SCS Summer School 2014

Emulsion
Technology
Russell Cox
 What is an emulsion?

• A dispersion of one or more immiscible liquid

phases in another, the distribution being in
the form of tiny droplets
 What is an emulsion?

• Emulsions are metastable –from a

thermodynamic standpoint they can exist in a
form that is not the state of lowest energy

• Gibbs stated that “the only point in time

where an emulsion is stable, is when it is
completely separated”
 Gibbs free energy equation
∆𝐺 = 𝛾𝐴 − 𝑇∆𝑆
ΔG is free energy of emulsification
γ is the interfacial tension
A is the interfacial area
T is temperature
ΔS is entropy of mixing

If ΔG is positive, the spontaneous emulsification is unlikely

If ΔG is negative, spontaneous emulsification will likely occur
The closer ΔG is to zero, the easier the formation of an
emulsion
 Simple emulsion types
Oil-in-water Water-in-oil

Water
Oil
(continuous phase)
Oil droplet (continuous phase) Water droplet
(dispersed phase) (dispersed phase)
 Emulsion orientation
• The phase that is added tends to become the internal
phase

• The predominant solubility of the emulsifier tends to

determine the external phase (Bancroft’s rule)

• Generally, the phase of the greatest volume tends to

become the external phase

• The phase in which the stirrer is placed tends to become

the external phase
 Identification of emulsion type
• Feel
• O/W emulsions tend to have a lighter feel than W/O

• Dispersibility
• Tested by dropping a small amount of emulsion in water –
O/W disperses easily while W/O remains whole

• Conductivity
• O/W emulsions conduct electricity well showing high levels
of conductance

• Dye penetration
• Water soluble dye is easily taken up in O/W system but not
in W/O
 Droplet size measurement
Laser method Laser Particle Analyser

Audio method Use of sound waves

(Malvern)

Optical method
 Microscopy
Uses

• Droplet size and size distribution

• Quality of manufacturing process e.g. undispersed
thickener
• Detecting unwanted crystallisation
• Early indications of instability e.g. flocculation,
coalescence, synerisis
• Comparison of different emulsions
• Liquid crystals
What does an emulsion look like?
What does an emulsion look like?
What does an emulsion look like?
Emulsifiers
 What is an emulsifier?

Water loving Oil loving

head tail

'Hydrophilic' 'Lipophilic'
'Lipophobic' 'Hydrophobic'
 What is an emulsifier?
• An emulsifier is a surface active agent with an
affinity for both the oil and the water phases on
the same molecule

• An emulsifier reduces the surface tension at the

oil / water interface and protects the newly
formed droplet interfaces from immediate
coalescence
 Droplet structures
 Within a droplet structure the emulsifier forms
a monomolecular layer on the surface of the
droplet
 The orientation of the emulsifier depends on
the type of emulsion formed

Oil - in - water
Water - in - oil
 Improving emulsion stability
Clearly the ability of the emulsifier to completely cover
the surface area of the droplet will be dependent on;

• The concentration of emulsifier in the formulation

• The size of the emulsifier
• The size of the droplet

Good coverage is vital to ensure longer term stability

 Types of emulsifiers
Anionics

The emulsifier carries a negative charge e.g. Sodium

Stearate soap

C H COO - Na +
17 35
 Types of emulsifiers - Anionic

Pros and Cons

• Were very common

• Old fashioned
• Not as versatile
• Cheap
• Limitations for actives due to high pH
• Give negative charge to the oil droplet
 Types of emulsifiers
Cationic

The emulsifier carries a positive charge e.g.

