Parylene polymerization growth mechanism

In the chain growth free radical polymerization of a vinyl monomer (conventional polymerization), the growth reaction is the repeated reaction of a free radical with numbers of monomer molecules. According to the termination by recombination of growing chains, 2 free radicals and 1000 monomer molecules leads to a polymer with the degree of polymerization of 1000. In contrast to this situation, the growth and deposition mechanisms of plasma polymerization as well as of parylene polymerization could be represented by recombinations of 1000 free radicals (some of them are diradicals) to form the three-dimensional network deposit via 1000 kinetic... 

So far as the growth mechanism is concerned, parylene polymerization is the closest kin of plasma polymerization. It is advantageous to go into a little details of parylene polymerization in order to understand how vacuum phase deposition of material occurs starting from a vapor phase material. 

The following aspects of parylene polymerization [3-9] seem to have important implications in an effort to understand the growth mechanisms of plasma... 

In both the polymerizations, free radicals are the species that are responsible for the formation of bonds in the depositing materials. The growth mechanism, however, is not by the conventional chain-growth free-radical polymerization. In a conventional free-radical chain-growth polymerization, two free radicals and 10,000 monomer molecules yield a polymer with degree of polymerization 10,000, which does not contain free radicals. In contrast to this situation, in plasma polymerization and Parylene polymerization, 10,000 species with free radical(s) recombine to yield a polymer matrix that has an equivalent degree of polymerization, and contains numbers of unreacted free radicals (dangling bonds). 

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