Bretherton 2019

Digital μ-fluidics
The flow of confined bubbles and drops

20-04-2009
Michiel Kreutzer
Department of Chemical Engineering
Delft University of Technology
Every drop/bubble is a test tube
Distribute Split-up
Optical valve
Baroud et al., Lab Chip (2007)

Link et al., Phys. Rev. Lett. (2004)
Synchronize Sort
Cristobal et al., App. Phys. Lett. (2006)
Merge
Feedback
Prakash et al., Science (2007)

Baroud et al., Lab Chip (2007)
Link et al., Ang. Chem. Int. Ed. (2006)
Prakash et al., Science (2007)
www.raindancetechnologies.com
2| Bretherton's problem - MT Kreutzer

Formation, mixing, merging, selection, …
Theberge, Angew. Chem. Int. Ed. 49 (2010), 2

Rapid variations with minimal sample use
Zheng JACS 125 (2003), 11170

High Throughput Nucleation Statistics
5| Segmented flow - MT Kreutzer

Single cell studies
Brouzes, PNAS 106 (2009), 14195

Lab-on-a-chip Chemistry
Ismagilov, 2006
Kreutzer et al., Chem Eng Sci 60 (2005) 5895
Gunther et al. , Lab Chip 6 (2006) 1487

Motivation – Plug Flow & Rapid Mixing
High-Throughput
Material Synthesis Analytical Chemistry
Khan, 2005
Res. Time Karger 2005
Distribution
=
Particle Size
Distribution
Kreutzer & Guenther, 2005
8
Residence Time distribution = Particle Size Distribution
Gas Gas
Colloidal Silica. Khan Langmuir 2005
Segmentation - Dispersion
9 Kreutzer Anal. Chem. 2008

Catalysis: film thickness key parameter
Excellent transport to wall
FLUENT 5.5 (axi, segregated, lam)

Jun 06, 2001
100-fold
better mass-xfer
d film
= O (Ca 2/3 ) ≈ 10 −2
d channel
Full CFD simulation
10
Segmented flow Synthesis
Kinetic tool, Ideal for
hazardous chemistry
Pd
N3 + H2 NH2
Azide hydrogenation
to form amines
Temperature low enough

To maintain stereo-
specificity
11
Monitoring conversion is easy
100
90 Camera
GC
80
70 GC Camera
Conversion [%]
60
50
40
30
20
10
0
run 1 run 2
12
Fast kinetics
Complete kinetics can be measured in a day
3.5
H2
Pd/Al2O3 0 th order in CE
3.0 kKC H C CE
r = 2
1 + KC CE
r ~ kC H
Ln(rate)
2
2.5
1 st order in CE 3.2
Ln((C-C0)/tau)
r ~ kKC H C CE 1
3.1 E a = -34 kJ/mol
2.0 2 3.0 R2 = 0.99
2.9
1 2.8
1.5 2.7
Ea = -32 kJ/mol (Boudart et al.1978)
2.6
0.392 0.397 0.402 0.407 0.412
1/RT*1000
1.0
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
Ln(Conc. CE)
13
Our basic questions for today
• Simplest case: bubble/droplet in a tube

– What is the flow resistance? Film thickness?
– Look at the basic problem of forced wetting (plate, capillary, all the same)
– Do the full matched-asymptotics that leads to the “BLL 2/3 law”
• More complex cases: inertia, marangoni effects?

– Basic features of the solutions
• Channel Shape?
14 | Bretherton's problem - MT Kreutzer

The Bretherton-Landau-Levich problem
Layer on flat plate coating on a wire coating in a tube
Characteristics:
• Film deposited, thickness depends on speed
(so called “2/3-law”, thickness scales with Ca2/3)
• Both on wetting and non-wetting surfaces
(the transition to forced wetting is NOT today’s topic)
• Matching of film to “outer” solution

Basic setup of the problem - Matching
∂u
Moving reference frame: bubble stands still: u (0) =−U , (h ) = 0
∂y
∂p ∂ 2u
Navier Stokes: =µ 2
∂x ∂y
h
∂h ∂q
Continuity + = 0, with q = ∫ u dy
∂t ∂x 0

