Surfactants classification,
features and
features and applications
applications
1. Classification of surfactants.
2. Particles as foam and emulsion stabilizers.
3. Role of surfactants for various foam and
emulsion properties:
(a) Thin film drainage and stability
(b) Foam rheology
(c) Foam drainage
(d) Ostwald ripening
4. Current directions.
1. Classification of surfactants
CnEOm
2. Ionic surfactants
(a) Anionic
Diffuse
electric
layer
(b) Cationic
(b) Betaines
Stabilization of foam films by surfactants
Temperature YES NO NO
pH NO NO YES
HLB =
20*M(hydrophilic) / M(surfactant)
Example
Brij 58 = Polyoxyethylene-20 hexadecyl ether
C16H33(C2H4O)20OH
M(hydrophylic) =20*44=880
M(surfactant) = 1120
(b) Block-copolymers
Synperonics, EOnPOmEOn
2. Natural polymers (proteins)
2. Particle monolayers
particles
Oil
Main factors:
• Particle hydrophobicity
• Particle size
• Particle shape
Dinsmore et al., Science, 2002
Stabilization of films
by capillary forces
12
F
qσQ1Q2 10
0
0 1 2 3 4
qL
Role of particle shape
Surface aggregation
Bulk aggregation
Antifoam effect
Antifoam effect
of hydrophobic
of hydrophobic particles
particles
TECHNOLOGY
Antifoam effect
• Pulp and paper production
• Oil industry (non-aqueous foams)
• Fermentation
• Textile colouring
CONSUMER PRODUCTS
• Powders for washing machines
• Paints
• Drugs
Composition of Typical Antifoams
1. Hydrophobic solid particles Silica particles Emulsified oil
¾ Silica (SiO2)
¾ Polymeric particles
2. Oil
¾ Silicone oils (PDMS)
¾ Hydrocarbons (mineral oil, 100 nm 30 μm
aliphatic oils)
3. Compound
Compound
¾ Oil + particles globule
30 μm
Film rupture by solid particles
bridging-dewetting mechanism
Key factors:
(1) Particle contact angle
(2) Particle size and shape
τV V
γ&
S ( t ) − S0 = δS sin ( ωt )
σ ( t ) − σ0 = δσ sin ( ϕ + ωt )
Storage modulus
S0 + δS0 ⇒ Γ < Γ0 δσ
GST = cos ϕ
σ > σ0 δS0
Loss modulus
δσ
GLS = sin ϕ
δS0
Experimental results for surface modulus
103
Total modulus
Soap ν = 0.2 Hz
T = 25 °C
( )
12
GD = G + G
2
ST
2
LS 102
GD, mN/m
101 Anionic
100
S0 S0 + δS S0
Friction in foam films Surface dissipation
τ V ∝ Ca
% 0.5
τ V ∝ Ca
% 0.2
Denkov et al., PRL, 2008; Soft Matter 2009; Tcholakova et al., PRE, 2008
Comparison with experimental data
for emulsions
Hexadecane, ηD = 3 mPa.s
Dimensionless viscous stress
Light oil, ηD = 30 mPa.s
10-1
Heavy oil, ηD = 150 mPa.s
10-2
n = 0.47
10-3
Φ = 0.8
EO8, EO20
10-4
10-7 10-6 10-5 10-4 10-3 10-2
Capillary number, Ca
Soap
Soap
τWR32/σ
10-2 n = 1/2 CAPB
Synthetic
surfactants
0 to 70 %
Glycerol
V0
n = 2/3 τW = kV0 n
10-3
10-6 10-5 10-4 10-3
Capillary number, Ca
Dimensionless
wall stress Capillary number
Lower friction for CAPB
τ W R32 μV0
τ% = Ca = compared to soap
σ σ surfactants
Bubble (drop) breakup in sheared foams
(emulsions)
Bubble breakup in a rheometer
Initial foam Final foam
35 R32 = 220 μm
Anionic+0.05 wt % MAc
Shear stress, Pa
30
25
20 Anionic
Anionic
15 R32 = 480 μm
Φ = 0.95
10
0 30 60 90 120 150 180
Time, sec
VS = VZ ( x = 0 ) = 0 τS = τV ( x = 0 ) = 0
Ostwald ripening in foams, R32(t)
2.6
Foam
2.4
2.2 Anionic
2.0
2
(R(t)/R0)
Anionic+LAc
1.8
1.6
1.4
1.2 Anionic+MAc
p1, V1 p2, V2
1.0
0 500 1000 1500 2000 2500 3000
Time, sec
dn DH
= AF ( C1 − C2 )
dt h + 2 D kML
C1(p1)
C1 I
DH
k=
C2 I h + 2 D kML
C2(p2)
D – diffusion coefficient
h
h – thickness of the film
H – Henry constant
kML – monolayer permeability
Arrest of Ostwald ripening by solid particles
Xu et al., Langmuir, 2005
P1 > P2
P1 P2
P1 > P2
P1 = P2
Applications:
Ice-cream, whipped cream,
chocolate mousse, …
Summary
• Biosurfactants:
• Polymers-surfactant mixtures.