allow

optimisation of the lubricant system.

The extrusion results for the filled additive series
vary

less

and

do

not

differentiate between

low levels

of

external lubricant or comparatively high levels of internal

lubricant
and

3EE

(3. 2. 3

incorporat e

indicated

by

the

characteristics
(02

and

Appendix D.4).

vast ly different

unfilled

remain

phr low m. pt.

Blends

series,

remarkably

paraffin wax)

3E-,

3ED,

3EC

lubricant systems

and

yet

similar.

the
The

as

extrusion
blend

3EA

was similar to the above

group but produced slightly higher extruder results.

The remaining two blends,

3EB and 3EF,

l' 0 phr of a strongly external lubricant

wax)
m. pt.

and

moderately

stearic

dramatically
"'50%

and

the

acid)

efficient

respectively.

increased

paraffinic

wax

(low m. pt.

external
These

processibility,
appeared

incorporated

lubricant
processed

1. e.

to

paraffin
(low
blends

Q reduced

reduce

to

by
a

Page 195

Discussion/6

great er

than

ext ent

the

stearic

acid

while

extrusion

pressures remained similar.

Therefore the introduction of a substantial level of
filler

appears to upset

proportion

of

the lubricant

balance and a higher

lubricant

required

external

acceptable processing conditions.

high levels of an int ernal

is

to

achieve

The introduction of quite

lubricant

has li t t le beneficial

effect and the under-lubricated systems do not discriminate

between

external

lubricant

types

at

low

proportions.

The

gross differences between the processibility of these filled

extrudates can be related to the level of filler dispersion
which will be discussed in !l6. 3.1. 3.
The
significantly
series.
ACR

increase

as

blend

the

in

(3EG)

The CPE system

modified

filled

modified,

impact

grades

case

of

did

the

not

unfilled

was similar to 3E- while the

had

higher

slightly

torque

characteristics.
6.3.1.3 EXTRUDATE HOMOGENEITY

The optical microscopy of the additive series again

revealed that residual grains were an important feature for
the

unfilled

series,

while

filler

dispersion

varied

significantly for the filled extrudates (4.4. 1>.

Grain content
The

residual

grain

structure

for

these

extrudates

varied significantly between the additive series and since

the

processing

throughout
of

the series at

residual

variable.

temperature

grains

must

remained

"185-189C

be

virtually

(4.2),

explained

by

constant

then the level

another

process

A relationship was observed between the extrusion

characteristics

such

as

Q and

quant it Y of residual grains.

head

pressure

High pressures

versus

the

and mechanical

energy inputs resulted in low levels of residual grains as

shown in the following comparison:

Page 196

Discussion/6

POOR ----- grain content ----- GOOD

OEB

OEF

OEA _ OE-

OEC _ OED

OEE

OEB

OEF

OEA

OEC

OEE

LOW
A

high

pipe

OED

----- head pressure ----- HIGH

lubrication

external

tendency to retain a
t he

OE-

efficiency

while

reduced

involves greater mechanical energy,

ext ernal

lubricant

increasing

(external:

proportion

of

levels

stearic

unfused

efficiency

higher backpressures and

a tendency for a more homogeneous extrudate.

that

high proportion of residual grains in

extrudat e,

observed

has

of

acid)

grains'.

Gale (146] also

non-compatible

lead

He

to

referred

greater
to

these

entities as unfused since intergrain fusion 1s clearly not

developed,

but

the

effect

of

intragrain

fusion

was

not

considered.
The influence of
with

respect

to

grain

impact

memory;

modifier produced extremes

the

CPE

modified

extrudate

exhibiting the highest proportion of grains for the unfilled

additive

series

(figure

whilst

4.33),

the

ACR

modified

system exhibited a few highly elongated grains (figure 4.37)

and

was

clearly

series.

The

consequence
modifier.

the

gross

most

homogeneous

extrudate

differences' can

be

produced

of

the

type

of

The

ACR

system

network
should

exist

for

this

considered
by

each

discrete

as

crosslinked rubbery particles distributed in a homogeneous

network;
impact

the

well

energy

distributed

through

dispersive

cavi t at ion and shear yielding

pressures
(cf.

and

other

torque

members

were
of

rubbery
(1.

mechanisms

2. 5. 2).

required

the

particles

to

series),

increase
such

as

Since higher melt

process

then

this

the

resulted in a low level of residual grain content.

blend

extrudate
The CPE

system is considered to form a continuous phase of CPE which

encapsulates
in this case,

inhomogeneities such as

primary particles or,

residual grains and the improvement in impact

performance is related to enhanced deformation mechanisms.

slight increase in melt viscosity is observed on processing,

Page 197

Discussion/6

however the grains are encapsulated in a continuous network

resulting in lower intergrain frictional contact and thus a
higher

retention

analogous

to

lubricant

of

grain

external

prevents

memory.

lubrication

This

where

frictional

behaviour

forces

coating
at

is

of

the

the

grain

boundaries.
Filler dispersion
In a similar manner to the earlier extrudate study,
the microscopy of
of

dispersion

these extrudates revealed that

was

an

important

feature

the level

and

that

measurable traces of grain content were observed.

of

filler

dispersion

agglomerates
homogeneous

of

"'20-30 flm for

system with

The order of

varied

greatly

The level

from

3EA and 3ED

distinct

to virtually

few agglomerates for 3EF

improving filler

no

(4. 4.1>.

dispersion can be ranked as

follows and also compared with the resultant head pressure

observed during processing:
POOR

(3EA _ 3ED)
3EA

3ED

HIGH

----- filler dfspersion

GOOD

(3EE

3E-

3EC)

(3EB)

(3EF)

3EC

3E-

3EE

3EB

3EF

----- head pressure ---------

LOW

The visual examination of these microscopy sections

indicated little difference in dispersion between 3EA & 3ED
and also the group,

3EE,

3E- & 3EC.

Thus

four

groups are

indicated by the brackets and a micrograph of each group is

shown in figures 4.38-4.41 inclusive.
The
seen,

high

dispersion.
amount

of

lubricant

interaction
head
Again

of

pressures
these

external

head

were

results

lubricants;

(3EF & 3EB)

pressure

ensures that

be

concurrent

can
a

can

be

high
a

wi t h

attributed
level

clearly

of

sufficient

poor

to

the

external
amount

is

available to coat the filler particles and prevent the fine

particle size filler from agglomeration.

The well lubricated

Page 198

Discussion/6

blends exhibit good flow properties with low torques and low
pressure build-up.
For
pressure
which

other

vary

is

less,

to

external
level

of

systems,

the

values

of

head

however 3EA yields high head pressure

attributed

efficient
moderate

lubricant
poor

dispersion

lubricant.
internal

The

and

low

level

incorporation

lubricant

(3EC & 3ED)

of

of
a

has some

effect but is not equivalent to a low level of a high m. pt.

The values obtained for Q generally bear

paraffin wax (3E-).

out the above trends with the notable exception that 3EB and
3EF

are

reversed.

efficiently
possible

This

lubricated

would
in

interaction

is

suggest

the

head

envisaged

that

3EF

is

more

region

than

3EB.

between

the

calcium

stearate surface treated filler and the chemically similar

lubricant stearic acid producing a more efficient system at
high temperatures.
The
extrudates

int roduct ion

with

the

of

impact

filler

being

modi fiers

well

resul t ed

dispersed

in

(4. 4.1);

the acrylic modifier system produced the best dispersion of

filler

for

all

the

series

(figure

extrudate was equivalent to 3EF.

for

the

ACR

significant

modified

increase

in

system

4.42)

and

energy

input

leads

can

be

related

mechanical energy
to

(6. 2. 2.1).

The reason for

system

analogous

is

unfilled

to

system given

CPE

The good filler dispersion

better

to

input

compared to 3E- (base lubricant composition).

of

the

(Q)

the
when

The high level

dispersive

action

the good dispersion in the CPE

that

above,

for
that

the
is,

behaviour
the

CPE

of

the

continuous

phase encapsulates the fine particles of the filler ensuring

that

the

particles

remain

discrete

and

'well

lubricated'

from other particles.

Surface appearance
The aesthetic appearance of the pipes outer surface
was

assessed

by

visual

examination

scanning electron microscopy

(3. 3.1)

(4. 4. 3).

and

also

The results of

via
both

Page 199

DiscussionIS

techniques confirm the groups obtained in table 3.5

(3.3).

Little difference in surface quality was observed with the

exception of
two blends

the blends containing the ACR modifier.

