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DETERMINATION OF ZERO-SHEAR
VISCOSITY OF MOLTEN POLYMERS
By
Mlanie Boudreault
Department of Chemical Engineering
McGili University, l\'lontreal
November 1997
A Thesis submitted to the faculty of Graduate Studies and Research in partial fuifillment
ofthe requirements ofthe degree ofMaster of Engineering
co Mlanie Boudreault 1997
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ABSTRACT
Measuring the zero-shear viscosity of a molten polymer is not at all
straightforward. Available rheometers are unable to operate at shear rates low
enough to measure this important property, especially for polymers that have a very
broad molecular weight distribution or a high degree of long chain branching. A new
falling baIl viscometer, the Magnetoviscometer (MVM), has recently been developed
in Austria for the measurement of melt viscosity at very low shear rates.. The
primary objective of the research was to evaluate this instrument as a tool for the
routine measurement of the zero-shear viscosity. Another objective was ta develop a
reliable and convenient method to prepare samples. Experiments performed near the
maximum allowable stresses for various resins are in good agreement with dynamic
data obtained using a rotational rheometer. The tvlVM allows for the measurement of
viscosity in a range of shear rates not accessible ta MOst rheometers.

Il
RSUM
Mesurer la viscosit newtonienne d'un p o l y m ~ r e fondu s'avre difficile dans
la plupart des cas. Les rhomtres disponibles commercialement sont souvent
incapables d'oprer des taux de cisaillement assez bas pour mesurer cette
importante proprit, surtout pour les matriaux ayant une distribution de masses
molculaires trs large ou un haut degr de branchements. Le magntoviscosimtre
(MVM), un nouveau rhomtre utilisant le principe de Stokes, a rcemment t
dvelopp en Autriche. Le premier objectif de cette recherche tait d'valuer cet
instrument lors de mesures de routine de la viscosit newtonienne. Un deuxime
objectif tait de mettre au point une mthode fiable et pratique pour la prparation des
les chantillons. Les mesures effectues pour diffrents polymres sont en accord
avec les donnes dynamiques obtenues l'aide d'un rhomtre rotationnel. Le MVM
mesure donc la viscosit des polymres fondus dans un intervalle de taux de
cisaillement qui n'est pas accessible la plupart des autres rhomtres.

III
ACKNOWLEDGEMENTS 1REMERCIMENTS
J'aimerai tout d'abord remercier le directeur de mes travaux, Dr Dealy. Son
excellente supervision et son dvouement pour ses tudiants ont contribu faire de
cette matrise une merveilleuse exprience et un moyen d' apprentisage exceptionnel.
1would like to thank Bernhard Pammer, Michael Ringhotr from Anton Paar,
and Sean Race from Paar Physica. Their great help and patience in answering my
numerous questions was much appreciated. They gave me aU the additional
information about the MVM and the press that 1needed.
Je voudrais aussi remercier les tudiants qui m'ont entour et encourag :
Franois, Marie-Claude, Paula, Ranjit. Merci pour toutes ces petites discussions qui
m'ont beaucoup servi orienter le cours de mes recherches.
Pour terminer, j'aimerai remercier ma famille et mes amis: ma mre, mon
pre, Thierry, Sophie, Marc-Antoine et tous ceux que je ne nomme pas mais qui ont
t l et qui ont su m'encourager et me conseiller.

TABLE OF CONTENTS
ABSTRACT
RsUM
ACKNOWLEDGEMENTSlRElvRCIMENTS
TABLE OF CONTENTS
LIST Of FIGURES
LIST OF TABLES
1. lNTRODUCTION
2. ~ O R T ANCE OF THE ZERO-SHEAR VISCOSITY
2.1 Dependence of viscosity on shear rate
2.2 Dependence of viscosity on molecular weight
3. METHOOS Of MEASUREING VISCOSITY AT LOW SHEAR-RATES
3.1 Falling body viscometer
3.1.1 Falling ball viscometer
3.1.2 Falling needle viscometer
3.1.3 Centrifuge ball viscometer
3.2 The Magnetoviscometer
3.2.1 Principle of operation
IV
i.
Il.
iii.
vi.
vii.
1.
3.
5.
7.
10.
10.
Il.

3.2.2 Peak/Peak measurements


3.2.3 Middle Range measurements
3.2.4 High-pressure ceU for the magnetoviscometer
4. EXPERIMENTAL lVIETHOOS
4.1 Experimental Materials
4.2 Sample Preparation Techpique
4.2.1 Design of the press
4.2.2 Procedure
4.3 Magnetoviscometer operation
5. RESULTS AND DISCUSSION
5.1 Temperature in MVM
5.2 Effect ofSample Preparation Technique on the zero-shear
viscosity measurements
5.3 MVM versus RDA II values
5.4 Reproducibility
6. SUMMARY AND RECOMMENDATIONS
REFERENCES
APPENDIX A: Experimental data
v
19.
21.
21.
23.
24.
27.
30.
33.
36.
40.
46.
49.
51.
53.

LIST OF FIGURES
vi
Figure 2.1 Viscosity versus shear rate for several temperatures - l\;leissner' s
data for low density polyethylene. 4.
Figure 2.2 Log 110 versus log Mfor several palymers. The data are shifted ta
avoid overlap. The lines shown have slopes of 1.0 (lefi portion)
and 3.4 (right portion). 6.
Figure 3.1 Faxen correction of different order. 9.
Figure 3.2 CentrifugaI acceleration. 12.
Figure 3.3 Measurement principle. 14.
Figure 3.4 Pieture of the magnetoviscometer 15.

Figure 3.5 MVM arm with the magnets 15.


Figure 3.6 Shear rate distribution around the bail 18.
Figure 3.7 PeaklPeak measurement evaluation. 20.
Figure 3.8 Middle range measurement evaluation. 20.
Figure 4.1 a) Mother cell for pp measurements, b) Mother cell tor
MR measurements. 25.
Figure 4.2 Picture ofthe cells: the measuring cells are on the left and the
mother cell is on the right 26.
Figure 4.3 Design ofthe MVM press. 28.
Figure 4.4 Picture ofthe MVM press 29.
Figure 4.5 a) eut for a pp measurement, b) cuts for a MR measurements. 31.

Figure 5.1 Temperature in MVM.


33.
vii

Figure 5.2 Variation of the room temperature near the MVNI arm: eftct
of air conditioning. 35.
Figure 5.3 Parameter Analysis, before elimination of defective samples. 38.
Figure 5.4 Parameter Analysis, defective samples eliminated. 39.
Figure 5.5 Viscosity curves for 0803-1 at a temperature of 150
a
C. 42.
Figure 5.6 Viscosity curves for 335A at a temperature of 150
a
C 43.
Figure 5.7 Viscosity curves for 335B at a temperature of 150
a
C 44.
Figure 5.8 Viscosity curves for 335C at a temperature of ISOaC 45.
Figure 5.9 PDMS at 30C. 48.

LIST OF TABLES
Table 1 List of the resins tested. 23.
Table 2 Temperature in the MVM peak/peak arm: with and without cover. 34.
Table 3 One-halt fraction ofthe 2
k
design. 36.
Table 4 Evaluation of the noise. 37.
Table 5 Viscosity results for 335A, 3358, and 335C. 46.

CHAPTERI
INTRODUCTION
A rheological property that is frequently used ta characterize thermoplastic resins
is viscosity, because it is relatively easy to measure. Using severaI instruments e.g.
capillary rheometer, cane-plate rheometer, etc., the viscosity can be measured over severa!
decades of shear rate, but to obtain the complete curve is impractical as a tool for routine
quality control, as tao much time and labor are required. For this type of application, a
single-point measurement is preferred. The zero shear viscosity is an attractive candidate,
because it is very sensitive to molecular weight.
However, measuring the zero-shear viscosity is not straightforward, as available
rheometers are unable to operate at shear rates low enough ta measure the zero shear
viscosity. It is particularly difficult to measure this quantity for polymers that have a very
broad molecular weight distribution or a high degree of long chain branching. The basic
problems are the detection ofvery slow motions and very small forces. [n sorne cases, the
motion of the fixture is sa slow that it cannat be detected, or a rneasurement takes sa
much times that the polymer degrades.
The magnetoviscometer (MVM) was recently developed in Austria for the express
purpose ofmeasuring the zero-shear viscosity, and a prototype has been loaned to McGiU
University for evaluation.

