Introduction to colloidal

dispersions
R.A.L. Jones, 4
Colloid
A colloid or colloidal dispersion is a system of two or
more components; a type of mixture intermediate between
homogeneous solution and heterogeneous mixtures with
properties also intermediate between a solution and a
mixture.
Examples: butter, milk, cream, aerosols (fog, smog,
smoke), asphalt, inks, paints, glues and sea foam, are
colloids.
This field of study was introduced in 1861 by Scottish
scientist Thomas Graham.
The size of dispersed phase particles in a colloid range
from 0.001 to 1 micrometers.
Milk
Cow's milk contains, on average, 3.4% protein, 3.6%
fat, and 4.6% lactose
Milk supplies 66 kcal of energy per 100 grams.
Butter
Commercial butter is about 80% butterfat and 15% water;
traditionally-made butter may have as little as 65% fat and
30% water.
Butterfat consists of many moderate-sized, saturated
hydrocarbon chain fatty acids. It is a triglyceride, an ester
derived from glycerol and three fatty acid groups.
http://www.scientificpsychic.com/fitness/fattyacids.html
Properties of colloids
High area of interface
Dispersion, aggregation, sedimentation
Stabilation: charge, cover by polymer etc.
Shear thickening or thinning
+
+
+
+
-
-
-
-
-
-
-
- -
-
-
-
-
-
A single colloidal particle in a liquid
Fluid mechanics point of view
Gravity
Grag is the force that resists the movement of a solid
object through a fluid (a liquid or gas).
Grag
Gravity
Randomly moving sphere in a liquid
Expression for the frictional
force exerted on small
spherical objects in a viscous
fluid. The force (Stokes law
1851) can be written as
F = 6nna v,
where v is the velocity, a the
radius of the particle, n
viscosity of a liquid.
Reynolds number
Re = pva/n
where p is the density.
The gravitation force for
one sphere is
F
g
= 4/3n a
3
Ap g,
where Ap is the density
difference between the
sphere and the liquid.
In balance F = F
g
. From this
the terminal velocity is
v
t
= 2a
2
Ap g/(9 n).
Suspension of colloidal spheres
Particles are in random motion
How this is characterized: random walk
The directions of the successive steps are not correlated.
The mean value of the square of the displacements is
proportional to the number of steps and thus the time t.
Denote the displacement vector by R(t). Then
<R(t)
2
> = a t.
The factor a is related to the diffusion coefficient D.
Randomly moving spheres in a liquid
Diffusion coefficient for the particles?
Equation of motion for a particle:
m d
2
R/dt
2
+ b dR/dt = F,
where F is random force resulting from collisions of the
spheres with the liquid molecules, m the mass and b the
drag coefficient.
Drag force proportional to the velocity (Stokes law):
b = 6nna.
Randomly moving sphere in a liquid
Use Cartesian coordinates x, y, z.
The sphere can move in random directions, all
coordinates behave the same way <x
2
> =<y
2
> =<z
2
> :
<R
2
> = 3 <x
2
>
Langevin equation of motion (x-direction)
m d
2
x/dt
2
+ b dx/dt = F,
The applied force is the random force F resulting from
collisions of the solute molecules with the sphere.
Inserting the relations
d(x
2
)/dt = 2x dx/dt and xd
2
x/dt
2
= d/dt(x dx/dt) – (dx/dt)
2
Randomly moving spheres in a liquid
Equation of motion
m/2 (d
2
x
2
/dt
2
) -m(dx/dt)
2
= -b/2(dx
2
/dt) + Fx
Take the average
b/2 d<x
2
>/dt = <xF> - m d/dt<xdx/dt> + 1/2m<dx/dt>
2
.
Because the direction of the random force is uncorrelated
with the position of the particle, <xF> = 0.
The position and the velocity of the particle are not
correlated, <x dx/dt> = 0.
From the equipartition theorem <1/2 m(dx/dt)
2
> = 1/2 kT
Equipartition theorem
The theorem of classical statistical mechanics and
thermodynamics states: the internal energy of a system
composed of a large number of particles at thermal
equilibrium will distribute itself evenly among each of the
quadratic degrees of freedom allowed to the particles of
the system.
For example, the equipartition theorem says that the
mean internal energy associated with each degree of
freedom of a monatomic ideal gas is the same.
For a molecule of gas, each component of velocity has an
associated kinetic energy. This kinetic energy is, on
average, kT/2, where k is Boltzmann constant and T
temperature.
Randomly moving spheres in a liquid
Denoting X = <dx
2
/dt>
one obtains a first order equation
(dX/dt) + b/mX = 2kT/m
The general solution is X = 2kT/b + C exp(-b/mt)
Assume that t >> b/m, one obtains
<x
2
> = 2kT/bt or <x
2
> = 2Dt.
Randomly moving sphere in a liquid
The motion is diffusive.
Einstein formula for the diffusion coefficient D = kT/b.