(unfilled and filled)

finish which might

temperature

produced

the best

These

surface

be explained by the slightly higher melt

observed

during

processing

(4.2)

and/or

dispersion of inhomogenei ties (see above discussion).

the original extrudates,
melt

fracture,

good

As for

no evidence was observed to suggest

lubricant

pl'ate-out

or

poor

filler

agglomeration on the surface.

The inner surface was also visually examined and the
results listed in table 3.7.

The introduction of 0<27 phr of

filler

inner

produced

attributed

to

manner

the

to

introduction

better

decrease
earlier

of

the

in melt
extrudate

acrylic

surface

which

elasticity in
series

modifier

may

similar

(6. 2. 2. 2).

also

be

reduces

The
melt

elasticity while the CPE modifier increases melt elasticity

(1. 2. 5. 1>.

6.3. 1. 4- ASSESSMENT OF THE DEGREE OF FUSION

In a similar manner to the original series of filled
extrudates,

the level of fusion for the additive extrudates

were assessed by thermal analysis and solvent tests.

Thermal analYsis
The thermograms for the additive series are similar
in appearance and characteristics to those obtained for the
filler

series

observed [27J.

(figure

6.5),

and

no

effect

TG

upon

was

Table 4-.2 lists the thermal analysis results

obtained and it can be seen that the processing temperature

(as

indicated

by

the

controlled

within

the

di fference

in

'B'

extruder,

lubricant

exception to good

melt

onset

temperature)
even

composition

control

containing the acrylic modifier;

can

is

be seen

though

is

well

wide

considered.

The

for the blends

these have slightly higher

Page 200

Discussion/6

melt temperatures due to higher levels of work input [201J.

The

values are compared to the maximum obtained

AH~

in the original series,

fusion
the

values,

and

predicted

3F:10'53 Jig,

the last
fusion

column of

using

temperature in equation 4.6.

suggests a
notable

the

table 4.2
measured

estimates
'B'

onset

Comparing the last two columns

reasonable agreement

exceptions.

to yield comparative %

The general

between values with a

few

agreement

the

infers

that

master curve plotted in figure 6.7 is also indicative of the

blends cont aining appreciable di fferences
lubricant
reports

systea
on

1 ubricant S;

This

fusions

suggestion

studies

and

137,200-202J

and

differs
their

previous

interactions

cont ent

lubricant

therefore,

from

all

things

[22-24, 29, 37-38,

being

equal,

fusion level of OEB should have been lower than OEA.

the common processing method used to assess
BrabenderM torque rheomet er.
by the material

with

a decrease in fusion level

most workers report

with increasing external

in the composi t e

the

However

fusion

is the

This uses the torque generat ed

to raise melt

temperature and thus enable

the fusion process to progress.

Since the introduction of an

external

acting

lubricant

initial torque [22,29J,

reduces

this,

the

in effect,

magnitude

of

the

reduces the amount

of work input via frictional forces 'leading to a decrease in

the

rate

of

heat

build-up.

The

ultimate

effect

of

the

decrease in the rate of work input is a lengthening of the

fusion time.

The use of a less externally lubricated system

does not have such a dramatic reduction upon initial torque,

alternatively,
initial
effect

calcium

torque [22,38J

stearate

is

reported

to

increase

and thus these lubricants have less

upon fusion time.

The application of results from a

Brabender torque rheometer to a process such as twin screw

extrusion

is

questionable

since:

firstly

the mechanism of

particulate breakdown may differ from comminution as seen in

a

high shear regime of a

'CDFE'

mechanism

[112-116J;

reported

secondly

the

torque rheometer
in
.twin

this
screw

study

1)

to the

and many

others

(1.

extruder

4.

offers

good

temperature control which ensures that the melt achieves the

Page 201

DiscussionIS

correct

processing

[131,181)

without

temperature

mainly

by

conduction

the prerequisite of a high degree of work

input.
Thus it can be seen that for many of the extrudates
the

level

curve at

of

fusion

can

be related

master

the appropriate processing temperature within the

bounds of experimental error.

6HA

to the original

values

plaques

(3-37

J/g)

containing

for

Obande [203)

range

substantial

of

reported similar

compression moulded

differences

in

external

lubricant

(10-45 phr) at moulding temperatures appropriate

to

study

this

temperatures
which

("'190C),

()200C)

indicated

although

at

higher

'B'

onset

discernible differences were obtained

that

higher

external

lubricant

content

lead to lower 6H A values.

The
between
st rong
level

unfilled series,

"'50-60%

with

dependence

on

of

secondary

primary

the

in general,

exception

of

had fusion
OEF

and

processing temperature

crystallite

crystallisation

breakdown

(6H A ).

Thus

levels

OEH.

The

controlled

and

the

considering

the

degree
the

of

CDFE

mechanism considerable intragrain fusion may develop before

complete

destruction

of

the

grains.

The

high

residual grains observed in some of these blends

does

not

suggested

indicate
by

that

Gale

[137),

pressures/mechanical
elongation

and

the
but

energy

eventual

entities
that

are

are

destruction.

to

residual grains were obtained for these blends,

as

extrusion

enable

Therefore

of

(6. 3. 1. 3)

'unfused',

insufficient

available

level

grain

although

the level of

intragrain fusion was similar.

The higher value of OEH
the high shear regime as
and

ext rusion

pressures

may be explained by

("'82%)

indicated by the high value of Q

(6. 3. 1. 2

were considerable higher than for

&

3. 2. 3);

these

val ues

the other members of

the

group and it may be envisaged that these conditions enhance

pressure

transfer

and

heat

conduction

leading

to

early

breakdown of the grains and possibly the primary particles.

The

partial

removal

of

boundaries

would

interdiffusion between primary particles and,

enhance

chain

possibly grain

Page 202.

Discussion/6

boundaries,

to allow further secondary recrystallisation and

hence higher values of 6HA.

The other anomaly was the extrudate OEF.

This pipe

yielded a higher 6H A value than might be expected from the

processing temperature.
variance since

the

It is difficult to account for this

extrusion conditions

were not

comparison to the acrylic modified blend

harsh

in

however it

(OEH),

is interesting to note that the high level of lubricant used

in t his blend

(1,

as

predicted

might

results

be

to

0 phr:

blends

external lubricant.
may interact

gave low val ues of Q

st earic acid)
but

retained

comparable

containing considerable

lower

pressure
levels

of

It may be possible that the stearic acid

with the similar lubricant,

calcium stearate,

to produce a higher fusion level at the moderate processing

temperature [22,38J.
The
levels

of

slightly
193 'C

filled

approximately
higher

general,

in

which

60-70%

average

processing

produced

were

fusion

attributed

temperatures

of

to

~190-

Again the fusion level can be related to the

(4.2).

extrusion

temperature

observed (3EB,
to

systems,

but

also

3ED and 3EG).

processing

conditions,

number

of

anomalies

are

These can not easily be related

lubrication

effects,

dispersion or melt temperature differences.

filler

3EB and 3ED had

considerable higher 6H A values than might be expected which

may involve substitution of the calcium stearate coating on
the

filler

interact,

and
and

'free'

further

work

is

curve

filled

additive
than

modified

in

similar

series.

expected

system

did

3EG

fusion
not

(10

to

to

the

filler

diluting

ascertain

to the original master

the

maj orit y

phr

CPE

modifier)

level

enhance

to

to

manner

indicated in the unfilled series.

due

calcium stearate

necessary

these blends can be fitted

fusion
lower

allowing

however no evidence is available to support this

speculation
whether

thus

and
the

also

level

the
of

of

the

had

acrylic

fusion

as

These differences may be

the

high

extrusion

characteristics of these modified systems (Appendix 0.4) and

thus reducing the expected benefit in fusion level.

Page 203

DiscussioniS

Therefore the thermal analysis technique appears to

be less dependent

upon the composition and allows a single

fusion curve for a part icular processing machine to be used

to

predict

fusion

materials.

levels

A number

of

for

range

mismatches

not fit the original master curve,

of vastly

were

different

obtained which did

these results may need to

be verified.

Acetone shearing test

The

acetone

shearing

results observed for

that

is,

unable

at

levels

to distinguish
Thus

the

support

thermal

(4. 4. 2)

confirmed

the original filled series

moderate

fusion.

test
of

fusion

between quite

test

provides

analysis

and

the

large

(6.2.2.3),

technique

increments

complementary

the

in 'Y.

evidence

the methylene chloride

is
to

tests

(3.4) but does not yield any further information other than
that the pipes are not poorly fused.
6.3.2 MECHANICAL PROPERTIES

6.3.2.1 TENSILE PROPERTIES

The tensile properties are listed in table 5.2 and

illustrated graphically in figures 5.6 and 5.7.

