Lecture 6 Emulsion Technology

Em lsion Technology
Emulsion Technolog
Dispersions
Di i in
i liliquids:
id suspensions,
i
emulsions, and foams
ACS National Meeting
March 21 – 22, 2009
Salt Lake City
Ian Morrison© 2009

Ian Morrison© 2009 Lecture 6 - Emulsion technology 1
*Dickenson in ”Food Structure”; Butterworths; 1988.
Emulsions, e.g.
g food!
Food Emulsio Dispersed phase Continuous phase Stabilization factors, etc.
n type
Milk, cream O/W Butterfat triglycerides partially Aqueous solution of milk Lipoprotein membrane, phospolipids,
crystalline
lli and d liquid
li id oils.
il proteins,
i salts,
l minerals,
i l and adsorbed casein.
Droplet size: 1 – 10 μm etc.
Volume fraction: Milk: 3-4%
Cream: 10- 30%
Ice cream O/W Butterfat (cream) or vegetable, Water and ice crystals, milk The foam structure is stabilized by
(aerated partially crystallized fat. proteins, carboxydrates agglomerated fat globules forming
to Volume fraction of air phase: 50% (sucrose corn syrup)
(sucrose, th surface
the f off air
i cells.
ll
foam) Approx. 85% of the water
content is frozen at – Added surfactants act as
20oC. “destabilizers” controlling fat
agglomeration. Semisolid frozen
phase.
Butter W/O Buttermilk: milk proteins,
proteins Butterfat triglycerides
triglycerides, Water droplets distrib
distributed
ted in semi-
semi
phospholipids, salts. partially crystallized and solid, plastic continuous fat phase.
Volume fraction: 16% liquid oils; genuine milk
fat globules are also
present.
Imitation O/W Vegetable oils and fats. Aqueous solution of proteins Before aeration: adsorbed protein
cream Droplet size: 1 – 5 μm. ((casein),
), sucrose,, salts,, film
film.
(to be aerated) Volume fraction: 10 – 30% hydrocolloids. After aeration: the foam structure is
stabilized by aggregated fat
globules, forming a network around
air cells; added lipophilic
surfactants promote the needed fat
globule aggregation
aggregation.

Where’s the emulsion science*?
*To be respectful – where can we add the “magic” of emulsion science?
http://www.seas.harvard.edu/projects/weitzlab/andersonresearch/

Terminology
gy - 1
Phase 1 Phase 2
Droplet Serum
Dispersed Medium
Di
Discontinuous
i C i
Continuous
Internal External

Terminology - 2
Macroemulsions At least one immiscible The stability by addition
liquid dispersed in of surfactants and/or
another as drops whose finely divided solids.
diameters generally Considered only
exceed 1000 nm. kineticallyy stable.
Miniemulsions An emulsion with Reportedly
droplets between 100 thermodynamically
and 1000 nm. stable.
Microemulsions A thermodynamically Usually requires a
stable, transparent surfactant and a
solution of micelles cosurfactant (e.g. short
swollen with solubilizate
solubilizate. chain alcohol)
alcohol).
Becher, P. Emulsions, theory and practice, 3rd ed.;

Oxford University Press: New York; 2001.

Manufacture of butter*
• Milk is a fairlyy dilute,, not veryy stable O/W emulsion,, about 4% fat.
• Creaming produces a concentrated, not very stable O/W emulsion,
about 36% fat.
• Gentle agitation,
agitation particularly when cool
cool, 13 – 18 C
C, inverts it to make a
W/O emulsion about 85% fat.
• Drain, add salt, and mix well.
• Voila – butter!
• What remains is buttermilk.
*Becher, Emulsions; Oxford; 2001, p. 291

Emulsion processes
A F
E
B
C D
A – Inversion C – Sedimentation E - Coalescence

B – Creaming D – Flocculation F - Ripening
Surface activity
y in emulsions
Emulsions are dispersions of droplets of one liquid in another.
Emulsifiers are soluble, to different degrees, in both phases.

