Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
These two parts bring together a number of authoritative, state-of-the-art reviews and
contributions, written by well recognized experts in the field of"flow and rheology of
non-Newtonian fluids." Knowledge of non-Newtonian behavior is of vital importance to
a variety of manufacturing processes including, for example, mixing, shear-thickening,
fibre spinning, coating, and molding.
This work covers areas such as bio- and food- rheology, electro-rheological fluids,
polymers, flow in porous media, and suspensions. Complex and industrial flow situations
are dealt with via analytical, as well as, numerical methods. In Chapter 1, a critical
account of advances made in the area of flow-induced interactions in circulation is
presented. Chapters 2 & 3 deal with shear-thickening in biopolymeric systems, and with
the rheology of food emulsions, respectively. The next six chapters are on complex flows,
in particular, Chapter 4 discusses worm-like micellar surfactant solutions. Chapter 5
covers time periodic flows. Chapter 6 communicates on secondary flows in tubes of
arbitrary shape. Chapter 7 relates effects of non-Newtonian fluids on cavitation. Chapter
8 discusses viscoelastic Taylor-Vortex flow. Chapter 9 deals with non-Newtonian mixing.
This is followed by two chapters on computational methods relevant to homogeneous
viscoelastic fluids at the macro-level. The next major section is on constitutive equations
and viscoelastic fluids. Chapter 12 discusses recent advances in transient network theory.
Chapter 13 deals with theories based on fractional derivatives and Chapter 14 involves
kinetic theory. Chapters 15 and 16 put forward new concepts approaching the constitutive
structure of polymeric melts. The next chapter communicates the theory of flow of
smectic liquid crystals. Part A ends with an overview of extensional flows.
Volume B starts with a section on electro-rheological fluids. The first two chapters in the
section summarize the constitutive theories for electro-rheological fluids from the
continuum and molecular points of view. Chapter 21 relates a comprehensive approach
to the constitutive structure of electromagnetic fluids, and the following two chapters deal
with the properties of electro-rheological fluids. The next section covers some industrial
flows related to drag reduction, and paper coating. Polymer processing and the related
rheology are discussed in Chapters 26-29. In particular, the rheology of long
discontinuous iber thermoplastic composites, thermo-mechanical modelling of polymer
processing, injection molding and flow of melts in channels with moving boundaries are
covered in Chapters 26-29 respectively. Free surface viscoelastic and liquid crystalline
polymer fibers and jets, and numerical sinmlation of melt spinning of polyethylene fibers
are the subject of Chapters )0 and 31, respectively.
vi
Section 9 contains two chapters dealing with foam flow and non-Newtonian flow in
porous media. Section 10 discusses four chapters on various aspects of
suspension.Chapter 34 reviews and puts forth new ideas on the fluid dynamics of fine
suspensions. Chapter 35 deals with concentrated suspensions. This section ends with a
discussion on fiber suspensions and fluidized beds.
With the publication of this work we hope to update and complement earlier work in a
diverse range of topics. These two volumes should be of interest to all those engaged in
basic, as well as applied research.
The information presented herein is equally valuable for practising engineers who are
constantly dealing with complex situations involving non-Newtonian materials. The
contents of the two volumes are accessible to those with a background in engineering
and/or pure sciences. We would like to take this opportunity to thank the contributors
who, despite their busy schedules, kindly agreed to participate.
Dennis A. Siginer
New Jersey Institute of Technology
Newark, NJ, USA
Daniel DeKee
Tulane University
New Orleans, LA, USA
Raj P. Chhabra
Indian Institute of Technology
Kanpur, UP, India
vii
LIST OF CONTRIBUTORS
Blumen, A. Couniot, A.
Theoretical Polymer Physics Siemens-Nixdorf Information Systems S.A.
Freiburg University LoB "Major Projects"
Rheinstr. 12, 79104 Freiburg, GERMANY Chaussee de Charleroi 116_
B- 1060 Brussels, BELGIUM
Dupret, F. lsayev, A. I.
CESAME Institute of Polymer Engineering
Unite de Mecanique Appliquee The University of Akron
Universite catholique de Louvain Akron, Ohio 44325-0301, USA
Avenue G. Lemaitre 4-6
B- 1348 Louvain-la-Neuve, BELGIUM Kanu, Rex C.
Department of Industry and Technology
Duming, Christopher J. Ball State University
Department of Chemical Engineering and Applied Chemistry Muncie, Indiana 47306, USA
Columbia University
New York, New York 10027, USA Khayat, Roger E.
Department of Mechanical & Materials Engineering
Fong, C. F. Chan Man The University of Western Ontario
Department of Chemical Engineering London, Ontario, CANADA N6A 5B9
Tulane University
New Orleans, Louisiana 70118, USA Kim, Kyoung Woo
Fiber Research Center
Forest, M. Gregory Sunkyong Industries
Department of Mathematics Su Won, 440-745, KOREA
University of North Carolina
Chapel Hill, North Carolina 27599-3250, USA Kim, Sang Yong
Department of Fiber and Polymer Science
Franco, J.M. College of Engineering
Departamento de Ingenieria Quimica Seoul National University
Universidad de Huelva San 56-1, Shinlim-Dong, Kwanak-Ku
Escuela Politecnica Superior Seoul 151-742, KOREA
La Rabida, 21819
Palos de la Ftra (Huelva), SPAIN Kornev, Konstantin G.
Institute for Problems in Mechanics
Friedrich, Chr. Russian Academy of Sciences
Freiburg Materials' Research Center 101 (1) Prospect Vemadskogo
Freiburg University Moscow 117526, RUSSIA
Stefan-Meier-Str.21
79104 Freiburg, GERMANY Kwon, Youngdon
Department of Textile Engineering
Fruman, Daniel H. Sung Kyun Kwan University
Groupe Phenomenes d'Interface Su Won, 440-746, KOREA
Ecole Nationale Superieure de Techniques Avancees
91761 Palaiseau Cedex - FRANCE
Lavoie, Paul Andre Prakash, J. Ravi
Center for Applied Research on Polymers Department of Chemical Engineering
CRASP Indian Institute of Technology
Department of Chemcical Engineering Madras, INDIA, 600 036
Ecole Polytechnique, Montreal
QC H3C 3A7, CANADA Rajagopal, K. R.
Texas A&M University
Leonov, Arkadii I. College Station, Texas, 77842-3014, USA
Department of Polymer Engineering
The University of Akron Rozhkov, Aleksey N.
Akron, OH 44325-0301, USA Institute for Problems in Mechanics
Russian Academy of Sciences
Leslie, Frank M. 101 (1) Prospect Vernadskogo
Mathematics Department Moscow 117526, RUSSIA
University of Strathclyde
Livingstone Tower Schiessel, H.
Richmond Street Theoretical Polymer Physics
Glasgow G 1 1XH, SCOTLAND Freiburg University
Rheinstr. 12, 79104 Freiburg, GERMANY
Letelier, Mario
Universidad de Santiago de Chile Shaw, Montgomery T.
Santiago Department of Chemical Engineering and Polymer Program
CHILE University of Connecticut
97 North Eagleville Road
Mal, O. U-136
CESAME Storrs, Connecticut 06269-3136, USA
Unite de Mecanique Appliquee
Universite catholique de Louvain Siginer, Dennis A.
Avenue G. Lemaitre 4-6 Department of Mechanical Engineering
B- 1348 Louvain-la-Neuve, BELGIUM New Jersey Institute of Technology
Newark, New Jersey 07102, USA
Neimark, Alexander V.
TRI/Princeton Steger, R.
601 Prospect Ave. Rheotest Medingen GmbH
P.O. Box 625 RodertalstraBe 1,
Princeton, New Jersey 08542-0625, USA D-01458 Medingen b. Dresden, GERMANY
Overfelt, R. A. Tang, P. H.
Space Power Institute Department of Chemical Engineering and Applied Chemistry
231 Leach Center Columbia University
Auburn University New York, New York 10027, USA
Auburn, Alabama 36849-5320, USA
Tanguy, Philippe A.
Padovan, J. Department of Chemical Engineering
Department of Mechanical Engineering Ecole Polytechnique Montreal
The University of Akron P.O. Box 6079
Akron, Ohio 44325-0301, USA Station Centre-ville
Montreal, H3C 3A7 CANADA
Petrie, Christopher J. S.
Department of Engineering Mathematics Tanner, R. I.
University of Newcastle upon Tyne Department of Mechanical and Mechatronic Engineering
Newcastle upon Tyne NE1 7RU, UNITED KINGDOM The University of Sydney
NSW 2006, AUSTRALIA
Phan-Thien, Nhan
Department of Mechanical and Mechatronic Engineering Tao, Rongjia
The University of Sydney Department of Physics
NSW 2006, AUSTRALIA Southern Illinois University at Carbondale
Carbondale, Illinois 62901, USA
Vanderschuren, L. Zhang, Y.
Shell Research S.A. Institute of Polymer Engineering
Avenue Jean Monnet 1, The University of Akron
B-1348 Louvain-la Neuve, BELGIUM Akron, Ohio 44325-0301, USA
Verleye, V.
TECHSPACE AERO
Route de Liers 121
B-4041 Milmort, BELGIUM
Vincent, M.
Centre de Mise en Forme des Materiaux
Ecole des Mines de Paris
URA CNRS 1374
BP 207, 06904, Sophia Antipolis, FRANCE
Vossoughi, Shapour
Department of Chemical and Petroleum Engineering
University of Kansas
4006 Learned Hall
Lawrence, Kansas 66045-2223, USA
Wang, Qi
Department of Mathematical Sciences
Indiana University-Purdue University at Indianapolis
Indianapolis, Indiana 46202, USA
Wu, C. W.
Research Institute of Engineering Mechanics
Dalian University of Technology
Dalian 116024
People's Republic of China
Yziquel, F.
Center for Applied Research on Polymers
CRASP
Department of Chemcical Engineering
Ecole Polytechnique, Montreal QC H3C 3A7, CANADA
FLOW-INDUCED INTERACTIONS IN THE CIRCULATION
Harry L. Goldsmith
1. I N T R O D U C T I O N
Many years ago, it was suggested to the English physiologist L.E. Bayliss by
the eminent Cambridge authority on fluid mechanics, G.I. Taylor, that rather
than work on the highly complex rheology of blood, he would be better
spending his time studying the flow of marmalade through sewage pipes. That
advice did not deter Dr. Bayliss [1,2] and a host of physiologists, rheologists,
chemical and mechanical engineers from engaging in the problem, which had,
after all, an honourable parentage in the person of Jean Leonard Marie
Poiseuille, who published as early as 1839 [3,4], and in this century, the
Swedish pathologist, Robin F~thraeus [5,6]. Quite apart from the clinical value
of discovering how blood cells travel in the vessels of the circulation, there is,
for the rheologist, a fascination about this fluid, since it is able to flow, even at
hematocrits (packed red blood cell (RBC) volume concentration) well above
40%, with such ease compared to other suspensions and emulsions [7]. Thus, it
is possible to pack a column of mammalian red cells containing less than 2%
trapped plasma into a 2 mm diameter glass tube, and then suck it out quite
easily into a micropipette whose tip has a diameter of only 0.5 mm. By
comparison, oil-in-water emulsions reach the quasi-solid consistency of
margarine at much lower concentrations.
Clearly, in such a concentrated suspension, interactions between the blood
corpuscles and between the corpuscles and the vessel walls play an important
role in determining the mechanics of the motion. This chapter is concerned
with a description of these interactions. We begin by taking the reader through
a brief description of blood, seen as a dispersion of charged colloidal-size
particles in a Newtonian suspending medium, and the main flow regimes to
which it is subjected. To understand the cell and cell-wall interactions, one
must begin with the macroscopic, overall non-Newtonian rheology of blood,
and then to correlate these rheological properties with the flow properties of
the individual cells, studied first in isolation, then at increasing concentrations
as interactions become increasingly important, i.e. the microrheology of the
blood. This part of the chapter will mainly involve the erythrocytes or red
cells, since they occupy >99% by volume and -96% by number of the
particulate phase of blood, and thus effectively determine both the macro- and
microrheology of the suspension. However, the most recent advances in the
field have been made at the submicroscopic level, where the molecules and the
forces involved in cell-cell and cell-wall adhesion have been investigated, thus
entering the realm of what has been called molecular rheology. At this level,
the chapter focusses not on the red cells but on the platelets and leukocytes,
since it is they that are involved in key physiological and pathophysiological
events through their role in blood coagulation and a g g r e g a t i o n - the platelet,
and in i n f l a m m a t i o n - adhesion of leukocytes to the vessel wall and their
passage into the extravascular space. In fact, adhesion processes between cells
and between cells and the vessel wall are particularly critical in the circulation
for all three classes of cells. The biophysics and rheology of certain of these
adhesive reactions and the means of measuring forces of adhesion are dealt
with in Sections 4 and 5. Where possible, the phenomena described are
discussed in terms of fluid mechanical and colloid chemical theory.
1.1 B l o o d as a colloidal d i s p e r s i o n
Mammalian blood is a dispersion of three classes of negatively charged
particles (the cells or corpuscles; Table 1) in an aqueous solution (the plasma)
containing dissolved salts and proteins (Table 2). As pointed out above, from
the point of view of its rheological properties, blood is essentially a
concentrated suspension of red blood cells
Table 2
Mean values of concentrations of ions and proteins in plasma
SALTS PROTEINS
Ion Concentration Name Molecular Concentration
meq./litre Weight gm/litre
2. M A C R O R H E O L O G Y OF BLOOD
10 3
>.,
r,o
o
o 10 2
..=., ~ " ' ~ ' ~ R B C in plasma
> Aggregation ~ Hardened cells in alb.-Ringer
(D
>
...=.
o......-o.........~ ......~ ...... ~. _ ~'~... Deformation ~ C>
........ v ......,~...... o......-':~.. / '----',.--~ " - ~
R B C in alb Ringer "'" 0 "--" (~)
rr
10-2 1 0 "1 1 10 10 2 10 3
Shear Rate, s ~
Figure 2. Relative apparent viscosity vs shear rate in suspensions
of normal RBC in plasma (aggregation and deformation), and in
Ringers-albumin (no aggregation) and hardened RBC in Ringers-
albumin (no aggregation or deformation). From Chien [29] with
permission.
where <u> is the average tube blood velocity, and <Up> and <Uc> are the
average plasma and blood cell velocities [6].
! v ,
o, i
HD
0.6
04 i ~ Critica,,lDiameter
92 I~)0 I000
Diameter, l~m
3. M I C R O S C O P I C C O R R E L A T E S OF M A C R O S C O P I C F L O W
BEHAVIOUR
where ~ is the azimuthal angle of the axis of revolution with the diametrical,
X2-axis (Figure 4; = + 90 ~ in positions 1 and 5, and 0 ~ in position 3 in Figure
5), B(re)= (r 2 - 1)/(r 2 + 1), r~ is the equivalent ellipsoidal axis ratio (axis of
revolution/diametrical axis) and T the period of rotation through 2n, given by
[47]:
T - 27r (re + re 1)
- G(r----~ (6)
Integration of Equation (5) yields:
tan~=re( Gt )
re + l / r e (7)
X
3
r
'
"-1' U ~ GX
2
X
2
Figure 4. Rotation of the axis of revolution of a spheroid (heavy line)
defined by the Cartesian (Xi) and polar (0, ~0) coordinates constructed
at the particle centre of rotation and origin of a Couette shear field.
360
A i _
B,| I ......
270 _ i
! 4~~ ~
i/1
i1) i Ot~" r red cell I
i
1~ 4-cell rouleau
90 - ,~ r'i 1"1 -
i
I
The vessel boundary exerts its influence on the flowing blood cells not only
by retarding their translational and rotational velocities, an effect appreciable
within one or two cell diameters from the wall, but also by generating radial
components in the cell velocity. There are two established mechanisms by
which migration across the streamlines can occur [45,47,53-55,57]: migration
due to particle deformation at low Reynolds number, and migration due to
inertia of the fluid at moderate and high Reynolds number. Here, we concern
ourselves mostly with the former mechanism.
Deformable particles (liquid drops, flexible fibers), suspended in
Newtonian media undergoing Poiseuille flow in the creeping flow regime,
migrate away from the wall towards the axis [45]. In the case of a fluid drop, it
has been shown to be an effect of the particle disturbance flow which generates
a flow with a radial component in the neighbourhood of the drop. In the
absence of fluid inertia, rigid spheres and spheroids do not migrate laterally
across the streamlines [45]. Under conditions of negligible fluid inertia,
particle Reynolds number < 10 -6, the latter defined in terms of the particle
translational slip velocity (particle [u] - fluid [U]) of a sphere, radius b at the
axis of a tube, radius R, in Poiseuille flow [58]:
Single human red cells and rouleaux also migrate radially inward, as illustrated
in Figure 6, for red cells in Ringers solution and in buffered dextran solutions
[55]. As previously found with fluid drops [45], the rate of migration increases
with particle deformation (it is much greater in dextran than in Ringer solution;
Figure 6) and increases rapidly with increasing ratio of particle to tube
diameter. Such migration, although severely inhibited by the particle-crowded
conditions in normal blood, nevertheless appears to result in a thin (-- 4 ktm
wide) cell-depleted layer at the wall and a significant lowering of the
hydrodynamic resistance in many blood vessels.
~ -; ~, ~ ~
!
r
RBC in
E 40~ Dextran Ceins
O 0.2
or)
I,,,,-
X
X
A 0.4
(.9
V
0.6 , 1 , I ....
O.072sec.
' - - - - 10 ~ - - - - ~
I II - 5 0 p m
v" ~--
I
I
I
E
1.0 ~ . l l l ' ]
Rigid ~ I
......~ Spheres ~ I
0.5
,~ " ~ ........... -
-I
r Complete Par
o
R Plug Flow , PlugFlow____~____;t~ ;
0 "- o 00000fO~176176
- : ~ e u , , , e -
0.5
9I .o~" Flow
......~ F'o'~
I .....~ i - Drops
1.0 L.... ................i
9 ~" ,
1.0 ' - ~ s I
t Cells~
-~ 0 Plug Flow
- .__L_
I
~]__t_- ~~ /
.(7""
0.5 ~ D -
iscs Q
U(O)
flow rate, Q [62]. In fact, it was shown that, despite the continual erratic
(Brownian diffusion-like) radial displacements of the spheres in those regions
of the tube in which shear-induced interactions occurred, over relatively short
time periods, the displacements were reversible in time and space [62,63].
At a given b / R , the degree of blunting increased with increasing volume
fraction, c, of the disperse phase, and at a given c, it increased with increasing
b/R. Blunting of the velocity distribution was not due to aggregation of the
spheres or discs whose interactions are due solely to hydrodynamic forces, nor
due to a redistribution of particles in the tube which could have resulted in the
two-phase flow of a more viscous and concentrated central core of suspension
surrounded by a less concentrated and less viscous peripheral layer. With the
exception of the exclusion layer closer than one particle radius from the wall,
sphere centres were shown to be uniformly distributed in the tube [62]. Rather,
the effect is due to particle interactions in the crowded suspension, and has been
treated by Skalak [64] who has interpreted the interactions of the particles in
terms of passing versus non-passing motions of adjacent particles. It should be
noted, however, that more recent work has shown that redistribution of rigid
particles in variable shear fields can and does occur in the creeping flow regime
providing particle interactions proceed for long enough times [65-69].
As shown in the lower panel of Figure 8, at comparable particle volume
concentrations, the ghost cell suspensions exhibited blunting of the velocity
profile, similar to that Of the discs, but with significantly lower r c [59,70]. As
with suspensions of rigid particles, r c increased with increasing b / R and
concentration. However, as expected, given the shear and concentration-
dependent deformation of the ghost and red cells, there is no quasi Newtonian
behaviour: the degree of blunting decreased with increasing Q as the parabolic
Poiseuille velocity profile was approached, accompanied by a decrease in
effective viscosity [71 ], and the motions were not reversible in time and space.
In this respect, the non-Newtonian behaviour of red cells and ghost cell
suspensions resembled that of concentrated emulsions of deformable liquid
droplets in which the droplets are also deformed not only by the shear stress,
but also through particle crowding. As shown by work in transparent oil-in-oil
emulsions, the droplets were distorted from prolate ellipsoids into irregular
shapes [72]. Moreover, the shear-induced deformation led to some migration
of the droplets away from the wall (opposed by an outward dispersive force
due to the continual interactions of droplets in the core of the emulsion), and as
with the red blood cells, such migration was not reversible in time and space.
In addition (see upper panel of Figure 8) the velocity distribution was less
blunted than that of a suspension of rigid spheres at the same particle volume
fraction and b / R , and was flow rate dependent: as the flow rate increased and
the droplets became increasingly deformed, the velocity distribution gradually
approached the parabolic Poiseuille velocity profile [72,73].
19
0.9
0.8
/
- 40
"l ~
"~
o.7
2
~PMN
5O 7O
Q
"
Q
5
~ 0. I .-i.
~ Q
"0 1,0~ u u , r I n
"- 35
"~ 0.9 "1:
tr 3
0.8 30
20
,
0 5 lO 15 20
Time,s
Figure 9. Radial dispersion of the paths of a polymorphonuclear
leukocyte (PMN) and an RBC in 40% ghost cell suspensions in tube
flow. Asterisks denote times when particles collided with the wall.
The slightly deformed PMN and markedly deformed RBC are
shapes seen while tracking the cells. From [74], with permission.
20
Brownian translational diffusion coefficient, Dr, for the isolated red cell
suspended in plasma, viscosity 7/- 1.8 mPa s at 23~
Dr = kBTr/K, ri = 4.4 x 10 -14 m E S -1 (9b)
where kB is the Boltzmann constant, TK the absolute temperature and
K, = 5.23x10 -5 m, the translational resistance coefficient for motion along or
transverse to the axis of revolution (2.4 l-tm) of a rigid spheroid, re = 0.38 [75].
The above values of radial diffusion coefficients in ghost cell suspensions are
in fair agreement with blood platelet translational diffusion coefficients
obtained from measurements of their dispersion in flowing blood, which
increased from < 1 0 -12 m 2 s -1 in plasma to 2.5 x 10 -~ m E s 1 at 50% hematocrit in
flowing blood at a mean tube shear rate <G> - 100 s -~ [76].
As a consequence of the enhanced radial dispersion of the other blood cells
by the red cell motions, is an increase in the two-body collision rate between
platelets in shear flow, which is discussed in Section 4. More important is the
effect of the red cells in increasing the frequency of platelet-wall collisions with
increasing hematocrit, an effect of considerable significance in hemostasis (the
normal plugging of cut or damaged vessel wall, a process initiated by platelets)
as well as in thrombosis (abnormal, pathological adhesion and growth of
platelet thrombi on the walls of arteries), particularly in regions of disturbed
flow, as described in Section 6. It has been shown that adhesion of platelets to
various artificial surfaces [77,78] as well as artery subendothelium [79,80]
(artery stripped of the endothelial layer thereby exposing collagen fibres to
which platelets strongly adhere) in flowing blood is markedly enhanced by the
introduction of red cell or ghosts cells into the suspending medium.
The extent to which red cell deformation or size may affect the increase in
the effective diffusion constant of cells and solute has also been studied. The
transport of molecular solute was found to increase slightly with cell size and
rigidity [81], and the wall adhesion of platelets observed to increase
substantially with red cell size [81]. Augmented transport in the shear flow of
concentrated suspensions of model particles and red blood cells has been
thoroughly reviewed by Zydney and Colton [82]. They proposed a model of
augmented solute transport based on shear-induced particle migrations and the
concomitant dispersive fluid motion induced by these particle migrations.
Augmented solute transport was defined as (D~e/DsF ) -- 1, where Dee is the
effective solute diffusion coefficient measured in the sheared suspension, and
D SF i s the solute diffusion coefficient in the absence of flow. If particle
rotations are assumed to be unimportant, D ~ - DSF + Dp, Op being the particle
diffusion constant. Augmented diffusion is predicted to vary as the Peclet
number, Pe - b2G/OsF.
peripheral layer of--4 gm thickness will likely have a negligible effect on the
distribution of red cells across the lumen. As mentioned in Section 2.2,
however, at low flow rates (corresponding to mean velocities <U> < 1 tube
diameter s-~) aggregation of red cells becomes an important factor.
Paradoxically, it is at low, and not high flow rates, that inward migration of
red cells in plasma or high molecular weight dextran buffer is most pronounced
in tube flow. Here, the formation and rapid inward drift of rouleaux of red
cells results in the two phase flow of an inner core of a network of rouleaux
surrounded by a peripheral cell-depleted layer in which can be seen single red
cells, small rouleaux and an apparently large number of platelets and leukocytes
[40,56,60,83-85]. Such two-phase flow has also been induced in small vessels in
the microcirculation of animals by intravenous injection of gelatin or
fibrinogen and of dextran. Both in vivo and in vitro it has been shown that the
formation of the red cell core is associated with the 'margination' (displacement
to the periphery) of white blood cells [56,84,85]. Cine films of blood flow
taken in tubes of 100-340 gm diameter clearly show that the effect is due to the
outward displacement of white cells by the inwardly migrating network of
packed red cell rouleaux [56,85]. Here, an "inverse" F~hraeus effect occurs:
since <u~> is less than <up> [Equation (4)], the leukocyte concentration in the
tube is greater than that in the infusing reservoir [56].
That such two-phase flow results in a decrease in hydrodynamic resistance,
R - AP/Q, had earlier been shown in studies of the oscillatory flow of
concentrated suspensions of rigid neutrally buoyant spheres where inertial
effects led to a small but significant inward migration of the particles from the
tube wall [86]. The effect was later demonstrated in the flow of mammalian
blood, where it was also shown that in vertically positioned tubes, enhanced red
cell aggregation in the presence of 250 kDa dextran resulted in a lower
effective viscosity at <U> < 2 s-~ [39]. By contrast, in horizontally positioned
tubes, where there is an asymmetric distribution of red cells and aggregates due
to sedimentation of the core, the effective viscosity continues to increase with
decreasing <U>. The relation between the radius of the core, r~, and
hydrodynamic resistance has been studied in buffered 110 kDa dextran
suspensions [40], and as shown in Figure 10 in a tube, R = 172 gm,
hydrodynamic resistance at first increased with decreasing <U> until
aggregation brought about syneresis and a shrinking diameter red cell core.
That the effect is due to aggregation was confirmed by experiments in 10%
buffered albumin in which rouleau formation was totally absent, and R
continued to increase with decreasing <U> down to < 0.2 s-~ [40]. As expected,
in buffered albumin suspensions there was no margination of leukocytes [56].
Redistribution of platelets in flowing blood has also been observed. In the
case of platelets in arterioles [87,88], and 1-2.5 gm diameter latex microspheres
in robes of-- 200 gm diameter [89,90], particle number concentrations near the
vessel wall have been shown to be higher than in the core of the flowing
22
1.0 ~ , ,
0.9
re
0.7
i i i i i i i i
3.0
co 0
,- 2.5
E
t~
Q- 2.0
.4 1.5
----it 9 1.5% Dextran ~
1.0 i i i i 1 i i i
suspension ("near wall excess"). The effect, which requires the presence of red
cells, has been modelled by adding a lateral drift term to the convective
diffusion equation for platelet transport in flowing blood [91]. The reason for
the net outward drift is believed to arise from the inward migration of the
more rapidly migrating red cells resulting in a marginal layer of lower red cell
concentration, whose width continuously fluctuates and should be viewed in a
statistical sense. The outward lateral drift of platelets or microspheres occurs
23
because of a net flux of particles from a region of higher red cell concentration
and hence higher red cell collision rate to a region of lower red cell
concentration and lower collision rate. Such a drift has been shown to occur in
alloys [92]. The fact that the location of the near wall excess of microspheres
occurs a few microns away from the wall is due to the fact that the particles are
physically repelled, and at sufficiently high Rep, fluid dynamically repelled
from the wall through inertial effects. It should be noted that the above
hypothesis does not attribute the motion of platelets toward the wall to their
exclusion by red cells in the interior of the tube, as is the case for leukocytes.
4. SHEAR-INDUCED TWO-BODY I N T E R A C T I O N S : F R O M
CHARGED C O L L O I D A L P A R T I C L E S TO BLOOD CELLS
C(s*)Fint(h) (10)
-~ = A ( s * ) G b sin20 sin2q~ +
dt 3 rcb rl
d~ 1
dt = -2 G[ 1 + B(s*) cos 2q~] (12)
-u(r) -u(r)
t t
i X3
i
i
i Repulsion
i
i
,, ,,
i Xm
8
X~
X3
Here, 0 and r are the respective polar and azimuthal angles relative to X1 as the
polar axis, as shown in Figure 11; A(s*) and C(s*) are known dimensionless
functions of s* = s/b, which have been documented [95,97,99]. Equation (12 is
identical with the Equation (5) describing the angular velocity of a rigid prolate
ellipsoid [46] with B(s*)= (r~(s*)- 1)/(r~(s*)+ 1). Asymptotic expressions for
r~(s*) have been given for large and small s* [97].
Rearrangement of Equation (10) yields the force equation:
where g(s*) and f(s*) are integral functions of s* for which numerical values
have been given [96,97]. When Fi,.(h) :r O, the paths of approach and recession
are no longer symmetrical, and D and E become functions of time, increasing
when F..t(h) > 0 (repulsion), and decreasing when Fi,.t(h) < 0 (attraction).
Fattr(h ) =
12h2
I(1+
where the van der Waals attractive force, Fattr(h ), is given by:
1 + 1.77p 2
p<l (15a)
and the double layer electrostatic repulsion force, Frep(h), is given by:
Frep(h) = 2~Kbe~ / /
1 + e -rh (16)
32 3
= --~ NoGb (17b)
for equal-sized spheres of radius b.
The classical Smoluchowski theory has been corrected using the rigorous
hydrodynamic theory of the curvilinear particle collision trajectories described
by Equation (10) with F~,~(h) = 0 [103]. The difficulties in defining a collision
were eliminated by defining a "curvilinear collision sphere" of radius p,,
around the reference sphere. Correction factors to be applied to the results of
the rectilinear theory (collision sphere radius = 2b) were then calculated for the
cross-sectional area of the collision sphere, the collision frequency and the
average doublet lifetime as a function of the ratio p,,,/b. Curvilinear and
rectilinear theories were shown to be compatible at p,,,/b = 2.38, which appears
to correspond to the minimum dimensionless distance of approach of the
spheres recognized experimentally by different observers as a collision [47].
=
8aocG
zc (18b)
concentrations chosen were those just able to induce aggregation, so that the
effects of shear and time of exposure to ADP would be at their most sensitive.
The magnitude and time of exposure to shear were varied independently by
using a double infusion system [112] in which the cells and agonist
simultaneously entered a tiny mixing chamber and flowed through preset
lengths of polyethylene tubing at mean transit times from 0.2 to 86 s and mean
tube shear rates, <G>, from 40 to 1920 s -~ (representative of those in the
circulation; Table 3). The suspensions were collected into glutaraldehyde to
arrest the reaction, and all particles in the volume range 1 to 105 ~tm 3 counted
and sized using an aperture impedance counter. Aggregation was measured by
the decrease in the number of singlets, and the number and size of aggregates.
Adenosine diphosphate-induced aggregation is known to be mediated by the
plasma protein fibrinogen which specifically binds to the activated form of the
platelet membrane integrin glycoprotein complex, GPIIb-IIIa [113]. Most
likely, aggregation occurs via cross-bridging of fibrinogen molecules between
receptors on adjacent cells, (Figure 12) [114]. Successful cross-linking requires
simultaneous binding of opposite ends of the fibrinogen molecule to two cells
immediately after activation of the GPIIb-IIIa complexes, and before their
saturation with fibrinogen, an unlikely scenario given the high plasma
fibrinogen concentration (2x107 molecules available per platelet) and receptor
surface density (5X104 sites per cell). A model of aggregation therefore
requires either a low affinity for fibrinogen binding with the continuous
breaking and making of bonds, or the time-dependent exposure of new
i
t'~, C
r
/ r
Figure 12. Schematic diagram of platelet activation by ADP causing shape
change from smooth discocyte (A) to spiny spheroid (B) with pseudopods,
and transformation of the membrane glycoprotein IIb-IIIa receptors
(inset) into active forms (o) capable of binding fibrinogen (Fb; C) which
can cross-link cells producing doublets. From [115], with permission.
30
335 S -1
~ 80
--~ 1335 S-1
-~ 60
t~
~ 40
r9~ 2o
0 20 40 60 80 100
M e a n Transit Time, s
Indeed, ao, computed from Equation (18b) over the first 4 seconds, was
greatest at the lowest shear rate (= 0.26), but decreased markedly to 0.017 and
<10 .3 at the intermediate and highest shear rates, respectively. Thus, it appears
that a weak bond between cells of the microaggregates formed within the first
few seconds, diminished in strength with time, and the low collision frequency
at low shear rate was unable to sustain a high rate of aggregation. As shear rate
increased, the initial decrease in ao led to a decrease in rate of aggregation, yet
at later times the high collision frequency, aided by the arrival of a more shear
stress-resistant bond sustained a high rate of aggregation.
In the presence of red cells at 40% hematocrit, the initial rate of single
platelet aggregation in whole blood is an order of magnitude greater than in
platelet-rich plasma [118,119]. There has been a long-standing discussion on
whether this is due to a chemical (release of ADP from the red cells) or a
physical effect of the red cells. As shown in Figure 14, some aggregation of
platelets in blood at low shear rate was observed in the absence of any added
ADP, and this could be abolished by the addition of an ADP scavenger enzyme
[119]. However, there remained a large effect believed to be a physical one.
An obvious candidate for the increased rate of aggregation is the increased
platelet diffusivity in blood, described in Section 3, which might lead to an
100 ._ - - - - _ - - = - _ - - -
8o
60
40
20
0
0 10 20 30 40 5O
M e a n Transit Time, s
- ~
TDtheor- 4"97 tan-l(1 tan q~0) (20)
where ~0 =-~00 is the collision angle when the spheres are first seen to make
apparent contact. In the absence of other interactions, the doublet is predicted
to rotate until the orientation q~ = +r the reflection of the collision angle, is
reached when spheres separate. Figure 15 illustrates the erratic time course of
the ~0-orientation of the axis of a collision doublet, compared to that computed
from Equation (20). For 320 doublets, the m e a n TDmea/'~Dtheor : 1.61 + 1.80
(S.D.) compared to 1.00 + 0.31 for 90 doublets in plasma. Analysis showed
that impedance of the rotation is the likely mechanism by which "~Dmeas > "~Dtheor"
A more sophisticated analysis of shear-induced platelet aggregation uses
population balance mathematics and a laminar shear coalescence equation
[120,121] in which a particle density function expresses the makeup of a
collection of singlets and aggregates of various sizes. The collision efficiency
and an aggregate void fraction (to avoid the problem that platelets and are not
spheres) are introduced and experimental data matched by computer analysis.
A population balance analysis has also been used to model the shear-induced
aggregation and disaggregation of activated neutrophils [122,123].
0 E F F E C T OF FORCE ON THE K I N E T I C S OF C E L L - C E L L A N D
CELL-WALL ADHESION
90
60 ] 9 _ .
Measured
30 I A Theoretical
I I
I I
-30 I 1
-60
-90 , ~ , " I , I i I
0 0.05 0.10 0.15 0.20 0.25
Time, s
Figure 15. Time course of the ~0-orientation of a collision doublet of
2.5 gm latex spheres in a 40% ghost cell suspension (O) compared to
that for an undisturbed doublet (A) formed at the same initial ~ = -~o
and G, predicted to separate at the mirror image q~ = +~Oo. Dashed
lines give time interval = "~Dmeas(> "~Dtheor) o f apparent contact between
the spheres. From [119], with permission.
long time. In contrast, the linkages quickly rupture when mechanical stress is
applied to the cells. Thus, molecular attachments appear to be maintained by
kinetic traps and bond rupture should be regarded as a kinetic process far from
equilibrium, with apparent bond strengths expected to depend on the rate of
force application. With the advent of ultrasensitive mechanical techniques such
as the atomic force microscope [124,125], the biomembrane force probe [126;
Section 5.3] and optical tweezers [127], the properties of single adhesive bonds
at cell interfaces can be tested with nanoscale resolution. In this Section, the
focus is on bonds made and broken in the flowing blood, and discussion is
limited to the kinetics of bond rupture between freely suspended cells in shear
flow, and to the kinetics of leukocyte rolling along, and adhesion to the vessel
wall. In both cases, the experimental results have been modelled using relations
for the effect of an external force on the off rate constant of a single bond.
applying to such bonds a model of Zhurkov [129] for the force dependence of
bond rupture based on empirical studies of the fracture of macroscopic solids.
This model is actually an extension of transition state theory in gases [130] in
which it was proposed that intermolecular forces in a gas could be treated as a
one dimensional random walk in a potential energy well. The probability of
escape depends on the depth, E 0, of the well and the natural frequency of the
bond in vacuum, "to (-- 10 -~3 s for atoms in a solid). For a parabolic energy
barrier it was shown that the escape or break-up time in the absence of an
extemal force is given by:
t o = "to exp (E o/kBTK) (24)
where the exponential represents the probability that thermal fluctuations
provide enough energy for the barrier to be surmounted (for the transition
state to be reached). Zhurkov introduced the force dependence by postulating
that the extemal force, f per bond, acts directly along the reaction coordinate x
to reach the value xa at the transition state, and that the force reduces the energy
barrier in a linear fashion; thus
tb= To exp (E 0 - f x ~ )/kBT K (25a)
= t o exp (-z'f) (25b)
where Z = xa/kBTK. Therefore, when f reaches the value f/3 - Eo/xa, t~ = "t'0, and
bond failure is almost instantaneous. By identifying tb with 1/~r the reverse,
or off-rate constant, the connection to bond reaction rates is made:
tr = tCog~ exp (z'f) (26)
where tCog~ = 1~to. The probability of bond breakage Pb in a short time interval,
At, is then given by [ 131 ]"
where ~:0 is again the time for rapid bond rupture and m was used to capture
variations in rupture behaviour from ductile (m < 1) to brittle failure (m > 1).
Evans et al. showed that any realistic technique for putting stress on bonds will
35
have a rise time or rate of loading and this, coupled with the inherent stochastic
nature of receptor-ligand bonds, will lead to the peaks observed in the
histograms of bond strength from mechanical probe experiments [132,133].
Hence, the strength of a single bond is governed by the rate of loading, and they
have used the Brownian dynamics theory of Kramers [130] to show that the rate
follows a general form given by:
to# = to#~ gff) exp [AEo(f)/kJK] (29)
which follows the required phenomenological descriptions for the force-driven
kinetics [134].
These models of bond rupture under force have been used to analyze
experimental data obtained on the break-up doublets of red cells, and on the
roiling of leukocytes on endothelium, as described below.
However, the bonds linking the red cell spheres are also subject to
hydrodynamic forces acting normal to the doublet axis, i.e. shear forces. The
general method of calculating forces, torques and translational velocities of
neutrally buoyant rigid spheres in a simple shear field [97], based on the matrix
formulation of hydrodynamic resistances in creeping flow [136], was used to
compute the normal force acting along, and the shear force, F~, acting
perpendicular to the axis of the doublet [137]:
F, = a,(h)rlGb 2 sinZO sin2dp [31]
F s = O~s(h)rlGb2 sin 0
1 - sin 20 COS2~)
/ (2sin20 cos2~- 1)2sin2r /-
+ cos20 C0S2~
1
[32]
where a,(h) and a,(h) are force coefficients weakly dependent on the minimum
distance of approach, h.
250 <>
58%
200 56?
Z
56%
150 50~ m
8 ~
49 o -,~ozx o
6 O
100 46% A ~ 0
5O
0
0.15 0.30 0.60 0.15
[IgM], nM [IgA], nM
Figure 16. Scattergram of the distribution of the normal hydrodynamic
force to separate doublets of SSRC cross-linked by monoclonal IgM and IgA
antibody, suspended in buffered 46-58% sucrose in an accelerating Poiseuille
flow. Also shown are mean values + 1 S.D. From [93], with permission.
0.25 0.25
F n <70pN F n = 55 p N
o
o
0.20
I
9.-o.. 70<F n<140pN , 0.20 I
I
9-.o..- Fn=lllpN
0.15 - I 0.15 1
O
..I l
9 l
o
- 0.10 0.10 -" I
0
0
A
-9 0.05 "~ 0.05 - i "A..-~ x ~' -~.~-]
o
/A \ "..,"1 9 *,,,4
ra~
0 0 | I I ,1 I I |
0 ] 2 3 4 5 67 8 910 0 1 2 3 4 5 6 7 8 9 10
Number of Rotations Number of Rotations
where R 0 and Rp are the radii of the membrane capsule and suction pipette,
respectively. When a small force, f, is applied to the probe, the capsule is
40
-p
Tm
Azt
Y
Figure 18. Schematic diagram of an ultrasensitive-
tunable force transducer formed by a pressurized
membrane capsule. From [140], with permission.
r b being the radius of circular contact between capsule and microbead. Since
stiffness is proportional to tension, the force sensitivity can be tuned in
operation between 1 l.tN m -~ and 10 mN m -~ simply by changing P, and Azt is
measurable down to 0.01 ~tm using optical techniques. The microbead is
chemically conjugated to separate ligands, one for macroscopic attachment to
the capsule surface and the other for focal bonding to receptors on a biological
surface. The microbead is brought towards the surface beating the receptor,
bond formation is signalled when fluctuations in height (which depend on the
rigidity of the receptor interface) diminish markedly; similarly bond release
shows up when the fluctuations return to the original level. The relative
frequency of formation and release then quantitates on/off rates. Finally, the
transducer can be retracted to load the force on the attachment until bond
rupture occurs.
leukocyte and E - and P-selectin on the endothelial cells). The ligand binding
sites on selectins are calcium-dependent lectin-like domains, carbohydrate
structures which recognize fucose containing oligosaccharide moieties known as
sialyl-Lewis x and sialyl-Lewis ~ on the leukocyte or endothelial cell. In the case
of neutrophils, L-selectin is concentrated on the tips of the microvillus-like
projection of the ruffled cell membrane, favouring the formation of the
selectin-carbohydrate bond with the endothelial cell.
Attempts have been made to determine the parameters of Bell's model from
experiments with rolling cells as well as receptor-linked latex spheres. Alon et
al. [ 150], using neutrophils rolling along lipid bilayers containing P-selectin on
the lower surface of a parallel plate flow chamber, measured the force
dependence of ~;oZ for the P-selectin-carbohydrate ligand bond using the
distribution of times during which cells were arrested. They found xt~ = 0.05
nm, an extremely small value, suggesting the linkage to be close to an "ideal"
bond, the lifetime of which varies little with applied force [131,151 ]. The work
also showed that both too, and tCog~ were fast compared to other known
macromolecular interactions [150]. This may be compared with xa = 0.40 nm,
obtained from computer simulation of the observed force dependence of
rupture of a protein-protein bond between doublets of latex spheres [152].
f
I~ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ lI I S ~ \ \ \ \ " ~ \ \ \ \ \ \ \ \ \ ~
i
I I
t . , 4 I 2R - - ~
Thus, Gw is zero at the stagnation point and increases linearly with radial
distance. The region where y is c o n s t a n t - a pure stagnation point flow,
extends out to r = 0.1h.. For greater r, corrections to the flow field can be
used. The particles are observed in epi-normal or interference contrast
illumination and events recorded on videotape.
Suspensions of cells or derivatized microspheres beating ligand flow onto the
surface, and the number of particles per unit surface area expressed as:
n, = n= [1 -exp(-t/cr)] [37]
where n is the number at t - oo and cr is given by the relation:
l/or = 1/cr,~ + l/crbt [38]
cr~ being the characteristic escape time of the cells and crb~that of slowing down
of the deposition by the presence of deposited particles [160]. Measurements of
n~ with time in various regions of the surface yield values of the initial adhesion
rate and the above parameters. The escape time (average lifetime of a cell on
the surface) is a measure of the cell-surface bond strength, and can be
compared for the different receptor-ligand systems.
Detachment experiments are carried out with the surface covered with
spheres, and then exposed to a stream of suspending medium of known viscosity
at various flow rates. The tangential hydrodynamic force, F~, exerted on a
particle of radius b adhering to a surface is given by [146]:
F~ = 1.7x6mS;wb 2 = 1.7x6n:yrb 2 [39]
can be related to the surface bond strength through the force dependence of the
time course of detachment, which is dependent on the surface density of ligand.
45
100~"
~ 50
=
r.~ 80 "~ 40
= E 30
o
= 60 ~ 20
"" "~ 10
E 40
r 1~ 0 20 40 60 80 100 120
" pN
0
0 10 20 30 40 50 60
Time, minutes
Figure 20. Shear-induced detachment of SSRC on a glass surface
having covalently-bound monoclonal IgM. Plot of the normalized
surface density against time. The average tangential hydrodynamic
force was 75 pN. Inset: plot of the surface density vs the average
hydrodynamic force. From [138], with permission.
a force of 3 nN [161], 30x greater than that found in the SSRC-IgM antibody
impinging jet experiments [138]. However, the surface density of rabbit IgG
antibody was 1-3 orders of magnitude greater and the number of bonds, rib, was
thought to be very high.
6. B L O O D C E L L I N T E R A C T I O N S IN R E G I O N S OF D I S T U R B E D
FLOW
Re = 37.8 ~
I
i
Q
the axial location of the vortex center and reattachment point oscillated in phase
with the upstream fluid velocity between maximum and minimum positions
about a mean which corresponded to that in steady flow. At hematocrits from
15 to 45%, migration of cells still occurred and resulted in a lowering of the
vortex hematocrit.
In part, particle migration in the vortex was likely due to the dilution effect
of cell-poor plasma taken into the vortex from the fluid layer adjacent to the
vessel wall upstream of the expansion. The mechanism for the trapping of
large aggregates in the vortex was qualitatively explained by using existing
fluid mechanical theory [57] for lateral particle migration near a tube wall due
to inertia of the fluid, and by the operation of a mechanical wall effect [ 168].
9 -:tF ~
'~ 1.0
B Re=
_ 37.5
U= 4 3 . 0 m m sec -!
o 0.8 ! ...... L.. ,... 5 x 1 0 5 p l a t e l e t s ~ e "1
\
,4-,
_.e 0.6
_
-q~ v - OI
o
"~ 0.4 Steady flow
o .......... Pulsatile flow
9 0.2 , AV=3~t
.Q f = 1.5 cycles sec -!
E
Lmin. IL Lmax.
l I; I I I I i i i i i i
Z 0
0 2 4 6 8 10 12
Distance from expansion, mm
Figure 22. Flow patterns and platelet adhesion in the annular vortex.
A: Streamlines in the expansion tube showing convective transport of
spheres on radially directed curved paths on either side of the
reattachment point (dash-dotted line). B: Plot of platelet adhesion
density on the collagen-coated tube in steady and pulsatile flow
(amplitude AV = 3 ~1) at the same mean Re0, with the reattachment point
oscillating between L,,z, and L,,~,. From [166], with permission.
Re=42.1
D=2.03mm
d =0.81 mm
0=53.3mm s-' R
Q1
Qo_~_.
~_~_~,i
9 ~_ ~ ~ ~ / ' ~ f ~ , ~ - - - . . ~ _ _~----------------~__~ ------------___.__~~
S R
Figure 24. Flow patterns (paths of tracer 50 l.tm PS spheres) in the common
median plane of a 3 mm diameter glass T-junction, made b_y fitting and glueing
2 pieces of tubing. Flow enters at left with mean velocity U o ; 80% left through
the side tube; points show sphere positions at 22 ms intervals, numbers the
velocities in mm s -~. From [175], with permission.
Q2
Abdominal aorta
Figure 25. Plot, as in Figure 24 of the flow patterns (paths of 200 l-tm PS
spheres) at the aortoceliac artery junction of a dog abdominal aorta, with a
considerably smaller flow disturbance (thin-layered recirculation zone) than in
Figure 24, as only 28% of flow entered the branch, curvature of wall opposite
flow divider is high, that at the divider is low. From [ 177], with permission.
53
was only a pair of recirculation zones, confined to a thin layer close to the wall
surrounding the mainstream. There was no side recirculation zone, no doubt
due to the gentle curvature of the bend opposite the flow divider. This
characteristic was shared by all the aortic T-junctions studied, as was the very
sharp curvature of the bend at the flow divider. From the results described
above in the glass model T-junctions, this represents the optimum condition for
minimizing the size of both regions of separated flow. Nevertheless, the curved
streamlines of the recirculation zone and secondary flows will bring blood cells
towards the vessel wall in a zone around the flow divider and in the side branch
on the outer wall.
Reo--592
U0=266 mm s-' Q2
Q~/Q. =0.613
Qo
i
2a3 :
QI
In pulsatile flow, the complex spiral secondary flows and the recirculation
zones oscillated in phase with the pulsatile flow velocity, and the locations of
the stagnation and separation points moved back and forth along the vessel wall.
However, the general flow patterns remained the same as those observed in
steady flow.
i il I~/
i [i
D, = 3.09 mm
Q.= 147 ml/min
tlillli !I ll|iJ!//iHtli|
~o
7. CONCLUDING REMARKS
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94. H.L. Goldsmith and S.G. Mason, Proc. Roy. Soc. (London), A 282 (1964)
569.
95. T.G.M. van de Ven and S.G. Mason, J. Colloid Interface Sci., 57 (1976)
505.
96. K. Takamura, H.L. Goldsmith and S.G. Mason, J. Colloid Interface Sci.,
82 (1981) 175.
97. P.A. Arp and S.G. Mason, J. Colloid Interface Sci., 61 (1977) 21.
98 C.Y. Lin, K.Y. Lee and N.F. Sather, J. Fluid Mech., 56 (1972) 375.
99. G.K. Batchelor and J.T. Green, J. Fluid. Mech., 56 (1972) 375.
60
S H E A R T H I C K E N I N G AND FLOW I N D U C E D S T R U C T U R E S
IN FOODS AND B I O P O L Y M E R SYSTEMS
1. INTRODUCTION
E
10 D
12_
10 -1
10-2
I I I I I I
r
10 -~ 1 10 10 2 10 3 10 4
?(S -1 )
Abstracts (American Chemical Society) did NOT result in listing of our own
publications pertaining to starch, although use of the search term, "starch," did.
This indexing situation was most surprising to us.
2. R H E O L O G I C A L M E A S U R E M E N T S AND R E L A T E D T H E O R Y
b
Shear thickening Shear Shear
thickening
thinning
J
/ / / Newtonian
~ thinning
Newtonian
? ?
plotted values of shear stress, shear rate and viscosity are steady state values.
This may not be the case and the appearance of shear thickening may be a
result of transient effects. Such effects are particularly likely with
instrumentation in which shear sweeps are performed, for example in a
Couette rheometer in which the shear rate may be cycled over a certain range
in a certain time. In a recent study of effects of processing on starch solution
properties, shear rate sweeps from zero to 750 reciprocal seconds and back
68
down to zero were carried out over a four minute period (Dimzis and Bagley
[8]). In such experiments the possibility of transient effects cannot be ignored.
Such a flow history is sometimes referred to as the thixotropic loop or T loop
(see Greener and Connelly [9]).
Other instrumental factors can be significant in the phenomena of shear
thickening. For example, a recent contribution by Chow and Zukoski [10]
deals with the effect of gap size in shear thickening of a suspension. The
possibility of such experimental artifacts must be kept firmly in mind in
interpreting complex rheological data.
Fluids for which viscosity depends not only on shear rate but also on time
can be subdivided into two classes, thixotropic and rheopectic (Tanner [6]).
Thixotropic fluids are generally regarded as ones in which there is a
breakdown of structure by shear while rheopectic fluids are ones (Tanner [6])
in which there is formation of structure due to shear. The history of the term
"thixotropy" has been reviewed briefly by Cheng and Evans [ 11 ] but they use
the additional term "antithixotropic" because in their view there are three
distinct types of structural changes brought about by shear: l) structural
breakdown under shear with recovery at rest (thixotropy); 2) structure buildup
under shear, disintegrating at rest (anti-thixotropy or negative thixotropy); 3)
structure breakdown at moderate and high rates of shear with recovery
accelerated at low shear rates, the recovered structure being stable at rest
(rheopexy).
The difficulty with the introduction of new terminology to describe particular
types of behavior is that nature keeps providing us with new phenomena
which do not fit into the accepted categories of the times. Thus, starch
systems (as will be discussed in more detail below) can show structure buildup
under shear but the structure so formed appears to be quite stable, both at rest
and under different shear fields (Dintzis and Bagley [8]). This type of
behavior is not covered by the three classifications proposed by Cheng and
Evans. Further, when the classifications become too numerous it often
happens that different workers use the terminology in different ways. A good
example of such confusion was given by Cheng and Evans, who noted in
their 1965 paper "At the present time thixotropy is still used by certain
rheologists to denote what is more commonly known as pseudoplasticity (that
is, the decrease in viscosity with increase in shear rate) without reference to
time dependence."
Barnes has recently reviewed shear thickening effects for nonaggregating
solid particle dispersions in Newtonian liquids (Barnes [12]). He summarizes
his views in the abstract of his article as follows" "The actual nature of the
shear thickening will depend on the parameters of the suspended phase: phase
volume, particle size and distribution, particle shape, as well as those of the
69
suspending phase (viscosity and the details of the deformation, i.e., shear or
extensional flow, steady or transient, time and rate of deformation)." Barnes
notes that shear thickening is defined in the British Standard Rheological
Nomenclature as "the increase in viscosity with increase in shear rate, and is
to be distinguished from rheopexy which is the increase of viscosity with time
at constant shear rate." Barnes also makes some interesting comments on, and
gives some references to, the practical implications of shear thickening.
60
.,..:::...:'.. : .........
50 , | ,,.. m" i~i =
CO
L~ ="" m""
30 . . . . . . . . . . . . . . . . . . . . . . . . ~..-':-'-'"- ;,.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(1)
(-" "
,~, ~"",:
~r 9 ,
,-" ,~0~,,,~
~ : : : : : :
n,~'.~., i.., i,.. i.., i... i,,, i,,, i . , ~
vO 1oo 200 300 400 500 600 700 800
Shear Rate[I/s]
3. SUSPENSIONS
10 4
LL
o 10 3 -
(n ro
0 .on
o >
.o LL
(/) t-
r c) 10 2 -
03 r
or)
thickening and dilatancy due to particle crowding and ordering into layers, as
discussed by Hoffman. Although not explicitly stated the viscosity data given
by Hoffman appear to be steady state values.
Starch particles in general, and certainly potato starch in particular, are not
uniform spheres and as Hoffman discusses one needs to consider that particle
size distribution and particle shape can both influence the thickening effects.
As Williamson and Heckert noted, and as was no doubt also true for the work
of Hoffman, the starch granules are little affected by solvent (water, glycerol)
at room temperature. In many actual food processing applications, though,
temperatures would be in the gelatinization range, high enough that swelling
of the starch may occur, or higher, where continued exposure to high enough
temperatures, pressures and shear would lead to starch granule disruption and
solubilization.
72
Further studies of the flow of potato starch suspensions have been reported
by Bang et al. [ 19]. They report dilatant behavior but caution that "Not all the
shear thickening is associated with a volume increase, but the term dilatancy
is more broadly used for the materials which increase viscosity with increase
of shear rate." However, the work of Bang et al. [19], while showing shear
thickening of potato starch suspensions at concentration levels of 14 to 30 wt
% at temperatures in the range of 20 ~ C-40 ~ C does not show the flow
discontinuity which Hoffman reports at concentration levels such as 50% or
greater. Bang et al. give a theoretical explanation that involves swelling of the
outer amylopectin molecules of the starch granule for the "dilatancy" in their
systems. This hypothetical swelling with the extension of the outer granule
amylopectin molecules into water is proposed as the mechanism for the
formation of a "three-dimensional scaffold structure" which results in the shear
thickening. More data on the partial swelling of the starch granules at these
low temperatures (below 40 ~ C) would be needed in establishing the validity
of the Bang et al. explanation for the thickening.
Rheological investigations of the "cooking" of starch granules have been
made (Bagley and Christianson [20]); Christianson and Bagley [21]). Figure
5 taken from the Christianson and Bagley [21] reference illustrates the type
of behavior observed. The dispersion was 25% com starch in water, heated
at 65 ~ C (on the lower end of the gelatinization temperature range for this
starch) for various times. After heating, a sample was removed from the
heating vessel and the viscosity measured in a Haake Rotovisco Couette
rheometer at 60 ~ C. The shear rate was raised from the low end (around 3
reciprocal seconds) to the high shear rate range in 3 to 5 minutes depending
on the upper shear rate reached (see Figure 5).
The initial uncooked dispersion had a very low viscosity which could not be
measured on the equipment used for the cooked samples. After 15 minutes
heating at 65 ~ C the starch granules had swollen enough that the viscosity
level was now well within the measurable range for the Rotovisco. As can be
seen from Figure 5 the viscosity initially decreases with increasing shear rate
but a region is reached just above 10 reciprocal seconds where the viscosity
begins to increase with increasing shear rate. This shear thickening is
interpreted as follows. After 15 minutes at 65 ~ C the effective volume fraction
of the water-swollen starch granules is now high enough to have a viscosity
in the range 500 to 1000 cp. However, the granules still have a relatively
rigid core and act as more or less rigid particles giving rise to the shear
thickening shown in the lower curve of Figure 5. After 30 minutes the
particles have swollen still more so that the effective volume fraction is such
that viscosities half a decade higher than the 15 minute cook are observed.
The particles, however, are more deformable, being much less rigid, more
73
100,000
At 60~ after cooking at 65~
| 15 min o 45 min
~e~ A 30 min 9 75 min
e~ 25% (db)corn starch in water
10,000 --0~0~ ~o
..=....
~
r
.....,.
Q~
"~'---A-- A.----A--A ~ A .
1,000
100 1 , I
1 10 100 1000
Shear Rate (sec-1)
Figure 5. Viscosity (cp) vs shear rate (sec l) for a 25% dispersion of normal
maize starch in water, measured at 60 ~ C after cooking in a Corn Industries
Viscometer at 65 ~ C for 15 (Q); 30 (A); 45 (n); and 75 ( e ) rain. (From
Christianson and Bagley [21].)
time required to ramp the shear rate from the low initial level to the upper
shear rate. Unfortunately, if the ramp time is varied to resolve this question
it means that the dispersion must be kept at 60 ~ C for longer periods of time
and the experimental result will be clouded by the effects of a longer cooking
period. However, the shear thickening observed for measurements made
around room temperature where the ratio of ramp time to relaxation times is
quite different from that at 60 ~ C suggests that the shear thickening observed
is not a result of time effects. More extensive investigation of the point would
be desirable. Nevertheless, the observation of shear thickening in these studies
certainly seems to provide information on the swelling process and the
changes in the deformability of swollen starch granules during the cooking
process.
4. S H E A R T H I C K E N I N G EFFECTS IN S O L U T I O N S / D I S P E R S I O N S
can be extremely large, of the order of one hundred million or more. This
means that starch, in terms of the number of monomer units per polymer
molecule, is much larger than most normal commercial thermoplastic polymers
such as polyethylene and polystyrene.
Starch is also interesting and challenging because of its solubility
characteristics. Common practice in the use of starch has been to "paste" the
material by heating with mechanical stirring at temperatures up to about
95 ~ C (Whistler et al. [28]). While well beyond the temperature range at
which gelatinization occurs (i.e., where starch crystalline melting occurs and
significant swelling due to water sorption takes place) the starch granules are
not by any means fully solubilized. Amylose may be largely in solution but
relatively little amylopectin can be fully solubilized, and starch granule
fragments may persist even to 100 ~ C and above. The gelatinization range
depends on numerous factors such as the type of starch (corn, rice, wheat,
etc.), the variety (e.g., waxy corn starch consisting primarily of amylopectin)
and various agronomic factors. For common starches this gelatinization range
is 60o-80 ~ C.
With so many hydrogen bonding sites it seems surprising that starch is not
more readily soluble in water. In fact, it is necessary to heat starch in water
well above 100 ~ C (to, say, 120 ~ to 140 ~ C in an autoclave, for example) to
approach polymer solubilization. Heating starch, with stirring, to such
temperatures produces "solutions" that are quite different in properties from
dispersion/solutions that have only been "pasted" by heating to around the
95 ~ C level (Christianson et al. [29]). Alternate routes to solubilizing starch
include jet cooking (in which a starch slurry is passed through a nozzle with
high pressure steam, Christianson et al. [30]) and the use of solvent systems
such as dimethyl sulfoxide (DMSO), water/NaOH, water/KOH and other
alkaline aqueous systems.
Starch is heated above 100 ~ C in aseptic food processing. This can be a
continuous sterilization process for viscous liquid foods in which high
temperature is applied for a short time. Dail and Steffe [31,32], in studying
this aseptic processing, found that solutions of cross-linked waxy maize starch
showed shear thickening effects and that this was probably due to dilatancy
instead of time-dependent thickening due to on-going pasting.
In investigations of the effect of thermo-mechanical processing on starch
structure and size it was found that the intrinsic viscosity of starch decreased
significantly as processing severity increased (Dintzis and Bagley [33]). At
the same time dilatancy was evident in samples that were not severely treated
(Dintzis and Bagley [8]). Since the viscosities were obtained with a shear
sweep the observed thickening could have been a result of time effects as
discussed by Krieger [13]. However, the thickening in these starch solutions
76
was of an unusual type, as indicated in Figure 6 taken from Dintzis et al. [34].
In a shear sweep from rest to 750 reciprocal seconds over a period of 2
minutes, and then without pause decelerating to zero shear rate in another 2
minutes, with several subsequent repeats of this cycle, results as shown in
Figure 6 were obtained. The solution freshly placed in the fixture was initially
shear thinning but just beyond 100 s~ shear thickening was observed. After
an increase of nearly half a decade in viscosity, the solution became again
shear thinning. Subsequent lowering of the shear rate gave a viscosity/shear
rate plot following a power law all the way down to the lower shear rate limits
of the machine. Subsequent cycling gave viscosity/shear rate curves which to
101
o o . Fresh c o o k
60 ~C F l o w
.x. 3 hrs. old, stored in D e w a r
f/)
C 0
rl
v
x o
>, 10 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
o,.~. x i
or) x
x
0
o
O x
x
o
x
o o
~
O x x ,,, :"Ooc b
x ~,,,, "o
>
o o o
o c>! o 0.~. om~ (~
1 0 -1 . . . . . . . . , . . . . . . . . i . . . . . . . .
10 0 10 ~ 10 2 10 3
. .i~
....
9,:<~,~,,, ,,
i:~(,"':
C ~
~,~ ~,
" 7"'
. ...
9~"" ,~,,;;
.~
E. . . . ..,.,.
~ ' . F .........
. . . . . . .~ :,~. . .
... ....
... :
lOpm ..,,,,,..,,
.:
Figure 7. Phase Contrast micrographs of sheared (in cone and plate) vs not
sheared starches in 90% DMSO-H20. A, 2.0% waxy maize starch sheared;
B, 2.0% waxy maize starch not sheared; C, 2.0% dull waxy maize starch
sheared; D, 2.0% dull waxy maize starch not sheared; E, 2.6% normal maize
starch sheared; F, 2.6% normal maize starch not sheared. Starch
concentrations chosen to provide approximately equal amylopectin amounts
in each fluid. (From Dintzis et al. [34]).
systems but other biopolymer systems can also show surprising behavior.
Thus, Yalpani et al. [36] reported on the complex rheological behavior of a
branched, water-soluble chitosan derivative, 1-deoxylactit-l-yl chitosan, a
comb-like polymer. The complexities reported included shear thickening seen
in viscosity versus shear rate plots for 1 and 2% (wt/wt) concentration levels
of this chitosan derivative in water. The authors emphasized that steady state
values of shear stress were obtained in their Brabender Rheotron viscometer
and used in calculation of viscosities. The onset of the observed viscosity
increase occurred at a lower shear rate for the 2% than for the 1% solution.
Lower concentrations (0.5% and 0.1%) showed approximately Newtonian
behavior over the shear rate range of 10 to 3000 s -~.
Rising temperature reduces the shear thickening exhibited by this chitosan
derivative. For a 1% solution an approximately five-fold viscosity increase
occurs in the shear thickening region at 25 ~ C. The shear rate at which
thickening occurs increases with increasing temperature over the range 25 ~
35 ~ C. Specifically, the viscosity peak occurs at 40 s -~ at 25 ~ C and at 35 ~ C
at about 350 s -1. The magnitude of the viscosity increase in the shear
thickening region decreases with increasing temperature. At 43 ~ and 50 ~ C
evidence of shear thickening has pretty well disappeared and the solutions are
only slightly shear thinning in character, or in the authors' words " .... at
43 ~ C, essentially Newtonian flow is again observed."
Yalpani et al. also report some unusual time effects for these chitosan
derivative solutions, in particular showing oscillatory "shear stress-time
dependency at steady shear." To illustrate, for the 2% solution, at a shear rate
beyond the peak of the viscosity-shear rate plot, oscillations in shear stress at
constant shear rate is seen. The corresponding viscosity variation is quite
large, from 800 to 2000 Pa.s, "without any appreciable damping being
apparent over the periods (few minutes) .... investigated." The phenomenon
was not observed with the 1% solution.
are several reasons for this. Food systems are always subjected to shear field
(mechanical) treatments during processing. This occurs particularly during
mixing, stirring, shaking, pouring, homogenization, pumping, extruding and
cutting. Normally, the larger scale and greater efficiency of food industrial
processes are related to the more intense shear forces. The mechanism of
shear effect on protein recovery from dilute solutions is of significance for the
improvement of technologies for protein isolation from different raw materials,
for scaling up and for wider use of continuous precipitation." The same
authors also note that proteins together with polysaccharides are the main
components responsible for the properties and quality of foods. Mechanical
treatment is an important part of the processing of these components, alone
and in combination, and the rheological characteristics are critical aspects of
protein/polysaccharide-based foods. Clearly, structure formation during
shearing, as indicated by shear thickening effects, can be critical in influencing
the final physical and organoleptic properties of processed foods.
~ o o o-1
T
0-2
2O
E
00
~ 15 -i
/
7
10 I I I ... I
0 10 C* 20 30 40
Cpr, % wt.
The work of Suchkov et al. is of significance in the food area because they
examined both the rheological and phase behavior of an important protein
system, specifically salt solutions of the 11S globulin protein from broad beans
(legumin). Stable single phase salt solutions of this protein "can undergo a
reversible transition from the single phase to the two phase state .......... either
on cooling or diluting the protein solution with water." A concentrated
"mesophase" and a dilute phase are formed so that in effect the water solution
changes into a water-in-water emulsion.
Figure 8 (Figure 3 of Suchkov et al. [37]) shows the phase diagram for 11S
broad bean globulin-NaCl-water system. Viscosity measurements of a 19.6
wt % system were made at temperatures from 11 ~ C to 29 ~ C in 1.5 ~ C
intervals, and the results for temperatures 14.0 ~ to 21.5 ~ are shown in Figure
9 (Figure 2 of Suchkov et al.). The authors note that above the binodal the
single phase legumin/salt solutions showed Newtonian behavior while within
a range of temperatures below the binodal the system exhibited non-
Newtonian behavior and specifically showed shear thickening effects. It is
evident from Figures 8 and 9 that the onset of apparent shear thickening does
not coincide very exactly with the development of two phases. It is not until
17.0 ~ C, well below the maximum of the phase diagram plot, that the shear
thickening is seen. The author's comment (V. Ya. Grinberg, personal
0,2 --
6 (14~
0,1
oo -5
n
4 (17~
E 3
2 (20~
~" 0,02 1
I ...... I ! I
0,01
0 600 1200 1800 2400
~/, S-1
communication) that the shear sweep cycle time was about 40 rain. and that
each of the coexisting phases in the protein system was a Newtonian liquid
suggests that the observed shear thickening was not the result of time effects.
It is also interesting to observe in Figure 9 that viscosities can be lower, at
the lower shear rates, for the low temperature measurements than at the
higher temperatures; for example at 14.0 ~ C the viscosity below about 750
sl is lower than the Newtonian viscosities at 17 to 21.5 ~ C. Such a reversal
could be indicative of a shear dissolving process. Certainly, the results are
extremely interesting and potentially valuable for process design applications.
Considerably more work and extensive investigation of protein and food
systems is needed along lines discussed in the literature, for example, by Wolf
and Horst [38] and Tolstoguzov [39].
7. H O N E Y
Scott Blair [40] in Chapter VI, The Rheology of Honey, from his well-
known book on "Foodstuffs, Their Plasticity, Fluidity and Consistency" notes
that the term "dilatancy" had been expanded "of recent years" to include
"any system whose viscosity increases with increasing rate of shear beyond a
certain minimum value". He noted that "the system need not contain any solid
particles but can be a true solution such as gum arabic in water to which a
small amount of borax has been added." He then went on to reference the
work of Pryce-Jones [41 ], who, using a twin-Couette rheometer, demonstrated
that a large number of honeys showed the property of shear thickening.
Specific honeys, such as honey from Eucalyptus ficifolia, also possessed the
property of being easily drawn into long strings, the property of
"Spinnbarkeit". Scott Blair further emphasized that dilatant honey systems
displayed the Weissenberg effect, as evidenced by the fact that when a glass
rod is immersed in honey and rotated at certain speeds the honey will climb
up the rod. This certainly implies that the system is exhibiting considerable
elasticity so that one evidently is dealing with viscoelastic fluids for these
dilatant honeys. Honey dilatancy is also emphasized in more recent texts, for
example in Sone [42].
Honeys are essentially concentrated sugar solutions. However, for the 15
dilatant honeys investigated by Pryce-Jones [43] all contained dextran
(C6H1005) n with n of the order of 8000. This would mean the dextran is a
relatively high molecular weight material, approximately 1.3X106 Daltons.
The concentrations of dextran are relatively low, quoted by Scott Blair as
7.2% dextran for the Eucalyptus ficifolia and 6.4% for Eucalyptus eugeniodes
honeys, respectively. Of course, for molecules of molecular weights over a
83
8. RECENT MODELS
Dr. Craig Carriere kindly called our attention to some recent papers
describing theoretical models for the development of shear thickening. There
is the phenomenological model of Hess and Hess [47]. Wang examined a
model treating the dynamics of coexistence between a physically cross-linked
network with temporary junctions and unbound chains [48]. Hatzekiriakos et
al. [49] modeled polymer macromolecules as Hookean elastic dumbbells
deforming affinely during flow. While not exhaustive, these references are of
fundamental interest and computational investigation of the applicability of
these approaches to specific shear thickening systems is clearly warranted. It
must be noted, though, that these models imply structural reversibility which
is not observed in the behavior of amylopectin.
9. A C K N O W L E D G E M E N T
REFERENCES
36. M. Yalpani, L.D. Hall, M.A. Tung and D.E. Brooks, Nature, 302 (1983)
812.
37. V.V. Suchkov, I.A. Popello, V.Y. Grinberg and V.B. Tolstoguzov, Food
Hydrocolloids 11(2) (1997) 135.
38. B.A. Wolf and R. Horst, "Flow Induced Dissolution/Demixing in
Polymer Systems - A Predictive Scheme" in Rheo-Physics of
Multiphase Polymer Systems, K. Sondergaard and J. Lyngaae-Jorgensen
(eds.), Technomic Pub. Co. Inc., Lancaster, Pennsylvania, 1995.
39. V. Tolstoguzov, Gums and Stabilizers for the Food Industry, G.O.
Phillips, P.A. Williams and D.J. Wedlock (eds.), "Applications of phase
separated biopolymer systems," IRL Press, Oxford 1996.
40. J.W. Scott Blair, Foodstuffs, Their Plasticity, Fluidity and Consistency,
Interscience Pub., Inc., New York (1953).
41. J. Pryce-Jones, J. Sci. Inst., 18 (1941) 39.
42. T. Sone, in "Consistency of Foodstuffs," D. Reidel Co,, Dordrecht,
Holland, 1972.
43. J. Pryce-Jones, Bee World 33(9) (1952) 147.
44. J. Sabati6 and L. Choplin, "Shear Induced Structure in Dextran
Solutions" in Proceedings of the Symposium on Recent Developments
in Structured Continua, D. DeKee and P.N Kaloni (eds.), Longman
Scientific and Technical, (1985) 165.
45. L. Choplin and J. Sabati6, Rheol. Acta 25 (1986) 570.
46. J. Sabati6, L. Choplin, F. Paul and P. Monsan, Rheol. Acta 25 (1986)
287.
47. Hess, Ortwin and Hess, Siegfried, Physics A., 207 (1994) 517.
48. Wang, Shi-Qing, Macromolecules 25 (1992) 7003.
49. Hatzekiriakos, G. Savvas and D. Vlassopoulos, Rheol. Acta 35 (1996)
274.
87
R H E O L O G Y OF FOOD EMULSIONS
1. INTRODUCTION
2. EMULSION STABILITY
EMULSION
STABILITY
STRUCTURAL PARAMETERS
- deformability
- internal viscosity
- surface viscoelasticity
- concentration
* interparticle interactions
PROCESSING CONDITIONS
* temperature
* residence time
* agitation speed
* etc.
stabilization takes place by the formation of a particulate network being the yield
stress of this structural network the decisive factor to stabilize the emulsion [41 ].
In relation to this, another important aspect to be taken into account is the
thermodynamic compatibility between the hydrocolloid and the emulsifier used
[5, 38, 42]. Thus, added biopolymer may have a positive or negative effect on
stability depending on its concentration and the nature of the droplet-biopolymer
interactions.
n 1 + 2,5 (1)
fir - r l c -
where r/~ is the viscosity of the continuous phase.
The classical Taylor's treatment [48] takes into account the internal circulation
of the dispersed fluid:
(1 + 0.4(nc / n j ) )
qrel -1+2.5~ l+(qc/qd) JOO (2)
where rk is the continuous phase viscosity and r/a is the dispersed phase
viscosity.
92
( 25~ "~
fir = exP/1 +am,J (4)
( 1.25~) )
fir-~1 + 1_ aEd~) (5)
- (6)
In addition to these, equations proposed for solid suspensions have been also
used to describe the influence of ~ on the relative viscosity, with the following
form [54-57]:
qr = qr ($ / d~m ) (7)
-[nl*m
Krieger-Dougherty
F ,
qr = [1 - ~ m
(9)
1- * 7-2
Maron-Pierce-Kitano f i r - ~mJ (10)
11oo _ exp 2 , 5 , ) (1 1)
qc 1- k~)
Pal and Rhodes [62] have proposed an empirical equation to correlate results
obtained with both Newtonian and non-Newtonian emulsions:
where (~b),~,.=;00is the disperse phase volume fraction at which fir- 100.
The same authors [36] have developed a theoretical equation for non-
Newtonian emulsions. They explain the non-Newtonian behaviour as a
consequence of the formation of flocs, yielding the immobilization of an
important amount of continuous phase, and, consequently, increasing the effective
concentration of disperse phase. In addition to this, the effective concentration
increases due to the hydration effect, that causes an association between
continuous phase and emulsifier molecules. The equation results:
f i r -- 1 - k o k F (3)),1-2'5' (13)
where ko is the hydration factor, and ky is the flocculation factor, that depends on
shear rate (being unity at high shear rates).
Another method to describe the viscosity dependence with both shear rate and
oil volume fraction has been proposed by Partal et al. [60]. This method is based
on the superposition of the flow curves of emulsions with different oil volume
fraction, using an empirical shift factor. The relationship between the shift factor,
a(~), and the oil volume fraction is described by a Frankel-Acrivos type equation:
(14)
where 4)o is the reference oil volume fraction. The master curve shown in Figure 2
also contains the flow curves of emulsions having different emulsifier
concentration. In this case the superposition was carried out by using another
shift factor, which varies exponentially with the emulsifier concentration.
When considering the influence of ~ on emulsion viscosity it is also necessary
to know that there is a simultaneous influence of droplet size. In fact, rlrel
increases as the mean droplet size decreases. Thus, for example, k in equation
95
(11) increases as droplet size decreases [63]. In addition to this, an emulsion with
a broad distribution of droplet sizes will have a lower viscosity than those with a
narrower distribution of particle size [29]. In this case, a model that relates the
relative viscosity and ~) for emulsions containing an i-model size distribution has
been proposed [46].
~rel(~; ) = .L_Lexp
i=l 1 - ki~ i (15)
100
~ Carreau modd I
10 9
il-
a+asE+ (s-1)
Figure 2. Master flow curve for emulsions containing 1-10% wt. sucrose ester
and 55-85% wt. oil. Reproduced, with permission, from ref. 60.
This fact has been confirmed by different authors [9, 28, 32]. Thus, Figure 3
shows that the viscosity of salad dressing emulsions containing a mixture of
emulsifiers increases as mean droplet size and polydispersity decreases. This has
been attributed to the fact that narrower droplet size distribution and lower mean
diameter yield stronger interparticle interactions [28]. On the other hand, Partal et
al. [60] have found a linear correlation between some rheological parameters
(high-shear-rate-limiting viscosity and flow index) and polydispersity. However,
in other cases this correlation fails, because, for instance, the emulsifier that is in
96
excess may form a gel-like continuous phase. This structuration may be favoured
by increasing the droplet size, and consequently the emulsifier concentration in
the continuous phase [64].
1
ra~
,,..a
9
~ ().1
[ ~Carreaulnodel ]
0.01 . . . . . . . . I . . . . . . . . ~ .......... i . . . . . . .
0.1 1 10 100 1000
25
20
15
0 5 10 15 20 25 3O
diameter (~.m)
Figure 3. Steady-state viscosity (a) and droplet size distribution (b) of salad
dressing emulsions (emulsification time: r'l 3 min, O 5 min, A 10 min). Adapted,
with permission, from ref. 8.
97
A large majority of food emulsions may show slip effects under steady-state
shear [61, 65-68]. It has been demonstrated that multiphase systems show slip
effects because of a displacement of the disperse phase away form the solid walls
of the sensor system in a rheometer or the walls of pipes or tubes [69]. In the case
of emulsions, this effect is even more dramatic due to the deformability of the
droplets and is also enhanced when creaming process becomes important. Figure
4 shows a typical example of a flow curve showing slip phenomena. As Barnes
[69] has pointed out we normally expect a single drop from a lower-shear rate
Newtonian plateau through a shear thinning region towards the high-shear-rate-
Newtonian plateau. However, if slip occurs, an intermediate false pseudo-
Newtonian region is observed as Figure 4 indicates.
9 lip flowcuwe
log (stress)
As has been reported [61], the extension of slip is clearly dependent on the
emulsion composition due to the existence of different interparticle interactions
that influence emulsion microstructure. Thus, an emulsion containing a very
soluble low-molecular-weight emulsifier shows wall slip (determined by
comparison of the flow curves obtained with sensor systems having smooth and
rough surfaces respectively), in contrast to an emulsion containing an only slightly
soluble emulsifier which practically does not show slip effects. This difference
98
must be related to the aqueous phase behaviour. Thus, in the first case the
droplets are suspended in a low viscosity continuous phase favouring their
mobility, but in the other emulsion a very structured continuous phase (gel-like)
takes place, apparently reducing the slip problem.
However, the differences found in the steady-state flow curves carried out with
different types of surfaces are much higher when the viscosity is plotted versus
shear stress than those found when viscosity is plotted versus shear rate. In fact,
in many cases the differences found in the viscosity-shear rate plots are not
significant [61 ] and slip effects may be not taking into account if the experimental
flow curves are obtained using a controlled-shear rate rheometer. This can be
observed in Table I where the Carreau model parameters are compared for an
emulsion measured with rough and smooth surface sensor systems respectively.
3.2. L i n e a r viscoelasticity
The linear viscoelastic properties of food emulsions are usually confined to that
range of strains below any perceivable visual movement during measurement, and
though not generally applicable to large strain and stress technical applications,
are nevertheless useful in assesing the microstructure and even possible the long-
term stability of an emulsion [45].
The first studies on the response of concentrated emulsions in the linear region
were done by creep-recovery experiments [46]. The creep behaviour of a
concentrated emulsion, as a function of disperse phase fraction, often looks as
despicted in Figure 5. Consequently, food emulsions behave as viscoelastic
liquids, even highly concentrated emulsions such as mayonnaise [28]. This
response has been modelled using different analogycal models, being the simplest
combination one Maxwell element combined with one Voigt element in series,
that is "one retardation process" model:
t e(_t/~)
.! ( t ) - do + + J1 (16)
qo
99
This model has been used by Kiosseoglou and Sherman [18] to describe the
response of an egg-yolk film at a groundnut oil-water interface and by Matsumoto
and Sherman [70] for nonionic surfactant films at an olive oil-water interface.
2.0x102
1.5x10"2
,f--,
~ l.OxlO_2 m
5.0x10-3
0.0 I , I ~ I , I ,
(-t/z 1) (-t/z 2)
J (t)= Jo + J1 e + J2 e + t /rio (17)
This model has been used to describe the creep behaviour of a wide variety of
emulsions [72-76].
On the contrary, oscillatory shear tests have not been extensively used for
emulsion rheology [28]. As a consequence, only very little data were available in
the literature until a few years ago [77], when several authors started to use this
technique on different types of emulsions [37, 45, 78]. A general overview of
these studies demonstrates that the frequency dependence of the storage and loss
100
103 ....... '1 ' ' ...... I ........ I ' ....... I .......
0121O
~ (rad/s)
Figure 6. Storage and loss moduli vs. frequency for model mayonnaise with
different oil contents. I"1 75% wt., O 77.5% wt., A 80% wt., ( G ' open symbols,
G " solid symbols). Adapted, with permission, from ref. 78.
0.54. The same tendency is observed in the evolution of G" with ~. These results
are explained on the basis that at ~ < 0.56, the droplet-droplet separation is
probably larger than twice the adsorbed layer thickness and hence the adsorbed
layers are not forced to overlap or compress. In this case, the repulsive interaction
between the adsorbed layer thickness is relatively weak and the emulsion shows
predominantly viscous response. However, when ~) > 0.56, the droplet-droplet
separation may become smaller than twice the adsorbed layer thickness and the
chains are forced to compress. This leads to strong steric repulsion and the
emulsion shows predominantly elastic response.
Similar behaviour has been found for vegetable oil-in-water emulsions (~)
comprised between 0.7 and 0.8) stabilized by a nonionic-low molecular-weight
elnu|sifier highly soluble in the aqueous phase, at very low concentration (1%
wt.) [791.
lO 1 ' ' ' ' ' ' " I ' ' ' ' ' ' " I ' ' ' ' ' ' " I ' ' . . . . . 'I ' . . . . . . . I ' ' ' ' ' ' "
10~
~Z
~z
10-1
GN~ (P a)
45 % 0 3590
50 % 0 4345
55 % 0 5300
c0 (rad/s)
However, when a high HLB sucrose ester (slightly soluble in water at low
temperature) is used as the only emulsifier [80], or in addition to a
macromolecular emulsifier [10], in concentrated food emulsions three
characteristic regions were observed: (i) a pseudoterminal region at low
102
-
EI/m I+)nl + for Xmin < ~ < XP (18)
where ~ and ~ are the characteristic relaxation times for the onset of the plateau
and pseudo-terminal regions, respectively, Xm~ and )~m~ are the reciprocal of the
minimum and maximum experimental frequencies attained, m, n and c are the
power-law exponents for the three different regions, and A is an empirical
constant.
Madiedo and Gallegos [82] have proposed a different empirical model that
describes the three regions of the relaxation spectra of oil-in-water emulsions
stabilized by a mixture of two sucrose esters with different HLB values:
a x m +13xn
H ()~)- p (20)
In this model, m, n and p are, respectively, the slopes of the transition, plateau
and pseudo-terminal regions, ~p is the pseudo-terminal relaxation time, and the
parameters a and [3 are given by the following relationships
Homm (21)
a= (m-n) )~o
103
1 n Ho (22)
- m)
Ho is the minimum value of the relaxation spectrum, which appears between the
transition and the plateau regions, and ~o is the relaxation time that corresponds
to this minimum. This model allows a smooth transition between the plateau and
pseudo-terminal regions, in contrast to the BSW-CW equation.
Studies carried out on model mayonnaise (emulsions using egg yolk as the only
emulsifier) demonstrated that an increase in oil concentration (75-80% wt.)
produces a wider linear viscoelasticity range and larger values of the dynamic
linear viscoelasticity functions [78]. Only the transition and plateau regions of the
relaxation spectra appeared. The same influence was found when the emu|sion
was stabilized by a nonionic surfactant, with a high solubility in the aqueous
phase, for emulsifier concentrations higher than 1% wt. [79]. In this case, a
dramatic decrease in the loss tangent as oil concentration increases (60-80% wt.)
was noticed in the low frequency range. This is due to the fact that a decrease in
oil concentration favours the development of a pseudo-terminal region in the
relaxation spectra of these emulsions, as previously mentioned.
Guerrero et al. [80] have studied model emulsions stabilized by a sucrose
palmitate. The tendency showed by the linear viscoelasticity functions was
practically the same in the whole oil concentration range studied (60-80% wt.),
although their relaxation spectra always displayed three different regions.
Furthermore, the values of the loss tangent were practically independent of oil
content. This fact allowed to superpose the linear viscoelasticity functions using
the plateau modulus as normalization factor and a horizontal shift factor only for
the less concentrated systems. The superposition obtained was good enough,
although some scatter in the plateau region was shown.
Similar results have been obtained by Franco et al. [10] studying salad dressing
emulsions (35%-55% wt. oil) stabilized by a mixture of egg yolk and a high HLB
sucrose ester. Thus, the linear viscoelasticity functions at different concentrations
can be superposed using the plateau modulus as normalization factor, which
increases with oil concentration. However, there is a slight, but significant
increase in the slope of the plateau region as oil concentration increases, which
may be related to the development of the entanglement network. On the contrary,
there is no significant influence of the oil concentration on the relaxation time that
defines the onset of the pseudo-terminal region of the relaxation spectra. The
addition of 2% wt. starch, although favouring the emulsion stabilization at lower
oil concentrations (down to 35% wt.), dampens the influence of oil content on the
104
been explained from two different points of view: thixotropy and non-linear
viscoelasticity.
101 . . . . . . . . n . . . . . . . . I . . . . . . . . I . . . . . . . . I . . . . . . . . t | i | ||111
10~
10_1
o o00 t~
10-2 . . . . . . . . . . n
10-3 10-2 10 -1 10 0 101 10 2 10 3
c0(rad/s)
3500 -
3400
f
3300 J
320(I I
J
J
3100 J
o
Z
O 3000
2900 I J
2800
Figoni and Shoemaker [87] and Gallegos et al. [89] tried to describe the stress
decay after the overshoot by using a kinetic model, sum of two first order kinetic
functions, as follows:
cy- cye - (%1 - eye1) exp (-klt) + (%2 - eye2) exp (-k2t) (23)
The kinetic constants of this model have been related to different shear-induced
processes: deflocculation and coalescence of oil droplets.
However, others authors [88, 90-92] have tried to describe the above
mentioned behaviour using a non-linear viscoelasticity model, the Wagner model
[93], a class of strain-dependent K-BKZ-type constitutive equation [94]. Mackley
et al. [95] and Madiedo et al. [96] have also used this model to predict the
steady-state flow of oil-in-water food emulsions.
Considering simple shear, and assuming that the memory function can be
separated into time and strain-dependent components (Figure 9), the Wagner
model would be reduced to the following equation:
t d G ( t t'
cy (t) - -~ - ) h (~,) y (t,t') dt' (24)
-oo dt' "
where G (t-t') is the linear relaxation modulus and h (y) is the damping function:
1
h ( 7 ) - l + a 7b (26)
t ~gi -(t-t')/~.
cy (t) - - "f =~1~ e 1 h (Y) Y(t,t') dt' (27)
-ooi l
107
Introducing equation (25), the apparent viscosity for a shear rate, +, can be
calculated as
n gi Xi
= z (28)
i= 1 (l+kXi~;) 2
10 3
10 2
~" 101 El
i D~ [] nclc~tan_,.,_~
o
~ lOo
10 -]
time(s)
Figure 9. Linear and non-linear relaxation moduli for a salad dressing emulsion,
( i G(t) from H(X), X G(t) from the Ninomiya-Ferry approximation).
In other cases [78, 90] a power-law equation was used, yielding the following
integral equation:
Figure 10 shows the experimental and calculated values of R(t) (ratio between
the shear stress after instantaneous imposition of shear rate, ~(t), and the steady-
state stress, r~(oo)) for a transient flow test carried out at 0.6 s-~ As can be
observed, the fit of the model is acceptable at low shear rates. Higher shear rates
produce increasing differences between experimental and calculated values.
108
Other authors [96] have used a continuous relaxation spectrum, calculated from
the experimental values of the dynamic moduli, using the Tikhonov regularization
method [97, 98], to predict the steady-state flow behaviour of different emulsions.
In this case the Wagner model results
t oo e_(t_t,)/Z (30)
cr (t) - - ~ ~ H (X) h (~,) qt(t,t') dlnkdt'
--o0 --o0
and the steady-state viscosity may be calculated from the following integral
equation:
oo X H(:X)
11 ( f ) - [ d lnX (31)
-oo (1 + kXf)2
2~F
~ = 0 . 6 s -1
1.5
0.5
0.0 , I ~ I ~ I ~ I ~ I ~ I
time (s)
domain movement, chaining and changes in droplet size distribution, were all
observed under different shear conditions and depending on the nature of the
emulsifier used.
The authors conclude [96] that the Wagner model gives acceptable results, in a
relatively wide shear rate range for vegetable protein-stabilized emulsions. The
overestimation of the apparent viscosity at low shear rates is thought to be due to
sample slipping between the rheometer plates. On the contrary, the model largely
fails for a whole egg-stabilized commercial mayonnaise. This difference is
explained on the basis that the shear rate is inducing significant changes in the
droplet size distribution of mayonnaise throughout practically the entire
rheological range studied. On the contrary, the vegetable protein-stabilized
emulsion only shows a significant change in droplet size distribution at very high
shear rates. The authors remark this fact may indicate that the applicability of the
Wagner model is closely related to shear-induced structural changes in emulsion
microstructure.
maximum was found when the emulsion was prepared with a rotor-stator turbine
(4000 rpm). These DSD curves determine the linear viscoelastic response of the
emulsions. As can be observed in Figure 12, the systems prepared with the
anchor impeller show higher values of the loss modulus at low frequencies,
althought G' and G" curves crossover at a frequency O3c.Above this characteristic
frequency, a plateau region in G' develops as agitation speed increases. Similar
behaviour was also found by Tadros [37] for weakly flocculated emulsions. On
the contrary, the emulsion prepared with the rotor-stator turbine only shows a
plateau region, similar behaviour to that found for highly concentrated o/w
emulsions stabilized by a macromolecular emulsifier [78]. This behaviour
corresponds to an emulsion having much smaller sizes and narrower droplet
distribution than those prepared with the anchor impeller.
An increase in temperature favours the coalescence process, leading to larger
droplet sizes and broader distributions. In the same way, the plateau region in G'
tends to vanish and the crossover frequency increases. On the contrary, an
increase in the emulsification time enhances the development of the plateau
region.
l0
O. ~ ~
Diameter (~m)
Figure 11. Droplet size distributions for emulsions containing NPE-PEG-10,
prepared with different process conditions, (m 1oo rpm, 9 150 rpm, A 200 rpm, V
250 rpm, I"! 300 rpm, 4000rpm). Reproduced, with permission, from ref. 64.
111
1000
100
IIIIQIll
10 ~ o ~ O O Q o ~ ~ ~~
m o
u oo
oo
oQ
~oooooo~
Oo O DB
0
Oo []
[]
9
9
O~ o 9
mm
m
~ ........ o.o ' ........ o11 ........ ........ ........ oo' ......
Figure ]2. Evolution of the storage and loss modu]i with frequency, for an
emulsion containing NPE-PEG-] 0 as emulsifier, prepared with different process
conditions, (I-I ]00 rpm, O150 rpm, V 250 rpm, X 300 rpm, + 4000 rpm).
Reproduced, with permission, from ref. 64.
properties, both effects being related to the formation of a gel structure. Similar
results have been obtained by Gallegos et al. [64], using vegetable protein as
emulsifier.
6000 , , , , , , , , , , , , , , 100
5000
o
9 m u m m n
80
oo 9 %
4000 9 00000 9
,,I 9
l
/ 9 ~ O9
3000 %
o'
o~
uNNN 9
9 9 []
",p
9 9 O O0 9 DO OOO 0 40
20OO 9 O go O 0
9 n []
o
9 [] 0 0 0 0 O0 0 O0
[]
1000
9
[] O O 0
[]
0
O0 0 20
9 [] ooO o @@@ @@@@ @@@ @
O00 .A@
0_ - - ~ B ~ . ? * *, * I , I , I , I
0 ~" ~ 2 ~ v ~. 40 60 80 100 120 140
time (min)
Figure 13. Effect of the lecithin/protein molar ratio (R) on developing storage
modulus (1 Hz) of whey protein emulsions. Lecithin/protein molar ratio (R): II
R=I6, 9 R=6, I"1 R=4, O R=2, 9 R=0. Dashed line shows temperature
programme. Adapted, with permission, from ref. 102.
Dickinson [106, 107] has also studied emulsion gelation by covalent cross-
linking of proteins using an enzyme. The resulting values of the storage modulus
are compared to those obtained by heat treatment of the emulsion. Furthermore,
data for some protein gels without emulsion droplets were also obtained. It is
concluded that, whereas the enzyme treatment produces stronger protein gels than
the heat treatment, the opposite is the case for emulsion gels. This is attributed to
topological constraints imposed by the permanent nature of the covalent
crosslinks in the enzyme-set system which restricts further reinforcement of the
network structure [106]. However, the G' values for enzyme-set emulsions gels
are slightly less frequency-dependent than those of equivalent heat-set emulsion
gels. This is explained by the fact that enzyme-set system theology is more
113
similar to that of a classical polymer gel with "chemical" bonds, whilst the heat-
set system rheology is typical of a "physical" gel with breakable bonds.
r 102
BSW-CW model
10-2 1 0 -1 i0 ~ 101 10 2 10 3
10 a . . . . . . "1 . . . . . ' " I ' ' ' ' ' ' " 1 ' ' ' . . . . 'i ' ' ' ' ' ' " -
lO 3 i::1 rn
t~
io ~
:2
101
BSW-CW model
10 0 0 "z . . . . . . . . , . . . . . . . . I . . . . . . . . , . . . . . . . . , . . . . . . . .
1 10 -1 10 ~ 101 10 z 10 s
)~ (s)
Figure 14. Influence of the processing variables on the relaxation time spectra of
salad dressing emulsions, a) Influence of emulsification temperature: 1"I 20~ 9
without thermal control, A 50~ b) Influence of emulsification time and agitation
speed: [21 8000rpm-5min, O8000rpm-3min, A 5000rpm-5min, V 5000rpm-3min.
Reproduced, with permission, from ref. 8.
114
The same author has also investigated the effect of low-molecular weight
emulsifiers, added after emulsification but prior to thermal processing, on the
linear viscoelasticity functions of protein-stabilized emulsions [84, 108, 109]. The
results indicate that the rheology of the emulsion gel, produced by in situ heat
processing, is significantly influenced by the surfactant used. Thus, Figure 13
shows the evolution of the storage modulus during the thermal processing, as a
function of temperature, for different lecithin/protein molar ration, R. These
results are consistent with lecithin-protein complexation at the oil-water interface
and in the bulk aqueous phase.
Much more complicated behaviour was found when a polyoxyethylene sorbitan
monolaurate was used. In this case, the values of the storage modulus present a
maximum for R = 1, which is related to a partial displacement of protein from the
oil-water interface by the water-soluble surfactant [110].
The influence of processing on emulsions stabilized by a mixture of
macromolecular and low-molecular-weight emulsifiers has been also studied by
Franco et al. [8]. Figure 14 shows the linear relaxation spectra of emulsions,
prepared in a pilot-plant colloidal mill or with a rotor-stator turbine (lab-scale), as
a function of rotational speed, residence time and temperature of emulsification.
As can be observed the slope of the plateau region increases with the processing
variables, because of the development of an entanglement network. This is related
to a decrease in mean droplet size and polydispersity of the emulsion, yielding
stronger inter-droplet interactions [28].
5. CONCLUDING REMARKS
REFERENCES
2007.
58. R. Pal, J. Rheol., 36 (1992), 1245.
59.Y. Otsubo, R.K. Prud'homme, Rheol. Acta, 33 (1994), 29.
60. P. Partal, A. Guerrero, M. Berjano, J. Mufioz, C. Gallegos, J. Texture Stud.,
25 (1994), 331.
61. J.M. Franco, C. Gallegos, H.A. Barnes, J. Food Eng., submitted for
publication.
62. R. Pal, E. Rhodes, J. Colloid Interface Sci., 107 (1985), 301.
63. F.L. Saunders, J. Colloid Sci., 16 (1961), 13.
64. C. Gallegos, M.C. Sfinchez, A. Guerrero, J.M. Franco, In Rheology and Fluid
Mechanics of Nonlinear Materials, Siginer, D.A. and Advani, S.G. (eds.),
ASME, New York 1996, 177.
65 A. Yoshimura, R.K. Prud'homme, J. Rheol., 32 (1988), 53.
66 J. Carnali, H.A. Barnes, J. Rheol., 34 (1990), 841.
67 R. Pal, Chem. Eng. Commun., 98 (1990), 211.
68 R. Pal, Chem. Eng. Sci., 52 (1997), 1177.
69 H.A. Barnes, J. Non-Newtonian Fluid. Mech., 56 (1995), 221.
70 S. Matsumoto, P. Sherman, J. Texture Stud., 12 (1981), 243.
71 N. Gladwell, R.R. Rahalkar, P. Richmond, J. Food Sci., 50 (1985), 1477.
72 H.J. Rivas, P. Sherman, J. Texture Stud., 14 (1983), 251.
73 H.J. Rivas, P. Sherman, J. Texture Stud., 14 (1983), 267.
74. V.D. Kiosseoglou, P. Sherman, J. Texture Stud., 14 (1983), 397.
75 N. Gladwell, R.R. Rahalkar, P. Richmond, Rheol. Acta, 25 (1986), 55.
76 J.M. Madiedo, J. Mufioz, M. Berjano, C. Gallegos, In Progress and Trends
in Rheology IV, Gallegos C. (ed.) Steinkopff, Darmstadt 1994, 281.
77. T. van Vliet, J. Lyklema, M. van den Tempel, J. Colloid Interface Sci., 65
(1978), 505.
78. C. Gallegos, M. Berjano, L. Choplin, J. Rheol. 36 (1992), 465.
79. M.C. Sfinchez, M. Berjano, C. Gallegos, Afinidad, submitted for publication.
80. A. Guerrero, P. Partal, M. Berjano, C. Gallegos, Prog. Colloid Polym.
Sci., 100 (1996), 246.
81 M.E. de Rosa, H.H. Winter, Rheol. Acta, 33 (1994), 220.
82 J.M. Madiedo, C. Gallegos, Applied Rheol. 7 (1997), 161.
83 D.E. Graham, M.C. Phillips, J. Colloid Interface Sci., 76 (1980), 240.
84 E. Dickinson, S.T. Hong, J. Agric. Food Chem., 43 (1995), 2560.
85 A. Yoshimura, R.K. Prud'homme, J. Rheol., 32 (1988), 575.
86 L. Ma, G.V. Barbosa-Cfinovas, J. Food Eng., 25 (1995) 397.
87 P.I. Figoni, C.F. Shoemaker, J. Texture Stud., 14 (1983), 431.
88 O.H. Campanella, M. Peleg, J. Rheol., 31 (1987), 439.
118
R. Steger a a n d P.O. B r u n n b
1. INTRODUCTION
In aqueous surfactant solutions the surfactant molecules form aggregates
(termed micelles) at some critical concentration cmc (= critical micelle
concentration). Its exact value depends on the size of the hydrophobic part of the
molecule. The hydrophilic group plays also a role, in particular whether it is ionic
or nonionic. At concentrations above cmc surfactants are present in the form of
micelles and monomers. Micelles are fragile dynamic objects which are
constantly formed and destroyed by the addition and loss of monomers. This
permanem exchange of material is in real thermodynamic equilibrium.
Usually the miceUes formed above cmc are of globular shape and remain so up
to rather high surfactant concentrations. Yet, some systems exist for which, even
at high dilution, a second critical concentration, termed ct. (transition
concentration), ct > cmc, exists at which rod- (or worm-) like micelles are being
formed. This usually happens when additives like oppositly charged surfactants,
organic counterions or uncharged components like aromatic hydrocarbons are
added [1,2].
Thus, above c, the rod- (or worm-) like micelles are thermodynamically more
stable than globular micelles. The dynamic nature of their creation and breakup
implies that micellar solutions cannot be regarded as suspensions of well-def'med
particles with a given size. Some of the kinetics, which govern these processes, is
well understood (e.g.[3]).
As soon as rod like micelles are present in the solution, viscoelastic behavior is
encountered in viscometric measurements [4,5]. In addition, the solutions then
120
show the ability of drag reduction in turbulent pipe flow [2,6,7] as well as
enhanced resistance in porous medium flow [8,9].
The system studied in this paper is the surfactant N-cetyl-N,N,N-
trimethylammoniumbromide (C~6TMA-Br) with sodiumsalicylate (Na-Sal) as
counterion (equimolar solution). Most of the results reported will refer to a
concentration of 1000 weight-ppm (___-2.3 mmol), a concentration well above ct
(at least in the temperature range tested by us, 25~ _< T _<50~ [ 10].
2. RHEOLOGY
2.1. Experimental
The viscometric results reported have all been obtained by the commercial
Couette viscometer Haake CV 100 - RV20. It is of the CR type (constant rate),
the outer cylinder being the rotating one. Details about the measuring systems
employed (dimensions) have been given before [ 10].
10 -~
Surfactant o 4 h
I000 p p m 9 20 rain
T=35"(3 0 4 min
DA45 x 1 min
EiO000D~%
o ~ i
1 0 -2
-,==4
0
r
o o 0
-,,...4
-3 XXXXX x
10 i .v 9 9 i~ 9 in|
.~ . v . . . .v' I ~
1
." . r 9 9 9 '~l
10
= ' " 9 9 ~
10 z
l
lb a
Using the software provided by the manufacturer a sweep test reveals time
dependent behavior up to a sweep time of four hours (Sweep times longer than
this do not change anything). Starting essentially from the base line of the solvent
viscosity, 11~, the apparent shear viscosity 11 shows sudden shear thickening at a
critical apparent shear rate ~, ~, from 11 ~ 11, up to some value rl p. The apparent
viscosity will then stay essentially at that plateau value 1"1p up to an apparent
shear rate, termed ~,,.
Increasing the shear rate fin-ther leads to shear thinning behavior (see figure 1).
On a double-logarithmic plot the slope for ~ > ~,, is minus one, which in terms of
shear stress x means that there exists a critical shear stress ~ ~ ( = 11p ~,~), at
which rl ,,jumps" from its plateau value 1"1p to some lower value (see figure 2).
10-1 . . . . . . . . .
- Surfactant o 4h
. 1000 ppm 2 0 min
. T=35 C r 4 min
13., DA45 x 1 min
~ r-.,I
1 0 "2 },
r,/3 r
0
0
~
o 0 x
>. - ~ r
xXXXX X X
'w- r w: i : w T C I
IO- - .... . . ...-.,,= , ...... . , , . , . , ....... , - , - . . . . . ,
I 0-3 10 2 10-I I lO
Shear Stress T in Pa
Surfactant a DB45
co 1000 ppm * ME4-5
T=35 C A ME46
t3-, 10-1
9r-',,I o000~
o o~o
t~ -2
10
" O
~ & & A A A A A
Q A
9 r-,,,ll D
0 o
0 -3 kAk
r 10 - dk' **~0~ I~II AAA A A
r~
9r,-,I
b,.
-4
10 11 - - It "l-- 9 : I I-i n1011
! .... Iv '" Iv-~-I --IV -II ~11 i ~ 2 - -W~ '' W-- 9 ~ W W W31~01
Figure 3. Influence of the relative gap width ~con the apparent flow curve
jump on the basis of a phase transition (like a sol-gel phase transition). Readers
interested in this subject are referred to the excellent papers of H. Hoffmann and,
repectively, H. Rehage [5,11,12].
The viscometric results of our solution show a dependence of 1"1upon the"type
and the size of the measuring system used. For example, by using three systems
of different relative size (indicated by the fact that K:, the ratio of the outer to
inner cylinder, 1<-R o /R] > 1, differs) we find that )~ increases while "iqp
simultaneously decreases with decreasing 1< (figure 3). If for 1<~ 1 there is any
jump (rl p > 1"1s) at all then this jump is bound to be rather small.
Interesting is another, and totally unexpected, fact namely that there is also a
dependence upon the actual gap width. Figure 4 shows that three systems with
the same K - 1.078 furnish (rather unsystematic) results. Two Mooney Evert
systems (termed ME) imply an increase of 11with increasing gap width, the
double gap device (DA) contradicting that somewhat, since the gap widths
(1.375mm and 1.63 ram) are between the others. We conclude from these results
that the apparent flow curves depend upon the details of the measuring system
used.
10-1 _
Surfactant o DA45
1000 oppm * ME45
T=35 e ME30
ooo
12., . oooooo O
%'*******~o ~
17~ 10 -2- Oo
B I,,,,-f
0
~ ~ oo o
0 0
B
~r,,,I
-3
10
O
to
r~
~
10 -40-1 1 ...... 'i' ' ' ' ' ' ~' 10'" . . . . . "i~) 2 ' ' "' '"10 3
Shear R a t e ~ in 1//s
Figure 4. Influence of actual gap width AR- R - R, on the apparent flow curve
o. AR=l.085 mm; , AR=l.63 mm; o- AR=1.375 and 1.63 mm
(K = 1.078 in all three cases)
124
with "r., t h e shear stress at the inner cylinder. Expressed in terms of measurable
quantities it is given by
M (3)
x ~ = 27r.hRiZ
For the measuring systems employed by us the shear stress thus varies across the
gap width by 7.5, 16.2 and by 38.3 % (~: =1.037, 1.078 and 1.176).
Assuming the fluid to adhere at a solid surface the other measurable quantity,
namely f~, is given by
Ro do 1 "ci (4)
Rj dr 2 r" 2 T,
Ti/
Thus, in a plot of f2 versus log~: the slope will be ~,. It is clear that such a
procedure will be extremely time consuming (to obtain from experimental data
the slope rather accurately will require many measurements) and we know of no
attempt that this procedure has ever been tried.
An alternate way is to employ a mean value theorem to equation (4) with the
result
2K2 ~ (6)
K2 -1 xi
where u is the appropriate mean shear stress, x o _<u _<x,. If the fluids rheology is
known then u can be calculated. Note that one can write u / x,= ~'~, I < ~ <_K .
This result implies for the shear viscosity the relation
q-rl(T)-~=x C M (7)
f2
with
9 -1 (8)
C _ _
4n~:2hR 2
which by equation (6) corresponds to the choice u = x,. While correct for a
Newtonian fluid as well as in the limit of infinitely small gap width (~: ~ 1 ) it
will for f'mite gap widths in general be incorrect. Not the fluid-specific shear
viscosity rl but an apparent viscosity rio, which depends on relative gap width as
well, is the consequence,
126
M (10)
f2
All experimental results reported thus far are apparent ones (since all results
reported in the last chapter are apparent ones we have for simplicity omitted the
subscript a ~ w h i c h emphasizes this fact ~ on q and ~. When we now compare
the theoretical results with experimental ones the latter results will get this
subscript) so that the observed dependence upon K (see figure 3) was to be
expected. Since these results point towards decrease in the height of the jump for
decreasing K (see figure 3) and since ~t and ~ coincide in the limit K ~ 1, the
question arises whether the jump seen in rio (see figure 3) is indeed consistent
with a jump in rl at some critical rate ~,~.
Such a jump of q implies a jump of rio at a critical apparent shear rate ~ a~, which
by equation (4) is given by
K 2 InK2 (11)
r - - ~gC
1( 2 --1
with f~e given by equation (4) and f2~(f~,o) the angular slip velocity at the inner
(outer) cylinder. The relations 4-10 would involve the rheologically relevant
127
angular velocity f21 -f2~(x,,K) rather than the angular velocity f2of the outer
cylinder. To obtain it, the slip contribution has to be known.
Making the usual assumption that the angular slip velocity can be written as
shear stress dependent slip velocity u divided by the radius of the corresponding
cylinder, i.e.
f2,~ + f~,o = ~ ,[ , 2]
u,(x~) +-u,(x~~: / K )
(13)
shows that slip effects become more and more important the smaller system
(small R~) is. This was to be expected and the experimental results presented in
figure 4 for the two Mooney -Evart systems (ME) are in accord with this feature.
That the results for the double gap device (DA) do not follow this vend could
possibly be of different origin. Labeling for the DA system the radii of the
cylinders (in increasing order)/~ to R,, we have (with ~c=/~ //~ = R~ / R3)
~"~-- ~"~fl (~1, K) + (~'~S1 + ~"~$2) (14 a)
for the 1-2 gap, and simultaneously
for the 3-4 gap. If no slipping takes place then f~z,- f2z:and consequently
x3 - x,. It is this very fact which ~ without slip ~ allows one to cast the result
for rl = rl(~ ) (for rl, = 1"1a (~t,,, K )) in the form of equation 7 (or 10) with the
system constant C given by
(K 2 -1) (15)
C~
47tK2h(R~ + R32)
With slip, however, (f2~,+ t~:) will, in general, not equal (~"~S3"~~"~$4) SO that the
relation between x3and x~is not known (Using the fact that f2~ cannot decrease
with increasing shear stress and that u should increase with x requires
128
(f2s3 + f2s,)<__(f2s~ + f2s,) and consequemly x~ >_x,. This implies that slip effects
in the 1-2 gap are larger than in the 3-4 gap. Since K =/~ //~ - R3 / R, the 1-2
gap is the smaller one so that this result was to be expected.)
This being the case there is no possibility to list a formula for the shear
viscosity. Using a double gap device in viscometric measurements in cases where
slip might occur is an extremely poor choice. Formally using equation (10) (with
C given by equation (15), as was used to obtain the corresponding results
displayed in figure 4) and f'mding odd results could possibly be traced back to
this feature.
Since f2eaccording to equation (4) stays constant at constant shear stress
x, (equation (4)) the sudden decrease of rl~ at x would require a sudden increase
of (f2" + f2o ) . In other words on reaching x any increase in f2 would leave f2I
unaffected but merely serve to increase the slip. Physically such a possibility
cannot be discarded.
3. SLIT FLOW
To possibly shed light on some of the puzzles presented we arm to slit flow
(dimensions of the channel: length l m, height: 3 mm, width 30 mm). Previous
investigations, employing a modification of the customary Laser Doppler
velocimetry (termed GRLDA-method [14]) such that local shear rates can
directly be determined, revealed that the jump of the shear viscosity, determined
via the relation
where Ap / L is the applied pressure drop per unit length, u is the (axial) velocity
in the x direction and y is the traverse direction measured from the midplane, is
accompanied by a sudden jump of the local axial velocity fluctuations, u'. Prior
to the jump the root mean square (RMS)-values are in the 2 % range, while they
suddenly jump into the 10% range exactly at that point, where rlsuddenly
increases, too [14]. The fact that RMS-values in the 2% range are found for low
shear rates already is astonishing and most likely a reflection of the dynamic
129
nature of surfactant solutions. The sudden jump to values of about 10% does
come a big surprise. From a fluid mechanical point of view this hints more in the
direction of turbulent flow. Since the Reynolds number was 81 (based on 1"1+)
this would be associated with some type of structural (or early) turbulence.
Proceeding along that fluid mechanical line of thought one would put for the
axial velocity u,
u=~+u' (17)
(with ~ ' - 0 ), where ~ denotes the mean. The average of the equation of motion
(in the average flow direction, x) thus reads (Here we have assumed that the
mean of fluctuating quantities show no systematic variations in the axial
direction, i.e. ~ ~2 _ ~ - f , = 0).
d -p~'v-') (t8)
0=@+ (~v+-'
Here xxy - ~ + X~yis the x-y component of the extra stress tensor and v' denotes
the traverse velocity fluctuation.
Equation 18 implies for the average shear stress ~+ the relation
It was shown elsewhere [14] that if isotropic tm'bulence prevails (v'= u', i.e.
pu'v'=-p~ '2) Newtonian behavior ('t~,=rls(du/dy), i.e. ~'~v= 0) would
quantitatively account for our results. In other words, the observed increase in q,
as determined via equation 16, would be fictitious, since that increase is solely
due to the (sudden) occurrence of the Reynolds shear stress 9u'v'=-p~ '2. The
viscosity remains constant, 1"1-- q~. (According to equation (19)
q satisfies rl~(d-a/ dy)= -(Ap / L)y if ~ < ~ and - -(Ap / L)-O~ '2 if ~ > Yc)
To study the hypothesis of isotropic turbulence, v' ,~-u', Laser Doppler
velocimetry (in the backward scattering mode) was employed, which allowed us
not only to determine the axial velocity u but also (by rotation of the optical
system by 90 ~ the traverse velocity v - v'[ 15]. Figure 5 shows a typical result. It
130
0.16
I"-"-I
C,6TMA-Sal + NaBr
-~0.14 1000 wppm
25 ~
~"JO. 12
1:3 ~ -~- - m -
~o.~o -
"~ 0 0. 8 -
t.,.~
9
> 0.02 -
0.030
t C,eTMA-Sal + NaBr
0.025 : I000 wppm
- 25 ~
/ =~
U~
rn 0.020
0.015
-
. ,,~,,,,,~ RMS~
o o o o o RMS v - c o m p o n e n t
0 . 0 1 0 -2_ ~
_ o o
0.005 0---.- 0
o o o
0.000
o., o.~ o.~ o.~ o.~ o~. 1.b 1.'1 1~. 1~. 1~. 1.~ 1.o
y - p o s i t i o n [mini
Figure 6. The RMS-values for, respectively, u' and v', close to the wall
131
follows from these results that Iv'l << lu'l (even close to the wall, figure 6)i.e. the
Reynolds shear stress, though non zero, is too small to account for the observed
increase. If the flow is indeed ,,turbulent", then it has to be a rather anisotropic
type of turbulence. Interesting in this connection is the fact that the surfactant
solutions investigated here do indeed show an essentially one-dimensional type of
turbulence under truly turbulent conditions (high Reynolds number) e.g. [16].
Since isotropic turbulence would, in our case, imply Newtonian behavior and
vice versa, we conclude that the fluids rheology is definitely non-Newtonian.
Thus, the observed increase in ,, q" as given by equation 16,should mainly be
due to a sudden increase in average shear stress fluctuations. Formally assuming
for the shear stress an arbitrary functional dependence f to the shear rate
~, ~ - f ( ~ ) , we, get, by Taylor expanding the right hand side around ~ and then
averaging
essemially plateau like for high shear rates (figure 7). In this latter case the
arithmetic mean used in LDA studies,
1 (22)
-W- , U , N .
"0
1:::;
<8.1@
O. 05
@.1 " 1@
4
@@
Ve]ocity [era/s]
in which N, is the number of measurements, for which the velocity u, has been
measured ( N = ~ N, ) seems highly questionable. Considering the logarithmic
i
scale of the abscissa of figure 7 it becomes clear that equation (17) is not
representative of the average behavior for high shear rates.
These results point more in the direction of some kind of multiphase flow, for
which it is (almost) equally likely to find velocity values well below fi (according
to equation (17)) as well as above. This hints in the direction of a shear induced
state, (SIS), in which monomers, micelles and, for the most part, larger entities
133
(SIS) are in thermodynamic equilibrium. Thus, if we assume that there is, after
some critical shear rate, ~,, an additional SIS state, and that this SIS state is far
more dynamic (Since turbulent flow is customarily associated with vortices of
different size and since we have no evidence of such vortices in our case we
refrain from calling the flow turbulent.) then the state of wormlike micelles
existing up to ~c, then the viscometric results make sense. What we have to
abandon totally is that after onset there is viscometric flow. Quite the contrary,
for ~ > ~ c, the flow is definitely non-viscometric. It may be viscometric in the
mean (even this is open to question, see figure 7), but it is fluctuations around the
mean which bring in the strong (or odd) dependence upon the actual geometry in
relations valid only for truely viscometric flow. Since even prior to onset the
flow is not strictly viscometric (~'2/~2 ~ 2% for slit flow), we expect the critical
shear rate 1'c (actually ~ ) to be geometry dependent, too.
! .00
>a
oo 0 . 6 ~
~ I ' 0
o~
i:> I '
20 "
O 1O 2O 30 4~ 50 60
Time Is]
The fact that after onset the flow cannot be viscometric (at least not in its
classical terms) is strengthened further by two additional observations. According
134
to the SIS hypothesis the micelles are all lined up in the flow direction after the
critical shear rate ~ h a s been reached [e.g. 11]. Flow birefringence
measurements will thus produce the extinction angle %- 0 ~ . While we fred this
to be true on average there are rather huge instantaneous fluctuations around this
mean (see figure 8). Corresponding measurements of the instantaneous pressure
difference fluctuations also hint at an extremely dynamic behavior (one-
dimensional) of the flow after onset (figure 9). Attempts to study (after onset)
such behavior by considerations restricted to truly laminar viscometric flow seem
futile.
1 .013 ~,
~0.60
For completeness we note that slip effects can def'mitely be discarded. In slit flow
we never observed any tendency of slip, irrespective of the volume flow rate
used. Figure 5 is a representative example for this fact.
135
Since the tendency for slip has to be discarded the results presented revealed
the non-viscometric flow behavior (at least in its classical sense) under seemingly
viscometric flow conditions. We do believe that these results reflect the dynamic
behavior of micellar surfactant solutions, especially in the so called SIS state.
This state is a rather dynamic one such that classical viscometric studies, though
useful if performed under identical conditions, may be of little use, if an
engineering attempt is made to use the data in any other system or for,
respectively, upscaling.
ACKNOWLEDGEMENT
REFERENCES
14. A.M. Wunderlich, P.O. Brunn and F. Durst, 1989, Rheol Acta 28, 473
15. R. Steger, 1994, Dissertation, Universit~it Edangen-Ntirnberg
16. H.W. Bewerdorff and D Ohlendorf, 1985, Proc 5 Symp Turb Shear
Flows, (ed. J. Lumley), Ithaca, NY, 241
17. G. B0hme, 1981, Str0mungsmechank nicht Newtonscher Fluide, Teubner,
Stuttgart
137
1. I N T R O D U C T I O N
2. V I S C O M E T R I C FLOW
The geometry of the most commonly used viscometers (cf. Ferry [1])
is such that the flow may be considered to be one of the curvilineal flows
described by Truesdell & Noll[6], in which the particle paths are con-
veniently expressed in terms of orthogonal curvilinear co-ordinates. For
the viscometer flows these are invariably rectangular Cartesian, cylindri-
cal polar or spherical polar co-ordinates. In general these flows may be
time dependent, and in particular time periodic in the sense that the flow
characteristics at a given point in the flow repeat after a given period of
time.
In the appropriate set of orthogonal curvilinear co-ordinates the ve-
locity of a fluid particle at x and time t has the contravariant components
with respect to base vectors ei(x):
v - o , v - v t) , - v 1, t ) , (1)
Ov 2 Ov 3
Ox ~ = f (x * )q(x 1 , t) , OX 1 -- h ( x 1 ) q ( x 1 , t ) (3)
As seen below, this is necessary for the physical components of the shear
stress on the surfaces x I constant to be in time independent ratio, so
that while fluctuating in magnitude they maintain their directions at
each point on the surfaces x 1 constant.
For these motions the displacement vector u(x, r; t) of a particle at
past time r relative to its position x at present time t has the components
,,1_0, u2 _ v 2 (x 1 , a ) d a , u a-
S v2(x 1,a)da ,-oc < r <_ t . (4)
where
{ -- x + u(x, r; t) (6)
and the base vectors
(r)
are orthonormal. For these orthonormal vectors there exists a time de-
pendent orthogonal tensor Qt(x, r) such that
,/
q~(x, ~).F,(x, ~) - v 77)(~) ~ (9)
Vg-~JJ)({) ~j + k(~; t)
/O00/
Equivalently, the tensor defined by (9) has the matrix of components
g(kk) (x) k
~ o o (10)
/300
140
where
,/ 11
,.)/--1 lg22f, - - 7--1 v/ g111g 33 h ,
for all 7-, and the ratio c~ 9 fl is then independent of time, being dependent
on x only as is clear from (ii). At each point x at present time t a basis
i~:
may be defined such that the relative right Cauchy-Green strain tensor is
where N has the component matrix with respect to the basis ik"
O 0 0/
1 0 0 (16)
0 0 0
141
For the class of incompressible simple fluids with constitutive law ex-
pressing the stress tensor T as a non-linear tensor valued function of the
strain tensor history:
Q . T . Q T - - p I + S~%o ( q . c t ( t - s ) . q T - I) (18)
with similar relations obtainable for T~23> , T < l l > - T<33> and 7'<22> -
T<33>. Hence, in these time dependent curvilineal flows the physical
components of the rate of strain tensor
2.1 T i m e P e r i o d i c Flow
By a suitable choice of Q in (18) it is readily established that the
shear stress functional in (19) and (21) is odd in the history k(.; t), i.e.
Also, if the non-zero components of the velocity are time periodic, i.e.
271 i
v i ( x 1, t ~- - - 1-- V (X 1 t) for i -- (2, 3), (25)
a2
then
q ( x 1, t "F- -271"
) -- q ( x 1 , t ) (26)
a2
and
k ( s ; t + 2a- ) - -7 ~o ~ q ( x 1, t -~- -27r
- - r)dr
~d CO
(27)
-- --'7
/o q ( x 1 , t -- r ) d r - k ( s ; t)
Hence, time periodic curvilineal flows have the property that the shear
stress components defined in (21) are periodic:
271
T<li> (x 1, t -}- - - ) -- T<li> (x 1, t) for i -- (2, 3). (28)
a)
In passing it is noted that SlsC~__0 (k(8; t)) and 8 2 ~ 0 (k(s; t)) are even func-
tionals of their arguments, so that all the stress components are periodic.
If the velocity is anti-periodic,
k(8; t -~- - - ) -- - - 7
~d
/o s q(x 1, t + ~d
r)dr
(30)
-- "7
/o q ( x 1, t -- r ) d r - - k ( s ; t)
for all 0 _ s < ~ . It follows from (21) that if (29) applies then
71"
T<lk> (X 1, t -~ - - ) -- - - T < l k > (X 1, t) fo r k - (2,3), (31)
a2
i.e. the shear stresses are anti-periodic. However the normal stress dif-
ferences are not(cf. Coleman & Noll[8]).
143
)U--
{ k(s;t)"
/0 e-P~k(s;t)ds < o o , ~ ( p ) > 0
} , (33)
and
k(t; p) -- e-P~k(s; t)ds < e ~ , ~(p) > 0 (34)
j~0~176
is an element of a Fr(~chet space of functions analytic in a right half-plane
of the complex plane. Further, it is assumed that E is a subset of the
domain of the functionals in (19). All k(s; t) such that
satisfy this requirement for all p such that ~(p) > 0 through proper choice
1
of v q ( t - s) -- 2 (t rD 2) ~. In addition
27r - 27r -
q(t + - - - s) - q ( t - s) 4, k(t + ;p) - k(t; p) (37)
cO CO
144
2.2 Equations of M o t i o n
It is assumed that each of the stress functionals appearing in (17)
and (19) is Fr~chet differentiable over its domain in some normed vector
space of functions on [0, ~ ) , which intersects with (33). For example,
corresponding to T~0(. ) there exists a linear functional dT~=o(.) defined
by
dT (/c(t; p)). Ak(t; p) - lim 7 (k(t; p) + eAk(t; p)) - r (k(t; p)) (41)
e----~0 6
where
T (k(t; p)) -- ~'s~ (/~-1 [k(t; p)]) , }
(42)
dT (~(t; p)) -- d~/-s~ (/~-1 [k(t; p)])./~-1
are compositions of operators.
Also, if
Vi (xl , t; p) _ --[c~ e -psv i(x I t -- s)ds (43)
Jo
145
it follows that
O~ i
Vi = _~_pOi i -- (2 3) (44)
Ot ' '
and
0 ~2 0~3
~1~ Ox 1 = -apk(t; p) g_33_
v lOxl
= -flpk(t;p). (45)
S-T+pI (46)
I g( ii) i (47)
S<ij> - g(JJ) Sj - v/g(ii)g(jj)S ij
0S<11> OP = o
~x Ox
0S<~2> @ Ov 2
(~0)
Ox N P-gi-
Op o
Oz
It follows from (50) that if a pressure
v~ - ~ {~y(x)}, ~- r (54)
lim ~ ,, (1 - e r O. (56)
w--~0 b(M
If this condition does not hold then the possible effects of hysteresis must
be considered(cf. Hunter &: Slemrod[9]).
The second set of conditions relate to plane pulsatile flow, but the
condition that T ~ 0 is linear is very restrictive. Among the fluid types
satisfying it are the Navier- Stokes fluids and certain 'second order fluids'
(cf. Truesdell & Noll[6]). Of course if the strain amplitudes are infinitesi-
mal a linearized theory, which is compatible with both sets of conditions,
is applicable.
Existence of periodic solutions to (52), for a special model proposed
by Slemrod[14], is assured by a theorem of Rabinowitz [15] (cf. Dun-
woody[16]), if the nonlinearity in the equation is sufficiently weak.
so that the physical components of the extra stress tensor S are from (17)
s<~j> - ~<~j>(~). (58)
Hence, the equations (48) become for these flows
1 0 S<22> Op = -pro 2
rot (rS<ll>)- r Or
1 0 (~'S<12>)-~- S<12> 1 0p = - p r o
oo
(59)
r Or r r O0
10 Op oo
rot (rS<13>) Oz = - p z
148
The velocity components (t), i) are obtained as the solutions, if such exist,
to the equations
where
subject to
O 0 ( t - s) Ok(s; t) O i ( t - s) -
ok( ;t)
--r OF ~ oz.(r)~ ~ --
Os Or (63)
1 - c~(r) 2 +/3(r) 2
a(t) -- 0 (64)
, (66)
r
149
Given that the modulus of the right hand side of this relation, for all r
in a finite interval, is within the range of the functional T,~=0(-) over the
domain/C, then if the functional is one-to-one and invertible over/C the
shear strain history k(s; t) is periodic by (27) and uniquely determined by
(68). The velocity components are then determined by (63)1,2. However,
only in the case that the functional is linear would the shear strain history
be simple harmonic.
Couette flow corresponds to the degenerate case
Og -- 0 ~ C1 -- 0. (70)
Even for these cases there is no known physical device which could enforce
stresses of the form (66) at cylindrical boundaries.
Another interesting type of flow falling within this general class is
pulsatile (axial) flow in a tube or annular pipe. However, for it
b(t) 7k 0 (71)
in (61), so that the stresses (66) no longer satisfy the equations of mo-
tion. Most often practical interest has been centred on small oscillations
superimposed on steady flow and inertial effects are not always neglected
(cf. Barnes, Townsend & Walters [17]). Mena, Serrania & Van Ziegler
[18] have performed experiments in which perturbation flows of all the
above types have been superimposed on steady axial flow.
150
so that
S<12> -- "~s~ (~:(8; t)) -- S < 1 2 > ( r , Z, t) (73)
while from (14) and (19)
0S<11> OF = 0
Oz Oz
0S<12> 10p = pr iiv (75)
Oz r O0
0S<33> S<33> -- S<22> 019 02
Or + r Or = - p r
subject to
0k(,; t) O~(z, t - ~)
~r (76)
Ot Oz
From the first and second of these
Therefore,
S<12> - fir f (:u(z,t)dz + h(r, t) (79)
and it is clear that (73) and (76) are incompatible with (79) in general,
unless some simplifying assumptions are made.
If the inertial terms in the right side of (75) are neglected then (73),
00
(76) and (79) are compatible if in (76) ~z is independent of z. In partic-
ular this is true if the velocity ~) has the time periodic, separable, linear
form
O - N(az + b)e *"~ (80)
which corresponds to the physical condition of 'gap loading' again. The
analysis for the steady flow case and references to experimental work is
to be found in Truesdell & Noll[6].
The restriction that time periodic flows of this type may only occur
under gap loading conditions also applies to the following type of flows.
and
v3 - - / ~ .-j0~
k ( s ; t ) - -sinO
0 (0, t -
~
u)
du.
(83)
while
S<12> - g < 1 2 > ( 0 , t ) . (85)
The flows envisaged could be generated by the independent rotations
of a circular plate and half-cone about the axis of the cone which is
perpindicular to the plate surface, the fluid being contained between.
152
0S<33> 1 {S<II> -~- S < 2 2 > -- 2 S < 3 3 > } Op --pr sin 2 0 ~2.
Or r Or
(86)
It is clear from (85) and (86)2 that if
0p
= o, (87)
or
which is the condition necessary for the pressure to be single valued in r
there is incompatibility between (83) and (86)2 unless the inertial term
is zero, which is the case for steady flow. In addition,the relations (19)
and (83) imply that
0 (S<11>- S<33>)-
o-7 ~0 ( s < ~ > - s<~>) - 0 (88)
0
(~----~{Sis%0 (]9(8" t)) -~- $2c~ 0 (]9(8" t))} - 2 p r 2 sin 2 0r O~ (89)
' ~= ' 00'
which cannot be satisfied for all r and 0 since
O0 r O. (90)
c(t)
~<12> = - 2
sln 0
(91)
0 {SiCs=O
00
c~ (k(8"
~ (k(8", t))-~- $2 s=O .,
t))} - O.
153
These conditions are satisfied for all fluids, but only approximately, when
3. S M A L L A M P L I T U D E FLOWS
In the case of oscillatory plane shear flow an appropriate value for E is the
A
ratio ~ , where A is the amplitude of the oscillations of one of a pair of
parallel plates which are a distance L apart, the other being fixed. There
is then no motion when A - 0 (cf. Dunwoody [21]).
Also, for a periodic flow of the form (54) with f ( x ) - V' (x) constant,
a complex valued dynamic viscosity may be defined by
ak
-~/ak (102)
k=l
then
n n
k=l k=l
To facilitate estimation of the importance of the inertial forces rela-
tive to the viscoelastic forces in these motions it is convenient to introduce
a set of nondimensional variables as follows:
Oa = R* O--v-v R* = PwL2
o~ oi' I~*(~)1 ' (105)
(7 -- --(O2]T]*(a2)l) -1 d T 2 o ( O ) 9 f0 ~ 0~(~,-0~i - r d+.
which are the equivalents of a Reynolds Number and Mach Number re-
spectively.
A separable solution to (105) of the form
'*-(~) v"
I~*(~)1 ( ~ ) - m*v(~) - o, (lO8)
156
since from (98)
and then
V(2)- 2 (112)
approximately. The shear stress arising from the motion (110) is
- ~
[~*(~)cos~]
i-~*-~-)lsin3 ' (113)
q*(co) ] (114)
(l -- O'g - - ~1~ Iv*(~)l "
respectively.
If
arg [r/*(co)] -- - r (116)
157
/~COS/~20Zl(1--~a2)COS{Ctl(1--~c~---~-2)
2 } a l al
(120)
sin/3 sin (OZl (1 - ~2-~-)}
Then, assuming 0 < r < 2, values of the ratios in the left hand sides of
(115) are plotted in Figure 1 and Figure 2 as functions of 2 for various
values of ~_x
O~1
in the range [0 ~ 1] and al > 0 9
158
0~1 -- 0 . 2 5 O~ 1 - - 0.5
1 . 0 4 ~
1.00 1.02
. . . . . . . . . ' X
~ . . .~ . . . . . . . 1i x
0 99 " " "~\"K~ " 0.98 0.2 0.4 0"~'N.~K"-5 0.75
0.9~ ~ 0.75 0.96
0.98 0.50 0.94 0.5
0.98 0.25 0.92 0.25
a 1 -- 0.75 a 1 -- 1.0
1.05 0.75
/
. . . . . . . X ' ' " " " " ~ X
-0.01 ~ . . . . . . . .
.6 0.8 I
X
- 0 . 0 5
~ . . . . . .
.6 0.8 I
X
~
. . . . . . . . . . .
. . . . . . . X
_ 0 . 1 ~ . 6 0.8 1 .6 0.8 i
-0.2
same values of a l and a___22_ 0.25, 0.5, 0.75 again in each plot.
C~l
159
3.2 A s y m p t o t i c a p p r o x i m a t i o n s
In the case of small strain oscillating cylinder flows the constraint
(94) is satisfied and the relations (96) and (97) again hold. Thus, the
equations of motion (59), with/3 - 0 , reduce with errors O(e 2) to the
single equation
1 0 S<12> "
/" C~" ( / ' S < 1 2 > ) - t " -- - p r o (121)
r
and
P - po + . / p r O 2 d r (122)
k ( s ; t ) - - / r O 0 (Os*
t - S*)ds, _ ek(s; t). (123)
The flows envisaged are contained by two cylinders of radii a and b, a < b,
so that the gap width is
L - ( b - a). (124)
Therefore, there are two fundamental lengths which must figure in the
considerations of dimensional analysis, viz. the the inner radius a and the
gap width L. It is evident from (41), (97) and (123) that, as in the case
of plane flows, a separable solution to (121) may be sought which is time
periodic. Since equation (121) is explicit in r it is appropriate to choose
a as the more fundamental of these two lengths, and so corrresponding
to (104) the non- dimensional set of variables
where
pwa 2
~ _ _~R:I,*(~)I and R; = (~)1 (128)
,*(~) I,* "
The boundary conditions which are applied may be
d (~_lv(?~)) -- fl2:~V(1) -- 0
d
where the non-dimensional parameter S defined by the relation
aS= K-w2I
27rPw2a3L (131)
(1+L)
V ( ~ ) -- -- 2-W-(L-) { J l ( ~ r ) Y l ( f l ) - Yl(flr)Jl(fl)) ,
(133)
Jl(~) v~(~)
tL/- [ t1+ Lt] [ t1+ Lt]
161
~*(~)~E~ G(0)
~ , G'(0)
(~)~ ~ o(~co2) (1 35)
which is the equivalent of the 'gap loading' condition of plane flow. The
condition (135) is of course even more stringent than (136).
Under the conditions
3.2 P e r t u r b e d S t e a d y Flows
The flows considered in this subsection are most often described
as nearly viscometric flows (cf. Pipkin & Owen[29]). However, here
the term viscometric flow is inclusive of the time dependent curvilineal
flows described in w and indeed of all the time independent, or steady
viscometric flows which in turn include the steady curvilineal flows. Thus,
the terminology adopted is that of the critical reference work by Truesdell
163
?31 - - 0, Vi -- V(0
i ) (X 1 )-~-- V~I ) (X 1 , t)
"
where again equations (2), (3) and the analysis following them in w
applies. It is also assumed that the condition
[v(1)l
<<1 (142)
Iv(0)l
holds. The split (141) is compatible with (3) if and only if,
Ov 2 OV 3
Ox I - f ( x 1) [1 + q(x 1, t)] , Ox I = h(x 1) [1 + q(x l, t)] , (143)
where
[q[ << 1, (144)
so that in (11)
k(~; t) - -
( .~, + .y
/o q ( x ~, t - ,.)d~
and if q(x 1, t) is time periodic then all of w applies, i.e. k(1)(s; t) and
the extra stress tensor S are also time periodic.
where
S - S,% o ( C t - I) - S ~ = o ( k ( s ; t)) , (150)
V p (~ - V. S (~ , (152)
then S (1) and p(1) are the perturbation stress tensor and pressure which
must be substituted in (48) to balance the perturbing motion with veloc-
ity v(1) ( xl , t).
It follows from the above that all of the classes of flow considered in
~2 may be treated in this way, subject to the proviso of their existence in
the presence of inertia, as before.
The consistency relations of Pipkin & Owen[29] relate the 13 inde-
pendent components of the tensor valued linear functional in the expan-
sion
T -- "/'s=0(--")/8) ~1 - - S l c~ ~
- & e~
s=0
, (154)
- . - .
(155)
dS (o) / h 0G (o)
d7 07
(156)
= dS %o t)) t) "
07
The consistency relations quoted by Barnes et. a1.[17], attributed by
them to Pipkin[32], apply to a very special material class having a mul-
tilinear functional constitutive form. Bernstein[33] has obtained similar
consistency relations for the general K-BKZ fluid class by setting
in (145), substituting the corresponding g(s) in (152) and then taking the
limit a~ ~ 0, but again some of his relations are peculiar to K-BKZ flu-
ids. Coleman & Markovitz[34] using the same method obtained relations
similar to Bernstein's for a class of second order fluids approximating the
fading memory fluids of Coleman & Noll[8].
The flows which have been dealt with in the literature using this
type of approximate analysis fall within the classes described in w so
that in the case of torsional and cone and plate flows (cf. Jones & Wai-
ters[35]) inertial effects must be neglected. Bernstein[33] in his analysis
of sinusoidal oscillations superimposed on steady plane shear flow of K-
BKZ fluids has taken no account of inertia. Barnes et. al.[17] have taken
166
account of inertia in their analysis of pulsatile pipe flow and also 'second
order effects', but have employed a special second order theory in doing
so. Phan-Thien[36] and others have followed suit. Their aim of course
has been to match their results to specific observations.
In all cases a single ordinary differential equation governs the spatial
dependence of the time periodic perturbation, so that the analysis differs
little from that required for the equation resulting from letting 7 -~ 0.
Indeed, Osaki et. a1.[37] interpreted their experimental data in terms of
the analysis of Markovitz[4] referred to in w However, besides the effect
that 7 7~ 0 has on the perturbation functionals (154), the interaction of
the perturbation with the basic flow has considerable practical interest(cf.
Jones & Waiters[35]). Both of the two previous nondimensional analyses
leading to conditions for the use of the 'gap loading' approximation may
be modified to be applicable to the corresponding perturbed steady flows.
4. L A R G E A M P L I T U D E F L O W S
4.1 M o d e r a t e A m p l i t u d e Expansions
Considerable experimental data obtained from large amplitude os-
cillatory shear(LAOS) flows has quite recently been recorded by such as
Hatzikiriakos & Dealy[7], Giacomin, Jeyaseelan, Samarkas & Dealy[10].
Many of the perplexities which these investigators have attempted to ad-
167
~. 1.1. P l a n e S h e a r Flows.
For simplicity of presentation the shear stress is written in the form
(42)1 but as a function of the rate of strain using the identity
Then the equations of motion (52) and (53) governing plane shear flow
with a ( t ) - 0 reduce to the single equation in terms of ~(x, t)"
O" m
~ f (1 - e -2~/w'~k ) - 1 ak j[o27r/w -s k2r+l(s't)
,
r=0 k=l ~ e /ak (--a) ~ ds + R m
(165)
where the remainder
k2m+3(s;t)
Rm <E O<s<27r/~s
max ctm+l (166)
G -- -- M(8) ]~2r+1(8;t)
?n
7: :f::
~=o (_a)~ ds+Rm
(167)
= ~ _
g2r+l (Oxv,... OxV;p)-F nm.
r--O
In particular,
r/~)(co) -- r/* (aJ) (170)
is the dynamic viscosity defined by (98), and it has the limits (99) and
(100).
A nondimensional form of the equation (160) is obtained in terms of
the nondimensional variables (104) except that the quantity e is replaced
A
by the ratio ~ , where A is the amplitude of the displacement of the
'upper' of two plates, a distance L apart, which contain the fluid between
them. In addition to (104)
and
the definition of r/; (w) in (168) and the multilinear property of the oper-
ators g2~+l (',. 9 "; p) imply that
where
R*= pwL2 ( wA ) 2r r/r*(w))
I~;(~)1' D,.- -~ rl~)(w . (176)
2) ~
lim D ~ - aL 2 , (177)
CO--* OO
which corresponds with the limit (106)2 on R*. The low frequency limit
corresponds with (106)1 and is appropriate for 'retarded ' flow(cf. Dun-
woody[21]).
The set of D~, 1 _< r <_ m, where rn is arbitrary, have the norm
right side of (175), but it also contributes to the nonlinear effects caused
A
primarily by relatively large ~ .
A nontransient solution to (175) and the boundary conditions
O, - R* + -
D2 0~5 (0~ ~o,.. , 0~ ~o; t3)
D
The variable coefficients Xl(2k. t_1) in these finite harmonic series are found
by solving, by either of the above methods, the ordinary differential equa-
tions obtained by substitution of (183) in the appropriate equation in
172
(182) and equating coefficients of e (2k+l)Li. The left hand sides in the
resulting equations involve the dynamic viscosities with argument w re-
placed by (2k + 1)w. The details of the calculations are described by
Dunwoody[21], who computed the actual shear stress occurring at the
upper plate using the Luo & Tanner[22] model and two terms in the se-
ries (180) only. His numerical results obtained for A / L - 2 , w - 100
rad/sec, and various Reynolds numbers are plotted in Figure 3, where
the upper profile is obtained from the linear theory.
If the gap loading assumption is made, equivalently R* is set to zero,
then the series (179) reduces to the single term
eti ) ~. (184)
- p+
where
Dunwoody[21] has computed the value of the shear stress crg again using
the Luo & Tanner[22] model for the same frequency and amplitude ratio
as above, but retaining four harmonics and terms O ([A/v/--dL]S). For
comparison a plot from his results is shown in Figure 4,where again the
upper profile is obtained from the linear theory, and it is apparent that
the higher order harmonics have a significant effect. The shear softening
due to nonlinearity alone is also significant.
It is also observable by comparison of the shear stress profiles in
Figure 3 and Figure 4 that the effect of increased inertia is to increase the
shear softening at the upper plate, which bears out the general conclusion
to be drawn from Figure 1. This observation can be compared with the
effect that a pulsatile pressure has on the mass flux of a fluid through a
pipe(cf. Barnes et. al.[17]).
173
R* - 0.0 R* - 0.7
60000
40000
~/:~176176176
o
R * - - 1.0 R*-- 1.2
40000 40000
-40000
0.0
\
3
--
0j/OoZeS
~j~oooo
-- 0
0.010 3
~L
Figure 3. Profiles of measured in Pascals as calculated by
A
A
Dunwoody[21] f o r - - 2, w - l O O r a d / s e c , both fixed, and
L
R* -- 0.0, 0.7, 1.0, 1.2. The upper profile was obtained from
the linear theory, and the ordinate scale varies with each plot.
75000
50000
250
,'5/
, , . . . . | . . . . | , / / . . . . . , . . . . | .
000
-75000
P - Po - t5 [1 + ee ~'t] . (187)
For particular models they have shown via an analysis in which terms
O(e 3) are n e g l e c t e d - the theory is therefore a second order one - that
the mean flux of the fluid is enhanced by the presence of the oscillations in
the pressure, hence by inertia also, and that the effect is O(e2). Davies et.
a1.[39] highlighted the fact that there was disagreement between theory
and experiment in that the theory of Barnes et. a1.[17], as well as their
own based on a different model, predicted that flow enhancement should
decrease with the frequency of the oscillations while experiment showed
the opposite. Phan-Thien[36] used a generalised Maxwell fluid model
for the same problem, and he found that the mean flux enhancement
increased with frequency.
4.2 E x i s t e n c e of L A O S
In order that a time periodic flow exist it must be possible to repre-
sent the velocity with the property (25) in the form of a Fourier series
oo
not true in general that the shear stress in the left hand side will separate
into the form
S<12> -- ~ gk (f(x))e ~kwt , (189)
k'- -cx:,
where
f(z)-(...fl2(x ) , f l 1 (x) , f) (z) , fl (z) ,.. .) , (190)
in general.It is therefore surprising that a perturbation analysis for LAOS
on the assumption that R* << 1 has never been undertaken. It is the au-
thor's conjecture that plane, rectilineal, oscillatory shear flow of arbitrar-
ily large amplitude satisfying the standard no slip boundary conditions
does not exist, because the velocity must be two dimensional if plane
shear flow is to exist at all, i.e. it must be n o n r e c t i l i n e a l . If his con-
jecture is correct then it would explain the complexities encountered by
Hatzikiriakos & Dealy[7] and Adrian & Giacomin[44] arising from the
imposition of a unidirectional oscillatory displacement of large amplitude
on one plate of a parallel plate viscometer. Theories involving wallslip
(cf. Graham[45]) have been put forward to account for the complicated
'quasiperiodic' experimental data.
Nonrectilineal oscillatory plane shear of arbitrarily large amplitude,
based on work of Antman & Guo[46] on large amplitude shearing oscil-
lations of incompressible, nonlinearly elastic solids, is the subject of a
current study by the author.
REFERENCES
S E C O N D A R Y F L O W S IN T U B E S OF A R B I T R A R Y S H A P E
1. INTRODUCTION
Fully developed Newtonian flows in pipes are rectilinear when they are driven
by a longitudinal pressure gradient, properties are kept constant, no wall-suction
is considered, and the pipe is a straight cylinder of arbitrary cross-section. No
secondary flows are possible under these conditions.
The linearity of the equations of motion makes it possible to use a wide
variety of analytical methods that yield either exact closed-form, or approximate
solutions. In this section, a summary of these results is presented based on a
unified approach that is applicable to an infinite spectrum of cases where the
main differentiating factor is the pipe cross-section geometry.
2.1. Analysis
The flow of a Newtonian, incompressible, and isoviscous fluid through
straight tubes of constant-cross-section is governed by a linear form of the
Navier-Stokes equations when the flow is parallel and laminar. In this case,
velocity is of the form,
where w is the axial velocity. If z is the axial coordinate, then, the continuity
equation reduces to,
181
c~
- o, (2)
c~
319
= pf(t), (4)
3z
where f(t) is an arbitrary function of time, usually called the "forcing function"
of the flow.
The velocity shown in equation (3) is subject to the no-slip condition at an
arbitrarily curved boundary 3D~ and, in general, to an initial condition for t=O,
that is,
where v = ~ / 9 is the kinematic viscosity, and, where the forcing function has
been split into a steady-state, constant part f,, and, a time-dependent part f2 ( t ) .
The linearity of equation (6) allows one to define,
3Wa p
v V 2 w 2 p - f 2 ( t ), Wz = Wz h + w zp" (9)
dt
mn
-_
)2Om
[( ] +
~12J
oo oo
ao aO
W2p= ~_. ~_,Omn(t) Emn " (12)
m=O n=O
Only the particular solution in equation (13) applies, since the homogenous
solution has been already taken into account in equation (11). An example of this
kind of exact analysis is applied to the problem of a flow that decelerates under a
zero pressure gradient starting from a given initial steady state velocity W(x, y) in
a rectangular pipe of cross-section 2a(x-direction) and 2b(y-direction). It is
assumed that the z coordinate lies along the pipe axis, so that the initial and
boundary conditions are,
further,
(2m+l)x (2m+l)y
Emn = cos cos , m,n = 0,1,2... (15)
2a 2b
184
W= 64k
oo
Z ~
oo
( - - l ) m+n 2 Bran"
(2re+l) (2n+l) (2re+l) (2n+l)
a~ + b2
Since the pressure gradient driving the flow for t > 0 + is zero, the time-
dependent velocity obeys equation (8), whose solution is shown in equation (11).
Thus,
2, -
n~v I(2m+1)2 +
(2n+l)~
___
1. (16)
mn 4 a~ b~
The structure of equation (17) shows that the boundary condition is met, since
that condition is first imposed on ws. Also, the initial condition follows from W,,
that is,
The associated start-up velocity of the flow has to be worked out first in order
to apply equation (17). This is not necessary when the eigenfunction method is
used, since the transient response to any forcing is incorporated in equation (13).
f (R 2 r 2 (18)
w~ = 4 v - ) +e,w~,
Condition (19)1 makes the velocity unique at the center of the pipe, and
condition (19)2 restricts the absolute value of c~ to a value equal, or less than
some critical value e~c, in order that the contour be a closed curve. A convenient
set of functions to this end are,
= ~ pn sinnO (20)
Wlh
L r n cosnO
where n is any positive integer. For each value of n, the small parameter ~c1 has
some specific physical dimension stemming from the physical homogeneity of
equation (18). For the sake of convenience, a dimensionless form of equation
(18) can be used by selecting R as length scale for r, f l R 2 / 4 v for Wl, and
fl / 4 v R n-2 for OC'l.In dimensionless terms, equation (18) becomes,
1 - r 2 + ~ r n s i n n 0 = O. (22)
A wide variety of contour shapes develop from equation (22) according to the
given values of ~, and n [8]. As l e~ I increases starting from c1 =0, the circle
changes continuously up to a shape that exhibits a number of sharp corners, or
cusps, equal to the integer constant n, and is obtained for ]c, ]= ]~]. When
]c~ I is greater than its corresponding critical value, then equation (22) no longer
describes a closed contour. For appropriate values of Cl equation (22) describes
ellipses (n = 2), approximate equilateral triangles (n = 3), approximate squares
(n = 4), and so forth. The critical values of ~ can be found by applying the
boundary condition, and the condition that at a cusp the velocity gradient should
be zero. This leads to,
n-2
I~lcl= - ( ~ n-2-2
)n2 . (23)
w= ( 1 - r z + e~r" sin n 0 ) I we
-r ~ + c lF~ + c 2F z +... ), (24)
In the following, the analysis is carried out for the case of an oscillatory flow
superimposed on a steady flow. It is, thus, assumed,
where k, and k2 are constants. If the reciprocal of the angular velocity co is taken
as time scale, then equation (6) becomes, in dimensionless variables,
V 2 A - iA - iA, (28)
2
with
The functions al(r ) and a2(r ) can be obtained from equation (29)1 by splitting
the modified Bessel function I o into its real and imaginary parts. In this form, the
expression for the velocity is,
Different versions of equation (30) have been developed in the past by several
authors, among them Sexl [9], and Uchida [10]. Since ~, is a small parameter
188
( [ G ] < 1 for n _> 2), a perturbation approach can be used to find the unknown
functions Fj. To this end w is expanded as,
w (~ c = l - r z + 2 ( a ~ c o s t - a 2 sin 0 ,
where,
~3v~ d2 1d 1 d2
V 2 w (i) = 0 " i = 1,2, .. V2 - + -~ + (33)
v2 ' " ' 3r 2 r Or r 2 ~5~2 "
W(~)= (.4 (') eit+ A(')e-;' )sin nO+ Dr" sin nO, (34)
d2A(')2dr + rl dA(1)
(dr i ~ n_~) A <~) = 0. (35)
we obtain,
w (') = 2 (a( 'J cos cot - a z(~) sin cot) sin n 0 + D r n sin n 0. (38)
Setting D = 1 and equating equations (38) and (32) an equation for F/is found,
al a2
P ~ - l_r 2 , P2- l_r 2.
sin 2 nO = 1- cos2n0
The unknown functions b, (r), b2 (r) can be obtained from a 0 - free solution of
equation (33),
B(r) e i' + - B ( r ) e -it , B(r) = C o I o (x]~r), C O = Co, + i Co2, I o = Iol +ilo2, (43)
and similarly,
A ~2' : C ~2' 12, (x/-f-t-~r) = a~2) + ia~2' , C ~2) : C(2) + iC~2' , I2n : 12n I .qt_ //2n2 "
This method can be applied to flows other than oscillatory, as long as it is not
necessary to impose an initial condition. Such a condition cannot be satisfied by
the present analysis.
Steady, fully developed, viscoelastic pipe flows are rectilinear when the pipe is
a circular cylinder [11, 12]. This is true even when the flow is unsteady,
regardless the constitutive behavior. Some special results of practical interest
arise from non-linear effects. One of these results is flow enhancement in
periodic flows. Several authors have explored this important aspect both
theoretically and experimentally [1, 2, 14 - 18]. Integral models seem to simulate
experimental data better than other models.
