Microemulsions

Microemulsions
Microemulsions are thermodynamically stable, optically transparent, isotropic dispersions of aqueous and hydrocarbon liquids stabilized by an interfacial film of surfactant molecules Microemulsions are monodispersed spherical droplets (diameter < 100 nm) of water in oil or oil in water, depending on the nature of the surfactant.

Microemulsions and (Macro) emulsions are Different

Microemulsion
Thermodynamically Stable Droplet size 10 - 100 nm (transparent) High surface area: 200 m2/g Ultra Low O/W IFT (10-2 10-3 mN/m) W/O , O/W and Bicontinuous types Forms at CPP = 1

Macroemulsion
Kinetically Stable 1-10 Qm (opaque) Low surface area: 15 m2/g O/W IFT 1-10 mN/m W/O or O/W types Forms at CPP > or < 1

Formation of Microemulsions*
(Gm ! (G1  (G2  (G3  T (S

Oil

(Gm = free energy change for microemulsion formation (G1 = free energy change due to increase in total surface area (G2 = free energy change due to interaction between droplets (G3 = free energy change due to adsorption of surfactant at the oil/water interface from bulk oil or water (S = increase in entropy due to dispersion of oil as droplets
*

Ruckenstein, E, Chi, J. C., Faraday Trans. II 71 (1975) 1690.

Stability of Microemulsions
Why are microemulsions thermodynamically stable?*
Gm

Gm > 0 for C & D

emulsion formation

+ve

D C
0
R*

Unstable

Gm =

G1 +
R

G2 +

G3 - T S

B A
Stable

Gm*

-ve

Gm* < 0 for A & B in certain R range microemulsion formation in that R range

NOTE: Microemulsions form spontaneously only when IFT is small. (order of 10-3 mN/m)

* Ruckenstein,

E, Chi, J. C., Faraday Trans. II 71 (1975) 1690.

Watch the apparent dichotomy !

1 1  P! R R 2 1
The Young Laplace Equation predicts an inverse relation of pressure drop with droplet radius

2K (G ! V R

Further, free energy arguments should predict, a rapid coalescence of droplets that are < 100 nm Then why are microemulsions thermodynamically stable?

Microemulsions are formed because ... The penalty for the apparent increase in free energy is compensated by the lowering of IFT to ultra low levels (10-2 10-3 mN/m) The work done in lowering IFT is achieved through a gain in system entropy S due to the creation of a large number of sub-micron sized droplets All this occurs when at molecular levels, surfactants form the most condensed interfacial film between oil and water

Microemulsions form when CPP = 1

The most condensed interfacial film between oil and water is formed when maximum number of surfactants pack Occurs when surfactants orient vertically !

Formulating Microemulsions Bancrofts rules

Surfactant Surfactant

Oil

Water

Oil

Water

(CPP < 1) O/W emulsion

(CPP > 1) W/O emulsion

Change in variables (T, Salting out electrolyte etc.)

Formulating Microemulsions Bancrofts rules

Surfactant

1 phase microemulsion

3 phase domain (oil - QE -water) (Bicontinuous QE)

W/O or O/W Oil microemulsion

Water

CPP = 1 Sometimes, a co-surfactant such as a short chain alcohol is used in conjunction with the surfactant to facilitate condensed interfacial film formation

But! Watch what we just did !

Surfactant

1 phase microemulsion

3 phase domain (oil - Qm -water) (Bicontinuous QE)

W/O or O/W Oil microemulsion

CPP = 1

Water

We just happened to bring OIL AND WATER, 2 IMMISCIBLE LIQUIDS, INTO 1 SINGLE PHASE See the Potential for Enhanced Oil Recovery?

Tracking phase change using test tubes

Surfactant Surfactant Surfactant

Oil

T1

Water Oil

T2

Water Oil

T3

Water

Some Definitions / Conventions

Surfactant Surfactant Surfactant

Oil

T1 Winsor I

Water Oil

T2 Winsor III

Water Oil

Water T3 Winsor II

Lower phase QE

Middle/ 3 phase QE

Upper phase QE

Manipulating Micro-Emulsions Micro-

Variables to play with Salinity Oil chain length Alcohol conc. Temperature Total surfactant brine/oil ratio surfactant/oil ratio M Wt. of surfactant

Interfacial Tension with Salinity

Solubilization For middle phase microemulsion, 1 mol CaCl2 $ 16-19 moles of NaCl and for oil-external microemulsions, 1 mol CaCl2 $ 4 moles of NaCl Values of optimal salinity : LiCl > NaCl > KCl > NH4Cl At phase inversion, partition coefficient is near unity. Repulsion forces between micelles decreases due to the neutralization of surface charge of micelles by counterions.

Enhanced Oil Recovery by Microemulsion Flooding

Proper selection of chemicals in formulating the surfactant slug. Surfactant formulation- surfactant, alcohol and brine with or without added oil. Correlation between interfacial tension and interfacial charge.

Enhanced Oil Recovery by Microemulsion Flooding

Vol. fraction of middle phase TRS 10-410 wt. % Even at very low surfactant concentration, microscopic amount of middle phase remains. Oil recovery maximum near the optimal salinity of the system.

Enhanced Oil Recovery by Microemulsion Flooding

For high salinity reservoirs, mixed surfactants are promising for enhanced oil recovery. Electrophoretic Mobility Maximum mobility corresponds to minimum in interfacial tension at the crude oil/caustic interface. Transient Processes At optimal salinity Fastest coalescence occurs Minimum in pressure jump Minimum in apparent viscosity

Various phenomena occurring at the optimal salinity

Production of Complex Oxides/ nanoparticles through microemulsions

W/O microemulsions provide a novel vehicle for synthesis of a micro-particulate oxalate precursor which yields very high density sintered pellets of YBa2Cu3O7-x. Steric barrier by surfactant monolayer restricts the growth of precipitated particles and hinders intergrain coagulation.

Schematic of W/O microemulsion and the reaction mechanism

Microstructure of microemulsion method synthesis

Microstructures of sintered YBa2Cu3O7-x prepared by W/O microemulsion

Microstructures of Pd, Pt nanoparticles prepared using W/O microemulsion

Drug Detoxification by Microemulsion

Pluronic

Drug
Oil

Water

Fatty Acid

Test on Isolated Guinea-pig Heart Guinea-

Test on Isolated Guinea-pig Heart GuineaExperiment Detail: Measured QRS interval Infused Bupivacaine (5 M) to cause cardiotoxicity (QRS prolongation ~ 20 msec)
R

1) Control

2) Bupivacaine

3) Bupivacaine + ME

Isolated Guinea Pig Heart - Results

Type Oil concentration Particle size (nm) Removal toxicity

Commercial Emulsion 1% ~ 430 21%

ME-3 1% ~110 90%

ME-6 0.01% ~ 25 72%

DeDe-Emulsification Cotton, wool, glass fibers and teflon to promote coalescence Addition of acid/base neutralizes the particle charge and leads to coagulation Application of high voltages Heating of emulsion.