Emulsions Part 1

Definition Preparation methods (some) Properties

Klaus Tauer MPI Colloids and Interfaces Am Mhlenberg, D-14476 Golm, Germany

Dispersed Systems with Liquid Continuous Phases*

Dispersed phase Technical term
gas liquid solid foam emulsion sol, suspension

Example
meringue, whipped cream milk, mayonnaise, butter latex, paint, blood

Dispergere (Latin): to remove, to redistribute Emulgere (Latin): to milk out Suspendere (Latin): to keep in, to keep in floating
* water as continuous phase and an organic dispersed phase or vice versa (inverse emulsions)

What is an Emulsion?
an emulsion is a liquid in liquid dispersion a (polymer) solution is also a liquid

(polymer) solutions can form emulsions an emulsion droplet interface has at any point the same interfacial tension (in contrast to many suspension particles)

sometimes emulsions are subdivided arbitrarily regarding the droplet size (macro-, mini-, microemulsions) and hence general aspects might be lost

Emulsification
comminution
(destruction)

condensation
(construction)

mechanical energy or pressure is doing the job the most widely used procedure (making a salad

thermodynamics takes care swelling of colloidal systems such as micelles or solid (polymer) particles with liquids

dressing in the kitchen)

Emulsification - Basics
stirrer oil mediator: dishwashing liquid

water emulsion
this relation is (possibly) the oldest topic in colloid chemistry and much more also the oldest example of its practical application (pouring oil over water)

hydrophobe oily phase

mediator surfactants emulsifiers stabilizers

hydrophile water

Emulsion formation by comminution

Influenced by:
comminution power duration of the comminution viscosity of both phases interfacial tension
olive oil & water

degradation after comminution is stopped

a process with high complexity

Comminution - Structure of the Emulsion

Which liquid forms the dispersed phase and which will be the continuous one? ? ?

influenced by the volume ratio of the liquids, the kind of the emulsifying agent, and its concentration in strong connection with the temperature. most important property of the emulsifying agent is its solubility (in both phases) or in the case of the solid stabilizers the wetting behavior of both liquids

Bancrofts Rule (1912)

Tests for Identification of Emulsion Types:

Dilution test: emulsion can be diluted only with external phase Dye test: water or oil soluble dyes CoCl2/filter paper test: filter paper impregnated with CoCl2 and dried (blue) changes to pink when o/w emulsion is added Fluorescence: some oils fluoresce under UV light Conductivity: for ionic o/w emulsions (o/w emulsions conduct electric current)

Action of Emulsifiers
reducing the interfacial tension between the phases forming a barrier between the phases

main actions:

Action of Emulsifiers
- promoting the formation of an emulsion, - making it easier to prepare, - producing finer droplet size, - aiding stability to the dispersed state

controlling the type of emulsion that is to be formed: oil in water (O/W) or water in oil (W/O)

Work of Emulsion Formation:

The increase in the energy of an emulsion compared to the nonemulsified components is equal to W. This amount of energy can be considered as a measure of the thermodynamic instability of an emulsion.

W = A
W is the free energy of the interface and corresponds to the reversible work brought permanently into the system during the emulsification process . This makes an emulsion very prone to coalescence processes which lead to a decrease in A and subsequently in W. The conclusion is straightforward that ultimate stability against coalescence processes is only achieved if s approaches zero.

Preparation of Emulsions by Comminution

input of mechanical energy by stirrers is the most important case stirrers generate macro-eddies or macro-turbulences with a characteristic length in the order of the stirrer diameter. macro-eddies decompose into micro-eddies with a characteristic length which is also called Kolmogorov length micro-eddies are finally responsible for the energy transfer and hence the breakage of the macroscopic phase

1/ 4

relates to the kinematic viscosity of the solution

() and the dissipation rate () which is the power input by the stirrer (P) per mass (m)

The Comminution Progress

as soon as the shear exerted by the turbulent micro-eddies on the droplet interface exceeds the cohesive forces of the liquids in the drops they split up to smaller units
C B A D

/W
time

P = (ra + rb )

cleavage occurs as long as a balance between the external stress and the internal stress is reached