An example of integral models is Green and Rivlin's [19] simple fluid model
of the multiple integral type. For incompressible fluids, the total stress T, can be
expressed in terms of the strain history G, on a particle X,
where p, t and r are the pressure, time, and past time, respectively. Following
Green and Rivlin, the functional F is expressed as a Fr6chet series,
in terms of the small parameter e. S ~i) is defined as the Fr6chet stress at order i.
The first two terms in equation (46) are,
oo oo
S(2) "-- I 0 ~(S)G2 (s)ds -]- I o I o Pl (s1, $2 )al (s1)a2 ($2)dsldS2, (48)
where the history of the strain has already been expanded in a series in c,
c~3 OO
Ou
p --VP+VoS ; V.u=O inD,, (51)
Dt
D, - {(r, O,z).'O < r < R,O < 0 < 2rc, - m < z < +~},
u (R ,0 ,z) - O, u ( O , O , z ) < ~ .
~42 (1)
P - I o G ( s ) V2 w(')(r, t-s) ds + p f ( t ) . (52)
c~
Let,
where Jo is the Bessel function of first kind and order zero, and
Jo(bn) = 0; n = 1,2, .... Substitution of equation (53) into equation (52) gives,
193
with
oo
ZDnJ ~ (b n r
n:, ~):1.
R2
Cnl = (17"- p(oR 2 -ib2Dn#7'),
2[(b.2r/') 2 + (pooR 2 - r/") 2]
C= fo R2 D.
P bZ" , /.t = ~o G(s)ds, (56)
R 2
w ~'~ = Z c~ljoR~ Dn
. ~ 2 (b~. u')~ + (poor ~ _ u")~ [(u"- poor ~-) cos cot
n=l bn
194
The shear relaxation modulus G(s) determines the viscosity/z in equation (56)
and the complex viscosity 7-/*in equation (57). The constant parameters fo and
are assumed to be 0(1). Other cases can be analyzed for different forms of the
forcing function, provided it remains bounded.
Another analytical approach can be developed by exploiting the linearity of
equation (52), through an extension of Duhamel's principle, in the form,
t df (59)
w (') : I oWsv(r,t- 4 ) - : = ( 4 ) d 4 + f(O)w~v(r,t),
ag
where Ws~ is the start-up velocity for the viscoelastic fluid at O(E), and for a unit
pressure gradient given by,
02
Ow
p--=r
oo
0
G(s)V2w(r, O. t - s)ds + pf(t), V 2 - 3z 1 0
+ - /"
1 ~2 ~ (61)
c,-r2 O-9F + _ /,.2
where cylindrical coordinates (r, O, z) have been selected and the superscript in w
has been dropped. The condition at the boundary cO, is,
wl =0.
Where wo(R 2 - r 2) is the closed form axial velocity of the flow in a circular
tube. The analysis that makes it possible to find the unknown functions
H i ( r , O , t ) , i = 1,2,.., follows a close parallel to its counterpart for Newtonian
flow as presented in Section 2. The main steps that lead to the determination of
the velocity field for pulsating flow in pipes of arbitrary cross-section are
described in the following using dimensional variables. Flow is driven by the
pressure gradient defined in equation (55) with constants j~, and 2 of 0(1). The
base flow that is the flow in a circular pipe under the forcing given by equation
(55), has already been solved in Section 3, and is described by equation (58) in
exact form. Assuming c~ small, equation (62) can be rewritten as a series in ~ ,
~(J) (j)
P cTt -~o~G(s)V2w (r, O , t - s ) ds ; j _> 1. (65)
In order to take advantage of the similarity between this problem and its
Newtonian counterpart presented in Section 2, the velocity at zero order in ~,
will be written as,
w(O) _ Pfo (R2_r 2) + 2 [a 1(r) cos cot - a 2(r) sin co t], (66)
4/a
where a, (r) and a2(r ) a r e infinite polynomials explicitly available from equation
(58). Note that several symbols used in previous sections are used in this section
with equivalent meaning, but they do not necessarily have the same algebraic
structure. For example, the functions a, and a 2 have the same meaning in
equations (30) and (66), but their algebraic structure is not the same in both
equations. Assuming w ~ has the following structure,
196
w"' = (A ~'' (r) e i~ + --A(" (r) e -ia~ ) sin nO + D r" sin nO, (67)
ipco (68)
r]*'
with r/* given by equation (57). The admissible solution of equation (68) reads as
A (') = C (') I, (Ar) = a(') + ia~ '), C (') = C~ ') + i C~ '). (69)
2
H, = h, (r, 0 sin n O, h , - [(a( ~)- r ' p ~ ) coscot-(a~ ')- r ' p 2 ) sin cot],
R2_r 2
al a2 (70)
P ~ - R2_r 2 , P2- R2_r 2.
Similar to the steps which led to equation (40) in Section 2, the required
continuity of the function h~ for R = r leads to a set of algebraic equations for
the constants C(~) and c"<~) The expressions for wc~) j > 1 can be worked out
"'2 ~
Other parameters concerning the flow and the geometry are given as,
co = 10 r a d/s , P f o _ I,
2
The selected values of n and the associated values for E1 determine through
equation (22) pipe cross-section contours that are approximately triangular and
square. The longitudinal flow in these pipes exhibits a very complex pattern that
is very much dependent on time and on the effect of sharp corners.
In Figures 1 through 6 the isovels in the cross-section of the pipes are shown
for one value of the viscosity index k. The specific times at which the isovels
were drawn are such that the velocity profiles undergo several inflexion points,
as shown in the companion plots. At such times, local velocity extrema appear at
several points, a phenomenon that tends to increase as k decreases. All plots are
dimensionless. The length scale for r is R, and the velocity scale for u is
PR 2/4f10. Velocity profiles refer to the larger half symmetry axis, and to the
shorter half symmetry axis for all figures.
198
1 "
0.8
0.6
0.4
0.2
0 I I I, I " ~
0 0.002 0.004 0.006 0.008 0.01
2 ! . . . . . .....
~I
o ...... i
0 0.002 0.004 0.006 0.008 0.01
1-
r
0.8
0.6
0.4
0.2
0 I I
1.4
r
1.2
0.8 -
0.6-
0.4
0.2
o I I
5. SECONDARY FLOWS
8u (2)
=- VP (2) + V'S (2) ; V'u (2) - 0 in D,, (72)
c~
u I =0 ;u(O,O,z)<~. (73)
0D,
(75)
The transversal velocity components are u and v, and e, and e o represent the
radial and azimuthal unit vectors. At the second order the axial velocity
component is zero. G(s) and 7"(s1,s2) represent the shear relaxation and the
quadratic shear relaxation moduli, respectively. The first Rivlin-Ericksen tensor
A1O) is of the form
~
+J0JoY(S,,S2) { _l [rw, r(S,)W, (s2)]
r r
1 }
"~- V [w'r ($2) w'O (SI)])0- 13 W~o (SI) W'o ($2) NSI ds2, (79)
1 2 1 + ]
+~o~ G ( s ) (W'r ~:'0 + W'O ~, r )'r +----~'(W,O ~'0 )'0 +-'7(W' ~'0 W'O ~ ) ds
r r~ r- r ~r
1
+ J'O J'O~ Y (S1, $2) -1 [w, r (s,) w, o (s 2)],r +
r
~3- [W,o (S,)W,o (S~)],O
Equations (79) and (80) can be combined and the pressure field may be
eliminated using a stream function 5Udefined as,
u (2) = V x 7-'.
The resulting equation has driving terms both time independent and time
dependent of type e i~ and e 2i~. This means that the secondary field has a time
averaged mean part ~ (r, O) and oscillatory components with frequencies co and
2oo. The time averaged field ~ is thus defined by
where { }. refers to the mean, that is time independent terms in the expression
between { }, and the operator L has the following structure,
34 1 34 ~3 1 ~2 4 ~2 2 33 1 C
L = r ~-g + r3 ~5~04 ~t_ 2 c7r3 r cTr2 + r 3 302 r 2 drO02 + -rT ~dr" (82)
lC9~ cgk'
u [ - m [ =0, v [ - m [ = 0 , Wm =constant. (85)
cqD r 00 c~D~ cqD~ ~ cqD~ c~D~
204
where ~m has been expressed as a series in powers of the small parameter e,. To
0(~), the equation to be solved reads as,
where the known functions gl (r) and g2(r) are involved expressions in terms of r
and of the fluid constants. The solution of equation (88) can be found by
replicating the method of Section 4. It is convenient to develop the functions g/as
finite polynomials in r. This can be easily achieved since g, are continuous and
smooth functions and the applicable range is of the order of R. Given the
structure of equation (82), for any term of the form rmsin nO on the RHS of
equation (87), this equation provides a non-homogeneous solution of the form
Cm r .m+3 sin nO, the constant Cm being dependent on m and n. It also provides, in
r/r
c~r~cos (fl In -R'\cos n C2F sin (fl In rR)
sin n 0 )
cos n 0
(89)
where c,, c 2 are arbitrary constants, and a ~ ifl are complex powers of r, with
a_~O. The solution for ~ at 0 (c~), thus, reads
5u~1) = [Pl + clr~ cos(fl In R)] sin nO+ [~2 + c2 r~ cos ~ ln R)] cos n O. (90)
205
Only the cosine term in equation (89) has been used because subsequent steps
demand that the homogeneous solution should be non-zero at r = R. We note
that the functions Pi(r) are known polynomials of r. The function ~1 is
determined next by equating ~m') as defined in equations (90) and (87), where the
constants c~ and c2are found after putting r = R.
The expression for ~m2) follows from the equation at 0(e~),
in which all terms in the RHS have been rendered linear in sinjnO and cosjnO, j
= 1,2. The functions gt (i =3 .... 7) depend on r and on the material constants
embedded in the shear relaxation and the quadratic shear relaxation moduli G(s)
and y(s~,s2) which appear in equation (81). Equation (91) can be solved using a
similar technique as that applied in the first order problem. The functions g, are
approximated as finite polynomials of r. Computation of the homogeneous and
non-homogeneous solutions of equation (91) is straightforward. All arbitrary
constants are determined from the required spatial continuity for r = R, after
-equating ~m~) computed from equation (91), and its equivalent expression
obtained from equation (87).
Material constants involved in the driving terms in equation (81) were adopted
from Siginer in [2]. Plots of the streamlines for the same values of the fluid, flow
and geometry parameters used in Section 4 are shown in figures 7 and 8. A very
complex pattern of cells is common between the two cross-sectional shapes
chosen. The main cells appear a number of times equal to twice the number of
cross-sectional sides. Minor cells are present close to the corners, and to the
center of the pipe, depending on the value of k.
These results can be extended to other shapes by changing the values of n
and/or c~. Secondary flows appear for any value of ez ~ 0. They do not exist
only for c ~ - 0 , in which c a s e ~gCm ~ ~/0 =constant in the whole domain,
consequently u = v = 0.
206
ACKNOWLEDGEMENTS
This work was partially supported by grant 197-0810 of the Chilean National
Fund for Scientific and Technological Development. The authors acknowledge
important institutional support provided by the departments of Mechanical
Engineering at the University of Santiago of Chile, and the New Jersey Institute
of Technology.
REFERENCES
1. Siginer, D. A., J. Fluids and Structures, 6 (1992) 719.
2. Siginer, D. A., Int. J. Engng.Sci., 29 (1991) 1557.
3. Mueller, W., Z. Angew. Math. Mech., 16 (1936) 227.
4. Yih, C. S., Fluid Mechanics, McGraw-Hill, New York, NY 1969.
5. Fan, C., and Chao, B. T., Z. Angew. Math. Phys., 16 (1965) 351.
6. Hepworth, H. K., and Rice, W., J. Appl. Mech., 37 (1970) 861.
7. Letelier, M. F., and Leutheusser, H. J., J. Engng. Mech., 111 (1985) 768.
8. Letelier, M. F., Leutheusser, H. J., and M~rquez, G., J. Engng. Mech., 121
(1995) 1075.
9. Sexl, T., Z. Phys., 61 (1930) 349.
10. Uchida, S., Z. Agnew Math. Phys., 7 (1956) 413.
11. Oldroyd, J. G., Proc. R. Soc. London Ser. A, 283 (1965) 115.
12. Xue, S. C., Phan-Thien, N., and Tanner, R. I., J. Non-Newt. Fluid Mech.,
59 (1995) 191.
13. Rahaman, K. D. and Ramkissoon, H., J. Non-Newt. Fluid Mech., 57 (1995)
27.
14. Barnes, H. A., Townsend, P., and Waiters, K., Rheologica Acta, 10 (1971)
517.
15. Sundstrom, D. W., and Kaufman, A., Ind. Eng. Chem. Proc. Des. Dev., 16
(1977) 320.
16. Manero, O., and Waiters, K., Rheologica Acta, 19 (1980) 277.
17. Davies, J. M., Bhumiratana, S., and Bird, R. B., J. Non-Newt. Fluid Mech.,
3 (1977) 237.
18. Phan-Thien, N., J. Rheol., 25 (1981) 293.
19. Green, A. E., and Rivlin, R. S., Arch. Rat. Mech. Anal., 1 (1957) 1.
20. Letelier, M. F., and Siginer, D. A., Rheology and Fluid Mechanics of
Nonlinear Materials, S. G. Advani and D. A. Siginer (eds.), 121-128,
American Society of Mechanical Engineers, New York, NY 1997.
209
EFFECTS OF N O N - N E W T O N I A N FLUIDS ON
CAVITATION
D.H. Fruman
1. I N T R O D U C T I O N
The change of phase, from liquid to vapour, occurring when the temperature
is kept constant and the local pressure is decreased to become equal or less than
the vapour pressure of the liquid, is called cavitation. For this definition to
hold, it is necessary for the liquid to contain dispersed micro bubbles of non
condensable gas, called nuclei, offering interfaces where opportunities exist
for the change of phase. The liquid can be either stagnant or in movement. In
the first case, the pressure change is due to the propagation of pressure waves
generated by ultrasound generators, boundary vibrations, sudden valve
closures, underwater explosions, etc. In the second case, the pressure reduction
is associated, through the Bernoulli equation, with the increase of the liquid
velocity as it occurs in the flow around hydrofoils, and by extension in pumps,
turbines and propellers, in the contraction of pipes, in venturi tubes, etc. In
separated flows, such as jets and wakes, cavitation occurs in the low pressure
regions of the vortices developing in the free shear layers. Cavitation over
solid surfaces can occur in the form of either individual travelling bubbles or
sheets. The latter continuously shed bubbles which, when penetrating in a
region where the pressure has increased above the vapour pressure, will
collapse and rebound with an amplitude decaying with time as a result of,
essentially, viscous dissipation. The consequences of cavitation are the
reduction of the hydrodynamic performance of liquid machinery - pumps,
turbines and propellers - and hydraulic circuits, the emission of noise, the
generation of vibration and the erosion of materials.
Bubble cavitation occurrence is essentially determined by the vapour pressure
of the liquid. Surface tension opposes bubble growth and determines the level
of "tension" to which the fluid has to be subjected before the onset of cavita-
210
tion. Also, the viscosity of the liquid, assumed to behave as a Newtonian fluid,
will affect the bubble growth and contribute to the damping of the oscillations
following collapse. Even in the case of such liquids, characterized by the
simplest relation between strains and stresses, explaining and interpreting the
inception of cavitation and the consequences of its development on engineering
applications is not a simple task and numerous textbooks [1-4] have been
dedicated to consider these issues.
When the liquid displays a non-Newtonian behavior, as it often happens in the
chemical engineering processes and when polymer additives are dissolved in
Newtonian liquids, the problem becomes much more complex. It has to be
recognized that the larger impetus on the research concerning cavitation in
non-Newtonian fluids comes from the interest developed during the 1960's by
the use of dilute solutions of high molecular weight polymers, known as being
very effective turbulent drag reducers, in naval hydrodynamics and hydraulics
(see the review paper by Acosta and Parkin [5] for a summary of work on
cavitation in polymer solutions up to 1975). It was soon recognized that these
solutions were capable of modifying strongly the flow field on a length scale
characterizing the boundary layer for very small concentrations, even below
one ppm. As a consequence, the experimental investigations on the effect of
flowing drag reducing polymer solutions on cavitation were faced with the
following question, i.e. was the behavior of individual bubbles altered because
of:
i) the modification of the surface tension, the vapour pressure and the
rheological properties of the liquid phase, or,
ii) the changes of the local pressures, as a result of the modifications of the
flow structure and of the boundary layer.
In presenting the most remarkable results we will try to single out which of
these approaches is predominant.
The spherical growth and collapse of a gas bubble has interested rheologists
because it creates an extensional flow which can be used to estimate the
elongational viscosity of polymeric liquids. Although numerous theoretical and
experimental investigations have been conducted on this matter, we will only
talk about them occasionally because they belong, in our opinion, to the area of
characterization methods rather than to that of hydrodynamic cavitation.
In this presentation we consider first the theoretical approach of the dynamic
equilibrium of a single spherical bubble in an unbounded liquid. This is
followed by some theoretical results concerning the effect of Newtonian and
non-Newtonian properties on bubble growth and collapse. Because the
conclusion of this section is that these properties have a very limited impact on
the life of spherical bubbles, we move to the presentation of experimental
results obtained in the somehow academic conditions of a single bubble
interacting with solid walls or affected by shear flows. For these non-spherical
deformations it is shown that the viscoelastic properties have a significant
211
u-
R(t))
r
/~(t) (1)
where p is the liquid density, p is the pressure anywhere in the liquid, and
Trr, TOO and 7:~r are the normal components of the deviatoric stress tensor
related by,
Because of (1) and (3), expression (2) becomes, after integration between
infinity and R,
p ( RR + -
2
- p(R)- Poo (t) + Trr (oo)-- Tr r ( R ) + 3
JR r
dr (4)
where p ( R ) and poo (t) are, respectively, the pressure at the interface on the
liquid side and the pressure far from the bubble. The stress Trr (cx~) can be
212
assumed to vanish far from the bubble. The pressure at the interface on the
liquid side is given by,
2~
p(R) - Pv + Pg R + Trr (R) (5)
where pg is the non condensible gas pressure within the bubble, p v the vapour
pressure and 7' the surface tension. By determining p g from the initial
conditions of the nucleus of radius R0 and gas pressure PgO, expression (5)
becomes,
P(R ) - Pv +
( P O - P v + -~O
27'/(R~/ 3k 2~+Trr(R )
--R R
(6)
where k is the polytropic index and P0 the pressure at infinity at t = 0.
Substituting (6) into (4) we obtain the generalized Rayleigh-Plesset equation
3
) - - - - ( P o o ( t ) - - P v ) + ( P o - p v ) ( - R ~ ) 3k
2
(7)
R0 R
.01
R
+3
R r
--dr
allowing one to compute the time evolution of the radius of the bubble as a
function of p~ (t) under the assumption that the liquid is incompressible and
that thermal and mass transfer effects are negligible. The terms on the left
hand side represent the contribution of inertia, while, on the right, the first
term is the cause of the bubble growth, the second term the contribution of the
partial gas pressure, the third term the effect of surface tension and the last
term that of the rheological properties of the liquid.
We would like to point out here that, whatever the rheological behavior of
the liquid, for cavitation to exist, the pressure far from the bubble has to be
reduced to a value at least equal to a critical pressure for which an asymptotic
growth phase of the bubble, at constant velocity, will exist. In the case of the
static equilibrium of a bubble undergoing an isothermal expansion and
ignoring the contribution of the last term in equation (7), the critical pressure
is given by,
4 ?'
Pc - P ~ (8)
3 Rc
213
with,
Re-Ro
E3R0/ 2
-~ --~- P O - P v + -~o (9)
The order of magnitude of the asymptotic growth velocity when the bubble is
subjected to p~ < Pv is given by,
The characteristic time for a vapour bubble, having an initial radius Rch, to
collapse under the effect of a pressure step is,
[
where p~ > Pv. It is clear that the velocity at the interface during collapse can
reach values much higher than those of the velocity for asymptotic growth.
If the pressure is reduced but remains above the critical value obtained using
expressions (8) and (9) and a given radius of the nucleus, it will not achieve
the conditions for asymptotic growth and will oscillate before reaching its
equilibrium. Therefore, depending on the nuclei size distribution and the local
pressure, some bubbles will enter the asymptotic growth phase and cavitate and
others will only oscillate with limited amplitude.
3 ~'rr d r - - 4 1 ~ - - (13)
R r R
214
n-1
f S Zr__Zrdr = _4 ( 2 )n-1 m
r n R
where m and n are the power law parameters and 77(R,/~, m, n) the apparent
viscosity. They numerically investigate the collapse and rebound of bubbles of
different diameters to a sudden increase of the pressure far from the bubble
and do not consider the bubble growth phase. Their results do not allow one to
show that power law behavior is responsible for the acceleration of the
damping of the oscillations, as compared to those in water.
215
0.35 [- R, m m p, Pa
0.30 ~Pa.s /
0.25 t- 0 //~'/ \//
I 10 -3 ///" X \~ 101000
0.20 -3 /
o.15 /~
0.10
0.05 ~ f / lO0
ms
0 t t t
0 0.1 0.2 0.3 0.4
1.0
_R/Rma 1 b)
0.8
Pa.s
0.6 0
10-3
5x 10 -3
0.4
0.2
t-t(R max )
0 I rR
- 12 - 10 -8 -6 -4 -2 0 2
Figure 1 : a) Pressure and radius of the bubble for an inviscid fluid (~t = 0),
water (~t = 10-3 Pa.s) and a more viscous fluid (r = 5 10-3 Pa.s) as a
function of time, b) radius normalized with the maximum radius and time
normalized with the Rayleigh time (expression (11)) for the maximum radius.
The straight discontinuous line has a slope corresponding to the asymptotic
growth velocity, expression (10).
216
Table 1 9 Fluid properties and main characteristics of the radius versus time
evolution in Figure 2.
rn n R ( t = 0.3 ms) /~(t = 0.3 ms) tmax R A
mPa.s n mm m/s ms mm %o
0.895 1 0.3228 1.053 0.3332 0.1861
10 0.8 0.3203 1.047 0.3330 0.1848 4.24
50 0.65 0.3190 1.041 0.3328 0.1841 6.14
450 0.4 0.3192 1.037 0.3328 0.1847 4.48
0.35 R, m m
0.30
0.25
O.2O
0.15
0.10
0.05 r n = 0.4
I
0 I //jl I I I
/
0 0.1 0.2 0.3 0 0.1 0.2 0.3 0 0.1 0.2 0.3 t, m s
3. S I N G L E B U B B L E 9 E X P E R I M E N T A L
1.2
- Rcma x RA
_ A AAA 10
1.0
o ~ o 9 I
0.8
- o~ A ~ AA I
0.6 - ~ 0 9
0 Q
0.4
0 9 A
0.2 17= Rc max / L
0~
o 77 Fluid
o |zx 9 1.39 250ppmPEO
o o 1.25 Water
I I I I I
9 0.56 250ppmPEO
0.5 1.0 1.5 2.0 t /"t" R
A 0.50 Water
These results were confirmed by Chahine and Fruman [15] using the same
bubble production technique and distilled water and a 250 ppm solution of
PEO (Polyox WSR 301) as testing fluids. They also show that the time and
amplitude of the first and second rebounds were unaffected by the polymer
additive. Very recently, Brujan et al. [16] produced laser-induced cavitation
bubbles in solutions of CMC and polyacrylamide (PAM) with a concentration
twenty times larger than the one used by Fruman and Chahine. Even for this
very large concentration and for the very viscoelastic PAM solution, the
bubble behavior is "little affected by the rheology of the fluid and the most
important parameter for bubble oscillation is the infinite-shear viscosity".
Since it was substantiated that a re-entering jet developed if the bubble collap-
sed close enough to a solid wall, and hence the viscoelastic properties of the
polymer solution might affect the development of the perturbation initiating
the re-entering jet, Chahine and Fruman [15] also investigated this
configuration. Typical results are shown in Figure 3, and demonstrate that
when the distance to the wall decreases as compared to the maximum lateral
extension of the bubble, the polymer solution introduces a retardation effect
over the initiation of the re-entering jet. Notice in this figure that the position
of the interface is, at the end of the collapse, below the center of the bubble at
origin. This investigation was, we believe, the first to demonstrate that
polymer solutions seem to have a stabilizing effect on bubble dynamics,
especially with regard to deviation from sphericity. Brujan et al. [16] did also
experiments in the vicinity of a solid wall and confirmed these early results.
Chahine and Morine [17] and Morine [18] conducted tests with spark
generated bubbles confined between two parallel walls. This geometry offers a
rather peculiar situation of collapse because the bubble, initially spherical,
develops an hour-glass shape during the collapse phase and splits into two
bubbles which collapse against each wall. In this situation the departure from
sphericity occurs along the mid-plane between the two parallel walls. Figure 4
shows some of the results obtained with concentrations of 125 and 250 ppm of
PEO. Clearly, the lengthening effect on the bubble life duration as a result of
the presence of the walls is significantly reduced in the case of the polymer
solutions. The most striking is that, in these fluids, the departure from
sphericity of the bubbles is considerably delayed. Interestingly enough, results
obtained with a 50% glycerin/water mixture, having a viscosity about ten times
larger than water, demonstrate little change compared with those obtained in
pure water, in agreement with the results obtained by integration of the
Rayleigh-Plesset equation.
Chahine [19] published results concerning the behavior of bubbles in the
vicinity of a liquid-air interface and showed that, in this peculiar situation, the
deformation of the bubble in the polymer solution is enhanced and made more
non-spherical. This peculiarity can be associated to the fact that the free
surface also deforms considerably during the growing phase, forming a jet
220
1.2 m
CD I CD m a x
m a mcx nyi_n nl m
1.0 pOx. -o-o 9 []
m A I k v
_ AOAA O zx A []
0.8
AolLX o A D xe i
0.6 - 0 ~ 0 A
X @
o [] | m
0.4
OA x @
0 A [] Oi
0.2~
0 x
EX @ []
0 I I I I I I
0 0.5 1.0 1.5 2.0 2.5 3.0 t/TR
~N"~"N'~"~N'~NNN'~'N~ ]7 fluid fl fluid
I b 9
9
9
0.59
0.64
0.70
0.54
water
water
water
water +glycerin
o
A
[]
0.56
0.61
0.80
250 p p m
250 p p m
250 p p m
100
-~ ,~m 0
0
80
0 A
0
Fluid 60 0 A
A
Water O O DOn [] A
500 ppm PAM 40
6o [] 0
I000 ppm PAM o
500 ppm PEO A
20 []
1000 ppm PEO*
O r7
0 I I I
0 0.5 1.0 1.5 t/'C R
100
- ~ ,~m 0
R 3=ab 2 0
0
A =a-R 80 0
ml
m m o
5 60
oOm
o m
AA
A
IIO
o [] A A l
0 0 mll A
40
@ A A
20- B
o
A
I I I I
0 0.5 1.0 1.5 t / Z"R
concentrations, the bubbles remain spherical during all the process of growth
and collapse when the shear rate was absent.
Ligneul [21] performed experiments with spark-generated bubbles immersed
in the shear layer developed by a rotating cylinder, with velocities between 1
and 5 m/s, inside a reservoir of much larger dimensions. By comparing the
behavior in water and solutions of PEO with 50 and 250 ppm concentration,
he concludes that the influence of the polymer solution is to maintain
sphericity during bubble collapse (but not during bubble growth).
4. C A V I T A T I O N IN A M O V I N G F L U I D
with P r the pressure in the reservoir where the jet is discharging and V j the
bulk velocity of the jet. Depending on the way the experiments are performed,
either by decreasing the pressure from a non r situation until
cavitation is reached or by increasing the pressure from a r situation
until the non cavitating conditions are achieved, the inception, a i, or desinent,
a d , cavitation numbers are obtained respectively.
Hoyt [22-25] conducted experiments with a nozzle situated 60 r below the
free surface of an open reservoir. Preliminary test results [22] showed a sharp
decrease of the incipient cavitation number when the concentration of the
homogeneous polymer (PEO) solutions was increased up to 10 p p m ;
afterwards the reduction was not as rapid. These results were later confirmed
and extended by modifying the upstream turbulence level [25]. All the data is
plotted in Figure 6.
For these concentrations, the fluid behaves as Newtonian with an increase of
the viscosity of about 10 and 25%, as compared to the solvent, for respectively
10 and 100 ppm. The surface tension of the polymer solutions was reduced
very sharply, by as much as 10%, when the concentration increased from zero
to about 40 ppm and reached a plateau afterwards. The tensile strength, the
nuclei concentration and the air content, at saturation or very slightly below,
are practically unaffected in the polymer solutions for the concentrations
mentioned earlier. Because the surface tension is reduced we may expect,
based on equations (8) and (9), an increase of the critical pressure and an
advanced cavitation. Since all other properties are unchanged and the
cavitation inception is delayed, Hoyt concludes that the causes are of an
hydrodynamic origin.
223
~f
0.4
Inception cavitation index
) Turb. Turb.
generator level, %
0.3
No <2
nX Yes 2
0.2 Yes 2.2
Yes 2.6
0.1 Hoyt [21]
Polymer concentration, ppm
I I I I I I I I
0 10 20 30 40 50 60 70 80
Baker et al. [26] obtained the desinent cavitation numbers, o"d, instead of o"i
as in the case of Hoyt, for a constant concentration, 100 ppm, of the same
polymer, a nozzle diameter of 50.8 ram, and a Reynolds of 6 x 105, larger
than in the case of Hoyt's tests, for varying concentration of air in the
circulating fluids. When the concentration was below saturation (<4 ppm) the
polymer did not introduce any appreciable change, but, for supersaturated
conditions (>4 ppm) cavitation desinence was delayed. The considerable
difference in behavior between Baker's and Hoyt's results can be due to the
much larger size of the nozzle, by near a factor of ten, the reduction of the jet
velocity, by a factor of about three, and the choice of the desinent instead of
the incipient cavitation number as a reference. Indeed, even in the case of pure
water, increase of the total gas content causes a strong increase of c7d, in
particular for supersaturated conditions.
Hoyt and Taylor [27] conducted visualizations of cavitating events using a
nozzle of only 2.92 mm diameter for saturated and undersaturated conditions.
The photographs clearly demonstrated that, for cavitation numbers comparable
or lower than those for which the water jets show extensive cavitation in the
shear layer, the drag-reducing polymer solutions, with a concentration of only
25 ppm, drastically reduced the presence of individual cavities. Moreover, the
bubbles are larger and their surface is smoother than for the conditions of
limited cavitation in water jets.
224
1.4
- Desinent cavitation index
1.2
AA
1.0 -
e# Fluid
Jet
origine
0
0.8 - o o o ~ 0 0
Water Nozzle
0.6
4 Water Orifice
100 ppm PEO Nozzle
0.4 100 ppm PEO Orifice
0.2
Total gas content, ppm
0 I I I I I I I
0 2 4 6 8 10 12 14
Arndt [28] advanced an explanation of the Baker et al. [26] and Hoyt [22-25]
results based on the difference in the hydrodynamic behavior of jets depending
on the values of the Reynolds numbers. His analysis is based on the fact that,
for equal Reynolds number, the order of magnitude of the strain rate in the
contraction of the small nozzles, will be larger than for the large nozzle. Thus,
this effect, coupled to the transitional state of the jets in the Hoyt and Taylor
[27] experiments, is expected to lead to a significant viscoelastic effect on the
pressure field and to justify the inhibition of cavitation. However, no
explanation is given on why cavitation is delayed in the Baker et al. [26]
experiments in the supersaturated regime.
Already in 1974, Ting [29] correlated jet cavitation inhibition data by Hoyt
[23] with the drag-reducing properties of the polymer solutions. He showed
that the percent reduction of incipient cavitation and of drag reduction can be
expressed in the same way; as a function of the polymer concentration and an
intrinsic concentration, which is a measure of how rapidly cavitation surpres-
sion (drag reduction) increases with increasing concentration. The
characteristic numerical values obtained in both situations are in very good
agreement.
In conclusion, jet experiments do not show conclusively that cavitation is
inhibited under all flow conditions. It appears rather clearly, however, that
modification of the flow structure is the main effect with little, if any, contri-
bution from the fluid properties on inception. When cavitation is well develo-
225
ped, the cavities are larger than those existing in the solvent and their surface
is smoother. These modifications can be directly related to experiments
showing that polymer solutions delay the departure from sphericity of single
bubbles and, as a consequence, their eventual break-up due to surface defor-
mation and instability.
G- cQ (16)
rc D U Sts
where c is the concentration, Q the volume flow rate of the ejected solution, D
the diameter of the hemisphere, U the free stream velocity and 8ts the
boundary layer displacement thickness calculated at specified positions along
the body surface.
There is a marked reduction over the whole range of Reynolds numbers, but
the relative effect seems to decrease when the Reynolds number increases.
Moreover, when the concentration of the ejected fluid is increased, the
polymer effects increase also but seem to reach a saturation beyond which
further increase causes a reduction of the polymer efficiency. The saturation
effect is exemplified in Figure 9 where the cavitation inception number has
been plotted for a constant Reynolds number of 7.5 x 105 as a function of the
polymer solution injection rate (up) and the dimensionless polymer solution
injection rate (down). It is interesting to note that what seems to be really
important is the amount of polymer present in the reference thickness of the
boundary layer.
Gates and Acosta [35] have plotted the maximum percent reduction in
inception on the hemisphere nose as a function of the Reynolds number for
their results and those previously published (Figure 10). It is very interesting
to see that the effects are qualitatively comparable in spite of the differences in
the way the polymer molecules are brought to the body wall (carried by the
main flow or ejected at the nose). The differences, between the results of van
226
der Meulen [34] and Gates and Acosta [35], may be due to many factors and, in
particular, the level of turbulence and nuclei concentration of the cavitation
tunnels employed in their investigations.
0.7 - cyi
~ Hemisphere body
0.6 9 : 106x G
iBm i ~ o 0
[] 0.35
0.5
ii 1.75
. / Q 2.3
0.4 . o/.--. A
A
7
9
t 14.6
K/ 10-Sx Re
23.6
0.3 I I I I I I I
3 4 5 6 7 8 9
0.7
(3"i
NSRDC body
0.6 106 G
o 0
O 0.35
0.5
(9
0.4 O
|
o
1 0 - S x Re
0.3 I I I I I I I I I
3 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4
0.65 F O'i
D O
50 ppm
0.60 500 ppm
O
0.55 -0
- |
0.50
0.45
O Q, 10-6 m3/s
I I I I I I I I I I I I I I
0.40
0 5 10 15
0.65 ~- O"i
O 50 ppm
0.60 OO O 500 ppm
0.55
0.50
0.45
| 106 G
0.40 I I I I I I I I
0 1 2 3 4 5 6 7 8
In an attempt to interpret these results, van der Meulen [37] and Gates and
Acosta [35] visualized the boundary layer along the body surface in the region
of separation. They both come to the same conclusion: the polymer additives
remove "the laminar separation by stimulation of transition (Gates and Acosta
[35])", causing "transition to turbulence at much lower Reynolds numbers than
the pure solvent (van der Meulen [37])". This conclusion is further
substantiated by the results of tests performed by these authors with a Schiebe
body, which, theoretically, should not exhibit laminar boundary layer
separation. They showed that, indeed, the polymer solution ejection has no
effect whatsoever on either the type of cavitation or the inception index.
Moreover, as signalled by Gates and Acosta [35], tripping the boundary layer
transition on the hemispherical headform has been demonstrated to be more
228
60 - A o ' i ,o~
O"i
50 - A
conc.,
ppm Reference
40 500 van der Meulen [33]
o
30
O0
0 | o
@
@
@
[] A 2o} Ellis et al. [36]
A 0 o A 50
0 0 20 H o l l et al.
20-
0 0 0 @ @ 500 Gates & Acosta [34]
0 0 @ [] [] 2o } Baker et al. [31]
10- [] 80
10-SRe
0 1 I I I I I I I I I
0 1 2 3 4 5 6 7 8 9 10
14 l O - 3 x Pac ' P a
12
10 c = 0 ppm
c = 3 ppm
m
- (
- }~ 10-SxRe
o~ t
0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4
I I I I I I I I I I (7
15 10 9 8 7 6 5 4 3 2
Reitzer et al. [36] have also investigated the flow around a cylinder in an
open loop cavitation tunnel. A 1000 ppm PEO solution was ejected upstream
of the test section with a flow rate such that the concentration of the homoge-
neous solution in the test section reached an homogeneous concentration of
3 ppm after mixing. Their main results are summarized in Figure 11, where
the acoustic pressure is plotted as a function of the cavitation and Reynolds
numbers for water and for the homogeneous polymer solution. For water,
there is a region, zone I, where the flow is non cavitating, up to a Reynolds
number, defined with the free stream velocity and the diameter of the
cylinder, of 85 000, for which cavitation is initiated and isolated bubbles can
be seen. Beyond this Reynolds number, cavitation develops and the acoustic
pressure increases up to a maximum (zone II), after which it decreases over a
limited range of Reynolds (zone III). After a relative minimum, the noise
increases very sharply, reaches another maximum much larger than the
previous one (zone IV) and then decreases as sharply as it had increased (zone
V). By comparison, the polymer solution completely inhibits zone II, which is
replaced by the continuation of zone I, and zone III, where the noise was
decreasing in the case of water, is replaced by an increasing region that fits
perfectly zone IV. The polymer has no effect whatsoever on zones IV and V
where cavitation occurs respectively in the form of alternating bursts and an
elongated vapour cavity. From these and other data, the authors conclude, as in
other previous works, that the cavitation retardation associated with the
230
mm []
9 Am~
~pr Ipr V
v~mvvV []
A
100 ppm
250 ppm
0.50
m m V 500 ppm
0.45 [] A Ak A A y y y v
A A
V" 9 IPr
0.40
1 0 - S x Re
0.35 I I I I I I I !
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
0.40
10-5 Re
0.35 I I I I I I I I
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
where V o is the tangential velocity, and Tii the extra stresses (i = r, 0). The
pressure on the axis of the vortex is obtained by integrating equation (17),
from infinity to r = 0. It is easy to see that the contribution of the rotation,
whatever the velocity distribution, is to decrease the pressure on the vortex
axis. In a Newtonian fluid the extra stress terms cancel. In non-Newtonian
viscoelastic fluids, the experience shows, as stated above, that these terms
contribute to diminish the centrifugal effect.
Inge and Bark [42] conducted experiments with a specially designed elliptical
wing having a maximum chord of 0.16 m and a half span of 0.238 m. They
reported results obtained by ejecting concentrated polymer solution into the
water stream through a multiperforated injector situated one meter upstream
of the foil and for homogeneous polymer solutions with concentrations
232
between 0.01 and 12 ppm of PEO Union Carbide WSR-301. In Figure 13, the
values of a modified cavitation number, taking due account of the different
values of the incidence angle and of the free stream velocity, are plotted as a
function of the polymer concentration in the homogeneous solutions for three
conditions of cavitation development. The results show very clearly that the
incipient cavitation occurrence is significantly delayed for concentrations
larger than 1 ppm. The same is apparent for the other conditions of cavitation
although the changes are proportionally smaller. Interestingly enough, the
permanent cavity and the attached cavity situations cannot be distinguished for
the largest concentration. The experiments with the polymer ejection gave
qualitatively similar results.
o"n
O O Incipient cavitation
[] Appearance o f a p e r m a n e n t cavity
o
0 ~ ZX Cavity reaches the w i n g
[] o ....
El
c, ppm
0 I I I ] ,,,
0.01 0.1 1 10
Fruman [43] investigated the behavior of the tip vortex of a NACA 16020
cross section elliptical foil in water and in water with polymer solutions
ejected from a 0.5 mm diameter tube at a distance of 20 mm upstream of the
tip. Prior to the polymer tests, experiments conducted by ejecting a 50%
water + glycerin mixture, with a viscosity of 10-2 Pa.s, did not show any
significant contribution of the augmentation of the viscosity of an otherwise
Newtonian fluid. Ejecting a 500 ppm PEO solution when a quite large vapour
tube occupies the vortex core considerably modifies the appearance of the
cavitation. At an ejection velocity of about half of the free stream the
233
continuous very long cavity is reduced to a very short cavity of about half of a
maximum chord length and only scattered isolated bubbles are carried
downstream. By doubling the ejection velocity these entrained bubbles are
eliminated and only the shortened cavity remains. In terms of the incipient
cavitation number, Figure 14 shows inception results obtained with an ejection
of a 250 ppm PEO WSR 301 solution at an ejection velocity slightly larger
than the free stream.
2.5
cYi
no ejection
2.0
polymer
.....
1.5
1.0
0.5 I I I
5 7.5 10 12.5
Thus, it appears that the polymer solutions have a strong effect on the tip
vortex cavitation occurrence and development. However, it is not clear what is
the mechanism responsible for such changes because, in these experiments,
neither the tangential velocities of the vortex nor the lift of the wing have been
measured. The latter is a very important factor since the tip vortex intensity is
directly related to the mid-span circulation of the foil and, as shown by Wu
[44] and Kowalski [45], lifting surfaces immersed in flowing homogeneous
polymer solutions display a reduction of lift.
In order to elucidate these aspects, experiments were conducted by ejecting
the polymer solution from the tip of the wing through a small diameter orifice
(Fruman et al. [46]), measuring both the tangential velocity distributions and
the incipient cavitation numbers. The results show a significant reduction of
the incipient cavitation number and, more interesting, a decrease of the
234
maximum tangential velocity and of the slope of the velocities in the core
region when the polymer solution was ejected, Figure 15. Measurements of the
lift did not show any change during polymer ejection (Aflalo [47], Fruman and
Aflalo [48]) in agreement with the fact that the tangential velocities in the
potential region were unchanged.
V, m/s
2 qi, m 3/s
0
1 0 . 7 x 10 -6
2.2 x 10 -6
-1 - U o o = 5 m/s
~=10 ~
~2
I I I I I I I I I I
-12 -10 -8 -6 -4 -2 2 4 6 8 10
1.5
V, m/s
1.0
0.5
--0.5
U =5m/s
-1.0 - 0~=5 ~
I I I I I I I I I I
-1.5
-12 -10 -8 --6 -4 -2 0 2 4 6 8 10
[]
0.4 0 0
0.2
107x q-/
0 I I I I
0 0.5 1.0 1.5 2.0
Figure 16 9 Ratio of the pressure difference between infinity and the vortex
axis for the ejection of the polymer solution and the pure water as a function
of the reduced injection rate. 1000 ppm PEO solutions. From Aflalo [47].
m qi c
qi =
U~ b Cma x
The results show that the polymer ejection causes a reduction of the pressure
difference as compared to the pure water situation. This reduction is largely
sufficient to justify the delay on the cavitation occurrence even if the
contribution of the normal stresses in equation (17) is ignored.
An investigation on the effect of homogeneous polymer solution on tip vortex
cavitation was conducted by Fruman and Aflalo [48]. The homogeneous
solution, of about 10 ppm, was obtained by injecting, upstream of the water
tunnel recirculating pump, a concentrated polymer (1500 ppm).
236
0.90
0.85 -
At time t=O
Attime t= lOOs
At fin~ t = 9OO s
The photographs of Figure 17 show that, in spite of the fact that the
modification of the flow rate and the reference pressure caused a significant
reduction of the cavitation number during the process of mixing, for an
initially well developed cavity the build-up of the polymer concentration in the
cavitation tunnel recirculating water was responsible for a significant decrease
of the cavity length. It is interesting to note also that the polymer seems to be
more effective at distances from the tip of several maximum chords and do not
causes the cavity to detach from the foil.
3.0
8
0
@0 water
2.5 -- iO polymer (9
0
2.0- w~ [] 0 0
Om o o
[] 0 0~
1.5-
u o~
o
1.0- [] O~
~ c Z
0.5 I I I I I t I
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
The measurements of the lift of the foil showed that it was markedly reduced
in the homogeneous polymer solution. The tangential velocities were also
considerably reduced in both the core and the potential region. The latter is in
direct agreement with the reduction of the lift and hence of the mid-span
circulation. Figure 18 shows the desinent cavitation numbers as a function of
the measured lift coefficients in water and homogeneous polymer solution. The
effect of the polymer solution is to degrade the performance of the foil since,
for the same lift coefficient, the critical cavitation number is larger. The effect
of the polymer solution on the lift is largely more important than that on the
inhibition of cavitation inception. Since the boundary layer of the NACA
16020 section used in these tests is very sensitive to laminar-to-turbulent layer
transition (Pichon et al. [49]) it may well be that the extremely large decrease
238
w Cp llum
2.0
I / "~-- crd withoutejection
J 0,~ I0 no ejection
1.5 ~ _ .. ~ m e r
III
X /C max
0.5 I I I I I I I I I I
0 0.2 0.4 0.6 0.8 1.0
The ejection of polymer solutions at the tip of the foils to delay cavitation has
been applied with success by Chahine et al. [51 ] to a five blade screw propeller
of about 29 cm diameter. Because of the relatively low aspect ratio of the
blades, the position of the tip vortex detachment was not as easy to establish as
239
17 - C a v i t a t i o n n u m b e r
water + glycerin
16 injection
blade #5, no injection
15
blade #1 }injection
blade #3
14
13
12
~ ~ o l y m e r concentration, ppm
10 I I I I I I I
1000 2000 3000 4000 5000 6000 7000
the difference between the discharge pressure and the vapour pressure divided
by the pressure difference across the device, and the air content is non
dimensionalized by the value at saturation. There is a large inhibition effect
for the PEO solutions, even at very low concentrations. However, a non drag
reducing polymer, Carbopol, does not display an inhibition effect.
Table 2 : Incipient cavitation number and air content for tests in a vortex
chamber. From Hoyt [53].
Test liquid Incipient Cavitation Air content/Air
Number content at saturation
Dearated water 0.253 0.284
Tap water 1.480 0.701
1.330
PEO, 8.2 ppm 0.547 0.755
PEO, 12 ppm 0.513 0.709
PEO, 16 ppm 0.100 -
PEO, 17.5 ppm 0.107 0.709
Carbopol, 20 ppm 1.300 0.785
Bismuth [54] conducted tests in a long vortex chamber where the fluid was
introduced tangentially at one end through eight rectangular slits and evacuated
axially at the other end. The reference pressure was measured in a large
reservoir situated downstream of the vortex chamber and used to determine
the incipient cavitation number using, instead of the pressure drop across the
chamber as in Hoyt [53], the kinematic head at the exit section. For a 10 ppm
concentration of PEO, the cavitation onset was advanced, as compared to the
pure water results, Figure 21, in complete disagreement with the earlier
results by Hoyt [53]. It has to be pointed out that, because of the different
definition of the cavitation number, direct comparison of these results is
difficult. However, if it is accepted that the drag reducing properties of the
polymer solution should increase, at equal pressure drop, the flow rate, the
results by Hoyt [53] should correspond to much larger inhibition effects. On
the other hand, velocity measurements made by Bismuth [54] did show that the
tangential component of the velocity increased, as compared to pure water,
when moving from the wall towards the center of the vortex. This increase
was large enough to justify, by integration of the simplified radial momentum
equation (equation (17) without the normal stress terms), the enhanced
cavitation characteristic of this flow. Moreover, since the flow rate determines
the ejection tangential velocity, and hence the circulation, Figure 21 can be
compared to Figure 18, where the lift coefficient is also proportional to the tip
241
20
[] []
19
18
17 -
EO]
16 -
f I I IQ' 10-3m3/~
15
1.0 1.1 1.2 1.3 1.4
I I I I Ejection tangential
11 12 13 14 velocity, m/s
~Rp CrRw
1.00 PR
0.86
0.95
0.98
_ []
1.17
0.90 1.23
0
o 1.35
0.85
0.80 []
qi /Q x103
0.75 I I I I I I I I
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Prey -- Pv
or- I (18)
-~- P ( ( o R ) 2
243
O' i
-1.84
lO iw = 7287 Re
f O polymer
o water
Re
5 I llll I I I I
5 6 789 2 3 456789 2 2 3
10 10
arrowhead cavities analogous to the ones observed in the case of water. When
the cavitation number decreases, the trailing edge waviness increases while
oscillations occur in the flow and axial directions. For extreme conditions the
movement of the cavity trailing edge becomes chaotic.
In Figure 23, the inception cavitation numbers as a function of the Reynolds
number (computed using the solvent viscosity and the minimum gap) have
been plotted in logarithmic coordinates for e = 10 ~tm. As shown, the
initiation of the cavitation is delayed in the case of the polymer solution but the
slope remains the same as that in the case of water.
It can be hypothesized that the inhibition effect is associated with the elastic
contribution of the normal stresses, which has the net effect of reducing the
incipient cavitation number, that is to say, to increase the pressure over the
Newtonian contribution. The added pressure, APe, can be estimated thus from
the difference of incipient cavitation numbers at an equal Reynolds number,
by,
1
APe - 2 t% - tYiw l. (19)
Ou/Ox, s -1
10 I i I I i i I tt : 105
2 3 4 5 6789 2
10 3 10 4
In Figure 24, the values of APe have been plotted, together with an estimate
of the elongational viscosity defined as,
APe
~e = ~
c)u "/ Ox (20)
where c)u / Ox (=70 co) is the maximum elongational strain rate, as a function
of the latter. The elastic pressure contribution increases with the strain rate
increasing while the elongational viscosity decreases. The latter is up to four
orders of magnitude larger than the shear viscosity (a Trouton ratio as high as
104). These Trouton ratios and elongational viscosities are comparable to the
ones obtained for a variety of polymer solutions displaying an elastic behavior.
It seems that the effect of the polymer solution in the present situation is due to
the development of normal stresses in the elongational flow in the space
confined between the moving and the fixed wall.
5. C A V I T A T I O N EROSION
factor of three as compared to pure water and the erosion rate decreases
slightly.
W e i g h t loss, mg J []
50
Fluid
40
water
J )J
"o glycerol-distilled
water mixture
20 100 p p m P A M
1000 p p m P A M
10
E r o s i o n t i m e , rain
I I
0 10 20 30 40 50 60
Fluid
30
0 water
20 - .~/ [] 100 p p m P E O
A 500 p p m P E O
0 1000 p p m P E O
10
I i I I I I
0 10 20 30 40 50 60
Ten years after these early results, Shima et al. [57] conducted very similar
experiments, but used PEO instead of PAM and had the aluminium test
specimen attached to the vibrating rod. Their results are very much different
of those of Ashworth and Procter [56]. First, no incubation time seems to be
necessary either in water or polymer solution; second, a 100 ppm solution
shows a behavior similar to that of water with a slight increase of the weight
loss; third, for 500 and 1000 ppm solutions the weight loss increases for a
short time after initiation and decreases significantly thereafter, Figure 26.
When the 1000 ppm polymer solution is moderately degraded the weight loss
increased in the early stages and decreased afterwards while for a fully
degraded solution the results are very close to those for pure water. Again, a
water/glycerol mixture decreased the material removal. Tsujino [58] pursued
the research by Shima et al. [57] and investigated the effect of the peak-to-peak
amplitude. He showed that when the amplitude is decreased, from 38 to
25 ~trn, water and a 1000 ppm PEO solution have exactly the same behavior
during a very short duration (-10 min) after initiation and then differ, the
aggressiveness being much decreased in the polymer solution.
30 - ~ ~'0
9 Tsujino[58]
_ / / / / ~ ' \ A = 25 gm O Ashworth and
10 Procter [56]
As shown, the results obtained by Ashworth and Procter [56] on one side, and
Shima et al. [57] and Tsujino [58] on the other, are markedly different in spite
of the fact that the two polymers used in the tests are very effective drag
reducing agents, display analogous viscoelastic effects, and have, for equal
concentrations, comparable shear viscosities in solution. The major differences
248
have to do with the materials and with the position of the test specimens in the
ultrasonic pressure field. However, in the case of pure water, the weight loss
versus time remains nearly linear regardless of the specimen material, the
position of the sample and the amplitude of the ultrasound, Figure 27. In the
polymer solutions, a linear behavior has been shown to exist by Ashworth and
Procter, while a power law behavior, with a power of less than unity, has been
demonstrated by Shima et al. and Tsujino. In a quite recent work, Hoyt and
Morgan [59] have reported results analogous to those of the Japanese
researchers when a 200 ppm PAM was added to a 6% mixture of tomato
puree in water.
How then to interpret the changes in the case of the polymer solutions ? No
explanation has been proposed as yet, although the visualisation conducted by
Shima et al. and Tsujino show conclusively that the development of the
cavitation bubbles in the more concentrated PEO solutions is very different
from the one observed in pure water. In the latter case, a cloud of bubbles
develops in an orderly fashion on the surface of the horn with a thickness
increasing from the rim to the center and, away from this surface and around
the axis, a column of small bubbles extending quite far away (one to two times
the diameter of the horn). When the erosion progresses, the thickness of the
cloud seems to increase on the surface and, in particular, around the center of
the sample. In 500 and 1000 ppm polymer solutions, isolated bubbles, clouds
or filaments, occupying a cylinder of at least the diameter of the horn, occur
away the sample surface and on the side wall of it, in what can be said to be a
disorderly fashion (as compared to water). When time, and hence erosion,
progresses, bubble clouds become denser and thicker on the surface and on a
column extending away from it. Therefore, it seems that, in the polymer
solutions, low pressure regions, where cavitation can occur, are developed
because of macro scale (of the size of the sample diameter) changes in regions
which are not even supposed to be affected by the vibration, such as the side
wall of the sample and the column mentioned above. For the test conditions of
Shima et al. [57] and Tsu~ino [58], it seems reasonable to hypothesize that the
very dense and thick cavitation, developing on the test specimen surface when
erosion progresses, has a cushioning effect that reduces the damage due to
bubble (cloud) collapse. For the Ashworth and Procter test geometry, this
cushioning effect is reduced because of the distance between the sample and the
tip of the vibratory horn and the modification of the macro scale (which is in
this case of the order of magnitude of the space between the sample and the
tip). Ting [60] offered a completely different explanation of the Ashworth and
Procter results. He claimed that the enhanced erosion resulted from the "solid-
like" behavior of the reentering jet and the additional impact stress developed
in the extremely rapid deformation process undergone by the fluid. In view of
the results by Shima et al. [57], Tsu~ino [58] and Hoyt and Morgan [59] this
reentering jet erosion enhancement effect does not seem to be of primary
249
6. C O N C L U S I O N
ACKNOWLEDGEMENT
The authors wishes to thank the support he has received over many years by
the Ministry of Defence, France, to conduct research on polymer solutions
effects in hydrodynamics. He is deeply indebted to Professors Jack W. Hoyt
and William R. Schowalter for taking the time to read a drat version of this
chapter and provide the author with many correction and wise comments.
251
NOMENCLATURE
r concentration
D diameter of headforms
e minimum gap in lubrication tests
G non-dimensional injection rate of polymer fluid
k polytropic index
L distance between the center of a bubble and a wall
m,n power law parameters
P pressure
po pressure at infinity at t = 0
pc critical pressure
Pd pressure in a reservoir
Pg non-condensible gas pressure within the bubble
PgO non-condensible gas pressure at t = 0
p(R) pressure at the interface of a bubble on the liquid side
Pv vapour pressure
p~(t) pressure far from the bubble
Prez reference pressure
qi non-dimensional flow rate
Q volume flow rate of ejected solution
R radius of the rotating drum in lubrication tests
Ro radius of a nucleus
RA distance between the position of the bubble interface, opposite
to a wall, and the center
Re Reynolds number
Rc critical radius
Rch initial radius for a collapsing bubble
R(t) bubble radius at time t
(r, O, (p) spherical coordinate system
t time
U radial velocity component
U free stream velocity
vj bulk velocity of a jet
vo tangential velocity
elongational viscosity
P liquid density
O"d desinent cavitation number
O"i incipient cavitation number
"t'R Rayleigh time
Trr, TOO, T ~ normal components of the deviatoric stress tensor
CO angular velocity of the drum in lubrication tests
APe added pressure in lubrication tests
REFERENCES
~ R.T. Knapp, J.W. Daily and F.G. Hammit, Cavitation, McGraw-Hill, New
York, 1970.
. D.H. Trevena, Cavitation and tension in liquids, 1987, Adam Hilger,
Bristol and Philadelphia.
. W. Tillner et al., The avoidance of cavitation damage, Mechanical
Engineering Publications Limited, London, 1993.
. C.E. Brennen, Cavitation and bubble dynamics, Oxford University Press,
Oxford, 1995.
. A.J. Acosta and B.R. Parkin, J. of Ship Research, 19, 1975, pp. 193-205.
6. A. Shima and T. Tsujino, Chemical Engineering Science, 31, 1976, pp.
863-869.
~ H.S. Fogler and J.D. Goddard, Phys. Fluids, 13 (5), 1970, pp. 1135-1141.
8. H.S. Fogler and J.D. Goddard, J. Appl. Phys., 42 (1), 1971, pp. 259- 263.
9. A.T. Ellis and R.Y. Ting, NASA-SP 304, Pt. 1, 1974, pp. 403-420 (with
discussions).
10. W.J. Yang and M.L. Lawson, Journal of Applied Physics, 45 (2), 1974.
11. G.L. Chahine, 1974, Thesis, Univ. Paris VI, 1984, Rapport de recherche
ENSTA 042.
12. R.Y. Ting, Phys. Fluids, 20 (9), 1977, 1427-1431.
13. P.S. Kezios and W.R. Schowalter, Phys. Fluids, 29 (10), 1986, pp. 3172-
3181.
14. G. Riskin, J. Fluid. Mech., 218, 1990, pp. 239-263.
15. G.L. Chahine and D.H. Fruman, Phys. Fluids, 22 (7), 1979, pp. 1406-
1407.
16. E.A. Brujan, C.-D. Ohl, W. Lauterborn and A. Philipp, Acustica, 82,
1996, pp. 423-430.
17. G.L. Chahine and A.K. Morine, ASME Cavitation and Polyphase Flow
Forum, 1980, pp. 7-8.
18. A.K. Morine, 1982, Thesis, Univ. Paris VI, Rapport de recherche
ENSTA 179, 1983.
19. G.L. Chahine, Applied Scientific Research, 38, 1982, pp. 187-197.
253
Roger E. Khayat
1. INTRODUCTION
The influence of inertia and elasticity on the onset and stability of Taylor
vortex flow (TVF) is examined for an Oldroyd-B fluid. The rigid-flee (stick in
the azimuthal direction and slip along the axial direction) and rigid-rigid
boundary conditions are used. Both formulations lead to essentially the same
qualitative stability picture, but the former conditions allow a much simpler
formulation, more easily amenable to algebraic manipulation and analysis. The
resulting equations reduce to the Lorenz equations for a Newtonian fluid and
small number of modes. A truncated Fourier/Chandrasekhar representation of the
flow field, and the Galerkin projection, lead to a closed nonlinear dynamical
system with sixteen degrees of freedom. In contrast to the six-dimensional
system derived previously [Khayat, Phys. Fluids A 7 (1995) 2191 ], the present
model is capable of capturing the dynamical behavior observed experimentally
for a (Boger) fluid with negligible inertia. The improvement stems mainly from
the proper choice and inclusion of higher-order modes that account for normal
stress effects. For flow with dominant inertia, the stability picture is similar to
that for a Newtonian fluid: steady TVF sets in as the Reynolds number reaches a
critical value, Reo which decreases with fluid elasticity or normal stress effects,
and is strongly influenced by fluid retardation. As elasticity exceeds a critical
level, a subcritical bifurcation emerges at Re o similar to the one predicted by the
Landau-Ginzburg's equation and the previous six-dimensional model. It is found
that slip tends to be generally destabilizing. The coherence of the model is
established through comparison with existing linear stability analyses, and
experimental measurements and flow visualization.
256
solutions [23], he showed that the critical value of the Reynolds number at the
onset of Taylor vortices may be smaller or higher than the Newtonian value
depending on polymer concentration. At high polymer concentration, when
elastic effects become dominant, the critical Reynolds number was found to
decrease with the flow Deborah number, De. However, at high polymer
concentration, solutions may exhibit significant shear thinning. Thus, ideally,
both viscoelastic and shear thinning effects must be accounted for through a
suitable constitutive model. The later experiments of Haas & Biahler [24] tend to
show similar results. The experiments of Muller et al. [8] clearly demonstrate,
for the Taylor-Couette flow of a Boger fluid, the existence of a purely elastic
time-periodic instability at a critical rotation rate. The experiments were
conducted using Laser Doppler velocimetry (LDV) measurements of the axial
velocity component of a polyisobutylene-based fluid between two concentric
cylinders, with the outer cylinder being at rest and the inner cylinder rotating.
The results show an oscillatory flow at a vanishingly small Reynolds number (Re
-~ 7x 10-3). The flow appears to undergo a transition from the purely azimuthal
Couette flow to time periodic flow as the Deborah number exceeds a critical
value, which is in good agreement with the value based on earlier linear stability
analysis of an Oldroyd-B fluid [25]. The LDV measurements show that the
oscillatory behavior is not localized but appears to be spread throughout the
flow. As the Deborah number increases from the critical value, the amplitude of
oscillation increases monotonically with De. The corresponding power density
spectra show peaks, which are instrumentally sharp at the fundamental
frequency, the growth of harmonics, and eventually subharmonics, reflecting,
perhaps, the presence of period doubling or emergence of a second fundamental
frequency (quasiperiodicity). The influence of inertia (shear rate) on the
evolution of TVF was later examined by Baumert & Muller [9] who performed
flow visualization on Boger fluids using reflective mica platelet seeding.
Parallel theoretical work, for axisymmetric and non-axisymmetric flows, has
also been conducted on the linear stability of viscoelastic fluids [25-27] and
nonlinear calculations [28-30], with new phenomena being constantly attributed
to fluid elasticity [31,32]. Unlike Newtonian fluids, which obey Newton's law of
viscosity, viscoelastic fluids are not governed by a similar universal constitutive
law. The dependence of the predicted flow behavior on the particular choice of a
constitutive model adds another difficulty in our attempt to interpret an already
complex flow situation, particularly in the transition and turbulent regimes.
Larson [33] carried out a linear stability analysis in the narrow-gap limit,.using
the Doi-Edwards and K-BKZ constitutive equations. He found that the
dependence of the critical Reynolds number on De is generally non-monotonic,
but the flow is increasingly destabilized by fluid elasticity in the higher De range
259
[33]. Numerical calculations were carried out by Northey et al. [30] for the
Taylor-Couette flow of an upper-convected Maxwell (UCM) fluid neglecting
inertia. The non-axisymmetric flow solution was obtained by Avgousti & Beris
[28] and Avgousti et al. [29]. Elastic overstability was also proved through
various linear stability analyses [25,26], showing that the base (Couette) flow
can lose its stability via a Hopf bifurcation as the Deborah or Weissenberg
number exceeds a critical value. Most of existing analyses are, however, limited
to the linear regime.
In our quest to probe the nonlinear regime, we have undertaken the current
series of studies on the influence of fluid elasticity on Rayleigh-Benard thermal
convection and Taylor-Couette flow. Khayat [14-17] developed a four-
dimensional dynamical system for the thermal convection of strongly elastic
fluids of the Oldroyd-B type. Such a system constitutes a generalization of the
Lorenz equations [11] to include viscoelastic fluids. The critical Rayleigh
number at the onset of the convective cellular structure was found to be the same
as for Newtonian fluids. This is a direct consequence of the fact that the
nonlinear terms (at least to the degree of truncation adopted) are the same as
those in the Lorenz equations; no convective or upper-convective nonlinear
terms survive in the constitutive equations. The conductive state thus loses its
stability to the two steady convective branches C1 and C2, say, through a
supercritical bifurcation similarly to Newtonian fluids. The two convective
branches lose their stability in turn through a Hopf bifurcation as the Rayleigh
number exceeds a value that, this time, depends strongly on fluid elasticity and
retardation. It was also observed that fluid elasticity tends to precipitate the onset
of chaotic motion, while fluid retardation tends to delay it. Above a critical value
for the Deborah number, the flow behavior departs significantly from that of a
Newtonian fluid. All three fixed branches remain unstable in the supercritical
range for any value of the Rayleigh number. Thus, for D e > D e c, no steady
convection can set in, and the cellular structure is always periodic in time
(overstable), with the corresponding Fourier spectrum showing a sequence of
period doubling as D e is increased. The existence and stability of the Hopf
bifurcation corresponding to the onset of overstability were established in a later
paper [15] using center manifold theory. These findings have prompted us to
adopt a similar approach to the Taylor Couette flow of viscoelastic fluids in the
narrow gap limit [18,19].
Our earlier work [ 18] focused on the influence of elasticity and retardation on
the sfability and amplitude of the Taylor vortices with inertia dominating the
flow. A truncated Fourier representation with Galerkin projection of the flow
field similar to that of Kuhlmann and associates for a Newtonian fluid was
proposed. Kuhlmann [33], and later Kuhlmann et al. [35] examined the
260
stationary and time-periodic TVF, in the narrow-gap limit and arbitrary gap
width, respectively, with the inner cylinder rotating at constant and harmonically
modulated angular velocity. The solution to the full Navier-Stokes equations was
obtained by implementing a finite-difference scheme, and an approximate
approach based on the Galerkin projection. Comparison of flows based on the
two methods led to good agreement. In the approximate Galerkin projection [ 18],
the velocity and stress components assume a truncated Fourier representation in
space, with the expansion coefficients being functions of time alone. Since
elastic effects were assumed to be weak, higher-order normal stress terms were
neglected, thus leading to a six-dimensional nonlinear system, and reducing to
Kuhlmann's three-dimensional system for a Newtonian fluid [18]. In both
models, the velocity is assumed to adhere to the cylinder surfaces in the
azimuthal direction, while it slips in the axial direction (rigid-free boundary
conditions). The corresponding rigid-rigid boundary model leads to more
realistic values of the critical Taylor number and the corresponding wave
number, but to a less realistic value for the torque. Kuhlmann's three-dimensional
system turned out to be equivalent to the Lorenz system with the Prandtl number
equal to one. In this case, Kuhlmann's model cannot predict the destabilization of
the Taylor vortices, and therefore cannot account for the onset of chaotic
behavior. The situation is exactly similar for the Lorenz system when the Prandtl
number is less than or equal to one [36,37].
In the previous work [18], a similar level of truncation in the Fourier
representation for the velocity and stress was adopted for an Oldroyd-B fluid.
Similar levels of truncation have been widely used for the Navier-Stokes and
energy equations [13,38]. Examination of the influence of additional modes on
flow and temperature fields [39-42] indicates that many of the gross features
predicted by low level models are essentially recovered by the higher-order
models. In the viscoelastic model, there are two Fourier modes in the azimuthal
velocity and shear stress components that are expected to lead to nonlinear terms
in the stress equations. This is in contrast to thermal convection [14-17] where
the nonlinearities originate from the convective terms in the energy equation.
While the stability and bifurcation picture at the onset of the cellular structure in
the Rayleigh-Benard convection of viscoelastic fluids is similar to that of
Newtonian fluids, the presence of nonlinearities in the stress equations of the
Taylor-Couette flow of viscoelastic fluids has a drastic influence on the stability
of the Taylor vortices and the transition to chaos. While the two models suffer
from a similar level of truncation, the addition of viscoelastic effect, even to a
very weak extent, appears to alter dramatically the stability and bifurcation
picture. Most importantly, unlike the Newtonian model, elasticity tends to
destabilize the TVF leading to chaotic behavior and the emergence of a Lorenz
261
type attractor. As the Deborah number increases, the onset of TVF occurs at a
Reynolds number that decreases with De. Beyond a critical De value, the
exchange of stability takes place via a subcritical instead of a supercritical
bifurcation. Since the previous formulation [18] is not valid in the presence of
dominant elastic effects, most results from existing linear analyses, finite
amplitude numerical calculations, and experiments on the purely elastic
overstability could not be recovered.
The aim of this chapter is to investigate the onset and stability of finite
amplitude TVF with elastic effects dominating over inertia. It is shown that the
purely elastic overstability can only be predicted if the higher-order normal stress
terms, neglected in the previous formulation [18], are properly accounted for.
Particularly, the addition of the azimuthal normal stress component z00 leads to
additional coupling with higher-order eigenmodes that can no longer be
neglected. The resulting nonlinear dynamical system involves sixteen instead of
six degrees of freedom. Although more cumbersome, and therefore less
amenable to algebraic manipulations, the present expanded model is more
accurate in its predictions, and leads to good agreement with existing
formulations and experiments. Both the rigid-free and rigid-rigid boundary
conditions are used and the resulting flows are compared. It is found that the two
formulations lead essentially to similar qualitative flows. The former conditions
allow a much simpler formulation. It also allows the examination of the influence
of the higher-order normal stress terms when compared with the previous
formulation of Khayat [18]. Additional calculations are also carried out in the
absence of inertia, based on a dynamical system that accounts for yet higher
order normal stresses, in an attempt to reach a quantitative agreement with the
measurements of Muller et al. [8].
The chapter is organized as follows. In w the derivation of the nonlinear
dynamical system is discussed. The stationary solutions and their stability are
examined in w The influence of inertia for weakly and strongly elastic fluids is
examined through numerical calculations, which are presented in w Discussion
and concluding remarks are covered in w
where V is the gradient operator, t is the time, u is the velocity vector and x is the
elastic part of the deviatoric stress tensor obeying the following constitutive
equation [43]"
De + u. V r- (17u) t . z" -
1
r. Vu = - r - Vu- ( V u ) t . (2)
The various dimensionless groups in the problem, namely the Reynolds number,
Re, the Deborah number, D e , the solvent-to-polymer viscosity ratio, R v , and the
gap-to-radius ratio, ~ (not explicitly appearing in the equations above), are given
by:
dRi.O 2 R .O 22 d
Re - De = Rv = - , c= , (3)
w ' d " A1 - / Z 2 tip Ri
where qs and rip are the solvent and polymer viscosities, respectively, and
22 (0 <_22 < 21) is the fluid retardation time. Note that in this case q = rls + qp
and v= r//p. Other related dimensionless groups are the Taylor number, Ta, the
Elasticity number, E, and polymer-to-solution viscosity ratio, a:
Ta cRe 2 E- De Zip 1
9 (4)
Re" r/ Rv + l
263
arguments, one may then suspect that not much further insight would be gained
if rigid-rigid boundary conditions were used in the case of a viscoelastic fluid, at
least at the qualitative level. This is indeed confirmed in the present study
through comparisons with existing linear stability analysis results, experimental
measurements and flow visualization.
O0 OO
Zum(x,t)e imkz
ui(x,z,t) - 9 (5)
m - -oo m ~ ~oo
265
0 A
equations, u~and (3' become decoupled from the remaining variables. For
which satisfies the RF conditions, whereas the solution that satisfies the RR
conditions is expressed in terms of the even and odd Chandrasekhar functions
denoted, respectively, by @l(X) and @2(x) and defined in [55]:
)22/2
k6CiA2-(k 2 C2 ( k - C 3 =0, (7)
where C1, C2 and C3 are constants involving the inner product of the orthogonal
functions and their derivatives. These constants take, of course, different values
depending on whether equation (6a) or (6b) is used. The exact solution, when
compared with (6a) or (6b), gives an estimate of the magnitude of the error
resulting from the t~ncation in solution. One should expect that the error
remains of the same order when such a truncation is applied to the solution of the
full nonlinear equations for small departure from the base flow. It is clear from
eq. (7) that the neutral stability curves based on the approximate solutions 6a and
b, those based on the exact solution using the RF boundary conditions, and the
exact solution from [25] using the RR conditions exhibit similar behavior. At
small wave number, the critical Deborah number for overstability to set in
decreases sharply with k, reaches a minimum at k = kc, and increases again for k
> k c. All curves indicate a general flattening around kc, confirming the
experimentally observed wide range of wave numbers at which overstability sets
in [9,20].
On the basis of these observations, and further analysis of the influence of
inertia and fluid retardation (see section 3), one can now proceed and impose the
type and number of modes that may adequately describe the nonlinear flow field.
Although the solutions and results for both the RF and RR formulations are
presented in this work, more details will be given concerning the RF problem.
The RF formulation presents advantages as (i) the RF boundary conditions lead
to a much simpler formulation than the RR conditions, thus allowing further
algebraic manipulation and analytical investigation using various tools from the
theory of nonlinear dynamical systems, (ii) the resulting equations reduce to the
six-dimensional system studied earlier [ 18], thus allowing the examination of the
influence of the higher-order modes, previously neglected, (iii) these equations,
in turn, reduce further to the Lorenz system for a Newtonian fluid, a system
extensively investigated in the past thirty years or so [ 12].
It is first observed that, if only one fundamental eigenmode was kept in
expressions (6), one would obtain the trivial solution to the eigenvalue problem.
This corresponds exactly to the level of approximation adopted in the previous
work [18], where the flow of highly elastic fluids (De >> Re) could not be
treated. It will be seen later that this amounts to neglecting important normal
stress terms in the limit Re ~ O. The general solution, must then be chosen so
that (i) linear behavior is recovered for small deviation from the base flow, (ii)
268
the Newtonian flow is recovered in the double limit De, Rv ~ 0, and (iii) the
boundary conditions are satisfied.
Only two terms tumed out to be sufficient in the expansion in x for all the
velocity and stress coefficients u m ( x , t ) and rn~ij(x,t). For the RF conditions,
trigonometric (Fourier) functions are used, similarly to (6a), except that the
expansion coefficients are time dependent. For the RR conditions, hyperbolic
(Chandrasekhar) functions are used to satisfy the stick conditions, similarly to
(6b). There are thus sixteen independent modes that are retained. Higher-order
terms are included in the radial and axial velocity, and the normal stress
coefficients as opposed to keeping only one term in the previous six-dimensional
system [18]. The truncation level adopted in the previous work [ 18] is similar to
the one used by Kuhlmann [34] and Kuhlmann & Lficke [35] for a Newtonian
fluid, where two terms are kept only for the velocity and stress in the y direction,
and one term is retained for the remaining variables. This level of truncation does
not leads to the trivial solution of the (linearized) eigenvalue problem in the limit
Re ~ 0 [25].
Upon projection of the Fourier modes for the RF formulation, or the
Chandrasekhar modes for the RR formulation, a set of sixteen ODEs are
obtained, which govern the time dependent expansion coefficients. The two sets
of equations are complicated and will be given explicitly elsewhere [56]. In the
present study, each set of equations will be referred to as the sixteen-degree-of-
freedom nonlinear dynamical system (16NDS). The projection consists of
multiplying equations (1)-(2), in the narrow-gap limit, by the appropriate mode
and integrating with respect to x over the intervals [0, 1] and [- 1/2, + 1/2] for the
RF and RR formulations, respectively.
Upon elimination of higher-order axial and radial velocity, and normal stress
coefficients, the system can be reduced to the six-dimensional system derived
previously [ 18,56], which is given here for reference"
(J- V + X-aRvU,
l? - - U W + r U + Y - a R v V ,
- uv + b(Z- RvW), (8)
)( - - 5(X + aU),
]" - - b UZ - ~ WX - rX - 8 ( Y + a V ),
2 = fl(gY- r 5(Z + a W),
269
where U, V, W , X, Y and Z are time dependent and are related to the expansion
coefficients [18]. Note that a dot denotes differentiation with time. The
parameters in system (8) are given by:
1 1"
r = k 2 z'3Ta, r= 2 k 2' ~- E
+
(9)
b - 41r 2 r, ,
17= mb ( )
qo- 31r2 - k 2 r
In the double limit E, R v --~ 0, that is, in the case of a Newtonian fluid, equations
(8) reduce to the three-dimensional system derived by Kuhlmann [34], or to the
Lorenz system with the Prandtl number equal to one [ 11 ]"
It is important to observe that the nonlinear terms in the viscoelastic 16NDS stem
from both the convective terms in the momentum equations and upper-
convective terms in the constitutive equations. This is in sharp contrast to the
case of Rayleigh-Benard convection of a viscoelastic fluid [14-16] where no
nonlinear terms survive in the stress equations. The consequence of such
nonlinear terms in stress, as we shall see, is drastic on the flow behavior, as
opposed, for instance, to the cases of a convected Maxwellian fluid with less
nonlinear terms, or linear Maxwellian fluid with no nonlinear terms in stress. It is
at this point, perhaps, that one may begin to appreciate the difficulty with
analyzing viscoelastic fluids given the marked difference in flow behavior
subject to one constitutive model or the other.
3. L I N E A R S T A B I L I T Y ANALYSIS
Before proceeding with the numerical solution of the 16NDS, subject to some
appropriate initial conditions, it is useful to carry out local stability analysis in an
attempt to unravel some of the fundamental differences between Newtonian and
viscoelastic fluids. In section 2.4 the linear stability of the Couette flow was
already examined in the absence of inertia for a Maxwell fluid (Re = R v = 0).
Consider the influence of inertia on the stability of a viscoelastic fluid. For small
values of E (or De) and Rv, one expects the behavior of the flow in phase space
to be similar, in both the Newtonian and viscoelastic regimes, at least around the
fixed points. As E increases, the stability picture changes, giving rise to a
270
periodic solution, or overstability, which is the result of normal stress effects that
are usually not present in the case of a Newtonian fluid.
U s = G = + [ b ( r - 1)] 1 / 2 , Ws = r - 1. (11)
For the 16NDS, the critical value of r = r c (or T a c for the Taylor number) at the
emergence of the two fixed branches is not as transparent as for equations (8) or
(10). The value of r c tends to generally decrease as the level of elasticity
increases. The value of r c corresponding to system (8) gives a reasonable
estimate of this tendency [ 18]"
rc = ~
" a or Ta c =
k2+.21,i 1 i ,
k )2 1 + a rE (12)
where the term between square brackets constitutes the Newtonian contribution
from the Lorenz system. In this case, T a c has a minimmn at
!
. . . .
lr 2 n. 2 1] 1/2
k = km = ~[aE (aE + 1) + 1 Clearly, in t h e c a s e of a Newtonian fluid,
aE
rc = 1 and k m = h a l 2 . Similar conclusions are reached when the formulae are
cast in terms of the Reynolds number, R e , and Deborah number, D e . We shall
use whatever notations are convenient as the present results will be compared
271
with those based on existing linear stability analyses. Comparison will be made
with existing formulations that use exact solutions for the eigenvalue problem,
and with the previous model that involves a lower number of eigenmodes [ 18].
Joo & Shaqfeh [27] carried out the numerical solution of the linear stability
problem, using the RR boundary conditions, and examined the influence of
inertia and elasticity for a UCM fluid. It is thus helpful to assess the accuracy of
the present approximate method against their results. Fig. 1 displays the neutral
300 I I I I I I 'I I
De - 0.0
2.5 ..... /
5.0 .....
7.5 ..........
250 10.0 .....
200
~D
150
9f,,,,\ I ..-"
"('..', ,, I" ..'"
UNSTABLE _.."'I"" ...... . .... ""'""" . ....... .'"
100 ~ "r ,, , ...-'" ..- . .......... ..
"~ \ " ", ~ i-'" .- ~ 9........... .-'~'~"
50
" ' , ,
I I I I I , I
1 2 3 4 5 6 7 8
Fig. 1. Influence of fluid elasticity and marginal stability curves for a UCM fluid
(Rv = 0) based on the RR boundary conditions and e = 0.01.
stability curves in the (Re, k)-plane for the onset of steady TVF for 0 < De <_ 15
and e = 0.1. Note that these curves are based on the linear stability analysis of the
16NDS. For all De values, the critical Reynolds number Rec = Re(k = k )
decreases roughly like 1/k2 near k = 0, reaches a minimum, and then increases
roughly like k2 for large k. There is a shift in the value of km towards the fight as
272
approximate curves tend to give slightly lower values for Re c and ktn .
Neutral stability curves in the (Re, k) plane were also obtained using the RF
conditions. This enabled the assessment of the influence of the boundary
conditions on the stability picture. The RF marginal curves lead to essentially no
qualitative disagreement with the curves in fig. 1. Both figures show a localized
minimum at k -- km that increases with De, a tendency of the curves to flatten
around the minimum for the more elastic fluids, a general decrease in the critical
Reynolds number as fluid elasticity increases, and the narrowing range of
practical k values for the onset of steady TVF.
Consider now the important question whether there is any (at least qualitative)
change in the stability picture due to the inclusion of higher-order modes in the
16NDS as opposed to keeping only six modes as in system (8) [18]. A direct
quantitative comparison was carried out by examining the influence of fluid
inertia, elasticity and retardation through Re, E and Rv, respectively. Comparison
shows that the stability picture is qualitatively the same in both cases. The
inclusion of higher-order modes appears to make little difference for Newtonian
and weakly elastic fluids. In fact, the curves corresponding to small values of E
(E = 0 and 0.01) were essentially identical. Deviation between the two sets of
curves became more evident for the larger E values. This is expected, as
discussed above, since higher-order modes, previously neglected in [ 18], become
important as the level of fluid elasticity increases. In this case, the neutral
stability curves appear to be flatter as a result of the inclusion of higher-order
modes.
Similar conclusions are reached as to the influence of fluid retardation on the
critical Taylor number Tac for an Oldroyd-B fluid with E = 0.5. Fluid retardation
273
tends to delay the onset of Taylor vortices. Note that in the limit Rv ~ 0% one
recovers the Newtonian marginal stability curve (E = 0). The influence of Rv on
the loss of stability of the base flow is to be expected since retardation tends to
delay the onset of instability. Comparison shows a growing deviation and
flattening of the curves for the lower Rv values considered. Recall that as
retardation decreases, elasticity becomes relatively more dominant, and the
influence of the higher-order (normal stress) modes is expected to be stronger. It
is interesting to note that the curves in fig. 1 are reminiscent of those
corresponding to the onset of overstability obtained from the linear analysis of
Larson et al. [25] (see also fig. III-11 by Larson [20]). It is clear in both cases
that fluid retardation tends to prohibit the onset o f steady and oscillatory Taylor
vortices. Although the mechanism of onset of instability is different in the two
situations (given the absence of inertia in the analysis of Larson et al. [25]), the
role of fluid elasticity (at least for an Oldroyd-B fluid) appears to be very similar
to that of inertia. This is particularly obvious from fig. III-11 in [20], which
clearly shows the destabilizing influence of both inertia and elasticity.
Additional calculations and comparisons with existing results were also
carried out to closely examine the influence of fluid elasticity and retardation.
The results will only be commented upon here but not shown for lack of space.
The behavior of the minimum value of the critical Taylor number
Tacm(E,Rv)-Tac(k=km,E,Rv) as function of the Elasticity number and
viscosity ratio reveals a very similar trend as established previously (fig. 3 in
[18]) on the basis of model (8). It is found that Ta m drops sharply with E at
small elasticity in the case of a UCM fluid, in a manner similar to that predicted
by earlier linear analyses (see fig. 111-6 in [20] and fig. 8 in [57]) for the case of
corotating cylinders). The decrease in Ta m is considerably attenuated at the
larger E values. As to the influence of fluid retardation, there is a flattening in the
(Ta m , k) curves as Rv increases. This behavior agrees with that obtained from
the linear analysis of Thomas & Walters [58] in the case of a Maxwell fluid, and
those of Ginn & Denn [59] for a second-order fluid corresponding to a second
normal stress of zero value. In this case, the formulation based on the second-
order fluid is expected to lead to the same stability picture as that based on a
Maxwell fluid with small E value. Similar agreement is reached, as to the
influence of fluid elasticity on the value of the wave number km at which the
critical value of the Taylor number has a minimum, upon comparison with earlier
formulations [ 18].
274
(U 2 - 5b)(U 2 - 8 ) + ( a R v + a fa+ 5 ) ( b a R v - a f a + 5 ) U 2
r ~
a ( b R v - (a- 1)U 2 + b 5(a + 5 )
U Z + (a + 5 ) r - tY
Ws = baRv - a fa + tY ' Vs = Us, (13)
Xs = -aUs, Ys = ( a R v - r - W s ) U s , Z s = aRv Ws - b
It is thus clear that the solution of the first equation in (13) leads, similarly to the
Lorenz system, to two nontrivial solution branches corresponding the onset of
Taylor vortex flow. The steady-state solution of the 16NDS also leads to the
emergence of two nontrivial branches at r = rc(E, Rv, k), which will be referred
to as C 1 and C2, that are symmetric with respect to the r, and correspond to the
onset of Taylor vortices in the two opposite directions. Unlike the case of a
Newtonian fluid, the pitchfork bifurcation at r = rc is not always supercritical. In
fact, our previous study based on system (8) shows that the bifurcation is
supercritical only for weakly elastic fluids. When the Elasticity number E
exceeds a critical value, E = Esub, the bifurcation becomes subcritical. This
bifurcation picture is confirmed when higher-order modes are included as we
shall see next.
275
I " I !
i I I
I I I I I I .- ; E = 0.000
...............:.;.::.-..................... 0.006 .....
1.6
1.8 0.018 ......
..., ........
0 . 0 4 0 ...........
_ :.. 9
9
....
...-.
0.050 .....
1.2 '.
// 0.100 .....
1.6
0.8
.... --- .......................
1.4 .~ o.o. /.
0.4
..-'" s/.
. . - o. j . ../
1.2 0
I i I i il
rg rh rc r
the TVF loses its stability at some critical r value r h > r c (shown here for the
curve E = 0.05)
Consider the stability of the steady branches C 1 and C2 as r is increased from
r c. It is helpful, however, to first recall the situation for a Newtonian fluid. The
discussion is focused on the Lorenz system (10) since the inclusion of higher-
order mode does not alter the qualitative picture. Linearization of the Lorenz
equations around the steady-state solution leads to a characteristic equation of
the third degree. The conditions for the loss of stability of the toroidal TVF is of
particular interest here. For a Newtonian fluid, the two nontrivial fixed points C 1
277
Linear stability analysis, such as the one presented in the previous section,
determines the flow field as it is slightly perturbed from the base flow or from
the (steady) TVF. However, it fails to give the flow structure for a large
disturbance. The influence of the nonlinear terms must thus be examined through
the numerical solution of the 16NDS. The influence of inertia and elasticity on
weakly and strongly elastic flows is examined in some detail. A weakly
(strongly) elastic flow is defined as one whose Elasticity number is small (large)
enough for it to undergo a supercritical (subcritical) bifurcation at the onset of
Taylor vortices. Particularly, the emergence of super- and subcritical Taylor
vortices, as well as the onset of chaos, are investigated by determining the flow
spatio-temporal structure in phase space, through power spectra and/or time
278
The value of the relaxation time ~1 was found to be equal to Ls = 0.021 s or ~t--
0.11 s (with the corresponding Elasticity number equal to E = 0.164 or E t =
0.94), depending on whether steady shear or transient experiments were used [9].
The value of the viscosity ratio is set equal to R v = 6.5. Figure 3 shows the time
evolution of the (dimensional) axial velocity component U z at z = k/2, where it is
maximum, and x = 0.5, midway through the gap. The evolution of the velocity is
displayed for various values of the shear rate: 13 < D e < 14 (81.25 < R e < 87.5),
above the critical shear rate, D e c ~ 13 (Re c ~ 81.25). The curves in the figure are
similar to the results reported in fig. 1 of Avgousti et al. [28], and the trend is in
agreement with the observations of Baumert & Muller [9] for low and medium
0.01
0.009 -
9 ..../ ....................................................................................................
0.008 -
0.006-
0.005 -
: /,'- ....
: i
i /
0.004-
: tI
0.003 -
De = 13.09
13.18 .....
0.002
13.27 .....
i 9 , ,i 13.49 ..........
i :; ,' / 13.70 .....
ii ," ,'
0.001 J i / ,'" /
o I !
0 5;0 10b0 15;0 2000 25'00 30'00 3500
Time (s)
Fig. 3. Monotonic time evolution of the axial velocity for different shear rates
(13 < D e < 14) and small initial perturbation of the base flow (E = 0.16, R v = 6.5,
k = 3.5 and e = 0.093).
280
viscosity fluids. The initial condition taken for all the curves in fig. 3 is U1 = 0.01
with the remaining variables equal to zero. In this case, the transition from the
base flow to TVF occurs via a supercritical bifurcation similar to the branches E
< 0.018 in fig. 2 for a UCM fluid. In the precritical range (De < Dec), the origin
in phase space (base flow) is asymptotically stable to any perturbation, and the
numerical integration of the 16NDS, in the vicinity of the origin, follows simply
an oscillatory decay to the origin. As De (Re) exceeds Dec (Rec), an exchange of
stability occurs between the origin and the steady-state branch C1 (or C2),
coinciding with the emergence of steady TVF, with increasing amplitude as De
(Re) increases.
100
Theory +
+ +
+
...., -i-
[-.,
Experiment
10 100
De
Typically, the flow evolves monotonically from the base flow to steady TVF
over a period of time that decreases with increasing shear rate as depicted from
fig. 3. This appears to be in agreement with the observations of Baumert &
Muller [9] who monitored the dependence of onset time on the shear rate for a
fluid with medium viscosity. Figure 4 displays the time after shear initiation of
appearance of steady vortices as a function of the Deborah number (shear rate).
An inset showing the values from experiment is also included for comparison,
and reveals good qualitative agreement with theoretical predictions. The values
in the inset are based on measurements performed for a medium viscosity fluid,
with E = 44. As will be seen next, at higher shear rates, however, theory predicts
that the time TVF takes to set in begins to increase with De, a trend in
disagreement with what experiment suggests.
0.o45[ '~ . . . . . . . .
o li ,
0.0as
1 '11 " !
o.o i ii
0.0254 i1!/ it i :V~i :.\ i ,,:' '.. ..-,,
7h | 1 i ! l, i i :,i" :", ".,,':'.2.~,vc.':-.-~'c:- "----:---- ..... " ......... -............ ---"- .....
~ o.o2 I
1 i. i De = 17.47
0 9005 ' ".,.,i 17 81
17194
Time (s)
Fig. 5. Oscillatory time evolution of the axial velocity for different shear rates
(17 < D e < 18) and small initial perturbation of the base flow. The parameters
used are the same as in fig. 3.
282
0.028 -
(a)
0.026: 18.13
_ J
0.024-
16.78
0.022
0.02 De = 16.07
0.0 8
. , . -- ,. -
0.028
(b)
0.027 -
19.14
q7 0.026- [hh. 18.89
De = 18.77 11111#~r162 .... -
0.025 -
0.024-
.... 19.38 . . . . . . i
0.08- (c)
0.04-
0-
-0.04 -
-0.08 - i
..... 1 .... 010 "'! I I " I !
-0 2000 4000 6 0 8000 10000 12000 14000 16000 18000
Time (s)
Fig. 6. Time evolution of the axial velocity for 16 < De < 21. The flow for each
shear rate level is obtained using the flow of the previous (lower) level as initial
conditions. The parameters used are the same as in fig. 3. The figure is
subdivided into three segments of 18,000 s period each. Steady TVF is always
reached during the first period (a) for the range 16 < De < 18.7. Oscillatory
instability develops towards the end of the second period (b) for the range 18.6 <
De < 19.27. Transition to periodic behavior some time during the third period (c)
for the range 19.26 < De < 21.
283
The evolution of the flow loses its monotonicity as shearing exceeds a certain
level. This is depicted in fig. 3 for the curves corresponding to De > 13.2, which
show a local depression in the flow amplitude before steady TVF sets in. In fact,
as De is further increased, an oscillatory behavior emerges before the onset of
steady vortices as shown in fig. 5 for 17 < De < 18. The secondary flow gains
strength initially at a much faster rate than for the lower range of shear rates (fig.
3). The amplitude of oscillation decays with time until the onset of steady of
TVF, but the frequency appears to remain constant. As De increases, the overall
amplitude of oscillation increases, accompanied by a phase shift and delay in the
onset of steady TVF. Eventually, oscillatory behavior is sustained for longer time
for higher De values; in the limit, no steady TVF is found.
Before examining the onset of sustained oscillations, it is desirable to address
the issue of the influence of the initial conditions on the ensuing flow behavior.
Baumert & Muller [9] report that "flow behavior was not found to be particularly
sensitive to the type of velocity ramp imposed" initially. They indicate that the
flow behavior commencing at the start of the final velocity was indistinguishable
from the case when a plateau was imposed over a certain period. This
observation is presently confirmed through additional calculations carried out by
taking as initial conditions the steady TVF reached before increasing the shear
rate, instead of starting again from near the origin as in figs. 3 and 5. The
resulting sequence of initial flow transients, after the imposition of the higher
(new) shear rate, and subsequent final (steady or oscillatory) TVF are depicted in
fig. 6 for the range 16 < De < 21. The figure displays the evolution of flow over a
period of 54,000 s, subdivided into three equal periods of 18,000 s.
The first segment is shown in fig. 6a for the range of shear rates corresponding
to 16 < De < 19. Comparison between the curves in fig. 5 and those in fig. 6a
indicates that the flow behavior is essentially unaffected by initial conditions. It
is interesting to note the similarity in the emergence and decay of oscillatory
behavior between one steady level and the other. The figure clearly shows that
the time it takes steady TVF to set in increases with shear rate. This is a result of
the oscillatory transition that takes a longer time for the higher shear rate. This is
indeed even more evident from fig. 6b, which shows, for the range 18 < De < 20,
that steady TVF does not even set in over the time period a given shear rate is
applied. The oscillations tend to decay at a slower rate as De increases, and
eventually start to grow with time as indicated in the last portion of fig. 6b,
corresponding to De = 19.26. This growth, which is linear upon onset, does not
remain unstable over time as linear stability analysis suggests. At some time,
when the signal amplitude is large enough for nonlinear effects to become
significant and halt the (exponential) growth.
284
The bifurcation diagrams in fig. 2 suggest that steady TVF is reached as long
as r is below rh(E, Rv, k). This corresponds to the onset of a Hopf bifurcation at
De - Deh when steady TVF loses its stability to periodic behavior. For the
present flow in fig. 6, Deh is found to be approximately equal to 19. The
existence of a Hopf bifurcation at De = Deh is easily confirmed through linear
stability analysis around the nontrivial steady-state solution(s) when two
eigenvalues are purely imaginary, and no other eigenvalue possesses a zero real
part. The stability of the Hopf bifurcation, however, is difficult to establish for a
complex system like the 16NDS. Such an analysis is algebraically involved, but
a similar analysis, based on center manifold theory, was carried out previously
for the thermal convection of viscoelastic fluids [15]. Numerical integration, on
the other hand, shows that the Hopf bifurcation indeed exists, and is stable as
will be seen below. This situation is in sharp contrast to the case of the Lorenz
system (10) whereby no loss of stability of the steady TVF is predicted.
In figs. 6a and b, and for the range 16 < De < 19.15, the computation has been
limited to flows with final state, after transients have died out, that corresponds
to a standing wave. This also corresponds to most of the range of shear rates
examined in the experiment of Baumert & Muller [9] that led to steady TVF for
the low and medium viscosity fluids. However, they reported the observation of
coexistence of migrating bands and distorted vortices at the highest shear rate
considered. It is thus desirable to numerically examine the transition from steady
to oscillatory TVF. The sequence of flows displayed in fig. 6c is obtained for De
above Deh subject to the initial condition corresponding to the steady TVF at De
slightly below Deh. Avgousti et al. [28] reported having numerical difficulties
for a UCM fluid when they took the slightly perturbed standing wave as their
initial condition. Figure 6a shows the transition from steady to oscillatory TVF,
that is, from the flow at De = 19.26 to that at De = 19.38. The figure also shows
the transition to another oscillatory state at De = 20.56. The first transition is
preceded by a destabilization of the steady TVF to a traveling wave of amplitude
(exponentially) growing with time, which is reminiscent of the behavior reported
in figs. 6 and 9 of Avgousti et al. [28]. The exponential growth (instability)
ceases immediately upon increase of the shear rate, giving way to a regular and
stable oscillatory vortex structure. This structure is sustained for as long as the
shear rate is maintained at De = 19.38. Upon further increase of De, another
regular oscillatory structure sets in with a larger amplitude. The modulation of
the oscillation indicates the emergence of period doubling. Additional theoretical
and experimental investigations are obviously needed if the flow at still high
shear rate is to be explored. It is possible that the flow may not remain
285
for the investigation of the purely elastic overstability or even a flow at very
small Reynolds number. In general, however, the presence of inertia, no matter
how small it may be, prohibits the base flow from losing its stability to the
overstable mode. Instead, the base flow loses its stability first to steady (and not
oscillatory) TVF since there is always a finite range of r values over which the
branches C 1 and C2 are stable (see fig. 2).
The influence of fluid elasticity is now examined for vanishingly small inertia
in the postcritical range of the Deborah number, in an attempt to recover the flow
sequence observed in the experiment of Muller et al. [8]. One cannot expect full
quantitative agreement between theory and experiment given the level of
approximation in the 16NDS. Moreover, the wave number k needs to be imposed
in the present calculation. This quantity is not known from experiment; the wave
number is difficult to establish under unsteady conditions of flow [9]. The
comparison between theory and experiment is covered next for the RF and RR
formulations.
Consider the flow with negligible inertia, and set r = 10-6. Also let Rv = 3.75
and e = 0.0625 corresponding, respectively, to the viscosity ratio of the fluid and
the gap-to-radius ratio used in the experiment [8]. Although the wave number is
not specified in the experiment, it is set k = 4 based on wave numbers reported in
other experiments on Taylor-Couette flow of viscoelastic fluids [9]. Thus, only
the Deborah number will be varied. The flow is examined as De is increased
from zero, that is from the Newtonian level. Referring to fig. 2, it is seen that for
De = E = 0 the base flow is unconditionally stable to any perturbation since r <<
1 in the present case. This situation remains practically unchanged until De
reaches the theoretically predicted critical value, Dec = 29.7 or 29.3, depending
on whether the RF or RR boundary conditions are used. These values are based
on the purely elastic linear stability analysis. At this point, the base flow is
supposed to lose its stability, but this is numerically detected at slightly higher
De values. Since inertia effects are small (r = 10-6), one observes an exchange of
stability between the base flow and oscillatory TVF, since no steady TVF can set
in in the absence of inertia. As the Deborah number is increased beyond the
critical value, the amplitude of oscillation increases. The resulting sequence of
flows is identified through the Fourier spectra shown in figs. 7a and b for the
calculation based on the RF and RR boundary conditions, respectively. The
range of Deborah numbers studied is the same as in the experiment: 32 < De <
53, and should be compared with that reported in figs. 7-10 of Muller et al. [8],
where it is noted that De = 0. 911DeM~lle~.
288
0.14- 0.01
Experiment
0.008
0.006
0.12
O
0.004
0.002
0.1-
0
20 2; 3;
0.08 -
0.06-
0.04-
0.02-
!
020 2'5 30 35 40 45 5'o 55
De
fluid used throughout the experiment, and DeM was probably varied by varying
only the inner cylinder speed, f~. Hence, from the range of DeM values reported,
the corresponding value of the inner cylinder speed can be given by f~ =
DeM/77.06 for ~. - 4.4 s. Muller et al. [8] reported that the highest Reynolds
number, Re, reached in the experiment was of the order 7x 10-3. Indeed, if one
considers the value of f~ corresponding to the highest Deborah number reported
(De M = 54.5), one finds that Re = 2.86 x 10-3 (assuming the density 9 ~ 1
g/cm3). The experimental wave number, k (in units of d), at which overstability
is first observed, was also not reported by Mullet et al. [8]; its measurement may
have been difficult under transient conditions. Its exact value, however, is not
crucial in this case since the critical Deborah number for the onset of
overstability does not depend strongly on the wave number, over a wide range of
practical values: k e [4, 8] for Rv = 3.76 as linear analysis suggests [20]; this is
reflected by the flattening of the corresponding neutral stability curve in the (De,
k) plane around the critical value Dec. The wave number will be fixed to k = 4.85
for all subsequent calculations. This is the minimum value of the wave number
291
0.01 9 ! !
0.009 -
/t
Theory ,
0.008 -
,s
/
/'
0.007 -
9
O 9
0.006
O
0.005 -
,,'" Experiment
II
eq
ii s
i
i
I
it"
0.004 - i
i
,/
t
9"
0.003 - i
0.002 -
/
0.001 - r
,/
0 I I 9 I I I I ..... I
20 25 30 35 40 45 50 55 60
De
Fig. 9. Bifurcation diagram and comparison between theory (dashed line) and
experimental measurements (diamonds) of Muller et al. [8].
Dec) 1/2 in agreement with the prediction based on asymptotic analysis in the
limit D e --+ D e c. Figure 10 displays the dependence of the dominant frequency
and its harmonics on the Deborah number. The frequency tends to increase with
De almost linearly. Unlike the amplitude, the frequency exhibits a jump at the
critical Deborah number. This means that any initial weak velocity amplitude at
the onset of oscillatory TVF has a dominant frequency that is relatively easy to
detect. The agreement between the computed and measured frequencies is
obvious from the figure. The apparent growing disagreement for the higher
harmonics is to be expected. Any initial discrepancy at the dominant frequency
level is simply amplified as it is multiplied by two for the second harmonics, by
three for the third harmonics and so on.
A closer quantitative agreement between theory and experiment can hardly
be envisaged given, on the one hand, the uncertainty surrounding experimental
293
fl ~
f2 + .....
f3 [] ......
f4 x ...........
0.2 -
E T
x h X ....................
p e
e o X ...............
r r X .....................
l y
0.15 - m X ..........
e
"4" n
t ............................................................. []o.OO...o- . . I'. r.l. . . ..oo[] o o.o.--'"~176
b . o.O
.o~o.-OO~176
o
0.1 -
oO~176
..o" ........
0.05 -
I , I ,, l l_ I _. I I
0 "'
20 25 30 35 40 45 50 55 60
De
Fig. 10. Frequency diagram and comparison between theory (dashed line) and
experimental measurements (diamonds) of Muller et al. [8]. The figure shows
the square of the amplitude of axial velocity at x = 88 as a function of De.
conditions, and, on the other, the lack of a universal and accurate constitutive
model for viscoelastic fluids. The sources of discrepancy between theory and
experiment are related to limitations of both Newtonian and viscoelastic flow
formulations. The lack of a theory capable of predicting the value of the axial
wave number, k, constitutes a major difficulty. The prediction of the value of k
remains an unresolved issue (in a given formulation, it is usually simply imposed
from experimental observation). In the case of viscoelastic Taylor-Couette flow,
however, the measurement of k is difficult under transient flow conditions [9].
Other parameters and variables are also difficult to obtain from the experiment of
Muller et aL [9] and had to be deduced. Additional uncertainty originates from
the type of constitutive model used. Although the Oldroyd-B equation predicts
the behavior of constant viscosity highly elastic fluids, it does not incorporate the
spectrum of relaxation times that is characteristic of real fluids. More
294
problem, in the absence of inertia, using the direct method. In this case, the
eigenvalue problem is relatively simple to solve since only constant coefficients
are involved. Only two modes, given by (6), are retained in the approximate
solution, leading to good agreement with the exact solution, especially in the
lower wave number range. Comparison between the approximate solutions based
on rigid-rigid and rigid-flee boundary conditions indicates that the type of
boundary conditions used does not influence the overall stability picture. This
confirms the earlier conclusions reached in the case of a Newtonian fluid [34]. In
fact, most earlier results based on existing linear analyses are recovered (see fig.
2).
It is found that the critical Taylor number, Tao at the onset of axisymmetric
Taylor vortices, not only depends on the disturbance wave number, but also
decreases with increasing level of elasticity. At Ta - Ta c (r = rc), two
bifurcating steady-state solution branches C1 and C2 emerge, corresponding to
TVF in two opposite directions. These solutions lose their stability when the
Taylor number exceeds a critical value Tah (r = rh), coinciding with the birth of
a Hopf bifurcation. It is found that Tah also decreases with E. Thus, at least in
the absence of shear thinning, fluid elasticity appears to destabilize the base
flow, precipitating the onset o f Taylor vortices, which, in turn, tend to get
destabilized, leading (eventually) to chaotic motion, earlier in comparison with
the ease of a Newtonian fluid. The stability and bifurcation pictures are
summarized in fig. 2 for a UCM fluid.
The validity of the model is further assessed in the nonlinear regime by
examining the influence of higher-order modes, neglected in the previous model
[ 18], on the nontrivial steady-state solution branches C 1 and C2. The additional
modes stem from normal stress effects and are thus found to have most of their
influence on highly elastic flows, and are rather insignificant in the high
Reynolds number range or for a Newtonian fluid. Indeed, for a Newtonian or
weakly elastic fluid, the inclusion of the higher-order modes does not alter
significantly the results in both the linear and nonlinear (fig. 2) regimes.
From the analysis and numerical results based on the present model, fluid
elasticity appears to alter dramatically the flow behavior in comparison with the
flow of a Newtonian fluid. One of the most striking differences in flow behavior
between the two flows is the destabilization of the TVF for a viscoelastic fluid
that cannot be predicted on the basis of the (axisymmetric) Newtonian equations.
Thus, unlike the Newtonian model, the Oldroyd-B model predicts the onset of a
Hopf bifurcation (at Re = Reh) in the postcritical range of Reynolds or Taylor
number (Re > Rec). Hence, to the degree of the present truncation, the
Newtonian equations predict that the TVF is always stable regardless of the
297
value of the Reynolds or Taylor number. This is somewhat expected since, for a
Newtonian fluid, the destabilization of TVF coincides, in practice, with the loss
of axisymmetry. This coincidence does not seem to hold for viscoelastic fluids
[9]. If fluid elasticity is accounted for in the constitutive equation, a different
stability picture appears to emerge. In fact, linear stability analysis of the 20NDS
around the TVF leads to a characteristic equation (not presented in this chapter)
that happens to admit a pair of purely imaginary roots, coinciding with the birth
of a Hopf bifurcation at Re = Re h as discussed earlier. The value of Reh depends
strongly on fluid elasticity, fluid retardation and wave number as illustrated in
fig. 2.
In an effort to examine the role of inertia on the onset of TVF and its finite-
amplitude instability, numerical calculations are carried out at intermediate
elasticity level (E = 0.16) by varying the Deborah (or, equivalently, the
Reynolds) number. The results (shown in figs. 3-6) indicate that, for weakly
elastic flows, there is an exchange of stability at De = De c (Re = Rec) between
the base flow and TVF, through a supercritical bifurcation similar to that in
Newtonian fluids. At some point in the postcritical range (De > Dec), the steady
TVF loses its stability, in turn, as De (Re) is further increased to De = Deh (Re =
Reh) when a Hopf bifurcation sets in. The influence of shear rate (De) was
investigated experimentally by Baumert & Muller [9]. Their flow visualization
focused essentially on the early transient behavior once a shear rate is imposed.
They showed that steady TVF sets in after a period of monotonic or oscillatory
vortex growth depending on whether the imposed shear rate is low or high. The
results based on the present formulation lead to good qualitative agreement with
experiment and the nonlinear calculations of Avgousti et al. [28].
For a highly elastic fluid, of Elasticity number greater than the critical value,
Esub, the steady-state solution undergoes a subcritical bifurcation at Re = Rec
(fig. 2) similar to that predicted by the Landau-Ginzburg's equation [44]. In this
case, the range of stability of the TVF becomes increasingly narrower as E
increases, giving way to (time) oscillatory vortex structure. Indeed, beyond a
critical level of elasticity (E > 0.1 in fig. 2) and for vanishingly small Reynolds
number, the base flow loses its stability to oscillatory and not to steady TVF.
This prediction confirms the experimental observation of Muller et al. [8].
Unlike the previous model [18], the present system led to favorable comparison
with experiment (figs. 7 and 8). The present theory predicts the sequence of
periodic behaviors observed as the Deborah number is increased: (1) loss of
stability of the base flow to an oscillatory flow at a critical Deborah number (Dec
= 29.3 and 29.7 for the RF and RR formulations, respectively, as predicted by the
model vs. 32 from experiment), (2) growth of amplitude of the velocity signature
298
like (De - Dec) 1/2, in agreement with asymptotic analysis, with the
emergence of higher harmonics in the Fourier spectrum, and (3) emergence
of subharmonics as De is further increased, reflecting (most likely) the
bifurcation into period doubling and, eventually, chaos.
Finally, an augmented twenty-dimensional dynamical system,
20NDS, is also used to describe highly elastic TVF. The model is derived
without inertia effect, and higher normal stress terms are added. This
approach constitutes a first systematic and accurate theoretical prediction
for the purely elastic overstability observed by Muller et al. [8]. It is shown
that the finite amplitude TVF can be effectively described if higher-order
normal stress terms are properly accounted for. Particularly, the addition of
the azimuthal normal stress component leads to additional coupling with
higher-order eigenmodes that are of O(eDe). The resulting nonlinear
dynamical system involves only twenty degrees of freedom. The sequence
of flows predicted by the present model is comparable to that reported by
Muller et al. [8]. The model predicts the sequence of periodic behaviors
observed as the Deborah number is increased: (1) loss of stability of the
base flow to an oscillatory flow at a critical Deborah number (Dec = 32 as
predicted by the model vs. 32.3 from experiment), (2) growth of amplitude
of the velocity signature like (De - Dec) 1/2, in agreement with asymptotic
analysis, and (3) the emergence of higher harmonics in the Fourier spectrum
as De is further increased [ 19].
REFERENCES
1. INTRODUCTION
Re -
-
pND2 (1)
77
where p and 1] are the fluid density and dynamic viscosity respectively, N is
the rotational speed of the impeller and D its diameter. Below Re = 10, the
viscous effects predominate, yielding a quasi-creeping flow. The mixing
regime is laminar. At the other end of the Reynolds number scale, the
mixing regime is turbulent. Depending on the impeller, the turbulence
303
vessel. In the first category, there are radial discharge impellers (flat
turbine), axial discharge impellers (propellers) and tangential flow impellers
(anchors). If the diameter of an impeller is significantly smaller than the
diameter of the vessel, this impeller is an open impeller. On the contrary, if
the impeller exerts a scraping action at the vessel wall, it is called a close-
clearance impeller. We show in Figure 1 typical examples of open and
close-clearance impellers.
Figure 1: Flat blade turbine (open impeller) and helical ribbon screw (close-
clearance impeller)
In industry, the use of empirical correlations has been the standard for
the design of mixing systems. Nowadays, stringent process efficiency
requirements make the use of pilot experiments in association with
computer modelling an essential step of the development phase. From the
formulation developed in the laboratory by the chemists, the process is first
developed at pilot scale (typically 200 to 500 1) and then some scale-up
guidelines are used to design the industrial unit. Computer modeling can be
used at both steps, for the pilot scale and for the eventual production line.
The selection of the mixing scale-up criteria to be used for the design
of industrial facilities is an open issue. The fundamental question to address
is how a process changes when the scale is changed, the objective being
obviously to maintain process similarity irrespective of the scale.
There are two broad classes of similarity: flow and transport
phenomena. Flow similarity may involve the geometry (shape similarity),
the kinematics (speed similarity) and the dynamics (force similarity). As for
307
3. NON-NEWTONIAN MIXING F L O W S
Equation (4) gives the shear rate at the inner rotating cylinder (or
impeller):
I 1-(rl[r2)a/n2)1[ 2or2]
nO-(r, l r 2 r22-rl 2
(4)
7, - 4n:N 1 (5)
n
309
2 ~2 r 2 I (6)
~/ ~ 2 2
r 2 -- r1
The flow patterns around mixing impellers are fairly complex and the
controlling factors of the drag on an impeller are difficult to appraise. In
practice, simplified flow situations are used to estimate the viscous energy
dissipation, and then deduce the drag or power requirements. In non-
Newtonian mixing technology, the flow model around an impeller blade
must obviously include the shearing rates or shearing stresses. This is a
direct consequence of the fact that the viscosity of these fluids to an
imposed stress is not constant but depends on the magnitude of the
deformation rate.
The knowledge of shear rates in stirred mixing tanks is central to
power input calculations and equipment scale-up. Empirical and theoretical
approaches have been developed in the literature to estimate shear rates. In
the following paragraphs, these approaches are discussed and compared.
It is worth noting here that equation (7) is only valid for laminar
mixing, although it has been used for the transition regime. The value of Ks
is typically estimated by performing duplicate power input measurements,
one with a Newtonian fluid and one with a non-Newtonian fluid, in the
same mixing system. Thus, if the rheological behavior of the fluid is
expressed by a power-law model, then, from the experimental Newtonian
power input curve, at fixed N, an apparent or effective viscosity defined as:
is calculated by:
(9)
770-77
where 1"1is the Newtonian viscosity, PnN and PN are the non-Newtonian and
Newtonian power respectively.
From the apparent viscosity calculated in equation (9), the
corresponding value of )'av is estimated by equation (8). Upon repeating this
procedure for pairs of (N, ~/av)values, the value of Ks is determined.
It is worth nothing here that as n tends towards the limiting
Newtonian case (n=l), equation (5) gives 7 = 41-IN = 12.6N or Ks = 12.6.
This is very close to the universal value of Ks = 13, originally proposed in
the literature [9] for several fiat-blade turbines.
The Metzner-Otto correlation has been extensively used to
characterize the average shear rates of non-Newtonian inelastic fluids [ 10],
and it is routinely recommended as a standard procedure in mixing and unit
operations textbooks. This algorithm is considered a useful approach for
the estimate of hydrodynamic similarities on scale-up although it might not
represent the rheological properties existing in the mixing vessel. It is a
current practice to consider Ks as a constant for given impeller geometry.
However, some authors have reported that this constant might depend on the
power law index [11][12][13], in particular for highly shear thinning fluids.
A compilation of experimental Ks values for helical ribbon (HR) and helical
ribbon screw (HRS) impellers is shown in Table 3.
A detailed analysis on the correlations proposed for Ks clearly shows
that the effect of wall clearance might be the most important one. The value
of Ks increases as the wall clearance decreases and this becomes more
pronounced as the ratio r~/r2 approaches the limiting value of 1.0.
311
i
Type , D/d n Ks Comments
The authors used the Couette flow analogy to describe the highly
sheared zone substituting the impeller by a solid cylinder. Setting as a
characteristic fluid velocity the tip speed velocity ND, a particular form of
the Reynolds number for power law fluids was proposed:
pN2-nD2
R e p~ = K (10)
10 8 -- i. l I I I I I I I ' ' ' ' ' ' ' 1 ' ' ' ' ' ' ' ' 1 ' ' ' ' ' ' ' ' 1
_
-
_ Q
-
10 5 - "'..
.%
_
_
_
10 4 _--
"O
_
o ~ e o
Z _
10 3 _-
_
_
[] n = 1.0 (Newtonian) "'-.O.'.-.+ :-:
_ * n = 0.77 ~-~"
-, . . _
_
/x n = 0.70 ' O . ~I k . ' & ..
i
0 n = 0.5 3 " "',II~"Lx "J,
10 2 "O "'', " .
_ 9 n = 0.28 6A-
_
I I I I I I 'll I I I ' ' ' I l l I I I , , , , , I I i n i i i n i l -
1 0 .4 1 0 .3 1 0 .2 1 0 ~ 1 0 ~
Repl
_ P
Np Repl - - KN,,+~ 9 3 "- K p (n) - Kp(n=l) Ks n-1 (13)
314
or
Ks- mN--2-+]d3
1
II- Kp(n)
gp
n-1
1
(14)
G e l l a n 1.5 %
Xanthan 3%
180 X a n t h a n 2 % - C M C 1% J '
Xanthan 1.5%-CMC 1.5%
160 - Xanthan 1.75%-CMC 1.25%
Q Xanthan 1.65%-CMC 1.35% //
/
140 - 9 Xanthan I%-CMC 2% /
/
[] CMC 2.5% / /
120 - A CMC 1.5% /
Newtonian fluids /
100 -
Kp - -
a=
80 -
/
60
40
20 -
0 , I , I , I = I ,
0.0 0.2 0.4 0.6 0.8 1.0
Figure 4. Variation of the power constant with the power law index
10 6
dl
10 5 - 1
Np Re = 162.55 -!
[exp. Newtonian correlation]-
U3
"=t
10 4 -
Z
Q.
II 10 3 -
Z
9 Xanthan 3 % "~1~
-i
9 Gellan 1.5% ' ,I~~,
10 2 - 9 Xanthan 2%-CMC 1%
9 Xanthan 1.5%-CMC 1.5% Orn
9 Xanthan 1.75%-CMC 1.25%
[] CMC 2.5%
I I I I I I I
10 ~
10-3 1 0 -2 10 1 10 ~ 10 ~
It is worth noting that the functional form of equation (14) makes the
Ks function very sensitive to small variations in power consumption
measurements, particularly in the highly shear thinning region (0.5 < n).
This is illustrated in Figure 6 for a power measurement uncertainty of 10%.
It can be seen that the interpretation of the results on the actual value
of Ks is delicate. With the measurement uncertainty, all conclusions are
possible: Ks may be taken either as a constant (independent of the fluid
rheological properties), or as a decreasing or even an increasing function of
the flow index. The most significant variations of Ks are found in the highly
shear thinning region, 0.1 < n < 0.5. Undoubtedly, these results shed some
light on the apparent opposite findings shown in Table 3. In the opinion of
the present authors, the differences found in the literature could be easily
explained if the impact of experimental errors on power measurements had
been fully accounted for.
316
40 ''''1''''~'''1''''1''''1''''1''''1''''1''''1'''
35 \
c=l.1
30 -.
~Oo
c=l.O
25
20
/ c = 0.913 (exp. data)
15
10
5 i ,,,I,,,,I,,,,I,,,,I,,,,I,,,,I,,,,I,,,,I,,,,I,,,,
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P - z ( 2 ~ N ) - 2~rbNFdo (15)
where rb is the radius of the impeller blade, and Fd0 the drag force in the 9
direction. The drag force can be written in terms of the drag coefficient, Cd,
as"
317
( l pVo2~
F d - C d -~ (16)
fdivv = 0
-, (Irl)r
(17)
where v is the velocity vector, p the pressure, r the radial coordinate and
~0the angular velocity. The symbol o denotes the standard vector product.
This equation is written without considering the unsteady term. This
approach is valid provided the flow in the Eulerian viewpoint is periodic.
For completeness, the viscosity function in equation (17) must be made
explicit with a rheological model. Typical models used in mixing
simulations include the Newtonian model (constant viscosity), shear-
thinning (power law and Carreau models) and yield stress (Herschel-
Bulkey) fluids.
318
where K is the consistency index and the n the shear-thinning index. These
parameters can be readily obtained by performing a logarithmic regression
on the flow curve.
Carreau model
where 7/0 is the zero-shear viscosity, r/_ the high-shear viscosity, t, a fluid
characteristics time and s the slope of the viscosity curve. This slope is
related to the shear-thinning index of the power-law model by s = (1- n)/2.
Herschel-Bulkley model
TO 2 (n-l)/2 (19)
r/~'l)- 21/217,--~+ Klrl" '
where ~:0 is the yield stress, K the consistency index and n the shear-
thinning index. When the viscosity of the fluid is constant, the familiar
B ingham model is obtained:
TO
rTOy])-~21,2it
+ r ]
I (20)
The last boundary condition implies that the free surface in the vessel
is fiat. Experience shows that this assumption is valid in viscous mixing.
319
The above equations are solved using the Galerkine finite element
method. Let us recall briefly the principle of this method. We first rewrite
the equations of motion using tensor notations, namely:
f div FI = f (21)
div V = 0
II = - P 5 + 271)'
With help of the variational calculus, these equations may be written
as a saddle-point problem, namely:
fb(v, O) - O, V O e L 2 ( a )
a (v, N) - ~a/1 grad v grad N d ~
(u, v) - ~~ uvdf~
(23)
(24)
art elements [31]. Tetrahedral elements are a much better choice than
quadrilateral elements for several reasons:
9 they are more flexible for unstructured grids
9 their accuracy suffers less from distortion
9 they are less costly to use that their equal-order quadrilateral counterpart.
A
rv
i+1
--
BT p i = F
A r = A + rB rB (25)
pi+l _ p i _ r n v i + l
where A and B are the elliptic (viscous) matrix and the divergence matrix
respectively and r is the penalty parameter. The reader is referred to [32] or
an advanced textbook on finite element methods in fluid flow problems for
a detailed exposure of the above principles.
For very viscous fluids and pastes, a single impeller may not be
sufficient to mix the media and stagnant regions may occupy most of the
vessel volume. In such a case, multiple impeller kneaders and planetary
mixers must be used.
The fluid mechanics of mixing inside a planetary mixer is much more
complex than with a single impeller. From a simulation standpoint, the
complexity arises from the fact that there is no symmetry of revolution
usable to simplify the flow description. The most convenient viewpoint for
flow description is the classical Eulerian viewpoint of the laboratory and the
problem must be dealt as fully transient.
In order to tackle kneading flows, a new approach has been
developed called the virtual finite element method [33]. This method is
nothing but a subset of the broad category of domain imbedding finite
element method. In short, the idea is to represent in the volumic finite
element mesh, the impeller as kinematics constraints. For this purpose, the
impeller is discretized with control points on which the kinematics is
known. Then these additional constraints are implemented into the finite
element discretization. Mathematical optimization methods (penalty method
and Lagrange multipliers) are used to enforce these constrainnts. The final
matrix problem is modified accordingly and an extra step is required to
update the Lagrange multiplier iteratively.
321
4. R E S U L T S A N D D I S C U S S I O N
D s = 0.013 rn
W=0.03 m
C = 0.0125 m
P = 0 . 1 8 5 rn H = 0.24 m
D = 0.210 m ~I
1111111
I ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
. . . . . . . . . 9...............
.............. .~
~ ...........
...................
.:....... ,~~....
..... ~~-.:---i--!"-i/
........ :...,......
.................. ' ........... ' ....... ~. . . . . . : . . . . . ~ . . . . i . . . ~ . . x..:" ................... : ........... c. . . . . . . .~ . . . . . . . . . . . ~ . . . ~ . . . . ~ . . . : . .
. . . . . . . . . . . . .9. . . ..:~ . .. . ... . ... .: . . . . . . . . ,. .~. ., .: : ~ . . . . 1 .~. . *: . ..' . :. i .!. ' :~ . . . . . -. . . . . . . . . . . . . . :i . . . . . . . . . . . ,~: . . . . . . :" . . . . 2~. . . d . , . .:~ . . . ~ .: . J . - : "
................. ~........ ..~.-.~ ..... i--..;...,..,..--~. .................. .:. ....... ~........ --...*...+.--t---~--.,--
i---i-
10 tf
0.10
i
1.00
i! iii i 1 10.00
Re.
F i g u r e 8: P o w e r c u r v e in the l a m i n a r m i x i n g r e g i m e
W e p r e s e n t in F i g u r e 9 the i s o - s u r f a c e ( s u r f a c e o f c o n s t a n t v a l u e s ) o f
the p r o c e s s v i s c o s i t y for the s a m e C M C s o l u t i o n a n d a r o t a t i o n a l s p e e d o f
10 R P M . In this case, a v a l u e o f 3.37 s -~ w a s o b t a i n e d for the e f f e c t i v e rate-
o f - d e f o r m a t i o n y i e l d i n g a p r o c e s s v i s c o s i t y v a l u e o f 4 . 8 6 Pa.s.
F i g u r e 9: L o c a t i o n o f the p r o c e s s v i s c o s i t y
323
It can be seen that the process viscosity is located along the impeller
blade and not in the gap between the ribbon and the wall, as it could be
expected with the Couette flow analogy. This is to our knowledge the first
time such a result is presented.
The numerical prediction of the variation of Kp(n) vs the shear-
thinning index is compared with the experimental results in Figure 10.
150
-.-e- numedcal 1
-..a-- experimental
100
:Z
50
Figure 10: Variation of the power constant with the power law index
It can be seen that Kp(n) does not vary linearly with n. Indeed,
although the slope is constant above n=0.6 as already noted in [ 17], the
slope tends to decrease for higher shear-thinning fluids. The same trend is
observed numerically and experimentally, although to a lesser extent in the
latter case. In Figure 10, there is a discrepancy between the numerical
predictions and the experimental determination of Kp for the lower values
of n. The difference could be imputable to the larger numerical errors
inherent to the evaluation of stiff velocity gradients in the simulation.
We present in Figure 1 l a a plot of the normalized angular velocity
Vz/(Vr 2 q- Vz2)1/2. It corresponds to an isometric view of the cross section
plane intersecting the central shaft. Figure 1 lb shows a top view of the same
field at mid-height. The spectrum goes from dark grey (small angular
velocity) to light grey (high angular velocity). These two figures were
obtained for the CMC solution (1.5 wt.%, room temperature) at N= 10 RPM.
In Figure 11 a, the downward pumping zone appears clearly in the vicinity of
the shaft, where the rotational speed is negligible.
324
//
,jJ
Figure 11" Pumping zone of the HR impeller - a) side view; b) top view
Figure 15 shows the pumping pattern in the vessel from the top. This
figure is another way of looking at the circulation pattern. The pumping
down region (on the left) covers most of the region confined within the
helical ribbons while the pumping up phenomenon is restricted to the ribbon
region only. The "Couette" cylinder appears remarkably.
The carousel to plain blade speed ratio and plain blade to hollow
blade speed ratio are both 0.5 by construction. The results shown hereafter
were obtained with a carousel speed of 15 RPM, a plain blade speed of 30
RPM and an hollow blade speed of 60 RPM.
Contrary to the previous close-clearance impellers, the kinematics of
the blades is such that no convenient simplifying frame of reference can be
used. The virtual finite element method is then required to tackle the flow
simulation.
We show in Figures 17a and 17b the typical flowfield in the kneading
vessel for an industrial cross-linked polymer. In Figure 17a, a detailed flow
pattern in the region of the blade is shown. Although the blade has a twisted
shape similar to a screw, the circulation appears rather horizontal, an
indication of a poor top-to-bottom pumping. Figure 17b shows the general
circulation pattern at mid-height in the kneader. Intense shearing appears
between the blades and in the clearance between the blade tips and the wall.
Far from the blade, the flow is slow and almost stagnant near the wall.
. . . . . . . . . . . . .
good as shown by the very chaotic trajectory patterns that covers most of the
cross-section surface of the vessel. This proves if necessary the relevance of
using more than one impeller to break the flow symmetry in viscous mixing,
and therefore enhance the process efficiency.
Figure 18: Dispersion pattern; left: side view; fight: top view.
5. CONCLUSION
ACKNOWLEDGMENTS
REFERENCES
25. Bourne J.R. and H. Butler, 1969, Trans. IChem. E., 47, T11.
26. Brito-de la Fuente E., L. Choplin, A. Tecante, and P.A. Tanguy, 1994,
in Progress and Trends in Rheology IV, C. Gallegos, J. Munoz and
M. Berjano (Eds.), Darmstad-Steinkopff, Germany, 272.
27. Brito-De La Fuente E., J.A. Nava, L. Medina, G. Ascanio and P.A.
Tanguy, 1996, Proc. XII International Congress on Rheology, A. Ait-
Kadi, J.M. Dealy, D.F. James and M.C. Williams (eds.), Canadian
Rheology Group, 672.
28. Patterson W.I., P.J. Carreau and C.Y. Yap, 1979, AIChE J., 25, 508.
29. Tatterson G.B., 1991, Fluid Mixing and Gas Dispersion in Agitated
Tanks, McGraw-Hill.
30. Tanguy P.A., R. Lacroix, F. Bertrand, L. Choplin and E. B rito-De La
Fuente, 1992, AIChE J., 38, 939.
31. Bertrand F., M. Gadbois and P.A. Tanguy, 1992, Int. J. Num. Meth.
Eng., 33, 1251.
32. Tanguy P., L. Choplin and M. Fortin, 1984, Int. J. Num. Meth. Fluids,
4, 441.
33. Bertrand F, P. A. Tanguy and F. Thibault, 1997, Int. J. Num. Meth.
Fluids, 25, 719.
331
1. I N T R O D U C T I O N
2. F O R M U L A T I O N
p ( ~ - + V- (uu)) - V . a , (2)
where t is the time, u is the velocity vector with components {u, v, w}, and
a the Cauchy stress tensor, given by
a = - p l + S, (3)
with p being the hydrostatic pressure, 1 the unit tensor, and S the "ex-
tra" stress tensor (not necessarily traceless), which is related to kinematic
quantities by an appropriate constitutive equation.
C o n s t i t u t i v e equations
In most studies, either a differential (Maxwell-type) or an integral consti-
tutive equation is used to model the fluid rheology. Integral constitutive
equations are less popular because of the need of particle tracking. A
review of constitutive equations, covering both microstructural and con-
tinuum view points is given in Huilgol and Phan-Thien [10]. Here, we will
be mainly concerned with the P T T model [10, 11], where the extra stress
tensor is written as
S - 2~ND + 7", (4)
where ~N is the Newtonian-contribution viscosity, D - (Vu + Vu T)/2 is
the strain rate tensor, with T denoting the transpose operation, and 7- is
the polymer_contribution stress, which evolves according to the following
constitutive equation
g r + A v = 2r/m0D' (5)
333
v Or
v - ~ + V - ( u ~ ' ) - (L - ~D)7" - v (L - ~D) T , (6)
and
Ae
g = 1 +--tr (r), (7)
r/m0
2.3 B o u n d a r y C o n d i t i o n s
To the set of governing equations one must add a set of relevant bound-
ary and initial conditions.
Slip or no-slip on a solid surface
The no-slip boundary condition at a solid surface is usually adopted in
most studies, where the fluid velocity assumes the velocity of the solid
surface. This assumption works well for viscous fluids, but there is a large
amount of experimental data suggesting that it may not be relevant for
polymeric liquids in some circumstances. There are extrusion experiments
with polymer melts [14-18], which suggest that wall slip may be responsible
for melt fracture. In these experiments, the occurrence of the extrudate
irregularities occurs above a critical wall shear stress, which is accompanied
by a fluctuation in the pressure drop. A phenomenological approach to the
slip boundary condition has been proposed by Pearson and Petrie [19]
where the slip velocity is taken as an empirical function of the wall shear
stress. A polymer network model has been proposed recently to account
for the dynamic slip velocity [20]. Here, we just simply adopted the no-slip
boundary condition at a solid surface, and note that real progress in this
area will be made by a careful consideration of the microstructure near a
solid surface. With this (Dirichlet) boundary condition, the velocity field
is prescribed as
u=u0, OnSu,
where u0 is known on the boundary S~.
Traction boundary conditions
Sometimes the traction vector is given on a part of the boundary, say St.
This type of (Neumann) boundary conditions take the form
t=er-n=t0, on St,
where t is the traction vector. This yields the normal traction,
tn " - - n - O ' - n -- --p + S- n = n - to, o n St, (12)
335
where [er] 9n - (er + - er-) 9n is the jump in the normal traction, with er +
being the stress on the positive side of n, and or- the stress on the negative
side of n, and q is the unit vector normal to the boundary curve AC, but
tangential to the interface AS. This is the mathematical statement of zero
force on AS. From Stokes' theorem, the surface integral over A C can be
done by parts,
(p- - p + ) n + (S + - S - ) . n + V 7 - 7 ( V . n ) n - 0. (16)
Note that the mean curvature of the surface is given by [21]
1 1
V n . . . ~~
. . (17)
R1 R2
Symmetry boundary conditions
Very often the computational domain can be reduced with the help of
symmetry, these sylmnetry boundary conditions are quite easy to state: a
plane of symmetry has no normal velocity component, and no tangential
stress (tangential tractions or vorticity are zero), i.e.,
u-n=O, t-t.nn=O, (18)
where t is the surface traction.
Inflow outflow boundary conditions
At the inflow to the solution domain, we know something about the flow,
usually the velocity field. For viscoelastic fluids, the stresses are also re-
quired there (in essence, these represent the information carried with the
fluid from its previous deformation history). Therefore, the boundary con-
ditions at the inlet are usually Dirichlet boundary conditions. Note that all
components of the stress cannot be arbitrarily prescribed. First, the stress
components should be consistent with the specified kinematics (but need
not be), otherwise steep stress boundary layers will be set up. Secondly, if
traction boundary conditions are also given there, then the traction com-
ponent tangential to the boundary would involve the stress components
alone without the pressure terms, and therefore these stress components
cannot be prescribed arbitrarily. Finally, Renardy [22] has pointed out
that specifying all the stress components at the inflow may lead to an
over-determined mathematical problem. It may be prudent in practice to
retain the time derivative terms in the (differential) constitutive equations,
337
= '1 -p + u. Vu + v. s + pb , on (20)
of initial values for the stress components is also needed. Note that the in-
compressibility constraint also forbids an impulsive start and stop, normal
to the boundary, since
fs u.n dS-O.
3. F I N I T E V O L U M E M E T H O D (FVM)
The finite volume method has been very popular in computational fluid
dynamics dealing with Euler and Navier-Stokes flow problems. There are
two main approaches in the finite volume method.
3.2 S I M P L E R - T y p e Methods
The second approach in finite volume method is much more popular and
forms the basis of some commercial packages dealing with Navier-Stokes
equations. The resulting algorithms are known as SIMPLE (Semi-Implicit
Method for Pressure-Linked Equations), SIMPLER (SIMPLE Revised) [4],
339
1. First, all of the governing equations are cast into the form of a general
transport equation:
a
AO(I)
-b-/- + 0 (Auk,I)) -
k +
where (I) is the dependent variable which can be a component of a
vector or a tensor and even a constant. The coefficients A, F have
different meanings for each different dependent variable, and Sr is
called the source term, which lumps all the terms that cannot be
accommodated in the convective and diffusion terms, and is specific
to the particular variable (I).
2. Next, the general transport equation is integrated over the control
volume surrounding the node, namely node P, in the flow domain and
the time interval St, using the divergence theorem whenever possible,
340
\Oxk]p
0
while the coefficients ai.j and ap0 take a form like (24) with F - 0, A - A,
and
SpJ - - A V [g )~ (1 - ~ ) [ - (dpi + dJpJ), 0]] - E sign(nb)Fnb, (29)
nb
where Fnb -- ()~uiA)nb can b e thought of being the "mass" flux passing
through the corresponding face A normal to i direction of the control vol-
ume. The term Esign(nb)Fnb in 5'~J is actually the continuity constraint
nb
which should approach zero when the solution converges.
342
where Dub -- ((~A/6xi)nb denotes the local diffusion conductance, and func-
tion f ( I D ~ b l ) h a s the different form for different schemes. For example,
\1 I/
1 05, ,
343
Thus, with the scheme adopted, the convective term of the equation
can be thought of being always discretised using upwind difference, and
the diffusion term is discretised using central difference, but the resulting
local diffusion conductances are different for different schemes used, that
is
' + [sign(nb)Fnb, O~ - anb
anb -- Dub d + anb
~ , (34)
with D'nb -- D ~ b - 0.5 IFnbl for central difference and D'nb -- Dub for upwind
difference. Here, we use anb d to denote the contribution of the artificial
diffusion term discretisation, and a~b the contribution of the convective
term discretisation, that is:
d _ D n' b ~ anb
anb c _ [sign(nb)Fn~, O~ (35)
To ensure all of the contributions to be positive, we need
!
with Dub -- IFnbl and ~; is an arbitrary constant satisfying ~; _> 0.5. This can
be thought of being the criterion for the proper selection of the artificial
diffusion coefficient c~.
Similarly, the source term will contain an extra artificial diffusion term
_ f z x u _ ~ko \(c~~176 dV, and central difference is applied for its discretisation.
The discretised form for the extra source term will have the form:
~dj -- _ y~ DnbTnb
_ij + "fp3 ~ Dub. (39)
nb nb
Thus, the final discretised constitutive equation can be cast into the
form
(ap T ad T apO_ ~ipj) ~ "" _ E (anb
c + adnb) Tub
ij + s~J 2t- ~d
-"j, (40)
nb
where
apC :~-~ anb
C
and a d :~--~ anb,d (41)
nb nb
344
where
~ d _.i j ~.d _--dj q_ ~adJ
Y~ t.nb.nb ~ t~p'i p
/~ __ nb (43)
(a~ + a ~ - ~ J ) + a d
W w_ , ' ..O" / _ G e E
- O- - ,-s- =0- - - I - @
""'P [
Figure 2" An unstructured finite volume mesh for a flow past a cylinder
in a channel.
In the figure, the lower case letter refers to the interface between two
neighbouring cells, e.g., e refers to the interface between the control vol-
umes for P and for E. One ends up having four different types of control
volumes, three for the velocity components, and one for the pressure. The
staggered grid is designed to eliminate the checker-board pattern in the
pressure field [4]. With structured mesh, a linear interpolation scheme is
often used, resulting in an O(h) accuracy, where h is a typical linear di-
mension of the control volume. Although one ends up with four different
types of control volumes (three for the three velocity components and one
for the pressure), structured mesh has been very popular because of the
ease in implementation; in addition, iterative solvers like the tri-diagonal
Thomas algorithm (TDMA) can be readily applied along the coordinate
lines defining the mesh. Structured mesh is not very suitable for complex
geometry, however.
To provide the flexibility in fitting complex computational domains, un-
structured non-staggered triangle mesh have been developed by a number
of authors, for example, Prakash and Patankar [37], Masson et al. [38],
and Davidson [39]. An example for such an unstructured mesh for the
two-dimensional flow past a cylinder in a channel is given in Fig. 2. To
retain the basic structure of the iterative line-by-line tri-diagonal Thomas
solver (TDMA), lines of nodes from the entry to the exit boundaries are
introduced (Huang et al. [32]). If this is not possible, then the line is ter-
minated in the domain. The nodal information (neighbouring ID's, etc.) is
stored in a sweeping line array. Similar to a re-ordering of the nodes in the
finite element method to minimise the bandwidth of the system matrix,
this array stores all the information needed for the line-by-line tridiagonal-
matrix algorithm, which only requires computer storage and computer time
346
of O(N), where N is the number of unknowns. The method has been used
successfully on viscoelastic flows between two eccentric cylinders [32], and
past a cylinder in a channel [36].
Solver
In the S I M P L E R method and most of its variants, the kinematics are
determined by solving the momentum equations, assuming that the pres-
sure field in known. The pressure correction is then applied, by enforcing
mass conservation [4]. For the viscoelastic flow computations, the source
terms containing the extra stress OEik/OXk in the momentum equations are
treated as pseudo-body forces with the known dynamics field obtained from
the previous time (or iteration) level by solving the discretised constitutive
equations.
In each cycle of the algorithm, no system matrix needs to be solved, and
the coupled discretised equations for the dependent variables are solved se-
quentially from an initial guess for all field variables (typically quiescent
field for Newtonian computations). For the momentum equations, two
T D M A sweeps are performed, and for pressure correction and stress equa-
tions, four T D M A sweeps. In the iterative procedure, the calculations of
velocities and stresses are under-relaxed by a global factor of 0.85 ~ 0.5
depending on the elastic level, but no relaxation is need for the pressure
calculation.
The convergence criterion for terminating the calculation is that the
integral residual of the discretised equations over all control volumes for
any dependent variable is less than the input tolerance, of the order 10 -6
10 -s, and the relative changes in the values of flow field (typically the
velocities) near the solid wall from one iteration to the next are of the
order 10 -5 ~ 10 -7.
For viscoelastic computations, the corresponding Newtonian result (A - 0)
is used as the initial guessed field, and Wi is increased gradually by in-
creasing A. The under-relaxation mechanism due to adding artificial dif-
fusion is very effective in the stabilisation of the calculations at high elas-
ticity. To speed up the convergence rate and save some C P U time, a
three-dimensional block T D M A solver can be used, see [30].
The two-dimensional implementation was done with both structured
and unstructured mesh. The three-dimensional version was implemented
with structured mesh only, as three-dimensional automatic unstructured
mesh generation is still an active area of research. Both versions have
been well tested with simple flow problems where analytical solutions exist,
including Couette and Poiseuille flows, and proved to be very robust. In
the 2D Poiseuille flow, there seems to be no upper limiting Weissenberg
347
4. F L O W P A S T A C Y L I N D E R
The flow past a cylinder in a channel has been well investigated, both
experimentally and numerically, and therefore is a good candidate to test
the finite volume method. Here, the flow past a cylinder, of radius R,
placed on the centreline, or offset from the centreline by a distance e in a
channel of width 2L, is considered. No-slip boundary conditions are applied
at the walls. Along the centreline symmetry conditions are applied. The
length of the downstream section is 9L, and that of the upstream section
is 6L. All distances are normalised by cylinder radius R. Having fixed
the model parameters and the problem geometry, the only parameter left
to vary is the average velocity U of the fluid at the channel entry. The
Deborah number (De) and Reynolds number (Re) are defined as
De = AU/R, Re = pRU/Vo. (45)
Dhahir and Walters [40] reported some experiments and finite element
calculations (using Polyflow TM) on the effects of viscoelasticity and of the
wall on the flow of non-Newtonian liquids past a cylinder confined by two
plane walls, with particular attention to the drag force on the cylinder. In-
ertia effects were neglected in the calculations, and they found the stream-
lines nearly independent of the mean flow rate. In addition, they also found
the streamlines to be essentially independent of the Weissenberg number,
at low values of the latter.
Flows past an asymmetrically confined cylinder have also been investi-
gated and the effect of the eccentricity on the drag force has been obtained
both numerically and experimentally. Baaijens et al. [41] investigated the
same flow of a shear thinning solution PIB/C14 both numerically and ex-
perimentally. A number of constitutive equations were used in their FEM
simulations, including the PTT, the Giesekus and the UCM models. The
field variables were compared to experimental values, along the centre line
348
and over cross sections of the channel. In general, there was a good agree-
ment between measured and computed field variables. Measured and com-
puted birefringence was also presented in [42] and a qualitative agreement
was found. The wall effects were considered by placing the cylinder off
the centreline, and it was found that the elongational thickening of the
viscoelastic fluid causes a significantly larger flow rate through the broader
gap compared with inelastic fluids. Barakos and Mitsoulis [43] investigated
viscoelastic flow past a cylinder symmetrically confined by two parallel
plates using a K-BKZ integral constitutive equation, using FEM with a
path tracking scheme. A good agreement between their results and those
of [41] was found. Huang and Feng [44] also reported some numerical re-
sults, using PolyflowTM, for the flow of the Oldroyd-B fluid past a confined
and non-confined cylinder, retaining inertial terms.
In the finite volume simulation, the computational domain is divided
into non-overlapping polygonal control volumes, as shown in Fig. 2, and
the SIMPLER algorithm is adopted for the UCM model.
First, the accuracy of the Newtonian calculations is assessed by com-
paring the drag coefficient defined by
K=
4~0UR'
where F~ is the axial force acting on the cylinder, with mesh refinement.
The extensive mesh refinement studies are performed with different meshes
by reducing both the polar mesh size hp and the maximum mesh size hm
according to Table 1. By comparing the results within and across mesh
groups, the refinement of the polar mesh size is found to play a more
important role in producing a more accurate solution. In the table, the
errors are calculated relative to the result of the finest mesh L4.
Polar Maximum
Mesh Nodes Drag Force Error
Mesh Size Mesh Size
M2 0.069813 0.4 1067 10.0634 0.03740
M4 0.0349065 0.2222 3434 10.3178 0.01306
M6 0.02617 0.1538 6504 10.3060 0.01419
M7 0.02416 0.1818 7711 10.2927 0.01546
N1 0.021 0.2566 2392 10.3260 0.01228
N2 0.0175 0.2566 2806 10.3313 0.01177
N3 0.00873 0.2566 4296 10.3513 9.86e-3
N4 0.00714 0.2566 4996 10.4172 3.55e-3
L1 0.021 0.127 6991 10.4306 2.27e-3
L3 0.00873 0.127 9695 10.4543 8.19e-7
L4 0.00714 0.127 10977 10.4543 0
349
Table 1" Drag force and relative error computed for a Newtonian fluid.
3000
E
Vo 1500
LI_ 1000
500
% 30 40 50 60 70 80
FLOWRATE (cma/s)
Figure 3: A comparison between the FVM (symbols) and the FEM
results of Dhahir and Walters (solid and dotted lines).
' F
4- - 4[- '- 4- -
2 2
+ . ~
o ' :~.~
a
o,.-~-
~. Iz~.z-a o ~a
-2 - 2 .~--- . q -
9 , b
,I, _ -,JI I. I
. . . . . . . . . I"" -6 '" " " " . . . . . . . . . . .
-6_ -1 o 12 ~ 1 2 6-2 lo 12
Figure 4: A comparison between the computed (FVM: solid lines, FEM:
triangles and squares) and experiment (circle) results by H. Baaijens [42]
along several cross sections for P T T fluid with A - 0.0431 s, p - 0.8
g/cm 3 and e - 0.39. Left: axial velocity, middle: normal stress difference
and right: shear stress. The shear rate at entry is so chosen that
D e - 2.31.
We have chosen the same geometry, with L = 5/3R, and 2113 control
volumes were used over the full flow domain. Using the UCM model, the
force per unit length on the cylinder is computed at varying flow rates
and two values of A (0.0 and 0.06 s). Inertia effects are neglected by
assuming creeping flow. Figure 3 displays the variation of normalised force
components F* - F = / % (cm2/s) with the flow rate. The Deborah number
at the highest flow rate of 80 cm2/s is 0.64. It is seen that F= increases
with the flow rate in both Newtonian (A - 0) and UCM (A - 0.06 s) cases.
Increasing elasticity reduces the force on the cylinder. The direction of
the force is along the flow direction, as it must. The drag force in both
the Newtonian and UCM cases are in excellent agreement with the F E M
results of Dhahir and Walters [40].
The flow of a 5% P I B / C 1 4 solution past a symmetrically confined cylin-
der between two plates of a distance 2L apart is simulated. Following [41],
the P T T model is chosen. The density of the liquid is taken into account
and fixed at 0.8 g / c m 3, the relaxation time is fixed at 0.04313 s and P T T
351
5. T H R E E - D I M E N S I O N A L ENTRY FLOW
In the study of the entry flow problem, two types of the cross-sections,
circular and rectangular, are of particular interest. The corresponding flows
are referred to as axi-symmetric contraction and planar contraction flows,
respectively. A large number of experimental works and two-dimensional
numerical simulations on the flow behavior of various types of viscoelastic
fluids in both types of geometry have been performed. Most earlier work
has been reviewed in the literature (see, for example [47-49]). Here, we
352
3 4 1 2 3 4 3
(a) w =0.82 (b) W = 1.29 (c) w.-- 2.75
Figure 6: Streamlines for the Boger fluids fitted using the UCM model
with different elasticity under the same flow condition (Re - 2.1), (a)
W~ - 0.82; (b) We - 1.92; (a) We - 2.75. The aspect ratio is one.
In the axi-symmetric contraction flow for Newtonian fluids, it has been
clearly shown experimentally and computationally [50-51] that the pres-
ence (or absence) of the upstream corner vortex is determined by fluid
inertia only.
353
0.05 IIII II t i t
w. -- 3.40E-3 1/
0.00
- - ~ -~~;'[2 / / //
-0.05
- - - .----'m -
(a)
_ ItfJJ,{tf /I
0.05 Wmi. -8.73E-3 lilltfltt/t
li i/ /
0.00
(b)
0.05
Wm.~n--- 2 . 1 4 E - 2
0.00 ........
, --..----
-'--'7"--
(c)
shear properties alone is not adequate to explain the different behavior for
different viscoelastic fluids. It was argued that the extensional behavior
of the fluid plays a more important role on the vortex activities for vis-
coelastic fluids: strong vortex enhancement is expected to occur for fluids
with strain-rate thickening extensional viscosity; on the other hand, strain-
rate thinning extensional viscosity will reduce the strength of the vortex
activity [55-56].
In contrast to the axi-symmetric contraction flow, where a strong vor-
tex enhancement is expected for some Boger fluids, the vortex activity is
weak in planar contraction flows [57-59]; only under some extreme flow
conditions [53] does a lip vortex appear. While for some shear thinning
viscoelastic fluids, such as polyacrylamide aqueous (PAA) solutions, vortex
growth has been observed in both cases. More remarkably, at very high
flow rates, a non-trivial 3D unstable and alternate flow pattern is observed
40 - . , - . , - - , . . . . , - - 140 . . . .
-= we = 0.4 r We = 0.4
30 We = 1.88 We = 1.88
15
4O
20
o ..............
the half height and the mean flow rate in the downstream channel, respec-
tively. As we can seen from the figure, there is virtually no corner vortex,
which is in good agreement with experimental observation. However, upon
close-up inspection of the streamlines near the re-entrant corner, as shown
in Fig. 7, there exists a tiny lip vortex which spreads over several meshes
and increases in both size and strength with increasing fluid elasticity. AI-
though the lip vortex feature for Boger fluids in planar abrupt contraction
flows was observed only at very high elasticity (We at order of 100) in the
flow geometry with higher contraction ratio [53], the trend of our simu-
lation results is consistent with the experimental observation. There may
be two plausible reasons for the discrepancies. First, the lip vortex may
be very hard to discern in the flow visualisation due to its being small in
size. Secondly, the UCM model may not have all the relevant physics in
complex flows of Boger fluids.
Recently, Quinzani et al. [61] measured the detailed flow fields of a well-
characterised shear-thinning polymer solution (polyisobutylene dissolved
in tetradecane (PIB/C14)) flowing in a 3.97:1 planar abrupt contraction
with the Laser-Doppler velocimetry (LDV) and flow-induced birefringence
(FIB). Their experimental results have been partly simulated by some 2D
numerical simulations with the fluid modelled by an integral K-BKZ equa-
tion with a spectrum of four relaxation times [62], and by multi-mode PTT,
Giesekus and UCM models [63]. All of the simulations showed a good gen-
eral qualitative agreement with experimental data. But the agreement is
still semi-quantitative, especially for the extensional stress near the entry
section (up to 30 - 40% discrepancy depending on the level of elasticity).
The PIB/C14 shear-thinning solution used in the experiment work has
been well characterised by Quinzani [64] with several non-linear multi-mode
models, and they found that the best quantitative fit to the transient exten-
sional viscosity could be made using the P T T model with p - 0.8 g/cm 3,
/~ 1, ~0 - 1.424 Pa.s, A - 0.06 s, ~ - 0 (or 0.1), ~ - 0.25 (or 0.05). A
-
finite volume simulation has been performed with these parameters using a
graded mesh. A comparison between the computed values for the centreline
velocity (w), and the first normal stress difference (centreline birefringence)
is shown in Fig. 8. Generally, the numerical results agree reasonably with
experimental data; however, the peak values predicted for N1 are 20-40%
higher than the observed values (depending on (). The discrepancies are
believed to be mainly due to the inadequacy of the constitutive model.
356
6. C O N C L U S I O N S
The results of the finite volume calculations presented here are rather
encouraging for computations of complex flow with arbitrary geometry.
The method is very robust, allowing converged solutions to be obtained
at a high Weissenberg number. The results also compare favourably with
those obtained with traditional finite element methods. In addition, the
use of unstructured mesh allows us to handle more complex computational
domain, much the same way as the finite element method. Coupled with
"both-side" diffusion, which is basically an under-relaxation mechanism,
the finite volume method appears to us a valid way of computing stable
solutions at high Weissenberg number.
ACKNOWLEDGEMENTS
This research is supported by then Australian Research Council (ARC).
The calculations were performed using the facility of Sydney Distributed
Computing Laboratory (SyDCom).
REFERENCES
1. M.J. Crochet, A.R. Davies, and K. Walters, Numerical Solution of
Non-Newtonian Flow, Elsevier, Amsterdam, 1984.
2. J.N. Reddy and D.K. Gartling, The Finite Element Method in Heat
Transfer and Fluid Dynamics, CRC Press, Florida, 1994.
3. N. Phan-Thien and S. Kim, Microstructure in Elastic Media: Princi-
ples and Computational Methods, Oxford University Press, New York,
1994.
4. S.V. Patankar, Numerical Heat Transfer and Fluid Flow, Hemisphere
Publishing Corporation, New York, 1980.
