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5 6172670196868710628 PDF
5 6172670196868710628 PDF
Arne Thomas,
MPI of Colloids and Interfaces, Golm
thomas@mpikg.mpg.de
0331-567 9509
What is a Colloid?
Colloid science is the study of systems involving small particles of one substance suspended in another
Colloid chemistry is closing the gap between molecular chemistry and solid state properties!
Micelles (“Aggregation colloids”)
3 - 50 nm
Outline
Hydrophilic headgroup
Hydrophobic tail
H2O
1. Surfactants/Introduction
2. Basics of micellization: characterization and properties
3. Micelle formation mechanism
4. Semiquantitative predictive models of micellization
(Tanford, Israelachvili, Ruckenstein, Nagarajan)
5. What is the “deeper” reason for self-assembly?
1. Surfactants
cationic
Hydrophobic tail
Non-ionic surfactants (“Niotenside”) (“hates water”)
O OH „Brij“
n m
Pluronics: PEO - PPO - PEO
O
n m
ϕ
1. Surfactants
Phosphatidylcholin (Lecithin)
Introduction: Self-assembly of surfactants in water
2) Applications of surfactants:
Cleaning/Detergents (40%), Textiles, Cosmetics,
Paper Production, Paint, Food, Mining (Flotation)......
SiO2
Si(OH)4
Porous material
Washing / Solubilization of other substances
Solubilization by
micelles
Chiuz, 2003
2. Basics of micellization: characterization and properties
• Characterization of micelles
• Basic properties of micelles
• The critical micelle concentration
• The Krafft temperature
Different shapes of micelles
Wrong:
1. There is no denser core!
2. The heads are not so perfectly arranged
3. For normal surfactants, micelles
are not shape-persistent
H2O H2O H2 O
H2O
H2O ...
H2 O
H2O
Preparation:
1) Controlled environmental chamber to minimize compositional changes
2) rapid thermal quenching of a thin layer of the sample in a liquid ethane slush
(formation of vitrified ice).
Visualization of self-assembled structures
Cylindrical micelles forming a stable 2D hexagonal lattice in a SiO2 matrix
50 nm
SiO2
H2 O
H2O
H2O
H2O
Detector
Sample
X-ray or neutron
source
2θ I (2θ )
ρ(r)
r
Density profile
PS120,d8-P4VP118
PS
N
r
P4VP
toluene
hairy micelles
deuterated PS
Contrast matching technique for small-angle neutron scattering
Scattering of
the corona
Poly(styrene)-b-poly(4-pyrrolidone) forms a)
inverse micelles in toluene core
Toluene
PS120,d8-P4VP118
N PS I(2θ)
P4VP
toluene
b) core 2θ
hairy micelles
deuterated PS Scattering of the
micelle core
Toluened8
Results:
RCore= 12 nm, Rmicelle = 36 nm
cmc of nonionic
surfactants
is generally lower
compared to ionic
surfactants
Typical behavior
of selected physico-
chemical parameters such
as the equivalence
conductivity Λc or the
surface tension σ on
the surfactant
concentration
Ionic surfactants
Conductivity:
Λc ≈ μ (mobility)
Ionic surfactants
Conductivity:
Λc ≈ μ (mobility)
3 - 50 nm
1
Ionic surfactants
2
zA = 10-170
3
Nonionic surfactants
4
zA = 30-10.000
H2O
Binary
phase diagram
surfactant/water
S: surfactant molecule
• S + (n-1)S ⇔ S2 + (n-2)S ⇔
Sn-1 + S ⇔ Sn
• Distribution of species
cooperative phenomenon!
Kn=1030; n=20
[monomer]
Kn = [micelles]/[monomers]n = [Sn]/[S]n
c-[monomer]
CMC = (nKn)-1/n
4. Semiquantitative predictive models of micellization
Vcore = g V0 = 4πR3/3
A = g ae = 4πR2 R = 3 V0/ae
R
Common surfactants:
v0/l0 = const. = 0.21 nm2
(single tail)
• The tail does not have any influence on the shape and
size of the aggregate
The concept of the “packing parameter P” (Israelachvili)
Predictions of the “packing parameter concept”
lamellae
Predictions of the “packing parameter concept”
A model surfactant system
electro-deposition of gold
polymerization of polypyrrole
Chemical potential
H2O change
σ: interfacial tension
α: headgroup repulsion
parameter
g ∝ 1/ae
General aspects:
1) Tail transfer is responsible for aggregation, no influence on size and shape!
P=V0/(ae l0)
2) Ionic surfactants:
salt addition decreases the repulsion α decrease in ae
increase in V0/(ae l0)
P=V0/(ae l0)
3) Single tail / double tail surfactants
4) Influence of solvents
Interfacial tension σ decreases
H2O
EtOH
H2 O H 2O V0/(ae l0) decreases
H2 O H2 O ae increases
EtOH
H2O bilayer to micelles,
rodlike to spherical micelles
Some successful predictions of the packing model
P=V0/(ae l0)
5) Influence of temperature
ΔT Increasing the temperature decreases
O the steric repulsion of PEO headgroup
n m
α decreases ae decreases
P increases
Same aggregation
Small tail behavior ?
Large tail … obviously not!
Br
N
+
= ae
(Nagarajan, Ruckenstein)
Influence of tail packing constraints – Nagarajan/Ruckenstein
(for spheres)
Q ∝ L,v0
The tail length influences the head group area and thereby the
shape!
5. What is the “deeper” reason for self-assembly?
H 2O
2) Hydrocarbons in water
Why unfavorable?
H 2O
CH3 CH2 CH3
CH2
CH2
Entropie/enthalpy of micellization
ΔG = ΔH – T ΔS
The high cost in free energy comes from the difficulty of finding
an appropriate cavity in water, due to the small size of water molecules.
Free-volume water
distribution of
a simple liquid
(n-hexane) n-hexane
and water
Literature:
Thermodynamics:
• Nagarajan, R. and Ganesh, K.
Block copolymer self-assembly in selected solvents,
J. Chem. Phys. 1989, p. 5843.
Visualization of micelles:
• Evans et al., Langmuir, 1988, 34,1066.
• Böttcher et al., Angew. Chemie, 2004, early view.
Washing/surfactants:
Chiuz, 2003, 37, 336.
Hydrophobic effect:
Southall et al., J. Phys. Chem. B, 2002, 106, 521.
Thank you!!