Yield parameters
The yield properties of the unfilled series appear
relatively independent

of additive type

(with the exception

of OEG & OEH) and of similar values to the original unfilled

series

(6. 2. 3. 1).

stress [59)

The

two

impact

with the CPE system

modi fiers

(soft

reduce

CPE phase)

yield

having a

greater effect than the ACR blend.

The
yield

filled

measurements,

additive

albeit

series

is

at

lower

also

insensitive

value,

modifiers again causing a decrease in yield stress.

with

to
the

However,

Page 204

Discussion/6

in

this case,

the ACR blend has a

the CPE modified system (cf.

lower

OEG & OEH)

yield stress than

and also the level

of reduction is not as great as the unfilled extrudates.

value

of

yield

stress

for

3EG

(10

phr

CPE

The

modifier)

is

approximately the same as for the OEG and thus is possibly

related to the CPE network phase retaining properties even
though the effective cross sectional area of the polymer is
reduced by the introduction of the filler.
Post-yield parameters
It

is

elongation

evident

values

from
are

(8)

original series (cf.

table

5.2

that

significantly

the

ultimate

higher

than

the

table 5.1). These high extension values

are induced by a more stable neck formation with the filled

extrudates
the

unfilled.

filled

having comparable extension

(3E-~3EH)

The

additive

improved

series

behaviour

compared

to

at

the

values as

failure

for

the

original

~27

phr

extrudates can be related to improved dispersion (cf.

with

!l4. 3.1)

allowing

substantial

drawing

before

4. 4. 1
failure.

The modified systems exhibited high neck stability and thus

high

elongation

at

break

observed

in

ultimate

elongation

extensions

!l5. 2. 3. 1
(esp.

[57l.

between
(8)

was

modified

The tentative relationship

breaking
again

blends)

st ress

apparent,
lead

and

(0"8)

i. e.

to

high

high

0"8

measurements.
Therefore
with

any

tensile

certainty,

unless modified by a
and secondly,

the

properties

between

the

did

members

not
of

distinguish,
each

series

rubbery additive such as CPE and ACR,

introduction of

approximately 27

phr of

filler produced a step reduction in yield stress.

5.3.2.2 IMPACT PROPERTIES
The

instrumented

impact

testing

of

the

pipes

containing the range of additives revealed gross differences

(table 5. 4) and failure energy derived from the impact trace

Page 205

Discussion/6

provided a good indicator of the overall impact performance

(figure 5.12),
The results of the additive series differed from the
original series since the approximately 30 phr filled pipes
had far greater impact properties than the original 3E pipe
and also OE- has a lower value than OE.
performance of

The better overall

the filled additive series is attributed to

better dispersion,
between members;

but there is still considerable variation

the earlier series at this filler level had

very poor dispersion compared to the series discussed here

(4. 4. 1 & 4. 3.
The

impact

performance

of

the

original

unfilled

(OA-OO) was shown to be dependent upon the level

extrudates
of

1).

fusion,

differences

however
whilst

the

addi t i ve

fusion

apparently constant.

level

(via

in

turn,

extrusion characteristics

indicat es

gross

thermal analysis)

The behaviour of

shown to be critically dependent

extrudates which,

series

is

these extrudates was

on the homogeneity of the

can be related
(6. 3.1. 3)

to the measured

and hence the external

efficiency of the composite lubricant system.

The impact behaviour of the unfilled extrudates can
be compared to the level of residual grains assessed during
opt ical microscopy (4. 4.
LOW

----- impact energy ----

OEB

OEF _ OE-

OEB

OEF

A clear
grain

content

link between

1):

OE-

OEA

OEC

OEA

OEC

relationship

and

failure

is

OEE
~

OED

OED

observed

energy.

HIGH

OEE

between

6. 3.1. 3

residual

identified

processibility and grain retention,

similarly

the ease of processing was related to the composition.

higher levels of external lubricant

(eg.

the
Thus

OEB & OEF) resulted

in low head pressures giving poor residual grain content and

ultimately
failure.

poor

impact

resistance

and

brittle/ductile

Therefore impact performance is dependent upon the

Page 206

Discussion/6

level of processing and the external lubrication efficiency.

Thermal

analysis

(4.2)

suggested that,

in general,

level did not dramatically differ between blends

OEF)

and

therefore

the

presence

of

high

fusion

(excluding

levels

of

grain

inclusions does not necessary imply poor fusion.

The

influence

of

residual

resist ance has been observed:

fracture

toughness

residual grains)

of

Mai

well

versus a

et

processed

Gale (35J

pipe

B1

upon

(204]

processed

impact

measured the

(low

level

poorly processed eKtrudate

level of 'unmixed PVC granules');

poorly

grains

resulted

it
in

(high

was proposed that

low

toughness

of
the

value.

also considered that impact strength was directly

due to the presence of 'unfused'

material.

A number of reports have investigated the effect of

high levels of external lubricant upon impact properties and
most agree that a det riment al effect is obt ained (33-35, 113,
179J.

Marshall et 81 (113J suggested that a higher level of

external lubricant delays the fusion process and also delays

the

development

(34J

also

of

maximum impact

attributed

performance

with

the

performance.

observed

increasing

levels

Shaw

decrease
of

in

lubricant

et

B1

impact
to

the

fusion delaying effect 6f the external lubricant.

The impact

results for the additive series in this

study were directly attributable to the presence of residual

grains acting as stress concentrators,

and the concentration

of

level

these

Fusion

grains

level,

was

as

related

measured

to
by

the

thermal

of

processing.

analysis,

varied

slightly between the blends and was not associated with high
residual grain content.
The
significant
processed
produced

introduction
increase

pipes
the

<OEB,

best

of

in

impact

performance

OEF,

OE-

propert ies

of

OEA).
all

residual grains were detected and,

the

rubbery

gives

good

additive
impact

(1.

modifiers

2.5.2).

performance

over

the

the

blends;

CPE

compared

<OEH)

since no

the effect
extrudate
to

containing high levels of external lubricant,

poorly

The ACR blend

secondly,
The

produced

the

of

(OEG)
blends

yet the value

Page 207

Discussion/6

of OEG is marginally lower than for the well processed pipes

(OED & OEE).
grain

Optical microscopy

content

ext rudat es
related

of

and

to

this

thus

its

(4. 4.1)

system

t he

energy

is

revealed that

the

worst

observed

impact

absorbing

phase

of

all

behaviour
(1.

the
the

may

2. 5. 2)

be

which

encapsulates the poorly mixed residual grains.

The

testing

indicated that

of

filled

the

additive

the instrumented tester is a

series

also

viable machine

for detecting differences in the quality of processed UPVC.

In

this

case,

relationship

was

observed

between

filler

dispersion (4. 4. 1) and impact behaviour:

LOW

----- impact energy ----

3EA
3EA

POOR

HIGH

3ED

3EE

3E-

3EC

3EF

3EB

3ED

3EE

3E-

3EC

3EB

3EF

--- filler dispersion --

GOOD

It is clear from the above comparison that the level

of

filler dispersion is the main factor controlling impact

performance,
but,
lower

as

the failure energy values varying considerably

might

be expected,

always remaining significantly

than the unfilled series due to the substitution in

effect i ve polymer area by inert filler.

The agglomerat es of

poorly dispersed filler may act as stress concentrator loci

which assist s
6. 3.1. 3

crack

attributed

ini t iat ion and crack propagat ion [53J.

the

level

of

filler

dispersion

to

the

processing characteristics and proposed that good dispersion

is related to the external nature of the lubricants present.
3EB

and

3EF

lubricant

contain

and

can

relatively
be

seen

high

to

levels

yield

more

of

external

homogeneous

extrudates in terms of filler dispersion.

In

similar

manner

to

the

unfilled

series,

the

impact properties of the filled series were also related to

product

homogeneity

lubricants.

and

highly

Again the influence of

dependant
fusion

(esp.

upon

the

3EA & 3ED)

was not observed.

The

introduction

of

modifier

resulted

in

good

Page 208

Discussion/6

resul t sand,

impact

ext rudat es
ascert ain

as

discussed

t he

inherent

produced

It

is

difficult

mechanism

of

the

exhibiting good dispersion.

whether

6.3. 1,

in

to

modi fier

system also has a tangible effect upon impact performance in

conjunction with good filler dispersion.
6.4 INTERACTION OF FILLERS AND LUBRICANTS IN RIGID PVC
The
stage of

discussion

work

to-date

in detail;

has

considered

each

the following discussion

major

reviews

some of the major similarities between the stages of work.