5. M.A. Mendelson, P.-W. Yeh, R.A. Brown and R.C. Armstrong, J.
Non-Newtonian Fluid Mech., 10 (1982) 31.
6. J.M. Marchal and M.J. Crochet, J. Non-Newtonian Fluid Mech., 26
(1987) 77.
7. R.C. King, M.R. Apelian, R.C. Armstrong and R.A. Brown, J. Non-
Newtonian Fluid Mech., 29 (1988) 147.
8. D. Rajagopalan, R.C. Armstrong and R.A. Brown, J. Non-Newtonian
Fluid Mech., 36 (1990) 159.
9. J. Sun, N. Phan-Thien and R.I. Tanner, J. Non-Newtonian Fluid
Mech., 65 (1996) 75-91.
357
S E G R E G A T E D F O R M U L A T I O N S IN C O M P U T A T I O N A L
ASPECTS OF C O M P L E X V I S C O E L A S T I C F L O W S
1. INTRODUCTION
In the last decade, several coupled finite element methods have been devel-
oped for the solution of viscoelastic flow problems. They include the sub-ele-
ment method of Marchal and Crochet [6], the explicitly elliptic momentum
equation (EEME) method of King et al. [7], and the elastic-viscous split-stress
(EVSS) method of Rajagopalan et al. [8]. These techniques enabled the re-
searchers to develop f'mite element methods that were stable enough to obtain
converged solutions at Weissenberg numbers as high as possible. It seems that
the success of all these strategies resulted from applications of streamline up-
winding technique to the constitutive equations of hyperbolic type. However, it
is noted that these finite element methods were based on fully coupled algo-
rithms, in which the velocity, pressure and stress were solved simultaneously.
In addition, they were restricted to very simple geometries requiting modest
number of elements even with supercomputers. For example, in one of the cal-
culations reported in [6], the degrees of freedom for stresses were 14116 with
a mesh containing 210 elements.
In the meantime, another group of researchers have studied viscoelastic
flows in terms of decoupled strategies, in which the velocity, pressure and
stress are solved separately. In decoupled algorithms, the momentum equation
is solved separately from the constitutive equation, which is significantly less
expensive than their coupled counterparts. Decoupled technique is also a natu-
ral choice for integral viscoelastic models since it is not a simple task to devise
coupled algorithms for them [9]. Furthermore, a properly constructed decou-
pled scheme should in general have a larger radius of convergence than a cou-
pled scheme which often relies on Newton type iterations [10]. The numerical
accuracy and computer efficiency of a decoupled algorithm depends on three
aspects: (i) solution of the constitutive equation subject to a given velocity
field; (ii) solution of the Navier-Stokes equation subject to a given viscoelastic
stress field; (iii) the way how the two equations are decoupled.
There has been a traditional difficulty associated with solving the Navier-
Stokes equation for an incompressible flow, that is, the incompressibility con-
straint, or the coupling of the pressure and velocity. For an incompressible
flow, the continuity equation in itself does not have an explicit reference to the
pressure. Therefore, a pressure equation, which enables the segregation of the
solution procedure for the pressure from that for the velocity, must be devised
by some further manipulation of the governing equations. A very well-known
way of devising such an equation is the SIMPLE (semi-implicit method for
363
pressure linked equations) algorithm [11] used in the finite volume methods.
Another approach calls for a 'pressure correction', in which an initially
guessed pressure is corrected successively at each iteration by adding the pres-
sure correction obtained from the associated equation. This pressure correction
is also common to artificial compressibility [12] and augmented Lagrangian
[13, 14] techniques. In the framework of the FEM, this difficulty can be easily
overcome by using integrated formulations in which the velocity and the pres-
sure are obtained simultaneously. However, the global matrices become in-
evitably larger than those of the segregated formulations. Therefore, in segre-
gated formulations, one can save more memory and CPU time since the pres-
sure is obtained separately from the momentum equation.
Some time ago, Boger [15] pointed out that, experimentally, flows in two-
dimensional geometries tend to become time-dependent and three-dimensional
when viscoelasticity is important [16]. As was also discussed in the work of
Evans and Waiters [17], concerning the lip-vortex mechanism of vortex en-
hancement in planar contraction flows, it is clear that any numerical simulation
aimed at predicting the vortex growth in such flows should also be extended to
three space dimensions and time dependent behaviour. These features of the
flow have to be taken into account in the numerical simulation of such flows
[18]. Recent researches pay more and more attention to computationally effi-
cient algorithms, since the flows of recent interest are ultimately three-dimen-
sional and time dependent [16]. Decoupled and segregated methods, which
deemed insufficiently accurate when they first appeared, have been developed
so that they now can produce credible results. Furthermore they remain very
attractive because of significantly reduced core memory and CPU time re-
quirement, which are crucial in transient and three-dimensional problems.
The objectives of the present article are to examine the segregated formula-
tions currently adopted in numerical simulations of viscoelastic flows and to
discuss the possibilities of emerging algorithms. To avoid possible confusions
in the usage of terminologies in this article, the term 'decoupled' is to be used
for the decoupling of the extra stress into the viscoelastic component and the
optional Newtonian component as they appear in the momentum equations
(Keunings [9]), and the term 'segregatea~ is now used for the segregation of the
pressure from the momentum equations. In section 2, governing equations for
viscoelastic flows in conjunction with basic decoupled techniques for the extra-
stress are presented. In section 3, several strategies handling the hyperbolic
364
2. G O V E R N I N G EQUATIONS FOR V I S C O E L A S T I C F L O W S
V.u=O, (1)
~gu
(2)
v
r+A,~=2r/d, (3)
where u is the velocity, p is the pressure, d is the rate of strain, lr is the extra
stress, p is the density,/7 and A, are the viscosity and relaxation time, respec-
tively, and v denotes the upper-convected derivative def'med by
v 9
lr = - ~ + u . V l r - V u r . l r - lr. V u . (4)
When equations (3) and (4) are taken in conjunction with the momentum
equation (2) and the continuity equation (1), it is apparent that the extra-stress
components have to be calculated together with the velocity components and
the pressure. The concept of the decoupled method is based on splitting the
extra-stress into the Newtonian part and the viscoelastic part as
r=2rld+ (5)
365
By substituting equation (5) into equations (2) and (3), the momentum and
constitutive equations are now written as
81/
P-~ (6)
v v
I'E + A,l-e = - 2 ~ r/d . (7)
The above alternative formulation was first introduced by Perera and Wai-
ters [19-20], Mendelson et al. [21] and Crochet and Keunings [22]. This was
further modified by Rajagopalan et al. [8] to construct the elastic-viscous split
stress (EVSS) formulation, which is categorized as a coupled method. In this
coupled formulation of the EVSS, the convected derivative of d in the
Galerkin discrete form of equation (7) involves second-order spatial deriva-
tives of the interpolating function ~, which can be eliminated by performing
v
an integration by parts on the term O d, with the resulting boundary integral
containing the flux of d through the boundary. In a decoupled formulation,
however, this complication may be avoided by first calculating r/d at node
points from the known velocity field and then consistently interpolating r/d (as
part of the extra stress) in the same manner as 1:~ [10].
Now, the momentum equation turns out to be the Navier-Stokes equation
with a pseudo-body-force V. ~:~,so that the solution always reduces to that of a
Newtonian flow when A, vanishes. The velocity and the pressure can be ob-
tained by solving equation (6) with the continuity equation in the given stress
field, and the stress can be obtained by solving equation (7) in the given veloc-
ity field, iteratively. The main disadvantage of decoupled techniques lies in the
iterative procedure because Picard schemes usually used in decoupled methods
are often slow in convergence, which is not even guaranteed no matter how
closely the initial estimates are chosen to the solution. However the decoupled
technique generally requires less core memory than a coupled method, which
turns out to be more efficient for larger computations.
Another attractive feature of decoupled methods is the breakup of the
problem into the solution of an elliptic Newtonian-like flow with pseudo-body-
force, and the integration of constitutive equations using fixed flow kinematics.
366
3.1 Background
The main difficulty in dealing with the constitutive equation (7) is that its
type is hyperbolic. Even though this advection equation is linear in the stress
with its structure being much simpler than the Navier-Stokes equation, it is still
a challenge to computation because the advection equation has no built-in
mechanism to smooth discontinuities in directions normal to the flow [23]. This
problem is similar to that encountered in high Reynolds number flows of
Newtonian fluids where high velocity along streamlines generate wild oscilla-
tions in the numerical solution. Before the advancement of the upwinding
technique, the only way to eliminate these oscillations seemed to be to refine
the mesh, such that convection was made not to be dominant on an element
level. However, Keunings [24] showed in a study on the high Weissenberg
number problem that the use of a very f'me mesh rather reduced significantly
the range of the Weissenberg number for which the viscoelastic solutions could
be obtained. It is because the local Peclet number, which represents the ratio of
the convection to the diffi~ion, remains to be infinite from equation (7), no
matter how we ref'me the mesh. Furthermore, it is reminded that one must cal-
culate the stress closer to the comer singularity with a f'mer mesh in the case of
the problem involving corner singularity, such as the 4:1 contraction flow
problem.
dicular to the flow direction. The basic idea of the streamline upwind method
is to add diffusion which acts only in the flow direction. Although the SUPG
method has been highly successful in solving the Navier-Stokes equations for
Newtonian flows, it was never introduced into solving the constitutive equa-
tions of the viscoelastic flows, until the first attempt was made by Marchal and
Crochet [6] who adapted the SUPG method for their coupled method.
Following Brooks and Hughes [25] and Marchal and Crochet [6], we define
modified weighting function q~ as
. _ luAl+ ,eh
9 =T+ku~-v~P, k = 2 (8)
%= U hx)
(9)
2
q~+]T~-~-V~P ~ + , ~ 2~, = .
An alternative method for the solution of the constitutive equation is the in-
consistent streamline upwind method, in which the modified weighting func-
tion is applied solely to the advection term u. V~g of the constitutive equation:
368
advection treatment and the rest of the procedure for a time-dependent prob-
lem. A shared feature of the OS and DG method is the use of discontinuous
interpolations of the extra stress tensor. This allows the elimination of the ex-
tra stress variables on the element level, yielding an efficient algorithm for
multi-mode fluids. More recently, Fortin et al. [33] and Gurnette and Fortin
[34] have combined the DG method with the EVSS method, by which they
could obtain good convergence and oscillation-free solutions for higher Weis-
senberg numbers.
I u
I p,l: I
L . . . . _1
In recent works of Saramito [49, 50], the original finite volume element
(Figure 2) was proposed for the mixed FEM which was somewhat similar to
the staggered grid in the FVM. It is noticeable that the staggered formulation is
relatively difficult to discretize the governing equations and it nearly cannot be
used for an unstructured grid mostly because one cannot define a control vol-
ume consistently for arbitrarily shaped meshes. Therefore the non-staggered
371
grid system in which all dependent variables are located at the grid points be-
comes more and more popular in the Newtonian flow calculations. In the un-
structured FVM approach of Huang et al. [44], they used a non-staggered for-
mulation, which corresponds to equal-order element in the FEM.
19 0 E
[-] ~2
) 9 () Ou
0 "r "t'22,p
l
/ 0 E
This segregated formulation has been one of the most commonly used ap-
proaches in the finite difference procedure [51], since it does not solve the mo-
mentum and continuity equations simultaneously as in the integrated formula-
tion of the FEM. For the purpose of solving them simultaneously, Song and
Yoo [4], Choi et al. [41] and Sasmal [52] applied the stream function-vorticity
formulation to viscoelastic flow problems. However this approach cannot be
extended to three dimensional flows, and it needs assumptions on stream func-
tion and vorticity in treating the boundary conditions.
Derivation of a pressure equation is based on combining the momentum and
continuity equations. A pressure equation of Poisson type can be obtained by
taking the divergence of the momentum equation (2):
= v. +v. . (]2)
Sato and Richardson [45] used this formulation for their viscoelastic flow cal-
culation, in which MAC (Marker And Cell) method of Harlow and Welch [53]
was incorporated into a finite element solution. A similar procedure to this
formulation is also used in the three-dimensional FVM calculation of Mompean
and Deville [ 18].
However, the SIMPLE algorithm does not converge rapidly because the ve-
locity correction is obtained improperly. Its performance depends greatly on
the size of the time step, o r - for steady flows - on the value of the under-re-
laxation parameter used in the momentum equations. It was found by trial and
error that convergence characteristics can be improved by controlling the un-
der-relaxation. Thus some modifications to this conventional SIMPLE algo-
rithm were proposed. They are SIMPLER (SIMPLE Revised) of Patankar
[11], PISO (Pressure-Implicit with Splitting Operators) of Issa [55] and SIM-
PLEC (SIMPLE Consistent) [56] which do not need under-relaxation of the
pressure correction [57].
Recently, the FVM approaches based on these algorithms were adopted for
viscoelastic flow computations, because of their attractive features of space and
time savings, as well as their numerical stabilities. For steady flow problems,
Hu and Joseph [40], Yoo and Na [42] and Huang et al. [44] used SIMPLER al-
gorithm, and its modification is used in the work and Xue et al. [43], while
Gervang and Larsen [58] used PISO algorithm and Luo [59] used classical
SIMPLE algorithm. Note that in these algorithms the pressure and velocity
fields obtained at the end of each time step (or iteration step for steady flow
problems) do not satisfy one and the same momentum equation so that for
time-dependent computations, sub-iterations are necessary at each time step, or
very small time steps must be chosen, which accordingly degrades the effi-
ciency of these algorithms.
where m denotes the present iteration step and e is a step length for the itera-
tive procedure. Hadj and Tanguy [36] and Kabanemi et al. [39] used this classi-
cal Uzawa algorithm for the momentum and continuity equations. Fortin and
Fortin [26] and Gu6nette and Fortin [34] solved the Stokes flow problem by
this algorithm combined with a condensation method [60] that eliminates the
velocity degrees of freedom associated with the center of each element and the
pressure gradients. This is achieved by using the continuity equation at the el-
ement level, thanks to the discontinuous approximations of the pressure. This
method greatly reduces the number of unknowns, resulting in a very efficient
Stokes solver. However, the convergence properties of this algorithm are not
so good because the determination of e is not easy so that e is usually fixed
with the iterative procedure. The way around this is quite simple but requires a
few developments [13, 14, 23]. Fortin and Fortin [28] showed that an intro-
duction of the preconditioned residual for the dependent variables enhance the
convergence, but the computations still had to be performed in double preci-
sion.
In fact, the algorithm (13)-(14) can be interpreted as a gradient algorithm
applied to the minimization of the functional. With this interpretation in mind
it is natural to seek the more effective iterative methods for the minimization
of quadratic functionals, such as the steepest decent method, the minimum
residual method or the conjugate gradient method. In these modified methods,
the conjugate gradient method is especially attractive for solving quadratic
problems because theoretically it converges in a finite number of iterations and
moreover, it leads to quadratic convergence in the general case. These algo-
rithms require the additional presence in memory, but this increased memory
requirement will be justified if the automatic determination of the step length
e leads to a very clear improvement in the speed of convergence compared
with original algorithm (13)-(14) [ 13, 14, 23 ].
for a time-dependent problem. This method is also called the alternating direc-
tion implicit technique [13, 14, 23, 61], which separates the main two difficul-
ties in the computation of the Navier-Stokes equation: the non-linearities in the
momentum equation and the incompressibility constraint. In the conventional
numerical simulation of viscoelastic flows, the non-linear term is usually ne-
glected. In an attempt to answer some of the unresolved questions in their ear-
lier work, Evans and Walters [17] investigated aqueous solutions of polyacry-
lamide and concluded that a lip-vortex mechanism may be responsible for
vortex enhancement for all planar contraction ratios. These experimental stud-
ies consist of observations and measurements of the phenomena resulting from
the change of the flow rate of the same viscoelastic fluid. Therefore, in order
to simulate such flows numerically, the inertia must be retained in the momen-
tum equations.
Glowinski and Pironneau [23] proposed the 0-scheme based on the above-
mentioned OS method to treat the nonlinearity and the incompressibility of the
Newtonian flows. It consists of three step time marching technique such that
(i) First step
gl n+O _ II n
P Ok _aV..g,+o +Vpn+O =fn+O ..[_~V. ,[,n (/gn .V)/gn , (15)
un+l-O _ 11n+O
P (1 - 2 0 ) k - f l Y . Zn+l-O "b (U n+l-O" V ) U n+l-O : fn+l-O + O~V..[n+O _ V p " + ~ ,
(17)
U n+l _ ign+l-O
P Ok _ o ~ V . ,[n+l q_Vpn+l = f n + l + ~ V . , [ n + l - O (lln+l-O.v)lln+l-O , (18)
P At + 3(un'V)un-(un-l"V)un-1)=-2
where r is a pseudo-pressure and V~b#+~- Vp #+~+O(At2). One can see that the
third step is derived from taking the divergence of equation (21) and requiting
u n+~ to satisfy the continuity equation. There are many variants of the frac-
tional step method such as a fully implicit fractional step method [69], due to a
vast choice of approaches to time and space discretization, but they are all
based on the principles described above.
The fact that the pressure is segregated from the velocity in the fractional
step method was utilized in the finite element analysis of the incompressible
Navier-Stokes equation by several researchers [70-74]. Because the fractional
step method does not include any approximation procedure, such as adopted in
the SIMPLE algorithm based finite element methods [75-78], this approach is
more accurate than the SIMPLE algorithm based approach for the same grid.
Furthermore, in the fractional step method, the coefficients of the pressure
equation are fixed and the inverse matrix of the pressure equation does not
need to be calculated at every time step like the SIMPLE algorithm based ap-
proach [79].
Carew et al. [80] and Baloch et al. [81] used this fractional step method
combined with the Taylor-Galerkin method for the advection treatment. The
details of that scheme is described in the work of Hawken et al. [82]. Recently,
Baloch et al. [83] were able to carry out a numerical simulation of a three-di-
mensional viscoelastic 40:3:3 expansion flow, using the Phan-Thien and Tanner
378
(PTT) constitutive fluid model, where they showed the streamlines in the cen-
ter plane of the 3D expansion and made comments on the differences in the
vortex development from the 2D simulation. Recently, Sureshkumar et al. [84]
applied the fractional step method of Kim and Moin [66] to the DNS of the tur-
bulent channel flow of a polymer solution by spectral method.
The major difference between the 0-scheme with preconditioned conjugate
gradient (PCG) method (15)-(19) and the fractional step method (20)-(22) is
how to advance one time step. The two methods are both of order two in time
and the Poisson equations for the pressure are involved respectively. However,
sub-iterations for satisfying the convergence criteria of the momentum and
continuity equations, that is, equations (15)-(16) and equations (18)-(19), are
needed in the PCG method of the 0-scheme, while the Poisson equation is
solved just one time at the second step (21) in the fractional step method. It is
well-known that the Poisson equation for the pressure is the most time consum-
ing one in the segregated formulation of the Navier-Stokes equations. In view
of this, comparing with the fractional step method, the 0-scheme may be inef-
ficient, particularly for three-dimensional problems, despite the fact that the
Poisson equation is solved in the discrete pressure space whose dimension is
much smaller than the dimension of the discrete velocity space in mixed FEM
formulation. Note that the 0-scheme with Uzawa type PCG method cannot
avoid the Babuska-Brezzi condition [13], and thus it must be discretized via the
mixed formulation where the discrete pressure on a grid is defined twice
coarser than the one used to discretize the velocity. On the other hand, the
fractional step method can avoid the compatibility condition as shown in the
recent work of Choi et al. [79] which combined the SUPG with an equal-order
finite element formulation. This work was extended to the numerical analysis
of a Bingham plastic [85]. However, the boundary condition treatments for the
intermediate velocity ti and the pressure in the fractional step method is some-
what unclear and some further assumption is needed, while such an assumption
is not needed in the 0-scheme.
5. CONCLUDING REMARKS
Recently, the streamline upwind (SU) scheme for the control volume finite
element method (SUCV) [86] has been proposed. When we consider that the
379
ACKNOWLEDGEMENT
I would like to express my deepest thanks to Mr. Taegee Min for his in-
valuable efforts in preparing this manuscript.
REFERENCES
1. I N T R O D U C T I O N
2. B E A D - S P R I N G M O D E L
This model was proposed to describe dilute polymer solutions. The polymer
molecule is idealized as a dumbbell consisting of two beads, each of mass m,
joined by a spring. The beads are labeled 1 and 2; their vector positions are
r l a n d r 2 and R = ( r 2 - r l ) is the vector joining bead 1 to bead 2. The
number of dumbbells in the position range F__i t o F_.i + d r i and the beads have
difference between the average bead velocity and the velocity of the
solution at that point. Assuming that the velocity of the solution is not
affected by the other beads, _F}h~ can be written as
F{ B)-- - k T ( ~ 2 n W / ~ r i ) (6)
(c) the intramolecular force F~ ~ and, in the present model, it is the force
due to the spring. The forces on the two beads are equal and opposite
and a connector force F (c~ can be defined as
388
In the absence of external forces and neglecting inertia terms, the equations
of motion for the beads are
On subtracting we obtain
m 9
(L-R_) ~ - ( 2 k T / ~ ) ( ~ / ~ _ R ) - 2F(C)~/~I } (12)
~t
where =/-/sand Hp are respectively the contributions from the solvent and the
polymer.
The solvent is a Newtonian fluid and _/-/s is given by
Us - Ps---- ns ~ (14)
389
where Ps is the pressure associated with the solvent, 6 is the unit tensor, and
is the rate-of-strain tensor.
--(b)
The contributors to __/-/pare the connector, ~___p,
(c)/7 and the beads, l=lp . It is
shown in Bird et al. [6] that __/_/(pc)and __/_/(pb)are given by
(c) (c)
lip= = - n < R F ) (15a)
where < > denotes the average over the configuration space.
Combining equations (13, 14, 15a, b) yields
n ( R F~C)>0 = n k T ~ (17)
Equation (18b) is the Kramers expression for the stress tensor. To calculate
<R F(C)) we usually need to solve equation (12) for V and then evaluate
V
= ln~<RR> (20)
~P 4
Equation (20) is the Giesekus form of the stress tensor. For a Hookean
spring, we deduce from equation (18b) that =Vp is given by
V
Combining equations (19, 20, 21) and noting that =~ = - ~ yields
V
_'lYp + ~1 "l~p= - - n k T ~ , 1 "~ (22)
V
V
~-+ ~'I ~ = --nO (~r+ ~2 It) (23)
where 770 - 77s + n k T ~ 1 is the viscosity and ~ 2 = /]" 177s ] (77 s -I- n k T X 1) is the
retardation time.
Equation (23) is the constitutive equation of a dilute polymer solution
modeled as Hookean dumbbells suspended in a Newtonian solvent. Equation
(23) was also proposed by Oldroyd [ 1] from a continuum mechanics approach
and was labeled liquid B.
An integral form of equation (23) is (Bird et al. [6])
-1
m ( t - t') _C t (t') dt' (24b)
where C -l(t')
t is the relative Finger tensor, ~' ( t - t ' ) is the derivative with
respect to t' of the Dirac delta function , and m ( t - t') is the memory
function.
In this model, macromolecules are represented by single dumbbells.
Figure 1 illustrates a more realistic model for a macromolecule consisting of
N beads connected by ( N - 1) springs. In the Rouse model, the connectors are
Hookean springs and a constitutive equation can be deduced as in the case
where the macromolecules are assumed to be single dumbbells. Equation (24a)
is modified to obtain (Bird et al. [6])
_R2
3. R E P T A T I O N M O D E L
3.1. D o i - E d w a r d s Model
In the reptation theory proposed by de Gennes [8], the constraint that
polymer chains cannot pass through each other is interpreted such that each
chain is confined to move inside an imaginary tube, as shown in Figure 2. The
chain is assumed to be longer than the tube and the slack is considered to be a
defect capable of moving along the tube. As a result of such motion, part of
the chain can move out of the original tube and a new tube is created. This
type of motion is called reptation. Based on this concept, Doi and Edwards [9]
derived a constitutive equation for polymeric liquids.
Doi and Edwards [9] introduced the concept of a primitive chain which is
the center line of the tube, as shown in Figure 2. The motion of the real chain
is represented by the motion of the primitive chain. The real chain wriggles
around the primitive chain. This motion is very rapid and an equilibrium is
established after a time Teq (equilibration time) which is proportional to N 2,
where N O is the degree of polymerization of the real chain. On a time scale
393
greater than Teq , this wriggling motion can be ignored and the motion of the
real chain coincides with the motion of the primitive chain.
4,--,,
/ \
f
/
/
\ /
o"
f
\ ,"
,_/
respectively.
If the primitive chain is assumed to be continuous, any of its points at time t
can be denoted by R_ (s, t), where s is the contour length measured from one
end of the chain. The unit tangent u (s, t) to the primitive chain is given by
where Go is a constant.
Suppose that the material is deformed such that a material particle which is
at x at present time t, was at x' at an earlier time t'. The deformation _E is
defined by
E = (Ox/~x') (31)
Doi and Edwards [9] assumed that the unit tangent vector _u' (s) at time t' is
The length of the primitive chain L is assumed to be constant and the extra
stress tensor ~ can be written as
I: - - G o Q (33a)
(E 9 u) ( E - u)
Q - - = - (33b)
iE.ul ~
0
In equation (33a), the random motion of the primitive chain has not been
taken into account. The random motion of the chain is responsible for the
395
~== -
f_ t M 1 [ t - t ' , I i ( t , t ' ) , I 2 ( t , t ' ) ] C t - l ( t ' ) + M 2 [ t - t ' , I i , I 2 ] ( _ C2t_- l) 1 dt' (35a)
M 1 = ~(t-t')Hl[Ii(t,t'),I2(t,t')] (35b)
M 2 = ~ (t-t')H2[II(t,t'),I2(t,t')] (35c)
where I1 and 12 are the invariants of ~_Ct1, H1 and H2 are functions which are
related to Q.
Equation (35a) is known in continuum mechanics as the K-BKZ equation
(Carreau et al. [4]). Note that the memory functions M 1 and M2 are written as
a product of a function of ( t - t ' ) only [/2 ( t - t ' ) ] and a function of
deformation only [H 1(I1 ,I2), H2(11 ,I2)]" The function p ( t - t') can be
obtained from linear viscoelasticity. Equations (25, 35 a to c) are similar if we
set 7"/~= 0, H 1 = - 1 , and H 2 = 0. Various modifications have been proposed to
the present model and they are discussed in [4, 5, 10].
C)
r
_Fv(h+)1 _--(h)
gV -- -- ~
13~V . { l l r- - v + l r l l - [ v- -( r - - +Lv
----V +1
) - v t- -r --
+Lv)]} (36a)
~v = ~ [ ~ - ( 1 - e ) u v u v] (36b)
m
where N is the average number of beads per chain, r v is the vector position of
bead v relative to the center of mass (see Figure 3), fl, ~', and e are constants,
and u v is the unit vector joining bead v to bead v + 1.
If the link tension coefficient e is one and the friction tensor ~'v is isotropic,
397
F(h)
v+l --
F(h)
2_.V ~ --
Nlaa ~V
9 {iI -fi- V 11-[L- - 9 Uv] } (37)
and in order to do this, Curtiss and Bird [11] introduced the concept of
reptation. They assumed that
~ = = - N n k T I f _ t o o g ( t - t') =Q (E_)
f _ t dt'+
oo_ e ( t - t') S_=_(E; L__)dt'1 (39a)
4. NETWORK MODEL
= (_R W) + c - 2 (40)
3t 3R
where c and 2? are the rates of creation and loss of segments respectively.
399
Segment "~ )
~' choin
~-Dongling
Loose end Segment
Note that in equation (40), unlike in equation (4), we have allowed for the
loss and creation of segments. This loss and creation of segments is analogous
to the loss and creation of tubes in the Doi-Edwards model. In their model, the
loss and creation of tubes is due to the reptation of the primitive chain and in
the network model, there is as yet no definite molecular mechanism for the
creation and loss of segments. We need to assume empirically the form of c
and 2 .
If we assume that the junctions move affinely, it follows that
1~ = L o R (41)
For simplicity we assume that all the segments are alike and the tension
acting in each segment is F (c). The total stress/7 can be written as
To evaluate < if(c)_R> we need to solve for 7~ from equation (40) and this
implies that we need to postulate c and ,e. In the Lodge model, the following
assumptions are made
2 = W/~ (43b)
V
<RR> = I((RR> -<RR>) (45a)
where J is a constant.
Combining equations (42, 43c, 45a, b) yields
V
H+LH = -nil J8 (46)
Noting that
FI = P ~5 + "c (47a)
z_ = 0 at equilibrium (47b)
401
V
8 - - ~ (47c)
V
"c + )~'c - - r l "~ (48)
where 77 (= ~, n H J) is a constant.
Equation (48) is the constitutive equation of an upper convected Maxwell
fluid (Carreau et al. [4]) and an integral form of equation (48) is
We note that in this case, as in the bead-spring model, we have been able to
derive a constitutive equation without having to solve for 7~. The time constant
~, for the network model is empirical whereas the time constant ~,1 in the bead-
spring model is related to the structural parameters of the model (equation 22).
The two models yield identical constitutive equations if the solvent viscosity is
negligible.
For clarity we have so far considered the case of a single time constant ~,.
We can generalize from one time constant to a multitude of constants ~p. We
can associate /~p with the different ages of the junctions (Lodge [16]) and to
each ~p corresponds a __rp. Each __rp satisfies equation (48) and =r (= ~ __Vp) is
p
given by equation (49a) with m ( t - t') defined by
where ~up0and ~p are the distribution functions associated with the p-mode at
equilibrium and at time t.
Substituting equations (5 l a, b) into the balance equation [equation (20)] for
the p-mode, multiplying the resulting expression by R R and integrating over
v
< R R) p = Lp =8- < R R)p/~p (52a)
Following the usual procedure, it is deduced that the extra stress tensor T
can be written as
'
m ( t , t', 3~) - Z
YI pfp [~ (t')] exp
2
)~p ftt dt"
~,pgp [~(t")]
(55b)
The functions fp and gp cannot be deduced from the model and have to be
prescribed empirically. The following assumptions are made (De Kee [23])
Note that I 1T, 12v, and 13 r are the invariants of __vand Q1 is positive for all
'~"~
m (t,t',Q1, Q2) - ~
P I
TlPgP[QI(t')' Qz(t')] exp
~2
P
Iftt dt"
~pgp [QI (t,,), Q2(t,,)]
(6O)
tl
Kaye [24] considered one mode only (p = 1) and assumed g l to be a linear
function of Q1 and independent of Q2. In a viscometric flow, this model
predicts a viscosity which decreases with increasing shear rate and the ratio of
the first normal stress difference to the square of the shear stress is constant.
Phan-Thien and Tanner [25], Phan-Thien [26], and Tanner [27] have
assumed that the rates of loss and creation of junctions are functions of
<lR2]>p and (IRl2)p0 respectively. Since the segments are assumed to be
model is a stress dependent model. In addition they have assumed that the
deformation is non-affine and their model is discussed in section 4.6. The
Marrucci model [28] was proposed as a modification of the upper convected
Maxwell model but it has been shown that it is derivable from the network
theory (Jongschaap [29]) and is of the stress dependent type. Acierno et al. [28]
have also introduced a structural parameter related to the segment density in
their model and we shall discuss these models in section 7.
405
= h (II,I2) Z 2
('qp/~p) e_(t_t, )/~,p (62b)
P
Comparing equations (55a, 62a) with equations (35 a to c), we observe the
Wagner model is a special case of the Doi-Edwards model or the K-BKZ
model.
4.5. Y a m a m o t o Model
In all the transient network models considered so far, the functions c and A?
depend on the macroscopic variables and it was possible to deduce a
constitutive equation in a closed form. Yamamoto [14] proposed that the
rates of creation and loss of segments depend on the end-to-end vector
R. It is assumed that c and ,8 can be written as
3q'
- (R W) + f ( R ) ( W o - W) (66)
~)t ~)R - -
where f = fl - f2-
If we proceed as in the previous cases, that is by multiplying equation (66)
by R R and integrating over the configuration space, we are led to evaluate
<f(R_) R R ) and we can only evaluate this integral if !P is known. But so far
we have not been able to obtain an analytic solution to equation (66). The
Yamamoto model has no closed form constitutive equation.
Petruccione and Biller [32] and Herman and Petruccione [33] have solved
equation (66) and its multimode version by a numerical simulation method.
The process governing equation (66) is simulated as a stochastic process and
the amount of computation required to determine the stress in a given flow is
reasonable. The agreement between predictions and experimental data in the
case of an elongational flow is good.
1~ = Lo R (67a)
L = L - (112~) ~ (67b)
~=+~= = - r 1 7 (68a)
7 = (1 - ~) ~ (68b)
~2
__z"is the Gordon-Schowalter [37] derivative of =vand is given by
Equation (70) is a special case of the Oldroyd [1] model derived from
continuum considerations. Equation (70) predicts a variable viscosity and the
ratio of the secondary (N2) to the primary (N]) normal stress differences in
viscometric flows is given by
408
N2 _ ~ (71)
N1 2
Two empirical forms of Y (tr r=p) have been proposed and they are
1 - ~ (tr ~ p) ~ p/lip
y (73a, b)
exp [-~ (tr ~p) ~ p [ ] q p ]
M
Z Tip exp ( - t / ~ p )
p=k+ 1
= I]oo [1 - H ( t ) ] (77a)
M
2Z Tlp(t + ~p) exp ( - t / ~ p ) = ~tl~ [ 1 - H ( t ) ] (77b)
p=k+ 1
where 7/00and ~1oo are the limiting infinite viscosity and primary normal stress
coefficient respectively and H (t) is the Heaviside step function.
Note that equations (77a, b) imply a singularity at t = 0 and are valid for
~ p - - > 0. Further, it is not possible to distinguish the various modes
(p = k + 1, k + 2, ...) and there is no loss of generality in confining to one
mode only (p = M).
De Kee and Chan Man Fong [39] have shown that equations (77a, b) are
equivalent to introducing a singularity to the memory function m in equation
(55b). This equation is now written as
m = mL + m s (78a)
mL= ~
p=l l rlpfp
~p
2 exp
Iftt ~dt"
g
p p 1[ (78b)
where ~' and 6" are the first and second derivatives of the Dirac delta
function.
Within the network theory we can interpret m L as being the response of the
active segments associated with a time scale greater than Teq. The function ms
represents the response of the solvent molecules [see equation (24c)], the stray,
and the dangling segments and is associated with a time scale less than Teq. To
predict the stress jump phenomenon it is necessary to include the short term
response which is the Newtonian and possibly also slightly viscoelastic
responses [10]. This in turn implies that the memory function must have a
singularity [40].
Other models that can predict the stress jump are discussed in [38, 41, 42].
411
where k c, k l, and k~ are constants and the functions fl and f2 are prescribed
later.
To include the electrostatic force, they wrote F_(c) as
1;
~
= + )l, m I;
= = (1 - ~ ) )~mkT
/n o ~
= - b--E----
~
i n [2 (k 2 f 1 - k 1 fa) 7= + 7]
= (81)
where ~ m -" (kc + k ~ . f l - klf2) -1, E = ( k c + k l f 2 - k,e f l), n o and n are the
number density junctions at equilibrium and at present time respectively, ~ is
the slip parameter, k is Boltzmann's constant, T is the temperature, b and I
are constants.
412
5.3. Slip-Link N e t w o r k
In section 3.1 the reptation process is modeled as the motion of the primitive
chain inside a tube. Doi and Edwards [9] have also proposed two other
alternative models, namely the cage model and the slip-link model. Slip-links
are small rings through which the chain can pass freely, as shown in Figure 5.
Wagner and Schaeffer [49] have implanted the slip-link model in the transient
network theory. The transient slip-link network is a network of active
Gaussian segments between slip-links. Suppose that at equilibrium the distance
between two slip-links is 2' 0 with n o monomer units. The end-to-end vector
can be written as
L = 2 ou (82)
<D/S> = 1 (86)
414
6. C O M P A R I S O N WITH E X P E R I M E N T A L DATA
v x - y ~ (y), Vy = Vz = 0 (87a, b, c)
In equations (88a to c), the functions are defined when the equilibrium state
has been reached. For viscoelastic systems it takes a finite time to attain the
steady state. If a constant shear rate )'oo is applied at time t = 0, we define the
growth functions 77+, I/t~, and lit~ by
~g~ (t, "]'oo) - - [~yy (t, Too)- "c= (t, ~'oo)] / ~/2 (89c)
415
Similarly if a constant shear rate ~'0 is kept for a sufficiently long time until
the steady state is established and the applied shear rate is stopped, which can
be taken to be at time t = 0, the stress relaxation functions r/-, gt l, and ~2 are
defined by
~ (t, Yo) - - ['Cxx (t, ~'o)- '[yy (t, ~'o)] / ~/2 (90b)
+
I1/1 (t, "Yoo) -- /[/1 (~oo) 4- Z np k L {t [1-exp(-tpyoo(2 - c))] - 2t exp (-tp~/oo)
p=l
Figure 6 compares the predicted and measured values of 7"/and Iffl for a 6.0
mass % p o l y i s o b u t y l e n e solution in Primol 355, a pharmaceutical grade white
oil with a v i s c o s i t y of about 0.15 Pa~ at 298 K. Figures 7 to 9 s h o w the
theoretical and experimental values of r/-, gt 1 , a n d gt I for various values o f
shear rates for the PIB solution.
I I I I ! I
3 _ iO 4
I0
O
n
3
i0 2 - I0
D-
It"
I 10 2
I0 L ~ I ........ 1 I I 1 I
0 I 2 3 4 5 6 7
~' is-' ~
08 \\\~\
0.7
o ,o 2'0 3b
t(s)
,o1
09
Q8
~'ox~/~,,,,, ~ =4.34 S-t . . _
.-. 0.7-
=
._~_ 06.
.~ 0.5-
.,., 0.4-
0.0
0 20 4'0 6'0
t(s)
~=o = 4 . 3 4 S -I
~,00= 1.37S - I
*-0.6- I
~,0 = 0.137 s - !
"T- T T T
0 2O 40 6O
t(s)
It can be seen that the steady values of 7/and ~l are accurately predicted by
the model. Accurate transient data are difficult to obtain and the discrepancy
between the experimental data and theoretical predictions in Figures 7 to 9 can
be attributed to experimental error associated with the lack of stiffness of the
Weissenberg rheogoniometer model R-18 used for these experiments. High
rigidity is required to reduce coupling effects between the sample and the
instrument which should be capable of very rapid acceleration.
It was mentioned in section 5.1 that Liang and Mackay [38] have reported
measurements of shear stress jumps. They defined a stress jump ratio R as
follows
1.0
0.7
_ ~"~'~|~-.,,~, .,.-'..,
0.5
0.3 -- II
0.2 -
0. I I I I I I I I '.l
i I
0. I 0.2 0.5 I 2 5 I0 20 50
Figure 10. Predicted and measured stress jump ratio for solutions in xanthan
gum in a mixture of 75 mass % fructose and 25 mass % water.
0.05 mass % r/1 = 13.48 Pa.s, r/2 = 2.28 Pa.s, 77oo= 0.83 Pa-s,
t 1 = 1 0 . 1 3 s , t 2 = 0.28 s.
9 99 0.025 mass % r/~ = 3.13 Pa.s, q2 = 0.91 Pa.s, r/= = 0.64 Paos,
tl = 6.02 s, t2 = 0 . 1 6 s.
0.01 mass % r/~ = 0.61 Pa.s, 772 = 0.33 Pa.s, r/= = 0.53 Paos,
tl=4.69s, t2 = 0 . 2 1 s.
e , II, A : experimental data for 0.05, 0.025, and 0.01 mass % respectively.
Furthermore R - ( 0 + , 70) is less than 1 and this implies that r/= > r/s. This is
in accord with our interpretation that q= represents the viscosity of the solvent
and the stray and dangling segments.
420
-- 1 / k c (1 + d ~/m) (95c)
.-,..
tO
g.
0.5
i ,, ,, \A\ /
--2
- 0.5
g.
--3-
- 0.2
-0.1
Figure 11. Plot of viscosity (A) and primary normal stress coefficient (A)
versus shear rate (~) for a partially hydrolyzed polyacrylamide solution
containing 2 g/2, of NaC1. Model parameters are: 7/0- 0.50 Pa-s, kc =
0.040 s -1, ~ = 0.016 s, d = 0.13, m - 0.95.
421
6.2. M u l t i s t e p Flows
In section 6.1 we have considered the case of a constant shear rate being
applied or removed at time t = 0. It is also possible to apply finite increments
of shear rates and measure the corresponding stresses. Xu et al. [51, 52] have
tested the De Kee-Carreau model for various multi-rate-step flows. Figure 12
shows the calculated and the measured shear stress for a PDMS sample (a
viscoelastic standard material provided by Rheometrics) in a concave step
flow. In this flow a constant shear rate ~ is applied at t = 0 and is maintained
until the steady state is reached. The shear rate is then halved and is kept at this
value (~/2) for a finite time after which it is increased to its original value (~5).
When the steady state is reached, the shearing is stopped.
~6
'0
4 _
2
?
ol
o o o o o o
1 I I I
0 20 40 60 80 I00 120 140
t(s)
Figure 13 compares the theoretical and experimental values of "Cyx for the
same material in a reverse shear rate flow. In this flow the fluid is subjected to
a constant shear rate ~ at time t = 0 and after the steady state is attained the
shear rate is reversed in direction but equal in magnitude (-~). This cycle is
repeated.
10"
5 x 10 3
A
o
O.
-5xlO 3 _
I I I I I
0 20 40 60 80 I00 120 140
t (s)
Figure 13. Shear stress for reversed shear steps. Model predictions
equations (55a to 56c). The model parameters are those of Figure 12.
7. D I S C U S S I O N
9 9
I 1 1800
I 0"s i i , , ,,,l
K)* iO? _ sOe iO t
%Mw
Figure 14. Correlation between the parameters tp and the product 77o M w .
The reptation model (section 3.1) has been improved by the des Cloizeaux
[58, 59] double reptation model and he has been able to deduce that the
viscosity 77 is proportional to M 3.4, where M is the molecular weight. In the
double reptation model, the reptation of a stress point is considered in addition
to the reptation inside the tube. A stress point is a point of entanglement of two
polymers and if either of the two polymers reptates out of the stress point, the
stress disappears. The stress point is the junction in the network theory and this
prompts Mead [60] to state that "the evolution of molecular constitutive
equations has gone full circle in the short span of 35 years." In the next circle,
we need to examine the process of loss and creation of junctions and the
deformation of the segments. The works of Wagner and Schaeffer [49] and des
Cloizeaux [58, 59] which combine both the reptation and network models need
further exploration.
425
REFERENCES
~ Oldroyd, J.G., Proc. Roy. Soc., A200 (1950) 523; A245 (1958) 278.
2. Barnes, H.A., J.F. Hutton, and K. Walters, An Introduction to Rheology,
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Liquids, Vol. 1 - Fluid Mech., Second Ed., Wiley, New York, NY
(1987).
, Carreau, P.J., D. De Kee, and R.J. Chhabra, Polymer Rheology:
Principles and Applications, Hanser, New York, NY (1997).
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Butterworths, Boston, MA (1988).
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of Polymeric Liquids, Vol. 2 - Kinetic Theory, Second Ed., Wiley, New
York, NY (1987).
~ Rouse, P.E., J. Chem. Phys., 21 (1953) 1272.
8. de Gennes, P.G., J. Chem. Phys., 55 (1971) 572.
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1789, 1802, 1818; 75 (1979) 38.
10. Doi, M. and S.F. Edwards, The Theory of Polymer Dynamics, Oxford
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(1958) 1200.
15. Chan Man Fong, C.F. and D. De Kee, Physica, A218 (1995) 56.
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17. Bogue, D.C., Ind. Eng. Chem. Fund., 5 (1966) 253.
18. Bird, R.B. and P.J. Carreau, Chem. Eng. Sci., 23 (1968) 427.
19. Meister, B.J., Trans. Soc. Rheol., 15 (1971) 63.
20. Carreau, P.J., Trans. Soc. Rheol., 16 (1972) 99.
21. De Kee, D. and P.J. Carreau, J. Non-Newtonian Fluid Mech., 6 (1979)
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426
22. Chan Man Fong, C.F. and D. De Kee, J. Non-Newtonian Fluid Mech.,
57 (1995) 39.
23. De Kee, D., Ph.D. Thesis, University of Montreal, Quebec (1977).
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25. Phan-Thien, N. and R.I. Tanner, J. Non-Newtonian Fluid Mech., 2
(1977) 353.
26. Phan-Thien, N., J. Rheol., 22 (1978) 259.
27. Tanner, R.I., J. Non-Newtonian Fluid Mech., 5 (1979) 103.
28. Acierno, D., F.P. La Mantia, G. Marrucci, and G. Titomanlio, J. Non-
Newtonian Fluid Mech., 1 (1976) 125.
29. Jongschaap, R.J.J., J. Non-Newtonian Fluid Mech., 8 (1981) 183.
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31. Wagner, M.H. and S.E. Stephenson, J. Rheol., 23 (1979) 491.
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Appl. Chem., 54 (1982) 1349.
35. Giesekus, H., Viscoelasticity and Rheology, edited by A.S. Lodge, M.
Renardy, and J.A. Nohel, Academic Press, New York, NY (1985) 157.
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42. Hua, C.C. and J.D. Schieber, J. Non-Newtonian Fluid Mech., 56 (1995)
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Fluid Mech., 60 (1995) 303.
427
1. I N T R O D U C T I O N
The simplest decay behaviors are exponential, such as the dielectric relaxation
associated with Debye and the mechanical relaxation named after Maxwell.
Exponential decays depend on a single mode (or, equivalently, a single
characteristic time). But most relaxation processes are governed by a large variety
of characteristic times, see references [1-4] for reviews, and vast types of decay
patterns follow, most popular being stretched exponentials (Kohlrausch-Williams-
Watts [2,5,6]) and power law behaviors. In this review we focus on the cases in
which the decay function follows a power law for reasonably extended time or
frequency intervals. Note that too short time or frequency windows do not allow
to distinguish between different decay patterns [7].
The transition from the glassy relaxation zone to the transitional zone in the
case of stress relaxation of a glassy polymer is an example for power-law
relaxation. Consider polyisobutylene at the reference temperature To = 25~ In
Figure l(a) we reproduce, following reference [8] its shear storage and loss
moduli G' and G" as a ftmction of the frequency o~; in Figure 1(b) we display the
corresponding shear relaxation modulus G and the shear creep compliance J as a
function of time. As is evident by inspection, the high modulus plateau is
followed by a power law that covers about four decades in time (Figure 1(b)) and
frequency (Figure l(a)). Then a second plateau zone (called the entanglement
430
10 10 -4
G' -5
.~ 8~ ~. 8 -6 "7t~
O ~- 7 -7
o 6 -8 e~
@
O
o 5 -9 o
i i i i l i i
-10
-4 0 4 8 -12 -8 -4 0 4
~.~ 5
~o
3
2
* .ce, G~- PB302
O
,-- 1 ~ G'- PB304
l 1 1 I I I I I I
-5 -4 -3 -2 -1 0 1 2 3 4 5
Figure 2. Storage modulus G' and loss modulus G" of unmodified (PB300) and
urazole modified polybutadiene (PB302 and PB304) vs. the reduced frequency
aTa~. The molecular weight of all samples is Mw - 31 kg/mol; the samples 302
and 304 correspond to the 2 mol % and to the 4 mol % modification, respectively.
431
plateau) shows up. This transition from one plateau to another, generally via a
power law, is characteristic for amorphous polymers.
Furthermore, power law behaviors also appear in the terminal relaxation zone
of polymers. In the case of a single relaxation time one has a sharp transition from
the entanglemem plateau to the flow zone, which obeys a typical liquid-like
behavior, namely G'oc co2 and G"oc co. Physically or chemically cross-linked
polymers [9], polymers with star-, H-, or comb-like topologies (see e.g. [10-19])
show a more general pattern, namely an intermediate power-law domain with
G' oc co~ and G" oc coa , where cz and 13 lie between zero and one. In Figure 2 we
contrast the behavior of neat, monodisperse polybutadiene to that obtained by
attaching to its backbone active groups, which are able to form H-bonds. While
for neat polybutadiene the shear storage and loss moduli obey G'oc o92 and
G" oc co, the moduli of the modified polymers follow more general power laws.
The reason for this behavior is that the active groups form temporary, random
links between the polymers, fact which renders the relaxation process multimodal
and cooperative; this leads here to power laws. Such laws are not the hallmark of
polymers only; vast classes of substances, which range from inorganic glasses to
proteins show such behaviors [1], and we like to recall the early works of
Meinardi et al. [20-22] on power law relaxation in metals, in rocks and in glasses.
In this chapter we focus on the possibility to portray such complex viscoelastic
features of polymers by means of fractional calculus, a formalism which turns out
to be exceedingly well-suited for this purpose. To this effect we start here by
illustrating, using a simple example, how fractional calculus comes into play as a
result of the superposition principle. We start with G(t), the shear relaxation
modulus of a linear system. Now G(t) is defined as the response of the shear
stress r(t) to a jump in the shear strata y(t)-yoO(t) where O(t) is the unit step
function. We assume that G(t) obeys a power law, i.e.
G(t) - r ( 1 - p) (1)
with 0 _ 13< 1. In equation (1) E and ~, are constants and I-'(x) denotes the
Gamma function [23]; for convenience we chose in equation (1) the prefactors in
such a way as to conform to the mare body of the Chapter. Due to the lmearity of
the system, the response of the stress to a previous history of deformations y(t)
is given by the superposition integral [24,25]"
432
t
Eft ~dt' (t- t') -p dy(t') (3)
r(t)- r ( 1 - p ) at'
r ( t ) - E 2 p dP?'(t) (4)
dtp '
in which ~/dt ~ denotes the fractional derivative of order 13 [26,27] (see section 2
for details). Equation (4) with 0 <13 < 1 interpolates between Hooke's law
describing solid behavior (13 - 0), i.e.
dr(t)
r(t)- r/---~ (6)
d~f(t) _ 1 ~ f(t')
dt ~ F ( L a ) dt'(t-t,)~+l
(8)
One has only to realize that for a = - 1 , - 2 , - 3 , . . , equation (8) is nothing but
Cauchy's formula for repeated integration [26,27]; hence for these values of
equations (7) and (8) are equivalent. Now, the basic idea is that equation (8) can
be readily extended to all tx < 0; this defines fractional integration. The
extrapolation to the positive a-range, a > 0, is obtained by first picking an
integer n, n > ct, then performing a fractional integration of order ct - n, followed
by an ordinary differentiation of order n, i.e. [26,27]
d ~ d~f dV+~f
= (10)
dt " dt ~ dt "+~
(14)
G* ( co) -icol;dzG(z)exp(-icoz )
From the complex modulus G*(co) follow the storage and the loss moduli,
G'(co) = Re(G*(co) ) and G"(co)= Im(G*(co) ), the complex shear compliance
J*(co)=l/G*(co) as well as storage and the loss compliances, J'(co)
= Re(J*(co)) and J"(co) = -Im(J*(co)). Furthermore, we also consider the
shear creep compliance J(t) (the response of the strain to a stress jump
r(t) = r 0 tg(t)), which is given here by
J(t)-/-'(1+ fl)
As a direct consequence of the multiplication relation, equation (12), we can
easily derive the harmonic response functions G*(co) and J*(co) of a given
fractional RCE. On the other hand, the analytical evaluation of the step response
functions, namely of G(t) and J(t), turns out to be a hard task in many cases.
Nevertheless these responses can be derived explicitly for a whole series of
fractional RCEs of practical importance, cf. sections 5 and 6.
d'~r
X_ (17)
Viewing z as stress and ~/as strain, the property X is an extension of the usual
definition of viscosity, for which a = f l - 1 . Bosworth [39] made first
considerations concerning the use of equation (17).
After these basic pioneering works, rheology experienced a renewed surge of
activity on fractional calculus starting at the end of the '60ies. Thus Slonimsky
[40] applied the calculus to study rheological phenomena of polymers, a
materials' class of growing importance. He described by a fractional relation the
force acting on a polymer segment and the displacement experienced by it; in fact
the operator used by him can be represented as an infinite series of simple
fractional derivatives. Then Smit and deVries [41] investigated several material
functions, such as the complex shear modulus of the fractional Kelvin-Voigt
model (having a fractional derivative of the strain) and compared the results with
experimental data. Next, Memardi and Caputo [20-22] developed the ideas of
fractional calculus ft~her; they provided expressions for several material
functions for the fractional standard solid model (see below), for which the order
of fractional differentiation was the same for the stress and the strain. The
evaluation of the relaxation in this case was an important step towards the
understanding of the basic properties of the whole class of fractional models.
These results were not widely noticed, and later rederived in rheology by
Friedrich [11-13] and Nonnenmacher [42-44], who also solved the general case,
in which the two fractional derivatives are of different order. Memardi and
Caputo used their expressions [20-22] to describe relaxation measurements of
rock materials, metals and glasses.
A study of the fractional versions of the Maxwell and Kelvin-Voigt models,
where only the derivative of the stress was replaced by a fractional counterpart
was performed by Koeller [45]. He also considered the generalization to parallel
437
and serial arrangements, and also pointed out the close connection between the
Rabotnov calculus [46] and fractional integrodifferentiation. The Rabotnov
calculus, developed in the USSR in the '60ies, is based on the Rabotnov-operator
9t5~(f) (also called fractional-exponential operator), and was used widely for
portraying relaxation phenomena in solid mechanics [46]. Friedrich and Hazanov
poined out the relation between 9t-~(f) and fractional integrodifferentiation
[47]. One has namely:
w h e r e 0 _ a < l andfl>_0.
More recently, one of the goals of research in our field was the detailed
analysis of the fractional Maxwell and Kelvin-Voigt models. It was soon clear
that the analytical determination of the response functions of these models is a
mathematically difficult task (see below). Bagley and Torvik [48] connected the
molecular theory of viscoelasticity to the fractional calculus, and showed that
some aspects of the theory are mirrored by the fractional Kelvin-Voigt model.
Friedrich and Heymann [15,16] pointed out the intimate relation between the
order of differentiation in a fractional Kelvin-Voigt model and the degree of
conversion for the sol-gel transition of a crosslinking polydimethylsiloxane.
Later, in 1986, Bagley and Torvik [49] considered the fractional standard solid
model in more detail. They established that this model, which contains two
fractional derivatives- one of the stress and one of the strata- is compatible with
thermodynamics if the order of both derivatives is identical. Thermodynamical
admissibility of fractional order models was also analyzed by Friedrich for
several models [12].
In 1983, Rogers [50] formulated general RCEs containing a large number of
sums or products of fractional derivatives, both of the stress and also of the strain.
The analysis of these models was restricted to those containing mainly two
fractional derivatives, and dealt with (the more accessible) frequency domain.
Another use of fractional derivatives was put forward by VanArsdale who
generalized the Rivlin-Ericksen and White-Metzner tensors by including
fractional orders of differentiation [51 ].
Only in 1991 did Friedrich [11] as well as G1Ockle and Nonnenmacher [42]
succeed in obtaining G(t) and J(t) for the fractional Maxwell model containing
two fractional derivatives of different order. They showed that this solution can
be expressed through a special class of mathematical fimctions which will be
438
In equation (19) ~lk and ~2k are two sets of characteristic times. The authors of
reference [63] succeeded in deriving the corresponding fractional RCE. Note that
for m = 0 and n = 1 one recovers the Kobeko function [24].
We close this section by noting that nowadays fractional calculus is of
widespread use in describing different rheological phenomena for wide classes of
materials. As examples from the polymer literature we refer to [19,53,64-67]. In
the following section we analyze under which circumstances spring and dashpot
arrangements lead to power law relaxations.
Fractional RCEs may be formally derived from ordinary RCEs by replacing the
first-order derivatives (d/dt) by fractional derivatives (~/dt ~) of non-integer
order (0 < 13< 1). This formal procedure can, however, not assure a priori that the
resulting expressions are always physically reasonable. This aspect was pointed
out, for instance, in references [11,42,54]. Thus it is useful to have a procedure at
hand that automatically guarantees mechanical and thermodynamical stability.
As a first step Schiessel and Blumen [54-57] and Heymans and Bauwens [60]
have demonstrated that the fractional relation, equation (4), can be realized
physically through hierarchical arrangements of springs and dashpots, such as
ladders, trees or fractal structures (which we will discuss in this section). The
idea is that (disregarding for the moment the specific structure of the hierarchical
constructions, these will be detailed later) equation (4) is obeyed by a fractional
element (FE) which is specified by the triple (fl, E, 3,). We symbolize the FE by a
triangle, as shown it Figure 3(c), where also its classical counterparts are
depicted: the spring (cf. Figure 3(a)) obeying equation (5) and the dashpot (cf.
Figure 3(b)) with the stress-strain relationship equation (6). Then, as a second
step, more complicated RCEs can be constructed by combining two or more FEs
in serial, parallel or more complex arrangements; this was proposed by Schiessel
et al. [58] and by Heymans [61]. We will make use of this method in sections 5
and 6.
440
E __Lq
(a) (b) (c)
Figure 3. Single elements: (a) elastic, (b) viscous and (c) fractional.
Eo
E1
rio
E2
Eg/
r12
1//
where we set )~-rl/E. For a)2 <<1 equation (21) reduces to the form
G*(co) "~ E(ico2) ~/2 . Therefore having the same spring constants and viscosities
for the whole arrangement one gets a complex modulus with 13= 1/2, and thus the
ladder model with equal springs and dashpots leads to a FE with the parameters
(1/2, E, A). To extend the ladder model to arbitrary values of 13 with 0 < 13< 1, a
suitable distribution for the spring constants and viscosities has to be chosen; thus
an algebraic k-dependence of the material constants of the form
r
(5 2n G :n+lI
....
' (
6 r
n
Heyrnans and Bauwens [60] and Schiessel and Blumen [56] demonstrated that
values of 13 with 13r 1/2 can also be attained by arranging equal springs and
dashpots into a network with a more complex structure. Thus reference [60]
focuses on a class of iterated networks which are generalizations of a fractal tree
model; each FE (/3,E,2) can be represented by such an arrangement to any
desired accuracy. We show in Figure 5 the recursive construction of the model:
One starts from an element having the complex modulus G~; this element gets
then represented by four elements, two of which have G~, the two others G2 and
G 3 as moduli (of. Figure 5 with n = 1 ) so that the ensuing structure still has G~
as complex modulus. From Figure 5 it is easily seen that the relation between the
complex moduli of the elements has to be G,, = ~G~,, Gz,+~. In principle the
iteration proceeds for each element indefinitely. By this the complex modulus G~
of the whole arrangement is
(23)
c, - - (c4G, G6c ) ''4 - ..
c, - E --
(24)
with /3- ~ " M,,/2" and 2 = ~7/E. Thus one can reach any preset, arbitrary 13,
0 < 13 < 1 to any desired accuracy by a sufficiently fine decomposition. As a
special case, by taking G 2 = E and G3 = i corl we obtain a binary tree. This
network, which we depict in Figure 6, is again a FE with the parameters
(1/2,E,2).
The advantage of the "binary decomposition" of elastic and viscous elements is
its simple analytical tractability; in many cases, however, it leads to complicated
networks whose properties are difficult to grasp intuitively. Thus it is also
443
1 ', 1 1 1
I ', ', I I I I I
Figure 6. A special case of the iterated networks shown in Figure 5" binary
spring-dashpot tree.
In reference [56] Schiessel and Blumen showed that for given fractal networks
this relation is straightforward when the springs and dashpots are suitably chosen.
The construction starts by connecting each site r~ of the given network to
neighboring nodes rj by equal springs (with spring constant E) and linking each
r~ to the ground via a site-dependent dashpot (with viscosity r/~ - z(r~)r/, where
z(r i) is the coordination number of node r~ ). Furthermore, the nodes' motion is
perpendicular to the ground. To give an example we show in Figure 7 a section of
the infinite mechanical network constructed from the Sierpinski gasket. The
analogy to random walks can now be seen by comparing the stresses acting on
node r i (whose displacement is ~,~)
which governs the probability P(r~,t) of having a random walker at site r~. In
Eqs. (25) and (26) the sums run over all nearest neighbors rj of r~. The transition
probabilities w o. in Eq. (26) obey z(rj)w o - w - constant. Now one can identify
formally r/, y,(t) with P(r~,t). Furthermore, the probability for a random walker
to return to the origin at time t follows an algebraic form:
where d~ is the spectral dimension of the network [68]. A power law behavior of
the complex modulus, Eq. (15), follows, with ~ 3 - 1 - d ~ / 2 (cf. Ref. [56] for
details). The ladder model, Figure 2, is the special case of a one-dimensional
lattice with d s - 1 and thus 13- 1/2; the Sierpinski gasket in 2d (cf. Figure 7) has
d,. - 2 ln(3)/ln(5) and hence fl - 1 -ln(3)/ln(5) "- 0.317.
Figure 8(a) shows the standard Maxwell model, in which a spring and a
dashpot are arranged in series [24,25]. Now this model can be generalized by
replacing these elements by the FEs (a, E 1, 3,1) and (/3, E 2, 22), as shown in
Figure 8(b). Due to the sequential construction the stress v(t) is the same for both
elements. Their respective stress-strain relations are
Let us assume without loss of generality that ~z > ]3. Eq. (29) can be further
simplified by setting 2-(E~A~/Ez2~) v('~-~) and E - E~(A1/A) ~ . This leads to
q ,E1,21)
(a) (b)
Figure 8. The (a) ordinary and (b) the fractional Maxwell model
446
When one arranges the spring and the dashpot in parallel one obtains the
standard Kelvin-Voigt model [24,25], depicted in Figure 9(a). Its generalization,
which has two FEs, is shown in Figure 9(b). Because of the parallel arrangement,
the stresses acting on the two elements are. additive. Following a procedure
similar to that for the generalized Maxwell model (vide supra), one finds for the
RCE of the generalized Kelvm-Voigt model (FKVM) [58]
where we have used the same parameters X and E as for the FMM.
I I
(a) I (b) I
Figure 9. (a) The Kelvin-Voigt model and (b) its fractional generalization.
The basic material functions of the FMM and the FKVM were derived
elsewere [58]; we will restrict ourselves to their succinct display and to the
discussion of their basic properties. Table 1 presents for both models their
fundamental response functions.
In Table 1 E p(z) denotes the generalized Mittag-Leffier function of argument
z, whose definition and basic properties are given in the Appendix. This function
is of great importance for fractional RCEs, since it occurs in many material
functions in the time domain. The harmonic response functions, equations (36) to
(39), follow simply from the RCEs, equations (30) and (31), by means of the
multiplication rule, equation (12). Due to the sequential (parallel) construction of
the FEs in the FMM (FKVM), the response J(t) (G(t)) is simply the sum of the
corresponding responses of its structural parts, which obey equation (16)
(equation (1)).
447
Table 1
Material functions of the fractional Maxwell and Kelvin-Voigt models
FMM FKVM
10r /
[]
~-~ FMM
~ 8
~ ~.
41 ,
-3 0 3 6 9
log co / s-1
Figure 10. Description of the data of Figure 1(a) by the fractional Maxwell model
(solid lines) and the fractional Kelvin-Voigt model (dashed lines).
Table 2
Material parameters used in Figure 10
log E log L c~ 13
FMM 9.09 -8.36 0.583 0.593
FKVM 5.75 -2.96 0.057 0.885
good agreement between the experimental data and the analytical expressions for
FMM. On the other hand FKVM is unable to describe the observed features even
qualitatively. This is especially true for the G"(o~) data where FKVM can not
follow the decline found experimentally in the range of very low frequencies.
In Figure 11 (which is redrawn from Figure 2) we provide another example
which stresses the possibilities offered by FMM to depict relaxation data.
Whereas Figure 1 is concerned with polymers in the glassy and transitional zones,
here we deal with relaxation from the plateau towards the terminal relaxation
zone. Figure 11 shows the storage moduli, both of two modified polybutadienes
(PB302 and PB304) and also of the neat polymer, on which the modifications
were performed (PB300) [64]. Note that the FMM with the parameters given in
Table 3 describes in a quantitative way the observed relaxation- the focus lies
449
here on the power law behavior of the modified PBs at very low frequencies. We
note furthermore that both the storage and the loss module of the neat polymer
melt are quantitatively depicted by this model.
r FMM
-5 -4 -3 -2 -1 0 1 2 3 4
Figure 11. Description of the data of Figure 2 by the fractional Maxwell model
(solid lines).
Table 3
Material parameters used in Figure 11
. . . . . .
logE log)~ ~ 13
PB300 5.52 -1.87 0.882 0.994
PB302 5.60 -0.344 0.553 0.632
PB304 5.48 0.720 0.478 0.590
The same holds true for polystyrene, as shown in the following example, taken
from reference [65]. The situation is depicted in Figure 12; as is obvious, the
storage moduli of polystyrene filled with different amounts of silicagel (N20)
follow a power law in an intermediate region. Here the slope of the low frequency
450
3
k3 Model
e~o 0.5 and 5 vol. %
o 2
1 and 4 vol. %
2vol. %
PS 100 matrix ~ 3 vol. %
I I I I
-2 -1 0 1 2 3
1og (aTo3) / rad s- 1
Table 4
Material parameters used in Figure 12
log E log ;~ c~ 13 log G~
PS100 4.97 -0.877 0.812 1.000 -oo
0.5 vol. % 5.07 -1.06 0.808 0.988 1.54
1 vol. % 5.17 -1.08 0.749 0.907 2.62
2vol. % 5.26 -1.12 0.718 0.867 3.09
3 vol. % 5.40 -1.03 0.649 0.784 3.99
4 vol. % 5.47 -1.15 0.597 0.725 4.15
5vol. % 5.49 -0.814 0.613 0.768 4.85
451
6. MORE C O M P L E X MODELS
E3
q
I
(a) I " (b) - I
Figure 13. The (a) ordinary and (b) fractional Zener model.
452
(FPTM), respectively. We stop to note that Heymans [61] has also analyzed more
complex models, which are composed of FEs and additional conventional
elements.
The constitutive equations of FZM and of FPTM (these being our basic,
simplest models containing 3 FEs) can be derived along the lines of the previous
section.
We start with the analysis of the FZM. The mechanical representation of the
FZM is displayed in Figure 13; it consists of an FMM (with the same parameters
as in Figure 8) in parallel to an FE specified by (z, E3,A3). The stresses on the
left and right branches of the arrangement, x L and XR, obey the following stress-
strain-relationships:
( y , E3,23)
q ( a , El,21) E2,~)
(a) (b)
Figure 14. The (a) Poynting-Thomson model and (b) its fractional generalization.
Table 5
Material functions of the fractional Zener and the Pointing-Thomson models
FZM FPTM
(v)
go 2C;-2~am~vl(Gat)
G(t) G F ~ ( t ) + G~(t) (44) (45)
E
+~GvE(t), for 3' - [3
E+E o
2
"-'l ,1FKVM
J(t) (46) JFKVM(t) + Jm(t) (47)
+ ~Ej o~ ( t ) , for r -
E+E o
(ic~162 + (ic~ (49)
G*(co) G*Mu(co) + E o (ico2) r (48) E- 1-[- E;l(i(.0,~,)~z_.y --[-E;l(i(_.O/],)fl_y
J*(co) (~)-~'-~+(~'~)-~
E + Eo(i~:k) + Eo(i~X) ~-~ (50) J ~9v M (co) + Eo ~(ico,r -~ (51 )
454
t -~ for t<<)~
(52)
G(t) oc t -~ for )~ << t << )~,
t -Y for )~ <<t.
G'oc co~, G"oc co-~ behavior. In the example of Figure 2 13 "~ 1/4 and a is
positive and close to zero, hence G' displays a quasi-plateau. In the
corresponding relaxation experiment the stress decays then first according to a
power law with slope - a , which is followed by an exponential relaxation at
longer times. Figure 15 shows the relaxation function G(t) of a modified
polybutadiene [64] where the appearance of an intermediate power-law domain is
clearly evident. In Figure 15, due to experimental limitations, the plateau can not
be seen directly but it can be infered from its dynamic modulus (especially from
the range aTco > 10 ), displayed in Figure 16. Now, fluid behavior is associated
with the termination of all relaxation processes, say at the time )~m, and thus )~m is
a natural cut-off. This can be achieved phenomenologically by multiplying the
corresponding decay function with an exponential. As an example, starting from
GF~(t ) (cf. equation (32)) in reference [18] the following 6-parameter relaxation
function was put forward
J*(co) -
(55)
G O io)/~ (i0)/9~ "Jr"2/~l~m) fl-1 "
456
Especially the dynamic moduli turn out to be particularly useful, since they
lead to equations which are easy to use for fits to the data. Figure 16 shows
exemplarily both the data and the obtained fits. For the PB202 sample we obtain
f l - 0.578 and log/~ m = 2.48. This is in good agreement with the parameters
/3'- 0.556 and log2~ - 2 . 2 4 which are determined by fitting equation (53) to
the relaxation function of the sample displayed in Figure 15.
In Figure 15 the glassy short-time behavior (with the plateau modulus Go ) is
not in the experimentally accessible range. In such a case the data may be fitted
by a simpler relaxation function, which one obtains from equation (53) by letting
2 ~ 0. This leads to
(56)
G(t) - Go1. (t/2~) -p exp(-t/2m)
r ~ _ . .
,~ I PB 202
10s . ~ . .~ Tref= 30 ~
04 _
10 3
102
10l 10 ~ 101 10 2 10 3 10 4
t/s
Figure 15. Relaxation function G(t) of a modified polybutadiene (PB 202, Mw =
21 kg/mol). The solid line is equation (56) with log G0l = 4.68 Pa, log km = 2.24 s
and 13= 0.556.
457
10 6
10 5 Tref= 30 ~
r 10 4
~ 10 3 9 PB200
PB202
o PB204
10 2 Model
Equation (57) contains an explicit time dependence that can be removed using the
product rule for fractional differential operators (cf. equation (5.5.2) of [26]). In
this way, the RCE, equation (57) takes the form [10]"
458
oc oo
w i t h a, - c t - i, bj - f l - j and w - 2/2 m .
A RCE with a structure similar to equation (57) was given in reference [63]. A
mechanical model composed of spring, dashpots and fractional elements is not
k n o w n f o r this R C E .
10 6 _
10 5 -
10 4 -
o G'
10 3 -
t~ G t~
10 2 - Model
aTO) / r a d s -1
Figure 17. Storage G'(arco ) and loss modulus G"(arCO) for polybutadiene
(PB18), for details see reference [69]. The solid lines represent the fit of the
generalized fractional Maxwell model according to equation (54) to the data.
459
I I I I I I
0000(
QFIDI3D [
9
/
9
_
PB-M2 o~ o G'
O
2- o
o n G II
I
O
O
oo 1
l I I O I I I I,
-4 -3 -2 -! 0 ] 2 3
Figure 18. Storage G'(arCO) and loss modulus G"(arco ) for an unmodified (PB)
and a sidechain modified polybutadiene (PB-M2), for details see reference [70].
The solid lines represent the fit according to equation (59) to the data.
are depicted by the FMM; multiplying G'z,~ (co) with an additional relaxation
term leads to:
Now the other relaxation functions of the model can be calculated following
the procedures outlined above. The relaxation modulus G(t) and the creep
compliance J(t) turn out to be complex expressions, which can be found in
reference [70]. Figure 18 shows that equation (58) reproduces successfully the
data, as indicated by the fitting curve. We close by giving the RCE belonging to
equation (58) [70]:
7. CONCLUSIONS AND O U T L O O K
the Kelvin-Voigt, the Zener and the Poynting-Thomson models. The relaxation
patterns of these models can be used to fit the experimental results for large
classes of materials. Particularly noticeable candidates are polymeric materials
which display ramified structures (such as cross-linked polymers) or whose
dynamics is characterized by cooperativity (i.e. glasses). Using fractional
elements one can tailor viscoelastic models with given properties, while keeping
the number of parameters involved relatively low.
The representation of generalized viscoelastic models by fractional analogues
also allows a deeper insight into the physics behind fractional stress-strain
relations. Nevertheless, we are still far from a reductionistic understanding of the
fractional relaxation laws. Here, as well as in related areas, we expect much
additional work in the coming years.
ACKNOWLEDGEMENT
The support of the DFG through SFB 428 and of the Fonds der Chemischen
Industrie is gratefully acknowledged.
APPENDIX
z k
, with la > 0 and v > 0. (61)
The special case v - 1 yields the usual Mittag-Leffler function E~,(z). On the
basis of this definition, the generalized Mittag-Leffier functions for some special
cases, in which la and v equal 0.5, 1 or 2, follow readily"
462
Eo.5,1(z ~ - e ~ erfc(_z ~
- - e ~ erfc(-z ~ 1- 2 z
z
El,l ( Z 1 ) - e z
(62)
E1,2(zl) - l [e: - l]
z
E2,1 (z 2 ) - c h ( z )
la z -2 for l a ~ l (63)
V(1 -
1 -1
E,.~(-z) ~: F ( v - l a ) z for v > la.
Consider now the relaxation function G(t) of the FMM, equation (32). Here the
generalized Mittag-Leffier function has the parameters l a - a - 13 and v - 1-13.
From definition (61) and the asymptotic expansion (63) one obtains for the two
power-law regimes:
G ( t ) ~: t -~ for t <<
(64)
G ( t ) ~: {
t -~
t
(a<l)
- 1)
for t >> ~,.
In Figure 19 we show the relaxation function of the FMM, equation (32), for
r - 1 and 13- 0.5. For the sake of comparison two other relaxation functions are
added, which are different from the double power-law relaxation in the long time
range.
463
i i i i i i i i
o- " ~176176
~,-2
~-4
/\\
i
O -6
-8 - (a) x "0"5 e -x / / -
(b) x "0"5 e"xO5
-10 i i i ~ , ~ , i
-4 -3 -2 -1 0 1 2 3 4 5
log x
Figure 19. Dimensionless relaxation function G ( t ) / G o vs dimensionless time
t / 2 for three models corresponding to different asymptotic behaviors (a)
exponential, (b) stretched exponential and (c) power-law.
,~, 0
0
"~ -2
tzr
0 -4
-6 -
-5 -4 -3 -2 -1 0 1 2 3 4 5
log x
Figure 20. Comparison of a Mittag-Leffier function, lhs. of equation (65), with
one of its Pad6 approximants, rhs. of equation (65).
464
The result is presented in Figure 20; note that deviations from the exact result are
small and are restricted to the transition region between the power-law domains.
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Moscow, 1980.
47. Chr. Friedrich and S. Hazanov, in: D.A. SiNner and Y.G. Yanovsky (eds.),
Advances in Structured and Heterogeneous Continua, Allerton Press, New
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48 R.L. Bagley, J. Rheol., 27 (1983), 201.
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50 L. Rogers, J. Rheol., 27 (1983), 351.
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53 R. Metzler, W. Schick, H.-G. Kilian and T.F. Nonnenmacher, J. Chem. Phys.,
103 (1995), 7180.
54. H. Schiessel and A. Blumen, J. Phys. A, 26 (1993), 5057.
55. H. Schiessel, P. Alemany and A. Blumen, Progr. Colloid Polym. Sci., 96
(1994), 16.
56. H. Schiessel and A. Blumen, Macromolecules, 28 (1995), 4013.
57. H. Schiessel and A. Blumen, Fractals, 3 (1995), 483.
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(1995), 6567.
59 J.-C. Bauwens, Colloid Polyrn. Sci. 270 (1992), 537.
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61 N. Heymans, Rheol. Acta, 35 (1996), 508.
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Steinkopffverlag, Darmstadt, 1994, p. 45.
66. L.I. Palade, V. Vemey and P. Attane, Rheol. Acta, 35 (1996), 265.
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Disordered Systems, Springer, Berlin, 1991, p. 97.
69. M. Mours and H.H. Winter, Macromolecules, 29 (1996), 7221.
70. Chr. Friedrich, Acta Polymerica, 46 (1995), 385.
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467
T H E K I N E T I C T H E O R Y OF D I L U T E S O L U T I O N S OF
FLEXIBLE POLYMERS: HYDRODYNAMIC INTERACTION
J. R a v i P r a k a s h a
1. I N T R O D U C T I O N
for the macroscopic properties of the polymer solution. For instance, the
simplest theory based on a bead-spring model assumes that the solvent
influences the motion of the beads by exerting a drag force and a Brown-
ian force. Since this theory fails to predict a large number of the observed
features of polymer solutions, more advanced theories have been developed
which incorporate additional microscopic phenomena. Thus, theories have
been developed which (i) include the phenomenon of 'hydrodynamic inter-
action' between the beads, (ii) try to account for the finite extensibility of
the polymer molecule, (iii) attempt to ensure that two parts of the poly-
mer chain do not occupy the same place at the same time, (iv) consider
the internal friction experienced when two parts of a polymer chain close
to each other in space move apart, and so on. The aim of this chapter is
to present the unified framework within which these microscopic phenom-
ena may be treated, and to focus in particular on recent advances in the
treatment of the effect of hydrodynamic interaction. To a large extent, the
notation that is used here is the same as that in the treatise Dynamics of
Polymeric Liquids by Bird and co-authors [2].
2. T R A N S P O R T PROPERTIES OF D I L U T E S O L U T I O N S
2.1. D i l u t e s o l u t i o n s
A solution is considered dilute if the polymer chains are isolated from
each other and have negligible interactions with each other. In this regime
of concentration the polymer solution's properties are determined by the
nature of the interaction between the segments of a single polymer chain
with each other, and by the nature of the interaction between the segments
and the surrounding solvent molecules. As the concentration of polymers
is increased, a new threshold is reached where the polymer molecules begin
to interpenetrate and interact with each other. This threshold is reached
at a surprisingly low concentration, and heralds the inception of the semi-
dilute regime, where the polymer solution's properties have been found to
be significantly different. Beyond the semi-dilute regime lie concentrated
solutions and melts. In this chapter we are concerned exclusively with the
behavior of dilute solutions.
A discussion of the threshold concentration at which the semi-dilute
regime in initiated is helpful in introducing several concepts that are used
frequently in the description of polymer solutions.
469
where Up is the polymer contribution to the solution viscosity, and r/s is the
solvent viscosity.
470
2.2. H o m o g e n e o u s flows
Complex flow situations typically encountered in polymer processing fre-
quently involve a combination of shearing and extensional deformations.
The response of the polymer solution to these two modes of deformation
is very different. Consequently, predicting the rheological properties of the
solution under both shear and extensional deformation is considered to be
very important in order to properly characterise the solutions behavior.
Rather than considering flows where both these modes of deformation are
simultaneously present, it is common in polymer kinetic theory to anal-
yse simpler flow situations called homogeneous flows, where they may be
treated separately.
A flow is called homogeneous, if the rate of strain tensor, "~ - ( V v ) ( t ) +
(~7v)t(t), where v is the solution velocity field, is independent of position.
In other words, the solution velocity field v in homogeneous flows, can
always be represented as v = v0 + ~(t) -r, where v0 is a constant vector,
~(t) - Vv(t) is a traceless tensor for incompressible fluids, and r is the
position vector with respect to a laboratory fixed frame of reference. While
there is no spatial variation in the rate of strain tensor in homogeneous
flows, there is no restriction with regard to its variation in time. Therefore,
the response of dilute solutions to transient shear and extensional flows is
also used to probe its character as an alternative means of characterisation
independent of the steady state material functions.
Two homogeneous flows, steady simple shear flow and small amplitude
oscillatory shear flow, that are frequently used to validate the predictions
of molecular theories which incorporate hydrodynamic interaction, are de-
scribed briefly below. A comprehensive discussion of material functions in
various flow situations can be found in the book by Bird et al. [1].
vz-O (2)
where the velocity gradient ~yx can be a function of time. From consid-
erations of symmetry, one can show that the most general form that the
polymer contribution to the stress tensor can have in simple shear flows
is [1],
% % 0 (3)
o o rPzz
where the matrix of components in a Cartesian coordinate system is dis-
played. The form of the stress tensor implies that only three independent
combinations can be measured for an incompressible fluid. All simple shear
flows are consequently characterised by three material functions.
(~176/
tation in the laboratory-fixed coordinate system,
~-x/ 0 0 0 (4)
0 0 0
The three independent material functions used to characterize such flows
are the viscosity, rip, and the first and second normal stress difference co-
efficients, ~1 and ~2, respectively. These functions are defined by the fol-
lowing relations,
< _ _ - (5)
with increasing shear rate, and exhibit a pronounced power law region.
At very high shear rates, the viscosity has been observed to level off and
approach a constant value, r/p,~, called the infinite shear rate visosity. A
high shear rate limiting value has not been observed for the first normal
stress coefficient. The second normal stress coefficient is much smaller in
magnitude than the first normal stress coefficient, however its sign has not
been conclusively established experimentally. Note that the normal stress
differences are zero for a Newtonian fluid. The existence of non-zero normal
stress differences is an indication that the fluid is viscoelastic.
Experiments with very high molecular weight systems seem to suggest
that polymer solutions can also shear thicken. It has been observed that
the viscosity passes through a minimum with increasing shear rate, and
then increases until a plateau region before shear thinning again [17].
It is appropriate here to note that shear flow material functions are
usually displayed in terms of the reduced variables, ~?p/~?p,O,~1/~1,o and
~2/~1, versus a non-dimensional shear rate fl, which is defined by fl = )~ph/,
where, Ap = [r/J0M rl~/NA kB T, is a characteristic relaxation time. The
subscript 0 on the square bracket indicates that this quantity is evalu-
ated in the limit of vanishing shear rate, kB is Boltzmann's constant and
T is the absolute temperature. For dilute solutions one can show that,
[?7]/[?']]0 - - ?~p/?~p,O and ~ - ?~p,O ;y/np kB T.
0 1 0)
~(t)-%coswt 0 0 0 (6)
0 0 0
Since the polymer contribution to the shear stress in oscillatory shear
flow, ~-~,
p undergoes a phase shift with respect to the shear strain and the
strain rate, it is customary to represent its dependence on time through
473
- f0 (9)
Experimental plots of log G' and log G" versus nondimensional frequency
show three distinct power law regimes. The regime of interest is the in-
termediate regime [17], where for dilute solutions of high molecular weight
polymers in good or theta solvents, both G' and G" have been observed to
scale with frequency as w 2/3.
It is appropriate to note here that the zero shear rate viscosity ~p,0 and
the zero shear rate first normal stress difference ~1,0, which are linear
viscoelastic properties, can be obtained from the complex viscosity in the
limit of vanishing frequency,
2 rf(w) (10)
~p,0 - ~a-+0
lira r/',,(w) ; 91,0 - lira
~a-+0 03
474
2.4. Scaling w i t h m o l e c u l a r w e i g h t
We have already discussed the scaling of the root mean square end-to-end
distance of a polymer molecule with its molecular weight. In this section
we discuss the scaling of the zero shear rate intrinsic viscosity It/]0, and the
translational diffusion coefficient D, with the molecular weight, M. As we
shall see later, these have proven to be vitally important as experimental
benchmarks in attempts to improve predictions of molecular theories.
It has been found that the relationship between [y]0 and M can be ex-
pressed by the formula,
[~]o-KM a (11)
where the exponent # lies in the range 0.49 to 0.6. Most theta solutions
have values of # close to the lower limit. On the other hand, there is wide
variety in the value of # reported for good solvents. It appears that the
upper limit is attained only for very large molecular weight polymers and
the intermediate values, corresponding to a cross over region, are more
typical of real polymers with moderate molecular weights.
2.5. U n i v e r s a l b e h a v i o r
It is appropriate at this point to discuss the most important aspect of
the behavior of polymer solutions (as far as the theoretical modelling of
these solutions is concerned) that is revealed by the various experimental
observations. When the experimental data for high molecular weight sys-
tems is plotted in terms of appropriately normalized coordinates, the most
noticeable feature is the exhibition of u n i v e r s a l behavior. By this it is
475
meant that curves for different values of a parameter, such as the molec-
ular weight, the temperature, or even for different type8 of monomer8 can
be 8uperposed onto a 8ingle curve. For example, when the reduced intrin-
sic viscosity, [u]/[n]0 is plotted as a function of the reduced shear rate/ ,
the curves for polystyrene in different type8 of good solvent8 at various
temperatures collapse onto a 8ingle curve [1].
There is, however, an important point that must be noted. While poly-
mer8 dissolved in both theta solvents and good solvents show universal
behavior, the universal behavior is different in the two cases. An example
of this i8 the observed sca]ing behavior of various quantities with molecular
weight. The scaling is universal within the context of a particular type of
801vent. The term universality class is used to describe the set of systems
that exhibit common universal behavior [40]. Thus theta and good 80lvents
be]ong to different universality classes.
The existence of universality classes is very significant for the theoret-
ical description of polymer solutions. Any attempt made at modelling a
polymer so]ution's properties might expect that a proper description must
incorporate the chemical structure of the polymer into the model, since
this determines its microscopic behavior. Thus a detailed consideration of
bonds, sidegroups, etc. may be envisaged. However, the universal behav-
ior that i8 revealed by experiments suggests that macroscopic properties of
the polymer solution are determined by a few large scale properties of the
polymer molecule. Structural details may be ignored since at length scales
in the order of nanometer8, different polymer molecule8 become equivalent
to each other, and behave in the same manner. A8 a result, polymer 80-
lutions that differ from each other with regard to the chemical structure
or molecular weight of the polymer mo]ecu]es that are dissolved in it, the
temperature, and so on, still behave similarly as ]ong as a few parameter8
that describe molecular features are the same.
This universal behavior justifies the introduction of crude mechanical
models, such as the bead-spring chain, to represent real polymer molecules.
On the other hand, it is interesting to note that in many cases, the pre-
dictions of these models are not universal. It turns out that apart from a
basic length and time scale, there occur other parameters that need to be
prescribed, for example, the number of beads N in the chain, the strength
of hydrodynamic interaction h*, the finite spring extensibility parameter
476
b, and so on. It is perhaps not incorrect to state that any molecular the-
ory that is developed must ultimately verify that universal predictions of
transport properties are indeed obtained. The universal predictions of ki-
netic theory models with hydrodynamic interaction are discussed later on
in this chapter.
3. B E A D - S P R I N G CHAIN MODELS
The development of a kinetic theory for dilute solutions has been ap-
proached in two different ways. One of them is an intuitive approach in
the configuration space of a single molecule, with a particular mechanical
model chosen to represent the macromolecule, such as a freely rotating
bead-rod chain or a freely jointed bead-spring chain [13,36,45]. The other
approach is to develop a formal theory in the phase space of the entire
solution, with the polymer molecule represented by a general mechanical
model that may have internal constraints, such as constant bond lengths
and angles [16,5,2]. The results of the former method are completely con-
tained within the latter method, and several ad hoc assumptions made in
the intuitive treatment are clarified and placed in proper context by the
development of the rigorous phase space theory. Kinetic theories devel-
oped for flexible macromolecules in dilute solutions have generally pursued
the intuitive approach, with the bead-spring model proving to be the most
popular. This is because the lack of internal constaints in the model makes
the formulation of the theory simpler. Recently, Curtiss and Bird [4], ac-
knowledging the 'notational and mathematical' complexity of the rigorous
phase space theory for general mechanical models, have summarised the
results of phase space theory for the special case of bead-spring models
with arbitrary connectivity, ie. for linear chains, rings, stars, combs and
branched chains.
In this section, since we are primarily concerned with reviewing recent
developments in theories for flexible macromolecules, we describe the devel-
opment of kinetic theories in the configuration space of a single molecule.
However, readers who wish the understand the origin of the ad hoc expres-
sions used for the Brownian forces and the hydrodynamic force, and the
formal development of expressions for the momentum and mass flux, are
urged to read the article by Curtiss and Bird [4].
The general diffusion equation that governs the time evolution of the
477
jointed bead-rod chain [2]. The introduction of the beads is to account for
the mass of the polymer molecule a n d the viscous drag experienced by
the polymer molecule. While in reality the mass and drag are distributed
continuously along the length of the chain, the model assumes that the
total mass and drag may be distributed over a finite number of discrete
beads.
For a general chain model consisting of N beads, which have position
vectors r~, u = 1, 2 , . . . , N, in a laboratory fixed coordinate system, the
Hamiltonian is given by,
where K: is the kinetic energy of the system and r is the potential energy.
r depends on the location of all the particles.
The center of mass r~ of the chain, and its velocity i% are given by
1 N 1 N
rc = N ~=1
Er~ ; /'~= N E=/ ' ~ (14)
~-1
where/-~ = dr~/dt. The location of a bead with respect to the center of
mass is specified by the vector R~ = r~ - re.
If Q1, Q2, ... Qd denote the generalised internal coordinates required to
specify the configuration of the chain, then the kinetic energy of the chain
in terms of the velocity of the center of mass and the generalised velocities
Q ~ - dQ~/dt, is given by [2],
I c _ m N .2 1
2 rc + -2 V E g~t Qs Qt (15)
t
where the indices s and t vary from 1 to d, m is the mass of a bead, and
g~t is the metric matrix, defined by, g~t - m E~ (OR~/OQ~). (OR~/OQt).
In terms of the momentum of the center of mass, Pc = m N/%, and the
generalised momenta P~, defined by, P~ - (OIC]OQ~), the kinetic energy
has the form [2],
1 2 1
K: - 2m N p~ + 2 V y] G~t P~ Pt (16)
t
where, G st are the components of the matrix inverse to the metric matrix,
F~t G~t gtu - 5s~, and 5~u is the Kronecker delta.
479
For an N-bead chain whose potential energy does not depend on the loca-
tion of the center of mass, the following result is obtained by carrying out
the integrations over Pc and P [2],
where Oi and r are the polar angles for the ith link in the chain [2].
Since the polymer chain explores many states in the duration of an ob-
servation quantities observed on macroscopic length and time scales are
averages of functions of the configurations and momenta of the polymer
chain. A few definitions of averages are now introduced that are used
frequently subsequently in the chapter.
The average value of a function X (r~, Q, pc, P ), defined in the phase
space of a polymer molecule is given by,
For an N-bead chain whose potential energy does not depend on the loca-
tion of the center of mass, the integrations over rc, Pc and P can be carried
out to give,
Z(r)- C/5(r- ~
i
aui)r (28)
Comparing this equation with the equation for the end-to-end vector (25),
one can conclude that,
Z (r) -- C Peq (r) (29)
482
H- 3kBT (32)
(N- 1)a2
The equivalence of the behavior of an ideal chain to that of a Hookean
spring is responsible for the introduction of the bead-spring chain model.
Since long enough sub-chains within the ideal chain also have normally
distributed end-to-end vectors, the entire ideal chain may be replaced by
beads connected to each other by springs. Note that each bead in a bead-
spring chain represents the mass of a sub-chain of the ideal chain, while
the spring imitates the behavior of the end-to-end vector of the sub-chain.
The change in the Helmholtz free energy of an ideal chain due to a
change in the end-to-end vector is purely due to entropic considerations.
The internal energy, which has only the kinetic energy contribution, does
not depend on the end-to-end vector. Increasing the end-to-end vector of
483
the chain decreases the number of allowed configurations, and this change
is resisted by the chain. The entropic origin of the resistance is responsible
for the use of the phrase entropic spring to describe the springs of the
bead-spring chain model.
The potential energy S, of a bead-spring chain due to the presence of
Hookean springs is the sum of the potential energies of all the springs in
the chain. For a bead-spring chain with N beads, this is given by,
N-1
1H E qi" qi (33)
1 N-1 1 N
r - -~ H ~ Qi . Qi + -~v kBT Z 5(r~-ru) (35)
i--1 ~,~=1
tt#u
485
3.2. N o n - e q u i l i b r i u m c o n f i g u r a t i o n s
Unlike in the case of equilibrium solutions it is not possible to derive
the phase space distribution function for non-equilibrium solutions from
very general arguments. As we shall see here it is only possible to derive
a partial differential equation that governs the evolution of the configura-
tional distribution function by considering the conservation of probability
in phase space, and the equation of motion for the particular model chosen.
The arguments relevent to a bead-spring chain are developed below.
the theory. Note that the velocity of the solution at bead # has two com-
ponents, the imposed flow field vu - v0 + ~(t) 9r~, and the perturbation
of the flow field v~t due to the motion of the other beads of the chain. This
perturbation is called hydrodynamic interaction, and its incorporation in
molecular theories has proved to be of utmost importance in the prediction
of transport properties. The presence of hydrodynamic interaction couples
the motion of one bead in the chain to all the other beads, regardless of
the distance between the beads along the length of the chain. In this sense,
hydrodynamic interaction is a long range phenomena.
The perturbation to the flow field v~(r) at a point r due to the presence
of a point force F ( r ~) at the point r ~, can be found by solving the linearised
Navier-Stokes equation [1,8],
n(r)-
1
87rq,r
(1 + rr )
r-2
(46)
The effect of hydrodynamic interaction is taken into account in polymer
kinetic theory by treating the beads in the bead-spring chain as point
particles. As a result, in response to the hydrodynamic drag force acting
on each bead, each bead exerts an equal and opposite force on the solvent
at the point that defines its location. The disturbance to the velocity at
the bead v is the sum of the disturbances caused by all the other beads in
the chain, v" - - ~u ~ u ( r ~ - ru). F (h), where, ~ - ~v~ is given by,
~u~--
{ 87rrlsru~
1 (1+ ru~ru~)
r2 , ru~--ru-r~, for##v (47)
]zy
0 for # - - u
The Brownian force F(~b), on a bead # is the result of the irregular colli-
sions between the solvent molecules and the bead. Instead of representing
the Brownian force by a randomly varying force, it is common in polymer
kinetic theory to use an averaged Brownian force,
F(~)_ 0r (49)
(-
F ,(iv) = 99 ( r . + l - - r # ) ( r . + l l 2
[r.+l -- r.
rt~)).[~#+1__~#]]
1
[[Oj]] - ~" Q j - -~ Z Ajk" ( kBT 0 In 9 0r f(iv) (55)
k
where, Bku is defined by, -Bk~ -- 5k+1,~- 5k~, the internal viscosity force,
fk(i~), in the direction of the connector vector Qk is,
Q'Q* (56)
- I I ]]
and the tensor -Ajb which accounts for the presence of hydrodynamic in-
teraction is defined by,
The independence of 9 from the location of the center of mass for homo-
geneous flows, and the result tr ~ - 0, for an incompressible fluid, can be
shown to imply that the equation of continuity can be written in terms of
internal coordinates alone as [2],
0r 0
0~ - - E o q / [ [ Qj] r (60)
J
The general diffusion equation which governs the time evolution of the
instantaneous configurational distribution function r in the presence of hy-
drodynamic interaction, arbitrary spring and excluded volume forces, and
an internal viscosity force given by equation (56), is obtained by substitut-
ing the equation of motion for ~-(~j~J from equation (55) into equation (60).
It has the form,
0r 0 1 0r ~(i~)
: - j
0qj qJ - Ek [0q 1)
0
kBT ~ OQj Aik" 0r -
(61)
+ ~ j,k OQk
eral analytically insoluble. There have been very few attempts to di-
rectly solve diffusion equations with the help of a numerical solution proce-
dure [9,10]. In this context it is worth bearing in mind that what are usually
required are averages of configuration dependent quantities. However, in
general even averages cannot be obtained exactly by solving equation (62).
As a result, it is common in most molecular theories to obtain the averages
by means of various approximations.
In order to examine the validity of these approximations it is vitally
important to compare the approximate predictions of transport proper-
ties with the exact predictions of the models. One of the ways by which
exact numerical results may be obtained is by adopting a numerical pro-
cedure based on the mathematical equivalence of diffusion equations in
polymer configuration space and stochastic differential equations for the
polymer configuration [29]. Instead of numerically solving the analytically
intractable difusion equation for the distribution function, stochastic tra-
jectories can be generated by Brownian dynamics simulations based on a
numerical integration of the appropriate stochastic differential equation.
Averages calculated from stochastic trajectories (obtained as a solution of
the stochastic differential equations), are identical to the averages calcu-
lated from distribution functions (obtained as a solution of the diffusion
equations). It has now become fairly common for any new approximate
molecular theory of a microscopic phenomenon to establish the accuracy
of the results with the help of Brownian dynamics simulations. In this
chapter, while results of such simulations are cited, details of the develop:
ment of the appropriate stochastic differential equations are not discussed.
A comprehensive introduction to the development of stochastic differen-
tial equations which are equivalent to given diffusion equations for the
probability density in configuration space, can be found in the treatise by
Ottinger [29].
3.3. T h e R o u s e m o d e l
The Rouse model assumes that the springs of the bead-spring chain are
governed by a Hookean spring force law. The only solvent-polymer interac-
tions treated are that of hydrodynamic drag and Brownian bombardment.
The diffusion equation (61) with the effects of hydrodynamic interaction,
excluded volume and internal viscosity neglected, and with a Hookean
spring force law, has the form,
_ 0 H kBT 0 0r (66)
0 r _ _ ~ oqj" (~" Qj - --( ~-" Ajk Qk ) r + - - ~ ~ Ajk i)Qj'Oqk
Ot j k j,k
where Af(t) is the normalisation factor, and the tensor O)k which uniquely
characterises the Gaussian distribution is identical to the second moment,
o ) k - <QjQk) (68)
Note that the tensors O)k are not symmetric, but satisfy the relation
~k -- Jkj- (Further information on linear diffusion equations and Gaussian
distributions can be obtained in the extended discussion in Appendix A
of [22]).
Since the intramolecular potential in the Rouse model is only due to the
presence of Hookean springs, it is straight forward to see that the Kramers
expression for the stress tensor r p, is given by,
v p -- - n p H ~ ajj + ( N - 1)npkBT 1 (69)
J
The tensors ~ j are obtained by solving the second moment equation (65),
which becomes a closed equation for the second moments when the Rouse
assumptions are made. It has the form,
H
d t ~ k -- ~ " ajk -- erjk . ~ t _ 2 k u T A j k 1 - - -
-
~-~[ a j m A m k -b A i m ermk ] (70)
Note that the solution of equation (70) also leads to the complete specifi-
cation of the Gaussian configurational distribution function r
A H o o k e a n d u m b b e l l model, which is the simplest example of a bead-
spring chain, is obtained by setting N = 2. It is often used for preliminary
calculations since its simplicity makes it possible to obtain analytical so-
lutions where numerical solutions are unavoidable for longer chains. For
such a model, substituting for ~rll in terms of r p from equation (69) into
equation (70), leads to following equation for the polymer contribution to
the stress tensor,
~'P + A s rP(1) -- - - n p k B T A H ~/ (71)
Qj - ~ 1-IjkQk! (72)
where, I-Ijk are the elements of an orthogonal matrix with the property
(I-l-1)jk -- 1-Ikj , such that, ~ 1]mjYImk -- ~jk (73)
m
The orthogonal matrix Iljk , which will henceforth be referred to as the
Rouse orthogonal matrix, diagonalises the Rouse matrix Ajk,
IIjiAjkIIkl - at&t (74)
j,k
where, the Rouse eigenvalues at are given by at - 4sin2(17r/2N). The
elements of the Rouse orthogonal matrix are given by the expression,
2
(75)
where,
4. H Y D R O D Y N A M I C INTERACTION
0r 0 H kBT 0 - 0r (81)
Ot - -~j9 OQj " (~" Qj - --~ y~
k
Ayk "Qk)r + r
Y~ OQj "Ajk " OQk
j,k
Equation (82) is not a closed equation for the second moments since it
involves more complicated moments on the right hand side. This is the
central problem of all molecular theories which attempt to predict the
rheological properties of dilute polymer solutions and that incorporate hy-
drodynamic interaction. The different approximate treatments of hydro-
dynamic interaction, which are discussed roughly chronologically below,
basically reduce to finding a suitable closure approximation for the second
moment equation.
4.1. T h e Z i m m model
The Z i m m model was the first attempt at improving the Rouse model
by introducing the effect of hydrodynamic interaction in a preaveraged or
equilibrium-averaged form. The preaveraging approximation has been very
frequently used in polymer literature since its introduction by Kirkwood
and Riseman [14]. The approximation consists of evaluating the average of
the hydrodynamic tensor with the equilibrium distribution function (34),
and replacing the hydrodynamic interaction tensor Ajk, wherever it occurs
500
in the governing equations, with its equilibrium average Ajk. (Note that
the incorporation of the effect of hydrodynamic interaction does not alter
the equilibrium distribution function, which is still given by (34) for bead-
spring chains with Hookean springs.) The matrix Ajk is called the modified
Rouse matrix, and is given by,
--- 2 1 _ 1 ) (83)
- + h*(v/i j ki ~/iJ - k- 1[ v/Ij - k + 11
where, h* -- a v / ( H / z r k B T ) is the hydrodynamic interaction parameter. The
hydrodynamic interaction parameter is approximately equal to the ratio of
the bead radius to the equilibrium root mean square length of a single
spring of the bead-spring chain. This implies that h* < 0.5, since the
beads cannot overlap. Typical values used for h* are in the range 0.1 <
h* < 0.3 [22].
By including the hydrodynamic interaction in an averaged form, the dif-
fusion equation remains linear in the connector vectors, and consequently
is satisfied by a Gaussian distribution (67) as in the Rouse case. However,
the covariance tensors ~k are now governed by the set of differential equa-
tions (70) with the Rouse matrix Ajk replaced with the modified Rouse
matrix Ajk. Note that this modified second moment equation is also a
closed set of equations for the second moments.
As in the Rouse case, it is possible to simplify the solution of the Zimm
model by carrying out a diagonalisation procedure. This is achieved by
mapping the connector vectors to normal coordinates, as in (72), but in
this case the Zimm orthogonal matrix l-ljk, which diagonalises the modified
Rouse matrix,
N
stresses ~'jP as in equation (77), but the "FjP n o w satisfy equation (79) with
the 'Rouse' relaxation times Aj replaced with 'Zimm' relaxation times Aj.
The Zimm relaxation times are defined by )~j - ( ~ / 2 H ~j).
From the discussion above, it is clear that the Zimm model differs from
the Rouse model only in the spectrum of relaxation times. As we shall
see shortly, this leads to a significant improvement in the prediction of
linear viscoelastic properties and the scaling of transport properties with
molecular weight in theta solvents. The Zimm model therefore establishes
unequivocally the importance of the microscopic phenomenon of hydrody-
namic interaction. On the other hand, it does not lead to any improvement
in the prediction of nonlinear properties, and consequently subsequent
treatments of hydrodynamic interaction have concentrated on improving
this aspect of the Zimm model.
By considering the long chain limit of the Zimm model, ie., N --+ c~, it
is possible to discuss the universal properties predicted by the model. The
various power law dependences of transport properties on molecular weight,
characterised by universal exponents, and universal ratios formed from
the prefactors of these dependences can be obtained. These predictions
are ideal for comparison with experimental data on high molecular weight
polymer solutions since they are parameter free. We shall discuss some
universal exponents predicted by the Zimm model below, while universal
ratios are discussed later in the chapter.
As mentioned above, the first noticeable change upon the introduction of
hydrodynamic interaction is the change in the relaxation spectrum. In the
long chain limit, the longest relaxation times/~j scale with chain length as
N 3/2 [29], whereas we had found earlier that the chain length dependence
of the longest relaxation times in the Rouse model was N 2.
In steady simple shear flow, the Zimm model like the Rouse model, fails to
predict the experimentally observed occurance of non-zero second normal
stress differences and the experimentally observed shear rate dependence
of the viscometric functions. It does however lead to an improved predic-
tion of the scaling of the zero shear rate intrinsic viscosity with molecular
weight, [~]0 ~ N 1/2. This prediction is in agreement with experimental re-
sults for the Mark-Houwink exponent in theta solvents (see equation (11)).
As with the longest relaxation times, the characteristic relaxation time
Ap ~ N 3/2.
502
In small amplitude oscillatory shear, the Zimm model predicts that the
material functions G ~ and G " scale with frequency as w 2/3 in the interme-
diate frequency range. This is in exceedingly good agreement with experi-
mental results [2,17].
The translational diffusion coefficient D for chainlike molecules at equilib-
rium, with preaveraged hydrodynamic interaction, was originally obtained
by Kirkwood [14]. Subsequently, several workers obtained a correction to
the Kirkwood diffusion coefficient for the Zimm model [21]. The exact re-
sults differ by less than 2% from the Kirkwood value for all values of the
chain length and h*. Interestingly, three different approaches to obtaining
the diffusion coefficient, namely, the Nernst-Einstein equation, the calcu-
lation of the mean-square displacement caused by Brownian forces, and
the study of the time evolution of concentration gradients, lead to identi-
cal expressions for the diffusion coefficient [21]. In the limit of very long
chains, it can be shown that D ~ N -1/2. The Zimm model therefore gives
the correct dependence of translational diffusivity on molecular weight in
theta solvents.
The Zimm result for the translational diffusivity has been traditionally
interpreted to mean that the polymer coil in a theta solvent behaves like a
rigid sphere, with radius equal to the root mean square end-to-end distance.
This follows from the fact that the diffusion coefficient for a rigid sphere
scales as the inverse of the radius of the sphere, and in a theta solvent,
( r2)eq scales with chain length as N. The solvent inside the coil is believed
to be dragged along with the coil, and the inner most beads of the bead-
spring chain are considered to be shielded from the velocity field due to
the presence of hydrodynamic interaction [44,17]. This intuitive notion
has been used to point out the difference between the Zimm and the Rouse
model, where all the N beads of the polymer chain are considered to be
exposed to the applied velocity field. Recently, by explicitly calculating
the velocity field inside a polymer coil in the Zimm model, C)ttinger [30]
has shown that the solvent motion inside a polymer coil is different from
that of a rigid sphere throughout the polymer coil, and that shielding from
the velocity field occurs only to a certain extent.
-- [ H(&j,k) + H(&j+l,k+l)
Ajk -- Ajk I + x/~h* ~/IJ 5' k[
x/'lJ- kl
_ I (8s)
v/l)- k+ iI
where the tensors &,~ are given by,
1 H max(#w)-I
" --^ -- Z ~k (86)
O'l~V- ~ v 0"'1" II~- l/] ]gBr j,k=min(#w)
3 1 (l_kk 1
H(er) - 2(2rr)3/2 f e x p ( - k - o ' . k) (87)
504
Note that the convention H(~jj)/0 - 0 has been adopted in equation (85)
above.
The self-consistent closure approximation therefore consists of replacing
the hydrodynamic interaction tensor Ayk in equation (82) with its non-
equilibrium average A---jk. As in the earlier approximations, this leads to a
system of ( N - 1) 2 coupled ordinary differential equations for the compo-
nents of the covariance matrix a)k. Their solution permits the evaluation
of the stress tensor through the Kramers expression (69), and as a conse-
quence all the relevant material functions.
Viscometric functions in steady simple shear flows were obtained by
Ottinger [20] for chains with N ~ 25 beads, while material functions in
start-up of steady shear flow, cessation of steady shear flow, and stress re-
laxation after step-strain were obtained by Wedgewood and Ottinger [41]
for chains with N < 15 beads. The latter authors also include consistently-
averaged FENE springs in their model.
Shear rate dependent viscometric functions, and a nonzero positive sec-
ond normal stress difference are predicted by the self-consistent averaging
approximation; a marked improvement over the predictions of the Zimm
model. Both the reduced viscosity and the reduced first normal stress
difference initially decrease with increasing shear rate. However, for long
enough chains, they begin to rise monotonically at higher values of the
reduced shear rate ~. This rise is a consequence of the weakening of hy-
drodynamic interaction in strong flows due to an increase in the separation
between the beads of the chain. With increasing shear rate, the material
functions tend to the shear rate independent Rouse values, which (for long
enough chains), are higher than the zero shear rate consistently-averaged
values. The prediction of shear thickening behavior is not in agreement
with the shear thinning that is commonly observed experimentally. How-
ever, as mentioned earlier, some experiments with very high molecular
weight systems seem to suggest the existence of shear thinning followed by
shear thickening followed again by shear thinning as the shear rate is in-
creased. While only shear thickening at high shear rates is predicted with
Hookean springs, the inclusion of consistently-averaged FENE springs in
the model leads to predictions which are qualitatively in agreement with
these observations, with the FENE force becoming responsible for the shear
thinning at very high shear rates [41,15].
505
ration of the long chain limit in more accurate models of the hydrodynamic
interaction.
Short chains with consistently-averaged hydrodynamic interaction, as
noted earlier, do not show shear thickening behavior; this aspect is re-
vealed only with increasing chain length. Furthermore, it is not clear with
the kind of chain lengths that can be examined, whether the minimum in
the viscosity and first normal stress curves continue to exist in the long
chain limit [20]. The examination of long chain behavior is therefore im-
portant since aspects of polymer solution behavior might be revealed that
are otherwise hidden when only short chains are considered. The introduc-
tion of the decoupling approximation by Magda, Larson and Mackay [18]
and Kishbaugh and McHugh [15] made the examination of the shear rate
dependence of long chains feasible. The dccoupling approximation retains
the accuracy of the self-consistent averaging procedure, but is much more
computationally efficient.
4.3. T h e decoupling a p p r o x i m a t i o n
The decoupling approximation introduced by Magda et al. [18] and Kish-
baugh and McHugh [15] (who use FENE springs in place of the Hookean
springs of Magda et al.) consists of extending the 'diagonalise and de-
couple' procedure of the Rouse and Zimm theories to the case of the self
consistently averaged theory. They first transform the connector vectors
Qj to a new set of coordinates Q~ using the timc-invariant Rouse orthog-
onal matrix Iljk. (Kishbaugh and McHugh also use the Zimm orthogonal
matrix). The same orthogonal matrix Iljk is then assumed to diagonalise
the matrix of tensor components -Ajk. While the process of diagonalisa-
tion was exact in the Rouse and Zimm theories, it is an approximation in
the case of the decoupling approximation. It implies that even in the self
consistently averaged theory the diffusion equation can be solved by the
method of separation of variables, and only the ( N - 1 ) transformed coordi-
nate variances ~ are non-zero. The differential equations governing these
variances can be derived from the uncoupled diffusion equations and solved
numerically. The appropriate material functions are then obtained using
the Kramers expression in terms of the transformed coordinates, namely,
equations (77)and (78).
The decrease in the number of differential equations to be solved, from
( i - 1) 2 for the covariances ~jk to ( N - 1) for the variances dj, is suggested
507
by Kishbaugh and McHugh as the reason for the great reduction in com-
putational time achieved by the decoupling approximation. Prak.~sh and
Ottinger [33] discuss the reasons why this argument is incomplete, and
point out the inconsistencies in the decoupling procedure. Furthermore,
since the results are only as accurate as the consistent averaging approxi-
mation, the decoupling approximation is not superior to the consistent av-
eraging method. However, these papers are important since the means by
which a reduction in computational intensity may be achieved, without any
significant sacrifice in accuracy, was first proposed in them. Further, the
persistence of the minimum in the viscosity and first normal stress curves
even for very long chains, and the necessity of including FENE springs in
order to generate predictions in qualitative agreement with experimental
observations in high molecular weight systems, is clearly elucidated in these
papers.
The function 0(j, l, p, k) is unity if 1 and p lie between j and k, and zero
otherwise,
are discussed in great detail in the papers by Ottinger and coworkers [22,
24,25,48,47].
All the approximations discussed earlier (with the exception of the decou-
pling approximation) can be derived by a process of succesive simplification
of the explicit results for the Gaussian approximation given above. The
equations that govern the self consistently averaged theory can be obtained
by dropping the last term in equation (88), which accounts for the presence
of fluctuations. Replacing H(~r) by 1 in these truncated equations leads to
the governing equations of the Zimm model, while setting h* - 0 leads to
the Rouse model.
Material functions predicted by the Gaussian approximation in any arbi-
trary homogeneous flow may be obtained by solving the system of ( N - 1) 2
coupled ordinary differential equations for the components of the covari-
ance matrix O)k (88). Small amplitude oscillatory shear flows and steady
shear flow in the limit of zero shear rate have been examined by Ottinger
[24] for chains with N ~_ 30 beads, while Zylka [48] has obtained the ma-
terial functions in steady shear flow for chains with N _~ 15 beads and
compared his results with those of Brownian dynamics simulations (the
comparison was made for chains with N - 12 beads).
The curves predicted by the Gaussian approximation for the storage and
loss modulus, G ~and G", as a function of the frequency w, are nearly indis-
tinguishable from the predictions of the Zimm theory, suggesting that the
509
sults to the infinite chain limit, Ottinger has shown that this reduction
is by a factor of 72% - 73%, independent of the strength of the hydro-
dynamic interaction parameter. Other universal ratios predicted by the
Gaussian approximation in the limit of zero shear rate are discussed later
in the chapter.
A comparison of the predicted shear rate dependence of material func-
tions in simple shear flow with the results of Brownian dynamics simu-
lations reveals that of all the approximate treatments of hydrodynamic
interaction introduced so far, the Gaussian approximation is the most ac-
curate [48]. Indeed, at low shear rates, the negative second normal stress
difference predicted by the Gaussian approximation is in accordance with
the simulations results.
Inspite of the accuracy of the Gaussian approximation, its main drawback
is its computational intensity, which renders it difficult to examine chains
with large values of N. Apart from the need to examine long chains for
the reason cited earlier, it also necessary to do so in order to obtain the
universal predictions of the model. A recently introduced approximation
which enables the evaluation of universal viscometric functions in shear
flow is discussed in the section below. Before doing so, however, we first
discuss the significant difference that a refined treatment of hydrodynamic
interaction makes to the prediction of translational diffusivity in dilute
polymer solutions.
510
4.5. T h e twofold n o r m a l a p p r o x i m a t i o n
The twofold normal approximation borrows ideas from the decoupling
approximation of Magda et al. [18] and Kishbaugh and McHugh [15] in or-
der to reduce the computational intensity of the Gaussian approximation.
As in the case of the Gaussian approximation, and unlike in the case of the
consistent-averaging and decoupling approximations where it is neglected,
fluctuations in the hydrodynamic interaction are included. In a sense, the
twofold normal approximation is to the Gaussian approximation, what the
decoupling approximation is to the consistent-averaging approximation.
The computational efficiency of the decoupling approximation is due both
to the reduction in the set of differential equations that must be solved in
511
order to obtain the stress tensor, and to the procedure that is adopted to
solve them [33]. These aspects are also responsible for the computational
efficiency of the twofold normal approximation. However, the derivation of
the reduced set of equations in the twofold normal approximation is signifi-
cantly different from the scheme adopted in the decoupling approximation;
it is more straight forward, and avoids the inconsistencies that are present
in the decoupling approximation.
Essentially the twofold normal approximation, (a) assumes that the con-
figurational distribution function r is Gaussian, (b) uses the Rouse or the
Zimm orthogonal matrix 1-Ijk to map Qj to 'normal' coordinates Q~, and
(c) assumes that the covariance matrix ~k is diagonalised by the same
orthogonal matrix, ie. Ej, k 1-Ijp~k H k q - (Q~Q~q) - dpSm. This leads to
the following equations for the ( N - 1) variances dj,
d 2kBT Aj - H [dj . Aj + Aj . dj]
H H
A]
k
where, Aj = Ajj are the diagonal tensor components of the matrix Ajk,
Ajk- ~ 1-Ilj Alp l-Ipk (93)
1,p
and the matrix ~jk is given by,
Ajk -- ~ 1-Iljl]pk rip,ran l-Imj link (94)
l, m, n, p
In equations (93) and (94), the tensors Ajk and ~rr given by equa-
tions (85) and (89), respectively. However, the argument of the hydrody-
namic interaction functions is now given by,
1 H max(#,v)- 1
^ -- E E Him nkm o'~ (95)
a'tw Itt -- v ! kBT j,k=min(#,v) m
same result. However, Prakash and Ottinger [33] have shown that this is
512
in some sense a fortuitous result, and indeed the key assumption made in
the decoupling approximation regarding the diagonalisation of Ajk is not
tenable. The Zimm model in terms of normal modes may be obtained from
equation (92) by dropping the last term, and substituting Ajk in place of
A--jk. Of course the Zimm orthogonal matrix must be used to carry out the
diagonalisation in equation (93). The diagonalised Zimm model reduces
to the diagonalised Rouse model upon using the Rouse orthogonal matrix
and on setting h* - 0.
The evolution equations (92) have been solved to obtain the zero shear
rate properties for chains with N ~_ 150, when the Zimm orthogonal matrix
is used for the purpose of diagonalisation, and for chains with N _ 400,
when the Rouse orthogonal matrix is used. Viscometric functions at finite
shear rates in simple shear flows have been obtained for chains with N ~_
100 [33]. The results are very close to those of the Gaussian approximation;
this implies that they must also lie close to the results of exact Brownian
dynamics simulations. The reasons for the reduction in computational
intensity of the twofold normal approximation are discussed in some detail
in [33]. The most important consequence of introducing the twofold normal
approximation is that rheological data accumulated for chains with as many
as 100 beads can be extrapolated to the limit N -+ c~, and as a result,
universal predictions may be obtained.
that rheological data for finite chains must be generated for large enough
values of N so as to be able to extrapolate reliably, ie. with small enough
error, to the limit N --4 oc. The second is that some knowledge of the lead-
ing order corrections to the infinite chain length limit must be obtained in
order to carry out the extrapolation in an efficient manner. It is clear from
the discussion of the various approximate treatments of hydrodynamic
interaction above that it is possible to obtain universal ratios in the zero
shear rate limit in all the cases. Four universal ratios that are frequently
used to represent the rheological behavior of dilute polymer solutions in
the limit of zero shear rate are [29],
- lim 77P'~
U,p~ nkBTAI~TP'~ U,R n-~On~Ts(nTrR3g/3)
-
Ur
_ nkBT~l,o
2 Ur ~2,0 (96)
rl~,0 ~,0
where, )~1 is the longest relaxation time, and R 9 is the root-mean-square
radius of gyration at equilibrium. With regard to the leading order cor-
rections to these ratios, it has been possible to obtain them explicitly only
in the consistently-averaged case [20]. In both the Gaussian approxima-
tion and the twofold normal approximation it is assumed that the leading
order corrections are of the same order, and extrapolation is carried out
numerically by plotting the data as a function of (1/v/N). Because of their
computational intensity, it is not possible to to obtain the universal shear
rate dependence of the viscometric functions predicted by the consistent-
averaging and Gaussian approximations. However, it is possible to obtain
these master curves with the twofold normal approximation.
Table 1 presents the prediction of the universal ratios (96) by the various
approximate treatments. Miyaki et al. [19] have experimentally obtained
a value of UoR -- 1.49 (6) for polystyrene in cyclohexane at the theta tem-
perature. Figure 1 displays the viscometric functions predicted by the two
fold normal approximation. The coincidence of the curves for the different
values of h* indicate the parameter free nature of these results. Divergence
of the curves at high shear rates implies that the data accumulated for
chains with N _< 100 is insufficient to carry out an accurate extrapolation
at these shear rates. The incorporation of the effect of hydrodynamic inter-
action into kinetic theory clearly leads to the prediction of shear thickening
at high shear rates even in the long chain limit.
514
Table 1
Universal ratios in the limit of zero shear rate. The exact Zimm values
and the Gaussian approximation (GA) values for U,TR and Ur are repro-
duced from [29], the exact consistent-averaging values from [20], and the
renormalisation group (RG) results from [25]. The twofold normal approx-
imation values with the Zimm orthogonal matrix (TNZ) and the remaining
GA values are reproduced from [33]. Numbers in parentheses indicate the
uncertainity in the last figure.
.0 . . . . . . . . | . . . . . . . . !
0 ~ , .. . . . . . , . . . . . . .-., 9 9
2.0 8 "~
1.5
4 j
1.0[ . . . . . . . . . . . . . . . . . . . . . . . . . . 9 t -, " - r ,~.
0.005 .........
-0.005
9-
"~
r
-0.010
9-
-0.015
-0.020 ~ o h* = 0.25
...... RG
-0.025 . . . . . . . . . . . . . .
1(,-' " i0 ~ 10'
p
Figure 1. Universal viscometric functions in theta solvents. Reproduced
from [33].
small decrease from the zero shear rate value before the monotonic increase
at higher shear rates. The good comparison with the results of Brownian
dynamics simulations for short chains indicates that the twofold normal ap-
proximation is likely to be more accurate than the renormalisation group
calculations.
5. C O N C L U S I O N S
This chapter discusses the development of a unified basis for the treat-
ment of non-linear microscopic phenomena in molecular theories of dilute
polymer solutions and reviews the recent advances in the treatment of
hydrodynamic interaction. In particular, the successive refinements which
ultimately lead to the prediction of universal viscometric functions in theta
solvents have been highlighted.
516
REFERENCES
~
R. B. Bird, R. C. Armstrong and O. Hassager, Dynamics of Polymeric
Liquids, Vol. 1, Fluid Mechanics, 2nd edn., John Wiley, 1987.
.
R. B. Bird, C. F. Curtiss, R. C. Armstrong and O. Hassager, Dynamics
of Polymeric Liquids, Vol. 2, Kinetic Theory, 2nd edn., John Wiley,
1987.
.
R. B. Bird and H. C. (3ttinger, Annu. Rev. Phys. Chem., 43, (1992)
371-406.
.
C. F. Curtiss and R. B. Bird, Adv. Polymer Sci., 125, (1996), 1-101.
5. C. F. Curtiss, R. B. Bird and O. Hassager, Adv. Chem. Phys., 35 (1976)
31-117.
.
J. des Cloizeaux and G. Jannink, Polymers in Solution, Their Modelling
and Structure, Oxford Science Publishers, 1990.
.
P-G. de Gennes, Scaling Concepts in Polymer Physics, Cornell Univer-
sity Press, 1979.
.
M. Doi and S. F. Edwards, The Theory of Polymer Dynamics, Claren-
don Press, Oxford, 1986
.
X. J. Fan, J. Non-Newtonian Fluid Mech., 17 (1985) 125-144.
10. X. J. Fan, J. Chem. Phys., 85 (1986) 6237-6238.
11. M. Fixman, J. Chem. Phys., 45 (1966) 785-792, 793-803.
12. D. A. Hoagland and R. K. Prud'homme, J. Non-Newtonian Fluid
Mech., 27 (1988) 223-243.
13. J. G. Kirkwood, Macromolecules, Gordon and Breach, New York, 1967
14. J. G. Kirkwood and J. Riseman, J. Chem. Phys., 16 (1948) 565-573.
15. A. J. Kishbaugh and A. J. McHugh, J. Non-Newtonian Fluid Mech.,
34 (1990) 181-206.
16. H. A. Kramers, Physica, 11 (1944) 1-19.
17. R. G. Larson, Constitutive Equations for Polymer Melts and Solutions,
Butterworths, Boston, 1988.
18. J. J. Magda, R. G. Larson and M. E. Mackay, J. Chem. Phys., 89
(1988) 2504-2513.
19. Y. Miyaki, Y. Einaga, H. Fujita and M. Fukuda, Macromolecules, 13
(1980) 588.
20. H. C. Ottinger, J. Chem. Phys., 86 (1987) 3731-3749.
21. H. C. Ottinger, J. Chem. Phys., 87 (1987) 3156-3165.
22. H. C. Ottinger, J. Non-Newtonian Fluid Mech., 26 (1987) 207-246.
517
A. I. Leonov
1. INTRODUCTION
from its poor description of nonlinear data, the physical approaches are also not
free from empiricism in formulations and arbitrariness in overcoming
mathematical difficulties. Additionally, recent mathematical analyses and
numerical simulations revealed examples of unphysical and unstable behavior
of the CEs derived by these methods.
The fourth method of deriving CEs has been introduced by the author [23,24].
It investigated nonlinear viscoelastic phenomena by the methods of the quasi-
linear irreversible thermodynamics with the use of a "recoverable strain tensor"
as hidden parameter. By this approach, a class of Maxwell-type differential CEs
has been proposed under strict stability constraints which are based mainly on
thermodynamics. Later, similar approach was adopted by Dashner and
Vanarsdale [25] to formulate the general class of CEs almost equivalent to the
author's.
Almost all CEs proposed in the literature have a limited ability to describe
start-up, steady state and relaxation phenomena of polymer fluids in standard
rheometric flows, within a relatively narrow region of strain rates usually
employed in the tests [26]. However, there are two frustrating problems: (i)
none of viscoelastic CE proposed could describe the whole set of available data
with one specified set of parameters, (ii) in real modem processing the values of
Deborah number, De, may be at least two orders of magnitude higher than those
in usual rheological tests, and in that flow region almost all CEs exhibit various
instabilities, the reason for which still remains unclear.
There are a lot of speculations in the literature on how the instabilities in CEs
are related to those observed in flows of polymer fluids There are also contrary
opinions about the physical sense of non-evolutionary behavior of viscoelastic
constitutive equations (see, e.g. Refs. [27,28] with contrary views on the
subject). The temptation to relate the instability in CEs to real flow instability
was perhaps caused by the widely spread perception that no rheological
constitutive model is globally stable.
A few books [ 18,26,29-31 ] and a lot of papers on the polymer rheology do not
answer the question as to which CE should be chosen to solve fluid mechanical
problems of polymer processing in the usual case of large De number flows,
where the nonlinear effects of elasticity are important. Therefore, general
studies in this field should be aimed on searching for not only descriptive but
also reliable CEs. Thus in our opinion, the principles of choice of CEs should
also include, besides the descriptive ability of viscoelastic CEs, such
fundamental thermodynamic properties of these as formulation of dissipation
and free energy, along with stability constraints.
522
To study these fundamental properties, even for the relatively simple CEs, one
has to employ a general formalism within the framework of which it is feasible
to find some general stability constraints. Several formal approaches to the
viscoelastic CEs have been proposed relatively recently in the literature. One of
them is the local quasi-linear approach of non-equilibrium thermodynamics
developed by the author [23,24,32]. As mentioned, this approach has resulted in
derivation of a class of Maxwell-like CEs, with some thermodynamic
constraints. Almost 10 years later, the Poisson-bracket variational approach has
also been established. It was first introduced by Grmela [33,34] and then
elaborated by Beris and Edwards [35]. This approach, extending the
Hamiltonian formalism in classical mechanics to the case of continuum
mechanics, also employs the dissipative functional. It was proved [36] that both
the above approaches result in the same "canonical" formulation of general
Maxwell-like CEs. Another two general formal schemes, consistent with the
irreversible thermodynamics, have been developed by Jongschaap et a1.[37,38]
and by Kwon and Shen [39]. The first one employs a matrix representation in
the phenomenological relations between the thermodynamic forces and fluxes,
with additional relations between external and internal (hidden) thermodynamic
variables. The second one uses the notion of evolution of the temporary network
structure. Regardless of all the differences in their detailed schemes, their
equivalence to the general author's approach is evident.
Another objective that should be kept in mind when proposing the CEs for
polymeric liquids, is solving geometrically complicated flow problems under
high deformation rate, as related to industrial processing. Complexity of flow
problems for polymeric liquids is enhanced by the effects of fading memory
which do not exist in viscous liquids or elastic solids. Hence, viscoelastic
polymer fluids demonstrate many unique rheological effects, such as nonlinear
evolution of stress under steady deformation, which cannot be seen in the other
fluids. Because of this, even geometrically simple problems which may be
solved analytically for viscous fluids, have often to be treated numerically in the
viscoelastic case. This necessitates the elaboration of certain criteria for the
selection of CEs for practical applications. The following principles of choice
have been suggested [40,41 ] for the selection of CEs:
(i) Stability. However well an unstable CE can describe rheometric tests, it is
impossible to use it in modeling of polymer processing, since the Deborah
numbers there may be at least two order of magnitude higher and the flow much
more complicated. Extrapolation of the majority of CEs to the region of high
Deborah numbers and 3D flows usually results in several types of instabilities
in numerical flow simulations. These instabilities reflect the mathematical
523
structure of the proposed CEs. In the most cases, they are not related to the
physical instabilities observed in the flows of polymeric fluids, or poor
numerical algorithms, but rather to violations of some fundamental principles.
(ii) Descriptive ability and flexibility. It is now well recognized that polymer
melts with similar linear viscoelastic spectra can show qualitatively different
nonlinear behavior. For the proper description of various flows, this requires
some functions of the kinematic variables, and the associated nonlinear
parameters in the CE (which vanish in the linear limit) to be specified within the
stability constraints. Once these functional forms and parameters are specified
for a particular polymer, the CE must simultaneously describe the entire set of
available experimental data fairly accurately.
(iii) Computational economy. The proposed CE should allow for numerical
calculations in complex flows with as little computational effort as possible. For
example, despite the good descriptive ability, it is rather cumbersome to work
with models in which the elastic potential is specified in terms of the principal
values of a strain measure, and it is usually conceived that working with CEs of
differential type is preferable for numerical calculation than with integral ones.
(iv) Extensibility. Real polymer processing is confronted with a variety of
complications such as compressibility, non-isothermality, wall slip, phase
transitions and separations, chemical effects (degradation, curing), etc. In
principle, the CE of choice should be amenable to extension in order to
accommodate these phenomena.
Among the four principles listed above, the first two can be regarded as the
most fundamental properties which the CEs should possess.
There are two types of viscoelastic constitutive equations which are only in
use today for practical applications. These are of differential (Maxwell-like) and
single integral types. Therefore we discuss below only the formulation of these
two types of CEs, since only they have been tested up to present.
are the basic invariants of the tensor g. Then the "thermodynamic stress tensor"
0% associated with the free energy F, as in the quasi-equilibrium elastic case
[45], is introduced as follows"
(o~ = 2pg=.c3F/Oc = 2p[F,c_- + F2(I,c=- s + Ffl,6=] (Fj = OF/OIj) (2)
525
Here 9 is the density and fi is the unit tensor. The only physical reason to
operate with the equation (2) is the explicit assumption [23,24] that polymeric
liquids always possess an "elastic limit", a quasi-equilibrium situation achieved
on very rapid (instantaneous) deformations, where the temporary entanglements
in macromolecules act like cross-links in cross-linked rubbers. Thus, in this
limit, when g --+ _Cl the use of equation (2) can be justified. It should also be
noted that no assumption of incompressibility has been made.
We now briefly discuss the dissipative effects [23,24] which are associated
with flows of elastic liquids. By using the laws of mass and energy conservation
as well as the momentum balance, and separating the total entropy variation in
the flux and origin ("entropy production"), one can easily obtain the Clausius-
Duhem expression for the entropy production Ps in the case under study:
Here ~/is the thermal flux, __o-isthe actual stress tensor, g is the strain-rate tensor,
and the symbol d/dt means the time derivative in the frame of reference
associated with a moving particle of liquid. The first term on the right-hand side
of equation (3) reflects non-isothermal effects and could be considered as
independent of the other two, which are related to mechanical dissipation.
According to the Second Law, P~ should be positive for all non-equilibrium
processes and vanish at equilibrium. Considering further the isothermal
behavior of elastic liquids. Using equation (2), we can rewrite the dissipative
terms in (3) as follows"
procedure" to find the solution, e~, from the kinematic relation c=c.__e+e.__c,valid
for elastic solids (or for the total continuum) and hold the expression for the
o
which has been obtained in an explicit form [24], too awkward to be reproduced
here. It is easy to see from equation (5) that the term pdF/dt I T in equation (3) is
reduced to tr(o-.e~), which, in turn, can be represented in the form of the second
term in the dissipation equality (4). It should also be noted that this derivation,
being general enough, was confirmed by an independent specific analysis of
kinematics of viscoelastic deformations [24,46,47] when ___e= C~l. If the non-
equilibrium stress _O-pand strain rate ep are defined as follows,
strain rate ep (the second term in (6)). Using quasi-linear scheme of irreversible
thermodynamics, these were connected in [23,24,46] by phenomenological
relations with kinetic coefficients represented as some rank four tensors
depending on the internal parameter, tensor g. In presenting these relations, the
Onsager symmetry of kinetic coefficients, proved for quasi-linear case in [43],
has also been used. The structure of the kinetic rank-four tensor had also been
completely revealed [24]. An interested reader can find the details in papers
[24,46,47]. This strict, straightforward and complete approach can be compared
with somewhat controversial matrix approach [43,44].
V
c+~c)/0(T) = O, ~c)/O(T) = 2C-ep(T,c). (~j(T,c)/O(T) = 2CikMkist(T,c)O's,(_~._C))
(8)
V
Here c is the upper convected time derivative and ~ c ) is a non-dimensional
isotropic tensor function of tensor c defined as in equation (8) and related to the
dissipative processes in an elastic liquid. Additionally, in the rest state when c--+
=_8(I1--+I2---~3; I3---~1), we have" =d(T,c)---~=0. We assume that this limit transition is
regular, meaning that there is a limit to the linear Maxwell viscoelastic equation
when the intensity of strain rate is very low. In the incompressible case with
528
linear dependencies Cre(=e)and =d(=c), equations (2) and (8) are easily reduced to
the upper convected Maxwell model.
Multiplying the first eqation (8) from the right and from the left by g-~ reduces
the latter to the a "dual form'"
+ s = 0, (b = __e-') (8a)
where b is the lower convected time derivative of the tensor b. Also, in the
incompressible ease with linear dependencies of ~ and ~ ) , eqations (2)
and (8) are reduced to the usual form of the lower convected Maxwell model.
The difference between these is mainly in the dependence of stress on elastic
strain" =o-= G=e corresponds to the case of rubber elasticity, whereas =o-= -Gb can
describe the elasticity of crystals or metals.
Equations (1),(2) and (8) give rise to the energy relation:
Substituting equation (11) into (8) represents the latter in the form which
coincides with the evolution equation obtained by Beris and Edwards (see
equation (2.13) in the second part of Ref.[35]). The tensor L has the structure
[35] similar to that known for the tensor M.
We now analyze the compressibility condition in the general Maxwell model
described by equations (2) and (8). Multiplying equation (8) scalarly by (2=e)1
gives:
Here/90 is the density in the rest state. Then, combining equations (12) and (13)
yields:
Equation (14) shows that P---~Po when c--+_6, since in this limit, trep--+0. It also
shows [23,24] that
Surprisingly enough, in this case, the free energy remains the same, i.e.
F=F(T,II,I2,I3), because the tensor =e is not directly related to the density. By
introducing the modified free energy / ? - F - p lnI 3, the actual stress =0-can be
represented by
530
Here the isotropic term 'p'(a Lagrange multiplier) in equation (17) is introduced
to satisfy the condition of incompressibility tre = 0; the thermodynamic tensor
ere being still defined by equation (2). This means that the tensor cr~ is not
defined with the accuracy of an isotropic term as in the equilibrium case, and
isotropic pressure is not an equilibrium one. These features result in the fact
that, even in the incompressible case, the expression (6) for the dissipation is
now not invariant under the transformation, _o-e--~o-~+p__6.
When the constraint trep = 0 is used, equation (15) results in the
incompressibility condition [23,24],/3 = detc = 1. In this case, the modified
^
elastic potential is introduced as" W = W(T, II,I2)-f~(I 3- 1), where W = pie. The
magnitude ~ here is the isotropic pressure. It is used in differentiation in
equation (2) as the Lagrange multiplier, allowing us to consider all cij variables
as independent. Then equation (2) results in the Finger formula for the stress:
Here Wk= OWlOIk and p = ~-/;'2/2. Also in this case,/2 = trc l and the formulae
for free energy and the stress tensor are exactly the same as for elastic solids.
Also, isotropic pressure and the expression for dissipation (6) are invariant
under the transformation: _O-e--)Cr~+ p=6.
We finally stress that as shown in this section, any attempt to extend the
configuration tensor approach to the compressible case is thermodynamically
inconsistent. Since the Maxwell type models involving configuration tensor c
were derived from the evolution equation for distribution function, it simply
means that the later equation should be somehow modified. It is unknown at
present what should be done to rectify the situation.
Here ~ is a numerical parameter (-1 <~< 1, %~0). The case %= 0, related to the co-
rotational derivative, can be also easily considered but we shall omit this. Then
following the same procedure, described in the derivation of equation (8), we
can finally obtain [36]:
__o
-= -p__6+ __ere Crex= Cre(g)/~, _c- ~(e.e + =e.___c)+ &(T,g)/O(T) = 0, (19)
D = tr(Crex-&).
In equations (19), written here in so-called canonical form, the formula for the
extra stress tensor Crex is given due to some thermodynamic reasons [26]. Note
that when ~,~+1, equations (19) have no perfect elastic limit and therefore they
are non-equilibrium.
One can also ignore the thermodynamic origin in the stress formulation ere(C)
and consider formally the second formula in equation (19) as a general non-
potential stress-elastic strain relation O-~x= Crex(C,~). It can be formally done even
in the case ~,=+1, where there is a limit to elastic solid behavior, ~(T,_e_)--+=0.
However, in this case, it is always possible to consider such a loading-unloading
procedure that will create work from nothing [53]. It means that this approach
inevitably leads to the theoretical eternal motion machine and therefore is
thermodynamically forbidden.
where p and G are the shear modulus and density, equations (19) represent an
interpolated Maxwell or the Gordon/Schowalter [49] - Johnson/Segalman [50]
model. When ~=+1 or ~=0, it is respectively called the upper/lower convected
or co-rotational Maxwell model.
When
532
Here W(I~,Iz) (=pF) is the strain energy function for incompressible case. The
positive functions bi(Ii,I2) should have a proper linear viscoelastic limit and
their positive definiteness suffices the positive definiteness of the dissipation.
The convexity constraints,
533
imposed on the general form of potential F were also suggested [23,24,47]. The
important implication of inequalities (27) and the proper use of this class of CEs
are discussed in detail in [40]. In the simple case of bl=b2=l, with the neo-
Hookean potential for F, it reduces to the simplest "Leonov model" which
includes no nonlinear parameters.
N N
F - y'Fk(T, ck),
k=l
cy - ~ r
---ex -= --- ex,k
(T,c )
=k ~
(28)
Here Fk, Crex,kand Ck are the free energy, extra stress tensor and configuration
tensor, respectively, in "k"th relaxation mode. Additionally, the general form of
evolution equation presented in equation (18) holds for every configuration
tensor s In the limit of very low Deborah number, this approach shows the
linear viscoelastic behavior, with a discrete spectrum of relaxation times { Ok}. It
means that every nonlinear relaxation mode is generated by the corresponding
linear viscoelastic mode. The generalization to the multi-mode case can be
justified only if the various relaxation modes are well separated, i.e.
01>>02>>...>>ON (29)
In this case, it is reasonable to assume that the various relaxation modes act
independently. All the known experimental datatestify in favor of inequalities
(29). Additionally, the guess-independent Pade-Laplace method (see e.g. [57])
reveals the effective discrete linear relaxation spectrum in accord with (29).
Here _O-ex is the extra stress tensor, C is the Finger total strain tensor for
incompressible media, whose time evolution is described as follows"
v
C-dC/dt-C.Vv-(Vv_)
_ _ _._ _~_ ~
r -C-O;
___ =
C[
I = T
=8
- -
(31)
Here I l= trC, I2 = trC -1, and ~, and q32 are generally independent functions. We
can also introduce many other measures of deformations. One of them, the
Hencky measure, H = (l/2)lnC, will be used below.
Experiments show that the simplified time-strain separable version of equation
(31),
can be introduced. Here re(t-x)- dG(t-x)/dx, and G(t) is the relaxation modulus.
Equations (30) and (31) are not the only single integral form of CEs. When, for
example, the mixed convected time derivative is used, the CE can also be
represented in an integral form (see, e.g., Ref [26]). Also, Kaye [57] and
Bernstein et al. [60] proposed the potential form of equations (30) and (31):
Here G is the elastic Hookean modulus. Equations (33) or (34) constitute the K-
^
BKZ class of single integral CEs. The potential F in equations (33) denotes the
thermodynamic free energy with relaxation effects taken into account.
For the time-strain separable viscoelastic CEs with potential F, the basic
functionals such as the free energy W, the extra stress tensor o-e and the
dissipation D are of the form [61 ]:
535
t
o-~ = (2p/G) IC. c3F/~C(I,,I 2 ) m ( t - , ) d , (36)
--O0
A comparison of equations (2) and (8) with equations (35) and (36) clearly
shows that CEs of the differential type where the dissipation and free energy are
generally independent, are more flexible for rheological modeling than CEs of
the integral type where those quantities are roughly proportional.
We now describe some particular CEs of separable single integral type by
specifying q~, and q~2 in equation (30) or the potential F for the K-BKZ type in
equations (34).
Wagner et al. [62] proposed their first specification as:
where f, nl, /</2 and, fl are positive fitting parameters. Later, Wagner and
Demarmels [63] introduced a new factorable version:
Here again, a and, , are positive fitting parameters. We further refer to the
specification (38) as the Wagner model I, and (39) as the Wagner model II.
Luo and Tanner [64] proposed the modification of the CE originally presented
by Papanastasiou et al. [65] in the form:
where c~, /3 and ~: are fitting parameters and K>0. When K=0, this model
becomes identical to the one proposed by Papanastasiou et al. [65]. One can
easily see that no thermodynamic potential relation exists (q012 ~ q~21) in all of
the above three CEs (38)-(40).
536
is a particular case of the separable K-BKZ class (34) when the neo-Hookean
potential is used.
In order to describe better the viscometric data, Larson and Monroe [66]
suggested the following 4-parametric form ofF for the K-BKZ class:
2p/~=. G! t- G2 e x p ( - t
exp( -~- ). In[1 + ~( I , - 3)] + 21302 -~2 )" In[1 + 13(12 - 3)] +
2or0
G3 exp( - t (44)
20--7 O3 )" ( I , - 3)
than invariants of the total Finger deformation tensor. Below are several
examples of these potentials.
Here Gtn are numerical parameters which can be negative or positive, and Gn are
shear moduli. The potential (45) becomes identical to the Mooney potential [71]
if it contains only two modes corresponding to a 1=2 and cx2= -2.
2pF-- A I ~ + B
_ _ o m
IE, I E - 1 (C~,,/2
~
, + C ,~2
2 + C ,3/ 2 ) .
n n (47)
n n
Here A and B are the parameters with the dimensionality of modulus, whereas n
and m are numerical parameters.
As mentioned, the non-potential viscoelastic CEs proposed in the literature,
are unphysical, since when applying very fast deformations, it is possible to
create a perpetual motion machine from a hypothetical material subordinated to
this type of CE [53]. Nevertheless, we will analyze below this type of CEs too,
considering it as mathematical abstraction for the superficial data curve fitting.
To make the following analyses more efficient, we now introduce a unified set
of notations for both differential and single integral types of CEs which employ
only upper convected time derivatives in the evolution equations. The lower
convected time derivative (~=-1) in equation (19), can be equivalently rewritten
in the form of upper one (~=1) [36], as shown by equation (8a). We introduce a
modified pressure term defined as:
538
Here 8/8g is in general the partial Frechet derivative with respect to c, and with
the definition for q)i in equations (2) and (30). In this notation, c becomes the
total Finger strain tensor __Cin the case of integral CEs, and thus for the CEs of
integral type and the author's CEs, I3=1, q)3=0 automatically. Even though the
set (40) is written for hyper-viscoelastic equations, the non-potential
viscoelastic formulations can also be included into consideration.
The (elastic or total) strain tensor c is the solution of the following evolution
problem:
v t el,__o = =8 for differential CEs
(50)
= = = = [
Ct=t,
= C] t = t t = =8, ~(c) - =0
__ =
for integral CEs
Here ~bis the dissipative term which vanishes for integral CEs, and from now on
we consider only upper convected time derivatives even for differential models.
3.1. Background
In numerical simulations of viscoelastic flows, degradation of the numerical
solution or lack of convergence of computational schemes has been frequently
539
observed for large or even modest values of Deborah numbers. It is thought that
the main reason for this numerical malady is an improper choice of a CE which
possess some bad mathematical properties (e.g., see Ref. [74], p.314). Therefore
the analysis of such properties of various viscoelastic CEs as their stability and
boundedness seems to be a pre-requisite for any successful numerical modeling.
It will be shown in this Section that these properties are in turn, originated in
our capability to incorporate basic thermodynamics laws in formulation of the
CEs.
We discuss in this section recent results of stability analyses for isothermal
formulations of CEs for viscoelastic liquids. To begin with, we briefly describe
the basic aspects of stability analysis in general, and two types of instabilities
related to the formulation of viscoelastic CEs in particular.
The general purpose of the stability analyses is to find the conditions of
boundedness for a solution of a set of functional equations subordinate to some
additional (usually initial and boundary) conditions. In our case, the total set of
equations consists of momentum balance and continuity equations coupled with
viscoelastic CEs. No-slip boundary conditions are usually applied at the rigid
surfaces and the common set of kinematic and dynamic boundary conditions is
used at the unknown free surfaces. It is assumed a "basic" solution of the set
(generally, 3D and time dependent) to exist, subordinate to initial and boundary
conditions. The solution is said to be stable in the Lyapunov sense, if "small"
disturbances imposed on the solution at time to, which satisfy the homogeneous
boundary conditions, remain to be small at any time t (to<t<oo). The solution is
said to be stable relative to the arbitrary "large" initial disturbances if they
remain to be bounded at any time t (to<t<oo). The particular type of the latter
stability is the boundedness of the basic solution itself. It is in principle also
possible to analyze the stability of the solution relative to small or large
disturbances in boundary conditions and in parameters ("robustness"). These
types of stability analyses are not considered below.
The stability "under small disturbances" is usually considered by analyzing a
linearized total set of equations, if such a linearization is possible. In spite of
their linear character, the initial boundary-value problems for the evolution of
disturbances are very difficult to solve, even in the simplest cases. A great deal
of simplification can be achieved when spacetime scales of disturbances are
considerably less than those scales for the basic solution. In this case, one can
analyze locally, i.e. in the vicinity of any spacetime point, the linear stability
problem, using elementary waves of disturbances and ignoring the boundary
conditions. This is the method of "frozen coefficients", which is illustrated in
Section 3.2.
540
The purpose of the stability analyses discussed in the following sections is not
to describe the real physical instabilities observed in flows of viscoelastic
liquids, but rather to reveal some constraints which should be imposed on the
formulation of CEs to prevent them from the occurrence of unphysical
instabilities. Therefore, we call the stability considered in the subsequent
analyses not the stability of viscoelastic flows but the stability of CEs. These are
related to the formulation of CEs.
The formulation of nonlinear viscoelastic CEs is not as straightforward as it
appears at first sight. For many specifications of CEs in the above two classes,
numerical modeling of high Deborah number flows has displayed heavy
unphysical instabilities, regardless of the "true physics" employed in their
derivation. Two types of instabilities related to the formulation of CEs were
observed for large or even modest values of Deborah numbers, and have been
analyzed in the literature. These are the Hadamard and dissipative instabilities.
The case of Hadamard stability is the most understood. We define the
complete set of equations for viscoelastic liquids as Hadamard stable (or
evolutionary, or well-posed) when the solution of the boundary-value Cauchy
problems for the set at any time provides the complete initial conditions for
determining the solution at subsequent instants in time [75]. Thus, the
Hadamard stability allows one to continue the solutions in the positive direction
of the time axis. When this is impossible, very quick blow-up instability occurs,
with extremely short wave disturbances, which results in progressive failure in
numerical calculations: the finer the mesh, the worse will be the degradation of
the results [76]. In many cases, one can treat the Hadamard instability as a
blow-up type increase in the amplitude of initially infinitesimal waves of
disturbances as the wavelength tends to zero. In viscoelastic liquids, this type of
instability can be associated with a nonlinear rapid response of CEs. Hence, this
type of instability depends on such quasi-equilibrium properties of the CEs as
the type of differential operator in the evolution equation for differential models
and the elastic potential in the hyper-viscoelastic case.
Rutkevich [77] initiated the study of Hadamard stability for viscoelastic CEs.
Later, Godunov [78] analyzed some aspects of the stability in more detail. Some
significant results were obtained relatively recently by Dupret and Marchal [75]
and Joseph and co-workers (see, e.g., Joseph's monograph [76]). These studies
which have analyzed the Hadamard instabilities in particular flows for
particular specifications of differential viscoelastic CEs, can be summarized as
follows. Joseph and co-workers [79,80] and independently Dupret and Marchal
[75] proved that the interpolated Maxwell model, which involves the mixed
time derivative in the evolution equation, is Hadamard unstable, except for the
541
cases of upper and lower convected time derivatives. The ill-posedness of the
Gordon/Schowalter [49] or Johnson/Segalman [50], and the original Phan-
Thien/Tanner [51,52] CEs is subject to this type of instability. Using the general
method of characteristics, Dupret and Marchal [75] also showed that the White-
Metzner model [54] is nonevolutionary, which was again justified by Verdier
and Joseph [79], who employed a perturbation method in their analysis. It was
found that the dependence of the relaxation time on the invariant of strain rate
tensor is the cause of Hadamard instability in the White-Metzner model.
Analyzing the White-Metzner model in elongational flow, Verdier and Joseph
[81] also noticed a type of dissipative instability that occurs whenever the
extensional strain rate exceeds the half of the reciprocal relaxation time.
The method of characteristics is the most general mathematical tool for the
Hadamard stability analysis. This method is, however, sometimes complicated
and cumbersome. Fortunately, in the most interesting cases, it can be simplified
by using the "frozen coefficient" method (see, e.g. [76]), when analyzing only
extremely short and high frequency wave disturbances propagating with a finite
speed. Those cases are related to all the CEs of the quasi-linear differential type
as well as the time-strain separable single integral CEs. Then, the linear stability
analysis of the problem can be studied locally, without considering boundary
conditions. Although following Kreiss' examples [82], this local stability
condition is neither necessary nor sufficient for the overall stability in the
general case of nonlinear partial differential equations, for quasi-linear
differential (and time-strain separable single integral) equations, the local
stability analysis with the method of frozen coefficients can be employed
without loss of generality [83].
The studies of Hadamard stability have also a long history in the theory of
nonlinear elasticity, where many general results were obtained and understood
in great detail. Among the many general stability conditions suggested, the
simplest is known as the Baker-Ericksen inequality [84]. Its physical sense is
that the maximal principal stress always occurs in the direction of the maximal
principal strain. In the case of hyperelastic solids, the thermodynamic stability
criteria called "GCN + conditions" were also established long ago (see, e.g.,
Section 52 in Ref. [4]). Their physical sense is the convexity of the elastic
potential with respect to the Hencky strain measure. This has been also known
as a condition for strong monotonicity of stress with respect to strain. In
nonlinear elasticity, the Hadamard stability criteria of field equations
correspond to the conditions of strong ellipticity which coincide with the
stability requirements known for dynamic problems. The weaker conditions of
ordinary ellipticity deliver the stability constraints for static states [85].
542
stability that both the steady flow curves in simple shear and in simple
elongation have to be monotonously and unboundedly increasing.
The combined Hadamard and dissipative stabilities have also been analyzed in
paper [88] for incompressible viscoelastic CEs. The results of this analysis will
be discussed at the end of this Section.
We assume that the set has a solution {__c,v,p} which satisfies some proper initial
and boundary conditions, and impose on the solution extremely short and high
frequency, infinitesimal waves of disturbances"
Here c is a small amplitude parameter (leJ << 1), c, v, p and p are (generally
complex) amplitudes of the corresponding disturbances, k is a wave vector, and
co is the frequency.
Using just the local linear stability analysis, we can easily find the following
"dispersion relation", i.e. the dependence of the frequency co on the wave vector
k and the parameters of the basic flow:
Here ~ = co- k.v is the frequency of oscillations, with Doppler's shift on the
basic velocity field v taken into account. The last equation in (53) means that
due to the incompressibility condition in (51), the wave vector of disturbances k
is orthogonal to the amplitude of velocity dis.turbance v. The fourth rank tensor
Bijmn is defined in the principal axes of tensor __cwith principal values ck as:
Formulae (54) show that the tensor Bjjmn depends linearly on the constitutive
functions q0k and their second derivatives q0kj with respect to the basic invariants
Ik, independently of whether the approach is potential or not.