CHAPTER 1: lNTRODUCTION
The objectives ofthis work were as fol1ow:
1. Ta develop a methad to prepare samples for use in the MV1v1.
2. Ta evaluate the MVM and compare its results with low-trequency dynamic data.
3. To evaluate the suitability of the MVM as a tool for routine quality control.
4. To determine the limitations of the MVM.
2

3
CHAPTER2
IMPORTANCE OF THE ZERO-SHEAR VISCOSITY
2.1 Dependence of viscosity on shear rate
The viscosity of molten polymers depends on a number of factors, including shear rate,
temperature, pressure, and resin composition (chemical structure, molecular weight distribution
and presence of long chain branches, nature and concentration of additives, fillers, etc.). The
viscosity of a molten thennoplastic decreases sharply as the shear rate is increased
1
, but at
sufficiently low shear rates, it becomes independent of shear rate. The limiting low-shear rate
value is called the zero-shear viscosity, 110. Figure 2. 1is a plot of viscosity versus shear rate at
severa! temperatures for a typical, commercial, low-density polyethylene. These data were
obtained by Dr. J. Meissner with a specially modified Weissemberg Rheogoniometer. These
rnpressive measurements were never repeated, because of the enonnous time and expense
involved.
At high shear rates, data often fall very close ta a straight line on a log-log plot,
and a power law can thus be used to describe the dependence of the viscosity on shear rate
in this region:
k
'/1-1
Tl = r
(2-1)

For a Newtonian tluid, n=1 and K= vscosity. As written above, the power law has
severa! basic tlaws, and a better fOrOl is:
(2-2)

10
10 - 4 10 3 10 -2 10 -1 1 10 10
2
10
3
Y(5 ')
Figure 2.1. Viscosity versus shear rate for several temperature-
Meissner's data for low density polyethylene
l
. Temperatures, from top
ta battom are (OC) : 115, 130, 150, 170, 190, 210, 240.
.10
4
where . is a materia! constant with units of time. However, the zero-shear viscosity must
be know ta use this farm.
CHAPTER2: lMPORTANCE OF THE ZERO-SHEAR VISCOSITY
5

2.2 Dependence of viscosity on molecular weight


It is known that rheological properties depend on molecular weight distribution,
and it has been proposed
2
that viscosity or complex viscosity data can be used to infer the
MWD of linear commercial polymers. Knowing the rvlWD of a resin is sometimes very
critical, because a small change can render a resin useless for its intended application.
The strong dependence of polymer viscosity on shear rate is attributed to the strong effect
of shearing on the entanglement densityJ. At low molecular weights, there are no
entanglements, and the viscosity is proportional to the molecular weight and varies little
with r over a wide range of shear rates. As the molecular weight increases, a point is
reached where '1(1 starts to increase much more rapidly over a tirly narrow range of M.
Above this range, the slope of the curve of log 'lu versus log M reaches a value of about
3.4-3.5 for Many linear polymers. For monodisperse polymers, this implies:
'70 = k N / 3 ~ {2-3}
For polydisperse materials, it is often round that
(2-4)

where Mw is the weight average molecular weight. Figure 2.2 iIlustrates this behavior.
As the moiecular weight increases above the critical vaIue for entanglement, Mc,
where 110 starts to rise with M
w
l
.", the melt becomes strongly dependent on shear rate,
eventually approaching a power-Iaw (Eqn. 2-1).

o
~
C)
.2
+
1-
~
tJ)
z
o
o
o 1 2 3 4
CONSTANT + logM
5 6
6

Figure 2.2. Log 110 versus log Mfor several polymers. The data are
shifted ta avoid overlap. The lines shown have slopes of 1.0 (left
portion) and 3.4 (right portion)l. 1968 by Springer Verlag.

7
CHAPTER3
METHOOS OF MEASURING VISCOSITY AT LOW
SHEARRATE
3.1 Falling body viscometer
3.1.1 Falling ball viscometer
The absolute viscosity ofa Newtonian liquid can be determined tram a measurement of
the time required for a ball to faIl a certain distance in a cylinder containing the liquid
3
. It is
probably the simplest and certainly one of the oldest methods tbr measuring viscosity. The
viscosity is calculated trom:

where: t=
" = t . (Sb - Sl' ). B
time for ball to fall tram one mark to another on a glass cylinder
(3-1)

Sb= specifie gravity ofthe ball


SF specifie gravity ofthe tluid at the measuring temperature
B= ball constant
The ball constant can be determined by calibration for a given shape offalling body and
size ofcontainer. Stokes' equation can be used to derive an exact equation for a sphere falling
under the influence ofgravity in an infinite sea ofNewtonian liquid:
(3-2)
where VrxJ is the terminal velocity, d is the ball diameter, Pb and Pr are the densities of the ball
and tluid, and g is the acceleration due to gravity.
The presence of the cylinder walls reduces the terminal velocity, and the commonly

CHAPTER 3: METHOOS OF MEASURING VISCOSITY AT LOW SHEAR RATE


used Faxen equation[ol,SI gives the correeted velocity to the 5
th
arder:
VIJ =V!.:
where: le
D= measuring cell diameter
v = actual ball velocity as measured
VIl = correeted ball velocity, reJated to viscosity by (3-2)
8
(3-3)
(3-4)

The correction is actually an infinite series. One can show that the 5
th
order approximation
given by (3-4) is a good approximation for the ball diameters used in this work (2 and 3 mm).
The Faxen equation up ta order lOis shown in Fig. 3. 1.
le +r
(3-5)

Since the MVM is intended for use with me polymers, which are viscoelastic, it is
essential ta know how viscoelasticity affec1 the flow around a sphere in the limit of very
1\
et dl/.
slow flow. MeKiniey, RaSiliUSSeIi, and 1(a99ager (1994t
'
and Arido and McKinley
(1997)7 have shown that at very small Deborah numbers (ratio of relaxation time of fluid
ta charaeteristic time for the deformation) the flow of a viscoelastic tluid does, indeed,
approach that predicted by Stoke's equations, i.e., that of a Newtonian fluid at small
Reynolds numher.

9
0.5
op
..:... 0 ---- ---------- ----------------
.a
-
- --..
-........ ---..
--
-.
~
~

- - - - - -f1
-0.5
_.
.,_____ __ .0
--- f3
------_. --'"-- --
f5
----te
f8
_. - - f10
-1
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
d(mm)
Figure 3.1. Faxen correction for various arder ofapproximation.

CHAPTER3: METHOOS OF MEASURING VISCOSITY AT LOW SHEAR RATE


3.1.2 FaIling Needle Viscometer
10
ln this methocL a slender cylinder with hemispherical ends (the needle) is used instead
of a sphere, still under the influence of gravityH. 9. For Newtonian tluids, the creeping tlow
expression for the viscosity, incIuding the wall etfect, is:
(3-6)

with K < 0.03, where K =d/D, d is the diameter of the needle and D the diameter of the
container. This equation assumes an infinitely long needle.
For a power law tluid, r = K(y) n , the following equation gives the terminal velocityl:
3-7)
where A(n,K) is a function arising from the solution of the flow field bet\veen the needle and
the cylinder wall.
A laser is sometime used for the detection of the needle111, but this is not useful when
the melt is opaque or degrades with time.
3.1.3 Centrifuge Bali Viscometer
This is a variation of the falling baIl vscometer. Here, the tluid is contained in a
horizontal cylindrical glass tube and the ball is subjeeted to centrifugai acceleratian11. ln arder
ta maintain constant acceleration for a ball moving in the chamber (see figure 3.2), the
following relation must hold:
(3-8)
where RPM1 and RPM
2
are respectively, the revolutions per minutes of the rotor at position PI
(measured trom the center of rotation) and rime t = tl, and at position P:! and t = t2. The
centrifugai acceleration ac ofa ball at position P(cm) and motor speed RPl\4 is:

CHAPTER 3: METROnS OF MEASURING VISCOSITY AT LOW SHEAR RATE 11


(3-9)
The viscosity is calculated tram:
(3-10)

where 0) is the speed ofthe motor in RPM'I and band c are empirical constants.
This instrument has sorne good f e a t u r e s ~ the temperature can be maintained trom
ambient to over 400C, and only 0.5 ml ofsample is required. A wide range ofviscosities can
be accommodated, trom 10-
1
to lOS Pa-s. In theory, IOIU Pas is achievable, but ooly one-data
point per day can be obtained.
3.2 Magnetoviscometer
[n the falling ball method, gravity is the driving trce for the motion of the sphere. To
obtain the zero-shear viscosity of a typical polymer melt, this is often insufficient, because the
ternnal velocity is too small. By adding a magnetic field to the gravityl2. 13. 1", the time of
experiments becomes shorter, sa that degradation ofthe polymer can be avoided.
3.2.1 Principle of operation
The Magnetoviscometer is a falling ball instrument that makes use of a magnetic field
(15.
16
1. It was developed by Paar and others at the University oflinz to overcome the problems

12
1 1
1
1
0.8 ~
1
1
0.6 j
1
i
1
0.4 .,
CIo * constant
RPM =constant
/1
:i
!!.
u
..
08
06
04
a.l =constant
RPlVI ~ constant
PI(RPlVld
2
= P
2
(RPM2)2
O'v
O-----------.........-------l
0.8 06
Position la. u.)
04 02
08 0.6
Po""on (L u.J

a) b)
Figure 3.2. a) centrifugai acceieration is proportional to the baIl position
from rotation center at constant RPM; b) by decreasing the rotor RPM
according to Eqn. 3.9, a constant centrifugai acceleration cao be obtained.

of previous falling body viscometers, Le., to get to a very low shear rate with only gravity as

CHAPTER 3: METHOOS OF MEASURING VISCOSITY AT LOW SHEAR RATE


the driving force, the ball velocity is very small.
13
In arder ta increase the driving force for flow, and thus reduce the rime for an
experiment, an iron sphere is acted on by an inhomogeneous magnetic field in addition to the
gravitational force, within a measuring cell filled with the melt (see figure 3.3, 3.4 and 3.5).
Two permanent magnet fixtures generate the magnetic field. For example, the force for a 3 mm
sphere can be about 40 times stronger than the gravitational field. The magnetic trce F ~ I is:
cT!
F.'v/ = m%.\/ H c
where: m= ball mass
(3-11 )
;t\[ = magnetic susceptibility ofball material
H = magnetic field strength

aH
ax
x=
gradient of magnetic field strength in vertical direction
vertical distance abave the plane
It is assumed that the gradient of magnetic field is vertically uniform over the distance where
the time offall is measured.
The gravitational force, Fa, is given by:
(3-12)

The viscous resistance (drag), F


v
, of the melt opposes the force driving the ball. For a
Newtonian tluid this is:

14
F
v
=3 d
K
x-l1 V-o
~ .. - - ~ - - " - - - " - - - FM = mkx...HaHlx
or
F
G
=mt< 9
H..-----

POLESHOE
Figure 3.3. Measurement principle.

15
Figure 3.4. Picture of the magnetoviscometer.
Figure 3.5. MVM ann with the magnets.

CHAPTER 3: METHOOS OF MEASURING VISCOSITY AT LOW SHEAR RATE 16


(3-13)

The tenninal ball velocity, VJ, is detennined by the balance of viscous resistance and
magnetic force, F
v
= FM + Fa, or from the balance of viscous resistance and gravitational force,
F
v
= Fa in the absence ofthe field. It usually takes 0.01 to lOs for the baU to reach 99.9% ofits
tenninal velocity. The ball position is monitored by an induction coil. The inductance of the
coil increases when the ferromagnetic ball is introduced. At constant velocity, this produces a
sinusoidal function of time. There are two types of measurement: peak/peak measurement,
used for low viscosity fluids, and middle range measurement.. tor higher viscosity tluids.
Measurement procedure l\Jleasurable viscosity range "
Peak/Peak measurement
10 to 5x10-J Pa.s
Middle Range measurement IOxIOJto 5xl0
5
Pa.s
Anominal shear rate is detined as follows:
. V"
y=c--
d
(3-14)
Values ofthe factor c between 0.4 and 2.0 have been proposed in the literature and a value of
c=1.3 is used for the MVM.
The shear rate distribution around a sphere moving at constant velocity in a Newtonian
tluid can be derived as follows:

Y
= - r ~ ( ~ J +.!. cJv
r
rO... ao
or r r
The solution of Stokes equations gives the velocity distribution:
(3-15)
(3-16)

CHAPTER 3: METHOOS OF MEASURING VISCOSITY AT LOW SHEAR RATE


(
3a a
J
)
VII =-Vcosf) 1--+-.
4r 4r'
(
3a ,,3)
V
r
=V 'cos8 1--+-.
2r 2r'>
Thus, the shear rate is:
1. 1 ,[ ( 1. 3a a
3
1. .. ( 1 Ja li;)l
I r r t / l = ~ casB --"'--., ----;-)T:sm8 ---.""--l)J
r 2r - r r 2,. - 2,.
17
(3-17)
(3-18)
(3-19)
Figure 3.6 shows the shear rate distribution around the baIl. At the location r = a and
8 =0, the shear rate has its maximum value:

. f' f'
yTf1 I
nuL
\( ==:;- =-,
_a ,
The maximum shear stress is thus:
r==,,Y
(3-20)
(3-21 )

The MVM software calculates a shear rate". and it is of interest to see how this is related
to the maximum value for a Newtonian fluid. Using data l'rom this study: for 3mm bail,
40mm gap, polybutene, lI) = 13.2 s (a1ready corrected for the standardized distance of
6.5mm)
S 6.5mm
V=-= =0.492mm/s
1%J 13.2s
Faxen correction: VIX) =V . le =O.492mm1S 4.0 19 == 1. 979mm/ s
rl'niL\( == Va) = 0.66s-
1
(Newtonian equations)
d
rMm == C Va) = 0.858s-
1
when c = 1.3
d

18
3.5 3 2.5 2 1.5 1 0.5 o
3
2 --------1
1
o
3.5
-cercle i
rate of-50 1
"""'-shear rate of-4O 1
i
--"'-shear rale or-30 1
2.5 -Jl-shear rate of-20

rate=O
"""'-shear rate of1 0
0.5
1.5

x
Figure 3.6. Shear rate distribution around the bail.

CHAPTER 3: METHOOS OF MEASURING VISCOSITY AT LOW SHEAR RATE


Value calculated by the MVM software: YMVM == O.864s-
'
3.2.2 PeaklPeak Measurement
19
For this technique, the time required for the ball to tll from one peak ta the other is
measured (see figure 3.7). Knowing the viscosity ofa calibration substance (8), the viscosity of
the unknown tluid can he detennined as foUows:

V,,(B)
'1 == 'lB V"
One can also calculate the viscosity direetly from the faIling time:
II) K
'1='1B'--= '/,
r,,(B)
'18
where K =ln (B)'
(3-22)
(3-23)
The constant K is determined for a gravitationai field alone and tor defined spacings
between the magnets. Between these spacings, K is calculated by linear interpolation. and tr
longer spacings, by extrapolation.
The temperature dependence of the bail detection system is taken into account by
correcting the measured falling time ofthe ball to a standardized measuring distance of6.5mm.
When the temperature rses, the distance between the two colis (peaks) increases, and it is
corrected using the cell constants A and B.