The Comminution Process (1)

steady state DSD for different rotor / stator systems: = 0.1, 50 mM SDS
Machine STR a) Screw loop b) Ultra turrax c) Conditions for W V = 5106 J m-3 n = 500 rpm, td = 60 min n = 4000 rpm, v = 350 l h-1 n = 10.000 rpm, td = 2 min Maximum Dd in DSD 60 70 m 10 11 m and 2 m 10 11 m and 2 m

W = 5 10 6 ( J m 3 ) = 10 2 ( N m 1 ) A(m 2 m 3 )

A = 5 10 m m
8 2

D = 1.3nm

theory

a - STR stirred tank reactor consisting of a cylindrical vessel (diameter 30 cm, volume 21.2 l) with a flat bottom and four symmetrical baffles and a six blade disc impeller with a diameter of 10 cm b - Screw loop reactor, volume of the dispersing zone about 64 ml and reactor volume 1.67 l c - Ultra turrax T50 from IKA with a dispersing tool type S50-G45F used in a cylindrical vessel with a volume of 8 l Ludwig, A., U. Flechtner, J. Prss, H.-J. Warnecke, Formation of emulsions in a screw loop reactor, Chem. Eng. Technol., 20, 149 - 161 (1997)

experimental values

The Comminution Process (2)

0,4 g/ml PMMA in MeCl2 in a 0,2 g/ml BSA solution (v:v = 10:2) batch homogenizer

Y.-F. Maa, C. Hsu J. Controlled Release 38, 219-228 (1996)

a steady state DSD is reached

The Comminution Process (3)

stirred tank, turbine-type stirrer soya oil, screw loop reactor

SDS

self preserving pluronics DSD

A. Ludwig, U. Flechtner, J. Prss, H.-J. Warnecke Chem. Eng. Technol. 20, 149-161 (1997)

H.+ M. Polat, S. Chander AIChE Journal 45, 1866-1874 (1999)

The Comminution Process (4)

viscoelastic force of the dispersed phase solution viscosity is a direct measure of the viscoelastic force
emulsification of an aqueous bovine serum albumin solution in dichloromethane containing poly(methyl methacrylate) (PMMA) as stabilizer with different agitation machines

Agitation machine Rotor stator homogenizer Baffled mixed tank Static Mixture

Relation
Dd 0.11c0.43 d Dd 0.22c0.42 d Dd 0.004c0.56 d

viscosity of the dispersed phase (d) and of the continuous phase (c)

increasing c means increasing shear stress at a given comminution energy

Comminution by Ultrasound
(special kind of mechanical energy input )

Ultrasound means the application of high frequency vibrations. In a first step larger drops (Dd 100 m) are produced in a way that instabilities of interfacial waves will be enhanced leading finally to the crushing. These drops are subsequently fragmented into smaller ones by acoustic cavitation. The use of ultrasound in emulsification processes is much more efficient than the application of rotor / stator systems.
Physical and chemical effects of cavitation
[K. S. Suslick, University of Illinois, USA]

The energy of the ultrasonic wave is concentrated into highly localized temperature and pressure hot spots

[K. S. Suslick, University of Illinois, USA]

action of ultrasound

Cavitation
Acoustical energy is mechanical energy i.e. it is not absorbed by molecules. Ultrasound is transmitted through a medium via pressure waves by inducing vibrational motion of the molecules which alternately compress and stretch the molecular structure of the medium due to a time-varying pressure. Therefore, the distance among the molecules varies as the molecules oscillate around their mean position. If the intensity of ultrasound in a liquid is increased, a point is reached at which the intramolecular forces are not able to hold the molecular structure intact. Consequently, it breaks down and a cavity is formed. This cavity is called cavitation bubble as this process is called cavitation and the point where it starts cavitation threshold. A bubble responds to the sound field in the liquid by expanding and contracting, i.e. it is excited by a time-varying pressure. Two forms of cavitation are known: stable and transient. Stable cavitation means that the bubbles oscillate around their equilibrium position over several refraction/compression cycles. While transient cavitation, the bubbles grow over one (sometimes two or three) acoustic cycles to double their initial size and finally collapse violently.

comminution and reaction

[K. S. Suslick, University of Illinois, USA]

