現今高分子聚合材料與社會大眾的日常生活早已密不可分，而高分子材料中含有的許多不同種類的化學物質添加物，而這些添加物對該材料的特性以及環境亦會有極大的影響。因此如何有效地對高分子材料中所含的化學成分進行分析是一項相當重要的課題。但高分子材料本身的揮發性及在溶劑中的溶解度皆相當低；難以傳統的檢驗方法直接進行檢測。而分析高分子材料方法中最常見的便是使用熱重分析儀 (TGA) 對材料樣品中的易揮發組成及熱穩定性進行粗略的分析，近年來則是使用熱裂解 (Pyrolysis)裝置搭配氣相層析質譜(GC-MS)法來鑑定高分子材料中的主要化學物種，但此方法受限於氣相層析儀及GC-MS儀器本身的限制，僅能對極性較低的化學組成進行偵測，而大氣質譜法 (Ambient Mass Spectrometry) 能夠在常溫常壓下將分析物游離，並且不受樣品前處理過程及層析分離系統的限制，即可有效地偵測到目標分析物，不僅具有快速、即時偵測等特點，能夠進行即時且高通量的分析。本研究透過熱重分析結合大氣游離源 ( Atmospheric Pressure Ionization source ) 以線上的方式直接對高分子材料進行分析。
第一部分將會介紹TGA-ESI/plasma APCI-MS系統介面的建置過程，並對其進行相關參數的探討，而這套自製的ESI/PLASMA APCI游離源除了可單獨操作ESI或APCI游離外，也可以同時開啟ESI以及APCI游離源；在雙重模式下同時對較高極性及低極性的物種進行分析。第二部分則是以該系統對聚乙二醇 (PEG)、藥丸、矽膠 (silicon rubber)、共聚物等樣品進行分析所得之結果。本研究建立了熱重分析儀與大氣壓力質譜法的結合介面；透過自製的傳輸管線將熱重分析儀於不同溫度下所產生的逸散的裂解產物傳送至大氣游離源進行游離，隨後馬上以質譜儀偵測得到分析物訊號。。如此一來便可偵測於不同溫度環境下，樣品中所含的化學組成因為汽化溫度上的差異而在不同時間所產生的重量損失曲線及在其相對應時間所得之質譜圖，觀察到高分子樣品中所含之分析物的裂解產物訊息。
TGA-ESI/plasma APCI裝置的建立與於現今TGA/GC/MS最大的不同點在於所使用之游離源為大氣游離源，除了裝置不需要真空系統而被有效的簡化外，更可在不需樣品前處理的情況下即可同時觀察樣品經過TGA燃燒後所釋出之極性及非極性成分，因此TGA-ESI/PLASMA APCI的開發將可大幅提升TGA-MS的分析能力。

Thermalgravimetric analyzer (TGA) and pyrolysis gas chromatography mass spectrometry (Py-GC/MS) are commonly used to characterize polymers in plastic materials. The thermal decomposition fragments generated by pyrolysis are typically characterized by MS, and the identification is based on the MS library or the knowledge of the user. However, the reliance on the fragment spectra for compound identification is a critical problem. API methods such as electrospray ionization ( ESI ), and atmospheric pressure chemical ionization ( APCI ) would generate intact analyte ions. In the recent year, new ESI/plasma-APCI source that combines an ESI and plasma-APCI has been developed to simultaneously characterize polar and non-polar compounds, greatly improving the capability of MS detector.
In this study, we develop Thermogravimetric analyzer coupled with Electrospray ionization and Atmospheric Pressure Chemical Ionization Mass Spectrometry (TGA-ESI/APCI/MS) was used for characterization of polymer. The ESI/ plasma-APCI ion source was operated in ESI-only, dual ESI/plasma-APCI, or plasma-APCI-only mode to analyze the separated compounds. TGA-ESI/plasma APCI-MS system is affected by several parameter, such as DC and AC high voltage, source geometry, the solvent flow rate…etc. we obtain optimal operating parameters for TGA-ESI/ plasma APCI-MS system in this study, These method offer a simple method to realize decomposition mechanism for polymer materials..
This technique does not require any sample preparation. These polymer samples could be detected for a wide range of molecular weights. This system can obtained various pyrolysis products that can be used to further investigate more complex materials.

論文審定書 i
謝誌 ii
論文摘要 iv
Abstract vi
圖目錄 ix
表目錄 xiv
第一章 、緒論 1
一、 前言 1
二、 熱分析法 2
(一) 熱裂解法 2
(二) 熱重分析法（Thermogravimetric Analysis；TGA） 4
(三) 差式熱分析法（Differential Thermal Analysis；DTA） 8
(四) 差示掃描量熱法（differential scanning calorimetry, DSC) 12
(五) 逸氣檢測（Effluent gas detection, EGD）與逸氣分析（Effluent gas analysis, EGA） 15
三、 游離法 20
(一)、真空游離源 20
(二)、大氣游離源 22
四、 研究動機與論文目標 30
第二章 、熱重分析儀與大氣質譜法結合介面之開發 32
一、 實驗 32
(一) 實驗裝置 32
(二) 實驗藥品 34
(三) 實驗操作 34
二、 結果與討論 35
(一) 大氣壓力游離源之建立 35
(二) 熱重分析儀與大氣游離源結合介面之建立 38
(三) 熱重分析儀與大氣游離源結合介面實驗參數最適化之探討 40
第三章 、以熱重分析儀結合大氣游離質譜法進行樣品分析 52
一、 標準品分析： 53
二、 真實樣品分析 57
第四章 、結論 73
參考文獻 74

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