Vous êtes sur la page 1sur 26

Microemulsions

Stability of Microemulsions
Why are microemulsions thermodynamically stable?*
Gm

Gm > 0 for C & D

emulsion formation

+ve

D C
0
R*

Unstable

B A
Stable

Gm*

Gm = G1 + G2 + G3 - TS

-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.

Formation of Microemulsions*
G m = G1 + G 2 + 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.

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.

salinity Oil chain length Alcohol conc. Parameter increasing Temperature Total surfactant brine/oil ratio surfactant/oil ratio molecular Wt. of surfactant

Multiphase microemulsions A variety of phases can exist in equilibrium with each other.

Interfacial Tension

Interfacial tension

Partition coefficient

NaCl concentration

Effect of salinity on interfacial tension and partition coefficient. Minimum in ultra low interfacial tension occurs when the concentration of the surfactant monomers in aqueous phase is maximum.

Oil

Mechanism of l mu transition Freeze-fracture micrograph Brine

Middle phase microemulsion behaves like a water continuous system with respect to the effect of counterions.

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.

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.

Interfacial tension

NaCl conc. Wt%

For high salinity reservoirs, mixed surfactants are promising for enhanced oil recovery.

Effect of Microemulsions on Oil Recovery


Electrophoretic Mobility Maximum mobility corresponds to minimum in interfacial tension at the crude oil/caustic interface.

NaOH conc. Wt%

Pressure drop Emulsion flow rate

Transient Processes
At optimal salinity
Fastest coalescence occurs Minimum in pressure jump Minimum in apparent viscosity

NaCl conc.

t=0.5 min

t=25 min

t=5 min

t=60 min

t= 10 min

t=90 min

The flattening time reflects the rate at which surfactant molecules accumulate at the oil-brine interface. Flattening time decreases drastically in the presence of alcohol.

Polymer-surfactant incompatibility leading to phase separation.

Various phenomena occurring at the optimal salinity.

De-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.

Production of Complex Oxides through microemulsions


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

Log(conductivity) wt. fraction of aq. phase

Pseudoternary phase diagram determined by conductivity and bulk viscosity measurements.

Surfactant Hydrocarbon Aqueous phase phase phase Microemulsion CTAB + I 1-butanol Microemulsion CTAB + II 1-butanol Weight fraction 29.25% n-octane (Y,Ba,Cu) nitrate soln. (0.3 N) Ammonium oxalate soln. (0.45 N) 11.33%

n-octane

59.42%

Microstructures of sintered YBa2Cu3O7-x

Transmission electron micrograph of oxalate precursor powder.

Extraction of Drug by Microemulsion


Pluronic

Drug
Oil

Water

Fatty Acid

Test on Isolated Guinea-pig Heart

Test on Isolated Guinea-pig Heart


Experiment 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%

Vous aimerez peut-être aussi