Visco-Elasto-Capillary Thinning and Break-Up of Complex Fluids
Visco-Elasto-Capillary Thinning and Break-Up of Complex Fluids
Visco-Elasto-Capillary Thinning and Break-Up of Complex Fluids
. ....(2)
The actual stress in the filament can, in principle, be determined by numerical
integration of a chosen viscoelastic constitutive equation with the known deformation
profile ( ) t . In many of the similarity solutions obtained for capillary thinning of
slender fluid filaments (discussed in detail below in 4), the midpoint of the fluid
filament is found to evolve according to a relationship of the functional form
( )
m
0
( )
mid
R t C t t = where C and m are parameters determined from the analysis. For
example: for the Newtonian fluid m = 1; for a Second Order Fluid m = 2 and for a
power-law fluid the parameter m is the power law exponent n. The strain rate and total
Hencky strain of the fluid element at the mid-plane are then given by the expressions:
2
( )
( )
mid
c
m
t
t t
=
and
0
2
m
c
R
( t ) ln
C( t t )
| |
=
|
\ .
. ....(3)
It can be seen that both the fluid strain rate and the total strain therefore diverge as the
breakup event approaches. It is thus possible to probe the extensional properties of
complex fluids under conditions far from equilibrium and far beyond those attained in
conventional torsional rheometers.
Following early disappointing attempts at correlating measurements of the
extensional resistance of polymer solutions in different elongational devices
(summarized in [10]), it is now recognized that the extensional viscosity of a
viscoelastic fluid is best represented as a transient function of both the deformation
rate (or Weissenberg number) and the elapsed time, or strain (see Ferguson et al for
additional discussion).
To illustrate this, we consider for simplicity the particular case of the Oldroyd-
B model [19] and a constant deformation rate (
0
). The radius of a fluid thread (in the
9
absence of surface tension) decreases according to ( ) ( )
0 0
2
mid
R t R exp t = . If the
initial stress difference in the thread at time t = 0 is denoted
( )
0 0 0
p p,zz p,rr
= , then
the evolution of the tensile stress difference can be found analytically and is given by:
( )
0
0
2 (1 0.5 )
(1 0.5 ) (1 2 )
p
p,zz p,zz
2
G
exp Wi
Wi Wi
= + +
`
)
, ....(4)
( )
0
0
(1 1
(1 1 ) (1 )
p
p,rr p,rr
G
exp Wi )
Wi Wi
= + +
`
+ +
)
, ....(5)
where
p
G = is the elastic modulus, the Weissenberg number is
0
Wi = and the
Hencky strain is
0
t = . After incorporating the additional Newtonian stress
contribution from the solvents, the extensional stress growth function, or equivalently
the transient uniaxial extensional viscosity, can then be represented in the form:
0
0 0
( )
( )
( ) 3
p,zz p,rr
zz rr
E s
,t
+
= +
. ....(6)
Results are also often represented in dimensionless form as a transient Trouton ratio
0 0 0
( )
E
Tr ,t
+
= .
For small Weissenberg numbers (Wi < 0.5) the last terms in equations (4 - 5)
dominate; however at Wi = 0.5, the coil-stretch transition leads to unbounded stress
growth in time. It can be seen from equation (5) that the radial stresses typically decay
with strain () for all Wi; however for Weissenberg numbers Wi > 0.5 the axial tension
in a fluid filament grows without bound. It is this stress growth that results in the
formation of fibrils and connecting ligaments observed in the images of figure 1.
Ultimately this stress growth is truncated by the finite extensibility of the
molecules and can exceed viscous contributions to the stress by many orders of
magnitude. This limit can be described by molecular models such as the FENE-P
dumbbell model obtained from kinetic theory [20] and an additional finite extensibility
parameter denoted
2
L herein. The axial stress growth is then truncated at a maximum
value given by:
( )
2
0 0
2 1 1 2
p,zz, max E p
L Wi... = = . ....(7)
Finally, it can be seen from the expressions above that for 0.5 Wi < the effects
of any initial stresses decay, i.e. the fluid exhibits a fading memory as normally
expected for a viscoelastic fluid; however, for Wi 0.5, the initial axial stress does not
decay but affects the flow at all future times. This is particularly important in the study
of jet breakup the effects of an upstream shear flow (for example in a pipe and
nozzle) can significantly modify the dynamics of breakup. The role of pre-shear on
extensional flow is not well understood yet and has only been considered by a handful
of authors to date [21-23].
10
3. THE STABILITY OF FLUID JETS AND THREADS
Our understanding of visco-elasto-capillary thinning and break-up has
advanced significantly over the past 10-15 years, through the combination of careful
experimentation, numerical simulations of the governing equations and mathematical
analysis of the stability of these equations. Some of the many papers in the area are
collected in tabular form in table 1. This list is not intended to be exhaustive but rather
highlights some of the key studies.
As we discussed above, the number of material parameters influencing the
evolution of a fluid thread or jet can be rather large (cf. figure 2) and systematic
studies have therefore focused on specific parts of this parameter space. In table 1 we
indicate which contributions to the total force balance on the elongating thread
considered in each study control the dynamical evolution and necking of the thread. In
the present section we focus on experimental and theoretical studies of the linear
stability of jets and liquid bridges (denoted by LS in table 1). In 4 we proceed to
consider the nonlinear evolution of fluid threads through the use of self-similar
solutions to the equations of motion, as well as through simpler but approximate
local analyses. These studies are denoted respectively by an SS and L in table 1.
3.1 Linear and Nonlinear Stability of Jets
It has been known since the 1960s that the evolution of viscoelastic fluid jets
may be substantially different to common experience with Newtonian fluids. Linear
stability analysis [33] shows that the jet is less stable to perturbations than the
corresponding Newtonian viscous jet (because the fluid stresses that resist disturbance
growth are always retarded behind the instantaneous deformation). For weakly elastic
fluids this can result in jet breakup lengths that are shorter than those observed with a
Newtonian fluid [39]. However, for highly elastic solutions containing high molecular
weight additives, nonlinear effects can rapidly develop in the extensional flow that
evolves in the neck region and stabilize the breakup process. This leads to significantly
enhanced jet breakup lengths and the development of a beads-on-a-string morphology
[1]. Bousfield et al. [13] simulated the viscoelastic extensional flow of a free jet using
the Oldroyd-B model and showed that the elastic stresses grow exponentially in the
neck as a result of the squeezing flow induced by the ever-increasing capillary
pressure ( )
mid
R t . They also showed that the evolution in the filament profile can be
accurately described by a simplified one-dimensional set of slender filament equations.
