Colloids and Fine Particles (Introduction) Example : Removal colloidal particle

from raw water

Solids are present in water in three main forms:
suspended particles, colloids and dissolved molecules.
Suspended particles, such as sand, vegetable matter
and silts, range in size from very large particles down to
particles with a typical dimension of 10 m.

Colloids are very fine particles, typically ranging from 10 nm to

10 m.
Dissolved molecules are present as individual
molecules or as ions.
There are two types of colloids: hydrophilic colloids and hydrophobic colloids.
Hydrophobic colloids, including clay and non-hydrated metal oxides,
are unstable. The colloids are easily destabilized.
Hydrophilic colloids like soap are stable. When these colloids are mixed with
water, they form colloidal solutions that are not easily destabilized. Most
suspended solids smaller than 0.1 mm found in water carry negative
electrostatic charges.

Since the particles have similar negative electrical charges

and electrical forces to keep the individual particles separate,
the colloids stay in suspension as small particles.
The magnitude of the zeta potential (Zp) is usually
used to indicate colloidal particle stability. The higher the
zeta potential, the greater are the repulsion forces between
the colloidal particles and, therefore, the more stable is the
colloidal suspension. A high Zp represents strong forces of
separation (via electrostatic repulsion) and a stable system,
i.e. particles tend to suspend. Low Zp indicates relatively
unstable systems, i.e. Particles tend to aggregate.

To remove colloids, small particles have to be destabilized first and then

they will form larger and heavier flocks which can be removed by
conventional physical treatment. This process can be described by
clarification mechanisms, that includes: coagulation, flocculation and
sedimentation.
Coagulation is the process of decreasing or neutralizing the negative
charge on suspended particles or zeta potential. This allows the van der
Waals force of attraction to encourage initial aggregation of colloidal
and fine suspended materials to form microflock. Rapid, high energy
mixing is necessary to ensure the coagulant is fully mixed into the
process flow to maximize its effectiveness. The coagulation process
occurs very quickly, in a matter of fractions of a second.
Flocculation is the process of bringing together the particles to form
large agglomerations by physically mixing or through the bridging action
of
coagulant
aids,
such
as
long
chain
polymer.

Destabilization by bridging occurs when a polymer of a high molecular weight

becomes attached at a number of adsorption sites to the surface of negatively
charged particles along the polymer chain. The remainder of the polymer may
remain extended into the solution and may adsorb on available surface sites of
other particulates, thus creating a bridge between the surfaces.
Flocculation time is commonly 10-30 minutes; however the optimum flocculation
time will vary depending on the raw water quality and downstream
clarification
process.
Sedimentation is the process of allowing the flock formed during flocculation to
settle out and separate from the clarified water. Typical retention time is 4-6
hours
for
settling.

Colloids and Fine Particles

-emergence of nanotechnology and

microfluids
Colloids- very fine particles between 1
nm and 10 micron
Behaviour dominated by surface force
rather than body force

Surface force
Exhibited

cohesive nature of fine

particles
High viscosity of
concentrated suspensions
Slow sedimentation of
dispersed colloidal
suspensions

Body force vs surface foce

Mass of fine particles and
colloids is so smallmagnitude of their body
force is less than the
magnitude of the forces
acting between their
surfaces.

 Mass of a particle is
directly related to its
2

x
6
Surface area / Volume =
x volume by its density.
x3
As particle size
6
Drag force ~ x
decreases, surface
forces dominate
x is the particle diameter (1nm 10mm)

Body force
~ x3

Other surface forces: van der Waals, electrical double

layer, bridging and steric forces

Surface Force
Other surface foces:
Van der waals
Electrical double layer
Bridging and steric force
* Control behaviour of
fine powders and
colloidal suspensions

Result from either

attraction or repulsion
between two particles
Depend on
- material of the
particles
- type of fluid
- distance between the
particles

Brownian motion- colloids disperse in a

liquid

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

A kinetic model-determine the influence of key

parameters on the average velocity of
particles in suspension. Consider thermal
energy of the environment is transferred to
the particles as kinetic energy. Average
thermal energy is 3/2kT ( k is Boltmanns
constant =1.381 x 10-23J/K).Ignore
drag,collision..average velocity of the particle
can be estimated by equating the kinetic
energy 1/2mv2

3kT

3
1 2
kT mv
2
2

Random thermal energy

Ignoring drag, collision and other factors
Increase temperature or decrease mass, increase
Brownian motion

(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 6t

Surface Force
Force between two particles Therodynamics dictates
(F) may be either attractive
that the pair of particles
or repulsive which depends
move to separation
on
distance that results in
-surface to surface separation
the lowest energy
distance (D)
-between the particles and the configuration.
potential energy (V) at that
separation distance

dV
F
dD

Surface forces
dV
F
dD

Van der waals Forces-Wikipedia

van der Waals' force (or van der Waals' interaction),
named after Dutch scientist Johannes Diderik van der
Waals, is the sum of the attractive or repulsive forces
between molecules (or between parts of the same
molecule) other than those due to covalent bonds, the
hydrogen bonds, or the electrostatic interaction of ions
with one another or with neutral molecules or charged
molecules.[1] The term includes:
force between two permanent dipoles (Keesom force)
force between a permanent dipole and a corresponding
induced dipole (Debye force)
force between two instantaneously induced dipoles
(London dispersion force).

Van der waals Forces

Refer to group of
electrodynamics
interactions including
Keesom, Debye and
London dispersion
Dominant contribution to
van der Waals
interaction between
two particles is
dispersion force

Dispersion Force
- Result of Columbic
interactions between
correlated fluctuating
instantaneous dipole
moments within the
atom of the particles

Van der waals Forces

Van der waals interaction
can be attractive or
repulsive depend on
dielectric properties of
the two particles
Medium between the
particles
Hamaker constant : A
A>0 interaction is attractive
A<0, interaction is repulsive

Two spherical particles of

the same size: Van der
waals interaction energy,
Vvdw and van der waals
force, Fvdw

 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-when particles are immersed in an aqueos

solutions-oxide particles immersed in aqueous solution.

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 x02e 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

 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
2kT
L
3 xm

x
g

P
f

18m

216kT m

g P f x5
2

 Suspension rheology

Einstein (1906), < 7% volume solids)

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

Relative viscosity (ms / m)l of hard sphere silica particle

suspensions (black circles) and Einsteins 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