Interfacial Rheology

Theodor D. Gurkov
Department of Chemical Engineering, Faculty of Chemistry,
University of Sofia, Bulgaria
Lecture at COST P21 Student Training School
Physics of droplets: Basic and Advanced Topics
12 – 13 July, 2010, Borovets, Bulgaria

Contents:
Description of surface deformation (strain)
Types of surface rheological behavior (elastic,
viscous, plastic; combinations thereof)
Examples of measurements, methods

Sofia University
Training school 2010, p. 1
 Motivation – Dispersion Stability

Role of the interfacial rheology:

™At short times
-Slows down the drainage of films
-Damps fluctuations
of area expansion/compression, by opposing stresses
of adsorption layer density, δΓ, by the Marangoni effect (motion toward lower
surface pressure)
of film thickness
™At long times
-Plastic behavior of surfaces – fracture of fragile layers and exposure of bare fluid
interface

Driving force: ΔΠ

Training school 2010, p. 2

 Surface Deformations
u=
1
(u : U s )U s + ⎡⎢u − 1 (u : U s )U s ⎤⎥
2 ⎣ 2 ⎦
⎡ ⎤
Tr ⎢u − (u : U s )U s ⎥ = 0 deviatoric part
1
⎣ 2 ⎦
Tru = u : U s = u1 + u2 isotropic deformation
relative extensions:
δL δL2
u1 = 1 = δ ln L1 ; u2 = = δ ln L2
δα = u : U s L1 L2
relative dilatation:
δA
Dilatation [Expansion/Compression]; u1 + u2 = δ ln (L1L2 ) = = δ ln A = δα
Change of A A
how to describe shear deformation?
1 1
u − (u : U s )U s = (u1 − u2 )(e1e1 − e 2 e 2 )
2 2
relative shear:
δ(L1 / L2 )
u1 − u2 = δ ln (L1 / L2 ) = = δβ
L1 / L2

δβ = u : q U s = e1e1 + e 2e 2 ; q = e1e1 − e 2e 2
1
Shear (A = const.)
u= (δα)U s + 1 (δβ) q
2 2
Training school 2010, p. 3
 Surface Deformation – Curvature

b = −∇ s n = HU s + D q
In the basis of principal curvatures:
1 1
H = (c1 + c2 ) , D = (c1 − c2 )
2 2
δws = γδα + ξδβ + BδH + ΘδD

where B = M 1 + M 2 , Θ = M1 − M 2

The behavior of B (H ) , Θ(D ) is usually elastic:

if w f = 2k c (H − H 0 )2 + k c K (and K = c1c2 ),

⎛ ∂w f ⎞
then B = ⎜⎜ ⎟⎟ = B0 + 2(2k c + k c )H
⎝ ∂H ⎠D
⎛ ∂w f ⎞
Θ = ⎜⎜ ⎟⎟ = −2k c D (and B0 = −4k c H 0 )
⎝ ∂D ⎠H

kc ~10-20 kBT
for lipid bilayers
Training school 2010, p. 4
 Dilatational Surface Elasticity – Low MW Surfactants

Type of Surface tension isotherm

surface tension Gibbs elasticity, EG In presence of surfactant,
σ = σ 0 − kTJ
isotherm σ = σ(Γ )
Henry J = Γ1 E G = kT Γ1
Elasticity:
Γ Γ
Freundlich J= 1 EG = kT 1 dσ
m m E=
d ln A
⎛ Γ ⎞ Γ∞ Gibbs elasticity:
Langmuir J = − Γ∞ ln⎜⎜1 − 1 ⎟⎟ E G = kT Γ1
⎝ Γ∞ ⎠ Γ∞ − Γ1
dσ N
EG = − , Γ=
Γ∞ Γ1 Γ∞2
d ln Γ A
Volmer J= E G = kT Γ1
Γ∞ − Γ1 (Γ∞ − Γ1 )2 E = EG only when N= const.