This greatly simplifies the analytical and computational complexity of the task. The
resulting one-dimensional equation set can also be conveniently represented in
Lagrangian form [37] and a number of similarity solutions incorporating capillarity
and viscoelasticity as well as additional effects of inertia and finite extensibility have
been studied by Renardy [36]. The structure and development of the associated
methodology is summarized in last years Rheology Reviews 2004 [40] and discussed
further in 4 below.
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11
12
An important result from numerical study of the necking process is the
possibility of an elasto-capillary balance in the necking thread. The exponential
decrease in the radius (and concomitant exponential increase in the capillary pressure
in the cylindrical thread
( ) cap
p R t , results in a constant strain rate (from equation
(1)) and correspondingly an exponential growth in the axial tensile elastic stress (from
equation (4)). Detailed analysis shows that the filament radius evolves in the form:
( )
( )
1/3
0 0
2 2
3
3
mid
mid
mid
mid
R t
G dR
exp t
R R R dt
| |
= =
|
\ .
....(8)
The necking process thus corresponds to a homogeneous elongational flow with
2/3
mid
Wi = = . Schmmer and Tebel [41] used this principle to motivate
construction of a free jet elongational rheometer.
The elasto-capillary balance and resulting exponential stress growth obtained
with a quasilinear model such as the Upper-Convected Maxwell or Oldroyd models
precludes the possibility of filament breakup [42]. Ultimately we expect two additional
effects to modify the dynamics; (i) fluid inertia and (ii) finite extensibility of the
dissolved macromolecules. The interplay of these effects governs the tendency of the
elongating and thinning fluid thread to form satellite droplets. These smaller droplets
are of great importance commercially as they affect the delivery of inks and fertilizers
in spraying and inkjetting operations. Although the general principles controlling this
process are now well known, a quantitative and predictive theory or analysis for
viscoelastic fluids remains lacking at present.
Simulations [13] of the size of the primary and secondary droplets resulting
from the breakup of a Newtonian fluid jet as a function of the dimensionless
wavenumber
0
k R L = of the disturbance are in quantitative agreement with
experimental data as shown in figure 4(a). As the wavenumber of the disturbance
increases, the sizes of both the primary and secondary droplets decreases
monotonically; however a secondary droplet is always observed.
For the case of a dripping nozzle, Ambravaneswaran et al. [43] used a 1D
slender-body approximation similar to that in [13] to develop a complete operating
diagram for the formation of satellite droplets in terms of the Weber number and
Ohnesorge numbers. Figure 4(b) shows that by careful choice of the fluid viscosity (or
Ohnesorge number) it is possible to optimize the range of dripping velocities (or
Weber numbers) for which no secondary droplets are formed.
For polymeric jets there have been few quantitative comparisons of theory and
experiment. Christanti & Walker [44, 45] recently studied the droplet size
distribution and jet breakup length for a series of aqueous polyethylene oxide (PEO)
solutions. The jet was periodically excited using a piezo transducer element and the
corresponding evolution of the jet was captured using high-speed video as shown in
figure 5. As the molecular weight of the PEO solute increases, and elastic stresses in
the fluid become increasingly important, the jet breakup evolves from the classical
Rayleigh mode (which leads to formation of a primary droplet together with small
secondary droplets as shown in the top frame) towards the beads on a string
13
morphology shown in the lowermost frame. The wavenumber of the most unstable
mode is clearly decreased with increasing fluid elasticity.
The authors also developed a phase diagram showing the range of fluid
elasticities (as characterized by the longest or Zimm relaxation time) and
wavenumbers for which satellite droplets are eliminated (figure 5(b)). As the fluid
elasticity increases, the range of wavenumbers for which the viscoelastic jet is able to
suppress drop break grows rapidly. In dimensionless form, the elasticity of the
polymer solutions is characterized by the intrinsic Deborah number
0
De defined in 2.
For a fluid jet exiting a nozzle of radius 0.25mm, the fluid with measured relaxation
time of 0.5 ms (0.1% 310
5
g/mol PEO) corresponds to a Deborah
number
0
0.97 De = . For Deborah numbers below unity, elastic effects thus do not
stabilize the jet and Newtonian-like breakup dynamics are observed. Very similar
stabilization effects and suppression of satellite drops are also seen during the pinch-
off of PEO solutions dripping from nozzles [46, 47].
Figure 4: Formation of satellite drops during breakup of a Newtonian
liquid thread; (a) Dimensionless droplet sizes (scaled with initial jet
radius
0
R ) of the primary and secondary droplet size in breakup of a
continuous Newtonian jet are shown as a function of dimensionless
wavelength of disturbance,
0
2 k R L = . Reproduced from Bousfield
et al. JNNFM 1986 [13]; (b) operability diagram showing the range of
Weber numbers for which a satellite drop is/is not formed for different
Ohnesorge numbers. Reproduced from Ambravaneswaran et al. Phys
Fluids (2002) [43] .
(a) Jetting (b) Dripping
14
Figure 5: Effect of viscoelasticity on jet break up; (A) evolution in jet
profiles due to a forced disturbance with wavelength d = 4.5; (a) a
Newtonian 50/50 water/glycerol mixture; (b) 0.3% 100kg/mol PEO; (c)
0.1% 300kg/mol PEO, (d) 0.05% 1000kg/mol PEO, and (e) 0.043%
5000kg/mol PEO. Flow direction is from left to right and the image size
is 20 mm x 2 mm; (B) Stability diagram showing conditions which
form satellites () and conditions which form no satellites () as a
function of fluid relaxation time and wavelength of disturbance.
Reproduced from Christanti & Walker, J. Rheol, 2002 [45].
