Cosmetic Product Stability

Product Stability
or How to make sure your product stays as good as new
John Woodruff
Creative Developments (Cosmetics) Ltd
www.creative-developments.co.uk
Product Stability
What is it?
How do we test it?
How can we improve it?
2
Product Stability
What is it?
How do we test it?
3
Definition of Stability
In mathematics, stability theory addresses the

stability of solutions of differential equations and
of trajectories of dynamical systems under small
perturbations of initial conditions.
In probability theory, the stability of a random
variable is the property that a linear combination
of two independent copies of the variable has
the same distribution, up to location and scale
parameters. ...
John Woodruff; Creative Developments
(Cosmetics) Ltd.
- the quality of being enduring and free

from change or variation
- resistant to change of position or
condition
- firm and dependable; subject to little
fluctuation
- not taking part readily in chemical
change
(Cosmetics) Ltd.
What do we understand about it with regard to

cosmetic products?
That a product remain fit for purpose
Appearance
Purity including lack of microbial contamination
Efficacy
That it remains fit for purpose for a period of not

less than 36 months from manufacture and not
less than its PAO declaration
(Cosmetics) Ltd.
Examples of Instability
Obvious
Emulsion breakdown
Perfume changes
Colour changes
Viscosity changes
Fungal growth
Wax crystallisation
Sediment in clear lotions
(Cosmetics) Ltd.
Less Obvious
pH changes
Loss of activity
Vitamins
Antioxidants
Enzymes
Preservatives
Photo-degradation of UV filters
Microbial growth
(Cosmetics) Ltd.
Emulsion Creaming
10

(Cosmetics) Ltd.
Emulsion Breakdown
4 days at room temperature
1 month at room temperature
1 month at 45C
1 month at 45C
11

(Cosmetics) Ltd.
Viscosity Changes
Increasing
Decreasing
Stable
70
60
50
40
30
20
10
0
Initial
12
5 days
10
15
20
25
30 days

(Cosmetics) Ltd.
Worst Nightmare!
Atmospheric Mould Colonies
13

(Cosmetics) Ltd.
Crystal Growth
14

(Cosmetics) Ltd.
Product Stability
What is it?
How do we test it?
15
Testing for Stability
Prepare a pilot batch and store it in its

retail packaging and check that it remains
fit for purpose for a period of not less than
36 months from manufacture and not less
than its PAO declaration!
Impractical
What other options?
16

(Cosmetics) Ltd.
Testing Schedules
Examples of suitable schedules are given

in the IFSCC Monograph
Boots publishes a scheme that its

suppliers are expected to use - GR10
Distance Learning Course (DLC) includes

suggestions in its module on stability
17

(Cosmetics) Ltd.
Testing Schedules
IFSCC Monograph
40 ambient humidity
retain as control
200 / 250 ambient humidity
60 months
370 ambient humidity
6 months
450 ambient humidity
3 months
370 & 80% relative humidity
1 month
Freeze / Thaw
Light exposure
18

(Cosmetics) Ltd.
Testing Schedules
DLC Recommendations
19

(Cosmetics) Ltd.
DLC Recommendations
1 month assessment (all storage conditions)
1 year assessment (all storage conditions)
18 month assessment (5C and RT storage conditions only)
2 year assessment (5C and RT storage conditions only)
30 month assessment (5C and RT only)
3 year assessment (5C and RT storage conditions only).
20

(Cosmetics) Ltd.
Testing Schedules
Boots recommendation - Stability and final pack compatibility of all cosmetic
and toiletry products should be assessed to establish that they are stable
and that no separation, crystallisation, contamination, degradation or other
instability occurs within the claimed product shelf life
Must be safe to use,
effective
and stable in final pack
for at least 36 months at:
Must be safe to use,

effective
and stable in final pack
for at least 3 months at:
Products sold in temperate

climates
0C to 23C
30C
Products sold in tropical

climates
0C to 30C
40C
Stability Requirements
Product must also be safe to use within their specified Period After Opening (PAO),
no matter at what point in their shelf life they are first opened.
21

