Langmuir
■ THE FORCE BALANCE MODEL
In order to derive an equation of motion to describe a bubble’s
rise and collision with a liquid−liquid or compound interface,
the same force balance approach that has proven itself with free
surface12 and solid surface6,7 collisions is applied. Four forces
are considered in this analysis: buoyancy, FB, drag, FD, added
mass, FA, and a film force, FF. This same force balance is
applied to all three models outlined here, so it will be detailed
only once. The present models focus on dynamic collisions of
relatively large bubbles (0.1 < R < 1 mm) with Reynolds
numbers up to ∼700 but Weber numbers below ∼3. If the
Weber number exceeds this value, then bubbles no longer rise
in a rectilinear path but instead develop wake instabilities that
cause them to rise in a zigzag or spiral path.43,44 The present
model considers only pure liquids, so the liquid−gas interfaces
in the systems are considered to be fully mobile. The film
formed between the bubble and the interface during the
collision is expected to have a thickness on the order of
micrometers.6,11 As such, surface forces due to van der Waals
and electrical double layer interactions can be neglected as they
do not become significant until the film reduces to ∼100
nm.6,48 The history force, a result of the drag force requiring
some time to establish itself, can also be neglected since
bubbles with mobile surfaces are being considered.6,49
A constant buoyancy force acts upward on the bubble.
Neglecting the density of the gas inside the bubble, this can be
written in terms of the bubble volume, surrounding liquid
density, ρB, and the gravitational constant, g:
4 face, and as such, this previous work defining the added mass
FB = − πR3ρB g
3 (2)
Acting against the bubble’s direction of motion is the drag
force. This force steadily increases with the bubble’s rise
velocity, V, until it balances out the buoyancy force and the
bubble attains its terminal velocity. The drag force is written
as50
π be negligible, and the coefficient value used for free or solid
FD = C DRe μB RV
4 (3)
where μB is the viscosity of the liquid surrounding the bubble,
CD is the drag coefficient, and Re = ρB|V|2R/μB is the
instantaneous Reynolds number. As the velocity of the bubble
increases, the bubble deforms from a spherical shape to an
oblate spheroid. The degree of deformation is typically
characterized in terms of the aspect ratio, χ = Dh/Dv, using
the Reynolds number and the Weber number, We = ρBV22R/
σB, where σB is the surrounding liquid surface tension. The
drag coefficient in the present model is defined based on these
three parameters to take the shape deformation into account
using the theory compiled by Loth41 for a bubble rising with a
mobile surface. This theory is applicable for bubbles with
Reynolds numbers up to 10,000 and any Weber number. The
terminal velocity of the bubble can be determined based on a
balance of these two forces. Extensive experimental validation
of the terminal aspect ratio and drag coefficient was also
presented by Loth.41
When the bubble undergoes any sort of acceleration, the
surrounding liquid must also accelerate with it, giving rise to an
added mass force. This added mass force can be determined
from a potential flow theory using the kinetic energy associated
with the moving bubble and is written as6,7,51
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FA =
4 3
3
πR ρB Cm
dV
dt
1 4
2 3
dC
− ρB πR3 m V 2
dH (4)
where Cm is the added mass coefficient. This coefficient is not
constant but varies depending on the bubble deformation, i.e.,
the aspect ratio,52,53 and the nearness of the bubble to an
interface or wall.6,7,51,54 For the sake of simplicity, the influence
of bubble deformation has been neglected in the calculation of
the added mass coefficient. However, as this assumption was
also made in the previous free and solid surface collision
models,7,12 which demonstrate excellent accuracy, these effects
are likely insignificant. An analytical solution for the added
mass coefficient of a spherical bubble approaching a free
surface and a solid surface was derived by Miloh.54 When the
bubble is touching a free surface or a solid surface, this
coefficient is reduced to 0.4198 or increased to 0.8020,
respectively. In the previous free surface collision modeling,
however, a constant value of 0.5 was demonstrated to be
sufficient in reproducing experimental results.12 An approx-
imate solution for the added mass coefficient of a spherical
bubble nearing a solid surface is given as a function of the
distance between the bubble and solid surface at the axis of
symmetry, H, and the bubble radius using ζ = (H + R)/R:51
Cm = 0.5 + 0.19222ζ −3.019 + 0.06214ζ −8.331
+ 0.0348ζ −24.65 + 0.0139ζ −120.7 (5)
The present models consider a bubble colliding at either a
liquid−liquid, solid−liquid−liquid, or gas−liquid−liquid inter-
coefficient for free and solid surface collisions is not directly
applicable. When a bubble collides at a liquid−liquid interface,
the upper liquid will also undergo acceleration. Therefore, this
added mass coefficient should ideally take the movement of the
upper liquid during the collision into account as well. For
compound interface collisions, the thickness of the top liquid
layer will also play a role in determining this coefficient value.
If the film is very thin, then the influence of the top liquid may
surface collisions would be applicable. For thicker films, the
effect will become more apparent and instead approach the
coefficient value for liquid−liquid interface collisions. At
present, the authors are unaware of any existing theoretical
analysis defining the added mass coefficient for bubbles
interacting with the interface types considered here.
Furthermore, similar arguments can be made for the buoyancy
and drag forces that the nearness of the bubble to the interface,
along with the properties and thickness of the upper liquid
layer, will influence these forces to some degree. Attempting to
capture all these variables in such a point force model presents
a difficult challenge that would significantly increase the
complexity of the model. For the time being, we leave these
considerations for future works and instead focus on defining
an added mass coefficient capable of replicating the
experimental data. For the liquid−liquid interface collision