⎛ Γ1 ⎞ β Γ12 ⎛ Γ∞ 2βΓ1 ⎞ (insoluble surfactant, or

Frumkin ⎜
J = − Γ∞ ln⎜1 − ⎟⎟ − EG = kT Γ1 ⎜⎜ − ⎟⎟
⎝ Γ∞⎠ kT Γ
⎝ ∞ − Γ1 kT ⎠ absence of exchange with bulk)

Γ∞ Γ1 β Γ12 ⎡ Γ∞2 2βΓ1 ⎤

van der Waals J= − EG = kT Γ1 ⎢ − ⎥ In general,
Γ∞ − Γ1 kT ⎢⎣ (Γ∞ − Γ1 )
2 kT ⎥⎦
⎛ dσ ⎞⎛ d ln Γ ⎞
E =⎜ ⎟⎜ ⎟
⎝ d ln Γ ⎠⎝ d ln A ⎠

Interesting feature: At Γ1 →Γ∞ , EG →∞ (not observed – out-of-plane escape)

Training school 2010, p. 5

 Diffusional Exchange Model

With soluble surfactants, when the

interface is expanded, the
diffusion flux, j, brings new
molecules to the interface. For this
reason, the relative increase of the
area per one adsorbed molecule,
(δa)/a, is always smaller than the
relative increase of the total area,
(δA)/A.

Lucassen & van den Tempel, Chem. Eng. Sci., 27 (1972) 1283.
Sinusoidal oscillations of a barrier in the plane of the interface –
compression/expansion

⎛ dσ ⎞ d ln Γ
For small deformations ε=⎜ ⎟
⎝ d ln Γ ⎠ eq d ln A
Training school 2010, p. 6
 Diffusional Exchange Model

1
ζ=
ωτ D
2
2 ⎛ ∂Γ ⎞
τD = ⎜ ⎟
D ⎝ ∂c ⎠ eq

Visco-elastic behavior
™ The elasticity and viscosity depend on frequency, ω
™ ”Apparent” viscosity, due to the mass exchange
Training school 2010, p. 7
 Harmonic Oscillations

ΔAm iωt
Δσ m ei (ωt + ϕ ) = τ = E *γ = E * e
A0
Δσm
E * = E '2 + E ' '2 = = ratio of amplitudes
ΔAm / A0

E * = E '+iE ' ' ; E ' = E * cos ϕ ; E ' ' = E * sin ϕ

Δσ m , ϕ = measured quantities
Oscillating deformable drop

0.01%Dyn.+0.1%Solv., Deformation ~6%

Area
Surf. tension
From the experimentally
38
phase shift
measured amplitude ratio and
65
37 the phase shift, one determines

Surface tension, dyn/cm

E’, E”.
Drop area, mm2

36 60

35 Interpretation of the storage

55

34
modulus, E’, and the loss
50
modulus, E”, can only be made
33
in terms of rheological models.
32 45
2 3 4 5 6 7 8 9 10
time, s
Training school 2010, p. 8
 Linear Visco – Elasticity (Maxwell)

Maxwell model [summation of strains]

Constitutive relation: G1 η
dγ 1 dτ 1
= + τ
dt G1 dt η τ

Oscillatory γ(t) is substituted; the equation

is solved for τ.
E ' = G1
(ωt r )2
E ' ' = G1
ωt r
tr ≡
η
1 + (ωt r )2 1 + (ωt r )2 G1
LvdT; Maxwell
1
At high frequencies, the behavior
0.8
becomes fully elastic, with E’ =G1 .
E' /E G , E" /E G

E' LvdT Besides, G1 =EG .

0.6 E'' LvdT
E' Mxwl
0.4 E'' Mxwl
If γ (t ) = sin( ω t ) , then
0.2 τ(t ) = E ' sin( ω t ) + E" cos(ω t )

0
1.E-03 1.E-01 1.E+01 1.E+03
angular frequency, ω (rad/s) Training school 2010, p. 9
 A More Complex Linear Visco-Elastic Model

Presence of irreversibly adsorbed molecules (that cannot be exchanged with the

bulk phase)
Polymers, proteins, … G1 η
™Extended Maxwell model
Freer et al. (+Radke), Langmuir, 20 (2004) 10159
Saulnier et al. (+Panayotov), Langmuir, 17 (2001) 8104
τ
Constitutive equation: G2
⎛ G2 ⎞ dγ G2 1 dτ 1
⎜⎜1 + ⎟⎟ + γ= + τ
⎝ G1⎠ dt η G1 dt η

Very fast deformation:

 Elastic behavior, with elasticity = G1 + G2
The viscosity is “apparent”: related to the exchange of molecules with the bulk.
At fast deformation, this cannot happen.
Slow exchange ⇔ LARGE viscosity; t r = η / G1 is long
Very slow deformation:
 The elasticity = G2 ; it is due only to the irreversibly adsorbed molecules.
Full relaxation of the mass exchange (G1 is inactive); Γ of the exchangeable
molecules has equilibrium value.
Training school 2010, p. 10
 Langmuir Trough Method
Symmetric motion of the barriers
♦ Linear translation with constant speed
The deformation rate is relatively small (to avoid The surface pressure is
ripples); dγ / dt < 0.01 s−1. measured with Wilhelmy
plate (made of
UNI-AXIAL DEFORMATION – superposition of
chromatographic paper)
dilatation and shear.
If shear is not important for a particular system:
γ – the relative area expansion,
dγ = dA / A , γ = ln( A / A0 ) ≡ α
Dynakoll 0.01%, Solvitose 0.1%, barrier speed = 20 mm/min
22 170

165

21 160

155
Π, dyn/cm

Area, cm2
20 150

145

19 140

135

18 130
0 200 400 600 800 1000 1200 1400 1600 1800
Time, s
Training school 2010, p. 11
 Linear viscoelasticity – Extended Maxwell Model

Abietic acid Levopimaric acid Cationized starch

Dynakoll VS 50 FS from Akzo Nobel ~4-4.5% trimethylammonium-groups
Solvitose BPN from AVEBE Germany
The negatively charged acids adsorb easily; to them, polymer molecules with cationic
groups can attach
In the Langmuir trough:
For small deformations, dγ / dt ≈ constant. Hence,
for the particular rheological model:

We use the model dγ ⎧ ⎡ G1 ⎤⎫

τ=η ⎨1 − exp − γ
⎢ η( dγ / dt ) ⎥ ⎬ + G2 γ
with two elasticities dt ⎩ ⎣ ⎦⎭
and one (apparent)
The experimental dependence τ(γ) is fitted;
viscosity
G1 , G2 and η are determined.
Training school 2010, p. 12
 Rheological parameters (at dγ/dt = 0.00247 s-1) Data from
σ, G1+G2, G1, G2, η,
System
dyn/cm dyn/cm dyn/cm dyn/cm dyn.s/cm
Langmuir trough
1. Dyn. 0.01%, Solv. 0.1%,
51.1 27.37 19.02 8.35 427.8
40°C (expansion)
1a. Dyn. 0.01%, Solv. 0.1%,
50.9 32.88 22.20 10.68 244.3
40°C (compression)

-1
dγ/dt = 0.00247 s

3 G2

τ = Δσ, dyn/cm
2
3.5

3.0
1
2.5
τ, dyn/cm

measured
2.0
G1+G2 fit
1.5
0
1.0 0.00 0.05 0.10 0.15 0.20 0.25
expansion
0.5 compression
fit compression
α = ln(A / A0) = γ
0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
α = ln( A /A 0 ) Training school 2010, p. 13
 Oscillatory Stress
Area change in the trough
0.10
0.08
Alternative way to analyse data:
0.06 The oscillatory strain γ(t) is inserted
0.04 into the constitutive equation, and
Strain, γ = ln(A / A 0 )

0.02
the solution for τ(t) is found in the
0.00
-0.02-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 form of Fourier series.
-0.04
-0.06
Dynakoll 0.01%, Solvitose 0.1%, 40oC
-0.08
2.0
-0.10 Experiment
Model function experiment
-0.12
1.5 model fit
time/ T

1.0

τ = σ(γ)−σ(0)
0.5

0.0

-0.5
σ(γ=0)= 23.4 dyn/cm
-1.0
G1 = 12.8 dyn/cm
G2 = 13.6 dyn/cm -1.5
η= 206.4 dyn.s/cm
-2.0
It is impossible to fit the results -0.10 -0.05 0.00 0.05 0.10
with only one G and η. γ = ln(A / A 0 )
Training school 2010, p. 14
 Shear Elasticity – Entangled Gel-Like Layers

Proteins,
Polymers,
…

picture size – 100 nm

Training school 2010, p. 15

 Rheological Behavior under Shear

™ Specific conformation on the interface – irreversible adsorption

™ Aggregation – 2D network (≠ from phase transition – spots of condensed phase)
Shear elasticity → solid-like behavior