It is now seen that due to equation (52) and the definition of ~ , the
requirement for the stability is that the left-hand side of equation (53) should be
positive. Therefore, the necessary and sufficient condition for global Hadamard
stability is reduced to the following:
1 ~-~2V2
- BijnmvikjVmk n > 0 (55)
2
For the integral type constitutive equations, the condition (55) provides the
stability during relaxation, which is included in the global stability requirement.
On the other hand, the convexity of potential F, or the GCN + condition, can be
represented as follows"
-- 02 F = 4Cmq eip
B ~jmn[30]3,,m > 0, B ijmn -- Oh ~j0h,m 0c qn 0C pj
Here hij is the Hencky strain measure, h__ = (1/2) I n c . To guarantee the
thermodynamic stability, the inequality in (56) should be satisfied for any
arbitrary symmetric tensor ,fl,j with the condition of incompressibility, trl~ = 0.
In the potential (hyper-viscoelastic) case, the identity, Bijnm = B ijmn, holds. The
comparison between the inequalities (55) and (56) shows that due to the
symmetry of the tensor fl,j, the condition (56) is included in the inequality (55),
i.e. the condition (56) imposes weaker stability constraints than the inequality
545
(55). It means that the conditions for the Hadamard stability are stronger than
those of GCN +.
Employing the algebraic procedure which has been used in hyper-elasticity
[85], one can finally obtain the necessary and sufficient conditions for the
global Hadamard stability as the set of algebraic constraints imposed on the
functions q~k:
The additional constraint in (i), the positive definiteness of the tensor c, holds
by definition for the integral CEs. It was also proved for the Maxwell-like CEs
of differential type [36,102], however, only for the flow situations with a given
history.
The above approach to the global Hadamard stability has been recently
extended by Kwon [93] on the compressible case. The new quality which
occurs there is the possibility of longitudinal wave propagation. In the
incompressible case, the speed of the longitudinal wave approaches infinity,
whereas the speed of the transverse wave is finite. Hence, perturbation of basic
solutions by the longitudinal wave was not considered in this stability analysis.
The result was that the wave vector is always orthogonal to the vector of the
main velocity field. However, in the compressible case, the speeds of both
waves have finite values. Thus for stability, the initially infinitesimal amplitude
of disturbing waves of either type (or a mixed type) should remain small all the
time. It means that the conditions of Hadamard stability in compressible case
are more rigid than those for incompressible one. It was demonstrated [89] on
the simple example of Mooney-Rivlin potential with additional term dependent
on density.
Two sufficient conditions for the incompressible case have also been
proposed:
(1) The author's condition (27): the thermodynamic potential F for the author's
class of viscoelastic CEs is a monotonously increasing convex function of
invariants I1, and I2.
546
(2) Renardy's condition" the thermodynamic potential F for the K-BKZ class of
CEs is a monotonously increasing convex function of ~ and
Although Renardy's condition has been proved only for the K-BKZ class, it
also holds for the Maxwell-like CEs with upper convected time derivatives [88].
Since the author's condition (1) is stronger than Renardy's (2), it also guarantees
the global Hadamard stability for the K-BKZ class. The above sufficient
conditions are much more easier to employ than the necessary and sufficient
conditions for Hadamard stability (57). Therefore they are very useful for a brief
evaluation of the stability for new formulations of CEs. For the compressible
CEs, one sufficient condition for the global stability has also been suggested
[89], but it is too complicated to use.
holds, then in any regular flow, the configuration tensor =e and the stress tensor
ere are limited.
547
Detailed proofs and definitions are given in the papers [36,90]. While the
theorem 1.1 has been proved for differential CEs as a sufficient condition close
to the necessary one, theorem 1.2 provides the necessary and sufficient
condition for boundedness of single integral CEs.
The above theorems were motivated by the fact that the globally Hadamard
stable upper convected Maxwell model displays the unbounded growth of stress
in simple extension when the elongation rate exceeds the half of the reciprocal
relaxation time. As the consequences of the above theorems, (i) the upper
convected Maxwell model which violates Criterion I, and (ii) the K-BKZ class
with a potential F represented as an increasing rational polynomial function of
basic invariants Iu, are dissipative unstable. Therefore, the Mooney and the neo-
Hookean potentials as well as the potentials for the K-BKZ class of CEs which
are subordinate to Renardy's sufficient evolution criterion also violate Criterion
I of dissipative stability. Since the satisfaction of only Criterion I cannot prevent
the viscoelastic CEs from severe dissipative instability, an additional criterion
for dissipative stability has been introduced.
All the results of the stability analyses found in various studies for popular
viscoelastic CEs, are summarized in Table 1. An interested reader can find the
details of calculations in references also provided in the Table 1. It is
noteworthy that CEs derived from molecular approaches such as the Larson and
the Currie models, exhibit the most unstable behavior. Surprisingly enough,
none (to the authors' knowledge) of the time-strain separable single integral
models are evolutionary. Appendix A represents the explanation of the reasons
for that given by Simhambhatla [94]. He analyzed the time-strain separability
concept for CEs and concluded that the Hadamard unstable CEs of time-strain
separable type cannot properly describe the experimental data of stress
relaxation after step-wise loading. The instabilities revealed in Ref. [94] exactly
correspond to the results reviewed in this Section. It is astonishing that many
CEs become Hadamard unstable even in viscometric flows.
For the CEs of differential type, only three stable specifications exist. These
are the FENE, the upper convected Phan-Thien-Tanner models, and the author
class of CE's (8), (26) under convexity constraints (27). However, the FENE
and the upper convected Phan-Thien-Tanner models predict zero value for the
second normal stress difference in simple shear flow, which contradicts the
experimental evidence for polymer melts and concentrated polymer solutions.
It should be noted that all the necessary and sufficient conditions obtained for
single-mode CEs become, strictly speaking, only sufficient for the multi-modal
approach. Even though the necessity is not proved, it is thought that due to the
inequalities (29), i.e. well separateness in the relaxation times, the exact
conditions for Hadamard stability exposed above for a single mode CE, will be
closed to necessary for multi-mode approach. It is also evident that the
threshold of instability would only be delayed to some higher Deborah number
region in the multi-modal approach, if any single-mode is unstable.
For some viscoelastic CEs, regularization of ill-posedness may be achieved.
E.g., it is well-known that adding a small Newtonian term to the stress stabilizes
Hadamard unstable CEs. However, for complex flow simulations, this may not
be enough to suppress numerical instability, and when the Newtonian term
becomes larger, the description of the CE will deviate from the experimental
data. In the case of Hadamard stable but dissipative unstable CEs which violate
the Criterion II, one can also propose the more fundamental procedure of
stabilization by changing the elastic potential. For example, the Giesekus model
with or<l/2 in equations (24) will become evolutionary in both global
Hadamard and dissipative senses, if the potential is assigned to satisfy the
convexity constraint (27).
550
Table 1 shows that the combined stability criteria impose very tough
constraints on viscoelastic CEs. Therefore, the serious question arises as to
whether there exists a CE or a class of CEs which can properly describe all the
available rheometric data for concentrated polymer solutions and melts, when
satisfying all the stability constraints. We will describe such a class in the next
Section.
Table I
Stability of viscoelastic constitutive equations
Model (Eq. #) Type of CE Type of instability References
Upper convected Quasilinear Dissipative e.g.[36]
Maxwell (20) (~=1) differential unstable(Criterion I)
Interpolated Quasilinear Hadamard unstable [36,75,76,80]
Maxwell(20) differential (~,1)
(Johnson/Segalman
Gordon/Schowalter)
General Phan-Thien/ Quasilinear Hadamard unstable [36,75,76,80]
Tanner (21) differential (~.l)
Upper convected Quasilinear Hadamard stable; [88]
Phan-Thien-Tanner differential dissipative stability
(21) (~=1) depends on
dissipative term
White-Metzner(22) Nonlinear differential Hadamard unstable, [75,81]
dissipative unstable
(Criterion I)
FENE(23) Quasilinear Globally Hadamard [88]
differential and dissipative stable
Giesekus(24) Quasilinear Dissipative unstable [91]
differential (Criterion II)
Simplest Leonov(26) Quasilinear Dissipative unstable [91]
(bl, = b 2 = 1) differential (Criterion II)
Leonov class (26) Quasilinear Globally Hadamard [88]
under stability and differential dissipative stable
constraints (27)
Larson (25) Quasilinear Hadamard unstable [88]
differential
dissipative unstable [91]
(Criterion II)
Wagner I (38) Separable single Hadamard unstable [88]
integral
Wagner II (39) Separable single Hadamard unstable [88]
integral
Papanastasiou (40) Separable single Hadamard unstable [90]
(K=0) integral
551
Following mostly the paper [40], we demonstrate in this Section the class of
differential CEs [23,24,36] which is able to consistently describe simple flow
data for such basic polymers as HDPE II, PS I, PIB P-20, PIB L-80 and LDPE
Melt I/ IUPAC A/ IUPAC X, while complying with the global isothermal
stability constraints. For simplicity, only one or two nonlinear parameters
additional to the discretized linear viscoelastic spectra are introduced for the
description of data.
Instead of the simple "Leonov model" which uses only the parameters of the
discretized linear viscoelastic spectrum, we employ in the following sections a
highly nonlinear specification of the general class of Maxwell-type CEs
proposed by the author [23,24,36]. This specification subordinated to the
convexity conditions (27) guaranties the both Hadamard and dissipative
stabilities. Comparison of the descriptive ability of other models with
experimental data is not attempted in this Section.
i) b~ = b(I~,/2,T)/20(T), b2 = 0;
iii) b~ = b2 = b(I~,Iz,T)/20(T).
Here, 0 = 0(T) is the relaxation time in the linear Maxwell limit. The
specification i) with the Neo-Hookean elastic potential, results in a decreasing
branch of the flow curve in simple shear for b = 1. This poor quality, resulting
in dissipative instabilities, can be rectified by specifying more sophisticated
functional dependencies either for b(I~,I2,T), or the elastic potential. However,
this form was rejected due to the inconvenience for practical modeling. With the
specification ii), various simple flows can be described quite accurately for
several polymers. The only problem with ii) is the weak maxima of Nl predicted
during start up shear flow, in comparison with experimental observations. No
way of rectifying this malady was found and we therefore reject this
specification also. The form iii) for which the evolution equation (8), (26) can
be written as:
is the only one discussed and tested in the literature. It allows for plane
deformations in simple shear and endows the resulting equations with the
proper quality and flexibility for modeling a wide variety of polymers. Detailed
comparisons with experimental data have been made [40] with this
representation.
In order to relate the extra stress tensor to the elastic Finger tensor during the
deformation history, a functional form for the elastic potential W(I1,/z,T) = poF
must be provided. Here, Po is the density, and F is the specific Helmholtz free
energy. The following fairly general elastic potential:
3G(T)
W(II,I2,T) - 2(n+ 1) {( 1-[3)[(I~/3)n+1-1] + (1-13)[(I,/3)n +'-1 ], (62)
553
has been suggested in [40]. Here G(T) is linear Hookean elastic modulus, and 13
and n are numerical parameters. With the evolution equation (61) and potential
relation (62), the constitutive equations are Hadamard and dissipative stable for
0_< 13 <1 and n >0 (see the sufficient condition O for Hadamard stability and
criterion 'I +II' for dissipative stability) except when the criteria for "fluidity
loss" are met (see below). Equation (62) yields the Mooney potential for n = 0,
and the neo-Hookean potential for n = 13= 0. The extra stress tensor can then be
written due to equation (18) as:
with the simple model. Then, if there is disagreement with experimental data, an
appropriate functional form of b function required to bring the calculations into
qualitative agreement with the data, can be systematically determined. The
reason this procedure is straightforward is that for this class of equations, the
effects in various flows are well separated in the sense that there is some
measure of flexibility in modeling their qualitative behavior independently. This
is a direct consequence of the fact that whether the simple deformations are
steady or non-steady, the following relationships hold for the invariants of the
elastic Finger tensor c:
These relations also hold for the invariants of the total Finger deformation
tensor C. This is a remarkable feature of the evolution equation (61). The
experience [40] in modeling the viscoelastic behavior of several polymers
(LDPE, HDPE, PS, low and high molecular weight PIB) with the function
b(I~,/2) showed that simple power law or exponential functions of the invariants
with one or two adjustable parameters are sufficient for an accurate quantitative
description of all the available data. However, unlike the elastic potential (62),
no any unified form for b(I1,/2) has been found which could be used for the
description of data for all polymer melts.
Because of the flexibility which the modeling of the dissipative term permits,
one can operate with fairly simple forms of the general elastic potential (62),
such as the neo-Hookean and Mooney potentials for the description of the usual
rheometrical data. However, in simple shear, with this approach, cl2 generally
reaches a limit value of unity at high Deborah numbers leading to a saturation
of the shear stress and therefore to dissipative instability. One remedy is to
extend the discrete relaxation time spectrum at the small relaxation time end in
order to effect stability until the region where physical instabilities appear. A
simpler approach is to work with the existing discrete relaxation modes
obtained from the usual linear experiments, and to allow the parameter n in the
potential relation (62), to be a small positive number (e.g., n = 0.1). In this way,
we can preserve all the predictions in the rheometric regimes with simple
potentials and also effect the non-saturation of the stress at very high Deborah
numbers. Still, for concrete recommendations for quantitatively modeling high
555
Here, ~, is the shear rate, O"12 is the shear stress, Nl and N2 are the first and
second normal stress differences, respectively.
Startupflow
The initial conditions for startup flow are:
Stress relaxation
Here, ~, = 0. For stress relaxation following cessation of shear flow, the initial
conditions for equations (65) are:
c,j[ t_-o- cij]v,t , (70)
where ts is the shearing time prior to cessation of flow. For the stress relaxation
following the imposition of a step strain 7o, the initial conditions for equations
(65), are:
ell ]t = O * - 1 + 7 2.
o, ]
c22 t-o* -1; c 12 ]t=o* -70 9 (71)
For N modes, the set of 2N+ 1 differential equations, two per mode in equation
(65) and one in equation (72), can then be solved by using e.g., a Runge-Kutta
scheme with an automatically adapting step size. The conditions for recovery
following unloading can be similarly derived.
(73)
Startup flow
The initial condition for startup flow is:
Lit_ o - 1. (75)
Stress relaxation
Here, ~=0. For stress relaxation following cessation of elongation flow, the
initial conditions for equations (73) is:
The procedure for creep and recovery calculations is analogous to that for
simple shear.
Here ~p is the planar extension rate. The system of planar extension stresses is
558
)q t - o - 1 . (81)
Stress relaxation
Here, /~p= 0. For stress relaxation following cessation of planar extension
flow, the initial condition for equation (79) is:
Creep and recovery calculation can be performed as for the other simple flows.
~B - G[(1 - 13)(1, / 3) n (X: -- ~-4 ) ..1_ ]~(i 2 / 3) n (~4 __ X-2 )]. (86)
559
Startup flow
The initial condition for startup flow is"
)q t=o- 1. (87)
Stress relaxation
Here, ~B= 0. For stress relaxation following cessation of biaxial flow, the
initial condition for equation (85) is"
Creep and recovery calculation can be performed as for the other simple flows.
Eq.(91) means that the four first tested polymers demonstrate softening
behavior at high strain rates.
For describing the data for LDPE Melt I with the author's class of CEs, some
preliminary calculations were first performed with the simple model, as
suggested in the section 3.1 [40]. With this approach, the description of shear
flows was quite accurate. However, the biaxial extension damping function was
overpredicted, while the hardening effects in extension flow were
underpredicted. To rectify the observed discrepancies with the simple model,
the relations (60) suggest that b(11,I2) should be a decreasing function of (IJlz)
(see section 3.1 for the physical sense of the function b). A simple choice was
made as:
The parameter 'm' was chosen to be 1.4, for properly describing the extension
stress growth data. It was a hope [40] that with formula (93) for b(I1,I2) all the
available experimental data could be described reasonably well. Indeed, the
calculations according to this choice of b(I1,I2) could describe properly almost
all the data for the Melt I but they failed to describe the planar elongation tests
[107]. The reason for this was that in the planar elongation, as in the simple
shear, 11 = 12. Thus the hypothetical rheological behavior in the planar
elongation, as predicted by formula (92), is softening. However, this prediction
contradicts the hardening phenomena in planar elongation, observed
experimentally [ 107]. Therefore in Appendix B, a new, more physically related
attempt is presented to describe the whole set of data for LDPE Melt I.
5. CONCLUSIONS
General results on stability for both classes of CEs were demonstrated, which
included stability analyses of both the Hadamard and dissipative types. Results
of the stability analyses were applied to popular CEs.
The descriptive capability of a class of Maxwell-like CEs was demonstrated,
whose formulation satisfies all the stability constraints.
It should be noted that the data [98] for equi-biaxial extension were obtained
with using lubricated squeezing technique. Recent publications [113,114]
reported that experiments with this technique can involve undesirable side
effects, such as distortion of sample shape [113] or uncontrolled thinning of
lubricant layer [114]. Therefore there is still a need for independent equi-
biaxial extension data for polymers.
REFERENCES
81. Verdier and D.D. Joseph, J. Non-Newton. Fluid Mech., 31 (1989) 325.
82. Kreiss, Numerical Methods for Solving Time-Dependent Problems for
Partial Differential Equations, Les presses de l'Universite de Montreal,
Montreal, 1978.
83. Strang, J. Diff. Eq., 2 (1966) 107.
84. Baker and J.L. Ericksen, J. Wash. Acad. Sci., 44 (1954) 33.
85. Zee and E. Sternberg, Arch. Rat. Mech. Anal., 83 (1983) 53.
86. Knowles and E. Sternberg, Arch. Rat. Mech. Anal., 63 (1977) 321.
87. Kwon and A.I. Leonov, J. Non-Newton. Fluid Mech., 47 (1993) 77.
88. Kwon and A.I. Leonov, J. Non-Newton. Fluid Mech., 58 (1995) 25.
89. Kwon, J. Non-Newton. Fluid Mech., 65 (1996) 151.
90. Kwon and A. I. Leonov, Rheol. Acta, 33 (1994) 398.
91. Kwon and A. I. Leonov, J. Rheol., 36 (1992) 1515.
92. Hulsen, J. Non-Newton. Fluid Mech., 38 (1990) 93.
93. Renardy, Arch. Rat. Mech. Anal., 88 (1985) 83.
94. Simhambhatla, The Rheological Modeling of Simple Flows of Unfilled
and Filled Polymers, Ph.D. Dissertation, the University of Akron, 1994.
95. Kwon, Studies of Viscoelastic Constitutive Equations and Some Flow
Effects for Concentrated Polymeric Fluids, Ph.D. Dissertation, The
University of Akron, 1994.
96. Einaga, K. Osaki, M.Kurata, S. Kimura, and M. Tamura, Polym. J., 2
(1971)550.
97. Laun, Rheol. Acta, 17 (1978) 1.
98. Khan, R.K. Prud'homme and R.G. Larson, Rheol. Acta, 26 (1987) 144.
99. Soskey and H.H. Winter, J. Rheol., 28 (1984) 625.
100. Takahashi, K. Taku, and T. Masuda, J. Soc. Rheol., Japan, 18 (1990)18.
101. Laun, J. Rheol., 30 (1986) 459.
102. Leonov and A.N. Prokunin, Rheol. Acta, 19 (1983) 137.
103. Laun, Stress and recoverable strains of stretched polymer melts and their
prediction by means of a single integral constitutive equation. In"
Rheology, vol.2, Plenum Press, New York (1980).
104. Munstedt and H.M. Laun, Rheol. Acta, 20 (1981) 211.
105. Vinogradov and A.Ya. Malkin, J. Polym. Sci. A-2, 2 (1964) 2357; 4
(1966) 135.
106. Leonov and A.N. Prokunin, Rheol. Acta, 19 (1980)393.
107. Laun and H. Schuch, J. Rheol., 33 (1989) 119.
108. Wagner, J. Non-Newton. Fluid Mech., 4 (1978) 39.
109. Laun, Rheol. Acta, 21 (1982) 464.
110. Wagner and H.M. Laun, Rheol. Acta, 17 (1978) 138.
565
Appendix A
o(t,y) : yh(y)G(t), (A 1)
where h(7) is the shear damping function, and G(t) is the linear (Maxwellian)
relaxation function. This means that the stress relaxation curves (log(o(t)) vs.
log(t)) for various applied step strains will be parallel. This observation of
seemingly parallel stress relaxation curves has been reported for several
polymer melts and solutions (e.g., see [96], [97]).
Consider strain-time separable CEs with a perfect elastic limit. For these
equations, the step stress cl in response to a step strain 7, will be
With v - Ou/c~, and 3' = Ou/0y, equation (A3) can be rewritten in the elastic limit
as;
Here 'u' is the displacement in the 'x' direction, and M(T) - c36/0y. Let uo be a
basic solution satisfying equation (A4). Let us impose a small disturbance on
the basic solution, so that
u - Uo + ~ fi exp[i(ky-mt)/a21 (A5)
where ~ is the small amplitude parameter, 'k' the wave number, and co the
frequency of disturbance. Substituting for 'u' from formula (A5) into equation
(A4) and taking into account only the lowest order terms in g, yields"
If M(y o) > 0, m is real and the disturbances in equation (A5) will not grow with
time. However, if M(To) < 0, we have:
1.5
J~ " 0
MeltI
v
_L--
1.0
o5 [
o Experirnenfal Poinfs
----- h(7) = ,57exp(--.31T)+.43exp(--.10-67)
5 i0 ~ 5.. 20 25 50 55
Shear Stroin, -y
is presumably because data could not been obtained at very short times
following the imposition of the step strains (assuming no wall slip).
10 4
t0 3
0,,,.
v
o
p..
to2
v
r~
"10
(3)
,J~
101
r
1 1 0 `= 10 2 10 s 10 4
It should be noted that the deviations from the master curve of vertically shifted
stress relaxation curves are consistent with the requirement of Hadamard
stability.
Two conclusions can be drawn. The first is that strain-time separability holds
only in an approximate sense, if we are prepared to neglect the material
response to quick disturbances. The second is that any strain-time separable CE
is certainly unstable in the Hadamard sense in the limit of very rapid
disturbances, due to the universally observed maximum in the dependence ~,h(~/)
vs. ~,in those time regimes. This indicates that we cannot simultaneously
describe the experimental data in the rheometrical regimes, and have the
stability at high Deborah numbers for any strain-time separable CE. It is evident
that the above instabilities have no physical basis, but are simply rooted in the
improper extrapolation of strain-time separability to quick time scales. High
Deborah number flow simulations using these CEs should therefore be avoided.
569
Appendix B
In order to describe all available data for the LDPE Melt I we will use the
simple non-Hookean potential and two-parametric expression for the dissipative
term b"
sinh[v(I, - 3)1
b(I, ) - exp[-13(I, - 3)] + -1. (0<13 < 1, v > O) (B1)
vO, - 3 )
With the parameters shown in (B2), formula (B1) initially show only
hardening and only then, after decay of the first term, it describes "irreversible
softening". It should be also noted that in simple shearing, with typical data for
shear rates available in rotating instruments, the value b in formula (B 1) is all
the time near unity. This fact preserves the description of simple shear data
demonstrated in paper [40]. Nevertheless, we manifest in the following also
some important comparisons between our calculations and data for simple
shearing too.
Figure B 1 indicates a good description of the steady shear viscosity and first
normal stress difference over a wide range of shear rates. Descriptions of the
transient stress growth during shearing experiments are depicted in Figure B2.
The discrepancy for N~ at short times is probably due to the instrumental
problems for these measurements [97].
7 7
10 ~__...~_v . ~ u l ~ l l 10
Melfl o o
I 10 6
I ~eference Temp. 150 C - 10
6
13..
~..,.
o 10
5 10 5 c-,-
~j_~-~7~,,
,--~7_~~^,-, ~
121
O
>:, 4
104 ~
-~
.,..~ 10
"I3
0 Q
I
3 u~
m
5= 103 10 ,-,
t~
ol
c~ 02 _ 9
10 f-]
O
C~
1 O
10 .,. I I I I 1 I I 10 ~.~.
Reduced Shear R a t e , 7G T (s 1)
Figure B 1 .Steady shear viscosity and the first normal stress coefficient of LDPE
Melt I at reference shear rate of l s -1 [97] at various temperatures (symbols).
571
a 10 5 i i
n Melt l 0
Reference Temp. 150 C **t:~:~O ~
c~ z-
,~
9 -I
~ ~ o3 .-vaT - 1s
r" t..
~ 10 2
I0-' 10 0 10 1 10 2
Shear Strain, 7
Figure B2. Transient stress growth normal stress coefficient for LDPE Melt I
[97,109]. Various symbols correspond to different temperatures.
6
10 I I 10
Melt l
o
Reference Temp. 150 C
10 4
_ 105
o "~ - 10 Pa
12
d z
o--
0
N1
10 _ 10 4 ~" U,
121
l-
c"
(/3
10 0 _ 10 3
2
10 -~ u i i i 10
10 -2 10 -1 100 101 102 10 5
Figure B3. Shear strain and first normal stress difference in creep under
constant shear stress for LDPE Melt I [110]. Various symbols correspond to
experiments at various temperatures.
102 I
. . . .
I I I
105
1 104
10 - N, t
> z
0
~ 0 _ 10 3 ,~
-la
r ~~ 10
Q
r
o_
El
k_
(z)
10
-1
o 102
Reference Temp. 150 C
10 -2 I I I I 101
10 -2 10 -1 100 101 102 103
Figure B4. Shear strain recovery and first normal stress difference after
unloading following the experiment in Figure B3 [110]. Various symbols
correspond to various temperatures.
573
80 I I 1 I I I 1
60 - 70 = 5.0
Frequency = 1Hz
40 _
O~
-~ 2o
(o)
e 0
r~
-20
o~ -40 IUPAC X
o
-60 150 C
-80 I I I I I I I
-40 -30 -20 -10 0 10 20 50 40
-t
Shear Rate (s )
100 I I I I I I I
75
7o = 10.0
OQ
5O
Frequenc =
v 25 _
f/l
I1)
~ 0
(b)
-25 -
&)
rn -50 IUPAC X -
o
150 C
-75 _
I I I I I I I
-100
-80 -60 -40 -20 0 20 40 60 80
-1
Shear R a t e (s )
6I
I I I I
10 0.I
t 1.0 0.01
I
0
13_
1
..---2
.+r 10
v
+#
f Melt I (I50 ~
10
I I I I I
10 -I 100 101 102 103 10 4
Time (s)
Figure B6. Tensile stress growth coefficient vs. time for LDPE Melt I [112].
Finally, we also attempted to describe with the use of formulae (B1) and (B2),
the data [98] for equi-biaxial elongation for LDPE Melt I. The result of
comparison between our calculations and data is shown in Figure B8. It is
evident that the calculated curve predicts more hardening in the rheological
behavior of the Melt I as compared to the data. The possible reason for that was
discussed in the Section 5 of the paper's main text.
575
106 I
-1 -1
0.05 s 0.01 s
0
0
0~
E~
13_
5
10
.kp
+o_
4
10
t .. I
Figure B7. Planar tensile stress growth coefficient vs. time for LDPE Melt I
[107].
1.0
0
c 07
0
"~ C:
c" 0
0
= 0.5
x
~ l.a.
12I
~ ~o3
IUPAC A (150 ~
.1 '
,_ 9 I
A. I. Leonov*, J. Padovan**
1. INTRODUCTION
2. F O R M U L A T I O N
whose most important feature is that the velocity field v is the same for each
mode;
(ii) the n-th modal extra stress tensor formulation:
e
O'n -- Gn(T)sn(~n, Cn ) (2)
579
and
iii) the expression for the total stress tensor:
c~ - -p~_ + o e e e (3)
= _ -- ' (5" = 'Y'~ (5"
-- --n
n
Here 't' is time, v is the velocity vector, N and e are the vorticity and strain rate
tensors, ~ is the stress tensor, p is the isotropic pressure, fi is the unit tensor,
0n(T)and Gn(T) are the relaxation time and elastic (Hooke's) modulus for n-th
mode, ~,n is a numerical parameter for each mode, and T is temperature. The
elastic terms in the CEs include the evolution operators within the square
brackets in equation (1) and the formulation of the stress tensor with the aid of
equations (2) and (3). Here _Sn (~,,, _C_n)are some isotropic tensor functions of
tensors Cn for each n-th mode. The dissipative terms in the CEs are represented
by the set of isotropic tensor functions ~n(~,, ~ ) of tensors c for each n-th mode.
If the values of parameters n are equal to either -1, or 0, or +1, the evolution
operator in equation (1) converts to the lower convected, corotational, or upper
convected tensor time derivative, respectively. It is also generally assumed that
the above isotropic tensor functions _S_n(r _C_n) and ~. (~n, --C_n) satisfy the
dissipative inequality and provide the CEs with a regular limit to the linear
viscoelastic case.
The momentum balance and the continuity equations are of the form:
V.v =0 (5)
Here p is the density and g is the gravity acceleration directed along the unit
vector k.
Finally, there is also the heat equation, which using the entropy viscoelasticity
assumption (e.g., see [2]) takes the form"
Here C~ is the heat capacity under constant volume, J is the thermal heat
equivalent of power, and K is the thermal conductivity which is generally
represented as a second rank tensor. In the case of high-elastic cross-linked
580
Here To, T~ and T2 are known temperature fields, V and U are known solenoidal
vector fields, and S(t,x) is a known boundary stress. We assume below that a
solution of the problem (1)-(7) exists, and will make simplifying assumptions to
the above formulations.
We now make three similarity assumptions which reduce the set of CEs (1) -
(3) and Eq.(6) to a more simplified form.
Here an and 13n are numerical factors, and 0(T) and G(T) are some characteristic
relaxation time and modulus, taken e.g. either from the first relaxation mode, or
from a dominant mode, or considered as mean values averaged over the linear
relaxation spectrum. The assumption (8) usually holds for polymer fluids in a
restricted time-temperature region.
K = n:o(T)6__, (11)
(ii) the anisotropic heat conductivity for solids with finite elasticity,
K=K(T,C-'). (12)
Scaling theorem.
Assume that the flow history (i.e. the velocity field v(t,x)) is known. Let the
assumptions 1-3 with equations (9)-(11) hold. Assume that for a certain value
n-k, a solution { 7~,_fi,~,_~} has been obtained. It depends on coordinate x and a
"stretched" time ~, and satisfies the s i n g l e m o d e set of equations:
8 - -~ + G(T)s(_~), (15)
V__._fi- 0, (17)
bC vp[a, T + (_ft. __V)T]= R E . [K(~', a)- VT] + J. G(T)- tr[~(a) .~1, (18)
Let the stretched time x, parameters 'a' and 'b', and functions ~, IA, ]71, "I'2'
and ~ in equations (19), be defined as follows"
z-t/ak, 2
a = 1/~--'~[3nan, b _ l / Z ] 3 n, ]Tj (a:,X) - Tj (t / ak , x )
n n
^
Then the multi-mode solution of equations (1)-(6) for the initial boundary
problem (7) is found as follows:
Preliminary remarks.
1. There are two important features of the above CEs: (i) as mentioned, the
velocity field is mode independent and given, and (ii) due to the scaling
assumptions 1-3, all the equations (13)-(18) are also independent of the mode
number ' n'.
2. The following scaling properties are exposed in equations (20) and (21): (i)
the time in each n-th Maxwell mode is scaled by the relaxation ratio an (= 0n/0)
as: ~n= t/an; (ii) the velocity in each n-th mode is scaled by the ratio an as:
_fin(1;n,X)--anV(t,x); and (iii) the non-dimensional n-th modal extra stress
tensor is scaled by the modulus ratio, [~n (=Gn/G).
3. It should be noted that the velocity field, v(t,x) in nonlinear multi-mode CEs
cannot be found from the known solution of the problem (13)-(19) for a single
583
Maxwell mode. This can be easily proved for steady simple shearing or the
simple elongation case.
Proof of the scaling theorem.
Using the above features, it is easy to show that the functions defined in
formulae (21) through the single mode solution of the initial boundary problem
(13)-(19), satisfy equations (1)-(6) and initial and boundary conditions (7) for
the multi-mode approach.
Firstly, the evolution equation (1) for n=k immediately follows from equations
(13) and (14) after substituting there z = t/ak, and _fi(t,x) and ~(z,x) from
equation (21). Because value 'k' was taken arbitrarily, equation (1) follows
from equations (13) and (14) for arbitrary 'n'.
Secondly, introducing into equation (16) the expressions: x = t/ak, __fi(t,x) and
15(~,x) from equation (21), as well as the formulae for 'a' and 'b' from equation
(20), yields"
1 gP
--[Otv+(v'g)v]-
- Z~n ~ +g - [o(r)s(c k)]-t- ~-'f~ k (22)
~Y'~a~ ~ n
n n n
This equation holds for any (and all) values of 'k'. Then the momentum balance
equation (4) can be retrieved for the multi-mode approach by multiplying
equation (22) by 13kand summing over all 'k'.
Thirdly, introducing into equation (18) the respective variables from (20) and
(21) yields:
CvakP (23)
~[0tT + (v-V)T] = RV. [K(T,c k ). VT] + akG(T)J 9tr[s(c k ).e]
n
Multiplying equation (23) by 13k /ak taking the sum over all 'k', and using
equation (10), yields the expression (6) for heat equation in the multi-mode
approach.
To finalize the proof, the multi-modal version of the continuity equation (5), as
well as the initial and boundary conditions (7) must be retrieved. In particular,
equations (5) and (7) follow directly from equations (17) and (19) when
employing equations (20) and (21).
Since in the reality neither flow, nor stress fields are known, the requirement of
the theorem about the known velocity field seems at first sight quite artificial.
584
Yet, the situation with known flow field commonly happens when using any
iterative numerical scheme. This will be clarified in the following Section.
4. EXAMPLES
To calculate the extra stress tensor in any, say j-th mode, we do not need to
solve once again the initial problem, but simply use the scaling approach:
Here aj = 0j/01. Note that since in this example, aj< 1, we need only to
extrapolate the values of or1e, already computed, for different values of ~ which
are not equal to q?k. Thus, to calculate the extra stress tensor using the scaling
approach we just need to make 'n' calculations for a single (say, first) mode for
all chosen values of shear rates r k and then restore the values of extra stress
tensor by interpolation.
It seems that (especially) for homogeneous simple shearing, there is no
computational advantage, as compared to the conventional procedure. Indeed,
using scaling one needs to compute in this case, n+l coupled ordinary
differential equations for the first mode and also perform a time consuming
interpolation procedure. If Ks is the amount of operations required for solving
the start up problem for a single model with a single value of ~, k and Kj is the
amount of the interpolation operations, the total amount of operations, K, using
scaling is: Ks~ = (n~c+l)Ks + Ki. On the other hand, the conventional method of
computations is performed with the following amount of operations: Kcon
NKsn~o.. Here n~c and ncon are the numbers of shear rates ~ k we need to perform
the complete set of computations. In order to compare the numbers of
operations when using these methods, we note that the values of n~c and n~on
should be generally quite different from each other. The value noo, can be taken
arbitrarily and related usually to the compared data. To make the interpolation
valid, the value of ns~ however, should be twice-three time more than the
amount of modes, N, i.e. ns~ = (2-3)N. Thus the efficiency of scaling over
conventional method is estimated by the ratio:
N
o'im _ --pim ~ + e , m l + qa (e m
i - eim-1 ), 13"ie,m - Z Gn-S ( ~ ' c-n,i
m ); (29)
n=l
m e,m ~7 2 (V m m-1
~-Pi -- g ' o . + l"la i - vi ), V ' V im -- 0. (m > 0) (30)
Here equation (28) describes the evolution equation for n-th mode, equation
(29) is the formulation of the stress tensor in the N-mode model, with the
artificial Newtonian term (with 'viscosity' rla) included, and equation (30)
describes the momentum balance and continuity equations. In equations (28)-
(30), the subscript 'i' indicates the flow with the flow rate Qi and the superscript
'm', the number of iteration.
587
The above iterative scheme works as follows. For a given 'i', the "initial
oo oo
guess" for the virtual velocity field is obtained as" v ~ Xi vi_l,. Here vi_ 1, is
the solution of the problem with the flow rate Qi-1 and )v~ is a numerical
parameter ()vi > 1). Since the vector field v ~ is still solenoidal, there is the
relation: Qi = )vi Qi-1. Thus to guarantee that given flow rate values Qi-1, and Qi
should be close enough, one should take the value of )vi just slightly above 1.
Using the value _,v~, the strain rate and vorticity tensors for the initial guess, =,e.~
and mi~ are easily calculated. Then equations (28) should be solved with some
proper (usually given upstream) conditions to find the space distribution of
values for N six-component tensors c 1 ., and concomitantly, the extra stress
=n,l
tensor, ~i e'~. The last step in the first iteration is the determining of the first
iteration for the velocity field, vl, and the pressure p l at the first iteration.
These are found as the solution of the linear non-homogeneous Stokes problem
(30) under constraint Qi = const. Then one should repeat the iterative procedure
till it converges, if it possible. Obviously, for any value 'i', the artificial viscous
terms in equations (29) and (30) vanish at the convergence, m --+ oo. The
described iterative scheme works well [ 16], if the CEs have some good stability
properties. It allows to find effectively the velocity and stress distributions for
very high level of Deborah numbers (flow rates Qmax). It is evident that the
scaling approach can be applied to the computations at any step of iterative
procedure, since the velocity field here has been found from the calculations on
the previous step.
To solve equations (28)-(30), some numerical schemes employing various
discretization (e.g. pure FEM, or combined FEM and upstream) methods can be
applied. These are not the subject of discussion in this paper. Obviously in this
case, the highest computation burden is the numerical solution of the evolution
equations (28) for the N tensors =n,i
c m on any iterative step ' m ' with the given
flow rate Qi. This is because for any given values 'n', 'm' and 'i', equations (28)
is generally the set of six coupled nonlinear partial differential equations. Once
again, it is wise to start solving equations (28) with the highest relaxation mode,
n=l. Then using the scaling approach, one can find the distributed values of
tensors Cn,
im and extra stress tensor =13ie'm for any level of flow rate Qi and the
iterative step 'm', as follows"
588
m m
__Cn,i - Cl,i
{a n -vm-1 } (an
-- 0
n
/ 0 9 n-
1,
1,2,
"",
N)
N
r _ Z ans(r mi )
Cn, (31)
n=l
Here we need to compute equation (28) only once for n=l and then using an
cl,i {anvm-1}
interpolation procedure, obtain the values of the functionals =m - from
a search of already computed values. This is because in equations (31), an < an-1
(On < 0n-l). Since the flow rate Q is a linear functional of velocity v, the
respective values of flow rates corresponding to the velocity a~y_iv-can be found
as Qni = anQi. Since an<l, SO Qni<Qi. Thus the value of Qni belongs to an already
computed domain, [Qj,Qj+I] (j+l<i). Evidently, the described procedure
preserves the nonlinear relationship between the stress and flow fields.
We now estimate the efficiency of scaling type of computations as compared
m. be the amount of numerical computations
to the conventional one. Let s Kn,i,
for solving equation (28) for a given 'n'-th mode, at the given value of flow
rate, Qi, and for a given iteration, 'm'. To simplify the estimates, we assume that
these values are independent of 'n', 'i' and 'm', i.e. s Knmi ~ Ks. Let Kret be the
m
amount of operations for retrieving the distributions Cn,i (x). Finally, let Kvp be
the amount of numerical operations for solution of the Stokes problem (30).
Then neglecting the amount of operations needed for tabulations of extra stress
tensor, the total amount of operations for computing the problem using scaling
is:
which holds for complex flows. Inequality (33) simply displays the fact that in
complicated computations, the number of operations for retrieval of already
589
Then comparing formulae (32) and (34) in the cases when inequality(33) holds,
one can find that
Ks/'Kcon ~, 1 / N . (35)
Equation (35) shows that for calculations of complex flows with multi-mode
viscoelastic CEs, the scaling approach can provide with a significant
computational economy as compared to the straightforward computations. The
key element here is the inequality (33) which holds only for complex flows.
Finally, it can be demonstrated that almost the same computational economy
can be achieved with the scaling approach for solving non-steady problems for
complex viscoelastic flows. Here, the scaling approach can give more economy
when using more stable implicit methods.
5. CONCLUSIONS
5. We have proven the scaling theorem for very broad formulations of multi-
mode CEs of Maxwell type. However, the very existence and stability of
solutions of the CEs will highly depend on such fundamental properties as the
thermodynamic consistency and stability of CEs.
ACKNOWLEDGMENTS
This work was supported in part by the NSF Grant (No CTS-932-0037). The
authors would also like to thank Sunil Acharia for valuable discussions and Jay
Jeong for help.
REFERENCES
A T H E O R Y OF F L O W IN S M E C T I C LI Q U I D CRYSTALS
F. M . L e s l i e
Mathematics Department, University of Strathclyde, Livingstone Tower,
Richmond Street, Glasgow G1 1XH, Scotland
1. I N T R O D U C T I O N
The continuum theory for nematic liquid crystals proposed by Er-
icksen [1] and Leslie [2] has significantly improved our understanding of
flow phenomena in these anisotropic liquids. Initially it explained flow
alignment and non-Newtonian flow effects exhibited by these liquids, and
thereafter contributed greatly to our insight into a variety of instabili-
ties that can occur in these fascinating fluids under the application of
magnetic and electric fields, thermal gradients, and flow [3]. Also the
realisation that changes in alignment of the local anisotropic axis can
induce flow, which in turn influences the changing alignment, had seri-
ous implications for applications using these materials in display devices
[4-6], this leading to a greater appreciation of the theory.
More recently potential for fast switching display devices has led to
an increasing interest in smectic liquid crystals, and particularly smec-
tic C liquid crystals. These liquid crystals display translational order as
well as orientational order, and clearly their intrinsic layering presents
new problems in terms of the formulation of an appropriate mathemat-
ical model. Motivated largely by applications in display devices, Leslie,
Stewart and Nakagawa [7] have recently proposed a theory for smectic
liquid crystals, which may prove useful for the modelling of such appli-
cations. Essentially it invokes two simplifications in order to reduce the
mathematical complexity, assuming that the layer spacing in these ma-
terials remains constant, and also that the tilt of the alignment of the
anisotropic axis with respect to the layer normal also remains fixed. For
many situations these assumptions appear reasonable, but clearly there
are others where they are too restrictive. The assumption of fixed layer
spacing largely rests on the notion that variations in layer thickness re-
quire considerable energy, and consequently it seems reasonable when the
592
smectic is not under undue strain. Also the constant tilt presumably ex-
cludes certain thermal and pre-transitional effects. However, the theory
has already proved useful in a practical context [8,9], and in this article
we attempt to summarise its predictions relevant to rheology.
For readers not familiar with general properties of liquid crystals,
the books by de Gennes and Prost [10] and Chandrasekhar [11] give full
accounts of physical properties, while that by Collings [12] provides a
fairly gentle introduction.
2. S M E C T I C THEORY
This section presents a summary of the equations proposed by Leslie,
Stewart and Nakagawa [7] for smectic C liquid crystals. The theory is
somewhat restricted in that it assumes that the smectic layer spacing re-
mains constant, although the layers may bend and deform, and also that
the tilt of alignment with respect to the layer normal remains unchanged.
However, the theory differs from its predecessors in that it does allow for
finite bend and deformation of the layers, and for non-linear displace-
ments and flow. Like the theory for nematics it rests on the concepts of
classical mechanics.
With the above assumptions one can readily describe the layered
configurations by employing two orthogonal unit vectors, one the unit
layer normal a, and, following de Gennes [10], the second unit vector c
is perpendicular to the layer normal indicating the direction of tilt of the
alignment. Clearly this second vector is tangential to the smectic layer.
Hence the two vectors or directors are subject to
a.a-c.c--1 , a.c-0. (1)
Also, in the absence of any singularities or defects in the layering, as both
Oseen [13] and de Gennes [10] argue one must also impose the constraint
curl a = 0. (2)
A more familiar constraint arises from the customary assumption of in-
compressibility, and so the velocity vector v is subject to
d i v v - O, (3)
wherein
where the scalars V, # and r are arbitrary multipliers stemming from the
constraints (1). Also, with the aid of equations (115) the balance of linear
moment (4) can be expressed as
pi~i = pFi + a~,ak,i + G~ck,i - ~,i + (~ak,i + ~ c k , i + tij,j, (16)
596
where
#=p+W. (17)
The forms (15) and (16) are more convenient for our purposes in the
following sections. Also, employing the forms (12) allows one express the
viscous dissipation inequality as
t i8j D i j __
g a A i - gi
*~C C
i >_ O, (18)
which leads to some restrictions upon the viscous coefficients.
To conclude this section we attempt to clarify the physical role of
the vector/3 arising from the constraint (2). If we consider planar layers
subject to flow or external fields, equations (7) show that they are subject
to moments
~.i --- ~.ijaj -" ~ p a p a i -- ~i q- eipq ap Oaq,j -~- Cp-OCq,j" aj. (19)
Thus, if the layer normal coincides with the z-axis, one has
= + ..., 4 - + ..., - 0 + ... (20)
simply giving the/3 contributions explicitly. Hence, if the layers are con-
strained to be planar by for example confining parallel plates, this vector
provides a means by which the couple stress transmits the necessary
torques to maintain the parallel layering.
3. S I M P L E S H E A R F L O W
Given the layered structure always present in smectic liquid crystals
it is not clear as to how this class of liquid crystal will respond to flow in
general, there being little by way of clear experimental evidence to guide
us. Here, therefore, we choose to consider the simplest options, two cases
in which the layered structure appears to be compatible with the imposed
flow. In our first example our results appear to be consistent with our
premise, but in our second the question does remain somewhat open.
3.1 P l a n a r layers p a r a l l e l to t h e b o u n d i n g p l a t e s
Consider a smectic C liquid crystal confined between two parallel
plates with the smectic layers everywhere parallel to the plates, one of
which is at rest but the other moves with velocity V along a straight line
in its own plane. With Cartesian axes such that the z-axis is normal to
the plates and the x-axis parallel to the imposed motion, it is natural to
examine solutions of the equations of the previous section in which
597
with the angle r either symmetric or asymmetric. For the former the
angle r tends to either zero or r in the centre of the cell, dependent upon
whether T5 is greater or less than T~. For asymmetric solutions the results
are more interesting with the twist in the centre of the cell unwinding as
the shear rate increases, the flow causing the twist to concentrate near
the plates with a growing region of uniform alignment in the middle of the
cell. This result appears to be consistent with the early experiment by
Pieranski, Guyon and Keller [18]. Note that for this problem the equa-
tions are equally valid for chiral or non-chiral materials, the difference
between the two, if any, being in the initial equilibrium configuration.
3.2 P l a n a r layers p e r p e n d i c u l a r to t h e b o u n d i n g p l a t e s
Our second example considers what is commonly called the bookshelf
geometry with the layers planar but normal to the plates, and a shear
imposed parallel to the layers would appear to be compatible with the
smectic layering, as Carlsson, Leslie and Clark [17] discuss. In this case we
examine solutions referred to Cartesian axes with the z-axis perpendicular
to the plates of the form
a-(0,1,0) , c- (cosr ,sine(z)), v- (u(z), v(z), 0), (35)
this again satisfying the constraints (1), (2) and (3). Here, however,
we must confine attention to non-chiral materials, since chiral materials
would require the inclusion of a y dependence in the angle r and pre-
sumably also in the flow components, which would lead to an analysis
beyond the scope of an initial investigation of the simpler options.
As Gill and Leslie [16] discuss, the equations of linear momentum
(16) with the above choice yield
t'~z - #1 (r + #2(r cosr cl, (36)
t' z = + osr
where again Cl and c2 are constants, and there are no imposed pressure
gradients or fields. The viscosity functions in the above equations are
given by
2#1(r = ~Uo+ ~ 4 ~- )k5 "4- 2A2 cos 2r + 2#3 sin 2 r cos 2 r
2~t2(r -- tel -4- I"1 -4- "r2 -4- T5 -4- 2(n3 -4- 7"4)sin 2 r (37)
2~t3(r --/Zo 4-/z2 A- 2A1 + A4 + (~t4 -~- ~5 -- 2A2 + 2A3 d- A5
-I- )~6) sin 2 r
500
Here also one can solve the equations (36) to obtain the velocity gradients
in terms of the angle r and the imposed shear stresses. The equations of
angular momentum (15) reduce to
f ( r 1 6 2 -4 21 dr(C)
de r _ (~5 + ~2 cos 2r - (T1 -~- 7"5)v' c o s r 0, (38)
where
f(r - g ~ + g~ cos 2 r + g~ sin 2 r (39)
but this entails a choice of the vector/3 and the scalar 7 of the form
t3-(~(z)y , 0 , ~(z)y) , 7=~(z)-y~(z), (40)
the prime again denoting differentiation with respect to z.
There are two respects in which this solution differs from the former,
both giving rise to grounds for not pursuing it in any great detail at
least for the present. One is that the material parameters appear in
greater numbers, and our lack of knowledge of their relative magnitudes
therefore inhibits progress. The second is that the surprising dependence
of the vector/3 on the y coordinate means that the resulting torques
can become large, and therefore the material may seek to relax to a less
strained state, say by forming domain structures. Some guidance from
related experimental studies would not go amiss in this respect.
To close this section we consider the alignment dictated by shear flow
in this geometry. Here the options are
r162 rico , v'-0, (41)
where r is the acute angle defined by
cos2r - -~5/~2 , provided ~5 <_ [~21, (42)
otherwise uniform alignment is not possible in shear flow in this geometry.
Note that the viscosity )~5 is clearly positive as a consequence of the
inequality (18), as Carlsson, Leslie and Clark [17] discuss. Of the solutions
(41) we select on grounds of stability
r162162 , if)~2u'<0 , r162162 , if)~2u'>0,(43)
as Gill and Leslie [16] and Carlsson, Leslie and Clark [17] show. For
such uniform alignment without transverse flow it is of interest to note
from equations (36) and (37) that the transverse shear stress is in general
non-zero, this an aspect perhaps more readily amenable to experimental
observation.
601
4. F L O W I N S T A B I L I T I E S
Continuum theory for nematic liquid crystals quickly gained credibil-
ity through its success in describing satisfactorily a number of instabilities
that occur in these materials, when subject to external influences includ-
ing flow. Here our aim is to show that similar flow induced instabilities
are likely in smectic liquid crystals, being predicted by the present theory,
and naturally one hopes to stimulate relevant experimental studies. In
this section it suffices to give a simple illustration discussed by Leslie and
Blake [19].
We return to the geometry of our first example in the previous section
and thus consider smectic C layers confined between parallel plates, the
layers parallel to the plates, and subjected to simple shear flow. Here,
therefore, with the same choice of Cartesian axes, the z-axis normal to
the plates and the x-axis parallel to the imposed flow, we again examine
solutions of the form (21), and find as before that the governing equations
are
g~r + (T1 -- rs)(u' sin r v' cos C) - 0,
(r/~ + y2 cos 2 r + 7/2v' sin r cos r c~, (44)
(711 -~- 712 sin 2 r + ~/2u' sin r cos r - c2,
where v/1 and v/2 are again given by equations (23). Choosing the origin
midway between the plates, a distance 2d apart, the relevant boundary
conditions are
u(d) - Y , u(-d) = v(-4-d) - O , r162 (45)
where V is the velocity of the moving plate, and r is either zero or r.
Straightforwardly the equations (44) have simple solutions subject to
conditions (45) in which
r162 , u- Y(z + d)/2d , v-O, (46)
t~z - (~71 + r12)l//2d , tyz - O.
As remarked above the solution anticipated is
r 0 , if r~ > T~ , r , if 7"5 < T1, (47)
being unstable otherwise. Consider small perturbations to the solution
(46) in which
r r + r , u - Y ( z + d ) / 2 d + ~t(z) , v - ~(z), (48)
602
and the boundary conditions for ~ require that the last of equations (49)
yield
C~U 0 [ Ou Ov
P Ot - 0---~ (rh + 7?2 cos 2 r + r/2 sin r cos r
+ ( ~ - ~-~)si~ r
(61)
Ov 0 [ Ov ~U
P-~ - ~ t(r/~ + r/2 sin 2 r O--~z+ r/2 sin r cos r Oz
+ ( n - ~) r162
and an expression for the pressure p, the viscosities 771 and r/2 again given
by equations (23). From the above equations it is at once evident that one
must include both flow components in order to avoid an over-determinate
system. The boundary and initial conditions are
~(+d) - ~(+d) - r177 - 0, (62)
u ( z , 0) - ~ ( z , 0) - 0 , r 0) - r , Izl < d,
the cell gap again 2d, and r a known even function of z.
Introducing the notation
a - (7"5 - n ) sin r , b - (7"1 - r5) cos r (63)
m-r/l+r/2cos 2r , n - 7 ? l + r / 2 s i n 2r , r-7?2sinCicosr
where r is a constant angle associated with the initial alignment, Leslie
and Blake [19] replace the above equations by
02r 0r Ou Ov
g ~ -~z ~ - 2 ~ ~ -8-i - ~ -8-;z - b -8; - O ,
cgu c92u c92v 02r (64)
P~ - m~z~ + ~ - ~ + a OzO----i '
Ov 02u 02v 02r
p-~ -- r -~z 2 q- n -~z 2 + b cgz cgt ,
whose solution presumably gives at least a good approximation to the
initial relaxation. With the removal of a strong field, it would be ap-
propriate to select r to be r / 2 . By introducing dimensionless variables
given below, one finds that the inertial terms in the last two of equations
(64) are negligible, and therefore it is reasonable to set p equal to zero in
the above. As a consequence the last two equations quickly yield
c92u = ( r b - a n ) 02r (ran - r 2) c92v - (ra - bin) 02r (65)
(mn- ~)-~ ~ OzOt ' ~ o~Ot '
605
where
r -- A(cos q~ - cosq) , U(~) - Aq(an - r~-
br)i (sin q~ - ~ sin q),
#(mn J
(71)
v(r - Aq(bm ) (sin q~ - ~ sin q)
~ ( m ~ - - ~at)
oo
an ~ bT" oo
q ~ A n (sin q ~ - ~ sin q ~ ) e - q ~ / " , (73)
~t = t , ( m n _ r2 ) n=l
bm - ar oo 2 ~/#
= I , ( m n - r 2) y ~ q,A~(sin q~( - ( sin q n ) e - q " 9
n=l
A n ( c o s q ~ ( . - cosq~) - r , (74)
n--1
the 's' and ' f ' subscripts denoting slow and fast modes, respectively, the
former detected by light-scattering experiments. Thus we predict a decay
time rd given by
74 = f?(q, O)/a(q, 0), (94)
where
~ / - 2(X5~/- v2)/rl. (95)
The coefficient ~5 is positive as remarked earlier, but appeal to the viscous
dissipation inequality (18) also shows that r/and f/are both positive.
Galerne and coworkers [29] find that their data for the decay time
observed in their experiments fits an expression analogous to our result
(94), their expression for the elastic factor taking the form
B(O) = (B1 cos 2 0 -b B3 sin 2 0 + 2B13 sin 0 cos O)q2, (96)
the coefficients those occurring in the Orsay energy [26]. However, as
Leslie, Stewart, Carlsson and Nakagawa [31] show, the above expression
is identical to that given by equation (89). Galerne and colleagues find
also that their data is consistent with a viscosity function given by
1 1 cos2(0 -- 0 1 )
= -- + (97)
7g, #a and Vg are viscous constants, and 01 and 02 constant angles. While
the two viscosity functions appear to differ, they are in fact equivalent,
as one finds by setting
~o -[" ~4 -- 2X2 q- )15 -- ttg c o s 2 02 -[- vg q- 7g c ~ 01,
REFERENCES
.
J.L. Ericksen, Trans. Soc. Rheol., 5 (1961), 23.
2. F.M. Leslie, Arch. Rat. Mech. Anal., 28 (1968), 265.
3. F.M. Leslie, Adv. Liq. Cryst., 4 (1979), 1.
4. C.Z. Van Doorn, J. Appl. Phys., 46 (1975), 3738.
5. D.W. Berreman, J. Appl. Phys., 46 (1975), 3746.
6. M.G. Clark and F.M. Leslie, Proc. Roy. Soc. A, 361 (1978), 463.
7. F.M. Leslie, I.W. Stewart and M. Nakagawa, Mol. Cryst. Liq.
Cryst., 198 (1991), 443.
Q
C.V. Brown, P.E. Dunn and J.C. Jones, Europ. J. Appl. Math., 8
(1997) 281.
0
J.C. Jones and C.V. Brown, Proc. 16th Int. Displays Conference
(1996), 151.
10. P.G. de Gennes and J. Prost, The Physics of Liquid Crystals, 2nd
Ed. Oxford University Press, (1993).
11. S. Chandrasekhar, Liquid Crystals, 2nd Ed. Cambridge University
Press, (1992).
12. P.J. Collings, Liquid Crystals: Nature's Delicate Phase of Matter,
Princeton University Press, (1990).
13. C.W. Oseen, Trans. Faraday Soc., 29 (1933), 883.
14. F.M. Leslie, Contemporary Research in the Mechanics and Math-
ematics of Materials, Eds. R.C. Batra and M.F. Beatty, CIMNE,
Barcelona (1996), 226.
15. T. Carlsson, I.W. Stewart and F.M. Leslie, J. Phys. A, 25 (1992),
2371.
16. S.P.A. Gill and F.M. Leslie, Liq. Cryst., 14 (1993), 1905.
17. T. Carlsson, F.M. Leslie and N.A. Clark, Phys. Rev. E, 51 (1995),
4509.
611
EXTENSIONAL FLOWS
Christopher J S Petrie
1. I N T R O D U C T I O N
in a fixed rectangular Cartesian coordinate system, (x, y, z), where (u, v, w) are
the components of the velocity vector and el, e2 and e3 are the principal rates of
strain, (which may be functions of time). For an incompressible fluid, the sum
of the principal rates of strain is zero. Uniaxial extension is obtained when
el = k ; e2 = e3 = - 8 9 (2)
For many fluids, including all Newtonian fluids, there is no more difference
between shear and extension than there is in linear elasticity. Indeed, Trouton
[1] introduced what we now call the elongational viscosity (his "coefficient of
viscous traction") because he wished to obtain the conventional viscosity (the
shear viscosity) of some highly viscous fluids. The elongational viscosity is the
ratio of stress to rate of strain in the steady uniaxial extension of a uniform
cylinder of material. For an incompressible Newtonian liquid Trouton proved
theoretically (and demonstrated experimentally) that this is three times the shear
viscosity, r/o,
just as the Young's modulus is three times the shear modulus for an incompress-
ible Hookean solid.
1.1. Definitions
The Society of Rheology, in an effort to keep some sort of order in the use
of terms by rheologists, has provided an unambiguous definition of "tensile
viscosity" [2] - the quantity we have referred to as elongational viscosity, also
known as uniaxial extensional viscosity. Tensile viscosity is defined as follows:
A material is subjected to homogeneous simple extension, i.e. to a flow which
is spatially uniform, with constant rate of strain, ~, in the x~-direction and - 89
in every direction perpendicular to the x 1-axis. The ratio of "net tensile stress",
O'E ~ fill --flEE, to rate of strain is monitored as a function of time and the
"tensile viscosity" is defined as
(4)
This definition, of course, says nothing about methods of, or even the feasibility
of, experimental realization. The notation r/T is sometimes used, instead of r/E,
in honour of Trouton, and the elongational viscosity may be called the Trouton
viscosity.
If surface tension is significant, we need to be clear that the "net tensile stress"
a E in our definition, Equation (4), is the measured stress corrected for surface
tension according to
Applied force Coefficient of surface tension
O"E = -- . (5)
Area Radius
We also need to be clear that the use of O E ~ O l l - - a 2 2 i s , in any case, valid
only for incompressible fluids. This matter is discussed further elsewhere [3,4].
For simplicity, our discussion of other extensional flows, Equations (8), (10) and
(11) below, refers to incompressible fluids in the absence of surface tension.
,p(g) =
O'll -- 0"33
,
(10)
which refers to the tensile stress required to stretch the material in the x 1-
direction and a second "cross-viscosity"
r](0)(~ -) = O"22 -- O"33 (11)
which refers to the tensile stress required to prevent deformation in the neutral
direction (the x2-direction). The theoretical relations for a Newtonian fluid, with
shear viscosity r/0, are
The notation 7/(2~ is a simple example of the general notation [2,5-7] for general
extensional flows. If el = ~ is the largest (positive) rate of strain, then we may
define m such that e2 = m~ and then
el = ~ ; e2 = m~ ; e3 = - ( 1 + m)~ (13)
for an incompressible fluid. The parameter m, which we take to be independent
of time, describes the geometry of the extensional flow, with m = 1 for equibi-
axial extension, m = 0 for planar extension, m = - 89 for uniaxial extension and
616
< m < 1 in general. The two extensional viscosities for this general flow
2 --
are
and
Tl(m)(~.) = 0"22 - - 0"33 . (15)
These are equal to one another for equibiaxial extension and the second is zero
for uniaxial extension while for all other extensional flows we have the two
physical quantities which we may try to measure. As well as for the three
standard cases, m = - ~1, m = 0 and m = 1, experiments have been carded
out by Demarmels and Meissner [8] for m = +89 This flow has been referred
to as "ellipsoidal extension" but may best be visualized as an unequal biaxial
extension, with stretching at rates ~ and 1~ in two perpendicular directions.
2. T H E E X P E R I M E N T A L E V I D E N C E
The situation is much less clear for polymer solutions, as has been summa-
rized by James and Waiters [10]. The experiment which corresponds to the
definition of extensional viscosity has not been easy to perform for these mobile
(low viscosity) fluids - in fact it had been judged impractical until the work
of Matta [11] and Sridhar [12-14]. It is, however, generally accepted that the
Trouton ratio for polymer solutions is large. Even with the considerable uncer-
tainty surrounding interpretation, we believe that estimates of 100 or 1000 have
genuine physical significance, whether or not the measured quantity is truly an
extensional viscosity. Suspensions of long fibres generally behave in a similar
manner to polymer solutions.
In all cases, at least for fluids which are unoriented in their natural state (i.e.
when at rest and relaxed), the limiting values of extensional viscosity for small
rate of strain agree with the Newtonian predictions. There is no clear evidence
617
of what happens at high rates of strain, where experiments are difficult, but what
evidence there is supports the theoretical conclusion [7] that uniaxial and planar
extensional viscosities should be the same. This theoretical study shows two
classes of asymptotic behaviour at large rate of strain in planar and uniaxial
extension. When we use constitutive equations appropriate to polymer solutions
or fibre suspensions, there is an "upper Newtonian" r6gime with a constant
extensional viscosity corresponding to fully extended and fully aligned molecules
or fibres. With the constitutive equations that were developed for polymer melts
a decreasing extensional viscosity was found. The stress must grow with rate of
strain, but can do so at a rate less than linear (e.g. (rE ~ In ~ for the Phan-Thien-
Tanner model) [7]. This decrease sometimes follows a maximum in extensional
viscosity at some intermediate rate of strain.
For other geometrical forms of deformation, there are fewer results [5,8,18].
Most work until recently has been on polyisobutylene (PIB), because it can
be investigated at room temperature. PIB behaves in a similar way to LDPE
in uniaxial extension. In biaxial extension the response is closer to the linear
618
James and Waiters [10] have collected results for one polymer solution and
show, in their Figure 2.1, values claimed for the extensional viscosity over a
range of three decades (10-10,000 Pa.s) for rates of strain in the range 1-100
s -1, with experimental results scattered over the whole of this region. The
explanation of this is not that the experiments are all meaningless, but that,
since we are dealing with a viscoelastic material, the differing flow histories
and the fact that steady flow is not attained made considerable differences to
results. The various collaborative testing programmes reviewed in [4] (one of
which produced the results in [10] mentioned above) have made it clear that
differences in the material being tested do not explain these differences. In
short, the reported quantities are not "extensional viscosities".
Attempts have also been made to investigate further the fundamental difference
between shear and extension by looking at flows in which the history of the
principal extension ratio is the same for a shear flow and an extensional flow
[26,27]. Experiments were carried out by Ztille et al. [26] both with ~ increasing
exponentially and with ~ constant, where ~ is the principal extension ratio. In
each case both shear and uniaxial extension were used. The results for LDPE
showed that at large strains and large rates of strain the rheological behaviour is
determined primarily by the history of the principal extension ratio, ~(t), and not
by whether the flow is an extensional flow or a shear flow. This means that they
were able to show deformation hardening and deformation thinning behaviour in
extensional flow of LDPE, by choosing in the first case elongation at constant rate
(~ = ~f = ~ exp(~t)) and in the second case, elongation with ~ constant. Similarly
in shear the apparent viscosity (measured at constant shear rate) is a decreasing
function of shear rate while the corresponding quantity for "exponential shear"
increases with shear rate. Samurkas et al. [27] point out that to conclude from
this that the material is deformation hardening in exponential shear may be
misleading. Their point is that under exponential shear a Newtonian liquid will
show a similar behaviour. Indeed Ztille et al. [26] show (in their Figure 4) that
the measured stresses are generally lower than the predictions for exponential
shear of linear viscoelasticity. Samurkas et al. [27] compare exponential shear
with planar extension, and present their result in term of the damping function
for the Wagner model (see below). Their conclusion is that the damping function
obtained from steady shear flow measurements is better than that obtained from
planar extension in predicting behaviour in exponential shear. This tends to the
opposite conclusion to that reported above [26]. However neither set of results
is conclusive, and direct comparison is difficult because of the different ways in
which the data are presented.
The extensional viscosity (in uniaxial extension), as well as the planar and
equibiaxial extensional viscosities have been tabulated for a number of simple
constitutive equations [3]. We reproduce some of these results below (Table 1)
620
and discuss two classes of constitutive equation which have become popular in
recent years. These are the Wagner integral model [28] (often used for polymer
melts) and the FENE dumbbell models [29] for polymer solutions. Larson [30]
gives useful discussion of constitutive equations which is both more thorough
and more up-to-date than [3].
Many of the results in [3] are for special cases of the Oldroyd eight-constant
model,
In terms of molecular (or micro-structural) models, only the upper and lower
convected derivatives are obtained from so-called affine deformation models.
In these models, hypothetical micro-structural elements in the fluid, (such as,
for example, either network junctions or dumbbells) move affinely with the
fluid. The parameter ( can be interpreted in terms of a non-affine deformation
of elements in the fluid, i.e. a slip between micro-structural elements and the
surrounding fluid. This leads to some predictions in shear flow which are re-
garded as undesirable and in extreme cases are contrary to physical intuition
(e.g. negative stresses in response to a sudden large shear deformation). There
are other consequences in extensional flows, such as non-existence of solutions
to flows problems for some values of the parameter (, e.g. ( > 0.5 [3], but
the whole range of non-affine convected derivatives are by no means ruled out
621
The abbreviations in Table 1 for rheological model names are " U C M "
for the upper convected Maxwell model, "LCM" for the lower con-
vected Maxwell model, "GCM" for the generalized convected Maxwell
model. The corotational result applies to Maxwell and Jeffreys models.
The Oldroyd fluids B and A are exactly equivalent to upper and lower
convected Jeffreys models, respectively.
by this behaviour (unless one adopts a very strict position on the mathematical
requirements for a constitutive equation [31-33]).
1 + 47-2~2
r/p = 47/o 1 + 47-1~2 (21)
One interesting aspect of this is that all the parameter combinations which ap-
pear in the expressions for the extensional viscosities also appear in the expres-
sions for the viscometric functions so that, in principle at least, the extensional
flow behaviour of the eight-constant Oldroyd fluid can be predicted from com-
plete data on shear flow. In fact, data for shear flow allow the calculation of the
characteristic times A1 and A2, which do not appear in the extensional viscosity
formulae, so that in a sense, for this model, the viscometric functions contain
more information than the extensional viscosity functions. Note that the actual
calculation of the parameters from viscometric data is not a trivial task and, for
example, to obtain the parameters ttl and #2 which are essential for extensional
viscosities one must have very good data on the second normal stress function,
~2(k).
in which M ( t - t') is the memory function, c~-l(t ') the relative Finger deforma-
tion tensor and h(I1,12) the damping function, which introduces non-linearity of
dependence on deformation through the invariants I1 and 12 of the Finger tensor.
The product h(I1, I2)Ctl(t ') may be thought of as a non-linear measure of defor-
mation [30,34]. If h = 1 and M ( s ) = ( G / A ) e x p ( - s / A ) we recover the integral
equivalent of the upper convected Maxwell model. A sum of exponentials for
M ( s ) gives the usual discrete relaxation spectrum. Equation (28) is not, in fact,
623
ctl(t ')= 0
00 ) (30)
0 0 (-2(re+l)
with invariants
I1 = g2 + g2m + g-2(rn+l) , 12 = g-2 + ( - 2 m + ~2(m+l) . (31)
The damping function is chosen to fit data from shear or extensional viscom-
etry (or preferably both). Early attempts used functions like h = e x p ( - n ~ ) for a
shear strain of ~ = k ( t - t') (and we could write ~ = vql - 3, noting that I1 = 12
in simple shear). In order to fit data from different flows (shear and extension),
the introduction of an invariant
has been successful [35] and better fits to data have been obtained using a sum
of exponentials
Wagner and Laun [36] found that values f = 0.57, n l = 0.310 and n 2 = 0.106
gave a good fit to shear data for the LDPE Melt known as "IUPAC A", and
/3 = 0.032 gave a good fit for uniaxial extension also. Another form of damping
function which is popular is due to Papanastasiou [37]
1
h(I1,12) = 1 + a K 2 " (34)
Larson [30] notes that neither of these functions, Equations (33) and (34),
fits data for biaxial extension well and he proposes a model which is strictly of
the Kaye-BKZ form, with a potential function, U, and the Cauchy deformation
tensor, Ct(t~),
[ Cl (I2 -- I1)3 ]
a = CO+ C2 tan -1 1 +(12--I1)2 , (37)
Similarly, Demarmels found [8,38] that the Wagner equation does not give a
consistently good fit to data from shear and several different extensional flows
for PIB and that a better fit can be obtained with a model which introduces the
Cauchy deformation tensor, Ct(tt), as well as the Finger tensor. This gives us
an equation of the form proposed by Rivlin and Sawyers, which we write here
and Wagner and Demarmels [38] propose a form for the two damping functions,
for one particular PIB melt,
1
hl(I1, I2) = (1 +/3)h, h2(II,I2) =/3h, h = 1 + a'~*lv'k~- 3)(12 - 3) (40)
with constant values of the parameters a = 0.11 and 3 = - 0 . 2 7 for the particular
PIB melt studied in [8]. The parameter/3 in this model, which gives the ratio of
second to first normal stress differences in simple shear, is important in general
extensional flows but unimportant in uniaxial extension. This choice of functions
h l and h2 is not obtainable from a potential, so Equations (39) and (40) do not
give a Kaye-BKZ equation.
A variation in use of the Kaye-BKZ model [39] seeks to express the de-
pendence of the kernel on the invariants I1 and 12 through dependence on the
principal stretches (or their squares, which are the eigenvalues of the Finger
tensor). This is motivated by the success of some strain-energy functions for
rubbers, but has not been found to be successful so far. It has not proved pos-
sible to pick a simple dependence on the principal stretches which gives a good
fit to shear and extensional data with the same values of parameters.
625
One final, well-known, defect of these models has been considered by Wagner
[40]. This is the fact that even the best of the models with a damping function
or non-linear deformation measure has difficulty in fitting data obtained in flows
where the fluid experiences flow reversal. The simple example of this is one step
strain followed by a second step strain in the opposite direction. The problem
can be explained in terms of a temporary network model in terms of irreversible
loss of entanglements. This suggests a damping functional as a replacement for
the damping function. The damping functional proposed is the smallest value
over the time interval of the conventional damping function. For a motion with
a "nondecreasing deformation", defined as a deformation for which the damping
function is a nonincreasing function of time, the damping function is correct.
If the motion involves a "decreasing deformation", a smaller damping factor is
used. This approach has some success in predicting recovery (elastic recoil)
after uniaxial extension [40].
HR
Fa = 1 - ( R 2 / L 2) ' (41)
is used. Here R is the end-to-end vector for the dumbbell (the molecule), H
is the spring constant, R = IR] is the end-to-end length and L is the maximum
permitted end-to-end length for the dumbbell, so that R < L. The hydrodynamic
drag force on a bead is given by a drag coefficient (d multiplying the velocity
of the bead relative to the solvent. This gives us the relaxation time, A =
( d / ( 4 H ) , which is a characteristic time for an individual dumbbell to come to
equilibrium under the competing action of the drag and spring forces. There
is a second characteristic time, 0 = L 2 ( d / ( 1 2 k T ) which is associated with the
balance between hydrodynamic drag and Brownian diffusion and a modulus,
626
b = 30/A = n H L 2 / G (42)
a 2 = 3L2/b = 3 k T / H . (43)
This gives the equilibrium length of a dumbbell (when the solution is at rest),
possibly multiplied by a factor like b/(b + 5), depending on the precise details
of the FENE model.
These ideas are used to obtain a configuration tensor, A = (RR) and the
polymer contribution to the extra-stress tensor. The mean, ( ) , is an ensemble
average involving the distribution function, g,(R), and the trick is to obtain
equations without having to calculate if,. This is most usually done by making
the Peterlin approximation, which involves pre-averaging the end-to-end length,
so that
HR
Fd = (44)
1 -- ( ( R 2 ) / L 2)
instead of using the true ensemble average of Equation (41). This leads to the
FENE-P model, with configuration evolution equation
v 1 L2
XA + A = ~ I (45)
1 - ( R 2 / L 2) (b + 2)
T= G(b/L2)
[A - (L2/b)I] + 2~/,D. (48)
1 - ( R 2 / L 2)
This model has qualitatively the same behaviour in extensional flows as the
FENE-P model, as far as is known from investigations to date [4]. It has the
property of a constant viscosity in shear, unlike the FENE-P and FENE models
627
which are shear-thinning [41], which is both a simplification and is desirable for
modelling the behaviour of Boger fluids.
One shortcoming of all the FENE models discussed above, as far as fitting
data on polymer solutions is concerned, is that they have only a single relax-
ation time. A recent discussion of multimode models (i.e. bead-spring chains)
by Wedgewood, Ostrov and Bird [43] points out that a straightforward general-
ization of the simple dumbbell leads to a complicated set of coupled nonlinear
differential equations. They point out that some earlier attempts to analyse this
contain serious errors and go on to propose a further approximation, the FENE-
PM model. The model consists of a set of N - 1 nonlinear springs joining
N beads and the end-to-end vector for the i-th spring is denoted by Ri. The
FENE-PM force law is taken to be
Fi = HRi (49)
1 --(iV -- I) -I ~N~'((R2)/L2)
and the M in FENE-PM stands for the mean value taken in the denominator
of Equation (49). The M is also used to denote "multimode", but it is neces-
sar3, to remember that the FENE-PM model is not just a multimode FENE-P
model, for the reasons of complexity to which we have alluded. Even so, the
model obviously remains more difficult to use than the single mode FENE-P and
FENE-CR models and the questions to be settled are whether the extra effort is
adequately rewarded and whether the approximation introduces any undesirable
side-effects.
As examples of unwanted side-effects, the fact that the FENE-P model leads
to equations for steady extension with multiple solutions may be instanced.
This is a comparatively minor matter, which can be resolved [4] by analysis
of the full equations, as is discussed below. A more interesting matter is the
demonstration by Keunings [44] that the dumbbells in the FENE-P model do
not actually behave as finitely extensible dumbbells. A simulation shows that a
noticeable fraction of the dumbbells exceed the supposed maximum length L.
This arises from the fact that the approximation leads to a distribution function
for end-to-end lengths which is Gaussian (with an infinite tail), while for a true
FENE model the distribution must have a cut-off at L and hence must be non-
Gaussian. A comparison between the FENE-P and FENE model predictions
(using a stochastic simulation) [44] shows that the rheological effect of the
Peterlin pre-averaging approximation is seen in a much more rapid increase in
the tensile stress during the start-up of an extensional flow. The stress growth
is smoother and somewhat slower for the tree FENE model. The steady state
stresses are the same.
None of the FENE models yields explicit formulae for the extensional vis-
cosities (unless one wishes to write down formally the algebraic solution to a
628
cubic equation). It is therefore less easy to make simple statements about their
properties. In the limit of small extension rate, the Newtonian ratios between
the extensional viscosities and the shear viscosity are recovered. In uniaxial
extension the viscosity curve is S-shaped and at large extension rate, an "upper
Newtonian" rrgime is obtained [45],
tiE = 3q~ + 6 G ~ = 3rl~ + 2b~Tp (50)
where r/p = AG is the polymer contribution to the viscosity. As far as the FENE-
PM model is concemed, the model can be expected to improve the quantitative
fit to data. No surprises in the qualitative behaviour have come to light so far.
4. S O M E M A T H E M A T I C A L ASPECTS OF E X T E N S I O N A L F L O W
set to be U~, while the initial velocity is Uo at the spinnerette. If the volumet-
ric flow rate, Q, is given, we can relate the cross-sectional area, A ( X ) to the
velocity since we make the basic assumption that, to a first approximation, all
quantities are uniform across the fibre.
In the absence of gravity, inertia, surface tension and air drag, the five equa-
tions governing this flow for an isothermal incompressible upper convected
Maxwell model, Equation (17) with ( = 0 and A = 0, are mass conserva-
tion, equilibrium of forces axially and radially and axial and radial components
of the constitutive equation:
U(X)A(X) = Q, (51)
{Txx(X) - P(X)} A(X) = F, (52)
TRR(X) -- P ( X ) = O, (53)
T x x ( X ) + A {U(X)TJcx(X) - 2 U ' ( X ) T x x C u = 2r/U'(X) (54)
and
TRR(X) + A {U(X)T~RR(X)+ U'(X)TRR(X)} = - r l U ' ( X ) (55)
in which F is the constant force at any cross-section and P ( X ) is the consti-
tutively undetermined hydrostatic pressure (which is, in effect, calculated from
the radial force balance, Equation (53)). Equations (51)-(53) can be combined
to give
Txx(X)- TRR(X)= F U ( X ) / Q (56)
and so we have a second-order differential-algebraic system, Equations (54)-(56),
for the velocity and two extra-stress components, with three conditions,
Txx(O) = To, U(O) = Uo , U(L~) = U1, (57)
two of which are needed for the differential equations and the third to determine
the force, F, which has to be applied to maintain the specified take-up velocity.
The extra-stress value, To, is all that is required from the flow history, corre-
sponding to the internal structure of the fluid at X = 0, i.e. to that which has
been determined by the flow of the material upstream of the spinnerette.
u
u , x
x=-;--, c~=
~Uo t,= ,1Q , 7-o=
ToQ (58)
Uo ~s L~ AUoF FUo
630
What we can prove is that the value, u(1), of the solution of Equation (59) at
the take-up, x = 1, is bounded above by a function of the Deborah number, a,
whatever the values of To and #. This means that there is an upper limit to the
draw ratio, DR, for any given Deborah number, regardless of the flow history
and regardless of how great a take-up force is applied.
Finally a comparison theorem applied to Equations (59) and (61) shows that
DR = u(1; c~,#,go) < v(1; c~,go) < g,(1/~,0.5) (68)
which gives us an upper bound on DR for any chosen c~, irrespective of the
values of # and go.
631
A~=sz+
(1)
s 1-z y (72)
m,
~ = 2sy +c (73)
1-z
in which s = ~k is the dimensionless rate of strain (which may be regarded
as a Deborah number) and c = 3/(b + 2) is a constant depending on the finite
extensibility parameter, b. For large values of b, c ~ a 2 / L 2, the equilibrium
mean square end-to-end length of the dumbbells expressed as a fraction of their
maximum length (and this is small).
We may examine the steady-state solutions of this pair of equations and dis-
cover that there are three, of which only one satisfies Inequalities (70) and (71).
It is relatively straightforward, if tedious, show that the unphysical steady-state
solutions are unstable. A more important question is whether, if y and z have
initial values which satisfy Inequalities (70) and (71), i.e. are physically rea-
sonable, the subsequent solution, (y(t), z(t)), remains physically reasonable. We
answer the question by considering the behaviour of solutions represented by
curves in the phase-plane, (z(t), y(t)). We shall prove that solutions which start
632
in the triangle 0 < z < 1, - z / 2 < y < z, for t = 0, remain in that triangle for
all subsequent time, t > 0.
It is easy to see, from Equation (73), that ~. < 0 for z ~ 1 - , so that z cannot
reach the line z = 1 provided that z(0) < 1. Next we consider the angle between
the solution curve as it crosses the line y = z and the normal the that line which
points into the region V < z. If we denote this normal by the vector n, we have
n = ( 1 , - 1 ) . The tangent to the solution curve (in the direction of increasing t)
is parallel to the vector v, given by v = (~,, #). If the angle between these two
vectors is between - 7 r / 2 and 7r/2, i.e. if the scalar product n . v is positive, then
the solution curves all cross the line y = z from the region y > z to the region
Y < z. When Y = z, ~, = y + c so the scalar product is
n. v = (#+c) - (#) = c > 0 (74)
and therefore solutions cannot leave the physically sensible region across the
line y = z.
The same result may be proved for the FENE-CR model, Equations (47) and
(48). The differences from the FENE-P model are only in the coefficient of the
isotropic tensor, I, and the effect on the configuration evolution equations is that
c is replaced by c/(1 - z) in Equation (73). Equation (72) remains unaltered and
the arguments used above hold for the direction in which solution curves cross
the lines Y = z and Y = - z / 2 . The behaviour as z ~ 1 is the same, provided
that c < 1 and it is easy to see that this will be the case, since r > 1 would
require b <_ 1 and the model only makes sense for b > 3 (otherwise a 2 > L2).
Hence the result that solutions which start off in the physically sensible region
remain there for all time is established for this model too.
633
There are many unsolved problems in extensional flow, and so plenty of work
for rheologists to do. The choice of the best constitutive equation is still an open
question- to which the safest answer is often that it depends on the purpose for
which the constitutive equation is required. Good quantitative agreement with
extensional flow data, and data on linear viscoelastic and viscometric properties,
may usually be obtained only at the price of introducing a complicated equation
which may present too great a challenge in the computational simulation of
complex flows. There is, of course, the question of whether the need to choose
a constitutive equation may be avoided by computational methods involving
direct simulation of behaviour at a molecular or micro-structural level. My view
on this is that we still have a need for constitutive equations, as an aid to our
understanding, even if not for our use of computers to solve problems.
The second set of results is more convincing, showing how results from the
"Rheotens" apparatus (in effect a melt spinning device) may be presented in a set
of "mastercurves" and "super-mastercurves" [52,53]. This presents a challenge
to the theorist to explain why such behaviour is observed - does it tell us
something about the family of experiments or about the appropriate constitutive
634
The topic of approximations for nearly extensional flows [3,4,57] has several
connections both with stability and with the analysis of industrial processes like
fibre spinning and film manufacture, both by tubular film blowing and by film
casting. It is therefore not merely a topic of interest to theorists as a matter of
scientific curiosity, but a topic which could shed much light on our analysis of
a number of industrial processes.
REFERENCES
36. M.H. Wagner and H.M. Laun, Rheol. Acta, 17 (1978) 138-148.
37. A.C. Papanastasiou, L.E. Scriven and C.W. Macosko, J. Rheol., 27 (1983)
387-410.
38. M.H. Wagner and A. Demarmels, J. Rheol., 34 (1990) 943-958.
39. K. Feigl, H.C. 0ttinger and J. Meissner, Rheol. Acta, 32 (1993) 438-446.
40. M.H. Wagner and S.E. Stephenson, J. Rheol., 23 (1979) 489-504.
41. M.D. Chilcott and J.M. Rallison, J. Non-Newtonian Fluid Mech., 29 (1988)
381-432.
42. J.M. Rallison and E.J. Hinch, J. Non-Newtonian Fluid Mech., 29 (1988)
37-55.
43. L.E. Wedgewood, D.N. Ostrov and R.B. Bird, J. Non-Newtonian Fluid
Mech., 40 (1991) 119-139.
44. R. Keunings, J. Non-Newtonian Fluid Mech., 68 (1997) 85-100.
45. C.JoS. Petrie, J. Non-Newtonian Fluid Mech., 54 (1994) 251-267.
46. S.J. Kurtz, Some key challenges in polymer processing technology, in
Recent Advances in Non-Newtonian Flows, AMD-Vol 153/PED-Vol 14I,
ASME, New York, pp. 1-13, 1992.
47. C.J.S. Petrie, Recent ideas in extensional rheology, in Polymer Process-
ing Society Europe/Africa Regional Meeting - Extended Abstracts, Ed J.
Becker, Chalmers University of Technology, Gothenburg, Sweden, KN 4:2,
1997.
48. J. Ferguson and N.E. Hudson, European Polym. J., 29 (1993) 141-147.
49. J. Ferguson and N.E. Hudson, J. Non-Newtonian Fluid Mech., 52 (1994)
121-135.
50. J. Ferguson, N.E. Hudson and M.A. Odriozola, J. Non-Newtonian Fluid
Mech., 68 (1997) 241-257.
51. C.J.S. Petrie, J. Non-Newtonian Fluid Mech., 70 (1997) 205-218.
52. M.H. Wagner, V. Schulze and A. G6ttfert, Polym. Eng. Sci., 36 (1996)
925-935.
53. M.H. Wagner, B. Collignon and J. Verbeke, Rheol. Acta, 35 (1996) 117-126.
54. C.J.S. Petrie, Prog. Trends Rheol., II (1988) 9-14.
55. A.Ya. Malkin and C.J.S. Petrie, J. Rheol., 41 (1997) 1-25.
56. C.J.S. Petrie and M.M. Denn, AIChE J., 22 (1976) 209-236.
57. C.J.S. Petrie, Predominantly extensional flows, in 2nd Pacific Rim Confer-
ence on Rheology - Abstracts, Ed C. Tiu, P.H.T. Uhlerr, Y.L. Yeow and
R.J. Binnington, University of Melboume, Australia, pp.225-226, 1997.
637
K.R. Rajagopal
1. INTRODUCTION
Electrical and magnetic fields can significantly change the response characteristics
of many materials and electrorheology is the name given to the branch of mechanics
that is concerned with the flow of materials that are primarily affected by the action
of electrical fields. Usually, electrorheological materials are dielectrics or
semi-conductors in a non-conducting fluid, though recently Ferroelectrics have also
been used. Winslow's study (see [1 ]) of non aqueous silica suspensions under the
action of electrical fields seems to have been the first systematic analysis in
electrorheology, though the effect of an electrical field on the viscosity of pure liquids
was studied much earlier by Konig [2], Quinke [3] and Duff [4]. The work of
Winslow has been followed by a great deal of work in the field, and much of this
effort has been directed in fashioning such materials with a view towards producing
a better fluid in virtue of the potential applications for such materials in shock
absorbers, exercise equipment, valves, actuators and the like. However, for a variety
of reasons such applications have not met the perceived potential for such materials.
Initial attempts at manufacturing electrorheological materials were hampered by a
lack of understanding of the role of water in such suspensions. Other stumbling
blocks that have prevented the development of technological devices are the limited
operational temperature range, the abrasive properties of the suspension that erode
the devices that they flow through, the attrition of the particles, the stability of the
suspension and the enormous voltage requirements that are necessary to produce the
changes that are required. Much progress has been made to overcome these
limitations. Polymer based particles that mitigate the problem have been developed
638
(see Bloodworth [5]), and stabilizers have been found that increase the structural
stability of the suspension. Also, great strides have been made recently in decreasing
the voltage requirement.
Much of the modeling of the flows of electrorheological fluids have been restricted
to one-dimension, though there has been some work on three dimensional models.
Numerous three dimensional models can collapse to the same one dimensional model
and at the present moment there is not a sufficient body of experimental evidence in
general three dimensional flows which can be used to validate and select any one of
these models as the one that is best suited. In view of this, we shall restrict our
discussion to a reasonably general class of models. Experimental evidence suggests
that electrorheological fluids thicken significantly on the application of the electrical
field, respond in a Bingham like fashion with the yield depending on the applied field,
develop normal stress differences and stress relax (see Gamota and Filisko [ 16], Yen
and Achom [17], Gamota, Wineman and Filisko [18], Jordan and Shaw [ 19], Jordan,
Shaw and McLeish [20]). The response of electrorheological materials is also
significantly affected by the thermal conditions (Conrad, Sprecher, Choi and Chen
[21 ], Jordan and Shaw [22]). Here, we shall not consider thermal effects but restrict
ourselves to an isothermal analysis.
639
The fiber like structures that are formed on the application of the electrical field
suggest that such fluids ought to be modeled as anisotropic fluids. This leads to an
additional level of complexity which should be introduced after a better
understanding of such materials is achieved. However, this aspect of the modelling
is crucial and has to be reckoned with if one is to capture the behavior of
electrorheological fluids. For instance, the perceived viscoelasticity of the fluid that
is characterized by a time constant for the response could be due to the response time
associated with the alignment of the particles on the application of the field. The
electrorheological response of liquid crystals have also been studied (Carlsson and
Skarp [23], Yang and Shine [24]) where the material is anisotropic even before the
application of the electric field. We shall not consider these issues here, suffice it is
to say that the new framework that has been developed recently that allows for
variations in the synunetry of the body with various configurations that are natural to
the body can be used successfully to model such materials (see Rajagopal [25]).
Such an approach has been used to model crystal plasticity (Rajagopal and Srinivasa
[26]), twinning and solid to solid phase transition (Rajagopal and Srinivasa [27],
[28]), multi-network theory for polymers (Rajagopal and Wineman [29]) and
anisotropic viscoelastic fluids (Rajagopal and Srinivasa [30]).
The image of f] under X, denoted as ~"~t, is the configuration occupied by the body at
time t. We shall assume that X is sufficiently smooth to render all the following
operations meaningful. The velocity v and acceleration a are defined through
1Various properties ~ associated with a material point at different instants of time can be
O~ dx
v- - , (2.2)
Ot dt
and
a - 0 2 X - ~d 2.x (2.3)
Ot 2 dt 2
The deformation gradient F and the velocity gradient L are given respectively
through
F: OX:Vx, (2.4)
OX
and
We shall keep our kinematical definitions and the documentation of the basic
equations to a minimum while ensuring that the treatment be self-contained. A
complete and proper flame-work for the study of electrorheological fluids would
require the laws of electromagnetism in addition to the usual laws of
thermomechanics. There are many ways of expressing the equations of
electromagnetics and we shall use the Minkowskian formulation. A detailed
discussion of the basic laws of field dependant materials within the context of
continuum mechanics can be found in Truesdell and Toupin [31] and Eringen and
Maugin [32]. We shall use the dipole-current loop model (see Pao [33]).
641
where T is the Cauchy stress 3, f is the external mechanical body force, and
fo the electromagnetic force density given by
qo is the electric charge density, E is the electric field, J the conduction current, B the
magnetic flux, P the electric polarization, and M is defined through
dv
div(x T) +xx pf+Q = x x p (2.11)
dt'
where ~o is the electromagnetic angular momentum density given through
2 A documentation of the governing equations can be found in Rajagopal and Ruzicka [34]
3While the phenomenological continuum models assume that the stress is symmetric, some
models based on particle dynamics lead to expressions for the stress that are not symmetric. We
shall assume here that the stress is symmetric. A discussion of the asymmetry of stresses of
electrorheological materials can be found in Rosensweig [35]
642
g'=E+lvxB. (2.13)
c
pd(e+-~lvl
1 2) +div q -div(Tv) +Of-V+pr+We, (2.14)
where e is the specific internal energy, q the heat flux vector, r the radiant heating
and w~ is the energy production density given by
p drl
dt +div (O)+p -~>_0,
r (2.17)
The above balance laws are the usual laws of thermomechanics modified to account
643
for the effects of the electrical and magnetic fields. We have to augment the above
equations with Maxwell's equations in the Minkowskian form. The conservation of
electric charge is
(2.19)
div I)e=qe ,
1 0B
curl E +-- =0. (2.21)
c Ot
1 ODe 1
curl H- + (2.23)
c Ot c
H: =B-M. (2.24)
644
J=O, (2.25)
and
M=O. (2.26)
dv
div T+pf+f = p ~ (2.28)
dt
1 aB
curl E + - - ~ = 0 (2.32)
c at
divB=0, (2.33)
dqe
~+qe div v=0. (2.35)
dt
In the above equations we have assumed that the heat flux is given through Fourier's
law and ~ is the specific Helmholtz potential. The above equations can be further
simplified on the basis of dimensional arguments for problems of interest in
electrorheology. A detailed treatment of the same can be found in [36].
In general we will have to solve the coupled partial differential equations (2.27)-
(2.35) which is tantamount to fourteen partial differential equations and one
constraint inequality for the appropriate variables, a most arduous task even under
idealized conditions. Since in most problems of practical relevance, the gaps are
exceedingly small, it may be reasonable to assume the electric field to be a constant
(of course, this assumption could be totally inappropriate as the electric field could
vary tremendously within the short gap). Such an assumption is often made in
electrorheology and the electric field then plays the role of a parameter in the
problem. We shall further simplify the analysis by restricting ourselves to isothermal
processes and essentially ignoring the thermal variables. Even such a simplified
situation serves to highlight certain interesting features concerning the flows of
electrorheological fluids.
646
It is possible that there are some electrorheological fluids that undergo only isochoric
motions when the electric field E is held a constant, however the density changing
with the electric field. This situation is similar to fluids which can undergo isochoric
flows in isothermal processes while their densities can change with temperature.
Such an assumption is the starting point for the celebrated Oberbeck-Boussinesq
approximations in fluid mechanics. The fact that the density can change with the
electric field, but is a constant in all processes in which the electric field is a constant
can be expressed through
det F =f(E).
3. S I M P L I F I E D M O D E L S B A S E D O N T H E E L E C T R I C F I E L D AS
A PARAMETER: DIFFERENTIAL TYPE MODELS
where -pl is the indeterminate part of the stress due to the constraint of
incompressibility and D is the stretching tensor defined through (2.6). We shall
assume that the material is isotropic. The response of materials of the form (3.1) has
been studied in some detail by Rajagopal and Wineman [29].
T= -pl +aIE~)E+a2D+a3D2+a4(DE~)E+E~)DE)
(3.3)
+as(D2E| +E|
where a~, I=l, ...,5 are scalar functions that depend on the following invariants
On the other hand if we require that (3.2) holds for proper orthogonal
transformations O +, i.e., invariance under rigid body motions, then T has the
representation
T : -pl +&IE~E +tx2D+~3D2 +t~4(DE| +E|
+6cs(D2E| +E| +&6(MD +DM r) +&7(MD2+D2M 7,) (3.5)
+&8(DMD2+D2M rD) +&9(E(~)MA+MA| +&lo(E| +MB|
where e is the alternator tensor and the &; , i=l,... 10 are functions of the invariants
Here, we shall essentially outline the analysis of Wineman and Rajagopal [29] to
illustrate that the model (3.3) can describe normal stress differences, thickening and
other behavior characteristic of electrorheological fluids. Let us consider the simple
shear flow of an electrorheological fluid modeled by (3.3) with an electric field
applied transverse to the direction of flow, i.e.,
T11_ _p+_~ ~2
~5
TI3 =--~-YE2E3,
T23=o~2E2E3+~.~6]t2E2E3.
where
649
Y:u'0') (3.10)
First, suppose that E3=0. We notice that the shear stress T12 can be expressed as
where the generalized viscosity ~t is dependent on both the shear rate and the electric
field. Thus, for appropriate forms of ~t, the model can describe the increase in
viscosity that is observed in electrorheological fluids due to the application of an
electric field. Depending on the nature of the fluid, it can shear thin or shear thicken
and this can either enhance or ameliorate the thickening due to the electric field. It
is also worth noting that in general the normal stresses Tll , T22 and T33 would be
different and thus normal stress differences that are characteristics of non-Newtonian
fluids are also induced by the electric field. We note that
r, 1 -TY 2,
and thus in general the normal stress differences are distinct. We also notice that
there is a contribution to the normal stress differences due to the sheafing as well as
the electrical field. Moreover, we recognize that there is a coupling effect between
the mechanical and electrical fields that arises in the normal stress differences Tll-T22
and T22- T33.
Next, we shall illustrate the effect of the electrical field in a simple flow.
parallel plates along the x-axis due to an applied pressure gradient with the electric
field applied along the y-axis.
It follows from the balance of linear momenttLm, in the absence of body force fields,
To,=-Cy, (3.13)
[g(u',E2)lu'=Cy, (3.14)
It has been observed that in the presence of an electric field the fluid flows only
after a critical value is reached for the shear stress, i.e., it exhibits "Bingham type"
behavior. Of course, it is possible that the fluid flows ever so slowly even below the
"yield stress" in that its flow is imperceptible within the time frame of the
observation. To simplify the problem, we shall assume a Bingham type behavior.
Thus, we shall consider a representation for Txy of the form
Oo(E)+v(E)v,
T= 0, y=0 (3.16)
For a fixed value of E, the maximum value of the magnitude of the shear stress
occurs at y= and its value is Ch. If Ch < Oo(E), then the maximum value of the
stress is less than the yield stress and there will be no flow. Let C be such that Ch
> Oo(E). Then, there is some y* such that Cy *= Oo(E). It then follows that
It immediately follows from (3.17) and the no-slip boundary condition (3.15) that
l C 2 2)
u(Y)= t(E)[~(h -Y -Oo(E)(h-y)] , y*_<y<h
We notice that in the absence of the electric field, Oo(E)=0 and thus y*(E)=0, and
we obtain the classical Poiseuille solution
Other boundary value problems within the context of this theory can be found in
[29]. It is also shown there that a Mooney-Rabinowitch type of relationship can be
established for such models.
Models of the class discussed above do not exhibit viscoelasticity, and it has been
observed that certain electrorheological fluids exhibit viscoelastic response (Xu and
Liang [39], Thurston and Gaertner [40], McLeish, Gordon and Shaw [41]
Vinogradov et.al [42]). In the next section we discuss models that can describe the
viscoelastic behavior of electrorheological fluids.
652
We shall now discuss a class of models that have a fluid like response in a certain
regime and a solid like response otherwise.
We shall yet treat the electric field as a parameter and we shall use a transition
function A(T(t), E(t)) which delineates the regimes of response"
(i) A(T(t), E(t))=0 determines the transition (boundary) between solid-like and
fluid-like response;
We shall not get into a detailed discussion of such models here, the interested reader
can find a detailed treatment in [11 ]. In the solid-like regime, the stress has the form
to
(4.1)
T~olid(t)=.~'-[Fto(s),E(t)]
s=t o
where F (s) denotes the deformation gradient at time s with respect to the
configuration at time to when the transition function is met and the material starts to
exhibit solid-like behavior. Let us suppose that the material when it is solid-like is
isotropic. It follows from standard arguments the T (t) has the form
Then,
It is possible to define response functionals which can have a more general structure
(see Wineman and Rajagopal [11 ]):
co
T(t)= G [ F ( t - s ) , E ( t - s ) ] , (4.5)
s---O
which in the absence of the history of the electric field reduces to the definition of a
simple material (see Noll [43], Truesdell and Noll [44]). The above models are too
general to be of use. Thus, we shall turn our attention to a specific model which can
describe the viscoelastic behavior of electrorheological materials. Consider the
following representations for the solid-like and fluid-like part of the response (see
Wineman and Rajagopal[ 11]):
654
t t
t f
+: :M2(t-Sl,t-s2)[~'t(Sl)C-~t(s2)+f-,,(~2)C-,t(Sl)]dSldS2
tl t1
t (4.7)
+f M3(t-s)[Ct(s)E| +E|
t1
t t
+ff t(s2)E~)E+E~)(~t(s,)Ct(s2)]Edsids2,
t1 tI
where I~:B t (t)-I and Ct(s):Ct(s)-I . The scalars 13i,I= 1,--7, and Yi, I=1, 2 are
constants. Also, Li, i--1, - - 6 and M., i-1, --4 satisfy certain continuity and
monotonicity properties.
The model outlined above is too general to be useful and it is unlikely that an
experimental protocol can be devised where all the arbitrary material functions can
be determined. The purpose of documenting the model is to merely show general,
principles of continuum mechanics can be used to develop general enough models
can describe the response characteristics of electrorheological fluids. Of course, the
above model could be further simplified with the multiple integral terms ignored
which would then lead to models similar to those used in viscoelasticity to describe
the time dependant behavior of such materials. For instance, there has been
considerable interest in the response of electrorheological materials when subject to
oscillatory shears (see McLeish, Jordan and Shaw [42], Gamota and Filisko [16],
Otsubo, Sekine and Katayama [45]). Wineman and Rajagopal [11] use the above
model to study small simple shear and oscillatory shear in electrorheological fluids.
In the case of the oscillatory shear problem the stress oscillates with the frequency
to of the oscillatory shear, and G~ and G~ the storage and loss modulii of linear
viscoelasticity depend on the electric field and the phase angle depends on both the
frequency to and the electric field E. They are able to correlate and explain
phenomena observed in the oscillatory response of electrorheological fluids by
Gamota, Wineman and Filisko [16], and Gamota and Filisko [46], [47].
656
General three dimensional continnum models that can describe the response of
electrorheological materials such as thickening, stress-relaxation, normal stress
differences, yield etc., have been presented. The simple shear flow of such fluids
has been analysed and even in such a simple flow it is found that the models are
capable of describing the characteristics exhibited by real electrorheological
materials such as thickening due to the applied electric field, normal stress
differences and stress relaxation.
657
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659
R. Tao
1. INTRODUCTION
2. CONSTITUTIVE EQUATIONS
expression
. _.-~.[fiJ
Fi -- +fidrep ]+fi self +fi wall (2)
jr
where fij is the force acting on particle i by particle j and all of j's
images, firfp is a short-range repulsive force to prevent particles i and
j from overlapping, f~lf is the force on particle i due to all its own
images, and f~an is a short-range repulsive force to prevent particle i
from penetrating the two electrodes.
The dipolar force exerted by particle j on particle i is given by
3/) 2
(efr~j) [e~(1-3 cos 20ij)-eo sin 20ij] (3)
where rij - r i - rj and Oij is the angle between the z direction and the
joint line of the two dipoles. When a dipole is placed inside a capacitor at
r i - (xi, yi, zi), an infinite number of images are produced at (xi, yi,-zi)
and (xi, yi, 2Lk 4-zi)for k - -4-1, +2,--.. The force that the j t h particle
and its images exert on the ith particle is given by
where Pii - X/(xi - Xd)2 + (Yi yj)2 and Ko and Kt are modified Bessel
functions.
The force on a particle due to its own images is in the z-direction
and given by
To introduce hard spheres and hard walls into the simulation, we use a
662
and the short range repulsion between a particle and the electrodes as
fwall 3p2ez
-- e - ~ { e x p [ - l O O ( z i / a - O . 5 ) ] - e x p [ - l O O ( ( L - z i l / a - 0 . 5 ) ) } . (7)
W(X,) - (Trq)-'/2 e x p ( - X 2 / q )
N
1
pj - [ ~ ~ exp(ibj- ri)[ (12)
i=1
where the bj are the reciprocal lattice vectors of the bct lattice
Of the three unit vectors, ez is along the field direction and e~,ey~ are
along the intrinsic axes of the bct lattice. In the calculation of the order
parameters, we must rotate the coordinate system around the z axis to
find the intrinsic axes of the structure which maximizes pip2. The order
parameter P3 characterizes the structure along the z direction while pl
and p2 characterize structure in the x-y plane.
In the simulation, we assume that an electric field is applied at t - 0
instantaneously. Then we apply an adaptive step-size control Runge-
Kutta method to integrate the equation of motion. It is clear from
664
Eq.(11) that the final structure depends on the two parameters A and B.
We examine the dynamic process by monitoring the particles' positions,
velocities, and the structure's order parameters. In most cases, after
application of the field, the particles quickly move to form chains, then
the chains aggregate to form a thick structure. Afterwards, the particles
usually fluctuate slightly around their positions in the structure and the
order parameters of the system change very little. Hence we are able to
determine the solidification time and analyze the final structure. The
other interesting quantity is the chain formation time which is shorter
than the solidification time.
As seen from equations (6) and (7), collisions may interrupt the
structure formation if some particle's position change in the integration
is too big. Therefore, we specify a value 5r~. If the largest position
change among all the particles' motion during one time step 5t is greater
than 5r~, the next time step is reduced. Otherwise, 5t will be increased.
Our method speeds up the integration and effectively preVents possible
problems from the collisions because we control the position change by
selecting a proper 5r~. Since the time step changes at every step with
this method, we must employ Eq.(10) to handle the Brownian force.
There are some special situations which need to be discussed. In the
over-damped case, the viscous force becomes so strong that we have
d r * / d ( - F*+BR* (17)
electrodes. In our simulation, we have found that when A _< 10 -a, the
final structure has its three order parameters independent of A and the
solidification time is proportional to I / A , indicating that the system is
in the over-damped situation.
The effect of the random force B R* in Eq.(11) needs special atten-
tion. Since R,*. is a Gaussian deviate, we should compare the magnitude
of F/* with B. When the particles are randomly distributed, a typical
value of F/* in Eq.(11) is ,,~ n 4/a where n is the particle density. In our
simulation n - 0.3486 which gives an estimation of 0.2 for F/* at a random
distribution. When two particles get very close, their dipolar interaction
force has a typical value ,,~ 1. However, when the particles aggregate to
form a final structure, the joint forces on every particle are vanishingly
small. Therefore, it is easy to understand from E q . ( l l ) that if B << 0.2,
B R ~ has little effect on the early dynamic process, but may have some
effect on the final structure since the joint forces on each particle are
small. If B >> 1, B R ~ becomes the leading force in Eq.(11).
1.0
(a) 05 f , , , , , . , , , , . ~ ~ y- ry structure
0.8
04
0.6
BCT Lattice
13:1 07
0.4
2"
O~
x~.~~ass-like structure ,.< Glaas-like structure
0.2
O~ Nematic liquid crystal
BCT Lattice ~ ~ ----
Liquid
0.0 : 7 - / ' 7 7 " / 7 - . / 7 ./-7- 7 " 2 7 7" 7 O( , ! , l. , ! , ! ,
I . . . . . . . . I' ........ I ......... I ......... I "''''''~"
A o.o 0.2 0.4 0.6 0.8 1.0 A 0.0 0.2 0.4 0.6 03 1.0
4. STRUCTURE OF ER FLUIDS
If the ER system can always evolve into its equilibrium state after
666
an electric field is applied, the final structure may only depend on the
parameter A - p2/(e.la3ksT ). However, in the actual dynamic process,
the ER system may not be able to reach the ground state after it is
trapped in a local energy minimum state. The viscous force enhances
such a possibility by a quick reduction of the particles' kinetic energy.
z(~) z(~)
14.00 .~(: 14.00
!
,, ,7 0 / it ~
g.s3
7 O0 7.00
(
467 ( 4.67
2 ~3 2. ]3
liquid crystal and the boundary between the bct lattice structure and the
nematic liquid crystal structure seem to have A = 6.7 and A = 167 respec-
tively. Although this is expected for an equilibrium statistical physics,
we should note that the final structure in our simulation may not be an
equilibrium state. Therefore, Fig.1 may differ from a conventional phase
diagram.
4.1 BCT Lattice and Poly-crystalline Structure
As seen from Fig.l, the ordered state, a bct lattice, has been obtained
in quite a wide range of A and B. In Fig. 3, we plot a typical bct lattice
structure with order parameters p], p~ ~ 0.8 and p3 >_ 0.9. The projection
of tile three-dimensional structure onto the x-y plane shows a centered
square lattice (Fig.4), a typical characterization of the bct lattice [4]; the
marked square also has its side ~ lv/~.5.ha; and the characterization of
these chains is also correct for the bct lattice [4].
"1
.--/ .'7~
~ 3
/ " /.
~ 2
9 l
.... I ' ' ' ' 1 ' - ' ' " 1 .... I .... I
0 1 2 3 4 5
x (~)
Fig.4. Projection of the bct lattice on the x-y plane. The marked square
has its side ,-~ x/1--5a.
We also note that there is a small region inside this ordered region
where the system may likely develop into a poly-crystalline structure
(Fig.5). This small region has a very small B and a big A (___ 0.1).
Examination of this structure reveals that the system has thick columns
consisting of several bct lattice grains. However, these grains do not form
a single crystal. There is some mismatch, mainly caused by their rotation
around the z axis by slightly different angles. In Fig.6, we plot a part of
a thick column of poly-crystalline structure which clearly shows a twist
of bct lattice grains. Since these rotations do not affect P3 very much
but reduces p] and p~, P3 remains ,-, 0.9 while Pl and p2 are reduced to
,-, 0.5. The poly-crystalline structure is a produ~:t of fast solidification.
668
Because of very small B in this region, the E R system may not be able to
relax into a good crystal. It is thus easy to understand that in this region
the final structure is somehow sensitive to the initial random state. The
computer simulation confirms the conclusion, too: in this region from
some r a n d o m initial state the E R system may develop into a good bct
lattice, while from some other random initial state the system ends up in
a poly-crystalline structure.
To further understand the issue, we have paid special attention to
the situation of B = 0 which can be realized at zero temperature. If
A <__ 10 -a, the system is over-damped. The final structure has the three
order parameters independent of A: pl and p2 around 0.62, and P3 around
0.89.
ZCa)
z(,,) 14.oo
14.00
11.67
11.57
9.33
9.,]3
7.00
7.00
4.57
4.57
2.33
2.33
0.00
4.17 2.77 .9G
0.00 60 + i
4.
f~ I. 0 o ~ .L.o,
Fig.6. A thick column of poly-
Fig.5. A poly-crystalline struc- crystalline structure which clearly
ture. sllows a twist of bct lattice grains.
(:7.
14.00
14.0
11.67
11.6
9.3
9.J3
7.0 7.00
4.6
4.67
2.3
2.33
0.0 ,r
e
3.62
0.00 48
4. ~~
o.83
11.67
11.67
9. ,1,1 9.,13
7.00 1.00
4.67
4.67
2. ,I,1
2.33
o.o ,1.92
2.30
0.00 .x,
! ,68
] .... z.~l 1.15
x(~)
Fig.9. In a glass-like structure, Fig.lO. In a glass-like structure
D(x, y) is peaked in a small colum- tile ER fluids form thick columns
nar region, a main difference be- but t h e t h r e e order p a r a m e t e r s ar~
tween a glass-like structure and almost the same as that of tile ne
liquid. matic liquid crystal state.
4.2 Nematic Liquid Crystal and Glass-like Structure
W h e n we increase B, equivalent to raising the t e m p e r a t u r e , we come
from the region of the bct lattice to a region of final s t r u c t u r e with sig-
nificant P3, but small pl and p2. Typically, pl and p2 are around 0.3 while
P3 >_ 0.6. This implies t h a t the system has ordering in the z direction
with weak or no ordering in the x-y directions. From the definition of a
particle density
671
N
D(r) - E 5(r-rj) (18)
j=l
t~o,id 60/A.
- (20)
lOa o B=I
o B=0.1
k: " B=O.01
o'3
107
E
0
m
.+J
10e
.p..i
=
10s
o~.,4
104
Fig.13. The relationship between the solidification time and the param-
eters A and B.
674
'~ I%
lOe
%,.
o
o
B=I
s=o.1
I- \\ , s=o.ol
lO7 =
1 oe
"~ lOS
104
10a
1 o-e 10-S 10-4 10-a 10-2 10-I
A
Fig.14. The relationship between the chain formation time and the pa-
rameters A and B.
6. DISCUSSIONS
REFERENCES
ELECTRO-MAGNETO-HYDRODYNAMICS
AND SOLIDIFICATION
G. S. Dulikravich
1. INTRODUCTION
Fluid flow influenced by electric and magnetic fields has classically been
divided into two separate fields of study" electro-hydrodynamics (EHD)
studying fluid flows containing electric charges under the influence of an
electric field and no magnetic field, and magneto-hydrodynamics (MHD)
studying fluid flows containing no free electric charges under the influence of a
magnetic field and no electric field. Traditionally, this division was necessary
to reduce the extreme complexity of the coupled system of Navier-Stokes,
Maxwell's and constitutive equations describing combined electro-magneto-
hydrodynamic flows. Recent advances in numerical techniques and computing
technology, as well as fully rigorous theoretical treatments, have made analysis
of combined electro-magneto-hydrodynamic flows well within reach. A survey
of electro-magnetics and the theory describing combined electro-magneto-
hydrodynamic (EMHD) flows is presented with an emphasis on describing the
intricacies of the mathematical models and the corresponding boundary
conditions for fluid flows involving linear polarization and linear
magnetization. This survey concludes with a presentation of EHD and MHD
flow models involving solidification.
NOMENCLATURE
b - electric charge mobility coefficient, kg A s2
B_B_ = magnetic flux density vector, kg A 1 s2
678
(
d = Vv_ + Vv = a v e r a g e rate o f d e f o r m a t i o n t e n s o r , s -~
Do = e l e c t r i c c h a r g e d i f f u s i o n c o e f f i c i e n t , m 2 sl
D=eo_E+P = e l e c t r i c d i s p l a c e m e n t field v e c t o r , A s m -2
e : c~T + (v._v)/2 = total e n e r g y p e r u n i t m a s s , m 2 s ~
E = e l e c t r i c f i e l d v e c t o r , k g rn s 3 A -~, or V m ~
E=E+vxB = e l e c t r o m o t i v e i n t e n s i t y v e c t o r , k g m s 3 A -1
f = mechanical body force vector per unit mass, m s2
g = a c c e l e r a t i o n d u e to g r a v i t y , rn s -2
h = h e a t s o u r c e or s i n k p e r u n i t m a s s , m 2 s -3
a_=B_/ to-M = m a g n e t i c f i e l d i n t e n s i t y v e c t o r , A m -1
J= + Jd = electric current density vector, A m 2
J, = electric conduction current vector, A m 2
J d = V_qo = e l e c t r i c drift c u r r e n t v e c t o r , A m -2
M = total m a g n e t i z a t i o n v e c t o r p e r u n i t v o l u m e , A m ~
M=M+vxP = m a g n e t o m o t i v e i n t e n s i t y v e c t o r p e r u n i t v o l u m e , A m -1
P = p r e s s u r e , k g m -~ s -2
P = total p o l a r i z a t i o n v e c t o r p e r u n i t v o l u m e , A s m -2
qo = total or f r e e e l e c t r i c c h a r g e p e r u n i t v o l u m e , A s m -3
q = h e a t flux v e c t o r , k g s -3
S = e n t r o p y p e r u n i t m a s s , m 2 kg-' K" s -2
T = absolute temperature, K
V = fluid v e l o c i t y v e c t o r , m s -~
GREEK SYMBOLS
= v o l u m e t r i c t h e r m a l e x p a n s i o n c o e f f i c i e n t , K -1
= C h o r i n ' s ( 1 9 6 7 ) artificial c o m p r e s s i b i l i t y c o e f f i c i e n t
E = d i e l e c t r i c c o n s t a n t ( e l e c t r i c p e r m i t t i v i t y ) , k g -~ m -3 s 4 A 2
ro = 8 . 8 5 4 x 10 -12 = v a c u u m e l e c t r i c p e r m i t t i v i t y , k g ~ m 3 s4 A 2
8r = S / F , o = relative electric permittivity
K = thermal conductivity coefficient, kg m s3 K l
= e l e c t r i c c o n d u c t i v i t y c o e f f i c i e n t , k g -1 m -3 s 3 A 2
P = fluid d e n s i t y , k g m -3
_x_v = 2 g v d + g v E I ( V 9v ) - N e w t o n i a n v i s c o u s stress t e n s o r , k g m -1 s -2
EM
x = e l e c t r o m a g n e t i c stress t e n s o r , k g m -1 s -2
679
v EM
x__=x__ + x__ = stress tensor (viscous plus electromagnetic), kg m -~ s -2
~t = magnetic permeability coefficient, kg m A 2 s -2
~to = 4~ x 10 - 7 = magnetic permeability of vacuum, kg m A -2 s 2
ktr = ~t [ k t o = relative magnetic permeability
~tv = shear coefficient of viscosity, kg m ~ s -~
~tv2 = second coefficient of viscosity, kg m ~ s -~
E = er _ 1 = electric susceptibility
M = [t r _ 1 = magnetic susceptibility
= electric potential, V
= x__~'d = viscous dissipation function, kg m ~ s -3
2. BACKGROUND
The electric displacement vector then becomes [19, p.164] [9, p.178].
V.D_=qo (3)
or
At this point it is important to note that qo multiplied with the charged particle
drift velocity, v d , creates the convection or drift electric current, Jd [ 13, p.67],
while polarization current, J_p, is defined as the variation of the total
polarization with respect to time [ 19, p. 121 and p. 147].
4. M A G N E T I Z A T I O N AND A M P E R E - M A X W E L L ' S L A W
~M
Po ~1+
~M)
682
In addition to the electric currents arising from magnetization and direct charge
motion, other phenomenological currents have been observed and must be taken
into account when defining the total current, J [9, p.162-163]. Introducing the
effects of magnetization and polarization and rearranging constants, the
Ampere-Maxwell's law of electrodynamics may be rewritten as [ 13, p.30]
Magnetization and magnetic field vectors are often combined to form the
magnetic field strength vector, H__,defined as
H - B _ M (7)
~to
The total current, J, is defined as the sum of the apparent magnetization current,
V x M, charge drift current, Jd, and phenomenological polarization currents,
J, [13, p.26] since the contribution to the magnetization current by intrinsic
magnetization is zero. The Ampere-Maxwell's law for polarizable, magetizable
media can therefore be written as [ 19, p.132]
0D
- VxI-I=-j (8)
0t
Detailed descriptions of these equations can be found in any number of texts
[19,20,21].
The full system of equations governing unified EMGD flows consists of the
Maxwell's equations governing electro-magnetism, the Navier-Stokes equations
governing compressible fluid flow, and constitutive equations describing
material behavior. Assuming a single-phase fluid and only one type of charged
particles in the fluid, this set has a minimum of 12 partial differential equations
that contains 13 unknowns: p, qo, T, p, and the three vector components of _v, E__,
and B, respectively. The thirteenth equation is the equation of state for the
683
8D
- - VxH=-J (9)
Ot
OE Vx--=--- l+ - (10)
8t eo eo
Faraday's law
0B
- ~VxE=0 (11)
8t
8qo
~+ V._J_ = 0 (12)
8t
V.DD_ = qo (13)
V.B =0 (14)
is also a part of the Maxwell's subsystem, but is not solved for explicitly.
684
The second part of the unified EMGD is the viscous, compressible flow
Navier-Stokes subsystem consisting of five PDE's and an equation of state of a
perfect gas. It is composed of conservation of mass equation
OP + V.(p_v)- 0 (15)
0t
0p_v
+V (v_gv+pI-~)
9 _ --
V (v(P
9 __ X
B/) --
V ((B_B_M II+(___ P)I)
9 9 = " -"
P S V
(16)
0t
Here, I is the identity (unity) tensor and S v is a vector of source terms. The
following dyadic identifies were used in equation (16)
9 -+&.E
Ds _ oh +_______~@V.
_ -T5 J- Dt -- Dt (20)
9Dt- T T
v
1; - 21avd + ).tv2I(V. _v) + oqd 2 (21)
685
In the case of a media with non-linear physical properties, the unified EMGD
formulation for the electric conduction current and the heat flux can be
expressed as [9, p. 161-162].
EM
I; = ~2~ (~)E + ot3B (~)B + o~4VT (~)VT + or5(_E| d. E)s
+ 0~,6 (_E~)d 2 -~__.1+o~7(VT | d-VT)s+ ot8@T | 2- VT~
-ko~9(_d.'W-W-d)q-O,,loW.d-W -+-Otll(d=2 . W - W . d 2)
(24)
- w 2 . . w),- 0,3( | T/s + E | E-W/s
~ W" F)S -t- O~16~" ~(~)W2 9E_~ + oqv~W-(E| VT- VT |
+ O~15(___.~) s
+ o~,18d-(E (~ V T - VT | 0~,18(E 1~)VT - VT |
6. CONSERVATIVE FORMS OF E L E C T R O - M A G N E T O -
HYDRODYNAMIC (EMHD) SYSTEM
8B
+ VxE = 0 (26)
8t
Oqo
+v.J_ = 0 (27)
ot
V.v = 0 (28)
Ov
- + v . l v v + - (1p i - )) - 1 v . I v ( l , B)+(B.M)I+(_EE.p)!]=S v (29)
8t P P . . . . . -= -
-8e
- + - V1 .(pe_v+ ( p I - x=)-_v + _q ) = S e (30)
& p
1 1
F=/.to (r M) =--~t (31)
1 1
= =- (32)
Co(1+ Z E)
A= (1
p +
zEI+Pe p B . B (34)
_Dt=V IB /- -M_M_ - J _ = V x H - J _
go
(36)
Pt = A D t +A(VxE_)xx
80
(37)
+ p(1 + Z E Dt + x A[Rt
9 - P_P_x (V x E__)]x B
If we now assume that the fluid which is subjected to applied electric and
magnetic fields is of Newtonian type and if we allow only for linear
polarization (equation 1) and linear magnetization (equation 5), the constitutive
relations for the electric conduction current and for the heat flux vector become
[9, p.173-174]
Then, the EMHD source terms can be given in a compact vector form [6,26] as
Notice that these source terms have been formulated in such a way as not to
contain explicit time derivatives [6,26].
cqQ c3E0F 3G ~
~+ +~+~=S (43)
& 0x 0y 0z
{
Q= E x, Ey, E z, B x, By, B z, qo, p Vx Vy v z e
}" (44)
In equation (44), Chorin's [27] artificial compressibility coefficient, 13, was used
to create the unsteady term in the mass conservation since physical unsteady
term does not exist in the mass conservation for incompressible fluids.
By combining equations (5), (7), (1), and (31), the Cartesian components of
the magnetic field intensity vector can be defined [6,26] as
Hz/eo
-Hy/eo /~o
0
-Ez
Ey -Ex
Jx
Jy
E= Vx
~=Vy
Vx
2 l EP Evvx-txy+
VxVy--? [V~y--}-~~)--'lTyy-- N~BP-VyN~yB)
Ev,vzt z+vz y t
(47) (48)
690
Hy/eo
-nx/~o
0
0
Jz
G=,Vz
1
VzVx-~ (~xz+ Vx~ ~)
~z +!(p-~zz-~.~-Vz~z
p- ~)
(49)
eVz
Here, we have written components of (__Px B_B_) as
0T 0T 0T (53)
N ~ - ax ~ + ar ~ + az--~z
691
(~1 ~ 0"7 PB ~Z 0T
Jx=vxqo+~Px+~4 +~N x +cy9(- B z- B )
~p ~XX {~p ~- -~Z y
O'11
+ NBpB x + O'lzNBTBx
~;p
~1 OT
~Z B x - ~ - B z )
= Vyqo + - - e y +0" 4 +--N +(I 9
ep c~ Sp Y
{3"11
+ - NBpBy + o'12NBTBy
E;p
O"1 OT G7 PB OT OT
Jz - Vzqo + ~ P z + 0"4 + Nz + (I9 By - B x)
{~p ~ZZ ~p (~- ~-
_ KI ~ 1(7 PB 0T 0T
{ly -8pPy
- 1" K4 ~0y' 1 " ~8pN y + K9(-~-ZBx - ~ - Bz)+ 1(1!
8p
NBpBy + K12NBTBy (56)
0T K:7 Pa ~ aT Kll
Clz - }c--LPz+ K:4 +~Nz + 1(9( By - - ~ - B x ) + - N B p B z + K12NBTB z
~p ~Z 8p 8p
692
7. CHARACTERISTIC-BASED I N F L O W AND O U T F L O W
BOUNDARY CONDITIONS
+~ + +~ SEM (57)
at Ox Oy az
-
QEM--Ex,
{
Ey, E z, B x, By, B z, qo
}* (59)
For illustration, the flux vector EEM can be extracted from equation (47) as
0
Hz/eo
-Hy/8 o
EEM -- 0 (60)
-E z
Ey
Jx
For fluids with linear polarization and magnetization, Hz and Hy are the same as
in equations (46), while Jx is given in equation (55). The flux vector Jacobian
matrix A___EMis obtained as
0 0 0 0 0 0 0
azl a22 0 a24 a25 a26 0
a31 0 a33 a34 a35 a36 0
A EM -- 0EEM = 0 0 0 0 0 0 0 (61)
-- OQEM
0 0 -1 0 0 0 0
0 1 0 0 0 0 0
_a71 a72 a73 a74 a75 a76 Vx_
= -Z E
a25 - ~EVyVz a36 VyVz (65)
NBp ) /9"I'
a74 = t37(VyBy + VzBz) + Oll(ExB x + + O'I2(NBT +B x (69)
0"7 0T 0T
a76 =O,Vy + - s - ( P y - g p v x B z ) + 0 9 ~ + Ol,EzBx +Ol2B x (71)
~p vy 0z
Matrices BEM and CEM may be obtained in the same fashion as equation (61).
After tedious algebraic manipulations [26], the vector of eigenvalues of the
flux vector Jacobian matrix A s s is found as
- {
k~M = 0, Zk, k~, 0, Z~,, k~,, Vx
}" (72)
This means that the eigenvalues ~1 "- ~4 - - 0 , while ~'7 -- Vx" The remaining
four eigenvalues can be obtained from the fourth order algebraic equation
+ 10 fil 1 (78)
~E=--4 " EMI+-vi-602MI---2 (II/EM-I-nEM~
19 ~/'1 1 (79)
~'E=--~ EMI-- "i-~O2EMI--~(II/EM'F~-)EMo)
+ 1 ~1 1
~:~ - -~-r + igc, G - -~(v~,,, - a~.,,,o) (80)
i
~'B -- -- ~ (I)EM2 --
jm~ 0 2 M 2 -- -~1 (ll/EM -- ~"~EMo) (81)
2
(I) EM2 = ~ EM -- (g EM - 4 v EM + 4~4/EM = (X,EM --OEM o (83)
(86)
3
[
3
YEM = VEM (4~EM -- (XEM~tEM) I VEM xl4VEM6EM-- ~tEM
2 -- (XEM~EM)
2 (88)
6 27 2
For illustrative purposes, the following are the eigenvalues in the case of one-
dimensional EMHD flow where Vy - v , - 0 and a22 = a33 and a25 = 0. Hence
~-~-
;[E IE2 / 1
x Vx+ x Vx+4 ~;o~to(1 + X M ) -- ~EVx
2)] (89)
1
Since /~o~-~o equals the speed of light in vacuum, it seems that for most
practical applications the incoming and the outgoing electromagnetic waves will
not be influenced by the fluid except in the situations where the fluid is very
highly ionized or when the fluid moves with a speed comparable to the speed of
light. In the case of a pure electro-magnetics without any fluid motion,
polarization, magnetization, or electric charges (v = __P= M =qo =0), these
eigenvalues reduce to the eigenvalues of Maxwell's equations for electro-
magnetic fields in vacuum [35]
1 1 1 1 }*
(91)
- 0, 4 ' - S' 0, 4 ' -
After introducing the similarity transformation matrix S__EMof the flux vector
~" +
~EM diag[ 0, ~E, LE,0, L+B,L-B, v x ]
- -
(92)
propagation, because the flux vector Jacobian matrices AEM , BEM , CEM cannot
be simultaneously diagonalized. Therefore, characteristic boundary condition
analysis allows that only one of these matrices (relating to only one coordinate
direction) can be diagonalized at a time.
In the case that the x-coordinate is in the main flow direction, premultiplying
the equation (58) with the inverse of the similarity matrix, SEI~, gives
(96)
, 63x
698
63QNs + aENs
- -b aFN S -1 63GNs = SNS (97)
at ax as az
into its non-conservative (characteristic) form
-
QNS= P/~,
{
Vx, Vy, Vz, e
}* (99)
From equation (47) it can be seen that flux vector ENs becomes
Vx ~,~1
2 p % __I'~BM Vx~x /
Vx + /
P P P PB p |
VxVy
'l~xy VyNx / (100)
ENS=
~xz Vz x
VxVz !|
ev_~ N_~
'~
P P J
0 1 0 0 0
~[p a22 a23 a24 0
ANS - 0 a32 a33 a34 0 (101)
0 a42 a43 a44 0
_Vx[5/9 a52 a53 a54 Vx_
The coefficients in this matrix are given in detail by Dulikravich and Jing [26].
Eigenvalue vector of the flux vector Jacobian matrix ANs is
- {
~,NS = Vx, Uu, Z+v, Uw, Ue
}" (102)
The eigenvalues Uu, X~, Uw, Ue are obtained analytically by solving a fourth
order characteristic polynomial (similar to equation 73) where
~NS -- (a34a43
_
a33a44
)_~ (107)
9
1 ~/1 2 1
~+w -- -- 4 (I) Ns2 q" i--~(I)Ns2 -- 2 (V NS -- ~'~NSo) (110)
_lt9 ~1 2
)~+e- 4 NS2-- ~ ~Ns2 --2(~I/NS- ~'-~NSo) (111)
with the coefficients given by equations of the type similar to equations (82-88).
Characteristic waves defined by the Navier-Stokes equations in the EMHD
system have a great dependency on both fluid dynamics and electro-magneto-
dynamics, in particular, the electro-magnetic properties of the media and
electro-magnetic field quantities. When electric and magnetic fields are absent,
these eigenvalues reduce to the well-known eigenvalues of a classical Navier-
Stokes system for Newtonian, incompressible flows. These eigenvalues are
{Vx,V~VxV x + c, Vx - c }. Here, the equivalent local speed of sound is defined
as C - - 4 V 2 + (~/p)
X "
~ aQNs -1 ~
SN s r + ~NsSNIs ~ + S__NsHNs=0 (112)
& = 0x
Ot --1--/I
Si.NS O0NS + Li,NS + Si,NsHNs
x=a,b
-- 0 (115)
where Li,NS --0 for incoming waves, while for outgoing waves
,NS 0X (116)
c3Q 0E 0F 0G --
00 + ~ + ~ + ~ + ~ _ S (117)
c3z 0 t 0x 0y 0z
702
or as
aQ= aQ
_ & (118)
where ~ is a composite of the spatial and source terms and is called the
residual. Thus, given a physical time step the governing equations are time
marched in pseudo time, x. Upon convergence, the fight-hand side of equation
(118) becomes zero and the solution at the desired physical time level, t, is
obtained. Note that the pseudo-time dependent variable vector, 0 , does not
have to be the same as the physical time dependent variable vector, r
An additional concern of great importance is that the system of equations
develops zero terms in the pseudo-time dependent variable vector, 0 , for
incompressible fluids, fluids without electric charges, or systems in which the
electric and magnetic fields are non-interacting. This poses significant
problems for time-marching numerical solutions. This problem may be
alleviated, however, by proper selection of pseudo-time dependent variable
vector, 0 , and through the use of matrix preconditioning.
By premultiplying I~ with a properly selected matrix, it is possible to
directly control the system eigenvalues. This prevents development of zeros in
the pseudo-time dependent variable vector, 0 , and vastly improves iterative
convergence rates over a wide variety of flow regimes (low and high Mach and
Reynolds number combinations). The preconditioning matrix, F'(0), for the
EMHD system could be based on one developed by Merkle and Choi [42] for
the Navier-Stokes system. The preconditioned EMHD system may be written as
r, aQ_
= ax -- aQ
& (119)
0 ~ =(~" (120)
A'I~ "~/~ i
F'F-I+ a i -~ _
- ~ z- ~- r i m + l , i-1
_4,
m2,,t i=O (121)
(~ n-,-1= 0 4 (122)
where m=1,2,3,.., represents the physical time step, n=1,2,3,.., represents the
pseudo-time step, and i=1,2,3,4 is the Runge-Kutta stage number. Also,
F = 0 0 / / ~ and c~i are the Runge-Kutta coefficients. Note that the physical
time-dependent term on the right hand side of equation (121) is held constant
for all four Runge-Kutta stages.
8. S U B M O D E L S OF EMHD
different time scales for the electro-magnetic fields and the flow-field.
Consequently, a number of simplified versions of the EMHD system have been
traditionally used in practical applications. These submodels can be grouped in
two general categories: EHD models and MHD models [ 11-13,44].
From the unified EMHD model, it can be seen that the electromagnetic field
is not the only cause of electric current and that the temperature gradient is not
the only source of heat conduction as is commonly assumed. The electric field,
magnetic field, heat conduction, and deformation (strain) may couple to produce
charge motion and heat transfer. These couplings are called phenomenological
cross effects and may be placed in four general categories: 1) thermoelectric, 2)
galvanomagnetic, 3) thermomagnetic, and 4) second order effects [9, p.161-
163]. These categories are based on the source of the effect and each will be
described in turn, as will be a comparison between classical EHD and MHD
models and the unified EMHD theory. The comparison concentrates on
similarities and differences between electro-magnetic force and electric current
and heat conduction terms in the EHD, MHD, and EMHD models. The
inadequacies of simple superpositioning of classical simplified models to fully
describe the unified EMHD flows are also noted.
Couplings between the temperature gradient and the electric field cause
thermoelectric effects so that a temperature gradient in the material produces an
electric current (Thompson effect), while applied electric field produces heat
conduction in the material (Peltier effect). These two effects together are
known as the Seebeck effect and form the basis for thermocouples. Also note
that the or, term in the electric conduction current (equation 22) and the K4 term
in the heat conduction (equation 23) are the ohmic charge conduction and
Fourier heat transfer, respectively.
When the electric and magnetic fields are simultaneously applied but are not
parallel, electric current (Hall effect) and heat conduction (Ettingshausen effect)
perpendicular to the plane containing the electric and the magnetic fields are
induced in the media. These effects are termed galvanomagnetic [9, p. 161-163].
When the temperature gradient and the magnetic field are simultaneously
applied but are not parallel, electric current (Nernst effect) and heat conduction
(Righi-LeDuc effect) perpendicular to the plane containing the temperature
gradient and the magnetic field are induced in the material. These effects are
termed thermomagnetic.
It should be noticed (equation 22) that the interaction of the average rate of
deformation tensor and the electric field can also create the electric current,
while the interaction of the material deformation tensor and the electric field can
create the temperature gradient (equation 23). These piezo-electric and piezo-
magnetic effects can further be enhanced if the material is non-isotropic.
705
8.1 Classical e l e c t r o - h y d r o d y n a m i c s ( E H D )
As mentioned previously, EHD flows are those in which magnetic effects
may be neglected and charged particles are present, while only a quasi-static
electric field is applied so that the magnetic field, both applied and induced,
may be neglected [ 11 ]. One of the implied assumptions is that the flows are at
non-relativistic speeds, although in astrophysical flows this assumption cannot
be made [1]. Atten and Moreau [44] present a detailed coverage of classical
EHD modeling and discuss the relative importance of terms in the force and
electric current through stability analysis. With these assumptions, the
Maxwell' s system reduces to [ 11 ]
V . D - V.(~E_)- qo (123)
c3q~ ~ - V . , J - 0 (124)
&
This is not the form of the electro-magnetic force usually seen in classical EHD
formulations [11]. Through the use of thermodynamics and the material
constitutive equation of state, the electric force per unit volume in EHD is most
often used in the following equivalent forms [10, p.505-507][8, p.59-63]
The three terms in the equation are the electrophoretic, dielectrophoretic and
electrostrictive terms, respectively.
The electrophoretic force or Coulomb force is caused by the electric field
acting on free charges in the fluid. It is an irrotational force except when charge
gradients are present [45].
706
However, this is not the form seen in classical EHD models [ 11 ] which typically
define the conduction electric current as only the first term of equation (22).
However, more advanced classical EHD models define the current as [9, p.562]
The last two equations imply that the temperature gradient is directly related to
the electric charge gradient. This may be shown to be true based on the
Einstein-Fokker relationships, derived from studies of Brownian motion [25,
p.264-273], which relate any concentration gradient to a charge mobility and a
diffusion. Newman [48] also provides a detailed discussion of the concepts of
diffusion and mobility. The electric charge diffusion term is often neglected
where only limited amount of free charges are available [49].
By introducing classical EHD assumptions in the unified EMHD theory, the
equation (23) for heat flux reduces to
The classical EHD models neglect the contribution to heat transfer from the
electric field so that equation (130) reduces to Fourier's law of heat conduction.
Cl = -~:VT (131)
V.B_.= 0 (132)
0B
VxE= -- (133)
- 0t
Vxl-l= / (134)
V-J -0 (135)
frM = j x B (137)
708
Here, (5'4 is the Seebeck coefficient [9, p.174] which in some classical MHD
formulations is not used [11 ]. Clearly, the classical MHD formulations neglect
a significant number of physical effects [52,53].
Similarly, in classical MHD modeling, Joule heating is often included in the
energy relation, but the heat transfer constitutive relation remains the same as in
equation (131). In comparison, the unified EMHD model for the heat flux with
classical MHD assumptions can be expressed with equation (39).
It could be concluded that classical EHD models include many important
effects and correspond to the unified EMHD theory well, while classical MHD
formulations need improvements in the force, current, and heat transfer terms.
As in classical EHD modeling, it is important to be aware of the fact that
many force, current and heat transfer terms can be written in several different
forms, each of which is equivalent. It is, therefore, important to recognize the
potential danger of simply adding terms from different EHD and MHD models.
9. S O L I D I F I C A T I O N W I T H E L E C T R O - M A G N E T I C FIELDS
f = Ve =
( T - Tsolidus
/n = 0n (139)
v,+v, Wliquidus -- Wsolidus
p e - p ~ 1+ . . . . (140)
00
with a similar expression for the solid phase where the reference values are
designated with the subscript "r". In this work, we assumed that electric
conductivity and magnetic permeability do not vary with temperature.
The EHD and the MHD systems of equations including solidification can be
non-dimensionalized in a number of ways. The typical non-dimensional
numbers are [33,60]:
HT = grgrHr Or / )
\ l'tvr
Pm - gvrO'r~'l'r
Pr
~tvr
PrbrA~)r
(143)
1 0L
c~q = c~ (147)
STZ 00
so that latent heat is released in the mushy region according to equation (139).
V-v=O (150)
{
+ ( l - f ) V Fgvs(Vv+(Vv) * +
[Re - - ~
>]~ } PsO,.s0
g-
+SEqo.
O0 [ \ [_ \
Cmix
_ 1
- .Re----PT~If V" (KtVO)+ (1- f) V 9(KsVO)] (152)
+Sc(qov+qo,mix_
Electric charge conservation equation including migration and diffusion is
712
Ot
E( bmix)] 1
~V. qo v+
- ReP E
_E - ~
ReD E
V 9( b m i x V q o ) (153)
Since _E_E--V~, the electric potential equation resulting from equation (13)
V-_v=O (155)
63v
Pmix-~+ f P e V " (---VX+ PeI)+ (1- f)P~V "(XX+ PsI)
00 [ \
Cmix + fpt?V" tcf0__v)+ ( 1 - f)ps v . [csq0v)
1 1 HTE c (V x H)-(V x H
=f RePR V 9(Ks + 2 3 (158)
O"e PmRe
1 1 HTE c tV
+ ( l - f ) RePR V'(K:sV0)q--- 2 3 I-I).(VxI-I
o s VmRe
The magnetic field transport equation for the two-phase MHD flow in its non-
dimensional form becomes [ 1, p. 150]
ACKNOWLEDGMENTS
The author would like to thank Dr. Yimin Ruan and Dr. Owen Richmond of
the ALCOA Technical Center for the ALCOA Foundation Grant, Dr. Martin
Volz of Microgravity Program at NASA Marshall Space Flight Center for
partially supporting a student assistant, Professor Akhlesh Lakhtakia of the
Pennsylvania State University for stimulating technical discussions, and Mrs.
Sheila Corl and Professor Hyung-Jong Ko from Kumoh National University of
Technology, Korea for proofreading this chapter.
714
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Transfer, Vol. 19 (1976) p.545.
717
C O N D U C T I O N AND DIELECTRIC E F F E C T S
IN E L E C T R O R H E O L O G Y
1. I N T R O D U C T I O N
f =24na6aoKf(~dEo)2/R4 , (1)
(2)
where f//is the force component induced by the field component parallel
to the axial line of the chain, fr the component induced by the torque
attempting to align the line-of-centers with the field leading to the
formation of the chain, f~ the repulsive component induced by the field
component perpendicular to the axial line of the chain and 0 the angle
between the applied field and the axial line of the chain. Chen, Sprecher
and Conrad [8] gave for the axial attractive force between two adjacent
particles (R/a~2.05)
Finite element calculations [9,10] gave the same magnitude for the
interaction force, with the following empirical equation [10]"
61Ua - 4
fa = ~oa2K~d2Eo2 R/a -~d ~l-~d)/2(~)4 (5)
(6)
)/(%+2of), (7)
the model does not account for the fact that the electric field dependence
of the flow stress is frequently less than quadratic, as observed in some
experiments at dc field or low frequency ac field [ 14,18,21-24]. Also the
model does not explicitly explain that the flow stress generally correlates
with the associated current density [14,25]. These discrepancies
pertaining to the polarization models were first addressed by Foulc et al
[26,27] for the case when the conductivity of the particles is much
greater than that of the host oil. A new concept in their study was that
the host liquid exhibits non-ohmic (non-linear) behavior. They proposed
that the effect of the field on the conductivity of such oils was given by a
simplified expression of Onsager's theory [28]
where of(0) is the conductivity at low electric fields and A and Ec are
constants which depend on the oil. In their model the conductivity
mismatch F=Op/Of(0) between the particles and the host oil is the
important electrical parameter. Further, to make the necessary
calculations they defined two regions in the contact zone between
spherical particles: (a) for a distance from the center line x>6 the sphere
surface is equipotential and the electric current leaving the sphere is
negligible and (b) for x<6 the electric field in the host oil is enhanced due
to the increased conductivity of the thin oil film in this region and
therefore most of the current passes through this region. The enhanced
conductivity of the thin oil film results from the non-ohmic conductivity
of the common non-polar oils used in ER suspensions. Their conduction
model then predicts that the attractive force between the particles is
proportional to Eon, where the exponent n ~ 1 at very high applied field
and n ~ 2 at very low applied field. Qualitative experimental agreement
with their conduction model was obtained for polyamide half-spheres (14
mm dia.) in mineral oil [27] and for a suspension of cellulose particles in
mineral oil [22].
Tang, Wu and Conrad [29], and Wu and Conrad [30] derived the
attractive force and current between conducting particles suspended in
non-ohmic conduction oil using an approach (to be discussed below)
which differs from that of Felici, Foulc and Atten [27]. They obtained
good agreement between the predicted values of both the shear yield
stress and current density and those measured experimentally.
Furthermore in their conduction models, the force and current is derived
as a function of the separation of the particles. In more recent work,
Atten et al [31] have however extended their conductivity model to
include separation of the particles. They proposed that the interaction
721
V-(e*VV)=0 (9a)
or
V.(o*VV)=0, (9b)
v2V=0. (10)
Ep*(OVp/On)=ef*(OVf/On), or (12a)
(12b)
where n denotes the normal direction at the interface of two media, and
again the subscripts p and f refer to the particles and host fluid
respectively. Another boundary condition is that the electric potential
should be equal at the interface of particle and the host liquid, i.e.,
Vp=Vr (13)
If we assume that the particles and the host liquid are non-conducting
or the frequency is very high, Equations (10-13) reduce to those
describing the dielectric polarization model [7,8,10].
As mentioned above, the conductivity of the host oil in ER fluids
generally depends strongly on the electric field. In dc or low ac field, the
non-ohmic character of the host oil has a significant effect on the ER
response. In this case Equation (9), together with its boundary
conditions (11)or (12) and (13), gives a strong non-linear complex
differential equation, which makes the exact solution extremely difficult,
even if a numerical method is used where iteration is involved. However,
from the view-point of engineering application it is generally
unnecessary to get the exact solution requiring extensive computations.
Of importance is that we obtain a reasonable estimate for the ER
response with an acceptable accuracy. Once we have the local field
distribution between the particles, we can easily calculate the attractive
force between the particles, the shear yield stress and the current
density flowing through a chain of particles or the ER suspension.
where a is the sphere radius and F=~p/C~f(0) the ratio of the conductivity
of the sphere to that of the oil at low field. They then calculated the total
axial attractive force between the two spheres for low applied electric
field to be
fa = 4ua2~fF2Eo2/[uln(a/5]- (15)
fa = 2ua2~f'EcEm, (17)
where E m is the saturation field in the host oil due to the strong non-
ohmic behavior of the oil. They estimate that E m ranges from
30kV/mm to 40kV/mm for the mineral oil they used. Thus, they
concluded that for two nearly-touching spheres, under low dc applied
field, the attractive force is proportional to Eo2, while under very high dc
field the force is proportional to the applied field Eo. Their analysis gave
qualitative agreement with force measurements on two nearly-touching,
large scale, semiconducting half-spheres (a=7mm). It should be pointed
out that although their model and experiment show that when
Eo>lkV/mm the dependence of the attractive force on the electric field is
linear, the shear yield stress does not have a linear dependence on the
field. This is because when a chain is sheared the particles in the chain
will separate and thus are no longer nearly-touching (see section 2.3).
The saturation field E m in the host liquid is an important parameter in
the non-ohmic conduction model. Wu and Conrad [30] give the following
empirical equation as an estimate of the saturation field
725
F o Ec
E ~ / E o - 30(~) "1(~0-0)09 (18)
and Davis and Ginder [32] give for the radius of the saturation region of
two nearly-touching spheres
Felici, Foulc and Atten [27] gave the following expression for the
relationship between the axial attractive force fa and the current I
passing through the spherical particle:
- -~'I h(x)
of Ef _Io I eo
(a) (b)
Figure 1. Schematic of the conductivity model for two separated
spheres [29,30]: (a) The geometry and symbols employed; (b) an area
element in the horizontal plane, of is the conductivity of the host liquid,
Op the conductivity of the particles, Ef the dielectric permittivity of the
host liquid, epthe dielectric permittivity of the particles, a the radius of
the particles, s the separation of the particles, and h(x) the gap between
the two particles at location x.
727
It was found that most of the current passes through the contact zone,
which dominates the main behavior of an ER fluid. Good agreement
occurred between the predicted and experimental data [21] for the effect
of applied electric field on the quasi-static yield stress XE of a
zeolite/silicone oil suspension.
Based on the work of Felici, Foulc and Atten [27], Davis and Ginder
[32] predicted the shear modulus of an ER suspension with non-ohmic
conductivity at dc field to be
G= 3EoKf0EoE m (22)
4 1
XE = ~EoKfOE ~ . 5 ~ (23)
Figure 2. The ratio of the maximum local field in the fluid layer to the
applied field v s the normalized separation for different applied fields [30].
728
the saturation field varies with the normalized separation S and the
applied field E o.
Figure 3 shows the normalized attractive force F (f~=na2~oK~o2F)
between the two particles. If Em/Eo<I+i/S, no saturation of the field
occurs and the normalized attractive force
F = 0.955/S. (24)
If Em/Eo>I+I/S , a saturation field occurs in the liquid layer and the
normalized attractive force is
3 (~oK~o2F(?) ~ (27)
lO~ ~ " ' ' '''"'1 ' ' '''"'! ' ' .... "1 ' ' '"'~"_~
F=]O 7
A=0.007
]o3 ~- ~ Ec=0.21kV/mm
:: ~ j F=fa/[:n;eoKfEo 2a21
-_ 1 . "~ =0.955/S
102
101 - lO .....
(29a)
or
(5 = ~ a~(I+S)Eo/E m -S (29b)
(5 = a%]2Eo/~, (30)
which is same as that given by Davis and Ginder [32] for two nearly-
touching spheres; see Equation (19).
The average current density of a single chain is
a
J = 2(~f(Em)Eo (34)
730
with an error of less than ~10% compared with Equation (32). Equation
(34) gives a reasonable estimate for the current density of a common
ER fluid chain. For an ER suspension with particle volume fraction ~,
Equations (31-33) should be multiplied by 3~/2 for an ideal arrangement
of the particles.
Recently, Atten et al [31] presented an extension of their earlier
conductivity model [27] to the case of small separation between two
half-spheres (a=7mm) in the saturation regime of the liquid phase.
However, their prediction does not show good agreement with
experimental results; see Figure 4, which includes the prediction by the
conduction model of Wu and Conrad [30]. The conduction model by the
latter authors shows better agreement with the experiments than Atten
et al's model. The non-ohmic conductivity parameters of the oil employed
in Wu and Conrad's calculation were obtained by fitting the experimental
data of Atten, Foulc and Banqassmi [43] to Equation (8), which gives
of(0)=3xl013S/m, A=1.35 and E~=l.49kV/mm. The dielectric constant of
the oil is Kf=2.2 and the conductivity of the particles is o p= 1.7xl0SS/m.
Figure 5 further compares the dependence of the measured attractive
force on the applied field of two half-spheres [27] and that predicted by
the non-ohmic conduction model [30] and the polarization model [8].
Again the non-ohmic conduction model shows better agreement with
experiment than the polarization model. At low dc field and large
separation the attractive force is proportional to the square of the
applied field, and at high dc field or small separation it is approximately
proportional to the applied field. This behavior is in good accord with that
predicted by the non-ohmic conduction model. Davis [33] uses an
integral equation method to calculate the attractive force between two
conducting spheres suspended in a non-ohmic oil and gives a prediction
similar to that of Wu and Conrad [30]. However, his polarization model
gave a quadratic dependence of the attractive force on the applied field.
It should be pointed out that the non-ohmic conduction models
[29.30,32,33] predict that the shear yield stress of ER
suspension is proportional to approximately Eo 15 at dc applied field
ranging from 0.5kV/mm to 5kV/mm, which differs from the prediction for
the axial attractive force between particles. This is because the yield
stress in shear occurs when the particles are separated by the shear,
with the result that the saturation region of the local field in the liquid
between the particles decreases compared with the case of nearly-
touching particles.
As mentioned above, one of the most important differences between
the non-ohmic conduction model and the complex polarization model is
that the former predicts that the shear yield stress dependence on the
731
1.2
Atten et al [31]
Wu & Conrad [30]
0.8 Experiment [31]"
Z 9 1.357kV/mm
0.6
it 1.071kV/mm
9 0.714kV/mm
0.4 @ 0.357kV/mm
0.2
101 ' I I I I I I rl I ~ I I I I ~
0.1 1 10
E o (kV/mm)
400-- //"
" / ./A A "'A A ~,
: / ~ A \
200 " - 9 / ~ .--'~ ~ "~
- ~1~ ~ ) Eo=lkV/mm u"O..
0-, l, , I , , , , I , , , , I I I , ,
experiments [44] show that the interaction force first increases, reaches
a maximum and then decreases with F. Boissy, Atten and Foulc [45]
and Wu and Conrad [46] found that when F is small the ER response is
negligible and when F<<I a "negative" ER response occurs. However,
when F is very large a complete chain spanning the two electrodes does
not form and a weak ER response occurs [45]. They proposed that
when F is too large, the two contacting particles will exchange their
charges in a very short time and separate before a complete chain
forms.
I h(x)
E0
/xL r
100 ,. i i[lll i ! . . . . . . . [ i
1
_
i i ! i : , , 1
-
Experiments.:
, . 1 _T T i i.t , t |
o 3 Spheres ~,~[
~ 4 Spheres ...............................
~ ~ ~
~_,1~ 0 A 5 Spheres ~ ~ ! -
! i ii
I '!-...........J..........i-~-i-i~--i---
i-'-'~-i -!....!---i......Theoreticati
_ T h e o r e t i ..........
