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CHARACTERIZATION

Thesis

DISTRIBUTIVE

CO-ROTATING

COMPOUNDING

Dept,

JOHN

submitted

Doctor

of

MJa

Brunel

Uxbridge,

OF

DISPERSIVE

MIXING

TWIN-SCREW

EXTRUDER

t 3y

WILLIAM

ESS

IN

of

at

teria193

May

A

for

Philosophy

the

University

Midd1

1989

the

degree

Technology

Bex

A

AND

of

ABSTRACT

A

new

design

compounding

extruder,

in

the

development

of

closely

developed

of

quantitative

at

dispersive

by

extrusion

and

distributive

compounding.

mixing

Image

intermeshing

co-rotating

Brunel

University,

has

twin-screw

been

utilized

techniques

for

characterization

of

in

thermoplastics

materials

analysis

procedures

were

prepared

used

to

quantify

carbonate

mixing

filler

of

using

polypropylene

reflected

light

composites

microscopy

containing

on

polished

calcium

surfaces,

and

transmitted

Stereological

light

results

are

discussed

microscopy

statistics

in

relation

of

have

to

particle

agglomeration,

dispersion

microtomed

pigmented

been

applied

to

sections.

raw

sample

data;

mechanistic

phenomena

influencing

and

distribution

of

fillers

in

thermoplastics.

Dispersive

or

intensive

filled

polypropylene

significant

influence

machine

effect

although

on

the

rate

the

specimens

except

melting

of

filler

mixing

showed

determined

from

that

processing

calcium

parameters

when

zone

filler

was

was

highlighted

added

as

midway

having

carbonate

had

along

no

the

a marked

dispersion.

Premixing

of

filler

and

polymer

introduced

additional

of

model

experiments

specific

parameters.

having

the

single

Distributive

most

or

were

In

this

important

extensive

agglomeration

undertaken

context

effect

mixing

specimens

was

disc

elements

than

a

six-fold

very

at

significantly

the

end

of

increase

in

the

affected

screws.

distributive

to

into

the

assess

filler.

the

A series

influence

of

on

moisture

content

filler

of

by

compaction.

carbon

black

the

presence

of

emerged

as

pigmented

segmented

These

elements

produced

more

mixing

in

the

extrudate.

I

ACKNOWLEDGEMENTS

The

financial

Directorate

author

gratefully

acknowledges

and

of

material,

the

made to

this

Science

and

project

Engineering

the

by

the

contributions,

both

Polymer

Engineering

Research

Council,

and

Croxton

and

Garry

Appreciation

Ltd

for

the

to

the

late

supply

Mr

I

of

calcium

Boyne

for

carbonate

fillers.

his

considerable

efforts

during

the

twin-screw

Sincere

initial

extruder

thanks

proving

development

and

modification

programme.

to

Peter

Hornsby

for

his

trials

patience

and

of

the

TS40

perseverance

during

the

later

comments

during

stages

the

initial

of

this

phase.

project

The

Materials

by

Mr

J

technical

Technology

Felgate,

Mr

and

administrative

are

also

acknowledged,

K Johns

and

Mr

L Kellett.

and

for

facilities

particularly

his

of

assistance

and

the

those

Dept

of

provided

report

Assistance

with

was

provided

the

preparation,

by

Gwen and

Will.

