Celluloid artifacts are known by conservation professionals to be prone to degradation, threatening their own integrity and that of nearby heritage collections. Celluloid alteration can have a heterogeneous nature, and this research topic is still in its infancy for heritage science. This article investigates degradation gradients, both along depth and width, of artificially aged celluloid sheets, and compares them to three-dimensional (3D) historical objects with the aim of gaining a better insight into the nature and evolution of their decay. ATR-FTIR was used to systematically study different sampling points of the artificially and naturally aged specimens and allowed us to recognize better-preserved surfaces and more deteriorated cores. ATR-FTIR was found suitable for assessing the molecular changes induced by degradation, particularly denitration and formation of carbonyl-containing degradation products in severely aged specimens. Even though the severely artificially aged sheets displayed unusual alteration phenomena, they present a degradation gradient similar to the one observed for the naturally aged 3D objects under study. This research underlines that sampling at different depths and/or widths is relevant for characterizing the heterogeneity of degraded celluloid, and further investigation with chromatographic techniques would greatly benefit the understanding of the complex degradation of celluloid artifacts.

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Cellulose nitrate (CN) has been used in the past as support for photographic negatives and cinematographic films. This material is particularly unstable and can undergoes severe degradation due to thermal, photocatalytic and hydrolytic loss of nitro groups from the lateral chain. Thus, to prevent the disappearance of the movies, their scanning and digitalization become a priority.However, CN bases degradation may prevent the scanning of the films. The decrease in pH, for instance, lowers the viscosity of gelatin, which becomes softer. This causes the formation of gelatin residues which stick on the back of the superimposed frames inside the reels creating a deposit.Traditional approaches to clean gelatin residues from the surface of CN bases include the mechanical removal with scalpels and the use of organic solvents (such as isopropyl alcohol). However, these methods are either slow and ineffective or could potentially damage the degraded CN supports.To overcome these drawbacks, we have evaluated the performance of three choline chloride and betaine-based Deep Eutectic Solvent (DES) formulations as alternative for the removal of gelatine residues from CN supports. These solvents are inexpensive (when compared to traditional solvents), easy to prepare, green (non volatile, safe towards the operators and the environment, and potentially recyclable), non flammable and have been previously proposed for the extraction of proteinaceous materials, but their use for the restoration of photographic negatives or cinematographic films has not been reported yet.Selected areas over the frames of a real deteriorated CN cinematographic film were cleaned comparing the DES performances with the ones obtained using isopropyl alcohol as an example of a traditional method.In particular, the tested DES formulations showed superior cleaning power compared to isopropyl alcohol and, at the selected application times, resulted capable to remove the gelatin residues without affecting the CN film supports. Graphical abstract

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