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Polymer Melt Rheology

A Guide for Industrial "'''''''1"'#.'''''''

Polymer Melt Rheology

A Guide for Industrial Practice

F. N. Cogswell

Godwin Limited
Godwin Limited

ISBN 1 85573 198 3

Godwin Limited ISBN 1 85573 198 3 2003FN British A ,-alACllVJ~Uv record for this book is

2003FN

Godwin Limited ISBN 1 85573 198 3 2003FN British A ,-alACllVJ~Uv record for this book is

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A ,-alACllVJ~Uvrecord for this book is available from the British

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cQ[)vng:m owner.

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any means~

without

the
the

Printed

or Ath"""UftC"" cQ[)vng:m owner. PU[)Uc,atIcm may be reproduced, any means~ without the Printed

ext.enem:e of

lAn'!:l1"trnA."tCl

of leI

art of ~Y"£'C"'A;"_

pra,Ctlt:tODlers of that technology, and a academic contributors to this field.

ba'~k:Q"rOlmd SCl~en(:e o,eve:lot)eO

stimulation,

this book is respe(~tttlllV

PUBLISHER'S NOTE

While the pnlrlCll)leS of careful

sUl1tabtllty of caJI~uJ~itl(J.n

not be form or contents

person tnc;~re4::m.

in this book are the nr".l'tn.f'f'

the

solutions to inl"llultill'!:lJ problems and

out

any

pulblis,heJrs cannot in

any kind in or any error

of or

reliance

Contents

 

xi

Notation

 

xiii

Introduction

1

1 Fundamental concepts

 

5

1.1

2e('me~trv of deformation

2e('me~trv of deformation

5

6

rlleolo f 21cal response of materials

7

1.2

Thermal and tlle:rmtodymlmJic response

9

1.3

"'h\'<i;tI("~1 and chemical

10

1 Rheometry for polymer melts

15

2.1

Cat,aDle of measurement Vi~iCOjelal)tic response of melts to shear flow in a cone and rheometer

Cat,aDle of

measurement

Vi~iCOjelal)tic response of melts to

shear flow in a cone and

rheometer

J::,1(Jn~:atlon;al flow rheometers

17

deformation

17

19

23

2.2

Measurement of aplJarlent rlle:olctgical

" ,."'jr.A"
"
,."'jr.A"

24

2.2.1

API)are.nt

25

2.2.2

and exit effects

30

2.2.3

Inference of elastic respoillse

Observation of extrudlate am:.eal'an«:;e

Inference of elastic respoillse Observation of extrudlate am:.eal'an«:;e
 

30

2.2.4

31

2.2.5

for app,arelot rl1leOl4oglcaI DI~ODlertijes

31

2.2.6

to

rheometers

32

2.2.7

The Melt Flow

as rheometer

33

2.2.8

Miniaturisation

33

2.3

Process simulators

 

34

2.4

Priorities and costs for

upa

Priorities and costs for u p a
Priorities and costs for u p a

35

3 Physical features and Dow

39

3.1 'emtl)eJratl11re and rtu:~01()2V

3.2 Pressure effects

39

44

3.3

DepeIldence of rhe~01()2Y on time

 

46

3.4 Stress

 

49

 

3.4.1

behaviour

49

3.4.2

Elastic response as a function of stress

51

3.4.3

Viscous response as a function of stress

52

3.4.4

Modification of mechanical

53

3.5 Deformation 2e()mc:~trv and rh(~01()2V

 

54

 

3.5.1

Bulk deflormlatl<m

54

3.5.2

hlongatloIlLal flow

54

3.5.3

flow

56

3.6 Flows

 

57

 

3.6.1

flows

57

3.6.2

Pressure-driven flows in channels of other than circular cross-section

58

3.6.3

flows

60

3.6.4

sections of

thickness

63

3.6.5

Biaxial extensional flows

64

3.6.6

The interface

65

4 Rheology and structure

71

4.1 Chain stiffness and conformation

71

 

4.1.1

Chain

73

4.1.2

Chain diameter

 

73

4.1.3

Molecular aspect ratio

73

4.2 Chain

 

distribution

77

4.3 Chain branctlmg

81

4.4 M(uptloJl02Jical structure in melts

 

83

4.5 plasti(~sers and lubricants

84

5 Adventitious Dow phenomena

91

5.1 Plasticisation

 

92

5.2 Chemical

92

5.3 Instabilities associated with a

in vis,~ositv

93

 

ix

 

5.4

Instabilities in

 

93

5.5

Melt

94

5.6

Melt memory

 

95

5.7

in structured materia1s

 

97

5.8

effects

97

5.9

induced instabilities

 

99

5.10

Non~laminar flow

 

100

5.11

Die exit instabilities

101

5.12

Coextrusion instabilities

102

5.13

flow instabilities

104

5.14

Phenomena associated with solidification

 

106

6

in polymer

 

111

 

6.1

Introduction

111

6.2

Low flow processes

115

 

6.2.1

115

6.2.2

Deformation of an extrudate under

 

116

6.2.3

Processes associated with

relaxation of

after flow

118

6.2.4

of a surface

a

melt

118

 

6.3

119

 

6.3.1

119

6.3.2

Distributive

120

6.3.3

120

6.3.4

Work

120

 

6.4

Constrained flows

 

121

 

6.4.1 Screw extruders

121

6.4.2 Wire

123

6.4.3 Pressure-driven flows in dies and moulds

 

123

6.4.4 Constrained flows defined

pressure

124

 

6.5

Free surface flows

 

125

 

6.5.1

126

6.5.2

Film

and blow

127

6.5.3

Vacuum

127

 

6.6

Bulk deformations

 

128

6.7

Select

129

x

7 Future developments in polymer rheology

x 7 Future developments in polymer rheology 133 Appendix I: Additional sources of error in

133

Appendix I: Additional sources of error in l"llr'\lIl~~rvvisc;;onletlry 135 1 in the die 135 2
Appendix
I: Additional sources of error in l"llr'\lIl~~rvvisc;;onletlry
135
1
in the die
135
2
at
die wall
136
3
Pressure and
effects
137
4 Shear modification effects
139
5 Non-laminar flow
139
Appendix
2: Int,,,.rn,r,,.tl:ltl(,\n of extensional vi"{~n"jtv from flow through an orifice
die
141
Appendix
3:
The inference of elastic modulus from Dosit~extnlsicm s\lVellin2
143
Appendix
4:
RUlptUJre behaviour
145
Appendix
5: Data sheet for l"llflHI!::.rv flow
146
Appendix
6: COlnp(llris<)O
rhe:ololgic,al proJJtert:ies of two
of low-
148
Appendix
7:
152
Appendix
8:
154
Appendix
9:
prc.celisiIllg nrnr)eT1tv data for a geJler,al-I'urpol~e
156
Appendix 10:
prc)Celiislrlg property
nylon at 285°C
data for an
In Ilectlion
of
158
Appendix 11:
prC)Celisirlg property
data for an
In.l l ectllon
of
160
Appendix 12:
pr()Ce:sslrlg property data for a
and a
of
162
Appendix 13: Emlpirlcal observations of flow in channels of cOIlnplc,x cross-section
165
Appendix 14:
a
of extrusion with
Flow
slot or annular die to
thickness
uniform
170
Author index
173
index
176

Preface

sciences and tnc:~rD110a'v",amlC rc:~srx)nSie. which form the meaSlJlnl1tll the flow of rne:OI()IlV and
sciences
and tnc:~rD110a'v",amlC rc:~srx)nSie.
which
form
the
meaSlJlnl1tll
the
flow
of
rne:OI()IlV and the assoc].ate:d
DJIlVS]lCal and chemical
methods of
on the
of rne:OI()IlV and the assoc].ate:d DJIlVS]lCal and chemical methods of on the InS>UJflYU 1981 F .
InS>UJflYU
InS>UJflYU

1981

F.N.C.

