Chap.

3 Viscoelastic Response of Polymeric Fluids

Design of a Parison die for a Viscoelastic Fluids

Design a die that will allow one to extrude at the highest rate possible for
LDPE (NPE953) at 170 with (Fig 3.1)
Diameter B
p
= S.1S cm
Thickness B
p
= u.S6S cm
Specify die dia B
0
using rheology data in Appendix A.1
Gap B
0
= 772kgcm
3
170
Assume L=10B
0

Maximum feed to die, m = Suucch @melt fracture,
w
= 1.1S 1u
5
Pa
In your calculation consider the extrudate swell.
Die swell ratio =B
p
B
0



Fig 3.1 here.


3.1 Material Functions for Viscoelastic Fluids
3.1.1 Kinematics
Flows Shear flow
Shear-free flow (Elongational flow)
For rectilinear shear flow
v
x
= (t)y v
y
= v
z
= u (1)

0
=
yx
=
dv
x
dy
+
dv
y
dx
=
dv
x
dy
=
V
h

v
x
=
V
h
y + c @ y=0, v
x
=0 c=0
v
x
=
V
h
y = y

For shear-free flow:
v
x
=
1
2
(1 + b)x
v
y
=
1
2
(1 b)y
v
z
= + z (2)

=extrusion rate , b=0 or 1
b=0, > u => Uniaxial extension
b=0, < u => Equibiaxial extension
b=1, > u => Planar extrusion

Note (t
2
t
1
) = Shear strain
(t
2
t
1
) = Elongational strain
More generally:
(t
1
, t
2
) = (t
i
)ut
i
t
2
t
1

reference time
(t
1
, t
2
) = (t
i
)ut
i
t
2
t
1

Note for simple elongation:
v = _
v
x
v
y
v
z
_ = _
-
1
2
c x
-
1
2
c y
c z
_
v
x
=
1
2
x v
z
= z

dx
dt
=
1
2
x
dz
dt
= z

dx
x
=
1
2
ut
dz
z
= ut
ln x =
1
2
t + c
1
ln z = t + c
3

@ t=0, x = x
0

c
1
= ln x
0

ln
x
x
0
=
1
2
t Likewise, z = z
0
e
c t


x = x
0
e
-
1
2
c t
= e
-
c
2
(t
2
t
1
)
=
1
I
x
0
y
0
z
0
= 1
y = y
0
e
-
1
2
c t
= e
-
c
2
(t
2
t
1
)
=
1
I
(Mass conservation)
z = z
0
e
c t
= e
(t
2
t
1
)
= l xyz = 1

Fig 3.2




Components of rate of deformation tensor (Table 2.10)
Simple shear flow :
v
x
= y v
y
= v
z
= u

I j
=
0v
]
0x

+
0v

0x
]


xy
=
yx
=
0v
x
0y
+
0v
y
0x
=
0v
x
0y

Other
I j
= u

I j
= (t) _
u 1 u
1 u u
u u u
_ (S)
Shear-free flow :
v
x
=
1
2
(1 + b)x
0v
x
0x
=
1
2
(1 + b)
xx
= (1 + b)
v
y
=
1
2
(1 b)y
0v
y
0y
=
1
2
(1 b)
yy
= (1 b)
v
z
= z
0v
z
0z
=
zz
= 2


I j
=
0v
]
0x

+
0v

0x
]

So,

I j
= _
(1 +b) u u
u (1 b) u
u u 2
_ (4)

3.1.2 Stress tensor component
State of stress

_

xx
+ P
xy

xz

yx

yy
+ P
yz

zx

zy

zz
+ P
_ (S)
Shear stress Normal stress (diagonal)
P= Isotropic pressure

xx
,
yx
= Extra stress or molecular stress

xy
=
xy


xx
=
xx
+P = Total stress

I j
=
I j
+P
I j
..... (7)

I j
=1 for i = j
= u for i j (Kronecker Delta) (8)
Newtonian shear flow (incompressible):

I I
= 2
0v

0x

+
2
3
( v) (3.2-11)BSL

I j
= (
v
j
x
I
+
v
I
x
j
)


xx
=
yy
=
zz
= u (See Table 2.10)

State of stress (5) _
P
xy
u

yx
P u
u u P
_ (9)

Viscoelastic shear flow
_

xx
+ P
xy
u

yx

yy
+ P u
u u
zz
+ P
_ (1u)

(
I I
+P) has no rheological significance. So we difine three independent quantities
of stress of rheological significance which are directly measured:
yx
=
xy
, N
1
, N
2

Shear stress:
yx
=
xy
(symmetric) (11)
First normal stress difference: N
1
=
11

22
=
11

22
(11)
Second normal stress difference: N
2
=
22

33
=
22

33
(11)

Definition of directions:
Direction 1= flow direction
Direction 2= normal to the flow directio
Direction 3= neutral direction

There is no way to separate
I I
and P!
So, N
1
and N
2
are a way around to understand the normal stress.

