Polymer Melt Rheology

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

Polymer Melt Rheology
A Guide for Industrial Practice

F. N. Cogswell
 Godwin Limited

ISBN 1 85573 198 3

2003FN

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 ext.enem:e of
of leI
lAn'!:l1"trnA."tCl

art of ~Y"£'C"'A;"_
pra,Ctlt:tODlers of that technology, and a
ba'~k:Q"rOlmd SCl~en(:e o,eve:lot)eO academic contributors to this field.
stimulation, this book is respe(~tttlllV
PUBLISHER'S NOTE

While the pnlrlCll)leS in this book are the nr".l'tn.f'f'

of careful pulblis,heJrs cannot in the
sUl1tabtllty of caJI~uJ~itl(J.n solutions to inl"llultill'!:lJ problems and
not be any kind in of or out
form or contents or any error reliance any
person tnc;~re4::m.
Contents

xi

Notation xiii

Introduction 1

1 Fundamental concepts 5

1.1 5
2e('me~trv of deformation 6
rlleolof21cal 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 17

Vi~iCOjelal)tic response of melts to deformation 17
shear flow in a cone and rheometer 19
J::,1(Jn~:atlon;al flow rheometers 23

2.2 Measurement of aplJarlent rlle:olctgical ......" ....,."'jr.A" 24

2.2.1 API)are.nt 25
2.2.2 and exit effects 30
2.2.3 Inference of elastic respoillse 30
2.2.4 Observation of extrudlate am:.eal'an«:;e 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 35

3 Physical features and Dow 39

3.1 'emtl)eJratl11re and rtu:~01()2V 39

3.2 Pressure effects 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 133

Appendix I: Additional sources of error in l"llr'\lIl~~rv visc;;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 data for an In Ilectlion of
nylon at 285°C 158
Appendix 11: prC)Celisirlg property data for an In.l lectllon 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: Flow a slot or annular die to uniform
of extrusion with thickness 170

Author index 173

index 176
Preface

rne:OI()IlV and the assoc].ate:d

sciences and tnc:~rD110a'v",amlC rc:~srx)nSie. DJIlVS]lCal and chemical
which form the methods of
meaSlJlnl1tll the flow of on the

InS>UJflYU 1981 F.N.C.

Notation

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
na."m()flU)US raw
material.
literature both in trade and
m()flO'2fC1PtIS:.l-· I :.l have been

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

t"n~efi()m~en()IOjglCl(l1 and discuss effects
2

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 nlrnl","'Cc'

response of the

ort~all;:t the between ...n.j'",nr'",1 new or lrrU"rn11!",11

ohlecfl've~ has led to SImlpllltlcattOJilS

who are in the of
arise. Those who are not so sinlplilficaticlns are
mtJ~oauce:a where COJllPleXltlt~s and where the
circumstances future research will
dernOllstr'ate that are sut.stantullJy c(}r:'~.. c,~... but my
tion in this is to be rather than de1timtlv4e.

eXJ)en,em~e into a cOJllplex

nOlvn1er rnf~OI()OV cur'rerltlv ~nr,p~rcto be in and the first

the final clalntl(~atton.
 3
more
£1&>"'11"''.11'\1"" in a
then~
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 to
in the of irntlrO'IIl"fl

theoreti-
tun.dalnelltal des.cnlPU()ll of what would be
pnlctltlolllers, who are
tneoreUCl;ans the
SU!l[lltlCal1lce. To
nUI"rl"l.rtp(! all other

Each is concerned with his own truth, which both to be

same when the two are married we have a cornpJete
unl:lerstandJlng. To that to be consummated much has
been laid on construction of between those and several books
have aUempt(~d to build such a framework. The dit1tlC\llltv
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 even if it is not DOs.Sltlle
river is not so after alL
4
REFERENCES

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

2. IVI L;I'\LI:: I VI:: V

3. Nlel!iSen,
4. R"'lirl'h11".n \OiUltlVIl. '\JVIUWIU. 1981.
5.
6. MiddleJ1nan,
7, HOJm€~S- 'IV alKer
8. pp.~lr~ln
1966.
9.
10.
11.

12.
Fundamental Concepts

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

are necessary to the

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 which is most felt. We have all SQtlee:rea toc,thl)as1te
kneaded from our
of descnttlD2
readlDJg, but
nt't"'Il1rlp the

is to
..... .,.£'\11" . ."'"

geJleral1~;eamaterials
eQtlatllon of state. The
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 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 1

stress

strain y

1
rate
Ii

1.1 shear: area A and distance h remain constant deformation

(b) In simple extension stress is a01)l1e~a normal to the surface of the material

stress UE:=

strain (unity) E:=

rate of strain e
 7

extension: cross-sectional area A and I both vary

In bulk deformation the stress is aDl)Ue:eJ normal to all faces. The stress is the
apl)l1e:a pressure, and the strain the in per unit vollunlle.

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

1.1.2 Tbe Rbeological Response of Materials

There are three of response to an stress: viscous
eJetorrnatlon and rUDiture.
In viscous flow a material continues to deform as
and the in to flow is (llss1pateeJ
defined as of stress to rate of strain in
The of some common materials are

Table 1.1 Viscosities of some Common

Materials

Air 10-5
Water 10-3
Olive oil 10- 1
loo
1()2
1(lLl 06
1()9 stiff
Glass 1()21
8

Strain

Stress

Time
1.3 Newtonian behaviour

response of a material is to flow with a

stress the is said to hellla,re
low stress level many melts aDI)ro,!:lch

ms,tarltJv under stress and the

riA·............... '" is
material possesses an
ratio of stress to recoverable
If all the deformation is
reversible and is aDlc>l1e~d stress the material
is to a Hookean response 1.4). At deformations
approach Hookean and many nnlvn~pr melts have a lower mc,oulus
than

Stress

Time
1.4 Hookean behaviour

11..... 1"......
£0 .. melts delIDons1tra1te elastic:o-~rjsc~()US reSDO]tlSe to stress. The Max-
well model in in a
Hookean elastic <:tn'"lnc:,O
illustrated in

m(jltel~ial will 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 Dashpot Spring

Strain
Raversible
deformation

Stress

b Time
1.5 a Maxwell model
b Its response to stress
role in deterl1mnmg the maximum rate at which a deformation ....rr.I".,.'~e
carried out: it is the initiation process for that important

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

interactions
elastu;ity rupture phenomena which determine the

1.2 THERMAL AND THERMODYNAMIC RESPONSE

cOlnpres,sio'ilit:y of materials we have ~lr''''~£1I'll

and in viscous flow,
is as rI"" •.,."d'" and SPt'~Clt:lC

pressure. For a
aplueC:lation of
tOIl~etller with the
nowned as msulClltlJ1lj!
handled by the for COlllvelltl(Jlnal ma1tenals. APpeniOloes
include typical data for several polymers.
The rate of during is determined by thermal

which is readily aPI'lle:o the corlcel,t of Fourier number:

Fourier number

eX(:haJflgeo from both sides of the sectlolll,

transfer on the square of thl(:kmess, a sec1tlOn
 aDllro.ach thermal
minutes.
cOlnplexltv due to surface heat transfer .
....nl'l1.....,.,... melt and dlfter,ent

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 .............."" ..lh""c
techmQU(~S which have been de~ileh)ne~d
eSI.aOJIlSrleO technique for cr .. nu" .... n
ngl-2'I£'nl!l:rlll ..........1""..... "" .. melts-the ......,...... ,,"".....,

~erlenitlCm as as heat
streamlines of a
QUiescent: state and must

in .....c ...""'r"r
stable.
only be lost
It is also '.....,'...."1"2'<:>11'12'
solid to an !ltnnnr'ln{'Uul.
values of tnClU(Jlea in
APIPenOlCles 7-12.

1.3 PHYSICAL AND CHEMICAL CHANGE

The ..... ".t: .....,.
One iSPf()cesse~o
been demonstrated to have a flow That ....""1"'...",. ..
plaStl(!lse:o and lubricated to achieve easier flow and may further
mOlol1led whose method of their desired effects
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 resins and thermal

of process may allow some of that order to be retained.
we have seen the of
 11

a distinctive mc$ODnliSe
of a 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
"~a.~~£~~ nrnt\lplm when

m(]~le(:UUlr ",""'''''_HL. RUlnnmg the extruder cold

and so hot any material prone to
ooltimum machine tel1npc~rature.
are least severe in constrained
IDllectlon mCml(lme:. where the 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 more severe in extrusion processes where thickness
variations 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 result in amounts of stretch. The of
plastics in this field less than 20 per cent

If ae2raaaucm DJ~021'eSSjes
only ~I"'htllv rf~dUiced a 10V\'-mlOle~CUJlar··we:l1!l1tt.
volatile, tail may be "'V. "n.., ...... plas'ticlsin1! the flow and IP!l"'t1~O' ......"'....""'JU,,
brittle, low-molecular-weight or voids as mechanical weak11esses
product.
A laudable desire to exposure to heat as low as DO~iSlble
lead to too little consideration 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 ...".... n1~h
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
nrr\nprhl"'<l of it is
rnf~OI()1!V interacts with the
Fundamental Concepts 13

RBFBRENCBS

5.
6.
7.
8....."',.....".
prc)CelSSlrlg aids

I::"repar,atl(Jln and
Pn/vm4rJr Science
"-".U'"""""",, Two

Rheometry for Polymer Melts

Kl1leometry is the art of maKlnlg useful measurements of the deformation

flow Df()Dertl(~S of measurement which is may fall
one
nrr\nA.rtu of the material.

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

Demonstration of a pn~en('m(~n(Jln mvestllgalte its and its DOltentIal

effect.
The of new which 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 must be asked of method of measure-
ment are 'Is it and 'Is it sufficient?'. If a is the only one
which the information about the then it is
necessary, and if the which it is to resolve the
QUlestllon under then the sufficient. Thus if we wish to
the linear behaviour of a melt we
methods of measurement from those which would to
Tnr,hl1rp behaviour of melts in film that for
much more far less
so~)hil)tic:ate~d rtleometrv which would be unsuitable to the first task.
this review of rheometers is to define those areas in
teC:hnlqtle is most The review is biased
eXl)entenc;e and limited of a that my
PV1,.....,."·.A .... I"'A for a more review of rtu~onl1eters
undelrlyiin,g their use several texts are available ,1-4
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 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
PRECISE DATA Strain rate <1 s-1
Extrudate force
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
The and measurement of
of oDtalllllDl2 nrpr'IClP

mOlduJusarerreQuen4~-IOel)erldent.
amlpJlltu4je-.aepeJ()d4~nt because maximum strain
rate in sut:t1C1~entjly small that from
are rare, "U""'"F'.,U

.
'e
"0
C
y• fl·

••
••...
-
f /)

, where is the strain amlPlltlllde and

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

are ways of data. The differen~ces
int en:.re1tatjion rest on whether stress or strain assumed to be the co]tltr oUiin2
1 1

meCll~lm!)m. Most under strain but

response would be if stress were the mechanism. Most
COlmDilOlllv strain is assumed to be the the dVlrmrmc

11' = sin 0

and the modulus:

Of =-""T"jr:ns 0

ampWtudes, 0 is the and (J) is

1Ddlepc~ndentof
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 a
these
..... ".rt.li" lIJltelrchanjlea.ble and contain the same mt.onna1tl.ol[}.
rer're~;entatli.on of data is an in their <ll2.,estl.on

J.UUi...,...,,", at sul11Clenttlv
t.o a Maxwell m.odel.
noilvnler melts use the Maxwell
share the that the Maxwell mtcerpretcitlOJn
the an easier

.oSc:illaltOl"Y shear rhe.ometers9,1O,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 of the

of melts are:
.. h",.file,,,,,·.,

tecnmQuces have received and may be used to .obtain

on~Cls:e in the linear over a very wide range of treQU4enc:y
(ii) a direct measurement of elastic as well as viscous Dr()Oertu:~s--anld
 19

~~b~~~~ ~~~ ~~
COltllP'aflin2 elastic response.
between and
information relevant to the very short time·scale response of

POsslltlle to obtain a
strain
as all the data are g£'Tln<lifi'"

nr£"'I,.,-t",C! a solution-

have been

)ls~ld,ranta~~es which must be borne in of measurement

are:
(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 in standard texts),2.3 There are two
oel)en.01I112 on whether the is to under constant stress
or constant rate
The constant-stress is the is apl)Ue:d
direct and deformation measured from a scale.
probably the rheometer which can be made and is eSt)eCIalllV
useful as a since the can be felt and the deflection seen,
rather than measured with transducers.
The constant-rate in which one face is rotated at a series of
rates and the is measured on the
nr~"f"'rr... rI in most commercial instruments. If the instrument is
this method of has an <lirl'"<li.."tO€~'''
stress variant in that, when the reaches
constant re~IOlJn2.
Cone and instruments may also be used to determine the elastic
reSPO]llse of melts. Several measurements can be stress and
transients to and from normal stresses and recovery.
The between such responses and measurements has been
the subject of numerous those and .l.,.;v'""J'.'..,.
evidence can be found to of COI[lcIUSlon:s.
 a b
rbeometers
a COllstalnt-lstress
b Constant-rate type
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 faces
That thrust is most measured instruments in which the
strain rate is accounts the common for that class
of instrument. own use of normal stress measurements has been limited for
I have never been able to of their and
evidence-the normal force "",vf"."u,'1"'T"ll
can be related to TU·".,....,.'"I
nu,.rlr,,,, ..,,, take a different 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 and cessation of
shear flow also offer for de(Jucln}! the elastic Such
tranSlenlts can be of absolute
measurements demand
an effect 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 some
a close lnspe<;Uctn

Since the contribution to total an individual annulus of the

instrument face on the cube a small loss of adhesion near
Rheometry for Polymer Melts 21

Strain
rate

a Time

As set up and 'Overshoot'

running with no evident
b 'overshoot'

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

b ~eciondlarv cone and rheometer

the of the ""'.1"1"''''' and so on the stress

measured. in a double cone
rheometer ins,trtJlm~ent to be used at much
higher stress argument «~«lU"" the of the
stress OVcerSJno(lt for eX~imlple
for tbe £>"O'I"T_"'_ exist. My
is that, were very should be seen-but
they are not. The mterr.reltatJOn of apparent stress overshoot phenomena as an
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)1t remains doubt such observations must be treated with caution. The
nh~O::l"'rlHitlnn of adhesion failure may be of considerable in

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

which the stress may removed the observer to
record strain recovery as a function of time for stress histories. The
ratio of shear stress to recovered shear a simple comment on the elastic
respolnse which may be related to observations of frozen-in strain in
mOlul(lmJ~S and in that all a desire of the
Tt1!l'''~1'1!:l1 to revert to an earlier state. use of recoverable shear as the
measure of elastic has the additional while it is
meastJlreci, it is the thing which is nallJPCmlJng.
ae~;tgJ)ea to measure strain recovery after constant-rate aeJtormaltlOin
22 Yn.I\IJt1"1Pl' Melt K/1;eo,tolJ.'V

Measured

c
.~
(/)

Time Time

Applied

Time Time
CONSTANT STRESS 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' • •

ment at constant rate is that it time to reach equlllorlUln

response. This difference in demonstrated for a
Maxwell model under constant is attained instan-
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 rhc~OInetrv are:

nrf~Clselv defined flow at low shear stress.

on both aDd in a of

As a measure of under low stress it is sensitive to the

structural characteristics of the which structure may break down
under stress.
The limitation of this class of rnc~orneltrv for melts is associated with the very
 23

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

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 would still
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

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 with the
wall of the so that is not a Such measurements are of
direct as of the ............................... r1T'!:l'lll1nrtT
tions and are of considerable thf~orebcal sig,ni11cCllDc:e
ret)reSerltII1U! the of irrotational flows which are rurlaa.memt~:lUy
from shear flows. the of measurement
desirable to carry it out.
24

Stress
2.7 blongatlOnlal
strain rate, E

The and of constant stress or constant rate as the

controlling mode of deformation apply to extension as wen as shear. The
reduction of the time transient available when making measurements at constant
stress is of in flow when making measurements on
melts whose decreases In such f"Xl'f"r<l.
ments the small reSltOUal unrc:~coveJreo recovery
may be tnt'p.rr\ ..... lt... rt aDI)ar~ent rate of viscous
aetonnatlon in ClrlCUtnstaflices where Ul~lt1t'IIO conditions to be
achieved would allow the to neck.
The most important in favour of direct measurements of
elon~(Jltlonal flow is that such measurements can one
Oflieself of the between shear and extensional flows
between materials in flows. Both these a crucial
role in the which follow. 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 of
f t .......-.""' ..1· .... '"

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

measured should property

reCluurea so that it may be
The should be {,{,U'1VP'ntf"ntllv
(better than 5
It should be pm'SIO.le of less than 100 g and Drc:~feI'abllv as little
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

wall shear rate, y

By the of onrlrnr'U'tota eC~Ullpment POSSlltJle cOllVe~nl~~ntlv to measure

shear stresses in 0-001 to

operaLtlctn have been used: cOlltn)lIe~cl nrac-C'nl-'"

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

Barrel

'~..,.',lIn .... extrusion rheometer

reilat1()QshlP between flow rate and

associated
tnc:t10nal losses
l1a40ltr!:ih'.,. to make the

above the die rather than

reCIUllrecl to drive the

(eS1Dec:talllv when the

(iii) enf;!~lDeernlg tOllen:mce~s.

