Colloids and Rheology

Lecture 1

Introduction to colloid
& interface science

Mike Adams (m.j.adams@bham.ac.uk)

Colloid and interface science

Types of colloidal dispersions

Discrete phase
Continuous Phase Gas (bubbles) Liquid (droplets) Solid (particles)
Gas Molecular Liquid aerosol Solid aerosol
dispersion (mist) (smoke)
Liquid Liquid foam Emulsion Sol
(shampoo) (mayonnaise) (ink)
Solid Solid foam Solid emulsion Solid sol
(packaging) (butter) (stained glass)

• Colloids consist of at least two phases comprising a discrete or disperse phase and
a continuous phase.
• The disperse phase will be in the diameter range 1 nm to 1 m although some colloidal
properties can be observed up to 10 m.
• Interface science is concerned with the interfaces between liquids and solids, liquids
and gases and between solids and solids, liquids and gases.
• Emulsion droplets may be larger than 1 m, the wetting of solid surfaces and the
adsorption of gases may occur over large areas. These are topics in interface science
in which the length scale of the interface is less than 1 m.
 Colloid stability

• Colloids are classified as lyophilic (solvent loving) and lyophobic (solvent hating)
- originally based on the ease with which the colloids could be redispersed on drying.
• The terms hydrophilic and hydrophobic are used when water is the dispersion medium.
• Colloid dispersions are thermodynamically unstable and kinetically unstable because their high
free energy.
• A lyophobic colloid has to be stabilised by treating the surfaces of the disperse phase
to induce repulsion between the particles.
• Generally, stabilised lyophobic colloids are only kinetically stable.
• Instability leads to aggregation, which may evolve with time.
• An initially formed rather open aggregate is termed a floc and the process of formation
is termed flocculation. The floc may or may not separate out.
• If the floc rearranges to a denser form it is said to undergo coagulation with the formation
of a coagulum.
• An aggregate usually separates by a process of sedimentation (if it is more dense than the
dispersion medium) or by creaming (if it is less dense than the medium).
• Usually coagulation is irreversible whereas flocculation may be reversed by a process
of deflocculation.
The length scale in colloid science - I
Specific surface area
• The surface-to-volume ratio is high for colloids (surface and bulk molecules have
diff properties) - important since surface molecules
have different properties from the bulk phase eg energy, molecular conformation.
• Cannot describe such systems thermodynamically in terms of summing
contributions from bulk molecules.
• The surface associated with a given mass of material increases in inverse proportion
to a linear dimension of the particles and is termed the specific surface area
(typical values for a colloidal dispersion are 1 - 103 m2 g-1). Specific surf area
increases linearly with the size of partivle
Consider a cube of material with edges of length d correspond ing to a unit mass
so that the density is given by   m / v  1 / d 3  1 / v where m is the mass , v is the
volume and v is the specific volume or volume per unit mass :
Surface area 6 d 2 6
Specific surface area  As   
Unit mass d3 d
For a sphere of radius a and diameter d :
4 a 2 6
As  
4 a 3  / 3  d
The length scale in colloid science - II

If the surface molecules have a linear di m ension h

and volume h 3 , the number per unit length of a cube
is d / h  and the fraction of molecules in the surface layer is :
Surface number 6 d / h  h
2
  6  
Total number d / h  3
d 

• For a molar volume 0.05 nm3 (eg silver bromide), h = 0.37 nm.
• For a 1 cm cube, there are ~ 3 surface molecules per 10 million.
• For a 1 m particle, ~ 1 in 500 molecules are at the surface.
• For a 1 nm particle, ~ 1 in 4 molecules are at the surface.
• Particles < 100 nm are called nanoparticles and they have different
properties to larger colloidal particles.
• Particles < 1 nm would disperse such that the equivalent of a solution would
be formed.
• Macromolecules such as proteins are larger than 1 nm and they form colloidal
dispersions.
• Small molecules such as soaps may aggregate to form micelles with a sufficient
size to form a colloidal dispersion (an association colloid).
The length scale in colloid science - III

Variation of the percentage of molecules in the surface as a function of

particle size for a molar volume of 30 cm3 mol-1 (h = 0.37 nm).
 Brownian motion

•The attractive and repulsive forces between colloid particles act over a similar length
scale of 0.1 - 0.5 m.
• When colloids are examined by optical microscopy, the particles are observed to
undergo random motion - known as Brownian motion after the botanist Brown who studied
a suspension of pollen grains in water.
• The energies required to cause motion of the particles are of the order of the thermal
energies causes vibration in the continuous phase, which gives rise to the Brownian
motion.
• That is, colloid particles are significantly larger than the surrounding liquid molecules but
sufficiently small to show Brownian motion and not sediment due to gravity.
• Due to the thermal motion of the molecules in the fluid, at any instant of time the local
concentration in a control volume will be less or greater than the global average and the
colloid particles will tend to move in the direction of the smallest molecular density.
 Force and energy (work)

• Force (f), distance (r) and energy or work

Force, f
(w) are inter-related. df f*
slope  m   *
• Plot force - vs - distance graph. dr r

• Area under the curve equals energy. f*

• Example: straight line ‘triangular’ plot.

