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Chemfcol Engineering Scknce,

Printed in Great Britain.

Vol. 41, No.

I, pp. 65-72,




s3.00 + 0.00
1986. Pergamon Press Ltd.


P. K. DAS and R. KUMAR
Department of Chemical Engineering, Indian Institute of Science, Bangalore 560012, India
Department of Chemical Engineering, Indian Institute of Technology.

Kanpur 208016, India

(Received 15 February 1985)

model of breakage of drops in a stirred vessel has been proposed to account for the effect of
rheology of the dispersed phase. The deformation of the drop is represented by a Voigt element. A realistic
description of the role of interracial tension is incorporated by treating it as a restoring force which passes
through a maximum as the drop deforms and eventually reaching a zero value at the break point. It is
considered that the drop will break when the strain of the drop has reached a value equal to its diameter. An
expression for maximum stable drop diameter, d,.
is derived from the model and found to be applicable
over a wide range of variables, as well as to data already existing in literature. The model could be naturally
when the dispersed phase is a power law fluid or a Bingham
extended to predict observed values of d,,

two phases. The viscosity of the dispersed phase has,


however, been found to have a significant influence on

the drop size (Arai et al., 1977; Konno et al., 1982). The
viscous stress resists the flow inside the drop, leading to
its breakage, and sometimes this stress has the same
order of magnitude as the inertial stress due to pressure
fluctuation. There exists very limited information (Arai
et al., 1977; Konno et al., 1982) on the prediction of
maximum stable drop size taking into account the
effect of dispersed phase viscosity. Konno et al. (1977)
were the first to propose a model for predicting the
maximum stable drop diameter incorporating the
effect of dispersed phase viscosity. They considered
that the deformation of a drop under external stress
can be described by the Voigt model which simultaneously takes both interfacial tension (restoring
force) and viscous dissipation (due to resistance to flow
inside the drop) into account. In deriving the model
equations, they assumed that the pressure fluctuation
across a distance due to turbulent flow is periodic and
the break-up of a drop occurs when the deformation
strain (0) reaches a critical value, 13~~. They have
obtained a semi-empirical correlation for the maximum stable drop diameter in terms of two dimensionless groups, Weber number and viscous number.
Although their semi-empirical expression predicts
their experimental results reasonably well, the model is
open to criticism on several grounds. The Voigt model
has a maximum equilibrium deformation and it is
reversible. As such, it is hard to visualize the breaking
of a drop through a classical Voigt model. Arai ef al.
(1977) overcame this problem through the artifice of
associating drop breakage with a maximum deformation, Qr, which is left as an arbitrary parameter.
Further, the regular and periodic pattern assigned by
them to the turbulent flow around the drop does not

dispersions requires knowledge of the sizes of the drops

existing in the vessel. To estimate the drop sizes, it is
essential to know the break-up mechanism of a drop in
a turbulent dispersion. Hinze (1955) suggested a model
for predicting maximum stable drop diameter by
comparing the restoring elastic stress in the drop due
to interfacial tension with the inertial stress across the
drop diameter. He proposed that break-up of a drop
occurs when the ratio of the inertial stress to the elastic

The analysis

of rate processes

in liquid-liquid

exceeds a critical value.

stress, i.e. PCu* (4 40,
Assuming that turbulence is isotropic and that the
diameter d + 1 (Kolmogoroff length), the mean square
velocity fluctuation across distance, d, is given by
UZ(4) cc (&#3.


If the Reynolds number is sufficiently large, then for a

fully baffled vessel, the power dissipation per unit
mass, E, can be expressed as
E a N3D2.


Substituting eqs (1) and (2) in Hinzes proposed

criterion, Shinnar (1961) derived the following equation for the maximum stable drop diameter, d,,,:

= constant (We)-o.6


where We is the Weber number.