26 Melt Rheology
20 mm diameter barrel will take apl:UOXlIl£1ately 15 minutes to reach thermal
equilibrium, will take a of size to accommodate
a melt pressure transducer near to
Intlerpretl!ltlC'll of Cal)lll:ary rne:Ofiletlry the PoiseuiUe eOllatlon
aPI)ar,ent rather a true measure of uu:r....nc"f"u at the op,eraltlnl2 f"'.rn ..""'... :l_

of corrections is the true 'ittl;! ....nc:l ..u

..'V" .. """"' ...."u. is recommended:

aPtlarlent wall shear

aPJ)arlent wall shear stress, as
leaOlIll2 to

where is the pressure

thl'OU,2h an orifice die
rate.
It is further recommended that the die used in such measurement should
have a ratio of between and and 32.

calnU,ary flow

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

Ends pressure

at the die wall

Inlluc~nc:e of pressure on viscm~ltv
Influence of on volume
Influence of
IntJIUel£1ce of on tenloeratlure
Modification of the material due to work in the
 27

2.9 The Darrel··nel~nt effect

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

.,.,.,....... ,,~~ that a

nh~~p."'llP.<1

wall shear rate

shear stress

Pressure

L/R
correction
col're(~tlv as gn:ullcent may be
of several but this extensive
poL "',_,,"' _ _ , the choice of two dies The
colmlJ-im,ne; a die an orifice

where is the pressure

Some eX]:>erlm1ent:ers
 Error band
in pressure

L/R L/R
a 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

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 This is in
conjunction with a screw rather tbe
needed in the die to the transducer necessitates
rates whicb are mos.t conveniently acbieved in such an apl)aratus.

Presentation of Capillary Vl$lconrret,"y

For the measurement of apparent ",i."".,.....,·.+" flow tbe ends COITe(:tl(Jln
should be made and tbe metbod of sbould be noted witb
the data. An method is the two-die method one die witb
LIR = 32 and an orifice of tbe same Some of tbe
additional sources of error will be found in 1.
Tbe data be of
versus log wall versus
sbear stress are of flow
 t
Pressure

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

10" 105
Stress (N/m2)
2.13 A,ma,rellt .",.,,,,...,.1',, versus wall shear stress: IOVi/-oemmv DoJlve1tllvieilie at
30

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 rt""lr.o.'I".rn'T,,,,,rt dmectJlv

pOJateo from a series of several measurements

2.2.3 Inference of Elastic Response from Capillary Flow
The most obvious during capillary extrusion
sWielJtnil. The in SlDlpJest appears to be a reverSIon towards an
earlier state and as such is as evidence of recoverable
strain. Post-extrusion increases as flow rate and
decreases ratio increases

To make a measurement of swell

be taken into account For praLCUcal. n 'lIrnnc*,"c
measurement which most and an ao€~au.ate
obtained the extrudate flush with the
length the diameter of the solidified extrudate 5 mm
of the 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 how the
elastic modulus of the melt may be deduced from such measurements.

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

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

230/2 15 at 210°C
 Vr..h'"'Ior Melts 31

2.2.4 Observation of Extrudate Appearance

extrudate from ........""cu."".. ",,'rn'U,.rt.,. useful
non-laminar flow or sUlta(;e nnDer1:ec'tlons. non-laminar flow occurs the
for nr£,\n.,.rf'u"'C! no hold and data
f'r"'!:lf'",.rt with The extrudate
to deduce of the
DrC)Ce!,SlIlli and also to obtain evidence of
Cletauc;:CI dllSCU,ssi()fl of the of lrre:gui,ar

2.2.5 Equations for Apparent Rheological Properties

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

Extensional now

extensional stress

extensional ViSC05.itv

recoverable extension
modulus in extension
rupture stress onset of non-laminar

* This eqllation, while complex in app~arance,

Where .", are the index, shear viscosity
capillary 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
of in-line tension, and rate can of value in comparing
the stretchability of polymers. to carry
out such the use which has been in many
demonstrated that clipping a weight on a
sample and allowing it to draw it solidifies is a method of comparing
highly viscous in stretching flows, and no of measurement
could possibly be less that an extruder exists. The main
drawback of all such measurements is the difficulty of the flows,
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
in thinnest The measurement is thus most 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·
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 during flow.
The measurement of stress has been
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
Rheometry Polymer Melts 33

aWlntjitative measurements on the flow 'in vivo'. The introduc-

a qUlCllltatl"e IllldgJrnelrlt to be made of the strl~anrulJ'le
pa1:tern and authors how such can illuminate
differences between materials and the of various flow detectls.:J-,"

"''''' .. "........ of all leaks the rheometer

cornpJ·es~.jbi.lity of melts. In a study it is
cb~lrec~s different volume to allow correction for
tantgellt bulk modulus, is VdPldV where

2.. 2.7 The Melt Flow Indexer as Rheometer

The Melt Flow Index is a control test used to assess the of a
standard conditions. a melt flow rate is extremely
sensitive in between of the same polymerisation fami ..
IV--lllnm~r ideal conditions it can to within 3 per
....... '''' ......Ju'"'' of 1 cent in molecular polymers whose
is of the This 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
as 0·1 g of In a small the of
leaKa,~e become severe if a ram-driven is used: gas pressure is more
A of miniaturised and

Because wOlrKl11l2 with very small sa110pl,es,

abf;Ol1ltely necessary and then as
a COlnpanlUv'e test.
34
Conclusion
I have dwelt on rheometer as a tool for obtamme:
eflj~m4eermg data and for the assessment of materials. The
Ilm,ltaltlOllS of the data in fundamental terms must be rec:ogms1ed.
caJ,aOle of .......L",.,rh..,in
are ne~cessal~V
favour of
pnlctlcal flow in mOlulcts Avir ...n,rt~jr ... on which a

su[nec:n\ire assessment of

2.3 PROCESS SIMULATORS

a
shc)rtc:omlmjl~s:
the shortest time
time-scales often
so that the melt may

mlrlUte$. These
Sh(utlcolmrl2S mean
may aUow a true
response of the in out
rheometric measurements at a best
we can do with is at best an "'".............." nr~("..Il·A
The second alternative is to use a screw melter a
material at a on which rheometric measurements can
mc'tI1100:S.;):;! This is a solution'thr'u.n,n
measurement can be as versatile in terms of rate
there is the the flow rate also chalngc~s
A screw melter also a of mattelrlal
conventional ram extruder since it will take time for the eq'Ula:;_mcent
eqluiliibrliul1rt. The use of screw extruders to rheometers is unlctolJbted,lv
ae~ilfaOle ....... "'.("f'1I"... when material cm:ml!:e
tec:hnlqlles are at their when rh ...,,,"L'f';!,, 4i:tllnr\nrtPfl

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 of such teC:hnlqlles
rt ........... "'...

which may of itself ob~;CUlre

which may be prc~mlnerlt
pr()OllctltOn eql.npment, and versa.
Rheometry for Polymer Melts

The geJilitlOtn of all polymer prclceS.Slng.

AV~IUAnle to make qualitative and co[np~lral1ve measure-
nrr'I"AC~C The provides information on to
gerlenltiotn and time-scale to fusion sometimes to under
COIl(1I1tlOI1S which may approximate to under which melts
pr()Ce:SSlng. As with other instruments, and tolerances
and it is often to 'run in' the surface
is attained. Although it
the
instruments they are commonly used for
rate of gelation is a critical feature to the process.

2.4 PRIORITIES AND COSTS FOR SETTING UP A PLASTICS

PROCESSING RHEOLOGY LABORATORY

laboratory with all the equipment which would be

p]rocc.:~SSU12 could cost £250000 (1980
nnl'urn,ar
ctectllca1tea eXl0er'lmen1taUsts to make effective use of much
r13£1'I1U-13

the A much more modest sum-£8500-will serve to equip a

laboratory which will be able to meet most of the to it.

Essential. A Melt Flow Index tester for measurements and OUiuu:a-

tive assessment of behaviour. Such equipment is obtainable for about
Very highly desirable. A .. c~lPi1llarv rne:O[[lett~r
<3 ...... _ , , ,. ..,."';• . ,

ducer located in the barrel above including a

orifice die _ This will allow the measurement of enJnn4eerm2
erties according to Standard recommendation and is currently AV~ulAnle
at a cost of about

Highly desirable. Constant-stress cone of low

stress behaviour and direct measurement of V1S1£':OI1S orc.oelrtles. Such
equipment is available at a cost of about

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

menae:a in part for electrical and mechanical SlDlpliclt:y allows them
to maintained and with a minimum of eXI)erien,ce. From such a basis
it may be to develop to more and tech-
niques, the of which will depend much on the nature of the work
to be """.·... ""'n out.
established that it is POS.SlDle to have an effective rnt~014[)glcal labora-
tory for a modest a second becomes 'Can we
afford not to have such a labOratto['vT
 36
RBFBRBNCBS

1. 1975.
2. U/t1, ..... I ",n,
J(n~wl'~Klcal 1 j~chj~iql.teS, Ellis Horwood (di~.trit)Ute~d

dyrlamic response of
6.
7.
8. and

9.
10.
11.
12.

13.
14. HenDOw

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' built Rheometries, Frankfurt and
New
25. R. Extensional flow of nnllvlO:1'vrf'np
1965.
26. .....V11I."""'U. rhc:~ol()gy of ool'vmc~r melts under Plastics and
 37

27. Rheometer zur der deformationsmechanischen

schaften von Kunststoffschmelzen unter
8 1969.
28.

29. bl()n~:atlon.al behaviour of a low

30. elong~ltiofnal flow and failure of

1978.
31. "",.."",lVILI. Godwin, 1981.

32. 34,
1961.
33. Doilve'thv'lel1te melt l"h"..... II',..nr

34.
35.
36. t"vtl"l1".""n sWleUiln2. Journal

39. ""-Vj","""",u, 8

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

47. HJLQ<l'A"''', The realities of Pn/vlH...,. l<fleC»lo"rv and

Plastics and
48. :swcerclJ[ow ""-Vil:.i:ln,""u. F. N. and Krul,

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 Rheo~
Saddle
61. W pJ\lnrn Garden
Physical Features and Flow

The 'What is the of a nnll'l.11"r''''' ... ·,'

aP1,ropriate answer lie within four orders
pn~rslc:al environment. easy prC)Cel)SIl1Ill;
rotational one need is for a
environment of two is quite different so
that which is easier to mould is not nelc:essaIlly
,",u"a.J,.I",,-,.t 6 return to the Qu~estJlon

influence of the environment on

relevant to such processes.

3.1 TEMPERATURE AND RHEOLOGY

As heat is SUI)pll!ed nnll'l.1"'l""'" the molecules vibrate more ... ~:n"'11'111"
""",",£"',,,,,, curves for a

of
ll;re:att:~r
at low tenlPerature
very much less seIlsltlve

39
40

\
\
\
\
\
\
,
\

Shear stress

terno.~ratll1·eis the of close theoretical

de'velooiine: master curves have also
been oul:>lis,heci.
from one OO.lvnler
molecular
of tenloeratlure
which
Because the of VIS'C05!ltv
Table 3.1 compares that del:>endel!lce
the different are cOlnmlonllv orocesse<l.
several melts may be found in the aplt)elll<ll(~es.
Because of the non-Newtonian character melts the SUI)er'Dositllon
of flow curves at different a at constant stress means that
there is not a at constant shear rate. For a shear
material on appears to
decrease at shear rate
P,,"u"'I"'rll Features and Flow 41

,
" " ......
Modulus ......

- --

Temperature (OC)
TeIIDPIeratuf!e-deJ)Emd.en<;e of elastic modulus and VUU'0f;11'h.l at low shear:

(-

energy to raise a to a
time necessary to cool a material to a form-stable
are also to be avoided where these may lead to ae'COInpoSltlon
Thus, in we seek to process at the lowest po:ssllJJe tel1rlpc:,ra1tufC:!.
but the lowest often be o01talIleCl
heat The the
dis:sip~ltio.n of heat if the material can be softened
heat in process, excessive heat can
sometimes be avoided at a later
 Melt
Table 3.1 Relative Fluidity Index for an Increase in
of 10°C
Test
Polymer RFI*

Branched 150 1·35

200 1·3
250 1·25
Linear 200 1·2
200 1·2
200 1·7
200 2·5
250 1·9
250 1·5
350 1·5
6:6 275 1·35
275 1·35
200 1·2
200 3·0t

RFI --,-.!!!l~~~~~ at constant stress.

pol'vvirlylchlolride the 'melt' known to be

n:: 1

, ,-
Rate'" I
constant Str~ss
constant
: n =0.2

3.3 Deperlde:l1ce of vlSC:OSi'tv on terrlPelrat1.ire: polvethvllene ten~phthallate

Table 3.2 EX)Jerlmellltai Methods to the InOuence of Pressure on Viscosity
Tec:hnique Operator Problems
Rotational

Pressurised
concentric measurement lDClep'eneJellt
of pressUlrisirlg

Extrusion

Pressurised MaxweU9 Direct descendent of Friction losses.

Westover10 rheometer
l"1U'llll!"TV measurement
derived small
difference between two
pressures

Double-die Choi 11 modification of Pressure delpelldt~nt on flow

method rheometer
l"Q1'\ .. II,:.ru rate and die J?;eCJm.etr'y

Non-linear Porter12
plot
44

3.2 PRESSURE EFFECTS

pressure both free volume and

1"Arlln"",..,·

leaClullg to an in VISiCOS~ltv
of pressure on

measurement
results 3.2 and
Since the influence of pressure on is aua1l1tatlveJlv ""' ........ 1.,. ..
in to that of a suitable way Clel)enlClelnce is

Table 3.3 Increase of at Fixed Shear Stress by Hydrostatic

Pressure of 1000 atm

Maxwell' 50 4·8
Westover and Itow 1000 40 3·9-5·3
270 4·0
Porter12 250
200 30 4-0

nr~~c!c!ln"p may be corlSldlere:Cl

ore:SStlLre. increases the Vl!O:lr-nC:ltv'
necessary to bring the melt back to its on:gm.aJ '''IQr'r''QY,..'1T

turlctllon as

This function has the appearance of a function and it is

oaJrtlculatrlv intc~re:stiIlU~ to compare it with the Isoen1troDlC function

which is the instantaneous tenlperature rise resulting from the aplPlu;atJlon of

pre:sstltre. That function may be cOllVe:nic:mtlly rrleaSUl'eCl in a cat>U1::uv rheometer
3.4 and Table
close these functions that if no direct
measure of the influence of is then the thermo-
ClVlrlarmC function be as a The correlation also SUf~ge:sts
unreasonable between and entro[,v
which would seem to merit theoretical consideration.
Pln1.Q;p.,,1 Features and
Table 3.4 Ratio of VIQ4PNlttv

Polymer

5·3 X 10-1 1·6 X 10- 7 3·3

4·2 1·5 2·8
8·6 2·2 4·0
4·0 1-5 2·7
3·3 1·2 2·8
3·1 1·1 2·8
3·2 1·2 2-7
6·7 1·9 3·5
5·1 1·4 3·6
5·7
3·6
6·7
5·0 SO 1·7 1·4 SO 0-4 3·1 SO 0-5

Pressure
transducer Thermocouple

3.4 Measurement of temperature rise

It is easy to recoa:flise
on ternDleratUl~e
I"n."' ....,,,.1 within one or two de'!rec~s ccent:12r~l(te
theoretical texts asume that inc:olIlpr!essiblle, nrn1.rU1'lnn

excuSle for the

cOlmb.imlticm of high pressure and low temperature

cn'st,llllliatJlon of some so that in some cases
will the material flow
46 VA,h,,,.,,.:>.- Melt J(11:eO,lOIl'V

Strain

Stress

Time
3.5 Evaluation of creep under constant stress

3.3 DEPENDENCE OF RHEOLOGY ON TIME

Maxwell
is achieved.
time-scale of real
be filled
order of

have a cornplete aPlueC:latlon

how that rh""r.lr"nu mt'eralcts
essential to gn'nr~>"l~::t1'~
and
Evaluation of creep eXlpel"lm,ents under constant stress before flow is

......

0.11' l' 101'

Time
3.6 Im~e-aepfmC.1ent apparent Maxwell parameters
Ph\J(,I,f'nl Features 47

109

10·

107
/
106 /
/
105 / G
/
10· /
/
10- 2

Cvclic loading ~ (s/rad) Creep loading (s)

3.7 compan!mn of and osc:lllaltOl:y shear flow: at 20ne

established allows the mtC:!fPret,ltlo,n of tllTle-cler)endelflt alDoBlrellt

Maxwell pal~alTlet~~rs:

otc.Ue:d as a function of time these cornmonlly have the form shown in

where stress and strain are n r.."nr\rt1nn!:l1

evaluation of
as a first
llelrWf~en ani~UUU I1'eQUellCV and time
texts, for eXclm1ple 1-<1"'11*"11,)

a series measure-
at constant maximum
CH}SS'-DI10IS
tlnle-1C1el)erldent, response in the non-linear

t1vln~rnlr aplprC)ache:s, and from

are consistent
time-scale response is truncated.
48
Modulus (N/m2)

...... -- -
...... ......
Stress (N/m2)

--

10 10
Time (s' Time (s'
3.8 DVflamjc response data in the non-linear
0-3 at
retllectlna the of the time-
Df()Derti~~s is the memory which the
nmle-~iCaJLe for which a material has a
the natural time of the the
ratio the vU::,f"nc:tth, flow. the
time-scale of a mattet"tal 11""1'"'1'1\, ..,11 the

Deborah number,
mountains melted from

process
such that if > 1 the process is dominantly < 1 the
essent:lalllv In use of this COflceltn orC)CelSS a)lal~(SIS it
since the material
characteristic of the
material. If we COI1SI(ler of a low stress deformation round a
comer fol:loVl,ed we must
consider two Df()cesses:

= 10
I 100 s

(b) Flow in the die

time-scale of nr£',..p.lOt~
high shear stress, 0-01 s

In this case the remote small disturbance in the streamlines as the melt flows
round the bend will be remembered at the die the extrudate to
even the melt has
dominantly viscous flow in the die
with which we are concerned when collsi(lerling
P"'''~'rnl Features

a low stress deformation is remembered after a

3.4 STRESS

is stress, which may vary

3.4.1 Rupture Behaviour

the stress levels which liquid ~v~tenl~
cOlnp.an~,on with useful solids. water will cavltalte"U
even when all
contamnnants, the

Tnr'I"P/~rf"~ at

often an indication of telltsiotn tliinnilltg t)ien2IVI()Ur

and a transition to SU),ertlclalJly
lDcrealS1I112 the rate at

a b
3.10 a ~UI>erJtJClciUy brittle failure
b failure
50

Table 3.5 Results of RIIIBhlll"ec Stress Tests: Braucbed PoJyetbyl'eue MFI 0·3
Experiment

Constant-force
extension 24
Orifice flow 150 ::::=10 atm
190
die 150 ::::=100 atm
190

bmefrilnglenc;e at the entrance

nnll"C'f'''r~''np COJTef>Do'nome: to a maximum
IO\:4/-c1I~ns;ltv nnlh.lp·th'lI'lp."p the

Shear

0-3
Shear modified 0-7
There is also some indication slgmtlca.ntJy increased by
a small of crj"staJIlS'atJOn.
presence of toreuz:n V-V\.IJ,,,,.,, increases the
to
assoclate:o with such contaminants.
Physical Features and 51

0' 3.0
.,...
'';;

.,~...
"c: 2.0

••en...c:...

