Protection of ancient and historic bronzes by triazole derivatives

Abstract

Ancient and historic tin bronzes can be substantially affected by corrosion when submitted to non adequate storage conditions or more aggressive environments such as, for example, the marked increase of air pollution and of acidity of rainwater in urban medium recently affecting outdoor monuments. To protect them, some triazole compounds were tested as corrosion inhibitors of bronze covered with patina layer. As in the case of cultural artefacts, each specimen is unique, an accurate comparison of inhibiting effect of different molecules is therefore hard to realise. To overcome this difficulty, on the basis of a global understanding of the nature of natural bronze patinas, artificial patinas were synthesised on a contemporary bronze (Cu–Sn–Pb) having a similar composition to that of bronze coins dating of the post Roman Empire (5th–6th century AD). Surface characterization and electrochemical experiments were carried out both on contemporary bronze covered with artificial patina and on three ancient bronze coins discovered in Morocco. All triazole derivatives used, benzo-triazole (BTA), amino-triazole (ATA) and bi-triazole (BiTA), exhibited fairly good protective properties on the synthetic bronze. The BTA is efficient in an artificial patina isolated of the substrate bronze and an old bronze specimen covered with patina layer, but this substance is considered as toxic. The BiTA has shown only a slight inhibiting effect on the ancient bronze coin. The ATA is the most effective at 0.1 mM concentration, and the initial treatment of bronze at a higher concentration makes inhibiting effect lower. The ATA is therefore considered the most promising candidate to be applied to protect antique bronze artefacts covered with natural patina layer.