Emulsion stability
ΔF = σ Δ A < 0
Drops coalesce
spontaneously.
t l
ΔF = σΔA + work of desorption

+
If the work of desorption

is high, the coalescence
is prevented.

Stability
y of emulsions*
Types:
• Creaming – less dense phase rises
• Inversion – internal phase becomes external phase
• Ostwald ripening – small droplets get smaller
• Flocculation – droplets stick together
• Coalesence – droplets combine into larger ones
*Dickenson
Dickenson in ”Food
Food Structure
Structure”;; Butterworths; 1988; p
p. 43
43.

Ripening of Emulsions
Change in size distribution with aging, 0.005 M sodium oleate and

octane: 1a, measured on first day; 1b, measured on third day; 1c.
measured on seventh day, 0.005M cesium oleate; 2a, measured on
first day; 2b measured on third day; 2c
2c. Measured on seventh day
day.

Breaking
g of emulsions
An emulsion system with

an initial particle size of
235 nm was destabilized
by dilution in a solution of
an ionic surfactant
opposite in sign to that of
the particle charge
charge. The
three figures show the
resulting distributions at
times up to 4 days as
reported in the figures.

Creaming
g of emulsions
50
40
H eight/mm
m
30
20 18 hours
43 hours
127 hours
154 hours
10 223 hours
0
00
0.0 02
0.2 04
0.4 06
0.6
Volume fraction
Volume fraction at various heights

g and times was
determined by measuring the speed of sound.
Stabilityy of emulsions - II
Electrostatic stabilization – at lower volume fractions
Steric stabilization – at all volume fractions
Additional factors –
1. St
1 Steric
i stabilization
t bili ti iis
enhanced by solubility in
both phases:
2. Mixed emulsifiers (cosurfactants)

+
are common. They can come from
either phase. +
3 Temperature is important – solubility changes quickly

3. quickly.

Demulsification – breaking
g emulsions
First, determine type, O/W or W/O. Continuous phase will mix with
water or oil.
oil
• Chemical demulsification, i.e. change the HLB
• Add an emulsifier of opposite type.
• Add agent of opposite charge.
• Freeze-thaw cycles.
• Add electrolyte.
l t l t Ch Change th
the pH.
H
• Raise temperature.
• Apply
pp y electric field.
• Filter through fritted glass or fibers.
• Centrifugation.

Emulsion inversion
As the
A th
concentration
increases (A)
A
p
the droplets g
get
closer until they
pinch off into
smaller,
opposite type of B
emulsion (B).

Multiple emulsions
((a)) W/O/W double emulsion O/W/O double emulsion

Consider, for either diagram:
Each interface needs a different HLB value.
The curvature of each interface is different.
Ian Morrison© 2009 Lecture 6 - Emulsion technology (Rosen, p. 313) 17
Bancroft’s
Bancroft s Rule
“The emulsifier stabilizes

the emulsion type where the
continuous phase is the
medium in which it is most
soluble.”
A hydrophilic solute in an O/W emulsion.
The long tail on the

surfactant is to
represent the longer
range interaction of a
“hydrophilic”
molecule through
water.
A hydrophilic
y p solute in a W/O emulsion.

The HLB Schema
Variation of type and amount of
residual emulsion with HLB number
of emulsifier.
Optimum
for
O /W
Emulsion O/W
breaker
Volume
and
type of
10 HLB
emulsion
W /O
Optimum
for
W/O

HLB Scale
Lipophilic End of Scale Hydrophilic end of scale
Stearane Steric Acid Sodium Sodium Sucrose Sodium Sulfate
Stearate Laurate
Soluble in oil; Soluble in oil; Soluble in oil; Slightly oil- Insoluble in Insoluble in oil;
insoluble in insoluble in and in hot soluble; oil; soluble in water
water water water soluble in soluble in
water water
Nonspreading Spreads on Spreads on Reduces Does not Increases surface
on water water substrate water substrate surface affect the tension in aqueous
substrate tension of surface solution
aqueous tension in
solutions aqueous
solution
Does not affect Reduces Reduces Reduces Does not Increases interfacial
interfacial interfacial interfacial interfacial affect tension at oil–water
tension at oil– tension at oil– tension at oil– tension at oil– interfacial interface
water interface water interface water interface water tension at oil–
interface water
interface
Does not Stabilizes water Stabilizes Stabilizes Does not Decreases the
stabilize in oil emulsions either type of oil in water stabilize stability of
emulsions emulsion emulsions emulsions
emulsions
1 20
___________ HLB Scale ___________

