Acid-catalysed degradation of historic cellulose triacetate, cinematographic film: Influence of various film parameters

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

doi:10.1016/0014-3057(88)90002-x

Cited by 15 publications

(12 citation statements)

References 2 publications

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“…Tightly sealed storage containers have been found to prevent acetic acid from escaping from the film, increasing the potential for autocatalysis (19,52); ventilated containers facilitate the escape of acetic acid (53).…”

Section: Enclosure Designmentioning

confidence: 99%

“…Typically, other changes in the film properties will occur after the vinegar syndrome has been initiated. These include reduction in tensile strength or toughness due to degradation of the polymer (embrittlement), buckling of emulsion away from the base layer (shrinkage and channelling), and surface deposits caused by the migration of plasticiser (crystals or bubbles) (17)(18)(19)(20)(21). Emissions of acetic acid from degraded CTA films have also been shown to induce vinegar syndrome in undegraded films stored nearby, lending cellulose acetate its reputation as a 'malignant' plastic (22,23).…”

Section: Introductionmentioning

confidence: 99%

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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: Enclosure Designmentioning

confidence: 99%

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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show abstract

“…Among the different plasticisers, only TPP diffused from the inside of the film to the surface as the deterioration progressed and then recrystallised. Although we did not know the exact film composition, previous studies indicated that a typical TAC film contained 100 g of CA, 60 g of ethyl or methyl alcohol, and 15 g of TPP 17 . The melting point of TPP was 48–50 °C; therefore, the climate of many countries promoted TPP melting.…”

Section: Discussionmentioning

confidence: 98%

“…However, its gelatine emulsion did not shrink with the film as it did not undergo deterioration, leading to the separation of the emulsion from the film base (a so-called "channelling" effect). Once this process has begun, the remaining life of the film was shortened significantly due to the acceleration and autocatalysis of the degradation reaction [11][12][13][14] .To prevent such degradation, early diagnosis of the films stored under cool and humid conditions is required 10,[15][16][17][18][19][20][21][22] . Although standard storage conditions for TAC-based films have been established, chemical analysis of the degradation products was not performed, and efficient diagnostic techniques were not developed.…”

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confidence: 99%

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Composition of the white precipitate formed on the surface of damaged triacetyl cellulose-based motion picture films

Takahashi

Sasaki

Hayakawa

et al. 2021

Sci Rep

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To achieve a better understanding of the “vinegar syndrome” phenomenon, which has caused serious damage to triacetyl cellulose-based motion picture films, the white powder obtained from damaged film surfaces was analysed in this study. The powder was found to be soluble in acetone, diethyl ether, dimethylformamide, and chloroform, but insoluble in water. From the results of 1H, 13C and 31P nuclear magnetic resonance spectroscopy, mass spectrometry, and X-ray fluorescence measurements, it was concluded that the white precipitate had a molecular weight of 326 amu and was composed of triphenyl phosphate (C18H15O4P).

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Fluorescence and Fourier-transform infrared spectroscopy for the analysis of iconic Italian design lamps made of polymeric materials

et al. 2010

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The preservation of design object collections requires an understanding of their constituent materials which are often polymeric blends. Challenges associated with aging of complex polymers from objects with an unknown physical history may compromise the interpretation of data from analytical techniques, and therefore complicate the assessment of the condition of polymers in indoor museum environments. This study focuses on the analysis of polymeric materials from three well-known Italian design lamps from the 1960s. To assess the degree of chemical modifications in the polymers, non-destructive molecular spectroscopic techniques, Fourier-transform infrared (FTIR) and fluorescence spectroscopy, have been applied directly on the object surfaces using an optical fiber probe and through examination of micro samples. FTIR spectra of the different polymers, polyvinylacetate (PVAc) for the lamps Taraxacum and Fantasma, and both acrylonitrile-butadiene-styrene polymer (ABS) and cellulose acetate (CA) for the lamp Nesso, allowed the detection of ongoing deterioration processes. Fluorescence spectroscopy proved particularly sensitive for the detection of molecular changes in the polymeric objects, as the spectra obtained from the examined lamps differ significantly from those of the unaged reference materials. Differences in fluorescence spectra are also detected between different points on the same object further indicating the presence of different chemical species on the surfaces. With the aid of complementary data from FTIR spectroscopy, an interpretation of the emission spectra of the studied polymeric objects is here proposed, further suggesting that fluorescence spectroscopy may be useful for following the degradation of historical polymeric objects.

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Acid-catalysed degradation of historic cellulose triacetate, cinematographic film: Influence of various film parameters

Cited by 15 publications

References 2 publications

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

Composition of the white precipitate formed on the surface of damaged triacetyl cellulose-based motion picture films

Fluorescence and Fourier-transform infrared spectroscopy for the analysis of iconic Italian design lamps made of polymeric materials

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