A
B
15
Recent advances in numerical methods that retain high resolution descriptions
of the free surface can now enable the nonlinear dynamics of viscoelastic jets to be
simulated very accurately as shown in figure 6. A small (1%) initial disturbance is
supplied to the initial jet profile and the one-dimensional evolution equations for a
slender Oldroyd-B filament are integrated forward in time [48]. The simulations show
the growth of a large primary drop and a smaller secondary drop. Of particular
interest are the velocity field and stress distribution in the filament, which are shown in
figures 6(g) and 6(h). The velocity profiles show regions of homogeneous elongational
flow in the threads (in which
z mid
v z = ) interconnected by quasi-stagnant regions in
the drops. A detailed analysis of the force balance in the thread shows that the net axial
force is not identically zero as initially assumed in early theoretical analyses [34, 49]
but in fact decays in time with the same exponential decay rate as the radius of the
cylindrical regions. The contributions of capillary pressure and elastic stress in each
Figure 6: Numerical simulation of the formation and coalescence of
beads on a string in an Oldroyd-B fluid; De = 212.1; Oh = 1.41; (a)-(f)
filament profiles at dimensionless times (scaled with the Rayleigh time
t
R
) of t = 56.6, 141.4, 212.1, 353.6, 381.8 and 424.3; (g) axial velocity
profile as a function of axial position (
0
z / R ); (h) dimensionless total
axial force in the filament (scaled with surface tension
0
R ) as a
function of axial position. Reproduced from Li & Fontelos, Phys.
Fluids, 2003 [48].
(g)
(h)
16
axial segment of the beads-on-a-string morphology are different and depend on the
entire evolution history of the respective fluid elements. Consequently, small force
imbalances and the slow drainage of fluid from the cylindrical threads into the
interspersed droplets can result in a prolonged coalescence phase as shown in figure
6(a - f). Although the similarity between the experimental observations in figure 5 and
numerical simulations is striking, a quantitative comparison between jet
breakup/atomization experiments employing a well-characterized model polymer
solution and numerical simulations with predetermined physical parameters has yet to
be performed.
The simulations in figure 6 are appropriate for a dilute solution of infinitely
extensible macromolecules (which can be modeled as Hookean dumbbells and
described by the Oldroyd-B constitutive equations); however in a real fluid, at long
times the finite extensibility of the molecules must become important. Renardy [36]
and Fontelos & Li [50] have shown that in this limit a self-similar necking process (see
4) develops in which the radius no longer decays exponentially, but linearly in time
with ( )( )
mid E c
R 2 t t where
E
is the steady elongational viscosity and
c
t is
the critical time to breakup. Interestingly it is found [50] that the precise value of the
numerical front factor in this relationship depends on details of the specific
constitutive model, and this suggests that studies of elasto-capillary thinning and
breakup might provide sensitive probes of the extensional rheology of complex fluids
at large strains.
A recent theoretical stability analysis [35] has also shown that the elongated
beads-on-a-string structure shown in the last frame of figure 6(a) may itself be
unstable to a new mode of inertio-elasto-capillary instability. Numerical calculations
showed that the neck region connecting the primary droplet to the elastically-
dominated cylindrical ligament is unstable to small perturbations, leading to an elastic
recoil and formation of a smaller secondary droplet connected to the main droplet by a
finer-scale ligament. This structure is then itself unstable to perturbations and this
process of iterated stretching repeats indefinitely (for an infinitely extensible fluid
model such as the Oldroyd-B model), with a well-defined recursion relationship
between the size of each generation of beads. Iterated instabilities in fluid threads of
very viscous Newtonian fluids (Oh 1) have been observed previously [51], but due
to the lack of a wavelength selection mechanism this instability does not lead to well-
defined arrays of beads. Although hints of this iterated process have been noted in
some careful photographs of polymeric threads [35, 45] an iterated elastic instability
has yet to be observed definitively in experiments with polymer solutions. As noted by
Chang et al. [35] fluid inertial effects are also important in this iterated process; in
order to ensure that the growth rates of the beads (which scale with
1
R
t
| | | |
= =
| |
\ . \ .
. ....(10)
Later analysis has shown that this solution is only one of a countably infinite
set; however all the other solutions are less stable to perturbations [28]. Eggers [26,
64] showed that there is another important universal solution which incorporates
viscous, inertial and capillary effects in the necking filament. We might expect this
solution to be appropriate when the Ohnesorge number becomes 1 Oh ;
corresponding to length scales
2
0 E
l ~ ( ) . When the expression for the thinning
rate of the neck in this inertio-visco-capillary (IVC) solution is evaluated, it is found
that it only differs from the visco - capillary (VC) expression (equation (10)) by a
numerical coefficient ( as indicated in figure 8 ) and the neck radius again decreases
P
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30
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21
22
linearly in time (although it should be noted that in the IVC solution the location of the
neck also translates slowly in the axial direction; whereas in the VC solution it is
stationary). The fluid inertia does not appear in the expression for the necking rate
because velocities are very small near the necking point. However at greater distances
from the neck, the velocities become much larger and the IVC solution is strongly
asymmetric, in contrast to the symmetric VC solution. Experiments and finite element
simulations have shown the progressive cross-over from the inviscid PF solution to the
IVC solution as viscous effects become important [74], and also from the symmetric
VC to asymmetric IVC solution as the velocities in the neck diverge (according to
equation (8)) and inertial effects become increasingly important [75, 76].
On very small length scales, additional forces become important and these have
also been considered. It has been shown [29, 77] that ultimately viscous effects in the
surrounding fluid become important (even if the outer fluid has a viscosity
0 i
<< )
and although the filament neck still decreases linearly with time, the shape of the
filament in the neck region becomes conical and symmetric. If the viscosity of the
outer phase is sufficiently large, analysis shows that the symmetric VC solution may
crossover directly to this viscous-viscous balance without ever displaying the
universal IVC solution [29]. Interestingly, it has been noted very recently that in the
case of an inviscid inner fluid core surrounded by a viscous fluid (
0 i
<< ) that self-
similarity breaks down because the necking rate in the inviscid thread is faster than the
time scale required any for surface reconfiguration [78], and the thread never forgets
the initial experimental conditions.
Recent experiments [79] have shown that similarity solutions to the governing
equations of continuum mechanics are valid down to remarkably small length scales of
O(10 nm); however ultimately an additional length scale, corresponding to the
wavelength of natural thermocapillary waves on the interface,
1 2
( )
T B
l ~ k T
(typically a few nm) becomes important. Beyond this point, the additional fluctuating
stresses in the momentum balance must be considered [30] and these modify the
necking so that the minimum radius varies with the square root of time from
singularity.
