Basics of TiO2 sunscreen

Ultraviolet (UV) Radiation

Ultraviolet radiation can be divided into three regions: UVA (320–400 nm), UVB(290–320 nm) and UVC (200–290 nm). Although UVC is the most damaging UV radiation, it is filtered out by the ozone layer in the stratosphere before reaching the earth’s surface. The radiation in the UVB region (partially filtered by ozone) can penetrate both the stratum corneum and the epidermis of human skin. It has
sufficient energy to cause damage, such as sunburn, to human skin. This is particularly true for fair-skinned individuals. The UVA radiation, which is unfiltered by ozone, has deeper penetration of human skin to the dermis; it, thereby, stimulates the formation of melanin and produces a tan, which acts as the first line of defense for the protection from sunburn. UVA radiation, therefore, is also called the “tanning region.” Although having considerably lower energy than UVB, UVA photons can cause delayed damages to the skin.

The fundamental function of a sunscreen is to serve as a filter that can prevent the penetration of ultraviolet radiation. The substances most commonly used in commercial sunscreen preparations include p-aminobenzoic acids (PABA), cinnamates, oxybenzone, salicylates, and metal oxides, such as TiO2 and ZnO. In addition to their ability to scatter sunlight, inorganic particles, such as TiO2, do
absorb strongly in the UVA and UVB regions.

Rutile and Anatase TiO2

In addition to its amorphous state, two of the most common crystalline forms of TiO2 are rutile and anatase. The two crystalline forms share many similarities, such as their physical appearance, refractive index, density, low toxicity, and high stability in the presence of strong acids and bases. As a physical blocker for sunlight, bot
crystalline forms would serve the purpose well. Their photochemical properties, however, are very different. TiO2 is a semiconductor. When a semiconductor particle absorbs light, it promotes an electron from its valence band to its conduction band, leading to a charge separation. In rutile TiO2, the charge separation is quickly diminished through a charge recombination within the particle and the energy is released as heat. This translates to a low photoactivity and an effective conversion of UV light into heat. As a result, any photoinduced reactions that can pose damage to the skin are avoided. The low photoactivity and its desirable UV absorption spectrum, which cover the entire erythemal curve make rutile TiO2 an ideal choice as UV blocker for sunscreen preparations.

For amorphous and anatase TiO2, the lifetime of the charge separation is much longer than that on a rutile particle. The electron and electron hole, therefore, have greater opportunity to undergo redox reactions on the surface; therefore, anatase has been extensively used for applications involving such electron transfer processes as
photocatalysis for environmental waste treatment and photovoltaic design for solar energy storage. Extensive reviews on these interesting topics are available. Due to their photoactivity, amorphous and anatase TiO2 are not suitable for sunscreen applications.

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