Equation (3) has been used by a number of investigators. Coulaloglou and Tavlarides (1976) have discussed exhaustively all the correlations available to
predict d,
in a turbulent dispersion.
Equation (3) is based on the assumption that there is
hardly any difference in densities and viscosities of the



J. S. LAGISEITY et al.


appear realistic, especially on the length scale of drop

size being dealt with. Apart from this, their model does
not give rise to the low viscosity limit of the maximum
stable drop size naturally and had to be introduced in
an ad hoc manner. Finally, their model does not yield a
final expression which can be used directly for evaluating the two constants contained in the model. Instead,
the final expression is assumed and the two constants
involved in it are evaluated from their own experimental data. Such a procedure does not allow extension of
their model to other rheologically complex fluids.
The present work aims at proposing a new phenomenological model which accounts for the effect of
viscosity of the dispersed phase in a more rational way.
It also tests the validity of the model against experimental results.

drawn from the vessel and the particle sizes measured

with an optical microscope. At least 150 drop diameters were measured to obtain the value of d,.
avoid coalescence of drops during sampling and
subsequent size measurements, polyvinyl alcohol
(PVA) was added immediately before drawing the
sample. This was done when the aqueous phase was
continuous_ When the aqueous phase was dispersed,
PVA was added to it at the beginning itself.
The liquids used together with their properties and
experimental conditions are listed in Tables 1 and 2,
respectively. Interfacial tensions were determined by
the pendant drop method. Viscosities were measured
with a coaxial cylinder viscometer.


The experimental apparatus consisted of a glass

vessel of 14.5 cm i-d. and 20 cm height. The impeller
used was a six-bladed disk turbine, placed centrally in
the mixing vessel through a stainless-steel shaft, which
in turn was connected to a motor, the speed of which
could be regulated. A set of four, equally spaced
stainless-steel balIles, arranged vertically at the wall of
the vessel, was used. The width of each baffle was equal
to one-tenth of the diameter of the vessel. A schematic
diagram of the equipment is shown in Fig. 1.
The continuous phase was taken in the stirred vessel
and the stirrer speed raised to the desired value. The
dispersed phase was then added to the vessel. The
dispersed phase volume fraction was kept at less than
0.02 to minimize coalescence. The equipment was run
for 1 h to achieve steady state. Samples were then



Fig. 1. Diagram of the stirredvessel.



When a viscous droplet becomes deformed in a

turbulent flow field, the viscous stress due to the
internal flow will act simultaneously with the interfacial tension force to resist the deformation of the drop
against the external inertial stress arising from the
turbulent pressure fluctuations. If the inertial stress is
sufficiently large and sustained over a long enough
time interval, the drop will deform and a thin column
of liquid will appear somewhere in its bulk. The
column will break due to instability producing two
daughter droplets. This has been assumed to occur
when the magnitude of deformation is of the order of a
drop diameter. As the interfacial tension restoring
force is absent both at zero deformation and at the
breakage point, this restoring force should pass
through a maximum as deformation proceeds. In this
connection, it is interesting to note that based on
calculations for low Reynolds numbers, Rallison
(1984) states that for globular drops, surface tension
acts as a restoring force but that surface tension may
even promote breakage once the drop becomes
elongated. As the interfacial tension and viscous stress
simultaneously oppose the inertial stress, the Voigt
model offers a suitable description of drop deformation. However, the elastic stress due to interfacial
tension needs to be represented in a more realistic
fashion. The Voigt model corresponding to the process
of deformation is presented in Fig. 2.
In accordance with the Voigt. model, the applied
stress (T) must be equal to the opposing elastic stress
due to interfacial tension (rJ plus the viscous stress (7,).
The governing equation therefore has the following
7 =
7, + 7.

1. Experimental conditions

Impeller speed
Reynolds number of the
continuous phase
Dispersed phase volume

1.5 x l@-5

x 104


Breakage of drops in a stirred suspension

Table 2. Properties of the $ontinuous and dispersed phases for the systems studied
Dispersed phase

Continuous phase












in styrene
lO-30% by
lOOm1 of
CMC in water
(2.5 %I +
60ml of 2%

CaCO, aqueous
(59.5 % Caco3 +
2.00 y0 polyvinyl











The condition that 7, is zero for 0, > 1 explicates the

essential feature of the model, i.e. the drop has reached
its break point when the dimensionless strain has
reached the value of unity and surface tension can no
longer bring it back to its original state. Thus the Voigt
model proposed in the present work cannot retract to
its original state, once 0, & 1, even when the applied
stress is withdrawn.

