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:155 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.
1.臺灣地區道路交通事故統計,內政部警政署,2015
2.「交通管理機關」未能妥善辦理道路交通事故相關業務糾正案,
監察院公報2360期
3.ASTM(E1610-14, Forensic Paint Analysis and Comparison)
4.Yuzawa T., Watanabe C., Tsuge S, Shimane N., Imai H.,
Application of a pyrolysis-GC/MS system incorporating
with micro-UV irradiation to rapid evaluation of the
weatherability of acrylic coating paints for house
exterior walls, Polymer Degradation and Stability,
2011, 96, 91-96
5.Watanabe C., Tsuge S., Ohtani H., Development of new
pyrolysis-GC/MS system incorporated with on-line
micro-ultraviolet irradiation for rapid evaluation of
photo, thermal, and oxidative degradation of polymers,
Polymer Degradation and Stability, 2009, 94, 1467-1472
6.Allen T. J., The examination of thin sections of
coloured paints by light microscopy ,Forensic Science
International , Volume 57, Issue 1 , November 1992, 5-16
7.Beattie B., Dudley R. J., Smalldon K. W., The use of
morin staining for the microscopic characterisation of
multilayered white paint flakes, Forensic Science
International, 1979, 13, 41-49
8.Laing D. K. , Dudley R. J., Isaacs M. D. J., Colorimetric
measurements on small paint fragments using
microspectrophotometry, Forensic Science International,
1980, 16, 159-171
9.Nowicki, J., Patten, R., Examination of U.S. automotive
paints: I. Make and model determination of hit-and-run
vehicles by reflectance microspectrophotometry, Journal
of Forensic Sciences, 1986, 31, 464-470
10.Laing D. K., Dudley R. J., Janet M. H., Isaacs M. D. J.,
The discrimination of small fragments of household
gloss paint by microspectrophotometry, Forensic Science
International, 1982, 20, 191-200
11.Cousins D. R., Platoni C. R., L. W. Russell, The use of
microspectrophotometry for the identification of
pigments in small paint samples, Forensic Science
International, 1984, 24, 183-196
12.Fuller N. A., Analysis of thin-layer chromatograms of
paint pigments and dyes by direct microspectrophotometry,
Forensic Science International, 1985, 27, 189-204
13.ASTM(E1535-14, Standard Practice for Specifying
Color by the Munsell System)
14.ASTM(E308-13, Standard Practice for Computing the Colors
of Objects by Using the CIE System)
15.Janina Z., Beata T., Paweł K., Comparative analysis of
car paint traces in terms of color by
vismicrospectrometry for forensic needs,
Analytical Letters, 2010, 43, 436-445
16.Patrick B., Geneviève M., Stéphane B., Nicole M. E.,
Williams M., Annarita F., Survey of crowbar and
household paints in burglary cases-population studies,
transfer and interpretation, Forensic Science
International , 2005 ,152, 221-234
17.Ryland S, Bishea G., Brun-Conti L.,
Eyring M., Flanagan B., Jergovich T.,
MacDougall D., Suzuki E., Discrimination
of 1990s original automotive paint
systems: a collaborative study of black
nonmetallic base coat/clear coat finishes
using infrared spectroscopy, Journal of
Forensic Science, 2001, 46, 31-45
18.Suzuki E. M., Marshall W. P., Infrared
spectra of U.S. automobile original topcoats
(1974-1989): IV. Identification of some
organic pigments used in red and brown
nonmetallic and metallic monocoats
quinacridones, Journal of Forensic
Science, 1998, 43, 514-542
19.Suzuki EM, Infrared Spectra of U.S. Automobile Original
Topcoats (1974–1989): I. Differentiation and
Identification Based on Acrylonitrile and
Ferrocyanide C≣N Stretching Absorptions, Journal
of Forensic Science, 1996, 41, 376-392
20.Suzuki E. M., Infrared Spectra of U.S. Automobile
Original Topcoats (1974-1989): II. Identification
of Some Topcoat Inorganic Pigments Using an
Extended Range (4000~220 cm-1) Fourier Transform
Spectrometer, Journal of Forensic Science,
1996, 41, 393-406
21.Suzuki E. M., Infrared spectra of U.S. automobile
original topcoats (1974-1989): VI. Identification
and analysis of yellow organic automotive paint
pigments-isoindolinone yellow 3R, isoindoline
yellow, anthrapyrimidine yellow, and
miscellaneous yellows, Journal of Forensic Science,
1999, 44, 1151-1175
22.Suzuki E. M., Marshall W. P., Infrared spectra of U.S.
