Colloid chemistry

Lecture 9: Colloid stability

Theories of the stability of colloidal disperse systems

(1 nm 10 m)

Instability of liophobic colloids

aggregation:

coalescence:

Colloid stability requires repulsive forces between colliding particles

Main types of (de)stabilization of colloidal dispersions

electrostatic potential steric potential

Coulombic repulsion electrostatic stabilization

entropy hindrance steric stabilization

van der Waals attractive interactions; attraction potential : VA

r
attraction potential between plate-like particles:

attraction potential between spherical particles:

VA (x) =

Ar 12 x

VA (x) =
x

A 2 S 2 12 x

A: Hamaker constant (attraction parameter)

A: Hamaker constant (attraction parameter)

Hamaker constants of various materials

Hamaker constants of various materials

Combination of Hamaker constants

A132 A131 A232

A12 A11 A 22

A132: particle(1)-particle(2) interaction through medium (3) A12: particle(1)-particle(2) interaction in vacuum

A131 A 313 A11 + A 33 2 A13 ( A11 A 33 )

A132 ( A11 A 33 )( A 22 A 33 )

van der Waals attractions in colloidal disperse systems

The stability of a colloidal disperse system is strongly dependent on the attractive pair potential, VA, between the dispersed particles. VA is determined by the geometric arrangement, G, of the particles (e.g. lamella-lamella; sphere-sphere; sphere-lamella; etc. interactions, independently of the chemical composition), and the Hamaker constant, A, of the overall system (which depends on the chemical composition of the constituting species, but is independent of the geometrc arrangement). Formally: VA = A G The Hamaker constant A of the overall system originates from a combination of the individual Hamaker constants, Ai, of the dispersion medium and that of the dispersed particles. It can be derived from the summation of the der Waals dispersion forces between the constituting species (dispersion medium; dispersed particles).

Dependence of the van der Waals pair potential VA between two colliding particles on the overall Hamaker constant A of the system

VA, van der Waals interaction energy (kT)

two spherical particles, R=4m

surface separation, x (nm), of two interacting particles

DLVO theory: Electrostatic stability

Derjagin Landau Verwey Overbeek

van der Waals attraction

electrostatic repulsion Aggregation is hindered by electrostatic repulsion

DLVO theory: the theory of electrostatic stabilization

(Derjagin-Landau and Verwey-Overbeek) The electrostatic repulsion depends on the...
1. Stern potential St 2. thickness of the electric double layer, -1

Electric double layer interaction energies; repulsion energies VR

VA =
between two sheets (lamellae):

A 12 x 2

64 n kT x VR = e

VA =
between two spheres:

Ar 12 x
2 2

8 k T r x VR = e 2 2 e z

e 1 ze zkT e + 1
ze zkT

DLVO theory: the resultant (total) potential is: VT = VA + VR

x

attraction potential
(van der Waals forces)
VA kT

repulsion potential DLVO theory

Derjagin Landau Verwey Overbeek
(Coulombic repulsion; aqueous medium, large )
VR kT

total potential 0

VT kT

VT = VA + VR

(VT/kT) 10: colloid stabiliy

DLVO theory: conditions for colloid stability

Stability

Coagulation

repulsive forces overwhelm attractive forces

attractive forces overwhelm repulsive forces

DLVO theory: conditions for colloid stability

Colloid stability/flocculation/coagulation/ are controlled by the relative magnitudes of the van der Waals and the Coulombic forces

repulsion

potential

total

aqueous Al2O3 suspension at different pHs

attraction particle-particle distance (surface separation)

aqueous As2S3 sol with increasing background electrolyte concentraion (1:1 electrolyte, mM)

Colloid stability/flocculation/coagulation/ are controlled by the relative magnitudes of the van der Waals and the Coulombic forces
stable emulsion stable suspension

unstable (coagulation; creaming and coalescence)

unstable

(coagulation / flocculation; sedimentation)

For VT = 0, VR = -VA. In this case, the DLVO theory predicts the ccc ratio for 1:2:3 valence of charge of ions to be 1000:16:1.3.
1 Schulze-Hardy rule: ccc 6 z
electrolyte