Applications of the HLB scale
HLB Range Application
3.5–6 W/O emulsifier
7–9 Wetting agent
8–18 O/W emulsifier
13–15 Detergent
15–18 Solubilizer

Group
p Numbers for Calculating
g HLB Values
G rou p N u m b er
H yd rop h ilic G rou p s
− O S O 3- N a + 38.7
−C O O -K + 21.1
−COO -Na + 19.1
N ((tertiary
y amine)) 9.4
E ster (so rbitan ring) 6.8
HLB = 7 + ∑ ( H ) − ∑ ( L)
E ster (free) 2.4
−COOH 2.1
− O H (free) 1.9
−O − 1.3
− O H (sorbitan ring) 0.5
(− C H 2C H 2O − )n 0.33 n
L ip op h ilic G rou p s
−CH −
−CH 2 − 0.475
CH 3 −
= CH −
( − C H C H 3C H 2O − ) n 0.15 n

HLB and C.M.C.
40 s o d i u m a lk y l s u lf a
A e r o s o l s e r ie s
HLB
A t la s T w e e n s
20
H
A t la s S p a n s
α −m o n o g l y c e
0
-1 -2 -3 -4 -5
Log C.M.C.
Phase inversion temperature
p
30oC 40oC 50oC 60oC 70oC 75oC 80oC 90oC 100oC
Water Emulsion Oil

www.bias-net.com/chimica/pdf/set_baglioni.pdf
/ / f/ f

HLB and the Phase Inversion Temperature
p
16
25oC)
12 Cyclohexane/Water
umber (at 2
8
HLB nu
4
Water/Cyclohexane
0
0 30 60 90 120
Phase Inversion Temperature (oC)

Particles as emulsion stabilizers
Liquid 1
(oil)
r
θ θ
h
Liquid 2
(water)
Almost all particles are only partially wetted by either phase.
When particles are “adsorbed” at the surface, they are hard to
remove – the emulsion stability is high, sometimes thousands of kT.
Crude oil is a W/O emulsion and is old!!

Stabilityy as a function of contact angle
g
12000
ΔF2 ΔF1
ΔFddesorption / kT
9000
6000
3000
0
0 30 60 90 120 150 180
θ
The thermodynamics is rich
Figure 7. Sketch of a particle of radius a, which Figure 8. Definitions of phases, angles, and emulsions: By
is bridging between the surfaces of a film from definition the particles are initially dispersed in phase 2
definition, 2. The
phase 2 formed between two drops of phase 1. h contact angle, õ, is always measured across phase 2. The
is the film thickness. õ is the contact angle. emulsion 1-in-2 is a Bancroft-type emulsion, in which the
particles are dispersed in the continuous phase. In contrast, the
emulsion 2-in-1 is of anti-Bancroft type.
P A.
P. A Kralchevsky,*,†
K l h k * † II. B
B. IIvanov,†
†KK. P
P. A
Ananthapadmanabhan,‡
th d bh ‡ and
dAA. Li
Lips‡
‡ L
Langmuir
i 2005,
2005 21,
21 50-63
50 63

Wax dispersed
p with fumed silica
Hydrophilic silica stabilizing a wax/water emulsion
Figure 1. Microscopic image of a paraffin- Figure 3.