equation for TV
For the fluids considered in this work, the constitutive equation for viscous stress can be written in a
generalized form as
7v =
Fig. 2. Voigt model for the deformation of a drop.

equation for T,
When the drop suffers a small but finite strain, the
interfacial tension force generates a restoring stress
proportional to the strain. However, as the drop
undergoes further deformation and approaches the
breaking point, its structure will be more like that of a
dumb bell: two yet to be born daughter droplets
connected by a thin filament of liquid. The filament will
break because of its inherent instability. Thus near the
break point,- surface tension has no restoring effect.
Hence a more realistic description of the role of surface
tension must be to assign to it a retractive force that
increases for small deformations of the drop but
decreases afterwards and eventually reaches zero at the
break point. Assuming that the total deformation
undergone by the drop up to the point of breakage is of
the order of magnitude of d, the following simple
functional relationship between 5, and 0, has been
TS= $ es (1 -e,>
= 0

e, c 1

e, 3 I.


TV +



Equation (6) simplifies to the case of Newtonian,

Bingham plastic and power law models when appropriate simplifications are made.
Model equation
For a Voigt element, the total strain 8 = 8, = 0,.
Noting this and substituting eqs (5) and (6), respectively, in eq. (4), we obtain


e c



The flow inside the drop during breakage will be quite

complex. In the present model, however, it has been
assumed to be a simple shear flow.
of z
In eq. (4), T represents the dynamic pressure difference across the drop diameter. In a turbulent flow
field the pressure difference normally associated with
the arrival of eddies is a quantity which fluctuates with
time and distance over which it operates. However,
exact knowledge of the fluctuations is not yet available.
Therefore, it is assumed that the deformation takes
place under the influence of a mean stress which
remains constant over the average life time of an eddy.


J. S. Llsorszrrv et al.

for average values of 7 and T

Let the average values of 7 be + and the average life
time of an eddy beF The expressions for these average
values given by Hinze (1955) and Coulaloglou and
Tavlarides (1977) have been used in the present
investigation. They are


7 ~PcU2W

cannot show any instantaneous deformation on the

application of the stress. Hence


By separating the variables, eq. (15) can be written as




mass, E, and u2 (d)

Tavlarides (1977) are

a = C We (d/D)s3





E = 0.407 IV= D2


u2 (d) = 1.88 s23 d23.


Therefore + can be expressed as:
+ -_ C pc N2 D4/= d2j3


where C is a constant dependent only on the geometry

of the tank and agitator. The average life time is given



The drop experiences no stress prior to its coming

under the influence of an eddy and from then onwards,
a constant stress equal to + for a time interval of T

$213 _


d/u) -



solution of eq. (18) with the initial condition

depends on the constant a in eq. (19). There are two
possible solutions corresponding to a < 0 or a > 0. If
a -Z 0, it can be shown that when t -B co, 8 --r [l/2


- fi]_
Thus, Bean never reach a value of unity, and
breakage is not possible in the finite time interval ofT_
But tI can reach unity in a finite time period when a
> 0, and therefore to predict the maximum drop
diameter, only values of a greater than zero need to be
Our main concern is to know the maximum size of a
drop that can exist in the stirred vessel. All drops above
such a size will break. As stated earliei, the drop has
been assumed to deform under the influence of T for a
period of?? The maximum stable drop size therefore is
the maximum threshold drop size which reaches a
deformation of unity when exposed to a constant stress
F during the time interval F. Such a drop size can be
calculated as follows.
Equation (18) is integrated to find rl at 8 = 1. If rl at
8 = 1, the dimensionless time required to reach deformation corresponding to breakage, is more than the
nondimensional life time of the eddy, breakage would
not occur. Thus for breakage to occur, the following
condition must be satisfied:
q (0 = 1) < (u/dIQ1Z

Substituting these into eq. (7), we obtain



It is necessary to express u2 (d) in terms of the

parameters associated with the stirred vessel. The
expressions for the rate of energy dissipation per unit

Tg +1





(dlJ/dt# = C We (d/D)/

- (q,d/o)

