Browning Phenomenon of Medieval Stained Glass Windows

Ferrand, J.; Rossano, Stéphanie; Loisel, Catherine; Trcera, Nicolas; Hullebusch, Eric D. van; Bousta, Faisl; Pallot‐Frossard, Isabelle

doi:10.1021/ac504193z

Cited by 20 publications

(14 citation statements)

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“…The XAFS technique has also been used to study ancient and medieval glasses [ 154 , 155 , 156 , 157 , 158 , 159 , 160 , 161 , 162 , 163 , 164 ]. Different studies focused on the determination of the origin of color in ancient and medieval glasses because this kind of information is important to understand the manufacturing technique of ancient glassware and potteries [ 154 , 155 , 158 , 159 , 160 , 165 ]. Recently, Farges and Cotte published a chapter in a book where they update as compared to the most recent review papers published on the application of XAFS technique to study cultural heritage [ 166 ].…”

Section: Examples Of Using the Xafs Technique To Study The Atomic mentioning

confidence: 99%

“…Among different studies where XAFS was used to study medieval glasses, we can cite, for example the work by Ferrand et al [ 160 ] that analyzed by XAFS three pieces of historical on-site glass windows dated from the 13th to 16th century and one archeological sample from the 8th century that showed Mn-rich brown spots at their surface or subsurface [ 160 ]. Based on XAFS results, they observed that the oxidation state of Mn is different compared to fresh glass confirming that a modification of the Mn environment occurred.…”

Section: Examples Of Using the Xafs Technique To Study The Atomic mentioning

confidence: 99%

“…Based on XAFS results, they observed that the oxidation state of Mn is different compared to fresh glass confirming that a modification of the Mn environment occurred. No precise identification of the crystalline phase modification was possible from a fingerprint analysis of XANES spectra whereas EXAFS data analysis led to identifying a Mn environment in this crystalline phase modification [ 160 ].…”

Section: Examples Of Using the Xafs Technique To Study The Atomic mentioning

confidence: 99%

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X-ray Absorption Fine Structure (XAFS) Studies of Oxide Glasses—A 45-Year Overview

Mastelaro

Zanotto

2018

Materials

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X-ray Absorption Fine Structure (XAFS) spectroscopy has been widely used to characterize the short-range order of glassy materials since the theoretical basis was established 45 years ago. Soon after the technique became accessible, mainly due to the existence of Synchrotron laboratories, a wide range of glassy materials was characterized. Silicate glasses have been the most studied because they are easy to prepare, they have commercial value and are similar to natural glasses, but borate, germanate, phosphate, tellurite and other less frequent oxide glasses have also been studied. In this manuscript, we review reported advances in the structural characterization of oxide-based glasses using this technique. A focus is on structural characterization of transition metal ions, especially Ti, Fe, and Ni, and their role in different properties of synthetic oxide-based glasses, as well as their important function in the formation of natural glasses and magmas, and in nucleation and crystallization. We also give some examples of XAFS applications for structural characterization of glasses submitted to high pressure, glasses used to store radioactive waste and medieval glasses. This updated, comprehensive review will likely serve as a useful guide to clarify the details of the short-range structure of oxide glasses.

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Section: Examples Of Using the Xafs Technique To Study The Atomic mentioning

confidence: 99%

Section: Examples Of Using the Xafs Technique To Study The Atomic mentioning

confidence: 99%

Section: Examples Of Using the Xafs Technique To Study The Atomic mentioning

confidence: 99%

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X-ray Absorption Fine Structure (XAFS) Studies of Oxide Glasses—A 45-Year Overview

Mastelaro

Zanotto

2018

Materials

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“…The spotty brown coloration of the original incarnate glass is caused by precipitation of four‐valent manganese ions present as secondary pyrolusite . However, as observed by Ferrand et al on historical (13th‐16th century) window glass, extended brown coloration contains mainly Mn 3+ ions. Sometimes precipitation of the spinel hausmannite was observed…”

Section: Extension To Nuclear Waste Glassesmentioning

confidence: 92%

Weathering of ancient and medieval glasses—potential proxy for nuclear fuel waste glasses. A perennial challenge revisited

