Documente Academic
Documente Profesional
Documente Cultură
discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/262105845
CITATIONS
DOWNLOADS
VIEWS
78
28
2 AUTHORS, INCLUDING:
Savvas G Hatzikiriakos
University of British Columbia - Vancouver
217 PUBLICATIONS 2,506 CITATIONS
SEE PROFILE
ORIGINAL CONTRIBUTION
Received: 8 July 2009 / Accepted: 30 November 2009 / Published online: 15 December 2009
Springer-Verlag 2009
Introduction
Unlike Newtonian fluids, polymer melts slip over metal
surfaces when the wall shear stress exceeds a critical value (de Gennes 1979; Lau and Schowalter 1986;
I. B. Kazatchkov
Schulich School of Engineering, University of Calgary,
Calgary, AB, Canada
S. G. Hatzikiriakos (B)
Department of Chemical and Biological Engineering,
University of British Columbia, Vancouver, BC, Canada
e-mail: hatzikir@interchange.ubc.ca, hatzikir@apsc.ubc.ca
268
(1)
dus
= (w )
dt
(2)
dus
= awm
dt
(3)
where a is a slip coefficient and m is the slip powerlaw exponent of the order of 2 (Ramamurthy 1986) or 3
(Hatzikiriakos and Dealy 1991, 1992) or 6 (Kalika and
Denn 1987; Hill et al. 1990), depending on the molten
polymers molecular structure. In order to examine its
capabilities in predicting the transient behavior of a
molten polymer in start-up of steady shear experiments,
Eq. 3 will be coupled with the Wagner (1976) model,
which in simple shear flow can be written as:
t
(t) =
t, t
Gi tt
e i
dt
i
1 + (t, t )
(4)
d
= 0 ,
dt
(5)
di
= 0,i
dt
and =
i .
(6)
The total stress value, , is the sum of individual contributions, i , and its accuracy depends on the number
of the {i , 0,i } pairs.
By analogy to the derivation of the generalized
(or multimode) Maxwell model from its singlemode counterpart, the single-mode dynamic slip model
269
dus,i
= ai wm
dt
and
us =
us,i .
(7)
ai = a.
(8)
Experimental
Rheological experiments were carried out with polyethylene Dowlex 2049 (a linear low-density polyethylene resin) at several temperatures using first a
Rheometrics System IV to determine the dynamic
moduli G and G . The data were shifted to produce the
master curves at 200 C where most of the calculations
were performed. The data were subsequently used to
calculate the relaxation spectrum {Gi , i } of the polymer needed for calculations using the Wagners model
(Eq. 4).
An Interlaken true stress sliding plate rheometer was
used to determine the flow curve of Dowlex 2049 at two
different gap spacings at 200 C by performing steady
shear experiments. These two sets of data were needed
to determine the slip behavior of the polymer. Largeamplitude oscillatory shear (LAOS) experiments were
also used to determine the slip relaxation times and to
provide data for a stronger test of the multimode slip
velocity model.
The values of and of the damping function were
determined by measuring the stress relaxation after
imposition of step strains by means of the sliding plate
rheometer. The procedure involved the following steps:
A sudden shear strain, , was imposed on a sample initially at rest and the value of resulting shear stress, (t),
was monitored as a function of time. After allowing the
sample to rest, another step deformation was imposed
using a different value of . This was repeated until the
various values of covered a desired range, i.e., from
0.1 to 20.
G ( , t)
G (t)
(9)
100
Dowlex 2049
10
Moduli, kPa
us,i + s,i
0.1
G"
0.01
0.001
200 oC
210 oC, aT = 0.95
G'
0.01
based on spectra
0.1
10
100
1000
aT, rad/s
270
Others
422.8
137.6
46.78
10.16
1.439
0.155
9.30 104
6.97 103
0.03713
0.1992
1.127
7.527
a = 1.7106 mm kPa3.06
m = 3.06
= 0.12
= 1.80
Dowlex 2049
200 oC
h = 0.45 mm
10
G(,t) / h(), kPa
Gi (kPa)
100
= 0.1
0.1
= 0.2
= 0.5
=1
=2
=5
= 10
= 20
0.01
0.001
0.01
0.1
10
Time, s
1
100
Dowlex 2049
200 oC
h = 0.45 mm
Damping factor
10
= 0.1
0.1
= 0.2
= 0.5
=1
=2
=5
= 10
= 20
0.01
0.001
0.1
Dowlex 2049
T = 200 oC, h = 0.45 mm
experiment
1 / (1 + 0.12 1.8) - Soskey & Winter
2
1 / (1 + 0.12 ) - Zapas
0.01
0.1
0.01
0.1
10
Time, s
10
Strain
271
100
Dowlex 2049
T = 200
T = 200 oC
Slip velocity, mm/s
100
Dowlex 2049
oC
10
experiment
95% confidence
1
10
1
Mooney technique
based on Wagner model
Wagner's model
0.1
10
100
100
-1
Shear rate, s
stress was <90 kPa (critical shear stress for the onset of
slip).