.c...a tii-.......
i i---
i
I i ~. ~ ..... Tangetal[49]
i -----Wu & Conrad 13(
i i :
51_ . . . . I . . . . . . . . I . . . . I .... -I
~.~_. _Expefimen.tal_
: :._ _~
4 1: ~ ................i............J o 3 Spheres ]-]
~" ~ 0 \ I A 4Spheres/:t
~~i 0 5Spheres1
,~ 2 i iA i ......; ................................
*'~ 1 - ..... : ~.,...................... !...................... i ....... o .........
o ?ii i,, i, :i i i i i
0 0.1 0.2 0.3 0.4
,,1 0.5
u
Figure 9. Comparison of the measured current density of a sheared
single chain of humidified glass beads v s shear strain with that
predicted by non-ohmic conduction models under dc field" 9 Tang, Wu
and Conrad [49]; Wu and Conrad [30].
I L : 1 1 !i J
9 Experiment [51,55] J /, ~ ~
......... Wu & Conrad [30] J ~Z'.,~";"
E] " Tang etai [49] [IIIIZ]III]I]I::]I::I~]:I]L~~I!!!-_
[i:J - Davis & Ginger [32] J:::::::::::::::::::::..~ ~:::::::::-
[---J -- ---Klingenberget al [7] [........i - ~ .....!.............Z
k if!___.~..- .- --Conrad et al [54] ..........!2~iiiiiiiiiiiiiii~iiiiiii--
.......i:i_..:i:!i:i::::ii:ii~ii!:i::::::i~iiii:iiliZ.ii~:i:2:1111!iiiiii:i~ii:ii:ii
_:_:.i_i
0.1 ~ ,J'2" i
0.6 0.8 1 2 3 4
E o ( k W m m )
conductivity of the surface film and gf(0) the conductivity of the oil at
low field. Taking silicone oil as the host liquid (with of(0)=2.4x1012S/m,
Ec=0.21kV/mm, A=0.007), they found that increasing A (i.e., increasing
o I or decreasing 5) increases the ER response under dc applied field. If
the surface film is an ideal insulator and thick (i.e., ai=0), there is no ER
effect under dc field. If 5 is too thin, electric breakdown will occur in the
surface film when the applied field exceeds some value, which was
observed in the experiments [18,34]. Therefore, a reasonable thickness
of the surface film is desired to avoid breakdown. The shear yield stress,
shear modulus and the current density of an ER suspension with a
volume fraction ~ of particles suspended in silicone oil were determined to
be given by the following empirical equations:
103
- 1;EOc EO 1"46 .
l02
11~ lO 1
_. . . . . . . . . . ~
# f
I
f Experiment [18]
10 o Wu & Conrad [34]
.... Davis [17] (~c=0.5)
. . . . . . . Davis [17] (~c=l)
10-1 -- I I I
1 2 3 4 5
E o (kV/mm)
Figure 11. Comparison of the predicted shear yield stress [34] with that
measured [18] for a suspension of oxidized aluminum particles in silicone
oil (~=0.2) under dc electric field. Also shown are the analytical results
by Davis [17] assuming ~*=~c=0.5 and ~*=~c=l (the upper-limit),
respectively. The average particle diameter is 20;um and the surface
film thickness 5=0.2/1m.
739
~c=1/2, which is still smaller than the measured value. Furthermore, the
complex polarization model predicts that the shear yield stress is
proportional to E02 not ~Eo 15, the latter being predicted by the non-
ohmic conduction model and supported by Inoue's experiment. Of
interest is that Davis' analysis [17] provides a good prediction for the
shear yield stress with ac field. The reason for this may be that with ac
field (especially at high frequency) the conductivity effect will be weaker
than the dielectric effect. The dielectric constant of the materials
employed does not usually change considerably with the electric field and
thus Davis' linear analysis seems more reasonable for ac field than for
dc field. A detailed study of the frequency dependence of the ER response
will be given in sections 3.2 and 3.3.
Figure 12 compares the predicted yield stress with that measured
[34] for ER suspensions of silicon particles (l~5~um diameter) with an
oxide surface film in Dow Corning 200 silicone oil. The conductivity of
the silicon is 4.35x104S/m [56], giving Fp=l.83x10 s. The conductivity of
the oxide film was taken to be oi=4.8x10llS/m. The average diameter of
the particles is 2.5~um and the surface film thickness 5=0.2;um. Good
agreement between the predicted and measured values of the yield
stress is indicated in Figure 12. Figure 13 compares the effect of the
- O x i d i z e d S i / S i l i c o n e oil
_
r 6=0.2/~m J
_
10
Exp.
Pred.
I I ,, I I I i I i i ] I _I I I I i i
0.1 1 lO
E o (kV/mm)
Figure 12. Comparison of the predicted shear yield stress vs. applied dc
field with that measured for a suspension (r of oxidized silicon
particles in silicone oil. The particles are of average diameter ~2.51~m
and coated with an oxide skin of thickness 5=0.2~um [34].
740
5o i i i i i i i i ]
Eo=lkV/mm o Exp.
40 --- Pred.
- Oxidized Silicon/Silicone Oil-
"~" 30
o ,=0.23 :
20
10
, , , , , , ,,! , I I I I I I I
0.01 0.1 1
(t,m)
Figure 13. Comparison of the predicted effect of the oxide film thickness
6 on the yield stress with t h a t measured for a suspension (r of
oxidized silicon particles in silicone oil with applied field E o - l k V / m m [34].
10-1 _- 1 i ! i i i i I ]
1 0 -3
- o
10-4
F
10-5 I I ,, I I , , , ! ,
0.1 0.3 1 3
E 0 (kV/mm)
Figure 14. Comparison of the predicted and measured current densities
of a suspension (~=0.23)of oxidized silicon particles in silicone oil. The
averaged particle diameter is ~2.5/tm and the surface oxidized film
thickness 6=0.05/tm. o Experimental data without electrical breakdown
in the suspension; h Experimental data after several breakdowns;
Predicted by the non-ohmic conduction model [34].
741
lO 4
10 a
10 2 : 10 --"
lO far
1 01
10 o
lO o lO ~ lO2 lO3 l~
where fc has a solution only in two cases: (a) when 0<F~8.243 and
Fa_>8.243 or (b) 0<Fa<8.243 and Fe~8.243. The four regions in Figure 40
represent four kinds of ER response. Region I (F~<8.243 and Fa_<8.243)
is an inactive region, where 113"(o))12is always less than 0.5. Region II
(0<FE<8.243 and F~>8.243) is conductivity dominant, where ER fluids
only show a strong effect below a critical frequency fc" Region III
(0<Fo<8.243 and FE>8.243) is dielectric dominant, which becomes active
when the frequency exceeds f~. Region IV (Fa>8.243 and F~>8.243) is
always active independent of the frequency.
The above analysis is based on the assumption that the particles
have the same dielectric and conduction properties in the bulk and on
the surface. The polarization process becomes more complicated with
surfactants around the particles [15] or composite particles, e.g., highly
conducting particles coated with a thin dielectric surface film [17,18,34]
or dielectric particles with a conducting film [49]. Tang and Conrad [58]
also calculated 1~*(o))12 in the frequency domain for several conducting
surface film thickness ratios. In a special case a new type of frequency
response for the dielectric particles with surfactants was found, which
can not be obtained by bulk polarization alone.
Although the complex polarization analysis is supported qualitatively
by experimental observations [15,20], it does not give a reasonable
estimate of the magnitude of the shear yield stress of ER suspensions.
In the following we will introduce a simplified analysis for the ER
response considering both the dielectric and conduction effects under ac
applied field, which gives better agreement with experiment.
744
where co is the angular frequency of the applied voltage and t time. Let
E* denote the complex amplitude of electric field. Referring to Figure 1,
along the y-axis (x=0), we have the following approximate equations
with ac field [41]
so that
~ _ (~176
E*f = 2ao,f + SO,p - 2a(of +ic0~f) + s(o +ic0e ) (41a)
p P
E* - ~176 (~176163176
- = (41b)
P 2ao*f + SO*p 2a(of +ic0s + s(o p +ir163
When c0=0 (dc voltage), O*p - o and o*f = of, the fields are induced by
P
the particle/liquid conductivity mismatch and Equations (41a-b)
become
E* ~176 (42a)
f- 2aof + SOp
E* - ~176
- (42b)
p 2aof + SOp
745
which can be also obtained from Equations (21a-b) when x=0. When o) is
very high or o p =of =0, the field is determined by the particle/liquid
dielectric mismatch and Equations (41a-b) become
epVo
(43a)
E*f = 2aef + Sep
E* = efV~ (43b)
P 2aef + Sep
. (1 + S ) E o (I+S)E o
= (45)
E f : o,f/o, + s ~+ if]
+S
F o + iQF~
- 1, (46a)
where E is the rms value of the local field in the oil. Equation (47) is a
complex equation which can be solved by a computer. The electric field in
the host liquid layer is
Ef(x,t) - Re(Ef*e i~~ = ~E(x)cos(o~t+0 E (x)) (47)
746
IEf*l
where E(x)= ~r~ is the rms value of Ef(x,t) and
1 Im(Ef*)
0E = t a n [ ~ 1 (48)
is the phase angle shift from the applied field and is a function of the
location x.
Outside the contact center (x>0), an equation similar to Equations
(42a-b) can be used to estimate the local electric field distribution
between the two adjacent particles. However, a and s in Equations (42-
47) should be replaced by a'=a~/1-(x/a) 2 and s'=s+2a[1-~/i-(x/a)2].
Further, the normalized separation S should be replaced by
S'=(S+I)A/1-(x/a) 2 -1. This simplified analysis gives an estimate of the
local field with good accuracy [36].
Having obtained the distribution El* (x) of the complex amplitude of the
local electric field, we can get the complex amplitude of the current
density
9 $ $ $
fa(S,t ) = ~soKf
1 f 2 ~ IEl(X)* 12cos2(eot+0E(x))xdx
= e 0 g a 2 I ~ ~ 2 F(S,t), (53)
Here ~=x/a and E ~ is the rms value of the applied electric field. The
rms value of the normalized attractive force is
tl
or
In most experiments, the measuring meters give the rms value of the ac
signal; but some meters may give the mean value.
748
03
where j(a) is the current density (rms value) of the pure host liquid under
the applied electric field and is given by
lO3 _= I I I I I I I l l l I 10 3
1
r =ro=l~ l
=]02 ~
:
o'10] ~
7 r~=ro=lO . ~
, 10 ]
- r~=}, ro=]'O--.~ M
L s=o.oo5 r~=ro=s
10 ~ 9 ~ i i i i i I i i I 0o
10-4 10-2 10 o ]o2 lO4
Q
Figure 16. The normalized attractive force between two particles versus
the normalized frequency [35].
750
when [~'2- I~* COS0~[2 < 0.85, where 13 is the real component of 13",and
The mean and rms shear yield stresses of a single chain are predicted by
the following empirical equations when ~'2<0.85:
s-o.oos
~_..2--:-.~
10 ~ ~ I I I I I i I I ! ~
10-4 10-2 100 102 104 106 108
f~
Figure 17. The average current density of a single chain versus the
normalized frequency [35 ].
751
The conductivity of the oil and, therefore, the conductivity ratio Fo=
Op/Of was varied by adding an ionic surfactant (AOT) to the oil. The
dielectric permittivity ~_ of the half-spheres decreased with the
frequency of the applied efectric field. The dielectric constant of the oil is
Kf=2.2. Figure 18 compares the measured attractive forces [23] with
those predicted by our model [35]. In the experiments, the exact
separation of the two half-spheres was difficult to observe and thus no
data were reported on their separation. By taking the normalized
separation S=0.005 (R/a=2.01), good agreement occurs between the
predicted and measured attractive force of the two nearly-touching
polymer spheres. It should be pointed out that in the high frequency
regime (f>20Hz) the conductivity ratio has no effect on the ER response.
This is indicated by both prediction and the experiments. Furthermore,
the theoretical calculation shows that when the normalized separation
S<0.01 there is almost no effect of the frequency on the attractive force
at high frequency (compare curves a and a' in Figure 18). However, at
low frequency the separation of particles has a significant influence on
10 o
dr
~
j ' Erms=0.202kV/mm -
10-1<
( ....~ S = 0 . 0 0 5 ( R / a = 2 . 0 1 ) -=-
" a "'-,
...... Fmean :.
10-4 I _ . . . . . . . . I ........ J ........ I . . . . . . . ,! .......
0.01 O. 1 1 10 100 1000
f (Hz)
Figure 18. Comparison of the predicted attractive force between two
polymer half-spheres immersed in mineral oil (Elf TF50) with that
measured (radius of the particles a=7mm, S=0.005, i.e., tUa=2.01).
Experimental: open symbols; theoretical: solid curve for Frm~, dashed
curve for Fmean. Experimental [23,24]" O Fo=l.4xl04, EIF(j= 1.2x103, A
['0=300, ~ ['0=30. Theoretical [35]: (a) Fo=l.4xl04, (b) Fo=l.2xl03, (c)
I"o=300, (d) Fa=30 , and (a') S=0.001, Fo=l.4xl04.
752
| [ ' ! i !
10
Predicted [351
o/x r3 Experiment [38] ~-
1 , 1 , : I ,,J I,,,
0.8 1 2 3 4
Eo (kV/mm)
Figure 19. Comparison of the predicted (rms) [35] and measured [38]
shear yield stresses v s the amplitude of the 400Hz ac applied field for
three ceramic particles/dodecane suspensions" TiO2, Kp=70; SrTiO 3,
Kp=270; BaTiO3, Kp=2000; I~=2. In all the calculations Fo=10 and
of=10llS/m were taken.
753
Predicted [35]
Experiment [38]
~" 102 =
O O 0 O 0
101 BaTiO3/dodecane _
,=0.2 :"
Eo- 1kV/mm
100 I I I I I llJ I I I I I I lli I l I I I I II
about 1.2 times the mean value, which differs slightly from the
attractive force. The reason for this may be that the shear strains at
which yielding occurs varies with frequency. Of interest is that if the
dielectric effect is larger than the non-ohmic conductivity effect the
transition regime from conductivity domain to dielectric domain is larger
2.4
2
~, 1.5
1.6
(a) 1 . .
3
. .~ . 3 . V/~~l 1.2
0.8
~
0.5 - k
0 ~ 0"4
10-1 _ S=0.005
- . ~ Erms=3kV/mm
10-3 I I I I I I I I I
10-5 10-3 10-1 101 103 105
f (Hz)
F~=5 .-3.5
.. 5E~:~rms <102Hz 1
,~ 103 Fa=10~ df ~ 103Hz -
=104Hz (a)
-i_--
2
_- /ECrErms
lO 1 , I , I I I I '
0.8 1 2 3 4 5 6
E rm s (kV/mm)
lO 4 I I I ' I I I '__
Fo=106 _"
F~= 103 103 Hz -
50Hz _
dc
~, 10 3 (b)
la
10 2 I I I I I i
0.8 1 2 3 4 5
Erm s (kV/mm)
Figure 22. The shear yield stress (rms value) dependence on the applied
field for a single chain: (a) F~=5, F,j=10 a and (b) FE-10 a, I"o=106 [36].
756
Figure 22a shows the shear yield stress (rms value) dependence on
the applied field when the dielectric effect is smaller than the
conductivity effect (F <<Fa). It is seen that the ER response at low
frequency (f<102Hz) is stronger than that at high frequency and further
shows a field dependence of E r ~ 15. At high frequency (f>103Hz) the
shear yield stress shows a Erms2 dependence. It is interesting that,
although f=103Hz is in the transition regime (see Figure 22a), the shear
yield stress still shows a quadratic field dependence. In contrast to
Figure 22a, Figure 22b shows the case when the dielectric effect is larger
than the conductivity effect. This gives a weaker ER response at low
frequency compared with high frequency. The shear yield stress shows
a field dependence of E ~ 151 , E r ~ 153 and Em~ T M for the frequency
f=0, 50 and 103Hz, respectively.
Figure 23 compares the predicted [36] attractive force (rms value,
S=10 5) with that measured [23] on the two 7mm radius polyamide half-
spheres in mineral oil with electrode spacing of 14mm. The conductivity
parameters employed in the calculation are the same as given in section
op=l.7xl0-8S/m,of(O)=3xlO-13S/m,
2.5.1, i.e., A=1.35 and Ec=l.49kV/mm.
The dielectric constant of the particles decreases with the frequency.
When the frequency f=10, 50 and 1000Hz, the dielectric constant of the
particles is Kp=34, 24, and 18, respectively. It is seen in Figure 23 that
the predicted attractive force is in good agreement with that measured.
The reason the measured force at low field and high frequency is slightly
smaller than predicted is probably that the force was too small to
measure accurately.
Figure 24 compares the dependence of the attractive force (rms
value) on the applied field. With ac fields of frequency f=50Hz and 200Hz
respectively, Wu and Conrad [36] predict that the attractive force is
proportional to E~m~2, which is in good agreement with experiment. With
dc field they predict that the attractive force is proportional to E ~ 13 at
S=10 5, compared with the experimental F n ~ E ~ m ~1.6 . If S=10 2 is
taken, it is predicted that F r a t E r n a l 4 5 (dashed line in Figure 24), which
is in slightly better agreement with experiment. However, with ac field
there is no difference between the predicted and measured field exponent
for this range of S. The reason the field dependence of the attractive
force at de field depends slightly on S is that at high applied field the
saturation of local field occurs over a large range of S. Thus over this
range the attractive force has almost a constant value. At low field,
however, only within small range of S does saturation of the local field
757
~-, 10-3
- dr
10-1
10-2 50Hz
10-3 OHz
10-4
10-5 I I I I I I I I I I z t
-120
k
9~ -28o
~,~ 10 -4 10-3 10-2 10-1 10 0 101 10 2 10 3 LO4
f (Hz)
Figure 25. Comparison of the predicted gain of two polymer particles
immersed in mineral oil (Elf TF50 without AOT) versus the frequency
with those measured. Radius of the particles a=7mm, the normalized
separation S=0.10 "5. Experimental[23]: open symbols; theoretical[36]"
solid curves for non-ohmic conductivity and dashed curve for ohmic
conductivity.
759
lO3 -
0.1 1 10
Erm s (kV/mm)
Figure 26. Comparison of the predicted shear yield stress (rms value)
[36] with that measured by Miller, Randall and Bhalla [39] for
BaTiOs/silicone oil suspension (f=60Hz and ~=0.1, Kf=2.8, Kp=2000,
=10l~ of(0)=2.4x1012S/m, A=0.007, Ec=0.21kV/mm) and by
der and Davis [59] for BaTiOJdodecane suspension (f=20Hz and
r K~2.0, Kp=2000, ~p=10l~ of(0)=2.4xl012S/m, A=0.007,
Ec=0.2 lkV/mm).
3 ~/gla
- 2 *Q rm 2Ef (63)
f~ 20 - i , i i l i i _ 100
- I', I._lO 3
15- ' ~ - 80
- FoI= 10 2 _
-
~) 10 - Fo=IO~2 - 60
- Fs=lOl o - I[,~
_ _ 40
F I=IO 3
5 2
"~ - FoI=2~ 5/a=O.O1 - _ 20
~,~ -
_
0 I i I i 1 I i
1 0 - 5 1 0 - 4 1 0 - 3 1 0 - 2 10-1 10 0 101 10 2 10 3
fl=2n'fEf/af
Figure 27. Shear yield stress (rms value) of a single chain of highly
conducting particles coated with low conducting film vs the normalized
frequency. The right ordinate is the normalized shear yield stress YE------TE
/[e0KfErms 2] with Fa=(jp/(Jf=1012, F=~p/~f=lO 1~ FEI=ei/~f=103, 5/a=0.01.
The left ordinate is the dimensional shear yield stress XE for the special
case of coated metal particles suspended in silicone oil with (Jf=2.4xl0-
12S/m, Kf=2.5, Erms=3kV/mm and f=50Hz [37].
761
conductivity ratio F~ of the surface film to the host oil is less than the
permittivity ratio F J , the ER strength is higher at high frequency ac
field than at dc or low frequency. For the special case of coated metal
particles suspended in silicone oil with af=2.4xl012S/m, the transition
frequency fc is about 10 -4-10-2 Hz. This transition frequency is
proportional to the ratio of the conductivity af to the permittivity ef of
the host oil, i.e., fc=ff2c(Jf/(2~tef). If we take of=10SS/m and s163 fc=l -
100Hz, which is same as the estimate by Davis [17]. No effect of
frequency on the shear strength occurs when the conductivity ratio
F~ equals the permittivity ratio F I. However, it should be pointed out
that when the ratio FI is high, the local field in the liquid layer between
two particles increases. This increased local field will increase the
conductivity of the host oil if it exhibits super-ohmic behavior, and the
- ~=2897.5 5/a=0 01 :
15 F,pl012 " --: 80
- F=IOI 0
60
@) 1 0 - ro~=1.67
- -_ 4O I~
5
~ -_ 20
1 10 100 1000
FEI=ei/e f
Figure 28. Shear yield stress (rms) of a single chain of highly conducting
particles coated with low conducting film vs the permittivity ratio
F~I=ei/ef of the surface coating to the oil. The right ordinate is the
normalized shear yield stress YE---'~E][s 2] with ro=(~p/Of=1012,
F~=ep/ef=lO 1~ I4o=0i/0f=1.67, g~=2897.5. The left ordinate is the
dimensional shear yield stress ZE for the special case of coated metal
particles suspended in silicone oil with of=2.4xl012S/m, Kf=2.5,
Erms=3kV/mm and f=50Hz [37]
762
real conductivity ratio may be lower than suggested. In this case the
non-ohmic conduction effect of the host oil should be considered
especially at low frequency.
Figure 28 gives the shear yield stress versus the dielectric constant
ratio of the surface film to the host oil for a single chain of particles. The
yield stress increases with the dielectric constant ratio, which indicates
that conducting particles with a high dielectric constant surface film
can give an exciting ER response. For example, if the volume fraction of
the particles ~=0.4, the surface film thickness 8=0.01a and the surface
dielectric constant ratio FEI=I~/~1000, and if we choose a structure
parameter As=10 [54], we can get a shear yield stress of 100kPaI Even
if we consider the structure parameter A~=I, one still obtains a shear
yield stress of more than 10kPa. In their recent work [60], Wu and
Conrad give the following empirical equation to estimate the shear yield
stress of highly conducting particles coated with a dielectric film
suspended in ohmic oil (As = 1):
8 grE 2
x E (Pa) - O.O06+(~FEI)O.6 , (64)
where A=5/a and the units of the applied ac field Eros are in kV/mm.
Figure 29a compares the experimental shear yield stress [18] for
aluminum particles with an alumina surface film with t h a t predicted
[ 17,37]. The frequency of the applied field is 50Hz. Davis [ 17] assumed
that the surface dielectric constant KI=5 for A1203 , but Randall et al
[61] report I~=10, whereas Thurnauer [62] report Ki=8-9. In Figure 29a
we give two cases, when KI=5 and KI= 10. Both values give predictions in
good agreement with the measurements of the yield stress. Even though
the surface conductivity ratio FoI may range from 1.67 to 100, no
significant difference occurs in the predicted values of both the shear
yield stress and the current density. This indicates that when the
frequency f=50Hz the surface conductivity ratio has no effect on the ER
response, which is seen more clearly in Figure 27. Figure 29b compares
the measured [18] current density with that predicted [37]. Again good
agreement occurs.
Figure 30 compares the dependence of the measured shear yield
stress on the oxide film thickness with that predicted [37,17]. It is clear
that good agreement again occurs between the predicted and
experimental values. The term "EG yield stress" is defined by Inoue [ 18]
763
to mean that when the surface film thickness is too small a field higher
than the breakdown strength of the film material could not be applied.
From the analyses by Davis [17] and Davis and Ginder [32] and the
calculation by Wu and Conrad [37], the smaller the surface film
thickness 6 the higher the shear yield stress. However, a decrease in the
film thickness also raises the local field in the film, which increases the
possibility of dielectric breakdown. In this case a high field can not be
applied, the result being that the ER suspension exhibits a low shear
yield stress. This can be seen in Figure 30. According to the above
analysis, the surface film should have a high dielectric constant, a high
dielectric breakdown strength and a reasonably small thickness.
-~ 100 :::::::-,
i!::!!,'
...... , .............. <...:
t..--.............. , ............ :::::::::::::::::::::::::::::::::::::::::::::
i i:! (a)
:::::::::::::::::::::::: Wu & Conrad [371 (K,:5)
...... !...... !........... Wu & Conrad [37] (K,=10) [--
...... i ...... i........... Davis [17] (K,=5) ~-
10 i i i i
I "
i S=O.O01 ,'
10 ...........!.............................................~.........................................................
!i (b)
0.8 1 2 3 4 5
Erm s ( k V / m m )
Figure 29. Comparison of the measured ER response of oxidized
aluminum particles suspended in silicone oil [18] with those predicted
[17,37] (5=0.2/zm, a=10/zm, (I)=0.2, f=50Hz, of=2.4x1012S/m, Kf=2.5,
ro=Op/~f=1012, r~-ep/ef=101~ and FIo=oi/of=l.67): (a) the shear yield
stress and (b) the current density.
764
.-. 800 E,,,~l,,,,i .... i , , , i , ~ , i , , , ' t , ' " l " ' ~ ' -
~ i ---Wu & Conrad [37]-
~ .... Davis & Ginder[32]-
600 L- ! o o 9 Experiment [18]
Erms=3kV/mm
400 ... 50Hz -
: ""0 "
200 ~- i'~'-" :". .... / m c
0
0 0.2 0.4 0.6 0.8
5 (Hm)
15 I -I I i
Exp. [18]
- Pred.[37] (K~=5)
10 Pred.[371 ( K , - I _ ~ "
wooa~176176
5
f S=0.001
9 E~b=400kV/mm
0 I I I I I _1 I
0 0.1 0.2 0.3 0.4
a qum)
Figure 31. Comparison of the measured [18] a p p l i e d breakdown field
for oxidized aluminum particles suspended in silicone oil with those
predicted [37]: a=10/tm, ~=0.2, f=50Hz, of=2.4x10lZS/m, K~2.5,
Fo=Op/Of=1012, Fe=13p/Ef=1010 and FIo---oi/of=l.67.
765
3.4 T r a n s i e n t r e s p o n s e in E R fluids
In Section 1 it was pointed out that for dc field the conductivity
mismatch between particles and fluid is the dominant factor in
determining the ER strength. Using pulsed dc excitation, Ginder et al
[65-68] and Tang and Conrad [58] have demonstrated the separate roles
played by the conduction and dielectric properties of the particles and
host liquid in transient ER response. An interpretation of the
experiments, based for simplicity upon a point-dipole analysis, sheds
considerable light on the mechanism of ER activity. Recently, Davis [33]
studied the ohmic (linear) ER response to a pulsed field and the non-
ohmic (non-linear) ER effects at high dc fields using an integral equation
method. Based on the point-dipole approximation, Ginder, Davis and
Ceccio [68] proposed a model to qualitatively predict the transient
response. The most important prediction of Ginder, Davis and Ceccio
[68] is that the shape of transient stress curves depend sensitively on
the relative contribution to the particle polarization mechanism of the
dielectric mismatch ~d=(Kp-Kf)/(Kp-2Kf) and conductivity mismatch
~c=(CJp-~f)/(~p-2(~f). If the ER response is mainly induced by a
conductivity mismatch (~d/~c<<l), then when an electric field is suddenly
applied the shear stress will increase over a relaxation time
t*=~o(Kp+2Kf)/((~p+2af), and finally reaches a maximum in the steady
state. If the ER response is instead induced by a dielectric mismatch
(~d/~>>l), sudden increase in the field produces an instantaneous peak
766
in the stress, which then decays over a time t* because of the residual
conductivity mismatch. These distinct qualitative behaviors enable a
determination of the mechanisms of electrorheological transient
response. The predictions of the ER transient response were fitted to
the measured stress transients using nonlinear-least-squares curve-
fitting algorithm; the solid curves in Figures 32-34 demonstrate that
qualitative fits were obtained. Good agreement also occurred between
the values of ~d/~c and t* derived from independent fits of the unipolar
and bipolar transients in amorphous aluminosilicate and barium
titanate suspensions.
For the amorphous aluminosilicate fluid the fit to the date gives
~d/~c=0.15, which suggests that ~d/~c<<l. As stated above, a
#
O~ 1SO
200
100
lO 20
-lO -20
2 I 2 r-- ! "i
O'
I I I 1 --2 1 I l .
~ 80 , i 80 i i
o 0 "
-40 -40 7
8O
2 1 I
10 Hz I) _ _ ~ ~ 10 Hz
2 I) I
~ 0 -I
o I
I , | ~ 2 . , i | i I
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
t i m e (s) t i m e (s)
(a) (b)
Figure 33. The time dependence of (I) the shear 1: (dots); (II) the
current density j and (III) the applied field E o in the barium titanate ER
suspension. The sample was sheared in a Couette cell at a constant rate
Y=5s 1 and was excited by a 2kV/mm peak amplitude, 10Hz unipolar
square wave. The solid line in (I) is a fit to the stress by the dynamic ER
response model [68]. (a) 10Hz unipolar square wave; (b) 10Hz bipolar
square wave.
768
400
200
02 , , ,
~ o.1
~ o.0
-0.1
~-~ -0.2 '
10 Hz
1 . . . . .
o ! .. | I
t i m e (s)
Figure 34. The time dependence of (I) the shear x (dots); (II) the current
density j and (III) the applied field E 0 in the crystalline aluminosilicate,
or zeolite, ER suspension. The sample was sheared in a Couette cell at a
constant rate Y=5s1 and was excited by a lkV/mm peak amplitude,
10Hz unipolar square wave. The solid line in (I) is a fit to the stress by
the dynamic ER response model [68]. The relatively high conductivity of
this fluid is reflected in high current density in (II).
769
4. D E S I G N OF I M P R O V E D E R F L U I D S
and has high dielectric permittivity. For the particles, we desire that
they have both a reasonably high conductivity and a high dielectric
permittivity. To improve the electrical properties of the particles two
methods can be used: (a) improve the bulk electrical properties, (b)
improve the surface electrical properties. Our studies suggest the latter
to be an exciting possibility. In Table i some design guidelines are given
for the host oil. In Tables 2, 3 and 4, some recommended design
parameters are given for ER suspensions activated by: (a) bulk
conduction of the particles, (b) dielectric particles with a conducting
surface film and (c) highly conducting particles with an "insulating
surface film", respectively. The recommendations in Tables 1-4 are
based on the theoretical and experimental considerations reviewed
above.
REFERENCES
1. W. M. Winslow, U.S. Patent 25 (1947) No.2417850.
2. W. M. Winslow, J. Appl. Phys., 20 (1949) 1137
3. C.A. Coulson, Electricity (Interscience Publishers, Inc., New York,1961)
4. A. P. Gast and C. F. Zukoski, Advanced Colloid and Interface Sci. 30
(1989) 153
5. A. F. Sprecher, Y. Chen and H. Conrad, Proc. 2nd Int. Conf. ER Fluids,
ed. J. D. Carlson, A. F. Sprecher and H. Conrad (Technomic, Lancaster,
1990), pp. 82-89
6. T.C. Halsey and W. Toor, Phys. Rev. Lett. 65 (1990) 2820
7. D.J. Klingenberg and C. F. Zukoski, Langmuir, 6 (1990) 15
8. Y. Chen, A. F. Sprecher and H. Conrad, J. Appl. Phys. 70 (1991) 6796
9. L.C. Davis, Appl. Phys. Lett., 60 (1992) 319
10. R. Tao, Q. Jiang, H. K. Sim, Physical Review E, 52 (1995) 2727.
11. R.A. Anderson, Proc. 3th Int. Conf. ER Fluids, ed. R. Tao and G. D. Roy
(World Scientific, Singapore,1992), pp.81-92
12. L. C. Davis, J. Appl. Phys., 72 (1992) 1334
13. Y. Chen, and H. Conrad, Developments in Non-Newtonian Flows, ed.
D. Siginer, W. Van Arsdale, M. Aitan and A. Alexandrou (ASME AMD,
New York, 1993) 175, pp.199-208.
14. H. Conrad, and Y. Chen, Progress in Electrorheology, ed. K. O.
Havelka and F. E. Filisko (Plenum Press, New York and London,1995),
pp.55-86.
15. Y. D. Kim and D. J. Klingenberg, Progress in Electrorheology, ed. K. O.
Havelka and F. E. Filisko (Plenum Press, New York, 1995), pp.l15-130
16. R. M. Webber, Progress in Electrorheology, ed. K. O. Havelka and F. E.
Filisko (Plenum Press, New York, 1995), pp.171-184
17. L. C. Davis, J. Appl. Phys. 73 (1993) 680.
18. A. Inoue, Proc. 2nd Int. Conf. ER Fluids, ed. J. D. Carlson, A. F.
Sprecher and H. Conrad (Technomic Publ. Co., Lancaster-Basel, 1990),
pp.176-183
19. H. Conrad, and A. F. Sprecher, J. Statistical Phys. 64 (1991) 1073
20. W. J. Wen and K. Q. Lu, Appl. Phys. Lett., 67 (1995) 2147
21. H. Conrad, Y. Shih and Y. Chen, Development in Electrorheological
Flows and Measurement Uncertainty, ed. D. Siginer, J. Kim, S. Sherif,
and H. Coleman (ASME, New York, 1994), FED-Vol.2051, AMD
Vol.190, pp.69-82
22. J. N. Foulc and P. Atten, Proc. 4th Int. Conf. Electrorheological Fluids,
ed. R. Tao and G.D. Roy (World Scientific, Singapore, 1994) pp.358-371
23. C. Boissy, J. N. Foulc and P. Atten, ed. R. Tao and G. D. Roy (World
Scientific, Singapore, 1994), pp.453-462
24. C. Boissy, P. Atten and J, N. Foulc, J. Intelligent Material System and
Structures, 7 (1996) 599
25. H. Conrad, Y. Chen and A. F. Sprecher, Proc. 2nd Int. Conf.
Electrorheological Fluids, eds. J. B. Carlson, A. F. Sprecher and H.
Conrad (Technomic, Lancaster, 1990), pp.252-264
773
26. J. N. Foulc, N. Felici and P. Atten, C. R. Acad. Sci. Paris. 314 II (1992)
1279.
27. N. Felici, J. N. Foulc and P. Atten, Proc. 4th Int. Conf.
Electrorheological Fluids, ed. R. Tao and G. D. Roy (World Scientific,
Singapore, 1994), pp.139-152
28. L. Onsager, J. Chem. Phys., 2 (1934) 599
29. X. Tang, C. W. Wu and H. Conrad, J. Rheology, 39 (1995) 1059
30. C. W. Wu and H. Conrad, J. Phys. D: Appl. Phys., 29 (1996) 3147.
31. P. Atten, K. Q. Zhu, C. Boissy and J. N. Foulc, J. Intelligent Material
System and Structures, 7 (1996) 573
32. L. C. Davis and J. M. Ginder, Progress in Electrorheology, ed. K. O.
Havelka and F. E. Filisko (Plenum, New York, 1995), pp.107-114.
33. L. C. Davis, J. Appl. Phys., 81 (1997) 1985
34. C. W. Wu and H. Conrad, J. Appl. Phys., 81 (1997) 383.
35. C. W. Wu and H. Conrad, J. Phys. D: Appl. Phys., (1997) in print.
36. C. W. Wu and H. Conrad, "Dielectric and conduction effects in non-ohmic
electrorheological fluids", Submitted to Phys. Rev. E, (1997).
37. C.W. Wu and H. Conrad, J. Appl. Phys., 81 (1997) 8057
38. T. J. Garino, D. Adolf and B. Hance, Proc. 3rd Int. Conf. ER Fluids, ed.
R. Tao (World Scientific, Singapore, 1992), pp.167-174
39. D.V. Miller, C. A. Randall, A. S. Bhalla, et al, Ferroelectrics Letters, 15
(1993) 141
40. M. J. Chrzan, and J. P. Coulter, Proc. 3rd Int. Conf. ER Fluids, ed. R.
Tao (World Scientific, Singapore, 1992), pp.175-191
41. M. Zahn, Electromagnetic Field Theory: A Problem Solving Approach
(John Wiley and Sons Press, New York, 1979)
42. C.W. Wu and H. Conrad, Submitted to J. Materials Research, (1997).
43. P. Atten, J. N. Foulc and H. Banqassmi, Progress in Electrorheology,
ed. K. O. Havelka and F. E. Filisko (Plenum Press, New York and
London, 1995), pp.231-244.
44. H. Block, and J. P. Kelly, Proc. 1st Int. Symp. ER Fluids, ed. H. Conrad,
A. F. Sprecher and J. D. Carlson (North Carolina State University
Publications, Raleigh, 1989), pp.l-26
45. C. Boissy, P. Atten and J. N. Foulc, J. Electrostatics, 35 (1995) 13
46. C. W. Wu and H. Conrad, J. Rheol., 41 (1997) 267
47. W. C. Yu, M. T. Shaw, X. Y. Huang and F. W. Harris, J. Poly. Sci., 32
(1994) 481.
48. Y. H. Shih and H. Conrad, Proc. 4th Int. Conf. Electro-Rheological Fluids,
ed. R. Tao and G. D. Roy (World Scientific, Singapore, 1994), pp.294-313
49. X. Tang, C. W. Wu and H. Conrad, J. Appl. Phys., 78 (1995) 4183
50. C. W. Wu, Y. Chen, X. Tang and H. Conrad, Int. J. Modern Phys. B,
10 (1996) 3315.
51. C. W. Wu, Y. Chen, X. Tang and H. Conrad, Int. J. Modern Phys., B,
10 (1996) 3327
52. Stangroom, J. E., Phys. Tech., 14 (1983) 290.
53. C. W. Wu and H. Conrad, "Electrical properties of electrorheological
particle clusters", To be published (1997)o
774
R H E O M E T R Y OF E L E C T R O R H E O L O G I C A L F L U I D S
1. R H E O L O G I C A L M E A S U R E M E N T S
1.1 Introduction
The purpose of this section on rheometry of ER fluids is to describe
methods that have been used for rheological characterization of ER fluids in
enough detail so that the experimentalist interested in studying ER fluids will
have a good start on the designs that have been tried, along with an
appreciation of their strong and weak poims. We will exclude engineering
tests in this section unless they result in true theological information.
Auxiliary characterization such as electrical and optical properties will be
covered briefly.
The inclination in rheometry is to adapt existing equipment to the task, and
with ER fluids this has been followed successfully. Most investigators have
taken commercial instruments and replaced existing fixtures with ones that are
electrically isolated from each other and from the rest of the instrument. Both
rotary and linear motions have been used successfully. Pressure-driven flows
have generally required custom-built equipment.
When working with ER fluids, two precautions are necessary: (1)
potentially lethal voltage sources are needed for most ER experiments and
safety interlocks thus become very important, and (2) high voltage connected
to even well-isolated fixtures can create stray currents to parts of the
instrument that should not be exposed to any currem. This may require
auxiliary grounding of parts leading from the fixtures to the bulk of the
instrument. For example, rather than counting on a ground through a motor
shaft or a load cell, a separate ground lead should be used [1]. Janocha and
776
Rech [2] have described some additional problems with high-frequency, high-
voltage fields.
Aside from protecting the experimentalist and the instrument, one should be
aware that the geometry of the fixtures, along with the dielectric properties of
all materials in the electric field influence the direction and strength of the
electric field. For example, if the classical parallel-plate geometry is used,
then the field near the edges of the plates will be concentrated near the corners
unless the sharp corners are rounded. The strength of the field will further be
influenced by the nature of the dielectric surrounding the plates (e.g., air vs.
fluid). At the electrical stresses typically required, air may break down [3].
According to Paschen's law, the breakdown voltage is a function of the
product of pressure x distance. At 1 ram, a field of 1 kV will break down air,
and fields of half this value will create corona discharge, adding to any
observed current. Thus successful designs will reduce the field before
encountering a fluid-air interface. Details concerning the design of cup-and-
bob viscometers have been described [4].
Suspensions are the most common ER fluids. Suspended particles in fluids
subjected to fields polarize, and then migrate together by attraction of the
electric dipoles. This process is indistinguishable to a more general process
called dielectrophoresis. Dielectrophoresis forces result when there is a
gradient in the electric field. The general relationship for dielectrophoretic
force on a sphere is:
F - 2~g o a3 ~2 - g l VE 2 (1)
g2 + 2 9 1
AV (2)
E
2a In da
_ d 2 (3)
o" 21 Pg / 2 a
AV (4)
E
H
and
o 21 = H p g (5)
where H| is the gap between the plates. Stipanovic and Schoonmaker [7]added
a Teflon block above the fluid (Figure 1), which increases the shear stress to
778
where W is the weight of the block, w is the width of the device and t is the
depth of the fluid beneath the block. Assumed here is that the width of the
block is the same as the width of the fluid, and there is no resistance to motion
contributed by the fluid between the block and the electrode, a good|
approximation because of the low electric field in that region. The Teflon
block increases the stress range and gives one the ability to develop a ~ 2~ vs.
E relationship over a| wide range of stresses without changing anything but the
weight of the Teflon block.
An alternative geometry for measurement of this kind is the annulus. Some
advantages of the annulus would be the fairly well-defined electrical field
combined with the ability to drive the fluid with gas pressure, which can be
easily varied during the experiment. Such arrangements diverge, however,
from the simplicity offered by the gravitational flow devices already described.
PTFE
Block
j ,, z/
. , , /,
2 m m ~
a movable plate could be allowed to float between two other fixed electrodes-
most investigators have found it convenient to arrange the movable plate as
either the ground or the high-voltage electrode. Linear motions have been
applied by a variety of methods, usually using a tensile testing machine.
J:D jf-~,
~ j Microscope
) ~ To Microscope Stage
t E>
Shear
Light
Another similar concept uses the weight of the plate itself by suspending the
top electrode on a pendulum and moving the bottom plate underneath this
swing (Figure 2) [8]. This arrangement has gives a nonlinear change between
the movement of the bottom plate and the stress, which is advantage in the
accurate determination of yield stress at low fields. Clearly if the bottom plate
is confined to a horizontal plane, the gap will change slightly; compensation
would be possible by mounting the bottom plate on another pendulum.
Still another sliding plate design uses axial annular drag flow between a
fixed, double cup and a light sleeve attached to the load cell mounted on the
cross head of a tensile testing machine (Figure 3) [9]. This geometry lends
itself to installation of optical paths in the field direction. Block et al. [10]
780
(+)
Teflon Insulator
Crosshead
T Crosshead Motion
II 'QI ,an,
! !
ner Electrode
,1-rr
-mm Gap (h)
ER
Io - 5 0 m m Fluid
uter Electrode
Figure 3. Axial annular drag flow device attached to a testing machine. From
Sprecher, Conrad and Carlson [9].
parallel plates can give a nearly uniform electrical field, the deformation field
varies spatially. As important is the variation of the contribution of the
material at various radii to the observed torque. The outcome is that the
outermost edges of the fluid contribute the most to the torque reading, but may
experience the most nonuniform electric field. This will lead to torque
readings which will be difficult to interpret in terms of the stress in the fluid by
the conventional methods [11]. In addition, particle migration by
dielectrophoresis will be a problem. The advantages of the parallel plate
geometry include ease of construction, small sample size, and the relative ease
of adding optical paths. The normal force can also be measured. Under static
conditions the attractive normal force F provides a measure of the dielectric
properties of the fluid. The relevant equation is:
F- 1 ~cR2~ 0~ f E 2
-~ (7)
where 'R is the radius of the plates, and g f is the effective permittivity of the
ER fluid. Figure 4 shows the application of Equation 2 for an experimental
ER fluid. Note that the normal force is quite linear in E 2 up to quite high
fields. The value of g f derived from this plot is close to the value obtained
with a time-domain dielectric instrument [12].
different bob geometries, including ones with conical bottoms and insulating
flat bottoms. The use of an insulating bottom removed the influence of the
contribution from the bottom area. While true with all ER geometries, these
authors found that stirring the fluid with the field off between each
measurement was essential to counteract the effects of dielectrophoretic
migration of the particles.
The Couette geometry is one of the best choices for the determination of
yield stress. Because applications of ER fluids may call for holding of parts or
fluids in position for a considerable time, the measurement of yield stress is of
importance to the technology. The subject of yield stress itself, irrespective of
the fluid, has generated lively debate; the reader is referred to, for example,
Astarita [29], Bennington et al. [30], Bonnecaze and Brady [31], Harnett and
Hu [32], Nguyen and Boger [28], Schurz [33], and Yoshimura et al. [18] to
sample the arguments. For ER fluids, most investigators favor the application
of a steadily increasing stress to the solidified ER fluid, finding the value that
1600
4OO
I I I
0.0 5.0 10.0 15.0 20.0 25.0
(E, kV/mm} 2
%
0
~ J
-=-V
Figure 5. Pressure-driven, annular axial flow device for use with ER fluids
[37]. The annular gap is between parts A and B. This material has been
reproduced from the Proceedings of the Institution of Mechanical Engineers,
Part C, Journal of Mechanical Engineering Science, 16 1974 by J. Arguelles,
H. R. Martin and R. J. Pick by permission of the Council of the Institution of
Mechanical Engineers.
where P* is the complex pressure, H is the slit height and L is the length of the
slit.
1.60therSound Propagation
Korobko and Chernobai [40] depict a chamber in which a sending and
receiving transducer are arranged to propagate sound parallel to the electric
field. Both velocity and attenuation could be measured, although only velocity
measurements were reported. Fields ranged up to 2 kV/mm. The sound
velocity was linearly proportional to the field and did not show a threshold,
even at particle volume fractions as low as 2 %.
2. E L E C T R I C A L MEASUREMENTS
3. O P T I C A L P R O P E R T I E S
I
0
I Q
J
I
/
Delrinbase I
from the output of the accelerometer, whereas the current to the vibrator is
proportional to the load. The light passes parallel to the field, which is applied
to the suspension using tin-indium oxide coatings on the glass plates. The gap
between the two plates is kept small, e.g., 100-200 ~tm.
1 X o cos (~t - 6)
E , ; , ~ / / /i/
I
~ / 1
///Glass Plates
l .
. . . . .
. . .
/ ,/ //,
/
," ,, ,~
~_/ , i~///
Accelerometer ~
Figure 7. Design for observing the structure of ER fluids along the field
direction while subjecting the fluid to oscillatory deformation. From Bossis et
al. [6]
789
i i 11 Polarizer
Wave Plate
E-field ~ FlowCell
-I CPU I I I PMT
I ldc ~r4co
iI
LPF
XY A2
A1 -
Laser
"I - - ~
<
/ /
f
\
\
L1
L2
4. SUMMARY
Sample Box
HIGH
/ 0 VOLTAGE
1--.
IR Absorber
I l IR Filter
532nm IF
rY
w
< PMT
._1
0
<
i>-
BOXCAR
COMPUTER
REFERENCES
24. K. Smith and G. Fuller, J. Colloid Interface Sci., 155, (1993) 183.
25. M. Jordan, A. Schwendt, D. A. Hill, S. Burton, and N. Makris, J.
Rheol. 41 (1997) 75.
26. J. E. Martin and J. Odinek, J. Rheol. 39 (1995) 995.
27. K. Tanaka, R. Akiyama, and K. Takada, Polym. J., 28 (1996) 419.
28. Q. D. Nguyen and D. V. Boger, Rheol. Acta, 26 (1987) 508.
29. G. Astarita, J. Rheol., 34 (1990) 275.
30. C. P. J. Bennington. R. J Kerekes, and J. R Grace, Can. J. Chem. Eng.,
68 (1990) 748.
31. R. T. Bonnecaze and J. F. Brady, J. Rheol., 36 (1992) 73.
32. J. P. Harnett and R. Y. Z. Hu, J. Rheol., 33 (1989) 671.
33. J. Schurz, Rheol. Acta, 29 (1990) 170.
34. M. Nakano, R. Aizawa, and Y. Asako, paper presented at the 5th
International Conference on ER Fluids, Sheffield, UK, July, 1995.
35. M. Nakano and T. Yonekawa, in R. Tao and G. D. Roy (eds.)
Electrorheological Fluids, Mechanism, Properties, Technology and
Applications, World Scientific, Singapore, 1994, pp. 477-489.
36. D. Brooks, Int. J. Modern Phys. B, 6 (1992) 2705.
37. J. Arguelles, H. R. Martin and R. J. Pick, J. Mech. Eng. Sci. 16 (1974)
232.
38. K. D. Weiss and J. D. Carlson, in R. Tao (ed.), Proc. Int. Conf.
Electrorheol. Fluids, 1991, World Scientific, Singapore,1992, pp. 264-
279.
39. G. B. Thurston and E. B. Gaertner, J. Rheol. 35 (1991) 1327.
40. E. V. Korobko and I. A. Chernobai, J. Eng. Phys. 48 (1985) 153.
41. Y. Kim, and D. Klingenberg, in K. O. Havelka and F. E. Filisko (eds.),
Progress in Electrorheology, Plenum Press, New York, 1995. pp. 115-
130.
42. P. Placke, R. Richert, and E. W. Fischer, Colloid Polym. Sci. 273 (1995)
848.
43. E. Lemaire, G. Bossis, Y. Grasselli, and A. Meunier, in C. Gallegos, A.
Guerrero, J. Mufioz and M. Berjano (eds.), Progress and Trends in
Rheology IV, Verlag, Darmstadt, 1994, pp. 140-142.
44. G. G. Fuller, Optical Rheometry of Complex Fluids, Oxford University
Press, New York, 1995.
45. J. M. Ginder, Phys. Rev. E, 47 (1993) 3418.
795
J. w. Hoyt
1.1 Introduction
Drag reduction in the turbulent flow of solutions of polymers or
surfactants has been studied for almost 50 years, beginning with the
discoveries of Toms [1] and Mysels [2]. The scientific and technical aspects
of these non-Newtonian fluid flows are still under active study, since the
underlying mechanisms involved in these flow effects, like those of
turbulence itself, are only dimly understood.
Nevertheless, a great deal of empirical information has been obtained,
outlined in several recent books: Sellin and Moses [3]; Gyr and
Bewersdorff [4]; and Choi, et al [5].
There are also numerous reviews: Hoyt [6]; Virk [7]; Shenoy [8]; and
Kulicke, et al [9] among many others. A very comprehensive bibliography
listing over 4,900 references has recently appeared: Nadolink and Haigh
[10]. Conference proceedings are another excellent source of current
information: the most recent being sponsored by the American Society of
Mechanical Engineers (Hoyt, et al, eds., [11]).
where AP~ is the pressure drop per unit length in a pipe flowing the solvent
alone and APp is the pressure drop for the same flow rate, using additives.
Another commonly found term is the "engineering friction factor", ~,,
defined as:
1
= [D aP] / [Tp V2]
where D is the pipe diameter and p is the fluid density. Friction factor -
Reynolds number plots are extremely useful in demonstrating the presence
(or absence) of drag reduction, since for a Newtonian fluid, the
relationship was deduced by Karman and Prandtl. A convenient
computing formula for the Karman-Prandtl (pure solvent) value is:
799
2. OIL-PIPELINE FRICTION R E D U C T I O N
2.1 Introduction
The use of high-polymer additives to reduce the pipeline friction of
crude-oil and petroleum products has been a spectacular success, and
currently forms an important part of industrial petroleum transport
technology. Several factors account for this success. First, although the
drag-reducing polymers are not inexpensive, their use in parts-per-million
quantities to greatly increase the flow of a very high-value product is often
much more economical than the capital and operating expense of
installing additional pumping capacity. Secondly, the additive can be
applied with relatively minor portable equipment, which can be easily
removed in case flow augmentation is no longer needed. Another factor is
that there is no need to remove or treat the additive-containing product in
any special way - the additives disappear in the refining process, or are
innocuous in other pipeline products. Finally, of importance in crude-oil
transport in cold climates, the greatly reduced heat transfer of additive-
containing fluids helps keep the product viscosity at a lower level.
These advantages have led to installations of drag-reducing additives
at more than 80 locations worldwide (Motier, et al, [14]), since the initial
trials in the Trans Alaskan Pipeline in 1979. Steady improvements in
polymer properties have accelerated this use; Motier, et al, show that
currently only about 1/14 the quantity of polymer (compared with the 1979
additive) is needed for the same amount of friction reduction.
2.3 Applications
The first and probably the major success story in polymer drag
reduction was (and is) the Trans Alaskan Pipeline System (TAPS). The
highly competitive and proprietary nature of the petroleum industry has
meant that very little detail regarding applications is available in the open
literature, but Burger, et al [16] have given some actual test data on
flowing Alaskan crude through 2.66, 5.25, 33.4, and the TAPS 119.4 cm dia
pipes. From these d a t a , a rather convoluted scheme based on estimated
molecular parameters was used to predict the TAPS performance from
laboratory data on the smaller pipe sizes. Although the scheme worked
well enough to warrant installation of drag reduction in the TAPS
pipeline, the much simpler method described later in this Chapter, based
on hydrodynamics, leads to even better predictions as shown in Figure 1.
From Berretz, et al, [17]; Beaty, et al, [18]; Hom, et al, [19]; and Motier,
et al [14], we learn that the initial success of drag reduction lead to the
cancellation of plans to build two additional pumping stations on the TAPS
pipeline. The 1.45 million barrels per day pumping capacity of the pipeline
was raised to 2.1 mbpd by polymer injection. Above 50% drag reduction in
the 1287 km long pipeline is achieved with 28 ppm or less polymer. The
logistics of providing some 95,000 liters per day of 10% polymer solution in
kerosene to remote locations in Alaska are impressive.
802
0.100 II II I _ -- IIII I I
.<
d
o
.w
o
4-1
0.010
o
-r4
4J
O
h~
0.002 . ,I . I . . . . . . .
Reynolds number
Figure 1. Pipe-flow data for Alaska crude oil with 10 ppm drag-reducing
additive. Actual data for 3 pipe sizes, with scaling from the two smaller
(2.664 and 5.25 cm dia) to the full-scale (119.4 cm dia) pipeline. Adapted
from Burger, et al [16] tabulated data. I"1 2.664 cm pipe dia; O 5.250 cm dia;
A 119.4 cm dia; E1'119.4 cm prediction from 2.664 cm dia data; (~ 119.4 cm
prediction from 5.250 cm dia data; ---Karman-Prandtl friction line for
Newtonian fluids.
Similar formulations have now been applied to other crude oil pipelines
(Beaty, et al, [18,20]; Lester, [21]; Motier and Prilutski, [22]; Motier, et al,
[14], as a apparently viable commercial technique. The low installation
cost, and impressive flow increase performance, together with the "use
only when needed" feature has lead to increased acceptance in crude oil
production, replacing expensive fixed assets which may have only a short
usage requirement.
Polymer additives have been used with great success in petroleum
product pipelines. Carradine, et al, [23]; Motier, et al, [24]; Muth, et al,
[25-27]; and Motier and Carrier [15] describe applications to diesel oil,
803
gasoline, and natural gas liquids pipelines. Drag reductions of over 40%
appear to be routine, and this offers the possibility of eliminating marginal
pumping stations.
2.4 S u m m a r y
The use of high-polymer additives to enhance flow in petroleum pipe
lines has been a great commercial success. Additive effectiveness has been
improved so that only a few parts-per-million are required to give friction
reductions of 50% or more. The economics of polymer addition seem to be
very favorable in the pipeline transport of high value products such as
petroleum, reducing the need for pumpiv.g stations as well as increasing
throughput.
3.1 Introduction
Many regions are served with district-wide heating or cooling systems,
which, in the case of heating for example, may involve transporting hot
fluid over considerable distances. The heat source is usually lower-grade
energy from electrical generating stations or industrial operations which
would otherwise be rejected to the environment. Offsetting this low-cost
source is the energy requirement to pump the hot fluid, typically several
kilometers or more, to heat exchangers servhag domestic needs. The use of
surfactants as drag reducers to reduce this substantial pumping
requirement is under intensive study. Mound 7% of the heating
requirement in Germany, 35% in Sweden, and as much as 40% in Denmark
and Finland is centrally supplied, while district heating serves six hundred
thousand households in Seoul, Korea. Hence the opportunities for energy
saving are plentiful. Moreover, in new designs, smaller transmission
pipes might be used, if drag reduction by surfactants achieves acceptance.
3.2 Surfactants - Basics
Surfactants are a broad class of surface-tension reducing chemicals,
characterized by having both a hydrophilic (watersoluble) and a
hydrophobic (water-repelling), often oil-soluble, component in the same
molecule. In solution, depending on the detailed chemistry, surfactants
804
may be ionic or non-ionic. The anionic group forms the basis of household
detergents, which are produced in enormous quantifies world-wide.
Cationic and non-ionic surfactants are less well-known, but readily
available industrial chemicals.
Thirty years ago, Savins [28] showed that some anionic surfactants
could greatly reduce the turbulent pipe friction as compared with the
water in which they were dissolved. At higher shear stresses, the drag
reduction disappeared and the friction was identical to water.
Remarkably, when the shear stress was lowered, the solutions were again
found to be drag-reducing. Many surfactants of various ionic classes have
now been found to be friction-reducing. All studies show that pipe friction
reductions of up to 80% can be observed, but at higher shear stresses, the
drag reduction effect abruptly disappears, promptly reappearing when the
shear stress is lowered.
10
q ,mPa
m,
Y. ! s e c
0.1 !
I | ,i J |1
10 10 10 10 4
Figure 2. Viscosity versus wall shear rate for 0.1% solution of C~6 TASal a t
35~ adapted from Ohlendorf, et al [29].
Table 1
Drag-Reducing Surfactants
Cationic
Zwitterionic
0.080 I I ! I
I
0.040
X Water
o
~<
0.020
0
o
U.
r
0
o
Symbol
U.
A 0.090 in. - ~ ?
0.008
-
o 0.500 in.
0.004
10 3 10 4 10 5
Reynolds Number
[c,a
I I I iG jlll l ji . . . . it- iii i _ i i _
7",," N - - CH 3 Cl
I
CH 3
C
o6
u
- i
0 SYMBOL T ( o C) iL
i i
o .30
+ 40
Z 50
o 70
9 80
X 90
o 1 O0 D -- 0.243 iN.
6
f~
I 10" 10 5 10 a
Reynoi(:J$ Number
Arcluod 18/50 -~- NoSol (2000 / 2000 IDIDm)
DR
[%]
80-
L
6O
z.O i-
20
,,...,
3.8 Summary
The use of surfactants in district and building heating and cooling
systems is an emerging technology with great promise for significant
energy savings. While there seems no doubt that the pumping-power
requirements of such systems can be greatly reduced by the use of
surfactants, appropriate formulations to avoid environmental concerns
and equipment designs to enhance heat transfer are important next steps
in securing commercial acceptance.
4. SCALE-UP
24 ~ -
22
20 . - -
18 ---
16 . . . .
14 --
AB
12
/o
12 p p m I
10 ---
' J-
2 r
i1~
6 ppm
u+ =Alny
815
where A and B are constants having the approximate values of 2.5 and 5.0,
and AB is a function of the drag-reducing substance, its concentration, pipe
roughness, etc. The problem has been that AB is a highly non-linear (and
non-predictable) function which must be determined by experiment.
Figure 6 shows a typical result.
An assumption made in most scale-up techniques is that the value of AB
is the same for equal values of shear stress (or friction velocity, u*) in both
small and large pipes. Based on this assumption, Hoyt and Sellin [60]
introduced a relatively simple scale-up calculation method which views
the drag reduction as an "negative" analogy to the familiar pipe roughness
employed in Newtonian fluid flow. An even more recent advance has
obviated the need for such an analogy.
Anderson, et al, [61] provide data from a large-scale experiment which
demonstrates conclusively that, for equal values of shear stress, AB has the
same value in both small and large pipes. Figure 7 is an example of
measurements of AB plotted against the friction velocity (u*), for pipes
differing in diameter by a factor of 6. The same polymer solution was
delivered to the test pipes and the measurements made simultaneously,
side-by-side, so that the only difference was pipe size. Similar results were
obtained over a wide range of polymer concentrations. Scaling using the
invariance of the AB-u* relationship proved to be very precise. Hence we
can greatly simplify the scaling relations.
Extending Prandtl's logarithmic velocity distribution law by including
AB, we find that:
where X is the engineering friction factor for flow in pipes and Re is the
Reynolds number VD/v. Solving for AB, and letting subscript I indicate
the small pipe, and 2 the larger,
AB~ = q8[1/q~-2 log {Req~/2.51 } ]
and
5O
e D,4.IS'
40 0 0.,1~6"
30
m
g
<1
Oo
20
10
o
O , L , I . ,' 9 ! , I 9 1~ J . l , , , l ~ l ! ] , t , 1 . ~ , ! 9 I ~ I 9 J . [ . l . l . t , l '
U,-ftJs
Figure 7. Delta B as a function of u* for p o l y a c r y l a m i d e p o l y m e r solution
in two different size pipes. The m e a s u r e m e n t s were m a d e simultaneously,
side-by-side, using 33 p p m solution from the same reservoir.
Equating AB's and noting that Req~, - u*Dq8/v, where D is the pipe
diameter:
Hence
0
U o
0 o
c 10-2 0
0
.--
u
+ _
@@
@ 0=6.15" Meosured @
0 D=l.026"bteasured
0 0=6.15"Predicted
, : , t, t,l,t,l ! 1 t t t] , ', , t ,,,I,~,1 ! 1 ! I II t , t .,,!,~,
ReynoldsNumber
Figure 8. Friction factor as a function of Reynolds number for the data of
Figure 7, together with scaling predictions for the 6.15 inch dia pipe flow,
based on the data from the 1.026 pipe. Black dots are the actual test data
for 6.15 inch dia.
been scaled up to 6.15 inch diameter and compared with the four available
test points. Similar agreement of scaling and actual test data was
obtained for five other polymer concentrations, which suggests that the
procedure is reliable, as well as being grounded in fundamental
engineering relations. Astarita will be surprised!
The above scaling procedures work very well if the smaller pipe is 1/2
inch (13 mm) or more in diameter. As shown in Hoyt and Sel!in [60], the
velocity profile in pipes of lesser diameter is significantly different from
that of larger pipes, thus voiding similarity scaling. If only very small
diameter pipe-flow data are available, the empirical approach of Savins
and Seyer [58] has given useful results. Savins and Seyer replace the
actual shear stress of the polymer solution flow with that of the pure
solvent. In effect, this modifies the velocity profile to approximate that of
the larger-scale polymer pipe. If data from very small pipes are the only
available source of scaling information, the Savins and Sayer scheme
probably remains the only alternative. It has been used with considerable
success in off pipelines (Lester, [62]).
5. FLOW TRACERS
5.1 Introduction
Many techniques with varying levels of sophistication have been
proposed as methods of showing the flow path, vorficity, or velocities of
turbulent flow in boundary layers or around various objects. The simplest
idea is a dye streak, but dyes suffer from very rapid dissipation and are
almost useless in turbulent flow. Hence very elaborate techniques, such as
Particle Image Velocimetry, have been brought forward to provide
turbulent flow information. However, the equipment cost of the lasers,
shutters, cameras, etc., involved in these methods is beyond the reach of
many investigators.
By incorporating non-Newtonian properties into a dye-streak, a highly
effective flow tracer has been developed. Such a tracer is of great interest
since it allows one to follow turbulent and separated flows currently
inaccessible with simple methods.
819
2% C16TASal 500 ml
1/2% PEO 250 ml
Tap Water 1000 ml
White Paint 5 ml
DEDICATION
ACKNOWLEDGMENTS
The support of the University of Bristol and the U.S. National Science
Foundation in preparing this chapter is very greatly appreciated. The
confidence in this work expressed by Dr. Michael Roco of the N SF,
through Grant No. CTS-9508409, is gratefully acknowledged.
REFERENCES
2. K.J. Mysels, Flow of Thickened Fluids. U.S. Patent 2 492 173 (1949).
3. R.H.J. Sellin and R.T. Moses (eds.), Drag Reduction in Fluid Flows,
Ellis Horwood, Chichester, 1989.
4. A. Gyr and H.-W. Bewersdorff, Drag Reduction of Turbulent Flows by
Additives, Klewer Academic, Netherlands, 1995.
5. K.-S. Choi, K.K. Prasad, and T.V. Truong (eds.), Emerging
Techniques in Drag Reduction, IMechE, London, 1996.
6. J.W. Hoyt, Trans ASME, J. Basic Engrg., 94 (1972) 258.
7. P.S. Virk, AICHE Journal, 21 (1975) 625.
8. A.V. Shenoy, Colloid Polymer Sci., 262 (1984) 319.
9. W.-M. Kulicke, M. Kotter, and H. Grager, in Advances in Polymer
Science 89, Springer-Verlag, Berlin, (1989) 1.
10. R.H. Nadolink and W.W. Haigh, Applied Mechanics Reviews, 48
(1995) 351.
11. J.W. Hoyt, et al (eds.), Symposium on Turbulence Modification and
Drag Reduction, ASME, FED-Vol.237, New York, 1996.
12. J.G. Savins, Soc. Petrol. Eng. Journal, 4 (1964)203.
13. P.S. Virk, H.S. Mickley, and K.A. Smith, Trans ASME, J. Applied
Mechanics, 37 (1970) 488.
14. J.F. Motier, L.-C. Chou, and N. Kommareddi, in Proc. Symposium on
Turbulence Modification and Drag Reduction, ASME FED-Vol.237
(1996) 229.
15. J.F. Motier and A.M. Carrier, in Drag Reduction in Fluid Flows, Ellis
Horwood, Chichester (1989) 197.
16. E.D. Burger, L.G. Chorn, and T.K. Perkins, Journal of Rheology, 25
(1980) 603.
17. M. Berretz, J.G. Dopper, G.L. Horton, and G.J. Husen, Pipeline and
Gas Journal (September 1982).
18. W.R. Beaty, R.L. Johnston, R.L. Kramer, L.G. Wamock, and G.R.
Wheeler, in Third International Conf. on Drag Reduction, Bristol
University (1984) F.1.
19. A.F. Horn, J.F. Motier, and W.R. Munk, in Drag Reduction in Fluid
Flows, Ellis Horwood, Chichester (1989) 255.
20. W.R. Beaty, R.L. Johnston, R.L. Kramer, L.G. Warnock, and G.R.
Wheeler, Oil & Gas Journal, 82 (Aug. 13, 1984) 71.
21. C.B. Lester, Oil & Gas Journal, 83, (1985) 51; 76; 107; 116.
824
D. W. Bousfield and A. Co
1. INTRODUCTION
Paper and paperboard are often coated to improve the appearance of the sheet
and the quality of the print of the final product. Products such as magazines,
catalogs, labels, and consumer packaging are often coated. The coating is
normally composed of a pigment such as kaolin or calcium carbonate, a latex
binder, and a soluble binder such as starch. Coatings are formulated at high solids
content in order to minimize drying requirements and to improve quality. The
coating must be mixed, pumped, recirculated, and metered onto the moving paper
web. The final metering or coating operation is the critical step in the process; the
coated layer must be free from defects and near a target coat weight. The
rheology of the coating is an important issue in the control, design, and operation
of the coating process.
A roll applicator followed by a blade on the same roll is a common method to
apply coating onto the web. In the last 15 years, the short dwell applicator system
became popular; coating is pumped to a pond in front of the blade and the blade
meters on the final coating amount as depicted in Figure 1. The short dwell
applicator has one advantage short contact time and, consequently, minimal
water penetration into the web. Uses of fountain or jet applicators and "metered
size presses" are recent trends to apply coatings. High coat weights are normally
obtained by a rod metering step followed by an air knife component. However,
the blade metering element is a common last step to control coat weight and is the
focus of this chapter and much of recent research.
There are a number of unique aspects of paper coating that make this operation
complex. The web is rough, porous, and absorbent. In addition, it changes its
physical properties upon contact with water. The coating step is often
accomplished at speeds higher than 15 m/s. The final coating layer thickness
ranges from 7 - 30 ktm. The web is compressible, along with the rubber backing
828
~'\"\,\
Coated web
T
Excess to pond
Figm'e 1. Schematic of paper coating operation with a short dwell coater. The
region around the blade tip is enlarged to show the details of the blade tip.
Coating is applied to the web in the pond. The blade controls the final amount
of coating applied to the web.
that supports the blade loading. The blade is slightly flexible, it is mounted and
loaded in various ways, and it wears during operation. All of these factors,
including the high speeds, cause paper coating to be a complex operation.
Economic driving forces cause the coating to be applied at high solids.
Application at high solids reduces energy costs for drying and is known to
produce a better quality product in terms of light scattering and printing
properties, as reported by Van Gilder et al. [1 ]. Coating of high solids gives the
paper less chance to roughen upon contact with water and the coating layer does
not sink into the paper web. However, high solids content naturally brings
challenging rheological problems. There is a trade-off between solids and
operational speeds. Figure 2 shows data from Taylor [2] that is typical in the
industry; as the coating solids increase, the maximum speed for defect-flee
operation decreases. In order to increase the speed of a specific coating line, the
solids content of the coating often needs to be reduced. This reduction increases
drying costs and lowers quality of the product. Some pigments have different
"runnability" limits. Ground calcium carbonate pigments can often be coated at
arotmd 70% solids, whereas delaminated kaolin clays need to be coated at around
829
16 9 , , I 9 9 . I 9 . 9 I 9 I I I 9 9 9 I . , 9
-~ 14-
E
v 12-
.1
(J
1
o 10-
>
.o 8.
E 6.
.E 4. o
x
0
~ 2-
0 9 " " I " " ' I " " ' I " " " I " " " I " ' "
Figure 2. The relationship between coating solids and the maximum web
velocity. The open circles are data from Taylor [2]. The line is a model
calculation from Bousfield [3].
55% solids. In any case, there is a constant incentive to operate at high solids and
not to have operational difficulties.
The operational difficulties or "runnability" problems vary widely in the
industry, but common problems are the scratches, streaks, or skips in the coating
layer and the buildup of coating on the blade. The buildup on the blade in itself is
not a problem, but when the buildup breaks off the blade and ends up on the web,
problems in the calendering and printing operations develop. The blade buildups
are ot~en called "whiskers", "stalagmites", "weeps", or "spits", depending on the
operator and the nature of the building (dry or wet). Other operational problems
are related to coat weight control, both in the machine and cross-machine
directions. Another common problem is web breaks; these cause a loss of
production and correlate to high blade forces. Many of these problems are related
to rheology of the coating.
Newtonian fluids, it is used extensively in the coating industry because of its ease
of use and its value as a tool for quality control. However, to understand the
effects of the components of a coating formulation on its rheological
characteristics and to relate these rheological characteristics to its performance in
a coating operation, numerous researchers have made use of various standard
rheological tests. These include steady-state measurements in shear flow,
measurements in small-amplitude oscillatory shear flow, and transient
measurements in shear flow.
Of these measurements, viscosity measurement in steady-state shear flow is the
most commonly used. Examples of recent works are Triantafillopoulos and
Grankvist [4], Carreau and Lavoie [5], Purkayastha and Oja [6], Ghosh et al. [7],
and Ghosh [8]. To obtain the viscosity function over a wide range of shear rates,
one usually has to utilize several viscometers: the cone-and-plate system for low
shear rates, the concentric cylinders configuration for medium to high shear rates,
and the capillary type for high shear rates. An important experimental
consideration is that there is sufficient time for the coating to reach its equilibrium
configuration at a given shear rate. Also of interest is the yield stress of the
coating colors. Its importance in the actual coating operation is minimal since the
operation is performed at very high shear rates. However, it may play an
important role in the recovery stage after the coating application.
The behavior of the viscosity versus shear rate curve depends on the
components of the coating colors. Figure 3 shows the viscosity curves of a starch-
containing formulation and a formulation with latex particles (Roper and Attal
[9]). The curve of the starch-containing formulation exhibits a power-law shear-
thinning region and a region of almost constant viscosity at high shear rates. On
the other hand, the formulation with latex particles shows a region with shear-
thickening or dilatant behavior. Beyond the power-law shear-thinning region, the
viscosity rises sharply with increasing shear rate and then decreases slightly at
higher shear rates. Roper and Attal [9] indicated that the dilatant behavior
depended on the solids level and the latex particle size; the extent of dilatant
behavior was increased with higher solid levels and larger latex particle size.
Aside from the solid levels and the size and shape of solid particles, the
polymer additives dissolved in the suspending medium also have considerable
effects on the rheological behavior of the coating suspension. Examples are
shown in Figure 4, which depicts the viscosity curves of Carreau and Lavoie [5]
for kaolin suspensions with three different concentration levels of CMC (carboxy
methyl cellulose). They attributed the large increase in viscosity to the
interactions between kaolin and CMC, since the viscosity of the CMC solution
itself did not change significantly at these concentration levels.
831
101 I I , I I I I I
~, 1 0 o.
t~
n
(/)
O
o
.~-
> 10-1.. m
1 0 .2 I I ~) I I I I
10 -~ 10 0 101 1 2 10 3 10 4 10 s 10 s 1 7
Shear Rate (l/s)
10- [] 11'
2
A 10-
w,
n 1 []
-~- 10-
0
10-
10 "1.
-2
10 ; I I ;0 01 ;2 ;3
1 -3 10-2 10-1 1 1 1 1
7, to (1Is)
Figure 4. Effect of CMC content on the viscosity and the dynamic viscosity for
44% vol. Kaolin suspensions. Data are from Carreau and Lavoie [5].
832
Also shown on Figure 4 are the dynamic viscosity versus frequency curves of
the suspensions. These are obtained from small-amplitude oscillatory shear
experiments. The dynamic viscosity rt'((o) is determined from the componem of
the shear stress that is in-phase with the rate of deformation and rt"(oJ), from the
component that is out-of-phase. Figure 4 shows that the viscosity curves and the
dynamic viscosity curves coincide, that is, rl(8)--r/'((o~,:~. This is analogous to the
Cox-Merz rule for polymer solutions or melts, which predicts that the magnitude
of the complex viscosity (r rl * ((o)I-x/rt;' ((o)+ rt"((o)) is equal to the viscosity at
corresponding values of frequency and shear rates. This empirical analogy can be
useful in predicting viscosity data when only linear viscoelastic data are available.
Alternately, linear viscoelastic data can be expressed in terms of the storage
modulus G' (-rl'a, ) and the loss modulus G" (-rt'a,). Figure 5 shows the storage
modulus of kaolin suspensions at various concentration levels of CMC, as
reported by Carreau and Lavoie [5]. As in the viscosity curves, a small
concentration level of CMC increases the storage modulus drastically, again due
to the interaction between kaloin and CMC. Another observation is that the
storage modulus approaches a constant value at low frequencies, a behavior that
is more like a viscoelastic solid. Similar behavior was also observed for the
coating formulations considered recently by Ghosh [8].
3
10 a , ... , I ,
1%CMC
2
10-
A
n
0.25 % CMC
1
10-
I
~00---0-0-(~ 0 ~ ' 0 ~ ~ ~ CMc
!
o
10 j
10" 10 "1 1() ~ 101 10'
(l/s)
Figure 5. Effect of CMC content on the storage modulus for 44% vol. Kaolin
suspensions. Data are from Carreau and Lavoie [5].
833
G'
4O
100"
(.9
3O ~'
50
20
Figure 6. The dependence of the storage and loss moduli and phase angle on
the frequency for a clay-based coating color containing 1.25 part of CMC per
100 parts of clay. Data are from Fadat et al. [10].
Figure 6 shows the linear viscoelastic data of Fadat et al. [10] for a clay-based
coating color with a different grade of CMC. Here the behavior of the storage
modulus is more like that of a viscoelastic liquid. The reduction of the phase
angle 5 (-tan -~G"/G') with increasing frequencies indicates that the suspensions
becomes more solid-like at higher frequencies. These behaviors are different from
those exhibited by the coating suspensions studied by Carreau and Lavoie [5] and
Ghosh [8].
Transient shear-flow experiments have been used to elucidate the characteristic
times of structure formation or breakup in coating suspensions. A common
industrial practice is to generate a hysterisis loop from shear stress measurements
completed over a strain-rate sweep for a finite time interval. Although this type of
measurement is valuable for quality control, it is of little use in characterizing the
structure formation or breakup in the coating suspension. More useful transient
experiments are the stress growth measurement upon the inception of steady
shear flow, as described by Ghosh et al. [7] and Ghosh [8], and the stress
relaxation measurement after a sudden sheafing displacement, as reported by
Young and Fu [11] and Ghosh [8]. These experiments were able to yield
estimated characteristic times of the coating suspensions studied.
834
Normal stress measurements at very high shear rates were conducted by Windle
ad Beazley [12] using a jet-thrust technique for starch-based coatings. Calculation
of the first normal stress coefficient from their normal stress data gives very low
values, indicating that normal stress effects may not be significant at the high
shear rates encountered in coating operation. This is corroborated by
Triantafillopoulos and Grankvist [4], which did not observe any jet swell in their
high-shear capillary flow experiments for several coating formulations.
Due to the converging-diverging geometry in the coating operation, the flow is
both shearing and extensional. Elongational viscosity may therefore play a
significant role. Measurements of elongational viscosity at the high deformation
rates experienced in a coating operation have not yet been reported. However,
Carreau and Lavoie [5] claimed that they did not observe any significant elastic
or extensional effect in the results from their lubrication equipment at high
deformation rates.
numerical techniques. In the limit of small particle Reynolds number, the particle
velocities can be found through matrix techniques; the velocities must cause the
net force on every particle to be zero.
In a blade coating geometry, the clearance between the web and the blade can
be in the order of 15 ~xn. Bousfield [22] showed that structures of particles will
form in shear fields and that these structures can span the gap between the web
and the blade. This mechanism is the same as those reported by Brady and Bossis
[14] and by Boersma et al. [19]. When a cluster of particles forms in this
geometry, large forces are transmitted between the web and the blade. This
mechanism could be responsible for blade wear and blade deposits, if these
structures exit the blade. Figure 7 depicts this situation: particles are forced closer
together as the fast moving particles must past the slow moving particles near the
blade. If the electrostatic or steric repulsive forces are not significant to keep the
particles separated, particle clusters can span the gap between the blade and the
web.
A potential mechanism for the viscoelastic response of a highly dispersed
suspension was modeled by Toivakka et al. [23] with a Stokesian dynamics
calculation. When electrostatic or steric forces keep the suspended particles well
separated, an energy minimum is obtained by an ordered packing of the particles.
Any small flow field will disrupt the particle configuration and will push the
particles closer together in some regions, as demonstrated in Figure 8. If the
motion is slight, as in a small-amplitude oscillatory experiment, the suspension
Figure 7. Schematic of the results from a particle motion model showing the
clustering of pigments between the blade surface and the web at high shear
rates. This structure can transmit large forces between the web and the blade.
836
Static i| -i =v
I II
Figure 8. Slight motion caused by shear will bring some particles closer
together. This compression of the electrostatic or steric repulsive forces can
store energy and lead to a viscoelastic response of the suspension, even when
dissolved polymers are not present.
can store energy by the compression of the electrostatic or steric forces. This
storage of energy leads to the possible elastic nature of a suspension, even when
dissolved polymers are not present in the system. Example of this type of
experimental system was reported by Fadat et al. [10] for coating suspensions. If
the deformation is too large, particles move away from the static position and a
non-linear viscoelastic result is obtained.
The position of different sized pigments and particles in the coating layer has
been predicted by Stokesian dynamics calculations. Chang and Powell [17] show
how small particles can disrupt the formation of clusters and, thereby, reduce the
837
shear viscosity. Toivakka and Eklund [18] confirm this mechanism and show how
small particles can end up closer to the blade surface during shear. Fine particles
are able to be closer to the solid boundaries because of their size. In addition,
when particles are exposed to a flow field, larger particles must move faster than
the finer particles near the walls. This velocity difference causes the larger
particles to push the smaller particles even closer to the walls. After a number of
interactions, the larger particles migrate away from the walls. This would create a
separation of particles according to size, with the finer particles near the solid
boundaries. The coating layer could have gradients of particles from its surface to
the bulk. This mechanism is illustrated in Figure 9. Bousfield et al. [24] show that
the free surface after the blade may cause a similar separation of particles based
on size, with the smaller particles being located at the top surface. These results
may explain the high concentration of latex binder at the top layer of the coating
observed industrially.
4. M O D E L I N G OF BLADE COATING
Initial attempts to model the blade coating operation are based on Newtonian
fluids. Follette and Fowells [25], Bliesner [26], Turai [27], and others give simple
analyses to relate shear rates, viscosity, geometry, and web velocity to the force
generated on a blade during coating. Lubrication theory is used to reduce the
complexity of the equations. The pressure distribution under the blade is found to
be a strong function of the blade operating angle. Bliesner [26] and Saita and
Scriven [28] used lubrication theory to relate the details of the blade geometry or
blade deflection to the coat weight and blade loading.
The force on the blade required to reject coating due to inertial forces was
given by Eklund and Kahila [29]. This force can be obtained from a mechanical
energy balance on the flow upstream of the blade. The resulting force F on the
blade, for a roll applicator system, is estimated to be
mV(1 + eosa)
Y= (1)
sin a
where m is the incoming mass flow rate of the coating to the blade, Vis the web
velocity, and cx is the operating angle of the blade. This force seems to be
important for roll applicator systems, but it is not clear how to use this type of
equation for a short-dwell coater. This expression indicates that the blade loading
is not a function of the coat weight metered by the blade nor the viscosity level of
the coating. Therefore, some other viscous forces must be important, in addition
to this force, in the coating operation.
838
Pranckh and Scriven [30] used fimte element method to solve the two
dimensional Navier-Stokes equation for the flow near the blade. The solution is in
conjunction with a nonlinear beam equation that describes the deflection of the
blade and a spring model that describes the deformation of the rubber backing roll
and the web. Surface tension forces upstream from the blade and after the blade
were included in the analysis. In the flow field, there is a stagnation line that
separates the coating that is retm-ned and the coating that is metered onto the
web. The pressure distribution near the heal of the blade and under the blade tip
shows little pressure gradients in the vertical direction: this result indicates that
lubrication theory is valid in this region. Again, the operating angle of the blade is
found to be a critical issue in these flows. The pressure distribution shows a
stagnation pressure upstream of the blade, which is close to 89 p V 2 , and a
pressure increase near the blade heel due to viscous forces. This result links the
pressure pulse due to the inertial terms with that of lubrication theory.
The influence of the absorption of the coating into the porous web is first
accounted for by Chen and Scriven [31]. The pressure distribution of a roll
applicator and by a blade metering element from Pranckh and Scriven [30] is
used to calculate the penetration depth of the coating. The influence of air being
trapped into the web and the compression of the web are taken into account.
Assuming a specific pressure distribution under the blade, Letzelter and Eklund
[32] predict the filter cake thickness and the amount of dewatering. Bousfield [3]
proposed a model to describe the formation of a filter cake on the web during
blade coating. Lubrication theory was found to duplicate the pressure distribution
of Pranckh and Scriven [30] and was used to describe the dewatering and
subsequent filter cake buildup on the paper web. The model by Bousfield [3] is
shown to predict the onset of operational difficulties of literature data, if
dewatering parameters are known. These difficulties seem to be related to the
growth of a filter cake which had a thickness near the blade-paper gap. In Figure
2, the data of Taylor [2] are compared with the predictions of the model. This
show that high solids content increases the coating viscosity and reduces the
amount of water needed to be removed to generate a significant filter cake.
The influence of the shear thinning nature of coating was first modeled by
Modrak [33]. A power-law model was used in conjunction with lubrication
theory to describe the flow in a "rounded" blade. Viscosity data from a capillary
viscometer was fitted for a Newtonian-like fluid, a shear-thinning coating, and a
shear-thickening fluid. The power-law exponent varied from 0.675 to 1.3. The
stagnation point moved downstream under the blade tip as the coating became
shear thickening. The pressure distribution and the hydrodynamic litt on the blade
were an order of magnitude higher for the shear thickening fluid, even though at a
839
shear rate of 3 104 S-1, the shear viscosities were similar. However, the shear
rate under the blade tip must reach 106 s-1. For the three coatings, the shear-
thinning model did a reasonable job at predicting pilot scale data.
Finite element methods were used by Triantafillopoulos et al. [34], Roper and
Attal [9], and Isaksson and Rigdahl [35] to calculate the flow field in a short
dwell coater pond and near the blade tip for a roll-applicator system. Free
surfaces and inertial terms were included in the later analyses. The coating was
described as a power-law model with various values of the power-law index. The
circulation within the pond of the short dwell coater was calculated to change
from a single vortex at high viscosity values to two vortices at low viscosity
values. The shear thinning nature of the fluid was fotmd to reduce the pressure
distribution under the blade and decrease the total blade loading. In addition,
shear thinning fluids are found to produce a "plug flow" nature to the flow field,
where most of the shear can occur in a thin layer near the moving web. The
influence of blade angle and "slip" at the blade-coating interface are also
discussed in Isaksson and Rigdahl [35].
The importance of viscoelastic properties of coating was first brought up by
Windle and Beazley [12]. The discussion on viscoelastic properties was focussed
on the extra normal forces generated during shear: these normal forces could
contribute to the hydrodynamic lift forces during operation. An expression for the
extra force on the blade due to normal forces was proposed.
Two-dimensional solutions for a viscoelastic fluid are described in Sullivan et
al. [36], Olsson [37], and Olsson and Isaksson [38]. The results by Olsson use a
geometry that closely resembles the blade geometry of paper coating. An upper
convected Maxwell fluid, an Oldroyd-B fluid, and a Giesekus fluid are used as
constitutive equations. The pressure distributions and streamlines are significantly
influenced by the presence of viscoelasticity. A recirculation region is predicted
upstream from the blade tip and near the exit of the blade, as depicted in Figure
10. The pressure is predicted to decrease due to the extensional components of
the flow field. This result would produce a lower blade force to obtain the same
coat weight, as compared to a Newtonian fluid. The entrance region seems to be
"clogged" with a vortex, resulting in less fluid that is able to pass under the blade.
This result resembles the outcome of Sullivan et al. [36] where the force on the
blade is reduced because of the influence of viscoelasticity.
The K-BKZ constitutive equation was used by Mitsoulis and Triantafillopoulos
[39] to describe the flow under a blade with the influence of a free surface. The
K-BKZ constitutive equation has multiple relaxation times and predicts normal
forces. The pressure distributions and the net flow rate under the blade are
influenced by the viscoelastic nature of the constitutive equation.
840
5. CONCLUSIONS
With the recem advances in theological testing methods and computational
tools, our understanding of the blade coating of paper has improved considerably
in the last ten years. The importance of "water retention" on the ability of a
coating to operate at specific conditions has been one significant step. However,
paper coating still offers a number of challenges, as high speeds and high solids
are desired. Still the small scale between the blade and the web requires a better
understanding of the small-scale microstructures that can form under the blade.
The role of viscoelasticity is still open to debate. A direct comparison of a
complex fluid dynamics calculation and pilot scale results has yet to be
841
REFERENCES
1. R. Van Gilder, D.I. Lee, and R. Purfeerst, TAPPI J., 66 (1983) 49.
2. J.A. Taylor, Proceedings of the 1987 TAPPI Coating Conference, TAPPI
Press, Atlanta GA (1987) 1.
3. D.W. Bousfield, TAPPI J., 77 (1994) 161.
4. N. Triantafillopoulos and T. Grankvist, Proceedings of the 1992 TAPPI
Coating Conference, TAPPI Press, Atlanta GA (1992) 23.
5. P.J. Carreau and P.-A. Lavoie, Proceedings of the 1993 TAPPI Advanced
Coating Fundamentals Symposium, TAPPI Press, Atlanta GA (1993) 1.
. S. Purkayastha and M.E. Oja, Proceedings of the 1993 TAPPI Advanced
Coating Fundamentals Symposium, TAPPI Press, Atlanta GA (1993) 31.
7. T. Ghosh, P.J. Carreau, and P.-A. Lavoie, Proceedings of the 1996 TAPPI
Coating Conference, TAPPI Press, Atlanta GA (1996) 303.
8. T. Ghosh, Proceedings of the 1997 TAPPI Advanced Coating Fundamentals
Symposium, TAPPI Press, Atlanta GA (1997) 43.
9. J.A. Roper III and J.F. Attal, Proceedings of the1993 TAPPI Coating
Conference, TAPPI Press, Atlanta GA (1993) 107.
10. G. Fadat, G. Engstrom, and M. Rigdahl, Rheol. Acta, 27 (1988) 289.
11. T.S. Young and E. Fu, Proceedings of the 1991 TAPPI Coating Conference,
TAPPI Press, Atlanta GA (1991 ) 61.
12. W. Windle and K.M. Beazley, TAPPI J., 51 (1968) 340.
13. J.F. Brady and G. Bossis, J. Fluid Mech., 180 (1985) 105.
14. J.F. Brady and G. Bossis, Annual Rev. of Fluid Mech., 20 (1987) 111.
15. J.L. Durlofsky and J.F. Brady, J. of Fluid Mech., 200 (1989) 39.
16. M. Toivakka and D. Eklund, Nordic Pulp and Paper Res. J., 9 (1994) 143.
17. C. Chang and R.L. Powell, J. of Rheol., 38 (1994) 165.
18. M. Toivakka and D. Eklund, TAPPI J., 79 (1996) 211.
19. W.H. Boersma, J. Laven, and H.N. Stein, J. Rheol., 39 (1995) 841.
20. T.N. Phung, J.F. Brady, and G. Bossis, J. Fluid Mech. 313 (1996) 181.
842
21. D.W. Bousfield, Nordic Pulp and Paper Res. J., 8 (1993) 176.
22. D.W. Bousfield, Proceedings of the 1990 TAPPI Coating Conference,
TAPPI Press, Atlanta, GA. (1990) 325.
23. M. Toivakka, D. Eklund, and D.W. Bousfield, J. Non-Newt. Fluid Mech.,
56 (1995) 49.
24. D.W. Bousfield, P. Isaksson, and M. Rigdahl, J. Pulp and Paper Sci., 23
(1997) J293.
25. W.J. Follette and R.W. Fowells, TAPPI J., 43 (1960) 953.
26. W.C. Bliesner, TAPPI J., 54 (1971) 1673.
27. L.L. Turai, TAPPI J., 54 (1971) 1315.
28. F.A. Saita and L.E. Scriven, Proceedings of the 1988 TAPPI Coating
Conference, TAPPI Press, Atlanta, GA (1988) 13.
29. D. Eklund and S.J. Kahila, Wochbl. Papierfabr., 106 (1978) 661.
30. F.R. Pranckh and L.E. Scriven, TAPPI J., 73 (1990) 163.
31. K.S.A. Chen and L.E. Scriven, TAPPI J., 73 (1990) 151.
32. P. Letzelter and D. Eklund, TAPPI J., 76 (1993) 63
33. J.P. Modrak, TAPPI J., 56 (1973) 70.
34. N. Triantafillopoulos, G.R. Rudemiller, and T. Fanfngton, Proceedings of
the 1988 TAPPI Engineering Conference, TAPPI Press, Atlanta, GA (1988)
209.
35. P. Isaksson and M. Rigdahl, Rheol. Acta, 33 (1994) 454.
36. T. Sullivan, S. Middleman, R. Keunings, AIChE J., 33 (1987) 2047.
37. F. Olsson, J. Non-Newt. Fluid Mech., 51 (1994) 309.
38. F. Olsson and P. Isaksson, Nordic Pulp and Paper Res. J., 4 (1995) 234.
39. E. Mitsoulis and N. Triantafillopoulos, Proceedings of the 1997 TAPPI
Advanced Coating Fundamentals Symposium, TAPPI Press, Atlanta GA
(1997), 27.
40. N. Triantafillopoulos, Paper Coating Viscoelasticity, TAPPI Press, Atlanta,
GA (1996).
843
The total cost of installed composite components is high enough to keep these
materials out of many products that could benefit from them. This introduction
discusses the motivation for using discontinuous fibers to reduce this cost, the
status of research into the manufacturing behavior of these materials and the
scope of this chapter in presenting these properties.
1.1 Motivation
High performance composite materials are beneficial when compared with
other candidate materials by specific strength. But applying advanced composite
materials to mass market industrial products has a tremendous limiting factor: the
traditional high cost of producing parts. The benefits of high strength composites
emerge when controlled fiber placement optimizes the directional strength of the
material. Traditional construction techniques involve significant labor and time
costs. These costs must be reduced to increase the market for designed materials.
Burdensome hand-layup is the most expensive fiber placement method m,.d
must be avoided [ 1]. Tape laying machines, although automated, are too slow for
rapid production cycles [2]. Many industries use injection molding, transfer
molding or sheet molding of low to medium strength composites with particle or
short fiber reinforcement. These techniques rapidly produce items such as
electronic connectors or automotive panels. If high strength composites can be
formed in a manner analogous to sheet metal stamping new markets may benefit
from their use.
844
But strong materials require high volume fractions of either continuous fibers,
which cannot extend in the fiber direction [5], or well aligned arrays of long-
discontinuous fibers [4]. Continuous fiber materials have limitations in
thermofonning [5]. If the fibers remain unbroken--necessary to avoid an area with
a concentration of damaged fibers--the sheet conforms to the mold by interply slip
and by drawing extra fiber length from the edge of the panel toward the center of
the sheet. The sheet accommodates the entire distributed total strain in the
direction of a given fiber by drawing in that fiber. For large deformations a
845
suitably large flange region provides the needed fiber length. This fiber drawing
process produces buckling and wrinkling of the sheet [8]. If severe, buckling can
intrude upon the region of the finished part and decrease the quality of the
component.
Discontinuous fiber systems allow the fibers to move past one another during
forming. Since the fibers can move independently, different regions conform to
their total strain.
Creating a high strength discontinuous composite is challenging. Fibers must
be long enough to provide strength close to that obtained with continuous fibers
[9]. The discontinuous arrays must be well aligned to maintain the necessary high
fiber volume fraction. Fibers conforming to these requirements interact in typical
processes such as injection molding. Fibers will break and alignment will be
limited from fiber entanglement and flow field conditions. Innovative methods are
needed to create a high performance sheet product.
An example long discontinuous fiber thermoplastic melt system (LDFMS) is
LDF/PEKK. Here the matrix is poly-etherketoneketone (PEKK) [ 10, 11]. These 7
micron diameter, 5.6 cm long carbon fibers fall between typical short fiber fillers
and continuous fibers in length and performance. LDFMS material is an attempt
to approach high solid strength typical of highly aligned continuous fiber
composites with melt formability similar to short-fiber filled polymers by allowing
relative motion between adjacent discontinuous fibers. This material contains a
high volume fraction (60 %) of aligned fibers with an average aspect ratio (a r) of
8000, [1 ]. The transient and steady state rheological properties of this fluid are
expected to be different from the unfilled melt.
2. MATERIALS
Polymer science has grown rapidly since the 1940s as new synthesis methods,
experimental appliances and structural theories were introduced [12]. This section
stmunarizes the outcome of research into the response of polymer melts in shear
and elongation flows.
Shear Flows
Material functions in shearing flow can be defined under both steady state
conditions and as transient functions with time as an additional parameter. The
transient functions will approach the steady functions for large times trader steady
applied strain rate or stress. We begin with Newtonian material functions under
steady flow conditions. Modified, these functions handle polymeric fluids under
steady and also under transient conditions.
Steady Flow
The fluids of interest in sheet forming are usually non-Newtonian polymer
melts. For these complex fluids, the entanglement of the polymer macromolecules
produces a rate dependence of the steady viscosity [12, 14]. We define the rate
dependent steady viscosity, rls (Tyx), such that
Xyx - rlS(Tyx)Tyx (1)
Shear
Thickening
Newtonlan
_c
Shear
Thinning
LCP
In~
Figure 2. Steady viscosity of Newtonian and non-Newtonian fluids as a function
of shear strain rate. Newtonian fluids have a constant viscosity. Shear thickening
fluids increase in viscosity as strain rate grows. Shear thinning fluids and liquid
crystal polymers (LCP) have regions of decreasing viscosity for an increase in
shear rate. Some LCPs have two regions of thinning connected by a Newtonian
plateau between them as displayed here.
Transient Flow
The above discussion assumed that steady-state behavior applied to the
measured shear viscosity. Polymer fluids show time dependent properties when
flow starts from rest. The way that transient stress (or equivalently transient
viscosity by rl~ =xy~/'~y~) grows to its steady-state value as the flow progresses
+
Figure 3 demonstrates stress growth for both linear and nonlinear viscoelastic
fluids. For linear viscoelastic fluids the stress grows up to the steady stress level
monotonically. A constant relevant to the flow, usually denoted by ~,l and called
the "relaxation time," is a measure of the time required to reach the steady state
response of the system, e.g., the Maxwell fluid model [16]. The relaxation time
changes the arithmetic equation 1 into a differential equation on stress. Nonlinear
models, such as the White-Metzner fluid, incorporate rate-dependent viscosity
[17]:
+ .+
"l:yx(~'yx , t ) + G "l:Yx(~/yx,t) - rl s (~'yx )~/yx (3)
G is a constant stiffness term that models the elasticity of the fluid. The
solution to equation 3 defines the transient viscosity as
+
rl~(~y~,t) = xy~(5/yx,t)/~y~. Monotonic stress growth function still confines this
model to linear viscoelastic material functions.
o t1
Time
Figure 3. Transient stress in starting-up and stopping of simple shear for
Newtonian, linear viscoelastic and nonlinear viscoelastic fluids. At time t - 0 a
step value of Yyx is applied; at time t - tl, 5[yx - O .
+
~(y~ grows large enough it stimulates stress overshoot. As Figure 3 shows, Xyx
grows larger than Xy~ and then falls to reach the steady value. As ~yx increases
the ratio of the peak Xy+x to the steady Xyx increases. The peak value of Xy+x is the
yield stress x y . A set of rl~/TIo fimctions for a nonlinear viscoelastic fluid is
presented in Figure 4. The slowest ~/yx data form an "envelope" curve that is a
maximum TI~ fimetion for the fluid. As ~yx grows, each rl~ curve falls under
this envelope. The steady rls values reached at each strain rate are equivalent to
the steady-state shear thinning property shown in Figure 2.
1.0
~.0.1 ~ 1000~0
+W
o.01 10,ooo~o
0.01
Time
Figure 4. Transient viscosity function for a nonlinear viscoelastic fluid in shear.
This equation includes both shear thinning and stress overshoot with increasing
strain rate. The first strain rate is within the Newtonian plateau since rl~ / rio - 1.
The two highest rates fall within the power-law region of the Carreau curve so
that rl~ / 110 < 1.
enough to produce linear viscoelastic response -- stress growth and relaxation are
linear with relevant ~,1 9 That is, the strain rate is small enough that the melt can
adjust to the flow by the same diffusion processes that allow attainment and
maintenance of the rest conformation.
Higher ~/yx stimulates a rearrangement of the conformation. The fluid cannot
accommodate the greater strain rate with the diffusion processes. The stress
grows until sufficiently large to change the mechanism by which the molecules
adjust to the stress. The initial rest structure has a potential steady stress
9 + *
comparable to xyx = rl0 ~/yx which is large since rl0>>rls(~/y~). As xyx ~ Xyx
the stress level rises and the diffusion processes cannot adjust to the rapid flow.
The high stress level supplies the energy necessary to break up the network and
align the macromolecules to the flow. As the network tears apart the polymer
becomes less resistant to the applied strain rate. A catastrophic realignment
occurs. Stress falls to Xyx and becomes stable [14].
Elongational Flows
Shearing flows are not the only deformation mode possible in a fluid. Shear
free flows involve extension of the fluid without shearing. Before considering
flows that may contain both extension and shearing components, it is worthwhile
to study the sheerer flows separately when possible. Material functions
definitions for elongational flow follow by analogy to the shear functions. Reports
of steady elongational viscosity data are rare [18]. Many polymers seem never to
attain steady elongation. With this and the transient nature of thermoforming in
mind, we turn to the transient material functions.
1.
~'y = -~-ey (4)
Vy-- 1.
--'~.Z
2
852
0 0
1.
+ (w)r) _ _ 0 --E 0 (5)
2
1.
0 0 --E
2 _
With only terms along the diagonal nonzero, elongational flows are shear-free
flows. We define the shear free elongational flow function [13] as:
+ -- 'l;yy
~xx + - rl~; (6)
where each term with a superscript "'+" is a function of strain rate and time.
This equation defines rl~(/z,t) for measured stress difference under applied
strain rate.
A Newtonian fluid has the single-valued shear viscosity It. It can be shown
that there is a single-valued Newtonian elongational viscosity given by the
Trouton relation
tie = 31.t (7)
This equation also holds for unfilled polymer melts when t~ is small enough
(creeping flow) to keep the response within the linear viscoelastic limit. In this
+
case TIE -- 3 rl~. Building upon the discussion of transient shear behavior above,
one could presume that a shear thinning fluid in elongation shows increasing
deviation from Newtonian behavior as ~ increases. These differences are
discussed next.
lOs
O.lO~/,~o.o3
1.0 / / '~.01
A
!
gO 1S"1
I1. los_
104 , ,,J : ,,J i ''J ' ''d ' ''J - ' ''
i~" 10 8
g ,
10
+~10 6
10 5
10 "1 100 101 102 103
Time (s)
b)
Figure 5. Elongational stress growth function at strain rates between 103 and 1.0
s1 for a) PE [22], b) PS [23]. The linear viscoelastic curve in extension forms a
"floor" for the transient viscosity at increasing strain rate.
855
The shortest fibers elevated the steady stress to the same value as the spheres.
These fibers were so short that they aligned to the imposed flow and had the
same impact as the spheres. That is both spheres and fibers with L / D = 7.3
interrupt the streamlines of the flow by nearly the same amount [34]. The longer
fibers could not align completely as they interfered with each other. Their
imperfect alignment kept more of them interfering with the flow. The total stress
level can modify this entanglement effect by providing more energy to align the
fibers.
150 AspectRatio
~il 9 27
~, 100~ ~/ He 7.31
,
so
0
0 50 100 150
fiber interactions and rate effects modify the quality of the composite [39]. The
elongation of short-glass-fiber filled polypropylene demonstrated the effects of
moderately aligned approximately 150a r fibers on rl~ [40]. The stresses
fluctuated from + 5% to + 15% due to the fiber/fiber interactions from the
distributed fiber alignment within the transfer molded specimens.
10 lo
10 9
~ '10 8
10 7 9 0.(0063
+KI II 0.02
9 0.O63
106 20% Carbon black m o~
10 5 I I IIIIIII I I I llllll I I IIIIIII I I IIIII1
10-1 100 101 102 103
Time (s)
a)
1010
10
"~10 8
10 7 0~0063
+t~ 0.02
0.063
lOS ~ 25% Carbon black l.n_ 0.2
10 5 I I1111111 I IIIIIIII I I!111111 ! III!111
10-1 100 101 102 103
b) Time (s)
Figure 7. Elongation of polystyrene with carbon black particles, aspect ratio = 1,
at 170 ~ at particle volume fractions of a) 20 and b) 25 percent [23]. With a
filler the linear viscoelastic limit curve again forms an envelope under which the
curves at higher strain rate fall. The higher volume fraction shows this effect to a
greater degree.
857
creates a highly aligned system with a distribution of fiber lengths and overlap.
The matrix material is not that well characterized and the fiber interactions with
the matrix are complex. However the material is available in usable form. The
model material can be made with a simple matrix and a selected L / D ratio.
However the price to pay for this control is the labor required to construct the
fiber arrays. For the model system we required a simple polymer with a high
degree of fiber control at 50% volume fraction.
The next sections detail the idea of a novel technique for manufacturing these
highly aligned arrays for academic research and several areas in which the
technique may be applied to produce tailored composite sheets for rapid forming
of panels.
Consolidation
Two consolidation steps formed the panel. The first pressing combined the
fiber mat with 8 plys of the 0.025 mm thick PE film. A picture frame mold held
the sandwich of bottom release film (Kapton), bottom four film plys, fiber mat,
top four film plys and top release film. A Wabash press pressed the mold and its
contents at 795 kPa, 125 ~ for 45 min. Pressure remained on the mold during the
45 min water cooling cycle that returned it to room temperature.
Wherever the wett lifted some fibers above the others a razor blade cut the
raised fibers. The bridging filaments below each cut held the array together.
Pressing six of the preforms a second time under the same conditions produced
six-ply test panels.
859
Fiber Morphology
A breaking strategy converts the continuous fiber tow to discontinuous fibers
and creates a distribution of fiber lengths [44]. A lognormal distribution produced
an average fiber length of 5.07 cm with the longest measured fiber at 16 cm. The
fiber tow is Hercules AS-4 graphite with an average fibril diameter of 7 lam.
At this point we have two material systems to characterize. The model system
has well known matrix properties and a simple fiber arrangement. The
commercial system contains a new polymer and distributed discontinuous fibers.
In the next section details of the test methods and equipment are discussed. Each
system is characterized by rheometry of both the neat matrix fluid and the filled
composite.
3. TECHNIQUES TO C H A R A C T E R I Z E LDFMS
Constant elongation rate tests provide transient tensile stress growth coefficient
+
data, rl~ ( t , ~) = XE ( t , ~)/k. These data describe the difficulty that will be
encountered in forming a useful component at the high elongation rates desired
for mass production. Controlled strain rate forming occurs in matched dies [3].
The fluid sheet becomes trapped at two or more points between the dies and
stretches at a rate proportional to the closure speed of the dies.
v{l +
~(t) = -~0
-I -~:o {1 + ~:ot l_l (9)
L0J
with g(0)=~o=V/L 0, which is the coveted constant strain rate. Equation 9
establishes strain rate as a decreasing function under a constant velocity scheme.
An example from linear viscoelastic theory discloses the impact of this difference.
For LDPE the tensile stress growth at 0.001 sl can be obtained from [13, 22]"
"on- i 3rl~ }e(t')dt' (10)
The second problem is the conversion of the transient load data F(t,/;) into
tensile stress "c+
E . Engineering stress cannot be used for displacements of interest
to thermoforming. Instead, assuming constant volume of a melt the cross sectional
area decreases with extension as A ( t , g ) - Aoe-~t .
Sectioning the sample after an experiment and weighing it as described below
verifies this assumption. Thus equation 11 above determines the transient stress
and viscosity.
Third, the ends of the melt must be securely held during the test. Several
methods do this with neat fluids and particle or short fiber filled systems [48]. For
some L / D 25 tests detailed here we could use a short specimen with nylon
extensions bonded to its ends with high temperature epoxy. This specimen type
could only be used at the lowest strain rates. Larger L / D or faster testing rates
need another technique.
Adding long fibers to the melt makes each of these problems more challenging.
Long fibers greatly increase the elongational viscosity and the force on the
specimen is larger. In this study a phase change method held these specimens
securely. The extreme ends of the specimen remained solid so that standard
Instron grips could hold them. The specimen, when heated in the center, formed a
melt/fiber system in a gage length of approximately 200 mm within a total
specimen length of 305 mm.
This solution to the third problem affected the first two as well. With a
transition from solid to melt and back there is a distribution of strain rates from
zero to a maximum and back to zero again along the major axis of the specimen.
This distribution broadens with the presence of long fibers. Some fibers at each
end of the melt zone will have some part of their length stuck in the solid or semi-
solid polymer. With a distributed strain rate, the change in cross sectional area is
distributed also and must be determined before performing the conversion of load
to stress and displacement to strain rate. Since no simple assumption of the area
distribution is possible for these systems we determine the resulting strain rates
and cross section from a post-experiment analysis of the specimens. Since there is
a transition in strain rates from one end of the specimen to the other, this viscosity
must be designated as an apparent value [49, 50].
protected the melt from degradation during the long heating times required with
the fitmace used. With the heaters switched on, the specimen temperature rose to
the test temperature. The ends remained well below the Tg of the matrix so that
they provided a finn grip surface. After reaching the test temperature--following
20 min of heating--the sample rests for 5 min before the extension starts.
With the techniques developed here, we evaluated the filled fluid systems
proposed in section 2. In the next section the results of each experiment are
shown. First the neat polymers are characterized, then the filled systems are
extended and the data are discussed.
This section presents the experimental data for nylon/polyethylene (N/PE) and
long-discontinuous-fiber/poly-ether-ketone-ketone (LDF/PEKK) in series. First,
for each system, results for the neat polymer appear progressing to the filled
system in elongation.
[52]. The LDPE film corresponds to a Carreau curve with parameters 11o =
43,850 Pa-s, ~ = 5.40 s, n = 0.489.
2x10 5
osl_ :3o'c l
I
104 150~ "~"~"0 PE 140~
n
ffl
~' 103
102
10-4 10-3 10"2 10-1 100 101 102 103
t (s")
Figure 8. Steady shear viscosity of PE at 140 ~ in air as a fimction of strain rate.
Data are from rotational and capillary rheometers. Curve is a Carreau curve with
parameters: rl0 = 43,850; ;~ = 5.40; n = 0.489. Data at 130 and 150 ~ from
Meissner [52].
Controlled g Flow
Controlled g flow experiments on two types of N/PE produced the following
set of data. The extensional viscosity shows the impact of aligned fiber filler on
an isotropic melt in extension.
Elongational Viscosity
Nylon fibers with an aspect ratio of 25 raise the elongational viscosity of the
system to 57 times 311o for PE. Figure 9 displays the measured transient
elongational viscosity. For a total strain of 0.15 the average viscosity is 7.47
MPa-s. For strain rates covering one order of magnitude the viscosities are close.
The lowest viscosity was reached by the panel with the curved fibers.
866
Increasing the aspect ratio to 1O0 raises the extensional viscosity at the lowest
strain rate by another order of magnitude to 192 MPa-s. This is three orders of
magnitude above the 31"10 value of 0.132 MPa-s. Figure 10 shows this and it also
shows the drop in viscosity with increasing strain rate. Each rate increase by
about 10 drops the viscosity by a factor of 5 to 6. These changes are similar to
the function of a shear thinning fluid in the power-law region.
2x107
107
n
A n
W
!
m
0 0.0457s-1
I I 0.0257
El 0.00261
106
0.15 0.30
~t
Figure 9. Transient elongational viscosity of L / D 25 N/PE. The prior stress data
are divided by the extension strain rate to obtain viscosity. The data show that the
elongational viscosity is fairly consistent among the three tests. The wavy fiber
plys in the 0.0257 s"1 strain rate test make the viscosity increase less and the peak
occur later. The smooth curves are average curves for three repetitions; only one
set of data points is shown for each strain rate to clarify the chart.
Figure 11 shows "steady" type viscosity data. The error bars at each point
show the range of peak viscosity to the last viscosity attained at the end of the
experiment. Points are connected with straight lines to group them by aspect
ratio. The L / D 25 samples are rather fiat with strain rate--discounting the
sample with wavy fibers. The 100 L / D specimens look like a power-law region
response with decreasing viscosity.
106
tll
31"1o PE
+~ 105
104 [I m I m
0 0.15 0.30
~t
Figure 10. Transient elongational viscosity of L / D 100 N/PE at three strain
rates. The slowest strain rate shows an increase of viscosity of approximately 3
orders of magnitude from 3r10 of PE.
109
A
Io
t~
IL
I
108
107
0 100
I-! 25
~176
II
o. 106
m
3rio PE
10 5 m m m m m m mmmm mlmm mmm m
104 , , ,,I , , , ,I . . . . 1
0.001 0.01 0.1
(s)
Figure 11. Extensional viscosity of N/PE for two L / D ratios compared with
neat PE; points are connected with straight lines to group the aspect ratios. The
L / D 25 material, accounting for the wavy fibers in the middle sample, remains
fiat in terms of the viscosity/strain rate ratio. L / D 100 material shows a power-
law response to increasing strain rate.
868
expected for PE. The slowest shear rate was selected as 1/5th the slowest rate
used with PEKK. Here the PE did not reach steady-state within 3800 s; but, the
viscosity grew towards the steady value without any unusual viscosity change.
10 s Melt
- O - PEKK 3 7 0 ~
10 s PE 140 ~ C
I
0,, 10 4
10 s
10 =
10 4 10 -a 10-= 10-1 10 0 101 10 =
(S "1)
Figure 12. Steady shear viscosity of PEKK at 370 ~ PEKK has power-law
behavior at low shear rates up to 0.2 s -~ and at high shear rates above 2.0 s -]. A
plateau viscosity connects the two power-law regions at about 470 Pa-s. The PE
data shown were collected with the same rheometer to test its performance at low
shear rates.
through two post-shear runs ('i, = 1.0 sl). The post-shear experiments returned the
measured viscosity to the levels measured in the pre-shear plus an increase
expected from the aging results above. Thus the significant rise in viscosity at
2 x 10 -3 sl cannot be attributed to aging because the increase is reversible and
the exposure time in N2 was limited to the time in which viscosity would be
expected to increase by 60 % at the most.
($-1)
lO 4 9 0.02
? D 1.00
A 20.0
v
+
~. l O =
10 =
0 6 12 18
7
Figure 13. Transient viscosity of PEKK at 370 ~ N2 environment. The tests at 1
and 20 s~ strain rates respond as expected for shear thinning isotropic melts. The
drop of shear rate to 0.02 sl produced a dramatic rise in viscosity.
Controlled ~ Flow
Following the basic format used with N/PE, the next sections show the
reactions of LDF/PEKK to similar experiments and additional tests.
871
,,
_ ,,, ~ (,-1)
10 s
A 1.0 Pre-Shear
,~ 10 s D 0.002
m
el 10 4 9 1.0 1st Post-Shear
II 1.0 2nd Post-Shear
+t=-I 0 s
10 2
101
10 0 ~ , , I , , , ! . , , , ! , , , ,
Figure 14. Transient viscosity of PEKK at 2 x 10 -3 s"l compared with pre- and
post-shear transients of the same specimen, 370 ~ N2 environment. This shows
that the viscosity increase at the low shear rate was a reversible function of the
applied shear strain rate.
Interrupted Flow
In these experiments LDF/PEKK extended at a constant strain rate for a time
and then the extension stopped with the total displacement held constant.
Following a fixed rest period the flow resumed and the transient response
recorded. Repeated appearance of the peak stress is a function of the rest time
and applied strain rate. Also, the effect of slight fiber misalignment on the initial
stress growth was noted. Panels are produced by hand layup of prepreg sheets.
During the first extension step the fibers align to the drawing direction and
872
I
Q.
0.1
~o
x
oo
04 0.01
.3 -1
Ip 0 1.49x 10.4 s
+ UJ I I 1.66 x lOs
9 1.39x 10
0.001 9 I , I . I 9
0 100 200 300 400
Time (s)
+
Figure 15. Normalized elongational viscosity growth, rl~. , for three elongation
rates of LDF/PEKK. The curve for the 10s rate reaches a value of 1 at 994 sec.
The data in Figure 16 show the result for three extensions of a single specimen
at a target ~ of 0.001 s-1. For the first extension the specimen elongated 8% and
the stress relaxed for 165 s. This time allows over 90% of x E to dissipate. After
the 165 s relaxation period, x~ fell 92.8% to 12.4 MPa. Atter restarting the
extension the specimen again passed over a yield peak, although, at 231 MPa, it
is 5.0% lower than the peak in the first flow. Also, in the second flow the sample
did not attain the desired near-fiat quasi-steady plateau after passing x y . Instead,
4-
a near-linear decreasing x~.-e results. The lower x y is probably due to the
incomplete relaxation of x~. atter the first flow. The declining x~. atter the
second peak is due to an error in the assumed gage length of the sample during
the second flow.
The three elongation test was repeated at the next slowest rate, 10-4 s1. The
stress relaxation data above demonstrate that stress decay is much slower after
drawing at this rate. Thus, for a fixed rest period, less stress will dissipate before
the extension resumes and this should significantly influence the size and shape of
the peak during the second and third extension. Figure 17 shows that the peak is
less in the second and third flows.
873
250 i I
Extension
200
i~ ~ First
13.
v
150 '~ Second
Third
I.U
100
50
0 ii . . I,
0.00 0.05 0.10 0.15 0.20 0.25
Strain
+
Figure 16. 1; E for three step elongation of LDF/PEKK with g of 10"3. Each stress
relaxation period is 165 s. Peak stress returns after the second and third restart of
extension.After the second extension, x E decays from 54.1 to 5.38 MPa, a 90 %
+
decrease in 165 s. The third elongation step produces another peak in x E . By this
time the error in the apparatus is significant throughout the elongation. The
significance of the third extension is that a yield stress occurs again.
Since this is a new material with unique properties, two questions about the
+
test results come to mind: (i) What is the effect of the fiber alignment on the x E -
e behavior? (ii) To what extent might bridging fibers contribute to the peak stress
or the magnitude of the stress growth slope?
The effects of fiber alignment and fibers that bridge the gage length can be
studied with the multiple extension test data by shifting the second pull curve so
that it starts at zero relative e. After the first extension the stress growth slope
grows from 14.7 GPa in the first extension to 41.3 GPa in the second. This shows
that the minor misalignment that results from hand layup of the plies is significant
in its effect upon the initial slope of the stress growth. No further increase in
slope occurred in the third extension.
On the prospect of bridging fibers adding significantly to the slope of the stress
growth or the value of x y , the population of bridging fibers is much less than 2.6
% of the fibers in the cross section based upon the distribution data of Chang and
Pratte [1 ]. The work of Bums [44] shows that at most 0.5 % of the fibers have a
874
statistical chance of avoiding fracture and bridging a 30.5 cm melt zone. So the
bridging fibers alone could account for at the most 1/22 of the slope during the
first pull based upon the modulus of AS-4 carbon fiber. Then, during the first pull,
any bridging fibers break. The second and third pull stiffness and x~ are
therefore entirely due to the properties of the fluid and the shear strain rate
magnification within the material.
200 Extension
- 0 - First
150 A
! , ~ Second
Third
13.
v
IO0 I
,, ,
+~
J .
O' . . . . 9 i i
Figure 17. XE for three step elongation of LDF/PEKK with ~ of 10-4 The stress
"~ ~
relaxation period is the same as for the higher strain rate test. Less stress relaxes
and the peak stress is diminished.
The multiple flow test at 10-4 s-I ~, when combined with the prior discussion,
supports the view that x y is a nonlinear viscoelastic effect under constant ~.
Since x E had only decayed by 68.1% atter the 165 s pause the melt could not
move to its preferred rest conformation before the next pull started. Thus, x y
diminished.
5. MODELS OF R H E O L O G I C A L PERFORMANCE
Fibers placed in a matrix can dramatically shift the deformation mode of the
system. For the filled fluids discussed here the total data set of flow, relaxation
with cessation of flow and behavior with restart of flow must be considered.
Figure 18 shows micromechanics and constitutive domains for the aligned fiber
systems of interest. The left figure shows a fiber/polymer cell in scale for a 60 vol
~ fiber loading. The cell is globally deformed in extension. A fluid element from
the cell is displayed on the right to illustrate the applied global elongation and the
generated local shear deformation defined by the development that follows.
Micromechanics provide the local deformation. The constitutive relation must be
appropriate to the superimposed deformations of the fluid element.
The first analysis of the effect of long fibers on extension of Newtonian fluids
applied to dilute suspensions [42]. The shear strain rate is concentrated in the
near field of the fiber. This effect increases the extensional viscosity of the
system, which was verified by Mewis and Metzner [56]. A derivation for shear
thinning fluids finds that the effect of the localized shear rate removes the fibers
876
as a factor in extensional viscosity [57]. That is, the viscosity drop in the fiber
region compensates for the presence of the fibers. However, the systems
employed here are not dilute. There is a substantial difference in shear rate
distribution in a concentrated suspension. The shear rate is significant and of the
same magnitude along the entire cell radius Ri < r < R 0.
The relevant equations for the micromechanics start with the fiber pulling
speed. Figure 19 illustrates the relative motion of the top fiber with respect to the
lower neighbor fibers. Each fiber remains whole and therefore moves with the
velocity of its centroid within the global elongation flow [58]. The relative
velocity for ideally spaced fibers is VreI - ( x 2 - x l) - L / 2 . The Navier-Stokes
equations yield the x component of the velocity vector:
#-L ln(r / R~ (14)
vx (r) - 2 In k
where
vx (R i ) is the inner boundary condition vx = ~ / 2
Figure 19. Relative fiber motion forms a shear cell in the Batchelor model.
area of two shear cells (2A) as only half the fibers carry the tensile load with a
good choice of the free body diagram [60]. For any volume fraction
Fm = 2AfqE~. The fiber pulling force comes from the shear stress over the fiber
surface within the cell [58] or F f = x , . x ( 2 ~ i ) L / 2 = rl'~rx/~.L. Using equation 15
the tensile stress is:
XE "-
t,}
3(1- f)rl~ + Ink tie -~ (16)
with tiE = 311. The first term shows the elongation component and the second
term shows that the shear cell effect has a factor of (L / D)2. The portion of the
total stress due to the sheafing within the cell quickly becomes orders of
magnitude larger than the portion provided by elongation of the annulus. For
L / D greater than 5 the annulus stress is less than one percent of the total
measured stress.
where ~ is the stress tensor, ~ is the strain tensor, 11o is the zero shear rate
viscosity, ~l is the relaxation parameter, ~,2 ~ 1 / 1000 is the retardation
parameter, and tx is the parameter that determines the degree of nonlinear
behavior. This set of equations was solved with a 4th order Runge-Kutta
program.
879
The strain rate tensor acts as the driving element of the solution to equation 17.
These tensors arise from the micromechanics of the shear cell. The strain rate
tensor for the elongational flow of the polymer annulus comes from the velocity
vector: Y = Vr~.r + vo~o + Vx~x with v x = kx , v o = 0 and the boundary conditions
on radial velocity of v~(r= R i ) = 0 and v~(r= Ro)< 0. These BCs allow the
polymer to flow toward the center to correspond to the extension in X with the
fiber acting as a solid inner boundary. To satisfy continuity
R?
- Vv + {Vv} r 0 e(-~-l) 0 (18)
/
0 0 2~
105
A
104
0
u) Source
103
- PE
O N/PE L/D 100
I"! N/PE L/D 25 r
102
10 .3 10 .2 10 "1 1 10 102 103
(s "1)
Figure 20. Matrix viscosity of N/PE derived from the extensional viscosity data
for the system. Solid line is the steady viscosity of the PE film.
Under either mechanism this could create a "two fluid" system in the shear
cell. A viscosity difference of 10 or higher quickly concentrates the deformation
to the outer layer. This increases the shear rate for the outer fluid and increases
the effective fiber volume fraction. Changes in this direction would reduce the
difference in PEKK and system matrix viscosity as the strain rate decreases.
Thus the interaction of the TLCP melt with the carbon fiber surface may make
the shear cell model inapplicable at low shear rates. Some innovative techniques
would be needed to assess this effect. More of this is discussed in the modeling
that follows.
Allowing the Giesekus model to relax for 165 s would relax away most of the
stress at either strain rate. Instead, the relaxation period can be reduced to that
required to get the same residual stress prior to restarting the flow. Figure 22 and
Figure 23 show the predicted stress response to the resumption of flow when the
hold period drops to 30 and 35 s for the 10.3 and 104 models respectively.
Besides the error in the rheometer, in which steady strain rate flow was not
883
attained on the second extension, the model shows a good prediction of the
degree of stress overshoot upon resumption of flow for both strain rates.
10 o .
0
tO, 10 4
Ii
Source
lu
- Model
~ 10"= 9 10-5
E! lo-4
0 10-3
10 "=
0 100 200 300 400
Time(s)
Figure 21. Best Giesekus model fit with single parameter sets at all three strain
rates.
250
200 0 l~
000,~
13.. 150
50 Model
0 LDFMS
i ... i J
o
Figure 22. Giesekus model applied to predict response to interrupted flow, 1.49
10-3 s-1. The single parameter fit covered the initial flow. The model relaxed to the
same stress level as the experiment and the flow rate resumed using the same
Giesekus parameters fit to the first extension.
884
200
150
C)O00 D O 0 0 0
v lOO
u.I
Source
50 Model
O ,,
LDFMS
I ,
0 (~ = 9 i
Figure 23. Giesekus model applied to predict response to interrupted flow, 1.66
10-4 s"~. The single parameter fit covered the initial flow. The model relaxed to the
same stress level as the experiment and the flow rate resumed using the same
Giesekus parameters fit to the first extension.
6. OUTLOOK
This section first summarizes the test and model results for both the
nylon/polyethylene (N/PE) and long-discontinuous-fiber/polyetherketoneketone
(LDF/PEKK) systems. Then the implications of applying these results to process
models are discussed. The prospect of timber experiments with new fiber
patterns is presented. Finally, a method of investigating microrheology and
LCP/fiber interaction is presented.
6.1 Conclusions
The evidence discussed above leads to the following conclusions about the
model micromechanics, the suitability of the constitutive equation and the
LDFMS properties.
changing the dominant strain rate from stretching to shearing. The induced shear
strain rate, which rises directly as a factor of the fiber aspect ratio, can stimulate
conformation changes (shear thinning, nematic/isotropic transition) in the
polymer. For a fixed volume fraction of fibers, extensional viscosity increases as
the square of the fiber aspect ratio. Finally, the extensional data follow from the
shear properties of the matrix fluid by micromechanics.
misses the polymer's nonlinear response and the effects of large deformations in
contrast to the small deformations of solids. The Giesekus equation in a similar
matrix form is
f ([x],[~:],['i'],t)= g([~'],[~?],t) (23)
which is more involved. Numerical techniques must include the transient
effects since stress overshoots can be significant and we need the total stress
history to deal with changes in deformation rates in simulated tool contact.
6. 2.3 Deconsolidation
Two deconsolidation mechanisms occur in sheet forming. When melted in
open air without any applied deformation, N/PE and LDF/PEKK deconsolidate.
Residual stresses in the sheet separate the plys and lott the material. Tensile
experiments show that forming enhances deconsolidation without an applied
pressure. In the shear cell model, the relative motion of the fibers generates
substantial normal forces. This normal force would push fibers apart. Raising the
strain rate increases the effect.
At the low strain rates used here the specimens remained consolidated within
either the metal fixture or vacuum bag. Consolidation maintained the continumn
so that the analysis could be completed. In some industrial forming processes no
consolidation force keeps the sheet together. The fmal forming step
reconsolidates the panels. Although this lowers the effective viscosity of the sheet
with the addition of voids [71], the void content changes the fiber motions in
ways that are very complex to model.
Fiber Length
The material should contain the shortest possible average fiber length for the
application. This keeps the viscosity increase to the smallest level needed to
make a good part.
6. 2. 5 Microrheology
Recent research into the microrheology of polymers shows that thin film and
bulk properties may be very different [72, 73, 74, 75, 76, 77]. Since the flow
condition of interest to this research is annulus flow, we suggest a
microrheometer that simulates this condition. A capillary rheometer with a fiber
inserted through the hole of the capillary. With the proper selection of the fiber
diameter the device would span the range of bulk (no fiber inserted) to
microrheology. Two methods of measuring the viscosity of the polymer are
possible with this device. The first method would be to rtm the instrument as a
capillary rheometer with the analysis of the data accotmting for annular flow. The
fiber insert may be either stationary or moving. The difference in cross sectional
area between the reservoir and the annulus assures that the polymer flows at peak
velocities much greater than that of the fiber surface.
888
A second method for collecting the data is to use the filled capillary/polymer
system in a "pull-out" test. The filled capillary/polymer system would be placed
in a test machine and heated to the appropriate temperature. Then the fiber would
be withdrawn from the capillary at various speeds as the data acquisition system
records the load on the fiber. This device could also determine the effect of LCP
structure on microrheology as discussed in the next section.
REFERENCES
NOMENCLATURE
English
ar Aspect ratio of a particle, the major length divided by the minor
length.
H(~.) The height of the relaxation spectnun as relaxation parameter
increases from zero to infinity.
L/D Aspect ratio of a particle, the major length divided by the minor
length.
Greek
O~ Parameter controlling the non-linear response of the Giesekus
model. Varies from zero to one.
Axial density distribution with units of g/cm.
13(x) Axial density distribution as a function of position along the
specimen.
Shear strain rate in sec ~.
rx(r) Shear strain rate in cylindrical coordinates for the shear cell
model.
~yx Shear strain rate in cartesian coordinates.
s Extension strain.
Extension strain rate in secf1.
rio Zero shear rate viscosity; viscosity of a polymer melt in the linear
viscoelastic strain rate range.
I"IE Extension viscosity of a fluid in tension.
TlEapp Apparent extension viscosity measured in a region with a strain
rate gradient.
Transient extension viscosity measured from the startup of flow
from the rest state.
I"1S Shear viscosity in steady shear flow.
Transient shear viscosity measured during startup of flow from
the rest state.
892
rls Shear viscosity decay measured during the time following steady
shear flow.
Carreau equation parameter that controls the onset of shear
thinning.
Relaxation parameter in fluid constitutive equations.
Z'max Relaxation parameter value at which 99.9 % of the area udner the
relaxation distribution function H(E)is attained.
~p Relaxation parameter value at which H(~) attains its peak value.
"~yx Shear stress in units of Pa.
+
1;yx Transient shear stress measured from the start up of flow until
steady flow is obtained.
1;yx Shear stress decay following flow. Deformation held constant
during the decay.
The peak value of the transient shear stress. A 'yield' value for
the conformation change in the polymer.
'[E Extension stress in tension.
+
17E Transient extension stress measured from the start of flow from
rest.
Peak value of tensile stress.
Stress relaxation measured atter extension.
893
1. INTRODUCTION
Polymer processing involves complex flow geometries, in the plasticating
units (single or twin screw extrusion, injection) as well as in the shaping tools
(die, mold). Thermoplastic polymer processes started only around sixty years
ago and these processes have been firstly developed by trial and error.
Polymer processing modeling is a recent story and appears as a useful tool, not
only to limit the number of trials, but also to master all the thermomechanical
parameters which will induce, for example, crystallization, macromolecule
orientation and, as a consequence, end-use properties of the produced part.
Modelling polymer processes appears as a challenge for several reasons :
9 molten polymers are highly viscous materials, which leads to important
viscous dissipation ;
9 polymer processes may rarely be considered as isothermal;
9 molten polymers are non-Newtonian viscoelastic fluids, which means for
example:
- shear-thinning behavior for the viscosity ;
- transient effects ;
- normal stress differences in pure shearing flow.
9 the viscosity of molten polymers is temperature dependent, which implies
that mechanical and heat transfer equations have to be solved simultaneously.
9 polymers present a low thermal diffusivity, which may lead to important
temperature gradients, even when the polymer is flowing in very thin gaps;
9 most of the polymers are semi-crystalline materials and very specific
structure developments (spherulites, for example) may be observed
depending on the cooling rate and stress field encountered during the process.
In this chapter, we will only consider the flow of an homogeneous molten
polymer. Neither plastication mechanism nor crystallization kinetics will be
taken into account. In a continuum mechanics approach, the different equations
894
V.u : 0 (1)
where u is the velocity field. When very high pressures are encountered (as
for example in injection molding), the variation of the material density p in
time and space has to be taken into account :
@
0t + V.(pu) = 0 (2)
Re= p Uh
7/ (4)
where U is the characteristic velocity of the flow, h the flow gap and 7/the
viscosity. Generally, Re is negligible in polymer processing or, at a maximum,
of the order of magnitude of several units (this is the case around gates and
runners in injection molding or at high speed fiber spinning).
To compare gravity and viscous forces, an equivalent Stokes number is
defined:
St- pgLh
rl U (5t
where g is the gravity and L the vertical dimension of the flow. In horizontal
processes (extrusion, injection molding), gravity forces are negligible. This is
no more the case when large vertical stretching distances are considered (fiber
895
spinning, film blowing). When both gravity and inertia forces are neglected,
the momentum equation reduces to 9
V.o-= 0 (6)
= ~ (Vu + Vu t) (8)
a = - p l + 2 rl(T, ~) [~ (9)
42 '""'
92
(10)
ld
where n is the power-law index and K the consistency, which is only a function
of temperature, following for example an Arrhenius law 9
896
E 1 1
K ( T ) = Ko exp ~ (~ - ~00) (12)
E is the activation energy, which may vary significantly from one polymer to
another, R is the ideal gas constant and Ko is the value of the consistency at the
reference temperature To. The advantage of the power-law is to provide
analytical solutions in a wide range of flow geometries, but its main drawbacks
are an infinite viscosity at zero shear rate and the absence of Newtonian
plateau at low shear rate.
77 = r/0(T) [1 + (A 2]
(n-1)/a
= 00(73 [1 + (~ ~) a] (14)
cr = - p ' l + s (15.1)
as
s+2~=2r/ e (15.2)
where p ' is the isotropic part of the stress tensor, s the extra-stress tensor and
5 s / & the upper-convected derivative. It is to notice that this Maxwell model is
897
It allows to account for the two normal stress differences in simple shear
flow (a first normal stress difference, as for the Maxwell model, and a second
one), but also for strain transition after a stress step. Jeffreys models [6]
consist in introducing an additional function of the extra-stress tensor in
equation (15.2) :
&
f(s) s + A-~= 2 r/ e (17)
For example, for the well known Phan Thien-Tanner model [7], we have :
e2~
f ( s ) = (1 + - ~ tr s ) I (18)
a~
f(s) = I + s (19)
77
~si
S - ~. S i , f(si) Si + / ] , i - - ~ - 2 17i ~ (20)
1
where m(t, t') is a memory function and C t I the Finger tensor. This model is
equivalent to the Maxwell model by choosing :
898
h (I l, I2) = 1
1 + a [fl 11 + ( 1 - [ 3 ) I 2 - 3] b/2 (24)
de
p = - v.q + (25)
where Cp is the heat capacity. More complex equations are proposed for
compressible materials with phase transition [13].
q is the heat flux, which is proportional to the temperature gradient
following the Fourier law 9
q =- k V T (27)
km
hr--- l (30)
where km is the heat conductivity of the metal and l is the average distance
between the cooling channels and the mold wall. When the geometry of the
mold (or the die) is complex, l may be difficult to determine and it is
preferable to develop a global computation in the polymer domain and in the
tool (with, for example, an iterative loop between polymer flow and tool).
For free surface problems (fiber spinning - cast film - film blowing ...),
the determination of a realistic heat transfer coefficient remains a challenge
because coupled and complex phenomena may be encountered : free
convection, forced convection, radiation ... [13]. Very often, the heat transfer
coefficient (or the heat transfer function, because it can vary for example
between the die and the winding system in fiber spinning) will be considered as
an adjustable parameter.
V. u = 0 (31.2)
901
+ boundary conditions
Figure 2" External view of the mesh of a die extrusion geometry and
detail of the mesh in the exit section
where pk(f~e) and pl(f~e) are the set (or sub-set) of polynomials of degree k
and l on element f~e. n =2, 3 is the space dimension. If i = 0, the functions are
continuous, if i = -1, they are discontinuous.
V h and p h cannot be chosen independently. The inf-sup Brezzi-Babuska
condition must be checked (see [16] for a complete discussion of this
compatibility condition). A well established technique to ensure this condition
is to enrich the velocity interpolation with a bubble part [19, 24] (Figure 3).
The discrete velocity space is augmented (in the hierarchical form) by the
discrete bubble space denoted by :
v h = u h + b h ~ (V h + B h) (36)
904
The bubble has the advantage to be local and it can be condensed at element
level without changing the bandwidth of the global system. This technique gave
rise to the simplest mixed finite element : the mini-element [21 ]. In theory, the
shape of the bubble function is free and it has only to vanish at the element
boundary. We use a pyramidal bubble function (Figure 3) preserving the exact
integration property of a first order tetrahedral element. The bubble can be
chosen optimally [25] and it can be related to the stabilization technique [26].
The mini-element is used for the calculation of the three-dimensional examples
presented in this paragraph. It has four unknowns per node.
In two-dimensional calculations (viscoelastic examples presented later), we
used the Crouzeix-Raviart element (also known as the P2+/P1). When coupled
with an augmented Lagrangian technique [19], the pressure unknown can be
locally eliminated, which leads to two unknowns per node.
The main difference between mini and Crouzeix-Raviart elements is that the
pressure is continuous for the first one and discontinuous for the second one.
Despite the increase of degrees of freedom with the mini-element, the
continuous interpolation of the pressure is, in 3D, largely less expensive in
term of computational resources.
.;. . . . . .
.Q"
Under this stability condition, the numerical solution converges with respect
to the mesh refinement to the real solution. The approximation in velocity and
pressure are then dependent through the a priori following estimate :
and finally this can also be related to the error in stress by using the
constitutive relation"
For the example of extrusion die, Figure 4 shows how the flow rate evolves
with the mesh refinement for a fixed pressure drop.
700
~. 600
O~
500
E
400 ~
300
0 0
u. 200
Figure 4 9 Evolution of the calculated flow rate with the mesh refinement.
When the mesh is composed of more than 10 000 nodes (for instance the
mesh of Figure 2), it reaches an asymptotic value, independent of the mesh. In
this example we used a linear interpolation of the velocity (plus a pyramidal
bubble term for stability purpose) and a linear interpolation of the pressure,
giving a first order element.
Under these conditions, we obtain the results presented in Figure 5, which
are almost free of numerical approximation. The pressure remains quite
constant in the upstream die region and a high pressure gradient appears at the
die exit. The goal of such a calculation is to compute the velocity profile at the
die exit in order to predict the balance of the polymer flow and then to
validate or modify the proposed geometry.
906
Figure 5 : Pressure field in the whole die (a) and velocity field at the die
exit (b)
2.4 l t e r a t i v e solver
An attractive feature of the mini-element interpolation is the possibility to
solve the large linear discrete systems by an iterative method [27]. This is
crucial for 3D applications for which the use of direct solvers is too much
consuming, both in term of memory and in term of CPU.
By using a static condensation technique [19], the internal velocity bubble
terms vanish from the system. This elimination provides a new diagonal block
matrix C. The remaining linear parts of the velocity and the pressure are then
solution of the following system :
B
H _BC ) ( pV) = ( F ) (40)
where H and C are symmetric definite positive. The unknowns are thus the
three components of the velocity and the pressure for each vertex. The size of
907
the system is then 4 N, N being the number of mesh nodes. The new block -C
can be seen as the optimal stabilization matrix in the context of a stabilized
P1/P1 method [28]. The form of the blocks remains almost the same in the
non-linear case, with H = H(V) and F = F(V), V being fixed at each Newton
iteration. The global matrix is symmetric indefinite and an iterative approach
must be based on a residual method. The preconditioned conjugate residual
method (PCR) for the Stokes problem has been introduced in [29]. The PCR
method can be seen as a particular case of the generalized minimal residual
method (GMRES) [30], which can be used with indefinite possibly non-
symmetric matrices. However, from the practical point of view, it can be seen
as a preconditioned conjugate gradient extended to saddle point problems. The
method used in [27] for 3D forming applications is based on the hybrid
Orthomin/Orthodir form of the algorithm, as described in [31] for instance.
dT
pep = k AT+ (41)
d T OT
dt = oat + V T.u (42)
methods often fail when the temperature gradients are important. Among the
possible alternative method we can mention the streamline upwind technique
[33], which consists to add diffusive terms in the standard Galerkin finite
element method. These terms must be smaller of one order of magnitude to
preserve the consistency of the equations. The standard discontinuous Galerkin
method is well suited for hyperbolic equation, but restricted to purely
convective term. The method of characteristics [34] is well suited both for
convective and dissipative dominated problem.
f~ pCp -~
dT T* dE~ =- ~ kVr.Vr* dE~ + f W T* dE~, VT* ~ T O (43)
dTh
The evaluation of--d~ will differ from one scheme to another and will lead
to symmetric or non-symmetric systems. For instance"
f~pCp--~T*hdE~
0Th + ~ VTh.uhT*hd~ + ~EkVTh.VT*hdE~- f I~hT*h dE~
(46)
This method is quite natural but can show some instabilities and it is restricted
to small temperature gradients. The other difficulty is to solve such a non-
symmetric system by an iterative solver (direct 3D solutions by means of
Choleski factorization are too expensive to be really usable). The minimal
residual method (which can be adapted to non-symmetric system) works when
the gradient along the flow remains small enough. Afterwards, one can
observe loss of convergence, even with the GMRES method [30]. The direct
Galerkin method using a minimal residual method as iterative solution was
used for the profile die extrusion application [35].
Very recently, we have proposed an explicit thermal solution algorithm.
The heat flux is introduced in the general heat transfer equation as a new
unknown variable, leading to a two fields problem"
cgT
pCp Ot = - pCp V T.u - V . q + W (47.1)
q =- k V T (47.2)
~l~f(x't)=f 1 i f x ~ ~2f
0 if x ~ f2 e (48)
Figure 7-
3D finite element simulation of the filling of a grid cavity
911
The whole cavity is meshed. At each time step, the velocity and pressure
fields are calculated everywhere using the 3D Stokes solver previously
described. The empty part of the mold is represented by a zero velocity field
and a zero pressure field. The interpolated fluid position (one constant per
element) evolution is performed at element level by using a transport equation
finite element solver, based on an explicit Taylor discontinuous Galerkin
method. The basic idea of this scheme is that the successive time derivatives in
the Taylor development of the characteristic function 1 can be calculated
recursively by"
at ll n f = - V l o f .u
032 O
03/2 t[nf "-- V ~-~ a n f .U
69 3 02
0t 3 1 h i =_ 7 - & _ f ~ a / . u ... (50)
Figure 7 shows different steps of the filling of a thick 3D grid mold [36]. It
has been run on a single middle size workstation. There are 9 827 nodes,
which means 39 308 degrees of freedom and 50 739 elements. We can clearly
see the evolution of the free surface and the formation of the weld lines. This
method is not restricted to the flow front movement in confined mold filling
problems. It can be used to compute accurately transient free surfaces as
shown in Figure 8 where two jets of polymer collide each other, showing that
large moving free boundaries can be well rendered by this approach.
V.u = 0 (51.2)
S = {s E ( L 2 ( ~ ) ) nxn} (52)
The space 5 must contain the rate of strain space, denoted e (V). The finite
element approximate space 5h must be chosen in order to be compatible with
V h and p h previously introduced. An easy way to check these compatibility
condition is to ensure that 5 h contains the discrete space e (Vh), for example
by choosing S h = k( V h).
The discontinuous Galerkin method is a consequence of the above
construction. Indeed, if the velocity discrete space is based on C Oelements, the
913
W h = {u h E (C~ 2, u h l ~ e E (P2+(f2e))2}
In this case, the standard notation p2+ means that the velocity is enriched
with a bubble term. The bubble being made of a polynomial of degree three,
the gradient of the velocity is of degree two. The variational problem can be
written as :
Find (u h, ph, s h ) E V h x p h x s h , u h = Uo on o3~, u 0 being given, such as:
V (u h,ph) 6 V h x Ph (54.3)
2.8 Conclusions
Despite interesting and promising results, the use of direct 3D numerical
simulation remains today generally limited to purely viscous fluids and
requires high numerical resources. To solve industrial problems encountered
in polymer processes, the use of approximation methods remains very often
necessary. These methods, which will be presented in the next sections, require
less computer resources and corresponding software packages are now well
implanted in polymer processing industry. They may be roughly divided into
two categories 9
- the confined flow approximation, which is adapted to flows into narrow
channels or between nearly parallel plates, dominated by shear;
- the thin film (or fiber) approximation, devoted to free surfaces, for
which elongational flows are dominant.
Xl ~ . . . . . . -
3w
+ ~y + ~ z dz = o (55)
Assuming no slip conditions on upper and lower walls, equation (56) may
be written as"
~q~
Ox + ~Oy = 0 (57~
where qx and qy are the local flow rates per unit width in x and y directions,
defined by :
_~ O~2U 0p a21:
0X "- ~ 0Z2 ' Oy = 77 OZ2 (60, 61)
Introducing equations (62) and (63) in equation (57) leads to the well
known Hele-Shaw equation :
a
~xx [o3x h3] + [0y ] = 0 or 7.(h 3 V p ) = 0 (64)
This equation can be generalized for non-Newtonian fluids under the form :
V.(/~ V p ) = 0 (65)
where/3 may have different expressions depending on the selected viscous law.
For example, for a power-law fluid, we obtain [40-41] :
+ 1)/n (1-n)/n
/ 3 = 2 n + 1( ) Vp (66)
dp 12r/q
dx = - h(x)3 (67)
917
where q is the flow rate per unit width in x-direction. For a power-law fluid, a
similar expression is obtained"
dx = 2n q [h~) (68)
If the change in gap h(x) is known, the above expression allows to calculate
the pressure evolution along the flow direction and the pressure drop/flow rate
relationship. For example, for a dihedron with initial gap ho, final gap hi,
length L, and a linear variation of h between ho and hi, the pressure drop Ap
is expressed as :
ho+ hi
Ap - 6 71 q L ho 2 h l 2 (69)
where ~ is the mean velocity in x-direction. Using this expression, the energy
equation can be written under the form [13] 9
h(x)
Nu - hy k - (72)
918
OT 1 Op c?T 10p 2k Tw - T
-~h (-O-x-x + ~pcp Ox) + ~h (-~-y-y + ~pcp Oy) = pcp
~ Nu h (73)
It is clear that these simplifications will give pertinent results only if the
heat transfer is correctly estimated and the transverse temperature gradient is
limited. They are generally useful for computing the flows in extrusion dies or
in calender gaps, but inappropriate to the strong conditions encountered in
injection.
+ 2 OP 0P 002x~y
1-n Ox2 OxOy +
+ h = 0 (74)
2k Nu Tw- T (77)
u h (-ff~-x + ~pcp )+ v h ( + ~pcp ) = pcp h
919
E 1 1
K- Ko exp ~ ( ~ - ~-~o) (78)
This set of equations may be solved iteratively, using for example a finite
volume method [43-45].
Figure 11 presents an example of computed result, corresponding to the
extrusion of a polymer with a power-law index equal to 0.35. Flow lines and
isobars are drawn on Figure 1 l a. The pressure drop is mainly consumed in the
straining bar, located after the coat-hanger. The polymer flows preferably
along the coat-hanger and is progressively distributed throughout the lips. The
homogeneity of the exit flow rate may be evaluated by plotting the ratio of
local flow rate qx to mean flow rate q as a function of the position (Figure
lib). In the present case, the distribution is correct (+ 10 %), but it is
important to point out the strong dependence on the power-law index.
The temperature plays an important role in the flat die extrusion. Isovalues
of bulk temperature for an initial temperature of 200 ~ and for a wall
temperature of 200 ~ are shown in Figure 12a. Figure 12b indicates that the
exit flow rate distribution is very sensitive to the wall temperature. It proves
that it is possible to correct a flow rate heterogeneity just by changing the
regulation temperature.
100 bars
90.1bars . 70.3 bars
5o.s~
30.7"i ]
.zo.81"---T
10.9J--- 4
Po=l.o [ . . . .
bar
t 1.2
C~
~" 1.1------, ' i
d
a) n-0.2
t.
1,0 b) n:= 0.35
o c) n=0.5
~- 0.9
,~_.
C
~' 0.8
A B
Figure 11 9 Flow lines and isobars (a) and flow rate exit distribution (b) for
the flow in the coat-hanger fiat die
920
200.0 *C
t
"M~L
i 202.9
1 1.4
I -
203.3
,-~
1.3
I IB ;,
l
O
1.2
AF sS
Wail femperafure:
O a) T : 180 ~
c~ bl T = 200 ~
. 1.1 c) T : 220 ~
i /
1.0
Q,P
bx,......t , J/
"- 09
~u
0.8 a%,,"
/
s
..,,.,,"
O.7
A
Figure 12" Isovalues of bulk temperature (a) and exit flow rate distribution
(b) for the flow in the coat-hanger flat die
'z (z - z*)
13- ~ d z (79)
z* is the value of z for which the velocity is maximum. It is equal to h/2 with a
symmetric thermal regulation. In more general situations, it is defined by 9
921
~Z-Z*
o dz - o (8o)
pcp U
OT
+ V --~ + W
c)__~zI c) 2T 9
= k t~Z2 + W (81)
~9
& Jt~k h a d s =-kf~a h u.n ot dl (82)
Figure 14 shows the isovalues of the pressure and the fill factor ~ for the
filling of a box cavity. This kind of computation gives accurate results for the
pressure, the temperature, and the flow front. The location of weld lines is
usually correct. The equations can be generalized to compressible materials,
for the packing phase, or for a better resolution of the filling of large cavities
at high pressure.
where 0 is the dihedron angle and Ro and R1 the radius defining the entry and
exit, respectively. The approximated solution using the lubrication
approximation is given by equation (68). So, the ratio of flow rate between
exact and approximate solutions is only a function of the angle 0"
Qapprox 4 tg30
(84)
Qexact = 3 sin2 0
- 0 cos20
2
1,3
t,,.}
m
X
1,2
o
x
0 C,one
~ 1,1
0 9 dron
0 5 10 15 20
Angle (degree)
Figure 15 presents the evolution of the flow rate ratio as a function of the
angle. It can be seen that the error made in using the lubrication
approximation remains less than 5 % for an angle inferior to 10 ~ For an
axysymmetrical conical geometry, this limit is roughly equivalent but further
deviation is enhanced. These particular examples are representative of the
global validity of the confined flow approximation. Whatever the real
geometry and the polymer behavior, the upper limit of the relative angle
between the walls must not exceed 10 ~ to ensure a correct description of the
flow [53-54].
0,6
~.,
,-, 0,4 ----------- 2,~r~
D #,, F i n i t e e. l e m e n t
~ 2.D ~ A n a _ l y t i c a l - " ~ . .
0,2 ......... Pivot "kN
0 , , , , i , , , , i , ~ , , i , , , ,.i , , ,. , , i , , , ~ ' ' ' ' I ~ ' ' I
0 l 2 3 4 5 6 7 8
Flow length
0,6
~
0,4
....... ~D # A n a l y t i c a l "'.~
l~ 0,2 ......... Pivot I",
0 , , ~ i , , , i , , , i ,_i , i , , , i , , ~I i ,. , , i , ,..
0 2 4 6 8 10 12 14
Flow length
1 ....
N 0,2
~
0,6
0,4 1 ~
. . . . .
.........
2D #
2D # A n a l y t i c a l
Pivot
Finite element
F l o w front position 9 16
"-.,,.
""-
" 1 0
0
' ' ' ' I
5
' ' ' '
10
I ' ' ' '
15
I I I I
....
Flow length
] ~
0, 8 ~ ..........
_ ..-......., -
, \
0,6
0,4 2D Finite e l e m e n t
0,2 . . . . . 2D A n a l y t i c a l F l o w front position 9 40
......... Pivot
0 ' ' .... ' I ' ' ' I ' ' ' I ' ' ' I ' ' ' I ' ' '
0 8 16 24 32 40 48
Flow length
Confined flows considered in the previous section are mainly shear flows.
As the fluid is sticking at the wall, the flow is locally a plane Poiseuille flow
926
and this is the key point of the confined flow approximation. On the contrary,
for stretching flows, the normal stress is zero at the free surface and hence the
velocity is quite constant throughout the thickness. In the following, we
describe one and two dimensional kinematics and mechanical approximations
for the cast film process, considered as an example of free surface stretching
flow. The same basic ideas can be developed for melt spinning and blown film
processes.
In the cast film process, the molten polymer is stretched between the flat die
and the chill roll (Figure 17). The stretching process may be considered as
isothermal, and cooling is achieved very rapidly on the chill roll. A shrinkage
(neck-in) is observed in the transverse direction. The thickness is more
important on the lateral edge of the film (dog bone defect), so that it is
necessary to cut the edges after solidification. Challenge of modeling is to
predict width and thickness of the solidified film. We first describe a two-
dimensional model for the isothermal Newtonian cast-film. Coupled equations
for thickness and mean velocity in the thickness are derived from these
approximations. Then, a one-dimensional model is presented by introducing
additional approximations. This 1D model allows easy extension to viscoelastic
constitutive equations, non-isothermal conditions or multilayer film
processing. Finally, a stability analysis will be performed using different
techniques both for the 1D and 2D models.
