Colloid stability of lyophobic colloids

Mrta Berka, Istvn Bnyai, University of Debrecen Dept of Colloid and Environmental Chemistry

http://dragon.unideb.hu/~kolloid/
(Stability of lyophilic colloids see: macromolecular solutions)

Thermodynamically stable, unstable

Solutions are thermodynamically stable Dispersions are thermodynamically unstable

A most important physical property of Kinetic stable system Kinetics of unmixing? If slow enough colloid dispersions is the tendency of particles Protect dispersion particles against aggregation / coagulation to aggregate. / flocculation/ coalescence by repulsive interactions
Direction of spontaneous changes toward states with lower Gibbs energy Delta G (constant P,T) <0

Gsol > Ginitial Sols , because of large specific surface area Gold sol- gold ring

STABLE, UNSTABLE
Solutions: mixing is spontaneous Mixtures are thermodynamically stable Inhomogeneities on molecular levels Mixing is reversible Dispersions: mixing is non-spontaneous (requires mechanical energy) Thermodynamically unstable (requires stabilizing agent) i.e. unmix spontaneously. Inhomogeneities on length scales large compared to molecular dimensions Mixing is irreversible

Properties of solutions independent on the way is prepared

Properties are strongly dependent on the way is prepared Empirical preparations procedures

Kinetically stable* or unstable systems

In an unstable system the particles may adhere to one another and form aggregates of increasing size that may settle out under the influence of gravity. An initially formed aggregate is called a floc and the process of its formation flocculation. The floc may or may not separate out. If the aggregate changes to a much denser form, it is said to undergo coagulation. An aggregate usually separates out either by sedimentation (if it is more dense than the medium) or by creaming (if it less dense than the medium). The terms flocculation and coagulation have often been used interchangeably. Usually coagulation is irreversible whereas flocculation can be reversed by the process of deflocculation.

*In a kinetically stable system dispersity, morphology and spatial distribution are unchanged within the examination. This will depend upon the balance of the repulsive and attractive forces that exist between particles as they approach one another.

Coagulation or flocculation
much denser form, irreversible a cake a floc loosely adhering mass, it can be reversed by deflocculation

a) coagulated, b) flocculated particles b) The suspended particles form light, fluffy agglomerates held together by strong van der Waals forces. The flocculated particles settle rapidly forming a loosely adhering mass with a large sediment height instead of a cake. Gentle agitation will easily resuspend the particles. Weak flocculation requires strong adhesion and a zeta potential of almost zero. thistle's flowerheads with sharp prickles give a loosely adhering mass

Strength of interparticle forces

Encounters between particles occur as a result of Brownian motion and stability of a suspension is determined by the interaction between particles during these encounters

Stability depends on the balance of attractive and repulsive interactions

Attraction from van der Waals forces between particles. Repulsion is a consequence of interaction between similar charged electric double layers and/or particle -solvent affinity. Repulsion prevents particles to get close enough and attach

There is no repulsion

There is repulsion

Stability of lyophobic* colloids

DLVO theory (Derjaguin, Landau and Verwey, Overbeek): stability of lyophobic colloids The double layer, zeta potential, the balance of repulsion & attraction, the energy barrier. Rates of flocculation

*Lyophobic colloid includes charged particles of weak solvent affinity

Colloidal stability requires a repulsion force:

Lyophobic colloid may be stabilized by lyophilic colloid

VR

VS

Molecular origins of van der Waals Attraction between particles in vacuum.

Attraction between atoms/ molecules in vacuum r
VA ( r ) const. r6

Dispersion attraction between atoms / molecules is additive so it effects in case of macroscopic bodies too. depends on geometry! H H a

VA

A H2

VA ( H )

Aa 12 H

A Hamaker constant

Hamaker model - Calculate the attraction between particles from molecular attractions
Molecules in particle 1 Molecules in particle 2

depends on geometry!

The attraction of bodies arises from London (dispersion) attraction of molecules (all molecules act independently) The effect is additive; that is, one molecule of the first colloid has a van der Waals attraction to each molecule in the second colloid. This is repeated for each molecule in the first colloid, and the total force is the sum of all of these. An attractive energy curve is used to indicate the variation in van der Waals force with distance between the particles.