automobile original topcoats (1974-1989): III. In situ
identification of some organic pigments used in yellow,
orange, red, and brown nonmetallic and brown metallic
finishes-benzimidazolones, Journal of Forensic Science,
1997, 42, 619-648
23.Suzuki E. M., Infrared spectra of U.S. automobile
original topcoats (1974-1989): V. Identification of
organic pigments used in red nonmetallic and brown
nonmetallic and metallic monocoats-DPP red BO and
Thioindigo Bordeaux, Journal of Forensic Science,
1999, 44, 297-313
24.Parybyk A. E., Kobus H. J., The Characterization
of Plastic Automobile Bumper Bars Using Fourier
Transform Infrared Spectroscopy (FTIR), Pyrolysis
Gas Chromatography (PGC), and Energy Dispersive
X-Ray Microanalysis Combined with a Scanning
Electron Microscope (SEM-EDX), Journal of Forensic
Science, 1990, 35, 281-292
25.Jalbout A. F., Jiang T., Fengqi L., Ding C.,
Abdalla M. D., Quantitative analysis of
(styrene/acrylonitrile/methyl methacrylate)
co-polymer systems by infrared resonance
spectroscopy, Spectrochimica Acta Part A, 2002,
58, 525-536
26.Suzuki E. M., Forensic Science Applications of
Diffuse Reflectance Infrared Fourier Transform,
Spectroscopy (DRIFTS): IV. Direct Analysis of
Metallic Paints-Sampling Considerations,
Journal of Forensic Science, 1989, 34, 164-179
27.Guineau B, Microanalysis of Painted Manuscripts and
of Colored Archeological Materials by Raman Laser
Microprobe, Journal of Forensic Science, 1984,
29, 471-485
28.Suzuki E. M., Carrabba M., In situ identification
and analysis of automotive paint pigments using
line segment excitation raman spectroscopy:1.
Inorganic topcoat pigments, Journal of Forensic
Science, 2001, 46, 1053-1069
29.Kuptsov A. H., Applications of Fourier Transform
Raman Spectroscopy in Forensic Science, Journal
of Forensic Science, 1994, 39, 305-318
30.Janina Z., Jolanta W., An investigation into the
use of micro-Raman spectroscopy for the analysis
of car paints and single textile fibres, Journal
of Molecular Structure, 2011, 993, 127-133
31.Beam T. L., Willis W. V., Analysis Protocol for
Discrimination of Automotive Paints by SEM-EDXA
Using Beam Alignment by Current Centering, Journal
of Forensic Science , 1990, 35, 1055-1063
32.Zeichner A., Levin N., Landau E., A Study of Paint
Coat Characteristics Produced by Spray Paints from
Shaken and Nonshaken Spray Cans, Journal of
Forensic Science, 1992, 37, 542-555
33.Peter V., Bernhard W., Luc M., Brigitte D.,
Bert C., Alex von B., Reinhold K., Pigment
Investigation of A Late-Medieval Manuscript
with Total Reflection X-ray Fluorescence and
Micro-Raman Spectroscopy, Analyst, 1999,
124, 169-172
34.David F. R., X-Ray Diffraction in Forensic Science,
The Rigaku Journal, 2003, 19-20, 11-22
35.Esposito G. G., Swann M. H., Application of
Pyrolysis and Programmed Temperature Gas
Chromatography to the Analysis of Thermosetting
Acrylic Coating Resins, Journal of Gas
Chromatography, 1965, 3, 282-284
36.Jain, N. C., Fontan, C. R., Kirk P. L., The
Identification of Paints by Pyrolysis Gas
Chromatography, Journal of the Forensic
Science Society, 1965, 5, 102-109
37.Challinor, J.M., Forensic Applications of
Pyrolysis Capillary Gas Chromatography,
Forensic Science International, 1983, 21,
269-285.
38.Blackledge R. D., Pyrolysis Gas Chromatography
of Automobile Rubber Bumper Guard Samples,
Journal of Forensic Science, 1981,
26, 557-559
39.McMinn D. G., Carlson T. L., Munson T. O.,
Pyrolysis Capillary Gas Chromatography/Mass
Spectrometry for Analysis of Automotive
Paints, Journal of Forensic Science, 30, 1064-1073
40.Cardosi P. J., Pyrolysis-Gas Chromatographic
Examination of Paints, Journal of Forensic Science ,
1982 , 27, 695-703
41.Armitage S., Saywell S., Roux C., Lennard C.,
Greenwood P., The analysis of forensic samples
using laser micro-pyrolisis gas chromatography
mass Spectrometry, Journal of Forensic Science,
2001, 46, 1043-1052
42.Thornton J. I., Kraus S., Lerner B., Kahane D.,
Solubility Characterization of Automotive Paints,
Journal of Forensic Science, 1983, 28, 1004-1007.