Sphere diffusing in a liquid D = kT/(6nna)
(Stokes-Einstein equation)
Light scattering and diffusion coefficient
Let one consider solution of colloidal particles.
The random motion of the particles causes intensity
fluctuations of the scattered light.
The autocorrelation function of the scattering intensity
g(q,t) can be presented as
g(q,T) = <I(q,t) I(q, t+T)>/<I(q,t)>
2
.
Magnitude of the scattering vector q = 4nn sin0// where n
is the refractive index of the solution, / the wavelength
and 20 the scattering angle.
Light scattering and diffusion coefficient
The correlation function g
can be fitted by a sum of
exponential functions giving
the decay time t which is
related to the diffusion
coefficient of the particles D
as
1/t = q
2
D.
D is affected by the
interaction between the
particles as
D = D
0
(1+a¢)
where ¢ is the concentration
of the particles and a an
interaction parameter.
The hydrodynamic radius R
h
of the particles in associated
with D
0
as
D
0
= kT/(6nn R
h
)
Example. SAXS and DLS
For a solution of fluorinated colloidal particles about the
same particle size distribution was obtained by using
SAXS and DLS.
DLS: He/Ne laser
SAXS: 1.54 Å
J. Wagner et al. Langmuir 2000, 16, 4080-4085.
Diffusion Coefficients for Four Hydrocarbons
in Water
Price and Söderman. Self-diffusion coefficients of some
hydrocarbons in water: Measurements and scaling relations.
J. Phys.Chem. A 104, 5892-5894, 2000.
0.70 ± 0.06 201.3/3.6 1.45 0.764 o-xylene
0.77 ± 0.06 180.5/3.5 1.42 0.95 c-hexane
0.85 ± 0.33 218.5/3.7 4.26 0.294 n-hexane
0.86 ± 0.10 192.8/3.6 5.72 0.225 n-pentane
D
w
e
(10
-9
m
2
s
-1
) V (Å
3
)/R (Å)
d
D
bulk
c
(10
-9
m
2
s
-1
)
b
(10
-3
kg (ms)
-1
) molecule
Forces between colloidal particles
System with a large amount of surface
Interfacial energy is large.
Jones book estimate: may be much bigger than kT.
Are dispersions then unstable?
Other forces between particles of electrostatic origin.
Interactions in colloidal solution
Excluded Volume Repulsion: This refers to the
impossibility of any overlap between hard particles.
Electrostatic interaction: Colloidal particles often carry an
electrical charge and therefore attract or repel each other.
The charge of both the continuous and the dispersed
phase, as well as the mobility of the phases are factors
affecting this interaction.
Interactions in colloidal solution
van der Waals forces: This is due to interaction between
two dipoles that are either permanent or induced. Even if
the particles do not have a permanent dipole, fluctuations
of the electron density gives rise to a temporary dipole in
a particle. This temporary dipole induces a dipole in
particles nearby. The temporary dipole and the induced
dipoles are then attracted to each other. This is known as
van der Waals force, and is always present, is short-
range, and is attractive.
Interactions in colloidal solution
Entropic: According to the second law of thermodynamics,
a system progresses to a state in which entropy is
maximized. This can result in effective forces even
between hard spheres.
Steric: between polymer-covered surfaces or in solutions
containing non-adsorbing polymer can modulate
interparticle forces, producing an additional repulsive
steric repulsion force (which is predominantly entropic in
origin) or an attractive depletion force between them.
Example. Concentrated Silica Colloidal
Dispersions
The structure factors of colloidal silica dispersions at
rather high volume fractions (from 0.055 to 0.22) were
determined by small-angle X-ray scattering and fitted with
both the equivalent hard-sphere potential model (EHS)
and the Hayter-Penfold/Yukawa potential model (HPY).
Both of these models described the interactions in these
dispersions successfully, and the results were in
reasonable agreement.
D. Qiu et a. A Small-Angle X-ray Scattering Study of the Interactions
in Concentrated Silica Colloidal Dispersions.
. Langmuir, 22 (2), 546 -552, 2006.
SAXS of Concentrated Silica Colloidal
Dispersions
The strength and range of the interaction potentials
decreased with increasing particle volume fractions, which
suggests shrinkage of the electrical double layer arising
from an increase in the counterion concentration in the
bulk solution.
However, the interactions at the average interparticle
separation increased as the volume fraction increased.
D. Qiu et a. A Small-Angle X-ray Scattering Study of the Interactions in
Concentrated Silica Colloidal Dispersions.
. Langmuir, 22 (2), 546 -552, 2006.
Forces between colloidal particles: van der