Palmitamidopropyl Trimonium Chloride

O CH3
+ _
CH3(CH2)14C NH(CH2)3 N CH3 Cl
CH3
Types of emulsifiers - Cationic

Pros and Cons

• Usage is not high in Skincare

• Good barrier
• Excellent silky skin feel
• Give positive charge to oil droplet
• Can be used at lower pH
 Types of emulsifiers

Non-ionic
Emulsifier carries no overall charge and can be
made to form both Water-in-oil or Oil-in-water
emulsifiers e.g. Steareth-2

CH3 (CH2 )16 CH2 (OCH2 CH2)2 OH

Types of emulsifiers - Non-ionic

• Most common
• Wide range
• Versatile
• Strengthen the emulsion interface
• HLB system to predict choice
HLB system and selecting
emulsifiers
 HLB system

Hydrophile / Lipophile Balance

 HLB system

0 10 20

Lipophilic Hydrophilic
Oil loving Water loving
Non polar Polar
Oil soluble Water soluble
 HLB system

Emulsifier HLB 5 Water

phase

Emulsifier HLB 10

Oil Emulsifier HLB 15

phase
 Determining HLB value
• Calculate the water loving portion of the surfactant on
a molecular weight percent basis and then divide that
number by 5
• Dividing by 5 keeps the HLB number scale limited to a
maximum of 20 which makes the scale smaller, thus a
bit more manageable
• Once calculated assign this number to the non-ionic
surfactant
• This assigned number is the HLB VALUE

Source: Croda presentation (Croda’s time saving guide to emulsifier selection) 1

 Determining HLB value
• Run a simple practical test based on nine small
experiments
• Materials needed for this test:
• an HLB “kit”
• about 200 grams of your oil
• eight small jars
• the instructions
• and a little bit of time (actually a lot of time!)

Source: Croda presentation (Croda’s time saving guide to emulsifier selection) 1

 Determining HLB values

Source: Uniqema/ Croda2

 Determining HLB value

• Look at your formula

• Determine which are the oil soluble ingredients
– this does not include the emulsifiers
• Weigh each of the weight percents of the oil phase ingredients
together and divide each by the total
• Multiply these answers times the required HLB of the individual
oils
• Add these together to get the required HLB of your unique
blend

Source: Croda presentation (Croda’s time saving guide to emulsifier selection) 1

 Determining HLB value
• A simple O/W lotion formula
• Mineral oil 8%
• Caprylic/capric triglyceride 2%
• Isopropyl isostearate 2%
• Cetyl alcohol 4%
• Emulsifiers 4%
• Polyols 5%
• Water soluble active 1%
• Water 74 %
• Perfume q.s.
• Preservative q.s.

Source: Croda presentation (Croda’s time saving guide to emulsifier selection) 1

 Determining HLB value
• Mineral oil 8 / 16 = 50%

• Caprylic/cap. trig. 2 / 16 = 12.5%

• Isopropyl isostearate 2 / 16 = 12.5%

• Cetyl alcohol 4 / 16 = 25%

Source: Croda presentation (Croda’s time saving guide to emulsifier selection) 1

 Determining HLB value

Oil phase contribution X required equals

ingredient HLB of
ingredient
Mineral oil 50.0% 10.5 5.250

Caprylic cap. 12.5% 5 0.625

Trig.
Isopropyl 12.5% 11.5 1.437
isostearate
Cetyl alcohol 25.0% 15.5 3.875

Total 11.2

Source: Croda presentation (Croda’s time saving guide to emulsifier selection) 1

 Emulsifier selection using HLB

• Oil phase components can be given required HLB

values

• Required HLB and emulsifier HLB are matched up

• Each oil will have 2 required HLB’s, one for oil-in-water

emulsions, the other for water-in-oil emulsions

• The required HLB is published for some oils

 Emulsifier blends

In the HLB system the HLB of the emulsifier blend is

additive for example if an oil system had a required
HLB of 10 you could use either

Emulsifier Emulsifier Emulsifier

HLB 10 or HLB 5 HLB 15
 Emulsifier blends
For a given blend of non-ionic emulsifiers, where
Emulsifier A is more lipophilic than Emulsifier B

Emulsifier A Emulsifier B

Oil Oil

Tighter packing
at interface
Considerations when choosing an
emulsifier

 Type of emulsion
 Oils to be emulsified
 Processing - hot or cold
 Effect on skin
 Properties of the emulsion
 Cost
 Level of electrolyte
 Potential irritation
• Emulsifiers, since they are surface
active, may be a factor in increasing the
risk of irritation

therefore

• Excessive levels of emulsifier should be

avoided
 HLB Summary
• Pros • Cons
– Not good for anionics and
– Empirical system
cationics
giving starting
– Need to know HLB of oil
position which can vary
– Can be assessed – Can be time consuming
practically working out or measuring
– Does not determine the
amount of emulsifier
needed
Nothing can go wrong – can it?
 Nothing can go wrong – can it?
• Emulsions are thermodynamically unstable
• This means that their natural tendency is to
revert to a state of least energy i.e. separated into
two layers
• The process of emulsification is to produce
droplets but also to maintain them in this state
over a reasonable shelf life
• Accelerated stability testing may reveal some of
the following horrors…
PHASE
INVERSION
Factors that contribute to emulsion
instability

