Colloid chemistry: Nanoparticles and sunscreen

Marcoen, K; Billen, A. ; Sweeck, J. Published 2 of march, 2012

1. Abstract A comparison is made between a bulk solution of ZnOH and a microemulsion of ZnOH. The microemulsion is broken down by the addition of acetone. A hand lotion base is made, and sunscreen is prepared by adding microparticles of ZnO. The performance of these two is compared by use of a UV-lamp. The UV-blocking capabilities of ZnO micro- and nanoparticles is compared in the same fashion. 2. Introduction Particles with at least one dimension in the range of 1 to 100 nm can be classified as nanoparticles. Nanoparticles have interesting properties due to their large surface area. In this laboratory we will prepare a sunscreen based on ZnO nanoparticles. Since unprotected exposure to sunlight is the main cause of skin cancer, sunscreen is very important. Sunlight is essential for people to survive, but one must always take care to be protected when long exposured. The sun rays can be catalogued by their wavelength. UV light is the most dangerous for the skin. Since they have short wavelengths, they posses high energy and are very active. When sunlight passes through the atmosphere, it gets filtered by several components present, like ozone, dust particles, smoke and water vapor. Still, 10% of the radiation that reaches us, is UV light, which is enough to induce some serious damage. Three types of UV light exist. UVA light (320 to 400 nm), which is not filtered by the atmosphere, can go through glass and is proven to be harmful on long term. UVB light (280 to 320 nm) is partly filtered by the ozone layer and is causing skin cancer. UVC light (190 to 280 nm) also

causes skin cancer, but is almost completely filtered by the ozone layer, so when producing sunscreens, we must focus on blocking UVB and UVA sun rays. Different kinds of sunscreen exist, but which sunscreen one should use, depends on the skin type. A factor that normally should help choosing the appropriate sunscreen is the sun protector factor or SPF-factor. But this factor only takes in account the amount of blocked UVB radiation. So the SPF-factor is an inconvenient measure to prevent skin damage since it neglects the harmful UVA radiation. A sunscreen that filters both UVB and UVA radiation is called a broad spectrum sunscreen. There are a lot of different additives that can be used in sunscreens. Every additive has its own range of wavelengths which it filters. Organic filters usually consist of aromatic compounds conjugated with a carbonyl group. These compounds absorb UV light to attain a higher energy, and when the system returns to normal stable condition, VIS or IR emission takes place. Problem with these organic compounds is that they penetrate the skin easily and can cause allergic reactions. ZnO is a inorganic filter, which is very popular for use in sunscreens because it is insoluble and is not absorbed by the skin. The main reason why ZnO is beneficial for use in sunscreens is because its an efficient broad spectrum ingredient which absorbs both UVB and UVA light very well. Nanoparticles are interesting for the use in sunscreens, because the diameter of the particles is smaller than the wavelength of visible light, so they are unable to scatter visible light, and appear transparent. The white layer normally related to sunscreen is not observed, and people will use an appropriate amount of sunscreen, without being covered by a white film. 3. Experimental The first experiment is aimed to create a bulk solution of zinc hydroxide. To obtain this, 5 ml of NaOH (0.50 mol/l) is simply add to 5 ml of ZnO (0.25 mol/l) in a stirred cup.
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Secondly a micro-emulsion of zinc hydroxide is prepared. To achieve this, micelles must be formed as micro-reactors, preventing the particles from recombining. We need an aqueous fase, a hydrophobic phase and a surfactant to form the micelles. In this experiment, AOT is used as surfactant and n-heptane as hydrophobic phase. To make a solution of 1.5 mol/l of AOT in n-heptane, 16.67 grams of AOT is weighed off in 2 separate beakers. Both beakers are placed on a heating plate at 80C whilst being stirred, and 25 ml of n-heptane was added to each beaker. When the AOT is completely dissolved, 5 ml of ZnCl2 (0.25 mol/l) is added to the first beaker and 5 ml of NaOH (0.50 mol/l) is added to the second. After several minutes, the content of beaker 2 is added to beaker 1, causing the NaOH and the ZnCl2 to react in the formed micelles, forming zinc hydroxide. By simply adding 50 ml of acetone, the previously prepared micro-emulsion is almost immediately destroyed. In this way one can easily see that zinc hydroxide had indeed formed in the drops of the micro-emulsion. Next a sunscreen based on ZnO is prepared. To start, 7.50 grams of hexadecanol is weighed off in a beaker and heated at 70C to melt the white powder and receiving a cream while stirring. Subsequently 0.80 grams of dodecyl sodiumsulphate is weighed off in another beaker and 42ml of water is added. To dissolve the dodecyl sodiumsulphate, the beaker is placed on a warm heating plate while being stirred. The solution of dodecyl sodiumsulphate is slowly added to the molten hexadecanol whilst being stirred and additionally also a drop of fragrance is added. When one keeps stirring, a smooth cream is obtained. A little sample of the cream is put on a watch glass and 0.5 grams of ZnO powder is mixed homogeneously with the cream. The obtained sunscreen is tested in a UV box, and compared with the cream