- (0 - 02)


where rl is the nondimensional time given by

q = (o/dK)



stable drop size

The drop is exposed to a stress of i only for a time

period T After this time, the eddy would have dissipated its energy and the external stress on the drop
becomes zero once again. If at the end of the time
interval T the value of B -Z 1, then the surface tension
spring would still have a finite retractive stress and the
drop would return to its original state. Thus for the
drop to break it is not only necessary that 8 = 1 is
reached but also that it should be attained at some
point during the time intervalT. The time required to
reach 0 = 1 can be obtained by integrating eq. (15); an
initial condition is needed to do so. The dashpot


As the applied stress increases with diameter, q (0 = 1)

decreases with increasing diameter. The maximum
stable drop size is that for which

Equation (14) is more conveniently represented in

dimensionless form as





C PcN2


q (0 = 1) = (a/d_,



Thus eq. (18) can be integrated up to rl(0 = 1)

= (a/d_K)T
to find the maximum stable drop
size. Using the expression for T in eq. (9), ~(0 = 1) can
be written as
r.t(e = 1) = (Re/We)



D (NoI2 - nP,


integrated analytically; the solutions are listed in
Table 3. It should be noted that C = 8.0 has been used
in these results for both Newtonian and nonNewtonian fluids. This will be discussed further in the
Results and Discussion.
It should be noted that the model developed in the

Breakage of drops in a stirred suspension


Table 3. Solution of eq. (18) for non-Newtonian fluids

Solution of the model equation

[32 We (d_/D)s3

= (RejWe) (d-/D)-

- I]* tanm



(Re/We)3/2 (d-/D)-


We (d_/D)
x tan-


(32 We (d_/D)513

c32 We(d_;D)

- 1) + [32 We (d_/D)53


-l)* Wez(d_/D)o]
x tan-

[32 We (d_;D)=

- l]*

- l]3/2


+ (32 We(d,,,f/$


[Re/ We] (d-/D)

- 1)5f*
- j3

present work involves a single parameter whereas

the model proposed by Arai et al. (1977) requires the
knowledge of two parameters to be evaluated from
experimental data. A positive test that can be applied to
the present model is that the constant C involved in eq.
(12), which relates the turbulent pressure fluctuations
to d, N and D, should not depend on the rheological
properties of the dispersed phase. If this is satisfied,
then clearly the present model offers a distinct advantage over the model of Arai et al. (1977) which
requires the evaluation of two parameters.



Newtonian fluids

and inviscid limit

One of the interesting aspects of the model is that as
the dispersed phase viscosity becomes very small, i.e.
,ud+ 0, the solution of the model equation reduces to
the well-known and widely tested equation given by
Shinnar (1961). For example, looking at the equation
for a Newtonian fluid (n = 1) presented in Table 3, the
only solution that is possible as pd - 0 or Re -+ co is
-+ constant. This result is identical
that We (d_/D)53
to eq. (3) reported by Shinnar (1961).
Using the data of drop diameters against dispersed
phase viscosity for different speeds, the value of
constant C in eq. (12) has been determined. The value
of the constant worked out to be 8.0. Figures 3 and 4
show the experimental drop diameter, d,,
dispersed phase viscosity, pd. and impeller speed. The
results predicted by the model are shown as lines
whereas the points are experimental results. The
theoretical predictions are in good agreement with the
observations. From this, it can be seen that C is
dependent only on the geometry of the vessel and
agitator, and not on cl,,. Further, it is worth noting that
the effect of dispersed phase viscosity on d,
significant only after about 20 cP.
The predictions of the present model and the
numerical value of constant C can be further tested
using the experimental observations of other workers.

Fig. 3. Comparison of experimentalresultswith the present

model (effectof Jo)_

When the dispersed phase viscosity becomes small, i.e.

p, -V 0, the model predicts that

= 0.125 (We)-*6.

Sprow (1967) has given the following empirical relationship when the dispersed phase viscosity is small:

= a1 (We)-.6.

The value of a 1 lies between 0.126 and 0.15, which is in

agreement with the value found in the present work.
The present value of 0.125 is somewhat better because
it fits a large amount of other experimental data. For
instance, the experimental results of Arai et al. (1977)
also agree with the present model. This is shown in
Fig. 5.
The present model can be easily modified to incorporate the effect of the dispersed phase hold-up.
The value of the mean square velocity, u* (d), changes
with the change in the dispersed phase hold-up. The



et al.