model, the same approach used for free surface collision
modeling is applied here by using a constant value for the
added mass coefficient. As such, the second term in eq 4
reduces to zero. The specific value used is determined for each
liquid combination based on the experimental data. For the
solid−liquid−liquid interface collision model, the influence of
the solid surface is taken into account using eq 5. The
thickness between the bubble surface and solid surface, H, is
DOI: 10.1021/acs.langmuir.9b01209
Langmuir 2019, 35, 8294−8307
Langmuir
determined based on the combined thickness of the upper and
lower liquid layers at the axis of symmetry. For thinner initial
top film thicknesses, the equation is used as is, while for thicker
initial top film thicknesses, the nominal 0.5 value is replaced
with the value used in the associated liquid−liquid collision
model of the specific liquid combination. For the gas−liquid−
liquid interface collision model, the constant value of 0.5 is
used for thinner initial top film thicknesses, and the value used
in the liquid−liquid collision model of the specific liquid
combination is used for thicker initial top film thicknesses. The
exact thickness at which this transition occurs is determined
later based on the experimental data. As with the liquid−liquid
collision model, since a constant value for the added mass
coefficient is applied, the second term in eq 4 reduces to zero.
The final force to be considered is the film force. When the
bubble collides with the interface, the pressure, pB, in the thin
liquid film formed between the bubble surface and the liquid−
liquid interface will buildup, as customarily defined using
lubrication theory, and impart this film force onto the top
surface of the bubble. The exact value of this force is
determined by integrating the pressure profile over the
axisymmetric area:6,7,12
∞ rm
FF = ∫0 2πrpB dr ≈ ∫0 2πrpB dr
(6)
where rm is the radial location at which the film pressure has
reduced to zero. In the previous modeling of bubble collisions
at free and solid surfaces, the exact value of this location has
been taken as 0.7R − 1.2R and sometimes varied within the
modeling of the same collision.6−8,12,55 The location of this
boundary is critical as it influences this force calculation and
the film pressure profile and drainage rate through the
application of their respective boundary conditions. In the
present work, this location has been kept constant at rm = 1.2R,
as was done in the previous free surface collision model.12 The
disjoining pressure has been neglected in the calculation of the
film force since the film thickness is expected to be on the
order of micrometers until just prior to film rupture. For
compound interfaces where two thin films are formed, only the
pressure in the bottom liquid layer is needed in the calculation
of this film force as the pressure in the top film does not act
directly on the bubble. In order to calculate the thickness and
pressure of the film(s) formed during the bubble collision, the
Stokes−Reynolds−Young−Laplace equations are employed.
The specific form of these equations will vary depending on
the interface type and, as such, has been outlined separately
later in the paper.
The equation of motion for the bubble is determined by
equating the four forces acting on the bubble during its rise
and collision with the assumption that the mass of the bubble
itself is negligible:
FB + FD + FA + FF = ma ≈ 0 (7)
Substituting eqs 2, 3, 4, and 6 into eq 7, the following ordinary
differential equation is derived:
4 3 dV 4 π
πR ρB Cm = πR3ρB g − C DRe μB RV
3 dt 3 4 τT = −2μT
rm
2 dC
+ R3ρB m V 2 −
3 dH 0
2πrpB dr ∫ (8)
For the liquid−liquid and gas−liquid−liquid models, the third
term on the right side is reduced to zero since a constant value
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for the added mass coefficient is used. Since this is a first-order
ordinary differential equation, just a single initial condition is
needed. The initial velocity of the bubble is taken as either the
associated terminal velocity for bubbles released far from the
interface or zero for bubbles released near the interface.
■ LIQUID−LIQUID INTERFACE MODELING
A schematic of the proposed model for bubble collisions at a
liquid−liquid interface is presented in Figure 3. In order to
Figure 3. Schematic of the proposed model for bubble collisions at a
liquid−liquid interface.
determine the pressure buildup, pB, in the film, the same
technique used for bubble collisions at a free surface is
employed.12 The augmented Young−Laplace equation is used
to first define the axisymmetric shape of the liquid−liquid
interface, zI(r,t), and the bubble surface, zb(r,t). These
equations stem from a balance of normal forces acting on
the respective interfaces. These equations are in turn used to
define a partial differential equation describing the film
pressure. Assuming that the slope of the deformation is
small, |∂zI/∂r| ≪ 1, the following equation is used to describe
the liquid−liquid interface shape:56
σI ∂ ij ∂z I yz
jjr zz = Δρgz I − pB + τT
r ∂r k ∂r { (9)
In this equation, the interfacial tension, σI, times the curvature
of the interface is equated to the pressure differential across the
interface, which stems from the hydrostatic pressure, the
hydrodynamic pressure in the film, and the normal viscous
stress, which are represented by the three respective terms on
the right side of eq 9. Since the minimum film thickness is on
the order of micrometers until just before rupture, the
disjoining pressure is neglected. It is assumed that the inertial
pressure due to fluid motion above the interface is negligible.
Additionally, the normal viscous stress below the interface is
assumed negligible, as done in the previous free surface
model.12 The normal viscous stress imparted on the interface
by the top liquid, τT, is determined again assuming small
interface deformations and using the top liquid viscosity, μT,
and the normal velocity gradient of the top liquid at the
interface, ∂uz,T/∂z:56
∂uz,T
∂z (10)
This particular term poses a difficult challenge for this model
because the velocity fields around the interface are not solved
for as part of the model and are thus unknown. In order to
estimate the normal velocity gradient in the upper liquid, the
DOI: 10.1021/acs.langmuir.9b01209
Langmuir 2019, 35, 8294−8307
Langmuir Article

