Mechanisms of deterioration in cellulose nitrate base archival cinematograph film

Edge, Michèle; Allen, Norman S.; Hayes, M.; Riley, P. N. K.; Horie, C.V.; Luc-Gardette, Jean

doi:10.1016/0014-3057(90)90218-s

Cited by 35 publications

(21 citation statements)

References 4 publications

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“…The results obtained in this work (see especially Figure 1) demonstrate that the molar ratio of nitrite-to-nitrate ions could be very different from 3, as anticipated from previous literature [26,28], and varies in the time course of the denitration reaction. This provides a deeper insight into the understanding of the kinetics of the competing denitration reactions.…”

Section: Highlight On the Alkaline Denitration Reactionsupporting

confidence: 64%

“…Several works have already shown that the alkaline hydrolysis of NCs mainly results in NC denitration [18,19,24,26,27], with nitrite and nitrate ions being the very main compounds containing nitrogen [18,24,26,27]. The release of these anions has been so far explained by competitive reactional mechanisms [28]. Although this mechanism does not allow to specify a value for this ratio, a nitrite to nitrate molar ratio close to 3 has been set forth, regardless of the nitrogen content of the NC [26], and of hydrolysis time, suggesting a single step process [27].…”

Section: Influence Of the Nitrogen Content Of Nc On The Molar Ratio Omentioning

confidence: 99%

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A new method for the determination of the nitrogen content of nitrocellulose based on the molar ratio of nitrite-to-nitrate ions released after alkaline hydrolysis

Alinat

Delaunay

Archer

et al. 2015

Journal of Hazardous Materials

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A new method was proposed to determine the nitrogen content of nitrocelluloses (NCs). It is based on the finding of a linear relationship between the nitrogen content and the molar ratio of nitrite-to-nitrate ions released after alkaline hydrolysis. Capillary electrophoresis was used to monitor the concentration of nitrite and nitrate ions. The influences of hydrolysis time and molar mass of NC on the molar ratio of nitrite-to-nitrate ions were investigated, and new insights into the understanding of the alkaline denitration mechanism of NCs, underlying this analytical strategy is provided. The method was then tested successfully with various explosive and non-explosive NC-containing samples such as various daily products and smokeless gunpowders. Inherently to its principle exploiting a concentration ratio, this method shows very good repeatability in the determination of nitrogen content in real samples with relative standard deviation (n = 3) inferior to 1.5%, and also provides very significant advantages with respect to sample extraction, analysis time (1h for alkaline hydrolysis, 3 min for electrophoretic separation), which was about 5 times shorter than for the classical Devarda's method, currently used in industry, and safety conditions (no need for preliminary drying NC samples, mild hydrolysis conditions with 1M sodium hydroxide for 1h at 60 °C).

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Section: Highlight On the Alkaline Denitration Reactionsupporting

confidence: 64%

Section: Influence Of the Nitrogen Content Of Nc On The Molar Ratio Omentioning

confidence: 99%

A new method for the determination of the nitrogen content of nitrocellulose based on the molar ratio of nitrite-to-nitrate ions released after alkaline hydrolysis

Alinat

Delaunay

Archer

et al. 2015

Journal of Hazardous Materials

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“…The exact mechanism and reaction condi-tions that would have allowed control of nitrite production are not known. A possible scheme for the release of nitrate and nitrite by a partially nitrated NC monomer was suggested by Edge et al (1990). This mechanism, when properly modified and applied to fully nitrated NC, as illustrated in Figure 5, can explain the production of nitrite and nitrate during alkaline hydrolysis but leaves the question of nitrite control unresolved.…”

