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Surfactants –– classification,

Surfactants classification,
features and
features and applications
applications

N. D. Denkov and S. Tcholakova


Department of Chemical Engineering,
Faculty of Chemistry, Sofia University, Sofia, Bulgaria

Lecture at COST P21 Training School


“Physics of droplets: Basic and advanced topics”
Borovets, Bulgaria, 12–13 July, 2010
Contents
Contents

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

• Low molecular mass surfactants


9 Nonionic
9 Ionic
9 Amphoteric
• Polymeric surfactants
9 Synthetic
9 Natural
• Particles as surfactant species
9 Spherical vs. non-spherical
9 Hydrophilic vs. hydrophobic
Low-molecular mass surfactants
1. Nonionic surfactants
Tweens
Alkylpolyoxyethylenes Spans

CnEOm
2. Ionic surfactants
(a) Anionic

Diffuse
electric
layer

n=12 ⇒ sodium dodecyl sulfate, SDS

(b) Cationic

n=12 ⇒ dodecyl trimethyl ammonium chloride, DTAC


3. Amphoteric surfactants
(a) Natural soaps (alkylcarboxylates), Lipids

(b) Betaines
Stabilization of foam films by surfactants

Ionic surfactants Nonionic surfactants

Electrostatic stabilization Steric stabilization by


by ionic surfactants nonionic surfactants

Both can be explained as a result of higher


osmotic pressure in the foam film
Role of surfactant micelles
Structural forces in foam films:

Solution rheology (shampoos, dish-washing gels)

higher solution viscosity

Control of micelle shape: mixtures (SLES+CAPB),


counterions (Ca2+), temperature (for EO surfactants)
Comparison
of the low-molecular mass surfactants

Sensitivity* Nonionic Ionic Amphoteric


Electrolytes NO YES Depends on pH

Temperature YES NO NO

pH NO NO YES

*Adsorption, surface tension, CMC, micelle size and


shape, foam and emulsion stability

Mixtures are usually used in applications


(main surfactant + cosurfactant ± polymers)
Hydrophile Lipophile Balance
(HLB)

HLB =
20*M(hydrophilic) / M(surfactant)

Example
Brij 58 = Polyoxyethylene-20 hexadecyl ether
C16H33(C2H4O)20OH

M(hydrophylic) =20*44=880
M(surfactant) = 1120

⇒ HLB = (880*20)/1120 = 15.7


Relation between HLB
and surfactant applications
• Mixing unlike oils together
– surfactants with HLB’s of 1 to 3
• Preparing water-in-oil emulsions
HLB < 8
– surfactants with HLB’s of 4 to 6
• Preparing self emulsifying oils
– surfactants with HLB’s of 7 to 10
• Preparing oil-in-water emulsions
– surfactant blends with HLB’s of 8 to16
• Detergent solutions
– surfactants with HLB of 13 to 15
HLB > 10 • Solubilization of oil into water (microemulsion)
– surfactant blends with HLB of 13 to 18
Polymeric surfactants
1. Synthetic polymers
(a) Homopolymers Modified polysacharides

Polyvinyl alcohol, PVA

(b) Block-copolymers

Synperonics, EOnPOmEOn
2. Natural polymers (proteins)

(a) Globular (b) Fibrilar

Bovine serum albumin, BSA β-casein


β-lactoglobulin, BLG κ-casein

Very often mixtures of proteins + polysaccharides are


used in applications
Modes of foam stabilization
by polymeric surfactants

Synthetic polymers Natural polymers

Usually: combination of steric + electrostatic stabilization


2. Particles as surfactant species
1. Types of Solid particles
(a) Mineral - SiO2, Ore particles (b) Polymeric - latex

2. Particle monolayers

Particle adsorption energy = πR2σ(1-cosθ)2 >> kBT


Particle stabilized emulsions and foams

particles
Oil

Particle layer on drop surface

Main factors:
• Particle hydrophobicity
• Particle size
• Particle shape
Dinsmore et al., Science, 2002
Stabilization of films
by capillary forces

Relatively thick foam films that are very stable, if the


particle layers are complete
Problems with particle stabilized foams
Velikov et al., Langmuir, 1998

Strong capillary attraction between particles


⇒ Creation of “weak” spots (free of particles) in the films!
Lateral capillary forces

12
F
qσQ1Q2 10

0
0 1 2 3 4
qL
Role of particle shape

“Foam super-stabilization by polymer microrods”


Alargova et al., Langmuir 20 (2004) 10371.