When elastic effects become important, the dynamics of necking change
significantly due to the additional elastic stresses that grow exponentially with the total
strain in the fluid thread. For the Maxwell/Oldroyd-B model this leads to an
exponential decrease in the thread radius as we discussed above in 3 for the case of
viscoelastic fluid jets. The crossover to this elastic-capillary balance is to be expected
when the viscoelastic time scale () becomes of the same order as the visco-capillary
or inertio-capillary time scale, and this crossover has been observed in both numerical
simulations [13, 34, 49] and experiments [46, 47]. Ultimately, finite extensibility
modifies this solution and the precise form of the corresponding similarity solution
then depends on the relative importance of inertia and also on the precise form of the
constitutive model [36, 50]. The additional constitutive parameters arising from
viscoelastic constitutive models preclude a convenient representation on a two
dimensional plot such as figure 8. Two important limits can be noted however;
23
(i) If the extensional viscosity approaches a constant value at large strain rates,
then the corresponding tensile stress increases linearly with strain rate and the fluid
acts like a highly anisotropic Newtonian fluid thread [34, 50]. As noted, in 3, the
thread then necks linearly in time according to:
( ) ( )
( )
1
min
2 0.5
E c
h t t Oh Tr
=
, ....(11)
where
0 E
Tr
= = =
. ....(12)
In general, both the strain and the strain rate are changing as the thread necks and it is
thus proper to refer to this as an apparent extensional viscosity. The material function
defined in equation (12) is, however, the relevant one for studying and understanding
commercial processes involving jet and thread breakup. It is also worth noting that in
addition to serving as an extensional viscosity indexer, numerous recent studies have
shown that a capillary thinning and breakup device can, under certain conditions,
measure the true extensional viscosity. Just as in a conventional torsional rheometer, in
order to extract values for specific material parameters it is necessary to select an
appropriate constitutive model that can be regressed to the data. A diagnostic guide of
the most commonly-observed modes of capillary thinning and break-up is shown in
table 2, and the rest of this section focuses on a discussion of the different modes of
thinning that can be observed.
5.1 The Force Balance on a Slender Filament
The expected form of the break-up profile can be obtained from a simplified
one-dimensional form of the force balance on the thinning filament. In the limit of
vanishing inertial effects, the governing equations can be integrated once to give a set
of equations describing the forces acting on one-dimensional Lagrangian fluid slices.
A detailed discussion of this approach and the connection with inherently one-
dimensional Cosserat models is given in [64, 88]. A Lagrangian formulation of the
governing equations for fiber-spinning in the absence of surface tension and subject to
a constant axial force is discussed by Yarin [11]; however, the appropriate system of
equations for capillary-driven breakup of a viscoelastic fluid thread with a time-
varying tensile force was first discussed and analyzed by Renardy [37]. It has been
shown that these one-dimensional equations can accurately reproduce full two-
dimensional, time - dependent simulations with both the Newtonian and Giesekus
B
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25
26
constitutive equations [80]. As originally formulated, the equation derived by Renardy
is written in terms of a Lagrangian stretch for each axial slice of the column defined
as:
( )
2
2
0 0 0 0
( ) ( ) S Z ,t z Z R R z Z ,t = , .(13)
where
0
( ) z Z ,t denotes the Lagrangian position at time t of the one-dimensional fluid
slice located originally at axial position
0
Z at time
0
t . In experimental
measurements of the midpoint radius or in digitized video images of liquid bridge
shapes as a function of time, the radial profile ( ) 0
( ) R z Z ,t ,t is the primitive variable.
If the stretch S is eliminated from the slender filament equation using equation (13)
and the equation is extended to incorporate the effects of higher order axial curvature
terms [64] and also an axial gravity field
z
g = g we obtain the following stress
balance:
0
,
2
2
0 0
1/ 2 3/ 2 2
2 2
( ) 2
3 ,
1
,
1 ( ) 1 ( )
z
s p zz p rr
Z
F t R
R t
R
gR Z R R
R
R
R R
| |
( = +
`
|
\ .
)
+ +
`
( ( + +
)
....(14)
where ( ) R R z,t = and the terms on the right-hand side represent, respectively, the net
viscous extensional stress, the non-Newtonian tensile stress difference, capillary
pressure arising from radial and axial curvature and gravity. This equation can then be
combined with algebraic or differential equations for the axial and radial stress
components that are obtained from a particular constitutive model. The resulting
equation set can be then be solved analytically or numerically. The net force in the
filament is not zero but is independent of spatial position (i.e. the force along the
filament is constant at any instant in time); it can thus be found by an integral
constraint along the length of the evolving fluid column. Renardy [40] outlines a
number of solutions that are valid in the limit that the last two terms capturing the
higher order axial curvature and gravitational body force acting on the filament are
negligible.
An even simpler zero-dimensional solution is possible if a further
simplification is made: the fluid thread is approximated as an axially-uniform
cylindrical column of constant radius ( )
mid
R t which is necking down under the action
of a capillary pressure ( )
cap mid
p R t = . The fluid blobs at either end plate serve as
quasi-static reservoirs which soak up the fluid drained into them from the necking
region and also alleviate the no-slip boundary condition which would otherwise induce
a radial shear flow near the ends of the radially-contracting fluid thread. The line
tension acting at the junction of the cylindrical surface and spherical blob then results
in an axial force ( ) 2 ( )
z mid
F t R t = . Substituting these expressions into equation (14)
and neglecting the asymmetric driving force of gravity results in an even simpler
approximate stress balance of the form:
27
| |
2 ( )
3
( ) ( )
mid
s p,zz p,rr
mid mid
dR t
R t dt R t
`
)
. ....(15)
It can be seen from this expression that the capillary pressure ( )
mid
R t can be
balanced by a viscous extensional stress ~3 ( )
s mid
t
and/or by non-Newtonian
contributions to the tensile stress difference in the column. It is this reduced zero-
dimensional form of the force balance that is studied in most theoretical and
experimental work [34, 87, 89] and is used in obtaining the different analytic
expressions given in table 2.
In the first row of table 2, we indicate schematically the distinctive features and
qualitative profile of the liquid bridge. In the second and third rows of the table, the
expected temporal evolution of the midpoint filament diameter for a number of
constitutive models are shown. It can be seen that the functional form of the necking
profile can be very different and in each case is directly connected to the form of
extensional viscosity predicted by a given constitutive model.