Attraction. Effective Hamaker constant

H

VA ( H )

Aa 12 H

Hamaker constant: A in vacuum depends on material properties: density, polarizability

The effective Hamaker constant Aeff also depends on the dispersion medium

VA ( H ) , J

An attractive energy curve is used to indicate the variation in van der Waals force with distance between the particles.

VA ( H )

Aa 12 H

Similar charged particles

= St exp ( x )
St

Positive particle with negative ion atmosphere

St
x ~ distance from surface Plane of shear

Electrostatic repulsion between overlapping double layers

H ~ distance between surface

VR
The loosely held countercharges form electric double layers. The electrostatic repulsion results from the interpenetration of the diffuse part of the double layer around each charged particle.

2 VR ( H ) 0 exp ( H )

An electrostatic repulsion curve is used to indicate the energy that must be overcome if the particles are to be forced together

The Balance of Repulsion & Attraction

is the sum of the electrostatic repulsion and the dispersion attraction, DLVO theory: Notice the secondary minimum. The system flocculates, but the aggregates are weak. This may imply reversible flocculation. VT = VA + VR

VA ( H )

Aa 12 H

VR ( H ) a ( kT ) 2 2 z 2 exp ( H ) ze St exp 1 kT 2 = ze St +1 exp kT 2

The point of maximum repulsive energy is called the energy barrier. Energy is required to overcome this repulsion . The height of the barrier indicates how stable the system is .The electrostatic stabilization is highly sensitive with respect to surface charge (~~ pH) and salt concentration (, z).

VT

Total Interaction= sum of the attractive and repulsive interactions =V +V

A R

VT ,VA, VR (J) the total, attractive and repulsive energy of two spherical particles at distance d (m) The height of the energy barrier depends upon the zeta potential and 1/

sol

In the secondary minimum there is a reversible flocculation: sol- gel transformation

Precipitate, or cake

large sediment height or gel

coagulation van der Waals attraction will predominate at small and at large interparticle distances. At intermediate distances double layer repulsion may predominate, depending on the actual values of the forces. In order to agglomerate, two particles on a collision course must have sufficient kinetic energy due to their velocity and mass, to jump over this barrier.

Electrostatic stability of dispersions

1 < 2
An increase in electrolyte concentration leads to a compression of the double layer (kappa increase) and so the energy barrier to coagulation decreases or disappears. If the barrier is cleared, then the net interaction is all attractive, and as a result the particles coagulate. This inner region is after referred to as an energy trap since the colloids can be considered to be trapped together by van der Waals forces.

What concentration of salt (n0) just eliminates the repulsive barrier?

Curve 1: Low ionic strength: primary minimum and high maximum stable colloidal dispersion. Curve 2: High ionic strength: only primary minimum unstable colloidal dispersion.

Critical coagulation concentration

What concentration of salt (n0) eliminates the repulsive barrier? If the potential energy maximum is large compared with the thermal energy, kT of the particles, the system should be stable; otherwise, the system should coagulate.

Counter -ion valency c.c.c (in mol/L) ~z-6

c.c.c. is the concentration of salt just eliminates the repulsive barrier.

Schulze Hardy Rule

The Schulze Hardy Rule: the stability depends on the sixth power of the charge on the ions! c.c.c (in mol/L) ~z-6 1:1/26:1/36=1:0.015:0.0014 What concentration of salt (n0 or c.c.c.) just eliminates the repulsive barrier?

Strength of interparticle forces Rates of coagulation

Rates of coagulation can be measured by the change in the number of particles, Smoluchowski equation:

dN = 8 DaN 2 = kd N 2 dt

kd is the rate of the diffusion limited aggregation or rapid coagulation (no barrier, Vmax=0)

the stability ratio: If there is an energy barrier, Vmax to coagulate then a fraction () of collisions is unsuccessful, so the rate of coagulation slower, ks. The stability of dispersion is increased by: increase in Vmax particle radius, increase in surface potential ( >25mV), exp kT decrease in Hamaker constant, decrease in the ionic strength, decrease in temperature.
t is the time, Np the numbers of single particles per unit volume, D diffusion coefficient, kD rate constant, kBoltzman constant, T temperature, V max

kd W= ks

Elementary acts of coagulation: initial act

N / N0 =

1 1 + kN 0t / 2

N/N0

N decreases with time, while their size increases.