Notation

R L R' L' Q p y n 11 recoverable elong,lU(Jtnal
R
L
R'
L'
Q
p
y
n
11
recoverable elong,lU(Jtnal

Introduction

raw efficieltlcy in the de~U2rled nolvn1er to suit a move towards interaction ae\relCtn new or
raw
efficieltlcy in the
de~U2rled nolvn1er to suit a
move towards
interaction
ae\relCtn new or
na."m()flU)US raw

material.

ae\relCtn new or na."m()flU)US raw material. tne:or~v-ess,en1tlal as a basis from which we can progress

tne:or~v-ess,en1tlal as a basis from which we can progress and discuss effects

t"n~efi()m~en()IOjglCl(l1
t"n~efi()m~en()IOjglCl(l1

literature both in trade and

m()flO'2fC1PtIS:.l-· I :.l have been

2

2 The OOlectlvc:!s of the res:eaJrcn from which this book l1p.lrn.l~"C are: ext,erien(:e of a material

The OOlectlvc:!s of the res:eaJrcn from which this book l1p.lrn.l~"C are:

ext,erien(:e of a material in a t'"'ru'ulp.:I""irln response of the nlrnl","'Cc'
ext,erien(:e of a material in a t'"'ru'ulp.:I""irln
response of the
nlrnl","'Cc'
between
new or
ort~all;:t the
n.j'",nr'",1
lrrU"rn11!",11
ohlecfl've~ has led to SImlpllltlcattOJilS
who are
in the
of

arise. Those who are not so

mtJ~oauce:a where

circumstances dernOllstr'ate that tion in this

is to be

sinlplilficaticlns are

COJllPleXltlt~s and where the

will

future are sut.stantullJy c(}r:'~ rather than de1timtlv4e.

c,~

research

but my

eXJ)en,em~e into a cOJllplex nOlvn1er rnf~OI()OV cur'rerltlv ~nr,p~rc to be in and the first the
eXJ)en,em~e into a cOJllplex
nOlvn1er rnf~OI()OV cur'rerltlv ~nr,p~rc to
be in
and the first
the final clalntl(~atton.
into a cOJllplex nOlvn1er rnf~OI()OV cur'rerltlv ~nr,p~rc to be in and the first the final clalntl(~atton.

3

more £1&>"'11"''.11'\1"" then~ in a strletcnec[J. F.nrtnnl::ttl"lv nature
more
£1&>"'11"''.11'\1""
then~ in a
strletcnec[J. F.nrtnnl::ttl"lv nature
lead
f'1"~Ul1l"l(f of thin film. Our
UllICOIISCllOUS, of the unusual
0011eCltlVe is to assist in
in the
to
of irntlrO'IIl"fl
is to assist in in the to of irntlrO'IIl"fl theoreti- tun.dalnelltal des.cnlPU()ll of what would be
theoreti- tun.dalnelltal des.cnlPU()ll of what would be pnlctltlolllers, who are tneoreUCl;ans the SU!l[lltlCal1lce.
theoreti-
tun.dalnelltal des.cnlPU()ll of what would be
pnlctltlolllers, who are
tneoreUCl;ans the
SU!l[lltlCal1lce. To
all other
nUI"rl"l.rtp(!
Each is concerned with his own truth, which both
to be

same

that

been laid on

have aUempt(~d to build such a framework. The dit1tlC\llltv

when the two are married we have a cornpJete

has

and several books

unl:lerstandJlng. To

to be consummated much

between those

construction of

To to be consummated much between those construction of that the first is a secure base

that the first is a secure base on both foundation on bank so I shall not to build bnc[Jge:s. ohllecl]ve of this work to chart the nature of the river

demonstrate river is not so

even if it is not DOs.Sltlle after alL

4

REFERENCES

4 REFERENCES 1. 2. 3. 4. 5. 6. IVI L;I'\LI:: I VI:: V Nlel!iSen, R"'lirl'h11".n \OiUltlVIl.

1.

2.

3.

4.

5.

6.

IVI L;I'\LI:: I VI:: V Nlel!iSen, R"'lirl'h11".n \OiUltlVIl. '\JVIUWIU. MiddleJ1nan,
IVI L;I'\LI:: I VI:: V
Nlel!iSen,
R"'lirl'h11".n
\OiUltlVIl.
'\JVIUWIU.
MiddleJ1nan,
pp.~lr~ln

t"."f""" mlouJdinll. Plastics and Rubber

1981.

7, HOJm€~S-'IV alKer

8.

1966.

9.

10.

11.

12.

t"."f""" mlouJdinll. Plastics and Rubber 1981. 7, HOJm€~S- 'IV alKer 8. 1966. 9. 10. 11. 12.

Fundamental Concepts the~rmloplas1tlcs during prc,cel,SlllI2 we are con- the are necessary to are necessary to

Fundamental Concepts

Fundamental Concepts the~rmloplas1tlcs during prc,cel,SlllI2 we are con- the are necessary to are necessary to achieve

the~rmloplas1tlcs during prc,cel,SlllI2 we are con-

the

the~rmloplas1tlcs during prc,cel,SlllI2 we are con- the are necessary to are necessary to achieve which may

are necessary to

are necessary to achieve which may be del.lbe:rat:ely

1.1 RHEOLOGY

Kn~eOI4[)e:y is the of deformation and flow: of all the reS1OOl1lSeS it is the one
Kn~eOI4[)e:y is
the
of deformation and flow: of all the reS1OOl1lSeS
it is the one which is most
kneaded
felt. We have all SQtlee:rea toc,thl)as1te
from our
of descnttlD2
readlDJg, but
the
nt't"'Il1rlp
is to
.,.£'\11"
"'"
geJleral1~;ea materials
eQtlatllon of state. The
this is deformation history once the eqllatJIOn eX):lenmeJots. At the other of the " ".""4<
this
is
deformation history once the eqllatJIOn
eX):lenmeJots. At the other
of the "
".""4<
"'
cOlnplex materials and cOlnplex
course is to amllv~.e
which are Qual11:aUVeJlY
discover such ex):)en.ments
This text takes this
a01:lroacll-the quanltItu;;atlon

Three material states are relevant to nolu""Pt' pr()CeSSiloe::

llratnular-1the form in which materials are fed to the process

melt

-the form in which

-the form in which

are nC!11!:llllu Sllat:.e<1

solid

-the form of the final

one in which some Sbalpll1lg

may

6

de:formtiltictn occurs.

in iUfJlstI'ati:ne:

solid response are mc:lucled

dej'me:d as cn~:mSl'e

1.1.1 Tbe Geometry of Deformation

are three simple cleJtormaltlOifiS.

In

the stress is aOIC)lie:d t~m2entialJ

stress

strain

y

rate

1

Ii

1

1.1 shear: area A and distance h remain constant

deformation

(b) In simple extension

stress is a01)l1e~anormal to the surface of the material

stress

UE:=

strain (unity)

E:=

rate of strain

e

extension: cross-sectional area A and I both vary 7 In bulk deformation the stress is
extension: cross-sectional area A and I both vary 7 In bulk deformation the stress is
extension: cross-sectional area A and I both vary 7 In bulk deformation the stress is

extension: cross-sectional area A and

extension: cross-sectional area A and I both vary 7 In bulk deformation the stress is aDl)Ue:eJ

I both vary

7

In bulk deformation the stress is aDl)Ue:eJ normal to all faces. The stress is the

per unit vollunlle.

apl)l1e:a pressure,

and the strain

the

in

a normal stress. The nr£lNll"'!:l1 aeltorm(lltlcms lUH1'3111"U clomple:x flows COInO~OUIlaea stress
a
normal stress. The nr£lNll"'!:l1 aeltorm(lltlcms
lUH1'3111"U clomple:x flows COInO~OUIlaea
stress
SOlll1tlcm to this double cor:npliex11ty
slnllplifu~atllon of tensor notation which is the sta.rtl]nQ··DOlmt
For the
those
siRlpljtfic,ati()ns in the
of this work it is sufficient to reC'02Illse
exist:
with
response of

1.1.2 Tbe Rbeological Response of Materials

There are three of response to an eJetorrnatlon and rUDiture.

stress: viscous

response to an eJetorrnatlon and rUDiture. stress: viscous In viscous flow a material continues to deform

In viscous flow a material continues to deform as

and the

defined as

The

in to

material continues to deform as and the defined as The in to in flow is (llss1pateeJ

in

flow is (llss1pateeJ

of stress to rate of strain

of some common materials are

Table 1.1 Viscosities of some Common Materials

10- 5 10- 3 10- 1 loo 1()2 1(lLl 06
10-
5
10- 3
10- 1
loo
1()2
1(lLl 06

1()9

1()21

stiff

Air

Water

Olive oil

Viscosities of some Common Materials 10- 5 10- 3 10- 1 loo 1()2 1(lLl 06 1()9

Glass

8

Strain

Stress

8 Strain Stress Time 1.3 Newtonian behaviour response of a material is stress the low stress
8 Strain Stress Time 1.3 Newtonian behaviour response of a material is stress the low stress

