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?
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Product Stability
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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
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
Examples of Instability
Obvious

Emulsion breakdown Perfume changes Colour changes Viscosity changes Fungal growth Wax crystallisation Sediment in clear lotions
Less Obvious

pH changes Loss of activity

Vitamins Antioxidants Enzymes Preservatives
Photo-degradation of UV filters Microbial growth

Emulsion Creaming
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Emulsion Breakdown
4 days at room temperature
1 month at room temperature
1 month at 45C
1 month at 45C
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Viscosity Changes
Increasing 70 60 50 40 30 20 10 0 Initial 5 days 10 15 20 25 30 days Decreasing Stable
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Worst Nightmare!
Atmospheric Mould Colonies
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Crystal Growth
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Product Stability
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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?
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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
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Testing Schedules
IFSCC Monograph

40 ambient humidity 200 / 250 ambient humidity 370 ambient humidity 450 ambient humidity 370 & 80% relative humidity Freeze / Thaw Light exposure
retain as control 60 months 6 months 3 months 1 month
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Testing Schedules
DLC Recommendations
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DLC Recommendations
1 month assessment (all storage conditions) 2 month assessment (all storage conditions) 3 month assessment (all storage conditions) 6 month assessment (all storage conditions) 9 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).
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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
Stability Requirements Must be safe to use, effective and stable in final pack for at least 36 months at: 0C to 23C Must be safe to use, effective and stable in final pack for at least 3 months at: 30C
Products sold in temperate climates Products sold in tropical climates
0C to 30C
40C
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 John Woodruff; Creative Developments (Cosmetics) Ltd.
What should be checked?
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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
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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?
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Accelerated Testing for Stability

Prepare a pilot batch and store it in its retail packaging:
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
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Monitor for changes in appearance (Subjective measurements)
Homogeneity Colour Glass
slides Microscope Texture and skin feel Odour


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

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Emulsion Creaming
3 months at 40C
18 months at RT
What ways are available for quicker results
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Microscope Examination
1 month at 45C

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1 month at 45C
Viscosity Changes
These are actual viscosity graphs of 5 different w/o emulsions differing only in emulsifier used
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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
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Accelerated Stability Testing
Centrifuge
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!
Ultracentrifuge
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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
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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
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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
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Principle of Measurement
Particle migration Sedimentation or creaming Particle size variation Coalescence or flocculation
t=0 min t=15 min
t=0 min t=15 min

Monitor chemical changes

pH Loss of activity
Vitamins Antioxidants Enzymes Preservatives UV Filters
Photo-degradation of UV filters
38

Monitor preservative efficacy
Initial challenge test to accepted protocols
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
Head space test
Challenge testing of stability samples

It is recommended that this be done after 3 months stability testing at RT and 40C
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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.
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.
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Product Stability
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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
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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
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Emulsion Stability

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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.
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
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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
Liquid Crystal Emulsion
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Liquid Crystal Emulsion
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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
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Emulsion Stability

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Incompatible Ingredients
Carbomers and salts
Kathon CG contains a salt Many preservatives are formaldehyde donors
Dihydroxyacetone and formaldehyde
Enzymes and chelating agents

EDTA and its salts Parabens Ethoxylated emulsifiers
etc. etc.
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pH vs Viscosity
Typical carbomer system
100000 98000 96000 94000 92000 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
Viscosity
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Correct Mixing Methods

Use laboratory mixing equipment which represents that available in the factory
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Pilot Scale
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Correct Mixing Methods
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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

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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
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
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
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 9

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
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Stokes Law: Good stuff but what does it mean for emulsion stability
V = 2a2(cd)g 9 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 - viscosity of the continuous phase
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What droplet size?

Emulsion appearance and approximate particle size

milky-white greater than 1 blue-grey 1.0 - 0.1 translucent 0.1 - 0.05 transparent less than 0.05
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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.
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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
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Add Right Rheological Additive

Zinc Oxide nano particles
Carbomer
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Acrylic acid/VP Crosspolymer

Microscope Examination
Titanium Dioxide Nano particles
Carbomer
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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
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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
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Preventing Agglomeration
TiO2 Nano particles Zinc Oxide nano particles

Crystallising of Organic Sunscreens

Check solubility in oil phase
If using Phenylbenzimidazole Sulfonic Acid pH 7.3 - 7.7 is critical

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Photodegradation of BMDBM
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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
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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 Dont put to much faith in SPF boosters Use the Ciba Sunscreen Simulator then in-vitro then in-vivo Make sure the formula complies with latest EU Recommendation (UVA =>1/3rd UVB)
http://www.ciba.com/index/ind-index/ind-per_car/ind-pc-uv/ind-pc-uv-sss.htm
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Thank you for your time and may all your creations be stable
John Woodruff www.creative-developments.co.uk
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Cosmetic Product Stability

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Cosmetic Product Stability

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Product Stability

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

Appearance Purity including lack of microbial contamination Efficacy

pH changes Loss of activity

Photo-degradation of UV filters Microbial growth

John Woodruff; Creative Developments (Cosmetics) Ltd.

4 days at room temperature

1 month at room temperature

4 days at room temperature

1 month at room temperature

John Woodruff; Creative Developments (Cosmetics) Ltd.

John Woodruff; Creative Developments (Cosmetics) Ltd.

Atmospheric Mould Colonies

John Woodruff; Creative Developments (Cosmetics) Ltd.

John Woodruff; Creative Developments (Cosmetics) Ltd.

Testing for Stability

John Woodruff; Creative Developments (Cosmetics) Ltd.

John Woodruff; Creative Developments (Cosmetics) Ltd.

retain as control 60 months 6 months 3 months 1 month

John Woodruff; Creative Developments (Cosmetics) Ltd.

John Woodruff; Creative Developments (Cosmetics) Ltd.

John Woodruff; Creative Developments (Cosmetics) Ltd.

Products sold in temperate climates Products sold in tropical climates

What should be checked?

John Woodruff; Creative Developments (Cosmetics) Ltd.

John Woodruff; Creative Developments (Cosmetics) Ltd.

Minimum and maximum for each parameter

John Woodruff; Creative Developments (Cosmetics) Ltd.

Accelerated Testing for Stability

John Woodruff; Creative Developments (Cosmetics) Ltd.

Testing for Stability

slides Microscope Texture and skin feel Odour

Testing for Stability

Viscosity changes Rheological changes Centrifuge tests Turbiscan Lumifuge

What ways are available for quicker results

John Woodruff; Creative Developments (Cosmetics) Ltd.

4 days at room temperature

1 month at room temperature

4 days at room temperature

1 month at room temperature

John Woodruff; Creative Developments (Cosmetics) Ltd.

For suspensions measure yield values

Accelerated Stability Testing

John Woodruff; Creative Developments (Cosmetics) Ltd.

John Woodruff; Creative Developments (Cosmetics) Ltd.

t=0 min t=15 min

t=0 min t=15 min

Testing for Stability

Testing for Stability

Initial challenge test to accepted protocols

Head space test

Challenge testing of stability samples

John Woodruff; Creative Developments (Cosmetics) Ltd.

What makes it stable?

What makes it stable?

John Woodruff; Creative Developments (Cosmetics) Ltd.

Liquid Crystal Emulsion

John Woodruff; Creative Developments (Cosmetics) Ltd.

Liquid Crystal Emulsion

John Woodruff; Creative Developments (Cosmetics) Ltd.

What makes it stable?

Carbomers and salts

Kathon CG contains a salt Many preservatives are formaldehyde donors