/
t =---
<Il A+B.T
where ta == falling rime for standard distance
(3-24)
u

o
t
20

J ~
~
f

r
s.
s
Bali starts
fa/ling
Figure 3.7. Peak/Peak measurement evaluation, where U is the
sinusoidal voltage, t, the time, te, the peak/peak falling time and Sa:, the
standardize distance.
t
r,
~
~ .


s
BaIl enters
Iinear range
Figure 3.8. Middle range measurement evaiuatioD, where Uis the
sinusodal voltage, t, the tinte, S, the distance, fI, the linear range and
L\U/At. the gradient.
CHAPTER 3: METHODS OF MEASURING VISCOSlTY AT LOW SHEAR RATE

t= measured falling time


21
3.2.3 Middle Range Measurement
For this technique, only the gradient IixJlit (x being the distance and t the time),
detennined in the linear range between the two peaks, is used ta caIculate the velocity (see
figure 3.8).
This is a useful technique for a high viscosity materiaI. because it requires a shorter
measuring rime. The ball velocity can he calculated fram:
v = / * ll,-c
C - DT iiI
(3-25)

where C and D are empirical constants, that correct for the augmentation of the distance
between the two peaks when the temperature increases, T is the measurement
temperature, and V is the bail velocity. The viscosity is then calculated as tbIlows:
"
=K . ~ = K (C +D T}._I- ~ ~
V A-c!
I ~ l
(3-26)

The shear rate i and the shear stress rare calculated using equations 3- 14 and 3-21.
3.2.4 High-pressure cell for the Magnetoviscometer
A high-pressure cell has recendy been designed for the lVlVM by Gahleitner and
Sobczak
l1
for studying the pressure dependence of viscosity. The falling ball method is
advantageous here, because there are no rotating parts(requiring seals) or pressure
gradients. The cell is hermetically sealed by means of a gasket made of nylon or PTFE; no
supply lines to the inside of the sample cavity are therefore necessary. Heating the
specimen in the closed cell generates the required and a cIosing screw allows the
final setting of the pressure. When the screw is the pressure inside the cell rises
because the sample has a low compressibility. The cell can operate up to lOOO bar
(iXIO
s
Pa) and 523K.
The high-pressure cell has not been used in this project. but it is a very interesting
possibility for future research. It would be interesting to compare I1I1(P) data from the
MVM with lJ(r p) data from the new high-pressure sliding-plate rheometer recently
developed at McGill
lK

CHAPTER 3: METHOOS Of MEASURING VISCOSITY AT LOW SHEAR RATE 22

23
CHAPTER4
EXPERIMENTAL METHOS
4.1 Polymers Studied
The resins studied were polyethylenes made using metallocene Csingle site")
catalysts. The Exact resin was made by Exxon, and Dow Chemical made the athers.
Sorne resins were received as pellets and athers in pawder form. Exact resin was chosen
ta develop and study the sample preparation technique, because in the range of shear
stresses generated by the ~ , this resin is in its zero-shear viscosity region. The athers
resins, 0803-1, 335A, 335B, and 335C have similar molecular weights but various degrees
of branching.
Table 1. List ofthe resins tested.
Resin Manufacturer Density (glcm
J
) ~ I w LCD Comonomer
Exact EXXON 0.9100 119400 No Butene
0803-1 Dow Chemical 0.9374 100900 No Butene
335A Dow Chemical 0.9592 88900 Yes None
335B Dow Chemical 0.9583 92600 Yes None
335C Dow Chemical 0.9575 93400 Yes None
The resins that were received in powder form had to be transtrmed into pellets.
Powder is a problem when one applies vacuum to the press for molding, because it gets
aspirated by the vacuum pump. Here, the resins were molded into a rectangular sheets
with dimensions of 4 X 6 ~ X 0.025 inches using a Carver press. The mold was a
stainless steel plate with a reetangular hole in it. In compression malding, this mold is
filled with polyrner and sandwiched between two Mylar sheets and two steel plates, to
allow easy removal of the cooled product. The press is then heated until it reaches
thermal equilibrium at 150C. The mold and the pawder are placed in the press, and a low
pressure from 0 to 5 metric tons is applied for five minutes in arder [0 force out trapped
air and promote complete melting of the powder. Then the pressure is increased ta 15
tons in two steps of 5 metric tons at 5 minutes intervals. This is ta remove any remaining
air and ensuring good sample consistency. Finally, the mold is coaled to roam
temperature by circulating water through the press for 15 ta 20 minutes. The sample is
then removed, and using a blade or scissors, it is eut into small pieces. The pieces should
be less than 4mm in size in order ta fit into the MVM press.

CHAPTER4: EXPERIMENTAL METHODS


24

4.2 Sampie Preparation Technique


4.2. 1 Design of the press
[t was tirst necessary ta design and construct a press to make samples for the
MVM. The required sample size is about 3cm
3
The "'mother cell" (an inner mold) used
ta produce cylindrical samples of 6.9mm inside diameter and of 25mm in length, is shawn
in the Fig. 4.1 (see also figure 4.2). The mother cell is different from the measuring cell
mainly in that it has a magnet at its bottom ta ensure that the iron bail stays at the center
of the sample during molding. There are two types of mother cell: one for peak/peak
measurements and one for middJe range measurements. The peak/peak cell bas an angle
Figure 4.1 a) Mother cell for peak/peak measurements, b)
Mother cell for middle range measurement.

30
a)
r11CV'8t
6.9
b)
25

26

Figure 4.2. Picture of the cells: the measuring cells are on the left and
the mother cell is on the right.
at the bottom of 150
0
, and the middle range cell has an angle of 178
0
The angle in the
cells is very important. The angle in the peak/peak cell allows the bail to center itself for
the next experiment. This is not needed for the middle range, since the ball does not reach
the bottom of the cell. The bail starts further up and stops near the second peak as
explained in section 3.2.3. Both are made of stainless steel as opposed to the Hmeasuring
cells" which are made of brass. The mother cell needs to be strong to support the
pressure in the press. They are made of brass, mainly because it is cheap. SA if the
material under study is hard to remove (for example a highly viscous ail), one can simply
discard the cell.
Figure 4.3 shows the important features of the lVlVM press (see also figure 4.4). It
has a I200W, 120V heater band, which is controlled by the temperature controller. The
hydraulic cylinder has a maximum capacity of 10 000 psi (6. 9X10'Pa). [t has a plunger a
diameter of 1mm and long enough to eject the mother cell. It has a copper seaI support a
vacuum inside the press and to keep the resin inside. The mold is water-cooled. There is
aIso a hole for connection to a vacuum pump to prevent the tormation ofair bubbles in the
sample. A vacuum of 26 ioches of Mercury (660 mm Hg) can be generated. The press
aIso has a screw at the bottom of the mold to release the mother cell.

CHAPTER4: EXPERIMENTAL METHOOS


27

4.2.2 Procedure for Sample Preparation


The molding procedure that was developed is as follows. First, a release agent is
applied to the mother cell inner surface if the resin tends to stick ta the mold. Then an
iron ball (2 or 3 mm diameter) is placed inside. The bail is centered by the magnet. The
screw is put in its position, and the cell is pushed to the bottom of the mold with the help

28
hydraulic cylinder

secl
~
plunger
tovacuum
........----n- heating coil
-+'---....
coollng

Figure 4.3. Design of the MVM press.


of the piston. The pellets are poured ~ up to the vacuum hole. The mold is then sealed
by the p i s t o ~ and the vacuum pump is tumed on. A vacuum of about 660 mm Hg is
maintained for 10 min at room temperature. At this point, the heater is tumed on for 20
to 30min. A pressure of 1500 ta 2000 lbs (680-910 kg) is then applied for 5 to la min. It
is important that the pressure not exceed la 000 psi. because this would damage the
copper seaI. \Vhile \vaiting, the vacuum pump is tumed off. since the vacuum hole is
blocked.
Ta cool the mold, the heater is tumed off, and the water valve is opened. It
normally takes fram 2 ta 5 min ta cool the mold ta a temperature of 3DoC. To remove the
sample, the pressure is released, the screw is removed. and the cell is pushed out of the
cylinder using the piston. The sample shauld then come out of the cell easily.
Finally, the sample needs ta be eut ta fit in the measuriog cell. The first eut is
made at ISmm from the bottom (see figure 4.5a). When doing a middle range experiment,
the sample has to be eut again at 4.5mm. Theo the segment eontaining the baIl is tumed
180 (see figure 4.5b.). The sample and segments are placed in the measuring cell, and the
cap is screwed on.