liquid−liquid interface is assumed to be spherical with radius initial film thickness is written based on a given initial distance
R′. Using conservation of mass, the velocity gradient at the between the top of the bubble and the interface, hB,00:
interface in the radially outward direction, r′, can be written as
r2
∂ur′ 2 dR ′ hB(r , 0) = hB,00 +
=− 2R (17)
∂r′ r ′= R′ R ′ dt (11)
At the inner boundary, r = 0, the first spatial derivatives of zI,
In order to implement this estimation in the present model, the pB, and hB are assumed to be zero congruent with the
radius of curvature is calculated based on the interface shape, axisymmetric assumption. At this inner boundary, eqs 9, 15,
R′ = |(∂2zI/∂r2)−1|, and the interfacial velocity is estimated as and 16 describing these variables are undefined since r = 0 is
dR′/dt = ∂zI/∂t. With this approximation, the normal viscous part of the denominator in certain terms of each. L’Hôpital’s
stress is written as rule is used at this location to determine these values. The
outer boundary conditions are defined at the radial location r =
∂ 2z I ∂z I rm = 1.2R as previously noted. At this location, the film
τT ≈ 4μT
∂r 2 ∂t (12) pressure is assumed to have reduced to zero. The film
thickness boundary condition is determined based on the
From this equation, it can be seen that if the interface is temporal derivative of eq 14 with the assumption that the
perfectly flat, that is, the interface curvature is zero, then this bubble surface velocity is equal to the bubble center of mass
viscous stress will vanish as would be expected. As the interface velocity at this location:
becomes more curved, a velocity gradient is induced at the
interface, which results in an increase of this normal viscous ∂hB ∂z
stress. (rm , t ) = −V (t ) + I (rm , t )
∂t ∂t (18)
The axisymmetric shape of the top of the bubble, zb(r,t), is
given as previously defined for the free surface collision The outer boundary condition for the liquid−liquid interface
model12 with the assumption |∂zb/∂r| ≪ 1: shape is determined using the outline previously provided for
σB ∂ ij ∂z b yz
jjr zz = − B + p
the analytical shape of a free surface under an applied force,12

