Colloid chemistry

Lecture 13: Emulsions

Emulsions

food cosmetics pharmaceutics biological systems bituminous carpet (asphalt) etc.

Emulsion suitable for intravenous injection.

Balm: Water in oil emulsion

Emulsions

Sodas: Oil in Water emulsion Milk: Oil in Water emulsion

Dodecane droplets in a continuous phase of water/glycerol mixture.

Mayonnaise: Oil in Water emulsion

Emulsions encountered in everyday life!

pesticide

asphalt

skin cream

metal cutting oils

margarine

ice cream

Stability of emulsions may be engineered to vary from seconds to years depending on application

Introduction
Emulsion Suspension of liquid droplets (dispersed phase) of certain size within a second immiscible liquid (continuous phase). Classification of emulsions - Based on dispersed phase Oil in Water (O/W): Oil droplets dispersed in water Water in Oil (W/O): Water droplets dispersed in oil - Based on size of liquid droplets 0.2 50 mm Macroemulsions (Kinetically Stable) 0.01 0.2 mm Microemulsions (Thermodynamically Stable)

Emulsifying agents
Stable suspensions of liquids constituting the dispersed phase, in an immiscible liquid constituting the continuous phase is brought about using emulsifying agents such as surfactants Surfactants must exhibit the following characteristics to be effective as emulsifiers - good surface activity - should be able to form a condensed interfacial film - diffusion rates to interface comparable to emulsion forming time

Common Emulsifying Agents

Surfactants Anionic Nonionic Cationic Sodium stearate, Potassium laurate Sodium dodecyl sulfate, Sodium sulfosuccinate Polyglycol, Fatty acid esters, Lecithin Quaternary ammonium salts, Amine hydrochlorides

Solids Finely divided solids with amphiphilic properties such as soot, silica and clay, may also act as emulsifying agents (Pickering emulsions: attribute of high stability)

Making emulsions

surfactant oil droplet in water (unstable)

po lym

oil droplet in water (stabilized)

er

solid particles

oil droplet in water (stabilized)

G = H A >> 0 emulgeation requires large energy input

G = H A << 0 drop coalescence proceeds continuously

G = H A + desorption energy high desorption energy prevents/hinders coalescence

Making emulsions

O/W

W/O

Surfactant Packing Parameter

Conceptual framework that relates molecular parameters (head group area, chain length and hydrophobic tail volume) and intensive variables (temperature, ionic strength etc.) to surfactant microstructures Critical Packing Parameter / Packing Parameter

v CPP or P = l a0
v: volume of hydrocarbon core l: hydrocarbon chain length a0: effective head group area

Surfactant Packing Parameter

v CPP or P = l a0
v: volume of hydrocarbon chain= 0.027(nc + nMethyl) l: hydrocarbon chain length= 0.15 + 0.127nc where nc = number of carbon atoms without the methyl group nMethyl = number of methyl groups ao: effective head group area: difficult to calculate.

Surfactant Packing Parameter

Packing Parameter is inversely related to HLB

mid point of packing parameter P=1 analogous to HLB 10

at P = 1/ HLB = 10, surfactant has equal affinity for oil and water

W/O vs. O/W emulsions

Bancroft's rule Emulsion type depends more on the nature of the emulsifying agent than on the relative proportions of oil or water present or the methodology of preparing emulsion. The phase in which an emulsifier is more soluble constitutes the continuous phase In O/W emulsions emulsifying agents are more soluble in water than in oil (High HLB surfactants). In W/O emulsions emulsifying agents are more soluble in oil than in water (Low HLB surfactants).

optimum for O/W emulsions

HLB

oil optimum for W/O emulsions water oil water

The type of emulsion (O / W or W / O) is affected by:

the ratio of the oil to water (non-polar to polar) phase; the chemical properties and the concentration of the emulsification agent; the temperature; the presence of additives; for solid particles as the stabilizing agents (Pickering emulsions) the wetting conditions (contact angles of the oil and water phases on the solid) Bancrofts rule (1912): the dispersion medium of an O+W emulsion is the phase in which the solubility of the emulsifying agent is higher. HLB
1-3 3-8 7-9 10-16 13-16 15-18

APPLICATIONS
antifoaming agents; inverse micelles W/O emulsifiers wetting agents O/W emulsifiers detergents solubilizers

Application of surfactants on the basis of their HLB

Pickering emulsions
oil

water vz oil

oil

water water

HLB values for typical nonionic surfactants structures

tenzid kereskedelmi nv HLB

Bancrofts Rule: Relation to HLB & CPP of Surfactant

Surfactant Surfactant

Oil

Water

Oil

Water

Surfactant more soluble in water (CPP < 1, HLB > 10) O/W emulsion

Surfactant more soluble in oil (CPP > 1, HLB < 10) W/O emulsion

Bancrofts Rule: Relation to HLB & CPP of Surfactant

Surfactant Surfactant

Packing Parameter = 1
Oil Water Oil Water

Microemulsion
Surfactant more soluble in water (CPP < 1, HLB > 10) O/W emulsion Surfactant more soluble in oil (CPP > 1, HLB < 10) W/O emulsion

Tests for emulsion type (W/O or O/W emulsions ?)

