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研究生: 楊勝雄
Yang, Sheng-Hsiung
論文名稱: 車漆成分應用於鑑別刑事證據之研究
A Study on Paint Polymers for the Differentiation of Forensic Evidences
指導教授: 吳家誠
Wu, Jia-Cheng
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 2015
畢業學年度: 103
語文別: 中文
論文頁數: 162
中文關鍵詞: 車漆鑑定熱裂解氣相層析質譜分析法主成分分析集群分析苯乙烯定量
英文關鍵詞: Paint examination, Py-GC/MS, PCA, HCA, Styrene content
論文種類: 學術論文
相關次數: 點閱:178下載:5
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  • 本研究的目標在於開發一套有效的數據處理方法,可以針對車漆樣品的熱解資料得到其分佈的狀態,評估以平均質譜技術結合主成分分析及集群分析應用的可行性及實用性,並進一步延伸數據的價值,為此我們調查國內車漆的配方,並從中歸納15種常見添加成分質譜中的76個質量/電荷(m/z)訊息作為區分與合併樣品的多變量統計分析的指標。另一方面,聚苯乙烯為車漆中常見的成分,由於具有高質譜感受性,經熱裂解氣相層析質譜儀定量後,可發揮高靈敏度及低樣品消耗的優點,經探討聚苯乙烯的熱解性質及評估基質對於定量的干擾情形,我們發展了一套針對少量樣品可以適用的定量方法,可以鑑別不同來源的車漆樣品。本研究所建立的方法均通過國際能力試驗比對及盲樣的檢測以確認其有效性,且優化後的操作過程對例行檢驗的負擔可以減到最低。
    綜整以上研究內容,本研究建立的方法從比對個案的定量分析結果,到大範圍的樣品分類,透過仔細及深入的數據比較過程,提供評判證物彼此的關聯性,藉由結合熱裂解氣相層析質譜儀及多變量統計與化學計量分析的方式,解讀微小的車漆樣品在系統中的定位及意涵,展示其證據力的價值內涵與科學意義,相信對於刑事科學研究及實務工作應有相當的助益。

    The aim of this work was to evaluate the capabilities and feasibility of using the averaged mass spectra obtained from pyrograms for assessing the group distributions and similarities of vehicle paint samples. To achieve this, all the profiles of averaged mass spectra were examined using principal component analysis and hierarchical cluster analysis after data processing. The pyrograms of 54 vehicle top coating samples were characterized by mass fragments chosen from 15 major paint constituents commonly used in the paint industry and multivariate chemometric analysis based on 76 variables, used as indicators for the classification of paint samples. Besides, polystyrene (PS) , one of the commonly used ingredients in paint recipes, is quantified by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) which offers satisfactory performance with low sample consumption and high sensitivity. Not only the characteristics of PS during the various pyrolyzing process are discussed, but also the matrix effects on quantification are evaluated for better identification of paint sources. We design a method to identify and quantify paint samples of different sources with limited quantities and high similarities. Furthermore, the method developed was proved to be accurate and reliable by participating international proficiency tests and multi-blind sample comparisons. Under the suggested conditions, extra work and pretreatment in routine work can be minimized. Through careful quantification of styrene component and comparisons of representative mass fragments of the paint constituents, the instrumental data can be treated in more detailed ways for the evaluation of paint evidence. The results indicated that these methods were promising, efficient and time saving tools for examining top-coating paint traces, with the application of combined Py-GC/MS with multivariate chemometrics for forensic purposes. Therefore, this technique can assist forensic scientists in actual cases of traffic accidents with better accuracy and reliability.