CHAPTER -l: EXPERIMENTAL METHOOS 30

4.3 Magnetoviscometer operation


The settings of the MVM eontroller were the same for ail measurements. The
middle range arm was used, with a fibergIass caver avec it ta ensure that the temperature
inside was constant and uniform. The instrument cao be operated from room temperature
up to 300C. The distance between the two magnets cao range from 36mm to SOmm.

31
then

- """"
---------_-'_---1---
18mm
18mm
..... .. .
4.5
Figure 4.5. a) cut for a peak/peak measurement, b) cuts for a middle
range measurements.

a) b)

Based on experience with ather measurements were delayed for about 15 min
ta ensure that the sample had reached the set temperature.
Ta make a a measuring cell is Ioaded into the arm, and the tiberglass caver is
slid inta place. The parameters chosen for the test are entered, and the computer contrais
the operation.
Ta clean the it is taken out of the arm, the cap is unscrewed, and a
screwdriver is inserted in the sample. The cell is then caoled with water ta room
temperature, and the polymer is taken out by pulling on the screwdriver.

CHAPTER4: EXPERIMENTAL METHOOS 32

33
CHAPTER5
RESULTS AND DISCUSSION
S.l Temperature in MVM
The distribution of the temperature in the MVM arms was measured to learo if
there was a temperature gradient in the sample and if it was affected by the surroundings.
This study was done to ensure that there was no temperature gradient inside the sample.
It is known that a temperature variation of 1C, depending of the material used't can cause
variations in viscosity of 5 to 10%. A special cap was fabricated ta make it possible ta
insert a thermocouple inside the sample. Two hales were made: one in the center (which
was an enlargement of the hale already existing) and one at the edge. [\Ileasurements were
made at four points as shown in Fig. 5. 1: two from the center hole (one at the center and
one at the bottom), and two from the hole on the edge (one at the center and one at the
bottom). A caver made of fiberglass fabric was used ta provide additional insulation for
the arm.

Figure S. L Temperature in MVM.
A J-type thermocouple was used, the set temperature was 130C. and the Exact

CHAPTER5: RESULTS AND DISCUSSION


34

resin was used. The data were collected after 45min for the peak/peak arm.. and these are
shawn in table 2. One can see that when there was no caver. the variation in the
temperature was O.6C, and when there was a caver" the variation fell to O.3C. The
fiberglass caver was therefore used for aIl the experiments.
Table 2. Temperature in the MVM peak/peak arm, with and \vithout cover.
No Caver With Caver
A 136.2C 137.6C
8 136.3C 137.6C
C 136.S0C 137.9C
D 136.SoC 137.SoC
At the beginning ofthis research, the MVM was install in a room \vere there was
an air conditioner with an ON/OFF controller. Every 15 min or so.. there was a sudden
draft of cool air. Since there was a significant variation in the room temperature near the
MVM arm (due ta the convection of the air and its temperature) (see figure 5.2), [ tracked
the variation of temperature at the center of the sample. [t varied between 136.2C to
135.SoC when the air conditioner went ON or OFF with no cover on the peak/peak arm.
A cardboard box was placed aver the apparatus ta see the effeet of reducing the
forced convection. As shawn in Figure 5.2, the box damped the variation of temperature
near the arm, implying a reduced variation in sample temperature.
For the experiments whose data are reported here, the MVM was moved ta
another laboratory in which there was no major variation in temperature near the arm. It
was thus not necessary to use the box.

35
24.5 .,.----------------------------..

24 .
23.5 .
o 23
Ga
!

" 22.5 .
-
!
:2
! 22
Ga
~
E
~ 21.5 .
21 -
20.5 -
....
.. -
...
.. -
,

,
. ,
. ,
, .
~ ,
.
t
1
, r
.
.
o.
o
.,
~
'without the box:
-withthe box
2:30 2:00 1:30 1:00 0:30
20 ~ . -----.....----.......----------------....
0:00
lime (hrs)
Figure 5.2. Variation of the room temperature near the MVM arm:
effect of air conditioning.

A temperature calibration was done ta ensure the comparability of data with thase

CHAPTER 5: RESULTS AND DISCUSSION


from other instruments in the laboratory.
5.2 Effect of sample preparation technique on the zero-shear viscosity
measurements
36

A series of tests were carried out ta see if the sample preparation technique had an
effect on the viscosity measured by the MVM. A one-haif traction of the 2 ' ~ design was
used ta set the parameters for the operation of the press. With this type of design.. one can
use 8 samples instead of 16 ta compare the interactions of the parameters \vith each other.
Table 3 shows the parameter values used. [n the table.. a --+'" indicates the maximum
value of the pararneter, and a" indicates the minimum value.
Table 3. One-half fraction of the 2
k
design.
Run P T HP HT
1
-
-
.
-
2 +
.
-
+
3
- + -
+
4 + + - -
5
-
.
+ +
6 +
-
+ -
7
.
+ + -
8 + + + +
Where the minimum and maximum values are:
Min (-) Max(+)
P (pressure) 1500-2000 lbs 3000-3500 lbs
T (temperature) I50
a
C I8S
a
C
HP (compression time) Smin 10 min
KT (bestiol( time) 20mn 30 min
The vacuum was constant at 26"Hg, and the cooling time was bet\veen 2 and 5 min. The

CHAPTER 5: RESULTS AND DISCUSSION


37

ball diameter was 3mm, and the Exact resin was used.
The test conditions were kept constant.. and the middle range measurement was
adopted with the fiber glass caver in place. The magnetic field was used with a distance
between the poles of 36mm. The test temperature was 130C at the middle of the sample,
and the equilibration time was 800s. The sample was cut as xplain in sction 4.2.2.
A separate study was done to evaluate the noise level in the data. The experiment
design is shawn in table 4. Ten samples were made.. and aIl were used. even if they had
defects (such as aif bubbles before or after the measurement. baIl not centered. white
spots, etc.) (see figure 5.3" run 9). Eliminating the samples with defects left 4 samples
(see figure 5.4, run 9). Those samples had an average measured viscosity
Pas, and the variation was 2%.
Table 4. Evaluation of the noise.
RUD
9
p
T
+
HP
+
UT
+

About 4 samples were made for each experimental condition for a total of 28
samples (see figure 5.3). Ali the samples were used even if they had detcts. Eliminating
the samples with defects left ID (see figure 5.4). These samples had an average measured
viscosity of 2.64XI 0
4
Pas" and the variation coefficient was 3%. [t was concluded that
the effect of variation in sample preparation technique is negligible. because the variation
coefficient is below the reproducibility of the MVM, which is about 5%. The only factor
i From the technical Specifications orthe MVM

38
28000 ~ - - - - - - - - - - - - - - - - - - - - . ,
27000 -
0 0
~
0
0 0
0
1
0

8
26000 -
0
0
~
0
8
0
0
~
~ 25000 -
~ en
ni
0
Q.
0
'-'"
~ 24000 -
0
0
en
0
u
en

:>
23000 -
0
22000 -
21000 - 0
10 o
20000 -+------"r------r--1---r--1---.,.....1-----i
246 8
Runs number
Figure 5.3. Parameter Analysis, before elimination of defective samples.

