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Lecture 18: Colloid stability
This Lecture Covers
DLVO and extended DLVO theories
Force measurements
Effect of interparticle forces on suspension
behaviour
Chee 2940: Colloid stability and dispersion
18.1 INTRODUCTION
Important property of colloidal dispersions is •
•
•
Tendency of the particles to aggregate
Principal cause of aggregation is
The van der Waals attractive forces
(and hydrophobic attraction & polymer bridging)
Stability against aggregation is
The EDL repulsive force
(and other forces: steric repulsion, hydration)
Chee 3920: Colloid stability and dispersion
1
18.2 DLVO THEORY OF COLLOID STABILITY
Was independently developed by Deryagin and
Landau (1939) in Russia, and Verwey and
Overbeek (1948) in the Netherlands.
•
•
•
Explains the effect of salts on stability of
colloidal systems (known from the Faraday
time).
Involves estimation of the total interparticle
interaction energy, V
T
, from the van der Waals
and EDL interactions as
Chee 3920: Colloid stability and dispersion
2
T vdW dl
V V V
e
= +
Total Interaction Repulsion Attraction = +
V
vdW
… van der Waals interaction energy
between two particles (Lecture 16)
( )
12
vdW
AR
V D
D
= −
V
edl
… electrical doublelayer interaction energy
between two particles (low potential  Lecture 17)
( ) ( )
2
0 0
2 exp
edl
V D R D πεε ψ κ = −
Chee 3920: Colloid stability and dispersion
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where D … distance between particle surfaces
R … particle radius
A … Hamaker constant
0
ψ … particle surface potential
ε
0
… permittivity of vacuum (8.854×10
12
C J
1
m
1
)
ε … dielectric constant of solution (=80 for water)
κ … Debye constant
For high surface potential
0
ψ , the EDL energy is
( ) ( )
2
0
2 exp
edl
V D R D πεε γ κ = −
where the reduced potential, γ, is given as
Chee 3920: Colloid stability and dispersion
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0
4
tanh
4
B
B
k T ez
ez k T
ψ
γ
¦ ¹
=
´ `
¹ )
z … valency of ions
e… electronic charge (1.602×10
19
C)
… Boltzmann constant (= 1.381×10
B
k
23
J/K)
T … absolute temperature
tanh … hyperbolic tangent function
( )
( ) ( )
( ) ( )
exp exp
tanh
exp exp
x x
x
x x
− −
=
+ −
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Effect of salt concentration and pH on surface forces
between a particle and a substrate measured with AFM
Chee 3920: Colloid stability and dispersion
6
6
4
2
0
2
4
6
0 5 10 15
Separation distance, D (nm)
I
n
t
e
r
a
c
t
i
o
n
e
n
e
r
g
y
,
V
T
(
x
1
0

1
9
J
)
1.0E+08 2.0E+08 5.0E+08
7.0E+08 1.0E+09 5.0E+09
Debye constant, κ (1/m)
Effect of the Debye constant (salt conc.) on the total interaction
energy. A = 6.1x10
20
J, ψ
0
= 50 mV, T = 25
o
C, R = 0.1 micron.
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Salt concentration determined from the Debye constant
κ (1/m) 1×10
8
2×10
8
5×10
8
7×10
8
1×10
9
5×10
9
C
NaCl
(M) 0.00189 0.00755 0.0472 0.0925 0.189 4.719
Important properties of the interaction energies
van der Waals energy is almost independent of
salt concentration.
•
• EDL energy strongly depends on salt conc.
Chee 3920: Colloid stability and dispersion
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Total interaction energy can be regulated by
changing the added salt concentration.
•
•
• There exists an energy (maximum) barrier of
aggregation at low salt concentration.
There exist two local minima in the total energy
at high salt concentration.
o Primary minimum (deep) at short distances.
o Secondary minimum (shallow) at long distances.
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Chee 3920: Colloid stability and dispersion
10
6
4
2
0
2
4
6
0 5 10 15
Separation distance, D (nm)
I
n
t
e
r
a
c
t
i
o
n
e
n
e
r
g
y
,
V
T
(
x
1
0

