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研究生：	邱凰倩 Chiu, Huang-Chien
論文名稱：	以Core-Shell技術合成ZST粉末 Producing ZST powder by Core-Shell techniques
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：	2005
畢業學年度：	93
語文別：	中文
論文頁數：	51
中文關鍵詞：	(臉譜)技術
外文關鍵詞：	Core-Shell technique
相關次數：	點閱：100 下載：1
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　　本研究之目的在以core shell技術製作(Zr,Ti)沉澱物包覆在SnO2顆粒表面之共沉膠，以縮短固態反應製程製作ZST粉末時Zr、Ti、SnO2粒子間所需要的反應距離，採用此方式降低其合成溫度，於低溫合成ZST粉末。實驗中選擇尿素為沉澱劑，與起始原料Zr、Ti及SnO2混合均勻，並控制加熱、持溫條件讓尿素緩慢分解出OH-，使Zr4+、Ti4+可於SnO2表面析出形成包覆層。結果顯示：於85~90℃持溫13小時可獲得粒體約500 nm以SnO2為core，(Zr,Ti)沉澱物為shell的ZST起始粉末。
　　以此方式合成之ZST起始粉末，於600℃有ZrTiO4相生成，直到800℃ SnO2可與之反應產生ZST相，而在1150℃還存在之ZrTiO4相則造成高溫生成ZST相的反應。雖於1200℃/2hr之煆燒樣品經XRD分析已無其他結晶相存在，但由TEM照片中發現仍有少量ZrTiO4相粒體存在，這可能是製程中SnO2與Zr、Ti劑量之計算誤差所造成。未來，如在SnO2個數計算與Zr、Ti用量之計量比能更精準，則有望生產單一相之ZST粉末。

　Producing Zr-Ti co-precipitate coating on the surface of SnO2 particles by core-shell technique was investigated in this study. This process reduced the reaction distance between Zr, Ti, and SnO2 particles and decreased the synthetic temperature in manufacturing ZST powders. Urea, as a precipitant, mixed homogeneously with Zr, Ti, and SnO2 particles slowly decomposed OH- to precipitate a Zr4+-Ti4+ coat on SnO2 surface by controlling heating conditions.
　The results manifested that near 500 nm ZST starting powder with Zr-Ti co-precipitate as shell and SnO2 particles as core was obtained during 85~90℃ /13hrs. ZrTiO4 phase formed at 600℃, reacting with SnO2 to form ZST phase until 800℃. ZrTiO4 phase remained at 1150℃ result in the formation of ZST at higher temperature. There is no else phases except for ZST in XRD analysis of 1200℃/2hrs sample, but detectable amounts of ZrTiO4 particles were found in TEM/EDS analyses. This phenomenon probably caused by the error in Zr, Ti stoichiometric calculation. In future, a pure ZST phase can be able to produce by precise calculation in number of SnO2 particles and Zr, Ti stoichiometry.

目錄
摘要	         Ⅰ
Abstract 	         Ⅱ
致謝	         Ⅲ
目錄	         Ⅳ
List of Tables	Ⅶ
List of Figures	Ⅷ
附錄	         Ⅹ

第一章  緒論	1
1.1  前言	1
1.2  研究目的	3

第二章  理論基礎與前人研究	4
2.1  ZST之基本性質	4
2.1.1  ZrTiO4之結構	4
2.1.2  Zr0.8Sn0.2TiO4之結構及特性	4
2.2  主要之ZST合成法	5
2.2.1  固態法	5
2.2.2  共沉法	5
2.2.3  溶膠凝膠法	5
2.3  以Core shell法合成ZST粉末	5
2.3.1  Core shell合成理論	6
  2.3.1.1  聚合作用	6
  2.3.1.2  溶解析出方式	6
  2.3.1.3  電荷吸引方式	6
  2.3.1.4  異質成核	6
2.3.2  Core shell合成技術	6
2.3.3  SnO2-core-(Zr,Ti)沉澱物-shell之製備	8
第三章  實驗方法與步驟	14
3.1  實驗構想	14
3.2  實驗原料	14
3.3  實驗流程	15
3.3.1  SnO2的取樣及特性分析	15
  3.3.1.1  SnO2顆粒之粒徑及表面電位	15
3.3.2  反應溶液的製備	15
3.3.3  ZST共沉膠的製作	16
3.4  特性分析	16
3.4.1  粒徑分佈	16
3.4.2  水溶液中之元素分析	16
3.4.3  熱差分析	16
3.4.4  粉末結晶相分析	17
3.4.5  顯微影像及結構分析	17

第四章  結果與討論	23
4.1  製作ZST core shell起始粉末之製程條件	23
4.2  ZST之生成機制	26
4.2.1  DTA熱分析	26
4.2.2  XRD及TEM觀察	26
4.3  ZST粉末之顯微觀察及結晶相分析	27
4.3.1  ZST粉末之狀態	27
4.3.2	TEM中發現少量ZrTiO4相存在	27
第五章  結論	39