39
28000 -r------------------------,
21000 -
10 o
20000 - + - - - - - - - , . I - - - - - - , I . . . - - - - - . . - - I - - - ~ I - - - - f
246 8
Run number
Figure 5.4. Parameter Analysis, defective samples eliminated.

that has an appreciable effect on the measurement of the viscosity is the presence of air
bubbles. Ifair bubbles are presence, the measured viscosity is lower than the true value.
CHAPTER 5: RESULTS AND DISCUSSION 40

5.3 MVM versus RDA II values


Another set of experiments was done to compare the results of the MVM with
low-frequency dynamic data. The resins used were 0803-1. 335A. 3358. 335C. and the
test temperature was 150C. The ball diameter and the distance bet\veen the magnets
were varied to obtain a wide range of shear rates. The nominal shear rate (the value
indicated by the MVM) is dependent on the falling time. sa ta get a curve of viscosity
versus nominal shear rate.. the distance between the magnets is varied. (Using a smaller
ball diameter also extends the range, because the force applied varies \vith the mass of the
ball, but it was found that the 2mm baIl diameter could not be used tor the middle range
experiments.) Middle range experiments are usually used for high viscosity resins.. which
require a high magnetic force. High forces can only be achieved using "vith the 3mm ball.
(The 2mm baIl has not been calibrated for use with that arm. ) For middle range
measurements.. the gradient xll must be known ta calculate viscosity.. which means
that the amplitude of the signal (voltage in mV) must be knO\vn. but this had been
adjusted for the 3mm ball. For this reason viscosities determined using the 2mm ball
were not valid and have been excluded from the following analysis.
The low-frequency dynamic data were obtained using a Rheometrics Dynamic
Analyser II (RDA), a controlled strain rotational rheometer. By using the Cox-Merz
Rule, which is always valid in the limit of very low frequencies.. one can convert the
complex viscosity into a steady-shear viscosity. Each of the RDA curves is the average
of at least 5 runs. The MVM curves show data for 4 or 5 samples. Viscosities were
determined at several force levels (distances between magnets) using a 3mm baIl. In this
way, it was possible ta get a curve ofviscosity versus nominal shear rate.
Figure 5.5 shows the viscosity as a function of shear rate tor the 0803-1 resin.
This figure is particularly interesting, because it was possible to rncasure the true zero-
shear viscosity using the RDA. This value was 5.78X10
3
Pas. The average of the MVM
data was 6. 70X10
3
Pas. These include repetitions of the 5 samples. The points to the
right were obtained using the 36mm gap between the magnets. and the points situated
between 2.5XIO
2
and 6.5XIO-
2
SI were obtained using variOlls gaps between the
magnets. The shear rate decreases as the distance between the magnets increases. The
three points situated around 2.0X10-
3
Sl were obtained using the gravitational tield. The
difference between the two curves is about 15.90/0. It is possible that ail the data coming
from the RDA were measured, in faet, at 151C instead 0 f 150
e
C. which would lower the
value of the viscosity. This was found after the resins (OS03-L 335A. 3358, and 335C)
were tested, when a temperature calibration of the RDA was carried out. The effect of
temperature would be different for each resin t e s t e d ~ since each has a different shift
factor, aT. It would be interesting to measure these shifts to see the etfect on the figures,
but this was not within the scope ofthe present project.
Figure 5.6 shows the viscosity versus shear rate for polymer 335A. The MVM
data are for 4 samples and the average values are shown in table 5. In this case, for this
material, this is the value from the RDA curve. The difference between the two is about
1%.

CHAPTER5: RESULTS AND DISCUSSION 41

42
1.00E+04 - r - - - - - - . . , . . . - - - - - ~ - - - - - - - - - - - - - - - - - . . ,
o MVM. P6
A MVM. P7
C MVM. P9
+ MVM. P11
MVM. P13
- - RDA approx
RDA
E:I
t
1
1
1
1
1
IVlscosity Avetctge values:
~ m m : 6.70e03 Pa.s
RDA: 5.78eo3j Pa.5

1.00E+01 1.00E+OO 1.00E-02 1.00e-C1


Shear Rate (5-1)
1.00E.Q3
1.00E+03 .....-----......-----....-----------------....
1.00e-04
Figure S.S. Viscosity curves for 0803-1 at a temperature of 150
C
C.

43
1.00E+05 ...
1
!R
. _. - -_. _. - -1- _. _. _ ...........
-
-;;

1.00E+04 t---------+--- ----<.__


';i
o

>
<> MVM, A1
X MVM.A5
o MVM.A7
a MVM.A8
- - - - RDA approx
1 RDA
1.00E+OO 1.00E-01 1.00E-02
Shear Rate (5-1)
1.00E.Q3
1.00E+03 .....------........------......---------------'
1.00E-04
Figure 5.6. Viscosity curves for 335A at a temperature of 150C.

44
1.00E+OS ...
MVM. B1
Il MVM. B2 '1
C MVM. B4
Z MVM, B6 1
- - RDA approx 1
1
---RDA :
1

!
..
e:.
1.00E+Q4
lit
o

>

1.00E+OO 1.aOE-01 1.00E-02


Shear Rate (5-1)
1.00E-03
1.00E+03 .... ...
1.00E-04
Figure 5.7. Viscosity curves for 3358 at a temperature of I50
a
C.

45
1.00E+05 , . . . . . - - - - - - . . . " . . . - - - - - - ~ - - - - - - - - - - - - - - . . . .
1
, Il ~ ,
__ _ _ -. .-. -. - -- _ _ 0-. .-.j. ~ .. ~ _ _ ~ _ ~ .. .- _ _
o MVM. Cl
a MVM. C2
Z MVM. CS
o MVM. C6
RDA
- - - - RDA approx
-;r
iii
e:.
~ 1.00E+Q4 1-- ---4--- , '
1ft
o
~
~

1.00E+OO 1.00E-Dl 1.00e-D2


Shear Rate (5-11
1.00E-D3
1.00E+03 ....------.....------....---------------'"
1.00E-D4
Figure S.S. Viscosity curves for 335C at a temperature of 150C.

CHAPTER 5: RESULTS AND DISCUSSION


Table 5: Viscosity of resins 3 3 5 A ~ 335B. and 335C
nMVM.avl! 11 RDA. av!!
335A 1.18XIO" Pas 1.17Xl0
4
Pas
335B 3.93XIO" Pas 3.16Xl0
4
Pas
335C
6.35XIO" Pas '&:65XI0
4
Pas
46

Figures 5.7 and 5.8 show data for polymers 335B and tor 335C. and the averages
are tabulated in table 5. For resin 335B, the difference is 19.70/0. For resin 335C. the
difference is 10.9%. For these two polymers't the RDA value for the zero-shear viscosity
was estimated as it was not possible to get a low enough frequencies ta measure the true
zero-shear viscosity. [t is possible that the estimation gives a value of 110 that is tao low,
which would expIain at least partly the discrepancy between the values.
One can say that the comparison between the M V ~ l and RDA is reasonably good
when one consider the effect of the temperature on the RDA curves and the approximate
value of the RDA zero-shear viscosity.
5.4 Reprodueibility
There are two types of reproducibility: hetween sample and within sample. The
between sample reproducibility is shawn by Fig. 5.4. Since it was shawn that there is no
appreciable variation due to sample preparation, it is assumed that aIl he sarnples are the
same. The average for all samples is 2.62XIO" Pas, and the variation coefficient is 3%.
Fig. 5.9 shows the reproducibility within a sample. A PDMS sample was studied
at 30C using the peak/peak test. The measurement was repeated ten times with a 3mm
balL The average value was 2.70XI0
4
Pas, and the variation coefficient \vas 4%. Since
both types of reproducibility are within the value given by the technical specification of
precision of the MVM, which is 5%, one can say that the MVM gives the specified
precision as long as the sample selection criteria is follow..

CHAPTER 5: RESULTS AND DISCUSSION 47

48
2.85E+04 -,.-------------------------.
2.75E+04 .
2.80E+04 -+----------------:------------1
2.S0E+04
2.S5E+04
.-
en
t 2.7DE+04 -I-----_a__---II----,---J.--\_.

a-
oc;;
o
:;I2.65E+04 -1------f--1k----f----\--f----+--1-
>

10 8 6 4 2
2.S0E+04 .......-------------.......
a
number of repetitions
Figure 5.9. PDMS at 30C. The average is 2.669X10
4
Pas and the
variation coefficient is 4.0%.