Time

1.3 Newtonian behaviour

response of a material is stress the low stress level many riA·
response of a
material is
stress
the
low stress level many
riA·

to flow with

is said to hellla,re

melts aDI)ro,!:lch

reversible and

is

approach Hookean

than

is

to

a Hookean response

and

and is approach Hookean than is to a Hookean response and a '" ms,tarltJv under stress
a
a

'" ms,tarltJv under stress and the material possesses an

is

ratio of stress to recoverable If all the deformation is aDlc>l1e~d stress the material

deformations

is aDlc>l1e~d stress the material deformations 1.4). At many nnlvn~pr melts have a lower mc,oulus Stress

1.4). At

many nnlvn~pr melts have a lower mc,oulus

Stress

1.4). At many nnlvn~pr melts have a lower mc,oulus Stress Time 1.4 Hookean behaviour melts delIDons1tra1te

Time

1.4 Hookean behaviour

melts delIDons1tra1te well model in Hookean elastic <:tn'"lnc:,O illustrated in 11 1" £0
melts delIDons1tra1te
well model in
Hookean elastic <:tn'"lnc:,O
illustrated in
11
1"
£0
elastic:o-~rjsc~()US reSDO]tlSe to
stress. The Max-
in
a
m(jltel~ialwill
as a Matx\\reH
aOl)arlent "'""ro
:""'"
an
modulus which
tel1[)Dc~ra1tune. pressure, stress,
of deforma-
nrl'\np,rtll'"'<:t which we record and use are thus the nnJrlnf"pnt
anl')arent Maxwell modulus.
more viscous than most
very

Fundamental Lo,nce'DlS

9

a

Fundamental Lo,nce'DlS 9 a Dashpot Spring b Strain Stress Raversible deformation Time 1.5 a Maxwell model

Dashpot

Spring

b

Strain

Stress

Raversible deformation
Raversible
deformation

Time

1.5 a Maxwell model b Its response to stress

role in deterl1mnmg the maximum rate at which a deformation

carried out: it is

rr.I".,.'~e
rr.I".,.'~e

the initiation process for that important

elastu;ity
elastu;ity

h,"'''''.,. prc)Ce!,SlIllj! it is frequently interactions

phenomena which determine the

rupture

1.2 THERMAL AND THERMODYNAMIC RESPONSE

cOlnpres,sio'ilit:y of materials we have ~lr''''~£1I'll and in viscous flow, as pressure. For
cOlnpres,sio'ilit:y of materials we have ~lr''''~£1I'll
and in viscous flow,
as
pressure. For a
aplueC:lation of
is
rI"" •.,."d'" and SPt'~Clt:lC
tOIl~etller with the

nowned as msulClltlJ1lj! handled by the for COlllvelltl(Jlnal ma1tenals. APpeniOloes include typical data for several polymers.

The rate of
The
rate of

during

typical data for several polymers. The rate of during is determined by thermal the corlcel,t of

is determined by thermal

the corlcel,t of Fourier number: Fourier number
the corlcel,t of Fourier number:
Fourier number

which is readily aPI'lle:o

number: Fourier number which is readily aPI'lle:o t r a n s f e r eX(:haJflgeo

transfer

eX(:haJflgeo from both sides of the sectlolll,

on the square of

thl(:kmess, a sec1tlOn
thl(:kmess, a sec1tlOn

aDllro.ach thermal

minutes.

cOlnplexltv due to surface heat transfer.

melt and dlfter,ent

nl'l1

,.,

still air

=

10

air at 10 mls

50

metal surface =

400

water

2000

While it is POS,SIDIe to measure the thermal and the:rmlodVfiiilmlC

techmQU(~S which have been de~ileh)ne~d

""

lh""c

ngl-2'I£'nl!l:rlll

eSI.aOJIlSrleO technique for melts-the

1""

""

cr

nu"

n

,,""

, as heat streamlines of a QUiescent: state and must

,

~erlenitlCmas

in stable. only be lost It is also ' solid to an

values of APIPenOlCles 7-12.

c

""'r"r

,'

"1"2'<:>11'12'

!ltnnnr'ln{'Uul.

tnClU(Jlea in

1.3 PHYSICAL AND CHEMICAL CHANGE

The

One been demonstrated to have a

".t:

,.

iSPf()cesse~o

flow

That

""1"'

",

plaStl(!lse:o and lubricated to achieve easier flow and may

whose method of

further

their desired effects

mOlol1led

is near one extreme of PJastJ(~s include some additional co]np'on(~nt

pr()Ce:)Sll1l~ or to their service pe]:-tOJrm~tnce. &.I.nhJ1rn"

nolvtnpr" are now Dec;oI1nmtg mlcrc;~asllngJly used.

tnc;~nrlOJ;llasitlc melts derive from

of

process may allow some

we have

seen the

resins and

thermal

of that order to be retained. of

11 of a a distinctive mc$ODnliSe with its pr()ce~ssttl!~ clllar'acl:enStl4:!S between that pr()Ce::iSlrl~ an(~--OI

11

of a a distinctive mc$ODnliSe with its pr()ce~ssttl!~ clllar'acl:enStl4:!S between that pr()Ce::iSlrl~ an(~--OI
of a
a distinctive mc$ODnliSe
with its pr()ce~ssttl!~ clllar'acl:enStl4:!S
between that pr()Ce::iSlrl~
an(~--OI the en(i-Dlfoauct
are
in a meltll1l2 omnI-local hot when "~a.~~£~~ nrnt\lplm m(]~le(:UUlr ",""'''''_HL.
in a
meltll1l2 omnI-local hot
when
"~a.~~£~~ nrnt\lplm
m(]~le(:UUlr ",""'''''_HL.
RUlnnmg the extruder cold
and so hot any material prone to
ooltimum machine tel1npc~rature.
are least severe in
IDllectlon mCml(lme:. where the
constrained
are nC!tloll!u of discoloration

12

Rheology

or

mechanical weakness of the

The

of pla.stl(~S

as much as a factor of two

injection moulding but

 

products, although

 

care in handling.

 

The

problems are

severe

in

extrusion

processes where

thickness

variations

more as a result of

 

or of meJUIlUl instabilities in

the screw.

are at their most severe in

 

which

the extrudate

to be

or to

stretch

and blow

where

local variations in plastics in this field

result in

 

amounts of stretch. The less than 20 per cent

of

If ae2raaaucm DJ~021'eSSjes only ~I"'htllv rf~dUiced

a 10V\'-mlOle~CUJlar··we:l1!l1tt.

volatile, tail may be "'V. "n brittle, low-molecular-weight product. A laudable desire to

lead to too little consideration

plas'ticlsin1! the flow and IP!l"'t1~O'

"'

,

""'JU,,

or voids as mechanical weak11esses

exposure to heat as low as DO~iSlble

to hOlmolgelflls;atU)n: in a

degradable polymer, it is easy to extrude a

of unmolten

undegraded polymer in a matrix of

 

material. While the

overall molecular

of such a product

the

molecular

of

and so the "'t

"

much attlectled. molecular to a value Mw/MN of about (Molecular weight distribution is ext:Hallled

and del:onne4l. work is

nr."rtl1l~';:' structural

to obtain a full it is

rnf~OI()1!V interacts with the

nrr\nprhl"'<l of

Fundamental Concepts

13

RBFBRENCBS

5.

6.

7.

8

"',

".

prc)CelSSlrlg aids

I::"repar,atl(Jln and

Pn/vm4rJr

Science

"-".U'"""""",, Two

"-".U'"""""",, Two

Rheometry for Polymer Melts

Kl1leometry is the art of maKlnlg useful measurements of the deformation

may fall

one

flow Df()Dertl(~S of

of the deformation may fall one flow Df()Dertl(~S of measurement which is mvestllgalte its Demonstration of

measurement which is

mvestllgalte its
mvestllgalte its

Demonstration of a pn~en('m(~n(Jln effect.

The

of new

which

nrr\nA.rtu of the material.

