Degradation of historic cellulose triacetate cinematographic film: The vinegar syndrome

Allen, Norman S.; Edge, Michèle; Appleyard, John H.; Jewitt, T.S.; Horie, C.V.; Francis, Danny

doi:10.1016/0141-3910(87)90038-3

Cited by 40 publications

(22 citation statements)

References 1 publication

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“…However, CTA films also suffer from inherent instability. It has been extensively observed that one of the first signs of degradation in CTA films is emissions of acetic acid; this process is nicknamed 'vinegar syndrome' owing to its characteristic odour of acetic acid (3)(4)(5)(6). The issue is sufficiently infamous that at least ten patent applications dealing with film preservation mention the problem, if not claiming to tackle it directly (7)(8)(9)(10)(11)(12)(13)(14)(15)(16).…”

Section: Introductionmentioning

confidence: 99%

Are we overestimating the permanence of cellulose triacetate cinematographic films? A mathematical model for the vinegar syndrome

Ahmad

Cane²,

Townsend³

et al. 2020

Polymer Degradation and Stability

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Among the earliest signs of degradation in cellulose triacetate cinematographic films is the generation of acetic acid due to hydrolytic deacetylation of the polymer, marked by an increase in the acidity of the films and emissions of acetic acid leading to a characteristic vinegar odour. We propose a mathematical model for predicting the onset of the vinegar syndrome which accounts for the autocatalytic effect of acetic acid on the deacetylation reaction. Model parameters are estimated from previously published experimental data from other research groups. These show free acidity changes in cellulose triacetate films subjected to accelerated ageing at temperatures of 70-100 °C. The model is validated against a different set of previously published experimental data of cellulose triacetate films aged at 21 °C and 35 °C, at 20, 35 and 50% relative humidity. The model demonstrates good quantitative agreement with the published experimental data. Predictions of film permanence at lower temperatures, similar to those present in the archives in which the films are typically stored, are made and compared with the predictions of film conservation guidelines. The results indicate that film permanence may be overestimated by existing guidelines, which do not account for autocatalysis in their modelling of the deacetylation rate. Our results suggest that cold storage, a common film conservation strategy, may be less effective at inhibiting degradation than previously thought. As cold storage typically requires film to be kept in confined spaces with limited air movement, conditions which promote autocatalysis, the inclusion of autocatalysis in our model is highly applicable to simulating this environment.

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Section: Introductionmentioning

confidence: 99%

Are we overestimating the permanence of cellulose triacetate cinematographic films? A mathematical model for the vinegar syndrome

Ahmad

Cane²,

Townsend³

et al. 2020

Polymer Degradation and Stability

View full text Add to dashboard Cite

show abstract

“…For cellulose acetate (CA), early research found that cold storage reduces the auto-catalytic reaction rate of polymer hydrolysis or 'vinegar syndrome' [23,24]. Others recommend ventilated storage or scavengers to minimise a build-up of acidic species arising from hydrolysis of CA and CN [25,26].…”

Section: Conservation Strategies To Datementioning

confidence: 99%

Plasticiser loss in heritage collections: its prevalence, cause, effect, and methods for analysis

King¹,

Grau-Bové²,

Curran³

2020

Herit Sci

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Plasticiser loss is a topic frequently mentioned in discussions on the degradation of plastic artefacts in museum collections, particularly for plasticised poly (vinyl chloride) and cellulose acetate. Plasticisers may migrate to the plastic’s surface and remain as a deposit, or volatilise into the surrounding environment, both presenting an aesthetic issue and impacting the future stability of the plastic. This paper draws on the work of conservation science, materials degradation, and indoor air quality/emissions studies, to review our current understanding of plasticiser loss. The influence of the material’s intrinsic properties, and environmental factors on migration rates are discussed and related to preventive conservation practices. The methods by which plasticiser migration is studied, including characterisation, are also reviewed, with a particular focus on minimally invasive and non-destructive methods suitable for heritage science research.

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“…A fully deacetylated 1000 ft (305 m) roll of CTA-based photographic film can generate about 6.2 ml of acetic acid (Reilly, 1993). Major factors affecting CTA deacetylation include humidity, pH, temperature, storage conditions, photographic film-processing conditions (particularly how well the film was washed after processing), and environmental surroundings (Allen et al , 1987). Considering storage conditions, iron has been shown to act as a catalyst for the degradation reaction, with potential sources being steel film canisters and steel spools that were used for motion picture film storage, and even paper clips used to hold paper on film strips or sheets.…”

Section: Introductionmentioning

confidence: 99%

X-ray diffraction characterization of a distorted Debye–Scherrer film strip – the effect of deacetylation on cellulose triacetate and an improved structural model for cellulose II

Blanton

Kaduk

Johnson³

2014

Powder Diffr.

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A Debye–Scherrer film that had been stored for several years in an office environment file cabinet was observed to be shriveled and distorted in appearance. An investigation using X-ray diffraction was carried out to determine the cause of the physical change in the film strip. As expected, silver phases were detected, due to the photographic capture layer coated on the surface of all traditional X-ray films. An unexpected result was the presence of cellulose II, an indication that a chemical change had occurred in the original cellulose triacetate (CTA) polymer film base. Laboratory experiments used to demonstrate an accelerated method of deacetylation of CTA were carried out, resulting in phase pure cellulose II. A density functional geometry optimization allowed for the generation of an improved structural model for cellulose II. Calculated and experimental powder patterns for cellulose II have been submitted to the International Centre for Diffraction Data for inclusion in future releases of the Powder Diffraction File.

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Degradation of historic cellulose triacetate cinematographic film: The vinegar syndrome

Cited by 40 publications

References 1 publication

Are we overestimating the permanence of cellulose triacetate cinematographic films? A mathematical model for the vinegar syndrome

Are we overestimating the permanence of cellulose triacetate cinematographic films? A mathematical model for the vinegar syndrome

Plasticiser loss in heritage collections: its prevalence, cause, effect, and methods for analysis

X-ray diffraction characterization of a distorted Debye–Scherrer film strip – the effect of deacetylation on cellulose triacetate and an improved structural model for cellulose II

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