5.2 Elasto-Capillary Thinning of Dilute Polymer Solutions
Perhaps perversely, the elasto-capillary solution for a viscoelastic filament is
easier to understand and validate experimentally than the corresponding expression for
a viscous Newtonian fluid. This is because experiments (figure 5) and computations
(figure 6) show that the approximation of an axially-uniform cylindrical thread is very
good for a strongly-strain hardening fluid such as a dilute solution of a high molecular
weight polymer. In this case the filament radius decays exponentially at a rate of
-1
( ) 3 with a front factor that depends on the elastocapillary number ( Ec ).
Physically, this corresponds to the radius at which we obtain a balance of the elastic
modulus (
p
G = ) and the squeezing effects of capillary pressure [34, 35].
A representative series of early experiments with a range of polymer solutions
is shown in figure 9 [90]. In each case, regression to a single exponential yields a
characteristic relaxation time ( ) c . As the concentration (c) of polymer increases, the
elasto-capillary thinning process slows down as a consequence of the increase in the
material relaxation time. At late times, two effects become evident; first a systematic
deviation from exponential behavior, arising from finite extensibility; and secondly the
discrete resolution of the laser micrometer can be seen in the staircasing of the
measured evolution in the filament diameter.
Entov & Hinch [34] also presented generalized expressions for elasto-capillary
necking in a dilute solution of dumbbells with an arbitrary spectrum of relaxation
times, { 1 }
i
i ,...n = and showed that after a short transitional period, the column
selects a necking rate so that only the mode with the longest time constant is in fact
being stretched. Anna & McKinley [87] considered the specific distribution of
relaxation times expected for the Rouse-Zimm model
m
i
i = , with m = 1.5 or
m = 2 corresponding to the Zimm model or Rouse model respectively. They note that
because the longest mode achieves an elasto-capillary balance in which the
Weissenberg number is
1
2/3
mid
= , all other modes experience a weak stretching flow
28
with 2 3
m
i mid
i = which, for i 2, is less than the critical value of 0.5 required for a
coil-stretch transition in a uniaxial extensional flow. Because the stretching rate is
constant in the exponential necking phase, the true transient uniaxial extensional
viscosity is obtained; however, in contrast to a filament stretching device, it is not
possible to vary the imposed deformation rate. Measurements for a series of
polystyrene solutions with different high molecular weight solutes have shown the
expected scaling in the longest relaxation time and quantitative agreement with linear
viscoelastic measurements in small amplitude oscillatory shear flow [87]. An
outstanding remaining challenge, however, is to understand the strong dependence of
the experimentally-measured relaxation time on the polymer concentration even at
concentrations well below c* [38, 85].
5.3 Visco-Capillary Thinning of Newtonian Fluids
Dimensional analysis can be used to argue that in the absence of inertia (i.e.
so that Oh >> 1) a filament of Newtonian fluid (with viscosity
s
) should neck
down at a constant velocity
cap s
v ~ . If the surface tension is known from static
tensiometry, then it should be possible to use measured variations in ( )
mid
R t to find the
viscosity of the fluid. Liang and Mackley [90] also performed experiments for a
Figure 9: Elasto-capillary thinning for a series of semi-dilute
polyisobutylene solutions dissolved in decalin. The average molecular
weight of the PIB is 210
6
g/mol and the concentrations are 1% (A20),
2% (A40), 3% (A60), 4% (A80), 5% (A100) respectively. Reproduced
from Liang & Mackley, J. Non-Newt. Fluid Mech. (1994) [90].
29
Newtonian fluid but were unable to obtain agreement with independent measurements
of the shear viscosity and surface tension. Similar problems were experienced in other
early experiments with Newtonian fluids [89], and these findings limited the spread
and utility of capillary thinning instruments . A comparison of the full axial profiles
obtained from experimental capillary thinning experiments with a viscous oil and a
dilute polymer solution is shown in figure 10. It is clear that for a Newtonian fluid, the
approximation of an axially-uniform cylindrical filament is less appropriate.
Direct integration of the one-dimensional equation for a Newtonian fluid gives
a linear variation in the filament profile with
( ) ( ) ( ) (6 )
mid s c
R t t t = [34] and the
numerical factor of
0 s
6 R corresponds exactly to the growth rate of the fastest
growing mode (of infinite wavelength) in Rayleigh breakup of a viscous fluid jet of
radius R
0
[28, 64]. However this analysis is only applicable for infinitesimal
perturbations about a cylindrical configuration and neglects the axial variations in the
slenderness of the fluid thread and the long-range nature of viscous stresses in low
Reynolds number flows. McKinley & Tripathi [91] used numerical calculations of the
full one-dimensional governing equation (14) and experiments with Newtonian
Figure 10: Comparison of temporal evolution in filament profiles for a
viscous styrene oligomeric oil and the same oil containing 500ppm of a
high molecular weight monodisperse polystyrene (M = 210
6
g/mol).
Adapted from S.L. Anna, PhD Thesis 2000 [23].
1 mm
t = 0 s t = 2.1 s t = 4.2 s t = 6.3 s t = 8.6 s t = 10.5 s
t = 0 s t = 8.5 s t = 17.0 s t = 25.5 s t = 34.0 s t = 42.5 s
SM-1 Fluid: 0.05 wt% PS (M
w
= 2 x 10
6
g/mol.) in oligomeric styrene
PS Oil: Oligomeric styrene
Bo = gR
0
2
19
t
*
=
0
R
0
( )= 8.5s
t
*
= 9.8 s
30
calibration fluids to show that incorporating these axial variations as well as
gravitational effects leads to additional contributions to the total force on the thread.
At short times, gravitational sagging in the filament was found to be important (as can
clearly be seen from the loss of top-bottom symmetry in figure 10) and leads to
deviations from the similarity solution [91]. However, for sufficiently small radii so
that gravitational effects are no longer important, the midpoint radius of a Newtonian
fluid undergoing capillary thinning evolves according to the similarity solution of
Papageorgiou [27] for visco-capillary (VC) necking indicated in figure 8 and table 2.
In dimensional form this expression may be written:
( ) ( ) 0.0709
mid c
s
R t t t
= , for ( )
mid
R g . ....(16)
The critical time to breakup may be obtained by setting
0
( 0)
mid
R t R = = to be
0
14.1
c s
t R = . The numerical front factor in this equation changes by a factor of
more than 100% from the value of 6 obtained from a simple zero-dimensional
balance. Clearly, an accurate appreciation of this correction factor is critical if
measurements of ( )
mid
R t are to be used to extract quantitative values of fluid
parameters that are consistent those measured in shear flows.