1'AI •.,.1''''A oror.er1:tes of a series of

materials.

and its DOltentIal

oror.er1:tes of a series of materials. and its DOltentIal into novel mtleraCt14cms between a material and

into novel

mtleraCt14cms between a material and its en'virlonJlllent.

The different categ()nc~s of measurement may different ~nl·'\t·r1.~rl"'pc rne:olTletl'yand on any measurement it is necessary to what that measurement is to acJrneve.

The two critical ment are 'Is it which

necessary, and if the QUlestllon under

the

must be asked of and 'Is it sufficient?'. If a

which it

then the

is

method of measure- is the only one

information about the then it is

to resolve the

sufficient. Thus if we wish to

the linear

behaviour of a melt we

Thus if we wish to the linear behaviour of a melt we methods of measurement from
Thus if we wish to the linear behaviour of a melt we methods of measurement from

methods of measurement from those which would Tnr,hl1rp behaviour of melts in film

those which would Tnr,hl1rp behaviour of melts in film much more so~)hil)tic:ate~d rtleometrv which would be

much more so~)hil)tic:ate~d rtleometrv which would be

eXl)entenc;e and
eXl)entenc;e and

teC:hnlqtle is most limited

a more

for undelrlyiin,g their use several

PV1,

,."·.A

I"'A

to

that for

far less unsuitable to the first task.

this review of rheometers is to define those areas in

The review is of a

review of rtu~onl1eters

texts are available ,1-4

biased

that my

is to define those areas in The review is of a review of rtu~onl1eters texts are

16

Melt

Table 2.1 Classes of Rheometer for Melts in Common Use

Classllkation Method Variables Limitations ROTATIONAL Eccentric Strain shear Near to linear METHODS disc and
Classllkation
Method
Variables
Limitations
ROTATIONAL
Eccentric
Strain
shear
Near to linear
METHODS
disc and
and
and
'balance'
Strain
rheometer
PRECISE DATA
Strain
Strain rate
Strain recovery
Normal stress
Stress
PRECISE DATA
Stress
Stress relaxation
Time
Torsion
As above
SQUEEZING
Penetrometer
Parallel
EXTRUSION
Melt flow rate
flow
Flow rate
Pressure
flow
Swell ratio
Extrudate
APPARENT PROPERTIES
appearance
COMPARATIVE
ENGINEERING
DATA
TORQUE
Instrument
COMPARATIVE
extruder
'Brabender'type
force
Resistance to flow
volume
fREE
Extensional
SURFACE
and
FLOWS
to flow volume fREE Extensional SURFACE and FLOWS P R E C I S E D

PRECISE DATA

Strain rate <1 s-1

Extrudate

Extrudate force

force

 
  Drawing

Drawing

 

CoMPARATIVE

 

Sheet inflation

PRECISE DATA

difficulties

Bubble inflation

Biaxial extension

COMPARATIVE

17 2.1 RHEOMETERS CAPABLE OF PRECISE MEASUREMENT 2.1.1 Viscoelastic Response of Melts to SmaU.amplitude Deformation

17

2.1 RHEOMETERS CAPABLE OF PRECISE MEASUREMENT

2.1.1 Viscoelastic Response of Melts to SmaU.amplitude Deformation

The

and measurement of of oDtalllllDl2 nrpr'IClP

The and measurement of of oDtalllllDl2 nrpr'IClP mOlduJusarerreQuen4~-IOel)erldent.
mOlduJusarerreQuen4~-IOel)erldent. amlpJlltu4je-.aepeJ()d4~nt because maximum strain rate in sut:t1C1~entjly small
mOlduJusarerreQuen4~-IOel)erldent.
amlpJlltu4je-.aepeJ()d4~nt because
maximum strain
rate in
sut:t1C1~entjly small that
from
are rare,
"U""'"F'.,U
c 'e y • fl· "0 C • • • - • f/)
c
'e
y •
fl·
"0
C
-
f/)
'e y • fl· "0 C • • • - • f/) , where is the

, where

is the strain amlPlltlllde and

Such

• - • f/) , where is the strain amlPlltlllde and Such are data CllCllra(:tel"lSlJ12 the

are

data CllCllra(:tel"lSlJ12 the rnC:!0l()2V

and Such are data CllCllra(:tel"lSlJ12 the rnC:!0l()2V ways of data. The differen~ces int 1 en:.re1tatjion rest

ways of

data. The differen~ces

int 1 en:.re1tatjion rest on whether stress or strain

meCll~lm!)m. Most

assumed to be the co]tltr 1 oUiin2

under

strain but

response

COlmDilOlllv strain is assumed to be the

would

be

if stress were the mechanism. Most

the dVlrmrmc

would be if stress were the mechanism. Most the dVlrmrmc 11' = sin 0 and the

11' =

sin 0

and the modulus:

Of =-""T"jr:ns

0

ampWtudes, 0 is the
ampWtudes, 0 is the

and (J) is

1Ddlepc~ndent of

element

18

G'

b

2.2 a

model b Maxwell model

aeJ)en.<lel1t on treQujenc:y

ui~£"ru:!itu and m(~aUIUS

re~)re!)entat:i.on.of the same data may be made

the material is reS'P.on<lltn2 and .of these lIJltelrchanjlea.ble and contain the same mt.onna1tl.ol[}.

rer're~;entatli.on of data is an in their <ll2.,estl.on

a

".rt.li"

t.o

noilvnler melts

share the

the

a

J.UUi

,

,,",

at sul11Clenttlv

Maxwell

m.odel.

use the Maxwell

that the Maxwell mtcerpretcitlOJn

an

easier

.oSc:illaltOl"Y shear rhe.ometers 9 ,1O,H in the lirrlitaLtioln is .one .of time-scale of measurement frDm the inertial effects.12 the behaviour of liquids at

dVlnarmc measurements

with strain amlpUlu(leS

pnnclpal aa'vallltaJ~es of dVlnarmc measurements for the

h",.file,,,,,·., of melts are:

of the

on~Cls:e

tecnmQuces have received in the linear

over a

and

may be used to .obtain

very wide range of treQU4enc:y

(ii) a direct measurement of elastic as well as viscous Dr()Oertu:~s--anld

19 COltllP'aflin2 elastic response. between ~~b~~~~ ~~~ ~~ and information relevant to the very short

19

COltllP'aflin2 elastic response. between

~~b~~~~

~~~

~~

and information relevant to the very short time·scale response of POsslltlle to obtain a strain
and
information relevant to the very short time·scale response of
POsslltlle to obtain a
strain
as all the data are g£'Tln<lifi'"
a
solution-
nr£"'I,.,-t",C!
have been
of
measurement

)ls~ld,ranta~~es which must be borne in are:

(i) The the nOII1·nne;:lT response al>1)arlent SPt~CIJtllen pJrepfanlUOfn and accurate eC1tllpJtllel!1t can be
(i) The
the
nOII1·nne;:lT response al>1)arlent
SPt~CIJtllen pJrepfanlUOfn and accurate
eC1tllpJtllel!1t can be

2.1.2 Steady Shear Flow in a Cone and Plate Rheometer

The of the cone and every element of the is to an loenncal are described
The of the cone and
every element of the
is
to an loenncal
are described in standard texts),2.3 There are two
oel)en.01I112 on whether the
or constant rate
The constant-stress
is
to
under constant stress
is
the
is apl)Ue:d

direct probably the useful as a

rather than measured with transducers.

and

deformation measured from a

since the

scale.

and deformation measured from a since the scale. rheometer which can be made and is eSt)eCIalllV

rheometer which can be made and is eSt)eCIalllV

can be felt and the deflection seen,

The constant-rate rates and

be felt and the deflection seen, The constant-rate rates and in which one face is rotated

in which one face

is rotated

at

a

series of

the

is measured on

the <lirl'"<li "tO€~'''
the
<lirl'"<li
"tO€~'''

nr~"f"'rr rI in most commercial instruments. If the instrument is

this method of

has an

stress variant in that, when the reaches

constant re~IOlJn2.

Cone and

instruments may also be

used to determine the elastic

stress and

recovery. measurements has been

reSPO]llse of melts. Several measurements can be

transients to and from

normal stresses and

The

the subject of numerous

evidence can be found to of COI[lcIUSlon:s.

between such responses and

those

and .l.,.;v'""J'.'

,.

evidence can be found to of COI[lcIUSlon:s. between such responses and those and .l.,.;v'""J'.' ,.

a

b

a COllstalnt-lstress b Constant-rate type

rbeometers

Wc~iss,enlbel-g!O notes

when an elastic

as the shear stress there is a rheometer that pull

the

across the face of the instrument and a normal

accounts

measured

the common

I have never been able to

faces instruments in which the

for that class

own use of normal stress measurements has been limited for

and

That thrust is most strain rate is

of instrument.

of their

evidence-the normal force "",vf"."u,'1"'T"ll

 

can be

,.'"I

nu,.rlr,,,,

,,,

take

a different

related to TU·"., and the ht""

",t'lU-.,.

"'I.o,un,.,. Whatever the fundamental int,en::.reltatllon mal stress measurements unlclOl11bted,lv elastic response of melts. The measurement of the stress transients

shear flow also offer tranSlenlts can be of measurements demand an effect

and cessation of Such absolute

for de(Jucln}! the elastic

as the 'stress OV4erSJIlO()t Jlhell0I1t1el110n

stalrI-UlD of flow at a constant rate, the stress

realCbJlng its

condition and some WCtrkiers deduce :se(:onaal'V flows can also be that it a close lnspe<;Uctn

some

Since

the contribution

to

total

instrument face

on the cube

an individual annulus of the a small loss of adhesion near

Rheometry for Polymer Melts

21

Strain rate
Strain
rate

a

Rheometry for Polymer Melts 21 Strain rate a b As set up and running with no

b

As set up and running with no

'overshoot'

Time

a b As set up and running with no 'overshoot' Time 'Overshoot' evident 2.4 a The

'Overshoot'

evident

2.4 a The stress overshoot phcenOfme:no:n: stress passes thr,ou,!h a maximum and

phcenOfme:no:n: stress passes thr,ou,!h a maximum and b ~eciondlarv c o n e a n d

b ~eciondlarv

cone and

rheometer

the

measured.

rheometer

higher stress

exist. My should be seen-but

they are not. The mterr.reltatJOn of apparent stress overshoot phenomena as an

is that, were

for tbe £>"O'I"T_"'_

stress OVcerSJno(lt

£>"O'I"T_"'_ stress OVcerSJno(lt of the very

of the

very

""'.1"1"''''' and so on the stress in a double cone ins,trtJlm~entto be used at much argument «~«lU"" the of the

for eX~imlple

much argument «~«lU"" the of the for eX~imlple lnC1trl1tTt1~"'nt effect is able to raise in the
much argument «~«lU"" the of the for eX~imlple lnC1trl1tTt1~"'nt effect is able to raise in the
much argument «~«lU"" the of the for eX~imlple lnC1trl1tTt1~"'nt effect is able to raise in the

lnC1trl1tTt1~"'nt effect is able to raise

in the heart of

eXJ)er]lm~mt:al rheologist alike. While the resolution of that arJ~Ul1ne)1tremains doubt such observations must be treated with caution. The nh~O::l"'rlHitlnn of adhesion failure may be of considerable in

of adhesion failure may be of considerable in is the ease with which the stress may

is the ease with

which the stress may removed the observer to

record strain recovery as a function of time for

ratio of shear stress to recovered shear respolnse which may be related to

a simple comment on the elastic

observations of frozen-in strain in

Tt1!l'''~1'1!:l1 to revert to an earlier state.

stress histories. The

palrm;::uUlf a40vEmt::Ule of the constant-stress cone and

mOlul(lmJ~S and

in

that all

a desire of the

use of recoverable shear as the

while it is
while it is

measure of elastic meastJlreci, it is the

ae~;tgJ)ea to measure strain recovery after constant-rate aeJtormaltlOin

has the additional thing which is nallJPCmlJng.

to measure strain recovery after constant-rate aeJtormaltlOin has the additional thing which is nallJPCmlJng.

22

22 Yn.I\IJt1"1Pl' Melt K/1;eo,tolJ.'V

Yn.I\IJt1"1Pl' Melt K/1;eo,tolJ.'V

Measured

c

.~

(/)

Melt K/1;eo,tolJ.'V Measured c .~ (/) Time Applied Time CONSTANT STRESS Time Time CONSTANT RATE OF

Time

Melt K/1;eo,tolJ.'V Measured c .~ (/) Time Applied Time CONSTANT STRESS Time Time CONSTANT RATE OF

Applied

Time

CONSTANT STRESS

Measured c .~ (/) Time Applied Time CONSTANT STRESS Time Time CONSTANT RATE OF STRAIN 2.5

Time

Measured c .~ (/) Time Applied Time CONSTANT STRESS Time Time CONSTANT RATE OF STRAIN 2.5

Time

CONSTANT RATE OF STRAIN

2.5 Deformation of Maxwell model: under constant stress

flow is attained

A further

of the use of constant stress COJllpare:o with an .'''<'V.''' T' ••

time to reach equlllorlUln demonstrated for a is attained instan-

ment at constant rate is that it response. This difference in

Maxwell model

under constant

while under constant strain rate the to condi- slow oPleraltlOifl is that most
while under constant strain rate the to condi-
slow
oPleraltlOifl is that most

at constant shear stress are more Ois.criimj,natoJ~y shear rate in non-Newtonian svs;telns.

The

of cone

rate in non-Newtonian svs;telns. T h e o f c o n e rhc~OInetrv are: nrf~Clselv

rhc~OInetrv are:

svs;telns. T h e o f c o n e rhc~OInetrv are: nrf~Clselv defined flow at

nrf~Clselv defined flow at low shear stress.

on

both

aDd

nrf~Clselv defined flow at low shear stress. on both aDd in a of sensitive to the

in

a

of

sensitive to the

under stress. The limitation of this class of rnc~orneltrv for melts is associated with the very

which structure may break down

As a measure of

under low stress it is

structural characteristics of the

23

23

23 Shear stress shear flow data for melts at different temperatures or of different molectllar weil2hts:

Shear stress