checking

and

collation

of

this

ii

ABSTRACT

ACKNOWLEDGEMENTS

CONTENTS

FIGURES

CONTENTS

CHAPTER 1

CHAPTER 2

INTRODUCTION

LITERATURE REVIEW

1

6

2.1 TWIN-SCREW EXTRUSION,

6

2.1.1

2.1.1.1

2.1.1.2

2.1.2

Background,

6

Single-screw

extrusion,

Twin-screw

extrusion,

Different

Formats,

10

8

6

2.1.3

Operating

Characteristics,

11

2.1.3.1

2.1.3.2

2.2 MIXING

Counter-rotating

Co-rotating

THEORY, 14

machines,

machines,

12

2.2.1

2.2.2

2.2.2.1

2.2.2.2

Single-Screw

Twin-Screw

Machines,

Machines,

Counter-rotating,

Co-rotating,

17

16

14

16

2.3 COMPOUNDING, 18

2.3.1

Definitions,

18

2.3.2

Equipment,

19

iii

11

2.3.3

2.3.4

Applications,

Materials,

22

21

2.4 CHARACTERIZATION OF MIXING,

2.4.1

2.4.1.1

2.4.1.2

2.4.2

2.4.3

Representative

Parameters,

Indirect

Direct

measurement,

measurement,

Manual

Methods,

26

Automated

Methods,

27

25

25

25

25

CHAPTER 3

3.1 TS40

3.1.1

3.1.2

3.1.3

EXPERIMENTAL

TWIN-SCREW COMPOUNDINGEXTRUDER, 28

Background,

Design,

29

Development,

28

30

28

3.2 DEVELOPMENTOF CHARACTERIZATION TECHNIQUES, 34

3.2.1

3.2.1.1

3.2.1.2

Sample

Preparation,

Isolation

of

the

36

filler,

Thin

film

formation,

38

36

3.2.1.3

3.2.2

3.2.2.1

3.2.2.2

3.2.2.3

3.2.2.4

3.2.3

3.2.3.1

Polished

solid

Sample

Examination,

surfaces,

42

41

Light

microscopy,

Scanning

electron

42

microscopy,

Contact

Acoustic

microradiography,

microscopy,

44

43

Image

Analysis,

45

Introduction,

45

3.2.3.2

3.2.3.3

3.2.3.4

3.2.3.5

Assumptions,

46

Data

Data

acquisition,

assimilation,

47

49

Statistical

analysis,

50

iv

42

3.2.3.6

Estimation

of

errors,

57

3.3 DISPERSIVE

AND DISTRIBUTIVE

MIXING,

3.3.1

3.3.1.1

3.3.1.2

3.3.1.3

3.3.1.4

3.3.2

Dispersive

Mixing,

60

Characterization

procedure,

Premixing

conditions,

61

Material

variables,

61

Processing

Distributive

variables,

Mixing,

65

67

3.3.2.1

3.3.2.2

Characterization

Pigment

loading,

procedure,

67

3.3.2.3

Processing

variables,

67

60

60

65

3.4 MODEL EXPERIMENTS WITH PRECONDITIONED FILLER,

3.4.1

3.4.2

3.4.3

3.4.4

Preconditioning

Calcium

Calcium

Carbonate

Carbonate

Preconditioning

Pressure,

Moisture

70

Content,

Characteristics,

Temperature,

71

70

71

CHAPTER 4

DISCUSSION

4.1 CHARACTERIZATION OF MIXING,

72

4.2 AGGLOMERATION, 84

4.2.1

4.2.2

4.2.3

Agglomerate

Influence

Formation

of

Premixing

Agglomeration,

Effect

of

Solid

87

'Dry'

4.2.4

Filler

Preconditioning

4.3 MELTING AND WETTING,

92

4.4 DISPERSION,

4.4.1

Material

96

and

Processing

and

on

Strength,

Filler

Processing,

88

84

Parameters,

89

Variables,

97

4.4.2

Preconditioning

of

Filler,

101

V

70

72

4.5

DISTRIBUTION,

4.5.1

4.5.2

Processing

Distributive

4.5.3

Reorientation

Extruder,

103

Variables,

Mixing

107

within

CHAPTER 5

CONCLUSIONS

SUGGESTIONS FOR FURTHER WORK

104

Contribution

of

the

Twin-Screw

Discs,

REFERENCES

APPENDIX A

A. 1

A. 2

APPENDIX B

APPENDIX C

IMAGE ANALYZER COMPUTERPROGRAMSFOR

DISPERSIVE

MIXING

MEASUREMENTPROGRAM

STATISTICS

PROGRAM

IMAGE ANALYZER COMPUTERPROGRAMFOR

DISTRIBUTIVE

MIXING

NOMENCLATURE

vi

106

108

110

112

123

131

134

3.1.1

3.1.2

3.1.3

3.1.4

3.1.5

3.1.6

3.2.1

3.2.2

3.2.3

3.2.4

3.2.5

3.2.6

3.2.7

3.2.8

3.2.9

3.2.10

FIGURES

Side

elevation

of

the

TS40

twin-screw

extruder

Schematic

diagram

showing

standard

extended

-5

barrel

-

configurations

shown

for

The

modular

each

configuration)