Waals
Interaction between two atoms (particles)
Potential between two particles is assumed to be of
form -C/r
6
For two macroscopic bodies with separation h:
U(h) = íí -C/r
6
p
1
p
2
dV
1
dV
2
where p
1
and p
2
are the number densities of the
volume elements dV
1
and dV
2
.
.
Example.
An atom at the distance D from
medium of density p.
The interaction between the molecule
and a ring of radius x whose centre
is z away from the molecule is
-2npx dx dz C/(x
2
+z
2
)
3
.
The total interaction energy is
w(D) = -2npC í
D
×
dz í
0
×
x dx/(x
2
+z
3
)
3
= -2npC/(12 D
3
).
D
x
x
z
y
r
dxdz
Example.
Assume that instead of one atom there is a sheet of
atoms.
The unit area and thickness of this atomic sheet is dz at
the distance z from the semi-infinite sheet.
The energy per unit area is simply
-2¬p
2
C/12z
3
,
where p is the density.
The constant A = ¬p
2
C is called the Hamaker constant.
Then the interaction energy is
U(h) = -A/12¬h
2
í
h
z
-3
dz.
van der Waals and Hamaker constant
Surface-surface interaction
The total interaction energy per unit area between two
semi-infinite sheets of the same material was
U = ¬Cp
2
/12D
2
The constant A = np
2
C is the Hamaker constant. Magnitude
around 10
-19
J
vdW interaction energies between particles of
different geometries
Atoms w ~ -1/r
6
Two spheres w ~ -1/r
Atom-surface w ~ -1/r
3
Sphere-surface w ~ -1/r
Two parallel cylinders
w ~ -1/r
3/2
Two surfaces w ~ -1/r
2
Israelachvili p 177
;
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-10
12
-10
10
-10
8
-10
6
-10
4
-10
2
-10
0
r
w
(
r
)
atoms
spheres
cylinders
surfaces
Problems
Pairwise additivity of the forces. In practice all other atoms
in the system have to be taken into account.
For large separations, over 10 nm, the effects of the finite
speed of the propagation of fields arising from the
fluctuating dipoles become significant.
More powerful approach – Lifshitz theory.
Charged surfaces
Electrostatic interactions are important.
In water: counterions of the colloids float freely: Screening
Screened Coulomb interaction: exponential decay in
strength with distance
Consider two ionized parallel surfaces in the water.
Counter ions are in the solution, but provide charge
neutrality. The counter ions are attracted to the surfaces.
Their concentration profile is diffuse.
Charged surfaces in water
Temperature T
Let ¢ be the electrostatic potential and p the number density of
ions of valency z at any point between the surfaces.
Chemical potential u = ze¢ + kT lnp
Boltzmann distribution for the density of ions at any point
p = p
0
exp(-ze ¢/kT) (¢
0
is assumed 0)
Poisson-Bolzmann equation gives the
concentration profile for the counter ions.
-
-
-
-
-
-
-
- D
+
Poisson-Bolzmann equation
The charge of the ions is ze.
Poisson equation for the net charge density at point x:
zep = - s
0
s d
2
¢/dx
2
Combine with the Boltzmann distribution
d
2
¢/dx
2
= - zep/s
0
s = -(zep
0
/s
0
s) exp(-ze ¢/kT)
PB: d
2
¢/dx
2
= -(zep
0
/s
0
s) exp(-ze ¢/kT)
Poisson-Bolzmann equation is a non-linear second-order
differential equation.
Surface charge
PB equation
d
2
¢/dx
2
= -(zep
0
/s
0
s) exp(-ze ¢/kT)
Boundary conditions
Symmetry requirement: the field must vanish at the midplane
d¢/dx = 0
Overall electroneutrality: total charge in the gap must be
equal (opposite sign) to that at surfaces.
Let o be the charge density at surfaces. Then
o = -í
0
D/2
ze p dx = s
0
s í
0
D/2
d
2
¢/dx
2
dx = s
0
s (d¢/dx)
D/2
= s
0
s (d¢/dx)
s
The field E
s
at the surface is (d¢/dx)
s
= o/ s
0
s.
-D/2 D/2
Ionic distribution
1. Charge density p(x) = p
0
exp(-ze ¢(x)/kT)
2. PB equation d
2
¢/dx
2
= -(zep
0
/s
0
s) exp(-ze ¢/kT)
Differentiating (1) dp/dx = p
0
ze/kT exp(-ze ¢/kT) d¢/dx
Insert (2): dp/dx = s
0
s/(kT) (d¢/dx) (d
2
¢/dx
2
)
= s
0
s/(kT) d/dx (d¢/dx)
2
dp/dx = s
0
s/(kT) d/dx (d¢/dx)
2
.
Integration from 0 to x: p(x) = p
0
+ s
0
s/(2kT) (d¢/dx)
2
x
At the surface (x = D/2) the concentration of counter ions
is p
s
= p
0
+ o
2
/2s
0
skT
Thus the number density of ions p
s
depends on the
surface charge density o and the counter ion
concentration p
0
at midplane.
Counterion concentration profile away from a
surface
PB equation d
2
¢/dx
2
= -(zep
0
/s
0
s) exp(-ze ¢/kT)
Solution ¢(x,T) = (kT/ze) ln(cos
2
Kx),
where K(T)
2
= (ze)
2
p
0
/s
0
s kT
At x=0, ¢=0 and d¢/dx = 0 for all K
At any point x
E
x
= d¢/dx = 2kTK/ze tanKx
The counter ion distribution profile
p(x,T) = p
0
exp(-ze ¢/kT)
= p
0
/ cos
2
Kx
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
1
1.05
1.1
1.15
1.2
1.25
1.3
1.35
x
1
/
c
o
s
2

