Frozen, Cold, or Cool? Chemical Assessment of the Effectiveness of Storage Conditions for Celluloid 3D Objects

Preserving celluloid artifacts is challenging for museums, as this plastic is highly prone to degradation. Frozen, cold, and cool storage solutions are typically recommended for inhibiting the chemical degradation of celluloid. However, they are rarely implemented for three-dimensional celluloid (3D-CN) objects because low temperatures might cause irreversible effects (e.g., microcracking). This work presents the effects of four different storage temperatures (+23 °C, +13 °C, +9 °C, -15 °C) on the preservation of artificially aged 3D-CN mock-ups, aiming at understanding their effectiveness by measuring molecular weight distribution, camphor, and nitrogen contents after storage. Gel permeation chromatography (GPC) results showed that the least loss of camphor content and fewer polymer chain scissions happened at -15 °C, hinting that this temperature was the best for preservation. However, the heterogeneous nature of celluloid alteration, i.e., the development of degradation gradients in thicker 3D-CN objects (>0.5 mm), made it necessary to apply a novel sampling technique, which selectively considers several depths for analyses from the surface to the core (depth profiling). This depth profiling made monitoring the degradation evolution dependent on the storage conditions in the thicker mock-ups possible. This approach was also used for the first time to quantify the polymer chain scission, camphor loss, and denitration of historical artifacts, indicating a dramatic difference in the degradation stage between surface and core. The effectiveness of frozen storage on the chemical stability of 3D-CN after seven months could support museums to consider reducing the storage temperatures to preserve precious artifacts.