Comminution by Ultrasound - A Practical Example 1

ultra turrax (n = 10.000 rpm, 170 W)
surfactant concentration:

ultrasound horn (20 kHz, 130 W)

surfactant concentration:

(25 % kerosene volume fraction; total volume of 80 ml) with a polyethoxylated (20EO) sorbitan monostearate surfactant (interfacial tension kerosene to water 9.5 mN m-1
Abismail, B., J. P. Canselier, A. M. Wilhelm, H. Delmas, C. Gourdon, Emulsification by ultrasound. drop size distribution and stability, Ultrasonics Sonochemistry, 6, 75 - 83 (1999)

Comminution by Ultrasound - A Practical Example 2

Consecutive emulsification
What will happen if an emulsion which was prepared by a certain comminution technique is exposed to a different shear stress ???

shear stress

Note, the shear stress is the product of shear rate and viscosity and hence it combines emulsion properties with properties of the comminution technique.
Mason, T. G. and J. Bibette, Shear rupturing of droplets in complex fluids Langmuir, 13, 4600 - 4613 (1997)

Shear Rupturing of Emulsion Droplets

2. step (Couette)
The pre-emulsions consisted of poly(dimethylsiloxane) oil (volume fraction ) in water stabilized with a nonionic surfactant (nonylphenol with 7 ethylene oxide units (mass fraction with respect to water C).

1. step (STR)

At shear rates larger than 10 s-1 in the Couette flow the polydisperse pre-emulsion starts to convert into monodisperse ones.
Mason, T. G. and J. Bibette, Langmuir, 13, 4600 - 4613 (1997)

Shear Rupturing of Emulsion Droplets, practical examples

10 2 s 1

> 10 s-1 in the Couette flow the

surfactant

polydisperse pre-emulsion starts to convert into monodisperse ones. The dependence of the final droplet size on the emulsifier concentration is as expected: Dd decreases with increasing C but Dd decreases with increasing volume fraction of the organic phase

oil

Mason, T. G. and J. Bibette, Langmuir, 13, 4600 - 4613 (1997)

Dd decreases with increasing volume fraction of the organic phase. This is a remarkable result as it indicates fundamental differences in the comminution mechanisms.

Membrane Emulsification - Principle

This technique was first reported at the 1988 autumn conference of the Japanese Chemical Engineering Society utilizing a micro-porous glass (MPG) membrane made of CaO-Al2O3-B2O3-SiO2.
SPG info-material, Japan

Membrane Emulsification - Results

D d = f DM
f:2-8
Re > 4000 turbulent flow

DM - pore diameter Dd droplet diameter

Continuous phase: 66.7 w% water 3 w% triethanolamine 0.3 w% sodium nipastat Dispersed phase: 27 w% mineral oil 3 w% isosteric acid

Williams, R. A.; S. J. Peng, D. A. Wheeler, N. C. Morley, D. Taylor, M. Whalley and D. W. Houldsworth, Controlled production of emulsions using a crossflow membrane Part II: industrial scale manufacture, TransIChemE 76, 902 - 910 (1998)

Membrane Emulsification -

more

Results
monodispers drops

membrane
Oil phase: soy bean oil with 0.5 wt-% Span 80 Water phase: 1 wt-% NaCl solution Membrane: hydrophobic SPG Dm = 2,56 m; P = 25 kPa

SPG info-material, Japan

Comminution - Summary
this emulsification process is influenced by various parameters: - the volume phase ratio - the viscosity of both phases - the mutual solubility of both phases - the kind and concentration of additives - the diminution energy and the power input - the stirrer as well as the vessel geometry - thermodynamic changes during the emulsification process (reactions, temperature).

Particles as Stabilizers -Pickering Emulsions (1)

W. Ramsden Proc. R. Soc. Lond. 72 (1904) 156-164 S. U. Pickering J. Chem. Soc. 91 (1907) 2001

any kind of particles: minerals polymers

crucial is the wetting behavior: contact angle particle size solids concentration interparticular interaction

(R. Daniels)

Particles as Stabilizers -Pickering Emulsions (2)

Energy of attachment or removal of a particle to or from a fluid-fluid interface (E) is not only related to the contact angle () but also to the interfacial tension (). Small enough particles - no effect of gravity. The sign inside the bracket is negative for removal into the water phase, and positive for removal into the oil phase. If D~20 nm and ~36 mN/m the particle is most strongly held in the interface for = 90 with E = 2750 kT. Either side of 90, E falls rapidly for 0 - 20 and 160 - 180 to less than 10 kT. For < 90 the particle is more hydrophilic and for > 90 the particle is more hydrophobic. Note, E depends on the square of the particle size!

