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研究生：	李珮慈 Lee, Pei-Tzu
論文名稱：	以SnO2-core、(Zr+Ti)-shell技術合成Zr.8Sn.2TiO4的反應機制 The mechanisms of formation Zr.8Sn.2TiO4 (ZST) via the core-shell technique in which SnO2 was used as core and Ti-ZrO2 was used as shell
指導教授：	顏富士 Yen, Fu-Su
學位類別：	碩士 Master
系所名稱：	工學院 - 資源工程學系 Department of Resources Engineering
論文出版年：	2003
畢業學年度：	91
語文別：	中文
論文頁數：	41
中文關鍵詞：	臉譜技術、鈦酸錫鋯
外文關鍵詞：	ZST, core-shell technique
相關次數：	點閱：147 下載：1
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本研究利用core-shell技術以SnO2為核、Ti-ZrO2為殼合成Zr0.8Sn0.2TiO4 (ZST)微粉。製備方式是先將氯化氧鋯、氯化鈦溶入水中，再加入氨水調整溶液的pH至9，可使Ti及Zr析出於微粒(0.2~0.4μm)SnO2粒體表面形成具有核-殼(core-shell)構造的顆粒。加上不同的熱處理步驟可合成微粒單相的鈦酸錫鋯(ZST，Zr.8Sn.2TiO4)粉末。研究目的在觀察合成ZST粉末的機制。
根據DTA吸放熱峰曲線與XRD繞射分析結果，推測合成ZST的反應途徑有2種：(1)在650℃前後可由微粒或非晶質狀態的含Zr及Ti成份與微粒(< 200nm) SnO2直接反應生成。(2)在溫度超過900℃後主要經先得到ZT (ZrTiO4)結構再以類構造方式Sn進入ZT合成ZST。
由於在650℃後Zr-Ti會開始生成ZrTiO4中間相，並持續至1000℃左右。一旦ZT生成合成ZST的溫度需移至900℃以上，因此若要藉由core-shell技術於低溫合成ZST，必須使用粒徑< 200nm的氧化錫作為core，才有可能在650℃持溫合成ZST。所得ZST粒徑在500nm以下。

Observations of the mechanisms of formation Zr.8Sn.2TiO4 (ZST) via the core-shell technique in which SnO2 was used as core and Ti-ZrO2 was used as shell are the major objective of this study. In this study, ZrOCl2‧8H2O and TiCl4 were dissolved in water and then were precipitated on SnO2 powders via pH-adjusted by the addition of NH4OH solution to prepare ZST starting materials with core-shell structure which were then thermal treated with uvarious temperature and duration to synthesize ZST powders.
According to DTA/TG and XRD analysis, it was found that there could be two reaction routes for synthesizing ZST powders : (1) SnO2 cores with size 200nm in diameter would directly react with amorphous Zr-Ti compounds around 650℃； and (2) exceeding 900℃, Sn ions might diffuse into ZrTiO4 structure by topotatic reaction (TTR).
ZrTiO4 was formed by amorphous Zr-Ti compound would after thermal treated at 650℃ and it kept continuing to 1000℃, so that the synthesizing temperature of ZST powders would exceed 900℃. Therefore it is necessary that the ultra-fine SnO2 powders (<200nm) were used as core and calcined around 650℃ using core-shell technique for synthesizing of Zr.8Sn.2TiO4 (ZST) powders.

摘要………………………………………………………………………………...Ⅰ
Abstract…………………………………………………………………………….Ⅱ
致謝………………………………………………………………………………...Ⅲ
目錄…………………………………………………………….…………………..Ⅳ
表目錄……………………………………………………………………………...Ⅵ
圖目錄……………………………………………………………………………...Ⅶ
附圖目錄…………………………………………………………………………...Ⅷ

第一章 緒論……………………………………………………………………….	..1
1-1 前言…………………………………………………………………………….	1
1-2 研究目的………………………………………………………………………	.2

第二章 理論基礎與前人研究………………………………………..	…………….3
2-1 (Zr.8Sn.2)TiO4的基本性質………………………………………………………	3
2-1-1 ZrTiO4的結構…………………………………………………………	……3
2-1-2 (Zr.8 Sn.2)TiO4的構造及特性…………………………………………….	...3
2-2 類構造反應法(Topotatic Reaction/TTR)………………………………………	4
2-3 (Zr.8Sn.2)TiO4的合成方法…………………………………………………	……4
2-3-1 傳統固態反應法…………………………………………………………	..5
2-3-2 改良新製程………………………………………………………………..	5
2-4 Core-Shell法……………………………………………………………………	.6