Fi 3 Microscopic
Mi i image
i off a paraffin-in-water
ffi i t
in-water emulsion stabilized by CTAB emulsion stabilized by P2 particles. Inset: same image
alone. T ) 25 °C. taken at T ) 25 °C under crossed polarizers, confirming
the presence of crystals
in the droplets.
p
J. Giermanska-Kahn,† V. Laine,† S. Arditty,† V. Schmitt,† and F. Leal-Calderon Langmuir 2005, 21, 4316-4323

Bubbles stabilized with fumed silica
Hydrophobic silica stabilizing a foam in water with added salt.
Figure 1.
Fi 1 Fraction
F ti (F) off bubbles
b bbl
remaining as a function of time (t)
formed in dispersions of 1wt%of 33%
SiOR particles at different NaCl
concentrations: 3 mol dm-3 ([)
([), 2 mol
dm-3 (0), 1 mol dm-3 (2), and 0.5 mol
dm-3 (4).
Thomas Kostakis, Rammile Ettelaie, and Brent S. Murray Langmuir 2006, 22, 1273-1280

Physical
y p
properties
p of emulsions
• Identification of “internal” and “external” phases; W/O or O/W

• Droplet size and size distributions – generally greater than a
micron
• Concentration of dispersed phase – often quite high. g The viscosity,y
conductivity, etc, of emulsions are much different than the continuous
phase.
• Rheology – complex combinations of viscous (flowing) elastic (when
moved a little) and viscoelastic (when moved a lot) properties.
• Electrical properties – useful to characterize structure.
• Multiple phase emulsions – drops in drops in drops
drops, …

Variation in p
properties
p with concentration
Oil in water emulsion W/O

Polyhedral
on Property
droplets
Emulsio
Phase
Spherical droplets inversion
0 10 20 30 40 50 60 70 80 90 100
Volume Fraction Oil
The variation of properties of emulsions with changes in composition. If

inversion occurs, there is a discontinuity in properties, as they change
from one curve to the other. Above 74% there is either a phase
inversion or the droplets are deformed to polyhedra.

Conductivityy of emulsions
0 .2 5
Conducttivity (Ω m )
-11
-1 0 .2 0
0 .1 5
O /W
0 .1
10
0 .0 5 W /O
0 .0 0
0 20 40 60 80 100
P h e n o l (% V o lu m e )
Phenol in water Inversion Water in

zone Phenol
The specific conductivity of aqueous potassium iodide and phenol

emulsions
l i as a ffunction
ti off composition
iti (Manegold,
(M ld p. 30).
30)

Interfacial viscometer
Torsional wire
supporting bicone.
se r
La
Light reflects
off
ff mirror
i into
i t Position Detector
detector.
Mirror
Bicone suspended
at oil/water
interface.
Stepping
motor

Rheology
gy of O/W interfaces
By single-particle tracking
For viscous liquids:
k BT
Δr 2 (τ ) = 4 Dτ where D =
4πη a
Δr 2 (τ ) = 4 Dτ where D =
k BT For elastic liquids:
4πη a
2 k BT
Δr 2 =
3π aG′
The particles have to sit properly

at the O/W interface.
Wu and Dai, Langmuir, 23, 4324 – 4331, 2007.

Making emulsions
Method of phase e.g. Use a poor O/W emulsifier, go to
i
inversion
i hi h volume
high l ffractions,
ti th
the emulsion
l i
inverts to smaller droplets of W/O
Phase-inversion- e.g. Heat and emulsify O/W 2-4o below
temperature method the PIT, creates low σ and small drops,
cool to room temperature.
Solubilize vapor in The energies driving the condensation,
micelles drive Ostwald ripening, therefore a
formulation challenge.
Electric emulsification Charging
g g the surface p
produces
electrohydrodynamic instabilities.
Intermittent milling Surfactant adsorption is slow – waiting
helps.

Breaking emulsions
Creaming Especially with a centrifuge, taking
advantage of temperature and salt.
Mechanical Sometime high shear; filtering through

bed whose surfaces are wetted by
i t
internal
l phase;
h ultrafiltration;
lt filt ti di
dialysis;
l i
Thermal Most emulsion a less stable hot; At the
PIT many are quite unstable; freeze-
thaw.
Chemical Chemically change the emulsifier;
mismatch of HLB, pH; replace with
strong surfactant but not strong
emulsifier; addition of other solvents.
Menon, V.B.;
Menon V B ; Wasan,
Wasan DD.T.
T Demulsification,
Demulsification in Encyclopedia of emulsion
technology; Becher, P., Ed.; Marcel Dekker: New York; 1985, Vol. 2; pp 1-75.