B. P. Binks Curr. Op. Coll. Interf. Sci. 7 (2002) 21-41

Particles as Stabilizers -Pickering Emulsions (3a)

Inorganic particles as stabilizers

O/W emulsion stabilized with TiO2particles backscattered electron (BSE) imaging of cryo-fracture SEM
(high pressure frozen sample: -196 C and 2200 bar)

S. Wiesner, S. S. Biel, K. P. Wittern, U. Hintze, R. Wepf Microscop. Microanal. 9 (2003) 510

technical of importance for: pharmaceutical and cosmetic products, crude oil and oil recovery, waste products in soils (O/W), suspension polymerization of styrene (with CaCO3, BaSO4, Ca5[(OH)|(PO4)3])
hydroxylapatite

Particles as Stabilizers -Pickering Emulsions (3b)

Latex particles as stabilizer
B. P. Binks, S. O. Lumsdon Langmuir 17 (2001)4540-4547
a 760 m diameter hollow sphere consisting of a monolayer of 7.9 m monodisperse polystyrene particles flocculated onto a nitrogen bubble formed during seeded emulsion polymerization experiment aboard the space shuttle orbiter Challenger (STS 7, June 1983)
[J. W. Vanderhoff, O. Shaffer EPI Lehigh University, Bethlehem,USA]

Colloidosomes

D. A. Weitz Science 298 (2002) 1006-1009

Multiple Emulsions (1)

Emulsifying an emulsion in another continuous phase to get either W/O/W or O/W/O emulsions requires stabilizers with different HLB

secondary emulsifier

(M. Akhtar)

Multiple Emulsions (2)

membrane emulsification

hydrophilic and hydrophobic silica particles as stabilizer

O/W: Oil phase: soy bean oil with 1 wt-% PGCR Water phase: 5 wt-% Na2PO4/KH2PO4 4/1 Membrane: hydrophobic SPG Dm = 0.36 m; P = 300 kPa W/O/W: O/W in 1wt-% aqueous Tween 20 + 0.5 wt-% NaCl Membrane: hydrophilic SPG Dm = 2.8 m; P = 40 kPa
SPG info-material, Japan

B. P. Binks Curr. Op. Coll. Interf. Sci. 7 (2002) 21-41

Preparation of Emulsions by Condensation Techniques or The Gentle Way to Make Emulsions

condensation does not require mechanical energy except sometimes ggentle stirring to avoid creaming or settling due to density differences bbetween both phases mainly determined by thermodynamic principles swelling of preformed colloidal objects sometimes in the presence of emulsifying or swelling adjuvant

Microemulsions (1)

but todays knowledge:

Microemulsions (2)
apparently a single phase

more surfactant than dispersed phase frequently surfactant plus co-surfactant (alcohol) complicated phase diagrams

two phases

no direct contact between both phases

Microemulsions (3)
comparing emulsions and microemulsions:
lower amount of surfactant thermodynamically unstable direct phase contact interfacial tension 20-50 mN/m turbid

higher amount of surfactant thermodynamically stable no direct phase contact interfacial tension 10-4 mN/m transparent

rule of thumb: high HLB is needed to prepare O/W emulsions, low HLB is needed to produce W/O emulsion and intermediate HLB gives -emulsion

stability of -emulsions:

Helfrich free energy (HFE) introduced 1973 by W. Helfrich explains interface and topological fluctuations involving the interface curvatures c1, c2 and the spontaneous interface curvature c0. K and K are moduli and associated with these fluctuations.