43.Buckle J. L., Macdougall D. A., Grant R. R.,
PDQ-Paint Data Queries: The History and Technology
Behind the Development of the Royal Canadian
Mounted Police Forensic Laboratory Services
Automotive Paint Database, Canadian Society of
Forensic Science Journal, 1997, 30, 199-212
44.Lavine B.K., Fasasi A., Sandercock M., Improving
PDQ database search strategies to enhance
investigative lead information for automotive
paints, Microchemical Journal, 2014, 117, 133-137
45.Ryland, S. G., Bishea G., Brun-Conti L., Eyring M.,
Flanagan B. , Jergovich T., MacDougall D.,
Suzuki E., Discrimination of 1990s Original
Automotive Paint Systems: A Collaborative Study
Of Black Nonmetallic Base Coat/Clear Coat
Finishes Using Infrared Spectroscopy,
Journal of Forensic Sciences, 2001 , 46, 31-45
46.Giang Y. S., Wang S. M., Cho L. L. , Yang C. K.,
Lu C. C., Identification of tiny and thin smears
of automotive paint following a traffic accident,
Journal of Forensic Science, 2002, 47, 625-629
47.Dabdoub G., Severin P., The Identification of
Domestic and Foreign Automobile Manufacturers
Through Body Primer Characterization, J.
Forensic Science, 1989, 34, 1395-1404
48.Jacqueline M. W. , John L., David K. L.,
The examination of paints as thin sections
using visible microspectrophotometry and Fourier
transform infrared microscopy, Forensic Science
International, 1988, 38, 43-52
49.Bates J. W., Allinson T., Bal T. S., The
examination of paints as thin sections using
visible microspectrophotometry and Fourier
transform infrared microscopy, Forensic Science
International,1988, 38, 43-52
50.Govaert F., Bernard M.,Discriminating red spray
paints by optical microscopy, Fourier transform
infrared spectroscopy and X-ray fluorescence,
Forensic Science International, 2004, 40, 61-70
51.Burke P., Curry C. J., Davies L. M.,
Cousins D. R., A comparison of pyrolysis mass
spectrometry, pyrolysis gas chromatography and
infra-red spectroscopy for the analysis of paint
resins, Forensic Science International, 1985, 28,
201-219
52.Burns D.T., Doolan K. P., A comparison of
pyrolysis-gas chromatography-mass spectrometry
and Fourier transform infrared spectroscopy for
the analysis of a series of modified alkyd paint
resins ,Analytica Chimica Acta, 2000, 422, 217-230
53.Francesca C., THM-GCMS and FTIR for the study of
binding media in Yellow Islands by Jackson
Pollock and Break Point by Fiona Banner,
J.Anal.Apply.Pyrolysis, 2004, 71, 405-415
54.Janina Z., Rafał B., Marcin K., PRAXIS—combined
m-Raman and m-XRF spectrometers in the examination
of forensic samples, Forensic Science International,
2008, 175, 1-10
55.台灣區車輛工業同業公會, 2014
56.Karina L. S., Mark B., Jose G., Recent trends
and development in pyrolysis-gas chromatography,
Journal of Chromatography A, 2008, 1186, 51-66
57.Burns D. T., Doolan K.P., The discrimination
of automotive clear coat paints indistinguishable
by Fourier transform infrared spectroscopy via
pyrolysis–gas chromatography–mass spectrometry,
Analytica Chimica Acta, 2005, 539, 157–164
58.Bates J. W., Allinson T., Bal T. S., Capillary
pyrolysis gas chromatography: A system employing
a Curie point pyrolyser and a stationary phase
of intermediate polarity for the analysis of
paint resins and polymers, Forensic Science
International, 1989, 40, 25-43
59.Keffer F., Physik H. d., 18, pt. 2, New York:
Springer-Verlag, 1966 and P. Heller, Rep. Progr.
