Shipwreck glass reveals insights into waste-form durability

Historic glass artefacts, especially those submerged in marine environments for centuries, serve as natural testbeds for long-term material stability. Understanding how glasses corrode over decades or centuries is critical for a wide range of applications, from cultural heritage conservation to the safe immobilisation of nuclear waste.  

Until now, lab-based accelerated corrosion tests have been used as proxies – but how well do they mirror real-world behaviour? Researchers from the University of Sheffield and their marine archaeology and materials science collaborators tackled this question in their paper, published in Applied Geochemistry. The team analysed ancient lead-silicate glass ingots recovered from the 18th century shipwreck of the HMS Albion and compared them with laboratory-weathered analogues. Using micro-X-ray absorption spectroscopy at Diamond’s I18 beamline, they probed element redistribution and corrosion layer development.  

When glass is immersed in saline, i.e. oxygenated seawater for extended periods, its surface layers evolve through ion leaching, new phase formation (such as clays or zeolites) and structural collapse – all of which affect long-term durability. Accelerated lab tests simulate this but often differ in time scale, solution chemistry or mechanical stress, which raises the question: Do accelerated tests capture the full complexity of real glass corrosion?

In this study, the team analysed shipwreck-altered lead-silicate glass (with visible corrosion layers up to several hundred microns thick) and compared the leached layers, element migrations (e.g., Pb, Si, Ca) and secondary mineral formation with artificially corroded analogues in lab immersion tests.

At Diamond’s I18 beamline, the team used micro-focused  XAS and XRF to map elemental speciation and spatial distribution across corrosion layers.

Read more on the Diamond website

Synchrotron light helps study the past, prevent corrosion in future

Techniques developed by researchers from Western University for creating images of old, badly tarnished photographs could also be used to study other historic artifacts and fossils and prevent corrosion on modern materials.  

Professor T.K. Sham and colleagues recently confirmed that a new synchrotron imaging technique they developed is just as effective for retrieving corroded daguerreotypes (the earliest form of photographs) as a technique they first reported on back in 2018, and can also be used no matter how badly damaged the image surface is from natural corrosion or cleaning attempts. The new research, which used beamlines at the Canadian Light Source (CLS) at the University of Saskatchewan (USask), is published in the Journal of Cultural Heritage.

“This technique can be used widely in all walks of science, from looking at tissues to materials science,” said Sham. “For example, you could determine whether or how a metal may be corrosion-resistant, or in the case of an already corroded material you can learn what the product of that corrosion is and its distribution on the surface, and then you can work back and think about how to prevent that corrosion from happening.” 

Sham said many applications are possible because synchrotron X-ray is very tunable, which means it can pick out any element and find out what its chemical surrounding is and where it is placed in the sample, even imaging it layer by layer. 

When it comes to the conservation of antiques, Sham’s research could be a game changer too, especially for studying artifacts or fossils that have severe surface deterioration.  

As part of his new research, he uncovered images of a lady and a gentleman fashionably dressed in mid 1850s garments, and one of a baby peacefully wrapped in covers. All of these daguerreotypes, belonging to private collectors and the National Gallery of Canada, were badly damaged — slow deterioration mixed with cleaning attempts may have caused the tarnish. 

He proved that this synchrotron technique is always effective as long as the image particles underneath the tarnish remain intact, a discovery advancing his 2018 study in Scientific Reports. This research was done using the VESPERS and the SXRMB beamlines at the CLS and at the Advanced Photon Source at Argonne National Laboratory near Chicago.

Read more on CLS website

Synchrotron light reveals why modernist stained glass deteriorate

Stained glass is a fragile component of our Cultural Heritage since was used for the windows of buildings, and a large part of it is exposed to weathering and consequently to deterioration. The concern raised regarding the decay shown by the modernist enamelled glass has led the path to a long-term study and to the thesis presented today by Martí Beltrán González. “We are satisfied because totally new information have been obtained and, in particular, data that may help to better preserve the enamelled glass windows of this period ”, highlights Trinitat Pradell, director of the thesis.

Synchrotron light has important applications in the field of historical and artistic heritage and the Universitat Politècnica de Catalunya (UPC) group has been an ALBA user for years to carry out analyses for its research. In this case, the beamline where the experiments have been performed, MSPD, provides the use of microdiffraction technique. Stained glass samples cut into very thin sections (100 microns) have been analysed through X-rays to obtain high resolution diffraction patterns that give information about the chemical composition of the materials and enables the identification of the pigments and colorants used. The microstructure of the materials and the products formed as a result of corrosion can be detected too thanks to this synchrotron light technique.

Read more on the ALBA website

Image: Modernist stained glass from Museu d’Art de Cerdanyola (Les Dames de Cerdanyola) by L. Dietrich, 1888–1910, showing the characteristic green and blue enamels decay

Credit: Jordi Bonet