(Cosmetics) Ltd.
What should be checked?
22

(Cosmetics) Ltd.
23

(Cosmetics) Ltd.
What is Important
24
Consider the function of the product under test and

decide whether or not the changes observed could affect
this
Consider the safety of the product under test and decide
whether or not the changes observed could affect this
Consider whether the changes observed affect the
aesthetics of the product under test
Note under what storage conditions any changes
observed take place and try to relate these to the
environment in which the product is to be sold
Look for significant trends in changes of product
attributes
(Cosmetics) Ltd.
Talking Points
What is important for this product in this

packaging for this market?
Setting product specification
Minimum and maximum for each parameter

Why these numbers?
Have products been prepared and tested at
extreme specification limits?
Release specifications / shelf-life specifications
What matters?
25

(Cosmetics) Ltd.
Accelerated Testing for Stability

Prepare a pilot batch and store it in its retail
packaging:
26
Room Temperature (RT) for 24 months

4C for 3 months
40C for 3 months
4C/40C Cycle for a number of cycles
In a N-facing window or a light box for 3m

(Cosmetics) Ltd.

Monitor for changes in appearance
(Subjective measurements)
Homogeneity
Colour
Glass
slides
Microscope
Texture and skin feel
Odour
27

(Cosmetics) Ltd.

Monitor emulsion stability
(Physical changes)
Emulsion breakdown
Creaming or settling
28
Glass slides aeration and density/opacity

Microscope droplet size changes; crystals
Viscosity changes
Rheological changes
Centrifuge tests
Turbiscan
Lumifuge
(Cosmetics) Ltd.
Emulsion Creaming
3 months at 40C
18 months at RT
What ways are available for quicker results
29

(Cosmetics) Ltd.
Microscope Examination
30
1 month at 45C
1 month at 45C
(Cosmetics) Ltd.
Viscosity Changes
These are actual
viscosity graphs
of 5 different
w/o emulsions
differing only in
emulsifier used
31

(Cosmetics) Ltd.
Rheological Changes
For suspensions measure yield values
32
Yield value is the minimum force necessary to

induce flow
Measured using a rheometer or a Brookfield
Digital Viscometer with small sample adaptor
Yield values may be used to determine the
suspending power of a composition; very
useful when developing scrubs
http://www.connock.co.uk/articles_exfoliants.htm
(Cosmetics) Ltd.
Accelerated Stability Testing
Centrifuge
Ultracentrifuge
33
5 minutes or more at 5,000 rpm

A centrifuge designed to run at very high speeds and
thus generate very high centrifugal force is called an
ultracentrifuge.
Suspensions which would settle only very slowly or
not at all under gravity can be made to separate
quickly in such a device!

(Cosmetics) Ltd.
The LUMiFuge
Demixing phenomena, like sedimentation, flotation or consolidation
are directly measured by the LUMiReader, LUMiFuge or
LUMiSizer due to the patented cutting-edge STEP-Technology.
This permits to obtain Space- and Time-resolved Extinction Profiles
over the entire sample length of up to 12 different samples
simultaneously. Parallel light (I0) illuminates the entire sample cell
and the transmitted light I is detected by thousands of sensors
arranged linearly across your whole sample from top to bottom with
a microscale resolution. Transmission is converted into extinction by
lg I/I0 and particle concentration may be calculated.
www.lum-gmbh.com/pages/.../lumifuge/products_lumifuge.htm
34

(Cosmetics) Ltd.
The LumiFuge
The multisample
analytical centrifuge
LUMiFuge accelerates
the demixing process up
to 2300 times compared
to traditional test tube
tests. Stability tests and
shelf-life determinations
of original dispersions are
up to 2500 times faster
than performed in a test
tube under earth gravity.
http://www.lum-gmbh.com/pages/products/lumifuge/products_lumifuge.htm
35

(Cosmetics) Ltd.
Turbiscan
The Turbiscan
measures transmitted
and reflected light
passing through a
sample and graphs the
results. Differences
over time are due to
changes in droplet size
and distribution
www.formulaction.com/stab_lab_gb.htm
36

(Cosmetics) Ltd.
Principle of Measurement
Particle migration
Sedimentation or creaming
Particle size variation

Coalescence or flocculation
t=0 min
t=0 min
t=15 min
t=15 min

Monitor chemical changes
pH
Loss of activity
Vitamins
Antioxidants
Enzymes
Preservatives
UV Filters
38
Photo-degradation of UV filters
(Cosmetics) Ltd.

