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

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Product Stability
What is it?
How do we test it?
How can we improve it?
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Product Stability
What is it?
How do we test it?
How can we improve it?
3

In probability theory.Definition of Stability   4 In mathematics.. up to location and scale parameters. John Woodruff.. the stability of a random variable is the property that a linear combination of two independent copies of the variable has the same distribution. . Creative Developments (Cosmetics) Ltd. . stability theory addresses the stability of solutions of differential equations and of trajectories of dynamical systems under small perturbations of initial conditions.

resistant to change of position or condition . Creative Developments (Cosmetics) Ltd.the quality of being enduring and free from change or variation .not taking part readily in chemical change John Woodruff. subject to little fluctuation . .firm and dependable.Definition of Stability     5 .

. Creative Developments (Cosmetics) Ltd.Definition of Stability   What do we understand about it with regard to cosmetic products? That a product remain “fit for purpose”     6 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 John Woodruff.

Examples of Instability 7 .

Examples of Instability Obvious        8 Emulsion breakdown Perfume changes Colour changes Viscosity changes Fungal growth Wax crystallisation Sediment in clear lotions John Woodruff. Creative Developments (Cosmetics) Ltd. .

.Examples of Instability Less Obvious   pH changes Loss of activity Vitamins  Antioxidants  Enzymes  Preservatives    9 Photo-degradation of UV filters Microbial growth John Woodruff. Creative Developments (Cosmetics) Ltd.

.Emulsion Creaming 10 John Woodruff. Creative Developments (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 11 1 month at room temperature John Woodruff. Creative Developments (Cosmetics) Ltd. .

. Creative Developments (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 John Woodruff.

Worst Nightmare! Atmospheric Mould Colonies 13 John Woodruff. . Creative Developments (Cosmetics) Ltd.

. Creative Developments (Cosmetics) Ltd.Crystal Growth 14 John Woodruff.

Product Stability What is it? How do we test it? How can we improve 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 John Woodruff. Creative Developments (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 John Woodruff. Creative Developments (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 John Woodruff. Creative Developments (Cosmetics) Ltd.

Testing Schedules DLC Recommendations 19 John Woodruff. . Creative Developments (Cosmetics) Ltd.

.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 (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 John Woodruff. Creative Developments (Cosmetics) Ltd.

no matter at what point in their shelf life they are first opened.Stability and final pack compatibility of all cosmetic and toiletry products should be assessed to establish that they are stable and that no separation. effective and stable in final pack for at least 36 months at: Must be safe to use. crystallisation. effective and stable in final pack for at least 3 months at: Products sold in temperate climates 0°C to 23°C 30°C Products sold in tropical climates 0°C to 30°C 40°C Stability Requirements Product must also be safe to use within their specified Period After Opening (PAO). Creative Developments (Cosmetics) Ltd. 21 John Woodruff.Testing Schedules Boots recommendation . contamination. . degradation or other instability occurs within the claimed product shelf life Must be safe to use.

.What should be checked? 22 John Woodruff. Creative Developments (Cosmetics) Ltd.

23 John Woodruff. Creative Developments (Cosmetics) Ltd. .

Creative Developments (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 John Woodruff.

Creative Developments (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 John Woodruff. .

Accelerated Testing for Stability Prepare a pilot batch and store it in its retail packaging:     26 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 John Woodruff. . Creative Developments (Cosmetics) Ltd.

.Testing for Stability Monitor for changes in appearance (Subjective measurements)  Homogeneity  Colour  Glass slides  Microscope  Texture and skin feel  Odour 27 John Woodruff. Creative Developments (Cosmetics) Ltd.

crystals Viscosity changes Rheological changes Centrifuge tests Turbiscan Lumifuge John Woodruff. Creative Developments (Cosmetics) Ltd.Testing for Stability Monitor emulsion stability (Physical changes)  Emulsion breakdown  Creaming or settling        28 Glass slides – aeration and density/opacity Microscope – droplet size changes. .

Creative Developments (Cosmetics) Ltd. .Emulsion Creaming 3 months at 40C 18 months at RT What ways are available for quicker results 29 John Woodruff.