49
CHAPTER6
SUMMARY AND RECOMMENDATIONS
A special press was designed and fabricated to produce samples tor the MVM.
The sample preparation takes about 35 min to 50 min, and it can produce samples with no
air bubbles. This sample preparation technique has no effeet on the measurement of the
viscosity. The only factor that causes an appreciable effect is the presence of air bubbles
which causes the rneasured viscosity to be lower than the true value.
A fiberglass caver was made for the MVM arm ta reduce variations in sample
temperature due to conduction in the arm, and variation of air temperature.
The MVM results obtained by varying the gap between the magnets compared
reasonably well with dynamic data, and the sample to sarnple and ron-to-run variation of
in the measurements is near 5%.
The prototype MVM has severa! limitations. The maximum viscosity that can be
measured is 5XI0
s
Pas, and this is insufficient for sorne polymers. For example, sorne
high-density polyethylenes have viscosities above 5X10
6
Pas. The maximum viscosity
depends on the falling lime; the more viscous the f l u i d ~ the longer the tlling time. The
sinus curve used to calculate the falling lime becomes thick and (ess precise.. until the
signal is mostly noise. It would be interesting to explore the possibility of using stronger
magnets.
The MVM moving parts (the arm and the magnets) should be placed inside a box
to protect them from variations in room air temperature.
It would also be advantageous to merge the twa arrns into one to avoid the use of
different calibrations for each. For the temperature distributions are not the
same in the two arms.
[t would be advantageous to use the 2mm baIl for middle range as
this would broaden the available range of shear rate. Sometimes the resin under study is
not in the 10\\1- shear rate Newtonian region when one is using 3n1111 bail. This was the
case for a HDPE. MH07 (for a spacing of T=180C. 'l=1.926XIO
s
Pas and the
shear rate was 8.663XIO"" S-l). It would have been interesting to see the results with the
2mm, which would have extended the measurements to lower shear rates__
[t will also be interesting ta do sorne experiments with the high pressure cell
described in section 3.2.4 and to compare the results with those l'rom the high pressure
sliding plate rheometer recently developed at McGill.

CHAPTER6: SUMMARY AND RECOMMENDATIONS


50

51
REFERENCES
1 Dealy, J.M., Wissbnm, K.F., Rheology and its Role in Plastic Processing", Van
Nostrand Reinhold, New York (1990)
2 Wood-Adams, P., Dealy, lM., "'Use of rheological measurements to estimate the
molecular weight distribution of linear polyethylene'\ 1. Rheal. p.761-778 (1996)
3 Park, N.A., Irvine, T.F.Jr., Falling Needle Viscometer: A new technique for
viscometry measurements", American Laboratory, Nov. 1988
4 HappeI, l, Brenner, H., I.Low Reynolds number Martinus Nijhoff
Publisher, p.318 (1986)
Bohlin, T., 1.0n the drag on a rigid sphere moving in a viscous liqllid [nside a cylindrical
tube'\ Transactions ofthe Royal Institute ofTechnology.. (Stockholm).. 155, (1960)
6 Becker, L.E., McKinley, G.H., Rasmussen, H.K., Hassager.. "The llnsteady motion of
a sphere in a viscoelastic fluid".. 1. Rhea!., 38 (2), p.377-403 (1994)
7 Arigo, M.T., McKinley, G.H., '"The etfects ofviscoelasticity on the transient motion ofa
sphere in a shear-thinning fluid".1. Rheo/... 41 (1), p.l 03-128 (1997)
IC Park, N.A., [rvine, T.F.Jr... of rheological nuid properties with the
falling needle viscometer", Rev. Sci. /nstnlm., 59(9), p.2051-8 (1988)
9 Zheng, R., Phan-Thien, N." Hic, V., 'Falling Needle Rheometry for Viscoelastic
Fluids", J Fluids Eng., 116, p.619-624 (1994)
10 Chu, B., Wang, 1., Tuminello.. W.H., 'Fast Determination of Polymer Melt Viscosity by
Optical Falling Needle Viscometer", 1. Applied Polym. Sei., p.97-101 (1993)
II Linliu, K., Yeh, F., Shook, J.W., Tuminello, W.H., Chu. B... Development of a
centrifuge baIl viscometer for polymer melts", Rev. Sci. 65( 12).. p.3823-8 (1994)
12 Herman, W., Sobczak, R., "Falling Sphere Viscometry in Gravitational and Magnetic
Fields", Monatsheftefr Chemie, 117/6-7, p.753 (1986)
1] Gahleitner, M., Sobczak, R., "The Magnetoviscometer: From an idea to a Rheological
Instrument", Rhea/ogy 91, p.236..240, Dec. 1991
14 Ringhofer, M., Gahleitner, M., Sobczak, R., frequency/shear rate measurements
on polymer melts with a novel rheometer", Rheal Acta 35 (1996)
15 Sobczak, R., "Viscosity measurement by sphere falling in a magnetic field", Rheologica
Acta, 25:p.l75-179 (1986)

52
REFERENCES
16 Gahleitner, M., Sobczak, R., measurements ,vith a magnetoviscometer in the
zero-shear and transition region ofpolypropylenes". Rheologie"l Acta. p.371-374
(1987)
17 Sobczak" R., Mattischek" J.-P." "High pressure cell tor measuring the zero-shear
viscosity ofpolymer meits", Rev. Sei. /nstrum., 68(5)., p.2101-21 05 (1997)
18 Koran" F., Dealy, 1., Determination of viscosity and \vaU slip of molten polymers at
high pressure." To he published.

APPENDIX A: EXPERIMENTAL DATA


Faxen correction for ditTerent order.
53

d diD f
e
1 te 3 te 5 te 6 f
e
8 f
e
10
1 0.143 1.430 1.418 1.418 1.418 1.418 1.418
2 0.286 2.508 2.235 2.244 2.248 2.247 2.247
3 0.429 10.194 3.809 4.019 4.161 4.086 4.101
4 0.571 -4.938 5.342 7.725 12.243 7.957 9.081
d d/D (te1r
1
(f
e
3r
1
(te Sr
1
(te Sr
1
(te Sr
1
(te 10r
1
1 0.143 0.699 0.705 0.705 0.705 0.705 0.705
2 0.286 0.399 0.447 0.446 0.445 0.445 0.445
3 0.429 0.098 0.263 0.249 0.2403 0.245 0.244
4 0.571 -0.203 0.187 0.129 0.082 0.126 0.110
Variation ofroom temperature near the MVM arm: effect of air conditioning.
54

without the box with the box


Time (hrs) Temp.(OC) time (hrs) Temp.(OC)
0:00 22.9 0:00 23.9
0: Il 23 0:05 23.4
0:39 23.3 0:07 23.1
0:58 23.3 0: 12 ' " ' ~ ~ _.3 . .3
1: 12 23.3 0:27 23.8
1: 17 20.4 0:34 23.8
1:20 21.3 0:38 24
1:30 23 0:43 23.9
2:52 23.3 0:46 23.9
0:52
. , ~
_.3
0:58
. , ~
_.3
1:03
., "" ""
_.3 . .3
1: Il 23.5
1:24 23.6
1:30 23.6
1:37
. , ~
_.3
1:41 22.8
1:50 23.1
1:55
,","" ""
_.3 . .J
2:03 23.4
2: 17 23.5
2:24 22.9
2:25 22.7
2:25 22.8
Parameter Analysis data. before elimination of defective sampies.
55
Run 1 Run 2 Run3 Run4 RuoS Run6 RUB 7 RunS Run9
2.106e4 2.548e4 2.570e4 2.396e4 2.521e4 2.441e4 2.455e4 2.563e4 2.520e4
2.64ge4 2.50ge4 2.583e4 2.646e4 2.28ge4 2.570e4 2.524e4 2.591e4 2.494e4
2.648e4 2.404e4 2.593e4 2.676e4 2.658e4 2.623e4 2.541e4 2.613e4 2.625e4
2.686e4 2.840e4 2.624e4 2.633e4 2.60ge4
2.617e4
2.70ge4
2.64ge4
1
2.616e4
Viscosity in Pa s
2.635e4
1
2.561e4
Parameter Analysis data. defective samples eliminated.