The

dry

blending

process

and

dry

blend

characteristics revealed little effect upon the addition of

filler or primary lubricant substitution with the exception
of highly filled blends;
handling,

filler

loss,

these systems lead to poor powder

high tap density and longer blending

times.
The processing characteristics of blends containing
variations

in

appreciably.

filler
Figure

concentration
6.14-

illustrates

unfilled or lightly filled system

fusion

mechanism

and

and

final

additives

the

(~85

extrudate

phr)

differed

behaviour

of

an

in terms of the

homogeneity.

Figure

6.15 depicts the differences observed in this mechanism with

the

addition

simplistic

of

moderate

approach

densification,

is

to

high

based

levels

upon

fusion and elongation

of

filler.

Allsopp's
(CDFE)

This

compaction,

mechanism [112J

which can be extended to explain the observations obtained.

Figure
(

1. 4. 1)

with

of the grains.

6.14

describes

the

basic

CDFE

mechanism

intragrain fusion occurring before breakdown

The level of intragrain fusion was estimated

by the development of secondary crystallinity and was shown

to

be

highly

(!l6. 2. 2. 3).
particle

dependant

upon

the

processing

Low processing temperatures

structure

within

the

grain

temperature

retained a
which

fragmented during the acetone shearing test

primary

was

easily

(!l6. 2.2.3).

The

elongation and grain retention depended upon the processing

regime and composition.

High processing temperatures,

high

Page 209

Discussion/6

torque characteristics and an appropriate

tended

to

produce

(A).

grains

These

addition

to

involved

1. e.

One

efficiency,

then,

in

general,
were

fusion

determining properties
as

observed

then

in

properties

concent rat ors,

opposing

high

and

temperatures
and

the

and

high

as

of

fusion

If

are

level

are

level

of

lubricating

level

an

of

residual

series

by

few

important

at

grain

role

situation 8

lubricant

impact

conditions
low

characterised

(6. 2. 3. 2).

in

extrudates

had

residual
or

external

filled

level

number

such

few

system

singularly

input

The

inclusions

act ing

temperature,

obtained.

were

moderate

If

with

processing

low

energy

matrix

component s

another.

mechanical
grains

homogeneous

lubricant

in

prevails,

modified extrudates,

reduced due

is

not

to

stress

envisaged

as

controlling influence.
Figure
highly

illustrates

6.15

filled

blends.

the

similar

case

for

fusion

moderate
mechanism

to
is

envisaged and intragrain fusion is unlikely to be affected

by

the

addition

of

an

inert

filler.

The

elongation

destruction of the grain takes place quickly but

and

the level

of filler dispersion is dependent upon processing conditions

and composition as illustrated.

Good dispersion was related

to

forces,

adequate

dispersi ve

lubrication

and

agglomerat ion
extrusion

low

was

energy

processing

observed

temperatures,

temperatures.

wi th
low

suff icient

blends

While

processed

dispersive

ext ernal

energy

filler
at

high

forces,

increasing filler loadings and compositions which have a low

external lubricating nature.
to

interact.

Again these effects are likely

. performance

Impact

was

related

to

filler

agglomeration and the influence of fusion level is not well

defined.
The two figures discussed previously (figures 6. 14 &
6.15)

demonstrated that

critically
aspects.
be

dependent

properties and product quality are

upon

formulation

and

processing

The significant effect of lubricant composition can

highlighted

in

both 'unfilled

and

filled

extrudates;

suitable formulation in unfilled blends can yield properties

Page 210

Discussion/6

FIGURE 6. 14
Schematic mechanism of fusion for unfilled or
lightly filled extrudates

ORIGINAL GRAINS

COHPACTION &
DENSIFICATION

Cf.l

:=>

r..
z

<:

'"~
to

E-<

High processing temperature and high torque

characteristics with adequate lubricant system
~
Good impact properties related to
fusion level.

x
0:

<:

FINAL EXTRUDATE HOMOGENEITY

E:3

Ui
r..
0

E-<
0
(l

0:

=x

x= =

==

=X

X
0

c:::.

c:::::>

Cl

ELONGATION OF
GRAINS

X=Dc:::=:.Q
X c::::::. 0

Low processing temperature and low torque

characteristics with High external lubrication
~
Poor impact properties related to
grain inclusions.

Additive

Porosity

Page 211

Discussion/6

FIGURE 6. 15
Schematic mechanism of fusion for highly filled extrudates

ORIGINAL GRAINS

)t

l(

COHPACTION &
DENSIFICATION

X .;,;.,-_ _ot:

Cl)

>-'._._""~.~ ;c:

"

Low processing temperature with adequate

lubrication system and adequate dispersive
energy
~
Good impact related to volume fraction
of polymer.

>< .4-
><.
.'
~ )( >r..
>c.
...)(

)( '>('

..

1>1
"'0::"
~

)(

\(

Cl)

It

oX

FINAL EXTRUDATE HOHOGENEITY

o

><

>-

.,.

)<

)<

.>c

High filler loading and high processing

E-<
(0

1>1
~

H
Q

'If

ELONGATl'bN OF
GRAINS

Jr

)(

>I

""

z
o

)r

temperature with inadequate lubrication

~
Poor impact related to level of
filler agglomeration.

)(

Additive

Porosity

Filler

Page 212

DiscussionIS

which

approach

those

extrudates

containing

impact modifiers such as CPE and ACR.

highly

filled

blends,

the

traditional

In the case of qUite

interaction

between

lubricant

system and filler level can be developed to prevent serious

reduction in impact performance which generally occurs with
the addition of substantial
some

instances,

better
(~27

impact

levels of

optimisation

performance

of

for

the

an inert

filler.

formulation

In

induced

quite highly filled grade

phr) when compared with an unfilled extrudate produced

under similar extrusion conditions.

Thus
processing

it

can be

regime,

(i. e.

modification

level

of

likely

filler

that

each

seen

lubricant

the
of

for

primary

dispersion
system

is

and

given

filler

system must

lubricant)
ease

machine

of

be

level

tailored

to optimise
processing.

specific,

and

It

however

the
is
the

techniques outlined above can be used to assess the quality

of the final extrudate.

Page 213

CHAPTER SEVEN

CONCLUSIONS AND SUGGESTIONS

FOR FURTHER WORK

7. 1 CONCLUSIONS

Dry blending

filler

Dry

blending

10adings,

increased
filler

time

time.

values

content

constant

loss reduced

filler

blending

remained

Ash

and

the

charge

content

confirmed

at

until,

weight

provided

the

high
and

accurate

resultant

filler

loss at high f i l l e r 10adings.

the

Filler

pOlymer

loss in
grains

the mixer

being

completely

particles and leaving 'free'

Dry

attrition

blending

of

the

of

spherical grains with

to coincide with

covered

by

filler

to

slight

f i l l e r particles.

the

original

appeared

filled

polymer

the inherent

blends

lead

to produce

grains
folds in

more

the pericellular

membrane preferentially filled wi th filler.

Bulk

densi ty

measurements progressi vely

with increasing f i l l e r content until at

30 phr

the

value

increased

f i l l e r levels beyond

increased disproportionately due

to 'free'

f i l l e r yielding an efficiently packed powder.

not

Modification

significantly

to

the

affect

composite

dry

lubricant

blending

system

did

characteristics

or

bulk den si ty va1 ues .

. The
disrupted

free
by

flowing properties

the

introduction

filler;

high

10adings

feeding

modification

of
were

filler

of

of
the

the

calcium

prevented

required

to

dry blends

powder

aid

were

carbonate
flow

conveyance

and
in

hoppers.

Page 214

Conclusions/7

Twin screw extrusion

From

the

results

extruder

number

of

general

conclusions were obtained:

mass

steady

attained

extruder

The
quickly and

throughput

state

apparently

was

condi tions

unaffected

by

processing conditions or formulation aspects.

Acceptable pipe was produced for all

blends with the

exception of those extruded at extrusion profiles,

these

low

extrusion

temperBtures

the

pipe

A & Eo'

could

not

at
be

formed into pipe.

with

All
the

profiles,

passed

extrudates
exception

& Eo'

of

the

pipe

methylene

chloride

at

processed

test

temperature

these extrudates showed signs of excessive

swelling and disintegration.