1
9
J
)
1.0E+08 7.0E+08 5.0E+09
Debye constant,
κ (1/m)
Barrier of aggregation
Secondary minimum
Primary minimum
Critical Coagulation Concentration (CCC)
Is the minimum salt concentration required to
produce coagulation of a colloid suspension
•
•
•
Salt concentration lower than the CCC
produces stable suspensions
Mathematical description for the CCC:
o Critical coagulation occurs if the barrier of
coagulation is reduced to zero, giving
Chee 3920: Colloid stability and dispersion
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( )
0
T CCC
V D = (The condition of zero barrier)
0
CCC
T
D D
dV
dD
=
 
=

\ .
(The condition of maximum)
( ) ( )
2
0
2 exp
12
T
AR
V D R D
D
πεε γ κ = − + −
Solving the above equations gives •
( )
2
0
2 exp 1
12
AR
R 0
κ
πεε γ − − = and 1
CCC
D κ =
Chee 3920: Colloid stability and dispersion
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• From Lecture 17:
1/ 2
1/ 2
2
2
2 2
0 0
1000
2000
A i i
A
B B
N e z c
N e z c
k T k T
κ
εε εε
∞
¦ ¹
¦ ¹
¦ ¦
= =
´ ` ´ `
¹ ) ¦ ¦
¹ )
∑
( )
 
1/ 2
2 2
2
0
0
2000
2 exp 1
12
A
B
N e z CCC
AR
R
k T
πεε γ
εε
¦ ¹
− =
´ `
¹ )
 