lacking the ZnO nanoparticles. Both creams are smeared onto fluorescent squares on a piece of paper. This paper goes into the UV box and is observed. In the final experiment, the performance of micro zinc oxide particles is compared with that of nano zinc oxide particles. To accomplish this, 5 grams of glycerine is put into 2 separate beakers, after which 15 mg of micro zinc oxide particles are added to the first beaker, and 15 mg of nano zinc oxide particles to the second. After thorough stirring, a homogenous gelatinous substance is formed. Both substances are tested in a UV box. Applying a small amount of both substances to their respective fluorescent squares, the same method as earlier was used. 4. Results and discussion When preparing the bulk solution, zinc hydroxide is formed in the following reaction: ZnCl2 + NaOH Zn(OH)2 + NaCl The zinc hydroxide particles aggregate to larger particles. After a few minutes, a white gelatinous solution is observed, with slight precipitation on the bottom and sides. An emulsion is a mixture of two liquids who are unmixable. One liquid is dispersed into the other. A microemulsion is a clear, thermodynamically stable liquid mixture. It consists of a water phase and an oil phase, separated by a surfactant. In this case, the microemulsion is reversed, meaning that the water phase is dispersed in the oil phase, the micelles contain the water phase. When preparing the microemulsion, micelles are formed, and they act as microreactors, which means that small particles of zinc hydroxide are formed, and not allowed to aggregate into larger particles. The surfactant made sure that the particles could not agglomerate, by
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trapping them in small micelles. The micelles did not agglomerate because of steric repulsion. A homogenous solution was observed, with a slight white fog. Relative to the normal emulsion prepared in the first experiment, the particles were too small to observe individually. The microemulsion was successfully broken down by adding acetone. The acetone reacts with the formed micelles, breaking them apart, causing the microparticles to aggregate, forming a white, cloudy suspension, which slowly sinks to the bottom of the cup. The sunscreen that was prepared and was tested under a UV-lamp, held up in relation to the hand lotion that was prepared (consisting of the same ingredients, but without the ZnO microparticles). As seen on the picture below, the sunscreen manages to stop almost all of the UV-light, whereas the hand lotion is practically transparent to the UV-radiation.

Top left corner: hand lotion, bottom right corner: sunscreen. In the final experiment, the UV-stopping qualities of microparticles were compared to nanoparticles of ZnO. As one can see on the picture below, the difference is quite clear.

Left: microparticles, right: nanoparticles We observed that, when applied in equal quantities, the nanoparticles provided much better protection against harmful UV-rays than the microparticles. Also, the nanoparticle solution seemed to be more transparant to visible light. Because the nanoparticles are so small, smaller than the wavelengths of visible light, the light-scattering ability is greatly reduced. For use in sunscreens, this is good, because now a sufficient amount of sunscreen can be applied, but no white coating can be seen. The better performance in stopping UV-rays results from the higher surface area created by the smaller nanoparticles. Conclusion From these experiments, the conclusion can be made that a microemulsion can be an effective solution for the reactions that form microparticles. Also, microemulsions can be broken down by the use hydrophobic solvents,such as acetone. ZnO microparticles are effective for use in sunscreens. Nanoparticles are even better than microparticles, because they provide better coverage and are practically invisible.

References
http://www.uhasselt.be/Documents/uhasselt@school/lesmateriaal/chemie/Nanocosmetica.pdf http://en.wikipedia.org/wiki/Microemulsion http://www.cosmeticsinfo.org/ingredient_details.php?ingredient_id=629