K
x
K=0.5, 0.3333, 0.25, 0.2, 0.1667
Limitations of PB equation
Continuum, mean field
Breaks down at small distances
Ion-correlation effects (polarization, vdW)
Finite-ion size
Discreteness of surface charges
Solvation forces
Electrostatic double layer forces
Consider pair of parallel ionized surfaces
Overall charge neutralization achieved by counter ions.
Electrostatic potential ¢(x) at a distance x from the
surface.
Boltzmann equation gives the density of ions: n = n(0)
exp (-ze ¢(x)/(kT)) where k Boltzmann constant and T
temperature, ze ion charge and the potential ¢(x).
The potential is determined by the distribution of net
charge p(z) by the Poisson equation p = s0 s d
2
¢/dx
2
.
Counter ions balance the surface charge p = ze.
Poisson-Boltzmann equation
d
2
¢/dx
2
= -(ze n(0)/ s0 s) exp(-ze ¢ /kT)
Electrostatic double layer forces
Example. Surface is in contact with a solution of an
electrolyte which is a solution of a univalent salt (e.g.
sodium chloride).
Concentration of positive ions n
+
= n(0) exp(-ze ¢/kT)
Concentration of negative ions n
-
= n(0) exp(ze ¢/kT)
The net charge density p = ze(n
+
+n
-
)
d
2
¢/dx
2
= -(ze n(0)/ s0 s) sinh (-ze ¢/kT)
Debye-Hückel approximation
Boundary conditions for solution:
Isolated plate: ¢ and d¢ /dx approach 0 as x approaches
infinity.
If the potential is small one can approximate sinh x ~ x.
Debye-Hückel approximation for the potential
¢(x) = ¢(0) exp(-kx)
where
k = (2e
2
n(0)z
2
/(s
0
skT) )
1/2
.
Debye screening length
Electric fields are screened in an electrolyte.
Screening is the damping of electric fields caused by the
presence of mobile charge carriers.
The length which characterizes the screening 1/k is called
the Debye screening length.
Stabilizing colloids
Coating with a polymer layer.
When two particles approach each other, the
concentration of the polymer inside the gap increases.
This increases the osmotic pressure and causes a
repulsive force.
Spatial Correlation of Spherical Polyelectrolyte
Brushes in Salt-Free Solution As Observed by
Small-Angle X-ray Scattering
Linear chains of poly(acrylic acid) (PAA) are chemically
grafted onto the surface of a colloidal poly(styrene)
particle.
Robillard et al. Macromolecules
33, 9109-9114, 2000
Depleting interactions
A solution contains both particles and e.g. dissolved
polymer.
Polymer coils are excluded from a depletion zone bear the
surface of the colloid particles. When the depletion zones
of two particles overlap there is a net attractive force
between the particles arising from unbalanced osmotic
pressure.
Depleting interactions
Dilute solution of particles
Osmotic pressure P
osm
= N/V kT
N number of polymers in volume V of solution.
The net potential F
dep
= -P
osm
V
dep
V
dep
is the total volume of particles from which the
polymers are excluded.
Model potential describing the depletion effect
First theoretical consideration Asakura and Oosawa J.
Chem Phys. 22, 1255, 1954
Suspension of colloidal particles, radius a, and non-
absorbing polymer
Depletion potential
U = infinity for r > 2a
U = A for 2a < r < 2a+rg
U = 0 for r > 2a+rg
Here rg is the radius of the polymer molecule
The constant A is related to the polymer osmotic pressure
and the volume of the overlapping depletion zones
between two particles.
Results
With the model potential the phase behaviour of the
mixture could be predicted.
At low polymer concentrations fluidlike arrangement of
colloidal particles
At high polymer concentrations colloidal fluid-crystal
coexistence
Also metastable gel phases
S.MiIlett et al. Phys. Rev. E, 1995, 51, 1344-1352.
Stability and phase behaviour of colloids
Interaction from repulsive to attractive
Adding salt
Add poor solvent
Remove grafted chains from the surface
Add non-adsorbing polymer to increase the size of the
depletion zone.
Crystallization of hard sphere colloids
Stable suspension: the forces between colloidal particles
are repulsive at all distances.
Spherical particles: The systems crystallizes as the
concentration of particles reaches high enough level.
Colloidal crystals: true long range order
Simplest model: hard sphere model
Good model for colloidal particles stabilized by polymer
coating. The coating need to be thin compared to the
radius of the particles.
Origin of the phase transition
A way of thinking: excluded volume
Two spheres cannot overlap. This leads to repulsive force
between the spheres.
Ideal gas of N atoms in a volume V: S
i
= k ln(aV/N)
Gas atoms have a finite volume b. The volume accessible
to any given atom is V-Nb.
Now the entropy S = k ln(a(V-nb)/N) = S
i
– k ln(1-bN/V)
If the free volume of atoms is low S = S
i
– k b N/V
The corresponding free energy F = F
i
+ k T b N/V
There is effective repulsion between particles which
causes the crystallization.
Structures
Close packed: HCP or FCC
Colloids with weakly attractive interactions
Grafted colloids
Weak interaction: liquid-solid transition
Colloids with strongly attractive interactions
Aggregation
Crystal-nucleation rate (Auer and Frenkel
Nature 2001, 1020-1023
Probability (per particle) that a spontaneous fluctuation
will result in formation of a critical nucleus depends on the
free energy
AG
c
as P
c
= exp(-AG
c
/kT)
Free energy needed to form the nucleus
AG(r) = 4/3nr
3
p Au + 4nr
2
v,
where p is the number density of the solid and v the solid-
liquid interfacial energy density.
The maximum of AG at r = 2 v/(p |Au|) where |Au| is the
difference in chemical potential of the solid and the liquid.
The nucleation rate f per unit volume is proportional to the
probability P:
f = c P
c
= c exp(- AG
c
/kT) = c exp(-16 n/3 v
3
/(p |Au|)
2
)
Complementary Use of Simulations and Molecular-
Thermodynamic Theory to Model Micellization
Brian C. Stephenson, Kenneth Beers, and Daniel
Blankschtein. LANGMUIR Volume: 22 Issue: 4 Pages:
1500-1513 Published: 2006
Computer
simulation
Molecular-
thermodynamic
model
Thermodynamic
Description of
Micelle aggregation
Property
prediction
g
mic

