Rheol.

Acta 13, 223-227 (1974) I

From the Department of Chemical Engineering,McMaster University, Hamilton, Ontario ( Canada)

Die swell and melt fracture: Effects of molecular weight distribution

By J. V l a c h o p o u l o s
With 3 figures
(Received October 27, 1972)
When polymers are extruded at high stresses is often contradiction for various aspects of the
it is often observed that the surface or shape of problem in the literature. The objective of the
the extrudate is impaired by the presence of present paper is to present some new aspects of
certain flow defects. These flow defects are com- die swell and melt fracture, especially on the
monly known as swelling, mattness, sharkskin effects of the distribution of molecular weights
and melt fracture. Because of the great importance in the extruded polymer.
of these phenomena in polymer processing, many
investigations have been carried out with the The die swell equations
objective of determining the mechanism involved
Die swell is usually described quantitatively
and the influence of various processing variables
in terms of the swelling ratio (d/D), which is the
and material properties.
ratio of extrudate diameter over the die diameter.
Extrudate swelling is observed when a polymer
Several expressions have been proposed for the
emerges from an orifice or tube with a diameter
prediction of die swell, centered on the concept
larger than the ejection diameter. This phenomof elastic recovery of the swelling process. These
enon is sometimes called the "Barus effect" and
expressions relate the swelling ratio (d/D) to
is usually referred to industrially as "die swell".
the recoverable shear ().
This effect has variously been attributed to polyThe recoverable shear is usually defined from
mer memory conditions before the die, to shear
Hookes law, which seems to hold for most polyrecovery, to normal stresses and to velocity promers:
file changes at the tube exit.
Mattness consists of a loss of surface gloss of O" ----- z l 2 J O
[1]
the extrudate under certain processing condiwhere 212 is the shear stress and Jo the shear
tions. Sharkskin is the flow defect that gives
compliance.
finely spaced, sharp, circumferential ridges in
Coleman and Markovitz (2) have shown that:
the extrudate. Both mattness and sharkskin can
often be tolerated because they are not very 211 - ~22 = 2Jo222
[2]
catastrophic effects.
Melt fracture exhibits itself as a gross distor- where Zaa and T22 are the first and second normal
tion of the extrudate when molten polymers are stress respectively. Several questions have been
extruded at shear stresses of the order of raised in the past as to the numerical factor 2, but
106 dynes/cm2. A number of mechanisms have presently it is generally accepted for viscoelastic
been proposed for this phenomenon, which is fluids. From eqs. [1] and [2]:
often referred to as "melt flow instability", the T l l - - 1222
- .
[3]
most important of which are (1): Reynolds
2l:12
turbulence, outlet phenomena, viscous heating,
fracture hypothesis, stick-slip flow, elastic energy This expression led some authors to the definition
hypothesis.
of as "Stress Ratio".
Despite the many investigations that have
Nakajima and Shida (3) used the concepts of
been carried out on the flow defects, these phe- rubber elasticity to calculate the tensile stress
nomena are still not fully understood and there for the elastic deformation of the extrudate until
731

Rheologica Acta, Vol. 13, No. 2 (1974)

224

its diameter becomes that of the capillary. They

arrived at the equation:
: (d)Z-

( d ) -4

[4]

1 ~0
J 5d/(~/~)

2 '

3'

0
where is the recoverable shear averaged over
the cross sectional area. Bagley and Duffey (4)
following the analysis of Nakajima (3) and using
a one-constant stored energy function for a
Mooney material (5) obtained the relation:

~3 d~/(~/~o)

[9]

It can, then, be easily shown that

~w = l / g e .

E10]

Bagley and Duffey also carried out an energy

balance analysis along Graessleys (6) lines and
arrived at the expression:

This equation relates the recoverable shear at

the wall to the average recoverable shear. The
numerical factor ]/~ accounts for the velocity
and stress distribution.
Another expression relating recoverable shear
at the wall to the swelling ratio has been proposed
by Tanner (7), based on the elastic recovery concept of a Poiseuille flow of a BKZ fluid.