Wo
A
v
exit
W(x)
Chill roll
at x = L. The mean surface of the film is, for simplicity, assumed to be the
plane z = 0 .
4.1.1 Kinematics
Let us note h(x,y) and W(x) the film thickness and width. The polymer
flows in the volume defined by :
1 1
{- -~ h(x,y) <_ z <- -~ h(x,y), 0 <_x <_L, -W(x) ~_y ~_ W(x) } (85)
Oh Oh
<< 1,--~-<< 1 (86)
Ox oy
~w
w(x,y,z) = z ~ (x,y,O) + o(z) (89)
c)w c)u Ov OU 8V
c?z (x,y,O) =- -ffs (x,y,O)- -~y (x,y,O)=- -~x (x,y)- -~y (x,y) (90)
Using free surface conditions on upper and lower boundaries and estimating
integrals by a mean value formula, the previous equation becomes 9
9 ~
Exx Exy 0
1~ - g.xy Eyy 0 (93)
0 0 ezz
9 8U 9 9 I 8U OV 8V 9 8U 8V
with" 8xx = o3x ; gXy = 8yx = -~ ( - ~ +-~-x ) ; ~ y = ay ; eZZ = - a x - ay
8U 8V
f i z z - - 20 (-~x + ffyy ) - P (94)
Using the zero stress condition normal to the free surface, and identifying
the normal to the free surface to z-direction, we have :
8U 8V
p = - 2r/(fiX-
x + -~-y) (95)
Gxx r 0
and hence" ff =
I I
axy ayy 0
0 0 0
8U 8U 8V
(96)
8V 8U 8V
Gyy- 2~ Uy + 2~ (gx + 7y~ ;
8U 8V
~ y = 77 ( -~y + ~ ).
929
V.(hff) = 0 (97)
U nx + V ny = 0 (98)
We add classical boundary conditions at the die exit and on the chill roll (at
distance x = L):
UL
The draw ratio is defined as Dr =
u0
4.1.4 Results o f the two dimensional model
For a given value of the thickness distribution h ( x , y ) , the velocity
components U and V and the width W are solutions of a free surface elliptic
problem (equation (97)), associated with boundary conditions (98), (99) and
(100). For a given velocity field, thickness h is solution of a transport equation
(92). This coupled system of equations can be solved iteratively by using finite
element solvers for velocity and thickness, and a fixed point method to reach
convergence [61, 62].
The preceding analysis may be easily extended to a viscoelastic Maxwell
equation. The equations and the numerical resolution are detailed in [62]
(another viscoelastic 2D model has been recently proposed by Debbaut et al.
[63]). Figure 18 presents the final thickness distribution of the film. Figure 19
shows the shape of the film between the flat die and the chill roll [62]. When
introducing a viscoelastic equation, the neck-in phenomenon is less pronounced
and the dog bone defect remains located at the periphery of the film.
930
0,15
Newtonian
gl
(1)
e-
0,10
c" c-
O r
0,05
rr' Viscoelastic i.
Figure 18 9 Final film section for a Newtonian and for a Maxwell fluid
1 ~0 ' '
0,8
..~ 0,6
i
0,4
0,2
0,0
0,7 0,8 0,9 1,0
Reduced half-width (W(x)/W O)
4.2 A d d i t i o n a l
mechanical approximations 9 a ID model
A one-dimensional model may be obtained if the thickness and velocity are
assumed to be varying with x only. In this case the model predicts neck-in and
mean thickness of the solidified film.
931
0
~x (hWU) = 0 (101)
As we are neglecting mass and inertia forces, the balance equation (97)
becomes 9
OF
Ox = 0 (~03)
1,0
0,8
_J 0,6
!
"" 0,4
1D model
0,2
0,0 9 I 9 I 9
For that particular free surface flow, the kinematics assumption (1D or 2D)
and the constitutive equation (Newtonian or Maxwell) have a marked influence
on the shape of the film between the die and the chill roll and on the final
dimension of the film (thickness and width).
1,3
x__
0,9
to
0,7
o0
t~
E 0,5
.m
ii
0,3
/ UNSTABLE,
0,1 9 I I I I I
15 20 25 30 35 40 45
Draw ratio
Figure 21 9 Cast film stability curve 9 influence of the film aspect ratio.
933
5. C O N C L U S I O N
NOMENCLATURE
cp heat capacity
-/
C t Finger tensor
C matrix
Dr draw ratio
e mass density of internal energy
E activation energy of the viscosity
F,F force
g gravity
h flow gap or thickness, damping function, mesh size
hT heat transfer coefficient
I identity tensor
11,12 invariants of the Finger tensor
k, km heat conductivity
K,K 0 consistency
l distance
L length
m memory function
n power law index
n normal vector
Nu Nusselt number
P pressure
p' isotropic part of the stress tensor
P pressure space
q heat flux
q, qx, qy flow rates per unit width
R ideal gas constant
Ro, R 1 radius of a dihedron
Re Reynolds number
S extra stress tensor
T temperature
T* test function
Te, Tw controlled temperature, wall temperature
U, V, W velocity components
U velocity vector
U* test function
935
m
o~ fill factor
".L.
second invariant of the rate of strain tensor
acceleration
e rate of strain tensor
77, 7/0 shear viscosity
F/e elongational viscosity
r/s Newtonian viscosity
A, relaxation time
P density
o stress tensor
0 angle of dihedron
f~ domain
~-'~e element
~e empty part of the cavity
fluid domain
boundary of the domain
V~ divergence
V gradient
tr trace
d
material derivative
dt
6
& upper convective derivative
0
partial derivative
Ot
REFERENCES
1. INTRODUCTION
The last decades have been marked by the spectacular development of synthetic
polymers, which are now commonly used in all of the major market sectors 9con-
sumer appliances, automotive, industrial, electric and medical. This sensational
success arises not only from the cost effectiveness of plastic parts, but also from
the wide range and amazing balance of chemical, mechanical and electrical prop-
erties of polymers. The growth of the polymer industry has been conducive to the
development of various processing techniques, among which injection molding
remains one of the most widely employed.
Injection molding is used for the mass production of identical parts obtained by
introducing a polymer melt into a cooled cavity. A major advantage of this pro-
cess is its suitability for the production, in a single operation, of ready-to-use arti-
cles of considerable geometrical complexity. As a result, its field of application is
very broad, ranging from the production of small parts such as tiny watch gears or
electronic components to large objects such as boats or automotive parts. Most
polymers may be injection molded, including amorphous and semi-crystalline
thermoplastics, thermosets, elastomers and fiber-reinforced plastics.
Injection molding is considered to be one of the most complex polymer proces-
sing techniques. A sketch of a typical molding machine is shown in Figure 1.
Primarily, two parts may be distinguished 9an injection unit comprising a hopper,
940
a rotating screw and a heated barrel, and a clamping unit containing the mold
typically made of two plates. The injection unit melts the polymer and injects it
into the cavity, whereas the clamping unit ensures the closure and opening of the
mold together with the final part ejection. In the case of thermoplastics, which
this chapter essentially addresses, the material is supplied under the form of
granules or powders introduced into the hopper. During plasticization, the screw
rotates and acts as a mixer and a pump : the material is taken from the hopper,
melted, homogenized and conveyed towards the barrel head while, at the same
941
time, the screw moves backwards. During injection, the screw acts as a piston,
moves forward and pushes the molten material into the mold. This operation
includes the filling stage, during which the polymer is injected into the mold, and
the packing stage, during which a high pressure is exerted by the screw to force
in additional melt to compensate for subsequent shrinkage due to cooling and
solidification. These steps are followed by the cooling stage during which the
material solidifies, and the ejection stage where the mold plates are separated,
thereby allowing the ejection of the part.
We shall not describe this process any further ~ the reader will find a thorough
description in [1,2]. Let us however mention three related developments which
will be addressed in this chapter. The first one is compression molding, where a
polymer charge, initially placed inside the cavity, is forced into the desired shape
by squeezing it via the motion of one half of the mold relative to the other [3,4].
Compression molding offers several advantages, in particular the use of simple
molds, the application of a low stress level during processing and a reduced mate-
rial waste. The second process is Reaction Injection Molding (RIM), where two
or more low viscosity liquids, which become reactive when brought together, are
mixed just before filling, the polymerization taking place partly during but essen-
tially after injection [5,6]. This process is typically applied for the production of
large objects due to the lower pressures required. The third class of related pro-
cesses is formed by Structural Reaction Injection Molding (SRIM) and Resin
Transfer Molding (RTM), which are both used for producing continuous fiber
composite parts by injecting a thermosetting resin into a mold filled with a fiber
preform [7,8].
In all these cases, the design of a new mold is a delicate and time consuming
task, often requiring dedicated trials and experiments. The aim of numerical
modelling is to prevent this costly and lengthy approach by providing an easier
way to apprehend the physics involved and to assess the influence of the key pro-
cess parameters. Quite clearly, the ultimate objective is, given a polymer, an ap-
plication and a desired type of geometry, to allow the numerical determination of
an optimum mold design together with the most appropriate operating conditions.
However, the numerical modelling of the filling and packing stages of the injec-
tion molding process (which represents the subject of this chapter) is plagued
with various difficulties. For the sake of simplicity, let us restrict ourselves here
to non-reinforced thermoplastics. During filling (Figure 2), the mold plates are
maintained at a temperature lower than that at which the injected material solidi-
fies. The problem is thus transient and 3D, in view of the front motion and the
important heat transfer between the melt and the cavity walls. Another difficulty
arises from the temperature dependence of the polymer viscosity, which couples
942
jjjjjjjj..~W~alJ~jjjjjjjj
Te
Jt e
Gate I ~ ~ ~
................................. 9 ........ i .......................
Front
the kinematics and the temperature distribution, especially close to the walls
where the lower temperatures increase the viscosity and slow down the fluid or
lead to the formation of a frozen layer. An additional difficulty relates to the
theology of polymer melts, which exhibit a strong non-Newtonian behavior as a
result of the very high shear rates prevailing during filling. Finally, the high
temperature gradients and pressures involved induce significant compressibility
effects, in particular during the packing stage.
A comprehensive numerical simulation of injection molding therefore appears to
be an outstandingly difficult task. Nonetheless, the geometry of molded parts is
typically characterized by a small thickness compared to the other characteristic
lengths or radii of curvature. As a consequence, Generalized Newtonian (GN)
stresses may be assumed and the goveming equations can be considerably simpli-
fied over most of the flow domain. The rheology of molded polymers is analyzed
in Section 2, while Section 3 details the flow and heat transfer model resulting
from the thin cavity assumption. The numerical algorithm accordingly developed
at the University of Louvain (UCL) [9-26] is presented in Section 4, and illustrat-
ed in Section 5 by means of simulation examples and experimental validations. In
these sections, only the injection and compression molding of thermoplastic mate-
rials are addressed. Extensions of the model to the cases of reactive resins, semi-
crystalline polymers and the filling of fiber mats are considered in Section 6. The
molding of fiber-reinforced polymers is investigated in the companion chapter
"Suspensions : Modelling the Flow of Fiber Suspensions in Narrow Gaps" (which
will be referred to as "Chapter FS" in the sequel).
943
model will be presented. The elastic Finger strain tensor B (.e) and the symmet-
ric plastic rate of strain d o are defined to represent the partially relaxed elastic
deformation from initial to actual state and the irreversible relaxation rate of elas-
tic deformation, respectively (without volume change effect). Letting t , x i and
v i stand for time, Cartesian coordinates and velocity components, the constitu-
tive equations for B (.e) and dip can be put in the general form [57,111] 9
v
#~(e),4
B(;e),j + de pB(e),~ ,~J 4" "ik '*kjp -- 0 , (1)
v
where the convected derivative _Bij(e) is def'med to maintain d e t ( B ( e ) ) - I 9
and Rv ij(e)-a denote the deviatoric parts of R--ij(e) and B (.e)-I Extra-stresses are
defined as follows 9
"gij -- 2 ( B(e)d
""
awlat,--itl(e)-d~ ij
V/012) 9
(4)
while the shear viscosity 0 and the 1st and 2 "d normal stress coefficients ~1
and I[/2 are functions of temperature, pressure and shear rate (~'), with
t2 -- 2 dqdq . (8)
. - + , (9)
with a - 1 - n for the Cross mode! and a - 2 for the Carreau model, are suc-
cessful in describing the shear stress/shear rate relationship for a large variety of
polymer melts. This was demonstrated by Hieber et al. [52,59,114,115], Chiang
et al. [56,78], Chen and Liu [73], and Douven et al. [64], who obtained excellent
pressure validations in PP, PS, ABS, PC, nylon and PMMA filling and post-fill-
ing experiments. In (9), rl0 - ~10(T,p) and the constant v 0 are the zero shear
rate viscosity and shear stress, while n is the power-index (0< n < 1). The
Cross model adequately fits the viscosity curve for polymers of broad molecular
weight distribution [52,59,115] and should thus be generally preferred to the
Carreau model. In the log-log diagram, both laws exhibit a Newtonian plateau at
low shear rate and a power-law asymptote of slope ( n - 1) at high shear rate. It
is interesting to compare the shear viscosity of the Leonov model to the Cross and
Carreau laws. As an example, Simhambhatla and Leonov [111] propose to use
b(Ii,I2)-(I2/I1) m in (2) for LDPE melts. Equations (l-S) provide an equiv-
alent shear viscosity which exhibits the expected Newtonian plateau and power-
law asymptote. Other values can be obtained depending on the selection of
material fimctions.
A last simplification is often introduced. In view of the short process cycles in
injection and compression molding, the wall shear rate is generally quite high and
946
provides a fairly good viscosity estimate to calculate the shear stress ( ~ - r/~') in
the cavity. Let us point out that Verhoyen and Dupret [23] have shown that the
kinematics of GN fluid flow in a thin cavity is relatively insensitive to the
viscosity dependence upon shear rate, even at low flow rates, whereas stresses
are highly viscosity dependent (see Section 3.3).
The GN model has been extensively used in the simulation of molding pro-
cesses, especially with power-law and Cross law viscosities [9,10,14,17,23,26,
31,37,40,41,52,56,64,66,69,72-74,76,78,79,104]. The present chapter focuses
on these models. The calculations of flow stresses via viscoelastic rheology and
GN kinematics is discussed in Section 3.4.
In polymer melts, the heat flux can be modelled by the Fourier law,
qi - - k o~/oqxi , (11)
where k - k (T,p) is the thermal conductivity. An empirical role and data are
proposed in [56,64]. According to Douven [ 116], it is not necessary to consider
anisotropic conductivity effects in injection and compression molding, even when
molecular chains are highly oriented by shear, since heat conduction within the
fluid is dominated by the transverse flux contribution (and thus only one compo-
nent plays a non-negligible role). It should be noted that most of the available
data do not take into account the pressure dependence of k, whereas compari-
son with experiments seems to indicate that this effect can be non-negligible (see
Section 5).
To complete the model, constitutive equations are needed for p , H , and S.
During filling, most of the fluid is in the liquid state and, for amorphous thermo-
plastics, p is a function of p and T (with very fast relaxation). The Spencer-
Gilmore state equation was often used in early studies [37,68]. Nonetheless, it
seems that the empirical equation of Tait [56,60,64,73b,116,117],
l i P - ~/Po - - C/Po ln(1 + p / B ) , (12)
where C is a dimensionless constant while l i P o and B are material func-
tions, is more appropriate to model l i p in both the liquid and the glassy states.
The glass transition temperature Tg is assumed to depend linearly upon p,
while 1/p o and B are linear and exponential functions of T,
with different coefficients ~i used above and below Tg. This approach is not
completely satisfactory in the vicinity and below Tg, where relaxation is much
slower. According to Kabanemi and Crochet [118], both stress and thermal ex-
pansion relaxations must be considered during the cooling stage. This is achieved
by introducing the concept of fictitious temperature (i.e. the temperature of local
thermodynamic equilibrium), together with additional relaxation functions (for
pressure and for fictitious temperature).
Finally, H is in principle a function of T, p and the shear elastic deforma-
tion. In the case of a GN fluid, shear elastic effects are neglected and
c)H/c?f - Cp , OH/Op -(1-~g/')/p , (14)
3. MATHEMATICAL MODELLING
3.1.1 A s y m p t o t i c analysis
Scaling is very complex in molding processes in view of the many dimensionless
numbers involved, and we refer to the book of Pearson [2] for more detail. Our
aim is, following Van Wijngaarden et al. [31] and Dupret and Vanderschuren [9],
to treat the lubrication approximation as an asymptotic model in order to provide
a sound basis for the construction of the boundary conditions. Under the assump-
tion of a low and slowly varying gap thickness 2h, asymptotic equations are
obtained by letting the dimensionless number e = h o / L tend towards zero,
where h0 and L are characteristic dimensions of the gap and the part, respec-
tively. This approach clearly distinguishes two flow regions [12,33,120], namely
the outer zone where the lubrication approximation is valid, and the inner zones
which are formed by the flow front, side wall ... boundary layers, that will be
investigated in Section 3.2.
It is sufficient to consider a model problem, where the fluid is assumed to be
incompressible, with a power-law viscosity and constant thermal properties,
while the part is symmetric with respect to a planar midsurface (Figure 2). In-
plane coordinates are denoted by x a , with Greek indices going from 1 to 2,
while the gapwise coordinate is denoted by z or x 3. Latin indices go from 1 to
3. The injected or initial fluid temperature Ti and the wall temperature Te are
given constants. The filling duration is denoted by it. The mass, momentum and
energy equations read as :
Ov, = 0 , (17)
C~Xi
Ox i Ox j
949
The dynamic similitude assumption states that, when e--> 0, the dimensionless
fields v a' , w' p' and T' (as fimctions of x~, z' and t ' ) tend towards
given limits provided the function h'(x'#, t') is fixed and the less d e g e n e r a c y
principle is applied to determine the scaling factors w0 and P0 and to remove
any indeterminacy in the limiting process. Asymptotic equations are therefore
obtained by assuming that dimensionless pathlines tend towards given limits,
together with the fields p' and T ' , when the above conditions are satisfied.
Writing the mass equation (17) in the form
To remove any indeterminacy, a" and b" must be fixed asymptotically in such
a way that the products b'p" and a'T" do not degenerate when e---)0.
Further, considering equation (24.1), less degeneracy imposes to select P0 as
P0 - moe-ari/(El+n~n I . (26)
lk l
where the Graetz and Brinkman numbers (which represent the ratios between the
advected or dissipated heat and the heat which is diffused in the gapwise direc-
tion), are defined as
av a g4, = 0
3p = 0 , (29)
oaxa 0 , 0z
v cp + v ~ -&--~ + w - - g - o
,nl
~2 _ (0 v~ / 0 z) 2 . (30)
To consider the presence of a solidified layer along the walls, the viscosity law
must be modified and additional dimensionless numbers are needed. In early
951
studies [2,28b,31,33], a no-flow temperature was often introduced but this con-
cept is difficult to define rigorously. It is better to use a WLF-type viscosity law
(equations (15) and (16.2)) throughout the entire cavity. Asymptotic equations
are obtained in the same way as in the present section.
where Pr is the specific mass at the temperature Tr and zero pressure, while
fl(T) and 7(T) are material functions, the former being constrained to vanish
when T = Tr. Two kinds of gap average quantities will be used. Letting
~p(xa,z,t) stand for any physical field, the averages ~ and r are defined by
h
2h - f 0a , 0co, (32
-h
where to(x~,z,t) is a so-called profile function, which is proportional to the
velocity profile in the gap and will be defined later.
Consider first the in-plane momentum equations (29.2) (which are not affected
by compressibility). A first integration over the gap provides the relations
O~ ot _ Op z - z0
(33)
Oz 3x~ 71
where zo(x~ ,t) is the unknown level at which 3v~/Oz vanishes. From (33)
and (20), the viscosity is thus provided by the relation
o" mo - n-' . (34)
952
A second integration provides the in-plane velocity components from (33) and
(34), taking the wall no-slip boundary conditions into account"
2h pv a = - S o Opioaxa , (38)
where the fluidity S o is given from (31) and (32) by the expression
ap ~ ~ ( p v ~ ) + (~) - 0 (4~
oat Ox~
From (38), integration provides the 2D pressure equation"
c9 r (Sp O p ) (42)
~-(2hfi)- ~ ~, ,
where the derivatives a*/o~ and O*/o~ are carried out while f'~ing z / h
instead of z (as in the a/& and O / ~ derivations). This expression is
convenient in numerical calculations because z / h (and not z) is used to posi-
tion the nodes in the gap.
The thicknesses ~+ and c5- must be evaluated from the "no-flow" temperature
Tm. Discretization nodes are optimally placed at the "solid"-liquid interface
(where T - Tm), and the mesh or grid must be adapted to ~+ and S- [31]~
Finally, when compressibility effects are taken into account and the lubrication
approximation is used, the energy equation takes the form (from (14))
954
0% + + w--s - ccc + +
(46)
-t- m 0 e b p - a T ~)n+l
The heat transfer in the steel mold can be simplified in the same way and the
governing energy equation within the walls is
PsCs(V3T
~ +-oat
O h ~o~) = (z>h
, or
_ z <_ - h ) (47)
where Ps, Cs and k s denote the steel material properties. Equation (47) is
coupled with the heat transfer in the gap. This model was improved by Chiang et
al. [78], who superpose a steady 3D contribution obtained by averaging the
successive molding cycles, on the transient contribution provided by (47).
3.1.3 Extensions
Extending the Hele Shaw model to curved midsurfaces is very easy [9], since
asymptotic analysis can show that curvature effects are negligible in Hele Shaw
flows because the gapwise dimension is "infinitely thin" as compared with in-
plane dimensions. The goveming equations must be adapted, since the easiest
approach is to use a unique Cartesian system of axes Ox i to represent all the
vector and tensor components, together with curvilinear coordinates (~1,~2,~3)
to represent the position. Any vector field (such as velocity) has 3 in-plane com-
ponents v i and an additional out-of-plane component w. Letting ~a denote
the in-plane coordinates and ~3 represent the distance to the midsurface, the in-
plane gradient of a quantity such as T is calculated by the matrix formula
Oxi
] = A(ATA)-I O~1 c?~2 ' (48)
with A ( 3 - E "]
~ 0xi , while DT/Dt is calculated as follows"
DT o~ ~T (ip)
= ~ + Vi-'---'X---t- W ~ . (49)
Dt & oaxi c?~3
Another very important extension consists in considering other viscosity laws,
such as the Cross law (see equation (9)). If a pressure-temperature decoupled
955
~e~o
103 . . . . . . . . . . . . . . . . I ' ' 103 .... 'r, "1 ..... "'''1 /' ' "
lOl .............................
i...............................
i/ ........ ::.. 101 ............................ + ............................... ~ '.t.~"......... .1
..............................................
i .........i............... 10 ~ ............................ i....................
1~176
I ........ .~..................... ::j:i!..----':::i~ .... ..'--::..::b'"" . . . . . . . . . . "1
10 -2 ii..... 10-2 , ,
10 .2 10 4 10 ~ 10 -2 10 -1 10 ~
Z'/Z" 0 Z'/Z" 0
~/~o 1//1/o
10 x ........ t ........ J ........ I ........ t ...... ": 10~ ~: ........ ~ ........ i ........ ~ ' '"' ..... t ...... ".-
10 ~ 10 ~
! i ... f................!................i..............i
10 -1 . . . . . . . . . . . . . . . . . . . . . . .
1 0 -1
10 -2
10 3 10 -2 10 1 10 ~ 10 ~ 102
10-21
1( f3
!iii.i....iiiiiii10-2 10-1 100 101 102
numerical scheme is required, the approach of Verhoyen and Dupret [23] can be
used. The quantities 7/o and Vo are approximated as follows 9
where the number of terms in the 1 st expansion must be limited to reduce the
computational cost, while the 2 no decomposition is sufficient because ~:o is most
often close to a constant. According to (29), (30) and (33), the shear stress ~:
can be written in the form
On the other hand, from (9) and (50), the reduced shear stress z / z o is a given
function F n of the reduced shear rate (r/0 y/'c o )"
In the case of symmetric temperature and velocity profiles (z o = 0), each term of
(55) can be integrated as in the case of a power-law viscosity. The non-sym-
metric case requires to approximate [z - Zo[8i/n sign(z - z0) as a stun of powers
of z and z 0. At each time step, the gap integrations can therefore be performed
once and for all when the temperature profile is known.
3.2 B o u n d a r y conditions
X3
I
|
_ m R . ~
L
r Xt
Figure 5. Sketch of the fountain flow 9 relative motion of the fluid with respect to
the front.
(b)
0.0
.ok,
0.8 max ~ '
'~ 0.6
t~ 0.4
0.0 L
o 50 100 150 200 250 300
x [mm]
Figure 6. Cross-sectional space-time distributions obtained by (a) the isothermal
and (b) the non-isothermal filling of a rectangular plate. The residence time of the
material points is in seconds. The separation line (in bold) is not the line of maxi-
mum residence time when w is taken into account [20].
"infinitely zoomed snapshots" at any location and time on the from. More
precisely, letting the origin of the axes move with the front and selecting any
initial time during filling, physical quantities are scaled as follows :
X i -- hox i , t = e "C t ,
where the matching conditions impose (and this is a key point) to keep the same
pressure and temperature scaling as in the outer zone.
The mass equation is not affected by the scaling process. Its dimensional
asymptotic form is thus exactly (17). In a similar way, all the terms defining ~'
in (8) have the same order of magnitude and the dimensional asymptotic shear
rate is thus exactly given by this equation. Also, the viscosity is not affected by
the limiting process. The dimensionless momentum equations reduce to
959
o3p'/cgx[- O(e), which means that their asymptotic dimensional form is
o ~ / ~ i - O. Therefore, the 0th-order term of the pressure expansion is constant
in every inner front region. In a further step, the 1St-order terms of the dimension-
less momentum equations are considered :
eb'p'-a'T" e (onv[ + +
where, for matching purposes, Gz, B r , a" and b' have the same value when
e ~ 0 as in the outer flow. The dimensional asymptotic form of (59) is thus
O T / O t - OT/Ot + v i anT/oqxi - 0 . (60)
The temperature of each material point therefore remains constant when it crosses
the front region.
The matching conditions impose velocity, pressure and temperature "continuity"
between the inner and outer regions [120,124] :
lim ( v l , v 2 , v 3 , p , T ) -
HS , v 2 HS O, p HS T HS )
v1 (61)
xl-~-oo ' ' (xl =0) '
where the superscript (t-/s) indicates the Hele Shaw outer solution. The order
of magnitude of w in the Hele Shaw flow (equation (23)) imposes to match v 3
with 0. As different scales have been used for both x 2 and t in the inner and
outer expansions, the relations (61) indicate that inner flows are two-dimensional
and quasi-steady. This discussion indicates how to select appropriate front
boundary conditions in the Hele Shaw model :
9 The asymptotic front region is infinitely thin and consists of a set of straight
segments perpendicular to the midsurface.
9 The front pressure in the Hele Shaw flow is the atmospheric pressure when
960
In fact, the characteristics of the simplified energy equation (46) are leaving or
entering the flow domain depending on whether the material point is moving
faster or slower than the front. Hence, one thermal condition must be imposed
at the level z2 while no condition may be imposed at the level z~.
Zl~
w
The front condition (62) is not affected by compressibility effects, since the front
inner pressure is a constant. The pairs of levels associated through condition (62)
are governed by mass conservation. Letting r.of denote the mass averaged
profile function (see (36)),
p - ) - 0 (64
Note that (_Of provides the front in-plane velocity vaf from (35).
The above discussion shows that, according to the terminology of Garcia et al.
[58], the "mass balanced front model" introduced in [9,49] relies on a sound
mathematical basis and fits perfectly with the Hele Shaw approximation. Also,
this approach can be used to model the effect of fountain flow when fiber rein-
forced polymers are molded (see Chapter FS). All the "simplified and averaged
961
simplified front models", which set the front temperature uniform and equal to the
centerline [40b,69] or average temperature just upstream of the front, present
mathematical inconsistencies which can induce heat losses at the front. However,
these models generally behave quite well [58] since temperature variations are
weak in the front region. Hence, no significant problem can be detected with the
mesh or grid refinements typically used. Finally, the solution could be improved
by solving the simplified inner flow problem and improving matching between the
inner and outer solutions. This coupled technique is quite complex and, in this
respect, the simplified model of Castro and Macosko [32], as adapted to 3D
flows by Peters et al. [ 104], provides a good method to gain accuracy.
from an asymptotic analysis. This theory will not be detailed. Using the scale L
along the side wall and h in the other directions, it is easy to develop the inner
flow governing equations and to conclude that the following conditions must be
imposed on the Hele Shaw solution at the side walls :
9 free slip of the averaged flow, which provides the condition 0p / ~gn = 0 ;
9 no thermal condition, because the characteristics of the energy equation are
tangent to the side wall.
It is also possible to define along the side walls a classical displacement boundary
layer thickness, which does not increase in the flow direction.
The situation is totally different on the upper and lower cavity walls, since the
objective is to approximate their thermal effect by means of boundary conditions.
For that purpose, it is sufficient to consider the upper wall ( z - h). The heat
transfer in the metal is governed by the 1D equation (47), with the following
boundary conditions :
9 continuity of temperature T w at the solid-fluid interface (z = h);
9 balance of heat flux at the interface (the heat flux entering the wall is qw);
9 matching with the initial wall temperature Te 9 T - T e , if (t < tf , z >__h ) ,
where t f denotes the time at which the front reaches location x~;
9 matching with the regulation temperature T e 9 T = T e , if (t > t f , z - h + ec),
where ec is the distance between the interface and the thermal regulation
channels; e c can depend on position x a .
962
Zt
h+e c coolant
h + e(t) T
wall
o.(t) T :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
":::'::"":.'.".'5.'L':':.",':',':',':'.'L'.".':','L'.5"L
h . . . . . i ._
r
polymer
z)
Te Tw(O Temperature
Figure 8. Typical temperature profile and thermal penetration length.
An accurate wall thermal boundary condition can be established from the theory
developed by Dheur [16] (see also [9,26]), as long as a monotonic and smooth
behavior of qw prevails ( T w is generally higher than T e and qw is positive
and decreases with time with thermoplastics, while T w is lower than Te and
qw is negative and increases with time in the case of thermosets). In that case,
the temperature profile within the wall can be approximated by a linear function,
where e is the (unknown) thermal penetration length (Figure 8). The required
boundary condition is established by means of the Galerkin method, using linear
test functions and taking into account the flux conditions 9
- k s -a-T~ ( z = h ) = q w , -
- - ~ ( z - h + e) = 0 . (66)
The thermal behavior of the upper and lower walls is complicated by the foun-
tain flow, which generates a thermal shock between the core polymer and the
walls, with a resulting singularity on the front-wall intersection lines [28a]. This
effect can be analyzed by means of the thermal shock theory between two semi-
infinite rigid bodies of initial constant temperatures Te and TZ o [44], since the
fluid motion and the non-uniform temperature field play no role close to the sin-
gularity during the first instants following the shock. This theory shows that Tw
remains constant after the shock. In a similar way, when a thermal shock is con-
sidered between a semi-infinite body (the fluid) and a model body (the steel wall)
where conditions (67) hold, Tw again remains constant after the shock [26] 9
and where Tfo denotes the temperature of the fluid making contact with the
wall at time t f . After the shock, the temperature profile inside the "semi-infi-
nite" fluid is easily calculated in terms of the complementary error function, while
the thermal penetration length is
///// ~/i// I
I//11111/11111
(d) /
(c) f / / / / / /
IIII/
//////,
,,,..._
///I/IS
,,....-
/ / / / / / / / 7 / / / / / / / / 7 ~ 7 / / / / / / I / / / / / /
T(z2)=T(Zl ) 2h2
2h-
~'///////// 'j~
2h +
1
with respect to the singular line. Flow separation and junction can be simultane-
ously present along different segments of a bifurcation. In both cases, an impor-
tam consequence of (62) is that the temperature and velocity profiles are no
longer symmetric with respect to the midsurface in the downstream branch(es),
even when the upstream flow(s) is (are) symmetric [17,125]. This effect, which
can influence the flow far downstream from the singular line, will be investigated
in Section 5.1. It should also be noted that an internal thermal shock takes place
in the case of flow junction.
This theory has multiple extensions, in particular when dealing with semi-crys-
talline or reactive polymers, or with fiber suspensions, or with the filling of fiber
mats (see Section 6 and Chapter FS).
linity, fiber orientation ... non-uniformity, which is most often observed just
downstream from the gate(s), is a consequence of the flow kinematics in both the
runners and the gates. A typical example will be analyzed in Section 5.2. In
general, the complexity of the role of the feeding system can be explained by the
very low thermal conductivity and quasi-vanishing diffusion coefficients of com-
mon molten polymers, which result in a lack of mixing when the fluid crosses the
runners and the gates.
The flow in the gates is highly complex, since it is 3D and viscoelastic, with
high Deborah number [2,22,79]. Model simplifications are hardly conceivable.
Quasi-steady flow may be assumed and heat conduction may be neglected, while
the effects of polymer compressibility and thermal dilation can be simplified. The
main issue is to determine whether a model coupling extensional and shear
viscosities is sufficient to represent the main transfer effects. Similar, but less
critical, difficulties appear in the bifurcations of the runner system.
To accurately calculate the flow in the runners, their trapezoidal shape must be
taken into account since it induces transverse recirculations that can affect the
heat and mass transfer. The simplified mass and 3D energy equations are estab-
lished in the same way as in the mold cavity by means of the lubrication approxi-
mation, and all details will be omitted. Letting x a a n d z denote the transverse
and axial coordinates, it is again convenient to introduce a profile function oJ,
which depends upon temperature profile only [22]. The axial velocity component
w is proportional to o~, which obeys the equation
c) e_aT 0(.0 _
~x~ [l ll ~ -1 , (74)
with o~ = 0 along the boundary of the nmner section. Evaluation of the trans-
verse velocity components va in the energy equation must be performed care-
fully, since mass conservation provides a single equation. The system is closed
by taking the 2D c u r l of the non-simplified transverse momentum equations 9
3
[ (();
0 0v/~ Ovr rl~-~-
-,, -.j x2
'", , Front
I I
m~ ~ p ~ - ~t/(2 m +1)
...... ::- ..... ~: m, ...............
1; Oblique 0 * Horizontal p*
side wall side wall
\ \ \ \ \ \ \ \ \ \ \ \ \ \ \ ~ \ \ \ \ ~ ~ \ \ \ N \ \ \ \ \ \ \ \ \ \ ~ \ \ \ \
Figure 11. Hele Shaw flow past a comer" schematic diagram in the real and
complex potential spaces (top); successive fronts calculated from the analytical
solutions (bottom).
Hence, from the front pressure condition and equation (33), vcr is normal ev-
erywhere to the front line and the flow fronts are perpendicular to the side walls
(in Hele Shaw flows, side walls are equivalent to reflection symmetry lines).
In this section, the following problems will be addressed"
9 How does the front cross a side comer, or the vertex of a conical midsurface ?
9 How do weldlines form, and how does the front collide with the side walls ?
9 What is the effect of an abrupt change of thickness or a bifurcation ?
968
(77)
: Im(r : o, if - o, -Kt<_r
Im(~e-mn/) : 0, if lit-O, <-Kt, (79)
where 2hp K t / S o is the comer pressure and the constant K needs to be deter-
mined. After a few trials, the solution is found to be
( 1 1
~ + ~ ~
(8o)
rot 2m + l v0 t 2m + l v0 t
Hence, K - Vo2/(2m + 1) and the front velocity along the side wall Vfe is, from
(77) and (80) with r - ~ - 0 , V fe -- Vo/(Zm + 1).
969
Solutions are shown in Figure 11. When the front runs past a salient comer, or a
cone vertex whose total midsurface aperture angle is lower than 2Ir, a stagnation
point forms immediately at the comer or the vertex, and a material line joining the
comer to the front extremity, or the cone vertex to the closest front point, starts to
stretch out. This line is initially infinitely small and forms a weld line in the latter
case. When the front runs past a re-entrant comer, or a cone vertex whose aper-
ture angle is higher than 2zt, the velocity immediately becomes infinite at the
comer or the vertex, which are continually crossed by material points. These
conclusions are reinforced when the viscosity obeys a power-law. With a Cross
or Carreau law, the flow in the vicinity of a stagnation point is governed by the
Newtonian viscosity plateau.
Analytical solutions of the flow in Hele Shaw cells were investigated in detail by
Richardson [128] and Entov et al. [129], while Aronsson [130] develoved very
simple solutions for the limiting case of a zero power-index fluid (n - 0).
V+
+ + v~)
d/~ ~ffont
v;: ,
. ~__ x 1
Figure 12. Flow across an abrupt change of thickness" (a) sketch of the front
velocities; (b) uniqueness of the intersection of the front and the singular line.
When a front collides with a side wall, the kinematics are the same as when two
symmetric fronts meet. Boundary layers are however different.
EV +2]/v+ E 2
"k- V 2 f 2f Vlf q" V 2 f 21/v' 9 (83)
971
Equations (82) and (83) can be cast in a more convenient form. In the case of a
power-law viscosity, the fluidity is given by (39), or equivalently, from (38), (40)
and (76), by
= m0 -1 ( n - l + 2)-nh , (84)
while ][vaf[I- Vlf 2 -FY2f 2 )1/2 can be eliminated by means of (83). Hence,
after some calculations, the following relation is obtained :
v 2+f / h +2 -- V2T
- / h -2 . (85)
Also, multiplying (83) and (85) side by side provides the relation
-- + +
The 3 equations (81), (85) and (86) involve 4 tmknowns (vlf ,v2f, vlf, v2f ),
which can thus be determined to within a multiplying factor. In particular, the
angles o~- and t~ + formed by the upstream and downstream velocity direc-
tions with the singular line are functions of the ratio (h+/h -) only"
The same formulas apply whether h + is higher or lower than h-. Two patterns
are thus possible, depending on which is the feeding and which is the fed branch.
Also, it can be observed that a vanishing or infinite thickness ratio corresponds to
the case of a lateral side of the mold. When h + = h - , the angle a + = a- is
indeterminate and (87) is no longer valid. When h is close to h-, a front cur-
vature boundary layer is thus present near the singular line in the Hele Shaw flow.
The m-plane dimension of this boundary layer is governed by the flow pattern and
the thickness ratio, but not the actual thicknesses. Hence, although (87) is valid
in theory, numerical solutions can exhibit angles o~+ and a - that differ from
their theoretical values, except if a very strong mesh refinement is used. In
reality, the flow in the singular region is governed by the theory developed in
Section 3.2.3. The inner flow domain is partly or totally superposed on the front
curvature boundary layer, which can be absent from experimental results.
The analysis of a bifurcation can be handled in the same way. Two problems
972
must be set apart, viz. flow separation and junction. A different equation governs
mass conservation in these cases, while pressure continuity and uniqueness of the
intersection between the fronts and the singular line each provide a pair of
equations. A total of 5 equations with 6 unknowns is thus found and the same
conclusions can be drawn as in the case of an abrupt change of thickness.
Verhoyen and Dupret [23] have shown that this theory can be extended to more
general viscosities, including the Cross and Carreau laws. Indeed, the jump equa-
tions (81-83) remain valid, together with (33), (38) and (51) (from the lubrication
approximation). Hence, the following expressions are successively found for the
fluidity:
On the other hand, from (51) and (54), the shear rate is
However, from (88), H0p/Oxal[ S o h - ' [l~o~l[-1 i~ continuous across the singular
2 -I1 / 11 s;
since h+v;f / S ; - h-v2f / S ; , (94)
in view of the pressure continuity gradient. Therefore, comparing (91) and (93)
973
shows that H n (h [lOp/ oaxaIi/*0) is continuous across the singular line, since 7/0
and "ro are functions only of p. Hence, h IlOP/Oqxall/'r0 is itself continuous
since H n is strictly increasing, and thus from (93) :
Sp+ // h +3 - S p / h -3 , (95)
which also involves from (94) the continuity of v2f/h 2 (equation (85)).
Further developments proceed as with a power-law viscosity.
Similarly, it can be shown [23] that, when an unbalanced bifurcation is fed with
incompressible isothermal fluid through the upstream branch, and the incident
velocity is uniform and normal to the singular line, the motion of the fronts down-
stream of the bifurcation depends only upon the thickness ratio, but not on the
viscosity law. These considerations have far reaching consequences and explain
why the filling kinematics are, in general, only weakly dependent upon shear
thinning effects and dominated by thermal effects.
N1 (MPa)
0.1
Direct
- Indirect
6
0.06
0.04
0.02
tO
0
-' -0.5 0 0.5 1
4. N U M E R I C A L SOLUTIONS
over which the problem is discretized. There is no longer any free boundary,
with the drawback that it becomes very difficult to address the complexity of
typical industrial parts. Whereas conformal mapping was used in early studies
[44,128a], the Thompson algorithm seems to behave better, see the results
obtained by Gtigeri and co-workers [74,77,98,133]. Particular methods are de-
veloped in [77,98] to couple the 2lAD Hele Shaw model with full 3D calculations
in the singular flow regions (front zone and junctures). On the other hand, the 1st
remeshing algorithms were based on the generation of successive element layers
according to the 2D front progression [52,66,73a], but this technique can hardly
be extended to general shapes. The best approach, as used in the MOLDSYS
software (see the next section) and in [80,104,132,134], consists in tracking the
front(s), recovering as many elements as possible from a fixed mesh covering the
entire midsurface, and generating new elements in the remaining portion of the
filled area.
To close this review, it is worth recalling the various techniques elaborated to
simulate the packing stage [14,56a,60a,61,64,68,70,78,104,132] and to under-
stand the fountain flow goveming mechanisms [48,50,51,54,55,70,77,122,123].
rare evolution upstream of the initial front of the time step, which can be treated
as an outlet section (without thermal boundary condition). The characteristics of
(46) are indeed leaving the domain along this "initial" flow front. On the contra-
ry, the effect of fountain flow must be taken into account in the region located
between the initial and final fronts, since characteristics are leaving or entering
this region across the moving front depending on whether the material points
move faster or slower than the front. The extrapolation mesh is therefore built on
in the inter-front region and equation (62) is considered for the fluid layers that
re-enter the domain after having experienced fountain flow. This method is
general and can be applied to any field for which in-plane diffusion is neglected.
To describe the time-dependent algorithm, it is sufficient to consider a single
time step. Let M n, F n, ~ n denote the mesh, front(s) and discrete domain at
time t,, and [Phi, [T~] the associated column vectors of nodal pressures and
temperatures, while [Vn] and [Wn] stand for the discrete in-plane and out-of-
plane velocity components along the front(s) and inside the domain at the integra-
tion nodes. Additional fields [ A n ] represent the nodal crystallization or curing
degrees, or orientations ... if need be. While the flow fronts move from time t n
to tn+ 1 , they scan the "inter-front region" An+1 . This area is discretized as a
quadrilateral "extrapolation" mesh denoted by En+ 1. T h e sequence of operations
needed to calculate these quantities at time tn+ 1 is organized as follows :
9 Front displacement so as to obtain the extrapolation mesh En+ 1 together with
^
lation of [7~n+l], [/~n+l] on the inter-front zone An+1 , taking fountain flow
conditions into account. Correction of the temperature and other fields so as to
obtain I T n +l ] , [an+l] on M n +l .
9 Implicit pressure time integration so as to obtain [Pn+l]" Calculation of in-
plane and out-of-plane velocities [Vn+1] and [Wn+1].
4.2.1 D e t e r m i n a t i o n o f the n e x t c o m p u t a t i o n a l d o m a i n
Front velocities are oriented along the boundary for vertices lying on the side
walls, and along the bisectors at the front for other vertices. The fronts are
978
I |
moved using the Euler scheme [13]. A more sophisticated technique would be
very difficult to implement since, during the time step, not only can the shape of
the domain evolve, but so can its topology as flow fronts merge, divide, or meet
the boundaries. Also, it was shown by Couniot [13] that the present remeshing
algorithm is of a very low order and that there is no point in devising sophisticat-
ed techniques. The Euler scheme has the benefit that the area scanned by a front
segment is represented by a quadrilateral, possibly degenerating into a triangle.
The union of these elements defines the extrapolation mesh. In the case of thick-
ness discontinuities or bifurcations, as velocities undergo a transformation when
the material points cross the singularity (see Section 3.3.3), each quadrilateral
originating from an upstream facet (relative to the singularity) yields one trans-
formed quadrilateral per downstream facet (Figure 14). Managing the extra-
polation mesh then becomes relatively easy [ 17]. The situation is more complex
regarding front junctions.
Computing the new position of the fronts features the difficulties of computa-
tional geometry [ 13], these stemming from the discrepancy between pure geomet-
ry and its numerical transposition. As a consequence, geometrical algorithms
involve tolerances, which means that the transitivity of geometrical properties is
lost (e.g., two straight lines which are parallel to a third line to a given tolerance
are not necessarily parallel to each other to the same tolerance). The complexity
of these algorithms is therefore often dramatic, particularly in the simulation of
molding processes when a front tracking strategy is selected, since the size of the
element sides must be controlled in order to obtain well-behaved meshes. To
overcome these problems, the solution must be implemented as a mix of numeri-
cal and logical operations. In particular, the present front motion algorithm is
979
Completely filled
[ I Partially filled
based on the concepts of "virtual front nodes" and "events" [13], and uses as
reference the fixed mesh. Basically, a virtual node corresponds to the intersection
of one front segment with one side of a mesh element. As the front moves, the
virtual node moves along the element side until it reaches a mesh vertex, which
constitutes a first type of event. Other event types include the crossing of a mesh
boundary or a re-entrant comer along the boundary. All the events are sure to be
detected and simultaneous events can be processed asynchronously (which
consists in removing or inserting virtual nodes in the front description). Hence,
operations are mostly logical and not numerical.
4.2.2 Generation of the temporary mesh used for the next iteration
The discrete front description provides a partition of the elements of the fixed
mesh into three classes, viz. the elements which are (i) completely filled, (ii)
completely empty, and (iii) partially filled (Figure 15). A simple approach would
be to re-use as such the elements of class (i) and to generate additional elements
in the remaining portion of the filled area ~ the so-called generation zone. This
approach is workable with some enhancements. First, the discrete front descrip-
tion must be modified in order to handle front-side wall and front-front meetings,
and filtered to ensure that the local front discretization scale corresponds to the
local fixed mesh scale. Such conditioning can be achieved by redistributing the
front vertices so as to preserve mass balance. As front collisions are treated by
accepting a slight overlap between the colliding fronts, or a slight crossing of the
side walls, it is easy to detect and remove the dead front segments. Front filtering
must also remove the unfilled areas which are regarded as negligible and increase
the filled areas which are still negligible (removing matter can lead to a halt or a
non-natural motion of the fronts). The simulation time is finally adjusted on the
980
basis of a comparison between the total mass integrated at the nozzle and the
mass currently present in the mold.
After front filtering, the temporary mesh is generated. First, the fronts are
located with respect to the fixed mesh and, if strictions are detected, some totally
filled elements are considered as partially filled. Generation is then performed.
As a 1 st step, triangles are built using a Delaunay triangulation that is con-
strained to use the boundary vertices of the generation zone. This method, which
leads to optimal triangulations with respect to some criteria, can be implemented
quite efficiently and extended to curved surfaces. Preserving imposed boundaries
can be achieved in several ways [13]. As a 2 "d step, as many triangles as possible
are merged two by two into quadrilaterals. The temporary mesh Mn+ 1 is built
by merging the filled elements and the generated ones.
where the shape functions r are linear or bilinear on the parent element,
while T~i) (z,t) is the temperature profile approximation at node x~ ) .
Space discretization of the energy equation is performed by means of a hybrid
scheme combining a S UPG technique along the midsurface [ 11,25] and colloca-
tion in the gap. Weighted residuals of equation (46) are l~t integrated over f~n,
and are further considered for each node z (k) in the gap. The original SUPG
method [135] consisted in defining the test functions ~i)(xa ) as"
which replaces A~" va in (97). For triangular elements, the following ad hoc
expression was found to take triangular symmetry into account :
j
-1pCp OZ~ (k OZ
)l ~~mfiOjdS
m o ebp_aT~n+l o~
- I pc; - Oz pCp -~ + va ~i)dS , (100)
~-~m
where T(j) denotes the time derivative of T(j)(z,t). Following Mal et al. [25,
26], cubic spline collocation is performed in the gap by considering (100) for
each node z (t) and expressing the derivatives o32T(j)/oaz2 in terms of the
nodal values of T~j) and the end derivatives 31"~j)/cgz( z - 0 or h, or z - + h ) .
The latter are then eliminated using the wall conditions (67) or (68) and the rela-
tion -kOT(j)/Oz ( z - +h)= + qw (a vanishing derivative is imposed along the
midplane in the synmaetric case). When k is temperature dependent, oqT(j)/0z
is evaluated at internal nodes by a 2nd-order FD approximation. Eventually, the
semi-discrete energy equation takes the genetic form"
[r]- K([rl,[pl...)[rl - Y(VI,[P]-.-) , (101)
where the matrix K (related to heat diffusion) is block-diagonal, each block
being associated with a given midsurface node x~aj) and having dimension m
(the number of nodes in the gap), while the right-hand side includes all the terms
arising from heat advection, friction and compression. Moreover, K is of the
form A-1B, where A and B are block-tridiagonal matrices, while in (101) f
is of the form M-~q, where the mass matrix M consists of m equal blocks
982
+ [ 1 (lO2)
+ (T~,- T f o ) e f f c [ ( h + z ) ( 4 k o ( t - t f ) / P o C - ~ o ) - l / 2 ] ,
where Tw+ and Tw are the upper and lower shock temperatures (equations (69)
and (70)), while t f - t f (x~) is the time at which the front reaches x a , Tfo is
+
the temperature of the core fluid meeting the walls at time tf, and k~, p~, Cpo,
ko, Po and Cpo are the fluid properties at room pressure and temperatures Tw+
and Tw . A single contribution is considered in the symmetric case. The calcula-
tion of Ta requires to track Tfo and tf as functions of x a [25].
As the definite front(s) and mesh Fn+ 1 and Mn+ 1 differ from their provisional
counterparts /~n+l and MnUEn+l, t h e n o d a l v a l u e s o f [7~n+1] and JAn+l]
must be re-evaluated on Mn+l, together with tf and Tfo. This is performed
ypi mg te o,ate va,ues [an+l] on pro
cedure is more stable than least square approximation [16]. When a given node
of Mn+ 1 is located outside f~n u An+l, an appropriate extension of the ele-
ments of En+ 1 might be required [ 16]. In the presence of front-front collisions,
the extrapolated values are averaged in the overlap area and the weights are
obtained from the distances to the previous fronts F n provided by En+ 1 [ 10,16].
The elements of En+ 1 are generally quite flat, especially at the end of a short
shot. Therefore, letting ~l denote the inter-front distance and SXn+1 represent
a characteristic element size of Mn+ 1 in the direction normal to Fn+ 1, the ratio
984
where T(j)o and T(j)n represent the extrapolated profiles obtained just before
and after applying the condition (62), while the relaxation coefficient 0 is
defined by O-min(51/Sx,,+l,1). The normal characteristic element length
5x,,+1 and inter-front distance 51 are estimated for any node of Fn+1 on the
basis of the new mesh Mn+ 1 and the extrapolation mesh En+1 [16,25]. It
should be noted [16] that the exact value of 0 is not important, since extrapo-
lated values are already influenced by fountain flow before integration. Relaxa-
tion is a numerical stabilization procedure (likewise to upwinding), which is
indispensable at low flow rate.
5. S I M U L A T I O N R E S U L T S AND E X P E R I M E N T A L VALIDATION
Figure 16. Sketch of the test bifurcation and successive flow fronts, for a flow
rate of 60 cc/s. Upstream, and horizontal and vertical downstream branch thick-
nesses : (a) 4/4/4; (b) 4/5/3; (c) 4/6/2 (in mm).
986
35000
p (kPa)
30(0 - /6/2
25000
t = 1.3 s t = 3.52 s
20000
15000
I
10000 , , I , , , , , t(s)
Figure 18 (next pages). Layer by layer temperature field at the end of the filling,
from T = 400 K (black) to T = 600 K (white) (approximate range). The bifur-
cation (in bold) is located at the top of the upstream branch and the bottom of the
2 downstream branches. Flow rates : (a) 60 cc/s and (b) 120 cc/s.
987
988
989
injection molding (fountain flow, heat advection, viscous heating and heat dif-
fusion) do not occur at the same time. Fountain flow occurs first, when the poly-
mer reaches a given point in the cavity. Its main effect is to make the temperature
profile quite uniform. However, this situation is short-lived at a given Eulerian
location, in view of the effect of heat transport (which generates asytmnetric pro-
files far downstream from the bifurcation) and the viscous dissipation taking place
in the sheared fluid layers. Soon the temperature profile starts exhibiting a well-
known "seagull" shape. After a while, heat diffusion starts exerting an increasing
cooling influence, especially when the local flow rate is low.
Figure 18(a) shows the temperature field at the end of the filling, in different
layers across the thickness, each identified by its relative distance to the midsur-
face. In the core (layers 3 to 5), temperature is relatively uniform and has a value
close to injection temperature. Only at very few locations is this observation not
valid, viz. in stagnation areas (visible at the comer in layers 2 and 6 of the up-
stream branch) and in the region filled last, where the temperature is higher due to
viscous heating (see layer 3 of the vertical branch). On the other hand, near to
the skin, where the cold mold effect is higher, temperature distribution appears
more or less symmetric in the downstream branches, except in the bifurcation
vicinity. This is easily understood in view of the flow and temperature profiles
splitting at the bifurcation, where the inner skin layers are fed with a much hotter
material than on the outer side. In fact, the asymmetry tends to increase when the
front moves away, but it falls in competition with viscous heating or cooling.
Finally, between the core and the skin, a noticeable effect is the temperature
increase induced by viscous heating in layers 2, 3, 5, 6 of the thin vertical branch,
as a consequence of the sharp increase in velocity occurring after the thicker
branch has been filled. Also, the temperature profile appears to be highly non-
symmetric in these layers, due to the kinematic bifurcation. This effect is also
visible in the horizontal downstream branch (layers 2, 3, 5, 6). All these observa-
tions are confirmed by results obtained for other flow rates (Figure 18(b)).
Sprue Pressure
(a)
Heat flux
Optical fibers
r Gate / Pressure
--- ~ ~ _ _ - ~ ~ . . ~ e a t flux
pos. 5
pos. 4
pos. 3
pos. 2
pos. 1
after
gate gate
(b) Ill /
Ill I
-111 I
57 -la 51
qi
qH \
9 qll I
17 365
Figure 19. (a) Sketch of the injected plate with a close-up of the gate and the
locations of the sensors. (b) Finite element mesh representation (where use is
made of the symmetry of the part), together with the thickness distribution.
311
309
~ 307
305
~ 303
301
299
297
295 .....................................
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
time (s)
Figure 20. Filling of a rectangular PS plate. Comparison between predicted ( . )
and measured (---) mold surface temperatures for the first sensor in the cavity.
with a large rib. The delivery system consisted of a 11 cm sprue and a 32.5 cm
trapezoidal nmner. The steel mold temperature was regulated by water circula-
tion in channels situated 10 mm inside the walls. The mold was equipped with
transducers and optical fiber sensors. Pressure transducers were positioned at the
inlet of the sprue, just upstream and downstream from the linear gate, and in the
plane of symmetry of the cavity (40, 115, 189 and 264 mm downstream from the
inlet). Heat flux transducers consisted of pairs of thermocouples separated by a
steel cylinder (one positioned at the mold surface and the other 7 mm inside the
mold), which could produce a very fast response time of 0.2 ms with a precision
of 1 K. Heat flux transducers were placed at the inlet of the runner, just upstream
and downstream from the gate, and in the cavity at distances of 40, 115, 189, 264
and 319 mm downstream from the inlet, and 20 mm from the plane of synmaetry.
Although different polymers were injected, only the results obtained with PS
(Dow Styron 678E, for which the material parameters are given in [20,25,116]),
will be detailed. The injection and mold temperatures were 483 K and 294 K,
respectively, while the injection flow rate was 250 cm3/s. The evolution of the
mold surface temperature is presented in Figure 20. As filling progresses, the
temperature at the sprue rises first, followed by all the sensors. The increase is
sudden and accurately records the front motion. After the front has passed, the
polymer-wall interface temperature remains approximately constant during the
remainder of the filling. This effect, which is a direct consequence of the thermal
shock theory presented in Section 3.2.2, was obtained in both the numerical
predictions and the experiments, and for materials as different as PS, PC, PP and
992
Figure 21. Successive flow fronts obtained from simulation with a very simple
runner and gate model (top), and from short shot experiments (bottom).
PET, thereby validating the thermal model of Mal et al. [25,26]. Also, this shows
that in-plane heat conduction within the polymer and the walls is negligible,
whereas the effect of the thermal singularity caused by fountain flow is important.
Short shot experiments were performed in order to visualize the flow front pat-
tern (Figure 21). It is obvious that the gate, which was designed to ensure linear
injection into the cavity, is not efficient. The polymer first enters the cavity cen-
ter, before reaching the lateral extremities of the thick rib. Later on, a linear front
forms, while the polymer flows faster close to the lateral side walls. This finally
leads to a 'V'front shape, which grows when the flow rate is increased. Verho-
yen [20] has proved that this effect, which sometimes generates a front weldline
at the end of the filling and was observed with all other injected polymers, is a
direct consequence of the non-uniform viscous dissipation taking place in the
runner during filling, leading to a non-uniform and transient gate temperature
profile. The resulting non-uniform fluidity in the cavity is responsible for the flow
front 'V' shape (Figure 21).
-.
993
6. EXTENSIONS OF THE M O D E L
taken into account, especially in the vicinity of the so-called gel point where r/
rapidly tends to infinity. Even more critical is the accuracy of the model used for
reaction kinetics. When the resin formula may be considered fixed, simple n th-
order models can often be used, and all the information on the reaction is lumped
into a single variable called the degree of cure. When the influence of a modifica-
tion in the resin composition is to be investigated, mechanistic models are neces-
sary. A most interesting and widely used example of this approach is the model
developed by Stevenson [138] for unsaturated polyester, where the influences of
initiator and inhibitor concentrations and types on the reaction are considered.
This model is used in the example presented in Figure 22 (Mal [25]). In order to
reduce computational time, use is made of the part symmetry in the simulations.
The injection temperature is 356 K, the heating channels being kept at 423 K in
order to activate the curing reaction.
6.2 P o l y m e r crystallization
For semi-crystalline polymers, the thermo-mechanical conditions prevailing
during the different stages of the process interact with the development of micro-
995
structures that in turn affect the product end-use properties [139-147]. Polymer
crystallization has been extensively studied and several kinetic models developed
[24,148-151], most of them based on the Kolmogorov-Avrami-Evans approach
[152,153]. However, little work has been performed to introduce these models
into injection molding simulation. Dufoss6 [154] investigated the effect of non-
isothermality on PE molding. The effect of shearing on PPS crystallization was
analyzed by Hsiung et al. [87,91 ], who extended the Hele Shaw model to include
crystallization by means of the Nakamura model [155]. More recently, Isayev et
al. [88] simulated PP molding, taking shearing influence into account by combin-
ing the models of Liedauer et al [156] and Nakamura et al. [155]. The combined
effects of temperature, shear and pressure were analyzed by Ito et al. [92] and
Verhoyen et al. [20,93], in order to predict PP and PET molding.
Crystallization models can be implemented in Hele Shaw simulation by using
the scheme of Section 4.2. This requires (i) to introduce a kinetics model in order
to integrate the crystallization degree a v as an additional 3D field, and (ii) to
consider the effect of crystallization on r/, k, p and H. The goal of the
present section is to summarize the investigations carried out by Verhoyen et al.
[20,93], showing that combining crystallization modelling and simulation pro-
vides a very convenient methodology to better understand the crystallization
mechanisms under high pressure and shear conditions.
)
9
|
Q
9 9 "
(a) ( ~':
(b)
Figure 23. Sketch of the crystallization model. Interactions affect the nucleation
and growth of real spherulites, but have no effect on the fictive crystals.
Da~Cl c DV~
Dt = ( 1 - a V l ) Dt
DavC2
: (, )(
Dt
(106)
if 02>1 , else D C-aw = O,
Dt
Da v - Otv ( Wl DavlC + ~ c)
Dt Dt
(1- W1 j Dav2
Dt
(with the weight W 1 ), taking into account the asymptotic degree of crystallinity
oo
tzv . The model of [157,158] was not used for the secondary mechanism, whose
physical behavior is totally different. It is assumed that nuclei pre-exist in the
melt, and that, in static conditions, the number of activated nuclei /V1 is
independent of time (with instantaneous nucleation). Hence, /V1 is a given
function of T, ~' and p, which can be determined experimentally. When the
material undergoes a complex thermo-mechanical history, /V is obtained from
the relation /V - max (D1Vm(t)/Dt, 0), in order to avoid any decrease of N 1
when the polymer is heated. This expression should be improved.
This model can predict PET crystallization in typical laboratory apparatus (such
as DSC or cone and plate rheometer) in both isothermal and non-isothermal
conditions [20,93]. In principle, the dependence of PET material properties on
txv should be specified. Detailed material functions are given in [20]. However,
these effects may be neglected in PET injection molding since crystallization
develops mainly during the packing and cooling stages.
II ~ ~ . . . . . . . . . . ~ cr
0.4 .............................. ..-.................. x .............. :.....-.........::...........................
"~ rf/ k1~6l ~O: , 0
0.6 . . . . . . 1020
(b)
z
0.5 1018
cur
0.4
"~ 101s O
"9 0.3
o ,,,,,~
b
o.2 -/" 1014
1012
~,,~.
t i
, ,...r
1014 c~
r~ 0.2 i,,,~ 9
b 1012
0.1 L _ ~ ~ r % -
L--..-I
due to viscous heating in the nmner. Since nuclei are generated mainly upstream
from the delivery system (i.e. where p is the highest), they are partially destroy-
ed in the nmner under the action of the high peripheral temperature. Hence, their
inlet distribution is not uniform, and this strongly affects crystallization. Also, the
non-uniform inlet temperature profile again had a major impact on the front
shape. A simple model was developed to evaluate the distribution of nuclei
downstream from the gate [20]. The resulting profiles are shown in Figure 24(c),
which exhibits a much better agreement between calculation and experiments.
where q~ is the porosity (i.e. the liquid volume fraction), 7"/ is the resin vis-
cosity and Kij the permeability tensor. The Darcy law is useless in describing
how the resin penetrates the bundles and wets each individual fiber.
As in TIM and RIM, most SRIM or RTM parts are thin (see Section 3.1). Di-
mensional analysis thus leads to combining the mass and Darcy equations as
c~xa
1000
h
where S ao - I / ~ KaO dz . (109)
-h
Greek indices mean that the quantity is limited to its in-plane components.
Equation (109) has the same form as (42), the fluidity factor S being replaced
by a fluidity tensor Sag. The procedure outlined in Section 4.2 is thus applic-
able, provided minor modifications of the front tracking algorithm in singular
regions are introduced [21,25].
The in-plane permeability Ka# is generally determined by eigenvector-eigen-
value measurements in simple flows [7,97]. In addition, progress has been made
in relating the reinforcement geometry and draping with Ka~ (taking into
account in some cases the elasticity of the preform) [164-170]. To illustrate the
effect of permeability, the injection of an automobile front hood has been simulat-
ed using two different kinds of reinforcement (Figure 25). The filling time is
141 s. Crosses indicate where vents should be placed. This result shows that
permeability is a key factor in determining the geometrical and operating parame-
ters for a given part. It should be noted that, as perfect draping along the borders
or the junctions is difficult, high permeability zones are often found, resulting in
easy flow channels or race tracking [162,171-173].
In SRIM and RTM, solidification generally results from a chemical reaction
initiated by heat or mixing during filling. In order to reduce the cycle time, the
mold walls are set to a high temperature so as to enhance this mechanism; hence,
thermal effects must be taken into account in the model [ 100,102]. However, the
heat transfer in the porous medium is much more complex than in Section 3.1,
since hydrodynamic dispersion must be considered due to the tortuous nature of
the flow paths. Assuming local thermal equilibrium between the fiber bundles
and the resin, the energy equation [99,101] reads as :
(op, c, p,c, v,
O [Kij+Kii~o~I" 1 ap @ (11o)
where P ph and Cph denote the specific mass and specific heat (with subscripts
l and s referring to the liquid and the solid), Ki~ and Kia are the thermal
conductivity and mechanical dispersion tensors, and ~ is the specific heat
source due to chemical reactions. In (1 lO), K~ is a function of the conductivity
1001
(a) (b)
(c) (d)
Figure 25. Isothermal simulation of the filling of an automobile front hood" (a)
finite element mesh; (b) example of temporary mesh; (c and d) evolutions of the
flow front for a non-isotropic (Kxx/Kyy - 3 ) and an isotropic reinforcement.
of the two phases and the reinforcement geometry [21,174], while KiJ, which
formally accounts for the mixing convection heat transfer, is often considered to
be proportional to Uv,II
Mal et al. [21] propose the equation"
where Lijkt is a fourth order tensor. This relation can induce different mixing
effects parallel or perpendicular to the flow, in agreement with experimental
observations [175]. Also, it is observed that hydrodynamic dispersion is invariant
with respect to time scale changes, corresponding to a purely geometrical mixing
model. As for Kij, the symmetries required for Lijkl are not clear. A complex
dimensional analysis shows that, in SRIM and RTM, gapwise mixing is
1002
3 4 ~
305 305
t = 141s ,,,,315~-,,7"~ t = 141s ...315~ 5>
(end) 33~.~@r" (c) (end) 33~~, / (d)
3 4 ~ 345~~~~,,~
the results obtained with and without neglecting mechanical dispersion (Figu-
re 26). Even though Lzz is small, its effect on the average temperature distribu-
tion leads to a difference of up to 10 K in the entry zone when filling is faster. It
is essentially in the immediate vicinity of the gate that its effect is important,
because mechanical mixing is very effective in the regions where thermal
gradients and velocities are high. A complex balance between dispersive and
conductive heat transfer takes place during filling and, the higher the flow rate,
the less effective conductive heat transfer is (while mixing acts on higher thermal
gradients). In conclusion, the global heat transfer is increased in the vicinity of
the gate, while it is reduced in regions of lower velocities.
Two closing remarks are in order. First, chemical reactions can be modelled us-
ing the methodology of Sections 4.2 and 6.1, as long as the kinetics and material
data are known. The evolution equation of species concentration is similar to
(110), with an additional term relating to curing kinetics, while molecular dif-
fusion can generally be neglected and mechanical dispersion is governed by the
tensor Lijkt. Secondly, it is easy to extend to SRIM and RTM the theory of
abrupt changes of thickness and bifurcations developed in Sections 3.2.3 and
3.3.3. In the case of isothermal flow, tmiform material properties and a trans-
verse isotropic permeability, mass conservation exactly provides (81), while
pressure continuity across the singular line forces the continuity of the tangent
velocity (v2f +- v2f-), instead of (82) (see Figure 12). At the front, equation
(83) remains valid and thus, after a few calculations, (81) and (83) show that,
when h + ~ h - , the normal velocity component vanishes at the flow front
+
(Vlf -Vlf -0). This simple effect, which holds true in the case of bifurca-
tions, can be observed in practice. It can also be exploited for computational
purposes.
This chapter summarizes the models and numerical techniques that were elabo-
rated to develop the MOLDSYS simulation software. Combining sound physical
knowledge with rigorous mathematical approximations and accurate algorithms
proves efficient in addressing the main issues of process modelling. Various
polymer molding techniques, all based on the thin cavity assumption, have been
implemented in the simulation program. The numerical method, which is based
on front tracking, automatic remeshing and extrapolation (taking fountain flow
into account), has been successfully extended to the filling of complex parts.
1004
Results prove the validity of this approach. Also, it is shown that the simulation
tool can be used to better understand the tmderlying physics when complex
materials are molded.
Besides the authors of this chapter, several people participated in this research,
including Marcel Crochet, Luc Dheur, Olivier Hansen, Kali Kabanemi, Natasha
Van Rutten and Vincent Verleye, whom the authors wish to thank here for their
contributions. The work was carded out within the framework of the European
BRITE project RI1B-0087-F(CD), the "Multimat6riaux" project of the Walloon
Region of Belgium, and the program of Interuniversity Attraction Poles of the
Belgian state, and in collaboration with the Shell Research and Technology
Center in Amsterdam (the Netherlands) and the "P61e Europ6en de Plasturgie" of
Oyonnax (France). The experimental work was possible thanks to Rapha61
Favier's permission. Grants from the IRSIA (Belgium) and the FRIA (French
Commtmity of Belgium) are acknowledged. The authors wish to thank Jean-
Pierre Gazonnet, G6rard Dechavanne and Virginie Durand for their friendly help
and advice in performing the molding experiments. The efficient page setting
work of Victor Vermeulen was also appreciated.
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1010
1. I N T R O D U C T I O N
Ring
Valve o.~tflo~.~,( \ _Inflow
Outflow / Inflow
Figure 1. Sketch of typical ring type non-return valve for the injection molding of
thermoplastics.
A plot of the pressure traces in front of the valve on the barrel wall
(downstream) and behind the valve (upstream) in the screw section and screw
displacement during the injection and recovery stages is shown in Figure 2. At
the start of injection both pressures increase rapidly. The upstream pressure
reaches a steady value, while the downstream pressure in the screw metering
section decreases drastically. This decrease in pressure indicates the ring closing
the flow passage into the screw. Thus, the valve is closed. The closing time of
the valve can then be determined. For the recovery cycle, an oscillating pressure
is observed in the upstream pressure transducer. This is caused by the movement
of the flights of the rotating screw over the stationary pressure transducer. The
downstream pressure measurement has a steady pressure due to the accumulation
of polymer melt in the large reservoir (shot size) in front of the valve for the next
injection stage. The pressure drop across the valve/screw determines the amount
of resistance during the recovery stage, which affects the length of the recovery
time. The ability to simulate this process of the valve opening during the
recovery stage and closing during the injection stage will determine the time for
the valve to open, close and the forces acting on the ring, which will help in the
development of more efficient valves [1 ].
In order to understand the phenomena that takes place during the polymer
processing with moving boundaries, an experimental slit die with a moving
boundary has been designed (Figure 3). The polymer flows through the slit die as
a wall closes the flow passage. The transient pressure drop across this wall is
measured. To numerically simulate the transient channel flow with a moving
boundary, computational code based on the f'mite element method has been
developed using the Giesekus viscoelastic model. In addition, a commercial
computational package is utilized to understand the transient polymer flow using
a quasi-steady approach. The pressure drop from the die experiments and
numerical simulations will be compared in an attempt to validate the numerical
technique. The contribution of the elasticity of the polymer will be investigated
1013
30 14
Injection Recovery
25- Stage / -12~
/ -10~
~, 2 0 -
-a
15-
-- 6 ~
r~
~ 1==,4
10-
-4 ~
5 1--3" A ,. -2
~, i i i i I I I I I I
0 2 4 6 8 10 12 14 16 18 20
t, S
Figure 2. Pressure measurements across valve and screw displacement versus
time during the injection molding of HDPE with an injection speed of 2.54 cm/s
and a melt temperature of 204.4~
Galerkin method or method of virtual work. The equations are then solved by
standard elimination techniques such as Gauss or Gauss-Siedel elimination. The
solution of these equations gives approximations of the pressure, velocity
components, extra stress components, etc. The two techniques to solve these
equations are the decoupled and mixed/coupled methods.
In the decoupled method, the continuity and momentum equations are solved for
the Newtonian flow field. Then, the constitutive equation is solved separately
using some type of streamwise integration. Usually, a Picard iteration, which is
also called successive substitution, is applied to the constitutive equation to attain
convergence. The extra stress contribution from the constitutive equation is then
incorporated into the momentmn equations and then a new solution is found for
the momentum and continuity equation. This iterative procedure is repeated until
the convergence criteria is attained. Researchers to have used this method
include Upadhyay and Isayev [17,18], Isayev and Huang [19], Bush et al [20],
Lou and Tanner [21,22,23], Lou and Mitsoulis [24], and Hulsen and Van der
Zander [25,26]. Since the streamlines start as flow boundary, the recirculation
zones in contraction flows are solved by a numerical technique found in
Upadhyay and Isayev [17,18]. The use of decoupled techniques has also been
utilized for integral constitutive equations by Viriyayuthakom and Caswell [27],
and Dupont et al [28] using particle tracking and Lou [29] using the control
volume approach. Other methods include the Choleski decomposition method
with a Picard iteration by Mitsoulis et al [30,31 ], streamline upwinding (SU) and
Lesaint-Raviart methods by Fortin and Fortin [32], streamline-upwinding/Petrov-
Galerkin (SUPG) by Lou and Tanner [22], Barakos and Mitsoulis [33], and Lou
[34], the adaptive viscoelastic stress splitting/streamline integration (AVSS/SI)
scheme and adaptive viscoelastic stress splitting/streamline-upwind Petrov-
Galerkin (AVSS/SUPG) by Sun et al [35] and botmdary integral methods by
Bush and Phan-Thien [36,37].
The use of mixed methods to simulate viscoelastic flow has received a large
amount of attention due to the inability of these schemes to converge at high
Deborah numbers. Early work on these techniques employed the method
proposed by Kawahara and Takeuchi [38], where the Galerkin method and a
Newton-Raphson solver converged only at low Deborah numbers. Researhers to
have used this method include Crochet and Bezy [39], Crochet and Keunings
[40,41,42], Davies et al [43], Dupret et al [44], Debbaut and Crochet [45],
Keunings [46], Musarra and Keunings [47], Mendelson et al [48] and Kajiwara et
al [49]. Other earlier research of Yeh et al [50] applied numerical methods
designated as quadratic stress interpolation (QLL) and stress interpolation using
bilinear polynomials (QQL) with Newtons method to solve the system of
1016
equations. The QQL method was found to converge at higher Deborah numbers
and have a more stable convergence. This QQL method was also used by Brown
et al [51].
Later, Marchal and Crochet [52] developed a more advanced mixed method
where each element is divided into several bilinear sub-elements for stress to
improve the algorithms convergence ability. In addition, some authors used the
SU and SUPG methods introduced by Hughes and Brooks [53,54] to improve
convergence. Other authors to have used this method include Debbaut et al [55],
Pumode and Crochet [56], Hartt and Baird [57] and Yunm and Crochet [58].
Methods to improve the convergence of mixed numerical schemes have been
researched by Brown, Armstrong and coworkers [59,60,61,62]. King et al [59]
implemented a numerical method into the momenaun equations which makes the
elliptic property of this equation explicit called the Explicitly Elliptic Momentum
Equation (EEME). SUPG is also applied to this numerical scheme. This type of
method has also been utilized by Burdette et al [60] and Coates et al [61]. One
other formulation developed by Rajagopalan et al [62] is the elastic viscous split
stress (EVSS) where the viscoelastic stress is split into the viscous and elastic
stresses defined by x= _~ + ft. In addition, Sasmal [63] used this method.
Other methods applied to the mixed solution technique include the
spectral/fmite-element method by Beds et al [64], the time-
discontinuous/Galerkin least-squares (TD/GLS) method by Baaijens [65,66], the
Taylor-streamline upwind-Petrov-Galerkin/pressure correction formulation by
Townsend and Webster [67,68], and the modified EVSS by Geunette and Fortin
[69] and Azaiez [70]. Integral models have also been solved by mixed methods.
An example of this is the paper by Papanastasiou et al [71 ].
All of these numerical techniques incur some difficulties in the approximation of
viscoelastic flow. One problem studied by Holstein and Paddon [72] and
Lipscomb et al [73] is the singularities which occur at the re-entrant comer of
contraction flows. The extra stress terms can reach physically unrealistic values
since the flow behavior of the fluid at these comers is not well understood. The
gradients of the stresses at the boundaries can become excessively high. To
overcome this problem, either the mesh size is increased in the region of the re-
entrant comer or a slip condition is applied at the boundary. Another source of
instabilities is inherent in the constitutive equations themselves. Kwon and
Leonov [74,75] have investigated the Hadamard stability and the positive
def'miteness of the configuration tensor of different constitutive equations. Models
proposed by Larson, Leonov and Giesekus, which are known to accurately
predict viscoelastic flow, experience blow-up instabilities. These instabilities can
be overcome by properly modeling the dissipative terms, adding a small
1017
2. THEORETICAL
The modeling of polymer processing can be grouped into three particular areas
of research. One is based on the generalized Newtonian theory, which takes into
account only the nonlinear shear rate dependent viscosity of the material. The
other is based on the viscoelastic theory of polymer melts, which has many
different forms, but is mainly concerned with incorporating the non-linear stress
terms into some type of constitutive equation along with the nonlinear viscosity.
To complete the theory of viscoelastic modeling, the viscoelastic-plastic fluid
theory is also covered.
r~ = -ja~ (1)
(2)
where r/(~;) is the apparent viscosity, which is a function of shear rate 2, pressure
and temperature.
Many generalized Newtonian equations have been postulated since the
realization of this type of relation. The types of available models are the Cross-
Arrhenius, Power Law, Klein, Carreau-Yasuda, Spriggs tnmcated power law,
Eyring, Powell-Eyring, Sutterby, Ellis, and Bingham. Bird gives a good review of
many of these models in chapter 4 of reference [99].
Two very useful generalized Newtonian relations, are the power law and the
Cross-Arrhenius equations. The power law equation of Oswald and de Wade
[ 100,101 ] is written as
-n--1
r/=mg (3)
1020
where m is a constant and n is the power-law index. This equation can only fit the
high shear rate range of the viscosity curve called the power law region. This
equation is useful since many analytical solutions are available, which can be
easily understood. Many of these solutions can be found in the book of Bird
[99]. In addition, this equation is capable of being implemented into numerical
solutions easily. An example of this is a paper by Hieber and Shen [ 102] and also
in Hieber [103] in which a finite element/finite difference is used to simulate the
injection-molding filling process. Hieber [104] and Isayev and Upadyhay [97]
also used the power law equation along with the finite element method to
estimate the pressure drop and extra entrance length across planar and
axisymmetric contractions. The main drawback of this equation is the inability to
accurately model the Newtonian or low shear rate range of viscosity.
The model by Cross [ 105, 106] is a three parameter equation of the form
7/
n(Y) = o (4)
i-n
where rio is the zero shear viscosity and ~* is the shear-stress level at which rl is
in transition between the Newtonian limit rio and the power law region. The
effect of temperature and pressure on the melt viscosity can be taken into account
through an Arrhenius type dependence. Hieber gives a thorough description of
these types of equations in chapter 1 of reference [ 103].
The modeling of the injection molding process by the Cross-Arrhenius equation
has been well documented since the early 1980's. Hieber et al [107] used the
Cross-Arrhenius type equation to model material viscosity to understand the
effect of juncture losses resulting from the elasticity of the fluid. By comparing
the numerical viscous simulation and experimental data, they were able to deduce
the amount of juncture pressure from the elastic effects. Sobhanie, Deng and
Isayev [ 108,109,110,111 ] have extensively used the Cross-Arrhenius equation for
the injection molding of robber compotmds. An additional parameter was added
to this simulation to account for the cure kinetics of the rubber compounds during
injection molding. The numerical pressure predictions showed qualitative
agreement with the experimental pressure data.
Other researchers who have used generalized Newtonian models include Duda
and Vrentras [112]. These authors used the Powell-Eyring equation to
understand the effect nonlinear viscosity has on the amount of extra pressure loss
1021
in juncture regions. Kim-E, Brown and Armstrong [113] used a Carreau type
viscosity equation to simulate the flow through an axisymmetric contraction.
Results indicate steep velocity gradients occurring near the wall caused high
shear rates and a shear thinning viscosity. These steep gradients effect the
accuracy of the finite element approximations.
De = .3U ~, (5)
where 3U/b is the characteristic shear rate with U being an average velocity
downstream of the contraction and ~, is the mean relaxation time defined as
~rlkkk
k = x_-, (6)
N
with TIk being defined as 770= 77~+~ = k, TI~ is a parameter similar to the lower
Newtonian viscosity, and TIk, and Ek are the viscosity and the relaxation time in
the k th mode.
Most differential models are only an extension of the Maxwell [114,99,115]
type equations from the 1860's. The Maxwell model assumes a linear relation for
the viscous and elastic responses of the fluid. This relation can be written as
1022
where 17xy is the shear stress and G is the shear modulus. For steady-state
motions, the equation simplifies to the Newtonian fluid. This equation shows
time-dependent response upon an imposition of flow. In addition, other types of
constitutve equations can be explained depending on the type of time derivative
utilized for equation (7). For sudden changes with time, the equation simplifies to
a Hookean solid. One can introduce the time derivative 5/8t in the convected
coordinate system such as
V T
~-,__=a=$-Vv.a-~=.Vv (8)
where ~ is the substantial time derivative, which translates with the material
particle, Vv is the velocity gradient with Vv~ denoting the transpose. This
system is called the upper convected coordinate system where the base vectors
are parallel to material lines. Therefore, the vectors are stretched and rotated
with the material lines, t, the time derivative, is written as
D a
~ = b--Tx== ~-x=+ v__.Vx__ (9)
Limitations for this model exist which exclude it from properly predicting realistic
polymer flow at high Deborah numbers. For instance, the model does not include
any type of shear rate dependent viscosity. The first normal stress coefficient is
not shear rate dependent either. The elongational viscosity becomes infinite at
f'mite strains and moreover, the recoverable strain is over-predicted at high strain
rates. In addition, the model cannot predict polymer behavior after the imposition
displacements strains.
In later developments, Oldroyd [116] proposed a quasi-linear differential model
which was frame invariant called the Oldroyd-B model or the convected Jeffrey's
model [117]. This model included a time dependent deformation tensor and is
written as
For this equation, one needs to provide three parameters where rio is the zero
shear rate viscosity, D is the deformation tensor, s is the relaxation time, and
is the retardation time. This equation is capable of describing time-dependent
flows, but is still unable to correctly predict rheological behavior. Equations of
this type are limited to polymer flows with small deformation rates or low
Deborah numbers. To account for these deficiencies more elaborate differential
models have been developed such as the Maxwell corotational, White-Metzner,
Gordon-Schowalter, Johnson-Segalman and Oldroyd-8 constant models which
appear in Bird [99] and Larson [115]. These models were capable of describing
more of the rheological properties of melts, but were still unable to describe all of
the material properties correctly.
In the mid-1960's, models were proposed that could describe polymer flows
more accurately. All of these equations contain nonlinear stress terms. With the
incorporation of this term, the constitutive equations are more suitable in
predicting stresses in shear flow. One model which includes the quadratic stress
term is the nonlinear viscoelastic equations developed by Giesekus [118-122].
This constitutive equation is based on the concept of a deformation-dependent
tensorial mobility or drag. The equation is derived from the theory for
concentrated solutions and melts using the dumbbell theory for dilute solutions.
The assumption is made that the mobility is not dependent upon the individual
configuration of each polymer segment. Instead, an average configuration of all
the segments is used to relate the mobility tensor to the configuration tensors.
This averaging of the polymer segment configuration bridges the gap between the
molecular ideas from which the constitutive equation comes from and the treating
of the polymer chains as a continuum of polymer melt or solution. This equation
replaces the scalar mobility constants Bk with a non-isotropic mobility symmetric
second order tensor 13to give an equation of the form
where $ is the elastic stress term, I"1 is the shear rate dependent viscosity, G is the
shear modulus and D is the rate-of-deformation tensor. To achieve realistic
predictions, two assumptions are made on the dependencies of $ and l~ on the
elastic strain tensor C. First, the relation [G-5] of _ to ~ is of the neo-Hookean
type dependence and is written as
1024
where ~ is the unit tensor. The shear modulus, G, is related to nkT, where n is
the number of beads per unit volume, T is the temperature, and k, is Boltzmann's
constant. The second assumption [120] is that a linear relation exists between 13
to C and is written as
a 2 3
+ ~-~ + ~,~-~ = 2r/D (14)
When oc equals O, equation (14) reduces to an isotropic mobility tensor and the
UC Maxwell model is retained. When oc equals 1, the anisotropy is at its
maximum and equation (14) produces results in shear and extension similar to
those for the corotational Maxwell model. For the research presented in this
paper, the assumption of incompressibility of the polymer is assumed and oc is
equal to 1A. In addition, a multi-model approach is applied to equation (14)
resulting in
1 2 3
l: + ~ ~ k + 2,k-~_~ = 2 r/kD (15)
uniaxial and biaxial extension by Khan and Larson [129], steady and transient
shear flow by Quinzani et al [130], and tmiaxial, biaxial and elongational flow by
Isake et al [131]. Larson [132] has compared several different models including
the Giesekus model for steady-state flows, start-up steady straining, stress
relaxation following cessation of steady straining, single and double step strains,
and elastic recovery, in sheafing, or uiaxial, biaxial and planar extension. Other
work has discussed the compatibility of equations with equilibrium
thermodynamics by Grmela and Carreau [133] and the restriction of the extra
stress tensor and requirements that this tensor must be positive def'mite by Hulsen
[134,135].
Other differential equations which are often used in the modeling of viscoelastic
fluids are the Leonov [136,137] equations, the Phan-Thien Tanner (PTT) model
[138,139],the f'mite extensible nonlinear elastic (FENE) model [140,141] and the
Doi-Edwards [142] model. For practical purposes, constitutive equations
quadratic in stress are the most popular for today researchers. More complex
models can be derived, but the implementation of these models would probably
be to cumbersome due to the complexity of the mathematical equations. In
addition, to many parameters would need to be specified in order to implement
the models. Excellent reviews of constitutive equations and the relations between
the different models is available in the books by Bird et al [99] and Larson [115].
J2-Y
- - - - - - x = 2riD for J2 > Y (17)
J2 = -"
x = ~o..-/3o=
m J
8..
~J
(18)
J2 = 4~-1;. q; (19)
Later, HuRon [ 149] proposed a model which uses a yield criterion with a memory
function. White [150,151] also developed a more specific viscoplastic model
based on the combination of avon Mises yield criterion and a hereditary function.
To more accurately model the thixotropy of fluids, Suetsugu and White [152],
Montes and White [153] implemented a time dependent yield criterion. Isayev
and Fan [ 154] used a von Mises yield criterion and the Leonov viscoelastic model
to propose an equation for f'flled polymers. This model though does not predict
thixotropy. Often, filled systems will have time dependent properties caused by
the breadkown and build-up of particle structure. To account for this time
dependence, Cheng and Evans [155] have developed an isotropic,
1027
m p
x=x +x (23)
m
where _x_ is the mean stress in the polymer matrix and ~P is the mean stress in the
filler network. The mean stress in the polymer matrix is represented by the
equation
N
"rm= P~ + 2 r/~D + 2~.~(Wk.lCk - Wk,2Ck
-1) (24)
k=l
where ~ is the elastic strain tensor and Wk is the elastic potential. The mean
stress in the filler network is represented by a scalar yield function
p Y
x =--x (25)
= J2 =
3. N U M E R I C A L SIMULATIONS
V.v=O (26)
where v is the velocity vector and the isothermal, incompressible and steady form
of the conservation of momentum equations with no body forces is written as
V.~=O (27)
where ~ is the total stress acting on the fluid. The model implemented is the
Cross model defined by equation (4). To determine the shear rate dependent
viscosity of this model the local strain rate is determined by
=
3ui ~3u~ (28)
r'~ ~ + Ox,
where i and j represent the direction of the velocity or displacement. The scalar
invariant of this local strain rate is determined as the local shear rate.
The two dimensional continuity (26) and momentum equations (27) are solved
by integration. The differential form of the momentum equations are written as
1029
(OVx v OV ]
P v'-~"x + Y Oy )=--~-x + ~9-T- (29)
v Ov,]
P vx-~x + '/9y ) = /gx + i)---~ (30)
for the x and y directions respectively. The differential form of the continuity
equation is written as
~9v_._Lx ~)Vy
Ox +--~y = 0 (31)
~Vx
Oxx = - p + rl Ox (33)
~gvy
o . = -p + rl ~)y (34)
( Vx
~x, = -P + rlt--~-y + Ox ) (35)
assumed average mass balance. The mass balance is applied to ensure that
continuity exists between the variables in a given control volume and the
variables of neighboring control volumes.
node,. : node
(i,j+l) (i+l,j+l)
Cell Center
face Q
location of
variable storage
node node
(i,j) 9 (i+l,j)
In the solution of equations (29), (30) and (31) for each control volume,
FLUENT uses several different interpolation schemes to give a more accurate
approximation of the field variables across each control volume. The choice of
interpolation schemes includes the power law scheme [163], blended Second
Order Upwind/Central Difference [164] and QUICK [165]. The power law
scheme uses a one-dimensional convection-diffusion equations for interpolation.
The blended second order upwind/central difference and QUICK higher order
interpolation schemes, which determine the faces values between control volumes
based on the values stored at the centers of two control volumes and an adjacent
control volume upstream of the first two cell centers. The higher order
interpolations schemes result is more accurate approximations in the solution of
the flow domain.
occurl'ing. In addition, the assumption is made that the flow is isothermal. In the
simulations the position of the wall from fully open to eighty-five percent closed
is divided into a given number of displacements. A control volume grid is built
for each displacement using the FLUENT preprocessor. The boundary
conditions are applied to each grid including the flow rate, material properties,
and constant closing velocity of the wall. To approximate the velocity of the
moving wall, the sides of the wall use a wall boundary velocity, which is parallel
to the wall. The velocity of the bottom face uses a flow inlet condition with a
uniform velocity across the entire face. The velocity boundary conditions are
shown in Figure 5.
v~ =vy =0.0
Figure 5. Boundary conditions for numerical simulations of moving wall and die.
V.v =0 (36)
Dv
V.~= p Dt (37)
where v is the velocity vector, p is the fluid density, and r is the total stress
acting on the fluid. The operator D( )/Dt is the material time
derivative b( )/bt + v. V(). The constitutive equation to be solved is the multi-
mode Giesekus model with the incompressiblity condition a equal to 89
corresponding to the incompressibility condition. This equation is written as
1 2 0
"t" + - ~ k ~ + ~,k~-_Tk = 2r/kD (381
where ~.k is the relaxation time, Gk is the shear modulus and rlk is the viscosity of
the k th mode. The extra stress tensor is incorporated into the Cauchy stress tensor
and is written as
r +~ (39)
where p is the pressure, 5__is the unit tensor and r__L_is the extra-stress tensor. For
the Giesekus model, the Cauchy stress tensor will be written as
Npara
where w is the extra-stress tensor of the k th mode with Npara denoting the total
-'k
Ov, (44)
k
Ovy
o-,,,, = - p + r/,--~-- + ~ r,,,,,,, (45)
O-y-- 7r/,C(Bv~
T +~) (46)
k
The extra stress terms x~j,k are the contribution of stress from the constitutive
equation for different modes of relaxation.
3,v3,P3)
(Ul,Vl,P~.."........~ (u2'v2'P2)
Figure 6. Six-node triangular element for u-v-p formulation with triangular area
coordinate system.
L = Ai / A = (ai + bi x + Ci y) / 2A (47)
where A is the total area of the element, Ai is the are the area coordinates as
indicated in Figure 6 and ai, bi and ci are the coordinate values of the three comer
nodes. The three area coordinates satisfy the following relation
L, + L2 + L3 = 1 (48)
The area coordinates have the unique relation that L,= 1 when x = xj, and y = yj if
i= j. Furthermore, the area coordinates have the relation that L,= 0 when x = xj,
and y = yj if i ~ j. One other constraint is that 0 < Li < 1 w h e n x ~ x j and y ~ yj. The
velocity components use the same quadratic shape functions, which are def'med
by six different variables for each element such as
N=[N,,N2,N3,N4,N5,N6] (49)
with each Ni being def'med by the standard triangular quadratic basis relations of
The pressures use the linear shape functions defined by three different variables
for each element written as
M_M_=[M~,M2,M3] (51)
with each M being defined by the standard triangular linear basis relations of
1035
The derivaties of the velocity components and pressure shape functions are
defined as
(9Vx ON 0Vx 0N
- - (53.a)
~gx - igx u, iOy ~gy u
0Vy 0N 0Vy 0N
~ ~ ~ ~ V
0x 0x v, by by - (53.b)
Op OM Op a M
&- &- - p__, Oy- ~- - p__ (53.c)
Equations (41), (42) and (43) are written into the finite element formulation using
the method of virtual work in two dimensions as follows
The left-hand side of the momentum equation (54) can now be rewritten as
(~v,o.)+# (60)
I~(~v,.~)~-I~
[~v
o( ,)~. +.v,/}.
~y ~. (61)
where F is the integration along the boundary of the domain and T1 and T2 are a
simplified way to write the relations in the brackets. Substituting these relations
into the conservation of momentum equations (54) and (55) results in the
following set of equations
I, [~v
o( ,)oo+ ~(~v~,
Oy ~ ]dR+I,~v~.o~-~+v~-~+v,
~v~ ~vx ~)~ =
(62)
and
Introducing the shape functions for the velocity components from equations
(53.a) and (53.b), the conservation of momentum equations (54) and (55) can
now be written in the following form.
+ ay Ox, dR+j'u_ u _ _ . t , - ~ + u+ v =
(64)
1037
and
L- ~ 0y r /
dR +~R__
Nr N ' p /
"~ + u + -~z v
_dR =
r_ R r(ON o (66)
by introducing the pressure shape function from equation (53.c). The stress
components in the momentum equations are represented by the following
equations with an artificial damping parameter co to control the stability of the
equations. These equations are written as
a, = + co + - o~ 9 v7 -~ a Vy -~ m-~ (69)
ay + oe + T.:
where m is the variable to be solved and m-1 is the variable from the previous
solution. This set of equations can be simplified and written in a matrix
representation to form a set of equations, which will be solved for each element
to give the approximate solution of the flow domain. This matrix is written as
i ONr ON-~R r
m
r/'+m ax +
f N r ONdR
1038
fOv,, r O3Vx T m
- - I NrNdR + J-7--N NdR ---~-N_ N_aR 0
Rm - R o'x----
_ -
o 0
T T
og~ N o
2~~+~ -
R-L~ m-1
r ~N~
R_L ~, ~+2--~---~~ o
o o o]
1 r
~N NdR 0 o
R u
+p o
0
~ _NTNdR o
0 0
fi t"
_r ,~
~N ] + N r T2 (70)
L 0
0
In these matrix equations, the N r and N vectors indicate the shape functions for
the velocity components with six constants and the M indicates the shape
functions for the pressures with three constants. The terms which include the At
terms indicate the f'mite difference approximation of the time stepping. The
velocity components are the initial conditions for the time step. The fmite
difference representations of the velocity components are given as
1039
m+l m m+l m
Ou u -u Ov v -v
- - - - and - - - - (71)
Ot At & At
u~ TM][(R,)q
(72)
{K31}Um {K32}V TM 0- J
where the K matrix is banded and symmetric. Therefore, the matrix set is solved
using LU decomposition.
The system of equations can be numerically integrated for each element in the
flow domain using standard integration techniques. The integration across each
element can be summed to give the contribution of the velocity components,
stresses and pressure across the flow domain from the continuity and momentum
equations. This summation can be written as
NE
I F(x,y)dR = ~_, I F(x,y)dR (73)
R i=1 R,
where NE is the total number of elements, i is the element number from 1 to NE,
and Ri is the domain of the ith element.
dv )r o~ 1 ak 2 2rhD (
=k = Vv-~ + ~ 9( Vv - ~ - ~ - v. VL - ~-~'k~ - 2Gk AkL + Ak----= F Vv,
[v_J--~-- (74)
(n+l) ,l(n)
where ----k
x and ------k denote the stress tensor at two consecutive points n+l and n,
respectively, and As is the arc length between the two points. The integration
starts at the upstream boundary and continues along the streamlines of the extra
stresses. This integration can be performed for any relaxation time ~,k as long as
the streamwise coordinate is chosen such that ~ <<~,klV_J. However, if the
relaxation time is small, the assumption is made that xlVv_J<<l, and a
perturbation solution is determined by
x = Gk[~+ ~,k(VV+ V : ) - 11
------'k
(76)
which is related to the Giesekus constitutive equation. The accuracy of this extra
stress tensor is directly related to the accuracy of the velocity and rate of strain
tensors.
This method does have difficulties when calculating the flow in the recirculation
zones since the streamline for a vortex is closed and does not start or end at an
inflow boundary. Thus, no initial conditions can be applied to solve this
situation. The streamlines in these flow regions are solved separately. The
assumption is made that the velocity components and strain rates are very small
compared to the flow, which drives the recirculation. Thus, from the assumption
that Z,k[VV_Jis small, equation (74)is solved for the stresses. If ~.k[VV_J is much
larger than unity, the stresses are determined after the stresses of some of the
1041
of the triangle, three points are related to the midsides of the triangle and one
point is related to the centroid of the triangle. The stress tensor from the
Giesekus model is evaluated at the Gauss points using the streamline integration.
Each streamline from an individual Gauss point is traced backwards until the
botmdary of the elements. From this point, the values of the stress tensor are
computed from the adjoining upstream element by interpolating quadratically at
the side of this element. With these values determined, the integration is then
performed along the trace path up to the original point. The elements in the
recirculation zone are determined using equation (76) or the streamline
integration as mentioned previously. At the walls the velocity is zero or defined
by the velocity of the moving boundary and the values of the stress tensor are
found from the constitutuve equation.
The application of appropriate boundary conditions is required in order to
numerically solve the system of equations. Boundary conditions required include
the velocity and stress field at the upstream boundary. Knowing these values, the
velocities and pressure field can be detennined and the streamwise integration
can start. The flow field upstream is assumed to be one dimensional, steady, and
fully developed. The equations ofmotion are written as
~9pm ~22~
- ~ (78)
~gy k=l 33'
and
Generatemeshinitial I
I on ions I
solve Newtonian flow field
If tm = t~ , numerical solution
finished
the field variables is then applied with the appropriate boundary and initial
conditions until a converged solution is found. This process is repeated until the
time and displacement limits have been reached. Then, the velocity components,
stress components and pressure are discretely known at each time step or position
of the moving boundary.
103 -
IMM
102-
model
Giesekus 9
101 ' '" .... I ' '"'"'1 ' '"'"'1 ' '"'"~ ' '"'"'1 ' '"'"'
7w, S 1
Figure 9. Viscosity versus shear rate at the wall for HDPE at 204.4~ along with
Cross and Giesekus model fits.
4. E X P E R I M E N T A L RESULTS
4.1 Material
The polymer used in the experiments is a commercial grade high density
polyethylene (HDPE) Marlex (Lot # HMN 4550-03) supplied by Phillips. To
rheologically characterize this material for the Cross and Giesekus models,
viscosity measurements were conducted on a Rheometrics mechanical
spectrometer (RMS-800) in the plate-and-plate mode in the low shear rate range
from 10 -1 to 10 2 S-1. For higher shear rates, experiments were conducted on an
Instron capillary rheometer (Model 3211) for the shear rate range from 101 to
3x103 s -1 and on an injection molding machine (Van Dora Demag 170 ton HT
series) fitted with a capillary type nozzle for the shear rate range from 2x103 to
4x104 s ~. Measurements have been made at three different temperatures
including 182.2, 204.4, and 232.2~ A plot of the viscosity curve for 204.4~
against the shear rate at the wall is shown in Figure 9.
1045
Ptunger
E
z _j_u
Ft-ow- .N~e~io ~-.------4~ . . . . . . . . ~ CO
/ ,,/3
Figure 10. Experimental Setup for the Slit Die with a Moving Boundary.
temperature control components (model E5CS-R1K JX-F) are from Omron Tatesi
Electronics Co. Cartridge heaters (Watlow firerod 9651M G4J33) are placed
symmetrically in the die. In addition, a band heater ( Watlow thinband STB5 1J2
T) is placed around the screen plate and adapter plate, which changes the flow
geometry from the circular geometry of the extruder to the slit die geometry.
Two inch Owens Coming lnsulwool insulates the slit die and the die to extruder
adapter.
Several processing parameters are varied in these experiments including the
flow rate through die and the closing speed of the wall. A data acquisition system
(1 KHz) is used to record data from the pressure transducers and LVDT for wall
movement, which consists of an A/D converter module ADM 12-11 (Quatech)
with in house software and an IBM compatible PC computer. In the experirnemal
testing of the wall closing, the pressure drop across the moving wall is recorded
as the wall moves from a fully open position to 85% of fully closed. The speed
of the moving wall is held at a constant rate for each experiment. The flow rate is
also constant for each experiment. The experimental test conditions are shown in
Table I.
Table I
Extrustion and Die Experimental Conditions
Melt temperature (~ 204.4
Barrel zone temperatures (~ 204.4, 204.4, 204.4
Die Temperature (~ 204.4
Flow Rates (g/min) 20,40,70
Wall Velocity (cm/s) -0.0287, -0.071, -0.154,
-0.317, -0.635
IIII I
0.0 - -
-~'-0.0287
-0.1 -
54
-0.2 -
-0.3 - J -0.317
> -0.4 -
-0.5 -
-0.6 -
[ . . . J V w = -0.635 cm/s
-0.7 ! ! | | w i ! | |
2 3 4 5 6 78910 20 30
Logt, s
ea~
le+6 - ".UJ
]~/] ~ A"0"071 -0.0287
le+5
b
! ! ! ! ! ! ! [ !
3 4 5 6 7 8 910 20 30
L o g t, s
Figure 11. Actual moving wall velocity (a) and experimental (solid lines) and
predicted (dashed lines) upstream pressure (b) as a function of time at the flow
rate of Q=20 grams/min and various imposed moving wall velocities, Vw.
1049
0.0
-0.1 -
--
; __.r'-
-0.0287
2 3 4 5 6 78910 20 30
Log t, s
le+6
le+5 b
w I
3 4 5 6 7 8 9 10 20 30
Log t, s
Figure 12. Actual moving wall velocity (a) and experimental (solid lines) and
predicted (dashed lines) upstream pressure (b) as a function of time at the flow
rate of Q=40 grams/min and various imposed moving wall velocities, Vw.
1050
0.0
J -0.0287
-0.1 - / - 5 ,.o.o71
-0.154
-0.2 -
-0.3 -
V w = - 0 . 3 1 7 cm/s
-0.4 -
-0.5 -
-0.6 -
-O.7 u u u u u u i
u
2 3 4 5 6 78910 20 30
Log t, s
le+7 -o.63s d
It I
-0.317
-0.154 -0.071 -o.o 1
/'
I
!
t~
!
/
le+6 ]
,J J
le+5 i "
i i i i i i i | I
2 3 4 5 6 7 8 910 20 30
Logt, s
Figure 13. Actual moving wall velocity (a) and experimental (solid lines) and
predicted (dashed lines) upstream pressure (b) as a function of time at the flow
rate of Q=70 grams/min and various imposed moving wall velocities, Vw.
1051
5. S I M U L A T I O N RESULTS
Calculations are conducted for the quasi-steady steps of the fully open position
and 85% closed position for a velocity of zero and with the specified closing
speed velocity. Thus, an instantaneous starting and stopping velocity is assumed.
The second type of analysis employed the actual velocity by determining the local
slope at each quasi-steady position. This variation of wall velocity during the
1052
closing of the slit channel is shown in Figure 1 la, 12a and 13a.
Results of the simulations of pressure traces with the ideal velocity are shown in
Figures 1 lb, 12b and 13b for the flow rates of 20, 40 and 70 g/min, respectively.
These figures indicate the pressure at each position during the closing of the
moving boundary. In all of the graphs, as the flow rate increases for a given
boundary velocity, the pressure increases, but not by a significant amount. As
the boundary velocity increases for a given flow rate, the pressure increase and
peak pressure increases drastically. This indicates that for a viscous quasi-steady
simulation the velocity of the moving boundary has a dominant effect on the
pressure as the moving boundary closes the slit channel. For the start-up and
stopping of the moving boundary, an abrupt change is seen in the value of the
pressure.
Results for viscous simulations with the actual wall velocity are shown in
Figures 14 and 15 for the various closing speeds and the flow rates of 20, 40 and
70 g/min, respectively. The simulated pressures show a sharp increase at the
start of the closing of the slit channel. This increase in pressure is not as drastic
in the case of the ideal velocity simulations since an instantaneous velocity is not
assumed. As the wall closed fiulher, the predicted pressure increases until the
end of the closing of the channel is reached. At this point, the pressure reaches a
maximum value. The location of this peak depends on the value of the wall
velocity at each quasi-steady position. Near the end of the closing simulations,
the actual velocity of the wall decreases rapidly. Thus, lower predicted pressures
are found when compared with the simulations which use the ideal velocity at the
end of the closing of the channel.
le+7 I
-0.317 ~ r . -0.154 .~ -0.071
t~
le+6 -
, j
- 4 - - Viscous w/Vw= -Vw(t)
7
le+5 - Viscoelastic w/Vw= -Vw(t)
Experimental Data
I I I I I I I i
3 4 5 6 7 8 9 10
Log t, s
Figure 14. Experimental and predicted pressure as a function of time for a flow
rate of 40g/min and various wall velocities.
a
le+5
! I I I I
3 4 5 6 7
Log t, s
le+7 -
- Viscous w/Vw= -Vw(t)
Viscoelastic w/Vw= -Vw(t)
9
_.l(~*,~ . . . .
9
r, le+6
o
-1
le+5 -- b
I I I I I
3 4 5 6 7 8
Log t, s
Figure 15. Experimental and predicted pressure as a function of time for a flow
rate of 20g/min (a) and 70/min (b) for the actual wall velocity with a set velocity
of -0.317 cm/s.
simulations that use the ideal and actual velocity. This pressure then reduces to a
steady value. After the wall has stopped moving the simulated pressure has not
reached the steady value as shown in Figures 14 and 15a. This would indicate
that a small amount of relaxation occurs in the viscoelastic simulations. In Figure
1055
15b, a large peak in the pressure development does not occur. The pressure
development for the viscoelastic simulation almost attain the steady pressure with
no overshoot.
different closing speeds due to the quasi-steady approach taken and the elastic
effects are ignored in these simulations. When no overshoot occurs, the pressure
development is delayed and the steady value of experimental pressure is not
reached until after the wall has stopped moving. This indicates the viscoelastic
effects of the polymer are relevant in the time dependent experiments, which the
viscous simulations cannot predict. For the other three closing speeds, an
overshoot is seen in the experimental pressure, but the numerical predictions for
the peak pressure are much higher.
For the flow rate of 70g/min in Figure 13, the experimental pressure for the four
closing speeds do not indicate any overshoot. In addition, when the pressure
development is delayed, the steady experimental pressure is not attained until
after the wall has stopped closing the slit channel. In addition, the time to reach
the steady pressure value has a longer time span for the experiments with a
slower wall velocity. Part of this delay observed in the experimental data could
come from the slowing of the moving wall during the end of each experiment. In
addition, the ideal velocity used in the simulations does not take into account the
slowing of the moving wall. The simulated pressures predict an overshoot as in
the previous numerical results. This reinforces the fact that the viscous
simulations cannot predict the pressure accurately for the flow of a viscoelastic
fluid, even though the relaxation modes of the polymer are relatively small. Thus,
the viscoelastic effects appear to be extremely important in the flow of a polymer
through a slit channel with a moving boundary.
For the viscous simulations where the actual velocity of the moving boundary is
applied, the predicted pressures indicate different results when compared with the
experimental values as shown in Figures 14 and 15. The prediction of the
pressure during start-up compares well with the experimental pressure since
enough quasi-steady increments were chosen to approximate this region. The
simulated pressures show good agreement with the experimental pressure after
the start-up region except at the end of the simulations. As with the viscous
simulations with an ideal velocity, the simulations predict a higher pressure even
thought the actual velocity is employed in the simulations. Thus, the simulations
based on the quasi-steady analysis cannot predict the experimental pressure at the
end of the closing.
For the viscoelastic simulations where the actual velocity of the moving
boundary is applied, the predicted pressure shows different results. The
predicted pressure compares well with the experimental pressure at the start of
the closing of the channel. Then, the pressure gradually increases and reaches a
maximum and after that reduces to the steady value of the pressure. The
experimental peak pressure is not predicted accurately, although, the viscoelastic
1057
2 4 5
0.6 --
scale: -
l cm/
0.5 --
0.4 --
~ 0.3-
0.2-
0.1-
0.0 --
'''' '' '' I ' ' ' ' ' ' ''' I'""'''''''' I' '' ''' '' ' I '' ' ' ' ' ' '' I''
8 10 12 14 16
x, cm
Figure 16. Predicted velocity profiles at five different cross sectional areas of the
flow channel at Q=40g/min and Vw= -0.317 cm/s for viscous (solid lines) and
viscoelastic (dashed lines) simulations.
simulations that use the actual wall velocity predict a much lower pressure than
the other simulations. The predicted peak pressure is always higher than the
experimental pressure except in some instances after the wall has stopped closing
the channel. The pressure jump at the start of the closing of the channel is
predicted well since the actual velocity of the moving boundary is employed and
a higher amount of time steps are used in this analysis when compared to the
viscous simulations which used the actual velocity. The viscoelastic simulations
offer the closest prediction to the experimental data. When an overshoot occurs
in the experimental pressure as seen in Figures 14 and 15, an overshoot occurs in
the viscoelastic predicted pressure. In addition, the relaxation of the pressure due
to viscoelasticity of the polymer occurs in this simulation. When a suppression of
the pressure development occurs in the experimental pressure, very little
overshoot occurs in the predicted pressure. Unforttmately, the simulations were
unable to predict this suppression of the pressure development. The predictions
of pressure can be improved by using a smaller time step. This would allow the
simulation to include all three relaxation modes of the Giesekus model.
The velocity vector profiles of the simulations are shown in Figure 16. The v
and u velocity components are shown in Figure 17a and 17b, respectively, for a
flow rate of 40 g/min, and the second fastest closing speed of-0.317 cm/s. The
moving wall is eighty percent closed for these figures. Figure 16 indicates that
lO58
0.6 --
0.5- /
t~ 0 . 4 -
ff~ 0 . 3 -
0.2-
3
O.1- a
0.6 --
0.5 i /5
0.4
if, 0.3 4
0.2
........ /3
0.1-
b
0.0 " '-'' ,;' '"":"' " -i ~ ' '
0 1 2 3 4 5
U, cm/s
Figure 17. Predicted profiles of v- (a) and u- (b) velocity component at different
cross sectional areas of the channel at Q - 40g/min and Vw- -0.317cm/s for
viscous (solid lines) and viscoelastic (dashed lines) simulations.
the variation in the velocity magnitudes across the gap are close for positions 1
and 2 and slight differences occur at positiom 3, 4 and 5 between the viscous and
viscoelastic simulations. It should be noted that the velocity magnitude at
position three in Figure 16 has a value greater than zero at the wall due to the
velocity contribution from the moving boundary. The velocity components in
Figure 17 indicate a good corr~adson between the viscous and viscoelastic
simulations for u-velocity components. However, some differences in the v-
velocity component are shown. This good agreement would indicate that the
1059
elastic effects of the polymer have little effect on the velocity profile of the
flowing polymer during the closing of the slit channel.
Thus, the viscoelastic simulations that use the actual moving boundary velocity
predict pressure better than the other simulations. The viscoelastic simulations
predict a lower pressure which is much closer to the experimental results. When
a suppression of the pressure occurs as seen in Figure 15b, the viscoelastic
simulation predicts a minimal amount of overshoot. When an overshoot occurs,
the viscoelastic simulations predict a lower pressure than the viscous simulations.
For the viscous simulations which implement the ideal velocity of the moving
boundary, the pressure development is poorly predicted. Thus, the variation in
the wall velocity has an important impact on the proper prediction of pressure
development. In addition, the predicted pressure overshoot is drastically higher
than the experimental overshoot of pressure. For the simulations where actual
velocity was employed, the viscoelastic simulations predict a lower pressure than
the viscous simulations. In both simulations, predicted pressures are lower than
in the simulations where the ideal wall velocity is used. The inclusion of the
elasticity of the polymer allows for a much better prediction of the pressure
development. The simulation predicts a pressure much closer to the experimental
data.
7. CONCLUSIONS
In the present study, experiments were conducted to measure the pressure drop
during the flow of a polymeric fluid through a slit die with a boundary moving at
a specified velocity, which is perpendicular to the direction of flow. The polymer
flows through the die as the wall closes the flow passage. The polymer used in
the experiments was HDPE. Experiments were conducted for three different flow
rates and five different moving wall velocities. A data acquisition system was
used to record the transient pressure drop as the wall closes the die channel. The
flow rate was held constant for each experiment. The velocity of the moving wall
was held constant, but was found to actually vary as the wall closes.
Experimental results indicate that for the flow rate of 20g/min an overshoot
occurs in the pressure as the wall closes the channel. For the flow rate of
40g/min, an overshoot does not occur for all of the closing speeds. This
overshoot occurs only for the two fastest closing speeds. For the flow rate of
70g/min no overshoot occurred for any of the wall closing speeds. When no
overshoot occurs, a delay is present in the development of the experimental
pressure. This delay was found to be a combination of the change in the velocity
1060
of the wall and a delay in the development of the pressure due to viscoelastic
effects.
The prediction of the experimental pressure was simulated using three different
types of numerical simulations. These simulations included viscous and
viscoelastic simulations that employed an ideal and actual wall velocity. The
viscous simulations used the generalized Newtonian fluid model according to the
Cross model. The viscoelastic simulations used the Giesekus model with a time-
dependent stress evolution. The viscous simulations were conducted with the
computational code FLUENT and used a quasi-steady approximation for the wall
movement. The viscoelastic simulations were conducted with in-house FEM
code, which is transient and accounts for the moving wall boundary.
The simulations that assumed an ideal wall velocity predicted a sharper increase
in the pressure development at the start-up of the wall velocity. In addition, these
simulations predicted a peak pressure which was drastically higher than the
experimental pressures. All simulations with the ideal wall velocity predicted an
overshoot in the pressure at the end of the closing of the channel. The
simulations which employed the actual wall velocity gave better predictions of
the experimental pressure. The viscous and viscoelastic simulations predicted the
start-up pressure very well. The prediction of the pressure overshoot for the
viscous case was much higher that the viscoelastic predictions. For the
simulations that used the actual wall velocity, a prediction of the pressure during
the start-up of the closing of the channel by the moving wall was found to be
accurate. The simulations, though, did not predict the delay in the development
of pressure. A small amount of overshoot in the pressure was predicted even in
the cases when no overshoot occurs in the experimental pressure traces. The use
of the actual velocity improves the prediction of the peak pressure. The
viscoelastic case was found to predict the transient pressure development better
than the other numerical simulations. The viscoelastic simulations which used the
actual velocity predict a lower pressure than the viscous simulations. This
indicates that the elastic nature of the polymer as described by the Giesekus
model helps in the prediction of pressure. These viscoelastic effects occur even
though the HDPE melt would seem to not exhibit a significant amount of
elasticity. The transient nature of the experiments make this elasticity become
more pronounced. For a better prediction of the pressure smaller time steps must
be implemented in the viscoelastic simulations.
The comparison of the velocity magnitudes and components across the gap
height for several different positions in the die at 80% closed indicate little
difference. Thus, the elasticity does not effect the velocity profiles. For the
simulations conducted, the viscoelastic FEM code can offer significant insight
1061
into the prediction of the experimental pressure. For polymers with higher
amounts of relaxation, this code could possibly help in the prediction of the
suppression of the pressure development. In these instances, a delay in pressure
could possibly be predicted. Research is currently being conducted on the
closing in the absence of flow through the slit or squeeze flow experiments. In
addition, polymers which have much higher relaxation times will be incorporated
into the current research on the channel flow of polymer with moving boundaries.
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1063
S t e p h e n E. B e c h t e P , M. Gregory Forest b, Qi W a n g r
and H o n g Zhou b
1. I N T R O D U C T I O N
viscoelastic [11, 12, 13], and liquid crystalline polymer [14, 15] constitu-
tive relations, together with surface tension, gravity, and inertia, we have
developed a slender fiber perturbation algorithm that produces all one-
dimensional slender, axisymmetric, isothermal and thermal models in the
literature, as well as several relevant new models. This approach posits
a separable radial and axial structure at every order in perturbation, and
therefore has one major advantage and disadvantage. The advantage is
that the method is algorithmic, can be implemented with symbolic ma-
nipulations, and works whenever there exist separable slender flows. The
disadvantage is that the method does not address whether the separable
flows it describes are uniquely specified by the slender longwave approx-
imation. For Newtonian flows this issue is resolved (private notes). But
for more complex constitutive laws of the types considered here, it is an
open problem to construct slender fiber flows which are not captured by
our posited radial/asymptotic expansions. We have also addressed how to
select the specific regimes and corresponding model which best fits a par-
ticular experiment or process. This modeling feature is essential both for
direct simulations of a given experiment/process, and for inverse material
characterization [16, 17, 18]. We refer to our original published work for
details of these developments over the past decade.
For this volume we survey a selection of leading order models for increas-
ingly complex physical regimes. Similar to work by [19] and [20, 21], we
have exploited the mathematical structure of transient models to deduce
which quantities can, or must, be specified at upstream and downstream
boundaries of the fiber spinline. In viscoelastic [13, 22] and liquid crys-
talline polymer [14] fiber models we have discovered a novel space-time
change-of-type in which the governing equations for the fiber flow may
experience a transition from a well-posed hyperbolic structure to a catas-
trophic elliptic structure. We have also identified this transient change-
of-type with predictions for the onset of polymeric fiber failure [23]. The
mathematical structure of the I-D models for our selection of physical
regimes will further be shown below to reflect on the stability of two very
different classes of steady states" cylindrical jets and noncylindrical fibers
under tension.
1071
2. S L E N D E R F I B E R M O D E L S F O R I N C O M P R E S S I B L E I N V I S C I D , N E W -
T O N I A N , V I S C O E L A S T I C , A N D LIQUID C R Y S T A L L I N E P O L Y M E R F I B E R
FLOWS
We refer the reader to our journal articles for the 3-D, incompress-
ible axisymmetric free surface formulation and slender fiber perturbation
theory. The fluid rheology is modeled in the 3-D equations by the consti-
tutive (i.e. stress vs. rate-of-strain) relation one posits. The I-D models
we survey below arise from the following constitutive assumptions for the
stress t e n s o r T:
Inviscid Fluids:
T -- - p I , (1)
T = - p I + 2~7D, (2)
where r/is the zero strain rate viscosity, D is the rate-of-strain tensor given
by
[Vv + (3)
with V denoting the Eulerian gradient and v the fluid velocity.
Viscoelastic Fluids:
T - - p I + q?, (4)
where
I
+ 2A(Vv 9 Q)(Q + 5) ]. (9)
R- pzg
r#o
(Reynolds number)
W- proz~to
2 (Weber number)
A1 - ~1
to
(Weissenberg number)
(12)
A2 - &
to
(dimensionless retardation time)
Ca - ~,to =
rFo
R/W (capillary number)
Pe- pCz~
Kto
(Peclet number)
Bi - hro
K (Biot number),
where a is the surface tension of the material interface, p is the density
of the fluid, r0 and z0 are respectively the characteristic scMes in radiM
1074
2.1 Model 1" Inviscid fibers dominated by surface tension and inertia
In the inviscid model [4, 6] the axial velocity v and the free surface ra-
dius r are decoupled at leading order, based on the inviscid constitutive
assumption (1)-
1 o v ~ r 0
v, 1-[o] (13)
Hence the model equations are elliptic, and ill-posed as an initial value
problem. This model has classical (Hadamard) catastrophic instability; it
results fi'om the longwave approximation of the free surface Euler equa-
tions and, of course, is not a property of the full 3-D equations. Refer
to [5, 13, 22, 23] for physical interpretations and cautionary remarks on
ill-posedness in slender models. Refer to [4] for similarity solutions which
yield predictions for the conical shape of an inviscid drop tip.
2.2 Model 2: Viscous fibers dominated by viscosity, surface tension and inertia
In this model, we promote viscosity and gravity to leading order. The
model equations are derived with the constitutive law (2):
0 r ~
__ 1
w
r
v
][v l I z ~
r 0
~zz+~r162
1 02 ] .(15)
where
B- fot (20)
Z = qr~
tofo' (21)
Here A is given by
1
/ k _ A I R 3 r q_ B (J'zz + 2 rrr) - - ~ r (23)
in which the first term (AI-~ r is the "gain" from high viscosity, the second
term (B (Tzz + 2 2~r)) is the "penalty" for compressive stresses (for which
1076
In this case, there are exactly 3 upstream boundary conditions and 1 down-
stream boundary condition. Therefore, the system is well-posed for mod-
eling fiber spinning processes as long as this inequality on the solution
is maintained. Moreover, the Riemann variables prescribe what process
quantities may be imposed upstream and downstream.
9 Hyperbolic type (4, 0) if and only if 0 < A < (~v)2 where all four
characteristic speeds sj are positive.
In this case all information moves downstream and one can only impose
upstream boundary conditions. This same system therefore describes ex-
trusion flows as long as the above constraints are satisfied.
The equations are not applicable for dynamical evolution in this regime.
The boundary between well-posed hyperbolic evolution and ill-posed
mixed-type behavior is A = 0, which is not an invariant condition (i.e. the
sign of A may change along exact solutions). [22] studies families of exact
model solutions which yield all varieties of hyperbolic to elliptic/hyperbolic
transitions. In Figure 1 we show one possible space-time boundary of this
well-posed/ill-posed transition, corresponding to the exact model solution:
(~ - - r V -- VO~
10-
61
2 4 6 8 10
Figure 1" The regions in the (z,t) plane of hyperbolic and mixed ellip-
tic/hyperbolic type which evolve from the Cauchy d a t a with the discrimi-
nant A - A ( e c ) + e-88 v0t), where v0 - A1 - 1, A(z) - 2 + sin(z) _>
0, ~ >- 0, z x ( ~ ) - 2wA~
~o ( ~- A
o 1) _ - 0 . 5 , so t h a t the system is hyperbolic
at time t - 0 for all z _> 0. A(ec) - - 0 . 5 implies t h a t the system becomes
mixed elliptic/hyperbolic as t --+ oc for all z > t. From [22].
1078
2.4 Model 4" Viscoelastic fibers dominated by surface tension, inertia, viscos-
ity, relaxation and retardation (a Johnson-Segalman fluid)
When an elastic retardation effect is included, the extra stress can be
decomposed into two parts,
A2
rr _ Tp + 2r/~ll D (25)
where Tp is the polymer part of the stress, A2 is the retardation time and
2 q ~ D is the Newtonian part of the stress. Substituting the decomposition
into the generalized Oldroyd Fluid-B model, the constitutive equation (5)
becomes a Maxwell-type equation for Tp,
v ~-
2
0 0
1
+ Tzz) -B B
C(u) - (28)
0 -2a~z - 2Z(1-~)_A~ v 0 '
Z(1-A1) 0 V
0 a Z , r + " A1
0 0 0 0 0
0 3 B Z ~A1 0 0 T1 + 6 BZ-~11dz
A,,
Vz
D f(u) - . (29)
_T_~
O0 O0 A1
0 0 0 0 T~
A1
1079
All the physical parameters are the same as before. Due to the decompo-
sition of the extra stress, the range of A2 is restricted to 0 _< A2/A1 _< 1.
ut + C ( u ) U z - f, (31)
h(s)-(1-s)(2s+l), (35)
1080
3ck0
(36)
which parametrizes the molecular kinetic energy per unit volume relative
to inertial energy per unit volume; and Catcp is the LCP capillary number,
(7
= 3ck07----- (37)
o r o
0 2a)~sr 2 0
v r2 0
M 1
W
2ogU(8) ~ V(~2 - o z U ' (8)(~ 2 (44)
0 - ( 1 - s ) ( 2 s + 1) v
AO -- 1 -- Oa/Omelt , (48)
which is a measure of the degree of nonisothermality. When Oa -- Omelt,
then A0 = 0 and our model reduces to the isothermal case. In [26] we
have varied this parameter to study the energy effects on our previous
isothermal LCP spin model predictions [15].
One can also formulate (45) into the general vector form (11) (see [26]).
Insight into the structure of the 1-D slender fiber models of the pre-
vious section can be deduced by linearizing the models about constant
cylindrical jet solutions when they exist (i.e. when gravity is negligible).
This calculation can then be compared against Lord Rayleigh's analysis of
the capillary instability of circular cylindrical jets [27]. The comparison
clarifies the nature of the slender, longwave model for each selection of
dominant physics.
First we recall exact 3-D results. Another discussion along these lines
may be found in [28]. Rayleigh's [27] linear stability analysis of a cylindrical
inviscid jet with radius r0, constant axial velocity v0, surface tension a, and
constant mass density p shows that an infinitesimal perturbation of the jet
free surface of wavelength 27r/k grows exponentially with rate
(49)
7(k)- pr~ Io(kro) '
where I0 and I1 are the modified Bessel functions of the first kind of order
0 and 1, respectively, indicating a longwave instability for all wavenumbers
k such that 0 < k < 1/ro, with a finite cutoff at the wavelength of the jet
circumference 27~r0.
1084
I1 k (1 - ~'2d)I1(~)
~n,(k)- W e Io(k'e) ' (51)
where
- ro/zo (52)
represents the radial to axial aspect ratio and W is the Weber number.
In nondimensional form, the exact linearized growth rate a/vi~c(k) for a
viscous fluid jet is described by the transcendental equation [29, 30]
where
7 ( : ) - : i0 (~-)
/l(Z) ' (54)
3~:2 / [3~2, 2 ~2
#visc(k) -- 2R + ~ [ ) - ~ + ~ + ~ (57)
1085
| . . . . | .
3.5 Inviscid,..E'~
xact
e2.5
c-
2
o
c,1.5 er . . . . . . . . . . . .
0.5
Oo 2
I
4
I I
6
I
8 10 12
k
The exact inviscid Rayleigh growth rate, together with the exact viscous
Rayleigh growth rate, the leading order approximate inviscid growth rate
(56) and the leading order approximate viscous growth rate (57) where
W - 1.0, e - 0.1, R - 10, is provided in Figure 2. As shown in Figure 2,
the inviscid and viscous growth rate share the same cutoff.
Now we investigate linear stability of constant cylinder equilibrium so-
lutions to all leading order slender fiber models presented in the previ-
ous section (with ~1 __ O) and display how these models approximate the
Rayleigh instability. The constant solutions always have radius r - 1,
axial velocity v0 - 1, with the remaining constant unknowns specific to
the model. For simplicity, we drop the superscripts. We posit that the
perturbation 5u of the constant solution is of the form
(~U ~ r
c, (5s)
where c is a constant vector. The linearized growth rate is given by the
real part of u, 7 - Re(u). The I - D linearized growth rate of each model
is given as follows (recall all the tilde overbars have been dropped)"
1086
,7 nv(k) - k ( 2 w ) (59)
Model 2" Viscous fibers dominated by viscosity, surface tension and inertia:
Note that these slender model growth rates agree, as they must, with
the leading order slender longwave approximation of the exact 3-D inviscid
and viscous growth rates (56) and (57) (Figure 2).
,7,~odd4(k ) _ _ 1 . (64)
A1
The three remaining growth rates satisfy the cubic polynomial equation:
1 3k2A2 k2 6 k2
~3 _[_ (All -+- AIR )3/2 4- 2WA1 (~aa - A1)~/- 2WA1 -- 0. (65)
The growth rates in the range of short waves are given by
~/Js "
( i
(WA1) -1 m -~- A 2 -~- RWA2 -t-O(]r A ~_ 0 for ]~-1 e,o 0
(66)
a~ ( - A
6RA2 + j A2 + RWA~ + O(k- 1) A < 0 for k -1
whereA-- 3 1 andR- 1
RA1 2W BZ"
In Figure 3 we plot the growth rates for the leading order inviscid, vis-
cous Rayleigh results and the growth rates for Maxwell, Johnson-Segalman
models with small (Ca = 1.0) and large (Ca = 10) capillary numbers Ca.
The remaining parameters are A1 = 2.0, A2 = 1.0, R = 10.0, e = 0.1,
and the Weber number is determined by the Reynolds number and the
capillary number through W = R/Ca.
u m . m i. m m 9
9
..'" ,'Maxwell (large Ca)
/
9 /
~2.5
-I~ ."
-'/"/ "
9 /
x: 2
o
o~1.5
0.5
m m m i i m
O0 2 4 6 8 10 12
k
0.5
U/>0
i
i
~ U ~ <0
$1 Ok
o
-0.5
U'>O
, , , , I , , J , I , , , , I , , , ' I , ,' , ,
-10 2 4 6 8 10
face tension, then the growth rates are identically zero, indicating neutral
stability.
Now this model couples Newtonian and effective LCP viscosity to the pre-
vious model. Intuitively, one expects a "viscous regularization", i.e., the
previous model growth rates should be lowered.
The linearized growth rates 71,2,3 are easily calculated in closed form:
If A(sj) > 0 then Re(")/1,2) a r e both negative for all k, with the remark-
able result that orientation contributions to the free surface energy, in the
limit of hyper-anisotropic drag ( a d - 0), completely stabilize the surface-
tension-driven Rayleigh instability.
If A(sj) < 0 then the growth rate Re(~/2), which reflects the Rayleigh
instability, is positive and bounded for all k, with qualitative behavior
similar to the viscous Newtonian 1-D Model 2 with surface tension and
inertia. Therefore, for such equilibria with sufficiently large Calcp, the
Rayleigh instability survives independent of the drag anisotropy.
This regime suggests that the degree of drag anisotropy plays a critical
role in the orientation-flow coupling, in particular with regard to the possi-
bility that orientation contributions to free surface energy may suppress the
Rayleigh capillary instability. This remarkable suggestion is made in the
mathematical limit, aa = 0, corresponding to zero drag along the dumbbell
axis relative to the drag orthogonal to the molecular axis.
Model 8" LCP fibers with all effects coupled at leading order:
This is the most general regime of LCP fibers, with all effects coupled at
leading order. The linearized dispersion relation for Model 8 is
dU'(sj)k 2
=0. (76)
2W~
In Figure 5 we compare the growth rates for all LCP slender models.
3.5 L ' ' ' .... ' ' /" ' ' ' ' -i
2.5
1.5
0.5
0 ~ N
Model 6 with s m a l l C a
\
'/
--1 -
-1.5 , , I .... , I , , I J
0 1 2 3 4 5 6 7 8 9 10
k
1 W'
different values of the parameters ~, 1 and T"
1 The upstream boundary
condition is chosen as
v ( O ) - 1, (77)
v ( 1 ) - 10. (78)
Figure 7 shows a typical steady state profile for a Maxwell liquid filament
(Model 3), while Figure 8 gives a typical steady state profile for a Johnson-
Segalman liquid filament (Model 4).
In Figure 9 we present a family of steady state solutions of the liquid
crystalline Model 8 reflecting variations due to changes in the initial degree
of orientation, s(0) = So. Note that there are uniform responses in 0, v, s to
1093
the maximum stable drawing speed (around Dr - 30.4) for this two-
parameter family of steady states.
Now we present steady fiber spinning solutions to Model 9. Consistent
with our nondimensionalization, the upstream conditions on fiber radius,
velocity, and temperature are fixed:
r 1, v ( 0 ) - 1,0(0)- 1. (79)
The downstream boundary condition is selected by the assumption that
axial thermal conduction is negligible downstream, i.e.,
0(r
Oz (1) - 0 . (80)
The remaining boundary conditions are free processing parameters to
be specified/varied in the simulations below"
s(0), v(1). (81)
The upstream degree of orientation (s(0)) is a function of spinneret design,
whereas the take-up speed (v(1) - draw ratio - Dr) is a measure of
process speed and throughput.
In Figure 12 we present typical steady state solutions of Model 9 due
to changes of A0. Here a two-phase model has been posited [26], where
the governing equations for the temperature above the glass transition
temperature (0 > 0g) are given in Model 9, and in the solid phase (0 _ 0g)
we employ a rigid cooling LCP fiber model so the velocity is constant
(fixed by the take-up speed) whereas the orientation and energy equations
are maintained. (The parameters used here are for academic illustrations,
and are not taken from experiments.)
Figure 13 depicts the critical draw ratio Dr* as a function of the non-
isothermal parameter A0. Three different forms of N have been used,
the constant value N - 4 and then two temperature-dependent forms
[26]. These forms are chosen so that the intermolecular potential f U(s)ds
has only the isotropic critical point for sufficiently high temperature, then
passes to a double-well potential for lower temperature.
As shown in Figure 13, the critical draw ratio grows with A0. As A0
increases from 0 to 0.4, there is 9.3% gain in Dr* for N c~ 9.7% gain
for N linear, and 9.5% gain for N quadratic. These predictions clearly indicate
that the cooling process increases stable spinning speeds.
Note that for A0 - 0, N c~ -" 4, N linear : 2.1, and N quadratic - - 2.52,
1,...
"'111111/I/1[[
. . . .
12
~
10
0.8
0.6
> 6
0.4
0.,~
Ill
..................... II iii|I |1|
.., ~ 9 o , 12
. ."""/. ////////,//////////,,,,:i~
0.8
0.{
O.z
0.~ 1 ..............
...... 11111111111111|I
1 i ! i I
(b) ~ o'.2 o:4 o:6 o'.8
CO 0.2 0.4 0.6 0.8 1
z z
12
0.!
10
/
/-.:y
0.6 if::
> 6
.../.! i /
0.4
........;:;r i ....
0.2
........... .,.,.,.,~.,~,-r~ . . . . .
Figure 6: The variation of fiber radius 4) and axial velocity v due to the
changes of: (a) l / F , where 1IF goes from 0 to 5 in increments of 0.5, with
1 / W - 1 / R - 1.0; (b) l / W , where 1/W goes from 0 to 5 in increments
of 0.5, with 1 / F - 1 / R - 1.0; (c) l / R , where 1 / R goes from 1.0 to 5 in
increments of 0.5, with 1/F - 1/W - 1.0.
1096
20
0.8 15
>,,
,,,,,,,,,,
0
~50.6 o10
L
>
0.4
0.2 ! ,,,
0 I
0 0.5 0 0.5 1
axial coordinate axial coordinate
30
25
-0.5
03
20
-I
9-~
X 15
L
-I .5
10
!
-2
0 0.5 1 0 0.5 1
axial coordinate axial coordinate
F i g u r e 7: A t y p i c a l s t e a d y s t a t e profile for a M a x w e l l l i q u i d f i l a m e n t in a
fiber spinning process. The parameter values are B - W - F - Z - a -
1, A1 - 0.05, 0 ( 0 ) - v(0) - 1, T,.,.(0) - 0, D r - 20.
1097
20 |
0.8 15
>.,
to,) ,,,..,.,
rj
~0.6 o10
(1)
>
0.4
0.2 I
0 I
0 0.5 0 0.5 1
axial coordinate axial coordinate
300
r,/) -2
200
L
(l)
,,,,,... ~-4
..,,,
~
"0
100 L
-6
0 0.5 1 0 0.5
axial coordinate axial coordinate
Figure 8" A typical steady state profile for a Johnson-Segalman liquid fila-
ment in a fiber spinning process.
1098
Figure 10: Variations in the steady spinning state due to changes in draw
ratio, Dr. All other parameter values and initial data are the same as
Figure 9. D r - v(1) is varied from 2 to 40, in unit increments.
1100
//i
-1.6 /
J I
1. /
// //
/ i
/
-1.7 /
t
/ /
/ /
/ /
/
/
-1.8 /
/ /
j/
l/max l/max /
//
/
/
-1.9 /
/J I
/
i
//
I
i
// i
l
/ I
j/
/ (b) l
l
-2.1 ...................... 9 , , , ~ . . . . : . . . . : ~ .
/ - ....... \
/' \,
3o / \
:
/ \ \
/ \
29.5 ',
'\
Dr*
29 \
28.5
(c)
0 0.2 0.4 0.6 0.8
80
1
10 : ""--:----:; ....-.....:...... -.... ;
0.9
0.8
B J/#I/Y ....... ................
0.7
0.6
:i!~i i
0.5
0.4
~) .... , ~ :i!;i:i:!:~:~:~''
0-30 0:2 ....0:4 0:6 0:8 ~ 0'2 o14 0'6 0'8 1
Z z
(b)
0.8 ..,~iii~!~
0.2
06;
f 0:2 0:4 0:6 0'8
. . . 11
z z
(d)
Figure 12" Steady state variations with respect to the nonisothermal pa-
rameter A0, 0 <_ A0 <_ 0.9, in increments of .045. All parameter values
are fixed at order one values" c~ - 5, R - 0.2, 1 / W - 1 / F - A - 1,
N- 4, a d - - 0 . 5 , P e - ~ c - c v - 1, 0 g - 0 . 8 . Boundary conditions are:
r v(0)- 0(0)- 1, s(0)- 0.5, v(1)- 10.
1102
43 9 9 n i
42
41
~
I,,--
D
.1~i" 5~
40 J ...
~ .. : 1~:'~
~... ""
39 ...
...
I ...
.~
......
.....
8 , i l I I
whereas the effect on process stability is on the order of 2%. Therefore, the
dimensionless LCP density parameter N has a bearing even in isothermal
stability of spinning states.
5. A P P L I C A T I O N S OF S L E N D E R F I L A M E N T M O D E L S
0 243.29 486.57
o
O~-'J
.,..4
M
o
,=;
~, .0 243.29 ' 486.57
,v--.q 0
'It' --.4
9,,.4 o
.,=4
r
.,,.~
"0
o .....
o ~.29 ~88.~7
axial c o o r d i n a t e
0 0.5002 1.0004
0 0.5002 1.0004
o
0 0.5002 1.0004
axial coordinate
Figure 15: A very brittle onset of failure: radius, axial force, and discrimi-
nant at the time of model failure t* - 0.951 x 10 -2 9 B - A - a - 1, W 1
=
114, T1 _ 20, Z - 20, v o l - 10/~; the number of mesh points n - 3200 and
the time step At -- 0.5 x 10 -5. Change-of-type occurs at z* - 0.78181 x 10 -3
near the ceiling; note T d A( z *-~ t* ) - - 9 3 . 2 9 8 and ~ ( z *+ t*) - 1070.1 are
large and of opposite sign, indicating a cusp-like behavior in A near (z*, t*).
At the m o m e n t of change-of-type the centroid of the filament is located at
Zcm(t*) = 0.50100. The suggested failure is brittle, with only 0.04 percent
strain at the m o m e n t of change-of-type.
1107
during the evolution from a slender uniform filament until the slenderness
assumption breaks down. In particular, the model fails whenever there is
a hyperbolic to elliptic transition, since at that time the model experiences
exponential growth in all lengthscales. The filament continues to stretch
up to and even after the change-of-type, and we conjecture this transition
equates to the onset of filament failure. Thus our model captures the
evolution into non-slender flow.
As long as the slenderness approximation is maintained and our assump-
tion as to the competing physical effects remains valid, we can confidently
predict details of the onset of failure: whether failure is approached through
uniform flow and profile or through a sharp, localized gradient; where the
onset of small scales occurs; whether the onset of failure is ductile (i.e.
the filament at onset of failure has stretched significantly from the orig-
inal length) or brittle (i.e. there is essentially no elongation before onset
of failure); and whether there is little mass redistribution or concentration
of mass. These are the aspects of polymeric filament behavior observed
in the model. Figure 14 depicts a ductile failure with significant mass
redistribution; whereas Figure 15 shows a brittle failure with little mass
redistribution.
Of importance to the application of this study, after the critical time of
ill-posed change-@ type our model is invalid. That is, if we apply the model
at all lengthscales, the full pdes are ill-posed. Effectively, the characteristic
axial scale goes to zero immediately after the elliptic change-of-type with
no argument for the radial scale converging to zero, so the slenderness con-
straint is immediately violated. As a result, we make no claims to capture
the detailed structure of breaks.
In [17] equations are derived for oscillating jets which allow for surface
tension and elongational viscosity to vary in space and time. Three specific
relations for the decay of surface tension with surface age are investigated"
exponential decay, the thin-film diffusion model derived by [35], and the al-
gebraic form proposed by [41]. For each form the direct problem is solved,
i.e. the governing integro-differential equations are numerically solved with
the particular specified function for the decay of surface tension with age
to obtain the free surface profile. In all forms initial and equilibrium values
of surface tension and decay rates were selected consistent with experimen-
tal values reported in [35] and [41]. See Figure 18. Important qualitative
differences in the oscillating jet behavior predicted under the three forms
are discovered, with a striking similarity: in all forms the nearfield decay
of surface tension, occurring in the first few wavelengths of oscillation or
over a fraction of the first wavelength determines the amplitude and wave-
lll0
B
-iV- R max
M
R mtt(
~, Ru
rain
E
R min
E
_~t_ R mcu
Figure 17: USDA measurements taken of the oscillating jet" from [16].
75
\
\~
,,,
60 \~
~ 55
E
\x 9
gso \X
x
g '\\ .
9~ 45 \
\
\
.
.
\ \\
4o \
.~ 35
..... Z.~_~.~ ....
25 i i i i i i i
0 0,005 0.01 0,015 0,02 0.025 0,03 0,035 0,04
surface age (s)
1,8
1,6
1,4
_1,2 i t
A /I,, I. /,' I, /,, /~,
/?',i,,
/,,/,', /,~ ,, t
-e-
. 1
\ I I I,' I', /'," t',,,Ii,'x,, I /,'t ,,,/
~u}0 , 8 \ I t I; ~',l',
\
\,,/.','
'\ ~
\,',/,,'
\
\,I, ~. '
.~_ 0,6
9~" 0 , 4
0.2
01 i i i i /
0 2 4 6 8 10 12
dimensionless axial distance z
Figure 18: (a). Surface tension vs. surface age. For all three decaying forms
- 72.8 dyne cm -1 at 0 ms and cr - 31.4 dyne cm -1 at 0.031ms. The
constant case is for a - 72.8 dyne cm -1 ( ); exponential decay ( - -
- - ) ; Brazee model ( . . . . . . ); Hua model ( . . . ) . (b) Free surface profiles
~1 with the variable surface tension given (a) and ~ ( 0 ) - 1.5, 01,z(0) - 0 .
1112
measurement of the axial force in the filament at the die exit, and (iii) an
accurate steady flow-rate control. In the analysis we admit many possible
physical effects. In the forward problem the known material properties and
boundary conditions dictate the dominant physical effects. In the inverse
problem considered in [18], the determination of which physical effects are
dominant is part of the solution.
The apparatus employed in [18], shown in Figure 19, was constructed
in collaboration with Prof. K.W. Koelling of the Department of Chemical
Engineering at the Ohio State. An infilsion/withdrawal syringe pump is
used to pump the fluid through a stainless steel delivery tube, controlled
to a specified value which ranges from 1.5 x 10 -s to 2 x 10 -1 ml/s. This
system avoids the variability in the volumetric flow rate of other types of
pumps, due to for instance the difficulty in controlling the pressure level in a
reservoir with falling fluid level, or the periodicity of a reciprocating pump.
The fluid is ejected from the delivery tube in the form of a vertical filament
which is taken up tangentially by a rotating drum of 5 cm diameter. The
take-up drum is mounted on a movable assembly which allows the fiber
length to be varied fi'om 0-19.6 cm. The drum is also connected to a flexible
torque transmission cable which allows the driving motor to be placed away
from the apparatus in order to minimize vibrations. A scraper is attached
to the bottom of the drum to remove excess fluid.
To avoid these errors, two sets of surface profiles and tube deflections are
recorded for each experiment, one for the filament with the take-up force,
and one, for the calibration, without windup falling only under the effect
of gravity. Analysis contained in [18] allows one to deduce the axial force
in the filament with windup at the tube exit from comparison of the two
sets of measurements.
Reference [18] demonstrates how the measurements provided by the ap-
paratus can be exploited to give quantitative information about rheological
material properties in isothermal elongational flows under applied tension.
The profile and force measurements fl'om a particular experiment are cou-
pled with a mathematical model formulated as an inverse problem, to de-
duce material properties. Referring to [18] for details, with the fiber profile
and upstream axial force experimentally known, the momentum and con-
stitutive equations decouple: the momentum balances reveal the evolution
of stresses that must be present in the jet to balance the effects of inertia,
gravity, and surface tension and produce the experimentally observed mea-
surements; and the constitutive equations deduce what stresses would be
produced by the measured kinematics and upstream boundary conditions
for a proposed rheological model of the fluid. The inverse problem consists
of searching through parameter space in the proposed rheological model
until the stresses generated by that model match those that must be there
to satisfy momentum considerations. Specifically, in [18] the elongational
rheology of a Boger test fluid is characterized within the assumption of a
single-relaxation-mode Giesekus constitutive model. Significantly different
values of the relaxation time and mobility parameter were obtained in the
elongational characterization than were obtained via shear rheometry: the
shear rheometer produced a relaxation time of 0.9148 s and a mobility pa-
rameter of 0.00035, whereas in the elongational flow the relaxation time
was found to be 1.323 s with one inversion technique and 1.303 s with
another, and the mobility factor was found to be zero, so that in the elon-
gational flow (but not shear flow) the proposed Giesekus model collapsed
to an Oldroyd-B fluid. The solvent and polymer viscosities deduced from
the elongational and shear experiments were the same.
ACKNOWLEDGEMENT
This work was funded in part by the Air Force Office of Scientific Re-
1115
REFERENCES
1. INTRODUCTION
two steps; one is spinning and the other is drawing. Later, for the
improvement of productivity, spin-draw process was developed, which
yields so called partially-oriented yarns (POY) at the spinning speed of
3 --- 3.5 km/min. They constitutes draw-textured yarns (DTY).
If one further increases the spinning speed, the drawing process hardly
affects mechanical properties of the fibers, and then the melt spinning can
be carried out in one step to get the final products. This high speed
spinning process was developed in the 1970's by modifying the
functionality of winders. In the 1980's, high speed spinning of PET, PP
and Nylon has been thoroughly investigated, and commercial products
manufactured at the speed of 6---8 km/min[1] become available. Under
such high speed spinning, one may occasionally observe some instability
like melt fracture and draw resonance, which deteriorates the filament
quality and reduces its productivity[2-3].
One can also notice neck-like deformation as the spinning speed
increases, and vast amount of research has been carried out to clarify the
origin of such phenomenon[4-5].
One of other peculiarities in high speed spinning is the crystallization
in the spinline, where according to the order of their appearance three
regions such as flow deformation, orientation crystallization and plastic
deformation can be defined[6].
Flow deformation occurs immediately after the exit of the spinneret,
and molecular orientation formed in the spinneret channel becomes
relaxed. Below this is the orientation crystallization region, where abrupt
increase in the orientation of amorphous region induces crystallization and
the filaments become thinner and necking may occur. Finally, in the
plastic deformation region, filaments are frozen and cold drawing under
the additional effect of air drag due to the increase in the filament speed
is also possible.
In the case of PET fibers spun at the speed of 3---4 kin/rain, even
though molecular orientation is high, the fibers are in low crystalline or
amorphous state[7,8]. Tensile strength and elasticity of the fibers are also
very low, but the breaking elongation is high, thus the fibers cannot be
applied for practical use without some additional processing like drawing
followed by heat treatment. However, if the spinning speed reaches 5---6
km/min, such produced filaments possess as high as 30---40% of
crystallinity and reasonable mechanical characteristics.
In general, with the increase of spinning speed, higher the tensile
strength of the filaments becomes and lower the breaking strain. When
the speed exceeds 5 km/min, necking in the cold-drawing process after
spinning disappears and the first yield point in the stress-strain curve
becomes obscure. Hence, the stress-strain curve becomes similar to that of
FDY. The tensile strength achieves maximum at the spinning speed of 6
---7 km/min and then decreases if it is further raised[9].
The high speed spun fibers have higher crystallinity and crystal
orientation than the low speed spun fibers with the treatment of cold or
hot drawing. They possess low total orientation due to lower molecular
orientation in the non-crystalline region and thus exhibit poorer
mechanical properties than the low speed spun and drawn fibers.
Thermal stability of high speed spun fibers is very high, and the
shrinkage in the boiling water is usually very low. Dye uptake of high
speed spun fibers is better than that of low speed spun and drawn
fibers[ 10].
however, if equation (1) is satisfied at one point, fracture may occur after
necking. On the other hand, if it holds at two points, the spinline
stabilizes and cold drawing will follow[18].
Necking phenomena at high speed spinning have been investigated since
Perez's study[19]. It has been reported that crystallization starts near the
neck point, which was confirmed through examining the data of X-ray
scattering for the PET filaments.
Necking has been explained in terms of the spinning instability and
draw resonance[20]. On the other hand, it has been also studied in view
of the structure formation, and it is claimed that necking occurs at the
point where the viscosity drops abruptly. Thus, necking point moves
upward along the spinline as the take-up speed increases[21].
Haberkorn et a1.[22] showed that crystallization rate is a function of
take-up speed for Nylon 6 and 66 in the high speed spinning. According
to their explanation, neck-like deformation occurs in the region above the
solidification point of the fiber, and then the polymer crystallizes after
neck formation. Thus, it is asserted that crystallization does not induce
neck-like deformation and the decrease of local viscosity due to the heat
of crystallization cannot be the cause of the necking.
A theoretical study of the neck-like deformation has been conducted
after the hypothetical division of the neck deformation into qualitative and
quantitative deformations.
Ziabicki[23] explained that an inflection point on the curve of velocity
variation along the spinline becomes a criterion for neck formation and
the cause of necking is the viscosity increase due to cooling of the melt.
However, the viscosity increase is only a necessary condition for the
stable spinning but not a sufficient condition for necking.
Even the existence of inflection point in the velocity distribution curve
may not be sufficient for the occurrence of necking, thus it can be said
that necking occurs if the radius variation exhibits two inflection
points[24]. The condition of neck formation is, thus, the appearance of
two inflection points, where
R"-- d2R
dz2 -- 0 (2).
Here R is the filament radius and z the axial coordinate.
1122
2. NUMERICAL SIMULATION
where F is the tensile force acting along the fiber, par is the air density,
1125
Do + Aft2 (12).
The values of parameters in the above equations have been specified by
Ziabicki[44] and Alfonso et a1.[46] as:
A = C1 - C2zIT
(~T) 3 (13)
AT: TOm- T (14)
where C1=3.09 l~ C 2 = - 1 . 5 5 t~/z=42s, T~176 D0=64~
v=v0, T= To, X = 0 at z = 0
v-- VL at z = L (15)
where v0 and To are the output velocity and the temperature at the die
exit, respectively, and vL is the take-up velocity.
The heat transfer coefficient was modeled by Kase and Matsuo[32] for
the forced convection by cooling air as:
0 D
[1 + ( 8 a;r) ]0
u (16)
where k~g~ is the thermal conductivity of air and its value is 5.50 10 -4
cal/cms~ v~ the velocity of cooling air, ReD is the Reynolds
number for the fiber diameter defined as:
vD
ReD = 0.29 (17).
The elongational viscosity ~e is in general a function of temperature
and crystallinity as assumed by equation (18) and the surface friction
coefficient is expressed in terms of Reynolds number[7] :
RO
Die i z:0
bl,, r 0 89 ( U, z -[- W, r)
D = 0 _u 0 (27)
l
(u,~+w,~) 0 w,~
where u , is defined as - Ou
~, etc.
The second invariant of D is defined as:
lid = u, 2~ + ( uT) 2 + w , 2~+ 1 ( u , ~ + w , ~ ) 2 (28)
and thus, the total set of equations in the 2-dimensional formulation can
be expressed as the following.
