臺灣博碩士論文加值系統

本研究是以99.97％的鋅（Zn）及鎢（W）金屬，利用電火花放電法以純水作為介電液備製奈米氧化鋅（ZnO）及奈米氧化鎢（WO3）膠體，此備製方式是屬綠色備製方法，在過去文獻中從未呈現。一般大多使用化學合成法備製，這也是本實驗室第一次以火花放電備製氧化鋅與氧化鎢；為了解所備製的奈米氧化鋅（ZnO）及奈米氧化鎢（WO3）膠體之特性及微結構，以雷射光散射儀(Zetasizer Nano System)、以紫外光/可見光分光光譜儀(UV-Visible Spectrophotometer，簡稱UV-Vis儀)、拉曼光譜分析儀(Raman Spectrometer)及螢光光譜分析儀(Photoluminescence, PL)、X光繞射分析儀(X-ray diffraction, XRD)、掃描式電子顯微鏡(Scanning Electron Microscope)、穿透式電子顯微鏡 (Through-type Scanning Electron Microscope) 、選區繞射(Selected area diffraction,SAED)等儀器分析其特性、成分及微結構。以火花放電法備製氧化鋅與氧化鎢為第一次實做，過去文獻極少呈現備製成品，測試結果與現有的其他化學合成方法生產的氧化鋅與氧化鎢之特性異同比較。
以火花放電法備製後的氧化鋅與氧化鎢膠體經各種儀器檢驗測，測得特性及微結構大略敘述如下：（一）以雷射光散射儀(Zetasizer Nano System)分析結果：氧化鋅（ZnO）顆粒大小分佈集中在1.117nm，而Zeta電位測量結果為-36.2mV，顯示其懸浮度良好；氧化鎢（WO3）膠體奈米粒子平均分佈在62.75nm，Zeta電位為-59.7mV，也顯示氧化鎢（WO3）膠體的懸浮性佳。（二）以紫外光/可見光分光光譜儀(UV-Visible Spectrophotometer，簡稱UV-Vis儀) 測得其光譜吸收強度分析：氧化鋅（ZnO）最大吸收強度在波長190nm以下，波長大於388nm時，其光吸收強度將近零；氧化鎢（WO3）測得兩個最大吸收峰值，其最大吸收強度會隨著膠體濃度升高產生紅移現象。（三）以XRD，SAED檢測氧化鎢（WO3）及氧化鋅（ZnO）所含成分及晶體結構，發現所備製的奈米氧化鋅（ZnO）膠體中含有鋅（Zn）及氧化鋅（ZnO）兩種元素，氧化鋅（ZnO）晶格間距(indice spacing）0.281nm對應晶面(Miller index）為(100)，晶格間距0.259nm對應為晶面為(002)，晶格間距0.247nm對應晶面為(101)是氧化鋅（ZnO）X光繞射的最大峰值；鋅（Zn）晶格間距0.230nm對應晶面為(100)，鋅（Zn）晶格間距0.209nm對應晶面為(101)是鋅（Zn）X光繞射的最大峰值；所備製的氧化鎢（WO3）膠體中含有鎢（W）及氧化鎢水合物（WO3•H2O）兩種元素，鎢（W）晶格間距0.223nm對應晶面為(110)，是鎢（W）X光繞射的最大峰值；氧化鎢水合物（WO3•H2O）晶格間距0.375nm對應為晶面為(120)，晶格間距0.347nm對應為晶面為(111)是氧化鎢水合物（WO3•H2O）X光繞射的最大峰值。
應用電火花放電法在備製氧化鋅膠體及氧化鎢膠體經成份分析結果為：氧化鋅（ZnO）膠體中含有鋅（Zn）及氧化鋅（ZnO）兩種成分；氧化鎢（WO3）膠體中含有鎢（W）及氧化鎢水合物（WO3．H2O）兩種成份。氧化鋅（ZnO）的拉曼(Raman)光譜產生E1(LO)及E2(H)兩個拉曼特徵峰在412 cm-1與570 cm-1位置上；以光致螢光光譜分析，氧化鋅奈米在波長366 nm及498nm兩處會發光可知本實驗備製之氧化鋅結構品質良好結晶度很高，無晶面方向不佳及的情形。WO3•H2O 經拉曼光譜分析，在247.5 cm-1、313.1 cm-1、706.8 cm-1及807.5 cm-1等四位置出現明顯的拉曼光譜特徵峰值；光致螢光(PL)分析，在PL光譜圖中發生以下五個特徵峰值，分別為446nm、470nm、489nm、520nm、570nm ，顯示本實驗備製之氧化鎢水合物結構品質良好。

In this study, with 99.97% of zinc (Zn), tungsten (W) metals and pure water as the dielectric liquid, spark discharge method is adopted to prepare nano zinc oxide (ZnO) and nano tungsten oxide (WO3) colloids. This is a green preparation method and has never been presented in the past literature. Generally, zinc oxide and tungsten oxide are mostly prepared by chemical synthesis. This is the first time that the laboratory made zinc oxide and tungsten oxide by spark discharge. In order to understand the characteristics and microstructure of the prepared nano zinc oxide (ZnO) and nano tungsten oxide (WO3) colloids, the analysis applied instruments such as Zetasizer Nano System, UV-Visible Spectrophotometer (abbreviated