Lubrication thin-film equation
∂p ⎡⎢ y 2 yh ⎤⎥ Laplace pressure
Navier Stokes: u =−U + −
⎢
∂x ⎣ 2µ µ ⎥⎦ ∂p ∂ ⎡ ∂ 2h ⎤
≈ ⎢γ ⎥
∂x ⎢
∂x ⎣ ∂x ⎦2⎥
h
γ 3 ∂3h
q = ∫ u dy = Uh − h
0
3 µ ∂x 3
∂h ∂h γ ∂ ⎛⎜ 3 ∂3h ⎞⎟
Continuity +U − ⎜⎜h 3⎟
=0
∂t ∂x 3µ ∂x ⎝ ∂x ⎠ ⎟
Scaling of the transition region: first relation
∂h ∂h γ ∂ ⎛⎜ 3 ∂3h ⎞⎟ x
+U − ⎜h ⎟= 0
∂t ∂x 3µ ∂x ⎜⎝ ∂x 3 ⎟⎠
Bubble stands still, ∂h γ ∂ ⎛ 3 ∂3h ⎞

so must be zero , we balance the 2nd and 3rd terms: ~ ⎜⎜h ⎟⎟
∂x 3µU ∂x ⎜⎝ ∂x ⎟⎠
3
x ~λ ⎫⎪ δ λ 1 ⎛⎜ 3 δ ⎞⎟ δ
⎪ ~ δ or Ca1/3
~
⎬
h ~δ ⎪⎪⎭ λ 3µU λ ⎜⎝ λ 3 ⎟⎠ λ

Matching to outer solution: second scaling relation
First scaling rule 1

κ=
r
δ
Ca1/ 3 ~
λ
∂ 2h δ 1
κ~ 2~ 2 κ=
∂x λ r
Scaling of the problem Second scaling rule
δ ~ r Ca2/ 3 δ 1
2
~
λ ~ r Ca1/ 3 λ r

The Bretherton-Landau-Levich problem
• Clean interface case:

– 2/3 law experimentally predicted by Morey (1940)
– Theoretical derivation of 2/3 law for flat plate by Landau-Levich (1942)
– Theoretical derivation of 2/3 law for capillaries by Bretherton (1961)
• Surfactant case
– Theoretical derivation by Bretherton (1961)
– Coating of flat surfaces by Groenveld (1970)
• Additional forces (on top of viscous-capillary)
– Inertia: Aussilous (2001), Heil (2001), Kreutzer (2005)
– Gravity & Partial wetting fluids by Snoeijer (2008)

Master equation
Again, using the film evolution equation y
∂h ∂ ⎛⎜ γ 3 ∂3h ⎞⎟ x
+ ⎜Uh − h ⎟= 0
∂t ∂x ⎜⎝ 3µ ∂x 3 ⎟⎠
Steady state, so drop the transient term
γ 3 ∂3h ∂3h 3µU h −c

In the flat region, h = 0
3
Uh − h =c = ∂
3µ ∂x 3 ∂x 3 γ h3 ∂x 3
δ −c
which gives c: 0= 3
,
h δ
η= c =δ
δ ∂3η η −1
= 3
x ∂ξ 3 η
ξ = (3Ca )1/3
δ
Forced Wetting Film Equation
∂3η η −1
“exponential range”
3
= 3 “parabolic range”
∂ξ η
η !1 η ≫1
∂3η ∂3η
 η −1 3
0
∂ξ 3 ∂ξ
which has an analytical solution which has an analytical solution
⎡ 31/2 ⎤ ⎡ 31/2 ⎤ P
ξ
η =1+ αe + βe −ξ
cos ⎢ ξ ⎥ + γ e sin ⎢
−ξ
ξ⎥ η = ξ 2 +Qξ + R
⎢⎣ 2 ⎥⎦ ⎢⎣ 2 ⎥⎦ 2

Four different regions with their scaling
∂3η η −1
3
= 3
∂ξ η y
“flat” “exponential” “parabolic” “spherical”
no no η η
η =1 η 1 η 1, 1 ~1
show show r /δ r /δ
∂ nη ∂3η ∂η 3
−1/3 ∂ η ∂ 2η δ
=0 ≈ η −1  (3Ca ) , ≈0 =
∂ξ n ∂ξ 3 ∂ξ ∂ξ 3
∂ξ 2 r (3Ca )2/3
Set up match of “exp” and “parabolic”
∂3η η −1 ∂3η
= 3 Exponential: = η −1
∂ξ 3
η ∂ξ 3 y
η(ξ ) =1+ αe ξ x
∂3η
parabolic: ≈0
∂ξ 3
P
η(ξ ) = ξ 2 + Q ξ + R
2
no no η η
η =1 η 1 η 1, 1 ~1
show show r /δ r /δ
∂ nη ∂3η ∂η 3
−1/3 ∂ η ∂ 2η δ
=0 ≈ η −1  (3Ca ) , ≈0 =
∂ξ n ∂ξ 3 ∂ξ ∂ξ 3
∂ξ 2 r (3Ca )2/3
Numerical Shooting
20
Use exponential for
initial conditions: 1+ 0.001e- ξ
η(ξ ) =1+ ae −ξ 15
η(0) =1+ a 0.643 2