Momentum equation:
-- D, r "[- rrr , r+ Z'rz,Z _+_ ~'rr--~r r O0 Af_ f r : P( UZr ?"-+- WU, z) in r-direction (29a)
__ 1), _~_ rrz r_~_ ~'rz _~_ rzz z_~_f z = P( 1,1W, -~- WW, z) in z-direction (29b)
where p is the pressure, fr and fz are r and z-components of gravity,
respectively, r0 the components of the stress tensor in the cylindrical
coordinate, and the second assumption assigns f~ = 0 and fz = p g.
Energy equation: pC~(uT, r+ wT, z ) - k(T, r~ + + T,r-'~" T , zz) -[- (/V (30)
where k is the thermal conductivity of polymer and I;V is the
crystallization heat.
1130
fQ [ 7"~J'i, rrrz q- 7"~i,z( -- p Jr rzz ) Ji- pT"~l"i( ZlW, r -t- WW, z ) ] d ~ (34b)
= f r~ipgds foar~i~Szds
where s denotes the boundary 0~2 of the domain ~ . ~r and ~z are the
components of air drag acting on the fiber surface in r- and z
-directions, respectively, and the related boundary conditions are expressed
as:
f, I"
(35a)
+ r+WU, Lo
f Y[ 7]~i, r( U, z "~- W, r) -~- ~i, z ( -- P "~ 2 7]W,z) -lt- i0 ~J'i( UW, r ~- WW, z)]d,~
f~
(35b).
= J r~, og d ~ + Jo,.car~i ~ z ds
Applying the product rule and the divergence theorem results in the
following form for the energy equation:
f~ [oCprgi( uT ~+ wT,~) + kr( ~ri,rT, r+ ~i, zT, z)]d~
f'l l'~
(36)
= J,.c2
[ r g i f V d f 2 + k [J O.(2
Y~i T , n ds
where
where ~e and ~" are coordinates in so called the master element and M
is the number of nodal points.
Substitution of the above relations for the governing equations gives us
a system of nonlinear algebraic equations. In order to solve this set of
nonlinear equations, we employed the simple Newton iteration method. In
this numerical computation, the iteration does not stop until the obtained
values lie within a desired tolerance limit.
method are illustrated in Figure 2. The line D-A in the figure denotes the
center line of the fiber, i.e. the line of symmetry axis.
Die Exit
A B
Fiber Free
Center , , ~ Surface
Line
C
Godet
Roller
50
1.0 (Newtonian) 6 km/min
4O
~
~ 30
~
r~
20
10 n=0.7
I I I
0.1
6 km/min
0.7
0.01 0.8
0.9
?5 (Newtonian)
0.001 I I I
300
6 km/min
n shift(cm)
200 //~ 0.7 30
~D
.+.a
0.8 20
0.9 10
._
100
I I [
6 km/min
6
n
0.7
4 0.8
o
0.9
CD
1.0 (Newtonian)
> 2
I I [
0.01 ~ 4 km/min
9 v,,,,q
"Q~ 6
\ ~ ~ _ :__,__:, . . . . . . . . . . . . . . . . . . . . . . . . ,
0.001 I I. . . . . I
0.1
v = 6 km/min
W = 1.5 g/min, hole
0
~-- 0 m/min
o 0.01 20
cO
3O
?5
0.001
0 50 100 150 200
Axial distance (cm)
Figure 8. Diameter distribution along the spinline at various quench air
speeds (symbols are for experimental results).
[] 0 m/min 9 20m/min o--- 30 m/min
0.1
v = 6 km/min
Uair = 20 m/min
(D \~"~'~
\
2.0 g/rain, hole
r 0.01 ',,\ ~_1.5
"\ 1.0
?5
.o _ ----- . . . . . . . . . . . . . _ . . . . . . . . . . . . . . . . . .
0.001 I I I
300
- v air = 20 m/min
', \ W = 1.5 g/min, hole
~ 200 shift(cm)
"- x\ 4km/min 0
"",, \ \ / / - - 5 10
" ~,</--- 6 20
100
% . %~
".o 9
I, I I
300
- v = 6 km/min
_ ~ W = 1.5 g/min, hole
~ 200
0 m/min
100
300
-', v = 6 km/min
~ v~i~ = 20 m/min
\,,,
200
\, \ \
100 -
~ "'",,%"",,2.0
~
g/min, hole
I I I
50
6 km/min
tl'"
40 #
!
I
I
o~..i
30 I
I
I
o~..~ I
/ ,;~
I
t~ /I ..~
20 I '
I :
r,.)
10 ,i"U
// Vair~" 2 0 m / m i n
50
40
o,.-i
.~.,i
t~
ra~
r,.)
30
20
! f 0 m/min
30
10 v = 6 km/min
W = 1.5 g/min, hole
1 I
50
2.0 g/min, hole
,'7 ..... ]'13- . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
40
'~ 1.0
30
///
4~
~ 20
'///
10
'J;,/
!,
;. ,
... i
v = 6 km/min
U ai r =
i
20 m/min
Figure 15. Crystallinity along the spinline at various mass flow rates
(symbols are for experimental results).
[] 1.0 g / m i n - h o l e 9 1.5 g/min, hole o--- 2.0 g/min- hole
300
v = 6 km/min
200
O
100 skin
1 I _ l
Figure 16. Temperature variation along the spinline in the skin and core of
the PET fiber.
1143
skin
core
.l..,a
~" 0.5
(D
~ 1,,,,i
v = 6 km/min
. I I
0
0 50 100 150 200
Axial distance (cm)
Figure 17. Relative crystallinity along the spinline in the skin and core of
the PET fiber.
300
v = 6 km/min
z = 20 cm
30
200
45
~' 100
75
115
I I I [
~ v
z =60 cm
v = 6 km/min
o
0.5
35
33 -----------
i i -----------'-~ -~
1.68 1.54
1.67 g/
x~
9 ,,,,-i
~ 1.66 1.535
9 ,-,,i
~ 1.65 v = 6 km/min
v~i~ = 30 m/min
W = 2.0 g/min, hole
I q q
1.64 1.53
0 0.2 0.4 0.6 0.8 1
Axial distance (cm)
Figure 20. Refractive index profile across the fiber cross-section for PET
fibers.
parallel (n/l) --- perpendicular ( n l )
1146
140
Pair = 30 m/min
_
x 120
I I 1 I
80
0 0.2 0.4 0.6 0.8 1
Axial distance (cm)
Figure21. Birefringence profile across the fiber cross-section for PET
fibers at various take-up speeds.
4 km/min ... 5 km/min --- 6 km/min
140
0 rn/min
30
x 120
em
100
cD
o~.~
v = 6 km/min
W = 1.5 g/min, hole
1 I I
80
0 0.2 0.4 0.6 0.8 1
Axial distance (cm)
Figure22. Birefringence profile across the fiber cross-section for PET
fibers at various quench air speeds.
0 m/min ... 20 m/min --- 30 m/min
1147
140
1.5
""
X
120 10 ...................
N loo
.~,,i
v = 6 km/min
Uair-- 3 0 m/min
I
80 I I
4. CONCLUSIONS
temperature variation along the spinline, its role diminishes in the case of
crystallinity and birefringence of the final products. The formation of the
fiber skin-core structure is simulated in this numerical procedure.
Effect of spinning conditions on the formation of skin-core structure is
estimated by observing the birefringence distribution in the cross-section.
The distinct skin-core structure builds up due to the combined effect of
high speed take-up and quench air. As the quench air velocity increases
at high speed spinning and the fiber diameter becomes thicker, this
structural inhomogeneity becomes severer.
REFERENCES
2223.
40. J. H. Bheda and J. E. Spruiell, J. Appl. Polymer Sci., 39 (1990),
447.
41. K. W. Hutchenson, D. D. Edie and D. M. Riggs, J. Appl. Polymer
Sci., 29 (1984), 3621.
42. W. P. Bell and D. D. Edie, J. Appl. Polymer Sci., 33 (1987), 1073.
43. A. Dutta, Text. Res. J., 57 (1987), 13.
44. K. Nakamura, K. Katayama and T. Amano, J. Appl. Polymer Sci., 17
(1993), 1031.
45. A. Ziabicki, Kolloid Z., 175 (1961), 14.
46. G. C. Alfonso, M. P. Verdona and A, Wasiak, Polymer, 19 (1978),
711.
47. I. Hamana, M. Matsui and S. Kato, Melliand Textilberichte, 50
(1969), 382.
48. I. Hamana, M. Matsui and S. Kato, Melliand Textilberichte, 50
(1969), 499.
49. J. H. Dumbleton, J. Polymer Sci. A-2, 6 (1968), 795.
50. T. Murayama, J. H. Dumbleton and M. L. Williams, J. Polymer Sci.,
A-2, 6 (1968), 787.
51. E. B. Becker, G. F. Carey and J. T. Oden, Finite Elements : An
Instruction Vol. 1, Prentice-Hall, 1981.
52. M. J. Crochet, A. R. Davies and K. Walters, Numerical Simulation of
Non-Newtonian Flow, Elsevier, 1984.
1151
PHYSICAL MECHANISMS O F F O A M F L O W IN P O R O U S
MEDIA
K o n s t a n t i n G . K o r n e v ~ , A l e x a n d e r V . N e i m a r k b , a n d A l e k s e y N. R o z h k o v ~
1. INTRODUCTION
Although bulk foam, as a matter for scientific inquiry, has a great history, the
problem of foam patterning in confining systems, such as porous media, drew the
attention of scientists only recently. Apparently Fried [20] was the first to show
that foam, because of its unique structuxe, reduces gas flow in porous media. In
recent decades, it has been recognized that foam within porous media indeed
possesses a unique structure and rheological properties. In particular, in both pre-
and in situ-generated foams, pore sizes impose some constraints on the foam
texture. If the characteristic bubble size is much smaller than the characteristic
pore size, the foam confined in pores does not differ from bulk foam. In the
opposite case, the foam in a porous medium is a system of thin liquid films
(lamellae) spanning the pore channels.
The transition from the bulk phase to the new "pore-confined" regime of foam
patterning is very complex, and is discussed, as a rule, for ideal homogeneous
capillaries or bead packs (Hirasaky and Lawson [21]; Nutt and Burley [22]).
However, a more reasonable conceptual model of natural porous media is a
network of interconnected capillaries of different sizes, which may contain
constrictions and enlargements. Recent experiments (Bazilevsky, et al [23]) show
that the motion of pregenerated foam through such a system demonstrates specific
characteristic patterns.
1153
Figure 1. The sequence of frames depicts the displacements of the lamellae in the
enlargement of the channel. The flow direction is from the bottom upwards. The
white and black arrows indicate the positions of the pertinent lamellae at different
moments of time. The channel consisted of 10 cubic cell elements, an 8 x 8 m m 2
cross-section, and 10 narrow elements 8 r a m long, and a 2.5 x 2 . 5 r a m 2 cross
section.
The main peculiarities of the phenomenon are as follows (Figure 1). Just after
the beginning of their injection, the lamellae move freely along the narrow part of
the channel. If the broad part is free of foam, the lamella, reaching this point,
stops for the present, not being able to overcome the enlargement of the channel.
Under the action of pressure supplied by the gas, the lamella swells, forming a
bubble. The bubble either disappears, and the bubble swelling process restarts
when the next lamella reaches this point; or, after touching the wall of the
enlargement, the lamella jumps to the free zone and stops, clinging to the walls of
the wide pore somewhere. The following lamella behaves similarly. The
advancing bubbles jump sequentially from the narrow to the wide part of the
channel and come to a standstill in the engagement with the walls or other
lamellae. This process continues until the wide part of the channel is filled
entirely with foam, whereupon the lamellae are free to pass through it. In the next
enlargement, the process of foam filling repeats itself. And all the wide parts of
the channel are gradually filled with bulk foam. In doing so, the specific film
channels of approximately the size of the narrow part of the original channel
arise. With all the broad parts filled, the lamella motion proceeds as follows. The
drift of lamellae along the narrow zone alternates with periods of motion through
1154
the effective channels in the enlargements. In the last case, lamellae are subjected
to transformation, and their motion is jumpy. (It is related to the tendency of the
lamella system to minimize its surface energy.) No processes of rupture or birth
of the moving lamellae are observed. Due to the manner of the foam generation,
the distance between the drifting lamellae is of the same order as the channel
period. When lamellae are passing each other, the bulk foam in the enlargements
also undergoes deformations. However, its structure is not changed. It seems to
be the same before and after each lamella passes.
Thus, the experiments show that, during the motion of foam through the channel
of an abruptly varying cross-section, a portion of it is used to form the effective
channel. Such a channel plays the role of a transport path for another portion of
foam. In the process, the foam lamellae demonstrate an astonishing stability.
This and other visual observations (Owete and Brigham [24]; Chambers and
Radke [25]) speak in favor of a crucial role of the solid skeleton in foam
patterning in porous media. Even excluding for the moment the hydrodynamic
features, foams in porous media or in contact with highly dispersed materials,
have a unique structure by virtue of the thermodynamic reasons. Indeed, in the
absence of external restraints, an interface between the gas and liquid phases
tends to minimize its surface free energy by adopting a particular ordered
structure. In the presence of solid surfaces, however, the interface between the
two fluids takes up configurations whose equilibrium and stability depend upon
the areas of contact and the interfaeial free energies of the surfaces separating the
various phases.
The solid skeleton imposes to the bubble system a multilevel hierarchical
structure, in which the surface and capillary forces are self-consistently
interconnected. The wetting films covering the pore walls interact with the
lamellae, while the general conditions of foam equilibrium include primarily the
conditions of equilibrium between these two type of thin films. In many instances,
the thermodynamic properties of lamellae and the wetting films may dominate the
foam behavior in porous media. This type of interactions especially concerns the
strong foams, in which all bubbles are bounded by the lamellae (bubble-bubble
interfaces) and the wetting films (bubble-solid interfaces) (Ettinger and Radke
[26]; Kovscek and Radke [27]; Rossen [14]) (see Figure 2). Namely the strong
foams play a major role in applications due to their strong blocking action.
1155
9 iii
Figure 2. The sketch of the gas and liquid distribution within a strong foam in a
granular medium.
Pore channels in real materials are not uniform. Alternating constrictions (pore
throats) and enlargements cause variations of the Laplacian pressure across a
lamella moving through the channel. Under these conditions, the resulting motion
of the lamella will be irregular. Indeed, just after the lamella has left the pore
throat, it bulges forward and resists the movement. But as it reaches a convergent
part of the pore, the lamella bulges backward and accelerates. Visual experiments
(Chambers and Radke [25]; Bazilevsky, et al [23]) do reveal that, when pushed at
a constant pressure drop, very often the lamellae do not move steadily, but by an
alternation of slides and periods of rest. This type of motion is called the stick-
slip motion (Rabinowicz [28]; Bowden and Tabor [29]).
Specific features of foam patterning within a porous medium can be revealed on
the simplest yet expository model of a one-dimensional foam, referred to as a
bubble chain or train, immersed into a wavy channel (Komev [30]; Komev, et al
[31 ]; Dautov, et al [32]). Imagine such a channel as a rigid capillary with a radius
(2~x
r=ro+~C~ 2 ~' (1)
1156
where the x - axis coincides with the axis of the symmetry of a capillary, to, ,~,
and J are some characteristic scales of the porous medium. Assume, for
simplicity, that the pore aspect ratio is a low ,~/ro << 1. This assumption,
however, can be altered without change in most of the physical conclusions.
I ~I a)
90 ~ Plateau border
b)
X
----~+i ~. ai
2
f e = xr21Pi+l - Pi ) (2)
Here P, is the gas pressure in the i-th bubble. Making use of the equation of the
state of the ideal gas, we have with the same accuracy the following equation
PgK2
Pi+l-Pi = p 2K , (4)
i+1
Note that the capillary force has the form, similar to equation (2), but, instead of
the pressure differential, the Laplacian pressure drop,
1158
R-1 (P'+I - P i )
ii+l = 4y (5)
should be inserted. Here 2y is the lamella tension, /~.,+,is the radius of curvature
of a lamella (Figure 3). Then the capillary pressure drop can be written with the
same accuracy of O(6/r o) as
Pi+l-Pi =
8Jr~
2r 0
sinl2~r;i)/ (6)
The stick-slip motion of the bubble tram can be qualitatively described by using
the following model
d2p i
m~ = ~rrgAP (7)
Of 2
2
where e2= 2mh~Pg/9r/;ppr o2 2 and a dimensionless time is introduced as follows
t-2~Pgi/32rL~. Here rl.,~ is an apparent viscosity of a lamella and h~ is the
wetting film thickness. The parameter
4y6 (9)
p = Pgro;~
1159
serves as a measure of the intensity of the capillary forces with respect to the
driving forces (e.g., in the case of a bubble chain, these forces will be the elastic
forces). The parameter zXp denotes an external pressure drop sealed by P~.
Equation (9) has a very broad range of interpretations. It is widely used and
describes various physical systems, depending on the choice of the parameters
(Landau and Lifshitz [41]; Barone and Paterno [39]; Lichtenberg and Lieberman
[40]; Zaslavsky and Sagdeev [42]). In application to the lamella motion, the
parameter G is usually small. Therefore, the first term in the left hand side of
equation (9) dominates the second only for initial instants of time. For an analysis
of the lamella dynamics during a long time interval, the inertial term may be
dropped and, as a result, equation (9) takes the form
This equation can be completely analyzed, because it has the explicit solution
(Aslamasov and Larkin [43]; see also Barone and Patemo [39])
27/"
r = . (12)
IJAp 2 - 4~r2p 2
steadily. The lamella velocity, averaged over the period T, becomes the following
nonlinear function of the external pressure drop
0.12
2~./,t~p=0.99
...... -2~Z~ =0.5
- - - 2~/gp =0.1
0.4
--. . . . . . . _ . . . . . . . . . . . - . . . . . . --- ~ 9. . . . . . .
, I , i , i , I , ,
with the expected threshold zXp~ p . Formula (13) displays the increase of the
apparent viscosity of the lamella along with the increase of the rate of shear, as
determined by the lamella speed (Figure 5). This is the so-called 'shear-
thickening' effect (Barnes, et al [44]). The averaging procedure which leads to
equation (13) somewhat disguises the cause of the 'shear-thickening' effect. The
physics of such a rheological behavior is as follows. In the vicinity of the critical
pressure drop, the capillary forces drive the lamella almost entirely. Figuratively
speaking, in this critical regime, a 'bare' external pressure drop is needed only to
compel the lamella to shift from its equilibrium position. Once shifted, the lamella
drifts almost autonomously. Only in a high-speed regime, does the apparent
viscosity of the lamella tend to its bare value. Therefore, this 'shear thickening'
behavior of a lamella is caused solely by irregularities of the channel. If we
increase the pressure drop ft~her and further, we will inevitably arrive at the
range of the validity of a Non-Newtonian friction law. The Bretherton friction law
1161
[45] is one of the possible candidates for description of the lamella friction in a
Non-Newtonian range of flow.
We recall that Bretherton [45] analyzed the motion of long bubbles in a
cylindrical capillary of the radius Rand computed the thickness of the film
between the bubble and the capillary wall h~ and the dynamic pressure drop
across the length of the bubble. Both depend on the capillary number
Ca (3Ur//cr), where U is the bubble velocity, 1/ is the viscosity of the wetting
=
film, and cr is the surface tension. Bretherton pointed out that the dynamic
pressure drop across such a bubble, additional to the Laplacian pressure drop, is
given by
(3r/U)2/3 cr
B =3.58.
0.05
J
<~> f
J
0.02
/-
J
0.01
, I I , I j , i ,,, 9 I
This result helps to explain the lamella mobility. In particular, Hirasaki and
Lawson [21] automatically spread Bretherton's analysis to a chain of bubbles
separated by lamellae. It is assumed that the bubble train moves through a
1162
changes to - 2 / 3 power of the velocity in the second. The latter result means
that the effect of the surface tension gradient governs the foam resistance in the
second flow regime (Hirasaki and Lawson [21 ]).
10
o / / /
8 ZX C17:~Pt=0 / / / _
0 2 4 6 8 10 12
Figure 6. Typical rheological curves. Foams from 0.5% Hostapur SAS carbon
number fractions. The length of the pack- 100 cm, the permeability-8 darcy, the
pressure at the exiting end -7 bar. AP, denotes the threshold pressure drop (after
Hanssen and Dalland [47]).
Thus, the key assumption in treating the experimental data concerns the form of
the contribution of the pore constrictions to lamella resistance. This term dictates
the tendency in the total changes of the apparent viscosity as a function of the gas
velocity. In the Bretherton flow regime, the 'shear thickening' behavior can be
changed by the 'shear-thinning' (i.e., the reduction of viscosity with increasing
rate of shear in an averaged steady flow). In particular, this fact can be checked
by performing an analysis similar to that expressed by equations (10) and (13),
but modified in accordance with the Bretherton theory (Komev [30]).
1164
I I I I I I I I I i i I
a)
,90
>-
l--
v/
0
o
**,/- OATA
50
m
>' 10"
Ld
THEORY,
V) rl# + Tleon
"I"
12.
I
(r
k-
Z
w
THEORY,J ' ' " ' " ' ' " -
< rl# ONLY ""-.
I
0.1 5
vn.ocrry (cm/,)
104 I i * m i i i m I I
b)
DATA,
F Xf<I
i--
THEORY,
0 TI. + Tlcon
10 3 q.. ,..
THEORY, "-.
1"Is ONLY "-.
10 z 9 , , , , , , . . . . . . . .
0.01 0.1
GAS-PHASE VELOCITY (cm/,)
Figure 7 Apparent foam viscosity in glass bead packs as a function of gas-phase
velocity. Physical conditions: the capillary pressure Pc ~ 1900 dynes cm -~ , the
1165
Ratulowski experiments fall into this range). In the opposite case, the effect of
chain elasticity cannot be ignored and the theory must be modified.
Just after the external pressure drop has overcome the threshold G - 4Vr--~
(Komev [30]; Dautov, et al [32]), the domain wall, which separates the stagnation
zones ahead of and behind the front of the wave, depins and runs forward.
Therefore, in soliton dynamics, the competition between the inertial, elastic, and
pinning forces is important, and the viscous forces do not crucially change the
character of the soliton propagation during a short period of time. If a bubble train
moves for a long period of time, the inertia forces are negligibly small with
respect to the three major forces - the elastic, viscous, and capillary forces. These
forces struggle among themselves and drive the displacement waves. Notably, if
the external pressure drop is maintained at a long time interval, the number of the
domain walls changes. In fact, the number of the domain walls is proportional to
the number of the channel periods over which the front domain wall has skipped.
Therefore, the longer is the bubble train, the greater is the number of domain
walls, and, consequently, the greater is the bubble train resistance.
ta il lam e Ila
124 ;.-
122 ~- N=80; I<=1
120 ~- #=10 .3
1.18
1.18
L
1.14.
middle lamella
~ 1.12
1.10
1D8
1.00
1.04
head lamella
102
= 9 ~ I ~, I =, I = ~ ~ r ~ ' , I
1J00
3.g5 3.g8 3.97 3.g8 3.98 4.00
time
Figure 8. Wave mechanism of foam motion. The head and tail lamellae move m
unison, while the middle lamella drifts in antiphase. Numerical experiment based
on equations (8) and (4), e -- 0 (after Musin [56]).
1168
Illustrating a priority of the collective effects in the bubble train friction, we shall
use a somewhat simplified model of lamella interactions. For clarity, a linear
elastic spring will represent the elastic interactions of the lamellae. Moreover,
because each individual domain wall plays a key role in the chain friction, we
shall focus on the motion of a solitary wave. Then, in a continuous limit, equation
(10) is written as (Kornev [30])
Here q' is a dimensionless external force which represents the total action of the
external pressure gradient onto each lamella in the chain. In the vicinity of the
threshold, the profile of a domain wall can be adequately approximated by the
Frenkel-Kontorova kink as
Then, rewriting equation (15) in a wave fixed reference frame, the velocity of the
domain wall is found as the solvability condition to equation (15) (Langer [54];
Kornev [30])
- ooL-d-x)dx = q~ ? dd~xX ,
--o0
(17)
the friction coefficient grows with the number of lalnellae in the chain (the
number of moving domain walls) and scales similarly to equation (18).
As shown in the previous section, during its motion, a bubble train is subdivided
into a system of domain walls. The domain walls separate the regions within
which the lamellae are displaced only slightly so that the principal part of the
dimensionless displacements, p,, remains at an almost the same constant level.
The size of each wall is much greater than the pore size. Therefore, on a
macroscale level of a sample, the train may again be imagined as a one-
dimensional coarse-grained foam in which the domain walls serve as
macrolamellae. Such lamellae interact between themselves via an renormalized
elastic potential. The potential incorporates all the microlevel elastic and pinning
interactions and displays the collective properties of the native chain (Lonngren
and Scott [52]; Dodd, et al [53]) . It is important that the distance between
neighboring effective lamellae crucially depends upon the history of loading. For
instance, if a piston is applied to the tail end of the chain, and if such a load is
maintained during a long period of time which is sufficient to shift the head
lamella of the chain, then the number of domain walls will be a well-def'med
constant. This constant is a universal characteristic of the given bubble train, the
pore channel and the applied pressure drop. The resulting structure of the chain
on the macroscale level of the sample will be periodic, i.e., the domain walls will
form a new perfect lattice. But if it is granted that the load is continuously
redistributed over the train (the situation which is most likely to occur in a natural
porous medium), then the chain acquires, generally speaking, a nonregular
structure: in the coarse-grained foam, the cell size will alter from one cell to
another.
A viewpoint which designates the bubble chain as a macroobject enables one to
construct a hydrodynamic theory for a so-called weak foam. For the latter, there
is a very small fraction of trapped bubbles, so that the gas and a system of bubble
trains flow together through a porous medium. The gas mobility is reduced due to
an enhanced friction of the bubble trains. We encounter a similar situation in the
hydrodynamics of polymer solutions (Doi and Edwards [57]). The action of
bubble trains on a free gas, which is flowing through a porous medium, resembles
the action of polymer molecules on a flowing solvent. Because the bubble train
resistance is accumulated almost entirely within the domain walls, and, at the
same time, each domain wall is much greater than a pore size, the hydrodynamics
of a weak foam may be considered as the hydrodynamics of an ensemble of the
1170
bubble chains 'dissolved' into a Darcian fluid, provided that the free gas flow
obeys the Darcy law ( i.e., the relation between the pressure gradient and the gas
velocity is linear).
In a non-uniform flow, where each bubble train undergoes the action of an
extemal pressure gradient which is imposed by the carrying free gas, any train
will be stretched or contracted (because each macrolamella in the chain acquires
a velocity imposed by the kinematics conditions). But, due to an inherent
elasticity, the chain will tend to restore its equilibrium length. By restoring its
equilibrium state, the chain draws into motion the surrounding gas and,
consequently, other chains. Therefore, the chains which are stretched only slightly
will flow to the regions in which the chains are more extended. As a result, a net
restoring force appears. A schematic picture of the phenomenon is presented in
Figure 9, where a dumbbell plays a role of a foam filled macrobubble or a bubble
train.
/crv-rrr O
2-rcrZ- "-
t
J = -cfl jds < u(s,t)u(s,t) > - V O , (19)
0
1171
here c is the concentration of the bubble trains, 1 is the length of the train, and p
is a phenomenological constant. In equation (19), the vector u(s) denotes a vector
which joins two adjacent macrolamellae, and arclength s is measured along the
train. The angle brackets denote an average over the orientations of the
macrobubbles which link the macrolamellae.
It is convenient to rewrite equation (19) in the following form
/,
J = J o - cp jd,sS. V P , (20)
0
Jo = - c - ~ - V P ,
1
S= < u(s,t)u(s,t)-;l >, I ij =6ij , S ' u = S i j u j , S : u = S i j u i u j ,
where tensor S is the tensor of the order parameter. One can see that the first
term on the right hand side of equation (20) may be included into the ordinary
Darcy law associated with the flow of flee gas. Thus, equation (20) is written in a
form in which it is convenient to treat the foam motion in a porous medium as a
flow of a "solution' of bubble chains (Doi and Edwards [57]).
For such a hypothetical system, the detailed derivation of the constitutive
equations has been presented by Kornev and Kurdyumov [50]. The system of
these equations contains a generalized Darcy law for gas flow in the presence of a
foam
and a kinetic equation which describes an evolution of the "blocking force' L due
to the action of the velocity gradients. In a one-dimensional case, e.g., for a foam
motion in a porous tube, the model has the following form
Ov
(22)
Ox
DL DL L
~ - l - V . . . . (23)
Dt Dx r
3t:'
v =-k ~-L . (24)
f 3x
1 1 1
r rt rh
AP
kf H = ( l + b ) v , v --->0, (25)
AP H
kf H =v+ b, v ~o (26)
1173
where AP is the applied pressure drop. The point at which the straight lines
intersect has the coordinates
W
5~
11 2/ 31 4
0 2 4 6 8 10 12 14 16
AP
Figure 10. The velocity as a function of the pressure drop. 1-b--1, 2 - b = 3,
3-b=5, 4-b=10.
The coordinates of the imersection poim can be used as the fitting parameters.
An additional parameter needed to specify the model is the breakthrough time
T* = t*r . At this instant, a from of the foam first reaches the exiting end of the
1= f t b 1 - exp(-(1 + b)t*)
H 2 1 + b + 1 +-~" 1+ b " (28)
10-
t*
u
1 " II 1 l b
0 2 4 6 8 1
AP
Figure 11. The breakthrough time as a function of the pressure drop. 1 - b = 1,
2-b=3, 3-b-5, 4-b=10.
1175
6. STRONG FOAMS
As follows from the previous sections, the main feature of foam rheology
concems its 'pseudoplasticity'. The foam pseudoplasticity is very sensitive to the
foam texture inside a porous medium and to a fraction of the pores blocked by
lamellae. The physical reasons of the blocking action of weak and strong foams
are different. For a weak foam, even in the absence of a start-up pressure
gradient, an enhanced friction of bubble chains will result in an apparent
pseudoplasticity of the gas-foam system. But for a strong foam, when the bubble
trains flow through a small fraction of the pore channels, the blocking effect is
originated from at least two mechanisms. The first is caused by trapped lamellae
which do not participate in the movement. Such a blockage leads to a
permeability that is orders of magnitude lower than that for the single phase flow.
The second contribution to a reduction of the gas flux in the presence of a strong
foam concerns an enhanced friction of the bubble trains. Thus, the total gas
mobility, i.e., the coefficient in the generalized Darcy law, is the product of
permeability divided by apparent viscosity. (If the liquid also participates in the
movement so that its saturation changes during the process and alters the fraction
of the trapped pores, then, instead of the absolute permeability, the relative
permeability to gas has to be considered). In addition to a nonlinearity of the gas
mobility, a start-up pressure gradient plays the key role in the treatment of the
hydrodynamic effects in strong foams. This is the pressure gradient which is
required to depin some bubble trains and to create a network of active channels
(Cottrell [61]; Read [62]; Hirth and Lothe [63]; Suzuki, et al [64], Komev [30],
Dautov, et al [32]).
Thus, the term plasticity, in its own physical meaning, must be attributed to
strong foams. Both, the bubble trains and the corresponding network of active
channels play the same role as the one prescribed to the dislocations and the
network of dislocations in solid state physics. In fact, studies have shown that the
trapped gas saturation of strong foams in porous media can be as high as 80%
(Rossen [14]). Therefore, the trapped foam forms an elastic field around the
network of active channels. In a short period of time, the trapped foam resides as
effectively motionless lamellae. However, the diffusion processes need to be
considered to characterize the long term behavior of a foam (Falls, et al [65];
Cohen, et al [66]). In particular, a mechanism like the Nabarro-Herring-Lifshitz
mechanism [67-69] of a diffusion-induced plasticity might play an important role
in the motion of trapped foam. Indeed, under a pressure gradient, the gas will
diffuse through the lamellae so that the gas pressure within the bubbles will
change with time. Because of a difference in the Laplacian and gas pressures, the
1176
obeying the same peculiarities as in the fiber system under consideration. For
example, the effective pore sizes are estimated from the experiments with
capillary equilibrium of immissible fluids (commonly, wetting liquid and gas) and
with steady or quasi-steady forced flow of a non-wetting fluid (commonly, gas)
within and/or through a fibrous sample. An advanced technique of liquid
porosimetry has been developed by Miller and Tyomkin [82] for determining
pore volume distributions in fiber systems and other materials. The method is
based on the consecutive, quasi-equilibrium wetting fluid - gas displacement
under precisely controlled pressure at isothermal environment. Therewith, the
effective radius of a pore, where the liquid and gas phases coexist at given
pressure, is operationally related to the mean radius of curvature of the
equilibrium meniscus between the phases through the Laplace equation.
During the process of gas-liquid displacement in fibrous materials, bubble
formation occurs mostly due to a hydrodynamic instability of the wetting film
clinging to the fibers. This is the common mechanism of lamella formation in any
porous media [27]. However, the fiber structure causes some peculiarities. It is
likely that in case of most of fibrous materials, we deal with strong foams with
the bubbles commensurate to the pores. This conclusion follows from the
experiments of Gido, et al [83], who examined the flow of foams through fibrous
mats by characterizing the bubble sizes before and after injection. The authors
observed that the size of the output bubbles exiting the fiber system was
independent of the bubble size of the input bulk foam. For fibrous mats with
different pore structure, the output bubble sizes were found correlated with the
pore size distributions measured by the liquid porosimetry [82]. This result can be
interpreted assuming that the foam bubbles, residing within the fiber network
during the foam flow through this network, are grouped basically into two
configurations: a system of immobilized bubbles strongly pinned to fibers and
system of unpinned bubbles, which are formed in the bubble trains sliding along
the active channels confined by the immobilized bubbles. The bubbles are
immobilized when they are transpired by several fibers which intersect or are not
collinear. These bubbles are crucified at fiber crossing and/or stretched by
differently oriented fibers. The mobile bubbles are commensurate with the pore
constrictions in order to pass through them without essential deformation. The
movement of lamellae in the active channels within a fibrous structure should be
like the lamella stick-slip motion within porous solids described in detail above.
However, foam flow through a fiber mat is more difficult to formalize than the
flow in a solid-wall porous body. At present, no quantitative approach exists to
describe foam flow in fibrous materials. This problem is still awaiting its solution.
1178
8. CONCLUSIONS
of the "weak foam" flow are discussed in detail. Careful analyses of the flow on
the scale of individual pores or channels are useful in exposing effects of various
physical parameters on foam motion and in identifying flow-induced patterns. In
addition, the basic physical mechanisms of foam microhydrodynamics tmderlie a
variety of technological processes in oil recovery, groundwater/soil remediation,
textile manufacturing, etc.
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1180
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1181
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Marcel Dekker, NY, 1995, p.339.
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Rebenfeld, J. Dispersion Sci. & Tech., 10 (1989) 785.
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1183
Shapour Vossoughi
University of Kansas
Department of Chemical and Petroleum Engineering
Lawrence, KS., USA
1. INTRODUCTION
2. NATURE OF FLUIDS
Non-Newtonian fluid flow through porous media is not limited to the polymer
solutions. There are a wide variety of non-Newtonian fluids that could be of
interest. Following are samples that have already established their association with
porous media.
polymers most commonly used for this purpose. Understanding the flow of aqueous
polymer solution through porous media is essential for producing a reliable model
for reservoir simulation.
2.4 Suspensions
Suspensions, sometimes called slurries, differ from emulsions in that one of the
two phases is solid. The dispersed phase, which is a solid, is finely ground and
mixed into a liquid. If the dispersion lasts, the mixture is called a suspension.
Surfactants are usually added to make the suspensions more stable by preventing
agglomeration of the solid particles. Suspensions at high volume concentrations are
affected by many factors, such as hydrodynamic interaction between particles,
doublet and high-order agglomerate formations, ultimately mechanical interference,
and surface chemical effects between the particles as packed bed concentrations are
approached. There is a critical concentration, after which, the viscosity increases
sharply [20,21]. The abrupt increase in the viscosity levels may be caused by the
strong inter-particle forces between the solid particles.
Vossoughi and AI-Husaini [22] studied rheological behavior of the coal, oil, water
slurries, and the effect of polymer as an additive. All the systems they studied were
pseudoplastic and showed shear thinning behavior. Slurries made of finer coal
particles were more viscous than those made of coarser grains. They studied the
dynamic properties of coal slurries with and without polymer, using a small
1187
amplitude oscillatory test. In general, for all slurries tested, the dynamic viscosity
was observed to be a decreasing function with frequency, and the modulus of
rigidity was found to be an increasing function with frequency. Their study was
limited to the frequency range of 0.24 to 6.0 cps.
Flow of suspensions and slurries through porous media involves many challenges
unique to this class of non-Newtonian fluids, and they need to be met. For example,
in the filtration of suspensions or drilling mud infiltration near the wellbore in the
petroleum drilling industry.
2.5 Gels
Placement of gel in petroleum reservoirs to improve oil recovery has become an
accepted practice. The technology is known as permeability modification or profile
modification. Water, or any other fluids that are injected into the reservoir to
displace oil, tends to pass through the more permeable zones leaving behind a
significant amount of oil in the reservoir. Gelling solutions are injected following
the waterflood to plug the already swept zones. Resumption of waterflood, forces
the water to find a new path which leads to additional oil recovery. Gelling
solutions are typically an aqueous polymer solution and some kind of heavy metal
ions, such as chromium or aluminum, as cross linkers. Gels are highly non-
Newtonian and their rheological properties are unique for each gel system [23].
A somewhat different process for profile modification, known as combination
process, consists of the sequential injection of polymer solution and aluminum
citrate solution [24]. The permeability reduction is believed to be due to the
formation of layers of polymer/aluminum ion structure onto the wall surface of the
pores. The adsorbed polymer molecules from the first polymer treatment acts as a
base for the buildup of the structure. To enhance creation of the base and to increase
adsorption of the polymer molecules to the rock, the rock was first treated by
cationic polymer before the injection of the first anionic polymer cycle [25].
In-depth Permeability modification for the oil reservoirs with high permeability
variation has also been achieved by injecting colloidal dispersion gels into the
reservoir [26-28]. This consists of polymer with aluminum citrate crosslinker
injected as a homogeneous solution.
Above examples clearly reveal the complexity of the non-Newtonian fluid flow
through porous media associated with the gel treatment. The fluid flow behavior is
not simply a function of the rheological properties of the fluids involved, but the
interaction between the porous media and the fluids plays an important role.
2.6 Foam
Foams are a dispersion of a gas phase into a liquid phase, are unstable, and break
easily. However, addition of surfactants can increase their stability and prolong the
life of the foams almost indefinitely. Foams are injected into the petroleum
1188
reservoirs for the same reasons as gels. The profile modification for the case of
foam injection is aimed toward the displacement processes where gas is being used
as the displacing phase such as carbon dioxide flood, steam flood, or any other gas
injection schemes [29,30]. Flow of foams through porous media has been studied
in the literature [31,32]. The apparent viscosity of the foams flowing through
sandpacks was measured [33] and was found to be significantly higher than the
viscosities of the constituent fluids. This is one major factor for its effectiveness in
profile modification. In some studies the permeability reduction for foam flow was
found to be an order of magnitude larger than the permeability reduction predicted
just based on the gas/brine mixture viscosity [34].
Foam rheology is crucial in designing an effective permeability modification for
a given reservoir. Foams are non-Newtonian pseudoplastic fluid. Viscosity
measurement in a capillary viscometer revealed that the data fit the Ostwald and de
Waele (power law) relationship [35]. It was noticed that the bubbles do not behave
as rigid particles but flow and slip at the same time. Therefore, a fixed-slip velocity
could not be determined from the data.
3. N A T U R E OF POROUS MEDIA
Any solid body containing space to hold a fluid can be considered a porous
medium. This can be as simple as a pipe or as complex as riving tissue. Only the
interconnected pores, which could contribute to the flow, is of interest to the study
of the fluid flow through porous media, but not all the dead pores should be ignored.
Those dead pores, which have connection to the main flow path, could act as sink
or source for the flow. Experimental investigation of the fluid flow through porous
media is frequently carried out on idealized porous medium to avoid the complexity
of the true nature of porous medium.
through the gap, and Figure 2 is when the gap is very small. This clearly shows that
by reducing the gap, a truly two-dimensional inviscid flow can be produced.
A Hele-Shaw model can be simply constructed by placing two parallel plates very
close together. Incompressible fluid flow through porous media and Hele-Shaw
model becomes analogous [37] and the average velocity components will be
identical if permeability in the Hele-Shaw model is defined as,
1190
h2
(i)
12
where, k is permeability and h is the spacing between the two plates of the Hele-
Shaw model.
Hele-Shaw cell has been used to study interface instability related to the viscous
fingering in porous media [38-45]. For example, Wiggert and Maxworthy [45]
injected air into a Hele-Shaw cell saturated with silicon oil. The unstable immiscible
interface resulted in a series of viscous fingering patterns that were photographed
and digitized. Their Hele-Shaw cell consisted of two glass plates separated by a gap
of 0.21 cm.
Viscous fingering is an interface instability which occurs when the displacing
phase is less viscous than the displaced phase. The creation of viscous fingers and
their growth have been visualized in Hele-Shaw models as well as sand packs.
Figure 3 is an example of the existence of the fingers even in laboratory systems
where porous media are much more uniform and much more homogeneous than the
actual reservoirs. Figure 3 is reproduction of one of the photographs taken by van
Meurs [46] in his transparent three-dimensional glass beads model where oil was
displaced by water.
Addition of a small amount of polymer to the displacing water has been shown to
have significant effect on the stability of the front [47] and, consequently, produces
much higher recovery efficiency.
visualize the flow path in porous media and to study the non-Newtonian flow
distribution in a porous bed. He used a regularly spaced matrix of 6 mm diameter
glass rods in a triangular arrangement. Figure 4 is a schematic top view of the bed
geometry used in this study.
d ~ X
@
0 T0 C) Flow
The cylindrical rods were positioned in a rectangular box of 5.2 by 6.5 cm inside
cross section. The box contained 40 rows of cylinders, each row containing 9 or 10
cylinders in width. The dimension of the smallest opening, d, varied randomly
between about 0.045 and 0.079 cm. Therefore, the bed is considered homogeneous
on a macroscopic scale, but on small or microscopic scale there are considerable
variations in pore diameter. A similar model with cylinders of shorter length and
larger diameter was used by Kyle and Perrine [50].
become significantly more important and will contribute much larger share to the
non-Newtonian flow behavior through porous media.
Figure 5. Cast of pore space of typical reservoir rock. (a) Fine intergranular
sandstone; (b) coarse intergranular sandstone. [55]
Teflon powder cores have also been used by others. For example, Mungan [66] and
Lefebre du Prey [67] used Teflon cores for their study of wettability effects and
Sarem [68] used them to study polymer retention. Domingues [65] measured
polymer retention for his Teflon core within the range of 10 to 21 gg/g of Teflon
powder. Other reported values in the literature [64, 69-72] for polymer retention in
1195
Figure 6. Typical carbonate reservoir rocks (From Core Laboratories, Inc.) [56]
porous media are from 6 gg/g to as high as 160 gg/g of sand grain.
Pye [73] and Sandiford [74], in their experimental investigation of the flow of
polyacrylamide solution through porous media, observed a reduction in water
mobility of 5 to 20 times more than would be expected from the solution viscosity
alone. The additional resistance to fluid flow is mainly attributed to the adsorption
1196
Fr=z <2)
p
where, ~, is the mobility and the indices w and p stand for water and polymer,
respectively. Mobility is defined as,
k
(3)
~w (4)
, wp
where, )~wis the mobility of brine before injection of polymer and Lw~is the mobility
of brine after the bed was exposed to polymer injection and all the mobile polymer
molecules have been displaced by subsequent brine injection. Residual resistance
factor in the range of 1.08 to 15 has been reported in literature [76-79]. A value of
residual resistance factor of 15 means that the porous medium permeability has
been permanently reduced by a factor of 15.
in the oil displacement processes where polymer solution is used as the displacing
phase. Unfortunately, it is not well documented in other disciplines when polymeric
fluid flow through porous media is discussed.
Dawson and Lantz [80] studied inaccessible pore volume in a consolidated
sandstone core by injecting polymer solution into the core. Two types of polymer
were studied. One was polyacrylamide-type polymer (Pusher 700, The Dow
Chemical Co.) and the other was a polysaccharide (XC biopolymer, Xanco, Div. Of
Kelco Co.). The cores were initially saturated with brine, then polymer solution was
injected continuously to satisfy the polymer retention. At complete equilibrium, i.e.
injected polymer concentration being the same as the effluent polymer
concentration, a slug of different polymer solution was injected. Injection of the
initial solution was resumed and continued till the end of the experiment. They
monitored the effluent polymer and the effluent salt concentrations and produced
concentration profiles as given in Figure 7. It is evident from Figure 7 that the salt
peak is arriving at 1 PV fluid injected as expected. However, the polymer peak is
arriving at 0.76 PV of fluid injected. The early arrival of polymer clearly indicates
that not all the pores are available for polymer to flow. This corresponds to an
inaccessible pore volume of 24%. Inaccessible pore volumes have been reported in
literature to range from 1 to 30% depending on the nature of the polymer and the
porous media involved [81,82].
t- 0.2 -
#
Jo
#
: j $
~0.1 p'o
~.g,.., o,
~ L 0.0
0.6 0.7 0.8 0.9 1.0 1.1 1.2
Fluid Injection, P V
Figure 7. Early arrival of polymer peak due to inaccessible pore volume [80]
That is, even if the polymer concentration profile appears at the same time as salt
concentration, this does not necessarily indicate that there is no inaccessible pore
volume and/or no adsorption and entrapment. It is possible that the dilution due to
adsorption and entrapment has been compensated and, therefore, concealed by the
inaccessible pore volume effect.
Inaccessible pore volume is an important, unavoidable phenomenon associated
with polymeric fluid flow through porous media and should not be ignored. Any
realistic fluid flow model for such a system should take into account all the
important fluid/rock interaction phenomena such as adsorption, entrapment, and
inaccessible pore volume.
5. MICROSCOPIC VIEW
Study of fluid flow through porous media at the microscopic level provides
information at the pore level. This information can be used to generate a predictive
model for the macroscopic behavior of the flow system. This obviously requires
significant simplification of the flow geometry. The idealized porous media
presented earlier can be taken advantage of for this purpose.
of fight. The fight was interrupted at known time intervals with a high-speed spoked
wheel. Therefore, velocity of fluid particles can be calculated by simply measuring
the length of an individual streak and dividing this measurement by the known time
interval. The schematic of the photomicrography assembly and the plan view of the
optical system used in this study are presented in Figures 8 and 9, respectively. The
photographs were projected onto a screen to achieve a magnification of
approximately 100X. The actual magnification was determined by projecting a
photograph of a precision steel rule.
@m
a era 9j - I~ Camera Stand
Phototubre ------.-....~~}
Microscope
J Flow Direction
! '" S! ,d
-] r
Microscope Stand Glass Rods Box
Fluid flow distribution with pore opening was studied for Newtonian as well as
Non-Newtonian fluid. Pure glycerol of 13.6 poise viscosity was used as a
Newtonian fluid. The non-Newtonian fluid was a polymer solution of 2% Separan
AP 273 (a partially hydrolyzed polyacrylamide supplied by Dow Chemical
Company). Relaxation time of the polymer solution, as estimated from normal
stress measurements, was approximately 0.1 sec. Viscosities of the two fluids,
measured with a Weissenberg Rheogoniometer, are presented in Figure 10. The
polymer solution used in this study was highly pseudoplastic with power-law
indices as given on the figure. Figures 11 and 12 are typical photographs taken at
three different flow rates for the Newtonian and the non-Newtonian fluid,
respectively.
Fluid Outle d
- q
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
L Fluid Inlet
,..__. ~.~
0 0 0 0
Variable Speed
Transmission
Light Beam and Motor
Adjustable Slit
Converging Lens
Source
r
Newtonian
.,..B
O
13_
:i.
~O Z:l
~
0
o
Polymer
>
(-. ]
m=7.5
< Power Law {
n = 0.43
0.1
1 10 100 1000
Shear Rate, 7, secl
,o I . i :o
~ Ai=0.360cm ~ ~ i =0.354cm
o
d = 0.0526 cm NCL = 0.0889 cm
In these plots, data points of all the four flow rates (whenever streaks are detected
at that particular pore opening) are included. The three profiles in each figure are
for three locations of the same pore. The profile designated by "d" is for the pore
throat (i.e. minimum opening between the two cylinders), and the one designated
by "NCL" (stands for Not Center Line) is for locations away from the pore throat.
The small variation in "d" values in the two figures is probably caused from the
small movement of the cylinders from one run to another. The fines in Figures 13
and 14 are eye-fitted curves through the data points. The graphical integration of the
1203
o Q = 3.42 cm3/s
"O5 9 Q = 6.82 cm3/s
r-
zx Q = 0.685 cm3/s
E
i5 ~'Ai = 0.236 cm 1 [] Q=1.717cm3/s
0 d = 0.0496cm
f
~_ ~,1: " A~ = 0.257 cm
t f
%1,, ~ ~,,~ A~ = 0.226 c
1
0 0
n NCL = 0.089 cm n NCL = 0.1016 cm
areas under the curves are shown by A~. It should be noted that the area under the
curve, which is proportional to the flow going through that pore, should be the same
for all the profiles generated for a given pore regardless of the position of the profile
with respect to the pore throat. The sum of the individual flow rates in every pores
of a single row should equal the total flow rate. This provides an independent check
on the consistency of the data. In general, this was within +5 % of the total flow rate
determined by the pump calibration.
The total number of velocity profiles at various positions and flow rates studied
in this work [48] was in excess of 400 and included approximately 5000 individual
data points. The range of variables covered in this study is given in Table 1. The
range of shear rate, given in Table 1, is within the power-law region of the
viscometric behavior of the polymer solution presented in Figure 10. Therefore, the
power-law parameters estimated from Figure 10 provide a reasonable
approximation to the viscous properties of the polymer solution during the
photographic experiments.
involved, Vossoughi [48] made further assumption that the flow geometry at the
pore level could be adequately simulated by flow through parallel plates. This
assumption was justified based on two observations: 1) Most of the pressure loss
will occur at the narrow openings between cylinders in a given row. 2) The narrow
openings between cylinders are small compared to the diameter of the cylinders
(0.05 cm compared to 0.6 cm). Thus, as shown by Figure 15, fluid flow at pore
level was approximated by flow between parallel flat plates with spacing d (the
narrow openings between the cylinders), but undetermined length in the flow
direction.
The equation of motion is then easily solved for creeping flow in the absence of
any elastic effects. Flow of power-law fluid in the z-direction between the parallel
plates produces [48,49]"
1 l+n n+l
u-( n ;~L d 2x (5)
n + l )(m )n(2 ) n [1-(--~-) n ]
or,
u -
[1 _(9_)
2x n+l
o] (6)
Umax
d12
= 2n ( kp ) ,1- (_~_.)
d l+2n
,
(8)
q P 1 + 2n m CAL
2 Ap d)3
qN -- ~ (#CA L)(-2 (9 )
Equations (8) and (9) predict the volumetric flow rate being a function of pore
opening to the power (l+2n)/n and 3 for power-law and Newtonian fluid
respectively. For the power-law exponent of n = 0.43, as given in Figure 10,
Equation (8) predicts a dependency of the volumetric flow rate on pore opening to
the power greater than 4. Figures 16 and 17 compare the predicted and the
measured flow distribution with pore opening for the Newtonian and polymeric
fluid, respectively. Experimental data in Figure 17 indicate that the flow is
distributed among the pores more uniformly than what is predicted from power-law
model. It is even less than the dependence on pore size for the Newtonian fluid.
6. MACROSCOPIC VIEW
Non-Newtonian fluid flow through porous media can also be studied from
macroscopic point of view. In this approach attention is shifted from the pore level
to the global behavior of the fluid flow. Flow parameters, such as pressure drop and
recovery efficiency, are measured to characterize the flow process. Single phase and
two-phase flow of non-Newtonian fluid through porous media will be considered
here.
0.4 i i I i
0.3
Theory
0
q
5 o2
0 0
O
8
OD" I I I I
0.1
1 2 3
d/d min
Figure 16. Flow distribution with pore opening for Newtonian fluid [49]
0.4 I I I I i
_ Theory d4
0.3
q
Q 0.2
0.1 I I I
1 2 3
did min
Figure 17. Flow distribution with pore opening for polymeric fluid [49]
1207
Of (io)
NDe b -- Op r
in which Of is a relaxation time of the fluid and 0pr is a measure of the rate of
elongational deformation in the flow. Intuitively, elastic effects are expected to be
felt when these two time scales become same order of magnitude. Vossoughi and
Seyer [49] defined Deborah number as following:
They estimated the Deborah number by considering the elongation rate of a fluid
element moving from point A in Figure 4 to a point at the minimum opening [91 ].
Thus
0u z v/~0~-0
(12)
1208
~sA z
Op r "-- (13)
%;
Ofv
NDeb = (14 )
CsaZ
Equation (14) allows estimation of the Deborah number from a knowledge of the
bed geometry and the fluid relaxation time. The choice of Deborah number and
even the choice of characteristic times are rather arbitrary. Some investigators have
used Ellis number instead, to correlate their pressure data [87]. There is no rigorous
treatment in the literature for additional pressure loss in porous media caused by
fluid elasticity. Kemblowski, et al. [92] provided a good review of the subject and
produced a table for the limiting values of Deborah number published in the
literature. The values, above which additional pressure drop due to elasticity has
been observed, range all the way from 0.05 to 3 with various definitions of Deborah
number.
Vossoughi and Seyer [49,91] presented data of friction factor plotted versus
Reynolds number for the Newtonian and polymeric fluid through their idealized
porous media consisted of glass rods. The upward deviation of the polymeric data
from the Newtonian data is clearly demonstrated in Figure 18. The data were also
presented in the form of friction factor multiplied by Reynolds number plotted as
a function of Deborah number. This is presented in Figure 19. In this figure data
from Marshal and Metzner [90] and the theoretical curve derived by Wissler [93]
are also included.
In a different study, Vossoughi [47] observed similar behavior for the flow of
polymer solution through glass beads pack.. The friction factor- Reynolds number
data of this study are reproduced in Figure 20. Two beds, one packed with large
glass beads and the other with small glass beads, were employed in this study. The
characteristics of the beds were presented earlier in Section 3.1.3. Data presented
in Figure 20 follow the linear dependency of friction factor with Reynolds number
for the Newtonian fluid. However, upward deviation from the straight line for
higher Reynolds number is evident for the polymeric data.
1209
10 5 i i
10 4
10 3
f 10 2
101 -
[] Polymer
10 0 - 0 Newtonian
f=l/N Re
10-1 1 I t 1 I
10-5 10-4 10-3 10-2 10-1 10 0 101
NRe
Figure 18. Friction factor - Reynolds number plot for glass rods bed [49]
As before, deviation from linearity can be also demonstrated by plotting the product
of friction factor by Reynolds number versus Deborah number. This is presented in
Figure 21. As observed from Figure 21, different polymer concentrations tend to
show independent trends of upward deviation. The polymer solutions of lower
polymer concentrations reveal earlier upward trend. This upward deviation is not
caused by adsorption, or plugging effects. Because, if this was the case, the more
concentrated solutions would have appeared to show higher upward deviation at an
even smaller Deborah number.
100 i i i liitil i i i itiiil i i i iiiii1 i i i~
9 Separan 273 (48)
- El
- zx
Carbopol (90)
Polyisobutylene (90) -I 1
10 _ O ET 597 (90)
- f ' N a e = 1 + 90N~)EB
f-NRe 1
1.0 zx ~ -
m
- [:n:IED n
f- NRe = 1 + 1 0 N b E B-
0.1 i i IIIIIII I I IIIIIII t t t titttl i i it
1-3 1-2 1-1 10
NDeb
Figure 19. Effect of Deborah number for glass rods bed [91 ]
1210
r 107 I I ! I i
00
o
t-
0
10 6
~
9 10 5
E
a
~
~ 10 4
0 Large Small
Beads Beads
o 10 a 9 O Tap Water
9 g~, 100 cs Dow Coming
t--
9 i-I 12500cs Dow Coming
.o 102 9 V 0.05% Separan AP 273
=m.
o (~ 0.1% Separan AP 273
t,...
u_ 1011 I I I
I =
10-7 10-6 10-5 10-4
10-3 10-2
Reynolds Number, NRe, Dimensionless
Figure 20. Friction factor- Reynolds number plot for glass-bead packs [47]
6.2 T w o - P h a s e F l o w
Two-phase flow through porous media is of significant interest in oil industry for
displacement of oil through the reservoir. Injection of non-Newtonian fluids, such
as polymer and micellar solutions, to displace oil is presently in practice.
Displacement process is an unsteady-state process because of the continuous
changes of the phase saturation with time. Displacement performance can be
predicted either by numerical solution of the partial differential equations involved,
or by the Buckley-Leverett model [94]. The Buckley-Leverett model, also called
frontal advance equation, is an old and systematic approach which can be solved
easily with graphical technique. The derivation of Buckley-Leverett model can be
achieved either by material balance, as discussed in detail by Willhite [95], or by
the method of characteristics applied by Sheldon, et al. [96], Scheidegger [97], and
Vossoughi [47]. The advantage of latter approach is its built-in sharp displacing
phase saturation gradient which must be entered arbitrarily in the other approach.
The method of characteristics is a powerful tool to deal with a system of linear
partial differential equations commonly encountered in the propagation of the plane
waves. Roughly speaking, a characteristic path is a propagation path along which
a physical disturbance, or entity, is propagated. The continuity equation for a one-
dimensional two-phase flow through porous media is given by,
(15)
1211
50 I I I I I i i t I i u
Large Beads Small Beads
or)
O 0.05% Sep. AP-273 9 0.05% Sep. AP-273
t.- o 0.1% Sep. AP-273 am 0.1% Sep. AP-273
.9 9 0.2% Sep. AP-273
. . . . . Newtonian Fluid Behavior
c'10
11)
.
E
m
_ O
CI
0 mm
$
- l l , i n
x
1 _o .,....o...
oo 9 or'&"
9 l_c~..li~. 4.~.,. tr--~'r-
.~...~
0.5 ,, i l i I i i I l i I i I
5x10 -4 10 -3 10-2 10-1 1 10 15
Deborah Number, NDe b, Dimensionless
Oqo=-oAOSo (16)
Ox &
qw (17)
L qo
----I (18)
where, f is fractional flow rate and q is total volumetric flow rate. By substituting
Equation (17) into (15), or Equation (18) into (16), the following partial differential
equation is obtained.
~+~~(s)~-0
~?S q ~?S
(19)
where,
1212
df
f ' (S) : - -
dS (20)
The subscripts are omitted, because similar equations are produced for displacing
and displaced phases. Since phase saturation is a function of position and time, total
derivative of S becomes,
as as
. s - --d +x dt (21)
1
#A
(22)
dt & ~ as
q f'(S)
~A
(23)
=0
dt dx
1 0
=0 (24)
dt dS
1213
q f ' (S)
oa
=0 (25)
dS dx
d x : q f , (S) (26)
dt ~A
dS = 0 (27)
That is,
S = Const. (2 8 )
which also satisfies Equation (25). Therefore, S is constant along the characteristic
path, the equation of which is given by Equation (26). Equation (26) is identical to
the equation derived by Buckley and Leverett [94] using the material balance
concept. In derivation of Equation 26, no assumption was made concerning
rheological behavior of the solutions involved. Therefore, by proper selection of
fractional flow function, Buckley and Leverett model is applicable for Newtonian
as well as non-Newtonian fluids.
Equation 26 implies that at constant volumetric flow rate, q, a given saturation
plane, S, moves at constant speed, dx/dt. Therefore, a plot of x, the position of each
saturation plane, versus qt/~A must yield a set of straight lines with slopes equal to
the first derivative of the fractional flow function evaluated at that specific
saturation. Vossoughi [47,98] performed linear displacement tests in a transparent
rectangular bed packed with either 0.15-cm or 0.47-cm diameter glass beads. Clear
silicone liquids, trade named Dow Coming 200 Fluid with kinematic viscosities of
100, 1000, and 12500 cs, were used as oil phases. Water, various concentrations of
glycerol solutions, and several concentrations of aqueous polyacrylamide-type
polymer solutions were used as displacing phases. He measured the position of the
zero-water-saturation plane, which corresponds to the tip of the longest finger, from
the moving pictures generated for each displacement test. The position of this plane,
Xo, was plotted against qt/#A for Newtonian and non-Newtonian displacing phase.
Figure 22 is an example of the linear advance of the zero-saturation plane of a
1214
polymeric flood. Similar linear behavior was obtained for Newtonian as well as
non-Newtonian displacing fluids.
To explore the possible effect of polymer solution elasticity on the displacement
process, Vossoughi [47] undertook the following approach. Two polymers, one
more elastic than the other, were chosen. These polymers were Separan AP-273 and
Pusher 500 from Dow Chemical. The former one had a molecular weight in the
range of 10 million and the latter in the range of 2-3 million. The concentrations of
the two polymer solutions were adjusted to obtain a similar viscosity level at shear
rates encountered in the displacement tests. The relaxation time defined by Bueche
theory was chosen as a criterion to compare the elasticity effect of the two polymer
solutions. Assuming a molecular weight ratio of Separan to Pusher of
approximately 3, this produced a relaxation time ratio of 7.9 [47]. That is the
relaxation time estimated for 0.1% Separan AP-273 solution is approximately eight
times that of the 0.2% Pusher 500 solution.
Displacement behavior, such as advancing rate of the zero saturation plane,
saturation profile, and breakthrough recovery efficiency, are compared in Figures
23 and 24 and Table 2, respectively. Data indicate similar behavior with small
differences attributed to the small variations in viscosity levels. Therefore, the effect
of polymer solution elasticity on the displacement process was concluded to be
insignificant for the two polymers studied in this work.
7. METHODS OF PREDICTION
I I I I I I
45
40
,[3
35
30
IE
o 25 o,,
x
2O
15 q,, Y
O Small Beads
10 O,~ D Large Beads
,e
,e
I I I I I I
0 5 10 15 20 25 30 35
qt/~A, cm
~ m m I jf/t
//
/,
40 //
s
// /
#
35 O
//
// o
30
l
Z
E 25
O #
X
20
--O 0.2% Pusher 500
q = 0.159 cm3/sec
15
- - .A - - 0.2% Pusher 500
q = 0.635 cm3/sec
10
--0-- 0.1% Sep. AP-273
q = 0.159 cm3/sec
100 I I I I I I I I I
~90
~8o I
9
o. 1% Separan AP-273
0.2% Pusher- 500
m 70
ff
o
60
9 9
~ 50
o
0
4-, 40 9 9
m 30 9 9
.-. 20
9 I 9 9 9 o9 ooo
NlO
i I i vt i 9 t v
10 15 20 25 30 35 40 45 5"0
Position in the Bed, x, cm
Y
|
lR
qi - 2 f f uzdydx (29)
00
qi
(30)
o
R R
Iu -u xl -IX .z (31)
o 0
UzXI~--0 (32)
From Equations (31) and (32), Equation (30) can be written as,
R
q__Li= - I xduz (33)
2l o
or,
R
(34)
2-ii _ - X ( ~ x ) d x
o
The equation of motion for the laminar flow of Figure (25) produces,
1219
P~-PL) x AP
-- ' X
v-( M~ M~ (35)
where, z represents xz-component of the stress tensor, z=. From Equation (35) the
wall shear stress, %, is obtained.
AP
Vw =~R
AL (36)
R
X----T
(37)
Tw
or,
R
dx - ~ d'c (38)
Tw
By substitution of Equations (37) and (38) into Equation (34), Equation (39) is
produced,
qi _ R2 ~ (dUz )d. c
~-- 2 T (39)
21 "t:w o dx
or,
qi (40)
--Um -- ,./72 "~" T
21R w 0
where, u mis average velocity and dUz/dXis shear rate and will be designated by y;
therefore,
um = T2 Ty d~" (41)
w o
For the assumed steady flow, z is a function of 7 only. For Newtonian fluids,
1220
v --~ty (42)
T - mlTl" (43)
where, ITI is the absolute value of 7, m and n are power-law indices. Let us define
F as an average nominal shear rate,
1-' -- um (44)
R
To modify Equation (45) for the multi-cylinder bed, it is sufficient to introduce v/~)~
in place of u m,
Um ~ ~ (46)
~8
~d
where, D is the diameter of the cylinder, and d is the minimum opening between
two adjacent cylinders of the same row. Therefore, Equations (44) and (45) become,
V 1 %
r
- =-~lv3 7dv (48)
G T, o
1221
where, subscript q~indicates that the equation has been modified for the porous bed.
Similarly, equation (36) can be modified for the porous bed as follows,
AP
-~R
T0- E (49)
L'=CL (50)
C is geometric constant which accounts for tormousity of the path of the fluid
particles. The magnitude of C could be approximately estimated as,
C = (zR)N
L (51)
where, ~R is half the circumference of the cylinder and N the number of rows. The
more accurate value of C must be determined experimentally by fitting the pressure
data to the model. Replacing L' in Equation (49) from Equation (50) gives,
AP
--R (52)
zo CL
Equation (48) can be integrated using Equation (42) for Newtonian fluid,
_TO
3p (53)
Solving for g,
T0
P - ~ (54)
3F 0
The expression found for g is defined as Darcy's viscosity. Substituting for z, and
F, from Equations (48) and (52),
1222
q~R 2 Ap
r 3C Lv (55)
l.l-k Ap
Lv (56)
k - ~0~R2
(57)
3C
y -- _(L) 1/n
m (58)
where, the minus sign is chosen because of the choice of coordinates. Equation (58)
is substituted into Equation (48) and then is integrated,
vo (59)
l+2n m
or,
Further, % and F, can be written in terms of k and C using Equations (48, 52, 57).
An
,r ~, - . , / ~ / COs -~ ~61~
L
Fo - v / a/3Ck~s (62)
1223
Equations (61) and (62) are substituted into Equation (60) and the resulting equation
is solved for v n,
From modified Darcy's law [85] for the flow of power-law model fluids through
porous media, Equation (64) is obtained,
(64)
H - m 1 + 2n). )(1-.)/2
7( ,, (3CkO (65)
2dO ~2Ap
f= pv2L (66)
where, f is friction factor and p is the density of the fluid. The Reynold's number,
NRo, is arbitrarily defined so that,
f - 1 / NRe (67)
Therefore, from Equations (57, 64, 66) and knowing that R = d/2, one could obtain
an expression for Reynold's number, NRo.
NR = Pdv2-~ (68)
24C0 H
1224
NR ~ _ pflv
24C0,r (69)
The experimental data of friction factors versus Reynold's numbers are compared
with the above derivation, i.e. equations (66,68,69) in Figure 18. A value of 0.682
was used for C in generating the data from pressure drop measurements. This was
determined experimentally using measured values of surface porosity and
permeability in equation (57). The inertia effect is felt around Reynold's number
equal to unity. The upward deviation due to elastic properties of the polymer
solution is observed long before the inertia effect is felt.
It should be realized that the opening between parallel plates are taken equal to the
minimum opening between the two neighboring cylinders of the same row. This
gives the highest possible value for a characteristic shear rate; therefore, smallest
value for viscosity. In fact, in the bed, there is a range of values of viscosity which
occurs and, therefore, the bed would have a somewhat higher value of average
viscosity. In terms of f - NRo, the low value of viscosity causes higher NRo which
makes the data points of polymeric solutions systematically shift to the fight of
Newtonian in Figure 18.
111111. .ILLL I
(70)
__ _ _ ]_ G~T rr -Jr 1 ~ q~rO ( T rr -- T O0) +Pgr
cgr 3r r 30
q - 2Io~rVr(r,O)dO (73)
c)z ~j 3 r ~j 3 v~_ 3U 2
- ~~'ki +-~(~'~l%)6ij] - 2rleij (74)
~J + ~ [ at + vk c) x k 3 x~ rkj 3 x~
ot~
Vi -- E ~n vi(n)
n=0
oo
p - E ~-p(.) (75)
n=0
oo
~ ij -- E ~ n z ij (n)
n=0
(76)
APviscoelasti c -- Apviscous [1 + A( - )2 ]
tJp
where, q/q~is the mean interstitial velocity, Dp is the average particle diameter, and
A is a constant. Equation (76) can be equally presented in terms of friction factor
- Reynolds number as given in equation (77).
fNR~-[I+A(r
Zq):
p ] (77)
fNRe -- 1 + A N 2 Deb (7 ~ )
Experimental data presented earlier in Figure 19 seem to follow the trend of the
above prediction.
Other investigators [102-104] have also observed significant increase in flow
resistance for polymer solutions flowing through porous media. It is believed that
elongational flow regime is dominant in porous media. This is because of the rapid
changes of cross-sectional area of the pore space in the direction of the flow. James
and McLaren [103] attributes the increased flow resistance to the increase in
1227
V --
kho
w m
(79)
qL
- m y (n-l) ( 80 )
Shear rate, 3' appearing in equation (80) is the average shear rate within the porous
media. There are different models to predict the average shear rate within a porous
media. In general they are a function of the superficial velocity and of an unknown
function of fluid and porous media properties, i. e.,
y = f(k,r (81)
~, Ap (82)
v"- P L
where,
1228
k (83)
A*p - m [ f (k'(~'n)ln- 1
3n+l 1
f (k,d?,n) = (84)
n ( 8 k ~ ) 1/2
1229
10 2 _ m
I I I llllll I I I llllll I I I lll___
m
~_. _
"ID
ml01
(.9 -
L_
kwp = 2,596 md _
Conc. = 3,000 ppm
t_
3n + 1)n_1 (85)
f ( k , O , n ) - ( 4n (0.5kq}) 1/2
1
f(k,r (86)
(0.5kr a/2
9n+3 1
[12( )-n]l-n
f(k,r n (87)
( 1 5 0 k q } ) 1/2
In general, the predicted values of the polymer mobility based on the above
models were poor compared to the experimental values. Hejri [76] correlated his
experimentally measured polymer mobility constants with those predicted by the
above models. His empirical correlations are as following,
1230
~p - 1.076~;~ 92 (88)
kwe Ap (92 )
V -- ~ m
71 L
Vn c _A;Ap s
(93)
where, kw~is the residual permeability, and no is the flow behavior index in porous
media. From equations (92,93), apparent viscosity, 1] can be derived as,
kwp
-- ,~p*vl-nc (9 4)
Assuming the apparent viscosity in a porous medium, rl, is the same as the bulk
viscosity, g, represented by power-law model given by equation (95), an expression
for the average shear rate in porous media can be derived as presented by equation
(96).
1231
] . / - m y "~-1 (9 5 )
m~p 1 1-n~
9' - v X-.v (96)
where, n~ is the flow behavior index, and m, consistency index determined from
viscometric measurements, ~p* and n are determined from porous media
experiments as presented in Figure (27).
DEDICATION
This chapter is dedicated to Dr. F.A. Seyer, the author's former M.Sc. and Ph.D.
advisor.
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1234
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1237
Y. A. Buyevich
Center for Risk Studies and Safety, University of California Santa Barbara,
6740 Cortona Dr., Santa Barbara, 6.4 93117
1. INTRODUCTION
Flows of colloids and suspensions of fme particles are important for a wide
variety of multifarious applications encountered in nature and in various fields of
modem industry. First of all, engineers and researchers are commonly interested
in global hydraulic characteristics of such flows. However, more subtle
peculiarities featured by such flows may be of great practical concern as well.
For instance, it is imperative to obtain a certain information on the kinetics of
flow stratification which would allow to evaluate the rate of particle deposition
on channel walls, the intensity of phase separation in vertical flows, etc. The
information of such a kind should also be of crucial significance in modifying
many widespread industrial processes with an ultimate purpose in view to
improve quality and performance characteristics of those processes.
However, theoretical study of suspension flow usually meets with formidable
difficulties of principal nature, even in cases where only comparatively sketchy
hydraulic characteristics pertaining to a smooth laminar flow as a whole are
under question. These difficulties, which are briefly indicated and discussed
below, are in the first place due to the obvious lack of a sufficiently reliable
hydrodynamic model even for laminar suspension flow. Such a model is at
present not available, despite considerable efforts undertaken during the last
decades in the field of both suspension hydrodynamics and rheology.
Correspondingly, the main intended objective of this Chapter consists in putting
forward some relatively simple considerations that hopefully will prove
themselves both beneficial and advantageous in the matter of developing the
needed fluid dynamic model for laminar flow of concentrated suspensions. A
1238
stresses acting in flow of the suspension phases are completely left out of
account.
As has been discussed in [1 ], the intrinsic inconsistency of conventional fluid
dynamic schemes of suspension flow which do not allow for stress contributions
due to the fluctuations consists in the fact that their governing equation do not
permit the concentration field to be found alongside the fields of mean phase
velocities and fluid pressure. The latter fields can be obtained merely on
condition that the former one is given beforehand. However, the mere fact of the
concentration field having been prescribed in advance decreases by unity the
number of unknown variables in the governing equations, so that one of these
equations cannot actually be satisfied and, in fact, has to be discarded.
The physical reason of this deficiency is usually due to the occurrence in a
flow of a transverse force experienced by suspended particles in the direction
normal to the flow streamlines. This force causes the particles to migrate in the
same direction and, inasmuch as the corresponding particle flux is not
compensated for by any diffusion flux, it must eventually give rise to the flow
stratification. The simplest example is provided by flows of not neutrally buoyant
suspensions in inclined channels. In such flows, the lateral component of gravity
as corrected for buoyancy brings about the initiation of both a region which is
filled with close-packed particles and a region which is entirely devoid of
particles. Under steady conditions, the whole flow domain must consist of only
such limiting regions, without any region containing suspended particles in
between [ 1].
In vertical flows, the similar particle migration is stipulated by the inertial
lateral lift force acting on particles that rotate in a sheared flow [2]. When being
not compensated by diffusion, this migration virtually results in the accumulation
of particles in either a central or a peripheral flow region, depending on whether
the particles are heavier or lighter than the suspending fluid.
Our primary purpose consists in demonstrating in the present Chapter what
has to be actually done in order to develop a consistent workable scheme aimed
at tackling stratified flows of colloids and freely dispersed suspensions. The term
"finely dispersed" insinuates that collisions of suspended particles are totally
irrelevant in the interparticle exchange by momentum and energy which is
therefore assumed to be carried out via the velocity and pressure fields of the
intervening fluid. The preference is given to simplicity and clarity of
presentation, rather than to strictness of our development which seems
unnecessary at its present stage . For this reason, we shall address only the
simplest possible type of dispersions, that is, a suspension of identical solid
spheres in an incompressible Newtonian fluid which exhibit steric and
hydrodynamic, but not any molecular mterparticle interactions that are usually
1240
3t ' 3t
+v.(ow)-0 (1)
C9
CPp(~
~ + w . V I w = f - qkppV ff~ (3)
where v and w are the mean fluid and particle velocities, ~b and e = 1 - ~b are
the particle concentration by volume and the void fraction, respectively, and (I)
is the potential of an external body force field. Vector f describes the average
mterphase interaction force per unit volume, and ~ is the effective stress tensor.
What happens to be of principally significance is that effective stresses
appear only in the equation (2) of continuous phase momentum conservation,
whereas averaged stresses that might be expected to affect mean flow of the
dispersed phase identically tum to zero [6,7]. Note, however, that this general
conclusion is valid only for disperse systems in flow of which the impact of
fluctuations on the phase stresses is negligible, so that it may be ignored.
'I 4 5
Pe = -~ P - -~ Pp + -~ M (3p - qkpp , p = ~pf + r M =~
1
(4)
1-2.50
pe a2
cr=-pi+ , o'~=21ufM 1+ T~ +w" ev , (5)
- F,S M
1244
where p is the mean interstitial pressure, I is the unit tensor, a is the sphere
radius, ktf is the ambient fluid viscosity, and e~ is the strain rate tensor
corresponding to the continuous phase mean velocity field. Quantity M plays the
role of relative suspension viscosity attained in steady flow, whereas Tu is a
specific relaxation time. If p~ is positive, as is the case for colloids and for the
majority of suspensions encountered in practice, an adjunct relaxation
relationship can be formulated as [10]
--
cgt
+ w- ev - ev,, - ev
' ev's 21ufM
= ~ (6)
Hence it follows that the strain rate tensor relaxes to its value which would
establish itself in steady flow characterized by a given actual tensor of mean
viscous stresses. In the opposite case of negative p~, which can be realized for
gas-solid mixtures, we have another relaxation relationship, instead of that in
equation (6),
According to this relationship, the mean viscous stress tensor now relaxes to
its steady value corresponding to a given strain rate tensor.
These relaxation phenomena come about as a natural consequence of the
frequency dispersion effect for the suspension viscosity. This effect means that
the effective suspension viscosity, as it manifests itself in unsteady
monochromatic suspension flow, happens to be dependent on flow frequency.
The frequency dispersion may be quite insignificant as far as the averaged
stresses are concerned. However, as is demonstrated below, it proves to be
rather important in the matter of influencing an inertial part of the total interphase
interaction force that is inherent in dense suspension flow.
The interphase interaction force attributed to a unit volume of the mixture is a
sum of a few contributions having different physical meaning
Expressions for the viscous drag force, the hereditary Basset force, and the
Faxen force due to flow non-uniformity are of exactly the same form as the
corresponding force constituents for a single sphere in an unbounded fluid [ 11 ],
save for the fluid viscosity and density being substituted by the effective
suspension viscosity and density. They are expressible as
1245
f_9r uzM
a 2
(v_w) (9)
fB -
9~2( .tllfMll/2i(~ VII
p Jra2 ) + w-
dr'
(v - w)t - t' 4 t - t'
(10)
--00
fi - /(
p - - ~ pp + 3~bPe ~ - + w v-w,
Supposedly, this force describes not only the effect of fluid virtual mass
acceleration and the effect of accelerated motion of the ambient fluid itself, but
also the influence on the interphase interaction force of the frequency dispersion
of effective suspension viscosity.
An equation for the effective buoyancy force contains two terms
The first term within the curly brackets describes a contribution to buoyancy
caused by the suspension being under action of an external body force field that
is characterized by potential O. This contribution is sensitive to changes in this
potential with time and (or) in space. This may be important for a centrifugal
force field that influences flow of suspensions rotating with either varying or
constant angular velocity. However, this contribution does not evince relaxation
if the specific acceleration of the external field is invariable, as is the case with
gravity. The second term in equation (13) represents a buoyancy force
contribution stipulated by an additional effective body force field that makes its
appearance owing to particle inertia. It is worth noting that an additional term
describing a relaxation effect associated with this buoyancy contribution makes
its appearance [10]. This term can be shown, however, to be of a higher order of
1246
magnitude that other terms retained in equations (9) - (13), and for this reason, it
must be omitted from equation (13).
At v = 0 and in the dilute limit ~ ~ 0, force (8) can be easily demonstrated
to reduce to the force that is experienced by a single Stokesian sphere moving in
an unbounded fluid and that was previously evaluated in [11 ].
To get a deeper insight into the nature of the inertial phenomena that affect
interphase interaction, we also reproduce an equation of motion for a single
suspended sphere that can be straightforwardly deduced from equations (3), and
(8) - (12). This equation can be written down in the following form
dw d ( w - v) dv
mp ~ = - m a +m- +R (14)
dt dt dt
Here, operator d/dt is understood as that of full time differentiation along the
averaged particle trajectory (or alternatively, along the dispersed flow
streamlines). Vector R stands for a sum of all forces experienced by the sphere
except for those proportional to the full time derivatives of the continuous and
dispersed phase velocities (that is, except for the inertial force (12) and the
second contribution to the buoyancy force (13)). The following effective masses
are introduced:
m = c r n f + q~mp , ma = k m f ,
1/
k =-~ e + (15)
pf
where mp and my are the sphere mass and the mass of the fluid replaced by the
sphere, respectively. In the dilute limit, m~ tends to m/2, and m tends to mf, so
that equation (14) with coefficients (15) reduces to the well-known equation for
unsteady motion of a body in an unsteadily flowing unbounded fluid [11, 12].
The first term on the right-hand side of equation (14) describes a combined
effect of the virtual suspension mass acceleration and of the frequency dispersion
phenomenon. Coefficient k can be conventionally interpreted as an effective
added mass coefficient. It depends not only on suspension concentration, but
also on the ratio of particle and fluid densities. This is due to the fact that the
suspension cannot apparently be regarded as a truly homogeneous effective
medium that surrounds an accelerating suspended particle when evaluating the
effective suspension mass that is carried along with this particle.
The second term in the right of equation (14) is due to the inertial force that
makes its appearance in the suspension momentum conservation equation when
this equation is formulated in a coordinate system that moves with velocity v, as
1247
is explained in [12]. This force must not be dependent on the suspension being a
two-phase system. Accordingly, coefficient m that appears in this term
represents the mass of the suspension that is replaced by a sphere, as if the
suspension were a homogeneous one-phase medium.
The determination of the added mass coefficient was a predominant subject of
many papers, beginning with that by Zuber [13], representative examples of
which have to be found in [14-18]. Nonetheless, conclusions inferred in these
and other papers on the subject with respect to the added mass coefficient can
hardly be unambiguously compared to our formula for k as listed in equation
(15). This is due to the fact that practically all such conclusions commonly refer
to a system of particles (most usually bubbles) immersed into a potential or
almost potential flow, where the frequency dispersion of viscosity and the
ensuing stress relaxation is of no consequence. At the same time, the contribution
to k appears to be quite significant for fine particles in viscous flow, and it
comes about as a result of the stress relaxation and which is not taken into
accotmt in the majority of available papers. (Admittedly, this contribution
correspond to the term in equation (15) that is proportional to effective density
p~ involved in the definition of relaxation time T, in accordance with equation
(5) .) At any rate, the added mass coefficient as detennined by equation (15)
increases with ~ considerably faster than similar coefficients calculated in [13-
18]. This point deserves attention in the future work.
It is significant that it is the mean suspension density, but not that of the pure
ambient fluid, that is involved in equation (13) expressing the effective buoyancy
force. As has been discussed in [10], this inference brings to an end a recent
rather hot debate on which density must be used in the mentioned context while
treating fluidized beds and other suspension flows (examples of different
controversial arguments used in this debate can be found in [19, 20]).
For future reference, we write down an expression for the sum of inertial and
buoyancy forces for a suspension in the gravity field. We have
(18)
model, etc. The local particle volume concentration distributions that stem from
two of such models at different values of mean suspension concentration are
plotted in Figure 1 as well.
1 5
0.5 4
0 !
1 2 3 4 r/a
Figure 1. Local particle volume concentration near test sphere surface related to
mean concentration as a function of relative distance from this sphere center; 1,
1" - model by Percus and Yevick at # = 0.4712 and 0.2612, respectively; 2, 2" -
model by Kirkwood at # = 0.484 and 0.2314; 3 - smoothed distribution
corresponding to neglect of interactions of more than two spheres; 4 -
approximation of the last distribution by a stepwise function; 5 - spheres are
permitted to overlap.
spheres that come closer together, are hardly avoidable in highly concentrated
suspensions, even if there are no interparticle collisions in the generally accepted
sense. Secondly, the inner structure of a flowing highly concentrated suspension
must be especially sensitive to various structure-ordering processes, up to those
of the formation of crystalline patterns. This means that the actual pair
distribution function as it establishes itself in dense suspension flow must be
essentially different fi'om its approximations resulting from equilibrium statistical
models, and it must depend on flow parameters. In particular, one can expect the
occurrence of shear-thinning even in flow of a suspension composed of identical
hard spheres without molecular colloid interaction, if suspension concentration is
large enough.
M ....., , ,/;
6
4 5
I __ !
0 0.2 0.4
l+ , (20)
2 2 ,of
For suspensions composed of particles that are lighter than the suspending
fluid, and in particular, for suspensions of gaseous bubbles in a liquid, the added
mass coefficient is illustrated by curves in Figure 3, a. This coefficient proves to
be a rapidly increasing function of suspension concentration, and this function's
recline slightly increases as the density ratio grows. For reasons that have been
pointed out in Subsection 3.1, this recline is considerably larger than those in
other existing models that treat particles in a potential flow. To show this, the
added mass coefficient as follows from the Zuber's model [13]
that were obtained in [15, 16], respectively, are also shown in Figure 3, a.
12 a. . . . . . 6 b
- , , , , , , , ,
0.1
b r 0.2
Figure 4. Variation of the virtual suspension mass for moderately concentrated
suspensions of heavy particles; the curves correspond, in descending order, to ~r
= 10, 30, 100 and 1000.
difficult to see from equations (9) - (13) that merely the buoyancy contribution to
the lateral component of f differs from zero in such a flow, so that the wanted
equation component reduces to a very simple form
where gt stands for the lateral component of the acceleration associated with an
external field of body forces that act on the suspension. It is easy to see that
equation (23) can never be fulfilled except for ~ - 0, if the suspension is not
neutrally buoyant, and if gt differs from zero.
Hence a conclusion seemingly follows that the steady uni-directional
suspension flow under consideration is impossible in the sense that the flow
domain must always separate into two regions. As has been already mentioned in
Introduction, one of these regions should be filled with pure fluid, where ~ = 0,
and equation (23) transforms into an identity. The other region should be
occupied with close-packed particles, where equation (23) is irrelevant because
certain direct interparticle forces arise which must be explicitly included in the
dispersed momentum conservation equation. Obviously, this conclusion is wrong
since it contradicts numerous experimental observations, if for no other reason.
In practice, the regular force that appears on the left-hand side of equation
(23) causes a particle convective flux in the direction of this force. Such a flux
modifies any initial spatial distribution of suspended particles. However, it not
necessarily leads to complete flow stratification with the formation of a region
totally devoid of particles, and of another region containing close-packed
particles. Indeed, the particles experience random fluctuations of different
physical origins. Particle displacements due to the fluctuations must result in the
occurrence of a specific particle migration, and a net particle flux stipulated by
migration must oppose the convective flux. Supposedly, the combined action of
these two fluxes prevents, or at least hampers, the flow domain separation into
the regions mentioned, and so it can result in establishing a steady suspension
concentration distribution. It is such a steady distribution that has actually to be
dealt with when considering steady flows.
If the particles undergo successive displacements that can be regarded as
mutually independent, the migration flux may be appropriately described as a
diffusion flux down a concentration gradient. It is rather tempting in such a case
to replace the dispersed phase momentum conservation equation by a convective
diffusion equation for suspended particles, as has been done more than once in
various papers on suspension flow. However, as will follow from the subsequent
analysis, this can be formally done only for one-dimensional suspension flows, in
which the suspension concentration depends on a single coordinate, and where it
1256
There are great many papers that deal with the problem of Brownian motion
in a system of many interacting suspended particles, as well as with the
elucidation of the influence that this motion is likely to cause on the suspension
rheological properties. Recent examples are provided by the beautiful papers by
Brady [25, 26] who has successfully addressed the statistics of a crowded
assemblage of Brownian spheres when placed into a thermal bath characterized
by temperature kT in energy units, and also the Brownian motion effect on the
rheological behavior of concentrated suspensions. However, within the
framework of the present treatment, we are surely unable to reproduce
conclusions of the type of those drawn in [25, 26]. This is due to the fact that we
have given up analyzing the influence of both suspension flow and particle
fluctuations on the pair distribution function, if for no other reason. Thus, here
we confine ourselves to a more modest aim of obtaining simpler conclusions
pertaining only to normal stresses caused by the thermal fluctuations. Within the
scope of our treatment, the effective suspension viscosity is regarded as a given
fimction of suspension concentration, no matter whether it is influenced or not by
particle Brownian motion, or either by other physical factors that happen to
originate a short order in the suspension flow.
As an alternative to ingenious methods used in [25, 26] and in other papers of
the same type, we are going to resort to the method that is based on introducing a
"thermodynamic" constituent of the interphase interaction force and that was
thoroughly substantiated by Batchelor [27]. When applied to suspensions of
interacting particles, this method represents a certain generalization of the
classical thermodynamic force method devised by Einstein for random migration
1257
of a single particle in an unbounded fluid due to the particle interaction with fluid
molecules.
As has been stated in [28], the influence of Brownian motion on suspension
statistics and rheology consists in smoothing out probability density function for
suspended particles, in contrast to a tendency of suspension flow to make these
functions non-uniform in their respective phase spaces. This influence is partially
revealed through mutually interdependent thermodynamic forces experienced by
different particles. They affect mean stresses in suspension flow in two ways.
First, they cause an immediate contribution to these stresses. Secondly, they
change the probability density functions, and in particular, the pair distribution
function, thus implicitly affecting the stresses (and the effective suspension
viscosity).
Before proceeding further, we wish once again to outline some limitations
inherent in the present paper. For reasons given above, below we concentrate
only upon the stress contribution due to the first mechanism, and we make use of
the analysis earlier forwarded in [27] for dilute suspensions and generalized to
concentrated suspensions in [1]. However, it is worth noting that the failure to
allow for the changes in probability density functions results in a slight difference
of the resultant relative suspension viscosity from its representations found on
the basis of more sophisticated schemes, even for suspensions of low and
moderate concentrations. Thus, the coefficient at q~2 in the Taylor expansion of
function M as defined in equation (4) equals 25/4 = 6.25, whereas the same
coefficient was found to be equal to 6.2 for shear suspension flow dominated by
intensive Brownian motion [9], and to 7.6 for flow of pure elongation without
Brownian motion [8].
approximately regard the fluctuating force, that is exerted on the particle by the
surrounding fluid and that depends on positions of all the neighboring particles,
as a stationary random process.
To begin with, we shall briefly reproduce the reasoning employed in [27]. If a
suspended particle is at equilibrium when an external force field is applied, the
Boltzman distribution must be valid, and the particle Gibbs free energy must be
spatially uniform. This means that an external force acting on the particle must be
statistically compensated by the thermodynamic force Ft which is equal to the
particle chemical potential gradient taken with a negative sign. The
thermodynamic forces produce a particle convective flux that is precisely equal
to the actual diffusion flux. Furthermore, the motion of the particle due to the
external forces and to its diffusion caused by thermal fluctuations can be
justifiably presumed to result in additive particle displacements. For this reason,
the particle diffusion flux must be determined by exactly the same
thermodynamic forces even under non-equilibrium conditions where there are no
external force [27].
By its very definition, the thermodynamic force in an isothermal flow can be
expressed in a general form as
(25)
On p,T p,T
V~ = _n_n_Ft (26)
F/=- On JP, f ~, Oqk ) p,T no
acts also upon each molecule of the ambient fluid, where flf and no are the
chemical potential and the number concentration of the molecules. It follows
1259
from equation (26) that the thermodynamic forces act simultaneously on both
phases of the suspension, and moreover, that their sum is zero for any suspension
volume, that is,
nF t + noF [ - 0 (27)
Equation (27) proves that the thermodynamic force per unit volume, ft = nFt,
has to be regarded as an additional constituent of the interphase interaction force.
In fact, equation (27) is a manifestation of the Gibbs - Duhem relation written out
for colloid particles dissolved in a fluid.
The chemical potential of hard spheres undergoing the Brownian motion can
be calculated with the help of the standard methods of statistical mechanics. The
calculation is trivial for very dilute suspensions of non-interacting spheres where
~tp coincides with the chemical potential of an ideal gas, in which case
the first term on the left standing for the inner chemical potential of a sphere.
If a suspension is dilute, but the mterparticle interaction is taken into account,
the application of the well-known group expansion technique seems to be
natural. The latter leads to an expression for the chemical potential in the form of
a series in powers of q~ that resembles the standard virial expansion~ Each term
of this series is associated with the collective interaction between the particles
being members of various possible groups composed of the fixed numbers of
particles. Allowance for merely pair interactions conforms to retaining also the
second virial coefficient of the expansion. This gives rise to the term of 8q~kT in
the series for ktp, which has been previously calculated in [27].
The group expansion technique is unlikely to be of much use, however, when
applied to crowded assemblages of suspended spheres, since this technique does
not in fact give a tangible opporttmity to advance in a region of large
concentrations. In such a case, the calculation is handicapped by the fact that no
reliable rigorous statistical physical theory of dense gases and liquids has been
elaborated to date, so that an approximate model has to be used. It seems
sensible to make use of one of versions of the Pereus- Yevich theory of liquids
because it makes it possible to obtain analytical results for assemblages
composed of hard spheres. Following [1 ], we employ the version of this theory
worked out by Carnahan and Starling [29], which gives the following equation of
state for a dense gas of identical rigid spheres
1260
where P is the osmotic pressure, and V is the volume occupied by the system
of N rigid spheres.
Roughly speaking, equation (29) brings to light corrections to the classical
equation of state for an ideal gas that are due to sterie interactions between
spheres having fufite volume of their own. It should be pointed out once again,
however, that this equation fails to account for the formation of a crystalline
phase in dense sphere assemblages. This failure calls in question applicability of
this equation of state to suspensions of high concentrations that are close enough
to a hypothetical concentration associated with the close-packed state.
Equation (29) serves as a sound basis while evaluating the particle chemical
potential and calculating the thermodynamic force for spheres suspended in a
fluid that plays the role of a solvent. The difference of the wanted chemical
potential from that of the same spheres forming a dilute system can be quite
straightforwardly written down as follows:
O I n ( V N QN)__~___P _ N G(~)
(31)
cTV kT V
lnQN = - N d ar
0
r (32)
=- fG(~)- 1 G(O)-I ( c7 _/
ON ,I -~ d ~k- N ~ p , T ,N o
p,T,No o
and this determines the chemical potential difference as defined by equation (30).
1261
Note that the differentiation is performed in equation (32) under the condition
that not only p and T, but also the total number No of solvent molecules are
maintained constant. By allowing for the expression of the osmotic pressure
function as shown in equation (29) and for evident relations
where o- and o0 are the specific volumes of one particle and one molecule,
respectively, we derive from equation (32)
cTlnQN) _ 8 - 50
ON - - (---i~ 0 (34)
p,r, No _~)2
Hence and from equations (28) and (30) follows the resultant formula
8 - 5______L~
/u p - 1.1,p + k T F ( q k ) , F(~b) - l n 0 - r + (1 - ~)e ~b (35)
d = dF(~b)
a---g- (37)
where F(r is the function defined in equation (35). Integrating equation (37) at
an evident initial condition yields
-
2 In(l-O) +3 1-20 +
1 15-8~-~ 2
- (38)
r 1-0 2 (1-~) 2
-f t = kT d
cr d e [r L(r V~b- - V H , H - kTo.r L(~) (39)
It is clear that the scalar quantity H may be identified with the effective
isotropic normal stress that is caused by the particle thermal fluctuations and that
manifest itself in mean flow of the dispersed phase. Physically, it describes a
momentmn flux density produced by the particle thermal fluctuations, and by its
very definition, such a density must be interpreted as a stress.
Instead of adding the thermodynamic constituent to interphase interaction
force (8) to describe the impact of Brownian motion on suspension flow, we can
alternatively include the isotropic particulate stress H into momentum
conservation equation (3) of the dispersed phase. Simultaneously, we must
include a component of - FI to mean interstitial pressure p involved in
accordance with equation (5) in the defirfition of the effective stresses that appear
in momentum conservation equation (2) for the continuous phase. This amounts
to introducing the following stress constituents that are caused by Brownian
motion and that must be added to the stresses acting in a suspension flow without
fluctuations:
/2
0 0.2 0.4 O
Figure 5. Functions of suspension concentration that determine the osmotic
pressure of a pseudo-gas of rigid spheres and the normal stress that affects
dispersed phase flow of a suspension of the same spheres without collisions and
that is due to thermal fluctuations.
(41)
of the actual random velocity of a particle from the averaged velocity of the
dispersed phase.
4~ , GE(~)= 1 - (45)
[34] and in some other papers. Shear-induced mutual diffusion of particles was
proven to induce the flow stratification, meaning that a non-tmiform particle
distribution develops in a shear flow as a result of the combined action of
external forces and particle mutual diffusion [35].
There are known many attempts to work out a comprehensive and reliable
model to treat suspension shear flows in general, and to determine particle
distributions specific to various concrete types of shear flow in particular.
Representative examples illustrating different trends of thought can be found in
[36, 37]. The authors of [36] developed a fluid dynamic model of shear
suspension flow, in which it was suggested to describe the shear-induced
migration in terms of a special particle diffusion equation introduced on purely
empirical grounds. In contrast to this, the authors of [37] deduced the steady
particle distribution in a pressure-driven one-dimensional flow in a channel from
the requirement that the total normal stress be constant in directions normal to
the mean flow. The model stemming from this requirement was well supported
by their numerical simulations performed on the basis of Stokesian dynamics
technique, and these simulations were, in their rum, in qualitative agreement with
experiment.
While setting aside a more detailed discussion of these issues until later, we
focus our attention on evaluating the normal stresses that are due to shear-
induced fluctuations within the framework of the approach being developed.
According to equation (46), this means that we have to calculate the tensor of
averaged particle velocity products, or particle velocity variance tensor (w'*w'),
in shear suspension flow as a function of suspension concentration, shear rates,
and particle radius. This has been done in [38], and we reproduce the main
results obtained in that paper.
above. To obtain a concise expression for this particle velocity variance tensor,
we make use of some tensor covariance methods as characteristic of the rational
mechanics.
The most general rational mechanical representation that satisfies both the
aforementioned requirements is of the form
/2 standing for the second tensor mvariant, and A and B being scalar
coefficients independent of the dispersed phase mean velocity field. To find a
relation between A and B, and thereby to reduce the uncertainty inherent in
equation (47) to a single unknown scalar coefficient, an analysis of a simple
shear flow sketched in Figure 6 appears to be helpful.
y
1 ly wx--]~
n'/2 R R,
{lyoclz
} ~dq9 fr dr(ycos~)Lsinqgjoc
Ic~176 {re~4}
1/2
fl * ( ~ 2 d na4ocr (48)
0 0
section. In a dense gas, as the particle volume fraction grows while the particle
number concentration is held constant, the collision frequency is known to
increase faster than is required by the last proportionality in equation (48). This
increase in collision frequency occurs due to the forcing the particles into a
confined space, and it is usually described with the help of the Enskog factor.
Although relative particle displacements in a sheared concentrated suspension
are affected by long-range hydrodynamic interactions involving many particles,
main contributions to the displacements may again be viewed approximately as
the result of particle pair interactions. As a first approximation, we hereupon
conceive elementary particle displacements as taking place in consequence of
two particles occasionally drawing close to each other, the influence of the other
particles being assumed to cause a secondary effect on pair interactions. This
amounts to viewing the complicated multiparticle interactions involving the
chosen sphere in a sheared concentrated suspension as a sequence of certain
effective pair interactions of this sphere with its neighboring spheres.
Within the scope of such an approximation, the pair interaction frequency in a
suspensions may be replaced by the collision frequency for the corresponding
pseudo-gase composed of hard spheres. Then the same factor Z(~) has to be
used to account for the increase in pair interaction frequency in concentrated
suspensions due to the particles being crowded in a confined space. Thus, the
last quantity in equation (48) has to be multiplied by the Enskog factor.
Obviously, components of the particle velocity variance tensor (47) represent,
by their very definition, averaged products of displacement velocity components.
The last velocity components equal the displacements per unit time, equation
(48), multiplied by the Enskog factor. Hence, we arrive at a general estimate
, 1 2
(50)
1271
A+B-(zc/
2 B 4) 1/2
~2
= 4 (51)
Using equations (49) and (51) enables us to reduce equation (47) to the
following form:
where C stands for an unknown coefficient having the order of unity. This
coefficient may slightly depend on the suspension concentration, due to the semi-
empirical nature of the model used to evaluate the shear-induced particle
fluctuation velocity, as well as owing to the fact that multiparticle interactions
have not been considered in an explicit form. A more sophisticated theory is
clearly needed to reveal such a dependence, in which multiparticle interactions
would not be replaced by a hypothetical sequence of pair interactions as far as
their impact on the said fluctuation velocity is concerned.
It is worthwhile to note that, by using simple rational mechanical
considerations, we have arrived at a rather informative inference pertaining to the
longitudinal fluctuations in the flow direction (that is, along the x-axis), in spite
of the fact that these fluctuations did not enter our reasoning in a direct explicit
way. Namely, as follows from equations (50) and (52), the velocity variance for
these fluctuations must be precisely equal to that for fluctuations in the direction
of shear (that is, along the y-axis).
As a reasonable first approximation, fluctuations of different particles can be
regarded as statistically independent. Then, on accord with the arguments
forwarded in the end of the preceding section, the normal stresses generated by
shear-induced fluctuations can be evaluated from equation (46).
variance tensors for the shear-induced fluctuations and for the thermal
fluctuations when taken alone. Such a superposition approximation corresponds
to an assumption that fluctuations of the types mentioned are mutually
independent, which appears to be quite credible in view of fluctuations of those
types being originated by different physical causes. The radial components of
momentum conservation equation (2) and (3), to which stresses due to thermal
and shear-reduced fluctuations are added, then reduce to
F
Y - M(r
~ ' R1 < r < R2 (54)
where R I and /?2 are radii of the internal and the external cylinders,
respectively, and F is an integration constant that can obviously be related to
the torque applied to the rotating cylinder.
Next, we have from the second equation (53) and equation (54)
0.6 0.6 9 aa
9 0
9 0
0.4 04 f ~
0.2 I 0.2I 4/ I t I
0.2 0.4 q} 0.6 0.2 0.4 ~0 0.6
The agreement between theoretical curves and experimental dots is not bad at
all. Nevertheless, the dots apparently corresponds to a dependence of # on
relative coordinate r/R2 which is more gently sloping than the dependence given
by the theoretical curves. The dots are all the more so gently sloping in a range
of high concentrations. These curves conform to the experimental data somewhat
better, if allowance is made for the singularity of osmotic pressure at # - ~ , in
conformity with equation (45). Comparison of the curves plotted in Figure 7, a
with those presented in Figure 7, b proves, however, this singularity to be
1274
important only at concentrations which are sufficiently close to that of close
packing.
It is worth emphasizing once again that no free adjustable parameters have
been used when drawing any curve in Figure 7, but for close-packed state
concentration ~,. The agreement of theoretical predictions with experimental
evidence as witnessed by Figure 7 can therefore be regarded as a weighty
agreement in favor of the model developed. This notwithstanding, this agreemem
is not altogether as conclusive as it might initially seem because of two
approximations used. First, equation (19) has been assumed adequate to
represent the relative suspension viscosity, and secondly, equations (44) or (45)
have been chosen to represent the Enskog factor. One might argue that viscosity
must increase infinitely as the particle volume fraction tends to its close-packed
state value, so that model predictions in Figure 7 may be somewhat fallacious.
At any rate, Brady [26] has obtained a theoretical limit for the relative
suspension viscosity of Brownian according to which M(r --} (1 - #~)-2 at
---} ~ suspensions that proves to excellently agree with experimental data by
many researchers. For instance, the well-known Krieger's formula [41] gives
1-
~m/_1.82 (57)
and the exponent is this formula differs quite negligibly from the exponent of 2
appearing in the Brady's theoretical result.
Moreover, the osmotic pressure function and the Enskog factor must also
diverge in the indicated limit, so that singularities of M ( ~ and Z(~ are likely
to cancel each other out. Moreover, comparison of the curves plotted in parts a
and b of Figure 7 evidences that the effect of divergencies at ~ ~ ~ is not as
high as it might have been anticipated.
The resultant diffusion-like equation that replaces the second equation (53)
looks as follows (it differs by a factor of (1- ~2 from the equation cited in [38]):
(1-#)2 d f
M(qk) dr 0[1+4r
I kT
6zc-pfa
+ C~b22,2 (~b) (7' a) 2 mp ]1 =0 (59)
6n'pfa 1!
This equation can be rewritten in a more familiar form, that is,
(DR + D,h)dq~
dr =0 (60)
where effective particle diffusivities caused by the thermal and the shear-induced
fluctuations are introduced by means of the following relationships:
DB = #)_____~2
(1- d {q~[1+ 4#Z(q~)]} D~ (61)
M(~) dq~
Ds~ _ ( 1 - ~ ) 2 d
- M(~--------~d~ {#3 Z2 (~)[1 + 4r162 } Ds~ (62)
kT (ya)2mp 2C 7'2a 4
D~ - 6 rc,uf a ' Ds~ = C 6 rc/.tf a = --9 K (63)
vf
Equation (60) involves two terms that must be interpreted as net diffusion
fluxes produced by the thermal and the shear-induced fluctuations. In equation
(63), DR~ is the familiar coefficient of Brownian diffusion for a single fine sphere
immersed into an unbounded fluid, whereas D,h ~ plays the role of a characteristic
scale for the coefficient of particle mutual diffusion caused by shear-induced
1276
2
o
2*
. . . . . _ . . . , ,
Curves 1 and 1" conform to using formula (38) when expressing the nonnal
stress in Brownian suspension flow. They essentially deviate from curves 2 and
2" that correspond to the usage in this context of the osmotic pressure function,
equation (29). Roughly speaking, curves 2 and 2* stem from the model
developed in [25], according to which the assemblage of suspended particles is
regarded as a pseudo-gas. In contrast to this, curves 1 and 1" arise out of our
modeling this assemblage like a system of molecules of a solute. The mere fact
that it is curve 1, but by no means curve 2, that satisfactorily agrees with
experimental data obtained for dilute suspensions serves as an implicit argument
in favor of our model.
As the suspension concentration increases beyond the range of moderately
concentrated suspensions, the mutual diffusion coefficient begins to decrease,
and it tends to zero as ~b~ ~ . This is undoubtedly due to an infinite increase in
viscosity in compliance with formula (57), and to the corresponding decrease of
particle mobility as suspension concentration grows.
Since a relative role played by direct particle contacts in momentum transfer
must grow with suspension concentration, one can justifiably expect that the
actual concentration dependence of the mutual Brownian diffusivity will
gradually undergo a smooth transition from curve 1 to curve 2* as concentration
increases.
It is worthwhile to mention in conclusion that a similar analysis can be
applied to calculation of the Brownian mutual diffusivity in colloids whose
particles exhibit molecular interactions of different origin [43], and also
electrostatic interaction [44]. The theoretical results derived in the papers cited
seem to be in a satisfactory agreement with experimental data. In principle, this
encouraging fact makes it possible to evaluate the particle diffusion flux, and
thereby to approach a difficult task of developing a rheological model for
colloids of interacting particles.
Figure 9 presents similar results for the dimensionless coefficient of mutual
diffusion of particles caused by shear-reduced fluctuations. This coefficient
appears to be rather negligible in dilute suspensions. However, it rapidly
increases with concentration, so that the particle migration generated by these
fluctuations becomes essential for highly concentrated suspensions.
In the case of shear-reduced diffusion, the distinction between the mutual
diffusivity and the self-diffusivity is even more drastic than that for Brownian
diffusion, since it touches upon the basic scaling of these coefficients. Indeed, in
conformity with equation (63), the coefficient of mutual shear-induced diffusion
scales with x 7' 2~vf , x being the density ratio. In contrast to this, the self-
diffusion coefficient is well known to scale with ?'a2 [33, 34].
1278
It has been noted already that there exist a number of attempts to model
particle distribution in shear-driven flows with the help of an equivalent diffusion
equation. Most commonly such attempts are based on an unwarrantable
assumption that the diffusion flux of suspended particles down a concentration
gradient is governed by the self-diffusion. Such an assumption is evidently
wrong, and without doubt, it is the mutual diffusion coefficient that must be used
in the indicated context. Moreover, in view of a so substantial difference
between these coefficients, conclusion drawn from models employing the self-
diffusion coefficient can be anticipated to be inadequate, both quantitatively and
qualitatively. A more detailed discussion of some shortcomings specific to such
models can be found in [38].
102 . . . . . '. . . . ,
2 ~t
ol
10-2
10-4 | I I i ,
we point out that various phenomenological approaches exist which are based on
such an analogy and which are primarily aimed at incorporating the effects of the
pseudoturbulent fluctuations on mean suspension and fluidized bed flow. Such
approaches are exemplified in a number of works, and in particular, in [47]. A
more sophisticated analytical kinetic theory approach is discussed in [48].
Another limiting case pertains to quiescent suspensions of fine particles which
exchange momentum and energy exclusively through random fields of ambient
fluid velocity and pressure, and collisions do not play a noticeable role in this
exchange. It is only this case that we are going to address below. A significant
feature of the pseudoturbulent motion generated in finely dispersed suspensions
consists in the fact that suspended particles are by no means statistically
independent. Long-ranged hydrodynamic interactions of the particles result in the
formation of group containing many particles that fluctuate in a correlated
manner. Such groups keep to incessantly originating and then disintegrating, so
that the fluctuating motion can be phenomenologically viewed as an ever altering
collection of intermittent flow patterns which are reminiscent of fluid moles in
one-phase turbulent flow.
In order to find out relevant statistic properties of the particulate groups, it is
necessary to develop an efficient model of multiparticle hydrodynamic
interactions. A generally accepted analytical approach to modeling flow of
quiescent suspensions consists in summing up all such interactions involving
different numbers of particles. In practice, such a summation has been effected
only for pairwise interactions, with the help of a nice renormalization procedure
as first invented by Batchelor to circumvent singularities and to get convergent
results for macroscopically homogeneous dilute suspensions (see, for example,
[8]). Unfortunately, some theoretical conclusions that have been obtained to
date while treating fluctuations by means of different versions of this
renormalization procedure seem to be unacceptable from the physical point of
view. Thus, analytical studies and numerical simulations of a sedimenting
suspension have shown that the variances for particle fluctuation velocity and
coefficients of particle pseudoturbulent self-diffusion in different directions
increase unboundedly with the size of the vessel that contains the suspension, if
the spatial distribution of particles is supposed to be random [49-51]. The last
inference is not supported by experimental data which prove the quantities
mentioned to be insensitive to the container size if it exceeds a certain critical
size [52,53]. These experiments found no systematic variation in the particle
velocity fluctuations with container size at all.
A possible explanation of this controversy might be founded on a stmmse that
a short-range order establishes itself in a sedimenting suspension, so that a non-
random suspension microstructure sets in. In particular, Koch and Shaqfeh [54]
1281
a a 3 1
Lg = c L -~ , Vg = cV ~-~ , Ng = c N 02 (65)
1282
Fr = - o t m p w ' , a = c a ppa2
luf CM(qk) (67)
dilute limit. It is evident that, as far as the divergence of the said quantities is
concerned, the dilute limit plays the same role at a given container size as an
infinite increase of the container size does at suspension concentration kept
constant.
where the convective coordinate system connected with the dispersed phase
motion is used again. To simplify the matter, we have ignored time and space
1284
dependence of the mean flow variables when formulating these equations. Thus,
strictly speaking, equation (70) has formally a bearing upon fluctuations
occurring in a macroscopically uniform steady suspension flow.
The fluctuations of mean flow variables that appear in equation (70) are also
sums of corresponding independent random contributions associated with
different particulate groups. In accordance with the central limit theorem of the
theory of probability, their variances equal the corresponding variances for one
group divided by the group number concentration that may be presumed large as
compared to unity. Thus, equations (69) and (70) can be thought of as the ones
related to the fluctuations of a single group.
Since stochastic equations (69) and (70) are linear in fluctuations, it is natural
to employ the correlation theory of stationary random processes, an informative
review of which is given in [57]. According to this theory, all fluctuations are
represented as Fourier-Stieltjes integrals over frequency co and throughout the
entire wave-number space k. Using these representation reduces differential
equations (69) and (70) to a set of linear algebraic equations in which the role of
tmknown quantities is played by random measures that are involved in the
Fourier-Stieltjes integrals. These last equations enable us to express all the
random measures as quantities proportional to the random measure for random
concentrational fluctuations, d Z~. Correspondingly, all spectral densities of
interest turn out to be proportional to the spectral density of the concentrational
fluctuations, q-'r (co,k), with proportionality coefficients being functions of co
and k. Using tile correlation theory of stationary random processes allows
various two-time two-point correlation functions to be found by standard means
characteristic of this theory [57].
An expression for the fluctuation force is to be determined from equations (8)
- (13). For the sake of simplicity, we take into account only the contributions to
the interphase interaction force that are due to viscous drag and to gravity
corrected for buoyancy. After a simple manipulation, we then arrive at the
following formula:
1 dM _ ~x - 1 g~, ] r = - ~2 a 2
nF'=qkPp[~r(v'-w')+~~ (71)
tcr dqk u~' x ' 9 vf
Using equations (71) and (72) in the algebraic equations for random measures
that obtain when the aforementioned Fourier-Stieltjes integrals are inserted into
1285
equations (69) and (70), and then solving these algebraic equation, result in final
formulae for the random measures of the pseudoturbulent fluctuations. In
particular, it is not difficult to derive general expressions for the random
measures of random fluid and particle velocity fluctuations v' and w'
o+u.kk
dZv = ck k S- dZ~
H
(73)
_ E { c, o + u . k _k r [s_(S'k)k] }
dZw ico+a+E ,~k k
where scalar and vector functions involved are introduced in accordance with the
following equations:
(io+a)E
e - terM , H = i (1- qkl Pf ( ~ + u "k ) + ttf M k Z + ~kPP i o + a + E
(74)
S= ico+a B+C, B=~u+c.dlnM C=(tc-1)r
ico + a + E dO ~bM
Equation (73) gives an opporttmity to derive equations for the spectral density
tensors of fluid and particle velocity fluctuations which express them as
quantities proportional to the scalar spectral density of concentrational
fluctuations. In order to be able to calculate the variances of particle velocity
components by integrating corresponding components of the spectral density
tensor over co and k, a trustworthy representation for the spectral density of
concentrational fluctuations is necessary. The wanted representation was
discussed at length in [56] where both particle velocity variances and self-
diffusivities were studied.
In what follows, we are interested in the determination of particle velocity
variances, but not of coefficients of particle pseudoturbulent self-diffusion. In
this ease, a detailed discussion of the eoneentrational fluctuation spectral density
proves to be excessive. As will become clear later on, only the variance of
coneentrational fluctuations is actually needed to get reasonable estimates for the
particle velocity variance under certain simplified conditions. The wanted
expression for this variance follows from [58] where the classical
Smoluehowski's combinatorial theory of fluctuations in dilute particulate systems
has been generalized to concentrated systems. This expression reads
1286
(75)
equation (65) having been taken into account when obtaining the second
equality.
At last, let us indicate sufficient conditions which must be fulfilled to allow us
to make use of a simple equation (75), instead of a much more complicated
representation for the concentrational fluctuation spectral density. As has been
discussed in [56], for this purpose in view we have to 1) replace fluid and
particle velocity spectral densities by their values at small frequencies, 2) assume
the integral of the concentrational fluctuation spectral density over frequency to
be dependent on modulus k of wave-number vector k, but not on this vector
direction (that is, not on angular coordinates of a spherical coordinate system in
the wave-number space), and 3) ignore viscosity effects.
The terms that involve frequency may be dropped out of equations (73) and
(74) if pseudoturbulent motion is quasi-stationary in a certain sense. This
condition of psedoturbulent fluctuations being quasi-stationary amounts in fact to
an assumption requiring a characteristic fluctuation frequency scale to be much
smaller than friction force coefficient a determined in equation (67). The
characteristic frequency scale for fluctuations must be of the order of vrMLg-2 ~
vf M~ 2/a2, whereas coefficient a ~ vf M ~ 2/1r 2. Thus, the condition trader
discussion must hold good for suspensions of sufficiently low concentrations, all
the more so, the larger the density ratio. In the generalized case, however, both
frequency scale and friction force coefficient are of the same order of magnitude,
and the said condition presents an approximation the adequacy of which has to
be specially checked.
The second condition requiting the integral of the concentrational fluctuation
spectral density over frequency to be independent of the wave-number vector
direction states that the concentrational fluctuations are nearly isotropic. This
represents a reasonable approximation that has its direct analogies in the theory
of fluctuations in molecular systems. At last, ignoring viscosity effects amounts
to the neglect in the expression for H in equation (74) of the term containing
fluid viscosity gf. This term can readily be shown to effect only quite a
negligible influence on the particle velocity variances.
For simplicity and definiteness, we shall consider the velocity variances only
in a vertical suspension flow (or in a fluidized bed). Vectors S, B and C
defined by equation (74) are collinear in such a flow, and it is easy to understand
that 1) only diagonal components of the fluid and particle velocity variance
tensors differ from zero, and 2) these tensors are axially symmetric with respect
1287
to the vertical axis. Thus, only diagonal components of the corresponding
spectral density tensors are actually necessary to evaluate the vertical and
horizontal velocity variances. Expressions for these diagonal components follow
from equation (73). Under the conditions enumerated above, these expressions
look as follows:
tlJvl'vl((~
{ (-~14(1-~u ) 2k?
2) $2
(76)
q2 qbC + sB - ~bC + s B + i -u~b qJ~,~(co.k)
~w2,w2(co,k)~ f1202(k~+q2
1 )
{(/2
s2 1_uo kl2
(77)
q2 r B+ k2 )
where
a
fl=~=cflqk, 2
cfl=-~Ca, s = ~ fl~
, q = - qbpp
- fl E (78)
l+fl o~pf l+fl u
Equations (76) and (77) are formulated in a coordinate system which first
coordinate axis is directed along u, its two other orthogonal axes being
arbitrarily chosen in a plane normal to u. Expressions for the spectral density
tensor components that correspond to the third coordinate axis are to be obtained
1288
from those corresponding to the second coordinate axis, if the third wave-number
vector component, k3, is substituted for the second one, k2.
,- dlnM 0 u, , c= u, (80)
1-# #(1-#)
tr - 1 (1 - r ga 3 (81)
~Fr<<l, Fr- 2
lo r vf
When formulating this inequality, the formula for relative suspension viscosity
from equation (4) and equations (78), (79) have been used. Condition (81) is
always satisfied if suspended particles are fine enough, so that their Froude
number, Fr, is small. However, inequality (81) becomes invalid, and it ultimately
transforms into an inverse strong inequality, in the dilute limit, as # approaches
zero.
If inequality (81) holds true, the terms proportional to k~2 in the denominator
and numerator of equations (76) and (77) can be ignored compared to the terms
that are proportional to q2. This simplifies the spectral density expressions
identified in equations (76) and (77) to quite a considerable extent, so that these
expressions can easily be integrated over the wave-number space. In particular,
by making use also of equation (80), we obtain from equation (77) the following
simple approximate formulae for the diagonal components of the particle velocity
variance tensor in a uniform vertical flow [56]:
1289
'
( / u_, ) 2
qJ~,~(co,k)
Wwl,wl(CO,k) ~ ]320 2 1- y ~-~-j 1 r
(82)
ca~ 2
%2,wz(co,k) ~r162 ~2 ) i - r %,q~(co,k), y = ~
l+c,ar
1/2
vt ~Cw 1 - 3 + 5 (1-~) s/2 1- ~
(83)
1
vt ~ Cw ~ 1- cw = cp r~-~
According to this equation, the ratio between lateral and longitudinal RMS
particle fluctuation velocities is equal to
iw+w211'2 iw ll,2 (
(wf21"2 _ (wf2) 1/2 -_ 15-107'+3y
2y2 2
11,2 (84)
In conformity with the formulae in equation (83), both longitudinal and lateral
RMS velocity components tend to finite limits as ~b comes to zero. Thus, the
pseudoturbulent particle velocity variances do not diverge in the dilute limit.
However, the adequacy of these formulae is conditioned by inequality (81) being
valid, so that they cease to be true in the dilute limit. It can be shown that these
formulae give way in the dilute limit to other relations for the said RMS velocity
components [56]. The last relations prove both lateral and longitudinal RMS
1290
0.6
0.5 9
Cq
0.4 I
~. o.3
0.2
0.1
0 . . . . . . . . . . . . . . . . . . . . . .
0 0.1 0.2 0.3 0.4 0.5
Figure 10. The longitudinal (vertical) particle velocity fluctuation scaled with
particle terminal velocity according to equation (80) at ~ = 0.6 and cp = 0.6;
the upper and lower curves correspond to c:v~/2 = 1.2 and 1.4, respectively; dots,
experiment in [53].
ambient fluid as well. For this reason, equation (42), that has relevance to
fluctuations of individual statistically independent particles which do not collide
but interact only with the fluctuating ambient fluid, certainly cannot be applied to
the description of stresses that originate due to pseudoturbulent fluctuations.
Thus, an alternative way to describe these stresses has to be put forward.
!.8
I hl.6
1.4
1.2
a -p< - s, = (85)
1292
that are supposed to act in flow of both continuous and dispersed phases due to
their pseudoturbulent fluctuations. The averages that appear in equation (85) can
be calculated from the model of pseudoturbulence as developed earlier in this
section. In particular, while dealing with equations (76) and (77), we can use
precisely the same assumptions that have led to formulae (83). In this case, we
shall obtain, atter a manipulation, expressions for normal pseudoturbulent
stresses that act in a nonuniform vertical suspension flow. We have for the
continuos phase
+ --+ pp (87)
15 cfl 2 c N (1 - ~b)2 U,
W l ( 0 ) = 8 - 4 s + 3 s 2, Wl(1)=2s(-2+3s)(h+l), Wl(2)=3s2(h+l) 2
V/(0) = (1 + s) 2 , V(1) = 2s(1 + s)(h + 1), V(2) = s 2 (h + 1)2 (88)
7. CONCLUSIONS
The two central notions advanced in the present Chapter are actually rather
trivial. The first notion represents a recognition of the simple fact that even
simplest suspension flows are subject to the stratification caused by forces
exerted on suspended particles in the direction normal to the dispersed phase
streamlines. If those forces are not opposed by dispersed phase stresses, this
stratification ultimately leads to the separation of the whole flow domain into
regions containing close-packed particles or altogether devoid of particles.
Consequently, steady suspension flows cannot be adequately and effectively
described with the help of existing conventional fluid dynamic models, if these
models do not allow for concentration-dependent stresses that are specific to the
dispersed phase and that condition this phase stratification.
The second notion intimates that the particulate stresses, which are capable of
hampering the flow stratification in unsteady flows and of bringing it to an end in
steady flows, are due to random fluctuations of the suspended particles. The
action of the particulate stresses results in the establishment of non-trivial
particle distributions that play a paramount role in evolving the fields of all the
flow mean variables and in making up the flow hydraulic characteristics.
1294
Apart from turbulent fluctuations of suspended particles which have not been
considered in this Chapter at all, fluctuations of three distinct types that owe their
origin to different physical mechanisms have been distinguished. These are the
thermal particle fluctuations, and also two types of hydrodynamically-induced
fluctuations: the shear-reduced and pseudoturbulent ones. The fluctuations of all
the types stimulate particle migration which in arm produces a net diffusion flux
down a particle concentration gradient. This flux partially compensate for the
convective flux of the particles caused by the forces directed normally to the
dispersed phase flow streamlines. As a result of the combined effect of these
fluxes, a particle distribution originates that, in steady flows, correspond to
dynamic equilibrium attained between convection and diffusion of particles.
When dealing with a suspension flow, simultaneous allowance for the
relevant fluctuations belonging to different types seems imperative. First, the
coupling of different fluctuations results in the occurrence of non-monotonous
dependencies of meaningful flow characteristics on parameters, such as the
particle size, which can significantly influence various technological processes.
This effect of the coupling is exemplified by a uniform shear layer flow that
has been considered at some length in [38]. A convenient measure of the ability
of uniform horizontal steady shear flow of a given shear rate to suspend particles
is the total mass (or volume) of suspended particles per unit area of the flow
bottom plate. This total mass has been proven to be a non-monotonous function
of particle size that has a minimum at a certain size value, all other physical
parameters being presumed fixed. For smaller particles, the flow suspending
ability increases owing to the corresponding enhancement of thermal
fluctuations. For larger particles, this ability also increases, but due to the
augmentation of shear-induced fluctuations. This conclusion has an immediate
bearing on manifold field-flow fractionation processes in practice.
A similar non-monotonous dependence on particle size can be proven to be
specific to fluidized beds and quiescent sedimenting suspensions of fine
particles. The total mass of particles that form an upper part of a fluidized bed
and that is situated above the approximately uniform bulk region of the bed has a
minimum for particles of a certain radius. This minimum has precisely the same
physical origin as that for the total mass of particles suspended by a uniform
shear flow, except for the fact that the role of shear-induced fluctuations is now
played by pseudoturbulent fluctuations.
Secondly, failure to simultaneously account for fluctuations of different origin
can lead to unwarrantable conclusions that may be erroneous not only
quantitatively, but also qualitatively. A convincing example is provided by a
pressure-driven one-dimensional steady suspension flow in a channel. Even if the
suspension is non-Brownian, neutrally buoyant and finely dispersed, allowance
1295
for the stresses due to both shear-induced and thermal fluctuations is vitally
important. If only shear-induced fluctuations were allowed for, we would come
with a conclusion that a close-packed core region always obtains in the flow, no
matter how low is the particle concentration averaged over the flow cross-section
[36,38]. Indeed, in such a case, the lateral particulate stress disappears at the
channel central axis (or plane) where the mean shear rate turns to zero. Hence it
follows that this lateral stress cannot be maintained uniform over the cross-
section, if the suspension concentration at the central axis (plane) is less than its
value associated with the close-packed state.
In the opposite case where only pseudoturbulem fluctuations were taken into
account, we would conclude, also erroneously, that the particles are uniformly
distributed in each cross-section. It is clearly the conditions of suspension
concentration and fluid slip velocity being invariable throughout any cross-
section that provides for the required tmifonmty of the lateral pseudoturbulent
stress. If the concentration does not vary in a cross-section, the fluid slip velocity
is also uniform. (Indeed, relative fluid flow is caused by the very same
longitudinal pressure gradient that produces the flow. This pressure gradient is
well-known to be uniform in a steady one-dimensional channel flow. Thus, given
that the pressure gradient is fixed, the distribution of fluid slip velocity over flow
cross-sections actually a function of suspension concentration alone.)
Simultaneous allowance for fluctuations of different types becomes even
more as far as general three-dimensional unsteady flows are concerned. In
particular, this is due to the fact that the corresponding particulate stresses
influence not only particle distributions as attained in various steady flows, but
also the rate with which these stationary distributions, and also the steady flows,
establish themselves. Besides, these stresses sometimes play a fundamental role
in making for hydrodynamic stability of steady flows [46, 48, 58].
It is expedient to emphasize in conclusion that much remains to be done in
order to develop a completely reliable, comprehensive and workable theory to
treat fine suspension flows. The point is that the tentative model as developed
and presented in this Chapter is not free of numerous semi-empirical assumptions
the validity of which must be examined in detail. To provide for such an
examination, tangible subsidiary models must be further elaborated and made
more precise for fluctuations of different origin, and also for stresses induced by
these fluctuations. Unavoidably, this task requires very serious efforts to be
applied in a specific research area bordering on mechanics of multiphase flow,
rheology and statistical physics. However, such efforts seem to be fairly justified
and worth being undertaken in view of important practical issues that are likely
to come about in connection with munerous branches of technology.
1296
REFERENCES
1. I N T R O D U C T I O N
1.1 Scope
In this chapter, we review the rheological behavior of multiphase systems
(suspensions in Newtonian fluids and polymers filled with or non interactive
particles). First, we present some basic definitions and concepts useful for the
understanding of the rheological properties of concentrated suspensions. Then, we
summarize problems encountered in rheometry, and review the main rheological
models proposed in the literature to describe the properties of concentrated
suspensions. Finally, we focus on non linear effects observed for concentrated
suspensions in small strain experiments using data of our laboratory, and conclude
with challenges and trends for future research.
and particle-particle interactions play a major role. The internal forces can be
subdivided in hydrodynamic and non hydrodynamic forces. The hydrodynamic
forces result from the relative motion of the suspending medium with respect to the
particles. These are the only forces considered in the Einstein [2] analysis of the
viscosity of a dilute suspension of rigid spheres in a Newtonian fluid, which led to
the well known result:
here fir, rl~ and I"1oare the reduced viscosity, the suspension and the fluid viscosity
respectively. The hydrodynamic forces are responsible for migration of particles,
alignment or orientation in the case of non spherical particles and finally structure
break-down in the cases of flocs and aggregates.
The non hydrodynamic internal forces consist namely of the Brownian forces,
responsible for the internal motion of the particles and diffusion, and forces arising
from physical and chemical interactions. These forces can affect the internal
structure of suspensions of colloidal particles, for concentrations well below that
of the maximum packing. Brownian motion allows low range attractive forces to
promote floc building, network and weak gel formation. Such attractive forces are
characterized by the Hamaker constant defined by the Israelachvili equation as
reported by Tsai and Ghazimorad [3]:
A 3 (c, c3/
- + +
3hVe , 2 23 (1.2)
via the Krieger-Dougherty model to be 0.72 and 0.96 using the values for the zero
shear viscosity, rio, and the high shear rate limiting viscosity, rl=, respectively. The
corresponding values for a suspension of spheres with a ratio 60 were 0.49 and
0.62.
External forces may affect the behavior of suspensions. Buoyancy effects
become important when the particle and the fluid densities are significantly
different. These effects are responsible for sedimentation or flotation, affecting the
stability of the suspensions and resulting in concentration profiles. As illustrated
in the next section, apparent thixotropy can be related to sedimentation. Other
external forces such as that due to an electric field can drastically modify the
rheological properties of suspensions. Table 1.1 summarizes the main forces acting
on colloidal particles and key expressions for calculating their order of magnitude
are presented.
Table 1.1 Forces acting on colloidal suspensions (Adapted from Russel et al.[ 10])
kT k: Boltzmann constant
Brownian dP T: temperature [K]
dp: particle diameter
with respect to the characteristic dimension of the measuring element (in cone-and-
plate geometry, gaps of less than 1O0 gm are common)"
dp
<< 1 (2.1)
h
where dpis a characteristic dimension of the particles and h is the gap of the
measuring device. Obviously it is not always possible to respect this criterion and
systematic experimental errors could result.
Inertial and gravitational effects must be negligible. The criteria for both effects
to be negligible can be written as"
4vp
<< 1 (2.2)
and:
The first criterion (Equation 2.2) just expresses that the Reynolds number based on
the particle and the average velocity of the fluid, V, has to be very small (creeping
flow regime). The second one relates the experimental time, t~ to a characteristic
time of gravitational or buoyancy effects. With large size particles, other effects are
to be expected such as due to a depletion layer at the wall and/or orientation along
the wall surface in the case of non spherical particles resulting in lubrication effects
or apparent slip.
complex viscosity curve and its value are drastically changed following the second
step mixing. The power-law behavior with a slope close to - 1 for this 31 vol %
suspension after mixing using the Brabender,is indicative of strong interactions
10 7
..x- 10 4
10 3
lO-a 10 -2 10 -1 10 ~ 101 10 2 10 3
o [s-q
100 9 9 9 . . . . . i 9 9 9 9 ..=.| 9 9 . 9 . . . . b
10-1
10-2
lO-I 10 ~ 101 10 2 10 3
[s-]l
between aggregates of rutile particles. The second mixing step broke down a large
portion of the aggregates and the behavior approaches that of a suspension made
of non imeractive particles. The complex viscosity remains, however, considerably
larger than predicted by a Maron-Pierce equation (Equation 3.1 with p = 2 and
assuming ~m = 0.68).
Another drastic effect of dispersion is illustrated in Figure 2.2 for a low
concentration suspension of fumed silica particles in water. These silica particles
have silanol groups at the surface which interact via water through hydrogen
bonding, forming very large aggregates and possibly a network. Following a
preparation via a manual mixing, the viscosity of an aqueous suspension containing
6 mass % of A200 (Degussa) particles (diameter of 12 nm) is shown in the figure
to be highly shear-thinning, typical of a gel-type structure which is broken down
under shear flow. However, the structure can be largely broken down prior the
rheological measurements using an ultrasonic vibrator. The values for the
suspension viscosity are drastically decreased and shear thinning is now very light.
103
13%
10
~_~ 10 2 7,~
2"~
~'1 0] 3-~
100 9 , I I
10 -3 10 -2 10 -! 10 0 10 l 10 2
[S "1]
Figure 2.4 reports simple shear viscosity data for suspensions of glass beads
(average diameter of 49 ~tm) in a 1 mass % aqueous solution of gellan (a
polysaccharide of molecular a weight of approximately 10~ kg/kmol). The unfilled
gellan solution is shown to behave as an homogeneous polymer solution,
describing a Newtonian plateau at low shear rate followed by a typical power-law
behavior. Adding 4.76 % per volume of glass beads did not change much the
rheological properties. The viscosity in the plateau region for the 4.76 %
suspension is, however, slightly lower than that of the suspending solution. Adding
more glass beads resulted finally in a large increase of the viscosity in the plateau
region, but strangely enough the viscosity is shown to be unaffected by the solids
content in the power-law region. To discriminate between the effects of polymer
adsorption at the glass bead surface (believed to be negligible here) and effects of
ionic content, we did measure the pH of the solution. It was found to increase from
6.79 for the unfilled solution to 11.53 for the 37.5 % suspension. Obviously, the
chemicals used for the surface treatment of the glass beads interact strongly and
change the polymer conformation in solution. Similar effects have been reported
previously by Carreau [22]. Figure 2.5 shows that the viscosity of the unfilled
aqueous solution of gellan is considerably reduced by increasing the pH of the
solution from 6.8 to 11.4.
1309
100
101
O001~ 9
. . . . . . . . I . . . . . . . . I . . . . . . . . I
mmlmmmmmm m 9
[] 9
r 10 0
9 9
9 pH = 6 . 8
9 pH =11.4 9 mo
9 9
lO-1
9 ..mm!
. . . . . . . . I . . . . . . . . I I I ...... I . . . . . . . . I
10 -2 1O 1 10 ~ 101 10 2 10 3
~/ [S -1]
Figure 2.5 Simple shear viscosity of unfilled aqueous 1 mass % gellan solutions
for pH values of 6.79 and 11.4 (Unpublished data).
diameters ranged from 125 to 150 ~tm and the density differences between that of
the particles and fluid were 0.03 and 0.04 g/mL. The second one consisted of
acrylic particles (diameter between 75 and 106 pm) in a Dow Coming fluid with
a density difference of 0.07 g/mL. A double gap Couette geometry was used for
measuring the viscosity. In the figure, the reduced viscosity as a function of a
reduced shear rate in steady-state conditions is reported for four different solids
volume fractions. The reduced shear rate is based on the fluid viscosity and gives
an order of magnitude of the ratio of viscous to buoyancy forces; ho is the height
of fluid in the Couette geometry. The apparent shear-thinning effects observed in
Figure 2.6 have nothing to do with shear-thinning properties of the suspensions.
Initially due to the small differences in density, sedimentation proceeds leading to
higher stresses in the lower part of the Couette geometry. But at higher stresses
particles are re-suspended by shear-induced diffusion and the particle concentration
reaches an equilibrium profile, which is a function of the applied shear rate. The
solid lines in the figure are the predictions of the model developed by Acrivos et
a1.[23] to account for sedimentation and shear-induced effects.
102
a, r 050
~- 101 0.40
0.30
10~ [_.,.,.,
10 -3 10 -2 10 -1 100 101 102
9rl~'
2h0gAp
Figure 2.6 Apparent reduced shear viscosity for suspensions of non colloidal
particles in Newtonian fluids, due to density differences between the
particles and the suspending fluid. The open symbols are for the first
suspensions; the close symbols are for the second type of suspensions
(Adapted from Acrivos et al. [23]).
1311
These simple results stress how careful one has to be in interpreting unusual
phenomena. Many other difficulties may be encountered, especially when using
polymer matrices. Other major problems are related to polymer degradation when
experimenting with polymer melts at high temperature. In the case of polymer
solutions, solvent evaporation could be a major nuisance as indicated by Acrivos
et a1.[23] when long experimental times are required to reach, for example, steady
conditions. For highly filled systems, it may just be impossible to make reasonable
measurements especially at high shear rates due to wall effects, fracture in the
suspensions, and other complications.
3. M O D E L I N G
(l m) -p
(3.1)
1312
where p = (l)m[]]], (])m is the maximum packing fraction and [11] the imrinsic
viscosity. The Krieger-Dougherty relation reduces to the Maron and Pierce [27]
expression for p = 2, which corresponds to the theoretical case of spherical particles
with [11] equal to 5/2 and ~ = 0.80. However, (I)m is usually kept as a fitting
parameter.
The viscosity models for concentrated suspensions are usually expressed as a
function of the maximum packing fraction ~ , which is a function of shape and size
distribution of the particles. The values reported in the literature range from 0.18
for carbon fibers with shape factor L/dp = 27 to 0.71 for uniform hard spheres.
Chang and Powell [28] have investigated the effect of size distribution using
particles of two well-defined sizes. The results were reported in terms of two
parameters K, the diameter ratio of the small particles, and r the volumetric
proportion of small particles. Their results and those of Storms et al. [29], Poslinski
et al. [ 14] and Shapiro et al. [30] show that for a fixed volume fraction, the relative
viscosity decreases as K decreases and a minimum in viscosity is observed around
= 0.25. The viscosity reduction could be quite spectacular as shown by Poslinski
et al. [14].
103[ .... I
102 ~t_,, 0
10 1
10~ I I I I I i
0.1 0.2 0.3 0.4 0.5 0.6
Figure 3.1 Relative viscosity versus dispersed phase volume fraction for latex
and silica suspensions (combined data of Krieger (1972) and de Kruif
et al. [31]). The solid lines are the best fits using the Krieger-
Dougherty equation (3.1) (Adapted from Barnes et al. [33]).
1313
The value of the maximum packing fraction also depends on the arrangement
of particles. The maximum packing value for monodisperse particles ranges from
0.52 for cubic arrangement to 0.74 for a hexagonal close packed one. The
maximum packing organization varies with flow: de Kruif et al. [31 ] and Krieger
[32] have shown that the maximum packing fraction and the intrinsic viscosity [1]]
vary with shear rate. Figure 3.1 reports the reduced viscosity as a function of the
volume fraction for the combined experimental data of de Kruif et al. [31 ] for silica
suspensions and of Krieger [32] for latex suspensions. The best fit of the Krieger-
Dougherty equation allows to obtain at high shear rates ~m== 0.71 and [rl]= = 2.71
and at low shear rates d~mo = 0.63 and [1]]o = 3.13.
Since only the hydrodynamic and the Brownian forces govern the behavior of
suspensions of colloidal hard spheres, the rheological properties can be scaled as
a function of the radius of the particles, a, the Boltzmann constant, k, and the
temperature T. Krieger [32] proposed a semi-empirical relation based on the Cross-
Williamson [34] model to describe the shear dependence for the viscosity of
concentrated suspensions viscosity. The viscosity is defined by the following
relation:
rl -rl~ 1
(3.2)
11o-r1= 1 +o/o c
26
O BZOH
22- -"~ 9 m-CRESOL "
~"18
14
10 ' , ,
]0-2 ]0-I ]0 0 ]01
O"r
Figure 3.2 Reduced viscosity versus reduced shear stress for 50 vol %
monodispersions of polystyrene latex particles in three different
media (Adapted from Krieger [32]).
1314
This equation describes shear-thinning effects from a zero shear rio to a high shear
limit rl=; Oc is a critical reduced stress for which the reduced viscosity,
(rl - rl=)/(rlo- rl=) - 1/2; %(- oa3/kT) is a reduced shear stress. Figure 3.2 reports the
reduced viscosity as a function of the reduced stress for suspensions containing
particles of two different diameters dispersed in two different media. A unique
curve is obtained, independent of particle sizes and of nature of the suspending
medium.
I I I I
101
rim -~--O
O
l0 0 .
10 -l o / a3G '
kT
[] []
10 -2
10 -3 m
10 "4 I I I
10-1 10 0 101 10 2 10 3
a20~
Do
Figure 3.3 Dimensionless elastic modulus and reduced dynamic viscosity versus
dimensionless frequency for a 46 vol % suspension of silica spheres
in cyclohexane- ffl a = 28 2 nm; (3 a - 76 + 2 nm. The solid lines
are the predictions using the Jeffreys model (Adapted from Mellema
et al. [35]).
off the charges on the particle surface. When electrostatic repulsion is dominant,
an agglomeration of particles is induced. At low shear rates, the viscous forces are
not sufficiently large to break down the structure, responsible for the rapidly
increasing viscosity with decreasing shear rate and for the existence of a yield
stress. At high shear rates, the flow is controlled by the hydrodynamic forces and
the shear viscosity becomes approximately independent of the electrolyte
concentration.
10 6
O
1.9xl04 M HCI ~ O deionized
ut.I O ~ . - -
10 4 D ~o
s..
9 1.9x10"3M HCI O
10 2 9.4xl(I2M HCI 9
A~ m
%Oo
. $ gA~llLemm~
1.9xl0"2M HC! ' ~
I
10 ~
10 .2 10 o 10 2
O'r
Figure 3.4 Reduced viscosity versus reduced shear rate for 40 vol % suspensions
of PVC latex particles in water containing HC1 at various molar
concentrations (Adapted from Krieger and Eguiluz [6]).
0o 1] 0
rl - IYI + (1 +(t,~/)2) (1-")/2 (3.4)
where the zero shear viscosity and the characteristic time are described by Maron-
Pierce expressions"
- - (3.5)
and
-2
(3.6)
rim and tlm are respectively the viscosity and the characteristic time of the polymeric
matrix. Poslinski et al. [ 14] obtained good agreement between the proposed model
and the experimental data for glass spheres suspended in thermoplastic matrix, as
shown in Figure 3.5. In this case, the glass spheres are not sufficiently interactive
compared to the viscous forces and no apparent yield stress is observed. The
rheological behavior of the suspensions is very similar to that of the unfilled
polymer. The zero shear viscosity increases and shear thinning occurs at smaller
shear rates as the glass spheres volume fraction increases.
5
lO
9 0%
104 O13%
m26%
r~
t~35%
10 3 A46 %
~x60 %
~" 102
101
10~
10-2 10-1 10o 101 102 10 3 10 4
"~ [S "l ]
Figure 3.5 Shear viscosity of glass spheres at various volume fractions, dispersed
in a thermoplastic polymer at 150~ (Adapted from Poslinski et al.
[14]).
1318
Doraiswamy et al. [17] proposed an extension of the Cox-Merz rule for
concentrated suspensions in polymer exhibiting a yield stress. They have shown
that the steady shear viscosity and the complex dynamic viscosity of a concentrated
suspension of silicon particles in polyethylene can be superimposed if the complex
viscosity is reported as a function of the strain rate amplitude coy~ for oscillatory
shear data obtained in the non linear domain.
- a(1-~)b-c~'~a (3.7)
at
l"lr (1
- - (D /-2 (3.8)
~)m(~)
where the maximum packing factor is given by the following function of the
structural parameter:
~),,,(r _ 1
( 1/~mo - 1/~,,,~,)+ 1/~,,,oo (3.9)
1319
Here the maximum packing factor varies from (~moat low shear rates to (I)mooat high
shear rates. The structural function ~ is obtained by solving the following kinetic
equation:
(3.10)
0t ta td
where t~ and td are characteristic times associated with the aggregation and
desegregation process respectively. The ratio t~/td is assumed to be a function of
the shear rate as follows:
a
t _
(3.11)
ta
where p ( > 0) is an empirical parameter and tc is a characteristic time.The
following expression is obtained for the steady shear viscosity:
1 +(tc~)P ]
(3.12)
where 1]o and ~1=are the limiting viscosity at low and high shear rate respectively.
Good agreement was obtained between the proposed model and experimental data
for blood and latex and silica particle suspensions.
Quemada [43] also proposed the following Jeffreys-type model to describe the
non linear viscoelastic behavior of concentrated suspensions"
-C [~ l d( ~ - ~equiZ) ~ (3.14)
at
o - op + o m (3.16)
106
PS/CB
5
~10
20%
10%
104 ......
10 -2 10-1 10o
'y [S-1]
Figure 3.6 The predictions of the Leonov model for the steady shear viscosity
compared with the data of Tanaka and White [40] for polystyrene-
carbon black (dp ~ 0.045 pro) compounds at various volume fractions
(Adapted from Leonov [45]).
107
PS/CaC03 [
106 1
z~ <--0.07 p m
~ - 10 5 9 _ -~'a~~ -~-" <--0.5 p m
9 9 - " " ' ~ . - - - - . ~ <-- 3 lam'
104 I
10-2 10-1 10o
? [s-l]
Figure 3.7 The predictions of the Leonov model for the steady shear viscosity
compared with the data of Suetsugu and White [46] for polystyrene-
calcium carbonate compounds with various particle sizes at constant
solids volume fraction, ~ - 0.3 (Adapted from Leonov [45]).
1322
Coussot et al. [47] proposed a model similar to that of Leonov to describe the
rheological properties of a granular grease and a clay platelet suspension. The
viscoelastic contribution is given by a modified Maxwell equation:
1 0o 1
P + ~ O - - ? (3.17)
G O at q(~) p
where Go is a constant elastic modulus and rl(~) is a viscosity function for the
viscous contribution of the particles, which depends on the structural factor ~,
determined from the following kinetic equation:
with
n
T](~) - T}p (3.19)
(1 - ~ ) - ' - 1
6 (3.20)
+ -- I + ~r - q~.
6t G(~) n(~) n(~) ~ G(~)
with
where Tl= and G= are respectively the viscosity and the elastic modulus for the
1323
1 / (1-n)/2
= 1 (3.23)
I
where ~, the structural parameter is related to the number of interparticle bonds
and ranges from 0 and 1. It is obtained by solving the following kinetic equation:
with
= rio (3.25)
0 Go +G oo
k I and ke are kinetic constants for the thermal build-up of the suspension
microstructure and for shear induced break-down respectively, )~ois a characteristic
relaxation time and I/, is the second invariant of the rate-of-strain tensor.
Figures 3.8 and 3.9 compare the experimental data for the elastic and viscous
moduli versus strain amplitude obtained for suspensions of fumed silica particles
in paraffin oil and the values predicted by the Yziquel et al. [48] model. Two types
of particles were used: Aerosil A200 (Degussa) particles have a diameter of 12 nm
and are hydrophilic with surface silanol groups that can participate in hydrogen
bonding. Aerosil R974 (Degussa) particles have also a diameter of 12 nm but are
1324
102
10 .3 10 .2 1 o-1
~,o
Figure 3.8 Elastic and loss moduli as a function of stain amplitude for
suspensions of A200 fumed silica particles in paraffin oil at different
solids loadings. The solid lines are the Yziquel et al. model
predictions. (Adapted from Yziquel et al. [48]).
1325
105 . . . . . . . . . . . . . . . . . . . . . . .
?
G
104
??
G
103
. . . . | . . . . . . . . ! . . . . . . . .
10.3 10 -2 10-1
3,o
Figure 3.9 Elastic and loss moduli as a function of stain amplitude for
suspensions ofR974 fumed silica particles in paraffin oil at different
solids loadings. The solid lines are the Yziquel et al. model
predictions. (Adapted from Yziquel et al. [48]).
Table 3.1 M o d e l parameters used for describing the data o f Figures 3.8 and 3.9
Suspensions in Go + G= ~.o Y C
nJ(Go + G3 k, / kl n
naraffin oil . (kPa~ ....
, ,, ,
(s) . . . . (S)
7.0 % A 200 15.6 1.19 0.0320 0.0030 0.0085
the loss modulus with strain. For example, the Coussot model [47] can describe as
well the decrease of the elastic modulus with strain reported here, but the
predictions for the loss modulus are considerably higher than the experimental
values [48].
As mentioned by Leonov [45], the main advantage of these approaches is that
no yield criterion is necessary to describe the transition from solid-like to liquid-
like behavior as in the Oldroyd model, discussed in Section 1.
presented in the figure was obtained using a controlled stress rheometer in the
viscosity mode and steady or pseudo steady viscosity is reported as a function of
the measured shear rate. A pre-shearing at different stress levels, but above the
maximum stress obtained in the viscosity mode, was applied to the sample
sufficiently long to reach steady states and erase previous shearing effects. Then
the subsequent viscosity curve was obtained. We observe in Figure 3.10 that the
low shear rate viscosity, the onset and the importance of the shear thickening
decrease with pre-shearing effect. At low shear rates, the behavior is slightly shear-
thinning. Above a critical shear rate, the viscosity rapidly increases due to
formation of aggregates. Under higher and higher stresses, the hydrodynamic forces
break down the aggregates and the hydrodynamic radius reduces with the
increasing stress level. Therefore, the viscosity is found to be considerably reduced
and the onset of the shear thickening occurs at a larger shear rate. Finally, we
observe that above a critical shear rate, the viscosity begins to decrease. This
subsequent shear thinning is attributed to a further reduction of the aggregate sizes
at higher shear rates.
101
.! , , 9 9 aiiOOOPa
c~
.9 YYvV9 9
' Wv ~Vv v V V v V V V v v v v v v v v v v v v W W Vv
Figure 3.10 Pre-shearing effects on the steady shear viscosity for a 8 mass %
suspension of fumed silica (A300) particles in polypropylene glycol
(Unpublished data).
_ + -IX o l
rI rl~ (1 (bf~ - cfz) e ) (3.26)
tXo
with
where rio, kc, b, c are contants and f~ and fe are functions of the shear rate. For
(b fl - cf2 ) > 0, the model predicts thixotropy and for (b f / - c f2) < 0 rheopexy is
predicted. For steady state, the viscosity becomes"
n(?) - (3.28)
tz
o
4. L O W S T R A I N H A R D E N I N G PHENOMENON
80
90 il
9 9 --
[]
Einstein's equation
Maron-Pierce(O., = . )
9% PVC / PB 1
0681
70 A 18%PVC/PB "~
~ - 60 _ Q 28% PVC / PB --I
, 50 "9 9V 437 % P V C / P B ~o 1d
40
30 mmmmmmmmImm~m_m
m
~=47
20
~ ~_ V
_ _" _ ~ ...~]E _ l"Itl?_'~..ll'..~ llt .ay_,~. , _ ~ _ 3-7~176~
10
o ...... , . . . . . . . . , 9 . 7 . . . . . , , ...7...#
10 -2 10-t 10 o 101 10 2
'~[S "1]
Figure 4.1 Specific viscosity for five different volume fractions of PVC/PB
suspensions vs. shear rate. The horizontal solid line at the value of 2.5
represents the Einstein result. The horizontal dashed lines are the
results calculated via the Maron-Pierce equation using a maximum
packing factor of 0.68 (Adapted from Carreau et al. [20]).
35
30 O 0 . 1 5 6 s -1
25 121 1.56 s -!
A 15.6 s-I
~. 20
V 39.3 s "j
15
10
5
0
0 10 20 30 40 50 60
r
Figure 4.2 Relative viscosity of PVC/PB suspensions for four different shear
rates as a function of the volume fraction. The solid lines represent the
Maron-Pierce model predictions using a maximum packing fraction
of 0.575, 0.629, 0.705 and 0.756 for the lowest to the highest shear
rate (Adapted from Carreau et al. [20]).
1331
represent the Maron-Pierce model predictions using the maximum packing factor
as an adjustable parameter. For each shear rate, the optimal values of ~)m equal to
0.575, 0.629, 0.705, 0.756 for each shear rate respectively. Hence, the steady state
viscosity of this PVC/PB system can be simply modeled by this Newtonian
empirical model using an adjustable maximum packing fraction or effective volume
fractions.
0.1
"~n' ...... ' '
! 9%
"<) . . . .4.5%r
. PVC/PB
18% _
28%
.~, 37%
,~ ,=.. I " ~ ~ Ha 47% ,
10~ 101 10 2 10 3
[s-q
Figure 4.3 Characteristic elastic time (~. - Nl/rlm?2) as a function of shear rate
for PVC/PB suspensions at six different concentrations (From Carreau
et al. [20].