 Forces of attraction between droplets

 Gravity

 Random movement of droplets

 Creaming / Sedimentation
• No change in droplet size
• Reversible
• Driven by density difference
• Usually results from gravitational forces

Creaming Sedimentation
 Stokes’ Law

Defined as:-

Velocity of droplet (v) = (2a2 g (ρ1 – ρ2)) / 9η

Where
a = Radius of dispersed phase droplet
ρ1= Density of continuous (external) phase
ρ2 = Density of continuous (internal) phase
g = Acceleration due to gravity
η = viscosity of the continuous (external) phase
 Coalescence

• Not reversible
• May lead from flocculation, creaming /
sedimentation or Brownian motion
• Involves 2 drops coming together

• May lead to complete separation

 Coalescence

Coalescence increases if:-

• Fat or ice crystals present

• Viscosity of continuous phase is decreased
• Emulsion is agitated
• Interfacial viscosity is decreased
 Van der Waals forces
Defined as

𝐴𝑎
𝐹=−
12𝐻
Where

F = Van der Waals forces of attractions

A = Hamaker constant
a = Radius of dispersed phase droplets
H = Distance between two adjacent dispersed phase droplets
Improving emulsion stability
• Charge stabilisation
• Interfacial film strengthening
• with powders
• with polymers
• with non-ionic emulsifiers
• Steric stabilisation
• Continuous phase viscosity
• Droplet size
• Co-emulsifiers / polar waxes
• Liquid crystals
 Improving emulsion stability
Charge stabilisation
+ +
+ + + - -+
+ - - -- + +-
- - +
+- - --
+ - - -
- - -- +- - -
--+ + + + +
+ - - + + - -
+ - - -- - - + +
+ - - +- - -
+ -- - + - - + +- -
+ + + - -
+ + + - - -- - -
- + - - -
+ + - -- + +
+ -
Negatively charged oil droplets repel each other

Stability affected by quantity of electrolyte and whether M+ or M++

 Improving Emulsion Stability

• In this system
• The negatively charged Stearate groups migrate to
the interface
• The positively charged Sodium ions in solution
(counter ions) are attracted to these now charged
droplets
• A layer is formed where the impact of the charge is
reduced
• This layer, called the Helmholtz double layer, can
reduce the repulsive effect and so stability
 Improving Emulsion Stability
Helmholtz double layer effect
+
+
- +
-
-
- + + -
- + -
- + - +
- -
+
- + -
- + - + - Water phase
Oil droplet
- + - +
-
- + - +
- +
- + -
- +
- - +
- +
-
+ - +

Electrical double layer

 Improving Emulsion Stability
• The double layer is likely to be more diffuse the further
away from the droplet you go (Gouy and Chapman and
Stern)
• Can the same happen for cationic and non-ionic
emulsifiers?
• The effect is impacted by the presence of electrolytes
• Adding electrolyte increases instability by reducing the
shielding effect
• The extent of this depends on the amount of
electrolyte added and the valency of the electrolyte
 Improving emulsion stability
• Interfacial film strengthening
• Reduces the probability of coalescence when
droplets collide
 Improving emulsion stability
Interfacial film strengthening
• with powders

Powder particle size must be

very small

Powder must have an affinity for

both the oil and water phase
Improving emulsion stability
Interfacial film strengthening
• with polymers

Polymer sits at emulsion interface

Polar groups orient into the water phase

e.g. Cetyl PEG/PPG-10/1 Dimethicone

Acrylates/vinyl isodecanoate
crosspolymer
Improving emulsion stability
Interfacial film strengthening
• with non-ionic emulsifiers

