Week # 3

MR Chapter 5
Colloids and Fine Particles

Drag force ~ x
x2  6
Surface area / Volume =  x3 x
6
x is the particle diameter (1nm – 10mm)

Body force Other surface forces: van der Waals, electrical double
~ x3 layer, bridging and steric forces
 Brownian motion
Robert Brown (1827)
Thermal energy from
environment causes the
molecules of the liquid to
vibrate.

These vibrating
molecules collide
with each other
and with the
surface of the
particles.

Illustration of the random walk of a Brownian particle.

The distance the particle has moved over a period of time is L
 3kT 3 1 2 Random thermal energy
 kT  mv Ignoring drag, collision and other factors
m 2 2
(Einstein, 1956)
Based on statistical analysis of 1-D random walk to determine root mean square
distance traveled.

k: Boltzmann constant = 1.381 x 10-23 J/K

f: friction coefficient = FD/U
x is the particle diameter

Extension to 3D case: L  6t

 Surface forces

dV
F 
dD
• Van der Waals Forces

A group of
electrohydrodynamic
interactions that occur
between the atoms in
two different particles.
Notation used to indicate the type of
material for each particle and the
intervening medium

Dielectric properties of medium 2 is between materials 1 & 3.

• Electrical double layer forces
Charged nanoparticles suspension
• Nanoparticles in polar liquid:
charge build up solid-liquid
interface
• Surface of particles- surface
ionization with the bulk solution
• Separation between surface and
bulk- potential difference,  (zeta
potential)
Theory of particle mobility in liquid

EPD Deposition model • Deposit particle;

lVcst Hamaker and
Y Avgustinik model
3 ln( a / b)
Electrophoretic mobility, m/s model (Huckel) • Yield (deposit layer), Y
depend on zeta
2ro
m potential. mass
3 particle concentration
Liquid flow, m/s (Electroosmosis) model in suspension.
 r o  1 
U 1  (1  E
2 
2  (1   / a ) 
Cylindrical electrode length, l, with radius, a, and counter electrode radius, b
(b>a). Permittivity, , zeta potential, , viscosity,  and particle mass
concentration, cs
9
P. M. Biesheuvel and H. Verweiji, J. Am. Ceram. Soc., 82(6) 1451-1455 (1999), H. Ohshima, Coll. Int. Sci., 248, 499-503 (2002)
H. Ohshima, Coll. Int. Sci., 210, 397-399 (1999)
Number density per unit area of neutral (M-OH), positive (M-OH2+)
and negative (M-O-) surface sites as a function of pH
A measure of the counterion cloud (thus the range of the repulsion)
is the Debye length , k-1
  3.29 [c] (nm-1 )
Approximate EDL potential energy
VEDL   0 x 02e D
Zeta potential of alumina particles as a function of pH and salt concentration
• Adsorbing polymers, bridging and steric forces

Schematic representation of (a) bridging flocculation and (b) steric repulsion

PAA polymer
• Net interaction force DLVO Theory:
• Result of surface forces on behaviour in air and water
• Influences of particle size and surface forces on
solid/liquid separation by sedimentation

L
2kT
t
  P   f  x 2
g
t
216kT m
 g   P   f  x5
t 2
3 xm 18m 2
• Suspension rheology
 Einstein (1906), < 7% volume solids)

Batchelor (1977), 7-15%, volume solids

Relative viscosity (m s / ml) of hard sphere silica particle

suspensions (black circles) and Einstein’s relationship (line)
The transition from Brownian dominated random structures to preferred flow structures
as shear rate is increased is the mechanism for the shear thinning behaviour of
concentrated suspensions of hard sphere colloids
Influences of surface forces on suspension flow
• Repulsive forces eff 
volume of solid + excluded volume
total volume
• Attractive forces
Force versus separation distance curves for alumina particles
Force versus separation distance curves for oil droplets