第三章 實驗設計與方法…………………………………………………………	.11
3-1 原料來源……………………………………………………………………	…11
3-2 實驗設計與流程………………………………………………………………	11
3-2-1 鋯、鈦水溶液的製備…………………………………………………	….12
3-2-2 SnO2(core)的製備………………………………………………………...	12
3-2-3 Zr、Ti包覆及core-shell製作…………………………………………..	.12
3-3 特性分析……………………………………………………………………...	13
3-3-1 水溶液中的元素分析………………………………………….…………	13
3-3-2 熱性質分析………………………………………………………………	13
3-3-3 粉末結晶相鑑定…………………………………………………………	13
3-3-4 粒徑分佈………………………………………………………………	…13
3-3-5 顯微結構分析……………………………………………………………	14

第四章 結果與討論……………………………………………………………….	17
4-1 鋯鈦包覆氧化錫之ZST起始粉末之基本特性……………………………..	17
4-1-1 SnO2(core)的粒徑分佈…………………………………………………...	17
4-1-2 ZST起始粉末(core-shell)之外觀………………………………………...	17
4-2 鋯鈦包覆氧化錫之ZST起始粉末之熱行為分析…………………………...	17
4-3 ZST之生成機制的探討……………………………………………………….	21
4-3-1 650℃生成ZST…………………………………………………………...	21
4-3-2 900~1150℃生成ZST…………………………………………………….	22
4-3-3 1200℃生成ZST………………………………………………………….	22
4-3-4 ZST合成溫度與SnO2粒徑之關係………………………………………	22

第五章結論………………………………………………………………………...	27

參考文獻…………………………………………………………………………...	28

附錄………………………………………………………………………………...	31

表目錄

Table 2-1	Compounds with the [α-PbO2] structure…………………………….8
Table 3-1	Reagents used in this study………………………………………….11
Table 4-1	The crystalline phase of the calcined powders identified using XRD techniques…………………………………………………………...	.23

圖目錄

Fig.2-1	Projection on (010) of the structure of ZrTiO4. The cations Zr4+ and Ti4+ 
occupy positions 4c of space group pbcn…………………………………	..9
Fig. 2-2	Rietveld refined structure of Zr0.8Sn0.2TiO4. All the cations, Zr4+, Ti4+ and Sn4+ occupy positions 4c of space group Pbcn………………..…………	...9
Fig. 2-3	Room-temperature phase diagram of ZrXTiYSnZO4 ceramics (x+y+z = 2). The existence range of a single phase compound ZrXTiYSnZO4 (ZTS) is tentatively indicated by the broken line. Locus of temperature coefficient TCf = 0 and preferred composition range for dielectric resonators…….…	10
Fig. 3-1	Flowchart of preparation of SnO2 particles…………………………….....15
Fig. 3-2	Flowchart of this study…………………………………………………...16
Fig. 4-1	(a)The particle size distribution of SnO2 powders used for preparing the core. (b)The TEM image of SnO2 powders……………………………….18
Fig. 4-2	The SEM images of ZST starting power………………………………….19
Fig. 4-3	The DTA/TG profiles of ZST starting powders with a heating rate of 20℃/min in air…………………………………………………………………20
Fig. 4-4	XRD patterns of calcined ZST starting powders…………………………24
Fig. 4-5	XRD patterns of calcined ZST starting powders…………………………25
Fig. 4-6	Schematic depiction of formation mechanisms of ZST powders using different SnO2 sizes………………………………………………………26

附圖目錄

AppendixⅠ	The titration curve for precipitation of Zr-Ti shell on SnO2 core using ammonia as the precipitator…………………………………………31
AppendixⅡ-(a)	The elemental analysis for ZST starting powders using SEM-EDS techniques………………………………………………………...32
AppendixⅡ-(b-1)	The elemental analysis for ZST starting powders using SEM-EDS techniques…………………………………………..33
AppendixⅡ-(b-2)	The elemental analysis for ZST starting powders using SEM-EDS techniques…………………………………………..34
AppendixⅡ-(c-1)	The elemental analysis for ZST starting powders using SEM-EDS techniques…………………………………………..35
AppendixⅡ-(c-2)	The elemental analysis for ZST starting powders using SEM-EDS techniques…………………………………………..36
AppendixⅢ	The DTA/TG profiles of Zr-Ti coprecipitate with a heating rate of 20℃/min in air………………………………………………………….37
AppendixⅣ	DTA/TG profiles of Zr- and Ti-gels with a heating rate 10℃/min in air…………………………………………………………………….38
AppendixⅤ	XRD patterns of ZST starting powders pretreated at 180℃/30min and 550℃/30min and then calcined at various temperatures and durations……………………………………………………………..39
                                    

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