The instrumented extruder can be used to compare the

processibi1ity

of

different

compositions

including

filler

and 1 ubr i ca t i on aspec t s.

Pressure

vB1ues

zone of the extrudero'

filler

content,

were

measurable

only

in

the

last

these values increBsed with increasing

decreasing

extrusion

temperature

and

decreasing external lubricant efficiency

Torque

and Q meBsurements

followed

similar

trend

as was exhibited in the head pressure results.

From

the

extruder

results

of

the

filled

extrudate

series it was concluded that:

upon

Extrusion

characteristics

compositiono'

increase
tr.ansducer

in
Bt

the

torque
the

were

incorporation
and

lJdaptor

of

pressures,
showing

criticBlly dependent
filler
with

an

lead

the

to

an

pressure

approximate

linear

relationship between pressure and f i l l e r content.

Page 215

Conclusions/7

levelling

loadings at

off

in

torque

high extrusion

values

with

high

temperatures was related

filler

to poor

dispersi on.

Surface appearance improved with increasing extruder

temperatures and was lowered by the introduction of moderate

levels of f i l l e r

08'5 phr).

A mathematical relationship was obtained to describe

head pressure as a

of melt temperature

function

and f i l l e r

content.

From the extruder results for

the additive extrudate

series it was concluded that:

some
for

Extrusion characteristics confirmed the behaviour of

common

lubricants

example paraffin

as external

wax has a

efficiency compared to,

say,

or internal

lubricants;

strong external

lubricating

OMS.

indicated
the
external
extrusion
results
The
behaviour of the composite lubricant system, a high external
nature leading to low t.orque and pressure values.

A high proportion of external

lubricant was required

to counteract the effect of f i l l e r addition.

lead

The incorporation of an impact

modifier, . in general,

to an increase in melt viscosity and thus an increase

in extrusion characteristics.

surface
modi f i er

modification

Lubricant
quali ty,

however

improved

surface

the

had

little

incorporation

appearance

in

effect

of

both

an

upon
impact

filled

and

unfilled extrudates.

Page 216

Conclus1ons/7

Microscopy
From

the

microscopy

study

of

the

filled

extrudate

series it was concluded that:

mi croscopy

Optical

the

of

filled

lightly

and

unfilled extrudates revealed residual grains which decreased

in number with
were

increasing extrusion

distributed

in

flow

band

temperature,.
and

at

high

the grains
processing

temperatures became highly elongated.

The

presence

mechanism and the

of

intrafused

of

final

residual

grains

mechanis~

stage of this

grains,

depended

supports

upon

the

CDFE

elongation

backpressure

and

extrusion temperat ure.

filled

Moderately

signi ficant

traces

di spersi on

fi 11 er

of

extrudates

residual

was

di d
but

grains,

dependen t

extrusion

tempera t ure,.

high

processing

temperatures

produced

upon

filler

exhi bi t

not

revealed

filler

level

contents

at

poorly

dispersed

that
and
high

filler

agglomerates within the polymer matrix.

UV fluorescence microscopy supports

the presence of

residual grain entities and f i l l e r agglomerates as indicated

by optical microscopy.

From the

microscopy at udy

of

the

addi t ive ext rudat e

series it was concluded that:

grain

The

unfilled

memory

characteristics,
function
external
pressures

of

the

which

additive
was

these
external

lubricated

related

extrusion
nature of

system

also

series
to

the

illustrated
head

characteristics
the lubricant.

yielded

low

torque

pressure
being

A highly
and

head

to produce a extrudate containing a high level of

resi dual grains.

Page 217

Conclusiona/7

The ACR modified unfilled blend produced the lowest

level of residual grains whilst the CPE system indicated the

highest level of grain inclusions for the series.

The filler dispersion of the filled additive series

was related to the external nature of the lubricant;

highly

external lubricants produced a well dispersed extrudate.

Both impact modified pipes containing filler yielded

well dispersed filler particles.

Fusion
From

the

fusion

assessment

of

the

filled

extrudate

series it was concluded that:

measurements
indicated
that
analysis
Thermal
secondary crystallinity increases with increasing extrusion
temperatures and

that

the amount

of primary crystallinity

decreases with increasing processing temperatures.

'B'

onset

temperature provided an accurate measure

of the maximum melt temperature achieved during processing.

upon

The

the

'B'

onset

setting

temperatures

had

of

temperature
pipe

little

head

effect

strongly

was

temperature;
upon

the

dependent

the

final

barrel

' B'

onset

tempera t ure.

A linear relationship was obtained between 'B' onset

and the temperature indicated by a

the

pipe

accurate

head,

however

calibration

as

the

thermocouple situated in

latter

opposed

to

method
the

relied

thermal

upon

analysis

technique.

versus

A
'B'

master
onset

fusion

curve

temperature

extrudates processed within

it

of
was

secondary
obtained

crystallinity

for

the

filled

wide processing window.

Page 218

Conclusionsl7

The

introduction

of

substantial

did not appear to influence the level

amounts

of

filler

of fusion

attained by

provides

qualitative

the extrudates.

The

acetone

to

evidence
analysis,

shearing

support

but

the

lacks

test

inferences

discriminating

gained
power

from

for

thermal

more

fused

extrudates.

From the fusion assessment of

the additive extrudate

series it was concluded that:

The

general,

pipes

seem

incorporat ing

to

insensitive

range

changes

of

in

addi t ives,

fusion

level.

in
In

cases in which high extrusion characteristics were obtained,

the level of fusion increases slightly.

The

thermal

analysis

estimating

fusion

level

relatively

insensitive

processing

condi t ions.

processing

behaviour

technique

from

to
may

fusion

changes

However

appears
curve

in

and

d:i fferences

modification

in

seems

formulation

signi f i can t

require

useful

of

and
:in
the

original master curve.

Mechanical propetties
From

the

tensile

testing

of

the

filled

extrudate

series it was concluded that:

Yield parameters

were

insensitive

to variations in

fusion level.

v'"

Yield

reduction

in

stress
stress

was

dependent

with

upon

increasing

filler
filler

attributed to a dilution effect of the inert

with

Yield

stress

increasing

of highly

processing

filled

temperature

level

a
was

filler.

extrudates
due

level;

decreased

to poor f i l l e r

di spersi on.

Page 219

Conclusionsl7

Post-yield

instabili ty
observed

properties

were

during

cold

drawing.

most

pipe

specimens

for

to

sensitive

Poor

neck

neck

stabili ty

to

leading

was

substantial

scattering of results.

~ High
poor

filler

filler

loadings reduce

dispersion

ul timate

affecting

neck

stress

to

due

stability

and

promoting premature failure

v-From

the

tensile

testing

of

the

additive

extrudate

series it was concluded that:

post-yield

and

Yield

parameters

were

not

significantly affected by changes in the primary lubricant.

The

stress,

introduction

of

impact

modifiers reduced

yield

especially for the unfilled pipes.

From the impact testing of the filled extrudate series

it was concluded that:

The

maximum
fusion

testing

at

levels

intermediate
improved

of

fusion
gave

the

level

poor

levels,

impact

reduces

resistance
at

to

resistance

destruction

mechanisms

extrudates

due
the

suggested a

approximately

At
of

70-75%.

failure

behaviour

performance.

the

absorption

of

ductile

temperatures,
impact

unfilled

while

Low
at

was noted giving

processing

high

particulate

network

to the elimination of energy

interfaces

of

the particulate

struct ures.

ductile

The introduction of f i l l e r delayed the attainment of

behaviour,

requiring

high

levels

of

fusion

to

promote ductile failure.

~_

High

loadings of f i l l e r with poor filler

yielded brittle behaviour with

approximately

10% of

very low impact

the maximum obtained for

dispersion

strengths of
the

unfilled

pipes at optimum fusion levels.

Page 220

Conclusions/7

At

high

filler

impBct

lOBdings,

properties

were

insensitive to fusion level.

ImpBct properties of filled pipes which

ductile

manner

were

considerably

lower

thBn

fBiled in B
for

unfilled

pipes fBiling in a similBr mBnner.

ImpBct

indicated

a wide range of test temperatures

testing Bt

different

brittle-ductile

unfilled and filled extrudates.

filler

increBsed

the

transitions

for

the

The introduction of an inert

brittle-ductile

temperature

Bnd

this

t ransi t i on occurred over B wi der t emperB t ure range.

higher

fusion

level

lowered

the

brittle-ductile

trBnsition temperature.

filler

Pipes

with

high

dispersion;

filler

loadings,

brittle-ductile

exhibited

trBnsition

poor

WBS

not

observed.

