Cosmetic Product Stability PDF

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
1
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

4 (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
5 (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

6 (Cosmetics) Ltd.
Examples of Instability
7
Obvious
 Emulsion breakdown
 Perfume changes
 Colour changes
 Viscosity changes
 Fungal growth
 Wax crystallisation
 Sediment in clear lotions

8 (Cosmetics) Ltd.
Less Obvious
 pH changes
 Loss of activity
 Vitamins
 Antioxidants
 Enzymes
 Preservatives
 Photo-degradation of UV filters
 Microbial growth
9 (Cosmetics) Ltd.
Emulsion Creaming

10 (Cosmetics) Ltd.
Emulsion Breakdown
4 days at room temperature 1 month at room temperature 1 month at 45°C
1 month at 45°C
4 days at room temperature 1 month at room temperature John Woodruff; Creative Developments
11 (Cosmetics) Ltd.
Viscosity Changes
Increasing Decreasing Stable
70
60
50
40
30
20
10
0
Initial 5 days 10 15 20 25 30 days

12 (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 (5°C and RT storage conditions only)
– 2 year assessment (5°C and RT storage conditions only)
– 30 month assessment (5°C and RT only)
– 3 year assessment (5°C 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, Must be safe to use,

Stability Requirements
effective effective
and stable in final pack and stable in final pack
for at least 36 months at: for at least 3 months at:
Products sold in temperate

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

0°C to 30°C 40°C
climates
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
 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

24 (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:-
 Room Temperature (RT) for 24 months
 4°C for 3 months
 40°C for 3 months
 4°C/40°C Cycle for a number of cycles
 In a N-facing window or a light box for 3m

26 (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
 Glass slides – aeration and density/opacity
 Microscope – droplet size changes; crystals
 Viscosity changes
 Rheological changes
 Centrifuge tests
 Turbiscan
 Lumifuge

28 (Cosmetics) Ltd.
Emulsion Creaming
3 months at 40C 18 months at RT
What ways are available for quicker results

29 (Cosmetics) Ltd.
Microscope Examination
4 days at room temperature 1 month at room temperature

1 month at 45°C
4 days at room temperature 1 month at room temperature 1 month at 45°C

30 (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
 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

32 (Cosmetics) Ltd.
Accelerated Stability Testing
 Centrifuge
 5 minutes or more at 5,000 rpm
 Ultracentrifuge
 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!

33 (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 Particle size variation
Sedimentation or creaming 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
 Photo-degradation of UV filters

38 (Cosmetics) Ltd.
Monitor preservative efficacy
 Initial challenge test to accepted protocols
 CTFA, CTPA, B.P. and European Pharmacopoeias
 Head space test
 It is recommended that this be done if wide-
mouthed 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 60°C 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
 Etc.

41 (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?
 Correct choice of emulsifier system
 Compatible ingredients
 Compatible pH
 Correct mixing method
 Compliance with specification
 Compatible packaging
 Understanding possible causes of instability

44 (Cosmetics) Ltd.
Emulsion Stability
 Compatible pH

45 (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
 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

51 (Cosmetics) Ltd.
Emulsion Stability
 Compatible pH

52 (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 etc. etc.

53 (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?
 One small laboratory batch?
 2 or more laboratory batches with
reproducible results?
 Pilot scale batch?
 Was stability tested on a product within
the specification set?
 Better still; were 2 or more batches at limits
of specification tested

58 (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(ρc–ρd)g
–––––––––––––
9μ
 V = velocity of the dispersed phase droplet

 a = radius of the dispersed phase droplet
 ρd = density of the dispersed phase
 ρc = density of the continuous phase
 g = acceleration due to gravity
 μ = viscosity of the continuous phase

62 (Cosmetics) Ltd.
Stokes Law: Good stuff but what
does it mean for emulsion stability
V = 2a2(ρc–ρd)g
–––––––––––––
9μ
To improve stability reduce V
 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 μ - viscosity of the continuous phase

63 (Cosmetics) Ltd.
What droplet size?
Emulsion appearance and approximate
particle size
 milky-white greater than 1μ
 blue-grey 1.0 - 0.1 μ
 translucent 0.1 - 0.05 μ
 transparent less than 0.05 μ

64 (Cosmetics) Ltd.
Emulsion Stability
 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.
65 (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™ P-
100
+ 0.5%
Cerasynt 945
Cerasynt 945 = Glyceryl stearate (&)

laureth-23 Ultrathix P100 =
Acrylic acid/VP Crosspolymer John Woodruff; Creative Developments
66 (Cosmetics) Ltd.
Add Right Rheological Additive
Zinc Oxide nano particles
Carbomer Acrylic acid/VP Crosspolymer

67 (Cosmetics) Ltd.
Microscope Examination
Titanium Dioxide Nano particles
Carbomer Acrylic acid/VP Crosspolymer

68 (Cosmetics) Ltd.
Sun Protection Products
These present special problems
 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

69 (Cosmetics) Ltd.
Agglomeration of micronised sunscreens can
be seen under a microscope at 1000x
magnification
 Use rheology modifiers to stop migration of
particles – Veegum is good. Acrylic acid/VP
Crosspolymer is recommended

70 (Cosmetics) Ltd.
Preventing Agglomeration
TiO2 Nano particles Zinc Oxide nano particles
Acrylic acid/VP Crosspolymer

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
 Study the suppliers literature and many articles on the
subject
 http://www.creative-developments.co.uk/papers/
 http://www.cosmeticsbusiness.com/section.asp?navcode=50
 Don’t 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
 Make sure the formula complies with latest EU
Recommendation (UVA =>1/3rd UVB)

75 (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

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

4 days at room temperature 1 month at room temperature 1 month at 45°C

John Woodruff; Creative Developments

Atmospheric Mould Colonies

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

Must be safe to use, Must be safe to use,

Products sold in temperate

Products sold in tropical

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

 Texture and skin feel

John Woodruff; Creative Developments

John Woodruff; Creative Developments

3 months at 40C 18 months at RT

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 1 month at 45°C

John Woodruff; Creative Developments

These are actual

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

This permits to obtain Space- and Time-resolved Extinction Profiles

John Woodruff; Creative Developments

John Woodruff; Creative Developments

Particle migration Particle size variation

Sedimentation or creaming Coalescence or flocculation

t=0 min t=0 min

t=15 min t=15 min

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

In the equation above the value (E+P) can take on any

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments

John Woodruff; Creative Developments