PVC at 170"C

o
1
3
5
10

OOSSll[)!e 2eller,al e~J(pl,amltlCJ~nof rupture behaviour is that it is associated

on a scale of about 100 nm. Provided the tensile stress
n""i~u1l'..... 1r
enOUJlln. surface tension suffices to such faults stable. Ho,mC.2elmSlil-
In'u'U'n1lTPri gel:atlCm in PVC achieved use of orC)Ce!iSllll2
nVIClrc.st::ttlc pressure all to reduce
characteristic of Whether
tun:Clalnelltal to material or an artefact remains to be estaOJIISJ"lteCS
theOff:tic.al work .
... , ....'V~'... L.., is the ultimate method of failure both in thin
sections such as and fibres due to rlr!UXT1ln('r thick sections
where the solidification stresses cause in both those
extremes normal is most cornmonlty an intermittent
effect with stress and is most ....:><::.£UII"
achieved notches both in the material and in the
is also the critical in the initiation of 10c:llmln2.

3.4.2 Elastic Response as a Function of Stress

When an elastic band is at low stress the deformation is ...."£, ....., ..1-....... ,,,1
to stress and at stress the a
The same qualitative reSPOI!1se nnl"n,,,,,,r melts.
For nn,l"rr.,,,,,,.. melts the bulk mc.csuJUS some five orders of
t1'''''''.'.:lt-.,.... than the shear mCJtCSutus for purposes,
 ratio may be taken as 1/2. The bulk modulus
""rulc!c!L'l.n'C! with hvclrm.tatic
accord!1D2 to:
+9P
When is the bulk modulus at pressure P above atnlosphc~nc and is the
bulk at atmlosptherlC pl'eSS111re.
The shear and

In may a critical role in

,",-"U.'U..,"'''''' 6), and the faster a process is
elastlc:JtV is also manifested in the
have a

3.4.3 Viscous Response as a Fundion of Stress

The non-Newtonian behaviour of polymer under both shear and exten-
rec:enred detailed treatment in the and models of
sotlhl~itlc~atl()fi have been to the del:>enidelllce

At the um.opJI11S1:Icated level it is worth nhCtPT'lI'lna that the model

des'cnll)es the qualitative of melts to both and extensional stress.

~
branched

Viscosity ~ Viscosity
linear

wide molecular
_ _ _ _ _ _ _.........;;w=eight distribution
Shear Stretch
3.12 shear and extension: the distinction between rotational and
irrotational flows
of course, to real rather than the cl1()Pt:)ed
"c!1.~111" lubricated with tomato sauce. If a bowlful real
h,P'!:I'lftiU

dj~:211112 in a fork and

move it from
,..I-ntc-'p,,.,1 Features and 53

3.4.4 Modification of Rheology by Mechanical History

rl4>l'!~T'int1,.... n~ of assume an state as the
nT'~'~Tl~~1 pr{)Ce~;su1Ig sItuattlO>DS, material response at any
nT'~.'t1U'Ul~ thermo-mechanical

reductIon in

eql1ilibri1um will reflect the eql1ilibrium nr...,.n""rt.,,,,~

eOl1ililbrilum may be Slgll1ltlcarltly imt>ro'ved
me~cn,am,cal urr,.rv,"nn may be the most effectIve

Table 3.6 Modification by Mechanical History: Branched Polyethylene

MFI 190°C/1'16
Melt Dow Swell
Thermomechanical rate ratio
0·28 1·47
Shear modified 0-66 1·14
After solution and 0-27 1·47
54

3.5 DEFORMATION GEOMETRY AND RHEOLOGY

There are three distinctive 1!e()metrJes of deformation: shear and

3.5.1 Bulk Deformation

When are to hvclrotstaltlc
in volume. If the stress is a hV41rotstalttC

mClenenl(1eIlt of such factors as

cnj:ln,~e in

solidifies
lead to most cornm,onllV ~t'\n!l,rpl'lt
frozen-in stress or cavitation.
An class of pr(.ce~~sU1lg olperatl(m
50 per cent eXt),anS:lOn
of gas reJ~~ase~a

3.5.2 Elongational Flow

material is drawn from one cross-sectional area to

3.13 Elclnglltlonal flow

Such flows dominate the and vacuum torJmlIlg

nroices,ses and indeed the whole class of be termed 'free surface
rn~·nlrul''!.1 in flow is QuaU1:atlveJtv different from that under
Physical Features 55

Cross·sectional area A
Draw distance s
v

Force F

3.14 Stress variation in ara.wU12 of an extrudate

volume flow rate
Vo at die
v
U.,.I,~t"ljr" at haul-off

stress
sut)lej~tof a

close approximation to
that the stress

(JE FIA
has its maximum at the nalLU·IOII where

The total in the process,

e
the time-scale of the process,
t slv
Comt)InJtn9; these we obtain aDllar,ent extensional vlscmntv

This derivation assumes that all the response is viscous flow, an aSSUlTlptlon
which be if the melt is inelastic or if the whole nrr~",.,..~c
the elastic is saturated
rellatl()flShlP will be
obvious siglnifilcallt tensile deformations can
constrained flows whenl~Vf~r the streamlines converge or
dl\l'en:ze--t()r e;"arnplte in the and exit of in calenders and in
3.
 , ,

I ,
a b c
3.15 Tensile deformation in constrained flow
section of extrusion die
' . 'n ....................

c InJection mOruldim~

3.S.3 Simple Shearing Flow

a deformation but also a
to the rneolo1fOc;al

a b
3.16 a Flow between reilltlv'eiv surfaces
b Pressure-driven flow

lrnlnrn·t~t1t t1lttl"·t'Plnt"I"·"::between such flows. First is the qUl~stllon

rel=:ttivelv mO'Vl1l12 surfaces there is the
adJlesilon lJet'wee~n the melt and the
nvclm,staktlc pressure COJnponc:!nt

nomc,genec)us so that is
exl:ra<;tecl. that heat must first traverse the
rpl~tivpliv mlOVlng surfaces ClOmlJna1:e
cornmonlly found in dies

are ImlDOJ1aIlt tensile contributions practical cc)nstailled flows

O/n,,,'''''''/ Features and

3.17 Shear effect a sQuleez:m2 flow

aDI)earS to

3.6 FLOWS HAVING COMPLEX GEOMETRY

of
UI",,,,"OIl"hi i(len'tifit~d the fact that
....,..1'11...... .,... pr{)celssil1l2 we find many flows

3.6.1 Superposed Shearing Flows

We have noted two
that between rel'lltiv'elv m(JIVU1Iil

3.18 Pressure-driven flow thriOull~h an annulus where the mandrel is rotated

how such flows may be treated we consider a pn~sslJre-dr'ive:n

an annulus
tnrlOlUlrn the mandrel is .." .. ,.. .. "",rl4,,*
is the volume flow rate and !J is the rate of rotatilon.
extrusion shear
rotational shear rate, =2n:RDIH
normal addition pr()celc:tur'es.
total shear rate, = +
 58 Polymer Melt Khleol47flV

The eftiectlve VISI~O!il:ttv

the

p=

aplJarem Vl(:t"n'~lhl COI~re!)Po.nd1D2 to the total shear rate in the

Table 3.7 Calculated aud Observed Pressure Drops io Helical Flow for a MC1IUJdliog
of PoIy(methyl at 230°C an annulus of
30 mm, H of radius 9·75 mm at an extrusion rate

Pressure drop, P
Rotatiooal Total shear

22
11
3·1

and and to mU'0(11uclllg

3.6.2 Pressure-driven Flows in Channels of other than Circular Cross-section

ideal cross·section. The fol.lm~ll1l~

For the of flow an:::tIV!i:l!i: cOll1lplex
3.
L of the channel land
A cross-sectional area
20 of the minor axis of the included of area
2b of the axis of the included of area
2c chord the axis of the die
PI"I'lHcir,nl Features and Flow

3,19 Flow anatlVSIIS: parameters descritting

From these pal~anlet~ers we may define the dinlensio:nle:ss
a
X=b~l

y= 1

WOlrklf:l2 re~latjion:)hiI~fur
can
cOlnolex cl1,mnels can

estjibli.she~d formulae:

Shear rate
Stress
Ull"..... tr ....u.. shear
y= +
shear

Pressure

= 1-0
Swell ratios for YR >

dies (
60

Swell ratio for zero ."",.,,~ ..... ,

( B.,Bb : (exponential (vii)

Dies of
zero

3.6..3 Converging Flows

In rnl'V""rOllno of a an extensional
flow is sUJ)el1po~,ed flows are much more
Jde~alJ:secl flows
in the as to
1) that when two ","".ar'ln ...
mtc~ra':tlOln and umloubtedlv
~hl'''~rllno and an extensional
dallnting cornplex11tv if the full were made. a
Quanltitaltive the strain rate histories shows that at the wall of the
,,""llnL"U"l1 is zero, the shear strain rate has its maximum and the

extensional strain rate zero, while maximum strain rate occurs

where the is at its maximum and the shear strain

PfC12nlatic view thus aIJows us to the interaction between the flows

COlDP'ute the flow as determined addition of the shear and extensional
One ilie fur
cyfmdlrtcal flow:
pressure +
where is the COfltrilt>utton due to Sh€~arl!Dg flow and is the contribution due
to ex1:en:SlOlnal flow and
tan 8

where ro is the die radius

rl is the die exit radius
8 is the half of convergence
OSI is the ,shear stress to the shear rate at die wall at the
Yt = the volume flow
n is power in the relation:ship
OBI is the extensional stress average extensional
strain rate, £1 = tan
1.1£.. , ..."",,1 Features and Flow 61

3.20 Extensional flow and sbearu12 flow in a .. "' ....""...,.1"1 die

shear is the dominant flow

rel:atl()nSblp between flow rate
COlnp()llelnt At about
If

stn~tcl1liD1:trate
rupture, the
At the
becomes
we

mm

130 S-1

for streamline

therefore
tan (J = 2 x 7/130 = 0-1
whence the half of convergence 6 rI"' ....."',"'.,
62 Melt Rheology

were used to effect the whole of the reduction from 20 mm to

the length of the would be such that 91L = tan
90 mm. For most purposes such a would be
ex(;ee,om2lv long and would to Thus we
a sut)SlCllaJ":V at what diameter is this "'ctor~"',..o.rlf·1
A taper would be 45° and so, since the
7 we have
tan i.e. 7
i.e. r=
we may dele1u(;e
14 = (4 x
m and ro=2·2mm
nr~,.tprrp,rI die for this extrusion is one that reduces the overall by
Further optimisation may in be by

"'"..",""."' ... '1 ....... flow, swell ratio is taken as

oOltential "'""..... ,...h........, ..." from """""'''1"''''''

and from extension;

exp ERI

COJrre:soCtndine to the stress at the die exit

COlrre!mcfndine to the extensional stress at

.... """,11""''''' and dies with contraction

from 0-01 to 1·57
U!:ll"'!t1'1i'"

for flow

value deviation
Pressure 16%
Swell ratio
taD.en:~C1
annular radial
In any of
I"'n1"''''''I" ...ii1'1O' flows it is necessary to bear in mind fact that the
ex1:en:sioJnal vi!itl~os:jtv may be several orders of "'''''''!:li'.", .. than the shear

thus, no matter how to the

extensional should never be since it is which are
likely to the stresses the material and so determine the
quality
Phll<'lr'fll Features Flow 63

3.22 Die that allows reduction of L

3.6.4 Extrusion of Sections of Varying Thickness

In such as extrusion blow it be desirable to extrude a
tube wan thickness so when tube inflated into the .......,......... ,
the final wall thickness can have a desired variation. A case is
the of a tube into a where a uniform wall
thickness is This can, of
the die to the
non-uniform jntlatllon

8 b
3.23 a Uniform parisoJ!l: thin-cornered mouldm2
b uniform thickness of mouldmg

one section of the the melt will flow more r~l'\u11Iu

may cause the paJ1SOin to 'banana' or the end to
cannot be To overcome this
an additional to flow is thick-section passage. Most
extrusion dies need to be well with a acceleration towards
the die In one the around the is so that
..... '.f'' '........ 'I.1""I,nr'11tu and variable and
can be calculated

relatlOn:Sblp shear stress to

of
SeCtlOllS <>,..",." ... the die we see a Qua1i1tatiive
£'1
64 I'rtl\1"",(1'" Melt KnleOlc:»gv

Pressure equa'
~
1
.. -'-"
"
1
Thick section
Thin section
at low -+ HN +-
Uniform velocity
c
at velocitv
velocity b

~tt"~lt,,"{nr has been used to obtain a variation of 50 per cent in

pal~ISOln tJlllCKness~ in it has to be to maCfilDllllg
has to be means of a

3.6.5 Biaxial Extensional Flows

makUllg direct measurement of extension
aplpre~claLtI()ln of such these are small in
encountered the of biaxial extension.
Measurements made on indicate that at low stress the
modulus are and shear response

Modulus
shear G
extension 3G
Pure shear or 4G
Uniform 6G
much less I.U'-''''""U some indication of the
(JeICluc!eO from studies on solids
Ilm.lUrlg elastic response in extension is the

in
this may be more

+
PhUC.Pfll Features

---.,.",.,.
10. 10'
Tensile stress (N/m2)
3.25 Biaxial (- - -) and uniaxial extension: toy balloon rubber at 200C

where D is the draw ratio in the direction of and B is the draw ratio in the
of the sheet normal to the direction of .....,"'nujlO,. This should be used as a
ull1.rlriinn since th"~nr"O" SUj~J!:e:sts
any
nel:essaI"lly be tension and
nV1Doltne:SlS which is of response
mono1tllalmelflt rllr~uJ'in{1' and film we may
rnt:~OI()2V of biaxial flows.
a dominant role in film DlOWlrU!

3.6.6 The Viscosity Interface

If a melt flows
dltter,ent one of two
uu:!,f'nc:!.tu

Slt1Jatlofls can occur. the

before whereas
through
If we cOllsuier the of the central of the interface then we
define an acceleration factor N such that of the interface is
where Vis the of the in uniform VISICOS,ltv tube.
if M is the of viscosities of new and old studies
mdlca1te values for N as shown in Table 3.8-a may be
 High vis1coslitv Low viscosity

3.26 Interface behaviour of melts of different uuu'nc1tv

Table 3.8 Effect of 'H£'........rih' Ratio on Centreline

Velocity Ratio

ratio, M Centreline
1()4 0·55
1()2 0-65
10 0-80
1 1·00 Stable
0·1 1·20
0-01 1·32
0·0001 1·40

Skin too viscous

Skin too fluid

8 b
3.27 Sandwich mould!m~
Phuc;ronl Features

of nr.I""",,,r
if
pffiPrtlvP
the new is of lower a
on the wall of the machine from which it
viSicm.ltv of melts is sensitive to teIlt1oe~ra1turc~,
own source of non-

The above
this
COlnoletle. it indicates that that
oot:imi~ationandex~.loi1tation,

REFERENCES

L N. and Bulk "tel'ne.t" of Dolvmc~ric ':)1'':)I',",U',:). Journal

37,
tJ(..lir;;;ru,;.r;;;.

2. J, D., Viscoelastic Prl'linprtiPfl Pn#Vn1prfl 2nd "''''''''U,II. ,",uat.Jt,",l

3.

5. Johnson.

6. Malrkm,ritz.

9. Ma~"weIL
68 Polymer Melt Rheology
to.

11. Determination of melt VIs(~OSlty

an extrusion Journal
12. R. R. S.

13. pb~rsic()·ctlemlical pro,perties of

14. Lm~SWE~1I

15.

16. MelLssnler extensional rheometer for uniaxial

extension of pOIvmc~r 16
1972.
17. Macdonald, I. Transactions
the Khlf!0IC1R'V Small deformations
International on
H. Influence of
non-Newtonian

18. J. J., '-'Vi~W""U. dVlllamlc response of

viscoelastic
19. Deborah and Barak in LJetorP1Ultiol't. Fracture and
H. K. 1960.
20. D. C. F. and

21.

22.

23.
24. Swcerdltow

Rip'pfr;no"pn/~p to Studies
communication, 1979.
27. me:tl:Ulcr:vla1te C4Do()lvlnelrs as aids
28. ShtJrrk.f,kin.
29. nolvmcer melts, Plastics and PnlvmpY<il.

Comparllion of the elongcltio:nal

constant strain

31. colnp;ari!son between

YnIVPn,r:-r bnJllrneC:!rtfllJl and Science.
Physical Features and Flow
32.

33.

(with 382

35. pOI,vm,ers in uni·

11

36.

rhe:olo~e;lcal ec::tuatl011S of state, rr()Cec~all'tgS

mtc~e;nltteastrain
1966.
39. AJ ...." ......"'.

40. Middleorlan,
41.

cornp()uI1ldlIle; and rheolo>e;lc;al

M tJ'tpriwl,fi: and Ap,pUc'atllms.

Applicatic)O No.

44.

45. elone;,ltIOtnal flow of nnlvml,,:r

46.
47. Plastics

48.

52.
70
53. "'--'VI~"WI;;U. ·nn\/.,.,.'lYln,n flow and flow: a cOl1npilabon. Journal
4, 23--38, 1978.
54. of melts in extrusion

55. '-AJ1i/:;:)WCU.

56. lDI1ectJIOn mould Plastics

57.

58.

59. R., Biaxial extension of an elastic

60.
61.

62. of non-Newtonian fluids-a

1971.
"T.J.J--.....u.

63. conlmutnic,abon, 1974.

64. Sandwich Plastics and Pn,fllnlfPY!.C 39,
Rheology and Structure

Easy

Difficult Service properties

Poor - - - - - 1___- - Excellent

4.1 ,h.,." and ease of prClcesismg: a common

.....n /....,. ..