5.4 Elasto-Capillary Thinning revisited; the approach to full extension
Although the deviation is less marked, recent analysis has shown that there are
also differences between the one-dimensional and zero-dimensional analyses for a
viscoelastic fluid. The small, but non-zero axial gradients in the cylindrical thread lead
to a net tensile force in the thread that scales with the thread radius ( ) ( )
z mid
F t ~ R t as
expected but has a numerical coefficient that is slightly different from that assumed in
the zero-dimensional analysis [48]. The self-similar nature of the necking process in a
highly elastic fluid thread is shown in figure 11.
High resolution video-microscopy imaging and an edge-detection algorithm is
used to image the junction region matching the cylindrical draining thread to the
hemispherical quasi-static end-drop [92] as shown in figure 12(a). As time progresses
this region becomes increasingly sharp. When plotted on a dimensionless scale
normalized with the neck radius ( )
mid
R t (here denoted ( )
min
h t ) it is clear that the
profiles progressively approach a single self-similar profile (figure 12(b)). These
experimental observations are in good agreement with the similarity solution to the
one-dimensional governing equation for the Oldroyd-B model shown by the dashed
line in figure 12(b). This similarity solution predicts the same necking rate as the zero-
dimensional elasto-capillary analysis (as given in equation (8)); however the front
factor is modified by a factor of
-1/3
2 as shown in table 2.
As we have noted in 4, when the molecules approach full stretch the necking
dynamics cross-over from exponential to linear decay as given by equation (11) and
indicated schematically by the dashed line in the rightmost figure of table 2. Entov &
Hinch [34] use the FENE-P model to provide a very approximate estimate of the
corresponding critical time to breakup.
31
Figure 11: High resolution videomicroscopy showing the progressive
formation of the corner region during capillary thinning in a PS/PS
Boger fluid; (a) digitized filament profiles; each profile is separated in
time by 2 0.4
Z
t s = ); (b) the profiles slowly approach a self-similar
shape when plotted in dimensionless form scaled with the minimum
filament radius. Reproduced from Clasen et al. J. Fluid Mech. In press,
(2005) [92].
(a)
(b)
32
Stelter et al. [93, 94] used careful measurements of the thinning dynamics in a
wide range of different drag-reducing polymer solutions to construct nomograms of
the measured relaxation time and the steady elongational viscosity; a representative
example is shown in figure 12. The measurements show that the data lie along two
distinct limiting curves; one for flexible non-ionic polymers (upper curve labeled 1)
and one for ionic polymers (labeled 2) which exhibit aspects of rigid-rod like
behavior as a result of charge repulsion along the chain.
This nomogram shows that as the relaxation time increases (either via
increasing the molecular weight of the chain or the concentration in solution) the
steady extensional viscosity also increases. The existence of two bounding curves
provides a convenient method of rapidly assessing the molecular extensibility of a
particular polymer chain. However the theoretical underpinnings of this empirical
correlation have not been firmly established yet. Substitution of the analytic
expression for the axial stress in a finitely-extensible dumbbell model given by
equation (7) into the zero-dimensional force balance (equation (15)) confirms that
observation of a linear radial decay in a capillary thinning experiment at long times
indeed corresponds to measurement of the true terminal extensional viscosity:
2
3 2
E,app E s p
L = + . If the solvent contribution given by the first term in this
expression is negligible then noting that the polymeric contribution to the viscosity is
Figure 12: Variation of the steady-state apparent extensional viscosity
(here denoted
E, t
) with the characteristic relaxation time () for a
number of aqueous solutions including polyacrylamide (Praestol);
polyethylene oxide (PEO); carboxymethycellulose (CMC) and
Xanthan gum. Curve 1 denotes flexible coil behavior; curve 2
denotes rigid rod behavior. Reproduced from Stelter et al. J. Rheology
(2002) [93].
33
p B
G nk T = , we find that the steady elongational viscosity is linearly dependent
on the relaxation time as shown in figure 12. However the molecular extensibility
parameter is an independent parameter and so a family of curves is perhaps to be
expected. The curves in figure 12 confirm the expectation that the molecular
extensibility of an expanded ionic polymer is smaller than for a non-ionic flexible
Gaussian chain. Stelter et al. [93] also show that as salt is progressively added to
polyacrylamide solutions and the intramolecular charge repulsions are screened out,
measurements of the
E
/ relationship move laterally from curve 2 to curve 1;
consistent with a decrease in relaxation time and an increase in molecular extensibility.
Recent drop pinch-off experiments with polyelectrolyte solutions including partially-
hydrolyzed polyacrylamide and DNA show that this increase in flexibility and the
concomitant increase in the elongational viscosity correlate with enhanced turbulent
drag reduction [95].
In general, molecular models such as the Rouse-Zimm model predict different
scalings with molecular weight for the polymer relaxation time and for the steady-state
extensional viscosity. The scaling of the former quantity with molecular weight is well
known,
3
w
~ M
, where is the solvent quality exponent [96] and the scaling for the
steady elongational viscosity can be found to be
2 3 2(1 ) 1
( )(
A B
E w w w
w
cN k T
G L ~ M M ) ~ M
M
+
. .....(17)
In the limit of a theta solvent ( 1/2 = ) the scaling of relaxation time and elongational
viscosity with
w
M is identical, in agreement with the linear variation in the
E
/
relationship observed in figure 12. For hydrodynamically-interacting chains in good
solvents ( 3/5 ) there is a small difference in the scaling of the steady elongational
viscosity
( )
1.6
w
M and the characteristic relaxation time
( )
1.8
w
M . However large
variations in the molecular weight would probably be needed to observe these effects
in capillary thinning experiments and this may explain why no discernable spread in
the data beyond a single line is seen in the experiments in [93]. Further considerations
regarding the steady elongational viscosity of flexible and rigid polymers in solution
are reviewed by James & Sridhar [97]. Repeated capillary breakup experiments on the
same sample have also been used as a means to monitor the effects of extensional flow
on the degradation of macromolecules commonly used in drag reduction studies [84,
89].