From

the

impact

testing

of

the

additive

extrudate

series it was concluded that:

The

significl3nt
High

presence
effect

of

residuBl

grBin

upon performl3nce. for

levels of residuBl

impBct

performBnce

WBS

the

structure

hBd

unfilled pipes.

grains caused poor properties;

directly.

linked

to

processing

thus
Bnd

formul B t i on aspec t s.

ImpBct modificBtion of the

unfilled pipes lead to B

drBmatic increase in performBnce with the ACR system showing

better improvement

than the CPE Bdditive.

~The impact
was
Poor

dependent

upon

dispersion

resistance

to

behaviour
the

of

the

qUBlity

of

yielded

impl3ct

was

poor

filled
the

filler

properties;

agBin

related

Bdditive series

to

dispersion.

therefore
processing

the
Bnd

formulBtion aspects.

Page 221

Conclusions/7

Modification

of

the

lubricant

system

can

play

an

important role in determining end performance properties .

Impact

modification

improved

impact

slightly

better

of

resistance,
improvement

the
the

than

filled
CPE

the

extrudates

modifier

ACR

again

producing

modifier

in

this

case.

7.2 SUGGESTIONS FOR FURTHER WORK

This
single

investigation

particle

properties.

size

considered

coated

fuller

filler

understanding

the

influence

upon

of

processing

might

be

gained

a
and
by

considering:
a) The influence of the particle size distribution.
b) The influence of coating and coating level.
These

factors

are

presently

under

investigation

at

IPTME.
The

lubricant

composite
performance

study suggested

lubricant
of

package

unfilled

and

upon

the

importance of

the

filled

processing
extrudatesj

the
and
the

application of factorial design experimentation might enable

optimum lubricant systems to be ident i fied.
Preliminary

work

(4. 1)

indicated

analysis testing provided a master fusion

that

thermal

curve which was

valid for a relatively large number of compositions.

Further

work might confirm these observations and relate the fusion

levels to mechanical properties.
The instrumented

extrude~

provided a convenient method

to investigate the processing behaviour of extruded pipe.

is envisaged that

processing window might

It

be identified

from the ext ruder charact erist ics which would ensure a good
quality extrudate.

Page 222

Conclusions/7

The
impact

application

tester

establish

the

of

demonstrated
quality

investigations might

an

instrumented

that
of

this
the

type

falling
of

extrudate;

test

weight
could
further

consider the suitability of this type

of test as a on-line quality control technique.

Page 223

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Reber,

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0,

SPE-ANTEC,

GM,

RAPRA J.,

J W,

TH Aachen (082) (1978)

Rabinovitch,

E B,

Vinyl Teehn.,

L 1, 32-35 (1985)

J W,

Rabinovitch, E B,

Summers,

Terselius,
Proe.

151.

68-72 (1974)

Phd Thesis,

N,

Vinyl Teehn.,
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708-710 (1974)

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Appl.,

Terselius,

Jansson,
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B,

J,

Quisenberry,

J G,

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67-69 (1982)

2,

J.

Quisenberry,

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Bystedt,

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P1Bst.

&

Rubb.

1-7 (1985)

Jansson,

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P1Bst.

& RUbb. Proe. Appl.,

J F,

P1Bst.

& Rubb. Proe. Appl.,

4 291-299 (1984)
152.

Terselius,

B,

Jansson,

4 4, 285-290 (1984)
153.

154.

Pezzin,

G,

Ajroldi,

G,

Vittadini,

G,

J.

Appl.

Humphreys,

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Volkmar,

Casiraghi,
Polym.
K,

T,

Sei.,

PVC Proe.

Garbuglio,
1..

C,

1839-1849 (1972)

Int.

Conf.,

P.4

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P E,

156.

Pat rick,

J.

S G,

Vinyl Techn.,
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in PVC technology',

M P,

4 3,

124-127 (1982)

PVC Symp.

'Current trends

Loughborough University of

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157.

Corvic Data Sheet:

158.

Polcarb Data Sheet:

159.

Associated Lead Manufacturers Ltd:

Data Sheet:

TBLS

160.

Associated Lead Manufacturers Ltd:

Data Sheet:

Lead

Data Sheet:

Calcium

S68/173

Polcarb S

Stearate
161.

Associated Lead Manufacturers Ltd:

Stearate

162.

Sasol Marketing Ltd:

Data Sheet:

163.

Hoechst:

PE520 (1977)

Data Sheet:

Sasolwaks H1

Page 232

References

164-.

Henkel:

Data Sheet:

Loxiol G15 (1982)

165.

Henkel:

Data Sheet:

Loxiol G12 (1982)

166.

Pristerene:

167.

Oletec:

Data Sheet:

168.

Pepper,

S T,

Data Sheet:

MSc

Stearic acid 4-903

Oletec 6009
Loughborough University of

Thesi~

Technology (1984-)
169.

Barth,

170.

Hemsley,

Kunstst.,

H J,

D "A,

Higgs,

71 10, 636-64-2 (1981)

R P,

Miadonye,

A,

Polymer Comm.,

24- 103-106 (1983)

171.

BS 903 Part A2,

<1971>

172.

Rosand Instrumented Impact Test Systems Company Manual

for Drop Weight Tester 5A,

173.

ISO/DP 6603/2.3:

174-.

Gutteridge,

175.

Draft

P A,

(1986)

(1987)

Hooley,

Will1ams,

M J,

Kunstst,

Bowerman,

H H,

McKelvey,

C J,

Moore,

D R, Turner,

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72 9, 54-3-54-7 (1982)

Polym. Eng. Sci.,

J M,

8 4,

310-318 (1968)
176.

den Otter,

PVC Technical Report (No 2>,

L,

Laboratorium TNO,
177.

Delft

(1974-)

Lead Industries Group Lt d.

Fillers,

Centraal

Report

' Cal ei um Carbonate

And Their Effect On The Fusion,

Strength Of PVC For Pipe',

And Impact

PM/25/82 Perivale,

London

(1982)
178.

Strijbos,

179.

Obande,

5,

0 P,

Powder Techn.,
Phd

Thesi~

1.. 209-214-

(1977)

Loughborough University of

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180.

Katchy,

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181.

Rauwendaal,

J.

C J,

Appl.

POlym.

Set.,

28 1847-1869 (1983)
~

POlym.

Eng.

Sci.,

Schultheis,

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1092-1100

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182.

Potente,

H,

77 4,

4-01-4-04

(1987)

Page 233

References

183.

Janssen,
Pub!.

184-.

'Twin Screw Extrusion', Elsevier Sc1.

L P B M,

Corp.

(1978)

'Polymer Melt Rheology',

F N,

Cogswell,

Oeorge Oodwin

(1981)
185.

Zolotor,

186.

Tadmor,

187.

McKelvey,

Mod.

A M,

Ind.

2,

New York

Eng.

4-7 12,

Ch em.

68-72

FundBm.,

(1970)
346 (1976)

'Polymer Processing', John Wiley & Sons,

M,

P1Bst.,

(1962)

188.

ICI Tech.

189.

Got ham,

Service Note W 121 ICI Vinyls group

K V,

Hitch,M J,

Brit.

Polym.

J.,

(1980)
4-7-52

( 1978)
190.

Pepper,

S T,

Unpublished results (1986)

191.

Howard,

0 J,

Shanks,

J.

R A,

Appl.

POlym. Sci.,

26 3099

<1981 )

L E,

192.

Nielsen,

193.

Alter,

194-.

Oberst,

H,

559-590

<1971>

195.

Gonze,

A,

317-351
196.

Cross,

J.

H,

J.

Appl.

Appl.

Polym.

Polym.

Retting,

W,

Set,

Set.,

J. MBcrom.

Chauffoureaux,

J C,

1Q. 97-103 (1966)

1525-1531

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Sci.-Phys.,

3,

Pure & Appl. Ch em. , 35

(1973)

A, Haward, R N, Mills, N J,

Polyme~

20 288-294-

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197.

Vincent,

198.

Parey,

199.

Marshall,

P I,

J,

Polyme~

Kruger,

0 P,

E,

P1Bst.

(1960)

Kunstst.,

74- 1, 39-42 (1984)

& Rubb. Proc. Appl.,

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169-182

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200.

Stapfer,
276

201.

C H,

Hampson, D 0,

Dworkin,

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Collins,

E A, Hartitz, E,

P1Bst.

Design & Proc.,

15-20

(1978)

Page 234

References

202.