Microemulsions (4)
O/W microemulsion

bicontinuous phase emulsion

as microemulsions appear transparent some people call them solutions

Spontaneous Emulsification
since 50 years: fatty alcohols (for instance lauryl alcohol) act as emulsifying adjuvant for ammonium fatty acids soaps during emulsion polymerizations [40] polymerizable miniemulsion droplets are formed

soap : alcohol in a 2 : 1 stoichiometry

This process obviously involves also the diffusion of the monomer through the aqueous phase into the structures formed by the mixed surfactant system.

action of the alcohol surfactant mixture results in a less power demand for the emulsification (gentle stirring is enough) and an enhanced droplet stability. This effect is called spontaneous emulsification and
its mechanism is still a matter of controversial discussion.
Dewald, R. C., L. H. Hart and W. F. Carroll, Jr., J. Polym. Sci.: Polym Chem. Ed., 22, 2923 2930 (1984) Ugelstad, J., P. C. Mork and A. Berge, Vinyl chloride polymerization in Emulsion Polymerization and Emulsion Polymers, (Eds. P. A. Lovell and M. S. El-Aasser), Wiley, Chichester, 1997

The synergistic

Surfactant Alcohol Mixtures

surfactant alcohol mixtures possess a variety of exceptional properties : highest packing density, lowest interfacial tension, highest surface viscosity, minimum in droplet / bubble size, and formation of the most stable microemulsions.
Jnsson, B., B. Lindman, K. Holmberg, and B. Kronberg, Surfactants and Polymers in Aqueous Solution, Wiley, Chichester, 1998 Patist, A.; T. Axelberd and D. O. Shah, J. Coll. Interf. Sci., 208, 259 - 265 (1998) Oh, S. G. , M. Jobalia and D. O. Shah, J. Coll. Interf. Sci., 155, 511 - 514 (1993)

small amounts of a highly water-insoluble compound in the monomer phase prevents the formation of a miniemulsion compound- 2 importance of diffusion processes through the aqueous phase for the spontaneous emulsification.

Swelling and Polymerization

shrinkage during polymerization
up tak eo fm

latex particles

on om er

mon Dp = pol

1/3

Dd

emulsion of swollen latex particles final latex particle after polymerization

promotion of swelling ???

Swelling Some Theory

ln 1 + (1 1 1 2 ) 2 + (1 )3 + 2 1,2 + 3 1,3 + 2 j3 j2 2,3 j2 )+ 4v1 Psw v1 + =0 D RT RT + 2 3 (1,2 + 1,3

j - degree of polymerization, c - interaction parameter, f - volume fraction, v - partial molar volume, D - equilibrium swollen particle size, RT - thermal energy 1 - monomer

entropy promotes swelling

2 - oligomer / compound- 2
3 - polymer

swelling promoter
J. Ugelstad, K.H. Kaggerud, F.K. Hansen, A. Berge Makromol. Chem. 180, 737-744 (1979 K. Tauer, H. Kaspar, M. Antonietti Coll. Polym. Sci. 278, 814-820 (2000)

Swelling Some Examples

seed particles emulsion droplets (swollen particles)

1. chloro-decane
(promoter)

2. chloro-benzene
(oil)

J. Ugelstad, K.H. Kaggerud, F.K. Hansen, A. Berge Makromol. Chem. 180, 737-744 (1979

Swelling of Latex Particles:

2 v1 2 v1 2 1/ 3 + P ( 2 2 / 2) = ln(1 2 ) + (1 1/ j 2 ) 2 + 2 + r RT MC

2 1 (r ) = 1 + r

3 2 (r, 2 ) = 1 + r

P* P = P0 + r

( 2 ) = 0.431 0.311 2 0.036 2 2

The factor (Z) is introduced taking into account the transition from the quasi homogeneous microgel system in toluene over to the heterogeneous aqueous systems of charged polystyrene in the presence of toluene. The factor Z acts directly on P0. P0 represents the swelling pressure of chemically identical bulk materials and P* can be considered as a modulus describing the pressure increase with decreasing size of the sample.

Coll. Polym. Sci. 278, 814-820 (2000)

Swelling of Latex Particles: Experimental Results

influence of particle surface chemistry

Coll. Polym. Sci. 278, 814-820 (2000)

Swelling Practical Meaning

in technical scale production semibatch procedure with feeding a monomer emulsion; normal swelling of seed particles

~25106 tons / y
(polymers worldwide)

Ugelstad

monodispers latexes for medical applications ; e.g. Dynabeads

Distler Distler

see you next week: a little (theory) on emulsion stability