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Suspensions Jim McElroy Lincoln, 2011
Suspensions - Definition Suspensions are classified on the basis of the dispersed phase and the dispersion medium. The former is essentially solid while the latter may either be a solid, a liquid or a gas.
Interparticleforces that can be controlled by formulation Electrostatic repulsive force – charged particles exert a force on one another.  Steric Repulsive force – arises from the adsorption of large molecules.  Can be controlled by formulation
Interparticulate forces that cannot be controlled by formulation Van de Waals force - attractions between atoms, molecules, and surfaces.   Repulsive Hydration force – arises from the structuring of water in the interfacial region. Operates over short distances.
Van der Waals Forces Colloid science has held that electrostatic and electrodynamic (van derwaals) forces are principle determinants of colloid systems. Interaction between two dipoles that are either permanent or induced. The temporary dipole and the induced dipoles are attracted to each other. It is always present, it is short-range, and it is attractive.
Repulsive Hydration Force Hydration repulsion is due to the work needed to remove water molecules from hydrophilic surfaces at small film thicknesses and is described by an exponentially decaying interaction potential.
Graph
How to Interpret the Graph Nernst Potential- charge at the true surface Stern Layer- adsorbed counterions tightly bound and move with the solid Diffuse Layer- complete neutralization of the surface charge Double Layer- complete neutralization of the Nernst potential.  Requires both the Stern Layer and Diffuse Layer i.e. the slipping plane Debye Length- thickness of the double layer is inversely related to ionic strength and ion valence
Flocculated Suspension Particles finer than 0.1 µm in water remain continuously in motion due to electrostatic charge (often negative) which causes them to repel each other.  The distance between particles is approximately 100 to 200 A. The network is easily disrupted by shaking but it reforms when the turbulence stops.
Properties of Flocculated Suspensions Rapid rate of sedimentation due to large size of floccules Clear supernatant as all particles are incorporated into floccules High sediment volume Sediment easily re-dispersed by shaking
Flocculation Formulation Approach Adjust electrostatic repulsive force  use an electrolyte Modify the Nernst (equilibrium) potential  reduce surface charge by adsorbing anions to it Adjust steric repulsive force  adsorb a neutral polymer Heteroflocculation Add small oppositely charged particles to produce a particle network
Flocculation Example:  Adjust or modify: the Nernst Potential using an ionic species such as phosphate anions the electrostatic repulsive force by using an electrolyte like sodium chloride The steric repulsive force adsorbing a neutral polymer like polyvinyl alcohol
Structured Vehicle Produce a liquid phase which exhibits shear thinning rheology, i.e. very viscous on the shelf to prevent settling and fluid when shaken. Usually contains a polymer and a clay (or several polymers) in order to produce a shear-thinning system.
Pseudoplastic Flow Exhibited by polymer solutions.  Increasing flow as the shear stress is increased.  The viscosity decreases as the shear stress is increased.
Dilantant Flow The system becomes more viscous as the shear stress is increased.   * can be a problem on scale-up.  Production equipment often introduce more shear than laboratory equipment.
Structured VehicleFormulation Approach Addition of “inert” small particles such as clays like montmorillonite or silica dioxide Mixture of polymers and “inert” small particles like sodium carboxymethycellulose with montmorillonite or silica dioxide Use of liquid-crystalline phases like surfactants at concentrations above the Critical Micelle Concentration (CMC).
Properties of Structured Vehicle Suspensions May appear as a semi-solid when undisturbed Fluid when shaken Thixatropic (becomes fluid when stirred or shaken and returning to the semisolid state upon standing ) No sedimentation
Conclusion Suspensions are complex systems that require an understanding of their basic chemistry for proper development and understanding. It is important to take into consideration all aspects of the formula before considering a preservative system.  This includes type of formula, bulk handling and packaging
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Suspensions Formulation Overview

  • 1. Suspensions Jim McElroy Lincoln, 2011
  • 2. Suspensions - Definition Suspensions are classified on the basis of the dispersed phase and the dispersion medium. The former is essentially solid while the latter may either be a solid, a liquid or a gas.
