New combined polymer/chromium approach for investigating the phototransformations involved in hologram formation in dichromated poly(vinyl alcohol)

The photochemical behavior of dichromated poly(vinyl alcohol) films has been analyzed upon exposure at 365 nm in relationship with the performances of holograms recorded in such photosensitive materials. The evolution of both involved species, poly(vinyl alcohol) and chromium, has been quantified by the implementation of an innovative approach. This approach combines the monitoring of the structural modification of the polymeric matrix and the fate of the various chromium species. For the first time, it has been established that chromium(V) not only is an indicator of the hologram quality, as previously assessed, but also appears to be responsible for the crosslinking implied in the hologram formation. Actually, the crosslinking has been proved to proceed through coordination bonds around chromium(V), which acts as a bridge between the polymeric chains. The role played by the ammonium cations in the hologram quality has also been elucidated. The improvement brought by ammonium dichromate with respect to potassium dichromate involves amide groups resulting from poly(vinyl alcohol) phototransformation. These groups provide additional chelating sites for chromium(V), leading to an increase in the matrix crosslinking. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1317–1325, 2006