4.1 CHAIN STIFFNESS AND CONFORMATION

,," ........·h .... "'1 alPP1reCIatlion of how chemical structure influences chain tleXJtJ.tll1:y
be obtained of molecules from
this means the molecule of is
fle,[ibl,e, with full freedom to rotate each of
nalrahvdroJrv benzoic acid has little freedom of
... "".rttl'" of the aromatic and intractable as a
72

H H H H H H
\ / \ / \ /
/C,/C,/C,
c C C/ Polyethylene
/ \ / \ /
H H H H H

Poly parahydroxy benzoic acid

4.2 bXclml)leS of Dolvmc~r chemical structure

To determine the influence of chain stiffness and conformation on rne~0l()2V

we must first seek some of molecular size2 and draw a
cOlnp.an~;on between and a of the of the
melt.
 73

4.1.1 Chain Length

For a nn·lun""" .. the is oDltaule<l
from
L=
where is the and is the molecular of the unit.

4.1.3 Molecular Aspect Ratio

Returning to the of molecular
we may an1ticioalte and diameter
to a first aPlprctxiJnaltiolll, COllsi(ierine; a constant
ratio of we may deduce
molecular

In the which follows we consider molecules of

of molecules useful ","'L"~ ""r"t.", ...
....

on
narrow mOtlec:uUlr
obtained in the polynlerlsatlon
Table 4.1 Rheology Parameters related to Molecular Aspect Ratio for Common Polymers
Aspect ratio tOOO
At Tg + 200"C
D M
Polymer (m)
9·1 x 10- 12 -20 180 770 5·5xl0- 10 60000 1-2x 1()3 2-0x 1()4 6·0x 1()4 3 0-06
6·0 10 210 770 6·7 110000 0-8 1·0 4·0 4 0-08
4-1 50 250 730 8·4 200000 0·4 0-5 2-0 4 0·08
2·4 100 300 950t 9·6 400000 0-3t 0-5t 2-0t 4 0-06
4-0 60 260 BOOt 6·4 160000 0-3t
8-1 -10 190 1190 4·7 58000 3·0 10-0 20·0 2 0-03
7·6 60 260 1010 5·3 69000 2-0 10-0 10-0 1 0-02
5·6 70 270 1210 5-6 100000 5-0 10-0 30-0 4 0-06
5·3 40 240 1086 6-1 120000 2·0t 10-0 30-0 3 0-02
2-6 110 310 1020 8-5 330000 3·0t 2·0 8-0 4 0-15
4·5 220 420 1060 6·7 150000 4-0 8-0 30·0 4 0-05
3·2 -120 80 950 8·3 260000 1-0 1-0 2-0 2

Estimated accuracy a factor of two_

t Indicates uncertainty because of either temperature or molecular
 Structure

For the sake of this cOlnp:aru;on we a sinlplifie:d view of

in the form of three pal'amlet{;~rs:
the at a shear stress of
the at a shear stress of 1()3
at, the shear stress at which
is a of non-Newtonian behaviour,
From these three terms we may derive the palranlet1ers
fO and
The former is a characteristic or natural time the latter an elastic shear
strain or function.
Melt rne~olol!V <l~eDen<ls makInlg as
necessary to make any
The choice

mc'le(:ult!S may
Intl"\t"tlun~ltpll,\l the calculation of can
metnet<l of measurement an the
",,,,,,... +1,;,,,•• ,,,,.,. values I work from that

Table 4.1
magmtueJle for rioT"''''''',,,,,,,,,,,, nnihln'&>r~'
we of the structure.
attribute the chain stiffness to the t1e'~ibilitv

ratio at 200°C above

but variation
so that the ratio
H.lVUU.JlU.".

From this we can deduce

on the stiffness of the chain.
the non-Newtonian of the as defined the shear
the has decreased to one-half its low shear also
varies with chain a correlation between
non-Newtonian flow and orientation,
The which seems least consistent with the is one
 Polymer Melt Rheology

Table 4.2 related to Molecular Weight: PoIy(metbyl

methacrylate) at 210°C
Weigbt ... .,..,.n"....,
molecular
34000 600 30 x 1()4
75000 2x1()4 16000 8 x 1()4
160000 400000 3xl()4
360000 8000000 2xl()4

tleJnlJlle comonomer in
tenlJ)erature and so the ",,,,£,,,,,£,"tu
and so is by
flexibility of the lJac:klJ4one by the use of the comonomer, or by lDCre(llSllll.2
effective cross-sectional area of the molecule the of pla,stic:Js~'r
the to an enhancement of non-
Newtonian behaviour and so a further reduction in under any
high shear condition.
Thus, as a aplprc.xnnalt1011l, we can observe a common n~t't"U"n
determined their cnt!ml[Cal
ture. may in two ways: as a which to Drc~dic:t
the of a melt from its chemical structure, and a of
dependent on chemical and as a framework within
more detailed to another.
is not a rule
consistent with an intuitive a01Pre:ci3ltloln
eXlstelnce of such an empirlical
to such a 'rule' and
and the~exc~pltlolns.
One such exception calculated that
rodlike
predlc1:lOn has
Xhleol<,R'Y and Structure 77
low 'H'c:!,f"'nC!1t'l state is only seen once the material is sheared
rest there to be evidence
results that it is not
which the 'H1c:!,f"'n,~1tv

4.2 CHAIN LENGTH AND LENGTH DISTRIBUTION

Molecular det.ermliniJlg the

eXI)rel)sictn as

That rell:lltIOlrlSnllJ) true for a narrow range of molecular wp:tottt~· a

sug,ges,ted aJ)l)earS more aJ)1:)r01Pn,lte:
+

that the 01"P'!:lt&> ..

the orCIOalJlllltv
down under
Molecular del:me:Cl in many ways, of which average
and number average are the most common:
Mw==
==
one which may
different m,ole,CUHlf weiolhtliL For
to
 104 105
Shear stress (N/m2)

ble~ndin~s8nllplces of different molecular

COlnoc)ul1ld blended
conrtoound blended

Number Oft
molecules

.....
",,
a

b
4.4 a Molecular
- - broad
b Narrow en1tan2lements per chain
c Broad MWD,
Rheology and Structure 79

Molecular Distribution
A major variant on molecular is molecular distribution (MWD),
usually poJlydlspiennty index as the ratio of to number
aVf~ra"e molecular
sarnplle has a narrow molecular
a similar of so that
stressed flow. In a of broad molecular
chain molecules appear to form a nriltp4"tnrp netvllork
hrA'thr~.. n 4.4).
assurrlptJlon that it is the which resist del:onna1tlOll,
nnlh,",,,,,," of broad molecular

amount of the total stress.

causes elastic response in those which is
retarded by viscous resistance as the smaller molecules conform. in a
<HU'nnll"" of broad molecular distribution there is more elastic
response than in a of with narrow mCllec:Ul,lr
dis.triltlut:iOll. but that elastic response is OelaVf!O
c:

-...
.~
( /)

j
- - - - -
Q.)
>
8
Q.)
~~ __L -____________________

Time
4.5 Effect of MWD on strain recovery after flow
~ - broad MWD, narrow MWD

If we assume that it is stress which orients the so reduces

enltangle~mc~nts, a second consequence of the uneven stress is that
the at a lower average
stress tail is in on of
a of low molecular the flow curve shows two distim:t
transl1tloIlS of non-Newtonian response: the first occurs at a low
~vp'r~('J"" stress is the few long molecules, pla.ClIllg
stress; and at the same stress
ummodllJled low molecular The more
response for of
tion shows a more .... r<:>£111·"'1
Note that while two nnl'Vn1f""rlO: Ill\JlstI'atf~d
VllO:f'n<r;!1hl under Melt Flow

be several orders of malgnltU.de tTr""<lf'~.. r

dis1triblubon. while at
sel,ectmg materials for such aplPllc::atlOI1lS
pf()ce:ss(llbi1lity low stress form I:!tl:lhilihT
the molecular distribution. Howe'ver these ad'vaf;lta,~es
str,eDllltn pr()perti~~s associated with the low mCIlec:ulclr
 Polymer Melt Rheology

-
", ,
,
" -
103 104 10'
a Shear stress (N/m2)

,,
,,
,
\
\
\
\

\
\
\ I• I

\' ,
I

•1\ •

104 106

b Shear stress (N/m 2 •

4.6 a

- -. 185000 15000
J(/i:eo,toR.'V and Structure 81

4.3 CHAIN BRANCHING

Linear molecule Branched molecule

--------- -+ .-
c
4.7 a Branched and linear molecules
b Shear flow
c flow
 N 106
E
'fii
~
~
8
.!! 10 6
>

104 10 6
a Stress (N/m2)

---'""1.""",----
Stress concentration

/ ~
Tension thinning Tension stiffening

Necking Uniform draw

b

strc;~tchin2 flow behaviour of linear (- - -) and

branched MFI 0·3 at Istre
b Effects of stress concentrations on flows

Thus similar in other tests

may be a to stress extensional
flows. The for the of to
increase with stress means that local stress concentrations are less in
H.1l~eolof}.~v and Structure 83

flow
br<llncJllln:g, it is far
trec]uency and how the OfalnCJlleS

"'.C,"'''U:'1t"U on ternplera,tU]"e

twice as sensitive to ternp~era.tUJ~e

clear that it is not the short l"U·"''''f't''oAC
ch~m2Ie. since the t"Al'nn,"'1"Q,tUI"A cs=>nCl'iti'l,rlhl

We may also note that the

sensitive to mechanical
There is also evidence
are rather more shear thinniln2
These ....++.....'An.,..""..

4.4 MORPHOLOGICAL STRUCTURE IN MELTS

find a basis either in continuum or in

substantial evidence that the molten
" ...... n1"..... h,"'> .. " but contain other levels of which

that is cornmonJly plroc~~sst~d

nnl11I'1'1''''''
content and for
,..,..,'"+'',110 ....''' there is
" ... ,... "",,,, of scales from
cluster flow
mC~lec:ulf~S are to accrete and flow
assurrlptiion for such flows. The size and
between" the clusters are assumed to be ,,1"1"£...... ""1'11 aepel[)aC~nt
for it is a feature of all where a
that the is very sensitive to such
84

cry'staJltIle polymers often po!)se~)s a remarkable memory of that

rec~ry!itajllisling in the same to tenrtpe:ra-
tures several tens of above
nnl!vrnIPr.;: is accentuated

to
In we noted three ditteren~t::es
in extensional flow h"",t'Hnl'I011r

in the of the rhe:ol()gy

history. features SUJ1~ge:)t
determined

me~ch:amsm is identified.
While all these responses are highly spe:CltllC be considered an
exception rather than a rule, there is nOltnlJ!1f.l. sensitivity to
thermomechanical which distmgUlSh(~s rlle(JllO'~Y of such "'v~tp",,,,
from that of 'normal' It presunrled
which can be djscolmt~ed:
dramatic effects onl~mlatll1lg
structural effects may
essential to note that a prC)Cel)Sll1lg opelratltOn
that the of a material

4.5 BLENDS, FILLERS, PLASTICISERS AND LUBRICANTS

It with be noticed that nnl'l1rnp.n:z
pla,stl(~S but combination with ad(llti'ves
serioulslv deficient.
 85

,,
\

,,\
103

" \
,\
102 '\\,
\\
\ \

104
Shear stress
higll1-visco:sitv incl[)mlpatjlble nnhilrnprc at 275°C

staOUlsers, mould release

nnllvrntprc aimed at
COfltiD:nilllg refine-
O'TP'!:ltl'"r S()Ptllstlc3ltion in the

and apt>ears
pr(,l)al)lv aSSOCJ,atc;~Cl with very
CllSpeJ:SlOin at a 1 ~m level. The flow
be deformed to an empS()lo.
lDCre(]lStrl2 the surface area . That work to be but
such work is recoverable on removal of the stress as the reverts to its

it is desirable that the continuous

"'n ... "'t ...nrot ..... n vu.,uu,.:t.
so that work is more
u.", .....-u,d-" done to j:lrtuP"'p
it is to construct a blend of a amount of 10vv~v]iscc)sl1:v
with a small amount of this most
86

.:......
.. ~
...
"...~
". "....

Shear stress (N/m2)

4.10 Blend of InUJr_v1'i:t"n.~ihl DOI,,,mers at 285°C
66
... "Irtn" ........ blend
lOW'-Vl!,CO!mv cornp!Jnfmt. The of blends is
the concentration of the
A review of the

- --
- ,
" \
\

10"
Shear stress (N/m2)
4.11 Effect of low ratio filler
Q
Base MFI 20 at 130 C
0·29 volume cone. aspect ratio filler
f(hlf!OIC1.2'V and Structure 87
mc)Ortlccltl()n, tend to increase the U1Co;,f"flC!ltU
prc~po:seo to describe
MalrOll·Ylerc:!e n~latl0nsllllf), that I have found eSP'ecI:aUv

"
",
---~-~ ...............
", ...
"
\
Stress
4.12 Effect of filler concentrations
Base pol'ymc~r
Low aspect ratio fiUer
Agglome]ratc~d low aspect ratio filler
aspect ratio fiUer
88
resistance to
COIIIUloction with

Molecular

----~r;::;.
lUb'ica1.1
Plasticiser Temperature

Log shear stress

4.13 SUlnmarv of factors afft:,ctiIlg the Vl!i:(~ositv of pol~rmers

SpatC1l1lg out the molecules. Their most obvious effect is to

tend to reduce the elastic modulus of the
stress. The effectiveness of a platstitcisc~r
cOIlcentI'ation, cOlnp:atit)ili1ty and "1C.(,l'\C~tf''I.1

or extenlau
The effects of fillers gellerau~,eCl with
the other factors mtluenC]lng 'liQ,('ru~thl

1'">-.,._.....,"', the mtJlueloce

microstructure of the ......".£'1.. "'1-
factor, The pr(.ce~)sil1lg ht",t", ....,
 89

structural is sometimes the shortest route to i"1~rit"l1tni(Y

a situation. To this a simple measurement such as Melt Flow Index on
base polymer and the end-product should be included in all studies.

REFERENCES

1. Courtauld Atomic IYIUUta:s.

2.
3.

4.
5.
6. Morgan,

7..HU"I\.~U.

8.
9. 11,
10. Uraesslc!v

12.

14. J a\.uv li\..

15 .......... '.h'VU.

on the Structure

Journal Pn/u.,...." .. Science

90
19. C02:swell. On the Formation Molecule
oresented at the Inrin"t,r'u C:on:ferienc:e on
1980.
20.

22.

25.
26.
27.
28.
29.
30.

31. sUS,peJIlSliOns from unimodal "l(:f'n<:lhr

32. of the effect of mIlectJlon

on fibre orientation in fibre filled nolvnl'onv-
Journal Materials Science, 13,
,-,"UIULI""'J. Five

Adventitious Flow Phenomena

The success of a plaS{I(~S pro(~eSSm2 opelratl!On not

.,.""run',-",£! the aclue'vln,(1
a desired of energy, but also
the The most obvious ex[)re~;sJ()'n
is the occurrence of in the
CO]npleX is the of order in the
dlt:ter~ent directions
92 Polymer Melt Rheology

5.1 PLASTICISATION

All machines have a limited cal,at'1111tv incidence of a

slightly surface flaws) above a critical output
rate, largely mClep,enlaellt of such factors as nominal melt tenlPeratlure nnlun"tpr
grade and die is most commonly ascribable to
this limit. The fact are continually pushed to
makes this a common form of defect but one which is ex1:relrne.lv
positively to ti1pntt1hr

S.2 CHEMICAL CHANGE

cn,lnll~e alters the structure and so nec:ess,anJlv

~ueo'r~CJP time of a melt prclce~.smig oner'abon--t1vnil~alllv

average dwell
broad time distribution which is eX~l22terated
scrap material. Further, the history is
elements pass a mechanical
proportion may be shear (for eX(llml)le,
the flight and wall). In a well streamlined flow
small spaces where material may remain static for very
but from which it may disturbed to enter the flow. In a normally
stable melt it is with such extreme elements of material (maybe less than 1 per
cent of the total that we must treat, and with their three products:
crosslinked gel particles, low-molecular-weight polymer and volatiles.
If crosslinked particles are formed in the they will <::In,....,.<'.:.r as
ne1ter!()2Eme:It1C~s in the final product. Because the are rubbery, can
deformed and attenuated and so with a remark-
As well as product quality, may act as
strless,-concc~ntrating features nucleate other such as rupture in film
or fibre pro~ce~isin2.
By serves to lubri-
cate the flow. held up in a dead space, may to
do no harm, but any continuous process has some instability
which serves to expel such material at random the main stream.
When this a local of the flow is lubricated and eases the
flow in that rise to a thicker with a long fading tail like a
comet. on the of and the with which
that enters the flow, defect may appear or mild
and continuous. In the latter case it is sometimes problem by
the deliberate addition of a lubricating well through the
polymer. Because the low-molecular-weight polymer is as a lubricant
it may be difficult to make a positive of this
nomenon, though it may be to construct lubricated
situations for comparison.
Extremes of may lead to volatile formation producing bubbles in
Adventitious

5.3 INSTABILITIES ASSOCIATED WITH A CHANGE IN VISCOSITY

"-'_ .. ,"'.....'.., .. 3 we noted that a melt of lower

while a one of
In the former case process is the latter may
to come to equilibrium, elements of the hlah_\J'1~1'.n~11rv
melt the flow for a prolonged period. In the flow of one n~il""""A"
another it may then appear that the flow of the lower UtQ,(>nCl'lhl
inferior-the meek often blamed for the ...1t"."'r""lo ..'1'f'u~"
extrusion to select an op1:imum material,

5.4 INSTABILITIES IN E.tA~L.lUJl::..l 'U:!.tUI..JCI SYSTEMS

or ntg~n-lrnelt1[lg
nQ,rl'tr'iA'"

of similar magmtu(jle
as in film or fibre
exalgg~erated in appearance and may act as
94

5.1 Flow in a disc

Maximum orientation
- - Orientation in final mouldliml
:5n,laU12 denotes orientation frozen

5.5 MELT ELASTICITY

U.I'''''''~,.V'' mouldine: by means of a

that it is
That
nr(1.C11](~e both
skin of the
""..."""'+"" ... + in the central

lDllectlon uV,c"L.J..",. The mae:ni.tucle

m<!lgnlitulde of the stress
the of the mouldmj?;.
orientation vary with ))Oslt1:on
mechanical n ...,(~n",.rl ..
::>",
Adventitious Flow Phenomena 95

Weld
line

5.2 ~el)afl:lttclD and reVl1eldlin2 of flow past an obstacle

to millimjsiflg
onenteo, but that OnC;!ntiCltlcm SllOSC~Quentlv
Because the relaxation of order is a low
the relaxation time of the materml--ttle
A indication of the relative rel,aXattlofn
to be of materials and under
different conditions is to COlnp,are the characteristic time of the material with the
time scale of the of Deborah Number low ratio
indicative effective relaxation.

