CHEE2940 Lecture 18 - Colloid Stability | Soft Matter | Materials Science

CHEE2940: Particle Processing

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 double-layer 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
3
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
4
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
− −
=
+ −

Chee 3920: Colloid stability and dispersion
5


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.
Chee 3920: Colloid stability and dispersion
7
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
8
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.
Chee 3920: Colloid stability and dispersion
9

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
11
( )
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
12
• 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
15
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 (non-DLVO) forces

Non-DLVO 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
16
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

= + +


• Non-DLVO forces have been determined by
subtracting the DLVO force from the (total)
measured force.
Chee 3920: Colloid stability and dispersion
17



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.
Chee 3920: Colloid stability and dispersion
19


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).
Chee 3920: Colloid stability and dispersion
21
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.
Chee 3920: Colloid stability and dispersion
22
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
Chee 3920: Colloid stability and dispersion
23

SFA designed by Drs. Israelachvili and Tabor at the
Cambridge University (UK) in 1978.
Chee 3920: Colloid stability and dispersion
24

Picture of SFA Mark II (Israelachvili)
Chee 3920: Colloid stability and dispersion
25
Chee 3920: Colloid stability and dispersion
26
Chee 3920: Colloid stability and dispersion
27
Chee 3920: Colloid stability and dispersion
28
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 position-sensitive photodiode
system.

Applied voltage vs photodiode voltage is
obtained and converted to force vs distance.
Operating principle of AFM with a sharp tip











Chee 3920: Colloid stability and dispersion
29
AFM tip can be replaced by a colloid particle











Chee 3920: Colloid stability and dispersion
30
AFM PicoForce system at ChemEng
Chee 3920: Colloid stability and dispersion
31

Schematic of our AFM PicoForce system
Chee 3920: Colloid stability and dispersion
32

A colloid probe: a 14 mm particle glued to an
AFM cantilever used in the force measurement
Chee 3920: Colloid stability and dispersion
33

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
Chee 3920: Colloid stability and dispersion
34
1micron 1micron
Nanobubbles Nanobubbles
Chee 3920: Colloid stability and dispersion
35
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
36
Summary of effect of interparticle forces on suspension


Chee 3920: Colloid stability and dispersion
37

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