r r k ∂r {
2σ which provides a means to reach an analytical solution to eq 9.
R B
(13) Since the film pressure is assumed to be zero at this location,
this equation can be rewritten as

1 ∂ ij ∂z I yz Δρgz I
In this equation, the bubble surface tension, σB, times the

jjr zz −
bubble surface curvature is balanced by the Laplace pressure of ∂ 2z I
r ∂r k ∂r {
1 ∂z I z τ
the bubble and the hydrodynamic pressure in the film. The = 2
+ − I2 = T
thickness of the film, hB, formed between the bubble and the σI ∂r r ∂r λI σI
interface is given by (19)

hB = z I − z b (14) where λI = σI/Δρg is a sort of interfacial capillary length.

Equations 9 and 13 are combined using eq 14 to describe the Equation 19 is truly a nonlinear second-order partial
film pressure using 1/σ̅ = (1/σI + 1/σB): differential equation, but in order to solve for an analytical

σ ∂ i ∂h y
+ ̅ τT + ̅ Δρgz I − ̅ jjjjr B zzzz
solution, the normal viscous stress is treated as a constant. The

r ∂r k ∂r {
2σ ̅ σ σ validity of the assumptions made in the analysis will be
pB = confirmed by comparing the solution with the experimental
R σI σI (15)
results. With this assumption, a solution can be written in
The drainage rate of the film thickness is determined using terms of the modified Bessel function of the second kind of
lubrication theory assuming immobile boundary conditions at order zero:58
ij r yz
z I = AK 0jjj zzz − T
the liquid−liquid interface and mobile conditions on the

j λ z Δρg
bubble surface. Although the true boundary condition at the τ
k I{
liquid−liquid interface is the continuity of shear stress and
(20)
velocity, the assumption that it is immobile is made to simplify
the analysis. The same assumption is made in the previous free To determine the constant, A, the asymptotic form of the
surface collision model with successful results.12 In lubrication modified Bessel function of the second kind of order zero for

ÄÅ ÉÑ
theory, the Navier−Stokes equation is simplified assuming that small arguments is used to rewrite eq 20 as
ÅÅ i r y ÑÑ
jij r zyz
the film thickness is much less than its radial size. This was first
jj zz
z I = AK 0jj zz − Å
≈ AÅÅ−lnjj zz − γE ÑÑÑÑ − T
Å
j λ z Δρg j z
done by Reynolds57 in his derivation of the classical lubrication
Å
ÅÅÇ k 2λI { Ñ
ÑÑÖ Δρg
τT τ
k I{
1 ∂ ijj 3 ∂pB yzz
theory and is given as

jrhB z
3μB r ∂r jjk ∂r zz{
∂hB (21)
=
∂t (16) where γE = 0.57721566 is the Euler constant. This form is then
In the liquid−liquid collision model, eqs 8, 9, 15, and 16 matched to an analytical solution for the interface shape in the
must be solved simultaneously for V(t), zI(r,t), pB(r,t), and inner region where the pressure can no longer be neglected but
hB(r,t), respectively. The initial condition for the bubble the hydrostatic pressure term can be. With this assumption, eq
9 becomes
σI ∂ ij ∂z I yz
velocity has already been described. Initial and boundary

jjr zz = −(pB − τT)

conditions must also be applied for zI, pB, and hB. To this
r ∂r k ∂r {
extent, the interface is assumed to be initially flat as defined by
zI = 0, and the film pressure is also taken as pB = 0 initially. The (22)

8299 DOI: 10.1021/acs.langmuir.9b01209

Langmuir 2019, 35, 8294−8307