1 1 1 : 6: 6 6 1 2 3

ccc (M) (As2S3 dispersion)

Schulze-Hardy-rule

NaCl KCl MgCl2 CaCl2 AlCl3

5,1 10-2 5,0 10-2 7,2 10-4 6,5 10-4 9,3 10-5 1000 16 16 1,3

1000 (980) (14) (13) (1,8)

ccc
c increases
interaction energy / 10-19 J
c = 1 mM

23 mM

4 mM

90 mM

360 mM 1500 mM

ccc = 65 mM

As2S3 sol in 1:1 electrolyte

r = 0.1m; T=298K; A212=10-19J; St=50mV; z = 1; =78.5

ccc

stable Fe(OH)3 sol

The sol undergoes coagulation upon the addition of Al2(SO4)3 solution

Mechanisms of coagulation

perikinetic

differential settling

orthokinetic

perikinetic: collisions by Brownian motion differential settling (polydisperse suspensions) orthokinetic: induced collisions through stirring; shear

The kinetics of coagulation

x r

Fast coagulation (Smoluchowski): each collision leads to aggregation (high electrolyte concentration, Vmin . 0, rate constant: kf)

no n = 1 + 4 (2 r + x ) D n o t

Slow coagulation (Fuchs): only part of the collisions leads to aggregation (low/intermediate electrolyte concentration, Vmin ~ kT, rate constant: ks)

no n = 1 + W 4 (2 r + x ) D n o t

t s,1 / 2 kf where W = = t f,1 / 2 ks

( t12: half life time )

Colloid stability: thermodynamic and kinetic aspects

W $ 1: stability ratio (Fuchs)
Vmax 1 V( x ) d x W = 2 r exp exp 2 kT 2r kT x 2r

t s,1 / 2 kf W = = t f,1 / 2 ks

log W

2:2 e

turbidity measurements W
fast coagulation region
log c
ly tro

1:1

lec

c ele

tro lyt e

logW = a b log c

te

Summary of main types of particle-particle interactions

x

(x > )

(x < 2), e.g.:

interactions.

Colloid stability requires repulsive forces between colliding particles

Main types of (de)stabilization of colloidal dispersions

electrostatic potential steric potential

Coulombic repulsion electrostatic stabilization

entropy hindrance steric stabilization

Conformations of adsorbed polymer chains

Conformations of adsorbed polymer chains

(a) polymer in solution; (b) chemisorbed (end-grafted) copolymer; (c) physisorbed homopolymer; (d) adsorption at low surface coverage with no neares neighbour overlap (mushrooms); (e) adsorption at high coverage (brush); (f) bridging

Typical Polymer Adsorption Isotherms

the effect of molecular weight Amount adsorbed, (mg/m2)
1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 100 200 300 400 500 600
MW > MW MW1 MW3 > MW2 > > MW1 3 2

Langmuir isotherm: = max

c K+ c
MW 3 MW3 MW 2 MW2 MW MW1 1

c (mg/L)

Typical thickness of the adsorption layer in case of electrostatic stabilization and steric stabilization
1:1 electrolyte c [mmol.dm-3] 0.01 0.1 1 10 100 1/ [nm] 100 30 10 3 1 (thickness of the electric double layer) polymer M [g.mol-1] 1,000,000 100,000 10,000 1,000 +ho,- [nm] 60 20 6 2 (end-to-end distance . polymer layer thickness)

Polymers at interfaces

Conditions for efficient steric stabilization

(1) large (point C in the Figure) (2) large (layer thickness) (3) large Ps (adsorption energy) (4) < 0.5 (good solvent for the polymer chain) (5) low c (free polymer concentration)
note: (3) may conflict with (4) for homopolymers; this conflict is absent for graft- and block copolymers

cpolymer

bridging flocculation

aggregation for small values of (below point B in the Figure)

Steric interaction

x/2

x = 2

Typical potential function of steric stabilization

VT
VS steric repulsion

~ coil diameter, rg

x
VA van der Waals attraction

Brownian movement/ agitation

electrolytes

polymers