5.6 MELT MEMORY

The fact that melts possess a memory, rise to such effects as orientation
and allows to remember non-uniform
ctetects. of which and lumpy
tre,QU(!ntJIV encountered.
pa~;Slfllg an obstacle and rewelds downstream of that
in the of the weld be
96
time for the relaxation of those local stresses. We may note that
mcrealSll1Ul the of the reduces the rate of rel,aXfJltJO,n
sec.anltIOfn occurs in the shear
teJ111pt~ralturc~, nor pressure will ehInin.ate
dlsltnbute weld such PflltlCl[)leS

i round
~ across

~ round
i across

aU across

5.3 Weld distribution means of a mandrel

considerations The
t>eJldlnf! of the streamlines under such if at die
may cause the extrudate to bend or 'banana' an effect which may sometimes be
nA ... " ...... "" the

...,&:•..." ....." of laminar flow fields.

the case at the of
oDmple:x and
""l"l1it'.1I'1'I;1

mtJrodluCltnf! a relax,ltio'n zone

In all these cases the relmjrernell1t in the material's

It matters not at all if that peJrturb,ttictn is small in to
strain histories: some memory of it will as as the
characteristic time of the material nPf'tnl't(!
Features such as 'choke' ... o.,~."£""''''
and so in the process, and can IffiIOr()Ve
wiJI do to relieve a heltero,g4em~OltS
cannot be de!il,grled
•...,.,,,....,. •.*<:"',* tool.
Adven:tittc,us Flow Phenomena 97
5.7 MEMORY IN STRUCTURED MATERIALS

ma1terials~ of
structured melts whose orJltartiSCllti(Jln
thermomechanical

tellll[)C~ra'tur!e.
oro(jtucces a easier tlo~Nmi!.
_'-"""'r",,,,,A each deformation
tenl0e:rature than the oreCe<llln2
should a ma1tenal
tp"'InPT!:ltuTP and shear than its ...... n •• ' .... .,

2eJlerate a new, smaller structure

it cases the act of down the eXlstuI2
structure to form new structure may not occur so that the matenal
is left with a he1terC)2e:ne~DUS structure which may to defects in the flow.
In such materials a of at a low ternJ)jera,tUJ~e
enhances tool in its

5.8 CRYSTALLISATION EFFECTS

..... QJt "",,",u.,,;u ... J high stress combined with

most

below the nominal

structures which
......"',rh".."'"

Such
and

appear as
and indicated that controlled
stress may lead to with enhanced
cnrst(lUll,atllon rate under stress is an In'1nr\lrt!:lI'lt
OJ),eraltll1l2 conditions of free surface flows such as
98 Polymer Melt J(nleot472V

Shear stress
5.4 'Forbidden' shear rates

material
the
While most cOInmlonly nl!'\~fI'rvf'·rt the effect has
also been detected in pojlytc~tf(lthJIOrlethyle:ne, nnlll.1nrnrn/ll"nfl' of
molecu1ar
in

associated the discOlltiIlU11ty

extrusion from an orifice die
defined shear stress in
suggests that it is indeed a pncenc.mt~nOln

BRII.lld-uO of

Low swell swell

Slow output output
5.5 Flow in unstable
 99

of notes that the

COilstl]ctlon on the die land near to the die
sufficiientlythenhC!tTn~tU\n

5.9 THERMALLY INDUCED INSTABILITIES

'lnc,£"oc' •• " cnj:m,~e can lead to unstable flow.
VISiCOS:ltV COCJtnR;ie. and viscous
"wnnof'"r-",... t source of

V"""!:l'f'cnn3": notes the which can occur "'1,',",""",I""U m()UI~clmll! or

extrusion when a hot melt flows a cooled Cmml1lel.
section flows slower than its section cools more ..", ..... £111"
becomes more while cools less .. .,.r'urlll..,
f'ln'irlit,,,· an unstable which can
Hot wan

--+
Coo, melt
--+

5.6 Effect of a constriction sublse()IUell1t to flow of cool melt tllr'ou~~ a hot section

While the flow of a hot melt Tn ..,,..,,,,,,,,,, a cooled sec:u(Jln ~1"np'~TC mlJlen~ntlv
um;tat)le. the flow of a cold melt a hot section can also
flow is tolloYveCl a constriction Here the VISiCOS:ltv ... 'f''''rI ••~n ..
eXl~O~leCl to the intense flow at the
break up the The flow
flow is slow the whole a ternp1eraltulre ... 'rgrUPlr'lY

> 1, where a is coefficient of thermal dltfus;i0I1.

x is the half or if it is fast en<)u~:n
100

5.10 NON-LAMINAR FLOW

More has probably written on the sut)Je~ct of 'melt fracture' than any other
rheological phenomenon of or notoriety, which might be
disputed by normal stresses.
As oligirlally 11.,,"Ci"'lMn,:,11

origil1latf~s with the very tensile stresses which accom-

pany COllstJ~airled i"'r\1",u~•.,.ftill'\c" flow at the entrance to extrusion dies

Recircullting
or'dead
.~I~ ~~~y ~ltJ
~(6 ~:;-Iamln.r ~~
\
I (,\>
1'"\
J \ .l
Rupture at entry Triggered in die

Chaotic Regular
(tension-stiffening melts' (tension-thinning melts)
5.7 Non-laminar flow
 Phenomena 101

Pn~:AihIA site of

initiation of
non-laminar flow
5.8 Restricted 'choke' section

may accumlUl~lte,
reduce the and so rate of extem,lOll,
not exceeded. While the should be sulJllected
other common sites are or bars to mc:re~ise
nrl"4:!~llrA in the of the relative flow rate in rt.t'·F"" ...,"' ......
the die Non-laminar flow defects at such
remote from die the flow.
As a result of many prc'ce~;Slllt~ Oloerat14:>ns
laminar flow at extrusion rates two
would cause in

5.11 DIE EXIT INSTABILITIES

tensile stresses may also exist at the die where the surface
accelerates from zero inside the die to the extrusion 'l1AI.nL'>.1~"
If the surface stress the then

surface breaks. The crack so formed into the I'>vl~ ..... rto1rl'>
surface from a loss to the texture of -"hal'''''''''',,"
be from a micro metre to several millimetres and of cmnp.araDle
ampli1tude. The is if the able to
ela.sti4:;allly so that skin can stretch and the stress SU[)SeICluc~ntJly relax wltholLit
ex<:eedilll2 the critical materials of low elastic are thus less
 also assists stress relaxation. Surface
filled or otherwise
cornmonJly observed in
less elastic.

aelDol>lts may not,

pf()CeSSlm~, when
corltarmnate the extrudate so

Somewhat to this class of defect is an mstat)ll11ty

front of an Here the front is Clllt'UPl"tp,t1
deformation 5.10) should the front rU[Jtture.
tnrou:g:n. The burst is transmitted to the surface as a
confer a decorative and the process of stress
......."'.I"A."'t1~ in a

5.12 COEXTRUSION INSTABILITIES

The search after desirable combinations of n ... np,rt" £ ... have led to
err"''''"11'n in coextrusion This tec:nnol(~2Y with it a new range

tenaeltlcy for a maltenal

makes it erA ..' ...... ':1'II1.1
'l11<>,('>n<>,.i"u4L. same

-
A

I ""
3
Shear rate
5.11 Inters,ecttnJ?; vis,:ositv/~,he(u rate curves of two oo)vmiers
Adventitious Flow t'n4~nOtmt:~na 103

As combined Shear rate profile After extrusion (rod)

After extrusion (sheet)

5.12 Shear rate may cause distorted interface

or lower than the main stream. If the two .....nl"I....,,"'".,."

families such that their flow curves intersect
difficult to obtain a SatlSnlct4Jry
in a 'black box' and sut>sel(luc~ntlY StlblC~ctt:~(l
driven flows nelcessal'UY
A match different
elasticities interface may
stress effects at the interface.

Secondary

Primary

5.13 """"JIJ""," formation where a stream meets a 'weak' stream

104 Polymer Melt Rheology
'normal' stresses at the 'I1AI .....",,,h, dllSC()ntmullty
for two streams of equal vi <:t.l"nc:!l hI
the other. Problems
pressure fluctuations in the
A further form of coextrusion defect is a thickness of COCltlIll2
... "",t."'l1ltl,,,lu observed in thin of a melt on one
ViSI~OSlltVJlS,44 (such are when the die tnrlous~n
melt flows is This class been attributed to
'draw resonance' associated with the flow of
the surface of critical thickness sheet
extrusion:

mSl:alJllIty if

where h is the H is the of the sheet and N is the

ratio of the of the to that of the main stream. An
alternative or a similar has been in terms of a
critical shear While as an event, as
a defect sometimes described as 'runny paint' other observers have that it
can a effect for decorative finishes'.

5.13 STRETCHING FLOW INSTABILITIES

processes
blow and vacuum TrU'rn"nn to
achieve a thin, and sometimes onentea, sectlolll.
If the stress in such a process exceeds the 1"lIl",tllt'P
catastroJ)hic:allly lr,t""'~1"1I'nt""ti or a hole is torlmelCl.
its own in pra,ctl(;e "'1nt'I1"""
OC(;aSlIOnal pJllerlonleIllon associated with stress raisers locally mc:re,lSlfU!
above the rupture threshold or that tlmeshold

Less which a continuous rl1"~l'\J.l1lnn nrc)Cp.l~~

becomes between thick and thin sections-a
sometimes as resonance' In processes such as blow
m(ml~ClUlIe: and vacuum thin may be observed. The
effect is most in where resistance to ex1:enSlonal
flow decreases as the stress level increases and is to 'neClune:'
Resistance to deformation of '"~t"rU:!tt'l1
while in some may as
int"rp!:I~pc at modest stress levels elastic modulus increases
mc:re~lSIfU! stress so that at stress the deformation may
In both ends of this n."·1'...·'"
observed if the process
COc,tUlle: is observed to
Adventitious Flow rh4~n(;~mEma

tralllsition to a more favQuJrabJle

~OS,SiblUtv of
c:
break bV
.~
';: \
tU
> \
:: Viscosity , Elasticity
~ dominated dominated
.¥
u
:.c
~ ',~---=~----------------------~~~~L-
Haul-off/extrusion rate
......

- Rupture

5.14 Thickness variation as a function of haul-off rate

local variations in Vlscm.ltv'-lthe

.,.'V...........,u·
£1T'!:tUTllno more the more vis:cous--l eaclID2 i

to local variations in Vlcf'nc:dv

relJtresent real dltitercmcles but may reflect diflrercmctes
ture or variations in structure from the thermomechanical the
process
The conlblflatU)n from a thin or narrow
annular die and a SUl)seawent dralWIlUZ may lead to a "'11.,·t-tu~T' form of
If the melt of the die or the

I
I
I

bead Curtaining
5.15 bead and ·cnrtaj.ninlJ;f

cirlculnfe~re)lCe
is unsu[)o(>rt(~d may cause it to fold inwards or 'curtain'
The eXistence phten()mc~na may a close control of
in certain critical processes.
The material from the middle of a flat film or sheet die is under a
constrained extensional flow to pure shear. That at the of
such a die is Thus a three element ap1pr()xilmation
106
... /
\
I
\
\ I
\ I
1 I

extension
5.16 Schematic nj~a"~1m of 'neck-in' and

",. - Long draw

......
,
Rupture
I I
I
I
....... -;

Haul-off/extrusion rate
5.17 'Neck-in' related to extension rate

5.14 PHENOMENA ASSOCIATED WITH SOLIDIFICATION

As a polymer solidifies its

"u"·t"" .....",, the difference between the nplrU;lH'v at room ternpleraltUlre
melt can be as much as 25 per cent.
:rYistaUls,atlion is a nucleated nu~cle;atlC)n, as a result either of
cOlnp()Sitlonorofpn)ce!~Slf;lg nom(]lgenec)us then the surface of the
be nlcrtnrtpn Such can
sut,)e1cteo to a deformation as it
Adventitious Phenomena 107

cr\l'sta,ll1s:es, since the alr~ea(JIV CJrYSlraume

deltormaltloln more than their ~1'n,nr1r'\h ..
'nlC sUl~roun~dilllgS.
and thick secltIOlltS. of the section

atllrlOS'llll,erelS. a
is es]:)ecIallIV PlnrrIUr!:.opi1 if there

elliptical section Void

5.18 Defects of thick sections

Conclusion
The and the
from the more
that of 'melt fracture' and rp£1I11U'P IIlst(;~ad phl.lOS,optlV of
more elusive del:ects, such as 'lulmptm~~ss'
delicate definition and SUl)DI·es~nOll1.
still of 'melt fracture'
used that there is still a
sur'nr~ess1ion and eXJ)IOI.tatlon
aSSOCJlat~~a with ....r.llu ..... "" ...

REFERENCES

1. Structural foam mouldm~ with surface

1979.
2. Note PP TD leI J..-IUIUI;#'U.
1972.
3. Borocz, L and Kubat, J., Phase seV1anltiotn
Plastics and Rubber 4
 4. flow of
19

5. :SChmldlt.

6. and
7.
8.
9.
10. Dollvolefitn films Modern Plastics

11. IntllUelrlCe of formulation on the cornD<)unidiI112

cornp()unds. Plastics and Rubber M(4~terjrats 4,

12.
13 . ...:"'... " .......

15.

16. .,,,...,....."' ...

17. MaCklc~v

18. :southern.

19. D.
behaviour of stress crvstailltsc;:d
1977.
20.

21.

22. Meltzger.
1964.
23. Unstable flow of amorplbOl11S n.nlv:me'rll: tttrmlgb caa:.. n~tnes,
l!,n.gmeermg and 11
Adve1i~titijC1US Flow t'hj~nO'mE~na

polvm~ers: a second site of melt frt}lr-tnlrp

1963.
discolltirluil~intheflowcu~esofool.vet:hvllene.

Transac-

27. "t:lIIUlcUU,

28.

29.
30.

3L Plastics

32.

33.

34.

Transactions and
Plastics
37. HulilmBLnn,

38. Journal
Transactions and

1975.
43.
110 Melt

44. Interfacial flow

35th Annual

45.

46.
47.

48.

49.

50.

51.

52. in molten 8

53. Science and

1967.
54. effects on

55.

56.

57. in MSc
Rheology in Polymer Processing

6.1 INTRODUCTION

The orecedltn2 cJla.pters have eXI)loJred

response in nnll"....""... melts. The
response may with """"I"'i-1I"'<l1
aD1,rO,aClles to such processes
material response so that the n'lllrr1!:U:rp
be most fruitful.
IJ'nl"ft'1i""r(.' are converted to en(l-oroclucts

prc.ce~iSU112 operatlO[lS are directed at 1l1".Up·UU110'

mCJWlng·-llut in many cases a orcJduct
I1nJ,prc~p tc:~cnnOJ021les. open container could

filament
welded from
vacuum formed from
blow moulded from tubular &l>vf· .... ,-i<lt""·

mould

pressure tec:hnolc)2V

Dn~c11.1de the
112
A

, 0
"'I,;

"
,---':IIp---A

-
Q!)
o
u c
Number of mouldings
MOluldllD~ costs related to ofclducticm rate

economics of the OfClce:ss.

available.
While there is a wide range sulJ'lectea to a
Four distinct

Material transfer-the tec~nnOl('2V

to that at
aplplu;atllon of deformation processes to achieve not
but also a orientation.
-lllStlalllv ro,,.rnru·.c",,,c the of removal of heat to achieve a
form-stable but can also involve such
CO<ltInlg to a substrate or oxidation to achieve a nrilnt~hl""
surface. is often the rate-cletl:!rnlininsz
process.
 concentrate on it in more
a problem, for the obsession that
extrudate on.gmate in the die may lead to a fruitless
detail in quite the wrong Personal eXt)efllen(!e
to the admission this is a easy thing to The
can be avoided is to the .......,,. ... 1&1> ......
While it is true to say that some may have SOI)hi!)tic:att:~d SC1Jutlons.

Freeze line

6.2 Pollvethvlene film blo,wiIUl process

JO{lI!CUUl in the right the solution is usually

consider the occurrence of a

or uneven because of
ex~cessiv'e reliance on heat l'f""""'1"<:at""rI local shear regIons, may as
a DOlrri(h!e-lil~e in

of the feedstock may uneven flow of the material

into hopper or the adventitious incorporation of amounts of or
other volatile materiaL
The screw
chosen .....,.Iu..... "'..
tives as lubricants and DUtmc:!nts.
A worn screw which oel~mits
114

the

flow tnriom;~n tc::m[)en:itUlre glraUlents

of the memory of a turbulent
screw-may all account for a extrudate.

to a U01"'",,~hfT
UraWtflQ' nrocess will to eX(llggc~ralte
and may itself

~ry:stajlhs,atj4[)n, which may vary with a

may be uneven.
CO()llDr2 rate interact-
or or result from

CO()JlDISt air may cause a of the

mspec;tlCtn of the ......r,rln,,..t and of the pr('ce~)s

the source of the
.rI""nt.lh" or to eliminate
Imme:(fUlteJIV obvious then eXlpet'lm,ents
pf()CelSsll1lg rate and tenlperature
COJ1CllJSU)nS can be checked
All the of proceS~>lnSt
and 1'h.,>",lr'..,."
 115

A---__'_,

Shear stress
Knieol~()~u~s alPPJ'oprialte to different processes

ln1,pl'''u~n mCluHltn:l!:. while C is most aPI)ropn:ate to blow mClul(ltnll!:. "-'"......."....,..

