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研究生: 王志嘉
Wang, Chih-Chia
論文名稱: 危害氣體捕集與化學偵測方法之研究
A Study of Hazardous Gases Sampling and Chemical Detection Methods
指導教授: 呂家榮
Lu, Chia-Jung
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 2017
畢業學年度: 105
語文別: 中文
論文頁數: 84
中文關鍵詞: 有機胺類離子層析氧化鋅石英微量天平有機揮發氣體
英文關鍵詞: Organic amines, Ion chromatography, Znic oxide (ZnO), quartz crystal microbalance (QCM), volatile organic compounds (VOCs)
DOI URL: https://doi.org/10.6345/NTNU202202783
論文種類: 學術論文
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  • 本研究結合氣體捕集與化學偵測之方法,期望能在環境中即時分析揮發性有機氣體 (VOCs),以增進氣體感測發展與建置具有良好再現性及迅速反應性之感測系統。
    本研究第一部分的主要工作內容:對於在工廠附近的周界空氣之現場測試結果所建立對於分析低濃度有機胺類混合物的方法。此本次實驗以甲胺等七種常用於工業上的有機胺類作為目標汙染物。使用兩個充滿去離子水的鐵弗龍衝擊瓶作為採集器。所有胺類的回收值是介於93.2% (三甲胺)到103.4% (丙胺)之間。所收集的樣本利用具有電導偵測器的離子層析儀進行分析。我們藉由分別操作兩種不同溫度的管柱(35.0和17.5 °C)將七種有機胺類分開。此方法的偵測極限範圍在0.11 ~ 0.48 ppb之間,對於環境氣味可以有效的控制。我們也研究了樣品準確值、保存時間及其他化合物的干擾。在電子化學廠外圍環境中,現場測試方法偵測到三種低濃度 ppb等級的目標胺類。我們使用相同方法來定量在其他印刷電路板 (PCB)製造工廠內濃度超過100 ppb的三甲胺。這種不用溶劑和花費合理的採樣方法可以有效地分析在環境上的低濃度胺類並適合不論是在工廠製成區或是其外圍等大範圍環境[69]。
    本研究的第二部分探討滴鍍於石英微量天平的奈米多孔性氧化鋅微球對於有機氣體之感測特性。多孔性微球組成的氧化鋅奈米粒子經由水相合成聚合成為具有微米等級直徑的球體。氧化鋅微球之多孔性結構同時提供氣體吸附之足夠表面積與作為氣體交換的擴散路徑,可逆的反應訊號說明完全無殘留的吸附與脫附作用。聚氯乙烯薄層在氧化鋅與石英微量天平的電極表面之間作為黏著層。本研究進行具有不同官能基的四種揮發性有機化合物測試以顯示在聚氯乙烯與多孔性氧化鋅粉末之間的選擇性區別。為了比較於聚異丁烯與奈米多孔性氧化鋅之間在選擇性方面的差別,我們使用有著不同官能基的五種揮發性有機化合物來測試在石英微量天平上的感測薄膜。此外,奈米多孔性氧化鋅鍍膜感測器的反應時間只有聚異丁烯鍍膜感測器的一半,此結果指出奈米多孔性氧化鋅微球可以作為石英微量天平具選擇性與迅速反應的材料選項之一[70,71]。

    This study presents the establishment and the field-test results of a method in order to analyze low levels of amine mixtures in the ambient air near industrial processes. Seven amines, which are commonly used in industrial processes, were selected as target contaminants. Two-stage Teflon impingers that were filled with deionized water were used as the samplers. The recoveries of all amines were between 93.2% (trimethyl amine) and 103.4% (propyl amine). After collecting the samples, the researchers analyzed the samples via ion-chromatograph with a conductivity detector. The seven amines was separated by operating the column at two different temperatures (35.0 and 17.5 ℃). The limitation of this detective method ranged from 0.11 to 0.48 ppb, which is sufficient for environmental odor control. While using this method, the accuracy, sample preservation time and interference of other chemicals were also studied. The field tests of this method detected three target amines at low ppb levels in the environment outside an electronic chemical plant. A level of trimethyl amine of more than 100 ppb was quantified inside another PCB production plant by the same method. This solvent-free sampling and cost-effective method can effectively analyze low concentrations of amines in the environment, which makes it suitable for large-scale investigations[69].
    The organic vapor-sensing properties of nano-porous ZnO microspheres coated onto a quartz crystal microbalance were studied. The porous microspheres consisted of ZnO nanoparticles aggregated via aqueous-phase synthesis into spheres with diameters in the micrometer range. The porous structure of ZnO microspheres provided both a sufficient surface area for vapor adsorption and a diffusion path for gas exchange. The reversible response signals suggested that complete desorption without contamination was achieved. A thin layer of poly vinyl chloride (PVC) serves as the adhesion layer between ZnO and the gold of QCM electrodes. The rapid and reversible response signals suggest that sensing process involved only physical adsorption. Four volatile organic compounds with various functional groups were tested to demonstrate the selectivity differences between poly vinyl chloride (PVC) and porous ZnO powder. Sensing films on a quartz crystal microbalance (QCM) were tested using five volatile organic compounds with different functional groups in order to compare the differences in selectivity between poly isobutylene (PIB) and nano-porous ZnO. In addition, the response time was half that of the PIB-coated sensor. The results of this study indicate that nano-porous ZnO microspheres represent an alternative material that could provide selectivity and rapid response for QCM[70,71].

    誌謝 I 摘要 II ABSTRACT IV 目錄 VI 表目錄 IX 圖目錄 X 第一章 緒論 1 1.1 前言 1 1.2 文獻探討 5 第二章 工業環境胺類之現場研究與分析方法 30 2.1 材料與方法 30 2.1.1 化學物質 30 2.1.2 實驗室校正與採樣儀器 30 2.1.3 胺類分析之離子層析儀 33 2.2 結果與討論 34 2.2.1 離子層析分離之溫度影響 34 2.2.2 其他離子之干擾 37 2.2.3 校正與偵測極限 40 2.2.4 鐵氟龍衝擊瓶之破出與採樣效率 42 2.2.5 保存樣品之耐久性測試 43 2.2.6 工業環境之現場研究 45 2.3 結論 50 第三章 氧化鋅石英微量天平應用於有機氣體感測之研究 51 3.1 材料與方法 51 3.1.1 多孔性氧化鋅之合成 51 3.1.2 石英微量天平感測器之準備 51 3.1.3 感測器之測試系統 53 3.2 結果與討論 55 3.2.1 感測材料之形貌 55 3.2.2 氧化鋅石英微量天平之反應訊號 58 3.2.3 氧化鋅石英微量天平之校正曲線 63 3.2.4 選擇性之比較 65 3.2.5 感測機制之探討 69 3.3 結論 72 第四章 總結 73 4.1 研究執行結論 73 4.2 參考文獻 75

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