  • 3. Interparticleforces that can be controlled by formulation Electrostatic repulsive force – charged particles exert a force on one another. Steric Repulsive force – arises from the adsorption of large molecules. Can be controlled by formulation
  • 4.
  • 5. Interparticulate forces that cannot be controlled by formulation Van de Waals force - attractions between atoms, molecules, and surfaces. Repulsive Hydration force – arises from the structuring of water in the interfacial region. Operates over short distances.
  • 6. Van der Waals Forces Colloid science has held that electrostatic and electrodynamic (van derwaals) forces are principle determinants of colloid systems. Interaction between two dipoles that are either permanent or induced. The temporary dipole and the induced dipoles are attracted to each other. It is always present, it is short-range, and it is attractive.
  • 7. Repulsive Hydration Force Hydration repulsion is due to the work needed to remove water molecules from hydrophilic surfaces at small film thicknesses and is described by an exponentially decaying interaction potential.
  • 9. How to Interpret the Graph Nernst Potential- charge at the true surface Stern Layer- adsorbed counterions tightly bound and move with the solid Diffuse Layer- complete neutralization of the surface charge Double Layer- complete neutralization of the Nernst potential. Requires both the Stern Layer and Diffuse Layer i.e. the slipping plane Debye Length- thickness of the double layer is inversely related to ionic strength and ion valence
  • 10. Flocculated Suspension Particles finer than 0.1 µm in water remain continuously in motion due to electrostatic charge (often negative) which causes them to repel each other. The distance between particles is approximately 100 to 200 A. The network is easily disrupted by shaking but it reforms when the turbulence stops.
  • 11. Properties of Flocculated Suspensions Rapid rate of sedimentation due to large size of floccules Clear supernatant as all particles are incorporated into floccules High sediment volume Sediment easily re-dispersed by shaking
  • 12.
  • 13. Flocculation Formulation Approach Adjust electrostatic repulsive force use an electrolyte Modify the Nernst (equilibrium) potential reduce surface charge by adsorbing anions to it Adjust steric repulsive force adsorb a neutral polymer Heteroflocculation Add small oppositely charged particles to produce a particle network
  • 14. Flocculation Example: Adjust or modify: the Nernst Potential using an ionic species such as phosphate anions the electrostatic repulsive force by using an electrolyte like sodium chloride The steric repulsive force adsorbing a neutral polymer like polyvinyl alcohol
  • 15. Structured Vehicle Produce a liquid phase which exhibits shear thinning rheology, i.e. very viscous on the shelf to prevent settling and fluid when shaken. Usually contains a polymer and a clay (or several polymers) in order to produce a shear-thinning system.
  • 16. Pseudoplastic Flow Exhibited by polymer solutions. Increasing flow as the shear stress is increased. The viscosity decreases as the shear stress is increased.
  • 17. Dilantant Flow The system becomes more viscous as the shear stress is increased. * can be a problem on scale-up. Production equipment often introduce more shear than laboratory equipment.
  • 18. Structured VehicleFormulation Approach Addition of “inert” small particles such as clays like montmorillonite or silica dioxide Mixture of polymers and “inert” small particles like sodium carboxymethycellulose with montmorillonite or silica dioxide Use of liquid-crystalline phases like surfactants at concentrations above the Critical Micelle Concentration (CMC).
  • 19. Properties of Structured Vehicle Suspensions May appear as a semi-solid when undisturbed Fluid when shaken Thixatropic (becomes fluid when stirred or shaken and returning to the semisolid state upon standing ) No sedimentation
  • 20. Conclusion Suspensions are complex systems that require an understanding of their basic chemistry for proper development and understanding. It is important to take into consideration all aspects of the formula before considering a preservative system. This includes type of formula, bulk handling and packaging