shear flow data for melts at different temperatures or of different23 Shear stress molectllar weil2hts: ratio of viscosities at constant stress is rate than that at

molectllar weil2hts: ratio of viscosities at constant stress is

rate

than that at constant

at constant stress is rate than that at constant surtac:e area to volume of the which
at constant stress is rate than that at constant surtac:e area to volume of the which

surtac:e area to volume of the which limit its usefulness to relatrvelv low stress measurements. OOSSllDle to overcome the associated with the nnnln'lPT:'-

the

rate of heat

associated with the nnnln'lPT:'- the rate of heat would still OI)eraltIOtn of the instrument at 2.1.3

would still

with the nnnln'lPT:'- the rate of heat would still OI)eraltIOtn of the instrument at 2.1.3 Elongational

OI)eraltIOtn of the instrument at

2.1.3 Elongational }i'low Rbeometers

No of has advanced more t"!u'\U11Iv than flows. This progress measurement are now COlrnntler'CUllUy
No
of
has advanced more t"!u'\U11Iv
than
flows.
This
progress
measurement are now COlrnntler'CUllUy
The slmtph~cltv
how it <lerrOrnlS
and the ten.<leltlcy
reh:ativelv crude lnstrume~nt~i.l;)"lO
while more SOt)hl~;:tlcate<l mlaCJt1lnleS""I-.;)V
on a broader range of ma:ter'lal:S,
flow
measurements
have
a

measurements in that the measurement does not involve an

wall of the direct tions ret)reSerltII1U! the from shear flows. desirable to carry it out.

of measurement

with the

so

that

as

and are

is not a

Such measurements are of

r1T'!:l'lll1nrtT
r1T'!:l'lll1nrtT

of the

of considerable thf~orebcal sig,ni11cCllDc:e

of irrotational flows which are rurlaa.memt~:lUy

the

24

24 2.7 blongatlOnlal strain rate, E Stress as controlling mode of deformation apply to extension as

2.7 blongatlOnlal strain rate, E

24 2.7 blongatlOnlal strain rate, E Stress as controlling mode of deformation apply to extension as

Stress

24 2.7 blongatlOnlal strain rate, E Stress as controlling mode of deformation apply to extension as

as controlling mode of deformation apply to extension as wen as shear. The

reduction of the time transient available when making measurements at constant

flow when making measurements on In such recovery aDI)ar~ent rate of viscous

the

The

and

of constant stress or constant

rate

stress is of

in

melts whose

decreases

f"Xl'f"r<l.

ments the small reSltOUal unrc:~coveJreo may be tnt'p.rr\ lt rt aetonnatlon in ClrlCUtnstaflices where
ments the small reSltOUal unrc:~coveJreo
may be tnt'p.rr\
lt
rt
aetonnatlon in ClrlCUtnstaflices where Ul~lt1t'IIO

conditions to be

achieved would allow the The most important

to neck. in favour of

direct measurements of

elon~(Jltlonal flow is that

Oflieself of the

materials in

which follow.

elon~(Jltlonal flow is that Oflieself of the materials in which follow.

such measurements can one between shear and extensional flows

 

between

flows. Both these

a crucial

role in the

The trenchant

such

that they require a

deal of

and that

is

a

very

2.2 MEASUREMENT OF APPARENT RHEOLOGICAL PROPERTIES BY CAPILLARY FLOW

The

that we can only determine the nrf"{'n~p rJle()lOI~IC;al ft

-.""'

'" of

polymer melts under a limited range of

are of

limited

interest leads to a quest for other

of measurement.

The criteria which these methods should meet are:

should cover the strain rate range of interest in PfilCtl.caJ prc.ce~)sml~ (up

rate range of interest in PfilCtl.caJ prc.ce~)sml~ (up The property be {,{,U'1VP'ntf"ntllv measured

The

property be {,{,U'1VP'ntf"ntllv
property
be
{,{,U'1VP'ntf"ntllv

measured should

of less than 100 g and Drc:~feI'abllvas little

reCluurea so that it may be

should

(better than 5 It should be pm'SIO.le as 1 g.

Capillary flow meets many of these reQluir·em,en1ts.

2.2.1 Apparent Shear Viscosity from Capillary Flow CapIUaJry flow will be in most wall shear

2.2.1 Apparent Shear Viscosity from Capillary Flow

2.2.1 Apparent Shear Viscosity from Capillary Flow CapIUaJry flow will be in most wall shear wall

CapIUaJry flow will be

in most

wall shear

wall shear

wall shear rate,

y

By the shear stresses in of onrlrnr'U'tota eC~Ullpment
By the
shear stresses in
of onrlrnr'U'tota
eC~Ullpment

POSSlltJle cOllVe~nl~~ntlv to measure 0-001 to

eC~Ullpment POSSlltJle cOllVe~nl~~ntlv to measure 0-001 to operaLtlctn have been used: cOlltn)lIe~cl

operaLtlctn have been used: cOlltn)lIe~cl nrac-C'nl-'" r"",,",ur'lrHT a measurement of

r"",,",ur'lrHT a measurement of re(~Ulnng a measurement of nr~~C:C:lllrp Barrel extrusion

re(~Ulnng a measurement of nr~~C:C:lllrp

Barrel

extrusion rheometer '~ ,.',lIn
extrusion rheometer
'~
,.',lIn
reilat1()QshlP between flow rate and associated tnc:t10nal losses to make the above the die rather
reilat1()QshlP between flow rate and
associated
tnc:t10nal losses
to make the
above the die rather than
reCIUllrecl to drive the
l1a40ltr!:ih'.,.
die rather than reCIUllrecl to drive the l1a40ltr!:ih'.,. (iii) (eS1Dec:talllv when the enf;!~lDeernlg tOllen:mce~s.

(iii)

die rather than reCIUllrecl to drive the l1a40ltr!:ih'.,. (iii) (eS1Dec:talllv when the enf;!~lDeernlg tOllen:mce~s.

(eS1Dec:talllv when the

enf;!~lDeernlg tOllen:mce~s.
enf;!~lDeernlg tOllen:mce~s.

26

26 Melt Rheology 20 mm diameter barrel will take apl:UOXlIl£1ately 15 minutes to reach thermal equilibrium,

Melt Rheology

20 mm diameter barrel will take apl:UOXlIl£1ately 15 minutes to reach thermal

equilibrium, will take a of a melt pressure transducer near to

size to accommodate

a of a melt pressure transducer near to size to accommodate Intlerpretl!ltlC'll of Cal)lll:ary rne:Ofiletlry the

Intlerpretl!ltlC'll of Cal)lll:ary rne:Ofiletlry

the PoiseuiUe eOllatlon at the op,eraltlnl2 f"'.rn

the true 'ittl;!

""' :l_ nc:l u
""'
:l_
nc:l u
aPI)ar,ent rather of corrections is
aPI)ar,ent rather
of corrections is

'V"

aPtlarlent wall shear aPJ)arlent wall shear stress,

a true measure of uu:r

nc"f"u

is recommended: """"' "u. as
is recommended:
""""'
"u.
as

leaOlIll2 to

""""' "u. as leaOlIll2 to where is the pressure thl'OU,2h an orifice die rate. It

where is the pressure thl'OU,2h an orifice die rate.

It is further recommended that the

have a

ratio of between

die used in such measurement should

and

and

32.

die used in such measurement should a n d a n d 3 2 . calnU,ary

calnU,ary flow

"'f.l~~"'l1nl" and

2 . calnU,ary flow "'f.l~~"'l1nl" and friction losses Ends pressure at the die wall Inlluc~nc:e

friction losses

Ends pressure at the die wall
Ends pressure
at the die wall

Inlluc~nc:e of pressure on viscm~ltv

at the die wall Inlluc~nc:e of pressure on viscm~ltv Influence of on volume Influence of IntJIUel£1ce

Influence of

on volume

Influence of

Influence of

IntJIUel£1ce of

on tenloeratlure

Modification of the material due to work in the

of on volume Influence of IntJIUel£1ce of on tenloeratlure Modification of the material due to work
of on volume Influence of IntJIUel£1ce of on tenloeratlure Modification of the material due to work

27 2.9 The Darrel··nel~nt effect Barrel radius R', die radius L POI,st[,le. measurements when the

27

27 2.9 The Darrel··nel~nt effect Barrel radius R', die radius L POI,st[,le. measurements when the measured

2.9 The Darrel··nel~nt effect

Barrel radius R', die radius L POI,st[,le. measurements when the measured
Barrel radius R',
die radius
L
POI,st[,le. measurements
when the measured
.,.,.,
.,.,.,

,,~~ nh~~p."'llP.<1 that a

the measured .,.,., ,,~~ nh~~p."'llP.<1 that a wall shear rate shear stress Pressure L/R correction

wall shear rate shear stress

Pressure
Pressure
that a wall shear rate shear stress Pressure L/R correction col're(~tlv as gn:ullcent may be of

L/R

correction

col're(~tlv as gn:ullcent may be of several but this extensive the choice of two dies
col're(~tlv as
gn:ullcent may be
of several
but this
extensive
the choice of two dies
The