Phys., 1967, 30, 731, (pt II)
60.Prati S., Fuentes D., Sciutto G., Mazzeo R.,
The use of laser pyrolysis-GC-MS for the analysis
of paint cross sections, Journal of Analytical and
Applied Pyrolysis, 2014, 105, 327-334
61.Sugimura Y., Tsuge S., Fundamental Splitting
Conditions for Pyrogram Measurements with Glass
Capillary Gas Chromatography ,Analytical Chemistry,
1978, 50, 1968-1972
62.Tsuge S., Takeuchi T. , Vertical Furnace-Type
Sampling Device for Pyrolysis Gas Chromatography ,
Analytical Chemistry, 1977, 49, 348-350
63.Sheng-Hsiung Y., Jermiah Y. S., Matt S. C.,
Gaston J. Wu, Quantification of vehicle paint
components containing polystyrene using
pyrolysis-gas chromatography/mass spectrometry,
Anal. Methods, 2012, 4, 1989-1995
64.Frontier laboratories LTD , double-shot pyrolyzer
model PY-2020id operational manual ver.2.01 ,1-4
65.Pearson, K., On Lines and Planes of Closest Fit to
Systems of Points in Space (PDF). Philosophical
Magazine, 1901, 2 (6), 559-572
66.Hotelling, H., Analysis of a complex of statistical
variables with principal components, Journal of
Educational Psychology, 1933, 24, 498-520
67.Moss, W. W., Posey, F. T., Peterson, P. C.,
A Multivariate Analysis of the Infrared Spectra of
Drugs of Abuse, Journal of Forensic Sciences, JFSCA,
1980, 25, 304-313
68.Sandercock P. M. L., Pasquier E. D., Chemical
fingerprinting of unevaporated automotive gasoline
samples, Forensic Science International, 2003, 134,
1-10
69.Beijing T., James K. H., Ralph E. S., Accelerant
classification by gas chromatography/mass spectrometry
and multivariate pattern recognition, Analytica
Chimica Acta, 2000, 422, 37-46
70.Craig D. A., Sarah L. S., Vladimir L. Z.,
Classification and individualisation of black ballpoint
pen inks using principal component analysis of UV-vis
absorption spectra, Forensic Science International,
2008, 174, 16-25
71.William J. E., Stephen L. M., Edward G. B.,
Rena A. M., Hollis J. T. III, Forensic discrimination
of photocopy and printer toners II. Discriminant
analysis applied to infrared reflection-absorption
spectroscopy, Anal Bioanal Chem ,2003, 376, 1279-1285
72.Elisa K. S., Jorge E. S. S., Osvaldo N. N.,
Marcelo Z. M., Reynaldo L. V., Sourcing Brazilian
marijuana by applying IRMS analysis to seized samples,
Forensic Science International, 2006, 160, 35-43
73.Vichet P., Narinee S., Juthamard P., Wiphada P.,
Tetsuro S., Ken T., Identification of impurities and
statistical classification of methamphetamine tablets
(Ya-Ba) seized in Thailand, Forensic Science
International, 2002, 126, 105-113
74.Johnston A., King L.A., Heroin profiling: Predicting the
country of origin of seized heroin, Forensic Science
International, 1998, 95, 47-55
75.Klemenc S., In common batch searching of illicit heroin
samples -evaluation of data by chemometrics methods,
Forensic Science International, 2001, 115, 43-52
76.Alan G. R Gerard M. O., Thomas J. G., Identifications
and Quantitative Measurements of Narcotics in Solid
Mixtures Using Near-IR Raman Spectroscopy and
Multivariate Analysis, Journal of Forensic Science,
1999, 44, 1013-1019
77.Bruno P., Ilaria L., Stefano D. T., Guido P.,
Maria G. C., Anders M., Ettore N., Antonio R.,
Use of NMR in profiling of cocaine seizures,
Forensic Science International, 2013, 231, 120-124
78.Cyril M., Genevieve M., Pierre E., The application of
chemometrics on Infrared and Raman spectra as a tool for
the forensic analysis of paints, Forensic Science
International, 2011, 209, 173-182
79.Janina Z., Grzegorz Z., Jakub M. M., Differentiation
and evaluation of evidence value of styrene acrylic
urethane topcoat car paints analysed by pyrolysis-gas
chromatography, Journal of Chromatography A, 2008,
1179, 47-58
80.Zadora G., Neocleous T., Likehood Ratio Model for
classification of forensic evidence Anal. Chim. Acta,
2009, 642, 266-278
81.Manahan, S. E., Environmental chemistry, Lewis Publisher
Inc., Michigan, 1991
82.Manahan, S. E., Environmental chemistry, PWS Publisher
Inc., Boston, 1984
83.Janina Z., Andrzej P., A statistical criterion for the
value of evidence: Application to the evaluation of the
results of paint spectral analysis, Forensic Science
International, Volume 17, Issue 2 , March-April 1981,
Pages 101-108
84.Voskertchian G. P., Quantitative Analysis of Organic
Pigments in Forensic Paint Examination, 1995, 40, 823-825
85.Tsuge S., Ohtani H., Structure characterization of
polymeric materials by Pyrolysis GC/MS, Polymer
Degradation and Stability ,1997, 58, 109-130
86.Jakab E., Uddin Md.A., Bhaskar T., Sakata Y., Thermal
decomposition of flame-retarded highimpact polystyrene,
Journal Anal. Appl. Pyrolysis, 2003, 68-69, 83-99
87.Nonobe T. , Ohtani H., Usami T., Mori T., Fukumori H.,
Hirata Y., Tsuge S., Characterization of stereoregular
polystyrenes by pyrolysis-gas chromatography, Journal
Anal. Apply. Pyrolysis , 1995, 33, 121-138
88.Tsuge S., Ohtani H., WatanabeC., Pyrolysis-GC/MS Data
Bookof Synthetic Polymers: Pyrograms, Thermograms and MS
of Pyrolyzates, Elseviers, Amsterdam, 2011.