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Photodégradation des résines naturelles : application au domaine artistique

机译:天然树脂的光降解:在艺术领域的应用

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摘要

This thesis presents a study on the photochemical degradation of natural resins used in the manufacture of painting varnishes. Following the literature, five resins were chosen for our experiments: sandarac, Manila copal, colophony, mastic and dammar. Varnishes were made from those resins dissolved in alcohol, oil or turpentine spirit, as found in old recipes. They were then photo-aged by irradiation under artificial light. The study by infrared spectrometry enabled the identification of the type of resin. Although various specific absorption bands were highlighted, they tend to disappear all along the photoageing process. Nevertheless, the C-H band situated between 2850 and 3050 cm-1 allows to separate diterpenic and triterpenic resins and the analysis by principal components can help the identification. Thanks to the study by GC-MS we could identify most of the molecules present in our varnishes by developing the fragmentation study in mass spectrometry. An advanced study of the molecules behaviour was done, especially by MS/MS experiments. Four photo-degradation reactions were observed: isomerisation, cleavage, hydroxylation and Norrish I oxidation of the terpenoids. The choice of the solvent used in the varnish can affect its composition and degradation kinetic, mostly for oil varnishes. Besides, a window pane placed before the varnish will influence the photochemical mechanisms. Ancient varnishes collected by conservator-restorers were analysed and identified thanks to the database elaborated from our results, validating our methodology. The first experiments of molecularly imprinted polymers were carried out with some encouraging results for the analysis of mixed terpenoids
机译:本文提出了一种用于制造油漆的天然树脂的光化学降解的研究。根据文献资料,我们选择了五种树脂作为我们的实验材料:山达拉克,马尼拉椰棕,树脂,胶泥和达玛。清漆是由溶解在酒精,油或松节油中的那些树脂制成的,这在旧食谱中是发现的。然后通过在人造光下照射使它们光老化。通过红外光谱法进行的研究可以识别树脂的类型。尽管突出了各种特定的吸收带,但它们在整个光老化过程中趋于消失。然而,位于2850至3050 cm-1之间的C-H带允许分离二萜和三萜树脂,并且通过主要成分进行的分析可以帮助识别。通过GC-MS的研究,我们可以通过开展质谱碎裂研究来鉴定清漆中存在的大多数分子。进行了分子行为的高级研究,尤其是通过MS / MS实验。观察到四个光降解反应:萜类的异构化,裂解,羟基化和Norrish I氧化。清漆中使用的溶剂的选择会影响其组成和降解动力学,主要是用于油性清漆。此外,放置在清漆前的窗玻璃会影响光化学机理。通过我们的结果精心制作的数据库,分析并鉴定了保存者-修复者收集的古代清漆,从而验证了我们的方法。进行分子印迹聚合物的首次实验,获得了一些令人鼓舞的结果,用于分析混合萜类化合物

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    Azemard Clara;

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  • 年度 2014
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  • 原文格式 PDF
  • 正文语种 fr
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