2 =

az = 2

+ 2

- 3.

[6]

Graessley, Glasscock, and Crawley (6) assumed

that the increase in the diameter of the extrudate
is due to the release of elastie energy stored in the
fluid inside the capillary. They obtained the
equation:

((~)6)

- 1 .

[11]

An experimental evaluation of the die swell

equations as to their predictive power has been
performed recently by Vlachopoulos et al. (8).
The results seem to favor Tanners expression but
definite conclusions cannot be made at present.

Critical conditions for melt fracture

1

S ~~d/(~/~o)

3 - J0 rg 0

[7]

2G~ i ~3d~/O1/qo)
o

where ~ = r/R is the dimensionless radial position, Jo is the experimental shear compliance and
Gs is the modulus of elasticity estimated from the
theory of rubber elasticity in terms of the average
molecular weight between entanglements:

Gs = QR T/M

[8]

Zw is the shear stress at the capillary wall. The

factor
1

2 i ~3d~/(rl/rlo)
o
accounts for the velocity and stress distribution
across the capillary.
By assuming a parabolic velocity profile inside
the capillary (Newtonian fluid), we have:
732

The onset of melt fracture is detected by the

appearance of gross distortions in the extrudate.
Several observations and conjectures for the
critical conditions have appeared in the polymer
literature.
Spencer and Dillons (9) results for polystyrene
show that the product of the shear stress (critical)
at the onset of melt fracture and the weight
average moleeular weight is eonstant, i.e.
r " )~w ~" 3 x 1011

[12]

Barnett (10) obtained that for polypropylene,

the critical stress rather than the product re" A4w
is constant, i.e.
z = const (of the order of 10 6 dynes/cm2). [13]

Bagley (11, 12) and White (13) conjectured

that melt fracture occurs at a constant value of
recoverable shear (critical), i.e.
= 7.

[14]

This criterion can be easily derived from the

definition of recoverable shear (eq. [1]) and the
expression for shear compliance J = Mw/eR T.

Vlachopoulos, Die swell and melt fracture : Eflects of molecular weight distribution
Bartos (14) suggested that at the onset of melt
fracture the ratio of apparent viscosity to zero
shear viscosity is constant
~/~o = 0.025.

[15]

Recently, Vlachopoulos and Alam (15) concluded that the critical recoverable shear at the
wall, as determined from die swell, is proportional to the factor (.M=M=+ 1/Mw)
-2 which represents the distribution of molecular weights,
i.e.

6w< = const/-

\M>~)

-I.

The die swell equations relate the swelling

index to the recoverable shear
= f(a).

[17]

The recoverable shear has been defined as the

product of shear stress (z 12) and shear compliance
(Jo). Therefore,
d
B = f(r12J0).

[18]

The shear compliance for a polydisperse collection of Rouse (17) molecules is

Jn = T \

,~T
Mw

"/ ~ T "

Polyslyreno

of~
ol
~
-~I~~Iw.600,000(~.8,07
~7
w
I
7

L/D
o 10,0
15,0
o 19,5

2q-,O

2,8

/o

/]"
/

1,5

q,

The importance of molecular weight distribution

2;5

.<

M/~____Mmo,
_
& &, es)
ooo(~oT,

10 6
Tw (dynes/cm 2)

[16]

This result was also interpreted in terms of the

equality of shear ware velocity and friction
velocity by Boger and Williams (16).

