Chemistry of The Drying Process
The "drying", hardening, or, more properly, curing of oils is the result of autoxidation, the addition of oxygen to an organic compound and the subsequent crosslinking. This process begins with an oxygen molecule (O2) in the air inserting into carbon-hydrogen (C-H) bonds adjacent to one of the double bonds within the unsaturated fatty acid. The resulting hydroperoxides are susceptible to crosslinking reactions. Bonds form between neighboring fatty acid chains, resulting in a polymer network, often visible by formation of a skin-like film on samples. This polymerization results in stable films that, while somewhat elastic, do not flow or deform readily. Diene-containing fatty acid derivatives, such as those derived from linoleic acid, are especially prone to this reaction because they generate pentadienyl radicals. Monounsaturated fatty acids, such as oleic acid, are slower to undergo drying because the allylic radical intermediates are less stable (i.e., slower to form).
The early stages of the drying process can be monitored by weight changes in an oil film. The film becomes heavier as it absorbs oxygen. Linseed oil, for instance, increases in weight by 17 percent. As oxygen uptake ceases, the weight of the film declines as volatile compounds evaporate. As the oil ages, further transitions occur. A large number of the original ester bonds in the oil molecules undergo hydrolysis, releasing individual fatty acids. Some portion of these free fatty acids (FFAs) react with metals in the pigment, producing metal carboxylates. Together, the various non-cross-linking substances associated with the polymer network constitute the mobile phases. Unlike the molecules that are part of the network itself, they are capable of moving and diffusing within the film, and can be removed using heat or a solvent. The mobile phase may play a role in plasticizing paint films, preventing them from becoming too brittle. Carboxyl groups in the polymers of the stationary phase ionize, becoming negatively charged and form complexes with metal cations present in the pigment. The original network, with its nonpolar, covalent bonds, is replaced by an ionomeric structure, held together by ionic interactions. The structure of these ionomeric networks is not well understood.
Most drying oils rapidly increase in viscosity after heating in the absence of air. If the oil is subjected to raised temperatures for a long time, it will become a rubbery oil-insoluble substance.
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