Colloid
A colloid or colloidal dispersion is a system of two or more components; a type of mixture intermediate between homogeneous solution and heterogeneous mixtures with properties also intermediate between a solution and a mixture. Examples: butter, milk, cream, aerosols (fog, smog, smoke), asphalt, inks, paints, glues and sea foam, are colloids. This field of study was introduced in 1861 by Scottish scientist Thomas Graham. The size of dispersed phase particles in a colloid range from 0.001 to 1 micrometers.

Milk
Cow's milk contains, on average, 3.4% protein, 3.6% fat, and 4.6% lactose Milk supplies 66 kcal of energy per 100 grams.

Butter
Commercial butter is about 80% butterfat and 15% water; traditionally-made butter may have as little as 65% fat and 30% water. Butterfat consists of many moderate-sized, saturated hydrocarbon chain fatty acids. It is a triglyceride, an ester derived from glycerol and three fatty acid groups.

http://www.scientificpsychic.com/fitness/fattyacids.html

Properties of colloids
High area of interface Dispersion, aggregation, sedimentation Stabilation: charge, cover by polymer etc. Shear thickening or thinning

+ -

-

+ + +

-

A single colloidal particle in a liquid Fluid mechanics point of view Gravity Grag is the force that resists the movement of a solid object through a fluid (a liquid or gas). Grag Gravity .

. is the density difference between the sphere and the liquid. a the radius of the particle. Reynolds number Re = va/ where is the density. The gravitation force for one sphere is Fg = 4/3 a3 where g. viscosity of a liquid. where v is the velocity. In balance F = Fg.Randomly moving sphere in a liquid Expression for the frictional force exerted on small spherical objects in a viscous fluid. From this the terminal velocity is vt = 2a2 g/(9 ). The force (Stokes law 1851) can be written as F=6 a v.

Suspension of colloidal spheres Particles are in random motion How this is characterized: random walk The directions of the successive steps are not correlated. The factor a is related to the diffusion coefficient D. Denote the displacement vector by R(t). . The mean value of the square of the displacements is proportional to the number of steps and thus the time t. Then <R(t)2> = a t.

. where F is random force resulting from collisions of the spheres with the liquid molecules. m the mass and b the drag coefficient.Randomly moving spheres in a liquid Diffusion coefficient for the particles? Equation of motion for a particle: m d2R/dt2 + b dR/dt = F. Drag force proportional to the velocity (Stokes law): b=6 a.

The applied force is the random force F resulting from collisions of the solute molecules with the sphere.Randomly moving sphere in a liquid Use Cartesian coordinates x. Inserting the relations d(x2)/dt = 2x dx/dt and xd2x/dt2 = d/dt(x dx/dt) – (dx/dt)2 . y. z. The sphere can move in random directions. all coordinates behave the same way <x2> =<y2> =<z2> : <R2> = 3 <x2> Langevin equation of motion (x-direction) m d2x/dt2 + b dx/dt = F.

The position and the velocity of the particle are not correlated. From the equipartition theorem <1/2 m(dx/dt)2> = 1/2 kT . Because the direction of the random force is uncorrelated with the position of the particle. <xF> = 0.Randomly moving spheres in a liquid Equation of motion m/2 (d2x2/dt2) -m(dx/dt)2 = -b/2(dx2/dt) + Fx Take the average b/2 d<x2>/dt = <xF> . <x dx/dt> = 0.m d/dt<xdx/dt> + 1/2m<dx/dt>2.

For example. on average. where k is Boltzmann constant and T temperature. the equipartition theorem says that the mean internal energy associated with each degree of freedom of a monatomic ideal gas is the same. kT/2. . For a molecule of gas.Equipartition theorem The theorem of classical statistical mechanics and thermodynamics states: the internal energy of a system composed of a large number of particles at thermal equilibrium will distribute itself evenly among each of the quadratic degrees of freedom allowed to the particles of the system. This kinetic energy is. each component of velocity has an associated kinetic energy.