225

I0 z

Fig. 1. Influence of molecular weight distribution on die

swell for several LID ratios (capillary length/capillary
diameter). Arrows indicate extrudate distortion
cr, and the approximate nature of the Rouse shear
compliance. However, the conclusion has been
reached that the broader the molecular weight
distribution the larger the swelling of the extrudates. Dependence on the factor M=Mz+ l/Mw-2
implies that the high molecular weight tail
influences greatly the swelling process.
By measuring the die swell at the onset of melt
fracture for a large number of polystyrene samples it was found (15) that the critical recoverable
shear at the wall was nearly proportional to the
factor M= M=+ a/Mw,
- 2 as stated in the previous
chapter and shown in fig. 2. This proportionality
70

Bo/y~tyrene

60

50

;o
[19]

By substituting r12 with the shear stress at the

wall (zw) and Jo with J s , we have

b30
20
lg
0

This implies that for the same shear stress at the

wall (%) and the same molecular weight Mw
the amount of swelling will be influenced by the
distribution of molecular weights as represented
by the factor .M=.~=+ 1/Mw.
-2 Vlachopoulos et al.
(8) results confirm this, as shown in fig. 1. No
attempt was made to check how well the experimental data fit the theoretical predictions because of the difficulty in choosing an accurate
expression for functional dependence of d/D on

10

12

~~ ~,/~~

1#

15

18

20

Fig. 2. Dependence of critical recoverable shear at the

wall on molecular weight distribution
was confirmed by using the critical swelling
ratios and any one of the die swell equations. The
numerical values of the constant, however,
varied with the different die swell equations.
Using Tanners equation the numerical constant
was estimated to be about 3, for polystyrene, i.e.
]~=+1) .
o'.---3\(]Q=~-~~

[211
15

733

Rheologica Acta, Vol. 13, No. 2 (1974)

226

This result can be used in Hookes law to explain

the polymer behavior at the onset ofmelt fracture.
Eq. [1] can be written for the shear stress at the
wall
aw = % J o -

E#UA2Z o , , /

"~"

Eo = 21ffl,/M
is the entanglement density at zero shear and E
is the entanglement density at finite shear. By
combining eqs. [19], [22], and [23] we have:

For polystyrene A = 2.2 and

and since the quantity

[24]

B/M = 2.1 x 10 -5

has a constant value ofabout 3 at the onset ofmelt

fracture we have:
z = 3 . 4 1 e R T

0 00
l

Z~ Potypropylene
Hiqh dens. Pol Kefhy[ene
Broad di~ftibuTion Polystyrene
0 Monodispe;$e Polystyrene
I
J
I
I
I

10

12

1#

16

18

20

Fig. 3. Dependence of critical shear stress on weight

average molecular weit

A, B are experimental constants

~, 2

[23]

~, 1+O(~oO
where

[22]

For the shear compliance Jo we use Graessleys

correlation (18) between experimental and Rouse
complianee, which is
J g_o=

/i f

2.1x 10 -5

[25]

For e ~ 0.976, R = 8.314 x 107, we obtain:

,c/T = 5.8x lO3(--o)+ 2.76x lOS/)('lw. [26]

Experimental measurements for several linear
polymers shown in fig. 3 resulted in the expression

zc/T = 1.717 x 103 + 2.67 x 10S/Mw .

[27]

From Graessleys molecular entanglement theory

(15, 18) we can calculate the corresponding
viscosity ratio for a monodisperse sample

q/rlo = 0.0065.

This result is equivalent to Bartos' criterion for

melt fracture (eq. [15]). The numerical value is
much smaller than Bartos' average (actual values
ranged from 0.006 to 0.0359). These discrepancies
are by no means disconcerting because of the
sensitivity of///r/o to changes in E/Eo for example
E/Eo = 0.486 corresponds to t//qo = 0.0302.
It is further interesting to observe that if
E < 1, from eq.[23], J = A J R
and therefore re. Mrw = const. If E 1, from eq. [23],
J=(A/B)JR/E and therefore rc=COnSt. This
suggests that no sound conclusions can be made
about the constancy of z or z" ~w unless
large molecular weight ranges are examined.
However, the use of Graessleys correlation for
Jo/JR seems to be very helpful in explaining the
seemingly contradictory results which are available in the literature.
It is also interesting to note that for the most
probable distribution )~=M=+ 1/Mw
-2 = 3 which
gives crwg 9. It is therefore not surprising that
many investigators who used commercial samples obtained a constant value of recoverable
shear of about 7 units. In the present investigation however special samples of narrow molecular weight distribution (M= M=+ 1/Mw
- 2 = 1.25)
were used and blends were prepared with
M=M=+x/Mw up to 16. Consequently, the
characterization of polymer samples as to the
distribution of molecular weights is very important both in melt fracture and die swell studies.
--