screw

sections

Screw

configuration

Dimensions

of

screw

used

in

mixing

configurations

experiments

Barrel

withdrawn

to

the

left

leaving

solidified

material

(Feed

enters

at

screws)

compounding

-4

barrel

(only

one

-

and

screw

experiments

used

in

screws

right

mixing

encased

hand

side

Transmitted

ashing

of

Transmitted

light

film

light

micrograph

micrograph

ashing

of

Transmitted

microtomed

section

light

micrograph

solvent

extraction

Bubble

blowing

apparatus

Transmitted

Extruder

of

light

micrograph

a

laboratory

film

Reflected

Transmitted

light

light

micrograph

micrograph

of

microtomed

surfaces

of

material

of

material

of

material

of

part

of

casting

extruded

remaining

remaining

remaining

blown

line

tape

bubble

showing

damage

to

Steel

bladed

Mechanical

RAPRA-designed

block

rotator

c ryomicrotome

vii

Page

No

 

33

33

33

33

33

in

of

 

33

after

 

59

after

 

59

after

 

59

59

59

59

59

59

59

59

3.2.11

3.2.12

3.2.13

3.2.14

3.2.15

3.2.16

3.3.1

3.3.2

3.3.3

3.3.4

3.3.5

3.3.6

3.3.7

SEM and

X-ray

dot-image

of

calcium

ions

detected

on

the

sample

X-ray

surface

micronegative

microscope

Specimens

compared

viewed

by

mode

viewed

through

a

transmitted

to

microtomed

section

acoustic

microscope

in

reflected

Principle

Optomax

components

image

analyser,

of

image

Apple

analysis

computer

and

Zeiss

light

microscope

The

effect

surface

of

(Graph

processing

A)

using

analysis

(Graph

B).

expressed

as

a

Mean volume

raw

data

measured

Schwartz-Saltykov

from

specimen

(diameter)

particle

diameter

volume

(MVD)

distribution

obtained

from

data

in

Graph

B

is

3i.

3um

Outline

calcium

The

effect

of

characterization

carbonate

filled

of

mixing

specimens

of

varying

calcium

carbonate

technique

for

characteristics

and

polymer

Dispersion

of

matrix

Durcal

2 along

at

standard

Dispersion,

extruder

of

Durcal

at

slow

screw

speed

settings

2 along

(60rpm)

Dispersion

of

at

high

screw

Comparison

of

Durcal

speed

2 along

(180rpm)

dispersion

of

of

the

screws

Dispersion

of

at

60,120

and

Durcal

2'along

the

the

length

length

of

of

the

length

of

Durcal

180rpm

2 along

the

length

of

the

the

the

the

the

screws

screws

screws

length

screws

at

low

temperature

profile

"

viii

59

59

59

59

59

59

69

69

69

69

69

69

69

3.3.8

3.3.9

3.3.10

3.3.11

3.3.12

3.3.13

3.3.14

3.3.15

3.3.16

3.3.17

3.3.18

Dispersion

of

Durcal

2

along

at

high

temperature

profile

Comparison

of

dispersion

of

of

the

screws

at

low,

normal

the

-

Durcal

and

length

of

the

2 along

the

high

temperature

screws

length

profiles

Dispersion

when

the

separately

of

Durcal

2 along

the

length

of

calcium

fed

at

carbonate

and

the

hopper

polypropylene

the

screws

were

Dispersion

screws

when

of

Durcal

2 along

the

the

calcium

carbonate

second

stage

of

and

polypropylene

the

separately

Comparison

fed

of

of

the

filler

screws

addition

at

the

dispersion

downstream

of

Durcal

entry

port

2 along

as

a

function

of

position

and

the

length

mode of

were

Comparison

of

the

second-stage

dispersion

metering

of

Durcal

screws

2

for

along

the

different

length

of

metering

screw

Outline

profiles

of

characterization

of

mixing

technique

for

carbon

black

Regression-lines

pigmented

specimens

of

area

fraction

on

screw

speed

showing

the

level

effect

of

Distributive

of

the

carbon'black

mixing,

presence

of

distributive

of

carbon

the

black

breaker

mixing

along

plate

the

the

'8mm pitch'