Monitor preservative efficacy
Initial challenge test to accepted protocols
Head space test
CTFA, CTPA, B.P. and European Pharmacopoeias

It is recommended that this be done if widemouthed container is used to assess risk of mould
and fungal growth
Challenge testing of stability samples

It is recommended that this be done after 3 months
stability testing at RT and 40C
39

(Cosmetics) Ltd.
Packaging Compatibility
STRESS CRACKING - The Hedley Test
Applied to detergent/oil based products which
are contained in polythene, PVC, PET.
12 samples filled to the declared volume and
closure fitted to the correct torque.
Stored at 60C for 48 hours, 6 upright and 6
inverted.
At the end of the test no containers should show
any signs of cracking.
40

(Cosmetics) Ltd.
Packaging Problems
Panelling of polyethylene
Dissolving of PVC
Oils causing brittle polystyrene
Corrosion of aluminium
Discolouration of plastic
Transpiration of perfume through plastic
Absorption of actives by pack wall
41
Etc.
(Cosmetics) Ltd.
Product Stability
What is it?
How do we test it?
42
Emulsion Stability
A two-phase system, consisting of two

completely immiscible or partially miscible
liquids, one being dispersed in the other in
the form of very fine droplets
Water-in-Oil = w/o
Oil-in-Water = o/w
Oil-in-Water-in-Silicone = o/w/Si
43

(Cosmetics) Ltd.
Emulsion Stability
What makes it stable?
44
Correct choice of emulsifier system

Compatible ingredients
Compatible pH
Correct mixing method
Compliance with specification
Compatible packaging
Understanding possible causes of instability
(Cosmetics) Ltd.
Emulsion Stability
45

Compatible pH
(Cosmetics) Ltd.
HLB System
HLB Number = E + P
5
where
E = molecular weight percent of ethylene oxide content
P = molecular weight percent of polyol content
In the equation above the value (E+P) can take on any
value up to a maximum of 100. This means that the HLB
number assigned to the emulsifier will lie within the
range of 0 to 20.
46

(Cosmetics) Ltd.
HLB System
HLB number of surfactant and type of
emulsion formed
< 3 none
3 8 water-in-oil (W/O)
8 15 oil-in-water (O/W)
> 15 solubilisation
47

(Cosmetics) Ltd.
Liquid Crystals
Some emulsifier systems form liquid crystal structures,
which contribute to stability
Examples:
Cetearyl glucoside with cetearyl alcohol
Sorbitan olivate and cetearyl olivate
Sorbitan stearate with sorbityl laurate
Sorbitan stearate with sucrose cocoate
Polyglyceryl-3 methylglucose distearate
Potassium cetyl phosphate and hydrogenated palm
glycerides
Lauryl glucoside & polyglyceryl-2 dipolyhydroxystearate
48

(Cosmetics) Ltd.
Liquid Crystal Emulsion
49

(Cosmetics) Ltd.
Liquid Crystal Emulsion
50

(Cosmetics) Ltd.
Other Emulsifiers
51
Polymers e.g. Acrylates/C10-30 Alkyl Acrylate

Crosspolymers
Polyethylene glycol ethers (Oleth-10; Laureth-10 etc)
Polysorbates with Sorbitan esters e.g. Polysorbate-20
with Sorbitan monolaurate
Glyceryl esters e.g. Glyceryl cocoate / laurate etc.
Alkolylated dimethicones (AKA Dimethicone copolyols)
Soaps e.g. triethanolamine stearate; Potassium
peanutate etc.
PG Esters e.g. Propylene glycol myristate etc.
Sucrose esters e.g. Sucrose laurate / myristate etc
(Cosmetics) Ltd.
Emulsion Stability
52

