DEFINITION OF A COLLOID

Mixtures of one material (the dispersoid) dispersed in another as particles in the size range of:

1nm 10m.

Since colloid is mainly a surface, the wetting liquid molecules are adsorbed rather than absorbed. The particle that adsorbs the external phase is called lyophilic. If the external phase is water it is called hydrophilic. A colloid that does not adsorb is called lyophobic or hydrophobic.

APPLICATION FIELDS OF COLLOIDS

Area
Industrial

Example
Paints, Adhesives, Floor polishes, Print inks, Carpet backing, Paper sizing, Water/sewage treatment, Secondary oil recovery, Rubberized concrete Size standard for electron microscopy High resolution chromatography column packing Magnetic particles targeted drug delivery Immunodiagnostics Controlled released drugs Catalysts, Colloids & surface chemistry, Coagulation kinetics Model liquid crystals, Rheology, Dielectric spectroscopy Particle interaction *Dispersion forces *Electrostatics *Steric stabilization

Research

Medical

Chemical

LYOPHOBIC COLLOIDS

IS COLLOID MAINLY A SURFACE MATERIAL..?

Divide 1cm cube into thin laminae, 10 nm thick, a colloidal distance. The cube becomes a million laminae, with a total surface area of 200 m2. Every molecule on the surface is now only a short distance apart and the material is now mainly surface. Note: Each transformation from cubic to laminae to fibril and eventually to corpuscular form causes an increase in number of particles by one million.

To some degree colloids are all surface. Their properties are that of their surfaces and almost no volume effects. This makes colloids different from bulk material.

CONTD

Surface-to-volume ratio increases. Significant proportion of the molecules are at the surface, creating high degree of inhomogeneity. Molecules at surface and bulk show great difference in energy and molecular conformation.

3 important characteristics which explain: (i) Why surface chemistry is important (ii) Why colloidal properties occurs below 1 micron

HOW DOES THE SURFACE CHARACTERISTICS OF A COLLOID INFLUENCE ITS PROPERTIES ?

Example1: Surface tension () - Free energy required per unit area to create new surface At 20C, water-air = 72.75 dyne/cm mercury-air = 450 dyne/cm mercury-water = 375 dyne/cm
If 1 cm3 mercury were divided into 10 nm cubes, then a new surface energy at least (1,000,000 x 375) dyne/cm. This amount of energy can warm the mercury by 143C if the corpuscles coalesce!!!

Example2: An aerosol of starch grains, with a density of 100g/m3, has a very large surface area, and
adsorbs O2 from the atmosphere. Starch grains in flour are from 5 nm to 200 nm in diameter. It is no wonder that it is a violet explosive!!!

Example3: Coal ground to pass through a 200-300 mesh sieve can be blown directly into a fire as a
convenient fuel. It can also make a sol with fuel oil to form a colloidal fuel that can be used exactly like fuel oil. Coal dust is reputed to be a fire hazard, but it is not as dangerous as starch dust.

Forces Between Two Approaching Colloidal Particles

London-van der Waals (VdW) force or dispersion force - forces due to synchronous oscillations of the electron clouds of nearby molecules causing strong attraction between their temporal dipoles.

Coulombic force associated with electrostatically charged particles Force arising from solvation, adsorbed layers, etc

LONG-RANGE VAN DER WAALS ATTRACTION

a
s0 r
Hamaker constant, A, proportional to intermolecular attraction constant

Potential energy of interaction

Attractive force of interaction

Aa = 12s0

Ftt = a

d A a = 2 d0 1 s s 20

s0

VdW interactions between molecules are extremely short ranged (potential -b/r6, b is a constant dependent on molecular properties). But the integrated effect between all of the molecules of one colloid particle with those of a nearby colloid particle are much longer ranged (potential -Aa/12s0). The constant A depends on b and the molecular density in the particles. The attractive forces are referred to as long range van der Waals forces. Long range van der Waals forces - important when ordinary colloid particles are within 100 nm of each other, and become very large as the particle surfaces approach one another. Result is - colloid particles will aggregate as fast as external effects (Brownian motion and/or bulk fluid motion such as stirring) bring them within range.

ELECTROSTATIC REPULSION RETARDS AGGREGATION

van der Waals attraction

electrostatic repulsion

INSTABILITY OF LYOPHOBIC COLLOIDS Aggregation:

etc.

Coalescence:

 What does the term stability/coagulation imply?

