Nano Calcium-Aluminum Layered Double Hydroxides for the Conservation of Earthen Immovable Cultural Heritage

Earthen immovable cultural relics, such as murals and painted clay sculptures, are prone to deterioration (e.g., efflorescence, flaking, and cracking) under long-term preservation conditions. While conventional restoration materials primarily offer reinforcement, they fail to regulate the migration of soluble salts within the relics, which is the main cause of such damage. Herein, aimed at protecting the painted sculptures and murals of the Yungang Grottoes, nano calcium-aluminum layered double hydroxides (Ca-Al LDHs) were prepared, and their effectiveness in regulating salt crystallization within the earthen ground layer, as well as their reinforcement performance were investigated. Simulated salt crystallization tests revealed that coating the ground layer with Ca-Al LDHs delayed salt-induced damage time by 150%. This can be attributed to the ability of Ca-Al LDHs to adsorb sulfate ions from soluble salts, thereby inhibiting the crystallization of magnesium sulfate on the surface of the ground layer. After curing Ca-Al LDHs-coated samples at 35 °C and 55% relative humidity (RH) for 7 days, their surface Leeb hardness increased by 3.1%, and the weight loss rate (measured via tape peeling test) decreased by 38.3%. These results indicate that the surface bonding strength was enhanced following Ca-Al LDHs coating, with the underlying mechanism being the transformation of part of the LDHs into calcium carbonate under the influence of water and carbon dioxide. This study demonstrates that Ca-Al LDHs not only suppress magnesium sulfate crystallization but also provide effective surface consolidation, showing promising potential for application in conserving painted sculptures and murals at the Yungang Grottoes.