In most of the careful studies of capillary thinning in polymer solutions the
fluids have been sufficiently viscous and elastic enough that gravitational drainage is
relatively unimportant; however if the aspect ratio of the imposed stretching
deformation is increased substantially then this can lead to pronounced asymmetries in
the filament [98]. As the Ohnesorge number is decreased, inertial effects can also
become important and careful control of the aspect ratio employed in experiments is
critical. Rodd et al. [99] have recently presented a series of experiments with low
viscosity aqueous solutions of polyethylene oxide in water and show that, in general,
successful measurements of capillary thinning require either
0
1 De (for polymer
solutions) or 1 Oh (for Newtonian fluids).
34
5.5 Concentrated Polymer Solutions
As the concentration of polymer is increased, coil overlap and entanglement
effects become increasingly important. Experimental measurements and constitutive
models for such systems show that the steady extensional viscosity may show both
extension-rate thickening and extensional-thinning depending on the imposed
extension rate [100]. Consequently capillary thinning and breakup measurements may
show pronounced deviations from the simple elasto-capillary balance appropriate for
dilute solutions. This can be seen in the experimental measurements at the highest
concentrations (A80, A100) in figure 9; the filament necking rate becomes
increasingly rapid as the chains become increasingly deformed and disentangled.
Capillary-thinning measurements on entangled polystyrene solutions show that the
filament evolves on time-scales corresponding to the Rouse time for molecular
stretching rather than on the longest (reptation) time scale [101]; however a
quantitative theory for this evolution is presently lacking. Numerical calculations
suggest that the Giesekus model provides a good qualitative description of entangled
solution response in transient extensional flows [80, 102]; however, no simple analytic
solution for the evolution in the midpoint radius is available for this, or any other
nonlinear differential constitutive model.
Renardy uses asymptotic analysis [40] to show that for many nonlinear models
the filament dynamics close to breakup change substantially and the radius can go to
zero uniformly over a finite region of space rather than at a single point. This
phenomenon has not been observed definitively yet but the consequences of
entanglement effects in capillary thinning can be illustrated by the experimental
images shown in figure 13. The fluid is a semi-dilute entangled solution of polystyrene
in tri-cresyl phosphate (TCP) which has been well-characterized in both steady and
oscillatory shear flows and is weakly strain-hardening in transient extensional flow
[103]. As the filament necks, the formation of a thin elastic filament can be observed.
However before the elasto-capillary similarity solution shown in figure 11 is fully
established, the maximum elongational viscosity is reached, the necking rate in the
central section increases and filament failure occurs. The enlargement of the final
frame suggests that the ultimate breakup event occurs simultaneously at several spatial
locations; however high speed and high resolution studies of breakup in entangled
solutions are needed for definitive assessment.
5.6 Weakly Viscoelastic Fluids
In the limit of very weakly elastic liquids, elongated filaments and strands are
not observed; however it can be seen from the form of equation (15) that any non-
Newtonian contribution to the total stress may be expected to retard the rate of
necking (as given by
mid
dR dt ). Since the flow is elongational in character, the use of
the Reiner-Rivlin class of models is appropriate to analyze the first effects of non-
Newtonian stresses [19]. Following specification of the form of the two functions of
the flow invariants in this model, the resulting equation set can then be integrated
forward in time. For the simplest case of a second order fluid, the extensional viscosity
can be expressed in the form 3 3
E s E
b = + . This expression can be combined with
35
equations (1) & (15) and solved analytically. The resulting solution is implicit in time
however, and is not given here. Instead we consider two appropriate asymptotic limits:
for low deformation rates and short times, the material response is Newtonian and the
necking rate is linear in time; however, close to breakup the quadratic term in the
extensional viscosity expression dominates. In this regime, the filament radius
decreases quadratically in time as indicated in the fourth column of table 2. The
filament still breaks in finite time and both the strain and the strain-rate diverge,
despite the extensional-thickening in the viscosity. Preliminary experiments in our lab
using STP oil (a prototypical weakly elastic fluid employed by Joseph and coworkers
in rod-climbing studies [104]) suggest that this is a simple but effective model for
interpreting the first non-Newtonian effects in capillary thinning [105].
5.7 Generalized Newtonian Fluids
Renardy [36] has considered the case of Generalized Newtonian Fluids and
shown that similarity solutions exist with an exponent that depends on the functional
form of the viscosity and how it varies with deformation rate in the necking fluid
thread. Recently Doshi et al. [106, 107] have considered the case of power-law fluids
Figure 13: Images of the elastocapillary necking of a concentrated
polystyrene solution (5wt% PS in tricresyl phosphate (TCP)). The shear
rheology of the fluid is well described by a single Giesekus model with
0
= 59 Pa.s,
s
= 2 Pa.s, = 0.6 s and = 0.2 Unpublished results;
courtesy of O. Brauner and A. Tripathi.
t-t
c
= 2.23 s
t-t
c
= 1.23 s
t-t
c
= 0.57 s
t-t
c
= 0.23 s
g
Bo = gR
0
2
3.1
36
and Carreau fluids in detail. In the region of the neck, the capillary pressure is high
and consequently so is the necking rate. The local decrease in the effective viscosity in
this region leads to a positive feedback effect and the necking rate accelerates
continuously. The fluid column thus shows enhanced axial gradients and a cusp-like
profile close to the pinch region as indicated schematically in table 2. In fact a detailed
analysis for the power-law fluid (both with and without inertia) shows that the
slenderness assumption (i.e. that 1 dR dz < ) is violated for a power law fluid with
exponent n 2/3 [107].
For a power-law fluid with constitutive equation
( )
n 1
K
= , the midpoint
radius varies as:
( )
0
( )
n
mid
c
R
n t t
R K
= , ....(18)
where n is the power-law exponent, K is the consistency index and ( ) n is a
numerical constant. A series of numerically-computed profiles are shown in figure
14(a).
As the filament necks down and approaches the singular point of breakup (at
( )
c R
t t t = = 0) the midpoint radius is well-described by a power-law of slope n.
Measurements with foods and consumer products which frequently exhibit inelastic
shear-thinning behavior show that the rate of filament necking is well-approximated
by this expression [108]. In figure 14(b) we show capillary thinning measurements in
two yoghurt samples; one a whole-fat sample and the other a low-fat formulation. The
image profiles (inset) from a high-speed video camera show the absence of a stringy
appearance and instead reveal the development of a cusp-like region in the neck.