4 identified how these different may be attained. To out
different are we may l"1<1C'C'liru
flow processes five groups:
Low flow prc1ces,ses
J,".UAJ,1llJ::. flows

Constrained flows
Free surface flows
Bulk deformations
Each class of flow may include viscous or elastic
response.

6.2 LOW FLOW PROCESSES

This class of is determined

material under low stress includes most of the prc)Ce~SSt~S
teIISl()n. gr~lvit.aUom:l1 forces and stress relaxation are
isms.

JiioJ
u u .. ,,""' ....... process, which determines the rate at which a rotational ""-~''''''''JiioJ
of are sucked into a of

2Jtrs
where s is the surface terISl()n.
and v the Each paI'tlcJle
of melt x is formed in a
t
116

Powder

resistance
Melt
tension
t t t , t t t t t t t t
Heat Heat
6.4 The smt:emlg process

This reJfltlOJDSh.ip is not heat transfer

nrt"V"A,t:'C! as it may
be if the n'2l1....1t"·I#'OC! are too eX3.mple is in Table 6. L

Table 6.1 Slnlerinl of Low-density Polyethylene MFI 20

Viscosity Time to form a

Temp- Surface at zero glossy surface
Thickness erature tension shear (s)

Calculated Observed
3 X 10-3 130 31 X 10-3 5·4 x 103 1600 1400
170 25 1·8 640 780
210 20 0-6 270 390
250 16 0-2 120 300

6.2.2 Deformation of an Extrudate under Gravity

Deformation of an extrudate is a low stress process. bX.amlplc:!s
flotation of a thick cable Co(ltlDt2 nn'l.lll'2lrt"lC! over a centra) core t>ec:aU!>e
the melt in a The shear stress level
Pf()celiS is of the
stress = (R- IU!cnnlinll' medium -

6.5 Buoyancy causes of a central core to float UmJlar4:is in a bath

For a melt 30 mm diameter t't"u,I#'Orino: a central core 10 mm

the stress level is of the 50 N/m2 that the
nrl'"\nI"lrlinn'!l1 to the thickness of The time for
del)end on the b"n1npr~tlln'p f,tnlldlc:!nt and the square of the
 117

I Cross-sectional area A

6.6 of an extruded tube under

thickness of coattm:~. Thus

total deformation = shear rate x time shear stress x tmle/'V1SI~m.1tv

and is
The sag an ~vt ...nrl~rI blow m()UIIQlIl12 is another
eX,lmlPJe of deformation under ,.,. . ".ud'u extensional
In such a process
stress
where I is the
A is
e is the rlPlrt<l:t1'v

g is the constant.
l'vrnr;;.Uv this stress is in the order
paJ'lSCJ1n taLPe1reo so that a
t)ec(J,mc:~s smanc:~r Clross·sc~ct]lon must c ............n ......

stress =i
Strain rate =i
Total strain =!
Total deformation =!
eX~lml)le, total deformation of 0-1 m
would be obltalIleO
l
118

6.2.3 Processes Associated with Relaxation of Orientation after Flow

Df{)ce!,S the stress levels and aetorlloatlon

QUlillt,atn'e rltleC)tol!!IC,al n~St"Omie in sJ1t~aflln2

and cJ1~lrajctelnstlc

Modulus /
(N/m 2;"

Characteristic
'time (s)
103
\T
,
\
10" 104 105
Shear stress Shear stress (N/m 2 J
6.7 Relaxation of orientation after flow: IO'W'-l1enSJltv ru:llv~~th"lef1te MFI 2·0 at

AJtJ1(m~.J1 the characteristic time is very short at

stress relaxes that relaxation is acc:OlrlPamed
the orientation molecules. The final of the molecules is a
when relaxation zones to allow a material to
or to form a uniform or when sel1ectm2 Dolvrniers
m()Uj OlIlL2 applltC:iltl<mS where a lack of orientation is ..""'e......""rf
I

rJ1(~Oll()glcal response which must

6.2.4 Wetting of a Surface by a Melt

The wettlllll!

Conclusion
Low flow and as a result have
received attention the literature. In such processes we tend to be ae~lllllig
with stresses which are either internal to the material or external to the process
 119

outside our control: it is thus difficult to find n¥~. . . ftrl

oel,lRller can manoeuvre. The need to locate
if low flow processes
have a very

6.3 MIXING PROCESSES

The of flows
unclerstalllOlnR. Almost every plasttC:IS1I1R lflaCJiUuery manujfac1tun~r
element so there is a
COlfl1PoundjlnJl: machines based on varied prInCIples.
discern four "~¥nAtC'·

apJ)llc:atl()Q of energy

6.3.1 Dispersion

He:SlO«es the method of actlllevlDll OlSlperSlOlll. at which it is attiempte:d

is also critical. If the lDs:reclleJllts h@l~~Vllrv worked

the matrix is moUeJIl. p:artJculate malteJ~lal aJl:J~10me:ra1:e or suffer "'f'f' ..·.f'.r.'"

and extended chain t"¥'l'C't~lC' nnllvlTl@lr11f' substances which are

sut)seIQuc~ntlv difficult to melt.

plasti(;isaltio,n and more difficult to In
. . .,o.,,:>Illu ideal to add fillers to the melt rather than to solid feeds.
120 Polymer Melt Rheology

dlsIPer:,e a small amount of low-viscosity material in a

U1(!j"'n~:ihl__, t easy to thin down porridge by adding milk
drc.ppine: lumps of into a bowl of milk and stirring
n1"£'I,rhu''''' appetising result-the skills of are, indeed,
c1e'.relc"lnf'~c1 in the kitchen.

6.3.2 Distributive Mixing

Distributive mixing, aimed at is achieved
the interruption of streamlines. by rows of
on a screw or by the use of static flow. Distributive
is of importance when the flow streams of different
u.,,('One,.f'u and, more when those different viscosities are the result of

6.3.3 Homogeneity
onllect:1Ve of all is homogeneity but nOlmogeIleI1:y
is not
n1"{"t1n,('f' mixing. A notable ex(;epltio1n
lOtlrO(1uctlon of the which the solid separa'te
from the melt the barrier flight, elements of the bed
may break be UlrlOUfl~n the extruder without melting. The barrier
nrt:~vent~ this and allows COJIS14deI'able increases in output rate to
achieved.
In the flow of ma'tenals, hOInO~tenc~ltv det,emls
also on f'",,",n"'1"af'II11"'"
the final
flow to
the die tp",np1"tltII1I'P to increase in the same way.

This nalrf'f~.lhl tenlPeratlure build-up due to heat n ... r''''1''~:lht'.n

and prOlmOttes which is more stable.
6.3.4 Work Input
All kinds of work input. Excessive work input is it
may also lead to heat generation and to If the work input
is uneven it may indeed be a source of in the wrong it
may defeat the of the or unwanted
attrition. There are many the work input during
UUJ'nUI"', but the in the final analysis, on the
lOQ~re'llents to be mixed.
 121
6.4 CONSTRAINED FLOWS

ConstlralIleCl flows are of two

mOIV1Jlli! surfaces and pressure
of r.Ollvp:vn1UJ

6.4.1 Screw Extruders

In the barrel of a screw extruder the flow is a COlnplex
In the power reomr,em,ent
ovi'..... , ...,.,.. the flow between the reilltiv'eiv t'n('1,Vll1,O'

where
shear rate =

where D is the screw diameter

H is between screw root and barrel wall
N is the screw in revolutions per minute.
The shear rate extruders is of the order 10-100
elements of the those which pass between the screw flight
and at very rates. The resJICleJIlCe
time of melts in the a screw extruder is of the order of 100
a total average of the order of 3000 units of
very considerable flow purposes.

6.9 One unit of shear

In dies and the nozzles of 10 I,ectlon moulCl1Oe; machines the flow is

pn~SS1ilre·ClI]V€m and the shear rates at much
SOlllletlmc~s e'tcec~atrle; 100 000 The shear rates
in such flows have described in an
kn<)wleClil~e of flow rate

shear rate =
where M is the
D is the
T is the time
N is the number of u .. " ........ "lIVU
122

6.10 Selection of die diameter for wire cm/eT'in~

a too restricted
b Die too
c Die correct size

.... """"' .... >

---

6.11 of convergence of die, 28

 123

While such formulae are no substitute for accurate cal,cullaticm

a of the of strain rate involved in a nrc'i"'p,~.:!C!
as a check that more have not gone

6.4.2 Wire Covering

i"'cnJP,r,na nrr,i"'P,c~C! the choice of diameter Iml)OSC~S a need to

shear at the i.,.+,.,.ri""'''A

I'h'~'Ult1lnU1n of the melt ..........
1'"1 . . "''''..,

With the correct die dll1neIlsl<)fi--u:suatUy about 10 per cent

coated wire-the at the with the conductor
and the outside surface of the material is
rel~~tl\l'elv easy to release such surface stresses

6.4.3 Pressure-driven Flows in Dies and Moulds

We have noted Dr€~SS1lfe-drwe:n flows in dies and moulds contain
COllnp(melots. If 2(J is the of of a die
then the tan (J for

tlHr"'!:lt"'r than 900 the melt will tend to

a 'dead' space in the comer of the die and
Pf()dUlCU1tg a 90° convergence, so that for such dies the stretch rate is
aplpro~xirnat:ely most constrained flows the extensional is
less than the shear strain. because the resistance to
eJong~ltional flow be very much due to shear the
stresses ty""."tAr~t""rI extensional than those
assoclate:d with the
to maintain the I10W---Hle Q1uarltitl:lthre
the shear flow cniuactens1tlc,
presence of flow or onentatllDn,
reSlPOl'1lse. No matter how small the stn:~tcllling
it never be Ig(]lOrled:
flow, the first QUlestllon
be re(luce~(l
124 Polymer Melt Rheology
...... ...

6.12 Strc~tcl1lina flows in inie~cti()D mIOu,IQUlf!;

warping or ..... Ir'..... n of the moulding. At the

<l' ... front of flow, the
stretching flow may lead to instability features in the
~nl,\p,!l,r~''' ...... of the of the product. While it is too to say that aU
prcJblen:lS of product in constrained flows are associated with strletchll1UZ
they should placed at the top of the list of causes for
elimination.

6.4.4 Constrained Flows Dermed by Pressure Gradients

A final dass of constrained flows occurs when relatively moving surfaces 2el1erate
which in turn
nrf~!il!ililre 2ra:(J1e~nts the This dass is ,,,...... '1'."'.£1
cal'efl(lerllD2 nrc)ce!;;s where the flow is constrained between r01:atlD2
Again there is a flow component r'nn,~ ... rI (ll1l''\ ...

,pumPing

#
I I
I

Drag I
I
I
I I
Pressure Shear stress Tensil!t
I I r
I
I

Pressure profile Shearing field Stretching flow

Figure 6.13 Constrained extensional flow in caumoienlllg
 125

to a dominant sn~~ar]tng flow 7 as a first aplprc.xlIna ltlolll,

y 2VIH
stretch rate, t =
where R is the calender bowl radius
H is the calender
V is the linear ,,""I,"....1h:r
Note the of the in rto.f'""rrntr\u'"y
from which we may

6, 14 Sq1Jlee~~ing flow

models for their

in this class include sallee:ZII1If!
Knc~adm2 flows found in COlnmlen:lal

6.5 FREE SURFACE FLOWS

Free flows are also of two kinds: those where the bulk of the material is
worked and those in which it is the surface which is affected. Free surface
flows are dominated
In we noted at the exit the extrusion die there is a sm:gulan1:y
the surface of the melt accelerates from zero to a finite "o.l,n","1t"
resulting in an intense strletchil112 flow of the surface leading to pm.SlOle
defects. In the streamlines of the surface near to exit
6. we observe a pattern which, even without is qualitative-
c!ln"1l1~" bubble blowing process in polythene film. Film blowing reaumes

b
6.15 Surface flow
a exit of extrusion die
b At front of moulding
a pressure inside the bubble and so, in a
re(Jluu~ed to induce the of the surface .~u,,,,,,,,,__·,, reOIUlrem!ent
to a die exit pressure studied by
the flow situation at the front of a mOUlO.lnf! nrc)ce!..s
where the melt conditions we can the stretch rate at
the front as E = where v is the of the front and h is the
QPt"'l!:l1"~lf'ti'.n between the surfaces. Should stretch rate that at the
rUJ:,tm:es, a defect will be observed in the surface of the moulding

In more obvious free surface flows of fibre spinnilng nlnWlrlO the

whole of material is to a strletchlI1lg the
of such processes is described in
maximum stress
total strain

u""l.nl"'.1tu at the freeze line and va is the

s is the draw distance.
be eStlmalteo.
are not lnClepenlCiellt vj:ln~lbt(~s
sec:uonal area of the and the die.
For most film or processes, is of the order 10 so that an estimate of
the strain rates in such a process is

strain rate = ariiWoortruiCe

1"Pl'llH1","'1O:t a very detailed of
tenlPerature profile the line is the most

6.5.1 Foaming
eX(im1ple of free surface extensional flow which is of "",,,'u'-'II,,
As with aU the critical
the defonnation
aplpr<J1xunalte stress in the tmlmltng nrC\{",l'>'i1(! one in
ISOllatlon. is where P is the pressure a bubble of radius r and wall
thickness h. The volume of to the volume of the
remains constant:

where 2R is the distance between the c\1"lcnn~1 nucleation sites. And so we

as an aplpr<J,xnna1tlolll,

stress "23
 n""'CCII ..':> remains constant, the stress bubble size
increases. characteristic allows
than smaller ones-a which is eSt)eClaJJIV e:"ag;gel'ate~d
deformation decreases with stress. In we observed that branched
materials have a resistance to deformation which increases with stress
that such materials should a more uniform cell
resistance to also tends to increase with stress if
carried out more when the material response is more

6.5.2 Film Blowing and Casting, and Blow Moulding

more terlslcm-stlJttell1lnig
the more elastic is
In the extrusion Co(ltnlig nrnl"':>cc
sus;celDtlltJle to 'neck-in'. In blow mouldme

process
deformation is dOlmUlaI1ltly elastic. Both these courses lead inevit-
stress and so to the of balance to
a delicate one. The ODltlOllS !t111!tIII!thilp to stabilise a are
in the of may not available.
However the context, we must defer to the advice of the
Bard: .. , 'twere well it were done '1'"
1'1 ...........

6.5.3 Vacuum Forming

One process which is almost ",nt', .. ",hl process,
where a sheet is sucked into a of the
the most extreme tlnlwllnf!
are at their minimum
thickness and strain

6.16 Vacuum IOflrnl11lg

 Polymer Melt Rheology

the sheet. In this process the stress is limited to about one atrnO!)pJ1lerc~,
(rlh) x for processes, rlh::::::: stress
level of 1()6 for the nl"r\l"p,~"
The ideal response for a material in such a process would allow
extension to strain and rapid after that. The aVf~ra~fe
in the much less than the maximum strain
reached in the average draw in a vacuum
maximum draw in the corners
material would tend to
m(mJlriUJIl! into the corners, leading to more even

6.17 Deformation response in vacuum toflmlllig

Ideal

Conclusion
Free surface strletcDJI1l2 to achieve thin sections: an
important sec:onoalry oblf~ctllve may to achieve enhancement
orientation, on the response of the melt.

6.6 BULK DEFORMATIONS

but
cnCllngC;!S of
COInOlres~)ed per

is al"~111111~1_
nl"l"""11rp

such an opti-
as PY{"P"':IVP the quality
usually better than that of

in building up or relteasin2
dlsplacernellt from an accumulator
 6.18 Observed in nmlla-tln to predeternlJnc~d flow rate

aettencls on the volume of the acc;unlul,atofr--a

the accumulator will ..",... :>Ilt",

relaxation will be more

prc:deterllDiIled flow rate. Bulk cornPl'ess,ibillity

Heat from the surface a moulded or so

that an outer shell first. As the molten interior shrinks it exerts a force
onto the solid skin, That force may the surface to buckle or or, if
the skin is a be the
melt. If that tension the melt may cavitate.

, ..7 SELECT BIBLIOGRAPHY

In this Ch,lptc~r
between and pr()CeSSJ10e:,
nre:seIlt across a wide

t'rul1cIJ)les of roti:ttl(J'nal mOuIOIne:

1972.
Extrusion
~xt'·UJll,(Jn. Van

H.F.
Fiber and Yam
130 Polymer Melt Rheology
Film Blowing
P. L. and Huck, N. D., Effect of .,.n...1"....l1c1nn variables on the IUDiOalnel'ltaJ
orooerties of tubular 26 114-120 and 26
1961.

moulctme: SYll!1p()S1l1m, Transactions the ." ..... 1 '• •;

1975.

C;alen(JrraR.~e, . . . '.. "' ........"" Francais . .

PL....... ,,.,"',, et
 131

REFERENCES

1. lDl lect:lon m()tul(llDJ~. Plastics and Rubber

2. Effect of extrusion variables on the fundamental

Dollve'thv'lel1le film, 26,

3.

4.

5.
6.

7. in Journee
Apph<=aUons des

8.
9.
1966.
Future Developments in Polymer Rheology

of the interaction between rnC;~OJ()1!V

decades

in
134
The last have seen a nrn,u" ... ",

mitigalte the major flow defects

such as
their train a new f(erlenltlCln
gnt,\pgrg"i"'p will COIltulUe

REFERENCE

1. ,V ....... cfv'ev J. Wiley, 1962.

