臺灣博碩士論文加值系統

本研究利用硝酸鈰及硝酸氧鋯作為先驅物，以沉澱法製備奈米結晶氧化鈰基粉體，並添加氧化鋯進行氧化鈰於氧氣感測特性之改質研究。其鋯離子添加量為0、5、10及15 at%，製備CeO2、5ZDC、10ZDC及15ZDC。本研究探討不同鋯離子添加量對氧化鈰之導電性質、氧分壓感測行為及電阻隨溫度變化的活化能之影響，最後將實驗結果運用於一只隨氧分壓改變、不隨溫度變化的氧氣感測器。
研究結果顯示：以沉澱法製得之氧化鈰基粉體皆呈現不規則形貌且具良好結晶性，晶粒尺寸約為67 nm，而粉體於900C及1200C熱處理後，鋯離子的添加有明顯抑制CeO2晶粒成長之效果，且其對於氧化鈰之晶格常數有縮小之趨勢，利於縮短電子跳躍之距離；同時促使氧化鈰之四價鈰離子還原成三價鈰離子的含量增加，藉此提升材料之導電率。利用網印技術以氧化鈰基粉體做為電阻式氧氣感測材料，其中以10ZDC於降低電阻及氧氣動態感測之應答表現最為突出。實驗結果發現，厚膜表面型態的粉體連結及多孔性對導電及氣體感測行為影響甚大。利用材料輸出電阻對應溫度所計算之活化能，選用5ZDC作為溫度補償材料(TCM)、10ZDC作為氧氣感測材料(OMM)運用於不隨溫度變化之電阻式氧氣感測器，顯現出良好的氧氣感測行為。

In this study, nanocrystalline zirconia-added ceria powder was prepared from cerium nitrate hydrate (CeNH) and zirconium nitrate hydrate (ZrNH) by precipitation method. Zirconia with various additions, 0, 5, 10, and 15 at.%, was added into ceria as CeO2, 5ZDC, 10ZDC and 5ZDC. The modification of the oxygen sensing characteristics of ceria powder was investigated. The influence of different amounts of zirconium ion additions on the electric conductivity, oxygen sensing behavior, and activation energy of electric resistance of ceria coating as a function of temperature was discussed. The experimental results were then applied to a temperature-independent oxygen sensor device in the final part of the study.
The experimental results indicated that the ceria powder obtained from precipitation showed an irregular shape with a good crytallinity. The crystallite size was ca. 6 to 7 nm. After heat-treating the powder at 900C and 1200C, zirconia could inhibit the growth of CeO2 crystals significantly and reduce the lattice constant of ceria, shortening the hopping distance of ions. In the mean time, the amount of Ce4+ reacted to Ce3+ was enhanced to cause the increase of electric conductivity of the composite. Ceria powders were then prepared as a resistive oxygen sensor by screen printing technique where the 10ZDC exhibited better electric resistance reduction and oxygen sensing kinetics in this system. The experimental result showed that the connection and porosity influence significantly the electric conduction and gas sensing behavior of the powder coatings. According to the calculation of the activation energy from the temperature vs. electric resistance plots, respective the 5ZDC and the 10ZDC were used as temperature compensating material (TCM) and oxygen partial pressure measurement material (OMM) for the fabrication of resistive oxygen sensor which would not be affected by temperature change. The results showed that the device exhibited excellent temperature-independence and oxygen sensing behaviors.

中文摘要.......................................I
Abstract......................................II
目錄.........................................III
圖目錄........................................VI
表目錄.........................................X
第一章、前言...................................1
第二章、文獻回顧...............................3
2.1　二氧化鈰之介紹與製備......................3
2.1.1　二氧化鈰的基本結構與特性................3
2.1.2　二氧化鈰的製備..........................4
2.2　氧氣感測器................................8
2.2.1　氧氣感測器種類..........................8
2.2.2　二氧化鈰的感測特性及改質...............12
2.2.3　添加鋯離子於二氧化鈰之優異性...........15
2.3　溫度補償材料之原理.......................19
第三章、實驗步驟..............................24
3.1　實驗設計與目的...........................24
3.2　感測材料製備.............................27
3.2.1　粉體製備...............................27
3.2.2　網印...................................28
3.2.3　熱處理.................................29
3.3　多孔感測材料之製備.......................29
3.4　感測材料之特性分析.......................29
3.4.1　熱重分析...............................29
3.4.2　X光繞射分析............................30
3.4.3　冷場發射掃描式電子顯微鏡表面型態分析...31
3.4.4　穿透式電子顯微鏡粉體結構分析...........31
3.4.5　化學分析電子能譜儀.....................32
3.5　氧氣感測行為之量測.......................32
3.5.1　氧分壓對應之電性量測...................32
3.5.2　應答速率之量測....................... 32
3.5.3　溫度補償感測器.........................33
第四章、結果與討論............................35
4.1　先驅物粉體之特性分析.....................35
4.1.1　TGA熱重分析............................35
4.2　沉澱法粉體之特性分析.....................36
4.2.1　XRD結晶結構分析........................36
4.2.2　TEM表面型態分析........................39
4.2.3　粉體成分分析...........................42
4.3　厚膜熱處理1200C之特性分析..............46
4.3.1　XRD結晶結構分析........................46
4.3.2　FESEM表面型態分析......................47
4.4　氧氣感測電性分析.........................52
4.4.1　氧分壓-導電率之行為....................52
4.4.2　應答時間...............................56
4.5　厚膜之多孔性對氧氣感測之影響測試.........60
4.5.1　多孔性厚膜製作與分析...................60
4.5.2　多孔性厚膜之氧分壓感測分析.............73
4.6　使用溫度補償材料對氧氣感測之影響.........80
4.6.1　溫度對電阻之活化能.....................80
4.6.2　氧分壓－輸出電壓之行為及應答時間.......83
第五章、結論..................................86
第六章、未來方向..............................88
參考文獻......................................89

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