參考文獻	40

Appendix I  以氨水為沉澱劑合成ZST起始粉末	43
List of Tables
Table 3-1 Reagents used in this study	                       14
Table 3-2 The physical and chemical properties of raw materials	     15
Table 4-1 The effect of different temperatures on precipitate of Zr4+、Ti4+ 
          was observed, using urea as precipitant	              25

List of Figures
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	(001) projection of ZrTiO4 structure：The ordered commensurate 
         ordered structure (aord＝2adis) of ZrTiO4	              9
Fig. 2-3	Rietveld refined structure of Zr0.8Sn0.2TiO4.All the cations, Zr4+, 
         Ti4+, and Sn4+ occupy positions 4c of space group Pbcn	     9
Fig. 2-4	Room temperature phase diagram of ZrxTiySnzO4 ceramics (x+y+z＝2).The 
         existence range of a single phase compound ZrxTiySnzO4 is tentatively 
         indicated by the broken line	                      10
Fig. 2-5	Schematic depiction of three types of chemical co-precipitation 
         models.(a) compound (b) mixing (c) coating	             11
Fig. 2-6	Solute concentration, reaction time and each step of crystalline 
         growth for the dissolution/precipitation mechanism	    12
Fig. 2-7	Change in pH by the hydrolysis of urea solution (0.5M)	    13
Fig. 2-8	Change of pH with time during precipitation of Sn (Ⅳ) with urea	                                                           13
Fig. 3-1	The XRD pattern of commercial SnO2 powders	             18
Fig. 3-2	a) The particle size distribution of SnO2 powders after 
         sedimentation. It reveals that (b) The TEM image of SnO2 powder shows 
         that SnO2 particles are nearly spherical	             19
Fig. 3-3	Schematic representation of zeta potential of SnO2 particles	20
Fig. 3-4	Schematic representation of the experimental tools	         21
Fig. 3-5	Flowchart of this study	                                    22
Fig. 4-1	The schematic representation of pH values of (Zr,Ti) solution with 
         some urea thermally treated at various durations	    28
Fig. 4-2	TEM micrographs of starting solution thermally treated above 95℃ for 
         (a)~(d) 2hrs (e,f) 3hrs, using urea as precipitant	    29
Fig. 4-3	TEM micrographs of starting solution thermally treated at 85~90℃ for 
         (a,b) 11hrs (c,d) 12hrs, using urea as precipitant     30
Fig. 4-4	TEM micrographs of starting solution thermally treated at 85~90℃    
         for (a)~(d) 13hrs, using urea as precipitant	         31
Fig. 4-5	TEM micrographs of starting solution thermally treated at 80~85℃ 
         for (a and b) 20hrs, using urea as precipitant. The corresponding EDS 
         patterns are shown in c and d, respectively	         32
Fig. 4-6	The DTA/TG profiles of ZST starting powders with a heating rate of  
         10℃/ min in air	                                    33
Fig. 4-7	XRD patterns of calcined ZST starting powders. The heating rate was 
         10℃/ min	                                             34
Fig. 4-8	TEM micrographs of examined samples thermally treated at (a and c) 
         600℃ for 30mins. The corresponding diffraction patterns are shown in 
         b and d, respectively	                           35
Fig. 4-9	XRD patterns of calcined ZST starting powders. The heating rate was 
         10℃/ min	                                             36
Fig. 4-10	SEM images (a,b) and TEM images (c,e) of examined samples calcined at 
         1150℃ for 2hrs. The corresponding diffraction patterns are shown in 
         d and f, respectively	                           37
Fig. 4-11	TEM images of examined samples calcined at 1150℃ for (a,b) 30mins, 
         (c,d) 2hrs, and (e,f) 1200℃ for 2hrs	         38 

附錄
AppendixⅡ TEM images of ZST starting powders using ammonia as precipitant	                                                       45
AppendixⅢ Element analysis of starting solution thermally treated
           above 95℃ for 2hrs using TEM-EDS techniques	46
AppendixⅣ Element analysis of starting solution thermally treated 
           above 95℃ for 3hrs using TEM-EDS techniques	47
AppendixⅤ Element analysis of starting solution thermally treated at   
           85~90℃ for 11hrs using TEM-EDS techniques	         48
AppendixⅥ Element analysis of starting solution thermally treated at 
           85~90℃ for 12hrs using TEM-EDS techniques	         49
AppendixⅦ The DTA/TG profiles of Zr-Ti coprecipitate with a heating 
           rate of 20℃/min in air	                           50
AppendixⅧ Element analysis of starting powders calcined at 
           1150℃ for 30 min using TEM-EDS techniques	         51

                                    

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2005-02-02公開

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