Langmuir 18 (2002) 1238

Plastic behavior (Bingham)

Training school 2010, p. 16
 Anisotropic Stress Method
y
The deformation is anisotropic
ΔA
Wilhelmy plate A0
movable ⇒ for solid-like layers, the
barrier
measured σ will depend on the
σ⊥ =σ22 orientation of the Wilhelmy
plate.
δL
σ|| =σ11 Langmuir trough:
x Uniaxial
x=0 L deformation =
In the case of pure elasticity: = Superposition
of dilatation and
⎡ ⎤
Δσ j = K (u1 + u2 ) + 2μ ⎢u j − (u1 + u2 )⎥
1
j =1,2 (1) shear
⎣ 2 ⎦
u1 refers to the direction perpendicular to the barriers, while u2 is in parallel
direction. For uni-axial deformation, u1 = ln ( A / A0 ) , u2 = 0 . With α ≡ ln ( A / A0 ) , Eq. (1)
becomes
Δσ1 = (K + μ ) α = Δσ|| ; Δσ 2 = (K − μ ) α = Δσ ⊥ (2)
Δσ1 , acting perpendicularly to the barriers, is measured when the Wilhelmy plate is
oriented in parallel with the barriers, hence the notation Δσ|| (similar reasoning holds
for Δσ ⊥ ). Dilatation (K) and shear (μ) elasticity moduli:

dσ|| dσ ⊥
K +μ = ; K −μ = (3)
d ln A d ln A Training school 2010, p. 17
 Anisotropic Stress Method

Dilatational and shear elasticity of BLG layers:

after ageing for hours, or at high concentrations

experiment - collinear plate

2.0 fit - collinear plate, K + μ = 78 dyn/cm
experiment - perpendicular plate
1.8 fit - perpendicular plate, K - μ = 63 dyn/cm
1.6
| σeq - σ(t) |, dyn/cm

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0
0.000 0.005 0.010 0.015 0.020
log(A(t)/A0)

Figure 2. Elastic stress response of the surface, as a function of the relative area de-
formation during expansion for two different orientations of the Wilhelmy plate:
collinear (squares), and perpendicular (circles). The system contains 1×10-4 wt%
BLG and 0.15 M NaCl (at the "natural" pH, 6.2). The interface was aged overnight.
Training school 2010, p. 18
 Anisotropic Stress – Visco-Elastic Behavior
τ11, el = ( K + μ ) u11, el τ 22, el = ( K − μ)u11, el
τ11, visc = ( ζ s + ηs ) D11, visc τ 22, visc = ( ζ s − ηs ) D11, visc
u11,el u11,visc
u11
In the frames of the Maxwell model:
τ11 = τ11, el = τ11, visc τ 22 = τ 22, el = τ 22, visc τ τ τ
u11 = u11, el + u11, visc D11 = D11, el + D11, visc
u22 =0
d d
where u11, el = D11, el ; u11, visc = D11, visc is the rate of strain.
dt dt
The displacement is a linear function of the x-coordinate, and u11, D11
do not depend on x. In such a case the rate of total deformation is
dα A
D11 = , where α = u11 = ln .
dt A0
dα 1 d τ11 τ11 dα 1 d τ 22 τ 22
= + ; = + Surface
dt K + μ dt ζ s + ηs dt K − μ dt ζ s − ηs Tension
Sensor
Investigated
Wilhelmy Plate Monolayer
(sand-blasted glass)
Barrier

PC Analogue-
Digital
Converter Vibration-Free Training
Tableschool 2010, p. 19
 Anisotropic Stress – Visco-Elastic Behavior
In the Langmuir trough, we carry out deformation with constant rate
(fixed d α / d t ). Then,

⎡ dα ⎤ ⎛ ⎞
τ11 (t ) = ⎢ τ11 (0) − (ζ s + ηs )⎥exp⎜⎜ − K + μ t ⎟⎟ + d α (ζ s + ηs )
⎣ dt ⎦ ⎝ ζ s + ηs ⎠ d t
⎡ dα ⎤ ⎛ ⎞
τ 22 (t ) = ⎢ τ 22 (0) − (ζ s − ηs )⎥exp⎜⎜ − K − μ t ⎟⎟ + d α (ζ s − ηs )
⎣ dt ⎦ ⎝ ζ s − ηs ⎠ d t

besides, τ11 = σ|| − σ eq ; τ 22 = σ ⊥ − σ eq

The functions τ11 (t ) , τ 22 (t ) are fitted
with the model expressions.