VN = constant = V0 N 0

V ~ 1/ N
1 1 =kt N N0

dN = k N2 dt

The decrease in the normalized number of total particles, singlets, doublets, and triplets according to Smoluchowski theory as a function of time.

If all flocculation rate constants are the same

1 N / N0 = 1 + kN 0t / 2

Rate can be measured through decreasing the total number -dN/dt or increasing the average volume, dV/dt for example by turbidity as a function of time. Turbidity~ V2N~ V (VN) ~V constant

http://apricot.polyu.edu.hk/~lam/dla/

Stability ratio vs. electrolyte conc.

the stability ratio:

kd W= ks

W 1 ln W 0

Stable and instable systems

The larger the negative voltage value of ZP, the more dispersing power it has.

Can you see this happening inside our bodies? [ A low Zeta Potential will cause blood cells to clump together. It is the force that maintains the discreteness of the billions of circulating cells, which nourish the organism ]

Coagulation in the human blood system

Numerical "Grade" (arbitrary) A low Zeta Potential will cause blood cells to clump together. Many types of cardiovascular disease are manifest in the early stages as "moderate to significant" intravascular coagulation, and in advanced stages as "heavy to very heavy" coagulation. (Clump: blood clotting sclera) "Degree" of Clump * (Observed in Sclera) Probable ZP of Red Blood Cells (in situ) mV

0 1 2 3 4 5 6 8 10

Absent Slight Moderate Significant Heavy Very Heavy Terminal (death) Fluid gel (5 min.) Rigid gel (10 min.)
http://www.hbci.com/~wenonah/riddick/chap22.htm

17 16 15 14 13 12 11 7 7

Colloidal stability requires a repulsion force:

Lyophobic colloid may be stabilized by lyophilic colloid

VR

VS

Steric stability: lyophilic colloids as stabilizers

Protective action of adsorbed macromolecules (natural or synthetic)

VS = VM + VVR

VM
Two effects

Entropic repulsion

VVR
Polymer thickness Work is required to push the particles closer together than their polymer layers keep them apart.

Steric stability
Steric + attractive interaction
VS+VA

One factor of steric stabilization is the tail size

Steric repulsion

Steric stabilization
Steric stabilization by surface bound polymers is: 1. not sensitive to surface charge and salt concentration 2. works also in non-aqueous media 3. (and works also in concentrated dispersions) Disadvantage: more difficult to prepare.

VT = VA + VS

VR=0

How to avoid coagulation

The stabilizing polymer must be a good solvent environment

VS = VM + VVR
VT = VA + VS

Effect temperature!

Segments in the tail can move freely or can not, the interaction between segments themselves are stronger or smaller than interaction between segment and solvent.

Configurations of adsorbed polymers

Sterically stabilized dispersions are stable when the polymer is soluble the one phase regions. The worse the solvent, the more unstable the colloidal dispersion. Cross-over from stabilization to flocculation: theta solvent, theta temperature

Chemical adsorption

Steric + electrostatic stabilization

It can be achieved by polyelectrolytes, gelatin, protein... or by charged surface + neutral polymers (caution about zeta potential)

VT = VA + VR

VT = VA + VR + VS Plane of shear is pushed out, farther

Bridging flocculation. Depletion flocculation lyophilic colloids as sensitizer

Good adsorbent, good solvent, (very) low polymer density, (very) long polymers

The long polymers bind the colloids together in open flocs. Application: water purification (in practice, a few ppm of cationic polyelectrolyte is added, since most natural colloid surfaces are negative)

Stability of lyophilic colloids

Lyophilic colloids are liquid loving colloids (Lyo means solvent and philic means loving)

lyophilic colloids:

isostable no precipitation at iep

isolabile precipitation at iep

Lyophilic sols stability comes from solvation + charge. If solvation interaction alone is strong enough the colloids stay stable at its isoelectric pH if it is not they coagulate at their isoelectric pH. Gelatin is stable at its isoelectric condition so called isostable colloids, but it can be precipitate with much more salt or dehydration agent (acetone, alcohol). Casein is unstable at this isoelectric pH where there is no charge, this is a isolabile protein. Casein precipitates at iep where there is no repulsion. The isoelectric point of casein is 4.6.

The fermentation of milk sugar (lactose) produces lactic acid, which acts on milk protein to give yoghurt its gel-like texture