CHEE2940 Lecture 18 - Colloid Stability

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, VT, from the van der Waals
and EDL interactions as
VT = VvdW + Vedl
Total Interaction = Repulsion + Attraction
VvdW … van der Waals interaction energy

between two particles (Lecture 16)
AR
VvdW ( D ) = −
12 D
Vedl … electrical double-layer interaction energy
between two particles (low potential - Lecture 17)
Vedl ( D ) = 2πεε 0 Rψ 0 exp ( −κ D )
2

where D … distance between particle surfaces
R … particle radius
A … Hamaker constant
ψ 0 … particle surface potential
-12 -1 -1
ε0… permittivity of vacuum (8.854×10 C J m )
ε … dielectric constant of solution (=80 for water)
κ … Debye constant
For high surface potential ψ 0 , the EDL energy is
Vedl ( D ) = 2πεε 0 Rγ exp ( −κ D )

2
where the reduced potential, γ, is given as

4k BT  ezψ 0 
γ= tanh  
ez  4k BT 
z … valency of ions
-19
e… electronic charge (1.602×10 C)
-23
k B … Boltzmann constant (= 1.381×10 J/K)
T … absolute temperature
tanh … hyperbolic tangent function
exp ( x ) − exp ( − x )
tanh ( x ) =
exp ( x ) + exp ( − x )

Effect of salt concentration and pH on surface forces
between a particle and a substrate measured with AFM

6
4
J)
-19
Interaction energy, VT (x10
-2
Debye constant, κ (1/m)
1.0E+08 2.0E+08 5.0E+08
-4
7.0E+08 1.0E+09 5.0E+09
-6
0 5 10 15
Separation distance, D (nm)
Effect of the Debye constant (salt conc.) on the total interaction

-20 o
energy. A = 6.1x10 J, ψ0 = -50 mV, T = 25 C, R = 0.1 micron.
Salt concentration determined from the Debye constant
κ (1/m) 1×108 2×108 5×108 7×108 1×109 5×109
CNaCl (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.

• 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.

6
4
Barrier of aggregation
J)
-19
Interaction energy, VT (x10
2
Secondary minimum
-2
Primary minimum
-4 Debye constant, κ (1/m)
1.0E+08 7.0E+08 5.0E+09
-6
0 5 10 15
Separation distance, D (nm)

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
VT ( DCCC ) = 0 (The condition of zero barrier)
 dVT 
  = 0 (The condition of maximum)
 dD  D = DCCC
AR
VT ( D ) = − + 2πεε 0 Rγ exp ( −κ D )
2
12 D
• Solving the above equations gives
ARκ
2πεε 0 Rγ exp ( −1) − 2
= 0 and κ DCCC = 1
12
• From Lecture 17:
1/ 2
1000 N Ae ∑ zi ci∞ 
2 2 1/ 2
 2000 N Ae z c 
2 2
κ =  = 
 εε 0 k BT   εε 0 k BT 
AR  2000 N Ae z [CCC ] 
2 2 1/ 2
2πεε 0 Rγ exp ( −1) = 2

 
12  εε 0 k BT 
288π ( εε 0 ) k BT γ
2 3 4
[CCC ] = 2 2 2
A N Ae z 1000exp ( 2 )

Surface potential (mV)
-19
A = 1×10 J
CCC (mol/L)
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.
Critical coagulation concentration in mmol/L for hydrophobic colloids (sols)
As2S colloid (-) AgI colloids (-) Al2O3 colloids (+)

LiCl 58 LiNO3 165 NaCl 43.5
NaCl 51 NaNO3 140 KCl 46
KCl 49.5 KNO3 136 KNO3 60
KNO3 50 RbNO3 126
K acetate 110 AgNO3 0.001
CaCl2 0.65 Ca(NO3)2 2.40 K2SO4 0.30
MgCl2 0.72 Mg(NO3)2 2.60 K2Cr2O7 0.63
MgSO4 0.81 Pb(NO3)2 2.43 K oxalate 0.69
AlCl3 0.093 Al(NO3)3 0.067 K3[Fe(CN)6] 0.08
Al2(SO4)2 0.096 La(NO3)3 0.069
Al(NO3)3 0.095 Ce(NO3)3 0.069
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
surfaces (short range, up to 10 nm)
o Polymeric bridging attraction (flocculation)
o Steric repulsion (due to polymers/surf’tants)
• Total interaction energy (force)
VT = VvdW + Vedl + Vnon− DLVO
• Non-DLVO forces have been determined by