N
1
, N
2
Related to die swell, elastic recoil, rod climbing (Elasticity)
N
1
= N
2
= u (For Newtonian)


Shear-free flow, the form of extra stress:

_

xx
+ P u u
u
yy
+ P u
u u
zz
+ P
_ (12)

Two normal stress differences:

zz

xx
,
yy

xx
(1S)

For b=0 in (2) (uniaxial, equal biaxial),
yy

xx
= u

So, the only nonzero normal stress difference is:


zz

xx
(14)

3.1.3 Material Functions for Shear Flows
Various types of shear flows used in the characterizations of polymeric fluids
(Fig 3.3)




Steady shear flows :

yx
=
o
= constant


xy
= ( )
o
(1S)

xx

yy
=
1
( )
o
2
(16)

yy

zz
=
2
( )
o
2
(17)

Shear viscosity

1
Primary normal stress difference coefficient

2
Secondary normal stress difference coefficient
See Fig. 3.4 for steady data as well as dynamic ones.

Fig. 3.4 here Note:

1
is more shear dependent than .

1
> u, large
2
< u onJ small => Neglected in processing
=>

1
, = u.1 ~ u.2

There are numerous transient shear flows (unsteady) where shear rate varies in a
specific way with time. One most frequently used is =
0
cos t (18).

------------------------Briefly discussed or skipped--------------------------------------

Constitutive Eq.
100% elastic solid
= u
100% viscous fluids
=
More commonly and are given in terms of complex variables to make
up for the phase lag between and .
So,

=
0
e
1mt
=
0
(cos t + 1 sin t)
=
i
+ 1

=
0
e
1(mt+8)
=
0
|cos(t + ) + 1 sin(t + )]
Then
Complex modulus (u

)
u

=
1

=
1
0
c
1(mt+6)
y
0
c
1mt
=
1
0
y
0
e
18
=
1
0
y
0
(cos +1 sin) = u
i
+1u
Storage modulus u
i
=
1
0
y
0
cos
Loss modulus u
ii
=
1
0
y
0
sin
Complex viscosity

=
1

=
1

1my
0
c
mt
=
1

1my

=
1
1m
1
0
y
0
e
18
=
1
m
1
0
y
0
(cos + 1 sin )
=
1
m
[
1
0
y
0
sin 1
1
m
[
1
0
y
0
cos = [
G
||
m
1(
G
|
m
)
=
i
1
So u
i
=
u

=
tan =
u

(
vI scous dI ssI patI on pcr cycI c
cI astI c cncrgy storcd pcr cycI c
)
G*=G+iG =i * (24)

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

Back to the text:
Viscous point of view
=
0
cos t (18)
=>
yx
= B()
u
cos(t )
= B()
u
cos cos t B()
0
ins sin t
This allows us to define a complex viscosity as
*= - i
where
=B()
u
cos
(in phase with (t)=dynamic viscosity=viscosity contribution)
= B()
0
ins
(90
o
out of

(t)=loss part of complex viscosity=elastic
contribution associated with energy storage per cycle)
See close correlation of * and in Fig 3.4.

Stress growth (Fig 3.3c)
Suddenly set in motion and stress is measured as a function of time (t)..

yx
(t) =
0
B(t)
Unit step function
B(t) = u; t < u anu B(t) = 1; t > u
Stress growth materials function (Fig 3.7)



xy
=
+
(t,
0
)
0
(26)

xx

yy
=
1
+
(t,
0
)
0
2
(27)

yy

zz
=
2
+
(t,
0
)
0
2
(28)




Stress relaxation after cessati
Deformation history (

yx
(t) =
0
|
B(t) = u; t <


yx
=
-
(

xx

yy
=

yy

zz
=

yx
relaxes faster than
As
0
increases, relaxation time becomes shorter

3.1.4 Shear Free Flow Material
=elongational or extensional flow

zz

xx
=

yy

xx
=

Steady uniaxial extrusion

yy

xx
=
=> ( ) =
1
( , u)
cessation of a steady shear flow (Fig 3.3d)
eformation history (See Fig 3.7)
|1 B(t)] (Su)
< u anu B(t) = 1; t > u

0
, t)
0
(S1)