Microscope Examination 4 days at room temperature 1 month at room temperature 4 days at room temperature 1 month at room temperature 30 1 month at 45°C 1 month at 45°C John Woodruff. Creative Developments (Cosmetics) Ltd. .

Viscosity Changes These are actual viscosity graphs of 5 different w/o emulsions differing only in emulsifier used 31 John Woodruff. . Creative Developments (Cosmetics) Ltd.

co.connock. Creative Developments (Cosmetics) Ltd.htm John Woodruff.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.uk/articles_exfoliants. . very useful when developing scrubs http://www.

Creative Developments (Cosmetics) Ltd. .000 rpm A centrifuge designed to run at very high speeds and thus generate very high centrifugal force is called an ultracentrifuge.Accelerated Stability Testing  Centrifuge   Ultracentrifuge   33 5 minutes or more at 5. Suspensions which would settle only very slowly or not at all under gravity can be made to separate quickly in such a device! John Woodruff.

Transmission is converted into extinction by lg I/I0 and particle concentration may be calculated.lum-gmbh.com/pages/.. LUMiFuge® or LUMiSizer® due to the patented cutting-edge STEP®-Technology.htm 34 John Woodruff. . www. 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.and Time-resolved Extinction Profiles over the entire sample length of up to 12 different samples simultaneously. flotation or consolidation are directly measured by the LUMiReader®. like sedimentation.. This permits to obtain Space. Creative Developments (Cosmetics) Ltd./lumifuge/products_lumifuge.The LUMiFuge Demixing phenomena.

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

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

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

Testing for Stability
Monitor chemical changes

pH
Loss of activity
Vitamins
 Antioxidants
 Enzymes
 Preservatives
 UV Filters

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Photo-degradation of UV filters
John Woodruff; Creative Developments
(Cosmetics) Ltd.

Testing for Stability
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

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John Woodruff; Creative Developments
(Cosmetics) Ltd.

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

John Woodruff.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. Creative Developments (Cosmetics) Ltd. .

Product Stability What is it? How do we test it? How can we improve it? 42 .

consisting of two completely immiscible or partially miscible liquids.    .Emulsion Stability  A two-phase system. Creative Developments (Cosmetics) Ltd. 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 John Woodruff.

. Creative Developments (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 John Woodruff.

Emulsion Stability  What makes it stable?        45 Correct choice of emulsifier system Compatible ingredients Compatible pH Correct mixing method Compliance with specification Compatible packaging Understanding possible causes of instability John Woodruff. Creative Developments (Cosmetics) Ltd. .

This means that the HLB number assigned to the emulsifier will lie within the range of 0 to 20.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. Creative Developments (Cosmetics) Ltd. 46 John Woodruff. .

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 John Woodruff. . Creative Developments (Cosmetics) Ltd.

Creative Developments (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 John Woodruff.

Creative Developments (Cosmetics) Ltd.Liquid Crystal Emulsion 49 John Woodruff. .

.Liquid Crystal Emulsion 50 John Woodruff. Creative Developments (Cosmetics) Ltd.

g. Creative Developments (Cosmetics) Ltd.g.g. Potassium peanutate etc.g. Propylene glycol myristate etc. Sucrose laurate / myristate etc John Woodruff. Acrylates/C10-30 Alkyl Acrylate Crosspolymers Polyethylene glycol ethers (Oleth-10. PG Esters e. Sucrose esters e. . Laureth-10 etc) Polysorbates with Sorbitan esters e. Alkolylated dimethicones (AKA Dimethicone copolyols) Soaps e. Polysorbate-20 with Sorbitan monolaurate Glyceryl esters e. triethanolamine stearate. Glyceryl cocoate / laurate etc.g.Other Emulsifiers         51 Polymers – e.g.

Creative Developments (Cosmetics) Ltd. .Emulsion Stability  What makes it stable?        52 Correct choice of emulsifier system Compatible ingredients Compatible pH Correct mixing method Compliance with specification Compatible packaging Understanding possible causes of instability John Woodruff.

Creative Developments (Cosmetics) Ltd. etc. John Woodruff.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. .

pH vs Viscosity Typical carbomer system 100000 98000 96000 94000 92000 Viscosity 90000 88000 86000 84000 pH 5.5 pH 6.5 pH 8.0 54 John Woodruff.5 pH 7.0 pH 7.0 pH 5.0 pH 6. . Creative Developments (Cosmetics) Ltd.