second-stage

Distributive

mixing

of

carbon

the

'12mm pitch'

second-stage

Distributive

mixing

of

carbon

metering

black

screws

along

the

metering

screws

black

along

the

on

length

length

length

the

of

of

of

the

'16mm

pitch'

second-stage

metering

screws

ix

69

69

69

69

69

69

69

69

69

69

69

3.3.19

3.3.20

3.3.21

3.3.22

3.4.1

3.4.2

4.1.1

Distributive

the

'8mm pitch

mixing

plus

of

carbon

2 mixing

black

elements'

along

the

length

second-stage

of

metering

Comparison

the

length

different

Distributive

screws

of

of

distributive

mixing

of

carbon

black

the

second-stage

metering

screws

for

along

metering

mixing

screw

profiles

of

carbon

black

along

the

length

of

the

'8mm pitch

metering

separately

Comparison

the

length

screws

into

of

of

plus

when

2 mixing

carbon

elements'

second-stage

black

masterbatch

dosed

the

downstream

entry

port

distributive

mixing

of

carbon

black

the

second-stage

metering

screws

for

along

different

positions

of

carbon

black

masterbatch

addition

The

and

effects

position

of

of

preconditioning

filler

entry

on

pressure,

moisture

the

dispersion

of

content

Durcal

2

pellets

in

polypropylene

extrudate

after

processing

Table

The

3.3.3)

effects

position

of

temperature

at

of

filler

standard

calcium

entry

extruder

carbonate

(Graph

settings

(See

characteristics

and

A)

and

preconditioning

(Graph

B)

on

the

dispersion

of

Durcal

2

pellets

standard

in

polypropylene

extruder

settings

extrudate

(See

after

processing

Table

3.3.3)

at

SEM and

processed

positions

X-ray

at

i

micrographs

of

standard

to

5

(See

extruder

Table

PP/Durcal

2

settings,

3.3.4

PP-D2)

samples,

taken

from,

X

69

69

69

69

71

71

83

4.1.2

4.1.3

4.1.4

4.4.1

Reflected

case

views

processed

to

8

(See

light

micrographs

encountered

for

showing

PP/Durcal

at

standard

Table

3.3.4

settings,

and

3.3.3)

taken

some of

the

worst

2

samples,

from

positions

I

Optical

microdensitometer

trace

from

micrograph

Transmitted

shown

light

above

(PPG-CB-BP-120

micrographs

showing

O. Swt% carbon

black

in

polypropylene,

8mm + 2D metering

1

to

6

(See

Table

section,

3.3.18

taken

from

and

3.3.19)

negative

in

Table

typical

processed

sampling

of

3.3.15)

fields

using

for

positions

Scanning

Durcal

(position

electron

2 agglomerate

2)

micrographs

found

at

showing

the

end

structure

of

the

of

screws

a

xi

83

83

83

102

CHAPTER

1

INTRODUCTION

Originally,

the

brief

for

this

research

work

entitled

'Twin-Screw

Extrusion

involving

However,

Compounding

both

as

the

material

project

of

Plastics'

investigation

progressed

implied

and

financial

acute

necessitating

compound

analysis.

placed

in

a

on

investigations

polymer

matrix.

This

investigation

polymer

processing

a

As

concentration

a

result

into

a

of

wide

of

industry's

mixing

desire

of

this

range

during

to

a

technological

study

engineering

development.

constraints.

became

more

resources

in

the

area

of

change,

more

of

materials

emphasis

was

for

inclusion

extrusion

stems

from

the

lower

materials

costs

while

enhancing

physical

this

philosophy

formulations

is

which

properties

to

be

found

employed

fibrous

fillers

have

found

of

with

end

the

products.

thermosetting

The

first

urea

example

of

formaldehyde

wood

favour

flour

as

as

a

means

filler.

of

More

reinforcing

recently,

polymer

matrices

The

mass

great

of

so

that

demands

research

they

can

required

work

being

compete

with

metals

of

engineering

as

engineering

materials

has

undertaken

to

accurately

specify

materials.

resulted

in

properties

a

and

to

satisfy

various

official

agencies

concerned

with

standards

and

safety.

