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Experimental Data

Rheology Lecture 22

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Shawn Waltz
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20 views

Experimental Data

Rheology Lecture 22

Uploaded by

Shawn Waltz
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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1

2
linear polymers, material effects,
temperature effects
Small strain - SAOS, step strain
Large strain - start-up, cessation, creep, large-
amplitude step strain
Experimental Data (continued)
Unsteady shear flow
Steady elongation
Unsteady elongation
later . ..
Faith A. Morrison, Michigan Tech U.
Time-
temperature
superposition
Next
1
1.E-10
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
10 100 1,000 10,000
(hz)
J
'

(
c
m
2
/
d
y
n
e
)
-14.3 -9.6
-5 -0.1
4 9.9
15.1 19.8
25.3 30
34.2 38.8
44.4 50.2
54.4 59.8
65.8 70.9
80.2 89.4
99.8 109.4
120.3 129.5
T (
o
C)
Figure 6.43, p. 202 Dannhauser
et al.; P-OctylMethacrylate
Faith A. Morrison, Michigan Tech U.
Small-Amplitude Oscillatory Shear -
temperature dependence
2
Time-Temperature Superposition
Material functions depend on g
i
,
i
) , , (
) , , (
i i
i i
g G G
g G G


=
=
relaxation times
relaxation moduli
g
i
,
i
are in turn functions of temperature and material properties
Theoretical result: in the linear-viscoelastic
regime, material functions are a function of

i
rather than of and
i
individually.
Faith A. Morrison, Michigan Tech U.
Example: plot a simple function
+ = ) sin( ) , ( f
0.01
0.1
1
10
0.01 0.1 1 10
or
s
i
n
(

)
+

0.2
0.3
0.4
0.5
0.6
1.0
=
Faith A. Morrison, Michigan Tech U.
. vs ) sin( +
3
Faith A. Morrison, Michigan Tech U.
In general,
) ), ( ), ( ), ( (
3 2 1
T T T G G =
Suppose that the temperature-dependence of
i
could be factored
out. Let a
Ti
(T) be the temperature-dependence of
i
.
i Ti i
T a T
~
) ( ) ( =
Then we could group the temperature-dependence function with the
frequency.
) ,
~
,
~
,
~
(
3 3 2 2 1 1

T T T
a a a G G =
not a function
of temperature
Time-Temperature Superposition
Relaxation times decrease strongly as temperature increases
Moduli associated with relaxations are proportional to
absolute temperature; depend on density
Empirical observation: for many materials,
all the relaxation times and moduli have the
same functional dependence on temperature
) (
~
) ( T a T
T i i
=
temperature dependence of all
relaxation times
) (
~
) ( T T g T g
i i
=
temperature dependence of all
moduli
Faith A. Morrison, Michigan Tech U.
4
Second theoretical result: the g
i
enter
into the functions for G, G such that T can
be factored out of the function
)
~
, (
~
)
~
, (
~
i T
i T
a h
T
G
a f
T
G

=

=

Therefore if we plot reduced variables, we can suppress


all of the temperature dependence of the moduli.
)
~
, (
) (
)
~
, (
) (
i T
ref ref
r
i T
ref ref
r
a h
T
T T G
G
a f
T
T T G
G

=


=


Plots of versus a
T
will therefore be independent of temperature.
r r
G G ,
Faith A. Morrison, Michigan Tech U.
(will still depend on the
material through the )
i

~
ref ref
r
ref ref
r
T
ref ref
T
ref ref
r
T
ref ref
T
ref ref
r
T
T T J
J
T
T T J
J
T a
T
T a
T T G
T a
T
T a
T T G

) (
) (
) (
) (



T a
T T
a
T
ref ref
T r
) (
) ( =
Shifting other Material Functions
linear viscoelastic steady shear
Faith A. Morrison, Michigan Tech U.
5
1.E-10
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1.E-07 1.E-05 1.E-03 1.E-01 1.E+01 1.E+03 1.E+05
a
T
(hz)
J
'

(
c
m
2
/
d
y
n
e
)
Figure 6.44, p. 202 Dannhauser
et al.; P-OctylMethacrylate
Faith A. Morrison, Michigan Tech U.
Small-Amplitude Oscillatory Shear -
temperature dependence
-50 0 50 100 150
T (
o
C)
a
T
experimental
WLF
10
-8
10
-6
10
-4
10
-2
10
0
Small-Amplitude Oscillatory Shear -
temperature dependence
Figure 6.45, p. 203 Dannhauser
et al.; P-OctylMethacrylate
Faith A. Morrison, Michigan Tech U.
6
Shift Factors
(
(

|
|
.
|

\
|


=
ref
T
T T R
H
a
1 1
exp
Arrhenius equation
( )
( )
ref
ref
T
T T c
T T c
a
+

=
0
2
0
1
log
Williams-Landel-Ferry (WLF) equation
found to be valid for
T > T
g +
100
o
C
found to be
valid w/in
100
o
C of T
g
Faith A. Morrison, Michigan Tech U.
0.01
0.1
1
10
0.01 0.1 1 10 100

r
,
Poise
1
,

s a
T

0.01
0.1
1
2 2.5 3 3.5
1000/T (K)
a
T
0.01
0.1
1
10
0.1 1 10 100
,
Poise
viscosity (Poise) 300 K
viscosity (Poise) 339 K
viscosity (Poise) 380 K
viscosity (Poise) 425 K
1
,

s
Steady shear viscosity -
Temperature dependence
Figure 6.46, p. 204 Gruver
and Kraus; PB melt
Faith A. Morrison, Michigan Tech U.
7
10
10000
10000000
10000000000
1E-13 1E-10 1E-07 0.0001 0.1 100 100000
G'
G''
10
7
10
10
10
4
modulus,
Pa
o
N
G
10
-4
10
-1
10
2
10
5
10
-7
10
-10
10
-13
frequency, rad/s
Another consequence of is the similarity
between log G() and log G(T).
Faith A. Morrison, Michigan Tech U.
) (
~
) ( T a T
T i i
=
Figure 6.39, p. 198 Cooper and
Tobolsky; SIS block and SBS random
Figure 6.30, p. 192 Plazek
and ORourke; PS
rad/s ,
C T
o
, C T
o
,
)
~
, (
) (
)
~
, (
) (
i T
ref ref
r
i T
ref ref
r
a h
T
T T G
G
a f
T
T T G
G

=


=


Faith A. Morrison, Michigan Tech U.
Take data for G, G at a fixed for a variety of T.
but, what is a
T
(T)?
We do not know.
But since log a
T
is approximately
a linear function of T,
-50 0 50 100 150
T (
o
C)
a
T
experimental
WLF
10
-8
10
-6
10
-4
10
-2
10
0
curves of log G versus T (not log T ) at constant
resemble slightly skewed plots of log G versus log a
T
.
(mirror image)
8
Using G(T) in
research on pressure-
sensitive adhesives
Faith A. Morrison, Michigan Tech U.
Figure 6.48, p. 207 Kim et al.; SIS
block copolymer with tackifier
Height of plateau modulus
and temperature of glass
transition are key
performance factors for
PSAs.
0
N
G
g
T

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