poL "',_,,"'
,
colmlJ-im,ne; a
die
an orifice
where
is the pressure
Some eX]:>erlm1ent:ers

a L/R Error band in pressure L/R b 2.11 Determination of pressure gra!Dle]lt a flreferJred
a L/R Error band in pressure L/R b 2.11 Determination of pressure gra!Dle]lt a flreferJred
a L/R Error band in pressure L/R b 2.11 Determination of pressure gra!Dle]lt a flreferJred

a

L/R

a L/R Error band in pressure L/R b 2.11 Determination of pressure gra!Dle]lt a flreferJred b

Error band

in pressure

L/R

b

2.11 Determination of pressure gra!Dle]lt a flreferJred b Dies of too similar LIR

Finally, the measurement of as a function of corrected

LIR Finally, the measurement of as a function of corrected Han,35 pressure situated in the has
LIR Finally, the measurement of as a function of corrected Han,35 pressure situated in the has

Han,35

pressure

situated in the

has dellDo,ns1:ra1ted

that the

ends correction is a

of an entrance and smaller exit pressure

drop

where

is attached to the exit pressure

drop as a measurement of conjunction with a screw rather needed in the die to

rates whicb are mos.t conveniently acbieved in such an apl)aratus.

This

is

in

tbe the transducer necessitates

an apl)aratus. This is in tbe the transducer necessitates Presentation ofCapillary Vl$lconrret,"y For the

Presentation ofCapillary Vl$lconrret,"y

necessitates Presentation ofCapillary Vl$lconrret,"y For the measurement of apparent ",i."".,

For the measurement of apparent ",i.""., should be made and tbe metbod of

the data. An

LIR = 32 and an orifice of tbe same Some of tbe

one die witb

flow tbe ends COITe(:tl(Jln sbould be noted witb

,·.+"

method is the two-die method

additional sources of error will be found in

Tbe data versus log wall

sbear

be

stress are

1.

of

method additional sources of error will be found in Tbe data versus log wall sbear be

versus

of flow

t Pressure
t
Pressure

Die land

Die exit

pressure drop

2.12 The ends correction is a COfnOC)Ullld of entrance and exit pressure

correction is a COfnOC)Ullld of entrance and exit pressure 2.13 A,ma,rellt .",.,,,, ,.1',, 10" 10 5
correction is a COfnOC)Ullld of entrance and exit pressure 2.13 A,ma,rellt .",.,,,, ,.1',, 10" 10 5

2.13 A,ma,rellt .",.,,,,

,.1',,

10"

10 5

Stress (N/m2)

versus wall shear stress: IOVi/-oemmv DoJlve1tllvieilie at

30

30 2.2.2 Entrance and Exit Effects exit nT*,"CC11T*," tool and and pressure drop and OO:st-f~xt]ruslon

2.2.2 Entrance and Exit Effects

exit nT*,"CC11T*," tool and and pressure drop and OO:st-f~xt]ruslon SWlelllnil. measurement cannot, at
exit
nT*,"CC11T*,"
tool and
and
pressure drop and OO:st-f~xt]ruslon SWlelllnil.
measurement cannot, at
dmectJlv
rt""lr.o.'I".rn'T,,,,,rt
pOJateo from a series of several measurements

2.2.3 Inference of Elastic Response from Capillary Flow

The most obvious sWielJtnil. The

earlier state and as such is

strain. Post-extrusion decreases

during capillary extrusion appears to be a reverSIon towards an as evidence of recoverable increases as flow rate and ratio increases

of recoverable increases as flow rate and ratio increases in SlDlpJest To make a be taken

in SlDlpJest

To make a be taken into account

measurement which most

obtained

length

of the

measurement of swell For praLCUcal. n 'lIrnnc*,"c

measurement of swell For praLCUcal. n 'lIrnnc*,"c and an ao€~au.ate the extrudate flush with the the

and an ao€~au.ate

the extrudate flush with the the diameter of the solidified extrudate 5 mm The two measurements of swell ratio from an orifice die

(Bo) and from a die of

ratio 32 (Bd

to the

maximum and minimum values of swell ratio. Appendix elastic modulus of the melt may be deduced from such measurements.

how the

Shear rate (,-1) 1000 • 100 • 10 •
Shear rate
(,-1)
1000
100
10
how the Shear rate (,-1) 1000 • 100 • 10 • ' i J fI) 2.14

'i

J

fI)

2.14 Effect of die lentnD-to··ra<uus ratio on po~.t-extrllsi(mSVveHlnil: DolvDf'OD'vlerle

230/2

15 at 210°C

Vr h'"'Ior
Vr
h'"'Ior

Melts

31

2.2.4 Observation of Extrudate Appearance

extrudate from non-laminar flow or sUlta(;e nnDer1:ec'tlons. for

""cu.""

",,'rn'U,.rt.,.

no

useful

",,'rn'U,.rt.,. no useful non-laminar flow occurs the hold and data The extrudate of

non-laminar flow occurs the

hold and data The extrudate of the

flow occurs the hold and data The extrudate of the nr£,\n.,.rf'u"'C!

nr£,\n.,.rf'u"'C!

f'r"'!:lf'",.rt with

to deduce

DrC)Ce!,SlIlli and also to obtain evidence of

of lrre:gui,ar

Cletauc;:CI dllSCU,ssi()fl of the

2.2.5 Equations for Apparent Rheological Properties

the eqllLauons recommenClc;~d a u.;}lri.,.1'u of measurements on Clltterlent DO,lvnler
the eqllLauons recommenClc;~d
a u.;}lri.,.1'u
of measurements on Clltterlent DO,lvnler

Table 2.2 Equations for Apparent Rheological Properties

Shear now

shear rate

shear stress

recoverable shear YR' from

shear U1Q£'£'\Ql'h,

shear modulus

pSt:~udopJtastici1:V index n from

shear modulus pSt:~udopJtastici1:V index n from Extensional now extensional stress extensional V i S C

Extensional now

extensional stress

extensional ViSC05.itv

extensional stress extensional V i S C 0 5 . i t v recoverable extension modulus

recoverable extension modulus in extension

rupture stress onset of non-laminar

* This eqllation, while complex in app~arance,

Where

capillary

.",

are the

index, shear viscosity

at the same volume flow rate.

32

Polymer Melt Rheology

2.2.6 Accessories to CapllJary Rheometers

Stretching Flow

An obvious access~orv to an extruder is an instrumented haul-off. Measurements

value in comparing

to carry the use which has been in many

demonstrated that clipping a weight on a

method of comparing of measurement exists. The main the flows,

sample and allowing it to draw

of in-line tension, the stretchability of polymers. out such

and rate can

of

it solidifies is a

highly viscous could possibly be less

in stretching flows, and no

that an extruder

drawback of all such measurements is the difficulty of

with velocity

and complex history and temperature

to yield

fundamental

The only

which are easy to

draw

ratio and maximum stress to

the material has been SUI)lectea ftnrr'p./~rp.::l

for studying

phenomena like rupture where maximum stress is the most important factor, or for comparative of the extensibility of mattelials.

Preshearing

The melt from a capillary rheometer the material is subjected to a well ael:lDe~a section may be used for preparing melts of different so that the influence of that important, though often parameter may be evalu·

The measurement is thus most

in thinnest

ated in Iilpl"!:lr!!:atp

eXl)erim~ents.

2.15 Pl'p~hp~riI'Hr

The Measurement of Velocity

Flow tJl1'etrtnllem:eand Streamlines

As well as mechanical measurements of stress it is to make

direct measurement of the streamlines and of stress

The measurement of stress

Wales: 50 such measurements 1'1"£111111'1" S()pl1llstllcaltea eql1Jp.ment, eXI)erllmc:mtlitiC)fl

and interpretation but the lDltOrnlatllon which they Improvements in tracer have reclentllv measurement of velocity distribution in COlnpllex

during flow.

has been

Rheometry

Polymer Melts

33

R h e o m e t r y Polymer Melts 33 pa1:tern and aWlntjitative measurements

pa1:tern and

aWlntjitative measurements on the flow 'in vivo'. The introduc- a qUlCllltatl"e IllldgJrnelrlt to be made of the strl~anrulJ'le

how such can illuminate of various flow detectls.:J-,"

authors

differences between materials and the

"''''' " cb~lrec~s
"'''''
"
cb~lrec~s

rheometer

cornpJ·es~.jbi.lity of melts. In a study it is

of all leaks the

different volume to allow correction for tantgellt bulk modulus, is VdPldV where

2 2.7

The Melt Flow Index

The Melt Flow Indexer as Rheometer

is a

control test used to assess the

of a