. one obtains <x2> = 2kT/bt or <x2> = 2Dt.Randomly moving spheres in a liquid Denoting X = <dx2/dt> one obtains a first order equation (dX/dt) + b/mX = 2kT/m The general solution is X = 2kT/b + C exp(-b/mt) Assume that t >> b/m.

Einstein formula for the diffusion coefficient D = kT/b. Sphere diffusing in a liquid D = kT/(6 (Stokes-Einstein equation) a) .Randomly moving sphere in a liquid The motion is diffusive.

t) can be presented as g(q. the wavelength . The random motion of the particles causes intensity fluctuations of the scattered light. Magnitude of the scattering vector q = 4 n sin / where n is the refractive index of the solution. t+T)>/<I(q.Light scattering and diffusion coefficient Let one consider solution of colloidal particles.t)>2. and the scattering angle.T) = <I(q. The autocorrelation function of the scattering intensity g(q.t) I(q.

D is affected by the interaction between the particles as D = D0 (1+a ) where is the concentration of the particles and a an interaction parameter. The hydrodynamic radius Rh of the particles in associated with D0 as D0 = kT/(6 Rh) .Light scattering and diffusion coefficient The correlation function g can be fitted by a sum of exponential functions giving the decay time t which is related to the diffusion coefficient of the particles D as 1/t = q2 D.

16. . SAXS and DLS For a solution of fluorinated colloidal particles about the same particle size distribution was obtained by using SAXS and DLS.Example.54 Å J. Wagner et al. DLS: He/Ne laser SAXS: 1. 4080-4085. Langmuir 2000.

33 0.70 ± 0. 2000.06 0.10 0.3/3.77 ± 0.06 0. J. 5892-5894.Chem.72 4.86 ± 0.294 0.45 V (Å3)/R (Å)d 192.5 201. A 104.7 180. Self-diffusion coefficients of some hydrocarbons in water: Measurements and scaling relations.764 Price and Söderman.225 0.8/3.5/3.85 ± 0.6 218.26 1. Phys.6 Dwe (10-9 m2 s-1) 0.42 1.5/3. .95 0.Diffusion Coefficients for Four Hydrocarbons in Water molecule n-pentane n-hexane c-hexane o-xylene b (10-3 kg (ms)-1) Dbulkc (10-9 m2 s-1) 5.

.Forces between colloidal particles System with a large amount of surface Interfacial energy is large. Are dispersions then unstable? Other forces between particles of electrostatic origin. Jones book estimate: may be much bigger than kT.

.Interactions in colloidal solution Excluded Volume Repulsion: This refers to the impossibility of any overlap between hard particles. as well as the mobility of the phases are factors affecting this interaction. The charge of both the continuous and the dispersed phase. Electrostatic interaction: Colloidal particles often carry an electrical charge and therefore attract or repel each other.

is shortrange. This temporary dipole induces a dipole in particles nearby. Even if the particles do not have a permanent dipole.Interactions in colloidal solution van der Waals forces: This is due to interaction between two dipoles that are either permanent or induced. . and is attractive. fluctuations of the electron density gives rise to a temporary dipole in a particle. This is known as van der Waals force. and is always present. The temporary dipole and the induced dipoles are then attracted to each other.

. a system progresses to a state in which entropy is maximized.Interactions in colloidal solution Entropic: According to the second law of thermodynamics. producing an additional repulsive steric repulsion force (which is predominantly entropic in origin) or an attractive depletion force between them. Steric: between polymer-covered surfaces or in solutions containing non-adsorbing polymer can modulate interparticle forces. This can result in effective forces even between hard spheres.

Example. . . 2006.22) were determined by small-angle X-ray scattering and fitted with both the equivalent hard-sphere potential model (EHS) and the Hayter-Penfold/Yukawa potential model (HPY). Concentrated Silica Colloidal Dispersions The structure factors of colloidal silica dispersions at rather high volume fractions (from 0. Both of these models described the interactions in these dispersions successfully. 546 -552. 22 (2). A Small-Angle X-ray Scattering Study of the Interactions in Concentrated Silica Colloidal Dispersions. Qiu et a. D. Langmuir.055 to 0. and the results were in reasonable agreement.

the interactions at the average interparticle separation increased as the volume fraction increased. . . D. Langmuir. Qiu et a. However. 546 -552. 22 (2). A Small-Angle X-ray Scattering Study of the Interactions in Concentrated Silica Colloidal Dispersions. which suggests shrinkage of the electrical double layer arising from an increase in the counterion concentration in the bulk solution.SAXS of Concentrated Silica Colloidal Dispersions The strength and range of the interaction potentials decreased with increasing particle volume fractions. 2006.

. -C/r6 1 1 2 2 dV1 dV2 and are the number densities of the volume elements dV1 and dV2 .Forces between colloidal particles: van der Waals Interaction between two atoms (particles) Potential between two particles is assumed to be of form -C/r6 For two macroscopic bodies with separation h: U(h) = where .

x r D x dxdz The total interaction energy is z w(D) = -2 = -2 C D dz 0 x dx/(x2+z3)3 C/(12 D3).Example. An atom at the distance D from medium of density . y . The interaction between the molecule and a ring of radius x whose centre is z away from the molecule is -2 x dx dz C/(x2+z2)3.