APpeJ:1!OlX 1

Additional Sources of Error in Capillary Viscometry

1 The Velocity Profile in tbe Die

A correction is freQuc~nt.lv made to take into account the fact that the
psc:::uaopJ.astlc nature of melt means that the aSSUITlea pa)~aJ:)jOl1c 'Us:>lnl"'l'hl
the die is DIUIl-lIKe. This ,..,..·..0''''..........

is form:

true waH shear rate,

rel.atl()nshlP shear stress ....................t ......... <31 to

............
......
......
......
......
.....
.....
""

0.1
shear rate

A1.l Effect of the Rabinowitsch correction on a flow curve

uncorrected data
corrected data

The of the correction term + tnt-tnl1t11 as n

goes from to 0, but in the error in VlSCOS,ltV nrt"'\nr1rt1nnlll to at

shear rate, that the COJrrec::;ticm a maximum value of
per cent when n
 Before whether it is aOilroonate to make this correction it is desirable
to the use to which are to be put.
(i) Where data are to be used for COlnOfilra1:tve n",~nn,Q"'<l aD11J1v]IDSZ the
correction win not alter the COlrnpanlbllllty
Where the data are to be used as enJllDleerlDi data to calculate pressure
iralOle~nts in different it can shown that the maximum
error in n""'QQ1!1"'" gra.Ole:nt, occurs when data from a are
takes the form + + has
accuracy of most
measurement.
Where the data are to be used as fundamental or for the of
other than the other ooltentlal sources of error

unlt1011bteOJly a proper one to from

aPl)earS unrf~W(lrOlDSZ in terms of the effort lDvolveO.
an index the of pse:uOioplastllc
rheol<ltglcal piarame:ter which may be
enJllD4eerlDg ",allfvUJ,aU\.JUi) and may nQl1~111"

2 Slip at the Die Wall

A rate is that
COlnm,OnJlY preS,URleO to occur with svstenlS
pal'Uc1ula1te rather than mC,le<;ulIU
"AI.n~'lh, n.en~lVl()Ur near the die wall is
is the treatment of die
Chamgc~S in the flow behaviour with to
obtained dies of different radii
aOl,arient shear rate at a pressure

volume flow +

ap)Jarlent shear rate,

where v := From this be oJOltteCl

indication of v from the the
indication on the assulIlotiion true
shear rate at die and must be treated with caution.
Several authors3.4.5 have an association between wall and flow
defects.
For geller;al OIUl1JiOS€~S it is sufficient to assume no at the die wall. If is
Of()oertv should be evaluated in discrete eX1Jerlmlents.
ADjfJen:au I 137

Inverse radius
A1.2 Apparent shear rate related to inverse radius: 4x velocity

J Pressure and Temperature Effects

assoCl.ate:o with and

extrusion leads to an Isoen1troPIC reduction in

for a pressure of could
and introduce an error of order 10 to 50 per cent in

A1.3 Exit temperature die wall at same ten'lperature as melt on

138

COlmbllDU1lll the tenloerature "',U,""""'''''''

ture be "f' ...r",\ ... II" (Jlst\lrbe(J,
the wall which are to llreatest
deterrnininll the resistance to
estima1te that
would cause an pff,Pt"'tnlP tenlperature
which would reduce the " •., ..."',,'.i-'"

I
--:;I---~---""":"-Average

I
I
I Low
I I
Entry Exit
AlA inside a t"~nll'~'n!

extent mULLUl::my carlcelllm:R.

magDltucle of the errors due to nrl~I:!'.!1!1rp and
ooltenUal ma,llDl,tucle of which effects out-

is to minimise the
the dies should not
pr(.ce~iSlt1Ig C()nClltU)nS are

Al.5 ~(]llan!-eIUrV die: streamlines and extrudate non-laminar flow

ADDell~alX 1 139

4 Shear Modification Effects

The action of &>cvlrru,rh'l1llJ' the melt may and/or mc.rpJ110Jogllcal
structure of the Thus excessive and so exc:esslv,elv
should be that the volume average total shear
4

5 Non-laminar Flow
the
NO]tl-l(!lmlJtlar flow
in the flow
lTH1lrlr,pnllu from those which are

is convenient to use
DOS;Slble .... ">1,.,,.., of extrudate
rnC~Ol~()JUCal information.
apl:Jropnate for studies.
made under non-laminar flow
c.11sUnJ~Ul:sne:c.1 as

REFERENCES

of molten
3.

4.

5. Ch~lUtf!ourleaux.

6.
Aottend.ix 2

Interpretation of Extensional Viscosity from Flow through

an Orifice Die

A2 Extensional flow thrlom~h an orifice die

so
def:orrnation is 1'3"."""__ ~'" a
flow
" ' ......... L_ ...... 4

received most use and value has been

eIoln2~iti(J'n rate, i =
at a flow rate
r
of = '1 is the
n is the power law
 Polymer Melt l(n~f!Ol(1JlV

If this is to must be taken over the

the orifice .... r"."" •• rt3 method is a transducer
.... r." .."'rr""rI

above the
U!:Ilirtii'u of the intC:!fPret:ati<m elcmg;atlonal response from i"i"I1!1Vl"rcrllncr
flow measurements is results so obtained must
be treated with caution. or
more tUflC1alm(mtaJ C1Dniunlatlon

REFERENCES

1. COl1l1ptlabon, Journal
A01penlClIx 3

The Inference of Elastic Modulus from Post-extrusion

Swelling

Several authors have sU2,ges:teCl intleroretinJ! DOI~t-c:~xt]rusllon SWf~lllIU!

able deformation. If
extensional flow is then it is apl)rOpnate
orifice flow as recoverable ex1:enlSlOltl,
is the ratio of extrudate/die Olame:ter

+
leadmlJ! to extensional mo,duJlus.

+ ]

swc:mUUl ratio from a die and rR is the recoverable shear at

 144 Polymer Melt Rheology

6. 0
1/
V

5. 0
V
/
.0 /
V
.0
/
/
.0 L
./
.0 ,/
/
/
~
1.0 1.2 1.4 1.6 1.8 2.0
Ratio of solidified extrudate to die diameter, BL
A3 Plot of recoverable shear swelling ratio

There are several possible ways of making a measurement of sweHllnil ratio.

One method is as follows:
L The extrudate is cut flush with the die.
2. A new is obtained which may be transferred to a water bath to
facilitate cooling.
3. The diameter is measurea with a mlC~rometer in two dtrc~cUons at right angles
within 1 cm of the end.
4. The readings are and the result is taken as the extrudate diameter.
Swell ratio is the ratio of extrudate to die diameter.
Certain corrections would be necessary to obtain a true sweUllnil ratio. These
arise from:
ShJrinJka~~e on CO()11I112
Sa~~2lfI2 under
to h'~'~7'lnn
Diametral increase to surface tension
flow conditions not established
These errors are, to some mutually carlcelUIll2 is that a
meaningful measurement can be obtained if the folJm'JlinlD CC)nClltlC)DS are met:
AD.Del1tarx 4

dI8.me:ter to die diameter >5: 1.

when

REFERENCES

elastic deformations in polymier melts. Plastics and Yolvm~ers •

.R.ppel1lOlX 4

Rupture Behaviour

Most observers now

at the stress COlllcc:~ntlratJlon
of flow into an orifice as a str()n21v e:x:tension:al
of 'melt through
stress at which the melt rUt)tUlres.
 AP1penl(llX 5

Data Sheet for Capillary Flow

Die diam. Extruder

2R

N/m 2 Ns/m 2

y= 0so = 1/=

By courtesy of lei Limited (Plastics """1"1;:>''''''"1

 AD.oen:au 5 147

Extrudate Extrudate
N/m2 L o

G + E=
APiDel11(11X 6

Comparison of the Rheological Properties of Two Samples

of Low-density Polyethylene

Fl(ltlres A6.1-6 COD1D3Jre

same as

Cone and plate

rheometry
103 10·
Shear stress (N/m2)
shear at 170°C
 10- 1

Angular velocity (rad/s)

A6.2 nvnalnlC viscoelastic nrClnp'rti,"''' at 170°C

The elastic modulus results

recovery on a cone and
inference of elastic response from Dost-«~xtJruslon swell:mS!
cone and plate measurements at low stress are agree-
ment with dynamic measurements and with the normal stress
measurements in flow A6.4), on the assumption l that

re.~o"erahle shear

N
E
"-
~ Cone and plate
(!) recovery measurements·
0'
:::J
"5 10'-
"0
0
E
"-
CIS
Q)
.t::.
en ---
10 3 10 4
Shear stress (N/m2)
reSl)On:se at 1700C
on work of S. Citroen at UCW 1979
Orifice die G == E/3 where E is the elong,ltional modulus
150

Table A6 Data for Post-extrusion Swelling

10 2-0 1·5 2·6

30 2·4 1·7 2·7
100 2·7 distorted

~ ).;'

/
If
V
'/
I
"
10'
Stress (N/m2)
A6.4 First normal stress difference at 17WC: results of P. J. Daniells2

Non~laminar
flow

104-
Stress (N/m2)
A6.5 Orifice pressure from ",a ...iU",r'l1 flow at 1700C
AO,oen:dLX 6 151

CD
Ii..
:s
....Q.
:s
3 x zero shear viscosity a:

----!---- -'"- ~~
10- .......
....... - -1-- __ •
1 .....
.....
I "',

Based on orifice flow

103
I 104 105
Elo'ng4!1tiCtnal stress (N/m2)

A6.6 Elcm2;lltiornal flow at 170°C

REFERENCES

Elastic L.tUIUI"u,J, 1964.

MSc Rubber Te(;hmcJlotzv 1977.
Appendix 7

Typical Processing Property Data for a General-purpose

Low-density Polyethylene Polymer with Moderate
Branching

Melt Flow 2-0

at

5·3 x

Table A7

Heat content Coefficient

Temperature Density Bulk modulus relative to of tbermal
lCrC dilTusion

3·1 x lOS
130 1·10 1()9 3·8 x lOS 1·1 x
170 762 0·96 x 1()9 4·8 x 105 1·1 10- 7
210 746 0·83 x 109 5·8 X 105 1·1 x
±10 ±0·03 x 1()9 ±0·1 lOS ±0·1 x 10- 7

Table A 7 lists bulk modulus and also beat content and

diffusivity data tbis polymer. otber tbermodynamic data we bave

Heat is cOl1l1plc~x near tbe but witbin tbe melt

in from above to below 70°C tbe beat eX(:hall1~e
adequately a of tbermal diffusivity of 1·1 x 10-7 m2/s
per
AO,rJen:atx 7

tel1[lpe:rat:un~s above the may tend to while

SClliSlc'n may dominate. These are minimised by the exclusion

coc~ftjlcleJr1t of friction rises from a value of 0-4 at 20°C to a of

and then faUs to a minimum of at
of about 0-45 as the polymer melts.

N
E
-,
~
Q.
...0
"a 10"
...:::J
II)

fII
:...
Q.
II)
(,)
!E
...

}I~
0

-1-_--

104 10&
Stress (N/m2)

A7 of a oprlpr~ll_nnrT'ln~p Dol.vethvllene with moderate oranctlung

Swell ratio at 15(f'C

10 1·4 2·1
100 1·6 2·5
Appendix S

Typical Processing Property Data for General-purpose

Grade Polypropylene Homopolymer

Melt Flow Rate 3-0

mcrealses the and its effect may be corlsJdlen:~d as a

neD'atj"e t"~'n1",\~"":lt"'''A such that
=S·6x
on uuu'nc't'tu as reclucJing tenlperat1ure

Table AS

Heat content Coefftcient

Temperature Density Bulk modulus relative to of thermal
20°C diffusion

20 0 1·4x
180 0·76 x 109 4·5 X 105 0·9 X 10- 7
200 0·70 X 109 5-0 X 105 0-9 X 10- 7
220 0·67 109 5·6 x 105 1-0 x
240 0·61 x 109 6·3 x 105 1-0 10- 7
260 1-0 x
±1O ±0·03 x 109 ±0·1 x 105

Table AS lists nAnC!li'u bulk modulus and also heat content and thermal

diffusivity data for this nolvmler

cornOl'esSlon or de(;Orrlprc~ssion:
= 2·2 x 10-7C>ClNm-2

Pressure bmld-l1n/lrele:ase ne~lttnlg or CO(U1n:2 at constant volume:

Polypropylene which melts at 165°C as a melt.

presence of intense stress may the of sut)erc::oollin,g.
most purposes it may assumed that polypropylene will at
Aooelltau 8 155

water.
The coettlcllent of of ooJvoJ'no'vlerle
other this value can be very

Q,
...
0
"0 106
...::::J
Q)

fI)
fI)

...
Q)
Q,
II)
(J

!E
0
105

.-<
C
0
';;

-
cII)
)(
II)

"0
A

'"s;::-
.:
..:
'"
II)
s::.
fI)

,5
=
s::.
fI)

,5

10'" 10 5
Stress (N/m2)
A8 Kheolo£!\! of a aelleral·l[JUJ''Oose oohi'Of{)o\rlerle homOOCllv1ner
Swell ratio at 2rxrC

10 1·5 2-0
100 1·6 2·6
Appendix 9

Typical Processing Property Data for a General-purpose

Grade Acrylic Polymer

Melt Flow Rate 4-0

HV4::irol§tatic DJress.ure IDCreal8eS melt "i'''''.n'''t" and it is cOIlVenient to coolsidler a

teorlpe:raturc:/p!'ess,ure equivalent

=3·3x

which implies that a hydrostatic pressure of 108 N/m 2 (1000 atm) the same
effect on as a drop in of

Table A9

Heat content Coefficient

Temperature Density Bulk modulus relative to of thermal
lOClC diffusion

20 1180 0 1·1 x 10-7

180 1130 1·35 x 1()9 2·7 x lOs 0-7 X 10- 7
200 1110 1·25 x 1()9 3·1 x lOS 0-7
220 1100 1·15 x 1()9 3·5 x lOS
240 1080 1·05 x 109 4·0 x lOS
260 1070 0-95 x 1()9 4·5 x lOS
280 1050 0·85 x 109 5·0 x lOS
±10 ±0·03 x 1()9 ±0·1 x lOS ±0'1 x 10-7

Table A9 lists typical bulk modulus and heat content and thermal
diffusivity data for this polymer_
OccasionaUy relevant are the thermodynamic tulllctl()oS:

= 1-2 x
and
iDl-,enau 9 157

C1eJlratClatlon can occur_

aPt)rmnmate.ly constant up to 1300C a
malXll1nUID value of 0-8 at about

-
N

~
E

Q.
...
0
"0 10'
!:J
,
=
!Q. /'
/'

8
~ 101i
0 200°C

..:
..,
«t
.s::.
fI)

.5
~ 102~--------r---------+---~----~--------~
-
~

104 105 10'

Stress (N/m2)
A9 ofaOp.flp.r:~I-rvlrnn':p

Swell ratio at 2(J(f'C

10 1·3 1·6
100 1·5 2·5
Apt)endlix 10

Typical Processing Property Data for an Injection

Moulding Grade of 6-6 Nylon at 285°C

Flow curves at different and pressures are SUt>erlPos,ablle

vertical at constant stress. Within the pr()Cel,SIIlI~
shift the axis is proportional to the tenl1pe:rature cmmge.
'(1t~{'n~11"'(1 is summarised by

1·36

Similar remarks pf()Ce:SSll1l~ range.

A hvc:1ro!datlc Vls(~ositv as a

=3·2x

Table AIO
Heat content Coemcient
Temperature Density Bulk modulus relative to of thermal
Q
20 C diffusion

285 1010 1·5 x 1()9 7-0 x lOS

±10 ±0'1 x 1()9 ±0·3 x lOs ±0·1 x 10-7

In form 6·6 11&>.,..c... t'(1of 1·14 x 103 at 20°C. The melt

bulk modulus at atnl0sphc~nc pressure and Quc~nCJllea heat content
relative to 20°C are AIO.
The rise in bulk cornPI'eSS,lOn
1·2 x 10- 7 °C/Nm- 2
AO.oen:QlX 10 159

melts at about may SUI)er·cO().

of
Drc;~sellce orientation 1"&:!>t'ilnt",:o",
by a reversible cOlule:nScltlcm so that
eClllilibri1Llm water content are reflected chja.n~~es in molecular
Above nylon 6·6 may to thermal

The coefficient of kinetic friction at 20°C is about but falls l"'.U"urlll" to 0·1
in the Above 200°C friction to a
maximum to a value of O· 25 at 250°C.

-
N
E
~
e.
0
I-
"0
106 /
I»
:;
rn
rn
V ",
/'

/ 1; and Ell
I»
l-
e. ",
I»
/'
,/
(,)
-.: "...
.....
'C 105
0
/
.<
C
0
W 104
: -
'0
C
0
c:::
... '0...c:::
I»
)(
I»
I»
)( I
"0
c:
ea
I»
"0
I
c:::
s;::- ea 103
t.: ci A
ea .:
I» ea
.c:
rn I»
.c:
.S rn

-----
.S

--
N
E
rn
N 102
E ~

~
~ ~
rn
:s
:;
"0
0
:e it
10 5 106
Stress (N/m2)
AIO KDleOI4Jgy of an lnl,F>l'i'1Inn mouldinJZ of 6·6 nylon
APtJen(lllX 11

Typical Processing Property Data for an Injection

Moulding Grade of Polyethersulphone

VIS(;OSltv on pressure is such

has the same effect on v ......,.tu'l1 • •

6·7 x

Table All

Heat content Coefficient

Temperature Density Bulk modulus relative to oftberma.
20°C dltTuslon

1·4 1()9 4·7 x lOS

+10 ±0·1 109 ±0·3 x lOS ±0·1 x 10-7

heat content and thermal

crO~):SllrIK after orolon2ec:l exposure to telTlpelratllLres

 11 161

-
N
E
~
Q.
0
"-
"0 106
f
:::s
en
en
f.)
"-
Q.
f.)
E/3
"
Ot:
't:
0
106
--
t< 320°C
C
0
'in
cf.)
....
)it(
f.)

