Oxygen Depletion Testing of Metals

The altered nature of archaeological metals means they deteriorate at much lower relative humidity (RH) conditions than historical metals. The study of deterioration for such materials is hampered by their complexity, variability and difficulties in measuring deterioration. Placing an object in a sealed container, controlling the RH and pollutant gases and measuring any decrease in oxygen concentration is an accessible method to measure the deterioration rate. It has been used for research into suitable environmental conditions to manage the deterioration rates of such artefacts, including the differences in the response of artefacts from different excavation sites. Some objects need the careful control of RH to low values; this is expensive to maintain and poses risks to other artefacts displayed together. Many objects are actually stable up to quite high RH values, and oxygen depletion testing has been used to identify those that can be safely displayed with minimal environmental control. The accelerated corrosion ‘Oddy’ test is frequently used to sift out unsuitable display materials. T the visual assessment is widely recognized to be subjective. the test container has been modified and oxygen depletion appears to give good quantitative measurements of corrosion that correspond with both visual comparison and corrosion loss measurement with linear stripping voltametry or chemical stripping for copper, lead and steel but not for silver.

Design and validation of tailored colour reference charts for monitoring cultural heritage degradation

Colour changes of cultural heritage objects can be related with degradation of materials, thus a proper colour monitoring system can be used to detect conservation problems. With this purpose, a monitoring methodology for cultural heritage preventive conservation based on tailored colour reference charts and image analysis is proposed.Reference colour charts have been designed and tested for use in museums. Charts containing 64 colour patches have been printed using high-stability inks on 4 different substrates: Acid-free paper SkyLight, Acid-free paper covered with a propylene film, FOREX® and GlassPack. The stability has been studied by accelerated ageing in an UV chamber, and the harmlessness of the materials by Oddy Test. The final selection of material, laminated paper, is a balance between the colour change upon ageing and the performance in the Oddy Test. Using this material and the proposed design, colour change of copper and silver coupons has been assessed using images that are adjusted and calibrated by an adaptive calibration framework employing a given set of reference colours which homogenises the visual information in the supplied images. Thus, regardless of the camera of origin, any processed picture will deliver reliable information of the state of the colour in the metal surfaces at the moment it was taken.Results demonstrate the adequacy of the approach and the design for colour calibration, so these charts can be used to monitor colour change of sensitive materials –metal coupons– using photographs. As colour change of reference metals is a consequence of corrosion by environmental factors this may be used as a measure of air quality in museum environments. This methodology can be used to design a low-cost preventive conservation tool, where colour change of metal coupons –or other reference materials– can be followed through image analysis of pictures taken periodically by conservators or visitors, introducing citizen science in the conservation strategy.

Oddy Tests: Adding the Analytical Dimension

The so-called “Oddy test” has gained popularity in art and archaeology collections because it is inexpensive to use, and the results are relatively easy to analyze. However, the method is also subjective and does not identify the pollutants. Here we present a modification to the traditional test that addresses these drawbacks and aims at providing solutions. Activated carbon was used to adsorb the volatile emissions generated within the standard Oddy test setup. Gas chromatography–mass spectrometry (GC-MS) analysis of the volatile organic compounds (VOCs) desorbed from the activated carbon detected pollutants within a considerably shorter time frame than the traditional Oddy test and provided both qualitative and quantitative data. GC-MS analysis of volatiles off-gassed during the Oddy test provided information about the VOCs from local brands of materials commonly used for conservation and storage of objects in collections. The use of GC-MS analysis of volatiles improves the Oddy test in a fast, sensitive, and quantitative manner.

Silver Nanoparticle Films as Sulfide Gas Sensors in Oddy Tests

The preparation and performance of a silver nanoparticle-based sensor for use in Oddy tests are reported. A suspension of spherical silver nanoparticles (Ag NPs) (mean diameter of 30 nm, absorption of surface plasmon resonance (SPR) at 428 nm) in methanol was synthesized and the Ag NPs were self-assembled into monolayer films on glass slides, using polyethylenimine as a linking agent. UV-vis spectrophotometry was employed to measure the SPR intensity of the Ag NP films in order to evaluate the extent of reaction. It was observed that the Ag NP films were quite stable under Oddy test conditions in a blank test, after a brief alteration of the spectrum due to particle dispersal, with no significant decrease in the SPR intensity after 1.5 months at 60°C and 100% RH. The sensitivity of Ag NP films to sulfide gases emitted from a test wool fabric in the Oddy test was investigated. UV-vis spectra taken after the Oddy tests showed the disappearance of the Ag NP SPR peak and the growth of the UV absorption due to Ag2S. Elemental analysis with energy dispersive x-ray spectroscopy confirmed that sulfur had been incorporated into the Ag NP film. Ag NP assemblies of lower NP density were created that indicated the presence of sulfide gases prior to significant tarnishing of a Ag foil. The results demonstrate that the Ag NP films can be used as sensitive, quantitative optical sensors to replace Ag foils in the Oddy test system.