Presented

By: Sumit K. Kiran and Edgar J. Acosta

Department of Chemical Engineering and Applied Chemistry, University
of Toronto, Canada

Denition:
Microemulsions are thermodynamically stable mixtures of surfactant,
oil, and water (diameter of dispersed domain < 100 nm)
Types of Morphology: Oil-in-Water (Type I, negative curvature)
Water

Oil
2

Denition:
Microemulsions are thermodynamically stable mixtures of surfactant,
oil, and water (diameter of dispersed domain < 100 nm)
Types of Morphology: Water-in-Oil (Type II, positive curvature)
Oil

Water
3

Denition:
Microemulsions are thermodynamically stable mixtures of surfactant,
oil, and water (diameter of dispersed domain < 100 nm)
Types of Morphology: Bicontinuous (Type III, net-zero curvature)

Important in various applications:

1) Patterning of nanoparticles

Replicated from: http://thegoldenspir

al .org/wp-content/uploads/2008/11/na
noparticles.jpg

Important in various applications:

1) Patterning of nanoparticles
2) Environmental remediation

Replicated from: http://www.ehponlin

e.org/members/2004/6932/fig4.jpg

Important in various applications:

1) Patterning of nanoparticles
2) Environmental remediation
3) Enhanced oil recovery
Replicated from: http://www.liteoilinv
estments.com/images/pores2.gif

Important in various applications:

1) Patterning of nanoparticles
2) Environmental remediation
3) Enhanced oil recovery
4) Drug delivery systems

Replicated from: http://www/integum

entarydisorder.com/images/skin.jpg

Transition in Microemulsion Shape:

Type I (O/W) Type III (Bicontinuous) Phase Behaviour Transition
Sphere

Rd

Ellipsoid

Cylinder

Ld

Ld

Ld >> Rd

Rd
Ld = 0

Ld > 0

Rd

Type II (W/O) Type III (Bicontinuous) Phase Behaviour Transition

Models for Spherical Droplets (Gradzielski et al., 1999):

Dilute liquid
sphere model

Concentrated hard
sphere model
Variable Description:
= Microemulsion viscosity = Volume fraction of dispersed
S = Viscosity of continuous phase phase
d = Viscosity of dispersed phase
10

Models for Non-Spherical Droplets (Gradzielski et al., 1999):

Dilute rigid
rods model

Rigid prolate
ellipsoids model

Variable Description:
Cg = Concentration of rigid rods a and b = major and minor
= Volume fraction of dispersed phase axes
L and d = Length and diameter
11

Denition (Acosta et al., 2003):

Semi-empirical equation of state which predicts microemulsion
properties according to their formulation conditions.
Hydrophilic-Lipophilic Deviation (HLD) (Salager et al., 1979)
Quanties the relative impact of the hydrophilic-lipophilic nature of
oils and surfactants on the observed phase behaviour:
HLD = ln(S)-KNC,O+CC
Electrolyte
concentration

Oil
hydrophobicity

@ f(A) = 0 & T = 0

Characteristic
curvature

12

Denition (Acosta et al., 2003):

Semi-empirical equation of state which predicts microemulsion
properties according to their formulation conditions.
Net Curvature (Hn)

Net curvature of the surfactant

at the oil-water interface

Average Curvature (Ha)

Size of the oil and water

regions

13

Denition (Acosta et al., 2003):

Semi-empirical equation of state which predicts microemulsion
properties according to their formulation conditions.
Net Curvature (Hn)

Length scaling
parameter

Average Curvature (Ha)

Radii of coexisting oil

and water droplets

Characteristic
length

14

1) 5 mL of toluene (NC,O=1) was added to 5 mL of an aqueous solution

consisting of 0.1 M SDHS (CC=-0.92) and 1-10 g/100 mL NaCl.
2) Formulations were mixed for 2 minutes at 3200 RPM and were
subsequently equilibrated for 2 weeks.
Electrolyte Concentration

Type I Type III Type II

15

Falling Ball Viscometer

Dynamic Light Scattering

Replicated From: http://www.malvern.de/LabGer/

technology/images/dynamic_light_scattering 16

Step 1: Calculate the HLD (f(A)=0 and T=0)

HLD = ln(S)-1.09
Step 2: Calculate the Fictitious Radii of Water (Type I) and Oil (Type II)

Surfactant
concentration

RW(O), I(II) = 3*VW(O)/AS

AS = CSi*VW*6.02*1023* ai

Volume of water
(ionic surfactant)

Total surfactant
interfacial area
Area per molecule
of surfactant
17

Step 3: Calculate the Net and Average Curvatures

Step 4: Calculate the Volume Fraction of the Dispersed Phase

18

Step 5: Predict the Length and Radius of the Dispersed Droplets

Step 6: Predict the Microemulsion Viscosity

Incorporate , Ld, and Rd within the previously described models
Step 7: Predict the Maximum Hydrodynamic Radii of Droplets 19

20

Type I Type III

Type II

21

22

Type I Type III

Type II

23

Derived Model:

24

Major Findings:
1) The HLD-NAC model successfully predicts the shape (Ld and Rd) of
Type I and Type II SDHS-toluene-water microemulsion droplets.
2) The predicted dimensions of microemulsion droplets were used to
accurately predict the maximum hydrodynamic radii (RH,max).
3) The experimental viscosity of the systems studied was closely
reproduced across multiple Type I/Type II formulation conditions.
4) Shape and viscosity of nonionic surfactant formulations were also
successfully predicted.
25

National Science and Engineering Research Council of Canada

(NSERC)

Institute for Applied Surfactant Research at the University of

Oklahoma

26

American Oil Chemists Society (AOCS)

27

Publication Information:
Kiran, S.K.; Acosta, E.J. Predicting the Morphology and Viscosity of
Microemulsions Using the HLD-NAC Model. Ind. Eng. Chem. Res. 2010,
49, 3424-3432.
Author Contact Information:
1) Sumit K. Kiran (Ph.D. Candidate), E-mail: sumit.kiran@utoronto.ca
2) Edgar J. Acosta (Supervisor), E-mail: edgar.acosta@utoronto.ca

28