Heimann¹

2017

Int J of Appl Glass Sci

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Ancient and medieval glasses that have survived the deleterious attack of the environment for millennia have long since proposed as proxy to estimate and predict the corrosion mechanism of nuclear waste glasses. However, because both composition and environmental burial conditions vastly differ between hydrolytically less stable ancient glasses and modern advanced nuclear waste glasses, only semiquantitative conclusions can be drawn about the likely performance of the latter as longterm stable immobilization matrices for high-level radioactive nuclear waste. In this contribution, special emphasis has been devoted to the behavior of manganese, present as both iron decolorant and coloring ions in ancient Roman and medieval glasses. Study of the behavior of manganese in ancient glasses during weathering may provide some limited clues to the behavior of long-lived radioactive technetium-99. Knowledge of the corrosion kinetics of ancient glasses will allow, eventually, a reasonable prediction of the long-term performance of glassy nuclear waste forms as function of their composition and environmental parameters, i.e. groundwater composition, flow rate, pH, solution volume, and surface area.corrosion, manganese, medieval glasses, nuclear waste glass, technetium | INTRODUCTIONGlass is a supercooled melt, a state that retains the statistical short-range order (SRO) of a liquid during cooling in lieu of the 3D-periodical long-range order (LRO) of a crystal.1 Key distinguishing properties of glass as opposed to crystalline ceramics include the following features:1. Glass shows isotropic properties, i.e. there are no direction-dependent variations of physical properties such as thermal expansion, index of refraction, hardness, modulus, electrical polarization, and others. The reason for this can be sought in the statistical distribution of structural elements such as tetrahedral glass-forming SiO 4 groups. 2. Glass shows reversible softening and solidification during transformation from brittle-solid to liquid state and vice versa, without formation of a new phase. Softening and solidification respectively occur within a more or less wide temperature interval, dependent on the composition, in particular on the silica content. Hence, in a thermodynamical sense glass has no fixed 'melting point'.In addition, the thermodynamic disequilibrium of glass leads to its composition-dependent leachability in the presence of water as well as minerals contained, for example in burial environment. Many ancient glasses buried under humic climatic conditions or exposed to deleterious environment such as external medieval church windows show surfaces depleted of leachable alkaline and/or alkaline earth ions. However, frequently those surface layers are strongly enriched in amorphous silica as well as silicate minerals such as clays or, rarely, zeolites.2

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“…To minimize photoreduction effects commonly reported for Mn-bearing phases (Bargar et al, 2005;Manceau et al, 2012;Ferrand, 2014;Ferrand et al, 2015), the beam size used was 50 × 50 µm 2 , and the photon flux was reduced together with data collection time. XANES spectra were collected from 6505 to 6630 eV with a 0.2 eV step size, and 0.4 s counting time per step.…”

Section: µ-X-ray Absorption Near Edge Structure (Xanes) Spectroscopymentioning

confidence: 99%

Characterization and origin of the Mn-rich patinas formed on Lunéville château sandstones

et al. 2021

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Abstract. The formation of iron- and/or manganese-rich dark patinas on sandstones is a common natural phenomenon that occurs also on building stones. Lunéville château, in eastern France, presents such patinas that developed either under natural conditions (rain and time) or after an accidental fire and exposure to significant amounts of water as part of attempts to extinguish the fire. The present study aimed at characterizing both types of patinas in an effort to determine their formation mechanisms and Mn sources. In both cases, Mn required for patina formation likely derives from the reductive dissolution of Mn-rich minerals present in pristine sandstones, as suggested by the contrasting mineralogy and chemistry of Mn-rich phases present in the bulk and in the patina of a given building block. Reduced Mn species then migrate to the exposed surface of building blocks where they are re-oxidized via undetermined processes. Patinas developing “naturally” over time result from the alternation of wetting-reducing and drying-oxidizing cycles and appear to be composed of birnessite. Patinas formed after the 2003 fire result from this single accidental event and form a much thinner, heterogeneous, and discontinuous layer of poorly crystalline lithiophorite at the sandstone surface (∼ 0–150 µm compared to ∼ 300–600 µm for “natural” patinas). The lack of Mn-rich patinas on areas of Lunéville château is likely related to the lower Mn content of pristine sandstone blocks.

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Browning Phenomenon of Medieval Stained Glass Windows

Cited by 20 publications

References 45 publications

X-ray Absorption Fine Structure (XAFS) Studies of Oxide Glasses—A 45-Year Overview

X-ray Absorption Fine Structure (XAFS) Studies of Oxide Glasses—A 45-Year Overview

Weathering of ancient and medieval glasses—potential proxy for nuclear fuel waste glasses. A perennial challenge revisited

Characterization and origin of the Mn-rich patinas formed on Lunéville château sandstones

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