Surfactants classification,

classification,
Surfactants
features and
and applications
applications
features
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, 1213 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
Alkylpolyoxyethylenes
CnEOm

Spans

Tweens

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

Electrostatic stabilization
by ionic surfactants

Nonionic surfactants

Steric stabilization by
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 HLBs of 1 to 3

HLB < 8

Preparing water-in-oil emulsions

surfactants with HLBs of 4 to 6
Preparing self emulsifying oils
surfactants with HLBs of 7 to 10
Preparing oil-in-water emulsions
surfactant blends with HLBs 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
Polyvinyl alcohol, PVA

(b) Block-copolymers

Synperonics, EOnPOmEOn

Modified polysacharides

2. Natural polymers (proteins)

(a) Globular

Bovine serum albumin, BSA

-lactoglobulin, BLG

(b) Fibrilar

-casein
-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 = R2(1-cos)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
qQ1Q2 10
8
6
4
2
0
0

2
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
effect
Antifoam
of hydrophobic
hydrophobic particles
particles
of
Antifoam effect

TECHNOLOGY
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

Silica (SiO2)
Polymeric particles

2. Oil
Silicone oils (PDMS)
Hydrocarbons (mineral oil,

100 nm

30 m

aliphatic oils)

3. Compound
Compound
globule

Oil + particles
30 m

Film rupture by solid particles

bridging-dewetting mechanism

Key factors:
(1) Particle contact angle
(2) Particle size and shape

> 90

> 45o

3. Role
Role of
of surfactants
surfactants for
for
3.
various foam
foam and
and
various
emulsion properties
properties
emulsion

Foam film drainage and thickness

Anionic
surfactant, SDS
Speed: 1

Polymeric
surfactant, PVA
Speed: 4

Protein,
Na caseinate
Speed: 8

hEQ 10 nm

hEQ 120 nm

hEQ 30 nm

DR 60 sec

DR 300 sec

DR 600 sec

Large vertical films

SLES+CAPB
real time

SLES+CAPB+MAc
accelerated 5 times

Much slower film drainage in MAc-containing system

Different mode of film drainage - no marginal regeneration

Foam rheology
rheology
Foam
V

&
1. Viscous friction in flowing foams.
2. Role of surface modulus (surfactant
dependent).
3. Bubble breakup.

Dimensionless viscous stress

Effect of surfactant type

100

10-1

Anionic+CTAC
+LOH
+LAc
+MAc
n
+PAc
+MAc/PAc

Soap

0.2
Anionic
+ 6 other
cosurfactants

10-2

10-3
10-7

n 0.5
Theoretical
curve
10-6

10-5

10-4

Capillary number, Ca

V R32 Dimensionless
%V =
viscous stress

10-3

10-2

Capillary number

& R32
Ca =

Role of surface modulus

Oscillating drop
S ( t ) S0 = S sin ( t )
( t ) 0 = sin ( + t )

Storage modulus

S0 + S0 < 0
> 0

GST =

cos
S0

Loss modulus

GLS =

sin
S0

Experimental results for surface modulus

103

Total modulus
2
LS

12

102
GD, mN/m

GD = G + G
2
ST

= 0.2 Hz
T = 25 C

Soap

101

Anionic

100
10-1

100
S/S0, %

Soap solutions: GD > 100 mN/m

CAPB, SDS, SLES, ... GD < 5 mN/m

101

Mechanisms of energy dissipation in

sheared foam

S0

Friction in foam films

0.5
%
V Ca

S0 + S

S0

Surface dissipation

0.2
%
V Ca

Denkov et al., PRL, 2008; Soft Matter 2009; Tcholakova et al., PRE, 2008

Dimensionless viscous stress

Comparison with experimental data

for emulsions
Hexadecane, D = 3 mPa.s
10-1

Light oil, D = 30 mPa.s

Heavy oil, D = 150 mPa.s

10-2

n = 0.47
10-3
= 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

WR32/

Soap
Soap

10-2

n = 1/2

Synthetic
CAPB
surfactants
0 to 70 %

Glycerol

V0
n = 2/3
10-3
10-6

10-5

W = kV0 n
10-4

10-3

Capillary number, Ca

Dimensionless
wall stress

Capillary number

W R32
% =

V0
Ca =

Lower friction for CAPB

compared to soap
surfactants

Bubble (drop) breakup in sheared foams

(emulsions)
Bubble breakup in a rheometer
Final foam

Initial foam

R32 = 730 m

& = const

R32 = 230 m

Shear stress as a function of time:

At & = const

1
~ n
R

Bubble breakup in steadily sheared foam

40

& = 150 s

Anionic+MAc

R32 = 220 m

Shear stress, Pa

35
Anionic+0.05 wt % MAc
30
25

Anionic

20
Anionic

R32 = 480 m

15

= 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

VS = VZ ( x = 0 ) = 0

Low surface modulus

S = V ( x = 0 ) = 0

Ostwald ripening in foams, R32(t)

2.6

Foam

2.4

Anionic

(R(t)/R0)

2.2
2.0

Anionic+LAc

1.8
1.6
1.4

p1, V1

p2, V2

Anionic+MAc

1.2
1.0
0

500

1000

1500 2000
Time, sec

2500

3000

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

k=
C2 I
C2(p2)
h

DH
h + 2 D kML

D diffusion coefficient
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

P2

P1
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
activity
Current

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 oilsolid compounds in aqueous foams, in Colloidal Particles at Liquid Interfaces,
B. P. Binks and T. S. Horozov Eds., Cambridge University Press, 2006.