• If the shear parameters are

negligible, then τ11 =τ22 .
•The viscous dissipation
leads to curvature of the plot.
• Difference between
compression and expansion.

Training school 2010, p. 20

 Anisotropic Stress – Visco-Elastic Behavior

Data fit ⇒
Values of the material parameters
K, μ, ζs , ηs
(see the Table below).

We observe different types

of rheological behavior

Training school 2010, p. 21

 Surface Rheological Behavior of Proteins

TABLE 1. Summary of results for the studied systems

Determined
Type of rheological
No. System parameters
behavior
(expansion)

BLG 1×10-4 wt% Dilatational elasticity only

K= 53.0 dyn/cm
1 + 0.15 M NaCl No shear elasticity
μ= 0 Globular protein –
Freshly prepared No viscous dissipation
the ageing and the
concentration are
BLG 1×10-4 wt% Dilatational and shear important.
K= 70.5 dyn/cm
2 + 0.15 M NaCl elasticity
μ= 7.5 dyn/cm
Aged overnight No viscous dissipation
Disordered protein –
absence of network.
K= 42.6 dyn/cm
Dilatational viscoelasticity
β-casein 0.001 wt% μ << K
3 Negligible shear elasticity
+ 1×10-5 M Tween 20 ζs = 127.9 dyn.s/cm
and viscosity
ηs << ζs

K= 83.2 dyn/cm
BLG 0.01 wt% Full dilatational and shear μ= 16.2 dyn/cm
4
+ 0.15 M NaCl visco-elasticity ζs = 1654.8 dyn.s/cm
ηs = 113.9 dyn.s/cm

Training school 2010, p. 22

 Method for Measuring the Surface Yield Stress

The barrier rises and the tangential

force on the particle increases
gradually, until the layer breaks.
The method is suitable for small
stresses (starting from Zero).

The layer breakdown is detected

when the position of the particle
starts to deviate from the predicted
position according to the Laplace
equation of capillarity (the curve).

Training school 2010, p. 23

 Yield Stress of Entangled Protein Layers

E
After the plastic element is
activated, the behavior is elastic.

With increasing protein

concentration, the layer gains more
strength (against disruption)
Training school 2010, p. 24
 Basic References
1. D.A. Edwards, H. Brenner, D.T. Wasan, Interfacial Transport Processes and
Rheology, Butterworth-Heinemann, Boston, 1991.

2. K.D. Danov, P.A. Kralchevsky, I.B. Ivanov, Equilibrium and dynamics of surfactant
adsorption monolayers and thin liquid films, Chapter 9 in: G. Broze (Ed.),
Handbook of Detergents. Part. A: Properties, Marcel Dekker, 1999, pp. 303–418.
3. J.C. Slattery, Interfacial Transport Phenomena, Springer-Verlag, New York, 1990;
Momentum, Energy, and Mass Transfer in Continua, R.E. Krieger Publishing Co.,
Huntington, New York, 1978.
4. L.E. Scriven, Dynamics of a Fluid Interface, Chem. Eng. Sci. 12 (1960) 98-108.
5. J. Hunter, Foundation of Colloid Science Vol. I, Clarendon Press, Oxford, 1987; Vol. II,
Clarendon Press, Oxford, 1989.

Training school 2010, p. 25

 Additional References
6. J.T. Davies, E.K. Rideal, Interfacial Phenomena, Academic Press, New York, 1963.

7. T.D. Gurkov, J.T. Petkov, B. Campbell, R.P. Borwankar, Dilatational and Shear
Rheology of Protein Layers on Water/Air Interface, In: "Food Colloids,
Fundamentals of Formulation" (E. Dickinson, R. Miller, Eds.), Royal Soc. Chem.,
Cambridge, UK, 2001, 181-190.

8. J.T. Petkov, T.D. Gurkov, B.E. Campbell, R.P. Borwankar, Dilatational and Shear
Elasticity of Gel-Like Protein Layers on Air/Water Interface, Langmuir 16 (2000)
3703-3711.