(1976) indicate that d,

= 1.5 dS2. Therefore

= 0.083 (1 + a2#).







N (r.p.m

pd c 3



z 20


= 4.5


Fig. 4. Effect of impeller speed on the maximum stable drop



i L-0

Figure 7 presents the experimental results of maximum stable drop diameter with change in impeller
speed for a power law fluid (2.5 0A CMC in water
+ PVA, n = 2/3). The grade of CMC used was the
same as that employed by Kumar and Saradhy (1972).
These authors used a test attributed to Philipoff to
ensure the absence of viscoelasticity in CMC solutions
up to a concentration of 4% by weight. The other
component of the solution used in the present work
was PVA, with a molecular weight of about 70,000. At
this molecular weight and low concentrations, PVA
will also not impart an elastic character to the solutions. Therefore the solution employed in this work
can be safely considered to be inelastic. The drop
diameter decreases with impeller speed in a nonlinear
fashion. As mentioned earlier, according to the model,




It is found that for a2 = 4.0, the model predictions

given by eq. (26) fit the experimental data of
Coulaloglou and Tavlarides (1976) on continuous
systems reasonably well. This is shown in Fig. 6.
It can be concluded that the value of 8.0 assigned to
constant C is related only to the geometry of the vessel
and agitator, and arises from the nature of the
turbulent fluctuations. It is not affected by the properties of the dispersed phase, which have been varied
over a wide range. The model itself can then be seen to
account for the variation of the viscosity of the
dispersed phase. This can be tested further by examining non-Newtonian fluids.


I/ /


















Fig. 5. Comparison of experimental results (Arai

the present model.

value of m
Tavlarides, 1977)


et al.)

4 as (Coulaloglou

= (1 +a2+)-2.0[uz(d)]+o.




Using the modified expression for u2 (d), the equation

for maximum drop size for Newtonian fluids in the
limit of small viscosity becomes

= 0.125

(1 + r~~+)~ (We)-.6.


The data available in the literature is in terms of dx2.

Sprow (1967) and Coulaloglou and Tavlarides (1976)
indicate that da2 is linearly related to d,.
continuous systems, Coulaloglou
and Tavlarides


0 05
z 4.0

Fig. 6. Comparison of Coulaloglou and Tavlarides experimental values (effect of 4) with those predicted by the present

Breakage of drops in a stirred suspension


numbers, i.e. at high values of p,, all the curves merge,

indicating that interfacial tension does not play a
significant role in the breakage of drops. This result is
expected, since when the drop is sufficiently viscous,
the applied force essentially overcomes
the mean
viscous resistance, compared to which the restoring
surface tension force is insignificant. On the other
hand, at high Reynolds numbers, the restoring force
due to interfacial tension is predominant compared to
the viscous forces and the applied force essentially has
to overcome the restoring interfacial tension forces.
That is why at high Reynolds numbers different lines
are obtained for different Weber numbers.



ti (r.p.m

Fig. 7. Comparison of experimental results with those predicted by the present model for a power law fluid.

constant C must be independent of the rheology of the

dispersed phase. The solid line represents the results
calculated from the model using constant C evaluated
with the experimental results of Newtonian fluids, i.e.
calculated from the second equation of Table 3. It was
found that the model predicts the results reasonably
well. This lends further credence to the model.
Generalized representation
The model predictions can be represented in generalized graphs by plotting (d-/D)
against the Reynolds
number, Re (defined on the basis of the viscosity of the
dispersed phase) with the Weber number, We, as a
parameter. Figure 8 shows plots of d-/D
against Re,
with We as a parameter for the values of n equal to I,
2j3 and 1j3. The plots show that at low Reynolds

Bin&am plastics
For Bingham plastic fluids the theoretical equations
can be easily developed by replacing 7 in the differential
equations for purely viscous fluids with (7 - 70)_ It is
easily shown that this corresponds to replacing
[32 We (d_jD)s3

- l]
[32 We (d_jD)5/3

- 4

(7,, d-/a)