Compatible pH
(Cosmetics) Ltd.
Incompatible Ingredients
Carbomers and salts
Kathon CG contains a salt
Dihydroxyacetone and formaldehyde
Many preservatives are formaldehyde donors
Enzymes and chelating agents
EDTA and its salts

Parabens
Ethoxylated emulsifiers
53
etc. etc.
(Cosmetics) Ltd.
pH vs Viscosity
Typical carbomer system
100000
98000
96000
94000
92000
Viscosity
90000
88000
86000
84000
pH 5.0 pH 5.5 pH 6.0 pH 6.5 pH 7.0 pH 7.5 pH 8.0
54

(Cosmetics) Ltd.
Correct Mixing Methods

Use laboratory
mixing equipment
which represents
that available
in the factory
55

(Cosmetics) Ltd.
Pilot Scale
56

(Cosmetics) Ltd.
Correct Mixing Methods
57

(Cosmetics) Ltd.
Compliance with Specification
How was the specification set?
Was stability tested on a product within

the specification set?
58
One small laboratory batch?

2 or more laboratory batches with
reproducible results?
Pilot scale batch?
Better still; were 2 or more batches at limits

of specification tested
(Cosmetics) Ltd.
Emulsion Stability
What causes instability?
For an emulsion to become unstable the
dispersed phase droplets must collide and
coalesce
Coalescence of two dispersed phase
droplets produces a bigger dispersed
phase droplet, and the ultimate outcome
of this process is complete phase
separation, indicating emulsion instability
59

(Cosmetics) Ltd.
Forces of Attraction
F = -Aa
12H
where
F = London-Van der Waals force of attraction
A = Hamaker constant
a = radius of the dispersed phase droplets
H = distance between two adjacent dispersed
phase droplets
60

(Cosmetics) Ltd.
F = -Aa
12H
Forces of Attraction
Good stuff but what does it mean for

emulsion stability
From the equation it can be seen that the
magnitude of the attractive force increases
as the radius of the dispersed phase
droplets becomes larger and less as the
distance between them is increased
Stability = Small droplets far apart
61

(Cosmetics) Ltd.
Stokes Law
Stokes Law describes the factors influencing the velocity
of a solid sphere, moving under the force of gravity, in a
continuous liquid medium
V = 2a2(cd)g
62
V = velocity of the dispersed phase droplet

a = radius of the dispersed phase droplet
d = density of the dispersed phase
c = density of the continuous phase
g = acceleration due to gravity
= viscosity of the continuous phase
(Cosmetics) Ltd.
Stokes Law: Good stuff but what

does it mean for emulsion stability
V = 2a2(cd)g
9
To improve stability reduce V
63
Reduce a - size of dispersed phase droplet

Reduce (pc-pd) by matching density of the dispersed
phase with that of the continuous phase
g = acceleration due to gravity difficult to alter
Increase - viscosity of the continuous phase
(Cosmetics) Ltd.
What droplet size?

Emulsion appearance and approximate
particle size
64
milky-white greater than 1
blue-grey 1.0 - 0.1
translucent 0.1 - 0.05
transparent less than 0.05

(Cosmetics) Ltd.
Emulsion Stability
65
Careful selection of emulsifiers

Small droplet size (High shear mixing; PIT
technology)
Lamellar structures by using emulsifiers
that form liquid crystals
Match SG of oil phase to aqueous phase
Adjust rheological properties by using
carbomers or xanthan gum, starch or CMC
derivatives etc.
(Cosmetics) Ltd.
Add Rheological Additive

0% UltraThix P-100
+ 0.5% Cerasynt 945
0.5% UltraThix P-100
+ 0.2% Cerasynt 945
0.5%
UltraThix P100
+ 0.5%
Cerasynt 945
Cerasynt 945 = Glyceryl stearate (&)
laureth-23 Ultrathix P100 =
Acrylic acid/VP Crosspolymer
66

(Cosmetics) Ltd.
Add Right Rheological Additive

Zinc Oxide nano particles
Carbomer
67

(Cosmetics) Ltd.
Microscope Examination
Titanium Dioxide Nano particles
Carbomer
68

(Cosmetics) Ltd.
Sun Protection Products

These present special problems
69
Emulsion stability
Agglomeration of micronised sunscreens
Crystallising of organic sunscreens
Failure to meet SPF declaration
Failure to meet UVA requirements
Failure to meet water resistance claims
Photodegradation of actives
(Cosmetics) Ltd.