Although the Polybutene matrix was inelastic in the measured shear rate domain,
significant primary normal stress differences, N1, w e r e measured for the PVC/PB
suspensions and increased rapidly with solids concentration. The results are
reported in Figure 4.3 in terms of a characteristic elastic time, ~. = N~/1]m:~2 , a s a
function of shear rate. For concentrations lower than 0.28, the elastic time is not
significantly different from zero. On the other hand, for higher concentrations the
elastic time is large at low shear rates and increases with concentration. However,
drops rapidly with increasing shear rate, as observed before for the specific
viscosity. Because of the nature of these suspensions, the elastic properties have to
be related to particle-particle steric interactions; the particles are large and not
affected by the Brownian motion and the matrix is purely viscous. The 47 vol %
suspension depicts the larger elastic characteristic and the stronger shear-thinning
behavior. To prove that shear thinning of such concentrated suspensions of non
colloidal particles is not due to hydrodynamic effects, we present in the next three
figures oscillatory data for the 47 vol % suspension. All experimems ,sere carried
out using a controlled stress rheometer (CSM of Bohlin) equipped with a 25 mm
1332
10 3 = 28
S-I.,
02
ro
~,.~" 10 l
10 ~ - -~
10 .4 10 .3 10 .2 10 1 10 ~ 101 102
yo
Figure 4.4 Elastic and loss moduli at 0.628 rad/s vs. strain amplitude for a 47 vol
% PVC/PB suspension (From Carreau et al. [20]).
Figures 4.5 and 4.6 report the elastic and loss moduli as functions of the strain
amplitude at ~ = 0.628 s~. The results of Figure 4.5 were obtained for 47 vol %
dispersion of coarse polypropylene (PP) particles in the same polybutene. The
average diameter of these PP particles was 300 lam and were spherical. To respect
criterion 2.1, a gap of 3.0 mm was used. The particles and the fluid had almost the
same density and measurement was not affected by settling, at least in the time
frame of the experiments. Obviously, particles of this size are not affected by any
type of colloidal forces. In this figure, a viscoelastic linear domain is observed until
the strain amplitude reaches 10%, then a large and rapid increase of G "is observed,
from a value of 13 to 160 Pa. Also G "is seen to start to increase at a larger strain
1333
103 a a I a 9 ! a l a i e 9 I i |
,,,
ff
102
101 . i I I I I I I I I I i i i
10 "1 ?o 10 ~
Figure 4.5 Elastic and loss moduli at 0.628 rad/s vs. strain amplitude for a 47 vol
% PP/PB suspension (Unpublished data [57]).
10 2 .
.
. .
.
.
.
.
. . . . .a .
G"
lO1
10 o
10-1 100
O
Figure 4.6 Elastic and loss moduli at 0.628 rad/s vs. strain amplitude for a 24 vol
% GB/PB suspension (Unpublished data [57]).
amplitude (~ 0.15) and increases from 230 to 370 Pa at a strain amplitude of 0.7,
but the maximum is not reached.
The results of Figure 4.6 were obtained for a 24 vol % of spherical glass beads
(GB) of average diameter equal to 10 gm in the same PB. Here again for the time
frame of the experiments, the effects of settling are believed to be negligible. The
general aspect of the curves remains the same. For the lower strain amplitude a
viscoelastic linear domain is observed, followed by slight decreases of the moduli
up to a deformation of about 0.7, which is the critical strain at which the structure
1334
-1
0 2 4 6 8 10
t[s]
Figure 4.7 Normalized strain and stress signal obtained at a frequency of 0.628
rad/s vs. time for a 47 vol % PP/PB, and a 24 vol % glass beads/PB
suspension. Also shown is the normalized strain output for the
Newtonian PB matrix (Unpublished data [57]).
1335
104 ~" ~
~~i,t,i~,ati,,,,i.m~ 63 s'l
103
6.3 s"l
ak
V ~ . 6 3 s-~
102
V
V
101 V V ~ . 0 6 3 s-~
........ I . . . . I ...I ........ I . ." .**.".'...I ........ I .......
10 4
10 3 constant shear
and model
o 102
D
10~ Jy c o []
A
V
0 6 3 s -1
6.3 s -1
0.63 s 1
0.063 s-1
10o ....................................
Figure 4.9 Steady shear stress and shear stress amplitude as functions of shear
rate and strain rate amplitude for the 47 vol % PVC/PB suspension
(From Carreau et al. [20].
[] r I , t ~ = 2 5 P a
O rl, cr = 10Pa
10 3
~x rl*, 03 = 0.63 s-1
102
These experimental observations allow us to make the assumption that the strain
hardening effects are included in the steady rheological properties. This
contribution for non colloidal particles could be significant compared to
hydrodynamic and other forces. As shown in Figure 4.9, the steady shear viscosity
of concentrated suspensions in a Newtonian matrix can be modeled by a Maron-
Pierce equation adding the contributions for the elastic yield stress, o o, and the
supplementary strain induced stress, Ooi. The induced yield stress was found, from
oscillatory shear experiments for the 47 vol % PVC/PB suspension, to be
proportional to the frequency at a power 0.65. Hence, we have proposed the
following extension of the Maron-Pierce model:
4.2 C o a t i n g c o l o r s
Many industrial processes are transient from a material point of view. Although
1338
the flow rate or deformation rate could be quite large, the total deformation
experienced by the material may remain relatively small. In general, restricting the
flow analysis of industrial processes by using time independent or steady state
viscosity could lead to a poor understanding of the phenomena envolved and
incorrect modeling. One example of such industrial applications is paper coating,
where a coating color is applied on the paper sheet and excess removed by a thin
trailing blade. The gap between the paper sheet and the blade is in the order of few
microns. As the blade is fixed and the speed of the paper sheet is in the range of
100 km/h, the calculated apparent deformation rate is of the order of 106 s~, but the
corresponding deformation or strain for the flow under the blade is less than 10.
Coating colors are concentrated colloidal suspensions. A typical formulation
consists of water, mineral pigments as kaolin and/or grinded calcium carbonate,
latex particles and/or starch used as binder and of different other additives playing
a role on the rheological properties. Brownian and other colloidal forces affect the
rheological behavior of this type of suspension. The results presented in this section
are extracted and adapted from a publication on rheological properties of coating
colors by Lavoie et al. [58]. The coating colors, used in this work, consisted of 100
parts by weight of pigments and 11 parts by weight of styrene butadiene
carboxylated latex particles of diameter equal to 0.13 lam. The pigments were a
standard #2 US kaolin and a standard delaminated US kaolin. The pH of the colors
was adjusted to 8.0. The Brookfield viscosity of each color was then adjusted to 1
Pa.s (1000 cP) at 100 rpm by adding a "high viscosity" type CMC as dry powder.
The coating colors containing the standard #2 kaolin were prepared at total solids
of 67 and 63 wt.%, and the coating colors made up of the standard delaminated
kaolin were prepared at 66, 64 and 62 wt. % solids. To emphasize the structure
induction (strain hardening) phenomenon presented in the previous section, results
obtained on two kaolin slurries at 68 and 71 wt. % and those of an industrial
coating color of unknown formation are also presented. The rheological properties
of the colors were determined using a strain-controlled Bohlin VOR and a stress-
controlled Bohlin CVO rheometer. A constant temperature of 20 ~ and a bob-and-
cup geometry (25 mm diameter and 1 mm gap) was used at all times. Steady shear
viscosity, transient viscosity (imposed shear rate) as well as strain and frequency
sweep measurements were conducted.
At low strain or low stress, the rheological behavior of a coating color
suspension is dictated by particle-particle (colloidal) interactions, it is strongly
related to the formulation. Figure 4.11 presents the complex modulus as a function
of the shear strain, for the coating color made with the delaminated US kaolin
containing 66 wt. % solids and for the industrial coating color. A linear viscoelastic
domain is observed for the complex modulus, characteristic of solid-like
1339
viscoelastic behavior. The limit of the viscoelastic domain corresponds to the yield
strain, Yo, which is related to the yield stress by Oo/Go. The rapid decrease of the
complex modulus corresponds to plastic flow behavior, and the strain hardening,
as discussed in the previous section, appears at a critical deformation.
10 ! =-- 000 9
Plastic ~ '
Msmelmtic Flow
100 . Dxr~
. . . . . . . . . . . . . . . . I ! i | | . . . .
10 -3 10-2 10-! 10 ~ 10 !
yo
Figure 4.11 Complex modulus as a function of strain amplitude for an industrial
and a 66 wt. % delaminated kaolin (model) color (From Lavoie et al.
[58]).
The oscillatory data for the industrial coating color, in terms of the amplitude of
the complex stress (o ~ G*y ~ as a function of the strain rate amplitude (y~ is
presented on Figure 4.11. Also shown are the steady shear stress vs. shear rate data.
As for the 47 vol % PVC/PB suspension, strain-hardening effects appear for the
101 Model
(5" Steady Shear
10 ~
o
co
~ 10 -! [] 31.4 s -1
cyo A 6.28 s -1
-2
V 0.628 s - !
10
10 -3 10-2 10-1 10 0 101 10 2 10 3
% 7~ [s-q
Figure 4.12 Steady shear stress and shear stress amplitude as functions of shear
rate and strain rate amplitude respectively for the same industrial
coating color as in Figure 4.11 (From Lavoie et al. [58]).
1340
three frequencies, and the stress amplitude at low frequencies approaches the steady
shear stress. The resistance to flow in steady shear situation is larger than that in
high frequency small amplitude shear case because of the stain induced structure.
The induction structure effect for the 68 wt. % standard American delaminated
kaolin suspension is presented in Figure 4.13. The complex viscosity (1"1")at o
equal to 0.628 rad/s and the transient viscosity (1]) in creep are presented as
functions of the strain amplitude (yo) and shear strain (y) respectively. These
rheological properties reflect strong particle-particle interactions. No linear
viscoelastic domain is shown and at low strain the elastic contribution is 5 times
larger than the viscous one, characteristic of a solid-like structure. At a strain
amplitude of 1.2, the structure induction phenomenon from the complex viscosity
becomes apparent. The creep experiments were conducted at three different shear
stresses, one lower than the yield stress (0.5 Pa), a second just above the yield stress
(1 Pa) and finally at a stress of 5 Pa for which the slurry behaves as a fluid. These
curves confirm the different flow regimes observed in oscillation. For a shear
stress of 0.5 Pa, the slurry behaves like a solid. The stress is large enough to deform
the material but not enough to make it flow. The large increase in the viscosity is
the reflect of the structure break-down under strain, as discussed in Section 3 in
terms of the loss modulus for fumed silica suspensions (see Figures 3.8 and 3.9).
For the second experiment (at 1 Pa) a large increase for the creep viscosity is also
observed, but at larger strains, in the domain of the induced structure phenomenon.
After reaching a maximum, the viscosity goes down as the material is beginning to
flow. Finally, the experiment at 5 Pa reveals the same type of behavior, but the
strain hardening effects are attenuated because the hydrodynamic forces dominate.
Comparable behavior would be observed for different types of concentrated
suspensions, including industrial coating colors.
During the paper coating process, coating color experiences a wide range of
deformation rates, the highest being in the nip of a roll or under a blade. However,
at high deformation rates, contact times are very short and, in these conditions, the
total deformation remains very small. Hence, the low strain behavior is as much
important as the steady flow properties for applications such as blade coating. We
stress that the coating process cannot be fully characterized using only steady state
rheological parameters. The magnitude of the deformation for the transient
experiments used to generate the data of Figure 4.13 is comparable to the total
deformation experienced in coating for the flow under the blade. The rheological
behavior under the blade is essentially that of a thixotropic material, which is time
dependent.
1341
|01
o" = 0.5 Pa
W
10~
r Pa
q
lO-1 O- = 5 p a
10 -2 10 1 10 ~ 101 10 2
T,T ~
Figure 4.13 Complex viscosity (60 = 0.628 rad/s) and creep viscosity as functions
of strain amplitude and strain respectively for a 68 wt. % delaminated
clay slurry (Adapted from Lavoie et al. [58]).
5. C O N C L U D I N G R E M A R K S
In this chapter, we have illustrated and discussed various aspects related to the
rheological behavior of concentrated suspensions. Concentrated colloidal
suspensions are characterized by yield stresses, shear thinning and thixotropic
behavior, and for small amplitude shear flow, the elastic moduli could be
significantly larger than the loss moduli. Obviously, colloidal forces and particle-
particle interactions play a major role on the properties. Changes in ionic strength
of the suspending fluid could lead to drastic differences in the viscosity and the
shear-thinning characteristic of colloidal suspensions. Suspensions of non colloidal
particles in Newtonian fluids are expected to be simpler to describe. This is done
using the concept of hard spheres and the increase of viscosity can be accounted for
by using the Krieger-Dougherty, Maron-Pierce or other equivalent expressions, in
terms of a maximum packing factor. For suspensions in non-Newtonian fluids, the
behavior is similar to that of the suspending fluid, provided particle-particle
interactions make negligible contributions to the stresses. The viscosity can then
be described combining viscosity models for polymers and Maron-Pierce
expressions for the filler effects.
We have shown that many experimental problems could lead to erroneous results
or results which lead to wrong interpretations. The dispersion of solids especially
in the case of colloidal particles could result in totally different rheological
properties. For example, an apparent yield stress and shear thinning may be caused
1342
REFERENCES
16. Yoshimura, A.S., and R.K. Prud'homme, Rheol. Acta, 26 (1987) 428.
17. Doraiswamy, D., A.N. Mujumbar, I. Tsao, A.N. Beris, S.C. Danford, and
A.B. Metzner, J. Rheol., 35 (1991) 647.
18. Husband, D.M, N. Askel, and W. Gleissle, J. Rheol., 37 (1993) 215.
19. De Kee, D., and C.J. Duming, in Polymer Rheology and Proceeding, edited
by A. Collyer and L.A. Utracki, Elsevier, New York, NY (1990).
20. Carreau, P.J., P.A. Lavoie, and M. Bagassi, in Macromolecular Symposia,
edited by E. Papirer and J.P. Trotignon, Huthig and Wepf Verlag, Oxford,
CT, 108 (1996) 111.
21. Otsubo, Y., J. Coll. Int. Sci., 112 (1986) 380.
22. Carreau, P.J., in Transport Processes in Bubbles, Drops and Particles, edited
by R.P. Chhabra and D. De Kee, Hemisphere Publishing Corporation,
Washington, DC (1992) 165.
23. Acrivos, A., X. Fan, and R. Mauri, J. Rheol., 38 (1994) 1285.
24. Batchelor, G.K., J. Fluid Mech., 83 (1947) 97.
25. Krieger, I.M. and I.J. Dougerthy, Trans. Soc. Rheol., 3 (1959) 137.
26. Mooney, M., J. Coll. Sci., 6 (1951) 162.
27. Maron, S.H. and P.E. Pierce, J. Coll. Sci, 11 (1956) 80.
28. Chang, C. and R.L. Powell, J. Rheol., 38 (1994) 85.
29. Storms, R.F., B.V. Ramarao, and R.H. Weiland, Powder Tech., 63 (1990)
247.
30. Shapiro, A.P. and R.F. Probstein, Phys. Rev. Lett., 68 (1992) 1422.
31. de Kruif, C.G., E.M.F. van Iersel, A. Vrij, and W.B. Russel, J. Chem. Phys.,
83 (1985) 4717.
32. Krieger, I.M., Adv. Coll. Int. Sci., 3 (1972) 111.
33. Barnes, H.A., J.F. Hutton, and K. Walters, An Introduction to Rheology,
Elsevier, New York, NY (1989).
34. Cross, M.M., J. Coll. Sci., 20 (1965) 417.
35. Mellema, J., C.G. de Kruif, C. Blom, and A. Vrij., Rheol. Acta, 26 (1987)
40.
36. Frith, W.J., J. Mewis, and T.A. Strivens, Powder Tech., 51, 27 (1987).
37. Nicodemo, L., L. Nicolais, and R.F. Landel, Chem. Eng Sci., 29 (1974) 729.
38. Mewis, J. and R. de Bleyser, Rheol. Acta, 14 (1975) 721.
39. Lobe, V.M. and J.L. White, Polym. Eng. Sci., 19 (1979) 617.
40. Tanaka, H. and J.L. White, Polym. Eng. Sci., 20 (1980) 949.
41. Barnes, H.A., J. Non-Newtonian Fluid Mech.,70 (1997) 1.
42. Quemada, D., Rheol. Acta, 17 (1978) 632.
43. Quemada, D., Rev. G6n. Therm. 279 (1985) 174.
44. De Kee, D., R.K. Code, and G. Turcotte, J. Rheol., 27 (1983) 581.
1345
1. INTRODUCTION
9 The effect of the solvent rheology is certainly essential [14,15]. However, the
available fiber motion models are basically limited to Newtonian solvents.
9 The fibers are first of all characterized by their aspect ratio A r - I/d, where
l and d are the fiber length and diameter [10-12]. In addition, the fiber
thermo-mechanical properties (including the fiber flexibility [16-17]) can play a
non-negligible role. Most theories are, however, restricted to rigid fibers.
9 The volume fraction of the fibers (r directly affects the mixture rheology [18].
General suspensions are classified as dilute (~O<O(Ar -2) ), semi-dilute
(O(Ar-2)<qb<O(Ar-1)) or concentrated (O(Ar-1)<~)), depending on
whether the particles do not interact, have only hydrodynamic interactions, or
interact through both hydrodynamic and direct kinematic effects [3,19-24].
Whereas the dilute and semi-dilute theories have been extensively investigated
[12,21-30], the much more frequent case of concentrated suspensions remains
limited to phenomenological models [1-3,6,20,31-33] and a theory in its begin-
ning stages [34-37].
9 In narrow gaps of thickness 2h, fiber out-of-plane rotation is basically gov-
erned by the ratio I/h (narrow meaning that e-h/L<<l, where L is a
characteristic in-plane dimension [1-3,6-9,38-42]).
9 Other dimensionless numbers characterize the processing conditions.
It is of course totally impossible to elaborate a model encompassing all these
phenomena. Nevertheless, most of the existing theories are based on the use of
orientation tensors [26b,43a] to represent the fiber orientation field and to model
the interaction of the fibers with themselves, the solvent or the walls. A common
presentation of the basic physical model for various kinds of suspensions and pro-
cesses will, therefore, be possible. As the use of orientation tensors requires to
solve the closure problem (i.e., to relate the (n+2)th-order orientation tensor to the
nth-order tensor by means of a sound physical approximation) [26b,40-46], this
issue will be carefully investigated. Another limitation, however, concerns the
numerical solution of the general orientation-flow coupled problem, which entails
significant difficulties [47,48]. In this respect, the recent development of coupled
lubrication models adapted to narrow gap flows [49,50], and of general two-di-
mensional (2D) coupled models with viscoelastic rheology [51] and three-dimen-
sional (3D) coupled models [52], should be emphasized. Hence, important pro-
gress can be expected in the near future concerning the orientation and flow
models that will be available for industrial use.
The objective of the present chapter is to review the state of the art in fiber ori-
entation modelling, with a particular attention bearing on the decoupled lubri-
cation model [2]. The algorithm elaborated by Dupret and co-workers [4,9,39-
1349
where ~, = (ArL 1)/(Ar 2+ 1) is the fiber shape factor and Pi denotes a mixed
convected derivative of Pi"
a OPi 1 (1 + ~) ~ 1 ~j (2)
Pi = Dt 2 ~ j j P J + -2 ( 1 - A ) -~ii P J "
The Einstein summation convention over repeated indices is used and t , x i and
Vi stand for time, Cartesian coordinates and velocity components, while the
1350
l
e1
Figure 1. Sketch of an ellipsoidal fiber and unit vector representing the fiber
orientation.
dS i - ( dSi ) + dS j - 0 , (4)
body theory, and Brenner (cf. the references in [12]), who highlighted the intrin-
sic tensors governing the motion of arbitrary particles under external forces and
torques. Vincent and Agassant [13] validated the Jeffery model by means of
extensional flow experiments, while Givler et al. [62, 63] and Henry de Frahan et
al. [39] developed numerical tools to solve (1) for plane and multi-faceted thin
shapes. From these investigations, it is worth recalling that, in extensional flow,
the fibers quickly align with the principal stretching direction. In shear flow, each
fiber rotates along a given "Jeffery orbit" at a non-uniform rate with a period
T-2zr (Ar + Ar-1)/y (where ~ ' , a s defined from )?2 2dijdij, denotes the
shear rate); for slender fibers (Ar >> 1), rapid tumbling motions separate long
periods of nearly in-plane orientation; for inf'mitely slender fibers ( Ar = oo ), each
in-plane orientation is an unstable equilibrium position and the motion is no
longer periodic (see also the stability analyses of MacMillan [64] and Szeri et al.
[60], and the investigation of the 3D transition from in-plane to uni-directional
orientation in shear flow in [9]).
The Jeffery model remains useful to evaluate closure approximations or other
effects by averaging the results obtained with a large set of fibers [65-67]. Ingber
and Mondy [59] have shown from exact flow calculations that Jeffery's theory is
robust for rigid fibers, even when weak hydrodynamic interactions with other
fibers or the walls are considered. Similar conclusions can be drawn for semi-
dilute suspensions from the analysis of Koch and Shaqfeh [23] and the experi-
ments of Stover et al. [68]. The theory should be further elaborated in order to
take the solvent viscoelasticity into account, since experiments indicate that vari-
ous behaviors exist, which often disagree with theoretical predictions (cf. Feng
and Joseph [14], Iso et al. [15] and the literature therein).
long fibers), dp is an element of length of the unit circle (which will also be
denoted by U ). The distribution function is normalized by the condition
~u ~ dp - 1, while the symmetry condition W(p) - q ' ( - p ) is introduced to
remove the indeterminacy between fibers oriented in the directions p and - p .
The evolution equation of W has the form [1,73] :
o%t - ,
(5)
that Hinch and Leal [69a] def'me the Brownian effect as strong, weak, or very
weak, according to whether DI/~/>> 1, 1 >> DI/~z >> (Ar + Ar -1)-3, or
(Ar + Ar -])-3 >> D , / y . The same scaling could thus be considered for C I .
=- C I =0 . 0 0 4 4 _
.9 2.0
Aspect ratio
=83
g ].5
Volume fraction
o'1 =0.013
?:51.o
O.5 (3
0
-rr/2 0 77"/2
Orientation Angle, c~
3.0
' ( y : 1.56)
0 Data Points (b) '
0 Data Points (7': 1.56)
(c)
- - Approximated Fit . . . . Initial Orientation (Exp.)
2.5 2.5 Approximated Fit
g~o ~'2.0
t.l. LI.
~0
1.5 C
.91,5
e~ C I: 0.004 .o
-~.
=-
ul
~1,0 -.,,
i:51.0 - CI: aO15 -
0.5
0 0.5 - 1~~
o_ D o o o
0 i 0 I
-~'/2 0 71"12 -71"12 0 ~'/2
Orientation Angle, ~) Orientation Angle,
sor Kij. The latter can be developed as a sum involving the 9 base syrrmaetric
tensors constructed from pi and dii (with coefficients depending on their
invariants and W ), and must respect invariance of fiber orientation with respect
to time scale changes. Hence, the general theory is very complicated.
FiA
where B 6 - Fia FjA is the Finger strain tensor from initial to actual state.
It is clear that W c has 5 degrees of freedom in the 3D case and 2 in the 2D
case, since Bij is symmetric and its determinant is 1 due to the suspension in-
compressibility. When the coefficients Bij are arbitrary numbers constrained by
these requirements, the distributions Wc(p) form a class called by Verleye et
al. [40-42,56] the class of canonical distribution functions, since they considered
that it is the simplest class of distribution functions and used it to build the natur-
al closure approximation by non-linear projection. This class was also used by
Szeri and Lin [46] to approximate the solution of the fiber orientation problem
(with Brownian motion) on the basis of the double-Lagrangian technique of Szeri
and Leal [44]. Lipscomb et al. [27] proved that the same class is generated by
the motion of finite aspect ratio fibers without fiber-fiber interaction, since an
equivalent strain tensor Fi,~q can be defmed from (2) by the relation
an - ~W(p,x,t)p| . (11)
u
From the normalization and synnnetry properties of W, it is clear that a 0 is the
constant 1 and that all odd-order orientation tensors vanish. We will restrict
1357
ourselves to the 2 nd-, 4 th- and 6 th- order tensors aij, aijkl and aijklmn, with
The basic properties of orientation tensors are full symmetry and normalization
[43a]. It is convenient to introduce the symmetrization operator S as follows :
for a genetic tensor b, S(b) is the average of all the transposes of b. Hence,
S (bij) and S (bijkl) are defined by
S ( b ij ) - /~2 ( b ij + a f t ) , (13)
with a similar expression (with 720 terms) for S(bijklmn ) . The full symmetry
property, which is a direct consequence of (12), writes as :
On the other hand, the normalization condition results from the fact that Pi is a
unit vector. Hence, from (12),
This shows that all the informations provided by aij are contained in aiju , and
the same for aijkt and aijklmn. Nevertheless, the deviatoric parts of the orienta-
tion tensors can be defined by the expressions [43a]
I,ta ij - a ij
_iS. .
N tj , (17)
3
d -- 6------~-S ) "k- S(~ij(~kl),
aijkl - aijkt 4 + N (Sijakt (4 + N)(2 + N)
ij - -2~aijktd~a - 2 C 1 ~ ' N a q ,
( d 3 N ) (20)
[aokt - - 4 X aokt,,, , dmn - 4 C r y ( N + 2)a01 a + ---S(a~6kl
+4)N "
I-1 rl
The mixed convected derivatives a ij and aokt are defined in the same way as
rl
P i in equation (2)"
[] V A
v a (21)
ijkl -- ~2(1 + Z) aijkt+/~2 (1 - X)aiykt,
V V A A
where a ij , a ijkt, a q and a ijkt denote the upper- and lower-convected deriva-
tives of aq and aqk l . In particular,
The 1~t and 2 "a equations (20) are embedded, in the sense that the trace of the
2 nd equation is exactly the 1st equation, whose trace is itself vanishing. Hence,
only one equation need be considered in a given model. Most authors select aij
as the basic variable (with 5 unknowns in 3D problems) [2,9,26b,27,39-41,43,45-
49,53,78,79,81 ], while Altan et al. [65,80,82,83,86,87] investigated the 2 "a option
(i.e., to solve for aijkt, with 14 unknowns in the 3D case), in view of the direct
effect of aijkt on the thermo-mechanical properties of the product [7].
1359
Solving the problem in terms of orientation tensors has the drawback that the ev-
olution equation of the 2nO-order orientation tensor involves the 4th-order tensor,
whose equation itself involves the 6th-order tensor, etc. To circumvent this diffi-
culty, a closure approximation expressing aijkl algebraically in terms of aij (or
aijklmn in terms of aijkt ) is required. In view of its importance, this issue is ex-
amined in a separate section.
where 7"/ is the solvent viscosity, while A, B, C and D are coefficients which
primarily depend upon the suspension concentration and the aspect ratio and
degree of alignment of the fibers, but might also be functions of the invariants of
ai# l and dij [93]. The dilute theory is well-established [10,12,25,27,58,61,69,
94] while, starting from the pioneer work of Batchelor [19] and Dinh and Ann-
strong [21], the semi-dilute theory has been developed by Shaqfeh, Koch, Fred-
rickson and co-workers [28-30,37,75], and validated by means of experiments
[68,92,95] and numerical simulations [29,30,37]. Mass, momentum and heat
transfer have been investigated. It is worth noting that, when A is put in the
form A - 1 / 2 ar 2 [ln(X/d)] -1 , the length X (which is thereby defined) scales
as the fiber length l for dilute suspensions, and as the screening length for semi-
dilute suspensions. Hence, as explained in Section 2.2, X is in this latter case
of the order of magnitude of the average inter-fiber spacing (and not the average
shortest distance between two fibers as in [21]), for any orientation distribution.
The coefficient B is negligible for slender fibers [27], while C = 2 and D
vanishes in the absence of Brownian motion.
No complete theory exists for concentrated suspensions. Semi-empirical values
of A, B, C and D are proposed in [96]. Phenomenological models combining
extensional and shear viscosities were developed by Gibson and co-workers [6,
31-33] (see also [97]), while Toll and M~nson [36] and Sundararajakumar and
1360
The use of orientation tensors to simulate fiber suspension flows represems the
best modelling methodology as long as an appropriate closure approximation is
developed (Hand [93], Hinch and Leal [26b], Advani and Tucker [43]). This
issue brings about the question of whether the (2n+2)th-order orientation tensor
can be expressed as a given function of the (2n)th-order tensor in such a way that
the predicted values of the 2nth-order tensor obtained by solving the associated
momem equations provide good results "in most circumstances of practical in-
terest" This question expresses the situation well. Exactly in the same way that
orientation tensors are summaries of the distribution function, the moment equa-
tions completed by a closure approximation represent summaries of the distribu-
tion function evolution equation, and summaries never provide full information.
Hence, the closure problem is not precisely posed in a mathematical sense, be-
cause this would necessitate to define the probability of the different states of the
system (each being represemed by a given distribution function), which is impos-
sible for there is a lack of sufficiem knowledge about the problem physics and
also because of the tremendous difficulty of the mathematical problem. There-
fore, heuristic methods, which combine theoretical and physical considerations
with numerical and real experimems, remain the only way to tackle the question.
1361
In the 2D case, the sum is limited to 12 terms and a single invariant needs to be
considered:
O - det (aij) . (25)
Note that symbols are selected in such a way that equations (24) and (25) match
when a 3D orientation state tends to becoming 2D.
Optimally, closure approximations should satisfy the f u l l normalization and sym-
metry conditions (16.2) and (15.2). However, this is not a constraint [26b,43b]
and it is sufficient to require p a r t i a l normalization and symmetry :
I101!1I1 I12o 4r
0
0
7
0
132 = -
133
0
7
1-6D
5
4(P-D)
2(3- 4D)_]
]Iil + , (30)
or I80 [-4D
depending on the problem dimension.
The first closure approximations that were successively proposed by various re-
search groups are listed below. All these formulae, which are discussed in [43b],
satisfy full normalization.
9 The linear closure (Hand [93]) writes as
3 6
aii~t = (4 + N)(2 + N) S (6iy6 ~ ) + 4 + N S (aij6~t ) , (32)
aijkl -- f , I 6 1
3 + N) S(t~ijt~kl)+ 4 + N S(aijt~kl ) + ( 1 - f ' )
(4 + N)(2 aijakl 1 (33)
where f ' - N N det (aij) . The hybrid closure is exact when the fibers are in a
random state or perfectly aligned, and never behaves badly (except that it
1363
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1
Figure 4. Left : space of possible orientation states in principal values and fitting
domain. Right: points generated by calculation of the distribution function and
used for the orthotropic fitted closure. (From [45]).
3 . 2 0 r t h o t r o p i c closures
The term "orthotropic" closure was introduced by Cintra and Tucker [45] to de-
note a 3D closure approximation of aijkl that has the same principal axes as aij.
Since aiykl must take all its directional information from aij, any closure ap-
proximation must be orthotropic. Hence, the closure relation expressing aijkt in
terms of aij can be considerably simplified. Letting ~, 7/ and ~" denote the
principal values of aij, it is easy to show by s ~ e t r y considerations that, for any
orthotropic closure satisfying the normalization and partial symmetry conditions
(16.2) and (27), there are, in principal axes, exactly 6 independent components
aij~l. This number reduces to 3 when full symmetry (equation (15.2)) is required.
Cintra and Tucker [45] selected allll, (/2222 and a3333 to provide these basic
1364
1.0 . . . .
all
/ [ an
/ ,--...-.- DFC ........... "~
0.2
. . . . i . . . . 9 . . . . ! . . . . ! . . . . ! . .
' . . . . ' . . . . * . . . . . 0.1 . . . . . ' . . . . ' . . . . . * . . . . ' . . . . * . . . .
5 10 15 20 25 30 0 5 10 15 20 25 30
Gt = reduced time Gt = reduced time
Figure 5. Tensor components obtained by means of the best fitted orthotropic
closure. The flow starts with simple shear, switches to shearing/stretching flow,
and finally shearing continues with a strong stretching in the 3 rd direction (DFC"
integration of distribution function; ORF" orthotropic fitted closure; NAT" nat-
ural closure approximation, 1 st version; HL1 and HL2" Hinch and Leal's 1 st and
2 no composite closures; HYB 9 hybrid closure). (From [45]).
aij is only possible (to date) in the 2D case [40]. Tuned numerical methods are
therefore required in the 3D case to obtain an accurate approximation of this rela-
tion. Hence, two levels of approximation must be considered, viz., the theoretical
natural closure, which provides an approximation of the 4th-order orientation ten-
sor aijkl, and its numerical approximation (which is thus an approximation of an
approximation). To avoid any misunderstanding in the sequel, the term "natural
closure" will concem the theoretical closure, while the term "natural closure
approximation" will be used for the numerical approximation of this theoretical
closure only.
It should be emphasized that the natural closure concept is based on establishing
a relationship between aij and aijkl by neglecting the effect of fiber-fiber inter-
action and starting from isotropic orientation in a hypothetical flow. These as-
sumptions are only necessary to define the closure, which is further used in situa-
tions where they are no longer valid. There is some physical evidence, which is
corroborated by the investigations of Verleye et al. [4,40-42,56,57] and Cintra
and Tucker [45] (see Figure 5), that the natural closure behaves well in many
circumstances, especially for molding problems. However, this cannot be always
true, and in particular the natural closure should not be used when two (or more)
preferential orientations of the fibers are present. These states are highly unlikely
in practical situations.
,5 i i i i ,I i i i
[FiA]_
[ J
F
0
0
F -1 '
- , (37)
F2+l 1
The 2D natural closure performs very well when compared with other 2D clo-
sures [4,40,51]. Figure 6 illustrates this behavior in simple elongational flow
(v 1 = ~ x 1, v2 = 0 , v3 = - ~ x 3 ) , starting from isotropic 2D orientation
(all =a22 = 0 5 , a12 = 0 ) and using the value C I =0.01. Impressive experi-
mental validations have been obtained in the prediction of Bulk Molding Com-
pound (BMC) injection molding with the 2D natural closure (see Section 5).
aijkq (~pm + a p#a (~im + a ipgq 3jm -- a pjmq tSik - a ipmq r -- aijmp t~qk +
which is a direct (but not obvious) consequence of equations (20.1) and (22) and
the definition of the natural closure. Indeed, from the identity
D F i A / D t - ~ V i / ~ X j FjA, and taking the conditions ~ - 1 and C t - 0 into
account, (20.1) and (22) can easily be combined as follows in differential form :
daij - dFiA FAT a kj - aik FAT dFjA - -aijkl (dFkA FAll + FAT dFia ) , (42)
where aijkt is a function of aij, which is itself a function of Fia. The key point
is to observe that the differential daij in (42) must be exact when aijkl depends
on aij through the natural closure. More precisely, the derivatives
o32aij/CgFkloqFmn and o32aij/cgFmn3Fkt provided by (42) must be equal for any
value of FiA when aijkt is defined by this closure. After quite long calculations
(which must be performed with care for aij is constrained by (15.1) and (16.1)),
this condition provides equation (41), which is the comerstone of the numerical
theory of the natural closure approximation. Also, (41) can be extended to
higher-order closures and, in particular, it could help in defining a closure approx-
imation for the 6th-order orientation tensor in terms of aijkl (by extending the
space of canonical distribution functions, since 14 degrees of freedom are re-
quired). This theory is under investigation.
At this stage, since the invariance properties of indicial tensor notation have
been used to provide (41), the calculations can be pursued with the tensors aij
and Fim in diagonal form. The following notations are used (Figure 7) :
r/=l
~-1/8
m
r r/=O ~=1
Figure 7. Left'triangular domain T of eigenvalues of aij. Right" isovalues of
Z-a1122 in T (the maximum Zmax is 1/8). (From [4]).
[ (4Z + X - r/)(2Z- ~) 1
+ (rt- r162 r L_(4 z + Y - , ~ ) ( 2 Z - r l ) _ ]
0.14 9 . . . . . . .
0.12 Analytical Z ~
Approximate Z - -
/
0.1
~,, / Anal.ytical Y - -
0.08
0.06
0.04
0.02
0.0
-0.02 i i i i i i i i
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.5 -
0.4 Analytical dY/d~
Approximate dY/dr
0.3 -
0.2
Analytical dZ/dr
0.1 Approximate dZ/d~ - -
0.0
-0.1
-0.2 ,,
-0.3
Figure 8. Comparison between the theoretical and approximated values of
Z -- a1122 and Y - a l l 3 3 (top), and dZ/d~ and dY/d~ (bottom), along
- 0 . The 2 "d strategy was used. (From [4]).
and the denominator of the approximants are increased (in [41,56], these degrees
were 8 and 1). This results from the singularity of the natural closure along the
boundary 3/" of the triangular domain T of admissible (~,r/,~') (Figure 7).
Altemative approaches, taking into account the theory of the natural closure,
were thus investigated.
In the 2 "a strategy [4], the following decomposition was introduced"
Z-/~2~r/+PZ , (50)
ae, g-r z - - ~ n , ar ac X - a~ ~) y = 1
2
(53)
a a)z_l~r
an ar
(aa~ ara] x - a(an 1
2
s+
coshs
16sinh4s (55)
S ~ ~ " if o<r (~<s<O),
sinh3s sinh2s
In both cases, (34) provides the relation ~ - 7 / - ~ 2 ( 1 - ~'), while it can also be
proved that X - Y - ~ (1 - u
8Z).
1373
The approximation (X ap, I?ap, Zap ) tested in the 2 nd strategy was of the form
lnD +(~
Zap ~
I l)I ll
1+/7 lnP In
(57)
with symmetricexpressions for f~ap and I~ap. In (57), P(v) and G(v) are
polynomials in 77= lnD/lnP, which vanish when "c = 0 and are selected in order
(i) to respect condition (51) when equation (52) holds :
and (ii) to provide a very close approximation of the axisymmetric natural closure
when ~ - U . This was achieved by constraining X ap, Yap and Zap to present
the same expansions (up to a given order) as )(, I7 and Z around ~ - 0,
= 1/3 and ~=1. In particular, complex calculations around ~ = 0 produce the
following expansions :
Whereas very good results were obtained by using this 2 nd method [4], the
solution adopted to remove the artificial singularities was not completely satisfac-
tory, since a closed analytical expression was expected for the closure approxi-
mation. Moreover, since in molding processes the fibers are most often strongly
aligned by shear and elongational effects, the vicinities of the comers of the do-
main T must be given particular attention. In particular, overlapping (and thus
non-regular) solutions must be avoided. This is the reason why a 3 rd strategy,
which is still under development [42], was investigated. Recent work also
suggests that non-linear algebraic relations linking fll to /56 can be obtained by
equaling the cross 2 "d derivatives of Z (obtained from (49)). Hence, a very high
accuracy should eventually be reached.
The results obtained by using the 1~t strategy (with rational approximants) were
compared by Cintra and Tucker [45] to their best fitted orthotropic closure (see
Figure 5). They showed that this natural closure approximation generally behaves
very well, whereas slightly better results are obtained with the optimal orthotropic
closure. We believe (but this needs confirmation) that this can be related to the
lower quality of the 1~t version of the natural closure approximation in the vicinity
of the boundary (and especially the comers) of the domain T. Further numerical
experiments are needed. On the other hand, the natural closure approximation
does not oscillate in the same way as the best fitted orthotropic closure for low
values of C I [45,88].
The isovalues of the approximate solution Zap obtained with the 2 nd strategy are
represented in Figure 7 along T. The good quality of this approximation is illus-
trated by Figure 8, which depicts the values of X, Z, X ap, Zap and their
1375
derivatives along the bisector ~ = 7/, and by Figure 9, where the relative error
(Zap- Z)/Zma x (in %)is represented over T. Near to the comers, the error is
more important because another approximation was used.
where 0pi/Op ~ (x ~ p0, t) represents the Jacobian matrix of the solution of (6),
while q'0 - W ( x~ p0,0). Hence, a system of ordinary differential equations is
found, which can be solved numerically by generating a large number of Lagrang-
ian fibers. Details are in reference [44b]. This serf-adaptive scheme is of particu-
lar interest for those problems where a good closure approximation is not availa-
ble, or when steep orientation gradients are present in the boundary layers.
In a subsequent work, Szeri and Lin [46] developed an accurate method to solve
the fiber orientation problem by tracking an equivalent deformation gradient
tensor FleAq (x,t) obeying the equation
Dt
where D/
- -~j + ( ~ - l)dij + 3hDI (BiJq(-1)-3B~c(-1) ~iJ) F ~
1 ,
4. A P P L I C A T I O N TO SUSPENSION F L O W S IN N A R R O W GAPS
provides a convenient way to define and understand the role of N o (the shear
number N s is negligible for slender particles). Tucker [2] proved that Pi, aij,
aiju ... are all of the order O(6S), where s is the number of out-of-plane com-
ponents among the indices i , j , k .... while, from (20.1), 6 - m a x ( e , C ~ i 3 ) .
(Note that aiju is scaled in [2] from the definition (12.2), without considering
the effect of the closure approximation. First inspection reveals that classical
closures such as the quadratic, hybrid ... closures, but not the linear closure, are
consistent with this scaling.)
The flow regimes identified by Tucker [2] are :
9 I. The decoupled lubrication regime ( N p S 2 << 1, S > e), which allows to
separate the flow and orientation calculations since the gapwise shear stresses
are governed by the solvent viscosity (without orientation effect) and dominate
the in-plane momentum balance.
. II. The coupled lubrication regime (Np 62 > _ 1 , e << 6 << 1), where the gap-
wise shear stresses dominate the in-plane balance, with orientation effects,
+ ~ S - 0 (65)
& 3x~
where 3h/oat is included to provide a single model for injection and compression
molding.
The Hele Shaw approximation, which is used to model problem P1, has been
presented in Chapter IM. Some points need to be recalled :
9 The pressure field is approximately constant across the gap.
9 Assuming a power-law viscosity 77- moe b p - a T ~ n - 1 , where T denotes tem-
perature while n, m0, a and b are material constants, the shear rate can
be approximated from the relation ~2 _ (oava/o3z)2 (with z - x3).
9 The fluidity is given by the expression
-
jz (e- z0) le- z0I1/n-1 eaT(~)/nd2 (67)
rhl eaT(z)/nd z
2h~- j_hlz -- Z01Vn+l . (68)
-- ~ e-bp/nmoVn(o(z,T(.)) . (69)
va - 3x a Oxt~
Letting 13+ and 13- denote the upper and lower lubricating layer thicknesses
(with ~ - / h , ~+/h << 1), the velocity gradient and shear rate in the skins are"
{ ~v~l~z
~v=/az
- - ~1~+
- ~-~/~,
, +
i, - I I ~ l l / ~
e -I1~=11/~
<h-~ + _<z<_h>,
(-h_<z_<-h + ~ ) ,
where v~ stands for the constant in-plane core velocity. Furthermore, assuming
a power-law skin viscosity, and using (70) and (71) with the approximation
"r3a - 7"10v a I O z , the core velocity norm I1~11 ca. be expressed in the form
where the temperatures T and T- in the upper and lower skin layers are
supposed to be constant (and this is a restrictive assumption). Introducing (71)
and (72) into (70), the core velocity is therefore approximated by the expression
V'-'a= ~ t I1~11
]I~ (2h)l/n mo-1/ne-bp/nle-aT+
~+~+n e-aT- I ' (73)
s I1~11
n-1(2h)l/n+lmo-Vne-bp/n~+~-~~+n
/ea+ / (74)
From this discussion, it results that the same equations (64) and (65) will be
used to predict the kinematics in P1 and P2. Thermal effects can play a non-
negligible role. The effect of chemical reactions could be easily considered (cf.
also [ 104]). The solution of these flow problems was investigated in Chapter IM,
1380
Recalling that aij is constrained by equations (15.1) and (16.1), while aij and
dij must have an equal number of degrees of freedom in order to produce an
equal number of discrete unknowns and equations, d o is itself constrained 9
(77)
& & h&&' 0x a oaxa h 0Xa 0z
1381
W - - - - +V a +w , (78)
h
it results from mass conservation and the wall no-slip condition that
9 3" 3" h
W ---~~hd2+<Sz zV~d2 . (79)
where n a denotes the in-plane outer normal along o ~ (m) . In the fight-hand
side of (81), the 1st term is easy to calculate in a layer-by-layer procedure, while
the 2 nd term is indispensable.
To complete the weak formulation of (20.1), boundary conditions must be treat-
ed. Along the gates, aij is specified by means of essential conditions. Along
the side walls, no treatment is mandatory because the characteristics of (20.1) are
tangent to the side walls. However, the normal in-plane velocity may be usefully
set to 0. The conditions to be applied at the flow front and along the singular
lines of the midsurface (namely, the edges, abrupt changes of thickness, bifurca-
tions ... of the part) are examined in a separate section.
After the evolution equation of aij has been put into a weak form and the
boundary conditions have been treated, the semi-discrete scheme is built up in
two steps. First, aij is approximated by the discrete sum
where aij (m) (z,t) and qb(m) (xa) denote the nodal values of aij and the shape
functions. The tensor a ijkt is discretized in the same way"
[ ~n) 0 0 0
^
0 0
o , o
o -r 0 -r
o 8(n) 0 0 0 ~(n) 0 0 0
o ; 0 o 0 (84)
o ~,., o o ~(n, 0
o -~n)' ~~ '
for a 3D or 2D problem, respectively. In (84) and (85), and (82) and (83), the
^
functions r and q~(l) differ, due to the effect of applying a modified SUPG
technique (cf. Chapter IM, Section 4).
4.2 Effect of the fountain flow; abrupt changes of thickness and bifurcations
In 3D Hele Shaw flows, the fountain effect results from the deflection of the
core fluid towards the walls of the narrow cavity when it approaches the flow
front, as a consequence of the fluid-wall no-slip condition. Modelling this effect
is an important issue, since appropriate temperature and orientation conditions
must be imposed at the front to obtain correct simulation results. Both the flow
and its influence on the fiber orientation must be considered.
The effect of the fountain flow on the kinematics has been thoroughly investigat-
ed in Chapter IM and only the principal results will be stunmarized. Basically,
the Hele Shaw approximation generates a singular perturbation problem [108],
whose outer zone comprises most of the flow domain and is governed by the
1383
\\\\\\\\\N\\~z\\\\\\
\\\\N\\
. . . . !
j--)
i
i
I
dx!2
\\\\'N\\\\\\\\
dZl~z ' 7 ...... a 2: . . . . . . . . . . . . . . . . .
dZl~z
I z z~ ~ ~ - ~ dz 2
__ l_l _~ /////// ,I t11111111111'1/
x1
Figure 10. Simplified models for the effect of fountain flow (left), and for the
flow across an abrupt change of thickness (fight).
lubrication approximation, whilst the inner front zone has a characteristic dimen-
sion of the same order of magnitude as the gap thickness. Matching the inner and
outer zones imposes to select precise front boundary conditions. The fountain
flow thermal model developed by Dupret and Vanderschuren [107] was thus
based on the theory of matched asymptotic expansions. The following points
should be stressed :
9 The Hele Shaw approximation governs the whole flow domain.
9 The front region is infinitely thin and consists of straight segments perpendicu-
lar to the midsurface.
9 Heat diffusion and viscous heating are negligible in the front zone. The core
material points entering the front at a given level leave the front at another level
while keeping the same temperature.
This model provides a front thermal boundary condition for each level in the gap
where the material points move slower than the front (according to the Hele Shaw
model). This agrees with the fact that the characteristics of the simplified energy
equation enter the flow domain in these layers [9].
Once the flow is modelled, its effect on the fiber orientation can be investigated.
This problem is complicated, since orientation is governed by the motion, rota-
tion and deformation of the elementary material volumes that cross the front re-
gion. Ideally, the effect of both the inner and outer asymptotic flows should be
taken into account. However, calculating the inner flow means solving a free
boundary problem at each time and position along the front, whereas a unique
inner solution can be determined once and for all only if the viscosity is a con-
stant. Approximating the viscosity by a constant in the inner zone and predicting
the fiber orientation by matching techniques thus represents an attractive solution,
which has not yet been implemented.
The method developed by Verleye and Dupret [4,9,40,53] (which is very close
to the model of Bay and Tucker [81 ]) extends the thermal model of [ 107]. Shear
1384
deformation is neglected when the suspension crosses the front region. Consider
in Figure 10 an elementary parallelipiped entering the front at level z 1 and leav-
ing it at level z 2 , and let (dx 1,dy 1,dz l) and (dx 2 ,dy E ,dz a) stand for the initial
and final side lengths of this material volume (which remains a parallelepiped
since shear deformation is neglected). The deformation gradient F~/(l-a) from
z I to z a can be expressed in terms of the profile function to and its average
defined by (67) and (68). Indeed, from mass conservation, the relation link-
ing the associated pairs (Zl, z2 ) is Sz 2 ( ~ - (3.)(Z))dz - O, from which it results
1
-- ~" -- ('O(Z2) 0 0
(.O(Zl) - ~
r__,lF,~l_2)/ _ 0 1 0 (86)
L -J j
0 0 - o~(zl)-~
~" _ (.D(Z 2 )
from (87.2), and then FiCA 1) from the result by means of (87.1) provides after
some calculations the relation
a (z) = (F(1-Z).a(1).a(1).F (1-2) T)l/2
(88)
tr[F ]
where the conditions (15.1) and (16.1) have been taken into account. The foun-
tain flow model of [40,53] consists in using the jump condition (88) as an orienta-
tion front condition for the layers moving slower than the front. Whereas quite
restrictive assumptions were introduced to establish (88), this model can efficient-
ly be used in more general situations, in particular when the fibers are not parallel
to the midsurface or when fiber-fiber interaction is not negligible.
The above model can also be used in the presence of other singular regions,
such as abrupt changes of thickness or midsurface bifurcations (Figure 10). Con-
sidering the theory of singular regions developed in Chapter IM, this methodolo-
gy provides a convenient way to treat all the boundary and jmnp conditions asso-
ciated with the prediction of fiber orientation in Hele Shaw flows.
On the other hand, there is, in principle, no fountain effect when the 2D plug
flow model applies. Nonetheless, bifurcations and abrupt changes of thickness
can be treated by using the above orientation jump model. As an example, the
deformation gradient tensor Fij(1-2) across an abrupt change of thickness is
0 0
/]7(1-2)/ -- 0 1 0 (89)
t'ij _
0 0 h2/h 1
where 2h 1 and 2h 2 denote the upstream and downstream thicknesses. The ex-
pression of Fij (1-2) provided by (89) can be introduced into (88) for calculating
the jump of aij. Applying this model to long-fiber suspensions however requires
some caution. In particular, experiments indicate that the velocity profile is not
completely flat in some circumstances [67,102,105], with a consequently low, but
non-vanishing fountain effect (in which case the fibers in the front zone can be
bent across the whole gap [33,105]), while a plug flow is clear in other cases
[38]. The model to be selected therefore depends on the material (SMC, BMC,
GMT ...) and the processing conditions. Additional modelling effort is needed.
1386
r
0.8
I
" Point A
Num. a~ m
Exp. al,
0.2
2h = 3.18 mm
0.0
-0.2
-0.4
-1.0 -0.6 -0.2 0.2 0.6 1.0
m
, 1.2 | i |
-0.2
i i i i i | I I I -0.4 i i i i I I I I i
- 1.0 -0.6 -0.2 0.2 0.6 1.0 - 1.0 -0.6 -0.2 0.2 0.6 1.0
z~ z~
Figure 11. Filling of a short-fiber reinforced nylon disk" sketch of the part, and
numerical and experimental profiles of a l l ( = arr ) and a13 ( - arz ) across the
gap 9 (a) r - 19.7 m m ; (b) r - 36.2 m m ; (c) r - 47.5 m m . (From [4]).
1387
(a) Num. a , l - -
W = 25.4 m m 1.0 Exp. al~ ,*--,
0.8
L = 20_3._2 m m
B
C 0.6 t
0.4
-0.2
-0.4 I I I I ,,,
Point B
9 I___
9 9 " " I L_ \' ~f~----' I ' ! I
9 !
, -0.2 ~ - - - - - - - - ~ - - - - - - - -
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
z~ z~
Figure 12 Filling of a short-fiber reinforced nylon strip" sketch of the part, and
numerical and experimental profiles of al 1 (-- axx ) and a13 (-- axz ) across the
gap 9 (a) x - 9.1 mm; (b) x - 54.1 mm; (c) x - 167.0 mm. (From [4]).
tions, except near to the gate. In Figure 11, the thickness of the core region and
its evolution are quite well predicted. Furthermore, the correct fountain flow and
frozen layer treatments induce very good prediction of the orientation in the skin
and shell layers (whose mastery is essential for realistic prediction of the product
thermo-mechanical properties [7]). Around the gate, orientation was never pre-
dicted accurately since, as the Hele Shaw model is no longer valid in its vicinity,
the temperature, pressure and orientation fields were approximated as inlet
boundary conditions into the cavity. Fortunately, the effects of shearing and elon-
gational flow rapidly erase the discrepancies downstream from the gate.
Bay and Tucker [81] also investigated the injection of a film-gated strip (Fig-
ure 12). The general orientation behavior was well captured by the simulations,
and some orientation components were correctly predicted, while the correlation
between experiments and simulation was of lower quality for the other compo-
nents (see Figure 5 in [8 lb]). The origin of this discrepancy must again be found
in the use of the hybrid closure. For the same problem, Verleye [4] obtained
excellent agreement by using the natural closure approximation, the only discrep-
ancies being observed near the gate (in point A of Figure 12).
It should be noted that the layered structure obtained by simulation and experi-
ments is similar to that of the center-gated disk, except that there is no longer a
skin layer. Along the mid-plane, the core orientation is not significantly modified
after the fibers exit the gate. Near the walls, in the shell layers, shearing aligns
the fibers in the flow direction. The thickness of the different layers changes
along the flow, this change being a function of the flow rate, the gap thickness
and the polymer material properties. Near to the cavity extremity, Bay and
Tucker [81b] predict a core layer thinner than the experimental one, and this
might be related to the fountain flow model implemented. However, the effect of
the packing stage, and possibly the in-plane viscosity, which are not considered in
[4,42,81 ], should be analyzed before drawing final conclusions.
The parameter analysis of Bay and Tucker [8 lb], confirmed by Verleye [4], pro-
vides key information, for various shapes, about the influence of the injection and
material parameters on the orientation field. The process parameters that
significantly affect fiber orientation are identified, together with the physics to be
included in the model for good orientation prediction. The influence of the wall
temperature proves to be limited [49,81b,104], although it has some impact that
will not be detailed. The inlet temperature has a reduced effect because it can
only vary over a narrow range. The effect of the flow rate is much more signifi-
cant, since it govems the thickness and orientation of the skin layer, which could
even disappear in very fast filling processes [81b,110,111]. This last conclusion
is directly drawn by comparing the fast filling of the film-gated strip and the slow
1390
filling of the center-gated disk. Conversely, the transition between the core and
shell layers is less stiff in the case of fast filling than for long injection times. Bay
and Tucker [81b] finally observed that the sensitivity of fiber orientation to the
velocity profile and the polymer rheology is high, basically since the orientation
profile cannot be accurately predicted if the velocity profile is inaccurate.
With a view to investigating the role of the suspension rheology, Chung and
Kwon [49,50] developed a simulation program to predict the injection of short-
fiber reinforced thermoplastics in arbitrary 3D mold cavities. Their lubrication
flow model was based on combining the Hele Shaw approximation with the Dinh-
Armstrong model, in order to couple the velocity and orientation predictions. The
hybrid closure approximation was used. The filling of a tension test specimen
and a center-gated disk was analyzed. The presence of different layers across the
thickness was well predicted, and the same conclusions as Bay and Tucker [8 l b]
were obtained from parametric analysis.
Figure 13 (next page). Filling of a thermoset box: (a) finite element mesh; (b)
successive fronts; (c, d) predicted fiber orientation from 2 viewpoints; (e) experi-
mental orientation. (From [4]).
1391
1392
Figure 14 (next page). Compression molding of a container" (a) initial load and
successive flow fronts; (b) final fiber orientation field; (c, d) comparison between
the mechanical effect of the flow-induced orientation (c) and a reference case
with planar isotropic orientation (d) (isovalues indicate the von Mises stress, and
w is the camber); (e) example of temporary mesh; (f) transient orientation field
during filling. (From [7]).
This section will be closed by recalling that the ultimate aim of fiber orientation
prediction in molding or other forming processes is to correlate the thermo-me-
chanical properties of the product with the final orientation distribution in the part
and the processing conditions. A single example, from the work of Lielens et al.
[7,112], will be considered to illustrate this issue, which is beyond the scope of
the chapter. See also [5,6]. Using the predicted fiber orientation distribution
represented by the 2nd-order tensor aij, the authors developed a homogenization
theory in order to evaluate the stiffness, thermal stress and thermal conductivity in
multiphase composite parts with inclusions of arbitrary orientations. It is worth
noting that orientation averaging over the aggregates was directly performed by
using the aij and aijkl tensors, the latter being estimated by means of the natural
closure approximation.
The simulation results, which concern the compression molding of a 5mm thick
container, are depicted in Figure 14. In view of the part's symmetry, only one
quarter of the geometry is represented. In this problem, the abrupt contraction
located at the border of the upper horizontal face, and whose thickness ratio
changes when compression progresses, has a strong impact on the downstream
orientation distribution, which in tum direcly affects the thermo-mechanical
properties in the molded part. Using these results, it was possible to calculate the
reaction of the container when clamped on its lower horizontal face and loaded
with an internal pressure of 1 bar [6,7,112]. The computation software SAMCEF
was used for that purpose.
This chapter was first devoted to analysing the general behavior of fiber
suspension flows, with a particular attention focusing on the decoupled prediction
of the fiber orientation evolution in a Newtonian solvent. Since orientation
1393
1394
tensors represent the best approach to model fiber orientation, the closure approx-
imation problem has been investigated, and the theory of the natural closure ap-
proximation has been thoroughly developed. The second objective of the chapter
was to review the models and numerical algorithms that are available to predict
the fiber orientation distribution in injection and compression molded parts. The
particular techniques implemented in the MOLDSYS software in order to per-
form decoupled orientation predictions have been detailed (the flow problem is
addressed in a companion chapter). Several examples, including successful
experimental validations, demonstrate the quality of the models and numerical
methods that have been elaborated
Besides the authors of this chapter, several people participated in this research,
including Marcel Crochet, Alain Couniot, Laurent Dewez, Hubert Henry de Fra-
han, Bernard Languillier, Gregory Lielens, Pascal Pirotte and Luc Vanderschuren,
whom the authors wish to thank here for their contributions. The work was
carded out within the framework of the "Multimat6riaux" project of the Walloon
Region of Belgium, the program of Intenmiversity Attraction Poles initiated by
the Belgian state and the COST 512 European project, and in collaboration with
the Shell Research and Technology Center in Amsterdam (the Netherlands) and
the Owens Coming company in Battice (Belgium). Grants from the IRSIA
(Belgium) are acknowledged. The authors wish to thank Natasha Van Rutten for
the drawing of several figures, and Jacques G6rard, Emile Franck and Jacques
Bleyfuesz for their help and advice in performing the molding experiments. The
efficient page setting work of Victor Vermeulen was also appreciated.
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Blends and Composites in Multiphase Systems, American Chemical Soc.,
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2. C.L. Tucker lJ/, J. Non-Newtonian Fluid Mech., 39 (1991) 239.
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in Polymer Composites Manufacturing, Elsevier, Amsterdam (1994) 147.
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1398
R E C E N T A D V A N C E S IN T H E R H E O L O G Y OF FLUIDIZED
MATERIALS
1. INTRODUCTION
Figure 1. Variation of the pressure drop as a function of the average air velocity
and height of the fixed silica sand bed [5].
Slugging is a flow regime in which gas bubbles increase to the diameter of the
fluidization chamber. The slugs of solid particles will move upward in a
pistonlike manner, reach a certain height, and then rain through the gas phase in
the form of aggregates or as individual particles. In group A of Hovmand-
Davidson's [ 16] classification, air slugs rise through the bed of particles which
rain down through the void to allow its upward motion. In group B, the upward
movement of the interface is slow and is caused by particles raining down
uniformly through the disperse regions. A slug flow of group A is analogous to
the flow of the two-phase (gas-liquid) system. Therefore the group A slug flow
has been studied thoroughly. A slug flow of group B occurs at certain values of
the bed height to diameter ratio (H/D) and the superficial velocity of gas. To
predict the slug flow regime some investigators introduce an "equivalent bubble
diameter" which is about 1/3 - 1/2 of the bed diameter.
The effect of slugging regime on the energy loss in fluidized beds has been
investigated analytically and experimentally by Bakhtiyarov and Overfelt [15].
Based on Meshchersky's model of motion of a body having variable mass and
the B lake-Kozeny-Carman equation of porous media flow, the following
expression for friction coefficient as a function of the Reynolds number, void
factor, gas velocity, sizes of the slug and fluidization chamber has been
obtained
1403
10000
0 h=7cm
o h=18.4cm
!_
A h=33.65cm
o - - " ' e q u a t i o n (2)
0
t~
lie
C" 1000
o
,m
~0
!._
lie
100
10 100
Reynolds Number
X = 321/{Re [1- [~4 -I- (1- 1~2)2 / In 13 + 8 e3 132/ 5 R z S 2 (1- e)2]}, (3)
Also experiments were run in the fluidization chamber (Figure 2) with silica
sand at different values of the fixed bed height, pressure and air flow rate [15].
The study of the slug motion dynamics demonstrated that both the drag
coefficient and the resistance factor decrease with increasing the Reynolds
number and the porosity of slug. At a given Reynolds number, the values of the
friction coefficient and the resistance factor are higher than for fluidized bed
with large value of the fixed bed height (Figure 4). There is a qualitative
agreement between the experimental data and predictions, with better agreement
at lower values of Reynolds number.
One of the major complications in the fluidization of materials is a tendency
towards radial segregation in the bed. Segregation is a state of the fluidized bed
in which a larger proportion of solid particles is found in one region than in
another one. In many experimental studies of gas-solid particles two-phase
flow the radial segregation phenomenon has been observed, where a fluidized
bed comprises a rapidly rising core with a low concentration of solids and an
annulus region near the column wall where the solids concentration is higher.
The research literature related to segregation phenomena and published before
1985 was reviewed by Nienow and Chiba [17]. Shape factor, density, moisture
content, size and size distribution of the solids are the main factors that affect
segregation tendencies.
Nienow, Naimer and Chiba, [18] concluded that the distributor design has a
significant effect on segregation tendencies. According to their results,
standpipe and perforated plate distributors provide better mixing than a porous
plate at the same superficial gas velocity. To predict the presence of
segregation during fluidized bed operations Delebarre, Pavinato and Leroy [19]
introduced an index based on pressure losses along the fluidized column.
Introducing suspended particle distribution coefficients, Hong and Tomita [20]
presented a model for high density gas-solid stratified pipe flow, in which the
particle-particle interactions between the suspension and the sliding bed were
taken into account. They found that particles begin to drop out of the gas phase
at the saltation point. The impact of the inlet configuration on the rate of
segregation of particles to the wall and the internal recirculation during the
steady, developing flow of gas-solid suspensions in a vertical tube were
investigated numerically by Pita and Sundaresan [21]. Examining the three
inlet configuration (uniform, core-annulus and circumferential), these authors
conclude that a circumferential injection of gas has a favorable effect on the
flow in the sense that it can decrease the extent of internal recirculation, and
hence, the segregation of particles to the wall. Dasgupta, Jackson and
Sundaresan [22] analyzed the time-smoothed equations for the motion of dense
1405
0 h=18.4cm
9 [] h=33.65cm
!....
o 10
.0 . . . h=18.4cm (eqn.3)
t~
tl. 9
~: h=33.65cm (eqn.3)
,,i.I
0
=
9 "~
,,_ 1
N
0.1 . . . . . . . . ~ ~- . . . . . .
10 100 1000
Reynolds Number
Figure 4. Variation of friction factor with Reynolds number at slug flow regime
[15].
Rhodes, Zhou and Benkreira [23] and Bakhtiyarov and Overfelt [24]
developed semi-empirical models for radial segregation of solid particles in a
circular tube. According to the models proposed, the radial distribution of
solids is dependent on the average solids concentration as
where C~, C 2 and n are constants (C~ = 1, [14, 15]; C2 = 2, [14, 15]; n = 2, [14];
n = 3, [15]).
In Figures 5 and 6 the radial solids concentration profiles predicted by
theoretical analysis [23, 24] are compared with experimental data of different
researchers [24-29]. As seen from these figures, there are qualitative and
quantitative agreements between the experimental data and the theoretical
predictions.
Spouting is a state of fluidized bed in which a fluid jet at high rate pierces
through the bed and a central channel is formed. The spouted bed is limited to
relatively large solid particles and mainly is affected by construction of the
1406
9 U=3.8m/s [27]
A
I
2.5
.= [] U=4.0m/s [28]
~o
!
2 9 U=3.3m/s [26]
A U=O.2m/s [25]
1.5
A
0 U=1.3m/s [24]
r! 1 0 U=l.7m/s [24]
qlI
[] U=2.3m/s [24]
~" 0.5
"~" --"theory [23]
theory [24]
0 0.2 0.4 0.6 0.8 1
rlR
fluidization chamber. Bakhtiyarov and Overfelt [30] reported the results of the
theoretical and experimental analyses of the spouted bed concerning the
influence of the design parameters of the fluidization chamber on the
hydrodynamic characteristics of the fluidized bed. The friction factor was
expressed as a function of Reynolds number, as following
Introducing a new mean drag law for the solid particles, Singh and Joseph [36]
proposed one dimensional model of fluidized beds where the fluid and solid
momentum equations are decoupled. The linear stability analysis of the model
shows that uniform fluidization is unstable even when the force acting on a
solid particle is assumed to depend on the area fraction. The results of this
analysis agree with the experimental results.
A theoretical model for the fully developed flow of gas-solid suspensions in a
vertical tube was developed by Sinclair and Jackson [37]. Over the whole range
of co-current and counter-current flows, they predicted the relation between gas
pressure gradient and the flow rates of the two phases. A drag force between
the gas and the solid particles is a function of their relative velocity. The
existence of the mutual interactions between the solid particles through inelastic
collisions has been reported. The model has been expanded by Pita and
Sundaresan [38] for gas-solid suspensions flow in vertical tubes of different
diameters.
The flow of gas-solid suspensions in ducts of arbitrary inclination was
considered by Ocone,Sundaresan and Jackson [39].These authors conclude that,
as a result of the compaction due to gravity, it is necessary to take into account
forces transmitted between particles at points of sustained, rolling and sliding
contact.
Tu and Fletcher [40] reported the results of numerical computations and
comparisons with the LDV measurements of earlier experiments for turbulent
gas-solid particle flow in a 90 ~ square-sectioned bend. The comparison of the
mean velocity profiles of both the gas and particulate phases gave good
agreement with the LDV measurements. Authors predicted the localized high
particulate concentration near the outer curve of the bend that occurs at large
Stokes numbers.
3. R H E O L O G Y OF FLUIDIZED MATERIALS
> 2.5 I xI
r
Q,)
i
2
qlm
1.5
A
I"
0.5
0
0 0.2 0.4 0.6 0.8 1
rlR
1000
It.
100
10 i i * * . * 9 .
was significantly less viscous as the gas flowrate was increased and particle size
was decreased. The addition of particles of large size had little effect on the
viscosity, but the addition of negligible amounts of fine particles significantly
lessened the viscosity. Trawinski [42] suggested an interesting model to
explain this phenomena. According to his model, fine particles act as "ball
bearings" between moving surfaces. Later, Kramers [43], Furukawa and Ohmae
[44], Shuster and Haas [45] and Grace [46] reported viscosity data also using
Stormer viscometers obtained with fluidized beds. The viscosity data actually
reported by a Stormer viscometer are the weights required to spin the immersed
paddle at a certain angular velocity. A different approach using a falling sphere
was applied by Peters and Schmidt [47] and Trawinski [42]. Applying the hole
of the liquid state, Trawinski [42] also analytically described the fluidized bed.
The following formula has been proposed to predict the effective viscosity of
the fluidized system
Estimated values of the apparent viscosity were found to coincide with those
obtained in [46, 54].
Murray [55] predicted the apparent viscosity of a fluidized materials by
estimating the friction factor for rising bubbles. A method based on pressure
measurements as a bubble rose through a fluidized bed was reported by Stewart
[56]. Row and Partridge [57] estimated the apparent viscosity of a fluidized bed
through the bubble size measurements.
According to Sch~gerl, Merz and Fetting [54] only the viscosity data
measured by a torsional pendulum oscillating at low amplitudes or by Couette
viscometer at low angular velocities of the inner cylinder can be considered as
quantitative. Capillary tube viscometers are preferred when the data are to be
used for pipe flow problems, and rotational viscometers, which subject the
material under the test to a precise and uniform rate of shear, have definite
advantages in the analysis of complex systems [58].
Simple mathematical models cannot at present describe the general flow
behavior of fluidized materials. The apparent viscosity of the fluidized material
is a multiparametric function and is dependent on the physical and chemical
properties of both the solids and the aerating fluid. Fluidized materials are
particularly complex and, if numerical simulations of the behavior are to be
reliable, it is critical that the measured values be consistent regardless of the
measurement techniques applied.
Bakhtiyarov, Overfelt and Reddy [58] presented the results of the experimental
study of the "apparent viscosity" of fluidized silica sand utilizing both
Poiseuille flows (capillary viscometer) and Couette flows (rotational
viscometer). Viscometric measurements by capillary tube viscometers were run
in the system shown schematically in Figure 8.
The system consists of a clear acrylic cylindrical chamber 457.2 mm long and
69.85 mm inside diameter which is sealed at the top and bottom. A funnel with
an angle of approach 57030 , was attached at the bottom of the cylinder.
Precision-bore copper capillary tubes of 4.7625 mm and 7.9375 mm inside
diameters and five different lengths (L/D = 15.328, 30.656, 61.333, 122.667 and
245.334) were screwed into the funnel exit. Air at a carefully controlled
constant pressure was admitted through the top plug of the chamber. The rate
of flow of solid particles is typically measured by collecting a sample over a
measured time and determining its mass. The experiments were run using both
non-coated capillary robes and capillary tubes coated (to prevent wall slippage)
by sand of the same particle diameter of sample to be tested. Water and 50/50
glycerol/water mixture were used as calibrating liquids.
1411
Ta=4 Q / p r ~ R 3 = 4 t ~ / R , (7)
Xa= AP R / 2 L . (8)
In the case of sand flow, the capillary viscometer technique determines the
apparent viscosity as the averaged value of all inner local viscosity. The value
of the apparent viscosity is obviously a function of the shear strain rate q(a-
1413
Figure 10 shows the results obtained using the Brookfield viscometer for silica
sand (0.212 mm < dp < 0.425 mm) at different bed void factors. As either the
shear rate or the bed void factor (air flow rate) increases, the apparent viscosity
decreases. The apparent viscosity is most sensitive to shear rate and voidage
effects near incipient fluidization. Thereafter, the rate of decrease lessens.
However, the measured viscosity was only slightly affected by changes in
particle diameter for the diameters investigated.
The apparent viscosity can be correlated with the apparent shear strain rate in
the usual way as [58]
Qp = kl d z'5 , (11)
Figure 10. Apparent viscosity of fluidized sand bed as a function of the shear
rate and void factor [58].
10000 0
W
o 50 rpm [58]
a.
E [] 100 rpm [58]
[] 0
~, [ 5 4 ]
o
0 oo
o 1000 []
(/) /1
[] /1
[]
e-
G)
12,
<
100 ' ' ' ' ''"~ ' ' . . . . . . . . . . . . . . .
~o ~oo ~ooo ~oooo
~ 0
.=
0.8
ll_
.=_o 0.6
0.4
...__.o...-.-=-.---
0
0.2
The apparent viscosity of sand particles (0.425 mm < dp < 0.710 mm) obtained
on both the rotational and the capillary viscometers as function of the apparent
shear rate is shown for comparison in Figure 13. Regardless of the method of
measurement, there is a general consistency in the data obtained with the
Brookfield viscometer (low shear rates) and capillary viscometer (high shear
rates). As seen from this figure, the apparent viscosity can be satisfactorily
correlated with the apparent shear rate by the following empirical power law
equation:
'qa = K~ ~r . (13)
forces by assuming that the interaction force between two solid particles is
equal to the overlapped volume force from the elastic contact between the
particles. To stabilize the numerical solution, they introduced a friction-like
energy-dissipation mechanism in the contact algorithm.
Figure 13. Apparent viscosity of sand bed as a function of the apparent shear
rate [58].
Hjertager [66] computed axial solid velocity, void factor and solid shear
viscosity in the riser of a circulating fluidized bed. The radial profile of solid
shear viscosity computed by the turbulent kinetic energy model was lower in the
core than that found experimentally, but with a linear function of solid volume
fraction in the measurement, the computed profile agrees well with experiments.
Delassade [67] considered the fluidized bed as a mixture of a micro-stretch fluid
representing the particulate phase, and a Newtonian fluid. The effect of particle
inertia and other consequences of non-negligible spatial gradients of velocities,
concentration and void factor on vertically propagating concentration waves of
small amplitude has been analyzed. Scht~gefl [68] carried out the flow equation
of fluidized systems from the shear diagrams using the method of Pawlowski
[69]. According to his results, the apparent viscosity of the particle-gas
suspension is independent of the flow rate at all particle diameters. However,
although the viscosity is independent of the particle diameter at particle
diameters dp > 0.100 mm, the viscosity decreases with decreasing particle
diameter at particle diameters dp < 0.100 mm. Reviewing a number of
expressions proposed for correlating fluidized bed viscosity with overall bed
void factor, Johnson [70] proposed that the fluidized bed viscosity is related to
bed voidage by
Figure 14. Viscosity ratio ~ = Tla.k.]Tla.sh.as a function of the apparent shear rate
and particle diameter [73].
An apparent viscosity model based on the integral characteristics of the radial
segregated fluidized beds has been developed by Bakhtiyarov and Overfelt [75].
Assuming that (i) the flow is laminar and steady on either side of the interface
between core and annular space, (ii) the interface is stable and smooth, (iii) the
pressure gradient is constant, (iv) end effects and a mass transfer between core
and annular flows are negligible, it has been determined that the apparent
viscosity of the segregated fluidized bed is a function of the viscosity and
density ratios of the core and annular flows. This embodies the effects of the
grain size and shape factor of particles, rheological characteristics and relative
velocity of the fluidizing fluid giving
where 1"1 and p are viscosity and density ratios of the core and annular flows,
respectively; and Xo is a dimensionless radius of the core.
50
m
Ix. 40
W
G)
L_
30
L_
m
0
I
I
... 20 I
G}
t_
m
Q.
a. lO
0
500 1000 1500 2000 2500 3000
Apparent Shear Rate, 1/s
16
w
== 12
o.
E
u 8 ,,~
-_ 9
13... " ~ -'~ .6 ~'' .'~;~ "
<
F.
I:_,. .- - , ' - " " "
ii ii ~ l " II ..... =_.,. . . . . . . . .
/
/
Figure 17. Variation of the dimensionless apparent viscosity (1/~t) with the
parameter 1"!, a ratio of the viscosities in core and annulus regions, and with the
dimensionless radius of the core (x0) [75].
acceleration cycles in all three directions for each parabola during the flight
maneuvers of the KC- 135.
250
200
150
=I.
100
50
0
0 20 40 60 80 100
Figure 18. Comparison of the experimental data [24] and theory [75] for the
dimensionless apparent viscosity as a function of the parameter 11" x0 = 0.5, !"! -
u0= 1.25 m/s, A - u0= 1.70 m/s, O - u0= 2.25 m/s.
The experimental set up, presented in Figure 19, was specifically designed and
built with the safety and portability requirements of the flight program. A
computer controlled Brookfield HADV-II+ rotational viscometer was used in
both the ground based proof and the flight experimental programs.
The advantage of the measurements in reduced or increased gravity conditions
is the possibility to change the buoyant weight of the system at the same fixed
bed height and voidage. Figures 20 and 21 show the variations of the
expanded bed height to the fixed bed height ratio and the overall voidage,
respectively, with the air velocity at three different values of the gravitational
acceleration during the fluidization of the silica sand particles tested (dp < 0.212
mm and 0.600 mm < dp < 0.710 mm) where data pertained to the g = 9.81 m/s 2
were obtained in the ground based experiments [78]. As seen from these
figures, the particle diameter plays a predominant role in expansion of the bed
and the void factor. The bed expansion and the voidage also show strong
dependence on the gravitational acceleration which has an increasingly larger
effect on bed expansion and the void factor with increasing values of the air
velocity. Figure 22 shows the gravity effects on the air velocity required for
1424
the incipient fluidization for two solid particle sizes [78]. The experimental data
show that increasing the gravitational acceleration causes suppression of the
bed and increases the amount of gas necessary to initiate fluidization.
acceleration at a wide range of the spindle angular velocity changes (10 to 100
rpm).
Recently, experimental results obtained by Hunt, Hsiau and Hong [79] show
that the expansion of the bed increases significantly beyond a critical frequency
(10 Hz), and that the expansion does not depend on the amplitude of the
vibration. The effect of the vibrational amplitude may be significant if the ratio
of vibrational amplitude to particle diameter is significantly larger or smaller
than unity. Therefore, a more detailed study of the fluidized beds in
microgravity should include the effects of small oscillations in acceleration
under the reduced gravity conditions, called g-jitter.
0.4
"o
m
._x 0.3
u.
O.o
rfl t m
~
"o 0.I
/,.;" I
m
I A I
-031 0.1 1 10
Air Velocity, m l s
Figure 20. Variation of the expanded bed height to the fixed bed height ratio
with imposed air velocity (dp< 0.212 mm: 9 - 9.81 m/s 2, I - 11.772 m/s 2, A -
17.658 m/s2; 0.600 mm < dp< 0.710 ram: -~- - 9.81 m/s 2, r-1 _ 11.772 m/s 2, A -
17.658 m/s 2) [781.
4. CONCLUSIONS
0.56
9 /
0.44
..;"
0.4 . 9 9 9 I'''l I l 9 ..,,.l . . . 9 ,.,.
0.01 0.1 1 10
Figure 21 Variation of the void factor with imposed air velocity [78] (dp<
0.212 mm: 9 - 9.81 m/s 2, i - 11.772 m/s 2, A - 17.658 m/s2; 0.600 m m < dp<
0.710 mm: + - 9.81 rn/s 2, r-I _ 11.772 m/s 2, A - 17.658 m/s2).
0.8
o
0.6
E
0
~ D4
O
_c 0.4 -~
m ! i
8 12 16 20
Figure 22. Variation of the incipient fluidization air velocity with imposed
gravitational acceleration ( i - dp<0.212 mm; r'i _ 0.60 mm< dp< 0.71 mm) [78].
1427
250
m 200
., 0o
"ILZ~:"
~ 100 I~ XT ~ ~"'~o " ~ ' " - I
< 50
E 9I , . ' ' ~ - . . " ~-.
"
0
0 20 40 60 80 100
Spindle Angular Velocity, RPM
600
w
te 500
Ix
>;
ul 400
o
u
.w_ 300
> Vi/x i
r 200 i II
D. ~Q
o. 100 "lOm D~
< _ -~" :." ~.-.:.-..~
0 20 40 60 80 100
Spindle Angular Velocity, RPM
250
ca 200
a.
100
0
0 5 10 15 20
G r a v i t a t i o n a l A c c e l e r a t i o n , nl/S 2
600
ca 500
(g
a.
_~ 400
(n
o
o
300
r~
9 2oo
D,,
,< 100
---I ..... x .....
0 5 10 15 20
REFERENCES
44. I. Furukawa and T. Ohmae, Ind. and Eng. Chem., 50 (1958) 821.
45. W. W. Shuster and F. C. Haas, J. Chem. Eng. Data, 5 (1960) 525.
46. J. R. Grace, Can. Joum. Chem. Eng., 48 (1970) 30.
47. K. Peters and A. Schmidt, (3st. Chem. Ztg., 54 (1953) 253.
48. W. Siemes, Chem. Ing. Techn., 24 (1959) 82.
49. W. Siemes and L. Hellmer, Chem. Eng. Sci., 17 (1962) 555.
50. X. L. Wu, K. J. Maloy, A. Hansen, M. Ammi and D. B ideau, Phys. Rev.
Lett., 71 (1993) 1363.
51. E. Manger, T. Solberg, B. H. Hjertager and D. Vareide, Int. J. Multiphase
Flow, 21 (1995) 561.
52. R. M. Davies and Sir G. I. Taylor, Proc. Roy. Soc., A 200 (1950) 375.
53. H. D. Mendelson, A. I. Ch. E. J., 13 (1967) 250.
54. K. Scht~gefl, M. Merz and F. Fetting, Chem. Eng. Sci., 15 (1961) 1.
55. J. D. Murray, Rheologica Acta, 6 (1967) 27.
56. P. S. B. Stewart, Trans. Inst. Chem. Eng., London, 46 (1968) 80.
57. P. N. Rowe and B. A. Partridge, J. Fluid Mech., 23 (1965) 583.
58. S. I. Bakhtiyarov, R. A. Overfelt and S. Reddy, ASME International
Mechanical Engineering Congress, Proceedings, AMD-217 (1996) 243.
59. S. A. Gregory, J. Applied Chemistry (London), 2 (1952) 1.
60. P. A. Cundall and O. D. L. Strack, G6otechnique, 29 (1979) 47.
61. T. Aizawa, S. Tamura and J. Kihara, ASME Proceedings, PED-61 (1992)
31.
62. T. B. Anderson and R. Jackson, Ind. Eng. Chem. Fund., 6 (1967) 527.
63. J. W. Pritchett, T. P. Black and S. K. Grag, A. I. Ch.E. Joumal, 74 (1978)
134.
64. D. Gidaspow, App. Mech. Rev., 39 (1986) 1.
65. Y. P. Tsuo and D. Gidaspow, A. I. Ch. E. Joumal, 36 (1990) 885.
66. A. Samuelsberg and B. H. Hjertager, A. I. Ch. E. Joumal, 42 (1996) 1536.
67. X. A. Delassade, ASME Proceedings, AMD, 217 (1996) 251.
68. K. Sch~gefl, in "Fluidization", J. F. Davidson and D. Harrison, ed.,
Academic Press Publishing Co., London-New York (1971) 261.
69. J. Pawlowski, Kolloidzschr, 30 (1953) 129.
70. E. Johnson, Institute of Gas Engineers (London), 378 (1950) 179.
71. H.-K. Tsao and D. L. Koch, J. Fluid Mech., 296 (1995) 211.
72. C. Li and V. Zakkay, Trans. of ASME, 116 (1884) 746.
73. S. I. Bakhtiyarov and R. A. Overfelt, ASME FED SM, Proceedings,
Vancouver, Canada (1997) $245.
74. S. Ergun, Chem. Eng. Progress, 48 (1952) 89.
1432
NOMENCLATURE
Ar Archimedes number
d diameter
g gravity
K expansion coefficient
L length
P pressure (AP is a pressure drop)
Q mass flow rate
R radius of fluidization chamber or tube
Re Reynolds number
S specific surface area (surface area per unit volume of medium)
U superficial velocity
13 angle of repose
e porosity
t~ sphericity of solid particles
), shear strain rate
consistency
~, friction factor
dynamic viscosity
1"1 structural viscosity
0 included angle
p density
x shear stress
velocity
viscosity ratio
Subscripts
a apparent
1433
av average value
b bulk
B bubble
g gas
k kinetic
mf minimum fluidization
P particle
S sphere
seg segregated fluidized bed
sh shear
W wall
1435
H E A T AND M A S S T R A N S F E R IN R H E O L O G I C A L L Y
COMPLEX SYSTEMS
R.P. Chhabra
1. INTRODUCTION
During the last four to five decades, considerable attention has been accorded to
the fluid mechanics of theologically complex materials and therefore significant
advances have been made in developing better insights into the underlying
physical processes. In contrast to this, the transport of heat and mass in non-
Newtonian materials have received much less attention. It is readily agreed that
most unit and processing operations encountered in the handling and processing
of non-Newtonian materials entail temperature and/or concentration gradients
within the fluid medium, thereby resulting in the net transport of heat (or mass)
from one region to another. For instance, in many industrial applications, process
streams need to be heated or cooled and a wide range of equipment may be
utilized for this purpose ,e.g., double pipe or tubular heat excl~angers or stirred
tanks fitted with cooling coils or steam jackets. Similarly, inter-phase mass
transfer between a non-Newtonian medium and a particulate please is frequently
encountered in fixed, fluidized bed and three phase reactors used to carry out a
range of polymerisation and biochemical reactions. Further examples are found
in devolatilization of thin films, de-gassing of molten polymers, drying and
aseptic processing of liquid food stuffs, concentration of fruit juices, oxygenation
of blood, etc. Solnetimes, heat is generated in the process itself, sucl~ as in
extrusion of polymers and foodstuffs. It may too be necessary to reduce the rate
of heat loss from a vessel or ensure that heat is removed at a sufficient rate in
equipment such as screw conveyors. In most applications, it is the rate of heat
transfer within the process equiplnent which is of plincipal interest, though with
thennally sensitive materials (such as food stuffs, fermentation broths, etc.), the
telnperature profiles must be known and maximum permissible temperatures must
1436
not be exceeded. Obviously, the rate of heat (or mass) transfer and the
temperature distribution in a given application are strongly dependent upon the
geometry of flow, kinematic conditions and the physical properties of the fluid.
Indeed this interplay between these factors is fi~rther accentuated in the case of
non-Newtonian fluids due to their non-linear flow behaviour. This chapter aims
to provide a state of the art review of the currently available body of infonnation
in this field.
2. SCOPE
3. THERMO-PItYSICAL PROPERTIES
-- + (] - )CpL (2)
where ~ is the volume fraction of the solids, and the subscripts L, s and sus refer
to the values for the liquid, the solid and the suspension respectively.
The thennal conductivity, k, of these systems, on the other hand, seems
generally to be well correlated by the following expression [24-26]:
1 + 0.5(ks/kL)-~b(l-(ks/kL) )
k sus = k L 1 + 0.5 (k S / k L ) ~+b ( 1 - (k S /kL) ) (3)
The scant experimental data [28] for suspensions (~ _<0.3) of alumina (0.5 - 0.8
l.tm) particles in a paraffin hydrocarbon are in line with the predictions of
equation (4). An exhaustive review on the thennal conductivity of structured
media including polymer solutions, filled and unfilled polymer melts, suspensions
and food stuffs has been published by Durra and Mashelkar [29].
Of all the physico-chemical properties, it is the rheology which shows the
strongest temperature dependence. For instance, the decrease is apparent
viscosity at a constant shear rate is well represented by the usual Arrhel~ius type
exponential expression; both the pre-exponential factor and the activation energy
are generally shear rate dependent. It is thus customary to denote the temperature
dependence using rheological constants such as the power law consistency index
and the flow behaviour index. It is now reasonably established that the power
law flow behaviour index, n, of suspensions, polymer melts and solutions is
nearly independent of temperature, at least over a 40-50~ temperature interval
whereas the consistency index follows the exponential dependence on
temperature, i.e.,
where mo and E are evaluated using experimental results in the temperature range
of interest. Similarly, for Bingham plastic fluids, both the plastic viscosity and
the yield stress decrease with temperature in a similar fashion but with different
values of the pre-exponential factors and the activation energies. Temperature
dependencies of the other rheological characteristics such as the first and second
nonnal stress differences, extensional viscosity, storage modulus, compliance,
etc., though studied less extensively, have been discussed by Ferry [30].
The study of flow and heat transfer to non-Newtonian fluids in ducts is of both
theoretical and practical importance, owing to its wide ranging applications in a
spectrum of industries including food, chemical and polymer processing. Though
process streams are heated or cooled in a wide variety of geometries, most
studies to date have employed circular tubes and occasionally triangular, square,
and elliptic tubes have also been used. Furthennore, owing to generally high
consistencies of polymeric and other non-Newtonian systems, laminar flow is
encountered much more frequently than in the case of Newtonian fluids. Hence,
the rates of heat transfer are inherently lower under these conditions than those
achievable under turbulent conditions. The rate of heat transfer is further
influenced by the type of boundary conditions imposed, e.g., constant
1440
0z T,,, - T b
where T = T(r, z) is the local fluid temperature, T,,. is tile duct wall temperature
and Tb is the bulk fluid or mixing cup temperature. Needless to say that the fully
developed temperature distribution implies fidly developed flow.
From engineering applications standpoint, the central problem in duct heat
transfer is to predict either the rate of heat transfer, q, fiom the duct walls to the
fluid for a known temperature difference, or the fluid-to-wall temperature
difference for a given rate of heat flow. In either case, it is convenient to
introduce a heat transfer coefficient, h:
From the scaling of the field equations and the relevant boundary conditions, it
can readily be shown that for flow in a tube, the dilnensionless heat transfer
coefficient is a fimction of the Reynolds and Prandtl numbers, i.e.,
hD
Nu = = f(Re, Pr) (8)
k
1441
where Nu is the Nusselt number, Re, the Reynolds number, and Pr is the Prandtl
number. Thus, the central objective of all theoretical and experimental
investigations is to establish this fimctional relationship.lt is convenienl to begin
with the discussion of heat transfer in circular tubes, followed by a similar
treatment for non-circular ducts.
5. H E A T T R A N S F E R IN C I R C U L A R T U B E S
5.1 L a m i n a r Flow
5. l. l Fully Developed and Constant Physical Properties Case
The first generation of analyses dealt with the thennally fiflly developed
conditions and for constant physical properties, with no viscous dissipation. For
the constant heat flux conditions at the tube wall, the asymptotic Nusselt number
for power law fluids is simply given by [36]:
It is not difficult to show that another form of tllis expression is possible as [37]"
3n + 1~ ~/3
Nu = 4.36 ~ , ~ j (1o)
Yet another version was presented by hunan [40]. All these expressions reduce
to file generally accepted value of Nu = 48/11 for n = 1 and for the plug flow
condition at n = 0, Nu = 8. Analogous results for the Bingham plastic fluids have
been presented by Grigull [37] and by Matsuhisa and Bird [41].
For tile case of constant wall temperature, the Nusselt number in the therlnally
fiflly developed region is given by:
2
Nu = /31 (12)
1442
where 13~ is the lowest eigen value for the boundary value problem governed by
the equation:
1 d dZ, l 3n+ 1 1
~- d---~ F,-~j+[3~ n + 1 -~,"JZ, : 0
-1
Nu = [ 3 InS + 43n2 + 13n + 1 n(6n + 2)" Br (14)
L8(5n + l)(3n + l)(n+ 1) 8n,,I
where the subscript "vp" refers to the temperature dependent viscosity value.
Equation (15) is applicable for tit < 6. In qualitative tenns, the overall effect of
temperature-dependent power law consistency index is to enhance the rate of
heat transfer for heating and to decrease it in the case of cooling of a fluid.
1443
The conesponding expression for the case of constant wall temperature is given
by:
where 8
1-1"1
4 111z
3 rl+-g.~
for Pe > 1000 [51]. Moudachirou et al. [52] have studied the flow of Herschel-
Bulkley fluids in tubes with constant heat flux at the tube wall and presented
correlations for pressure drop and Nusselt number.
As mentioned previously, for most non-Newtonian fluids, the consistency index
is strongly temperature dependent. Therefore, any serious analysis must take into
account at least the temperature dependence of consistency index. A common
practice in Newtonian flow studies is to account for the temperature dependent
viscosity via the Sieder-Tate type empirical correlation, namely, (~tb/~t,,,)~ In
the initial studies, this approach was assumed to be applicable for non-Newtonian
fluids also [53]. Subsequent extensive numerical computations, however, clearly
bring out the deficiencies of this empirical approach [54]. Many forms of
telnperature dependence of the non-Newtonian characteristics have been used in
the literature. For instance, in the early numerical studies [54-56], the shear
stress itself was written as a fimction of temperature as:
where E is the activation energy of viscous flow. With this fonn of temperature
dependence, Christiansen and Craig [54] solved the coupled field equations
numerically for different values of n and tlle parameter ~(E)= (E/R) (1/To -I/T,,.)
where To is the unifonn temperature of the fluid at the inlet. These calculations
show that for n = I and ~(E) = 2, the Sieder-Tate equation overpredicts the
Nusselt number by 10% at Gz = 50 while it underpredicts by 11% at Gz = 5000.
This divergence rises with increasing values of ~I~(E). Positive values of ~I~(E)
implies that the fluid is being heated, i.e., T,,, > To. Subsequently, these authors
have obtained similar results for the cooling of fluids, i.e., ~II(E) < 0 [57]. Figure
1 shows representative results illustrating the interplay between various factors.
On the other hand, Forrest and Wilkinson [58,59] denoted the telnperature
dependence of the apparent viscosity as:
(20)
la= [1 + flw (T - To)]"
where jao is the apparent viscosity at the fluid inlet temperature To and [3w is the
temperature-viscosity coefficient to be evaluated using experimental data. Figures
2a and 2b show their representative results for tile constant wall temperature and
the constant heat flux boundary conditions respectively when the viscous
dissipation effects are negligible. Broadly, the telnperature dependent
1445
consistency index facilitates the heating of fluids whereas the cooling is impeded.
The effect is, however, very weak for the constant wall flux conditions.
10 3
10
v(E)= -3 x - 2 . -1 0 1 2
L. 10 2
F
101
10 ~ ...... I ,, I , ~ I ,
10 ~ lO l 10 2 10 3 10 4 lO s
Graetz Number, Gz
Figure 1 .Nusselt number as a fimction of Graetz number and ~I~(E)for n = 0.3 and
(E/RTw) = 10.
(- Ap/L)w _ [ _ ~ 1 - ~'~b(T' v~
(- ap / - (21)
For heating of fluids, i.e., b(Tw- To) >_ 0, O~'k = 20tk n/(n + ]) with Otg values
given in Table 1 and for cooling, Ot'k takes on constant values as:
1446
" ' !
i
10 3 I
13w=0 13w= 1 0 , ~ = 1.2 _
n = 0.5
101
13w = 1 0 , 4 ) = 0.91
10 ~
10 2
13w = 0 .,.
Nu
13w= 1 0 , V = ' 0 " 1
10 ~ I .... I I 1
10 ~ 101 10 2 10 3 10 4
Gz
Figure 2. Mean and local Nusselt number for heating and cooling of power
law fluids with temperature dependent consistency index (11 = 0.5).
Table 1
Values of a'k for heating [60].
In addition to the extensive numerical results, Kwant et al.[60] argued that when
the consistency shows strong temperature dependence, the only significant
parameter governing the rate of heat transfer is the shear rate at the wall. Based
on this premise, Kwant et al. [60] reconciled their results for the constant wall
temperature condition as:
Nu vp
- 1 + 0.271 In ~o + 0.023 (In ~o)= (23)
Nu
Similar expressions, though somewhat more involved, have also been presented
by Joshi and Bergles [44].
The effect of viscous dissipation on entrance heat transfer has been examined by
numerous investigators [58,59,63-73]. Since detailed discussions are available
elsewhere [33,36,69,74], only the salient features are recapitulated here. In
practice, a fully developed entrance flow condition is accomplished by preceding
the healed section with another long section. Under the conditions of significant
viscous dissipation (large Brinkman numbers), Gill [64] argued that the
establishment of fully developed flow is not feasible under the constant wall
temperature condition and therefore a plausible boundary condition can be
provided by the solution of energy equation with viscous dissipation in an
infinitely long isothennal section. On the other hand, Forrest and Wilkinson
[58,59] solved the fifll energy equation with llle viscous dissipation as well as
internal source tenns. Figure 3 shows typical results elucidating the effect of
viscous dissipation on the mean Nusselt number. Qualitatively, the study of
Fo~Test and Wilkinson [58,59] shows that even though the mean temperature of
the fluid may be lower than that of the wall, for certain values of Brinkman
number there exists the possibility of a fluid layer in the wall region with an
average temperature higher than that at the wall thereby resulting in heat transfer
from the fluid to the wall. Under these conditions, the local Nusselt number
would obviously be negative.
Some idea about the role of viscous dissipation can also be gauged from
approximate solutions [74]. For instance, for the Poiseuille flow of constant
properties power law fluids, in the so called equilibrium regime, the temperature
of the fluid becomes independent of the axial coordinate z and is a function of r
1448
alone. Under these conditions, the maximum temperature rise occurs at the
center of the tube which is given by:
10 3 !
i ia
! !
i i
!
Br=l,~=l.2
~
B r = 1 0 , ~ = 1.2
B r = 10, ~ =0.91
Br=0
Nu h
I
/
/
101 /
B r = 1 , ~ = 0.91 t
I l
10 ~
10 ~ 101 10 3 lO s
Gz
nt n (25)
,ST ] ma -- k 3n + i)'-" v"+'
R"-!
Tb(z)-Tlr-o
411+1
\5n + I t 2 /Sn+,ll3n+,// l
ATm,~ 1 - exp -
Gzz n 4,1 + 1
(26)
2000
g
al
l::
1000
.<3
0
0 0.5 1.0
n u162
Figure 4. Maximum temperature rise due to viscous heating for a power law fluid
in thennal equilibrium regime.
Dakshina Murty [85]. Schenk and van Laar [86] investigated tl~e behaviour of
Prandtl-Eyring model fluids.
60 120 -
i i
9
i
1
i i|
40 80
Gr' / Re'
20 40
[
oi 0
' ,I
1
~, I,,
2
~ O!
0
, l
1
, . .I
2
Table 2
Local and mean Nusselt numbers for simultaneously developing flow of a power-
law fluid ofn = 0.5 in a circular pipe
From the foregoing brief account, it can thus be concluded that for tile constant
wall flux condition, the analytical predictions of Bird [105] provide good
estimates of the Nusselt number for viscous and viscoelastic systems for small
values of AT, the correlation of Mahalingam et al. [62] and Deshpande and
Bishop [98] might be the best ones to use in design calculations.
1453
Turbulent Regime
Despite the fact that turbulent flow is encountered much less frequently with
non-Newtonian systems (except with the so called drag reducing dilute polymer
Table 3
Experimental correlations for laminar heat transfer
ln b
[Gz + 0.0083 (GrPr)~] ''~
o3,:,,,o
IYIb
60 1 ! , ! I I I I ' i I I "1
43 < Re < 1780 , 105 < Pr < 231 B i r d 11051
t
! n=0.73
Nuz . , _
10 I-
I
Equation(9)
2_ I I I I I ! I ~ II I I I l
101 102 103 104
St = f /2 (27)
1.2 + l l . 8 4 f / 2 ( P r - 1) Pr ''~
where the fi-iction factor, f, fimction of the generalised Reynolds number (pV 2-"
D"~/8"-~m 6n) and the power law index, n, is given by the following
equation[ 108]
(l/f) ~ = 4 n ~ log (Re f(2-,)/2) _ 0.4 n "12 (28)
Equation (27) is restricted to the condition (Pr Re2)f > 5 x 105. Preliminary
comparisons showed equation (27) to be adequate. Since this pioneering study,
many workers have reported new experimental data and/or analysis for turbulent
heat transfer to non-Newtonian systems, see [2] for an exhaustive compilation.
Based oll a critical evaluation of most previous data oll heat transfer for purely
viscous fluids, Yoo [109] put forward the following empirical correlation:
1455
Equation (29) is based on data extending over the ranges 0.2 < n < 0.9 and 3000
_<Re,, < 90,000.
More recently, Kawase et al. [110] have examined the effect of pipe roughness
on heat transfer to power law fluids. Kawase and Moo-Young [111] also re-
analysed the data of Thomas [112] on turbulent heat transfer to thorium oxide
slurries and concluded that the yield stress had an adverse effect on heat transfer.
Analogous data on TiO2 suspensions [113] shows considerable scatter, though
they attempted to develop new correlations.
Considerable attention has also been accorded to heat transfer in drag reducing
systems [2,114]. Most developlnents in this field invoke the Reynolds analogy
without any justification. This coupled with the poor reproducibility of
experimental data has impeded the development of universally valid correlations
for calculating heat transfer in these systems. Therefore, all available correlations
are too tentative to be included here. Also, most mass transfer studies relate to
dilute drag reducing systems and therefore pose similar difficulties in devising
predictive correlations [2]. Kostic [115] has provided a critical review of the
pertinent literature in this field.
Thus, in conclusion though the turbulent heat transfer in non-Newtonian systems
is of considerable theoretical significance, it is perhaps of limited practical utility,
for turbulent conditions are encountered much less frequently than for Newtonian
fluids in industrial applications.
2(n+ 1) -
~( it 5n +
,In +
n n -!
NH = (30)
2n+l
[~ (32n'- + 17n + 2)
(4n + 1)(5n + 2) (31)
Nu = (4n + l)(5n + 2)
Payvar [116] also presented an analogous expression for Binghaln plastic fluids.
On the other hand, in the hydrodynamically and thennally developing flow
regime, when the classical separation of variables method is applied to the Graetz
problem for power law fluids, a series solution is possible only for certain values
of n. Tien [117] obviated fills difficulty by using the approximate velocity
distributions deduced from file variational principle. Richardson [66] investigated
fl~e similar problem wifl~ constant thennophysical properties but included viscous
dissipation effects. His solution, however, converges only for large values of Gz
and is fires restricted to very close to fl~e entrance. Numerous other studies of
laminar heat transfer in slit geometries have been reported but all have presented
fl~eir results in gn'aphical form and therefore reference must be made to original
papers [118-123]. However, Kwant and Van Ravenstein [123] extended flleir
previous study to channel flows and presented fl~e following expressions for
pressure loss and mean Nusselt number:
!
(- Ap / L)isothemlaI
For heating, i.e., b(Tw - To) _> 0, C~'k = 2 ak n/(n + 1) where ak is tabulated in
Table 4 while for cooling
The mean Nusselt number with temperature dependent viscosity is given by:
Ntl] vp
= 1 + 0.238 In~b, + 0.0224 (ln ~bo)-" (33)
Nu
Table 4
~k as a fimction of b(Tw- To) and n in a parallel plate geometry
b(Tw- To ) n --~ 1
.....
0.75 0.50 0.33 0.2
1 .
0.105
. . .
0.109
. .
0.123 0.134 0.132
2 0.10 ,,
0.102 0.100 0.88 0.070
3 0.095 0.096 0.082 0.061 0.049
Note the increasing effect of b(T,,,- To) with an increasing degree of shear
thinning behaviour.
Aside from these studies, Lin and Shah [91] and Shulman and Zaltsgendler
[124] have studied heat transfer to viscoplastic fluids whereas Yau and Tien
[125] studied developing flow heat transfer in power law fluids.
Table 5
Fully developed laminar flow in a square duct
Note that shear thinning behaviour only marginally enhances the value of the
Nusselt number. Chandraputla and Sastri [126] also computed the values of the
Nusselt number as a fimction of the Graetz number and power law index for the
thennally developing flow in square ducts. Finally, they [127,128] also tackled
the problem of heat transfer in simultaneously developing flows. Representative
results are shown in Figure 7 for the isothennal wall boundary condition. Lawal
and Mujumdar [129] have also studied heat transfer to power law fluids in square
ducts under silnultaneously developing conditions.
Analogous results for rectangular ducts are fi~rther compounded due to the
additional geometric factor, namely the aspect ratio [34]. Few numerical studies
[130-134] and experimental data [135-137] on laminar heat transfer to purely
viscous and viscoelastic polymer solutions are available. Most theoretical
analyses assume constant physical properties; however, a notable exception being
a recent study of Shin and Cho [138] for a 21 rectangular duct. The effect of
viscoelasticity on heat transfer has been found to be small in rectangular ducts
[139]. Limited data on turbulent heat transfer suggest the j factor to be smaller
for viscoelastic fluids in rectangular ducts [140].
12
n = 0.5 Pr'= 0
Nu 8
O0
10 20 50 100 200
Graetz Number , Gz
Figure 7. Mean Nusselt number as a fimction of Prandtl and Graetz numbers for
simultaneously developing profiles for isothermal condition.
Subsequently, Lawal and Mujumdar [143] and Etemad et al. [144] respectively
have elucidated the role of viscous dissipation and simultaneously developing
flow on the laminar heat transfer to power law fluids in equi-lateral triangular
ducts. Lawal [142] also paralleled a similar study for trapezoidal and pentagonal
ducts as encountered in the extrusion of polymers and food stuffs.
6.40iher Geomeiries
In addition to the aforementioned ideal flow geometries, industrial processes
entail a great variety of complex shapes of flow passages including helical,
double-sine [145], tapered tubes and these are not readily amenable to rigorous
analysis. For instance, Jarzebski and Wilkinson [146] solved the laminar 11o11-
isothennal developing flow, lemperature dependent consistency power law fluid
flow in a slightly tapered tube to simulate the flow in extrusion dies and they
developed a predictive expression for pressure drop. Similarly, sudden
contraction also represents a geometry of considerable theoretical and pragmatic
significance in polymer processing. Christiansen and Kelsey [147] analyzed the
1460
Table 6
Fully developed laminar flow Nusselt numbers for isosceles triangular ducts
where a and b are purely geolnetric factors introduced by Kozicki and Tiu [151]
and are reproduced here in Table 7. The advantage of this simple approach
which is restricted to laminar flow is obvious.
Dunwoody and Hamill [152,153] predicted enhancement in heat transfer for 3rd
grade Rivlin-Ericksen fluids in rectilinear flow in rectangular channels. Similarly,
1461
Table 7
Duct Flows: Geometric Constants
Geometry (x* a b
0.1 0.4455 0.9510
0.2 0.4693 0.9739
0.3 0.4817 0.9847
CONCENTRIC ANNULI 0.4 0.4890 0.9911
0.5 0.4935 0.9946
0.6 0.4965 0.9972
0t* = inner radius/outer radius 0.7 0.4983 0.9987
0.8 0.4992 0.9994
0.9 0.4997 1.0000
1.0 0.5000 1.0000
0.0 0.5000 1.0000
RECTANGULAR DUCT 0.25 0.3212 0.8482
0.50 0.2440 0.7276
a * = height / width 0.75 0.2178 0.6866
1.00 0.2121 0.8766
0.00 0.3084 0.9253
0.10 0.3018 0.9053
0.20 0.2907 0.8720
0.30 0.2796 0.8389
ELLIPTICAL DUCT 0.40 0.2702 0.8107
0.50 0.2629 0.7886
0.60 0.2575 0.7725
0t* = minor axis / major axis 0.70 0.2538 0.7614
0.80 0.2515 0.7546
0.90 0.2504 0.7510
1.00 0.2500 0.7500
2~(deg)
I0 0.1547 0.6278
ISOSCELES TRIANGULAR 20 0.1693 0.6332
40 0.1840 0.6422
Apex angle = 2 60 0.1875 0.6462
80 0.1849 0.6438
90 0.1830 0.6395
N
REGULAR POLYGON 4 0.2121 0.6771
5 0.2245 0.6966
with N sides 6 0.2316 0.7092
8 0.2391 0.7241
, secondary flow patterns in flattened tubes and coils have been shown to yield
higher heat transfer to non-Newtonian fluids [154-156]. Such enhancements ill
1462
heal transfer have been observed experimentally [157]. The scant results point to
fi~rlher increases in heat transfer due to free convection in non-circular conduits
for purely viscous and viscoelastic fluids [158-160].
This section is concluded by noting that the highest value of the Nusselt number
occurs in circular tubes and then progressively decreasing as the cross-section of
flow changes to pentagon, square, trapezoidal and triangular. This trend is seen
for both shear thinning and shear thickening materials. Furthermore, if the
various geometries are ranked on the basis of the ratio of heat transfer to pressure
drop, a large value of this ratio is desired. In this ranking, for n < 1, the circular
duct is evidently superior to other shapes while short square tubes are to be
preferred for shear thickening materials [33].
Considerable research effort has been expended in elucidating the role of non-
linear flow characteristics on the rates of heat and mass lransfer in boundary
layers over submerged objects. Though theoretical results are available for
highly idealised shapes such as plates, cylinders and spheres, often this treatment
serves as a useful starting point for more complex situations encotmtered in
engineering applications. The available voluminous literature on both forced and
flee convection has been reviewed by several authors [161-165], only key
findings are summarised here.
At the outset, it is instructive to point out l~re that the flow of shear lhinning
(usually modelled as power law fluids) and viscoplastic media have been studied
most extensively, followed by the flow of viscoelastic fluids. Furthennore,
though it is realised that the momentum boundary-layer analysis for non-
Newtonian fluid is gennane to the study of the convective heat and mass transfer
in these systems, these are not included here for the sake of brevity. However,
attention is drawn to the pioneering efforts of Schowalter (1960); Bizzell and
Slattery (1962); Na and Hansen (1966) ; Lee and Ames (1966); Chen and
Radulovic (1973), etc. for power law liquids and of others [171-173]for
viscoelastic boundary layers. A cursory examination of the available reviews
reveals that thermal convection has been investigated more extensively than the
analogous mass transfer process. The three geometries that have been accorded
the greatest amount of attention are spheres, cylinders and plates, although some
authors [174-178] have attempted to develop general framework for 2-D
boundary layer flows. The ensuing discussion is presented in tlu-ee sub-sections,
namely, spheres, cylinders and plates, with fiwther classification depending upon
the mechanism of transport, e.g., free, forced or mixed convection.
1463
7.1 Spheres
7.1.1 Free Convection
The general field equations describing fiee convective heat/mass transport in
external flows and the associated difficulties, due to non-linear viscosity models,
in seeking rigorous solutions have been alluded to by some authors[31,161],
Similarity solutions are not feasible even for the simplest non-Newtonian
viscosity model, namely, power law model [166,179]. Acrivos [179] employed a
Mangler-type transformation to derive the following expression for the mean
Nusselt number for the constant temperature condition in the laminar boundary
layer region:
| B
where c2(n) is another fimction of n. Tile values of both cl(n) and c2(n) are
available in respective papers. Equation (36) was stated to be particularly
appropriate for high Prandtl numbers, as is generally the case with non-
Newtonian fluids. The theoretical developments in this field have been matched
by excellent experimental studies. Both Liew and Adehnan [181] and Amato and
Tien [182] measured the temperature distributions and the mean Nusselt numbers
for electrically heated copper spheres immersed in polymer solutions. In the
range 0.66 _<n _< 1, Liew and Adelman [181 ] reported that a single value of cj(n)
= 0.56 in equation (35) correlated their data with an average deviation of 6%.
Likewise, the experimental [182] temperature distributions around the sphere are
in line with the predictions [179]. However, they put forward the following
correlations for Nusselt number:
and
Nu = 0.49 f2 (37b)
1464
| !1
k d c,' (Qr,,,Sc,)s"-'
Shl = = 2 + - 4
(38)
1 + (0.43/ Sr ~
Witll the diminishing value of Grin, one would intuitively expect the Sherwood
number to approach the pure diffi~sion limiting value of 2. However, due to the
thin boundary layer assumption inherent in the aforementioned dleories, neither
equation (35) nor (36) approaches fills limit whereas equation (38) does. Widl
fl~e generally large values of die Schmidt number for non-Newtonian fluids, Lee
and Donatelli [185] simplified equation (38) as:
and they found tl~at c2'(l) = 0.59 provided satisfactory conelation of their mass
transfer data in the range 0.58 _<n _< 1.
where V0* is the tangential velocity on the surface of the sphere. Kawase and
Ulbrecht [195] used the approximate stream fimctions available in the literature to
deduce the value of the Sherwood number. The predicted 50-70% enhancement
in mass transfer due to shear thinning viscosity (n --- 0.7) is in line with the scant
experimental results [197,198].Beyond the creeping flow regime, little theoretical
information is available on heat and mass transfer beween a non-Newtonian fluid
and spherical particles. Based on the penetration model [199,200], Kawase and
Ulbrecht [201 ]) derived the following formula for a sphere:
1466
1,-A n-*2 1
Shl = "~" = A(n) Re,,3~.,,> Sc ~ (41)
DAB
where the values of A(n) are available in their paper; A(n=l) = 0.85. The scant
experimental results on mass transfer from spheres [202] appear to be within
+30% of the predictions of equation (41) [165].Likewise, admittedly numerous
experimental studies on forced convection heat transfer between a sphere and
inelastic power law type polymer solutions have been reported but sufficient
details are not available to recalculate the experimental results in the form needed
by theoretical analyses mentioned in the preceding section. For instance in some
studies [203,204] particles were held stationary in moving polymer solutions
while in olher stLidies [205] particles were being conveyed in moving liquid
streams. Similarly, significant uncertainty also exists with regard to the effect of
particle-to-tube diameter ratio in exerimental results. Clearly there are some
variables which are not being duly accounted for. Similarly, based on their
experimental data, Yamanaka and Mitsuishi [206] put forward the following
semi-empirical correlation for mixed convection from a sphere to power law
fluids:
2 ! 3
hd
Nu = = 2 + { (0.866o- Pe~ - 0.553o-- 0.341) -~
k
!
I n 3 2 [ l l l b ] - -3n-,-!
+ (0.44 Gr~ <~ pr~"")2 }~ (42)
\ 111.
10 2
Equation (43a)
lO~
Equation (43b) i
10 -2
10. 3 L I I | I I I _ ! !
10 -7 10 -5 10 -3 I 0 -1 101 10 3
Figure 8. Overall correlation for heat and mass transfer from a sphere
(0.32 _< n <_ 0.93).
Nu = c(n) Ra 3~ (44)
1468
now becomes Ra ~3~ > 1. Since c(n) is a weak fimction of n, the Nusselt
number rises with the decreasing value of n at a fixed value of Ra. Analogous
results for constant properties Ellis model fluid are also available [215]. The
available limited experimental results for shear thinning polymer solutions [216]
are in fair agreement with theoretical predictions over the range 0.64 _< n _< 0.93.
It is also somewhat puzzling that their results of the surface averaged Nusselt
number in carbopol solutions are virtually indistinguishable from the Newtonian
correlations provided the cylinder diameter is used instead of cylinder radius! Ng
and co-workers [214,217-219] have reported extensive results on the free thermal
convection from horizontal (thin) wires to pseudoplastic and viscoelastic fluids
for the constant heat flux condition on the wire surface. These experimental
studies differ from the analysis of Acrivos [179] and the work of Gentry and
Wollersheim [216] in an important way that the wire diameters were of the same
order as the botmdary layer thickness. For pseudoplastic carbopol solutions, their
final correlation is:
i
Furthermore, Ng and Hartnett [217,219] reported that the fluid was virtually
stagnant as ascertained by the stationary air bubbles trapped in the liquid. Under
these conditions, pure conduction is the main mode of heat transfer, and this is
borne out by their experiments. Subsequent experiments suggested viscoelastic
effects to be minor [214,218].
where c(n) accounts for both varying degree of shear thinning behaviour, and
different shapes. Subsequently, many other investigators [224,225] have
employed different solution procedures to arrive at substantially similar
conclusions [165].Mizushina and Usui [226,227]argued that the aforementioned
analysis are flawed due to the so called zero defect at the separation and
stagnlation points. They obviated this difficulty by combining the approaches of
Kannan-Pohlhousen [228] for momentum boundary layer and of Dienemann
[229] for thermal boundary layer to obtain approximate results for the power law
and Powell-Eyring model fluids. Mixed convection from horizontal cylinders
submerged in power law fluids has been investigated amongst others by Shenoy
[230] and Wang and Kleinstreuer [231].
The first experimental study in this field is that of Shah et al. [223] who
measured the local values of heat transfer coefficient and reported good
agreement with theoretical predictions, especially for large Prandtl numbers.
Mizushina et al. [232,233] measured both the rate of heat and mass transfer from
horizontal cylinders oriented nonnal to flow. Their data show good
correspondence with equation (44) and they correlated the constant c(n) as:
where A = 2.26 and m = 1/3 for Rep < 10 and A = 0.785 and m = 1/2 for Rep >
10. Equalion (48) was fotmd to be successfid not only in bringing together the
heat and mass transfer data but also the resulls for Newtonian and power law
liquids up to Re--- 25000, as can be seen in Figure 9.
Considerable interest has also been shown in studying the forced convection
from horizonlral cylinders immersed in drag reducing polymer solutions, though
results of different investigators often do not agree even qualitatively. For
inslance, James and Acosta [239] and James and Gupta [240] found that at low
flow rates, the drag coefficient and heat transfer coefficient for cylinders placed
nonnal to the flow of PEO solutions virlually coincided with the values for water
but beyond a critical flowrate (presumably Deborah or Weissenberg number),
both levelled off to constant values whereas the more recent data[241] show no
such behaviour with a Separan AP-302 solution. Numerous plausible
mechanisms including the viscoelasticity, boundary-layer thickening due Io the
solid-like behaviour at high defonnation rates, etc. have been postulated;
however, while none of these has proved to be completely satisfactory,
Ruckenstein and Ramgopal [242] developed an empirical correlation for such
anomalous data. Likewise, a few investigators have studied heathnass transfer
from horizontal cylinders rotating in drag-reducing polymer solutions [243,244]
and immersed in boiling non-Newtonian polymer solutions [245].
7.3 Plates
7.3.1 Free Convection
The theoretical treatment of Acrivos [179] results in a qualitatively similar
expression for the mean Nusselt number as that for a cylinder, equation (44).
Shenoy and Mashelkar [161] have treated in great detail free convection fi'om
vertical and horizontal plates (with isolhennal as well as constant heat flux
boundary conditions) in non-Newtonian fluids whence only the key findings are
summarised here. For instance, the scant data [216,246,247] for isothermal
surface are in line with the predictions[179,248].Shenoy and Ulbrecht [249]
presented an inlegral solution for laminar thermal convection from a vertical
surface to power law fluids under a variety of boundary conditions on the plate
surface, i.e., constant heat flux, constant temperature and temperature varying
with distance. For the constant temperature condition, their expression for the
mean Nusselt number (averaged over the plate length) is given by:
(2n + I)
10 2
I
Ur~
_ Equa,, 8, 785 J
I0 ~
A = 2.26
,m m
1,1
m = 1/3
1 0 -2
10"3 I. I I _ I ..... i i
10 "3 10 4 I0 x I0 3
Figure 9. Alternate correlation for heat and mass transfer from a sphere to power
law fluids.
where
n
(50a)
2 A. (10/3) ~j"
1
with An = (50b)
3n
6
Shenoy and Ulbrecht [249] reported good agreement between their data and
predictions. No analogous mass transfer results are available in the literature.
This sub-section is concluded by noting that most theoretical studies in this field
may be regarded as direct descendants of the pioneering work of Acrivos [179],
except for the fact that a variety of teclmiques have been employed to seek
approximate solutions.
1472
7.3.2 F o r c e d Convection
Little work has been reported on the forced-convective transport fonn a
horizontal plate/plane surface to non-Newtonian media since the study of Acrivos
et al. [174,175]. For the conditions when the thermal boundary layer is thinner
than the momentum boundary layer (a condition which is fulfilled over a
substantial part of the plate except near the leading edge). In this region (x --+ 0),
Acrivos et al. derived the following expression for the local Nusselt number:
":
More recently, a complete numerical solution for laminar heat transfer from a
plane surface (aligned) immersed in Newtonian and power-law fluids has been
carried out by Pittman et ai. [250]. The predictions and experiments show good
match for detailed temperature profiles and the Nusselt number for the constant
heat flux condition on the plate in the range (30 < Re < 2000; 50 < Pr < 400).
The corresponding mass transfer problem has been studied by Mishra et al.
[251], who employed the von Kannan integral method to solve the approximate
boundary-layer equation for power law liquids. The average Sherwood number is
given by:
(53)
l n +
Both Ghosh et al. [252] and Luikov et al. [234,235] have re-cast the results of
Acrivos et al. [174] into the equivalent mass transfer problem. While the
expression of Acrivos et al. [174] is similar to equation (52), the one due to
Luikov et al. is given below:
Luikov et al. [234,235] reported good agreement between equation (52) and
limited data.
Subsequently, Ghosh et al. [252] have reconciled the limited data on mass
transfer from plane surfaces to a single correlation as:
1473
SIlL = 3.23 Re~ Sc~ L ,,3 0.2 < ReL < 100
= 1.12 Rel '': Scl ''~ 100 < ReL < 5000 (55)
10 3 -- i I
~ I I"l I I I I ~ ~ I I ~ 'I I
4m
10 ~
~ Slope = 1/3
10-1 I J ~_ I I ~ I J ~ ] t t .I l ~ ! t t
1 0 .2 10 ~ 10 2 10 4
Figure 10. Correlation for mass transfer from a plate to power law fluids (plate
length 10 - 90 ram).
Figure l0 shows the overall conelation for different lengths of plates immersed
in water as well as in a series of CMC solutions. The co~xesponding range of
Schmidt number is 840 _< Sc~, _<2 x ] 0 6 while the power law index varies fiom 1
to 0.89 only.
Analogous boundary layer-analyses from continuously moving surfaces and/or
to the other type of generalised Newtonian fluids have been reported by Sharma
and Adelman [253], Lin and Shih [254], Gorla [255,256]. On the other hand,
Skelland [257] and Mishra and Mishra [258] have used the Chilton-Colburn
analogy to obtain approximate expressions for heat and mass transfer in turbulent
boundary layers. Forced convective heat transfer to power law fluids flow over a
rotating non-isothermal sphere has been analyzed [259] and as expected the
rotation yields higher values of the Nusselt number, as also noted previously by
other investigators [231]. More recently, Ruckenstein [260] has re-examined
1474
Packed and fluidized beds are widely used in chemical and polymer processing
applications to affect a variety of operations including mixing, filtration and
chemical reactions. Despite their overwhelming pragmatic significance in the
handling of non-Newtonian materials, very little information is available on
liquid-solid as well as bed-to-wall heat and mass transport with non-Newtonian
systems. For instance, Kawase and Ulbrecht [201] developed a semi-theoretical
expression for Sherwood number describing the mass transfer between power
law liquids and a packed bed of spheres and they reported satisfactory
correspondence between their predictions and limited data. On the other hand,
Kumar and Upadhyay [262] and Wronski and Szembek-St6eger [263] carried out
experimental works on liquid-solid mass transfer in packed beds and put forward
the following empirical correlations.
Kumar-Upadhyay
0.765 0.365
ej = + (56)
Rel '~: Re, ~"
Wronski-Szembek-St0eger:
~j= 1
0.097 Re ~ + 0.75 Re~ 6' (57)
72000. Note that equations (56)and (57) are also valid for short cylindrical
pellets (L/D <--- 1) provided an equal volume sphere diameter is used in lieu of
sphere diameter. Hilal et al. [264], on the other hand, proposed the use of (6/a,.)
where av is the specific surface area. Coppola and BNam [265] have studied
mass transfer from a bed of screens to power law fluids.
500
Equation (56)
100
"~ 10
Equation (57)
1.0
0.1
I 1 I .... l I , r J
The effect of drag reducing additives on mass transfer in packed bed reactors
has been studied by Sedahmed et al. [266]. Depending upon the type and dose of
the additive, they reported up to 50% reduction in mass transfer. Similar
deterioration in gas-liquid mass transfer has also been reported by others [267].
Likewise, convective heat and mass transport in fluidised beds have received
only very scant attention. For instance, Kumar and Upadhyay [262] asserted
equation (56) to be applicable to fluidised beds also. More recently, Hwang et
al. [268] reported new experimental data on liquid-solid mass transfer in fluidised
beds and found equation (56) to over-estimate the value of j factor at low
Reynolds numbers (see Figure 12). They found it necessary to develop the
following new correlation (0.01 _<Re~ _<600; 0.915 >_n >__0.63):
No such results are available on heat transfer and for viscoelastic media.
50
Equation (58)
10
O
Equation (56)
0.1
|
0.01 [- I , ! t ~ .
Reynolds Number, Re I
Figure 12. Overall correlation for liquid-solid mass transfer in fluidized beds.
9. ]VIISCELLANEOUS GEOMETRIES
Beside the simplified geometries dealt with in the preceding sections, numerous
other configurations have been studied in the literature. While, it is not possible
to include all such studies in this review; some key references are provided here
for the benefit of the interested reader. The subject of heat transfer in
mechanically agitated vessels used for the heating/cooling of process streams has
been reviewed by several authors [74,269,270]. The CO~Tesponding literature on
gas-liquid mass transfer with non-Newtonian liquids in bubble columns and
packed towers has been summarized in many papers [271-274]. Heat transfer in
boiling non-Newtonian fluids has only begun to receive systelnatic attention [275-
280] and thus far only preliminary results are available on different flow patterns
and critical heat flux, etc. Similarly, the thennal perfonnance of compact heat
exchangers and their fouling characteristics with non-Newtonian polymer
solutions have been studied only in a cursory manner [145,281,282]. Thermal
effects in the extrusion of food and polymer extrusion have been reviewed
recently by Jaluria [283].
1477
From the aforementioned discussion, it is clear that in the laminar region tlle
shear thinning enhances heat transfer and reduces pressure drop as compared
with a Newtonian fluid. Shear thickening produces the opposite effect. The
temperature dependent viscosity facilitates the heating of fluids while it impedes
the efficacy of cooling of fluids for shear thinning materials. Likewise, a
significant degree of viscous dissipation aids in the cooling of fluids with the
opposite effect in the heating. Furthermore, in situations with Br > 0, inespeclive
of the heat transfer mechanism at the wall, the local Nusselt number attains an
asymptotic value, about three times the value predicted for forced convection. In
horizontal flow, the natural convection increases both heat transfer as well as
pressure loss above those expected from the pure forced convection analyses.
While from a heat transfer standpoint, the circular geometry is the most efficient
one but when pressure loss is also of concern, short pipe lengths are to be
preferred. Besides, under certain conditions, square pipes offer a good
compromise between high heat transfer rates and low pressure drops, particularly
for shear thickening fluids. Experimental work in this area of duct flow is trailing
behind the great strides made in theoretical developments.
Heat and mass transfer in laminar boundary layer flows have also witnessed
remarkable years of progress. Consequently, sound theoretical frameworks are
now available for the prediction of heat and mass transfer from simple geometries
such as spheres, cylinders and plates, at least to purely viscous type non-
Newtonian materials. Available experimental results, while essentially in
agreelnent with the predictions, do not seem to cover anywhere near as wide
ranges of kinematic conditions as encompassed by the corresponding expressions
for Newtonian media.
Considerable scope exists fi~rther developments in this rugged terrain of non-
Newtonian fluid mechanics. For instance, the role of fluid elasticity is not at all
clear both in internal flows in ducts as well as in boundary layer flows. For
instance, secondary flows are ta~own to exist in non-circular ducts even in
creeping regime but it is not yet fully known how these impact on heat/mass
transfer. The question of stability has hardly evoked any interest. Furthermore,
most heat transfer studies employ either the constant wall temperature or constant
heat flux condition, whereas in practice the actual conditions may be somewhere
in between these two idealizations. Also, the flow patterns and heat/mass
transfer phenomena in systems of practical importance including packed and
fluidized beds, heat exchangers, boiling, etc. merit much more attention than it
has received in the past.
1478
11. NOMENCLATURE
a geometric shape factor, Table 7
B width of plate, m
Br Brinkman number, = (D/2) x,,,("+l~"~/q,,,j.tl/",.
b geometric shape factor, Table 7, - or coefficient in temperature
dependent viscosity equation, I/K
Cp heat capacity, J/kg K
d particle diameter, m
D tube diameter, m
DAB molecular diffusivity of A in B, m2/s
DH hydraulic diameter, m
E activation energy for viscous flow, J/kg K, equation (5)
f fanning friction factor, D (- Ap)/2L 9V 2
Gr Grashof number, = I3AT D 3p2g/~teff2
Grh Grashof number, = (p2d3gl3AT/m2)(d2/002"2
Gro modified Grashof number for sphere/cylinder, =
p2Rn+2(13gAT)2-n/m2
Grl modified Grashof number, p2d3g[ST/m2(d2/ot)2'~-2
=
Pr Prandtl number, Cp
Pr' Prandtl number = Cp m (V/Dh)"-l/k
Pra Prandtlnumber'-Cpm
l k[ 3n4,,+ 8V]""D
r radial coordinate, m
SClm Schimdt number, = (mDAB/d2)"-J/pDAB
Scp Schimdt number, = (m/pDAB)(d/V)I-"
St Stanton number, h/pV Cv
T temperature, K
Tb bulk temperature of fluid, K
T~ outlet fluid temperature, K
To inlet fluid temperature, K
Zw wall temperature, K
V mean velocity in pipe, m/s
Vz point velocity in z-direction, m/s
Vo angular velocity in 0-direction, m/s
X dimensionless axial distance, x/D
X* dimensionless axial coordinate X/Pe
Z axial coordinate, m
Greek Symbols
ot thennal diffilsivity, m2/s
Ot.'k constant in equation (22)
coefficient of thennal expansion, K l
13W coefficient in viscosity equation (20), K -~
5 ((3n + 1)/4n)
Ap pressure drop, Pa
1480
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1485
1. I N T R O D U C T I O N
Very complex motions can result when a viscoelastic fluid is put under external
forces. In general, for a given set of forces one has to solve continuity, momentum
and constitutive equations simultaneously to determine the details. The majority
of effort along these lines has focused on incompressible media, which execute
isochoric motions; viscoelastic flows with a strong dilational component have not
received as much attention, primarily because there are relatively few applications
demanding their study. One situation involving viscoelastic media where the resulting
flow is dominated by the dilational component is inter-diffusion. Here, flow occurs
in a mixture with relative motion between components, driven by a combination
of thermodynamic and mechanical forces. The simplest case involves just two
components with no applied mechanical tractions; the relative motion is mutual
diffusion, generally resulting in flow of each component dominated by dilation. We
discuss this situation for one-dimensional motions in the case of a binary mixture with
one viscoelatic component and the other an ordinary viscous fluid.
A quantitative understanding of mutual diffusion in concentrated polymer/viscous-
fluid mixtures is of great practical importance, in order to understand and control a
number of polymer processing operations and end-use applications. For example, it
1490
2. MATHEMATICAL MODEL
0 t' OC' _,
Jx -- - D ( C ) ~ x - D'(C)-~-~g(C) r ;C')-~dt . (2)
Here, r characterizes the linear viscoelastic response of the mixture in shear; the
notation r t'; C') means that it is a functional of the concentration history between
t and t'. 9(C) - G(C)/Go with G(C) being the instantaneous shear modulus of
mixture and Go being G(C - 0), D(C) - D12(pzV2) 2 with D12 being the binary
mutual diffusion coefficient and
C - q~(t, 0; C')Co -
fo t -~
0r (t, t' ; C' )C'dt.
where Co is the initial fluid concentration in the polymer film; for an initially dry film
(4)
Co equals zero.
Boundary and initial conditions need to be specified in order to solve for C. For
the boundary conditions, at the interfaces between the mixture and the reservoir, we
assume continuity of the fluid chemical potential, #1, which can be written in terms
of the fluid activity in the reservoir, tfl, as
which requires an initial value for Cb. Taking the limit for t ~ 0 gives
In Cb + a ( cb Co ) - - 0 (7)
c or 1 - ~ Cgq co
defining the initial value.
So far, the development can accommodate any viscoelastic model. Hereafter, we
assume single exponential relaxation with a concentration dependem relaxation time
t dr"
r c') - - ~ s,, . - ~ . (8)
In order to include the most important nonlinearities in the simplest way, we adopt the
following assumptions, which approximate experimental results in the concentrated
regime.
(i) The relaxation time decreases exponentially with concentration:
D ( C ) = Do exp k C (10)
where k is a constant and Do is the diffusion coefficient of the dry polymer.
(iii) The instantaneous shear modulus of mixture, G, is independent of
concentration, which implies g(c) - 1.
Equation (3) then gives:
D~ -- DoGoV1 ~ p 2 V 2 C ~ (12)
2.2 Scaling
Introduce the dimensionless quantities
where l is the dry film thickness. After substituting the expressions for
D(C), "r(C), and r C'), and using equation (4), the diffusion equation
becomes:
Ou 0
Os --
- Ox (1 - a + au) exp K u OuO--x aOaO OI
. x u exp K u Ox (14)
with
I -- Ouo exp (/0
- s0 exp~- M u ~)
+
Jo~ exp(Mu') exp
x: M~ u " / u_' d s '
( I- , ~~ 0 e~'' (15)
where
a -- D6 0 - T0(D0 + D6) (16)
D~ + Do' 12
are dimensionless constants. Equation (6) becomes
lnr
~ ( Ub--
o) (17)
where ~ -- C~/C;~
For numerical solutions, it is easier to work with differential equations. Equation
(15) is the solution of
OI I
0---~= exp M u ( u - ~). (18)
The initial conditions at the boundaries can be obtained from the scaled form of
equation (7). The experimentally measurable relative fluid uptake, W(s), can be
calculated from
3. N U M E R I C A L M E T H O D S
We aimed to solve equations (14)-(21) for the broadest possible range of the
dimensionless parameters c~, 0, K, M, uo and ~b. In the Case II limit, steep moving
concentration fronts are expected. This demands a numerical scheme able to handle
"stiff" problems effectively. Consequently, finite element spatial discretization,
together with an ODE integrator designed to handle stiff initial value problems was
the approach chosen.
Two different finite-element schemes were used. The first employs orthogonal
collocation. The details are more or less the same as described by Fu and Duming
[23] and Tang et al. [ 12]. A solution is constructed by discretizing space into equal
subintervals and approximating the spatial dependence with piece-wise continuous
Hermite cubic polynomial basis functions. Orthogonal collocation is then applied to
each subinterval to convert the PDE system into a coupled system of ODEs for the
time dependent coefficients in the polynomial approximations to u(z, s) and I(z, s).
We used LSODI [24] for the ODE solver, which requires that the system be in linearly
implicit form; equations (14) and (18), employing equation (4), collapse to a linearly
implicit ODE system when discretized.
The second scheme is that discussed by Caimcross and Durning [22] . The
dimensionless form of the diffusion equation retaining the memory integral in
equation (2) is integrated directly by Galerkin's method, i.e. equation (4) is not
used, using quadratic basis functions and a differential/algebraic equations systems
solver, DASSL [25] . Actually, the boundary condition used with this scheme at
the reservoir/mixture interface is somewhat different from equation (19): A "surface
evaporation" condition is imposed where the external fluid flux is put proportional
1497
to the fluid activity drop between the film surface and the bulk phase and set equal to
the flux in the film at the surface, given by equation (2). The proportionality constant
appearing in the external flux at the surface is a mass transfer coefficient; for very
large values of the mass transfer coefficient, the surface evaporation condition gives
that the surface and bulk phase fluid activities nearly match, i.e. it reduces to our
surface condition, equation (19). In fact, calculations based on the two schemes agree
closely when the (dimensionless) external mass transfer coefficient in the second
scheme (a Biot number) is set to large values ( ~ O(103)) and all other model
parameters are set equal (see below). Values of the Biot number ~ O(103) were
used for all of the calculations by the Galerkin scheme.
4. N U M E R I C A L RESULTS
There are six dimensionless parameters in the model, a, 0, K, M, u0 and ~b. The
first four characterize the polymer-fluid system, while the last two define the driving
force for the sorption. For all the calculations, we fixed the number of subintervals
at 30. As a basic benchmark we solved the case a - 0, K - M - 0 and recovered
linear Fickian diffusion, as expected. By trial calculation, we found that the numerical
solutions were most suseptible to instabilities for integral sorption (u0 -- 0.0 and
= 1.0). In this case, when a is near 0, K and M must be less than 4 in order
to avoid instability of the collocation scheme. When a is away from 0, M can be
increased to 5, while K can go up to 12 before numerical instabilities occur with
collocation. The code based on Galerkin's method enjoyed a wider range of stability
in parameter space for integral sorptions than the one based on collocation, permitting
values of both M and K up to 12 for a wide range of a and 0.
A comparison of concentration profiles predicted by the collocation and Galerkin
schemes for the demanding case of integral sorption near the Case II limit (a =
0.9, 0 = 0.01, K = 5.0, M = 5.0, u0 = 0.0, and~b = 1.0)showed
excellent agreement between the two codes. Subsequent remarks refer to results from
collocation, except where noted.
system from published data; the details are given in Appendix D of Tang [26]. For
a 5# thick PS film, at 40~ we find c~ -~ 0.97, 0 ~ 432, M ~ 3 5 , / ( ~ 17.
To model the conditions where two-stage weight uptake was observed, we picked
u0 - 0.03, and ~ - 0.1, which corresponds to run R4 in reference [10] . This
choice corresponds to the solvent mass fraction starting at w I = 0.018 and ending
at w~- - 0.059, somewhat too large of a change for purely linear response, i.e. the
response is weakly non-linear. Figure (la) shows u(x, s) while figure (lb) shows
the corresponding dimensionless weight uptake, W(s) vs. x/~, which is clearly a
two -stage weight uptake curve. The concentration profiles show that the two-stage
sorption process is controlled by the viscoelastic response in surface concentration,
which which was first recognized by Long and Richman [27].
Consider next liquid methanol (MeOH) in poly(methylmethacrylate) (PMMA). It
is known that Case II transport occurs when liquid methanol contacts a relatively
thick ( ~ lmm) PMMA film at room temperature (see reference [ 14], for example).
Under these circumstance, u0 -- 0, and ~b = 1, i.e. we are considering an integral
sorption. From the physical properties provided by Thomas and Windle [14] we
find c~ ~ 0.86, 0 -~ 0.0087. We adopt K = 6.2, as suggested by Thomas and
Windle. According to Thomas and Windle, M = 13.0; however, M = 5.0 was used
due to the limitation of the collocation scheme. Consider the concentration profiles
predicted for this system, shown in figure (2a). Note two key features, characteristic
of Case II [ 14-16]. First, the surface concentration relaxes with time. Second, a steep
concentration front develops and propagates into the film at nearly constant speed
after the surface equilibrates. Figure (2b) shows the corresponding (dimensionless)
weight uptake, W(s) vs. s. The main, increasing part of the plot is nearly linear,
and there is an induction time visible as illustrated by the construction on the figure;
both features are additional signatures of the Case II process. Clearly, the predictions
for the PMMA-liquid MeOH system capture all the characteristic features of Case
II transport noted in previous work. The forgoing calculations demonstrate that the
model considered here can predict the two most well documented manifestations of
viscoelasticity in sorption experiments: Two-stage uptake in differential sorption and
Case II transport in integral sorption. The remaining sections focus on the effect of
the material parameters a, 0, M and K on the predictions of the model in the Case
II limit, assuming integral sorption, i.e. u0 - 0 and ~b = 1.
1499
0.12
0.10
-~. 0.08
9.08
0.06
0.04
0.02
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.20
0.16
0.12
0.08
0.04
0 3 6 9 12
S~r2
Figure 1. (a). Concentration profiles (u(z, s)) from the non-linear model with
parameters for the PS-EB system studied by Billovits and D u m i n g [ 10] 9a -- 0.97,
0 -- 432, K - 17, M - 35, uo = 0.03, ~b - 0.1; (b). Weight uptake kinetics ( W
vs. s) from the non-linear model with the same set of parameters.
1500
.0 _ _ . rM
0.8
0.6
g-
0.4 24
02 s=O.O 12
O0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1.0
0.8
0.6
0.4
0.2
0.0
0.00 si 0.01 0.02 0.03 0.04 0.05 0.06
Figure 2. (a). Concentration profiles (u(x, s)) from the non-linear model with
parameters for the PMMA-MeOH system studied by Thomas and Windle [14] :
c~ = 0.86, 0 = 0.0087, K = 6.2, M = 5, Uo = 0.0, ~ = 1.0.; (b). Weight
uptake kinetics ( W vs. s) from the non-linear model with the same set of parameters.
1501
si ~ 0 (24)
according to the TW model.
In the present model, three parameters a, 0, and M appear in the equation
governing surface concentration, equation (19). One sees that the effect of 0 is
only to rescale s, which implies that si ~ 0 as in the TW model (equation (24)).
The parameter M describes the dependence of the relaxation time on concentration.
Figure (3) shows its effect on surface swelling with a fixed at 0.99, and 0 set to 1.0;
lnM ranges from 2 to 3.25. When in M < 1.5 ( M < 4.48), there is no discemable
induction time; the Ub vs. s curves in this case do not show upward curvature. For
In M >_ 1.5 ( M >_ 4.48), autoacceleration of Ub occurs, and an induction time can be
calculated using a process analogous to that illustrated in figure (2b). Figure (4) plots
si vs. ( M in M ) -1 for a - 0.99 and shows a linear relationship. Taking differences
in 0 into account, the slope agrees in order of magnitude with the value obtained by
Fu and Duming [23] from the TW model.
In the current model the parameter a also affects the induction time. a shows up
as a measure of the instantaneous elasticity of the polymer in the mixture; there is
no analog for a in the TW model, since it presumes the polymer is purely viscous.
a -- 0 means a perfectly compliant polymer and corresponds to ordinary diffusion;
for finite a instantaneous elasticity and relaxation effects are switched on. Figure (5)
shows the effect of a on surface concentration with M fixed at 10.0. For finite a one
sees an initial jump, permitted by the instantaneous elasticity, which decreases with
1502
increasing c~. In the linearized version of the model, the surface concentration jumps
initially to 1 - a (Tang et al. [ 12] ). In the non-linear version, the value given by the
dimensionless version of equation (7) is near, but not exactly equal to 1 - c~. From
figure (5) one sees that when a is less than 0.1, the relaxation of UD is minimal and
there is no discernible induction time. As c~ increases from 0.1 to 0.9, the amplitude
of the relaxation in Ub increases, induction times si appear and increase with a. The si
increase monotonically with a, but the numerical data do not suggest an unambiguous
analytical representation for si(a).
1.0 ! I '
0.9
0.8
0.7
0.6
.Q
0.5
0.4
0.3
0.2 A M = 12.18
v M= 15.64
0.1
0.0 , ~ ~ I , ~ , I J , J I , J '
0 2 4 6 8
Figure 3. Effect of M on surface concentration (Ub vs. s) for a -- 0.99 and 0 -- 1.0.
1503
9 , , ! , , , !
0 i i I I = |
1/MIn(M)
Figure 4. Linear relation between induction time from surface concentration kinetics,
si, and ( M In M) -1.
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0"3 I a a=0.3
0.2 ~ " a=?.5
[ - a=0.7
0.1 [ o a=0.9
/
0.0
0.000 0.005 0.010 0.015 0.020
Figure 5. Effect of a on surface concentration kinetics (Ub VS. 8) for M - 10.0 and
O - 1.0.
1504
1.0
0.8
0.6
0.0 , I , , , ,
i. i ,
the sharp concentration front which establishes near the surface after the external
activity is switched on and propagates into the polymer film at a constant speed. We
conducted systematic calculations to investigate the effect of a on the key features of
OI
the from: The front speed v and the values of u and 8-; at the front (uf and (o~):),
with the front's position being defined by the position of the maximum in N. oI Figure
(8) displays a typical trace of u: and (oi) i with time, for M - / f i - 5.0, a - 0.9
and 0 = 0.01. The plot shows that, after an initial induction at the surface both u /
and ( ~ ) I achieve nearly steady values and move at nearly constant speed into the
film. When the front reaches the center of the film, (oi N ) : stops and sinks to zero
gradually. At the same time, uf relaxes to the equilibrium concentration.
Two measures of the moving front speed were calculated. One, v:, is the slope of
the linear part of front position versus time, and the other, Vw, is the slope of the linear
portion of W(s) vs. s. Since the moving front invades the film from both sides, vw
corresponds to about twice Vv (the values ofvf and vw/2 agree within 8%).
1506
1.0
0.8
0.6
0.4
0.2
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.20
0.18
0.16
s = 0.0004
0.14
o.12 s= 0.011
o.lo s=oos s=o.o3 /~/I
0.08
0.06
0.04
0.02
0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Figure 7. (a) Concentration profiles (u(z, s)) determined by two different numerical
schemes. Hollow symbols correspond to collocation method while filled symbols
correspond to Galerkin method. The model parameters are a = 0.9, 0 -- 0.01,
K = 5.0, M = 5.0, Uo = 0.0, ~b = 1.0.; (b). c9I/c3s profiles from collocation for
the same set of parameters.
1507
Results for effects of a on both v~ and "of with K = M = 5.0 and 0 = 0.01 are
summarized in figure (9), which shows that the v decrease linearly with increasing
a. That plot suggests v f ~ (1 - a) since the speed gets vanishly small near a - 1.
0.3 ~ Uf
0.2
?
0.1
0.0
0.0 0.1 0.2 0.3 0.4 0.5
4.3.2 Effect of O
0 is a Deborah number for this model. It corresponds to the ratio of a characteristic
relaxation time of the polymer to the characteristic diffusion time, evaluated for
the dry film. For nonlinear diffusion, the behavior cannot be anticipated from 0
along, as in the linear limit, since the actual relaxation and diffusion times vary with
concentration making the instantaneous, local value of the Deborah number vary
significantly. However, for this model in the special case M = K the concentration
dependence of the relaxation and diffusion times cancel, and 0 does correspond to the
dimensionless relaxation time at all compositions. It happens that M ___ K is required
for Case II (see later), so we may view 0 as a key parameter for Case II.
1508
10
8 [- ~. Vw
4_ vf
-2
0.90 0.92 0.94 0.96 0.98
Gt
We found that 0 must be _< O(0.01) in order to predict Case II, consistent with
Fu and Durning's [23] analysis which derived the TW model of Case II as a small
Deborah number limit of the model considered here. We picked the range 0.008 _< 0
_< 0.022 to study the effect of 0 on the process. From calculations of concentration
profiles and weight uptake with a -- 0.9, / ( = M = 5.0, one finds that an increase
of 0 causes a proportional increase in the induction time calculated from weight ~ain
kinetics, i.e. si ~ 0, exactly as anticipated from analysis of the surface concentration.
0 also decreases front speed, and therefore the slope of the linear portion of W ( s ) vs
s plots. The results for v f and vw are plotted in figure (10); we find v f ~ 0 -0.52 under
these conditions. Fu and Durning [23] studied the TW model numerically and found
v ~ 0 -~ identical with the dependence of in the current model in the Case II limit.
One can anticipate this result from dimensional analysis.
1509
1.2 9 9 l-- w 1 w i i w
1.1
1.0
0.9
c
0.8
b.O z
9
0.7
0.6 Iogvf
0.5 L
0.4 -
3 1 I I I I I
Figure 10. vf and v~ vs. 0 with a - 0.9, .K - 5.0, M - 5.0, Uo - 0.0, ~b - 1.0.
20
18 II
16 ~ vw
14
El
12 r-I 9 -
lO ~ n
_ o 9 -
- 0
8. [3 9 -
6~ 0 0 O0
4
. ooOO v, :
2 , = j , I , , , I 1 . . . . I , , , , I , , = i I . . . .
0 2 4 6 8 10 12
The numerical solutions give evidence that M has to be sufficiently large in order
to predict Case II 9 We calculated u and 0I profiles with 3/1 -- 2 and other parameters
as above. By comparing the results with figure (7), one finds that the decrease of
M from 5 to 2 suppresses the Case II features. The decrease results in considerable
broadening of the concentration front; at the same time, the peak in 0I continuously
decays at M = 2 and spreads progressively more along the spatial coordinate during
sorption.
The parameter K govems how fast the diffusion coefficient increases with
concentration and characterizes the other key nonlinearity in the model. Figure (12)
shows the dependence of induction time from weight gain on K with ce = 0.9, 0 =
0.01 and M = 5.0. The four data points in the high K range were generated
1511
by the Galerkin code. One expects that the induction time from weight gain be
independent of K, if it truly characterizes the surface relaxation process, i.e. if it
corresponds closely to the induction calculated from the surface relaxation kinetics
(e.g. figure (4)). However, we find that the induction time from weight gain increases
linearly with K until near the value of M (5.0 in figure (12)) after which it becomes
independent of K as expected. This indicates that diffusion in the surface layers can
limit the induction time determined from weight gain kinetics. We note, however, that
compared with the effect of M, which reduces the induction time even if the value
exceeds K, the influence of K on the induction from weight gain is much weaker, as
one expects intuitively.
Calculations show a roughly linear relationship between front speed and K, as
shown in figure (13) for M = 5, a - 0.9, 0 = 0.01. This finding is again consistent
with that by a perturbation analysis ofthe TW model, which predicts v ~ ( K + M ) 1/2.
Calculations showed that in order to have Case II, M needs to be at least 2 - 3
and K has to be at least equal to M. For example, it was found that if K is kept at
5.0, when M rises above 8, the predicted behavior deviates from Case II in that the
linear weight uptake kinetics were not predicted. This is because when M exceeds
K, the front speed becomes so fast that diffusion behind the front quickly becomes
rate limiting. Consequently, the front begins to show diffusive dynamics (v ~ sl/2).
5. C O N C L U S I O N
A one-dimensional nonlinear model for viscoelastic diffusion in concentrated
polymer-fluid mixtures was constructed by an ad-hoc generalization of the linear
response model by Durning and Tabor [18] . The nonlinearities were introduced
by retaining concentration dependencies of physical properties. In order to get a
numerical solution for sorption in films, the diffuson equation was cast as coupled
partial differential equations by introducing a new dependent variable. Finite element
methods were used to discretize the spatial domain, converting the PDEs into an ODE
system, which was solved by a time integrator package. In one scheme, orthogonal
collocation on Hermite cubic basis functions was used to discretize and LSODI was
adopted to do the time integration. An alternative integration technique employed
Galerkin's method on quadratic basis functions together with the DASSL integrator.
The two schemes were shown to agree.
There are six dimensionless parameters in the model, a, 0, M, K, u0 and ~b. The
1512
0.0092
0.0088
O
9 9 @
0.0084
0.0080
0.0076
0.0072
3 4 5 6 7 8
Figure 12. Dependence of the induction time from weight gain kinetics, si, on K with
a - 0.9, 0 - 0.01, K - 5.0, Uo - 0.0, ~b - 1.0. Filled symbols represent values
calculated by Galerkin's method.
first four characterize the mixture and the last two define the initial and final states for
sorption. We first investigated the predictions for two well-studied situations, where
all the parameters could be calculated apriori: Differential sorption in polystyrene-
ethylbenzene (PS-EB) solutions and integral sorption in poly(methylmethacrylate)-
liquid methanol (PMMA-MeOH). For PS-EB, the two-stage sorption process was
correctly predicted for differential sorptions in thin films at concentrations just below
Tg. For PMMA-MeOH, the Case II diffusion was correctly predicted for immersion
conditions in thick, dry plates at room temperature. The calculation shows that
the model can predict the most well documented and striking non-Fickian effects
observed in sorption w i t h o u t empiricism.
A systematic investigation was conducted of the effects of the materials parameters
1513
22 '"" ' ' I ' i , , I ' "' ' I ' ; ; ' I ' "' ' I ''w ' ' "
20 i
18
16
Vw
14
12
10
0 9
D 9 9 9
8
6 0 0
0 0 Vf
4
4 5 6 7 8 9
on Case II diffusion. The study should facilitate analytical asymptotic work, and
provide guidelines for design and control of systems relying on Case II. Case II
diffusion appears only when a, a measure of the instantaneous elasticity of the system,
is close to 1. This implies D~ > > Do and physically means that the osmotic modulus
is weak compared to the mixture's shear modulus. The situation occurs when the fluid
is a poor solvent or swelling agent. It was found that the front's speed decreases nearly
linearly with increasing a. 0, the diffusion Deborah number, has to be ~ O(0.01)
for Case II to appear, indicating that Case II is a slow-motion limit of the model. 0
affects the front speed according to v ~ 0 -1/2.
The numerical study shows that strong nonlinearities in the relaxation time and
diffusion coefficient, represented by large M and /4, are both essential for the
prediction of Case II transport. Importantly, the values of M and K should be about
the same, and at least 2 - 3. I f M exceeds K by too much, the process rapidly becomes
1514
6. Acknowledgment
1LAC acknowledges support from Sandia National Laboratory.
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