拉曼光譜技術在顏料鑑定及建立資料庫上的應用

Identifying pigments and creating database by Raman spectroscopy

簡佩妏(Chien Pei-Wen)

指導教授 ： 林震煌

國立臺灣師範大學/理學院/化學系/碩士(2020年)

https://doi.org/10.6345/NTNU202000589

摘要

白色顏料是繪畫上一個分常重要的顏料，加上畫家需要呈現不同的繪畫感覺，因此有許多以不同材料來源所製成的白色顏料。本論文選擇檢測快速且具有獨一無二的拉曼散射訊號的拉曼光譜技術對胡粉、鉛白、珍珠粉、白雲石、方解末、鋅白、鈦白、立德粉與水干雲母共9種白色顏料進行鑑定，並應用於畫作上的顏料分析
除了白色顏料的研究，本論文也選用7種碳酸鈣顏料，搭配本實驗室開發的LabVIEW拉曼光譜背景螢光減去程式，解決碳酸鈣顏料拉曼光譜螢光訊號干擾的問題。並且透過此程式具有將扣除的螢光訊號重新繪製成螢光光譜的特點。將7種碳酸鈣顏料被扣除的螢光訊號重新繪製成螢光光譜，並根據螢光最大波長的數值成功分辨出這7種碳酸鈣顏料。
本論文也進行畫作上顏料的鑑定。進行檢測的有五月雨以及奈良市登大路町十四這兩幅畫。透過拉曼光譜的結果，以及LabVIEW拉曼光譜背景螢光減去程式的應用。推測五月雨的白色蝴蝶可能使用胡粉或方解末這兩種以碳酸鈣為主成分的白色顏料。奈良市登大路町十四的打底層則推測出是使用鉛白，白色建築物則是使用鋅白。
本論文也會介紹LabVIEW文物修復專用光譜資料庫，此資料庫為國立臺灣師範大學美術系與化學系共同建立的資料庫，是國立台灣師範大學獨有的資料庫。與其他資料庫相比具有未知物光譜檢索功能。並且搭配Data thief圖檔轉換程式，能夠快速的擴充資料庫，目前資料庫內已有20種天然材料製成的顏料拉曼光譜。

關鍵字

拉曼光譜 ； 顏料 ； 碳酸鈣

並列摘要

White pigments are a very important pigment in painting. In addition, painters need to present different painting feelings, so there are many white pigments made from different materials sources. In this paper, the Raman spectroscopy technology that detects fast and has a unique Raman scattering signal is used to select 9 types of white powder, such as hu powder, lead white, pearl powder, dolomite, calcite, zinc white, titanium white, lithopone and hydromica. Identification of pigments and application of pigment analysis on paintings
In addition to the research of white pigments, seven calcium carbonate pigments were also selected in this thesis, which was used in conjunction with the LabVIEW Raman spectrum background fluorescence subtraction program developed by this laboratory to solve the problem of interference of the fluorescent signal of the calcium carbonate pigment Raman spectrum. And through this program has the feature of redrawing the deducted fluorescent signal into a fluorescent spectrum. The fluorescent signals deducted from the 7 kinds of calcium carbonate pigments are redrawn into the fluorescence spectrum, and the 7 kinds of calcium carbonate pigments are successfully distinguished according to the value of the maximum wavelength of fluorescence.
This paper also conducts the identification of the paint on the painting. Two paintings were tested, May Rain and No.14, Todaiji-cho, Nara City. Through the results of Raman spectroscopy and the application of LabVIEW Raman spectroscopy background fluorescence subtraction program. It is speculated that the white butterfly in May rain may use two kinds of white pigments with calcium carbonate as the main component. The ground floor of 14th Noboriojicho, Nara City speculates that lead white is used, and white buildings are zinc white.
This paper will also introduce the LabVIEW Spectral Database for the restoration of cultural relics. This database is a database jointly established by the Fine Arts Department and the Chemistry Department of the National Taiwan Normal University, and is a unique database of the National Taiwan Normal University. Compared with other databases, it has the spectral search function of unknown objects. And with the Data thief image file conversion program, the database can be quickly expanded. Currently, there are 20 kinds of pigment Raman spectra made of natural materials in the database.

並列關鍵字

Raman spectroscopy ； Pigments ； Calcium carbonate ； LabVIEW

參考文獻

1. Calza, C., et al., XRF applications in archaeometry: analysis of Marajoara pubic covers and pigments from the sarcophagus cartonage of an Egyptian mummy. X‐Ray Spectrometry: An International Journal, 2007, 36(5), 348-354.

2. Hochleitner, B., et al., Historical pigments: a collection analyzed with X-ray diffraction analysis and X-ray fluorescence analysis in order to create a database. Spectrochimica Acta Part B: Atomic Spectroscopy, 2003, 58(4), 641-649.

3. Neelmeijer, C., et al., Paintings—a challenge for XRF and PIXE analysis. X‐Ray Spectrometry: An International Journal, 2000, 29(1), 101-110.

4. Stos-Fertner, Z., Hedges R.E., and Evely R., The application of the XRF-XRD method to the analysis of the pigments of Minoan painted pottery. Archaeometry, 1979, 21(2), 187-194.

5. Van der Snickt, G., et al., μ-XRF/μ-RS vs. SR μ-XRD for pigment identification in illuminated manuscripts. Applied Physics A, 2008, 92(1), 59-68.