Section: Resultsmentioning

confidence: 99%

“…Instead, it involves a profound decomposition of the NC backbone to yield various biodegradable organics and inorganic substances including nitrates; nitrites; ammonia; cyanide; nitrogen oxides; carbon dioxide; malic, oxalic, glycolic, trioxyglutaric, dioxybutyric, malonic, tartonic, and other unidentified complex acids; sugar; modified cellulose and its nitrates; and partially denitrated cellulose nitrate. Edge et al (1990) studied the degradation of cinematographic films and proposed NC decomposition and nitrite-nitrate pathways caused by alkaline conditions. The probable mechanism suggested involves three types of decomposition reaction, namely (a) hydrolysis of nitrate ester (ϪONO 2 ) groups, (b) destruction of linkages between particular glucose units, and (c) intermolecular oxidation of particular anhydroglucose rings.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of the Alkaline Hydrolysis of Nitrocellulose

Christodoulatos¹,

Su²,

Koutsospyros³

2001

Water Environment Research

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Cellulose nitrate (nitrocellulose) is an explosive solid substance used in large quantities in various formulations of rocket and gun propellants. Safe destruction of nitrocellulose can be achieved by alkaline hydrolysis, which converts it to biodegradable products that can then be treated by conventional biological processes. The kinetics of the alkaline hydrolysis of munitions-grade nitrocellulose in sodium hydroxide solutions were investigated in completely mixed batch reactors. Experiments were conducted using solutions of alkaline strength ranging from 0.1 to 15% by mass and temperatures in the range of 30 to 90°C. Regression analysis of the kinetic data revealed that alkaline hydrolysis of nitrocellulose is of the order 1.0 and 1.5 with respect to nitrocellulose and hydroxide concentration, respectively. The activation energy of the hydrolysis reaction was found to be 100.9 kJ/mol with a preexponential Arrhenius constant of 4.73 ϫ 10 13 . Nitrite and nitrate, in a 3:1 ratio, were the primary nitrogen species present in the posthydrolysis solution. The kinetic information is pertinent to the development and optimization of nitrocellulose chemical-biological treatment systems. Water Environ. Res., 73, 185 (2001).

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“…Stupeň degradace nitrátu celulózy lze porovnávat zavedením tzv. indexu degradace CN, který lze určit z poměrů rostoucích intenzit pásů skupin -OH (3378 cm -1 ) a C=O (1715 cm -1 ) ku pásu příslušejícímu asymetrické valenční vibraci skupiny-NO 2 (1630 cm -1 [18].…”

Section: Laboratorně Vyrobený Acetát Celulózy (Cta Lab)unclassified

Study of triacetate cinematographic films and magnetic audio track by infrared spectroscopy

Knotek

Korandová

Kalousková

et al. 2018

Koroze a Ochrana Materialu

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Most of the cinematographic film collections stored in film archives are made on a triacetate base, and from the 1950s to the 1980s, a magnetic track was used to record sound. With a large number of archive materials, archives often do not know the chemical composition of film bases, history of use and degradation rates. Therefore, the chemical composition of three films with a magnetic audio track and one representative of the modern film FOMAPAN were investigated by infrared spectroscopy. Selected samples were artificially aged at elevated temperatures and humidity, and the rate of degradation of the film was evaluated by infrared spectroscopy, dimensional changes and gravimetric analysis. Based on the measurements, all of the examined films were made from cellulose triacetate and the binder of the magnetic trackswas cellulose nitrate. To determine the degree of degradation of the binder of the audio track and the triacetate base, a degradation index was created which expresses the ratio of the bandwidths of the characteristic groups in the infrared spectra. It is shown that infrared spectroscopy makes it easy to determine the chemical composition of cinematographic films and to quantify the rate of degradation and the current state of the film base using a suitably chosen degradation index.

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Mechanisms of deterioration in cellulose nitrate base archival cinematograph film

Cited by 35 publications

References 4 publications

A new method for the determination of the nitrogen content of nitrocellulose based on the molar ratio of nitrite-to-nitrate ions released after alkaline hydrolysis

A new method for the determination of the nitrogen content of nitrocellulose based on the molar ratio of nitrite-to-nitrate ions released after alkaline hydrolysis

Kinetics of the Alkaline Hydrolysis of Nitrocellulose

Study of triacetate cinematographic films and magnetic audio track by infrared spectroscopy

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