Creative Developments (Cosmetics) Ltd. .Correct Mixing Methods Use laboratory mixing equipment which represents that available in the factory 55 John Woodruff.

Creative Developments (Cosmetics) Ltd. .Pilot Scale 56 John Woodruff.

Correct Mixing Methods 57 John Woodruff. . Creative Developments (Cosmetics) Ltd.

Creative Developments (Cosmetics) Ltd. . were 2 or more batches at limits of specification tested John Woodruff.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.

and the ultimate outcome of this process is complete phase separation. Creative Developments (Cosmetics) Ltd. indicating emulsion instability 59 John Woodruff. .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.

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 John Woodruff. . Creative Developments (Cosmetics) Ltd.

. Creative Developments (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 John Woodruff.

in a continuous liquid medium V = 2a2(ρc–ρd)g ––––––––––––– 9μ       62 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 John Woodruff. Creative Developments (Cosmetics) Ltd. .Stokes’ Law Stokes Law describes the factors influencing the velocity of a solid sphere. moving under the force of gravity.

.Stokes Law: Good stuff but what does it mean for emulsion stability V = 2a2(ρc–ρd)g ––––––––––––– 9μ To improve stability reduce V     63 Reduce a . Creative Developments (Cosmetics) Ltd.viscosity of the continuous phase John Woodruff.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 .

0.05 μ John Woodruff.0. Creative Developments (Cosmetics) Ltd.1 .0 . .What droplet size? Emulsion appearance and approximate particle size 64  milky-white greater than 1μ  blue-grey 1.05 μ  transparent less than 0.1 μ  translucent 0.

John Woodruff.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. Creative Developments (Cosmetics) Ltd.

5% UltraThix™ P-100 + 0. Creative Developments (Cosmetics) Ltd.2% Cerasynt 945 0.5% Cerasynt 945 Cerasynt 945 = Glyceryl stearate (&) laureth-23 Ultrathix P100 = Acrylic acid/VP Crosspolymer 66 John Woodruff. .Add Rheological Additive 0% UltraThix™ P-100 + 0.5% UltraThix™ P100 + 0.5% Cerasynt 945 0.

. Creative Developments (Cosmetics) Ltd.Add Right Rheological Additive Zinc Oxide nano particles Carbomer 67 Acrylic acid/VP Crosspolymer John Woodruff.

Microscope Examination Titanium Dioxide Nano particles Carbomer 68 Acrylic acid/VP Crosspolymer John Woodruff. Creative Developments (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 John Woodruff. Creative Developments (Cosmetics) Ltd.

Acrylic acid/VP Crosspolymer is recommended John Woodruff.Sun Protection Products 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. Creative Developments (Cosmetics) Ltd. .

Preventing Agglomeration TiO2 Nano particles Zinc Oxide nano particles Acrylic acid/VP Crosspolymer 71 John Woodruff. Creative Developments (Cosmetics) Ltd. .

Creative Developments (Cosmetics) Ltd.7. .Crystallising of Organic Sunscreens Check solubility in oil phase If using Phenylbenzimidazole Sulfonic Acid pH 7.3 .7 is critical 72 John Woodruff.

. Creative Developments (Cosmetics) Ltd.Photodegradation of BMDBM 73 John Woodruff.

 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.  EHMC destabilises BMDBM / octocrylene mixtures  Benzophenone-3 stabilises BMDBM weakly.8. Creative Developments (Cosmetics) Ltd. . after which its rate of decay increases again 74 John Woodruff. octocrylene stabilises EHMC strongly but does not stabilise BMDBM and ethylhexyl methoxycrylene stabilises BMDBM strongly.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.

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.uk/papers/ http://www. .creative-developments.com/index/ind-index/ind-per_car/ind-pc-uv/ind-pc-uv-sss.co.cosmeticsbusiness.ciba. Creative Developments (Cosmetics) Ltd.Sun Protection Products  Failure to meet SPF declaration  Failure to meet UVA requirements       http://www.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) John Woodruff.

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