Based on the Bancrofts rule, many emulsion properties are governed by the properties of the continuous phase 1. 2. 3. 4. 5. dye test dilution test electrical conductivity measurements refractive index measurement filter paper test

Conductivity of emulsions

O/V

V/O

Emulsions are kinetically stable!

Rate of coalescence measure of emulsion stability. It depends on: (a) Physical nature of the interfacial surfactant film For Mechanical stability, surfactant films are characterized by strong lateral intermolecular forces and high elasticity (Analogous to stable foam bubbles) Mixed surfactant system preferred over single surfactant. (Lauryl alcohol + Sodium lauryl sulfate: hydrophobic interactions) NaCl added to increase stability (electrostatic screening)

Emulsions are kinetically stable!

(b) Electrical or steric barrier Significant only in O/W emulsions. In case of non-ionic emulsifying agents, charge may arise due to (i) adsorption of ions from the aqueous phase or (ii) contact charging (phase with higher dielectric constant is charged positively) No correlation between droplet charge and emulsion stability in W/O emulsions Steric barrier dehydration and change in hydrocarbon chain conformation.

Emulsions are kinetically stable!

(c) Viscosity of the continuous phase Higher viscosity reduces the diffusion coefficient Stoke-Einsteins Equation This results in reduced frequency of collision and therefore lower coalescence. Viscosity may be increased by adding natural or synthetic thickening agents. Further, as the no. of droplets (many emulsion are more stable in concentrated form than when diluted.)

Emulsions are kinetically stable!

(d) Size distribution of droplets Emulsion with a fairly uniform size distribution is more stable than with the same average droplet size but having a wider size distribution (e) Phase volume ratio As volume of dispersed phase stability of emulsion (eventually phase inversion can occur) (f) Temperature Temperature , usually emulsion stability Temp affects Interfacial tension, D, solubility of surfactant, Brownian motion, viscosity of liquid, phases of interfacial film.

Phase inversion in emulsions

Bancroft's rule Emulsion type depends more on the nature of the emulsifying agent than on the relative proportions of oil or water present or the methodology of preparing emulsion. Based on the Bancrofts rule, it is possible to change an emulsion from O/W type to W/O type by inducing changes in surfactant HLB / CPP. In other words... Phase Inversion May be Induced.

Phase inversion induced by the change in the HLB / CPP

Na-soap Ba-soap

water O/W

+ BaCl2 W/O

oil

O/W

W/O

Why does phase inversion take place for system with surfactants?
Surfactant Surfactant

Oil O/W emulsion

Water

Oil

Water W/O emulsion

temperature for non ionics, salting out electrolytes for ionics

Bancrofts rule: manifested in response of surfactant solubility

temperature for non ionics, salting out electrolytes for ionics
O/W emulsion W/O emulsion

Temperature and electrolytes disrupt the water molecules around non-ionic and ionic surfactants respectively, altering surfactant solubility in the process Also reflected by change in curvature of the interface

Inversion of emulsions (phase inversion)

O/W W/O 1. The order of addition of the phases W O + emulsifier W/O O W + emulsifier O/W Nature of emulsifier Making the emulsifier more oil soluble tends to produce a W/O emulsion and vice versa. Phase volume ratio Oil/Water ratio W/O emulsion and vice versa

2.

3.

Inversion of emulsions (phase inversion)

4. Temperature of the system Temperature of O/W (polyoxyethylenated nonionic surfactant) makes the emulsifier more hydrophobic and the emulsion may invert to W/O. 5. Addition of electrolytes and other additives. Strong electrolytes to O/W (stabilized by ionic surfactants) may invert to W/O Example. Inversion of O/W emulsion (stabilized by sodium cetyl sulfate and cholesterol) to a W/O type upon addition of polyvalent Ca.

Creaming of emulsions
Droplets larger than 1 mm may settle preferentially to the top or the bottom under gravitational forces. Creaming is an instability but not as serious as coalescence or breaking of emulsion Probability of creaming can be reduced if

4 3 a gH kT 3
a - droplet radius, - density difference, g - gravitational constant, H - height of the vessel, Creaming can be prevented by homogenization. Also by reducing , creaming may be prevented. This is achieved by producing a polyphase emulsion

Methods of destabilizing emulsions

1. Physical methods (i) Centrifuging (ii) Filtration media pores preferentially wetted by the continuous phase (iii) Gently shaking or stirring (iv) Low intensity ultrasonic vibrations 2. Heating Heating to ~ 700C will rapidly break most emulsions.

