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3/7/13 LECTURE 10 FORMULATION CHEMISTRY SHORT TEST (Formulation) March 12 FINALS Tues., March 19, 9:30-11:30, C114 FORMULATION CHEMISTRY FORMULATION CHEMISTRY n Formulation chemistry is the mixing of compounds/ substances that do not react with each other but n Many modern products contain a combination of several produce a mixture with the desired characteristics/ chemical substances, each contributing an advantage to properties to suit a particular application/use. the finished product for a particular application. 1 3/7/13 FORMULATION CHEMISTRY FORMULATION CHEMISTRY n Any developed product must be commercially viable i.e. a n Since no reactions happen in making the mixture, most useful profitable material, so, almost every example quoted formulations are prepared by measuring liquids by volume and below, you will actually find in your home i.e. a broad range of solids by mass ('weight'). It is perfectly possible for a marketed useful household products are the result of the science of product to go on sale without a chemical equation ever being formulation chemistry. written down! FORMULATION CHEMISTRY n Although there are no chemical reactions involved in n However, there may be much chemistry going on to actually preparing formulations, there are many chemical make some of the ingredients e.g. chemically synthesising a aspects to do with formulation. These include drug is one matter, mixing it with water and other ingredients thermodynamics (energy changes) of mixing, phase to make a liquid medicine for oral consumption is another! equilibria, solutions, surface chemistry, colloids, emulsions and suspensions. 2 3/7/13 FORMULATION CHEMISTRY FORMULATION CHEMISTRY n These important principles and ingredients may be n By changing the composition of the mixture, its related to properties such as adhesion, weather properties will change to be more or less suited to a resistance, texture, shelf-life, biodegradability, particular useful application. Quite a bit of trial and error allergenic response and many other properties. goes into product formulation research and even computer programes have been developed to model and therefore predict the properties a mixture may have - BUT its still got to be tested in the laboratory. EXAMPLES - PAINTS EXAMPLES - PAINTS n A paint is made up of a base pigment, a mixture of n Binders bind the pigment to the surface painted and compounds to give it a particular color, a binder and a pigments must be insoluble materials e.g. titanium solvent which evaporates to give a hard solid surface dioxide and zinc oxide are used as white pigments (and finish (matt or gloss depending on the composition). have replaced potentially harmful lead pigments). Paints may be water, latex, oil, acrylic or epoxy based. Sometimes the binding action involves a chemical House paints must be reasonably durable at a change e.g. polymerisation. Acrylic paints use polymer reasonable price but high durability paints used for car resins as a solvent and can be thinned with water, but and aircraft bodies are more costly. still dry easily. 3 3/7/13 EXAMPLES – INKS and DYES EXAMPLES – INKS and DYES There is a huge variety of inks available of different Good color quality is required for glossy magazines. As well compositions to suit different circumstances. Ink used for as colour composition, appropriate ink flow is important newspapers or paperback novels must be cheap and have for pens and computer printers. The performance and the consistency of a thick sludge to properly feed through formulation of a good photocopier or laser printer toner the ink rollers of a printing press. depends upon its electrostatic properties. COSMETICS AND OTHER 'PERSONAL PRODUCTS' OTHER EXAMPLES n The cosmetic industry provides a wide range of Petrolium Oil Products, Detergents (gels, formulated products. In the bathroom/bedroom you may find perfumes, moisturizers, lipstick, antiaging skin bars, liquids, granules), Soap (blocks/ products, face powder, nail polish, sunscreen/ powders, liquids), Perfumes and Flavors, sunblocker, hair gel, hair conditioning and colouring Pharmaceutical products, adhesives, products, aftershave and deodorants etc. pesticides, Food industry products, dietary supplements. 