1
-
(
0
, t)
0
2
(S2)

2
-
(
0
, t)
0
2
(SS)
relaxes faster than
xx

yy.
(Note from the figure)
increases, relaxation time becomes shorter (Observed)
aterial Functions
elongational or extensional flow

1
( , b) (S4)

2
( , b) (SS)

u =>
2
= u (Leaves one viscosity function)
) (S6) See Fig 3.9

figure)
(Observed).
ne viscosity function)



At steady state (Fig 3.9)
= S
0
at low shear (
(shear viscosity) shows shear thinning.
increases slightly w/ stress and then decrease

Stress growth
Two viscosity functions are defined

zz

xx
=

yy

xx
=

Uniaxial flow defines

1
+
=
+

2
+
= 0

Linear polymer tends
w/ branching or w/
at low shear (Trouton viscosity).
(shear viscosity) shows shear thinning.
increases slightly w/ stress and then decrease
Two viscosity functions are defined for stress growth.

1
+
(S7)

2
+
(S8)
defines only one viscosity function.
+
,
tends to reach steady value (Fig 3.10), but
w/ HMW tail to increase w/o bound (Fig 3.11
).



Fig 3.11)


Fig 3.11 here

3.2 Nonlinear Constitutive Eq.
Constant viscosity () does not describe shear dependence.
GNF uoes not describe time dependence (nonelastic).
Nonlinear constitutive eq describe time dependence + nonlinear behavior

Maxwell model-Review
= u
s

s
=
1
G
(Reversible deformation-Elastic)
=
d

d
=
1
q
(Dissipation-Viscous)

Stress =
s
=
d
(Needs a mechanic model for Maxwell here)
Strain
=
s
+
d


dy
dt
=
d
dt
(
s
+
d
) =
1
G
d1
dt
+
1
q

=> +
q
G
d1
dt
=
dy
dt
=
Define =

u
_
m
Lt
mL
t
2
L
2
= t_: Relaxation time
Then +
d1
dt
=
dy
dt
= (One dimensional model)
+
d1
dt
= (Tensor form)

I j
+
d1
]
dt
=
I j
(Component form) (S9)
For stress relaxation
=
dy
dt
= u,
d1
]
1
=
dt
\
ln =
t
\
+ c
@t = u, =
0
, c = ln
0
=> =
0
e
-t\


Generalized Maxwell model-linear viscoelastic model
(See LN 184 for the solution of (39) as)

GNF (power-law model etc) and linear viscoelastic models (generalized
Maxwell model ) do not predict the normal stress difference. For example
for steady SSF, v
x
=
yx
y, v
y
= v
z
= u

_

11

12

13

21

22

23

31

32

33
_ = _

11

12

13

21

22

23

31

32

33
_ = _
u u
u u
u u u
_
=
21
=
0v
1
0x
z

So,
12
=
21
=

11

22
= u Do not predict N
1
, N
2


22

33
= u


How can the model predict
Cast the time derivative (39) into codeforming or corotating coordinates

i) Codeformation model

Cast the time derivative
=>

I j
+
i j
=
where,

i j
=
1
]
t
+

Recognize the first two terms in RHS are
This CE is called UCM
White-Metzner (WM

See Table 3.1 for other models

ii) Corotational Model-CEF
Tadmor and Gogos (Ex 3.5
The CEF constitutive equation in
v
z
(r)=v
c
(1-(r/R)
2
).

ow can the model predict N
1
, N
2
?
ast the time derivative (39) into codeforming or corotating coordinates
Codeformation model
the time derivative (39) into codeforming (and translating

=
ij
(4u)
(v )
I j
|( v)
j k

kI
+
I k
( v)
kj
]
Recognize the first two terms in RHS are substantial time derivative.
UCM (upper convected Maxwell model) or
(WM) model ( )
for other models.

CEF (Criminale-Ericksen-Filbery) Eq
Ex 3.5)
quation in steady, fully developed flow in tube
ast the time derivative (39) into codeforming or corotating coordinates!
and translating) coordinate!
] (41)

or

ube:
= [
1
2

1
+
2

{ ] +
1
2

1
T
Tt
CEF (E3.5-1)

T
Tt
=Corotational derivative.

