Role of marble microstructure in near-infrared laser-induced damage during laser cleaning

When marble is cleaned by nanosecond neodymium yttrium-aluminum-garnet lasers (1064 nm), strongly absorbing surface contaminants are removed at fluences substantially below the damage threshold for the much less absorptive marble substrate. Recent studies have shown, however, that unacceptable roughening of the marble surface also may occur at low fluences due to removal of individual grains. In order to elucidate this effect, we have compared the low-fluence response of marbles with two different grain sizes and single-crystal calcite, in the fluence range 0.12-1.25 J cm-2. Damage was greater in fine-grained than coarse-grained marble, and did not occur in the single-crystal calcite at these fluences. The temperature rise following defect-mediated absorption triggers thermal plasma emission and generates shock waves; the concomitant surface damage depends on the size and crystallographic orientation of the crystals. Laser irradiation anneals the defects and increases ''crystallite size.'' The implications for the laser-assisted cleaning of marble artworks are outlined