η(ξ ) = ξ + 2.79
η′(0) = a 2 10
η′′(0) = a
And integrate full equation
with that 5
Numerical solution
∂3η η −1
3
= 3
∂ξ η - 10 -5 0 5 10
P
η(ξ ) = ξ 2 + Q ξ + R
2
Move numerical solution P = η′′(ξ )
to left and right, such that Q = 0
Fitting: Q = η′(ξ )− ξη′′(ξ )
P = 0.643, R = 2.79 R = η(ξ )−(ξ 2 + ξ )η′′(ξ )−η′(ξ )
Note: MTK gets a = 0.001, P = 0.643, Q=0, R = 2.90
25 | with Mathematica’s NDSolve Bretherton's problem - MT Kreutzer
2/3 law for film thickness
∂3η η −1 ∂ 2h 1 is the same as
3
= 3 =
∂ξ η ∂x 2 r
y
∂ 2η δ x
=
∂ξ 2 r (3Ca )2/3
Parabola matches to the sphere:

δ δ
0.643 = = 0.643(3Ca)2/ 3
r (3Ca)2/ 3 r
no a η
η =1 η = 1+ αe ξ η = 0.643ξ 2 +2.79 ~1
show n r /δ
∂ nη ∂ 2η ∂ 2η δ
=0 = 0.643 =
∂ξ n ∂ξ 2 ∂ξ 2 r (3Ca )2/3
Perturbation of Laplace pressure
⎛x2 ⎞
The parabola h = ⎜⎜ +1.79(3Ca )2/3 ⎟⎟r matches y
⎜⎝ 2 ⎟⎠
to a sphere of curvature ⎡ (2 / r )(1+1.79(3Ca )2/3 ⎤ x
⎣ ⎦
no a η
η =1 η = 1+ αe ξ η = 0.643ξ 2 +2.79 ~1
show n r /δ
∂ nη ∂ 2η ∂ 2η δ
=0 = 0.643 =
∂ξ n ∂ξ 2 ∂ξ 2 r (3Ca )2/3
Rear of the bubble
8
6
0.643 2
η(ξ ) = ξ - 0.8
2
4
Numerical solution
-4 -2 2 4
-2
Start numerical solution with exponential function
⎡ 31/2 ⎤ ⎡ 31/2 ⎤
η =1+ αe −ξ
cos ⎢ ξ ⎥ + βe sin ⎢
−ξ
ξ⎥
⎢⎣ 2 ⎥⎦ ⎢⎣ 2 ⎥⎦

Pressure drop over the bubble:
2γ
Δp = [1+1.79(3Ca)2/ 3 ]
r
2γ
Δp = [1- 0.46(3Ca)2/ 3 ]
r
γ
Δp = 4.52(3Ca)2/ 3
r

Experiments
Taylor, J Fluid Mech 10 (1961), 161

Bretherton, J Fluid Mech 10 (1961), 166
Why the maximum?
First matching rule

δ
Ca1/ 3 ~
λ
Second matching rule
δ 1 Thick film decreases radius of curvature!

2
~
λ r- δ
Scaling of the problem
Ca2/ 3
δ ~r
1+ Ca2/ 3
Ca2/ 3
λ ~r
[1+ Ca2/ 3 ]1/ 2
Aussilous, Phys Fluids 12 (2000) 2367
Taylor, J Fluid Mech 10 (1961), 161
The not-so-simple cases
Marangoni, Inertia, non-round, thick films, …

Marangoni Effects
∂u
Moving reference frame: bubble stands still: u (0) =- U , (h) = 0
∂y
u(0) =- U, u(h) = 0
∂h ∂h γ ∂ ⎛⎜ 3 ∂3 h ⎞⎟
+U − ⎜h ⎟= 0
∂t ∂ x 3µ ∂ x ⎜⎝ ∂ x 3 ⎟⎠
δ = 0.643 r (3Ca)2/ 3
γ δ = 0.643 r (12Ca)2/ 3
12μ
Inertia changes bubble shape
Ca = 0.04
Re = 1,10,100,200
Kreutzer et al, AIChE J 51 (2005) 2428

