Disperse Systems: Emulsions 8 Flashcards

1
Q

Emulsions

A
  • Dispersion consisting of
    • Insoluble Liquid Globules
      • (POLAR LIQUID phase)
    • Liquid/semisolid dispersing medium
      • (NON-polar liquid phase)
    • w/ aid of Emulsifying agent
      • ​(surfactant), typically 2+ emulsifyers
  • Primarily Coarse Dispersions
    • 500-1000nm
  • Sometimes Colloidal Dispersions
    • ​10-200nm globule sizes
      • ​nanoemulsions / microemulsions
  • ​​NOT THERMODYNAMICALLY STABLE
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2
Q

When is a colloid not a Colloid?

A

When it is an EMULSION

  • Milk is an COARSE dispersion
    • we base it on size, the droplets need to be
    • <500nm (<0.5um)
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3
Q

Oil in Water

O/W

Emulsions

A
  • Most Emulsions are Oil in water (THINK MAYONAISE)
    • Oil droplets are dispersed as globules (nonpolar)
    • throughout a Continious aqeuous phase (polar)
  • Pharmacy practice uses mainly O/W emulsions
    • Creams & Lotions
    • Oral to mask taste or convenient liquid dosage form
      • protect from degradation
    • Prenteral administration
  • GOOD ELECTRICAL CONDUCTION
  • ​​Rinse out jar of mayo with WATER
    • adding water will NOT cause PHASE SEPERATION
  • Water soluble dyes work for OW
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4
Q

Water in Oil

W/O

Emulsions

A
  • Think BUTTER
    • Water droplets are dispersed as globules
    • throughout a Continious oil phase
  • Topical Drug formulations, Rare in pharmacy
    • Ointments / sunscreen / sensitive skin
  • Poor electrical conductance
  • You can’t clean up butter with WATER
    • ​need to add more OIL in order to not get phase seperation
  • Oil souluble dyes ( paprika / turmeric )
    • will work for W/O emulsions
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5
Q

Desired Properties

of Emulsions

A
  • Emulsified material (=what comes first, O in O/W or W in W/o)
    • SHOULD NOT seperate from the dispersing medium rapidly
    • Globules should FLOCCULATE not coalesce
    • Readily redispersed into UNIFORM mixture by MIXING
  • Globule size distribution & Specific surface area
    • SHOULD NOT CHANGE
  • Formulations should be prepared using readily available ingredients
  • Should NOT BE too Viscous so it can pour freely
    • but viscous enough to PREVENT settling
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6
Q

Flocculation

for Emulsions

A
  • Type of Agglomeration that is PREFERRED
    • loose/fluffy conglomerate held together by VDW forces
    • surface area is only slightly reduced
  • Zeta Potential is close to zero
  • Analagous to suspension except for:
    • globules of the dispersed LIQUID phase
      • vs particles of the dispersed SOLID phase
    • ​​​are clustering together without caking in flocculation
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7
Q

Coalescence

in Emulsions

A
  • Type of Agglomeration that is Not preferred
    • compact liquid formed in which globule structure is lost
    • interfacial surface area is minimized
  • ​Zeta Potential is FAR from zero​
  • Analagous to suspension’s AGGREGATION except for:
    • glubules of the dispersed LIQUID phase agglomerate to form a single mass as a seperate fused layer
      • vs particles of the dispersed SOLID phase agglomerate to form a CAKE OF DENSELY PACKED PARTICLES
    • –>TWO BULK LIQUID PHASES
    • vs –> One bulk liquid phase + Compacted solid particles
      *
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8
Q

Creaming

in emulsions

A
  • Creaming = Sedementation in suspensions
  • Precurser to Coalescense
    • vs sedementation as a precursor to aggregation
  • When creaming occurs,
    • ​the emulsion MAY or MAY NOT be easily reformed
  • In O/W emulsions, oil is lense dense than water so…
    • Creaming –> FLOAT TO THE TOP
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9
Q

