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从绿色到棕色:玻璃窗中现代绿色釉质快速变化的特征

From Green to Brown: Characterization of the Fast Alteration of Modern Greenish Enamels in Glass Windows.

作者信息

Palomar Teresa, Calatayud David G, Oujja Mohamed, Maestro-Guijarro Laura, Aparicio Mario, Mosa Jadra, Koppermann Bettina, Seliger Léonie

机构信息

Instituto de Cerámica y Vidrio (ICV), CSIC, c/Kelsen 5. Campus de Cantoblanco, 28049, Madrid, Spain.

Unidade de Investigação VICARTE-Vidro e Cerâmica para as Artes, NOVA School of Science and Technology, Universidade Nova de Lisboa, Hangar III-Campus da Caparica, 2829-516, Caparica, Portugal.

出版信息

Chempluschem. 2025 Sep;90(9):e202500205. doi: 10.1002/cplu.202500205. Epub 2025 Aug 7.

Abstract

In 2009-2014, new glass panels were produced by the Stained-Glass Studio of Canterbury Cathedral (UK) and installed in St Peter's Church (Little Barrington, Burford), St Lawrence's Church (Mereworth, Kent), and Canterbury Cathedral. After a few years, some spots and stains have appeared on the greenish areas of the panels. The common factor is that the panels were produced using the same green enamel. The present work reports on the studies of the observed alterations in green enamels to propose possible degradation mechanisms. These studies are based on using different analytical techniques such as optical microscopy, scanning electron microscopy energy dispersive X-ray spectroscopy, inductively coupled plasma mass spectrometry, laser-induced breakdown spectroscopy, X-ray diffraction, µ-Raman spectroscopy, profilometry, X-ray photoelectron spectroscopy, and UV-vis spectroscopy. The characterization of the fragments from the original panels showed that a brown layer of dark lead compounds was formed on the green enamel. The alteration occurred in a 3-step alteration mechanism divided into Pb lixiviation from the enamel, formation of hydrocerussite (2PbCO·Pb(OH)), and transformation into scrutinyite (α-PbO) and plattnerite (β-PbO).

摘要

2009年至2014年期间,英国坎特伯雷大教堂的彩色玻璃工作室制作了新的玻璃面板,并安装在小巴林顿的圣彼得教堂(伯福德)、梅勒沃思的圣劳伦斯教堂(肯特)和坎特伯雷大教堂。几年后,面板的绿色区域出现了一些斑点和污渍。共同因素是这些面板使用了相同的绿色珐琅。本研究报告了对绿色珐琅中观察到的变化的研究,以提出可能的降解机制。这些研究基于使用不同的分析技术,如光学显微镜、扫描电子显微镜能谱仪、电感耦合等离子体质谱仪、激光诱导击穿光谱仪、X射线衍射仪、μ-拉曼光谱仪、轮廓仪、X射线光电子能谱仪和紫外可见光谱仪。对原始面板碎片的表征表明,绿色珐琅上形成了一层棕色的深色铅化合物层。这种变化发生在一个三步变化机制中,分为珐琅中铅的浸出、水白铅矿(2PbCO·Pb(OH))的形成,以及向方铅矿(α-PbO)和块黑铅矿(β-PbO)的转变。

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