臺灣博碩士論文加值系統

摘 要
發射火藥主要分為無機成份及有機成份，無機成份分析方法中，主要以掃瞄電子顯微/X-射線能譜分析法（SEM/EDX）為主，可非破壤性地分析發射火藥所含之無機元素，並利用所測得元素之差異辨別不同來源之火藥。有機成份分析方法，主要由各種層析法配合不同偵測器進行，目前常用於鑑識發射火藥之層析法為高效液相層析法（HPLC），其主要優點為可一次完成硝化甘油、二硝基甲苯、安定劑及可塑劑之分析，相對於其他層析法在發射火藥鑑識上之應用較具實用性。
本研究首先利用SEM/EDX分析發射火藥無機元素成份，瞭解發射火藥無機元素的組成，比較兩兩不同發射火藥間所含無機元素組成之差異性問題，並分析發射前與發射後之無機元素組成，瞭解發射後之火藥樣品無機元素分析可否作為研判發射前發射火藥來源之依據。
結果發現，來自同一發子彈及來自同一批子彈之射擊前火藥樣品均無法區別其不同。若將採自同一發或同一批子彈之發射火藥視為同一來源，將來自同一批子彈之射擊前火藥和射擊後火藥殘留視為不同來源，則來自不同來源之火藥樣品經區別成功率為87.83%。
若僅就就射擊前發射火藥樣品進行區別分析，則區別成功率為84.72%。
接著利用HPLC分析發射火藥所含有機成份，先就各有機成份標準品在不同層析條件上之分離情形、各分析物偵測極限、定量極限及檢量曲線等問題進行研究。接著就採自未發射子彈之真實發射火藥樣品進行分析，根據分析結果比較不同來源發射火藥間有機成份之差異性，以區別不同來源之發射火藥。最後，並就HPLC在發射火藥之應用分析上的優缺點作一探討。
以有機成份樣品峰面積比值之平均值進行t-test來區別不同來源火藥，結果發現當P=0.01時，極少數來自同一發子彈內之發射火藥顆粒會誤認為不同，但如以P=0.005檢定時就無法區別其不同。來自同一批但不同發子彈之發射火藥在P=0.01及P=0.005時，均有一半之樣品被判定為不同來源。其可能原因為：各發子彈存放環境的差異造成子彈內發射火藥之劣化程度不同，產生各種安定劑（二苯胺）硝化衍生物比例不同，而使得兩兩樣品峰間之面積比值有所差異，導致檢定時區別為不同來源。
若將採自同一發或同一批子彈之發射火藥視為同一來源，則來自不同來源之火藥樣品以P=0.01為判定標準時，區別成功率為96.8%。
以P=0.005為判定標準時，區別成功率為92.0%。以有機成份區別不同來源發射火藥之成功率顯然較以無機元素分析進行區別之成功率為高。

ABSTRACT
Ammunition propellants are composed of organic and inorganic constituents. The inorganic ingredients are usually analyzed using scanning electron microscopy / energy dispersive X-ray analysis (SEM/EDX) in order to differentiate the propellants from different sources. On the other hand, the organic ingredients are analyzed using various chromatographic methods where HPLC is the most frequently employed method. Both analytical methods mentioned above were employed in this work for the analysis of pre- and post-discharge propellant samples.
At first, thirty-one pre- or post-discharge propellant samples from a variety of sources were analyzed by SEM/EDX to obtain inorganic elemental composition of each sample. The elements most commonly detected in these samples are Al, Si, S, Cl, K, Ca, Fe, and Cu. Unique spherical particles with characteristic elemental composition of inorganic gunshot residues were observed on the surface of post-discharge propellant flakes.
Relative concentrations of Al, Si, S, Cl, K, and Ca were calculated using standards and software contained in the instrument. All samples were firstly classified into four groups according to the difference in the most concentrated element in each sample. Concentration ratios between different elements were employed to differentiate samples within each group. A t test was used to establish the significance of difference between concentration ratios of compared sample pairs, a confidence level of 90% was chosen for the test. The results indicated that pre-discharge samples from the same round of ammunition or those from the same lot of ammunition were not differentiated by the procedure mentioned above. Pre- and post-discharge samples from the same lot of ammunition were significantly different in inorganic elemental composition and were differentiated as being from different sources. Using elemental analysis results to postulate the original elemental composition of discharged propellant flakes is impractical and useless. The successful rate of the differentiation of pre-discharge propellant samples from different sources is 84.72%.
In the second part of this work, twenty-eight propellant flake samples from a variety of sources were analyzed by microbore HPLC to obtain organic composition of each sample. The organic constituents most commonly detected in these samples are diphenylamine (DPA), N-NODPA, 4-NDPA, 2-NDPA, ethyl centralite (EC), nitroglycerine (NG), dinitrotoluene (DNT), and dibutyl phthalate (DBP).
All samples were firstly classified into four groups according to the presence or absence of NG, EC, and 2-NDPA in each sample. Peak area ratios between different constituents were employed to differentiate samples within each group. A t test was used to establish the significance of difference between peak area ratios of compared sample pairs. When p=0.01 was chosen for the test the successful rate of the differentiation of propellant samples from different sources was 96.8%. However, a few samples from the same round of ammunition were also differentiated as samples from different sources. When p=0.005 was chosen for the test, the successful rate of the differentiation of propellant samples from different sources was reduced to 92.0% that is still much higher than the successful rate of differentiation using concentration ratios of elements. And none of the samples from the same round of ammunition were differentiated. However, There were always some samples from the same lot of ammunition being differentiated as being from different sources. The possible explanation of this phenomenon is that propellants in different rounds of ammunition were subjected to various storage conditions and resulted in different degree of nitration of stabilizers. Which further resulted in significant variation of analysis results.

目 錄
第一章 緒綸………………………………………………1
第二章 發射火藥中無機元素分析之研究………………4
壹、前言……………………………………………………….4
貳、實驗部份………………………………………………….6
一、 實驗器材……………………………………………6
二、 實驗步驟……………………………………………6
參、結果與討論……………………………………………….7
一、SEM/EDX下發射火藥樣品測得之無機元素種類………..7
二、樣品分類……………………………….………………..9
三、不同來源火藥之區別………………………… ……….13
肆、小結……………………………………..………………17
第三章 發射火藥中有機成份分析之研究……..…………26
壹、前言……………………………………………………..26
貳、實驗部份…………………………………..……………30
一、 實驗器材…………..…………………………….30
二、 實驗步驟………………………………………….33
參、結果與討論………………………………..……………36
一、有機成份標準品之HPLC分析……………….………….36
二、有機成份標準品滯留時間再現性之評估………………42
三、有機成份標準品HPLC法分析之偵測極限……………..47
四、有機成份標準品HPLC法分析之定量極限…….……….52
五、有機成份標準品檢量曲線試驗…………………………52
六、發射火藥樣品分析…………………….…….…………57
肆、小結………………………………………..……………62
第四章 結論…………….………………………………….73
參考資料……………………………………….…………….76
附錄一
附錄二

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