4 3/7/13 What form? What form? Consumer preferred Solid (granular, block), encapsulated solids Ease of formulation Gels and Paste Cost. Liquids (solutions, emulsions) (dispersions) (dilute or concentrated) MODE OF USE/DELIVERY PRODUCT AESTHETICS - direct application - odor, flavor - dilute and use - Color - - Spray-on - Form - With implements (tooth brush, foam) - others 5 MANUFACTURING IN COSMETICS FROM THE LABORATORY TO 3/7/13 FULL PRODUCTION PRIMARY AND SECONDARY BENEFITS Two in one shampoo Detergents for cleaning but can claim antibacterial benefit. Dishwashing with glass repair Emulsion Chemistry Emulsion Chemistry OUTLINE – WHAT YOU SHOULD LEARN n Learn about emulsions Cosmetic Formulation n What they are n Where they are used n How you make them n Practical information 23 24 6 3/7/13 Emulsion Chemistry: Emulsion Chemistry: Cosmetics The Problem - OILS n Oils are excellent cosmetic materials n Cosmetics are all about changing / n Improve surface feel improving surfaces n Protect n Aid in moisturization n Reduce static n Shine n Don’t wash away n Oils have drawbacks n Tacky, greasy 25 26 n Cost too much Emulsion Chemistry: Emulsion Chemistry: The Solution – Dilution! The Problem n Oil & Water Do Not Stay Mixed n Why? n Lower free energy when separate n Why? n Hydrogen Bonding n Oils are non-polar n Size of molecules 27 28 7 3/7/13 Emulsion Chemistry: Emulsion Chemistry The Solution Emulsifier – The Stabilizer n Add energy to the system n Lipophilic tails & Hydrophilic heads n Agitation n Heat n Need something to stabilize Reduce interfacial surface tension n Surfactants or Emulsifiers Helps disperse oil in water 29 Forms micelles in solution 30 Emulsion Chemistry: Emulsion Chemistry: Micelle formation The Solution n Oil breaks into tiny droplets (particles) Molecules in Motion n Hydrophilic heads align with water n Lipophilic tails align with oil 31 32 n Note: More structures than this formed in solution. Depends on surfactant concentration 8 3/7/13 Emulsion! Common Emulsions Peanut Butter 33 Milk Salad Dressing 34 Emulsion Chemistry Emulsion Chemistry EMULSIONS EMULSIONS n Pseudo-Stable mixtures of oils & water n Why are they useful? n Three phases n Improved feel n Internal Phase n Easier to apply – Shear thinning n External Phase n Less chemical exposure = safer n Emulsifier n Use the right amount n It’s generally cheaper! 35 36 9 3/7/13 Emulsion Chemistry Emulsion Chemistry EMULSIONS - PARTICLES Emulsions – Particle Size n The importance of particle size Type Particle Size n Clarity Macroemulsion >1000 nm n Stability Microemulsion 10 – 300 nm n Characterization Micelles 5 – 10 nm n Macroemulsions Solutions <5 nm n Microemulsions (also Nanoemulsions) 37 38 Emulsion Chemistry Emulsion Chemistry EMULSIONS - TYPES Oil in Water – O/W n Type of emulsions n Internal phase = oil n Oil in Water n External phase = water n Water in Oil n Advantages n n Multiple emulsions Easiest to formulate n Least expensive n Best feel – cooling effect n Disadvantages 39 40 n Less oil delivered n Not as effective for dry skin n Not water-resistant 10 3/7/13 Emulsion Chemistry Example Product – O/W Water in Oil – W/O n Internal phase = water St. Ives Vitamin E Lotion n External phase = oil Water (Aqua), Glycerin, Mineral Oil (Paraffinum Liquidum), Stearic n Advantages Acid, Glycol Stearate, Stearamide AMP, Petrolatum, Dimethicone, n Waterproofing possible Tocopherol, Tocopheryl Acetate, Chamomilla Recutita Flower Extract (Matricaria), Helianthus Annuus Extract (Sunflower), Sambucus n Most effective for dry skin Nigra Flower Extract, Primula Veris Extract, Theobroma Cacao Seed n Better stability Butter (Cocoa), Glyceryl Stearate, Cetyl Alcohol, Triethanolamine, Other Products Acetylated Lanolin Alcohol, Cetyl Acetate, Magnesium Aluminum n Disadvantages Hair conditioners Silicate, Carbomer, Propylene Glycol, Propylparaben, Methylparaben, Sunscreen n Oily, tacky feel Wrinkle Creams DMDM Hydantoin, Disodium EDTA, Sorbitol, Fragrance (Parfum), Yellow 5 (CI 19140) n More expensive 41 42 Emulsion Chemistry Example Product – W/O Emulsions – Differences Philosophy hope in a tube, Firming cream Water (aqua), Squalane, Mineral Oil, Glycerin, Isocetyl n Is it O/W or W/O? Stearoyl Stearate, Petrolatum, Butylene Glycol, Polyglyceryl 2 Diisostearate, PEG 30 Dipolyhydroxystearate, Ceresin, n Dilution – O/W disperses more easily Polyethylene, Microcrystalline Wax, Magnesium Sulfate, Phytosteryl/Octyldodecyl/Lauroyl Glutamate, Dipalmitoyl n pH – O/W has consistent pH Hydroxyproline, Tocopheryl Acetate, Polysorbate 80, Bisabolol, Potassium Ascorbyl Tocopheryl Phosphate, Iron n Conductivity – O/W conducts electricity Oxide (CI 77492, CI 77491 and CI77499), Methylparaben, Diazolidinyl Urea, Ethylparaben, Tetrasodium EDTA 43 44 11 3/7/13 Emulsion Chemistry Multiple Emulsions EMULSION STABILITY n Multiple phases n Oil in Water in Oil (O/W/O) n Water in Oil in Water (W/O/W) n Advantages n More effective than Oil in Water n Less greasy than Water in oil n Time release, active delivery possible n Disadvantages n Hard to manufacture 45 46 n Not always stable Emulsion Chemistry Emulsion Chemistry: Emulsion - Stability Emulsions - Stability Problems n Emulsions are inherently unstable n Second Law of Thermodynamics Flocculation Coalescence n Good emulsions last a long time Creaming Inversion n But