----------------------------------------------------------------------------------------
Rate-of-deformation tensor is obtained from : v
z
(r)=v
c
(1-(r/R)
2
).

y =Vv +(Vv)
t
= _
u u

rz
u u u

rz
u u
_ (E3.5-2)
{ ] = _

rz
2
u u
u u u
u u
rz
2
_ (E3.5-3)

Next we calculate

T
Tt
=
0
0t
+ {v ] +
1
2
({ ] { ]) (E3.5-4)

0
0t
= u (ss)

The components of v

is obtained from Table (Table 3.2, T&G)

(v )
rz
= (v )
rz

v

i

z

= [v
r

0
0

+
v
0
r
0
0
+ v
z

0
0
z

rz

v
0
r

z
(E3.5-5)

Since v
r
= u, v

= u, and v
z
z = u , (v )
rz
= u.

The vorticity tensor m can be obtained as

m = Vv (Vv)
|
= _
u u
rz
u u u

rz
u u
_ (E3.5-6)

Then,

{ ] = _
u u
rz
u u u

rz
u u
_ _
u u
rz
u u u

rz
u u
_ = _

rz
2
u u
u u u
u u
rz
2
_ (E3.5-7)
And
{ ] = _

rz
2
u u
u u u
u u
rz
2
_ (E3.5-8)

Thus, Eq. E3.5-4 reduces to
T
Tt
=
1
2
({ ] { ]) = _

rz
2
u u
u u u
u u
rz
2
_ (E3.5-9)

Finally, we substitute Eqs. E3.5-2, E3.5-3, and E3.5-9 into Eq. E3.5-1(CEF) to obtain
the stress field

_

rr

r

rz

zr

z

zz
_ = ( ) _
u u
rz
u u u

rz
u u
_ j
1
2

1
( ) +
2
( )[ _

rz
2
u u
u u u
u u
rz
2
_

+
1
2

1
( ) _

rz
2
u u
u u u
u u
rz
2
_ (E3.5-10)

rz
=
zr
=
rz

rr
= _
1
2

1
+
2
]
rz
2
+
1
2

rz
2
=
2

rz
2

= u

zz
= _
1
2

1
+
2
]
rz
2

1
2

rz
2
= (
1
+
2
)
rz
2

(E3.5-11)

12
=
21
=
21
(E3.5-12)

11

22
=
zz

rr
=
1

21
2
(E3.5-13)

22

33
=
rr

=
2

21
2
(E3.5-14)

Viscoelastic model is used to predict die swell (Tanner)


D

D
0
= u.1 + |1.u +
1
2
(
N
1
,w
21
v
)
2
]
1
2
(S.89)
D
p
=Extrudate diameter, D
o
=Capillary diameter
Cases where nonlinear viscoelastic model is used = Unsteady flow

Viscoelastic effect is also important in steady flow in capillary flow, slit die flow if
residence time (t) < longest relaxation time (), or Deborah number
B
c

\
t
av
1 Elastic effect is important.
For example in injection molding if the melt stress relaxes slowly relative to the
heat transfer rate => Residual stress are frozen into the part

3.3 Rheometry
3.3.1 Shear flow measurement
Low shear property => rotatry rheometry
ie cone-and-plate (Fig 3.18) and parallel plate (Fig 3.19)
High shear property => capillary rheometer














Rotatry Rheometry



Fig 3.19 here

Steady property =( ), u( )
Dynamic property =

(
i
, ), u

(u
i
, u
ii
), tan =
G
||
G
|
=
q
|
q
||
(= f())
=
3T
2R
3
y

1
=
2F
R
2
y
2
=
v = Rm
Rq
0
=
m
q
0
(cone and plate)
cone angle



Capillary Rheometry



R
= (
dp
dz
)
R
2
(91)
Pressure drop across the capillary+end effect (Fig 3.21)
(
dp
dz
) =
AP
L
P
cnd
= P
cx
+P
cnt
(92)
Capillary length

R
=
PR
2L
(Wall shear stress)

End effect and wall shear rate corrections

End effect correction
1) Plot P
totaI
vs
L
B
, at various for several
L
B
, capillaries
=>Get P = P
cnd
at
L
B
, = u
=>
R
= (
AP
tot
-AP
end
L
)
R
2
(See Fig 3.22)


2) Correction by equivalent dia length required to produce P
tot

Extrapolation of P
tot
to 0 => Read
L
B
, value
(
L
B
, )
C
=
|L +Nent x (
B
2
, )|
B
_
(94)

Corrected

=>
R
=
AP
tot
(
L
D
, )
c
1
D
[
R
2
=
AP
tot
4(
L
D
, )
c
(9S)

Wall shear rate correction u uv = uv v uu
Volumetric flow rate
Q = v
z
us = 2i
s
v
z
ui = v
z
(i
2
)|
0
R
i
2
uv
z