Emulsifiers

A
  • Needed to PREVENT coalescence
    • because emulsions are thermodynamically UNSTABLE
  • Ways to create a barrier on the surface of dispersed globules:
    • SURFACTANT
      • monomolecular layer of surfactant to alter interfacial tension
    • HydroPHILIC colloid particles, multimolecular layer
      • Acacia, gelatin
      • ONLY FOR O/W emulsions
    • Adsorb finely divided solids to the globules
      • bentonite veegum for O/W
      • carbon black for W/O
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10
Q

Using Surfactants

A
  • Typically TWO OR MORE surfactants to form stable O/W emulsion
    • HydroPHILIC surfactant –> in aquous phase
      • Help form outerlayer around electric double layer
    • HydroPHOBIC / lipophilic surfactant
      • adsorb to the surface of oil globule
  • Want film to be Densely packed
    • cover the ENTIRE Surface
  • We DO NOT have a good predective theory
    • ​Trial and error experimentation to determine whats good
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11
Q

HLB Values

(hydrophile-lipophile balance)

for surfactants

A
  • For O/W emulsions
    • moderately HIGH HLB VALUES ( 9-12 )
  • ​​​For W/O emulsions
    • ​moderately low HLB values ( 3-6 )
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12
Q

Technique Matters!

A
  • Emulsion like GRAVY is stabilized by hydrophilic colloid
  • SHEER FORCE MATTERS
  • TEMPERATURE MATERS
  • Lumpy gravy is formed from failure to properly form the starch colloid.
    • Caking starch particles
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13
Q

Velosity of CREAMING

V

A
  • Expressed by Stoke’s Law for dispersions containing less than 0.5% - 2% suspended material
  • NEGATIVE V = particles FLOAT ON TOP
  • Velocity is determined by:
    • Diameter of globule
    • Difference between densisties of globule/medium
    • Gravity acceleration
    • INVERSELY related to VISCOSITY of medium
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14
Q

Breaking the Emulsion

=

Coalescense

A
  • Coalescence to form a continuous phase from the formerly dispersed globules depends on multiple factors:
    • Globule Volume/Size
      • ​Reducing size does NOT always improve stability
        • below 3-5um DOES, because brownian motion
      • Uniform size retards creaming
    • Dispersion medium viscosity
      • Increasing Viscosity retards creaming
    • Phase Volume Ratio
      • Phase Volume can NOT exceed 74% of total volume
        • ​limiting to 50% increases stability
    • Zeta Potential
      • ​Increasing globule zeta potential improves physical stability
      • make globules more highly charged to increase electrostatic repulsion
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15
Q

Preservatives

A
  • Most pharmaceutical emulsions have ingredients that SUPPORT GROWTH of microorgamnisms
  • Preservatives are added for Antibacterial properties
    • Prefer preservatives that prefer partion into the depersing medium
      • Ex. Water in the O/W emulsion
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16
Q

Rheology

(flow properties)

A
  • Emulsion flow properties are LARGELY determined by the VISCOSITY of the DISPERSING MEDIUM
  • Structured vehicles w/ HIGH VISCOSITY can be formulated
    • by adding excess emulsifiers
17
Q

Microemulsions

A
  • Emulsions with globule size in the colloidal particle size range of:
    • .005-.14um (5-140nm)
    • prepared with 20-25% by volume of dispersed phase
  • Stable against creaming due to BROWNIAN MOTION
  • Optically Transparent
  • Will SELF EMULSIFY SPONTANEOUSLY upon dilution w/ dispersing medium
  • SMEDD’s
    • self-microemulsifying drug delivery systems
  • SWOLLEN MICELLES
    • differ from micelles
18
Q

Nanoemulsions

A
  • Similar to microemulsions, BUT
    • Cannot be prepared by self-emulsification techniques
  • require EXTREME HIGH SHEER FORCES
    • ie. ultrasound
  • Globule size <0.1um (<100nm) are produced
  • Have properties of colloids