Interface strengthening is
dependent
on the number of molecules that
are packed into the interface
Oil

Tighter packing
at interface
Interface stabilisation using non-ionic
emulsifiers
• Stabilises both oil-in-water and water-in-oil emulsions
through reducing interfacial forces
– Aids dispersion
– Reduces particle size

• Appropriate blends optimise stabilisation

– Reducing the energy imbalance
– Providing a barrier to coalescence
Steric stabilisation
• Polymer molecules adsorb on
the surface of oil droplets,
leaving tails and loops
extending into the water phase
• Polymer molecules must be
strongly adsorbed at interface
• There must be high coverage of
droplet surface with polymer
• The 'tails and loops' must be
soluble in the water phase
• e.g. Cetyl PEG/PPG-10/1
Dimethicone
Improving emulsion stability
• Continuous phase viscosity
• Thickening the water phase restricts
movement of oil droplets
• Thickeners with yield points are most
effective

• Droplet size

Increasing stability
Improving emulsion stability
• Co-emulsifiers / polar waxes
• e.g. Cetyl alcohol
• Co-emulsifiers have weaker surface activity
than primary emulsifiers
• Adds body and helps prevent coalescence
Stability testing -available tests
• Freeze thaw cycling
• Accelerated stability testing
• Tests at various temperatures
• Good guidance at www.ich.org

• Ultra centrifuge
• High speeds (>25,000 rpm) required

• Visual assessment
• As part of other techniques
• Use microscope
 Stability testing
• Low shear evaluation

• Use sophisticated rheology machines

• Shake for several days

• Other tests as required

• Light
• Humidity
• Microbiological
 Stability testing

 Examining stability samples

 Actual pack and clear container samples

 Visual assessment in pack
 Microscopic assessment
 Viscosity, pH etc
Emulsion manufacture
 How are emulsions formed?
 In order to overcome the barrier between the oil
and water we need to add energy
 This is derived from two sources:-

Chemical energy + Mechanical energy

(emulsifier) (homogeniser)

 For long term stability both forms are needed

Two key requirements for creating
a stable emulsion
 Apply enough energy to the two phases to
create a dispersion

 Stabilise the created dispersion

 Maintain a small droplet size

 Increase the external phase viscosity to reduce
movement
 Reduce phase density difference
Two stages of creating an emulsion
Stage 1 – apply energy to the two phases to
create a dispersion
 Generally heat to 70 - 75°C

Stage 2 – stabilise the created dispersion

 Maintain the small droplet size
 Increase the external phase viscosity
 Reduce phase density difference
 Emulsion manufacture
 Heating to this temperature can change the
level of the oil phase e.g. Cyclomethicone
 If you need to add sensitive ingredients hot e.g.
sunscreens, then do it just prior to
emulsification
 Watch out for tea breaks and shift changes and
build these into your considerations!
 Avoid post emulsification addition of
preservatives etc that partition between oil and
water
 Emulsion manufacture
 After cooling the remaining ingredients are
added e.g. heat sensitive preservatives,
perfumes.
 For W/O emulsions if you have to add
preservatives these MUST be added prior to
emulsification
 Only Oil-in-water emulsions can be made to
weight easily
 BUT you must start thinking about scale up
from the first formulation attempt
 Emulsion manufacture
 Laboratory  Factory
– Oil phase added with – Oil phase added with
Silverson mixing gate stirring followed
by homogeniser
mixing
Size and distance

– Beaker placed in – Cold water passed

bowl of cold water through water jacket
and stir cooled with gate stirring

Takes approx 15 min Takes hours!