Integrate force = work, differentiation work = force
r* Distance, r
r* f *
Work or energy w   Area under curve area of triangle   J 
2
*
2 r
1  f * *2 
Alternatively , w r  
r* f *
mr
J 
* *
r r
 f dr   m r dr    * r  
*
0 0 2 0
2 r  2
d  mr 2 
Therefore, f r  
f* *
  m r  * r  f * N 
dw
*
 
dr dr  2  r
 The Boltzmann distribution

Equilibrium between liq and gas phase

If the molecular in teraction energy of a specific molecule or particle  j  has

different values 1j and  2j in two regions of a system (eg vapour in equilibriu m with the
liquid or two coexisting phases ) the equilibriu m di mensionles s concentrations X 1 and X 2
in these two regions are given by the Boltmann distributi on :
 
X 1  X 2 exp  1j   2j / kT  
 X 1  then 1j   2j 
or : 1j  kT ln X 1   2j  kT ln X 2
 
where k is Boltzmann ' s consta nt 1.38110  23 JK 1 , X n is the mole fraction
or volume fraction. These equations applicable to the dilute state ideal mixing .
For n regions :  nj  kT ln X n  const ant   ()
where  is the chemical potential (total free energy per molecule including
i nteraction energies ) and k ln X n is the entropy.
 Molecules will diffuse between the regions until () is satisfied .
 Here  refers to molecules. On a molar basis the energy has to be multipled
by Advogadro' s const ant N A  6.022 10 23 mol 1.
 Activities and molar masses

 Activities are a means of ex pressi ng the chemical potential of a species

in a mixture or solution :
i  i0  RT ln ai
where ai is the activity in state i , i0 is a reference state and R is the gas const ant
R  N A k  8.314 JK 1 mol 1
Activities may be given on the molar concentration scale :
 c
ai  i 0 i
c

where c 0 is the sta ndard value of the molar concentration 1 mol L1 1 mol/dm 3 and
 i is the activity coefficien t such that :
lim ci  0   i  1
 The molar mass M is related to the molecular mass m by : M  N A m
where the mass of a molecule  MW 1.66110  27 Kg MW  molecular weight 
eg for water M 18  1.66110  27  6.022 10 23  1.8 10  2 Kg mol -1
alternatively the concentration of pure water may be ex pressed as 55.5 mol L1
Diffusion I
The mean square displaceme nt of a colloid particle x 2 after time t is given by :
x 2  2 k T / B  t (1)
where B is the friction factor.
For a spherical particle : B  6   a ( Stokes law)
where  is the visco sity of the dispersion medium and a is the particle radius .
Note that the mean displaceme nt x is zero.
A local var iation in the chemical potential  i will cause particles to diffuse
in a way that equalises the values throughout the phase. The one di mensional
driving force is given by the spatial gradient of  i : Fd  d  i / d x
 i   i0  R T ln ai   i0  R T ln ci (2)

Fd 
d
dx
 
 i0  R T ln ci 
R T d ci
ci d x

 kT / ci  d ci / d x
Fd
Diffusion force per molecule : f d  (3)
NA
The viscous drag force resisting diffusion :
f v  B u (u  particle velocity)
 Settling under gravity

A particle of mass m settling under gravity in a liquid is acted on by three forces :

the gravitational force m g , the buoyancy force m g and the viscous force f v ( m  mass of
fluid displaced by the particle ). From Newton' s law the net force is :
mg  m g  f v  m d u / d t but a small particle will quickly reach its terminal velocity ut , thus
f v  B u  6   a ut
Then  s   l  4  a 3 g / 3  6   a ut
2  s   l  a 2 g
And ut  applies to dilute solutions  1 % 
9
A 1μm particle with  s  2  10 3 kg m 3 in water would travel about 2 μm in 1s due to
gravitational settling .
 k T / 3  a 
1/ 2 1/ 2
From (1) : x2 t which correspond s to a comparable
displaceme nt of about 0.7 μm for such a particle.
Thus gravitational sedi mentation is only importa nt for dense / lar ge particles .
Centrifugation : replace g by  2 r where   radial frequency of centrifuge ( 2  ( rpm / 60))
& r  dista nce from axis of rotation.
Settling under gravity

z  h  h0 , c  c
z

z  h 0 , c  c0
 Sedimentation and creaming

Sedi mentation and creami ng will cause a concentration gradient . Gravitational forces
acting on the particles   s   l  v g  * will be opposed by diffusion attempting
to restore a uniform distributi on. The driving force per particle for diffusion
is d  / d h  where h is the height above some datum h0 and    0  kT ln c
At steady state :   s   l  v g  d  / d h   k T d ln c / d h 
k T d ln c    s   l  v g d h
Integrating between h and h0 :
c / c0  exp   s   l  v g h  h0  / kT 
Note that the particle velocities are small so that viscous drag is negligible .
An example of a physico  chemical balance of potential energy
( gravitational ) and thermal energy (diffusion or Browian motion).

*
The positive direction is taken as up ie h  h 0
Learning outcomes – Lecture 1

• Define colloids, give examples and describe how they become unstable
• Origin and importance of the critical colloidal length scale
• Define Brownian motion
• Understand the Boltzmann distribution
• Activities and molar masses
• Diffusion in the absence of gravity
• Settling under gravity
• Sedimentation and creaming