(uv = 2iui, v = i
2
)
Q = i
2
u
R
0
v
z

= + i
2
(
dv
z
dr
) ui = + i
2
u
R
0
i ( =
dv
z
dr
> u)
Chang of variable:
= i
1
m
R

i =
R
1
m
, ui =
R
1
m
u
Q = (
R
1
m
)
2
1
m
0
(
R
1
m
) u =
R
3
1
m
3

2
1
m
0
u
(
4Q
R
3
)
m
3

m
3
= 4
2
1
m
0
u

4Q
R
3
= Newtonian shear rate @ wall

Differentiation wrt
m

0

d(1
m
3
)
d1
m
= 4_
d
d1
m
1
m
0
(
2
)u +
2
|
1
m
d1
m
d1
m

2

0
d0
d1
m
_
= 4
m
2

m
true shear rate @ wall
Leibnitz formula applied

0
0t
f(x, t)
a
2
(t)
a
1
(t)
ux =
0
0t
f(x, t)ux +f(a
2
, t)
0a
2
0t
f(a
1
, t)
0a
1
0t



m
=
1
41
m
2
d(1
m
3
)
d1
m

=
1
41
m
2
]S
m
2
d1
m
d1
m
+
m
3
d
d1
m

= ]
3
4
+
1
4
1
m

d
d1
m

=
3
di
m
i
m
+
d

4
di
m
i
m
= ]
3 dI n 1
m
+dI n
4 dI n 1
m

=
3n
|
+1
4ni

where n =
dI n 1
m
dI n
From pressure drop measurement
i.e.,
m
= (
3n
|
+1
4ni
)
Newtonian shear rate @ wall =
4Q
R
3
(Measured)
True shear rate @ wall
From Newtonians law of viscosity

m
=
m

=
1
m
y
m
(Calculated)

3.3.2 Shear free flow measurement
Measurement of uniaxial viscosity (Fig 3.24)


Ballmen method (a)
Polymer melt is either glued or clamped at both ends, and then one end is
moved in such a way as to generate a uniform extension rate ( ). That is, the
length of sample should increase exponentially with time as L=L
o
exp( t).


zz

xx
=
1
( , b)
1
=
1
zz
-1
xx
c


For uniaxial extrusion
b = u, > u,
2
= u
-> ( ) =
1
( , u)

Viscosity measured by this method is the startup viscosity.

ZZ
= (F(t) A(t)) +P
a
(102)

rr
= P
a


ZZ

rr
=
ZZ

rr
= (F(t) A(t) ) (103)
Volume=A (t) L= A
o
L
o
(= 1), L=L
o
exp( t)=e
st
A = A
o
/e
st

+
=
1
ZZ
-1

s
=
F(t)c
st
A
0
s
(104)

Meissner method (b)
Both ends of the materials are pulled at a constant velocity or a constant stress.

3.4 Useful Relationships for Material Functions

0
N foi N < N
c

critical mol.wt

0
N
3.4
foi N > N
c


The power is
3.4 for nonpolar polymer (PE,PP)
>3.4 for polar polymer (SAN)

For u

1,0

0
2
N
7


Cox-Merz rule
( ) =

()|
m=y
|=]
rad
s
, |=] 1s

(N
1
2)|
y =m
= u
N
1
= 2 () j(1 +(
qii
qi
)
2
)
0.7
[
m=y




Solution to the design problem?
Design a die that will allow one to extrude at the highest rate possible for
LDPE (NPE953) with (Fig 3.1), diameter B
p
= S.1S cm, thickness B
p
= u.S6S .
Specify die dia B
0
and Gap B
0
using rheology data in Appendix A.1.
Assume L=10B
0

Maximum feed to die, m = Suucch @melt fracture,
w
= 1.1S 1u
5
Pa
In your calculation consider the extrudate swell:
Die swell ratio =B
p
B
0



Die swell is given by Tanner eq as
D

D
0
= u.1 + |1.u +
1
2
(
N
1
,w
21
v
)
2
]
1
2
(S.89)
Shear stress of annular flow is derived in class as

rz
==
[P
u

P
L

2L
R_
i
R

(1k
2
)
2ln
1
k
R
i
_ (2.29) or Table 2.7
Maximum stress occurs at r=R, i.e.,

rz
(R) =
w,1
=
(P
0
i
P
L
i
)
2L
R_1
(1 k
2
)
2ln
1
k
_
Wall sheai iate is then obtained by

w,1
=

m
=
w,1
/
Then, N
1,w
is obtained from the rheology data (
1
( ))
Bo fiom (89), Bo fiom mass flow iate(m ) data.

Now you are able to design an annular die with desired product dimension.