Stability (Macro/nano) Flashcards
Emulsion stability
- Droplets retain their initial character and
remain uniformly distributed throughout the continuous phase
Cause of emultion instability
- Phase inversion
- Creaming
- Flocculation
- Coalescence
- Ostwald ripening
How do you stablise an oil in water emultion
- ionic surfactant/co-surfactant
- If charge on emulsion droplet is reduced
(with the addition of ions through buffer
or drug), emulsion droplets will come
together
Phase inversion
Once droplets are in contact, interfacial
surfactant film re-aligns forming water-in-
oil droplets and phase inversion occurs from oil in water
Creaming
- Density is lighter than the continuous phase forming a layer on top cream on milk
- To avoid this, increase the oil density or viscosity of the emulsion
Flocculation
- Two or more emulsion droplets aggregate
without losing their individual identity - Larger droplets (> 2 μm) flocculate fastest and flocculation is promoted by creaming
- Addition of salt (Na3PO4) causes flocculation aggregation occours
Coalescence
- Coalescence occurs when two or more droplets collide and form one larger droplet and is irreversible
- It is caused by various factors, including surfactant type and concentration, pH, temperature
- Arrested coalescence of adjoining inner cores
Ostwald ripening
- Collision between two droplets may
cause one bigger droplet and one smaller droplet - Repeated collisions, the small droplets become very small becomes solubilised in the continuous medium
- Eventually diffuse and re-deposit on larger droplets making them even larger in size
Asspumtion of DLVO
- Van der Waals forces of attraction (VA)
- Electrostatic repulsive forces (VR)
Energy of attraction
- Vary with distance (H) between pains of atoms and molecules inverse of 6th power
Electrical repulsion
- Arises from the interaction of the electrical double layers surrounding pairs of particles
- Repulsive forces decay exponentially with distance
- Repulsive forces decay more rapidly than attractive forces therefore the attractive forces predominate over longer distances
Increasing charges on double layer causes…
- Optimise the concentration of
surfactant (don’t forget about
the associated counterions) - Optimise the pH
Zeta potential of particle depends on stability
- 0-5mV is rapid coagualtion
- 10-30mV incipient instability
- 30-40mV Moderate stability
- 40-60mV Good stability
- 61< mV Excellent stability
What does DVLO show?
- Van der Waals attraction explains why some of the colloidal particles aggregate e.g. suspension to floc
- Electrical repulsion explains why some colloidal particles stay seperate
Secondary minimum
- Large distance seperated particles experience minimal attraction
- Forces of attraction are weak, flocculation occours and this can be redispersed when shaking
Primary maximum
- As the particles get closer together start to experience repulsion this peaks at primary maximum
- Vmax (height of primary max) determines the stability of the system
- High value means coagulation is slow long term stability
- Energy barrier that leads to irreversible particle aggregation
Primary maximum heigh is determined by
- Diffrent surfacant
Elecrolyte concentration: - Neutralisation or reduction of charge on droplets
- Decrease in Vmax
- Destabilisation of the emulsion
Primary minimum
- At close approach, van der Waals forces always dominate over repulsive electrostatic forces
- A deep primary minimum is present
- At this short inter-particle distance, particles/droplets coagulate irreversibly
Non-ionic surfacant
- No electrostatic charge is present to stabilise the droplet
- Entropic (steric) effects
- Osmotic (solvation) forces
Entropic (steric) effects
- When two particles come into close contact, the polymer chains start to overlap
- This leads to a loss in the freedom of motion of the polymer chains decrease of entropy
This situation is thermodynamically unfavourable and forces the droplets apart again
Osmotic (solvation) forces
- When two particles come into close contact the polymer chains start to overlap, effectively leading to a concentrated polymer solution
- This induces an osmotic gradient in the solution: a concentrated polymer solution in the overlap region and a dilute solution in the bulk solution
- Water enters the concentrated region in an attempt to dilute it and in doing so forces the polymer chains apart
Steric stabilisation
- Vt = Va + Vs
- Surfactants are used, electrostatic forces are more efficient at stabilising emulsion droplets than steric/solvation forces alone
What are the important forces for charged colloids
- Vander waals and electrostatic forces
What are the important forces for uncharged colloids
- Vander waals and steric and solvation forces