Emulsion manufacture
Emulsion properties
 Phase ratio
 In simple terms the ratio of one phase to
another
 BUT, in order to accurately describe the phase
ratio you need to know the type of emulsion
you are dealing with so

 For an o/w emulsion a 30:70 ratio is 30% oil/

70% water
 But for a w/o emulsion the opposite is true!
 Phase inversion
 It is possible to influence the orientation of an
emulsion in a number of ways including
 Change the phase ratio of the emulsion
 Influencing the behaviour of the emulsifier in the
emulsion
 Phase inverted emulsions tend to have smaller
particle size and so improved chances of
longer term stability
 Often used in wipes systems where low
viscosity is required
 Phase inversion - phase ratio
 In practical terms this could happen if

 Phases are mixed opposite to convention

e.g. adding water to oil is expected to give a
water in oil emulsion but could give oil in
water
 Deliberately making a water in oil emulsion
then adding water to increase the internal
phase and causing inversion e.g. low
energy emulsification
 Phase Inversion Temperature
(PIT)
 Occurs in some non-ionic emulsifier systems

 Linked to solubility of emulsifier in the

respective phases
 At different temperatures
 In the presence of electrolyte

 Mostly used to transition water in oil to oil in water

at a given temperature to produce desired small
particle size
 Phase Inversion Temperature
(PIT)
 Unique for any given emulsifier or blend of
emulsifiers

 Useful for explaining behaviour of emulsion

systems

 Helps to understand formation of differing types

of emulsion observed for a given blend of
emulsifiers
 Phase Inversion Temperature
 Within the marked band a complex three phase
mixture is found
 Above TU a W/O emulsion exists, below TL O/W
 This temperature and band will be different for
different systems
75o

TU
Temperature oC

2 phase

T 3 phase 1 phase

2 phase
TL

0o
Source: Kahlweit4
0 % emulsifier blend 20
 Phase Inversion Temperature
 Why might this be the case?
 Solubility of ethoxylated emulsifiers
increases with increasing ethoxylation
Solubility

8 20
Number of ethoxylate groups
 Phase Inversion Temperature
 Bancroft’s rule suggests that the emulsion
formed will depend on where the emulsifier is
most soluble
 Oil in water where most water soluble (hydrophilic)
 Water in Oil where most lipid soluble (lipophilic)
 Consequently changes the effective HLB observed

 By correct choice of emulsifier conversion from a

W/O to an O/W is possible
 Emulsion rheology
• Shear deformation Shear Deformation

• Is a change due to force

F being applied across
the top surface of area A.
• The ratio of force F to
area,A gives us a shear
stress across the liquid
• The liquid's response to
this applied shear stress
is to flow
 Emulsion rheology
• Shear deformation
Shear Deformation
• The medium behaves as
a pack of cards
• At velocity V the liquid
spread and thins (T falls)
• It is this velocity gradient
that gives us the shear
rate
• Viscosity is simply the
ratio of the shear stress
to the shear rate
Emulsion rheology
 Emulsion rheology
 Thixotropy
 Reduced viscosity when shear applied
 Viscosity recovers when shear removed
 Dilatancy
 Increased viscosity when shear applied
 May recover when shear removed
 Shear thinning
 Complete loss of viscosity when shear or
excess shear applied
 Emulsion rheology
• A detailed study can yield information about

• Predicted stability

• Flow
• during application
• during pumping
• time dependency
• effect of temperature on
 Emulsion rheology

http://en.wikipedia.org/wiki/File:Rheometer.jpg accessed 6 July 2010

 Emulsion rheology
 Can pictorially describe the properties that the
emulsion might exhibit
Complex Modulas,
1
G* (Pa)
1000
900
800
700
600
500
Rate Index (from Power
400 Significant Yield Stress Pa (x10)
Law model)
5 300 2

200
100
0

4 3
Viscosity with Shear Phase Angle, Delta (x100)
(rubbing) Pa (x1000)
 Emulsion rheology
 Observed rheology is linked to extent of
continuous phase
 Large, major continuous phase/ small
dispersed phase
 Properties similar to that of continuous

phase
 Small continuous phase/ large dispersed
phase
 Interparticle reactions more important

 High resting viscosity observed

 Exhibits yield point

 Emulsion rheology
 Electroviscous effect
 The apparent increase in viscosity when

shear is applied to charged particles

 Pulling charged particles between two others

requires greater force

-
-
-
 Sources and further reading
1. “Croda’s time saving guide to emulsifier selection” - training course
available from Croda PLC
2. www.crodalubricants.com/download.aspx?s=133&m=doc&id=267
accessed 22 June 2009
3. Uniqema technology training document (unpublished)
4. Kahlweit M: Microemulsions, Science 29 April 1998, p671-621