Cookson plc Central Research Laboratories Report

'Perf-

ormance of Hydrocarbon Lubricants in a High Speed Mixer

in Filled and Unfilled PVC Formulations',

Perivale,

London (1984)

203.

Obande, 0 P, Gilbert,

204-.

Mai,

Y W,

PM/5/84

Kerr,

P R,

M,
J.

To be published (1988)
Vinyl

Techn.,

7 4, 130-139

(1985)

Page 235

APPENDIX A

FORMULATION DETAILS

Al. 1 COMPOSITE STABILISER/LUBRICANT SYSTEM

TABLE A.l

Properties of TBLS.

Property

TBLS
[ 159]

NLSt and Cast

NLSt
[ 150]

Formula

3PbO. PbSO . H2 O Pb(CH.(CH 2 ),.COO),

Appearance

cream/whi te

soft white

53

l' 4

PbO content (%)

82-84

27-29

Safe PbO

51-53

27-29

Specific gravity
(%)

Melt ing point ( 'C)

Moisture content (%)
t

02

Cast
[ 15t]
Ca (CH. (CH,) "COO),
white
105

102-108

121

025

30

Determined by DSC

Page 235

Appendix/A

Al.2 LUBRICANT DETAILS

TABLE A.2
PrimarY lubricant properties

Sasol
HI
[162]
Manufacturer
Description
Addi tion (phr)
Solidlf icatlon
point ('C)
Drop point ('C)
Melting point t
Acid value
(mg KDH/g)
S.a/Density
(-/gem l )
Vi scoslty
(m.pa.s/cs)

Hoechst
PE520
[163]

Loxiol
815
[ 164]

Loxiol
812
[ 165]

Pristerene Oletec
4903
6009
[ 166]
[167]

Henkol
Pristerene Dletec
Sasol
Hoechst
Henkol
High M.pt Polyethylene Hydrogenated Fatty acid ester Stearic
Low M.pt
of glycerine
castor oil
ac id
paraffin
Paraffin wax
1-0
1-0
0-2 l 1-0
0- 1
0-2
1-0
98

118-123

95
(0- 1

=108
105
0

094

0,92-0-94

~25'C

59
64-90
82
(5
0-895

~20'C

~100'C

=1000
WO'C

~100'C

24

57-60
60
(2
0-5-0-915
a80'C
25-35
~80'C

53-55
54
=2

56

4-25 cs
!100'C

t DSC measurement ('C)

Page 237

APPENDIX B

ASH ANALYSIS

Bl. 1 CALIBRATION GRAPH FOR ASH CONTENT

A number
from

O~120

!l2. 5.1.

phr

of

blends

with

were hand mixed

filler

and

ashed

The resultant graph and fitted

content

ranging

as described

in

curve was then used

to calculate the filler content of the Henschel dry blended

samples.

FIGURE B.l ASH CALIBRATION

Filler Content (phr)

, r-------------------,

le

2IiJ

r.

lit

..8

50

Ash Content

Polynomial regression equation:

Y = 0078 + 0353x + 00792x. - 0'0032x' + O'0000051x'

Correlation (rl

= 09987

Standard deviation of errors [adel

= 1.886
Page 238

APPENDIX C

SKETCH OF SPLIT PIPE IMPACT RIG

o
j---H-----

o
r---H-- --------

-- ---- -I----i

-- - --

-0

-------I

ALLEN BOLT
CLAMP

'-r-~jIIIIIIII'-l7l=-l~

____ SPECIMEN

TITLE

Roeand impact rig

SCALE

1: 2 (mm)

DRAWN

S.T.Pepper IPT

MATERIAL: Mild steel

Page 239

APPENDIX D

EXTRUDER RESUL TS

TABLE D. 1
Extruder temBeratures
Pipe
code

Zone
one
( 'C)

EXTRUDER
Zone
two
( 'C)

TEMPERATURES
Oil
Adaptor
reservoir TMl
( 'C)
( 'C)

He6d
TM2
(. C)

OA
lA
2A
3A
4A
5A

160
158
. 158
158
158
158

160
160
161
160
161
162

142
141
141
141
141
141

156
153
152
157
159
152

170
168
164
168
164
165

OB
lB
2B
3B
4B
5B

160
158
158
158
158
159

160
160
161
160
162
162

142
141
141
141
142
141

156
153
158
157
160
155

175
170
168
168
169
169

OC
IC
2C
3C
4C
5C

160
159
158
159
159
159

160
161
161
161
161
162

142
141
141
141
141
141

156
158
158
158
158
160

183
176
177
177
178
177

OD
ID
2D
3D
4D
5D

173
172
173
172
172
173

173
175
176
176
175
175

142
141
142
141
142
142

168
165
165
165
166
167

183
180
181
182
183
182

OE
lE
2E
3E
4E
5E

173
173
173
173
173
173

173
175
175
175
175
175

142
142
141
142
142
142

168
169
169
170
171
171

192
187
186
187
187
188

OF
IF
2F
3F
4F
5F

193
191
190
191
191
191

191
193
193
193
193
193

142
142
142
143
143
143

184
185
185
186
186
187

203
194
197
197
198
198

Page 240

Appendix/D

TABLE D. 1 (cont)

Extruder temperatures

Pipe
code

Zone
one
( 'C)

EXTRUDER
Zone
two
( 'C)

TEMPERATURES
Adaptor
reservoir TM1
( 'C)
( 'C)

011

Head
TM2
('C)

OEOEA
OEB
OEC
OED
OEE
OEF
OEG
OEH

172
172
172
172
173
173
173
173
173

172
172
172
172
173
173
173
173
173

142
142
142
14-2
14-2
142
142
142
142

169
169
170
170
169
170
170
169
170

187
187
186
186
187
186
187
187
187

3E3EA
3EB
3EC
3ED
3EE
3EF
3EG
3EH

173
173
173
172
173
172
173
173
173

173
173
173
172
173
172
173
173
173

143
143
143
143
14-4
143
143
143
143

171
171
171
170
171
170
170
170
171

189
189
190
188
189
188
189
189
190

Page 241

Appendix/D

TABLE D.2

Mechanical energy:

Pipe
code

EXPERIMENTAL VALUE
Torque Output
Q
(rev, %/g)
TQ
Jb
(%)
(g/min)

filler content

Pipe
code

EXPERIMENTAL VALUE
Torque Output
Q
(rev,%/g)
TQ
III
(%)
(g/min)

OA
OB
OC
OD
OE
OF

62
53
47,5
43
42
38

130
130
130
131
131
130

40' 1
31' 4
26, 1
21' 6
20'6
16'9

lA
lB
lC
ID
lE
IF

65
57
48,5
45
42
35'5

130
127
131
136
136
136

42,0
34,0
26,9
22,6
,19'3
13,9

2A
2B
2C
2D
2E
2F

74
66
51
47,5
44' 5
37'5

133
134
128
125
134
135

49 1
42'7
29,9
27, 1
22'5
15'8

3A
3B
3C
3D
3E
3F

84
78
59
54
51
42,5

127
129
127
126
135
130

628
56'0
38' 1
33'4
28'4
21 '3

4A
4B
4C
4D
4E
4F

94
91
67
59
60
48,5

133
141
129
135
132
132

69'4
62,8
45' 3
35'8
37,6
26,7

5A
5B
5C
50
5E
5F

109
105
83
62
62
53

134
134
139
140
138
135

83'0
79,2
56'5
37,2
37,8
30'2

Page 242

Appendix/D

TABLE D.3
Extrusion pressure:

Pipe
code

EXPERIMENTAL VALUE
PI
Inlet
Head
pressure pressure pressure
(Bar)
(Bar)
(Bar)

filler content

Pipe
code

EXPERIMENTAL VALUE
Inlet
PI
Head
pressure
pressure
pressure
(Bar)
(Bar)
(bar)

OA
OB
OC
OD
OE
OF

31
25
0
0
0
0

269
236
202
175
165
127

164
131
105
97
92
80

lA
lB
lC
10
lE
IF

39
6
0
0
0
0

307
280
242
223
212
154

167
141
123
123
100
74

2A
2B
2C
20
2E
2F

62
27
0
0
0
0

348
329
274
265
246
191

192
170
145
145
122
95

3A
38
3C
30
3E
3F

77

49
0
0
0
0

415
394
334
317
286
217

226
207
184
174
152
122

4A
4B
4C
40
4E
4F

87
73
0
0
0
0

436
420
374
362
333
237

266
248
217
206
193
152

5A
5B
SC
50
5E
5F

139
120
27
0
0
0

518
496
432
400
360
260

315
290
241
228
203
179

Page 243

Appendix/D

TABLE D.4.