Comparison to eq. [26] shows that the analysis

predicts the correct slope of the straight line.
From the intercept at the z/T axis we can calculate the value of the entanglement density
ratio

[29]

--

- 2

A cknowledgements
Financial assistance from the National Research

E/Eo = 0.34.
734

[28]

Council of Canada is gratefully acknowledged.

Vlachopoulos, Die swell and melt fracture : Effects of molecular wei9ht distribution
Summary
The equations for determining die swell of molten
polymers are discussed. The critical conditions for melt
fracture and die swell results are combined in order to
explain the flow behavior at the onset of instability. It is
shown that the factor ~~'zM~+1/M"2 is the most important
parameter in die swell and melt fracture studies.
Zusammenfassuny
Die Formeln fr die Bestimmung der Schwellrate von
Kunststoffschmelzen wurden behandelt. Die kritischen
Bedingungen fr die Ergebnisse von Schmelzbruch und
Schwellrate sind kombiniert, um das Fluverhalten beim
Einsetzen der Instabilitt zu erklren. Es wurde dargestellt,
da der Faktor/~z/~~+l/MZ~ in der Schwe~rate sowie
im Schmelzbruch der wichtigste Parameter ist.
References
1) Tordella,J. P., Unstable Flow of Molten Polymers.
Chapter 2, in: Rheology, vol. 5 (Ed. Eirich) (New York
1969).
2) Coleman, B. D. and H. Markovitz, J. Appl. Phys.
35, 1 (1964).
3) Nakajima, N. and M. Shida, Trans. Soc. Rheol. 10,
299 (1966).
4) Bacjley, E. B. and H. J. Duffey, Trans. Soc. Rheol.
14, 545 (1970).

227

5) Treloar, L. R. G., The Physics of Rubber Elasticity

(Oxford Univ. Press 1967).
6) Graessley, W. W., S. D. Glasscock, and R. L. Crawley,
Trans. Soc. Rheol. 14, 519 (1970).
7) Tanner, R. I, J. Poly. Sci. (A2), 8, 2067 (1970).
8) Vlachopoulos, J., M. Horie, and S. Lidorikis, Trans.
Soc. Rheol. 16, 669 (1972).
9) Spencer, R. S. and R. E. Dillon, J. Coll. Sci. 4, 241
(1949).
10) Barnett, S. M., Polym. Eng. Sci. 7, 168 (1967).
1t) Bagley, E. B., J. Appl, Phys. 31, 1126 (1960).
12) Bagley, E. B., Trans. Soc. Rheol. 5, 355 (1961).
13) White, J. L., J. Appl. Sci. 8, 2339 (1964).
14) Bartos, O., J. Appl. Phys. 35, 2767 (1964).
15) Vlachopoulos, J. and M. Alam, Polym. Eng. Sci. 12,
184 (1972).
16) Bo9er , D. V. and H. L. Williams, Polym. Eng. Sci.
12, 309 (1972).
17) Ferry, J. D., Viscoelastic Properties of Polymers.
(New York 1970.)
18) Graessley, I41.. W. and L. Seoal, Macromol. 2, 49
(1969).

Dr. John Vlachopoulos

Ass. Professor
Dept. of Chemical Engineering
McMaster University
Hamilton, Ontario L8S 4L7 (Canada)

15"

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