Nonlinear regression of equation (18) to the data allows determination of the power-
law exponent characterizing the fluid rheology (n) and also the time to failure (t
c
)
which is important in package-filling operations.
In general the front factor ( ) n in equation (18) is a function of n and must be
found numerically. The zero-dimensional model of equation (15) gives 2 3
n
1D
=
and a polynomial regression to the numerical solution of the full similarity equations
[107] gives:
2 3
0.0709 0.2388(1 0.5479(1 ) 0.2848(1 )
num
n ) n n = + + + .(19)
for 0.6 n .
In each of the above expressions, the correct Newtonian result is obtained for
n = 1. In the case of a Carreau fluid, this power law-like necking is ultimately cut-off
by the background Newtonian viscosity (
(
| |
=
( |
|
(
\ .
, ....(20)
with a critical radius 3
y y
R = . Validation of the accuracy of this equation has yet
to be performed.
6. CONCLUSIONS AND FUTURE WORK
In this review we have surveyed recent experimental, numerical and theoretical
advances in our understanding of the capillary-thinning and breakup of complex
fluids. In addition we have attempted to note in each discussion some specific
technical questions that remain outstanding. In this section we highlight more broadly
some important areas for future research.
The liquid bridge geometry shown in figure 3(c) has become a standard
laboratory configuration for studying visco-elasto-capillary thinning for the reasons
highlighted above. However the other geometries are more relevant to commercial
processing operations and additional computational and theoretical analysis of these
configurations is needed. The addition of polymer to dripping jets and drop-on-
demand inkjet printing configurations can inhibit breakup and completely eliminate
satellite droplets [46, 47, 110].
39
An illustration of the dramatic effect of elasticity is shown in figure 15. The
left-hand image shows the pinch-off of a droplet in a low viscosity Newtonian fluid
(Oh << 1) and is now well-understood, both theoretically and numerically [43, 51, 64].
However the addition of high molecular weight polymer inhibits the singularity.
Figure 15: The effect of polymeric additive on drop pinchoff. (a) The
image on left shows the pinch-off of a water droplet; (b) the inhibition
of pinchoff through addition of 100ppm of PEO (M 4 10
6
g/mol). (c)
The measured evolution in the neck radius initially shows rapid necking
with
2/3
min
h ~ before crossing over to a slower exponential decay at
t 0.07s. Reproduced from Amarouchene et al., Phys Rev. Lett. (2001)
[46].
(a) (b)
(c)
40
Measurements of the neck radius shown in figure 15(c) show that at short times the
polymer does not modify the initial necking; however, there is an abrupt crossover
from inviscid-like dynamics (
2/3
h ~ ) to exponential elasto-capillary decay
( ( 3 ) h ~ exp t ) as expected from figure 8. A simple zero-dimensional model of the
neck evolution has recently been presented [38] but no numerical simulation of the
complete one- or two-dimensional equations has yet been possible. Interestingly the
system passes from an inertio-capillary to an elasto-capillary balance and viscous
effects are thus irrelevant throughout. This suggests that studies of the dynamics of
inviscid elastic fluids (or more accurately potential flows of viscoelastic fluids)
may be a viable avenue for future research. Joseph and coworkers have recently used
such an approach to consider the linear stability of viscoelastic jets and find excellent
agreement with the full linear theory [111, 112]; however, the extension to large
amplitude deformations and nonlinear viscoelastic effects remains to be considered.
Other liquid bridge configurations have also been proposed as potential
elongational rheometers for probing the response of complex fluids. In particular, the
filancemeter has been developed as a method of probing the spinnability of
viscoelastic biological fluids such as respiratory and cervical mucus [113, 114]. It has
been known since the early work of Scott-Blair with bovine mucus that the apparent
extensional rheology of these fluids varies significantly with hormonal cycles [115].
This has lead to patented devices that use ex-vivo measurements of the extensional
viscoelasticity for probing fertility in both cows and humans [116]. The filancemeter
uses an axial drive system to elongate a cylindrical liquid bridge linearly in time
beyond its Plateau stability limit. The force in the stretched fluid column is not
measured; however the variation in the total lifetime as the pulling velocity is varied
can be determined with high accuracy by measuring the electrical conductivity
between the upper and lower plates. Numerical calculations with Newtonian [68] and
Generalized Newtonian Fluids [67] show that the length to breakup increases
monotonically with the capillary number and also depends on the extensional rheology
of the fluid. James has recently shown that measurements of the increased length to
breakup resulting from non-Newtonian stresses can also be used to probe the
extensional rheology of weakly elastic fluids such as printing inks and coating colors
[117]. Careful experiments with Newtonian fluids suggest that the length to break
increases beyond the Plateau stability limit with the square root of the separation
velocity [118]; however, there is presently no analytic theory for Newtonian or non-
Newtonian fluids.
Although we have reviewed experimental measurements for a large number of
different materials in this article, the extensional rheology of several classes of
complex fluids that have not been studied extensively to date; especially surfactant-
based systems. Theoretical analysis of the necking of a viscous Newtonian thread in
the presence of an insoluble surfactant shows that Marangoni stresses dramatically
affect the necking dynamics and satellite formation; however ultimately the surfactant
is convected out of the neck sufficiently fast that the visco-capillary solution of
Papageorgiou is regained [119]. Linear stretching experiments with a soluble
surfactant [120] show that, depending on the viscosity of the bridge, the presence of
surfactant can either increase the length to breakup (if Oh >> 1) or decrease it (if
41
Oh <<1). It will be interesting in the future to study other surfactant systems such as
worm-like micellar solutions which exhibit strong strain-hardening in filament
stretching experiments followed by sudden rupture events at high stresses [121].
7. ACKNOWLEDGEMENTS
I would like to acknowledge the stimulating discussions on this subject over a
number of years with Oliver Harlen, Howard Stone, Vladimir Entov, Ole Hassager,
Jens Eggers, Jie Li, Christian Clasen and Anubhav Tripathi. In addition I would like to
acknowledge the assistance of the following people in my laboratory for providing me
with unpublished results: A. Park, Dr. C. Clasen and Dr. J. Bico. Research on
extensional rheology in my laboratory is supported by NASA, NSF and the
Schlumberger Foundation and I gratefully acknowledge their support.
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