Inertia increases film thickness
Ca2/ 3
δ ~r
1+ Ca2/ 3 - We
ρU 2 (r - δ )
We =
γ
Kreutzer et al, AIChE J 51 (2005) 2428

Han and Shikazono, Int J. Heat Fluid Flow (2009) Aussilous, Phys Fluids 12 (2000) 2367

Square Channels

Hydrostatics
Without flow, there cannot be

a gradient of (Laplace) pressure
∇p = 0
For a channel of width W and

height H, we have at the nose
−1
⎡2 2⎤
Δp = γ ⎢ + ⎥ In the gutter, no curvature
⎣⎢ H W ⎥⎦ in the axial direction, so
−1
⎡ 1 1⎤
Δp = γ ⎢ + ⎥
⎢⎣ ∞ α ⎥⎦
−1
⎡2 2⎤
α=⎢ + ⎥
⎢⎣W H ⎥⎦
Ajaev & Homsy, Ann Rev. Fluid Mech 38 (2006) 277

Wong, Radke & Morris, J Fluid Mech 292 (1995) 71
Film Deposition

The non-uniformity starts at the nose
0.643
δ= (3Cacosφ )2/ 3
α

What have we learned
• Scaling in flow of long bubbles / droplets in cylindrical tubes
(basically the same as Landau Levich)
• Marangoni effects increase film thickness and pressure drop by a factor 42/3
• There is a maximum film thickness at high Ca

(this does not happen with a flat plate LL scaling)
• Inertia increases film thickness, numerical solution needed
• Square channels have highly non-uniform films

Further Reading
• Recent reviews
Ajaev & Homsy, Ann Rev. Fluid Mech 38 (2006) 277
Kreutzer et al., Chem Eng Sci 60 (2005) 5895
Gunther et al. , Lab Chip 6 (2006) 1487
• Microfluidics: a couple of key papers
Aussilous, Phys Fluids 12 (2000) 2367

EXTRA – DEWETTING
In Bretherton’s problem in square channels

43
Non-Flat Dewetting
Human eye
Wong, 1996, JColl Int Sci
Grooves Coffee (?) cup

Seeman, 2005, Proc Nat Acad Sci Brinkmann, 2002, Eur Phys J E
44 |
Topology: interface and surface
GL interface: flat GL interface: round GL interface: round

Solid surface: flat Solid surface: round Solid surface: round
Always two regimes:

- stable (full) non-wetting
- metastable forced (full) wetting
NB: here we are interested in the topology

on the capillary length scale.
45 |
Experimental
46 | Segmented flow - MT Kreutzer

Resistance to Flow – Partial wetting
47 |
c theory = 2.88
(Wong 1995) a b
c exp ≈16 c
(Stone 2007)
48
Film Dynamics

Controlled experiments to study instability
Accurate creation of films with initial thickness 10-1000 nm,

connected to a Plateau border
Measurement of rupture time

under flow conditions

Constant dewetting velocity
γ 3 1
Vd = kθe k=
µ 12 2 ln(r / a )

Relation to Foam films
Choice of boundary conditions

leads to very different solutions
- mobility or not, at free surface

- Symmetry or no-slip
Howell & Stone Eur. J Appl. Math 16 (2005) 569
Denkov Soft Matter 5 (2009) 3389 Aradian EPL 55 (2001) 834
52 |
Film rupture
∂h ∂ ⎛⎜ γ 3 ∂3h A ∂h ⎞⎟
+ ⎜ h + ⎟= 0
∂t ∂x ⎜⎝ 3µ ∂x 3 6πh ∂x ⎟⎠
Oron et al, Rev Mod Phys 69 (1997) 931

Film rupture
h
H= ,
h0
x
X= 2 1/2
h0 (2πγ / A)
A2
T= t
12π µγ h0
2 5
πh03γ −1
κ= r
A
Forcing term
∂h ∂ ÊÁ γ 3 ∂ 3h A ∂h ˆ˜
+ Á h + ˜˜= 0
H (Hx ËH3μXXX ∂+xH 6HπhX )∂x=¯ 0
∂tT +∂ Á
3 3 −1
X
Oron et al, Rev Mod Phys 69 (1997) 931