The energy per unit area is simply -2 where 2C/12z3. Then the interaction energy is h z-3 dz. is the density. The unit area and thickness of this atomic sheet is dz at the distance z from the semi-infinite sheet. . 2C The constant A = U(h) = -A/12 h2 is called the Hamaker constant.Example. Assume that instead of one atom there is a sheet of atoms.

van der Waals and Hamaker constant Surface-surface interaction The total interaction energy per unit area between two semi-infinite sheets of the same material was U= 2 /12D2 2 The constant A = around 10-19 J C is the Hamaker constant. Magnitude .

1 0.2 0.8 0.4 0. -10 -10 4 w ~ -1/r3/2 Two surfaces w ~ -1/r2 -10 6 -10 8 -10 10 atoms spheres cylinders surfaces Israelachvili p 177 -10 12 0 0.7 0.3 0.5 r 0.6 0.9 1 .vdW interaction energies between particles of different geometries Atoms w ~ -1/r6 Two spheres w ~ -1/r Atom-surface w ~ -1/r3 Sphere-surface w ~ -1/r Two parallel cylinders w(r) -10 2 0 .

For large separations. . over 10 nm. In practice all other atoms in the system have to be taken into account. More powerful approach – Lifshitz theory.Problems Pairwise additivity of the forces. the effects of the finite speed of the propagation of fields arising from the fluctuating dipoles become significant.

Their concentration profile is diffuse. In water: counterions of the colloids float freely: Screening Screened Coulomb interaction: exponential decay in strength with distance Consider two ionized parallel surfaces in the water.Charged surfaces Electrostatic interactions are important. but provide charge neutrality. Counter ions are in the solution. The counter ions are attracted to the surfaces. .

Charged surfaces in water Temperature T Let be the electrostatic potential and = ze + kT ln ( is assumed 0) the number density of ions of valency z at any point between the surfaces. Chemical potential = exp(-ze /kT) Boltzmann distribution for the density of ions at any point 0 0 - + - Poisson-Bolzmann equation gives the concentration profile for the counter ions. D - .

ze PB: 0 0 0 d2 /dx2= -(ze 0 0 ) exp(-ze /kT) Poisson-Bolzmann equation is a non-linear second-order differential equation. Poisson equation for the net charge density at point x: ze =0 d2 /dx2 = -(ze ) exp(-ze /kT) Combine with the Boltzmann distribution d2 /dx2 = . .Poisson-Bolzmann equation The charge of the ions is ze.

Let = be the charge density at surfaces. Then dx = 0 D/2 0 = . The field Es at the surface is (d /dx)s = / .0D/2 ze 0 d2 /dx2 dx = 0 (d /dx)D/2 0 (d /dx)s .Surface charge -D/2 D/2 PB equation d2 /dx2= -(ze 0 0 ) exp(-ze /kT) Boundary conditions Symmetry requirement: the field must vanish at the midplane /dx = 0 Overall electroneutrality: total charge in the gap must be equal (opposite sign) to that at surfaces.

.Ionic distribution 1. Charge density (x) = 0 exp(-ze (x)/kT) 2. PB equation d2 /dx2 = -(ze 0 0 ) exp(-ze /kT) Differentiating (1) Insert (2): /dx = /dx = = 0 0 0 /dx = 0ze/kT exp(-ze /kT) d /dx /(kT) (d /dx) (d2 /dx2 ) /(kT) d/dx (d /dx)2 /(kT) d/dx (d /dx)2. (x) = + /(2kT) (d /dx)2x Integration from 0 to x: is s= 0 0 At the surface (x = D/2) the concentration of counter ions 0 + 2 /2 0 kT s Thus the number density of ions surface charge density concentration 0 depends on the and the counter ion at midplane.

0.25.35 /dx = 0 for all K 1.3333. 0 0 0 /kT) where K(T)2 = (ze)2 At x=0.15 1.4 -0.Counterion concentration profile away from a surface PB equation d2 /dx2 = -(ze Solution (x.2 0.8 -0.T) = (kT/ze) 0 ) exp(-ze ln(cos2Kx).T) = = 0 0/ 1/cos2 Kx 1. =0 and At any point x Ex = d /dx = 2kTK/ze tanKx kT 1.6 -0. 0.2 0 x 0.1667 1.5.1 1.05 1 -1 -0. 0.3 K=0.25 The counter ion distribution profile (x.6 0.8 1 . 0.2 exp(-ze /kT) cos2Kx 1.4 0.2.

vdW) Finite-ion size Discreteness of surface charges Solvation forces . mean field Breaks down at small distances Ion-correlation effects (polarization.Limitations of PB equation Continuum.

Electrostatic potential (x) at a distance x from the surface.Electrostatic double layer forces Consider pair of parallel ionized surfaces Overall charge neutralization achieved by counter ions. ze ion charge and the potential (x). /dx2. Boltzmann equation gives the density of ions: n = n(0) exp (-ze (x)/(kT)) where k Boltzmann constant and T temperature. The potential is determined by the distribution of net charge (z) by the Poisson equation Poisson-Boltzmann equation d2 /dx2 = -(ze n(0)/ ) exp(-ze /kT) = d2 = ze. Counter ions balance the surface charge .