Methods of destabilizing emulsions

3. Electrical methods Most widely used on large scale 20 kV results in coalescence of entrained water droplets (W/O) e.g. in oil field emulsions and jet fuels. (mechanism deformation of water drops into long streamers) For O/W, electrophoretic migration of charged groups to one of the electrodes. Ex. Removing traces of lubricating oil emulsified in condensed water.

Selection of emulsifiers
Correlation between chemical structure of surfactants and their emulsifying power is complicated because (i) Both phases oil and water are of variable compositions. (ii) Surfactant conc. determines emulsifier power as well as the type of emulsion. Basic requirements: 1. Good surface activity 2. Ability to form a condensed interfacial film 3. Appropriate diffusion rate (to interface)

General guidelines:
1. Type of emulsion determined by the phase in which emulsifier is placed. Emulsifying agents that are preferentially oil soluble form W/O emulsions and vice versa. More polar the oil phase, the more hydrophilic the emulsifier should be. More non-polar the oil phase more lipophilic the emulsifier should be.

2.

3.

General guidelines
1. HLB method HLB indicative of emulsification behavior. HLB 3-6 8-18 for for W/O O/W

HLB no. of a surfactant depend on which phase of the final emulsion it will become. Limitation does not take into account the effect of temperature.

General guidelines
2. PIT method At phase inversion temperature, the hydrophilic and lipophilic tendencies are balanced. Phase inversion temperature of an emulsion is determined using equal amounts of oil and aqueous phase + 3-5% surfactant. For O/W emulsion, emulsifier should yield PIT of 20-600C higher than the storage temperature. For W/O emulsion, PIT of 10-400C lower than the storage temperature is desired.

General guidelines
3. Cohesive energy ratio (CER) method Involves matching HLBs of oil and emulsifying agents; also molecular volumes, shapes and chemical nature. Limitation necessary information is available only for a limited no. of compounds.

Breaking emulsions

1 phase separation (creaming/sedimentation) 2 Ostwald ripening 3 aggregation processes (flocculation; coagulation; coalescence) 4 phase inversion

Breaking emulsions
coalescence breaking

primary emulsion

flocculation

creaming

Stabilization of emulsions
emulsifiers: mostly surfactants

hydration forces: O / W steric forces: W / O electrostratic forces: ionic surfactants polymers: steric forces (entropy stabilization) solid powders: hydrophobic forces (+ wetting)

Breaking emulsions
sedimentation centrifugation filtration thermal coagulation electric treatment ultrasonication chemical additives (e.g. salting out)

Complex (multiphase) emulsions

aqueous phase

stirring

step 1
oil + lipophilic surfactant W / O emulsion

W / O emulsion

stirring

step 2
hidrophilic surfactant W/O/W complex emulsion

primary emulsifier oil phase inner aqueous phase szekunder emulgelszer secondary emulsifier outer aqueous phase W / O / W emulsion

Complex (multiphase) emulsions

W/O/W

O/W/O

10 m W/O/W O/W/O

20 m

Hypothetic phase diagram

surfactant

water

oil

unstable
ma c ro em

metastable

stable

uls io

ns

miniemu

lsions

microemulsions

stability

Micelles, solubilizates, emulsions

normal micelle thermodynamically stable

solubilizate

thermodynamically unstable

microemulsion

O/W macroemulsion

Emulsions microemulsions - internal structure

O/W W/O Bicontinuous structure (E)

- bicontinuous Es do exist; - bicontinuos emulsions do not exist!

The interfacial tension (IFT) for microemulsions is ca. 1000-times less than the IFT of O/W or W/O emulsions !!!
IFT [mN/m]

O/W

W/O

100 % water

100 % oil

Appearance and properties

microemulsion

emulsion

Physico-chemical properties
property
formation type stability

microemulsions
spontaneous, no energy input requied O/W; W/O; bicontinuous structure thermodynamically stable transparent; translucent surfactants; co-surfactants (.0 20-400 nm

emulsions
energy input required O/W; W/O; + complex: O/W/O; W/O/W thermodynamically unstable; kinetically stable turbid; milky surfactants; polymers; solid particles (.90) ($1 mJ/m2 1-20 m

optical properties stabilizing agents interfacial tension size

Winsor-microemulsions
phase inversion may be generated by the variations of temperature/salinity

nonionic surfactants: temperature increases ionic surfactants: electrolyte (NaCl) concentration increases

Winsor-microemulsions

pure oil

pure water

O/W Winsor-I

bicontinuous Winsor-III

W/O Winsor-II