    中文摘要 (Ⅰ) 英文摘要 (Ⅱ) 目錄 (Ⅳ) 表目錄 (ⅩⅠ) 圖目錄 (ⅩⅣ) 附件目錄 (ⅩⅦ) 第一章緒論 (1) 1-1研究動機 (1) 1-2國內交通事故鑑定現況 (1) 1-3車漆證物鑑定流程 (4) 1-4車漆成分鑑定技術 (7) 1-4-1實體顯微鏡檢視 (8) 1-4-2顯微分光光譜法與顏色比對 (8) 1-4-3紅外線光譜分析 (10) 1-4-4拉曼光譜分析法 (10) 1-4-5掃瞄式電子顯微鏡/X射線能譜分析法 (11) 1-4-6熱裂解氣相層析質譜分析法 (12) 1-4-7顯微溶解試驗法 (12) 1-4-8資料庫建檔比對法 (13) 1-4-9交叉比對分析方法 (14) 1-5汽車原漆之組成及塗裝 (14) 1-5-1汽車塗料的組成 (15) 1-5-2各年代汽車塗料之演進 (16) 1-5-3目前常用車漆原料組成成分 (18) 1-5-4汽車原漆之塗裝過程 (19) 1-6熱裂解器之演進及介紹 (22) 1-6-1熱裂解原理 (22) 1-6-2熱裂解器的種類 (25) 1-6-3本研究所使用的熱裂解器 (30) 1-7多變量統計分析 (31) 1-7-1主成分分析 (32) 1-7-2群集分析 (32) 1-7-3多變量分析應用於刑事科學之研究 (33) 1-8本研究構想 (34) 第二章實驗內容與儀器設備 (36) 2-1歸納國內車漆塗料中常見樹脂成分 (36) 2-2汽車原漆樣品層次觀察及透明層取樣 (36) 2-2-1所需設備 (36) 2-2-2所需工具 (37) 2-3利用紅外線光譜儀分析汽車原漆組成及分類 (37) 2-3-1所需設備 (37) 2-3-2所需耗材 (37) 2-4建立熱裂解氣相層析質譜儀分析汽車原漆條件 (37) 2-4-1所需設備及配件 (38) 2-4-2所需耗材 (39) 2-5針對15種車漆添加成分進行氣相層析質譜分析 (39) 2-5-1所需試劑 (39) 2-5-2所需標準品 (40) 2-6歸納15種車漆添加成分之質譜碎片及豐度資訊,提取可供使用的變數指標 (41) 2-7以建立的熱裂解氣相層析儀條件分析汽車原漆樣品 (41) 2-7-1所需比對車漆樣品 (41) 2-8建立汽車原漆樣品經裂解分析後之數據處理原則 (42) 2-9能力試驗比對樣品及盲樣分析 (42) 2-9-1所需三組能力試驗比對樣品資訊 (43) 2-9-2所需盲樣及其他任意組合之樣品資訊 (45) 2-10相關統計軟體參數設定 (45) 2-10-1所需軟體 (46) 2-11苯乙烯、聚苯乙烯在本研究中的角色 (46) 2-12主成分分析 (46) 2-13集群分析 (47) 2-14運用熱裂解氣相層析質譜分析法對於苯乙烯成分定量探討 (47) 2-14-1所需設備、器具 (47) 2-14-2所需實際樣品 (48) 2-15苯乙烯定量結果納入評估樣品的變數之可行性及結果討論 (48) 第三章結果與討論 (49) 3-1歸納國內車漆塗料中常見的成分 (49) 3-1-1理由 (49) 3-1-2選擇研究標的原則 (50) 3-2車漆樣品的觀察與透明層取樣方法 (51) 3-2-1樣品觀察與紀錄 (51) 3-2-2樣品前處理 (51) 3-3利用紅外線光譜儀分析汽車面漆組成及分類 (52) 3-4熱裂解氣相層析質譜儀分析汽車面漆條件 (53) 3-4-1熱裂解器參數設定 (53) 3-4-2氣相層析質譜儀條件設定 (53) 3-5針對15種車漆添加成分進行氣相層析質譜分析 (54) 3-5-1實驗步驟 (54) 3-5-2 15種車漆添加成分標準品進行氣相層析質譜分析 (55) 3-6歸納15種車漆添加成分之質譜碎片及豐度資訊,提取可供使用的變數指標 (59) 3-6-1分析15種車漆添加成分之質譜圖,並建立質譜碎片取樣規則 (59) 3-6-2提取76個質譜碎片作為評估樣品分佈的變數 (61) 3-6-3提取之質譜碎片可能隱含之意義 (62) 3-7汽車原漆樣品、能力試驗比對樣品及盲樣以建立的條件分析 (63) 3-8建立汽車原漆樣品經裂解分析後之數據處理原則 (63) 3-8-1平均質譜 (63) 3-8-2選擇平均質譜法的理由 (63) 3-9 SPSS統計軟體計算結果 (67) 3-9-1變量的共同度 (67) 3-9-2主成分分析 (69) 3-9-3未經旋轉的因子負荷矩陣 (74) 3-9-4旋轉後的因子負荷矩陣 (78) 3-10集群分析 (88) 3-10-1 Q型的集群分析 (89) 3-10-2 R型的集群分析 (91) 3-11真實樣品在統計模型的分析結果 (93) 3-12能力試驗比對樣品及盲樣分析 (97) 3-12-1使用能力試驗比對樣品的理由與結果分析 (97) 3-12-2盲樣分析對於模型評估的結果 (100) 3-13熱裂解氣相層析質譜分析法針對車漆中特定成分之定量探討 (107) 3-13-1車漆成分定量想法之理由 (107) 3-13-2文獻探討 (109) 3-13-3實驗目標 (109) 3-13-4苯乙烯性質研究及待解決之問題 (109) 3-13-5聚苯乙烯熱裂解性質之探討 (111) 3-13-6熱裂解氣相層析質譜儀之條件建立 (121) 3-13-7苯乙烯單體成分之定性、定量結果 (127) 3-13-8能力試驗樣品定量結果 (131) 3-13-9影響定量因素之探討 (134) 3-14評估車漆中苯乙烯定量結果增列為統計分析變數之可行性 (137) 3-15苯乙烯定量結果納入評估樣品的變數及結果討論 (139) 3-15-1車漆樣品的定量程序 (139) 3-15-2增列車漆樣品之定量結果為新的變數及結果討論 (141) 第四章結論 (150) 第五章參考文獻 (154)

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