There is no change in the number of particles with time. A system is said to be colloidally unstable if collisions lead to the formation of aggregates; such a process is called coagulation or flocculation.

Two ways to prevent particles from forming aggregates with

one another during their colliding
1) Electrostatic stabilization by charged group on the particle surface - Origin of the charged group initiator fragment (COOH, OSO3-, NH4, OH, etc) ionic surfactant (cationic or anionic) ionic co-monomer (AA, MAA, etc) 2) Steric stabilization by an adsorbed layer of some substance 3) Solvation stabilization

STABILIZATION MECHANISM
Electrostatic stabilization
- Electrostatic stabilization Balancing the charge on the particle surface by the charges on small ions of opposite sign in the solution phase (counter ions) - Surface potential

r = s (a / r ) exp[( x(r a)]

x = (8e e n A / 1000kT ) I

1/x : Thickness of electrical double layer : dielectric constant of the medium I : Ionic strength

Steric stabilization
- Hairy particles with uncharged hairs extending into nonaqueous medium as noncharged polymer chain

Electrosteric stabilization
- Combination of electrostatic and steric stabilization by grafting to a polymer core particle polyelectrolyte chains

ELECTROSTATIC STABILIZATION
DLVO (Derjaguin, Landau, Verwey, Overbeek) theory
- Attraction decays as the inverse power of distance of separation. - Repulsion decays as an exponential of distance. - At both short and long distances of separation : Attraction > Repulsion - Critical coagulation concentration; a concentration at which the primary maximum becomes zero.

Advantages of electrostatic stabilization

- Providing stability in nonaqueous systems where electrical effects are week. - Providing tolerance against high level of electrolyte - Stabilizing much greater particle concentrations

Disadvantages of electrostatic stabilization

- Flocculation if coverage of particle is low

GUOY-CHAPMAN DOUBLE LAYER MODEL (1914)

+ 0 + + + + + + + + + + + + + + + + C+(x) +

-- - - - - C (x) - (x) - - - x

Assumptions: 1. The surface charge is smeared 2. Ions are point charges 3. No specific ion adsorption 4. Dielectric constant is constant

z en (x)
i i i

Poisson equation
(describes variation of potential in a spatial charge distribution)

Boltzmann equation
(describes variation of ion concentration in an electric field)

d 1 = d2 x 0 e
2

space charge distribution

w ze ( ) n( ) x i x = x i= x i ep ep k k n( ) T T i

Poisson-Boltzmann equation
2 ze d 1 = e i( )e p i z n x k d2 x 0 i T

STERN MODEL (1924)

0

Surface potential

Stern potential

+++ +++++ +++++ +++++

- thickness Stern layer

Problems with G-C model:

Characterizes the ions only by their charge (i.e., they have no chemistry), they cannot adsorb to surfaces in excess of the charge required for neutralization, nor can they adsorb to surfaces of the same charge. It regards ions solely as point charges, and permits them to pack without limit into the layer adjoining the surface.

(x)

These problems are relieved by Stern model

Stern layer
STERN MODEL
Assumes existence of a monolayer of ions (the Stern layer) directly adjacent to the surface and generally (but not always) effecting partial neutralization of the surface charge. Remainder of the surface charge is neutralized in a Guoy-Chapman diffuse layer adjacent to the Stern layer. Stern layer assumed to reside between the surface and a plane (the Stern plane) passing through the centers of the first layer of hydrated ions, a distance from the surface. The distance d is generally 2 3 , and potential at this location, the Stern potential, is . The Stern potential is the effective surface potential.

ELECTROSTATIC REPULSION DEPENDS ON.

The Stern potential, The thickness of the diffuse double layer, -1

1. 2.

DLVO (Derjaguin, Landau, Verwey, Overbeek) THEORY

s

Attractive forces
van der Waals forces
kT

DLVO Theory
kT

Repulsive forces
electrostatic forces (aqueous or high media)
kT

Forces between particles (surfaces)

s 0 s 0

When (/kT) 10, stability

Controlling DLVO interactions

e 0 6 Nv . 4 a AC 2 z s A2 0 1a = t n 2 ah e 2 4 T k T k 1k s 2T
water, 25C

2 2z2n e 2 2z2C F -1 = = 0 2 C .3 9z 0kT 0R T

For a given colloid, barrier height depends on the ion concentration and valence, and on the effective surface potential (the Stern potential). All are subject to external control.