以拉曼光譜技術及基質輔助雷射脫附游離質譜法分析藍色水彩顏料及應用在畫作上的鑑定

Abstract

本論文以拉曼光譜技術建立各種藍色顏料的標準參考拉曼圖譜，使用的藍色顏料包括群青、酞青藍、鈷藍、普魯士藍、靛藍等，共8種常用的藍色顏料。再分析87支市售的藍色水彩顏料，發現較多水彩顏料是以群青及酞青藍為成分製作，甚至能發現有些藍色是與白色、紫色或綠色顏料混和而成。而有些無法以拉曼光譜儀直接測量到的顏料，以水洗方式純化顏料後再進行測量，洗去顏料中的甘油、阿拉伯膠等物質後，便能成功檢測出該顏料的拉曼光譜。建立標準參考拉曼圖譜後，本論文也實際應用於畫作上的鑑定，分析由國立台灣師範大學文物保存中心提供的畫作，鑑定出畫作上的藍色顏料為群青，紅色顏料為朱紅，黃色顏料為鉻黃，而綠色顏料為普魯士藍混和鉻黃。除了使用拉曼光譜技術之外，本論文也利用基質輔助雷射脫附游離飛行時間質譜技術(MALDI-TOF MS)針對藍色水彩顏料進行分析的研究，因為MALDI-TOF MS具有可大量分析樣品的優勢，未來可能用於大量分析未知顏料或建立顏料質譜數據庫，實驗結果發現酞青藍、陰丹酮藍以及靛藍顏料均能得到質譜圖。

In this paper, Raman spectroscopy is used to establish the standard reference Raman spectra of various blue pigments. The blue pigments used include ultramarine blue, phthalocyanine blue, cobalt blue, Prussian blue, indigo, etc., a total of 8 commonly used blue pigments. After analyzing 87 commercially available blue watercolor paints, it was found that most of the watercolor paints were made of ultramarine blue and phthalocyanine blue, and even some blues were mixed with white paints. For some pigments that cannot be directly measured by Raman spectroscopy, the pigments are purified by washing with water and then measured. After washing away the glycerin, gum arabic and other substances in the pigment, the Raman spectrum of the pigment can be successfully detected.After the establishment of the standard reference Raman spectrum, this thesis was also applied to the identification of paintings. The paintings provided by the National Taiwan Normal University Cultural Relics Preservation Center were analyzed, and the blue pigments on the paintings were identified as ultramarine blue, the red pigments were cinnabar, the yellow pigment were chrome yellow, and the green pigment as Prussian blue mixed with chrome yellow.In addition to using Raman spectroscopy, this paper also used matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) to analyze blue watercolor pigments, because MALDI-TOF MS has the ability to analyze a large number of samples. In the future, it may be used to analyze a large number of unknown pigments or establish a pigment mass spectrometry database. The experimental results found that phthalocyanine blue, indanthrone blue and indigo pigments can all obtain mass spectra.