Agglomeration of micronised sunscreens can
be seen under a microscope at 1000x
magnification
70
Use rheology modifiers to stop migration of

particles Veegum is good. Acrylic acid/VP
Crosspolymer is recommended

(Cosmetics) Ltd.
Preventing Agglomeration
TiO2 Nano particles
Zinc Oxide nano particles

71

(Cosmetics) Ltd.
Crystallising of Organic Sunscreens

Check solubility in oil phase
If using Phenylbenzimidazole Sulfonic Acid

pH 7.3 - 7.7 is critical
72

(Cosmetics) Ltd.
Photodegradation of BMDBM
73

(Cosmetics) Ltd.
Improve UV Absorber Stability
The UVA filter BMDBM is not photostable and may lose 60% or
more of its activity at 360nm when exposed to solar radiation.
EHMC destabilises BMDBM / octocrylene mixtures
Benzophenone-3 stabilises BMDBM weakly; octocrylene stabilises

EHMC strongly but does not stabilise BMDBM and ethylhexyl
methoxycrylene stabilises BMDBM strongly.
There is a relationship between the rate of photo decay of BMDBM

and the dielectric constant of the oil phase. As the dielectric
constant increases BMDBM is progressively more stable until it
reaches maximum stability at about 8.8, after which its rate of
decay increases again
74

(Cosmetics) Ltd.
Failure to meet SPF declaration
Failure to meet UVA requirements
http://www.creative-developments.co.uk/papers/
http://www.cosmeticsbusiness.com/section.asp?navcode=50
Dont put to much faith in SPF boosters
Use the Ciba Sunscreen Simulator then in-vitro then in-vivo
http://www.ciba.com/index/ind-index/ind-per_car/ind-pc-uv/ind-pc-uv-sss.htm
75
Study the suppliers literature and many articles on the

subject
Make sure the formula complies with latest EU

Recommendation (UVA =>1/3rd UVB)

(Cosmetics) Ltd.
Thank you for your time

and may all your creations
be stable
John Woodruff
www.creative-developments.co.uk
76

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Product Stability

or How to make sure your product stays as good as new

In mathematics, stability theory addresses the

- the quality of being enduring and free

What do we understand about it with regard to

That it remains fit for purpose for a period of not

John Woodruff; Creative Developments

4 days at room temperature

1 month at room temperature

1 month at room temperature

John Woodruff; Creative Developments

John Woodruff; Creative Developments

Atmospheric Mould Colonies

John Woodruff; Creative Developments

John Woodruff; Creative Developments

Testing for Stability

Prepare a pilot batch and store it in its

John Woodruff; Creative Developments

Examples of suitable schedules are given

Boots publishes a scheme that its

Distance Learning Course (DLC) includes

John Woodruff; Creative Developments

200 / 250 ambient humidity

370 ambient humidity

450 ambient humidity

370 & 80% relative humidity

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

Must be safe to use,

Products sold in temperate

Products sold in tropical

John Woodruff; Creative Developments

What should be checked?

John Woodruff; Creative Developments

John Woodruff; Creative Developments

Consider the function of the product under test and

What is important for this product in this

Minimum and maximum for each parameter

John Woodruff; Creative Developments

Accelerated Testing for Stability

Room Temperature (RT) for 24 months

John Woodruff; Creative Developments

Testing for Stability

John Woodruff; Creative Developments

Testing for Stability

Glass slides aeration and density/opacity

What ways are available for quicker results

John Woodruff; Creative Developments

4 days at room temperature

1 month at room temperature

4 days at room temperature

1 month at room temperature

John Woodruff; Creative Developments

For suspensions measure yield values

Yield value is the minimum force necessary to

Accelerated Stability Testing

5 minutes or more at 5,000 rpm

John Woodruff; Creative Developments