as Rheometer is a control test used to assess the of a standard conditions. between a

standard conditions. between

a

melt flow rate is extremely of the same polymerisation fami to within 3 per

sensitive in

IV--lllnm~r ideal conditions it can

of 1 is of the '''' Ju'"'' cent in molecular This polymers whose not ne(~e~,ariily
of 1
is of the
''''
Ju'"''
cent in molecular
This
polymers whose
not ne(~e~,ariily
which have been made by different routes
nnl'vtnprliO: having the same melt flow rate may vary by more than an
maeDJttU(le under other conditions
of capiUalry
after prolceS,SIDJi. e~.pe4:1allv
eSt)eClalJIV useful indication of cnalng4~s
Flow Indexer invites the eXJ)eliime:ntE~r
eO(X)uraging him to
the nT't'~nJ:>,T'tu

2.2.8 MiDiaturisatioD

The

can be miniaturised to allow measurements to be made

In

a

small

the

of

is used: gas pressure is more

and

made In a small the of is used: gas pressure is more and as 0·1 g
made In a small the of is used: gas pressure is more and as 0·1 g

as

0·1 g of

leaKa,~e become severe if a ram-driven

A of miniaturised Because
A of miniaturised
Because

wOlrKl11l2 with very small sa110pl,es, abf;Ol1ltely necessary and then as

a COlnpanlUv'e test.

34

34

Conclusion

on eflj~m4eermg data and for the

I have dwelt

rheometer as a tool for obtamme:

assessment of materials. The L",.,rh ,in on which a Avir n,rt~jr
assessment of materials. The
L",.,rh
,in
on which a
Avir
n,rt~jr

Ilm,ltaltlOllS of the data in fundamental terms must be rec:ogms1ed. caJ,aOle of

are ne~cessal~V

favour of pnlctlcal flow in mOlulcts su[nec:n\ire assessment of

2.3 PROCESS SIMULATORS

shc)rtc:omlmjl~s: a
shc)rtc:omlmjl~s: a

Sh(utlcolmrl2S mean may aUow a response of the

rheometric measurements at a

we can do with

in

is at best an "'"

"

nr~(" Il·A

the shortest time time-scales often so that the melt may

mlrlUte$. These

true

out

best

The second alternative is to use a screw melter

material at a

a solution'thr'u.n,n rheometers is unlctolJbted,lv ,,,"L'f';!,, 4i:tllnr\nrtPfl
a
solution'thr'u.n,n
rheometers is unlctolJbted,lv
,,,"L'f';!,,
4i:tllnr\nrtPfl

on which rheometric measurements can

4i:tllnr\nrtPfl on which rheometric measurements can measurement can the A screw melter also ae~ilfaOle
4i:tllnr\nrtPfl on which rheometric measurements can measurement can the A screw melter also ae~ilfaOle

measurement can the A screw melter also

ae~ilfaOle

"'.("f'1I"

mc'tI1100:S.;):;! This is a

be as versatile in terms of rate the flow rate also chalngc~s of mattelrlal

there is

a conventional ram extruder since it will take time for the eq'Ula:;_mcent

eqluiliibrliul1rt. The use of screw extruders to when material cm:ml!:e

tec:hnlqlles are at their

when rh

to when material cm:ml!:e tec:hnlqlles are at their when rh The use of such as film
The use of such as film and as <>10"" control tests when eV~llmltjrlg .,,,,o.l'''I~-UU of
The use of
such as film
and
as
<>10"" control tests when eV~llmltjrlg
.,,,,o.l'''I~-UU of ext:)enefl(~e
value in establlshmg
two materials.
The
rt
"'
which
of such teC:hnlqlles
may of itself ob~;CUlre
which may be prc~mlnerlt
pr()OllctltOn eql.npment, and
versa.

Rheometry for Polymer Melts

The geJilitlOtn nrr'I"AC~C The
The geJilitlOtn
nrr'I"AC~C The

gerlenltiotn and time-scale to fusion COIl(1I1tlOI1S which may approximate to pr()Ce:SSlng. As with other

and it is often
and it is often

of all polymer prclceS.Slng. AV~IUAnle to make qualitative and co[np~lral1ve measure-

to

under

melts

and tolerances

measure- to under melts and tolerances provides information on sometimes to under which

provides information on

sometimes to under which instruments, to 'run in' the surface

to under which instruments, to 'run in' the surface is attained. Although it the instruments they

is attained. Although it the instruments they are commonly used for rate of gelation is a critical feature to the process.

for rate of gelation is a critical feature to the process. 2.4 PRIORITIES AND COSTS FOR
for rate of gelation is a critical feature to the process. 2.4 PRIORITIES AND COSTS FOR

2.4 PRIORITIES AND COSTS FOR SETTING UP A PLASTICS PROCESSING RHEOLOGY LABORATORY

FOR SETTING UP A PLASTICS PROCESSING RHEOLOGY LABORATORY laboratory with all the equipment which would be

laboratory with all the equipment which would be nnl'urn,ar p]rocc.:~SSU12could cost £250000 (1980 r13£1'I1U-13 ctectllca1tea eXl0er'lmen1taUsts to make effective use of much A much more modest sum-£8500-will serve to equip a

to it.

the

laboratory which will be able to meet most of the

Essential. A Melt Flow Index tester for

tive assessment of behaviour. Such equipment is obtainable for about

Very highly desirable. A ducer located in the barrel

orifice die _ This will allow the measurement of enJnn4eerm2

erties according to at a cost of about

measurements and OUiuu:a-

according to at a cost of about measurements and OUiuu:a- <3 _,,, .,."'; • ., c~lPi1llarv
according to at a cost of about measurements and OUiuu:a- <3 _,,, .,."'; • ., c~lPi1llarv

<3

_,,,

.,."'; • ., c~lPi1llarv

above

rne:O[[lett~r

including a

Standard recommendation and is currently AV~ulAnle

a Standard recommendation and is currently AV~ulAnle Highly desirable. Constant-stress cone stress behaviour and

Highly desirable. Constant-stress cone stress behaviour and direct measurement of V1S1£':OI1S equipment is available at a cost of about

: O I 1 S equipment is available at a cost of about of low orc.oelrtles.

of low

orc.oelrtles. Such

These instruments will nrrnl1rt"" an excellent basic eQ1Lupme:nt.

are recom-

menae:a in part for

electrical and mechanical SlDlpliclt:y

allows them

to

it may be niques, the to be """.·

maintained and

""'n

out.

with a minimum of eXI)erien,ce. From such a basis

tech-

much on the nature of the work

to develop to more of which will depend

and

established that it is POS.SlDle to have an effective rnt~014[)glcal labora-

'Can we

tory for a modest

afford not to have such a labOratto['vT

a second

becomes

36

RBFBRBNCBS

1.

2.

6.

7.

8.

9.

10.

11.

12.

U/t1,

I ",n,

13.

14. HenDOw

1975.

J(n~wl'~Klcal 1 j~chj~iql.teS, Ellis Horwood (di~.trit)Ute~d

dyrlamic response of

and

15.

16.

IS9,

17.

Plastics J::.,n,~lneer'InK

18.

19.

20.

21. MaJrcwell.

22. Coi!'sweIL

23.

Research Notes in Mathematics No.

1979.

24. 'Munstedt hl()ntl;atl0nlll Flow Rheometer'

New

built

Rheometries, Frankfurt and

25. R.

1965.

26. V11I."""'U.

Extensional flow of nnllvlO:1'vrf'np

rhc:~ol()gy of ool'vmc~r melts under

Plastics and

37 27. 28. 29. 30. 31. 32. schaften von Rheometer zur Kunststoffschmelzen der deformationsmechanischen unter

37

27.

28.

29.

30.

31.

32.

schaften

von

Rheometer zur Kunststoffschmelzen

der deformationsmechanischen

unter

zur Kunststoffschmelzen der deformationsmechanischen unter 8 1969. bl()n~:atlon.al behaviour of a low elong~ltiofnal
8 1969. bl()n~:atlon.al behaviour of a low elong~ltiofnal flow and failure of 1978. Godwin, 1981.
8
1969.
bl()n~:atlon.al behaviour of a low
elong~ltiofnal flow and failure of
1978.
Godwin, 1981.
"",
"",lVILI.
34,

1961.

33. Doilve'thv'lel1te melt l"h" II', nr 34. 35. 36. t"vtl"l1".""n
33.
Doilve'thv'lel1te melt l"h"
II',
nr
34.
35.
36.
t"vtl"l1".""n sWleUiln2. Journal
39.
8
""-Vj","""",u,
40.
41.
42.
43.
phcenc~m(m(J~n of draw resonance in
1966.
44.
SpiJlnillg of molten oolvetJllvl4enes.
1972.
'"TJ.r".J.l.Lh
45.
spInning, Transactions
Dolvethvliene melts in
and Rubber
The realities of Plastics and Pn/vlH ,. l<fleC»lo"rv and 47. HJLQ<l'A"''', 48.
The realities of
Plastics and
Pn/vlH
,.
l<fleC»lo"rv and
47. HJLQ<l'A"''',
48. :swcerclJ[ow
F.
N.
and Krul,
""-Vil:.i:ln,""u.
biaxial extensional
49.
50.
51.
nolvtl1lene. in The J(fl,eoliO"RV

38

53.

l,;Ofl:sweU.

55.

1975.

60. 'Brabender PJ~COltnar~nh7, made Saddle

61. W pJ\lnrn Garden

Rheo~