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.
Air pollution is one of the environmental influences that degrade cultural heritage objects situated indoors. Other essential influences, such as temperature, relative humidity, and light are often well monitored. The presence of air pollutants is less often measured or included in risk assessment. The MEMORI ® technology presented in this paper was developed as a tool for easy measurement and assessment of the general risk of degradation of heritage objects situated indoors due to indoor exposure to air pollutants. MEMORI dosimetry was performed in locations belonging to English Heritage and Tate (both located in London) and the National Archives of Norway in Oslo, to assess air quality. The related damage risk for collection objects and the protection offered by display and storage designs was assessed. A high level of acidic effect was observed inside a number of showcases, and a high level of oxidizing effect was observed in some room locations. Relatively simple mitigation measures, such as constructing tightly sealed showcases using low emitting materials, installing active carbon absorbing media inside a 'microclimate' frame, and using cardboard storage boxes for paper, significantly improved air quality. Overall, implementation of such measures is likely to improve the preservation of objects and reduce conservation costs.
The design and experimental method for the use of a novel instrument for lightfastness measurements on artwork is presented. The new microfadometer design offers increased durability and portability over the previous, published design, broadening the scope of locations at which data can be acquired. This reduces the need for art handling or transportation in order to gain evidence-based risk assessments for the display of light-sensitive artworks. The instrument focuses a stabilized high powered xenon lamp to a spot 0.25 millimeters (FWHM) while simultaneously monitoring color change. This makes it possible to identify pigments and determine the lightfastness of materials effectively and non-destructively. With 2.59mW or 0.82 lumens (1.7 x10 7 lux for a 0.25mm focused spot) the instrument is capable of fading Blue Wool 1 to a measured 11 ∆E ab value (using CIE standard illuminant D65) in 15 minutes. The temperature increase created by focused radiation was measured to be 3 to 4°C above room temperature. The system was stable within 0.12 ∆E ab over 1 hour and 0.31 ∆E ab over 7 hours . A safety evaluation of the technique is discussed which concludes that some caution should be employed when fading smooth, uniform areas of artworks. The instrument can also incorporate a linear variable filter. This enables the researcher to identify the active wavebands that cause certain degradation reactions and determine the degree of wavelength dependence of fading. Some preliminary results of fading experiments on Prussian blue samples from the paint box of J. M. W Turner (1755-1851) are presented.
A modified microfading spectrometer incorporating a linear variable filter is used to investigate the wavelength dependence of fading of traditional watercolour pigments, dosimeters and fading standards at a higher spectral resolution and/or sampling than had previously been attempted. While the wavelength dependence of photochemical damage was largely found to correlate well with the absorption spectra of each material, exceptions were found in the case of Prussian blue and Prussian green pigments (the latter includes Prussian blue), for which an anti-correlation between the spectral colour change and the absorption spectrum was found.
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