9. J.T. Petkov, T.D. Gurkov, B.E. Campbell, Measurement of the Yield Stress of Gellike
Protein Layers on Liquid Surfaces by Means of an Attached Particle, Langmuir 17
(2001) 4556-4563.

10. J.T. Petkov, K.D. Danov, N.D. Denkov, R. Aust, F. Durst, Precise Method for
Measuring the Shear Surface Viscosity of Surfactant Monolayers, Langmuir 12
(1996) 2650-2653.

11. J. Lucassen, and M. van den Tempel, Longitudinal Waves on Visco-Elastic Surfaces,
J. Colloid Interface Sci. 41 (1972) 491-498.

Training school 2010, p. 26

 Additional References
12. R. Dimova, K. Danov, B. Pouligny, I.B. Ivanov, Drag of a Solid Particle Trapped in a
Thin Film, or at an Interface: Influence of Surface Viscosity and Elasticity, J.
Colloid Interface Sci. 226 (2000) 35-43.

13. K.D. Danov, R. Aust, F. Durst, U. Lange, Influence of the Surface Viscosity on the
Hydrodynamic Resistance and Surface Diffusivity of a Large Brownian Particle, J.
Colloid Interface Sci. 175 (1995) 36-45.

14. J.T. Petkov, N.D. Denkov, K.D. Danov, O.D. Velev, R. Aust, F. Durst, Measurement of
the Drag Coefficient of Spherical Particles Attached to Fluid Interfaces, J. Colloid
Interface Sci. 172 (1995) 147-154.

15. T.S. Horozov, P.A. Kralchevsky, K.D. Danov, I.B. Ivanov, Interfacial Rheology and
Kinetics of Adsorption from Surfactant Solutions, J. Dispersion Sci. Technol. 18
(1997) 593-607.

16. T.S. Horozov, K.D. Danov, P.A. Kralchevsky, I.B. Ivanov, R.P. Borwankar, A Local
Approach in Interfacial Rheology: Theory and Experiment, Proceedings of the First
World Congress on Emulsions, Vol. 2, Paris, 1993, paper 3-20-137.

17. A.M. Poskanzer, F.C. Goodrich, Surface Viscosity of Sodium Dodecyl Sulfate
Solutions with and without Added Dodecanol, J. Phys. Chem. 79 (1975) 2122-2126.

Training school 2010, p. 27

 Additional References
18. I.B. Ivanov, K.D. Danov, K.P. Ananthapadmanabhan, A. Lips, Interfacial Rheology of
Adsorbed Layers with Surface Reaction: On the Origin of the Dilatational Surface
Viscosity, Adv. Colloid Interface Sci. 114-115 (2005) 61-92.
19. F. Ravera, G. Loglio, V.I. Kovalchuk, Interfacial dilational rheology by oscillating
bubble/drop methods, Curr. Opinion Colloid Interface Sci. 15 (2010) 217–228.
20. F. Boury, Tz. Ivanova, I. Panaïotov, J. E. Proust, A. Bois, and J. Richou, Dilatational
Properties of Adsorbed Poly(D,L-lactide) and Bovine Serum Albumin Monolayers
at the Dichloromethane/Water Interface, Langmuir 11 (1995) 1636-1644.
21. D. Langevin, F. Monroy, Interfacial rheology of polyelectrolytes and polymer
monolayers at the air–water interface, Curr. Opinion Colloid Interface Sci. 15 (2010)
283-293.
22. H. Brenner, L.G. Leal, Conservation and Constitutive Equations for Adsorbed
Species Undergoing Surface Diffusion and Convection at a Fluid-Fluid Interface, J.
Colloid Interface Sci. 88 (1982) 136.
23. R. Miller, R. Wustneck, J. Krägel, G. Kretzschmar, Dilational and Shear Rheology of
Adsorption Layers at Liquid Interface, Colloids Surf. A 111 (1996) 75-118.
24. K.S. Yim, B. Rahaii, G.G. Fuller, Surface Rheological Transitions in Langmuir
Monolayers of Bi-Competitive Fatty Acids, Langmuir 18 (2002) 6597-6601.
Training school 2010, p. 28