Conservation of marble artifacts by phosphate treatments: influence of gypsum contamination

The use of ammonium phosphate solutions has proven to be very promising for protection and conservation of marble. However, all the studies carried out so far have been performed on uncontaminated marble. Unfortunately, this is rarely the case in the field, because marble artifacts exposed outdoors are often affected by sulfation, i.e. formation of a gypsum crust on the surface. Because gypsum is much more soluble than calcite, the outcome of the ammonium phosphate treatment is expected to be sensibly altered by the presence of gypsum. Therefore, in this study the nature and morphology of the new calcium phosphate phases formed by reacting gypsum with aqueous solutions of diammonium hydrogen phosphate (DAP) were investigated. In particular, the effect of DAP concentration, ethanol addition (aimed at reducing gypsum solubility), and pH were explored. The result is that phase formation can be controlled by suitably tuning the above mentioned parameters. Phases with low solubility (such as tricalcium phosphate and hydroxyapatite) can be obtained by increasing the ethanol concentration, the DAP concentration or the pH. However, their formation is associated with diffused cracking, likely because of excessive growth of the new phases. Among the investigated formulations, treatment with a 0.1 M DAP solution with 30 vol% ethanol at pH=8 seems to be the most suitable one, as it leads to formation of brushite (about 30 times less soluble than gypsum), without cracking, so that a reduction in gypsum solubility in rain is expected.