Emulsion technology

SCS Summer school July 13,

2013

Steve Boothroyd
Thinking about how you would develop
any sort of product what are the key
things you should consider during
development?
My thoughts in no particular order of
importance

Does your Consumer love it?

Does it meet the Claims you want to
make for it?
Is it safe?
Is it stable?
Can you make it on a larger scale
consistently?
Can you afford it?
Does you consumer love it?

Why would you choose to use an

emulsion instead of another
technology?

Take a few minutes in your tables to

come up with 5 possible answers
Does you consumer love it?
Possible answers…

•They feel good!

•You can pack different actives in different
phases
•You have the option to change lots of things
•They can take a range of formats
•They are cost effective
 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?

A dispersion of one or more

immiscible liquid phases in another,
the distribution being in the form of tiny
droplets.
 Simple emulsion types
Oil-in-water Water-in-oil

Water
(continuous phase) Oil
(continuous phase) Water droplet
Oil 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
 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?
What don’t you want to see?
 Is it Stable?

What are the stability risks

associated with emulsions?

Take a few minutes in your tables to

come up with some possible answers
 Is it Stable?
What are the stability risks associated
with emulsions?

•Creaming
•Sedimentation
•Flocculation
•Coalescence
•Phase Inversion
•Ostwald Ripening
 Is it Stable?
Why is that?

•Emulsions are thermodynamically unstable

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

Creaming Sedimentation
 Coalescence

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

• May lead to complete separation

 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
 Van der Waals forces
Defined as

F = - Aa
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
 Is it Stable?

What can these two equations tell us

that will help us make formulating
decisions to improve stability?

Take a few minutes in your tables to

come up with some possible answers
• From Stokes’ Law
• Thicken the continuous phase. This increase η
and reduces the velocity
• Reduce the particle size by greater or more
effective mixing.This has a major effect as a is
squared
• Reduce the difference in specific gravity
between the phases
• Additionally from Van der Waal
• Increase the distance between droplets either
through thickening the water phase to reduce
mobility, reducing particle size, or introducing
materials that avoid droplets getting too close
e.g. polymers
 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
• 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
Oil are packed into the interface

Tighter packing
at interface
 Improving emulsion stability
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
 Is it Safe?

What are the key components of an

emulsion that contribute to safety
risk?
 Is it Safe?
What are the key components of an
emulsion that contribute to safety risk?
Here are some possibilities

•Preservatives
•Fragrance
•Actives
•Emulsifiers
What is an emulsifier?

Water loving Oil loving

head tail

'Hydrophilic' 'Lipophilic'
'Lipophobic' 'Hydrophobic'
 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
• The most appropriate type of emulsfier
should be chosen
 Types of emulsifiers
• Anionics

The emulsifier carries a negative charge e.g.

Sodium Stearate soap

C H COO - Na +
17 35
 Types of emulsifiers

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

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

• Most common
• Wide range
• Versatile
• Strengthen the emulsion interface
• HLB system to predict choice
 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 values

Source: Croda ( Taken from Croda’s time saving guide to emulsifier selection” - training course available from Croda PLC)
How can you tell the difference?

• Measure conductivity – conductivity is

higher with an O/W emulsion than a W/O
emulsion
• Dye uptake - a water soluble dye will be
taken up by an O/W emulsion
• Dispersion – an O/W emulsion will easily
disperse in water
 HLB system
Required HLB for oil-in-water emulsion

Benzophenone-3 7
Mineral oil 10 - 11
Caprylic/Capric triglyceride 5
Cetyl alcohol 15 - 16
Vitamin E 6

Required HLB for water-in-oil emulsion

Mineral oil 4
 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

 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 time consuming
– Can be assessed
working out or measuring
practically – Does not determine the
amount of emulsifier
needed
 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

Tighter packing
Oil Oil 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
Can you make it on a larger
scale consistently?
What are the differences that would
impact on the manufacture of an
emulsion between lab and factory?

Take a few minutes in your tables to

come up with some possible answers
Can you make it on a larger scale
consistently?
What are the differences that would
impact on the manufacture of an emulsion
between lab and factory?

Heating/ Cooling rates

Stirring/ Shear rates
 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
• 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 30 min Can take hours!

Emulsion manufacture
 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
0 % emulsifier blend 20
Source: Kahlweit M: Microemulsions, Science 29 April 1998, p671-621
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