Figure 9 shows the start-up of steady shear of
Dowlex at the nominal shear rate of n = 110 s1 and
temperature of 200 C and the Wagners model predictions under no slip, static slip, and single-mode dynamic
slip. The Wagner model under the assumption of no
slip well overpredicts the actual experimental response
since, at this high shear rate, slip becomes significant.
Note that the steady-state stress is well above the critical shear rate of about 90 kPa and slip effects become
noticeable. To improve the prediction of the model,
the steady-state slip should be taken into account. A
300
200
100
-1
36 s-1
h = 0.45 mm
110 s
80
150
h = 0.19 mm
100
50
Dowlex 2049
200 oC
0
0.0
0.1
0.2
0.3
0.4
Time, s
200
Wall shear stress, kPa
18 s-1
60
10 s-1
40
20
Dowlex 2049
o
200 C
0.45 mm
0
0.0
0.5
1.0
Time, s
1.5
272
180
160
140
Experiment
Wagner model, no slip
Wagner model, static slip
Wagner model, dynamic slip
120
100
80
Dowlex 2049
o
200 C
0.45 mm
110 s-1
60
40
0.0
0.1
Time, s
0.2
Strain
amplitude
1
2
4
8
16
16
8
4
2
1
100.5
100.5
100.5
100.5
100.5
273
Slip model
Parameters
Steady-state us =
Stress, kPa
100
50
0
single-model and
two-mode depart
-50
-100
-150
static
single-mode
2-mode
Experiment
1.0
1.2
Time, s
200
Stress, kPa
Frequency sweep,
multiparameter
estimation
180
50
0
-50
-150
1.4
100
-100
kPam ,
instantaneously to reduce the shear stress to its steadystate value. The single-mode model provides a better prediction, but fails when the stress value exceeds
the critical stress for the onset of slip for prolonged
periods of time. For example, in the upper graph in
Fig. 10 ( = 2 Hz, 0 = 8), the predictions of the
single-mode and two-mode models coincide until 0.06 s
(marked with an arrow). At this point, 0.06 s, the shear
stress has already reached 130 kPa, i.e., well above the
critical level (90 kPa). This means that a single-mode
slip model is capable of accurate predictions only at
very short time scales. The addition of a second set of
parameters {ai , s,i } has greatly improved the accuracy
of the prediction. Note that s,2 (which is greater than
s,1 ) is responsible for that improvement and allows
accurate predictions at longer time scales.
Figure 11 shows the prediction of the multimode
dynamic slip model for start-up of steady shear. Comparing it to the prediction of a single-mode dynamic
slip model (see Fig. 9), one can see that a significant
improvement in the accuracy of prediction is achieved.
As a final concluding remark, it is noted that
the procedure described above for the parameter
150
s1
a = 6.5
mm
m = 2.8
a = 6.5 106 mm s1 kPam ,
s = 0.017 s, m = 2.8
a1 = 5.1 106 mm s1 kPam ,
s,1 = 0.011 s, a2 = 1.4
106 mm s1 kPam ,
s,2 = 0.86 s, m = 2.8
Single-mode dynamic
m
s
us + s du
dt = aw
Multimode dynamic
du
us,i + s,i dts,i = ai wm
150
Methods
106
awm
static
single-mode
2-mode
Experiment
160
140
120
Dynamic multimode slip model
experiment
100
80
Dowlex 2049
o
200 C
0.45 mm
110 s-1
60
40
0.0
0.5
0.6
Time, s
0.1
Time, s
0.2
Fig. 11 Start-up of steady shear experiment at 200 C and comparison with predictions of the Wagner model coupled with a
multimode dynamic slip model
274
Conclusions
The slip behavior of linear polymers may involve dynamics which are complicated by the viscoelastic nature
of these materials. As discussed above, experimental
evidence indicated that the assumption of a slip relaxation time is necessary to explain the transient response
of linear polymers under slip conditions. Furthermore,
while a single relaxation time can explain the experimental results qualitatively, it may be necessary to
take into account multimode effects for a quantitative
description.
In order to investigate these effects, steady shear experiments were performed for Dowlex 2049 in a sliding
plate rheometer using two different gap spacings. A gap
dependence of the flow curves was obtained. Using the
Mooney technique, the slip velocity was calculated as
a function of shear stress and fitted to a steady-state
slip velocity model. A constitutive equation, Wagners
model, was then used together with the steady-state slip
model and a dynamic slip model to predict the shear
stress response in start-up of steady shear experiments.
Although the steady-state predictions were in good
agreement with the experimental data, both models
failed to accurately describe the dynamic behavior. By
the analogy to the derivation of a generalized Maxwell
model from a simple mechanical two-element model,
a multimode slip velocity model was formulated to
take into account multiple slip relaxation times. A general procedure for the determination of its parameters
based on comparisons with the LAOS data was described. The new multimode dynamic slip model was
found to provide considerably better predictions of the
shear stress in dynamic flow conditions, such as LAOS.
References
Archer LA (2005) Wall slip: measurement and modeling issues.
In: Hatzikiriakos SG, Migler KB (eds) Polymer processing
instabilities. Marcel Dekker, New York
Baumgaertel M, Winter HH (1989) Determination of discrete relaxation and retardation time spectra from dynamic
mechanical data. Rheol Acta 28:511519