Nevertheless,

remain

with

the

higher

a carefully

non-reinforcing

volume

chosen

area

offering

polymer/filler

(extending)

large

fillers

potential

combination.

in

cost

The

polymers

savings

result

of

incorporating

properties,

minimized.

systems,

viz.

extending

so

ways

have

Two possibilities

fibrous

and

fillers,

been

is

found

arise:

-

particulate

usually

whereby

(a)

the

some

these-

use

of

combined,

in

loss

of

problems

composite

physical

can

filler

be

the

same polymer

I

matrix;

or

agglomeration

The

use

difficulties

(b)

the

elimination

of

of

the

because,

particulate

composite

in

order

filler.

filler

for

the

the

fibre

length

attrition

must

not

be

of

stress

raisers,

systems

fibrous

excessive

creates

element

while

to

the

viz.

any

additional

be

effective,

shear

stress

must

be

sufficient

masterbatch

of

the

to

eliminate

particulate

gross

filler,

agglomeration.

or

a

higher

shear

A pre-dispersed

first

stage

of

a

three

element

then

only

Composite

stage

will

extruder

be

required

at

a

significant

systems

do,

screw,

for

with

this

downstream

strategy

to

be

feeding

of

the

property-efficient

fibrous

and

cost

however,

penalty

prove

compared

tenable

in

to

extended

systems.

demanding

engineering

situations.

Polymers

employed

for

their

aesthetic

properties

or

in

non-load

bearing

situations

require

an

extending

filler

displacing

The

aesthetic

undermined

expensive

nature,

polymer

while

together

by

agglomeration

of

perhaps

also

with

physical

the

filler:

to

provide

pigmenting

a means

the

matrix.

properties,

will

various

means

exist

of

be

to

eliminate

these

agglomerates:

-

(1)

use

of

pre-dispersed

masterbatch

systems

which

require

only

blending

(ii) use

of

and

shear

(iii)

(iv)

above

a

size

use

of

screen

use

of

surface

distribution

within

the

polymer

matrix;

stresses

determined

packs

to

high

by

filter

coatings,

enough

to

the

severity

disperse

of

all

agglomerates

specification;

out

applied

the

to

offending

the

filler

particles;

during

its

manufacture,

which

inhibit

filler

particle-particle

agglomeration.

The

masterbatch

system

particularly

raw

material

for

or

common fillers,

if

the

non-specialized

equipment.

A

of

when

filler

prime

filler

it

is

is

example

addition

not

desirable

difficult

to

of

this

type

is

to

employed,

handle

the

disperse

of

filler

on

is

2

carbon

state

black

and

dispersion.

in

a matrix

route

around

which

requires

presents

very

formidable

high

shear

handling

rates

to

A masterbatch

of

of

the

these

same polymer

difficulties

pre-dispersed

as

that

in

carbon

the

final

but

increases

problems

achieve

black

in

its

raw

acceptable

concentrated

product

provides

raw

material

costs.

a

Nevertheless,

it

is

particularly

cost-effective

for

producers

using

standard

formulations

when

compared

to

outlay

It

necessary

for

specialized

dispersion

the

formulation

required

has

ingredients

there

are

a

number

of

options

equipment.

unusual

open

to

or

a Polymer

Most

frequently

a

Banbury

intensive

mixer

is

utilized

low

the

volume

capital

confidential

Processor.

to

produce

batches

to

batch

twin-screw

processing

of

dispersed

variation

material

for

subsequent

and

contamination

can

processing;

arise.

however,

More

recently

batch

the

compounding

'difficult

extruder

to

disperse'

has

been

materials

developed

without

for

the

directly

need

for

pre-conditioning.

The

main

limitation

a

specified

size

after

a

related

period

to

the

of

is

that

time.

concentration

itself

a

function

of

distribution

and

pore

size

of

filtering

the

filter

out

will

any

agglomerates

inevitably

larger

than

become

blocked

The

the

of

suitability

of

filler

the

particles

filter.

of

to

a

be

concentration,

Use

of

filtering

restrained

system

which

is

is

a

particle

filter

is

size

tenable

when

a cheap

method

is