Rod-like particles seem to be a better option for


foam stabilization
Role of particle aggregation

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

θ > 90 o θ > 45o


3. Role
3. Role of
of surfactants
surfactants for
for
various foam
various foam and
and
emulsion properties
emulsion properties
Foam film drainage and thickness
Anionic Polymeric Protein,
surfactant, SDS surfactant, PVA Na caseinate
Speed: ×1 Speed: ×4 Speed: ×8

hEQ ≈ 10 nm hEQ ≈ 120 nm hEQ ≈ 30 nm


τDR ≈ 60 sec τDR ≈ 300 sec τDR ≈ 600 sec
Large vertical films
SLES+CAPB SLES+CAPB+MAc
real time accelerated 5 times

Much slower film drainage in MAc-containing system


Different mode of film drainage - no marginal regeneration
Foam rheology
Foam rheology

τV V

γ&

1. Viscous friction in flowing foams.


2. Role of surface modulus (surfactant
dependent).
3. Bubble breakup.
Effect of surfactant type
100

Dimensionless viscous stress


Anionic+CTAC
+LOH
+LAc Soap
+MAc n ≈ 0.2
10-1 +PAc
+MAc/PAc
Anionic
+ 6 other
cosurfactants
10-2
n ≈ 0.5
Theoretical
curve
10-3
10-7 10-6 10-5 10-4 10-3 10-2
Capillary number, Ca Capillary number
⎛ τV R32 ⎞ Dimensionless ⎛ μγ& R32 ⎞
τ%V = ⎜ ⎟ viscous stress Ca = ⎜ ⎟
⎝ σ ⎠ ⎝ σ ⎠
Role of surface modulus
Oscillating drop

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

10-1 100 101


δS/S0, %

Soap solutions: GD > 100 mN/m


CAPB, SDS, SLES, ... GD < 5 mN/m
Mechanisms of energy dissipation in
sheared foam

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

Very good description without any adjustable parameter


Foam-wall friction
10-1

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

R32 = 730 μm γ& = const R32 = 230 μm

Shear stress as a function of time:


1
At γ& = const τ~ n
R
Bubble breakup in steadily sheared foam
40 Anionic+MAc
γ& = 150 s −1

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

Smaller and less polydisperse bubbles are formed at high


surface modulus
Foam drainage
Surface stress in foam drainage
Longitudinal section of
the Plateau channel

High surface modulus Low surface modulus

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

Much slower bubble coarsening in FAc-containing system


Effect of surfactants on film permeability
(Princen & Mason, 1965)

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

Surfactants with low surface modulus


(anionic, cationic, nonionic; HLB concept; …):
SDS, SLES, CAPB, CTAC, EO7, ...

Surfactants with high surface modulus:


Fatty acids, fatty alcohols and acids as cosurfactants, …

Mixtures are often preferred in applications:


SDS+LaOH, DTAB+LaOH, SLES+CAPB, CAPB+FAc, LAS+EO7, ...
Surfactant + Polymer, Surfactant + Particles

Particles (in combination) give new options:


Arrest of Ostwald ripening, different rheology, …
Current activity
Current activity

• Biosurfactants:

• Polymers-surfactant mixtures.

• Other dynamic phenomena – acoustic response,


foam extrusion, ...

• Role of surfactants and polymers in emulsions.


Relevant References
Basic Literature
K. Tsujii, “Surface Activity: Principles, Phenomena And Applications”,
Academic Press, 1998.
D. J. McClements, “Food Emulsions: Principles, Practices, and
Techniques”, CRC Press, 2nd ed., 2005.
K. Robert Lange, “Surfactants: A Practical Handbook”, Hanser, 1999.
J. Goodwin, “Colloids and interfaces with surfactants and polymers”, Wiley
2nd ed., 2009.
B. P. Binks,” Particles as surfactants – similarities and differences”,
Current Opinion Colloid Interface Sci. 7 (2002) 21 (review).
S. Tcholakova et al., “Comparison of solid particles, globular proteins, and
surfactants as emulsifiers”, Phys. Chem. Chem. Phys. 12 (2008) 1608
(review).
N. D. Denkov et al., “Role of surfactant type and bubble surface mobility in
foam rheology”, Soft Matter 5 (2009) 3389 (review).
Additional Literature
S. Tcholakova et al., “Role of surfactant type and concentration for the mean drop
size during emulsification in turbulent flow”, Langmuir 20 (2004) 7444.
S. Tcholakova et al., “Coalescence stability of emulsions containing globular milk
proteins”, Adv. Colloid Interface Sci. 123-126 (2006) 259.
K. Golemanov et al., “Selection of surfactants for stable paraffin-in-water
dispersions, undergoing solid-liquid transition of the dispersed particles”
Langmuir 22 (2006) 3560.
N. D. Denkov et al., "Wall slip and viscous dissipation in sheared foams: effect of
surface mobility", Colloids Surfaces A 263 (2005) 129.
S. Tcholakova et al., “Theoretical model of viscous friction inside steadily sheared
foams and concentrated emulsions”, Phys. Rev. E 78 (2008) 011405.
K. Golemanov et al., “Surfactant mixtures for control of bubble surface mobility in
foam studies”, Langmuir 24 (2008) 9956.
K. Golemanov et al., “Breakup of bubbles and drops in steadily sheared foams and
concentrated emulsions”, Phys. Rev. E 78 (2008) 051405.
N. D. Denkov, K. G. Marinova, “Antifoam effects of solid particles, oil drops and oil-
solid compounds in aqueous foams”, in Colloidal Particles at Liquid Interfaces,
B. P. Binks and T. S. Horozov Eds., Cambridge University Press, 2006.