subtracting the DLVO force from the (total)
measured force.
In absence of
EDL repulsion:
VT = Vvdw + Vsteric VT
Vsteric
Interaction energy
Vsteric
VT
Vvdw +
V
VvdW In presence of EDL
repulsion:
VT = Vvdw + Vedl + Vsteric
Schematic interaction energy for sterically

stabilised particles.
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).
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: F = kx
• Measurements of separation distance between
surfaces are different.
o SFA uses the optical (interferometric)
principle. It can give the absolute zero
separation.
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
SFA designed by Drs. Israelachvili and Tabor at the
Cambridge University (UK) in 1978.
Picture of SFA Mark II (Israelachvili)
ATOMIC FORCE MICROSCOPE
Measures the surface force between a small
surface (AFM sharp tip with R ~ 10 nm or
colloidal probe with R ~ 10 µm) 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

AFM tip can be replaced by a colloid particle

AFM PicoForce system at ChemEng
Schematic of our AFM PicoForce system
A colloid probe: a 14 mm particle glued to an
AFM cantilever used in the force measurement
0
-10
Steps in the force curves
Force/Radius [ mN/m]
-20 5
are due to nanobubbles
of dissolved gases in water
-30
F/R (mN/m)
-5
-40 Pure ethanol

-15 17% ethanol
-50 Pure water
-25
-60 0 50 100 150 200
Separation distance (nm)
-70
0 40 80 120 160 200

Separation [nm]
Effect of soluble gases on attraction between

hydrophobic surfaces
Nanobubbles
1micron
AFM image of nanobubbles formed at hydrophobic (graphite)
surface in water.
18.5 EFFECTS OF INTERPARTICLE FORCES
ON SUSPENSION BEHAVIOUR
Loose sediment
Dense sediment bed & low solid
bed & high solid volume fraction
volume fraction
Settling rate and final bed structure depend on interparticle

forces
Summary of effect of interparticle forces on suspension

CHEE2940 Lecture 18 - Colloid Stability

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CHEE2940: Particle Processing

Lecture 18: Colloid stability

This Lecture Covers

DLVO and extended DLVO theories

Chee 2940: Colloid stability and dispersion

• Principal cause of aggregation is

• Was independently developed by Deryagin and

• Involves estimation of the total interparticle

VvdW … van der Waals interaction energy

Chee 3920: Colloid stability and dispersion 3

For high surface potential ψ 0 , the EDL energy is

Vedl ( D ) = 2πεε 0 Rγ exp ( −κ D )

where the reduced potential, γ, is given as

Chee 3920: Colloid stability and dispersion 5

Chee 3920: Colloid stability and dispersion 6

Effect of the Debye constant (salt conc.) on the total interaction

κ (1/m) 1×108 2×108 5×108 7×108 1×109 5×109

CNaCl (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

• EDL energy strongly depends on salt conc.

Chee 3920: Colloid stability and dispersion 8

• There exists an energy (maximum) barrier of

• There exist two local minima in the total energy

o Primary minimum (deep) at short distances.

o Secondary minimum (shallow) at long distances.

-4 Debye constant, κ (1/m)

1.0E+08 7.0E+08 5.0E+09

Chee 3920: Colloid stability and dispersion 10

• Is the minimum salt concentration required to

• Salt concentration lower than the CCC

• Mathematical description for the CCC:

o Critical coagulation occurs if the barrier of

• Solving the above equations gives

2πεε 0 Rγ exp ( −1) = 2

Chee 3920: Colloid stability and dispersion 13

As2S colloid (-) AgI colloids (-) Al2O3 colloids (+)

• DLVO theory considered only two forces:

• Deviation from the DLVO theory has been

• Non-DLVO forces include:

• Total interaction energy (force)

VT = VvdW + Vedl + Vnon− DLVO

• Non-DLVO forces have been determined by

Schematic interaction energy for sterically

Chee 3920: Colloid stability and dispersion 29

Chee 3920: Colloid stability and dispersion 30

Steps in the force curves

-40 Pure ethanol

0 40 80 120 160 200

Effect of soluble gases on attraction between

Settling rate and final bed structure depend on interparticle

Chee 3920: Colloid stability and dispersion 37

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