Free radical oxidation, ultraviolet light

Light. Ultraviolet (uv) light promotes free-radical oxidation at the mbber surface which produces discoloration and a brittle film of oxidized mbber (35). This skin cracks in random directions to form a pattern called crazing, which can be prevented by the addition of carbon black fillers or uv stabilizers. Black stocks are more resistant to uv light than are gum or light-colored stocks. Nonblack compounds require larger quantities of nonstaining antioxidants which should bloom to the surface as the surface uv stabilizers deplete. 

Ultraviolet light promotes free-radical oxidation at the rubber surface which produces discolouration and a brittle film of oxidized rubber. This skin cracks in random directions to form a pattern called crazing, which can be prevented by the addition of carbon... 

In addition, hght, particularly ultraviolet light, may be involved in initiation of the classical free radical oxidation of lipids and catalyze other stages of the process. 

Ultraviolet light initiates free radical oxidation at the exposed surface of an elastomeric product to generate a layer of oxidized rubber. Heat, moisture, or high humidity can then initiate crazing of the surface, which subsequently can be abraded off. Such degradation of the surface is more severe with nonblack stocks than with black compounds. Nonblack compounds such as white tire sidewalls thus require higher levels of nonstaining antioxidants than carbon black-loaded formulations. 

The solvent-borne clearcoat is spray-applied over the basecoat at a dry film thickness of 1.8 to 2.0 mils. The clearcoat, responsible for UV protection, chemical resistance, chip resistance, and so on, is most often composed of a hydroxy functional acrylic binder together with a melamine or an isocyanate cross-linker. Ultraviolet light absorbers and hindered amine light stabilizers also are added to achieve better free-radical oxidative degrada-... 

The most important reactions of trichloroethylene are atmospheric oxidation and degradation by aluminum chloride. Atmospheric oxidation is cataly2ed by free radicals and accelerated with heat and with light, especially ultraviolet. The addition of oxygen leads to intermediates (1) and (2). 

Moore and Hemmens [119] studied the photosensitization of primaquine and other antimalarial agents. The drugs were tested for in vitro photosensitizing capability by irradiation with 365 nm ultraviolet light in aqueous solutions. The ability of these compounds to photosensitize the oxidation of 2,5-dimethylfuran, histidine, trypotophan, or xanthine, and to initiate the free radical polymerization of acrylamide was examined in the pH range 2 12. Primaquine does not have significant photochemical activity in aqueous solution. 

The second way in which fats deteriorate is oxidative lipolysis. This is an entirely different process in which oxygen free radicals add across double bonds. Oxidative rancidity can be prevented or reduced by several different routes. One way is to ensure that no double bonds are present. Another is to use anti-oxidants that act as free radical traps. Exposure to oxygen and ultraviolet light should be avoided. Reducing the temperature has no effect since free radical processes have a zero activation energy. 

Role of Antioxidants. The inhibition of color development by phenolic antioxidants is rather interesting since it points out the relationship between discoloration and oxidation. It is generally assumed that the photooxidation of polystyrene is a free radical reaction involving oxygen attack on a polymer radical, produced by the action of ultraviolet light. 

Thermal oxidation is also autocatalytic and considered as metal-catalyzed because it is very difficult to eliminate trace metals (from fats and oils or food) that act as catalysts and may occur as proposed in Equation 4. Redox metals of variable valency may also catalyze decomposition of hydroperoxides (Scheme 2, Equations [6] and [7]). Direct photooxidation is caused by free radicals produced by ultraviolet radiation that catalyzes the decomposition of hydroperoxides and peroxides. This oxidation proceeds as a free radical chain reaction. Although there should be direct irradiation from ultraviolet light for the hpid substrate, which is usually uncommon under normal practices, the presence of metals and metal complexes of oxygen can become activated and generate free radicals or singlet oxygen. 

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