RUDS
Viscositvin Pa s
1 2.64ge4
2 2.840e4
3 2.570e4
4 2.676e4
5 2.658e4 2.624e4
6 2.633e4
7 2.524e4
8 2.563e4 2.613e4
9 2.60ge4 2.617e4 2.635e4 2.S61e4

Viscosity data from MVM for 0803-1 resin


Shear stress Shear Rate Viscosity
(pa)
( s ~ t )
(Pa-s)
P6 3.88E02 S.62E-02 6.90E+03
P7 3.88E02 S.40E-02 7.19E+03
P9 1.66E02 2.S3E-02 6.60E+03
1.66E02 2.S0E-02 6.67E+03
1.59EOI 2.0SE-03 7.75E+03
1.66E02 2.S5E-02 6.54E+03
PlI 1.66E02 2.62E-02 6.37E+03
1. 59EO1 2.26E-03 7.03E+03
3.88E02 S.70E-02 6.81E+03
2.96E02 4.70E-02 6.3IE+03
PI3 1.66E02 2.S9E-02 6.44E+03
3.88E02 2.3IE-03 6.79E+03
I.59EOI 3.86E-02 6.46E+03
2.49E02 6.50E-02 S.97E+03
Viscosity data from MVM for 335A resin.
Shear stress Shear rate Viscosity
(pa)
(Sl)
(Pas)
Al 3.38E+02 3.IIE-02 1.2SE+04
3.38E+02 3.S8E-02 1.09E+04
2.96E+02 2.46E-02 1.21E+04
2.96E+02 2.60E-02 L14E+04
1.67E+02 1.47E-02 LI4E+04
AS 1.S9E+OI 1.20E-03 1.33E+04
1.67E+02 1.41E-02 1.19E+04
2.96E+02 2.36E-02 1.26E+04
A7 1.67E+02 1.42E-02 1.18E+04
1.67E+02 1.41E-02 LI8E+04
1.67E+02 1.44E-02 1.16E+04
AS 2.96E+02 2.64E-02 1.12E+04
1.67E+02 1.48E-02 1.13E+04
1.59E+Ol 1.18E-03 1.35E+04
3.88E+02 4. 27E-02 9.09E+03
3.88E+02 3.09E-02 1.26E+04
56

Viscosity data from MVM for 3358 resin.


Shear stress Shear rate Viscosity
(pa)
(S-l)
(Pas)
BI 3.88E+02 9.36E-03 4.15E+04
3.88E+02 1.06E-02 3.66E+04
2.96E+02 7.54E-03 3.93E+04
1.67E+02 4.45E-03 3.75E+04
82 3.88E+02 9.85E-03 3.94E+04
2.49E+02 6.78E-03 3.68E+04
1.59E+O1 3.36E-04 4. 74E+04
84 1.67E+02 4.26E-03 3.92E+04
2.96E+02 7.61E-03 3.89E+04
3.88E+02 9.02E-03 4.3IE+04
3.88E+02 l.04E-02 3.72E+04
86 3.88E+02 9.47E-03 4.10E+04
2.96E+02 8.06E-03 3.68E+04
1.67E+02 4.59E-03 3.63E+04
Viscosity data from MVM for 335C resin.
Shear stress Shear rate Viscosity
(pa)
(fl)
(Pas)
Cl 3.88E+02 5.99E-03 6.48E+04
2.96E+02 5.07E-03 5.8SE+04
C2 3.88E+02 S.74E-03 6. 76E+04
2.49E+02 3.99E-03 6.24E+04
1.67E+02 2.75E-03 6.07E+04
CS 3.88E+02 5.69E-03 6.89E+04
2.69E+02 4.55E-03 6.51E+04
1.67E+02 2.64E-03 6.32E+04
C6 3.88E+02 5.91E-03 6.S7E+04
2.96E+02 S.05E-03 5.87E+04
57
Viscosity data from RDA. Values are the average viscosity of 5 samples.
58

0883-1 335A 3358 335C


m
Freq. Viscosity Viscosity Viscosity Viscosity
(radIs)
(S-I)
(Pas) (Pa5) (Pas) (Pas)
1.86E-02 5.93E-03 1.15E+04 3.14E+04 S.OOE+04
2.59E-02 8.24E-03 1.14E+04 2.96E+04 4.76E+04
3.60E-02 1.I5E-02 5.79E+03 1.12E+04 2.76E+04 4.48E+04
S.OOE-02 1.59E-02 5.78E+03 1.IOE+04 2.66E+04 4.19E+04
6.95E-02 2.2IE-02 5.77E+03 I.08E+04 2.53E+04 3.88E+04
9.65E-02 3.07E-02 S.75E+03 I.04E+04 2.36E+04 3.S6E+04
1.34E-O1 4.27E-02 5.73E+03 I.OOE+04 2.19E+04 3.23E+04
1.86E-O1 S.93E-02 5.70E+03 9.6IE+03 2.00E+04 2.91E+04
2.59E-O1 8.24E-02 5.66E+03 9.IIE+03 1.83E+04 2.60E+04
3.60E-OI l.I5E-OI 5.6IE+03 8.58E+03 1.65E+04 2.3IE+04
5.00E-OI 1.59E-OI 5.58E+03 8.04E+03 1. 49E+04 1.04E+04
6.95E-OI 2.2IE-OI 5.52E+03 7.47E+03 I.J3E+04 1. 79E+04
9.65E-OI 3.07E-Ol S.45E+03 6.90E+03 1.18E+04 1. 57E+04
I.34E+OO 4.27E-Ol 5.36E+03 6.34E+03 l.OSE+04 1.J7E+04
1.86E+OO 5.93E-Ol 5.26E+03 5.80E+03 9.30E+03 1.19E+04
2.59E+OO 8.24E-O1 5.15E+03 5.30E+OJ 8.24E+03 1. 03E+04
3.60E+OO 1.15E+OO 5.0IE+03 4.83E+03 7.32E+03 9.0IE+03
5.00E+OO 1.59E+OO 4.85E+03 4.40E+03 6.52E+03 7. 86E+03
6.95E+OO 2.2IE+OO 4.66E+03 4.01E+OJ 5.82E+03 6. 87E+03
9.65E+OO 3.07E+OO 4.44E+03 3.65E+03 5.19E+03 6.0IE+03
1.34E+OI 4.27E+OO 4.20E+03 3.32E+03 4.66E+03 5.29E+03
l.86E+OI 5.93E+OO 3.92E+03 3.02E+03 4.13E+03 4.62E+03
2.59E+OI 8.24E+OO 3.63E+03 2. 74E+03 3.67E+03 4.05E+03
3.60E+OI 1.15E+O1 3.31E+03 2.47E+03 3.25E+03 3.54E+03
5.00E+OI I.59E+OI 2.98E+03 2.22E+03 2.86E+03 3.08E+03
6.95E+OI 2.2IE+OI 2.65E+03 1.98E+03 2.50E+03 2.67E+03
9.65E+Ol 3.07E+O1 2.J3E+03 1.75E+03 2.17E+03 2.29E+03
1.34E+02 4.27E+Ol 2.0IE+03 1.53E+03 1.86E+03 1.96E+OJ
1.86E+02 5.93E+OI 1.72E+03 1.33E+03 1.59E+03 1.66E+03
2.59E+02 8.24E+Ol 1.44E+03 1. 14E+03 1.34E+03 l.39E+03
3.60E+02 1. 15E+02 1.20E+03 9.60E+02 1.11E+03 l. 15E+03
5.00E+02 1.59E+02 9. 83E+02 8.02E+02 9.15E+02 9.42E+02

PDMS al30
o
e.
Test condition: peak/peak artn, 3mm ball, 36mm gap and Exact resin. No cover.
falling time shear rate Viscosity
(5)
(s-1 )
(Pas)
1 7.46E+02 1.53E..02 2.54E+04
2 7.93E+02 1.44E..02 2.70E+04
3 7.53E+02 1.52E..Q2 2.56E+04
4 8.12E+02 1.40E..Q2 2.77E+04
5 7.63E+02 1.50E..02 2.60E+04
6 8.21E+02 1.39E..02 2.80E+04
7 7.60E+02 1.50E..02 2.59E+04
8 8.18E+02 1.39E-02 2.78E+04
9 7.58E+02 1.51E-02 2.58E+04
10 8.18E+02 1.39E-D2 2.78E+04
59