Extrusion results:

Pipe
code

Torque
TQ
(1.)

additive study

EXTRUDER RESULTS
Output
Inlet
PI
Q
(rev.1./g) pressure pressure
Ih
(Bar>
(Bar)
(g/m1n)

Head
pressure
(Bar)

OEOEA
OEB
OEC
OED
OEE
OEF
OEG
OEH

39
38
305
38
395
49
35
39
60

118
117
117
113
112
118
117
107
112

19'7
188
107
19'5
213
302
156
21 7
44'1

0
0
0
0
0
6
0
0
30

112
113
100
127
135
179
123
126
228

85
85
74
106
110
142
84
100
190

3E3EA
3EB
3EC
3ED
3EE
3EF
3EG
3EH

33'5
36
27
34
35
35
28
31
33

50
50
52
52
57
55
50

327
390
156
32'9
32'0
33'0
189
322
385

0
0
0
0
0
0
0
0
0

131
154

119
136
75
125
127
119
70
101
105

41

41

77

143
134
138
74
79
114

Page 244

APPENDIX E

FIL TERING OF IMPACT TRACES

FIGURE E. 1
Impact trace of 5e:

unfiltered

Drive: 3
Sample:
Details:
Date: 07/05/86
Time: 23:39:08
Mass: 25KQ:
Temp: 20'C
PEAK INFORMATION
Force=275.2 N
Deflection=1.587 mm
Energy=0.196 J
Gradient=21.92 KN/m
FAILURE INFORMATION
Deflection=44.68 mm
Energy=4.265 J

699.9

Force-Distance

...................................................................................................................... .

....................................................................,.

499.0H1

29:99

49.89

68.88

........

Page 245

Appendix/E

FIGURE E.2
Impact trace of 5C: Over-filtered

Drive:

Samp~e:

Detai~s;

Date: 07/05/86
Time: 23:39:08
Mass: 25Kg
Temp: 20'C
PEAK INFORMATION
Force=173.5 N
Def~ection=2.117

mm

EnergY=0.235 J
FAILURE INFORMATION
Def~ection=U9.80 mm
Energy=U.382 J

H
3 .

Force-Distance

rir r...............................

tfr\ I ~ I ........

188. 8

I I

., ................. \ ........... - .......

I,

/1

L.._.

\\ Lr\_....
"

I~

/~<.\

. . . . . . . _. . . . . . . . . . . . . . . . ..
:

L_, / ..., :
...-

,:
..}__. . .
\ ,

. - - --\~

8~-----------'+':------------~:------~----~-8

28.88

48.98

68.88

.........

Page 246

Appendix/E

FIGURE E.3
Impact trace of 5C:

Drive:

Moderate filter

Samp~e:

Detai~s:

Date: 07/05/86
Time: 23:39:08
Mass: 25K&
Temp: 20'C
PEAK INFORMATION
Force=211.0 N
Def~ection=1.588

mm

Energy=0.198 J
FAILURE INFORMATION
Def~ection=43.62 mm
Energy=4.242 J

Force-Distance

288.8'

It
I
!
V
I :
i.

!:

r',
I~I '/1

i.

~.;........... T.... +.I:{ ..... \.............. i... ..................................

\:
.}-./"..... :
\1,.,. I~l. t'v,
L~L"'II !
'.,:
i
....
8~------------~'~'--------------~'--~'----------__~__
8
28.88

188 .8 . .............

48.88

......

68.88

Page 247

APPENDIX F
IMPACT PROPERTIES

TABLE F. 1
ImBact Brol:lert 1 es:
Test
temp
( 'C)

Peak
Peak
Force Deflection
(N/mm)
(mm)

Influence of test t eml:lerat ure

Peak
Energy
(J Imm)

Failure
Deflection
(mm)

Failure
Energy
(J Imm)

Er

Maximum
Gradient
(KNmm/m)

Type
of
Failure

s.dt

OF:O Ilhr
-20
-10
0
10
20
41
60
80
100

166
198
1117
1170
1261
1317
1140
994
921

1 54
3' 19
1163
12'67
1490
16'45
1657
17 15
1837

O' 1
0'4
60
7 1
99
11' 2
10 1
9'5
9'4

7'21
8'41
14'43
15'97
2064
19'79
2005
2074
2398

08
l' 0
76
9 1
125
14' 1
125
11'8
123

O' 1
0'2
1 6
0'8
0'7
0'9
1'0
0'4
l' 2

152
161
150
130
119
117
110
96
76

B
B

2 11
1057
1176
12'78
15'46
1731
1727
1786
18'40

0'3
57
62
7'2
10 4
11' 7
10 6
95
9' 1

6'33
12 12
1351
15'35
17'89
19'82
21' 11
21'31
23'14

0'9
66
73
87
12 1
13'6
133
11'4
119

0'2
l' 2
l' 2
l' 0
0'7
0'5
0'2
0'6
0'5

162
lU
126
123
127
105
99
84

451
5 44
3'08
926
11 84
1386
16'82
16'84
1788

06
08
0'4
36
58
72
88
83
87

718
722
926
10'45
1305
15'85
1988
2021
21 11

09
l' 0
l' 2
4' 1
63
8' 1
10' 1
97
10 1

O' 1
O' 1
0'3
1'0
0'7
l' 3
0'6
0'3
0'5

131
148
142
119
116
100
81
78

BID
BID
D
D
D
D
D

IF:8'5 Ilhr
-20
-10
0
10
20
41
60
80
100

217
1134
1117
1182
1293
1250
1158
937
869

72

BID
BID
BID
D
D
D
D
D

2F: 18' 1 Ilhr

-20
-10
0
10
20
41
60
80
100

191
203
180
829
1034
1059
1002
908
876

B = Brit t le. BID = Brit t le/Duct ile. D

t s.d = Sample standard deviation

72

B
B
B

BID
BID
BID
D
D
D

= Ductile

Page 248

Appendix/F

TABLE F.l Cont.

Impact properties:

Test
temp
("C)

Peak
Peak
Force Deflection
(mm)
(N/mm)

Peak
Energy
(J Imm)

Influence of test temperature

Failure
Deflection
(mm)

Failure
Energy
(J I mm)

Maximum
Gradient
(KNmmlm)

Type
of
Failure

EF

s.dt

l' 0
08
0'9
l' 0
l' 0
l' 7
2'4
4'5
6' 1

0'2
O' 1
O' 1
O' 1
0'2
0'4
l' 0
0'8
0'8

113
107
119
107
137
96
71
66
60

B
B
B
B
B

l' 2 0'2
. l' 1 0'2
l' 3 0'3
l' 5 0'4
l' 3 O' 1
l' 1 0'2
l' 1 O' 1
2,.2 O' 1
26 0'5

238
114
120
101
155
107
87
60
48

B
B
B
B
B
B
B

254
110
108
99
151
102
81
37
44

B
B
B
B
B
B
B
B

3F: 27'3 phr

-20
-10
0
10
20
41
60
80
100

163
161
188
185
198
402
467
624
691

580
5'59
504
5' 12
5'39
662
8'32
1206
15' 12

0'7
06
07
07
0'7
l' 4
'2'0
38
52

354
5'84
6 15
6'74
571
6'96
591
770
855

0'5
0'7
0'9
0'9
0'9
0'8
0'8
l' 5
l' 5

1 11
5'39
595
6 12
6 15
660
5'44
5'84
599

O' 1
0'7
07
0'7
09
09
0'6
0'7
0'8

8'57
7'44
7'48
7'70
7'75
8'62
10'36
14'81
18 11

BID
BID
BID
D

4F:35'6 phr
-20
-10
0
10
20
41
60
80
100

214
172
195
183
166
180
191
371
344

7'94
8'90
9'45
11'86
8'03
10'30
8'49
11' 61
17'14

BID
BID

5F:40 phr
-20 .
-10
0
10
20
41
60
80
100

188
166
168
167
184
180
183
194
238

7'00
8'30
9'09
8'48
9'00
12'57
8'52
15'00
13'90

l' 0
l' 0
l' 1
10
l' 2
l' 6
1'0
l' 8
18

O' 1
0'1
0'2
0'1
0'3
0'3
0'3
0'2
0'2

BID

B = Brittle. BID
Brit tle/Duct ile. D = Ductile
t s.d = Sample standard del(iation

Page 249