Concentration of positive ions n+ = n(0) exp(-ze /kT) Concentration of negative ions n. sodium chloride). Surface is in contact with a solution of an electrolyte which is a solution of a univalent salt (e.= n(0) exp(ze /kT) The net charge density d2 /dx2 = -(ze n(0)/ = ze(n++n-) ) sinh (-ze /kT) .Electrostatic double layer forces Example.g.

.x) where = (2e2n(0)z2/( 0 and /dx approach 0 as x approaches kT) )1/2. If the potential is small one can approximate sinh x ~ x.Debye-Hückel approximation Boundary conditions for solution: Isolated plate: infinity. Debye-Hückel approximation for the potential (x) = (0) exp(.

The length which characterizes the screening 1/ is called the Debye screening length.Debye screening length Electric fields are screened in an electrolyte. . Screening is the damping of electric fields caused by the presence of mobile charge carriers.

Stabilizing colloids Coating with a polymer layer. This increases the osmotic pressure and causes a repulsive force. the concentration of the polymer inside the gap increases. . When two particles approach each other.

Robillard et al.Spatial Correlation of Spherical Polyelectrolyte Brushes in Salt-Free Solution As Observed by Small-Angle X-ray Scattering Linear chains of poly(acrylic acid) (PAA) are chemically grafted onto the surface of a colloidal poly(styrene) particle. 9109-9114. Macromolecules 33. 2000 .

When the depletion zones of two particles overlap there is a net attractive force between the particles arising from unbalanced osmotic pressure.Depleting interactions A solution contains both particles and e. . Polymer coils are excluded from a depletion zone bear the surface of the colloid particles.g. dissolved polymer.

.Depleting interactions Dilute solution of particles Osmotic pressure Posm = N/V kT N number of polymers in volume V of solution. The net potential Fdep = -Posm Vdep Vdep is the total volume of particles from which the polymers are excluded.

.Model potential describing the depletion effect First theoretical consideration Asakura and Oosawa J. Chem Phys. and nonabsorbing polymer Depletion potential U = infinity for r 2a U = A for 2a < r < 2a+rg U = 0 for r > 2a+rg Here rg is the radius of the polymer molecule The constant A is related to the polymer osmotic pressure and the volume of the overlapping depletion zones between two particles. radius a. 1954 Suspension of colloidal particles. 22. 1255.

Phys. . At low polymer concentrations fluidlike arrangement of colloidal particles At high polymer concentrations colloidal fluid-crystal coexistence Also metastable gel phases S. 51. 1344-1352.Results With the model potential the phase behaviour of the mixture could be predicted.MiIlett et al. E. 1995. Rev.

.Stability and phase behaviour of colloids Interaction from repulsive to attractive Adding salt Add poor solvent Remove grafted chains from the surface Add non-adsorbing polymer to increase the size of the depletion zone.

The coating need to be thin compared to the radius of the particles. . Colloidal crystals: true long range order Simplest model: hard sphere model Good model for colloidal particles stabilized by polymer coating.Crystallization of hard sphere colloids Stable suspension: the forces between colloidal particles are repulsive at all distances. Spherical particles: The systems crystallizes as the concentration of particles reaches high enough level.

The volume accessible to any given atom is V-Nb. . Ideal gas of N atoms in a volume V: Si = k ln(aV/N) Gas atoms have a finite volume b. This leads to repulsive force between the spheres. Now the entropy S = k ln(a(V-nb)/N) = Si – k ln(1-bN/V) If the free volume of atoms is low S = Si – k b N/V The corresponding free energy F = Fi + k T b N/V There is effective repulsion between particles which causes the crystallization.Origin of the phase transition A way of thinking: excluded volume Two spheres cannot overlap.

Structures Close packed: HCP or FCC .

Colloids with weakly attractive interactions Grafted colloids Weak interaction: liquid-solid transition .

Colloids with strongly attractive interactions Aggregation .

1020-1023 Probability (per particle) that a spontaneous fluctuation will result in formation of a critical nucleus depends on the free energy Gc as Pc = exp(. the solid| is the is the number density of the solid and |) where liquid interfacial energy density.Crystal-nucleation rate (Auer and Frenkel Nature 2001. The nucleation rate f per unit volume is proportional to the probability P: f = c Pc = c exp(.Gc/kT) Free energy needed to form the nucleus G(r) = 4/3 r3 where + 4 r2 . The maximum of G at r = 2 /( difference in chemical potential of the solid and the liquid.Gc/kT) = c exp(-16 /3 3/( |)2) .

Kenneth Beers. and Daniel Blankschtein. LANGMUIR Volume: 22 Issue: 4 Pages: 1500-1513 Published: 2006 Computer simulation gmic Molecularthermodynamic model Thermodynamic Description of Micelle aggregation Property prediction .Complementary Use of Simulations and MolecularThermodynamic Theory to Model Micellization Brian C. Stephenson.

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