本研究針對十字型同軸雙游離源進行特性分析，改善開發階段所設計不便之處，並以此架構量測的最佳化參數做樣本分析檢測。首先利用計算流體力學的數值分析方法運算常壓介電質放電氦氣電漿之流場，並透過質譜儀量測氦氣電漿總離子濃度進行實驗驗證。本研究利用實驗室前人之設計，用來產生介電質放電氦氣電漿之對稱十字型玻璃管架構作為模型，透過ANSYS軟體分析氦氣從玻璃管噴出的流場行為，並繪製出流體速度分佈方便觀察。此外，本研究燃燒市售的香製造出可視化流場並與模擬結果相互比對，進而確認模擬邊界條件的正確性。模擬結果可觀察到玻璃管出口最高速度範圍，而因氦氣質量密度低，由此也可觀察出口流速急劇下降、氣體擴散情形。然而，因氦氣介穩態離子將隨著氣體至流場所及之處，本研究模擬改變玻璃管出口及毛細管擺放位置，並利用質譜儀偵測，最終獲得與模擬匹配之總離子濃度，且最高訊號達5.25×(10^10) ion/cm^3，相較於前人的10^9濃度訊號高於一個數量級。另外，在以往同軸式電噴灑及大氣壓力化學雙游離源實驗上最大的問題，電噴灑離子濃度會遠高於電漿所產生之離子兩至三個數量級訊號，導致在同時量測極性與非極性分析物時，極性物質會強烈得壓低非極性物質的訊號，故此部分參考本研究特性參數的收集，提高電漿離子濃度、降低電噴灑離子濃度之訊號調整，成功使雙游離源模式同時開啟時，離子濃度維持在相同次方訊號，並以毛細管內伸3 - 4 mm，由玻璃管去限制電噴灑噴霧，玻璃外管徑升溫至60℃加熱氣體，氦氣氣體流量0.15 SLM，正對質譜入口偏移2 mm位置，透過實驗證實上述參數為此架構之最佳化參數。
　　在天然樣本檢測應用方面，樣本選擇人們每天需攝取的蔬果作為檢測樣本，針對表皮所殘留之農藥做物質分析，成功使用改良式熱脫附探針，在蔬果表皮上，同時量測到不同範圍之極性及弱極性化合物。

This study focuses on analyzing the characteristics of the crisscross symmetric coaxial dual ion source in order to discard the weakness of the initial design. Moreover, the optimized parameters obtained from this survey would be taken for the sample analysis. Computational fluid dynamics (CFD), a numerical analysis method to compute the flow field of the ambient dielectric discharge helium plasma, is adopted with the use of the ANSYS software. Hence, mass spectrometry is carried out to measure the total ion concentration of the helium plasma as the experimental verification. According to the experiment design of previous researchers, a crisscross symmetric coaxial glass tube is used as model to produce ambient dielectric discharge helium plasma. ANSYS is used to analyze the flow field movement of the helium jetted from the glass tube outlet as well as outputting the fluid velocity profile for observation. In order to confirm the accuracy of the analog border conditions, joss sticks are burnt to demonstrate a visualized flow field for the comparison with the simulation results. The simulation results show that the gases have maximum speed at glass tube outlet due to the low mass and the low density of helium gas, and the diffusion speed of the gas particles is drastically reduced at glass tube outlet. In order to get the optimized parameters, the glass tube outlet and capillary tube position are relocated so as to minimize the possibility of helium metastable ions flowing to the flow field. Eventually, a result of high ion intensity of 5.25×(10^10) ions/cm3 is obtained, matching to the results from the simulation and MS detection. During the previous experiment of the coaxial ESI+APCI source, the ion concentration of ESI are 2 to 3 orders higher than the ion concentration of APCI such that the signals of the nonpolar compounds are covered by the intense signal of the polar ones during the simultaneous detection. Therefore, ESI intensity is reduced by placing capillary in glass tube for 3 to 4 mm deeper to limit electrospray, moving the plasma gas outlet towards the MS inlet with 0.15 SLM flow rate, and heating the gas to 60℃ to increase plasma ion intensity. Results show that the pesticide on the surface of fruits and vegetables can be detected successfully. In addition, the polar and weak polar chemical compounds on the sample skin could also be detected simultaneously via the modified thermal desorption probe.

論文審定書 i
論文公開授權書 ii
致謝 iii
中文摘要 iv
Abstract v
目錄 vii
圖目錄 x
表目錄 xiii
符號表 xiv
簡寫表 xvi
第一章 緒論 1
1.1 前言 1
1.2 常壓電漿與電噴灑游離質譜法之介紹 3
1.2.1 常壓電漿之介電質放電電漿游離源 5
1.2.2 電噴灑游離源 9
1.3 大氣壓力及熱脫附游離質譜法 13
1.3.1 大氣壓力游離步驟 13
1.3.2 熱脫附游離法文獻回顧 17
1.4 雙游離源整合質譜分析 21
1.4.1 整合型雙游離源 22
1.4.2 同軸型雙游離源 22
1.5 流體力學數值模擬分析 24
1.6 論文架構 25
第二章 原理及動機目的 26
2.1 電噴灑游離原理 26
2.2 電漿游離機制 30
2.3 計算流體力學數學模型 33
2.3.1 統御方程式 33
2.3.2 數學模型 33
2.4 十字對稱型同軸式雙游離源 35
2.4.1 電漿游離之十字對稱型設計介紹 35
2.5 研究動機與目的 37
2.5.1 研究動機 37
2.5.2 研究目的 37
第三章 研究方法 38
3.1 數值模型 38
3.1.1 模型介紹 38
3.1.2 分析流程介紹 38
3.1.3 參數測試 40
3.2 系統架設與實驗設備 42
3.2.1 實驗裝置 42
3.2.2 實驗系統及檢測流程 46
3.3 實驗藥品與試劑 47


第四章 實驗結果與討論 48
4.1 實驗最佳化參數與流場優化分析 48
4.1.1 實驗數據分析與流場模擬 49
4.1.2 平衡電噴灑游離源及電漿游離源之偵測訊號 55
4.2 熱脫附探針檢測複方樣本 57
4.3.1 單電噴灑模式檢測市售感冒糖漿 58
4.3.2 單電漿模式偵測複方中草藥 60
4.3 蔬果農藥殘留檢測 61
4.3.1 雙游離源模式檢測蔬果表皮之農藥殘留 61
第五章 結論與未來展望 65
5.1 結論 65
5.2 未來展望 67
參考文獻 68
自述 73

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