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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
Chee 3920: Colloid stability and dispersion 2
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

Chee 3920: Colloid stability and dispersion 3


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


Chee 3920: Colloid stability and dispersion 4
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 )

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
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.
Chee 3920: Colloid stability and dispersion 7
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.

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
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)

Chee 3920: Colloid stability and dispersion 10


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
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
Chee 3920: Colloid stability and dispersion 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 )

Chee 3920: Colloid stability and dispersion 13


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.
Chee 3920: Colloid stability and dispersion 14
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
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)

VT = VvdW + Vedl + Vnon− DLVO

• 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:
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.
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: F = kx
• 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
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.
Chee 3920: Colloid stability and dispersion 28
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

-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
Chee 3920: Colloid stability and dispersion 34
Nanobubbles

1micron
AFM image of nanobubbles formed at hydrophobic (graphite)
surface in water.
Chee 3920: Colloid stability and dispersion 35
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
Chee 3920: Colloid stability and dispersion 36
Summary of effect of interparticle forces on suspension

Chee 3920: Colloid stability and dispersion 37