Intermittent milling
Well stabilized drops

p
Mill to smaller size,

hence larger area.
Marginally
Dilute into
+ stable drops.
stable dispersion.
Continued
milling.
Smaller,
stable drops.
Unstable
drops coalesce.


Lecture 6 Emulsion Technology

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Em lsion Technology

Ian Morrison© 2009

Ian Morrison© 2009 Lecture 6 - Emulsion technology 2

*To be respectful – where can we add the “magic” of emulsion science?

Ian Morrison© 2009 Lecture 6 - Emulsion technology 3

Ian Morrison© 2009 Lecture 6 - Emulsion technology 4

Becher, P. Emulsions, theory and practice, 3rd ed.;

Ian Morrison© 2009 Lecture 6 - Emulsion technology 5

*Becher, Emulsions; Oxford; 2001, p. 291

Ian Morrison© 2009 Lecture 6 - Emulsion technology 6

A – Inversion C – Sedimentation E - Coalescence

Ian Morrison© 2009 Lecture 6 - Emulsion technology 8

ΔF = σΔA + work of desorption

If the work of desorption

Ian Morrison© 2009 Lecture 6 - Emulsion technology 9

Ian Morrison© 2009 Lecture 6 - Emulsion technology 10

Change in size distribution with aging, 0.005 M sodium oleate and

Ian Morrison© 2009 Lecture 6 - Emulsion technology 11

An emulsion system with

Ian Morrison© 2009 Lecture 6 - Emulsion technology 12

Volume fraction at various heights

2. Mixed emulsifiers (cosurfactants)

3 Temperature is important – solubility changes quickly

Ian Morrison© 2009 Lecture 6 - Emulsion technology 14

Ian Morrison© 2009 Lecture 6 - Emulsion technology 15

Ian Morrison© 2009 Lecture 6 - Emulsion technology 16

((a)) W/O/W double emulsion O/W/O double emulsion

“The emulsifier stabilizes

The long tail on the

Ian Morrison© 2009 Lecture 6 - Emulsion technology 18

Ian Morrison© 2009 Lecture 6 - Emulsion technology 19

Ian Morrison© 2009 Lecture 6 - Emulsion technology 20

3.5–6 W/O emulsifier

7–9 Wetting agent

8–18 O/W emulsifier

Ian Morrison© 2009 Lecture 6 - Emulsion technology 21

Ian Morrison© 2009 Lecture 6 - Emulsion technology 22

30oC 40oC 50oC 60oC 70oC 75oC 80oC 90oC 100oC

Water Emulsion Oil

Ian Morrison© 2009 Lecture 6 - Emulsion technology 24

Phase Inversion Temperature (oC)

Ian Morrison© 2009 Lecture 6 - Emulsion technology 25

Ian Morrison© 2009 Lecture 6 - Emulsion technology 26

Ian Morrison© 2009 Lecture 6 - Emulsion technology 28

Figure 1. Microscopic image of a paraffin- Figure 3.

Ian Morrison© 2009 Lecture 6 - Emulsion technology 29

Hydrophobic silica stabilizing a foam in water with added salt.

Ian Morrison© 2009 Lecture 6 - Emulsion technology 30

• Identification of “internal” and “external” phases; W/O or O/W

Ian Morrison© 2009 Lecture 6 - Emulsion technology 31

Oil in water emulsion W/O

Volume Fraction Oil

The variation of properties of emulsions with changes in composition. If

Ian Morrison© 2009 Lecture 6 - Emulsion technology 32

Phenol in water Inversion Water in

The specific conductivity of aqueous potassium iodide and phenol

Ian Morrison© 2009 Lecture 6 - Emulsion technology 33

Ian Morrison© 2009 Lecture 6 - Emulsion technology 34

For viscous liquids:

The particles have to sit properly

Wu and Dai, Langmuir, 23, 4324 – 4331, 2007.

Ian Morrison© 2009 Lecture 6 - Emulsion technology 36

Mechanical Sometime high shear; filtering through