- l]

in equations of Table 3. This implies the usage of the

same value of C determined from Newtonian fluids.
Figure 9 presents the experimental results of the
maximum stable drop diameter with change in the
impeller speeds for a Bingham plastic fluid (aqueous
CaCOS suspension with PVA, c = 45.2 dynes/cm T,,
= 75 dynes/cm, n = 1, p,, = 13.7 cP). It is found that
the drop diameter decreases with increase in the
impeller speed in a nonlinear fashion. The solid line
represents the theoretical results calculated from the
first equation of Table 3 with the modification
described above. The dashed line represents the drop
diameters that would have been observed if the fluid
had been Newtonian,
i.e. 7. = 0. The experimental
results are higher than those for a Newtonian fluid
since the effective applied stress is now lower. The
model reflects this and predicts the d,
values quite
well, thus accruing more evidence in its favour.

Fig. 8. Effect of the Reynolds number on d,,, /D with the Weber number as a parameter.



et al.



u= (d)





Fig. 9. Effect of impeller speed on the maximum stable drop

diameter for a Bingham plastic fluid.

Kolmogoroff length scale, cm

power law index
impeller speed, rev/s
D (ND)- pJ(2- (3 + l/n) K), Reynolds
time, s
average life time of eddy, s
mean square velocity fluctuation across distance d, cm2/s2
N2 D p,/a, Weber number

Greek letters
energy dissipation rate/mass, cm2/s3
dimensionless time
dispersed phase hold up
density of the continuous phase, g/cm
viscosity of the dispersed phase, poise
dimensionless strain; subscripts s and v refer
to spring and viscous parts
dynamic pressure difference across the dis
ameter of the drop, dynes/cm2
average value of t, dynes/cm
yield stress, dynes/cm
resistive stresses due to spring and viscous
dashpot, respectively, dynes/cm2
interfacial tension, dynes/cm


A model of breakage of drops which accounts for

the effect of interfacial tension in a realistic way has
been used to predict the maximum size of a stable drop
in a turbulent stirred dispersion. Separation of the
rheology of the dispersed phase and representation of
the turbulence characteristics of the stirred vessel by a
constant, dependent only on the geometry of the vessel
and agitator, are the essential features of the model.
Measurements on Newtonian fluids, power law fluids
and Bingham plastics show the efficacy of the predictions of the model and confirm its main features.


Arai, K.,Konno,

M., Matunga, Y. and Saito, S., 1977, Effect of

dispersed phase viscosity on the maximum stable drop size
for break-up in turbulent flow. .I. them. Engng Jap. IO,
Coulaloglou, C. A. and Tavlarides. L. L., 1976. Drop size
distributions and coalescence frequencies of liquid-liquid
dispersions in flow vessels. A.1.Ch.E. J. 22, 289-297.
Coulaloglou, C. A. and Tavlarides, L. L., 1977, Description of
interaction processes in agitated liquid-liquid dispersions.
Chem. Engng Sci. 32, 1289-1297.
Hinze, J. O., 1955, Fundamentals of the hydrodynamic
mechanism of splitting up in dispersion process. A.I.Ch.E.
J. 1, 289-295.

Konno, M., Arai, K. and Saito, S., 1982, The effect of stabilizer




constant dependent only on the geometry of
vessel and agitator
drop diameter, cm
Sauter mean diameter, c nid:/C n,df,cm
maximum drop diameter, cm
impeller diameter, cm
power law constant, g/(cm s*-)

on coalescence of dispersed drops in suspension polymerization of styrene. J. &em. Engng Jap. 15, 131-135.
Kumar, R. and Saradhy, Y. P., 1972, Drop formation in nonNewtonian fluids. I.E.C. (Fund.) 11, 307-311.
Rallison, J. M., 1984, The deformation of small viscous drops
and bubbles in shear flow. Ann. Reu. Fiuid Mech. 16,4%X
Shinnar, R., 1961, On the behaviour of liquid-dispersions in
mixing vessels. J. Fluid Mech. 10, 259-275.
Sprow, F. B., 1967, Distribution of drop sizes produced in
turbulent liquid-liquid dispersion. Chem. Engng Sci. 22,