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 small-
magnitude 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
volume by its density.
As particle size
decreases, surface
forces dominate
Body force
~ x
3
Drag force ~ x
Surface area / Volume =
x
x
x 6
3
6
2
=
t
t
Other surface forces: van der Waals, electrical double
layer, bridging and steric forces
x is the particle diameter (1nm 10m)
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
Illustration of the random walk of a Brownian particle.
The distance the particle has moved over a period of time is L
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.
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
x is the particle diameter
3kT
m
u =
(Einstein, 1956)
f: friction coefficient = FD/U
k: Boltzmann constant = 1.381 x 10
-23
J/K
Extension to 3D case:
t L o 6 =
2
2
1
2
3
mv kT =
Random thermal energy
Ignoring drag, collision and other factors
Increase temperature or decrease mass, increase
Brownian motion
Based on statistical analysis of 1-D random walk to determine root mean square
distance traveled.
Surface Force
Force between two particles
(F) may be either attractive
or repulsive which depends
on
-surface to surface separation
distance (D)
-between the particles and the
potential energy (V) at that
separation distance
dV
F
dD
=
Therodynamics dictates
that the pair of particles
move to separation
distance that results in
the lowest energy
configuration.
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-OH
2
+
)
and negative (M-O
-
) surface sites as a function of pH
-1
3.29 [ ] (nm ) c k =
2
EDL 0 0

D
V x e
k
tcc

= +
A measure of the counterion cloud (thus the range of the repulsion)
is the Debye length , k
-1

Approximate EDL potential energy
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
( )
2
2 5
216
P f
kT
t
g x

t
=

( )
2
2
3 18
P f
x g
kT
L t t
x

t

= =
Suspension rheology
Relative viscosity ( ) of hard sphere silica particle
suspensions (black circles) and Einsteins relationship (line)
/
s l

Einstein (1906), < 7% volume solids)
Batchelor (1977), 7-15%, volume solids
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
Repulsive forces
Influences of surface forces on suspension flow

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