"0 320°C
c "0
cc C 370'C } A
cc
F" ci 103
.:
CC
f.)
.:
CC
.c
en
f.)
.c
.: (I)

370°C
N ,:
E N
fh
~
....>
"iii
-
E
~
(I)
:::s
102

0 3
:>"
"0
en 0
::E
104 105 105
Stress (N/m2)

All of an of
APt,endllX 12

Typical Processing Property Data for a Rigid and a

Plasticised Grade of PVC

ViSC:OS11tv on pressure is such that tnCJrea~;tnJl the pressure

has the same effect on at recluc:mJl tenlperatlure

=3,1 x

Table Al2

Heat content Coemdent

Temperature Density Bulk modulus relative to of thermal
20°C dift'usion

1·9x1()9 1·6 105

1·6x1()9 2·1 x lOS
+10 ±O'l x 1()9 ±O·1 x lOS

heat content and thermal

and ......."""' ........"" nIIIUC1-nn lle,ltuluz at constant volume

2000C.
The friction of PVC dec'emis CIulcauy on the lubricant formulation.
ADl'ena~lX 12

t<
w
C
0 C 104

..
'ii
c:
Ci
)(
Ci
0
'ii
c:
....Ci
)(
Ci
"0
c: "0
ca c:
ca
F" 103
.: C)
ca .:
Ci
.c:
fA
.S =
.c:
fA

N .S

-E
fA
~
102

fA
:::J
:;
"0
0
:E
104 105 106
Stress (N/m2)

A12.1 Rh,eoll()2V of a PVC

Swell ratio at 17(f'C

10 1·05 1·35
100 1·10 1·50
164 """.1""",,,,,. Melt Rheology

-
e
~
Q.
...
0
'C po /""I.-
e... 10&

1~
:::J
0
0
...e \
""
Q.
e 190°C
(J
It:
'l:
0 10 6 """,'
...
'"
,,\
\
G and E/3

1 /
/ \
,.. \
\170 0 C
.< A\
C w
'"
0
'0
c
....e
)(
e
C 104
0
'0
c
....e)(
\
,
'C e 170°C '\190 0 C
c
as 'C
c
as
ci 103
\ \

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to:
as
e
.t::.
0
.52
.52

-
N

~
e 10
0
:::J
2

\~
"S
'C
0
::!
10 4 10 5 106
Stress (N/m2)

A12.2 Rheology of a highly PVC on K69 nol1vme:r 1

APJ,endtlx 13

Empirical Observations of Flow in Channels of Complex

Cross-section

\
\

AB.l Flow 9n~llv~!I~' p~lral1[lete:rs dleSCtibiI12 die channels

For the PUJ~OOl~e c0I111plc~x channels may desc;;ribc~d by

of area
of area

From these Pat'ameters we may the dmlen.Slo'oie:ss ratios

x
y

and for a slot die X = 0 and Y = 1.

a set of for
the two flows can
col111plc~x cJltaIJlDels can
166
In ae(lUCJn2 relati4ems.hil)S we note the established !or:mu.lae:
Slot
rate 4QlaA
Stress
~ .......lru'.... shear
y= + (i)
shear stress,
0s= +
Pressure drop through dies of zero ."".. ,.po, ...... ,
=4(1+ + 1)

= = = 1-0
Swell for YR>

1 + 0'4(1 -0-8)
B~b
(iv)
{
=
dies
(Br) x = (vi)

Swell for dies of zero

aBb

r Ba =
Dies of (viii)
zero
(Br)X =
nr~..C!'alrp drop in a long die and
Sigllific~s the ratio of extrudate to
is the in n is the power in
YR is the recoverable shear and eR the recoverable extension as
.....,.U.'~IJL''"'.1 2. The to y have values 0

been determined in addition to standard

and short dies cross-section and
cornbi.nil112 three rods to form a tn~mgle with concave sides.
and
that their

tension-
 Shear rate (8- 1 )

utl:!..'nc:!ttu flow curves

stifJfeDllng, nolvnrnm/lerle temsion-tlmlnlllg and in-

Working Shear Rate

The intersection of the flow curves Ol)ltalIleCl
reference at wc.rk:lD2 shear rate is ael:lDe~a

Table At3.t Data for Calculation of Working Shear Rate

Shear rates at Intersections

p == 1 and q== i
DIe cross-section
x y
Circle 1-00 1-00 3·2 23 380
0-80 1·28 3-8 28 300
0-28 1·06 2·2 32 420
0-11 1-00 2·3 23 360
Concave
I tOO 1·62 3-8 35 480

factors
points Ol)1tau1leCl
Table All.2 Data for Calculation of WorkiDg Shear Stress
Shear stress
PoIy(methyJ methacrylate) Polyethylene Polypropylene
X y 10 S-1 100 S~l 1000 8- 1 10 S-l 100 8- 1 1000 8- 1 108- 1 100 8- 1 1000 S-l
Circle 1-00 26 110 260 17 61 160 31 84 130
1·28 26 120 18 64 34 80
1·06 25 110 15 55 32 77
1-00 27 100 250 17 56 150 31 82 110
Concave 1·62 24 90 230 18 59 140 38 81 130

Table All.l Predicted Value Compared with Table A13.4 Predicted Value Compared with
Observed in Dies Observed in Dies of Zero Length
Standard Standard
Function deviation deviation
1% high 8% 7%
2% high 8% 10%
as observed 7% 7%
 169

calculated are on average 9 cent with a stand,ard deviation 26 per

cent.

WOlrkJlnJ! shear Y= .lI..-_.-+---==-

Working Shear Stress

From the at defined values of WOlriOllJ!
for rand s of equation
obtained r =s =i
obtained of cif(;uhu CJrOSl;-se~CtJi[)n.
are, on average, 2 per cent
Thus

wOlrkuU! shear

Other Rheological Functions

In a similar manner the other empUllcal IUIlICtll:ms are defined such that
pressure

mf~aS1L1re;d value of Cal,CuJlatc~d, standard deviation 8 per cent.

Post·extrusion from <YR<10:

0-8)

{ =

Dies of
zero
length (
above may be used as a to oornol1tulJ!
tbrl()uJl~bC4()mple:x ducts and also as an aid to
The same and in nQ1rtll"nhu"
intterslectin2 flow curves, may be used ,to the shear rates of
cOJnp,lex svs,terns--f()r e;"antlpl1e, in mixing devices where torque may be
AOttenClllX 14

Flow through a Tapered Slot or Annular Die to give

Uniform Velocity of Extrusion with Varying Thickness
Profile

-+ HN ........
A14 die

For small cp,

tan cp = --w,__...t.:.
(i)

In section N,
pressure

= constant in all seCtlOllS

shear rate, y
where is volume flow rate per unit width
shear stress, (J =
'tl""I£1I£11TV at die

velocity of oar'isOlrl, VN = =1 (¥1A N

= constant (v)

swell B, assumed constant (but variable in principle) (vi)

AD,venaLX 14 171

From (vi) and (v),

BVN constant

whence

From (iii),

= x
From (iv),

From and (i),

~~......-;;.;..;;;;;.;.""":' ~ -(~JJ= constant

Then

Example. Wall thickness in side walls approximately double reCluurect thu;Kfiiess.

With a variable thickness inflation will first occur in
If the side wall thickness were reduced to half, on mtJlahon,
these walls would become thin. SU22ests that a side wall
thickness of about IW()-I1UTlIS the 2: 1 on
inflation.
Original
=10mm
= 4 mm-f> 2·7mm
15mm
n=O·3
To equation
(247)O'31~"""""-
0·82
whence 12·3 mm.
Author Index

the tOllc')wuzg in Darlenth'l!St!3

Ballman, R. L.
Barrie, L T. 1
130
Bartos, O. 98
Benbow, J. J. 18,19 56
101,102
Berens, A. R. 10 (13)
(38)
Berl~ol12:oni. A. 32 104 (110)
Bird, R. B. 1 (4), 52 Daniells, P. l.
BloodeD, D. J. 97 35
L. L. 104
D. C. 52
Bol1ltinck. W. J. 32, 33
H.C. 47
Borocz, L. 93

Edwards, S. 73
E. 91
Busse, W.F. ~lI":Ui:lu.R.

Caron. I. M. ,cVC;;li:ljl!,C;;, A. E. 102

Cancio. L. V.
H.
Casson,N.
R.V.
Chauffoureaux, J. C. 136 40 47 (68)
Chen,S.l. 120(131)
Chen, Y. 87 (90)
Choi, S. Y. 44(68)
Christiansen, R. L. 52
Oark, H. O. 58
P. L. 33 105 113 130
Oallo, R. l. 64
174
Galvin, P. 21 Kratz, R. F. 52
Gieniewski, C. 104 Kraus,G. 84
VU111:>1:'1::>. A. 84 Krul, N. 32,33 49, 104 (110)
Gottfert Feinwerke-Buchen 32 Kubat, J. 93
Gould, R. W. 10 50 Kuhfuss, H. F. 11
Ura,essliey W. W.
Lamb,P. 32 84
97,98,99
Lamonte, R. R.
Landel, R. F.
34 58 Laun, H. M. 23
102,103 (109), Leblanc, J. L. 34
Lee,B. L. 93
Lenk, R. S. 1
A.S. 7
84 Lord, H. A. 130
Lund, J. K. 32
Maack, H. 104
Macdonald, I. F. 47
McGowan, J. C. 44
Hessenbruch, H.
McFarlane, F. E. 76,84
Hirai, N.
McJ!Celvlev J. M. 1
Holdsworth, P. J. 97
Mackie, P. 32
Holmes-Walker, W. A.
Mackley, M. R.
Hoiomek, J. 136
Maerker,J. M.
Hori, Y.
MaiUeffer. C.
Howells, E. R. 102
Markovitz, H.
Hubbard, D. 49
Masken, S. G. 130
Huck,N. D. 113
Matovich, M. A. 104
Hudson, N. E. 32
Matsuo, T. 32
Hulimann, H. P. 101
Maxwell, B. 21,24
T.W. 98
Meier,D. J. 84
Hutton, J. F. 20
Meissner. J. 20 23, 32 47
Huxtable. J. 87.88 (90)
Mendelson, R. A. 40 (67)
Ide, Y. 23 Menges, G. 94
..... ,"""u... Chemical In(j!ustrie:r-Welw~rn Garden Men, E. H. 98
54 91 A.P. 98
Ito, K. 44 Metzner, A. B. 32
Ito, Y. 52 Mewis,J. 87
Jackson, W. J. 11 76,84 Middleman, S. 52 83
Jacovic, M. S. 83 MilIer,J. C. 104
J. C. 64 (70) Miller, W. R.
Janieschitz-)'rie:gl, H. 130 Minnick, L. A. 18
Johnson, J. F. Moore, D. R. 47,52 97
"UV'I.!f,GU, P. W. 76
Jones, T. E. R. 18
Jung,A. 44 M.E. 98

Kamal, M. R. 138
Karl, U. H. 44 Nakajima, N. 130
Kase, S. 32 Nazem, F. 20 (36)
Khan, A. A. 103 Newman, S. 86, 87 (90)
Klein, I. 129 Nicely, V. A. 76,84
W. 101 Nielssen, L. E. 1
 175
Schulken, R. M. 18
Scott Blair, G. W. 5
W.E.
Semljonl[)V V. 44
86,87
Shah, Y. T. 99
Sbc:t>bc::rd. G. W.
Shida, M. 141
Shishido, S. 52
136 Shroff, R. N. 141
den Otter, J. L. 34
Smit, P. P. A. 84
D.F. 67
Y. 87
" V i t l • .,..,,,, . .
Southern, J. H. 97
A.J.B. 87
J. 62 J.A. 32
Paul, D. R. 86,87 J.E. 97
Pearsall, G. W. 58 Swerdlow, M. S. 32,33 49,50 104
Pearson, J. R. A. 1 104
129
Tadmor, Z. 94
C. 44
Throne, J. L. 129
Petrie, C. J. S. 23 55 104 130
Tordella. J. P. 98,100,101
Trevena, D. H. 49
J. M. 10 50
Truesdell, C. 5
Plazek, D. J. 52
Turner, S. 87,88
Plochocki, A. P. 86, 87
Tyabin, N. V. 57
Pollock, D. 83
Poolak, T. 83 Uhland, E. 98
Porter, R. S. 44 85 97
Prest, W. N. 85 98
Pritchett, R. J. 62
Proctor, B. 96
H.
Raadsen, J. 84 L.S. 50 58
Rabinowitsch, B. 135 136
Ra~:upa,tbi. N. 52 Walters, K. 15, 18, 19
Rao, A. 129 Warner, H. R. 52
Reid, G. C. 18 Wasiak, A. 97
Reiner,M. 5,8 van Wazer,J. R. 15,19 26
Reinhard, R. H. Webb, P. C. 130
Rheometrics--Frankfurt 18,23 Weeks, J. C. 18
Rice, P. D. R. 62 130 WeilsSellbeJ]t, K.
van J. 136 West,D. 98
Rokudai, M. 53 Westover, R. F.
Rubin,1. 130 White, J. L. 23 33
87 93,97

18 Whorlow. R. W. 15,19,21 25
Williams, G. 130
Williams, M. L. 40
Willmouth, F. M. 97
Winter, H. H. 57
Schmidt, L. Wissbrun, K. F. 105
Schowalter. W. R. 64 Worth, R. A. 58
Schrenk, W. J. 104 Yearsley, F. 72
Schroeder, E. 83 Ziabicki, A. 97
Subject Index

Adhesion 21,56,101,118 152-163

Weld lines spaces 11,61,92,101,114
Deborah number 48,95. 127
11,35,92,102,120
Density 9, 10,54, 106
26 2
63,95,96
screw 120
10,78,84,93
11,12,54,63,65,79,104,105, 'Draw resonance' 104
112,115, Shear, oscillal:ory
detailed studies 130
52,81,84
adventitious effects of 94
Bulk coolpre:ssi(JD de)>endelrlce on stress 51
enhancement 97
55,100,124 inferred 30
detailed studies 130 in filled systems
E '"".... 11 ..... ," H ....,_, rheometers 24, 146 limited 52
amranlta2ces and limitations 34 measurement of 22,28, 143
errors and corrections 56 of 104,127
Cavitation 54, 107. 129 see also M(J.duJlus; Orientation; Strain
Chemical 11,41,92 recovery
Chemical structure 2, 71 Elc,ngliltioinal flow, see flows
Choke sections 96 11,150
Cluster flow 83 Entropy 44
Coextrusion 102 5
Strt~tcl:ling flows
Compression moulding 112 Extrusion 12, 56, 100, 121
Cone rheometer 19 detailed studies 129
advantages and limitations 22 of monofilament 61
Contamination 50, 67, 104, 107 58,63,167,170
2 105
100
Fibre 11,51,54,91,93,97,104,126,
1,111 127
106,114,119.123 detailed studies 129
Fillers 10, 87. 102, 119
Data Film 11,12,34,51,53,54,65,93,104.
representation of 18,28, 146 113, 127
 177
detailed studies 130 Normalstress 7.19,20,103
rupture in 15
Film casting 11,104,127
Flow 32 Orientation 3,21,46,52,54,58, 75,91,94,
9, 54,126 118
Fourier number 9 Orifice flow 30, 141
Friction 113 U~ciHlrdOlry flow
and short time-scales 47
Gelation 35 superposit:i.on on steady flow 47
Gell)m4~trv of deformation 54 Shear, oSCliJlatory

Heat transfer 9. 34 111

at surface 10 Ph~ ~para1tion 93
34,50,53.81,93,120 Plastici~rs 88
114 Poisson'STatio 52
42,45
42,45,76,86
data 158
10,11,34,52,53,54,55, 98
56,67,100, 107,112,115,121,123,128 42,45,85
detailed studies 130 Pol,ydime1thyl siloxane 45,76
orientation in 46,54,81,94,118 42,45,16
Instrumentation 2,34,39,133 data 160
94 Polyetl~ylc;~ne, branched 3,29,42,44,45,48,
50,55,61,81,83,86,106,113,111.148,
crystal 10, 76, 83 167
Lubricallts 88
42,45,71,74,80,81,98
Maron~Pierce 87 42,45,16,83
Maxwell model 8, 18, 74,78,85
Mechanical 32,53,83,84,88,97,105, Pol;v(meth:yl mlethacr:vlatle) 40,41,42.45,58,
133,139 83, 167
Melt Flow Indexer 33
'Melt fracture' 100
see also Non-laminar flow 11,76
92,113 Polyptlen:ylelle oxide 45, 85
52,75 30,42,45.74,83,86,97,98,
definition 8
Molecular dimensions 73
Molecular models 71
Molecularstructure 2,71
Molecular theories 11 74,83
73, 77 10,42,45,50,53,74,83,91
distribution 52, 73, 78. 102 Droces!~in2 aids for 10, 50
11, 71, 83, 91,133 typical data 162
Post~extrusion 21,30,93,94,91,105,
'Neck-in' 106 143
Newtonian behaviour 8 32
Non-laminar flow 31,50,56,97,99,100,114, see also Mechanical
139,145 Pressure 44,96,97,137
Non-Newtonian flow 2,22,40,47, 75, 76 43
de~~n(lenc~onmo'leculajr~ej21~t
79
178
Rabinowitsch correction 135 concentration 82, 107
Reclaim 11 overshoot 20
Rheometers Stretch rate
classes of 16 125
35 123
in fibre and film 126
coDilparisc1n of data from different 52,81,125
148
purposes of 15 instabilities in 24, 52, 104, 127
112,113 rheometers for 23,32, 141
detailed studies 129 Structural foam 91
8,15,49,93, 127,145 Structure, see Chemical structure; Molecular
structure; MClrpll0l«lgy
Sandwich 67 Surface 91,
11,34 Surface 31,99,101,104,105,106,114
Screw extruder 56,57,113,121 Surface 133
as rheometer 34 Surface tension 51
effects of scale 11 Swell ratio, see Post-extrusion
twin 125
and 20 39,41
3, 11, 71, 79, 88, 91, 97, 134 transition 75
97,101 99
Shear 6,56 TeDSCIr notation 7
see Viscous diSlsiplilticln Thermal diffusion 9
oSClillatory 17, 18, 19 Time 46
57 of 95
52, see also Non-Newtonian flow natural or characteristic of material 48,75,
Shear rate
95
forbidden 98
natural 11,34,48
in 125
rbeometers 35
in extrusion 121
Transients of stress and strain 19
in 121
in screw extruder 121
Shrink 3 54,65,104,127
Sink marks 91 32
115
Slip 23,98,129,136 oatcn-i[O-[)aI(:n variation 93
see also Adhesion
Spaghetti model 52, 73 dellendellce on stress 52
heat 9 common materials 7
mandrel 96 Viscous dissipation 9, 10,23,41,56, 120, 137
93 Voiding, see Cavitation
Strain 6 Voigt model 17
rateof 6
recovery 8,19,21,75,79,143 3,52,81,107,124
Streamlines 32, 100, 101, 114 3,11,93,95,96,114,118,133
Stress 6,49 116,123
 11111111111111111111111111
9 781855 731981