( )
( )
3
2 4
0
2 2 2
288
1000exp 2
B
A
k T
CCC
A N e z
π εε γ
=
Chee 3920: Colloid stability and dispersion
13
A = 1×10
19
J
Chee 3920:
S
u
r
f
a
c
e
p
o
t
e
n
t
i
a
l
(
m
V
)
Dependence of critical coagulation on CCC and surface potential and salt
valency. The colloids are to be stable above and to left of each curve and
coagulated below and to the right.
CCC (mol/L)
Colloid stability and dispersion
14
Critical coagulation concentration in mmol/L for hydrophobic colloids (sols)
As
2
S colloid () AgI colloids () Al
2
O
3
colloids (+)
LiCl 58 LiNO
3
165 NaCl 43.5
NaCl
51 NaNO
3
140 KCl 46
KCl 49.5 KNO
3
136 KNO
3
60
KNO
3
50 RbNO
3
126
K acetate
110 AgNO
3
0.001
CaCl
2
0.65 Ca(NO
3
)
2
2.40 K
2
SO
4
0.30
MgCl
2
0.72 Mg(NO
3
)
2
2.60 K
2
Cr
2
O
7
0.63
MgSO
4
0.81 Pb(NO
3
)
2
2.43 K oxalate 0.69
AlCl
3
0.093 Al(NO
3
)
3
0.067
K
3
[Fe(CN)
6
]
0.08
Al
2
(SO
4
)
2
0.096 La(NO
3
)
3
0.069
Al(NO
3
)
3
0.095 Ce(NO
3
)
3
0.069
Chee 3920: Colloid stability and dispersion
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18.3 EXTENDED DLVO THEORY
DLVO theory considered only two forces: •
•
•
o (vdW & EDL forces: DLVO forces)
Deviation from the DLVO theory has been
observed, due to additional (nonDLVO) forces
NonDLVO forces include:
o Hydrophobic forces between hydrophobic
surfaces (long range, up to 100 nm)
o Hydration repulsion between hydrophilic
Chee 3920: Colloid stability and dispersion
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surfaces (short range, up to 10 nm)
o Polymeric bridging attraction (flocculation)
o Steric repulsion (due to polymers/surf’tants)
Total interaction energy (force) •
T vdW edl non DLVO
V V V V
−
= + +
• NonDLVO forces have been determined by
subtracting the DLVO force from the (total)
measured force.
Chee 3920: Colloid stability and dispersion
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Chee 3920: Colloid stability and dispersion
18
In absence of
EDL repulsion:
V
T
= V
vdw
+ V
steric
V
T
I
n
t
e
r
a
c
t
i
o
n
e
n
e
r
g
y
V
steric
V
steric
V
T
In presence of EDL
repulsion:
V
T
= V
vdw
+ V
edl
+ V
steric
V
vdw
+
V
V
vdW
Schematic interaction energy for sterically
stabilised particles.
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Chee 3920: Colloid stability and dispersion
20
Stabilisation of colloidal systems: Create a
total repulsion between particles by
• Electrostatic stabilisation  EDL (charge)
repulsion by changing pH or increasing surface
potential (via surface cleaning).
Steric stabilisation  repulsion by polymer or
surfactant adsorption.
•
•
Destabilisation of stable colloidal systems:
Create a total attraction between particles by
• Surface hydrophobisation by the surfactant
adsorption or deposition.
Increasing salt concentration (not practical).
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18.4 FORCE MEASUREMENTS
There are two major types of equipment for
measuring surface forces, including
•
•
o Surface Force Apparatus (SFA)
o Atomic Force Microscope (AFM)
Force measurements use Hook’s law: x F k =
Measurements of separation distance between
surfaces are different.
•
o SFA uses the optical (interferometric)
principle. It can give the absolute zero
separation.
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o AFM uses the piezoelectric calibration:
zero separation cannot be precisely
determined.
SURFACE FORCE APPARATUS
Measures the surface force between two large
(radii ~ 1 cm, nearly flat) mica surfaces.
Major parts: variable stiffness spring for force
measurement, spectrometer for distance
measurement.
Sensitivity: 1 nN for force & 0.1 nm for distance
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SFA designed by Drs. Israelachvili and Tabor at the
Cambridge University (UK) in 1978.
Chee 3920: Colloid stability and dispersion
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Picture of SFA Mark II (Israelachvili)
Chee 3920: Colloid stability and dispersion
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Chee 3920: Colloid stability and dispersion
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Chee 3920: Colloid stability and dispersion
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Chee 3920: Colloid stability and dispersion
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ATOMIC FORCE MICROSCOPE
Measures the surface force between a small
surface (AFM sharp tip with R ~ 10 nm or
colloidal probe with R ~ 10 um) and flat surface.
The surfaces are approached and retracted
periodically by the piezoelectric tube
Cantilever deflection is measured by the laser
reflection on the positionsensitive photodiode
system.
Applied voltage vs photodiode voltage is
obtained and converted to force vs distance.
Operating principle of AFM with a sharp tip
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AFM tip can be replaced by a colloid particle
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AFM PicoForce system at ChemEng
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Schematic of our AFM PicoForce system
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A colloid probe: a 14 mm particle glued to an
AFM cantilever used in the force measurement
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0 40 80 120 160 200
Separation [nm]
70
60
50
40
30
20
10
0
F
o
r
c
e
/
R
a
d
i
u
s
[
m
N
/
m
]
25
15
5
5
0 50 100 150 200
Separation distance (nm)
F
/
R
(
m
N
/
m
)
Pure ethanol
17% ethanol
Pure water
0 40 80 120 160 200
Separation [nm]
70
60
50
40
30
20
10
0
F
o
r
c
e
/
R
a
d
i
u
s
[
m
N
/
m
]
25
15
5
5
0 50 100 150 200
Separation distance (nm)
F
/
R
(
m
N
/
m
)
Pure ethanol
17% ethanol
Pure water
Steps in the force curves
are due to nanobubbles
of dissolved gases in water
Effect of soluble gases on attraction between
hydrophobic surfaces
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1micron 1micron
Nanobubbles Nanobubbles
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AFM image of nanobubbles formed at hydrophobic (graphite)
surface in water.
18.5 EFFECTS OF INTERPARTICLE FORCES
ON SUSPENSION BEHAVIOUR
Settling rate and final bed structure depend on interparticle
forces
Dense sediment
bed & high solid
volume fraction
Loose sediment
bed & low solid
volume fraction
Chee 3920: Colloid stability and dispersion
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Summary of effect of interparticle forces on suspension
Chee 3920: Colloid stability and dispersion
37
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