Boundary conditions
x 0: x ≫0:
1 2 h = h0
h = h0 + x
2r hx = 0
hxx = r −1
four parameters : h0 , r , γ , A
scaling choices for : h, x ,t
AradianEPL 55 (2001) 834
Evolution of dimple

Self-similar solution near pinch-off
x
H = (T −TC ) S (η ),
1/5
η=
(T −TC )2/5
Zhang & Lister, Phys Fluids, 11 (1999) 2454

Matching
mN
γ = 20 , A =10−21 J, r =10µm, h0 = 0.1µm, µ =10 -3 Pa s
58 |
m Segmented flow - MT Kreutzer
Time to Film Rupture
Tc ~ κ −10/7

Agreement with Experiments

Regime map

Pressure drop - partial wetting
Front: Bretherton’s law
Δp
= 1+ O (Ca2 3 )
γ r
Rear: Cox-Voinov
Δp
= 1− cos[θE + O (Ca1 3 )]
γ r
θE2 13 Ca2 3
≈ + θECa +
2 2
62
Conclusions
Dewetting on surfaces that have acute corners (on capillary length

scale) described
Multiple, stable, regimes possible, dictated by a delicate balance

between forced wetting and dewetting
Small deviations from complete wetting significantly impact fluidic

resistance of bubbles in microfluidic networks
Dewetting in rectangular channels
– Plateau borders drive rapid film rupture

– Rupture time depends on forcing term (gutter curvature) only

Bretherton 2019

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Digital μ-fluidics

The flow of confined bubbles and drops

Baroud et al., Lab Chip (2007)

Prakash et al., Science (2007)

2| Bretherton's problem - MT Kreutzer

Theberge, Angew. Chem. Int. Ed. 49 (2010), 2

3| Bretherton's problem - MT Kreutzer

Zheng JACS 125 (2003), 11170

4| Bretherton's problem - MT Kreutzer

5| Segmented flow - MT Kreutzer

Brouzes, PNAS 106 (2009), 14195

6| Bretherton's problem - MT Kreutzer

7| Bretherton's problem - MT Kreutzer

Colloidal Silica. Khan Langmuir 2005

9 Kreutzer Anal. Chem. 2008

FLUENT 5.5 (axi, segregated, lam)

Full CFD simulation

Temperature low enough

• Simplest case: bubble/droplet in a tube

• More complex cases: inertia, marangoni effects?

14 | Bretherton's problem - MT Kreutzer

Layer on flat plate coating on a wire coating in a tube

• Matching of film to “outer” solution

15 | Bretherton's problem - MT Kreutzer

16 | Bretherton's problem - MT Kreutzer

Bubble stands still, ∂h γ ∂ ⎛ 3 ∂3h ⎞

18 | Bretherton's problem - MT Kreutzer

First scaling rule 1

19 | Bretherton's problem - MT Kreutzer

• Clean interface case:

20 | Bretherton's problem - MT Kreutzer

Again, using the film evolution equation y

Steady state, so drop the transient term

γ 3 ∂3h ∂3h 3µU h −c

22 | Bretherton's problem - MT Kreutzer

“flat” “exponential” “parabolic” “spherical”

“flat” “exponential” “parabolic” “spherical”

η(0) =1+ a 0.643 2

Parabola matches to the sphere:

“flat” “exponential” “parabolic” “spherical”

“flat” “exponential” “parabolic” “spherical”

28 | Bretherton's problem - MT Kreutzer

29 | Bretherton's problem - MT Kreutzer

Taylor, J Fluid Mech 10 (1961), 161

First matching rule

Second matching rule

δ 1 Thick film decreases radius of curvature!

Scaling of the problem

Marangoni, Inertia, non-round, thick films, …

Kreutzer et al, AIChE J 51 (2005) 2428

34 | Bretherton's problem - MT Kreutzer

Kreutzer et al, AIChE J 51 (2005) 2428

35 | Bretherton's problem - MT Kreutzer

36 | Bretherton's problem - MT Kreutzer

Without flow, there cannot be

For a channel of width W and

Ajaev & Homsy, Ann Rev. Fluid Mech 38 (2006) 277

Wong, Radke & Morris, J Fluid Mech 292 (1995) 71

Wong, Radke & Morris, J Fluid Mech 292 (1995) 71

• There is a maximum film thickness at high Ca

• Inertia increases film thickness, numerical solution needed

• Square channels have highly non-uniform films

40 | Bretherton's problem - MT Kreutzer