as UV-Vis Spectrophotometer), Raman spectroscopy, Photoluminescence (abbreviated as PL), X-ray diffraction (abbreviated as XRD), Selected area diffraction (abbreviated as SAED), Scanning Electron Microscope, Through-type Scanning Electron Microscope and so on. The initial experiment of preparing zinc oxide and tungsten oxide by spark discharge method is rarely presented in the past literature, and so are the compared similarities and differences between the characteristics of zinc oxide and tungsten oxide in this method and that in other synthetic methods.
The zinc oxide and tungsten oxide colloid prepared by the spark discharge method were tested by various instruments, and the measured characteristics and microstructure are roughly described as follows: (1) Analysis results from the Zetasizer Nano System: The particle size distribution of zinc oxide (ZnO) is concentrated at 1.117 nm, and the zeta potential measurement is -36.2 mV, indicating good levitation. Tungsten oxide (WO3) colloidal nanoparticles have an average distribution of 62.75 nm and a zeta potential of -59.7 mV, which also shows good suspension of tungsten oxide (WO3) colloid. (2) Analysis of spectral absorbance intensity measured by UV-Visible Spectrophotometer (UV-Vis instrument)：The maximum absorbance intensity of zinc oxide (ZnO) is near zero when the wavelength is below 190 nm and greater than 388 nm. There are two maximum absorbance peaks measured in Tungsten oxide (WO3) and its maximum absorbance intensity red-shifst as the colloid concentration increases. (3) XRD and SAED were used to detect the composition and crystal structure of tungsten oxide (WO3) and zinc oxide (ZnO). And it is found that the prepared zinc oxide (ZnO) colloid contains the two elements, including zinc (Zn) and zinc oxide (ZnO). The Miller index of Zinc oxide (ZnO) with a indice spacing of 0.281nm is (100), while the Miller index of Zinc oxide (ZnO) with a indice spacing of 0.259nm is (002). The Miller index of Zinc oxide (ZnO) with a indice spacing of 0.247nm is (101), which is the maximum peak of zinc oxide (ZnO) X-ray diffraction. The Miller index of zinc (Zn) with a indice spacing of 0.230 nm is (100) and the Miller index of zinc (Zn) with a indice spacing of 0.209 nm is (101), which is the maximum peak of zinc (Zn) X light diffraction. The prepared tungsten oxide (WO3) colloid contains two elements, including tungsten (W) and tungsten oxide hydrate (WO3•H2O). The Miller index of tungsten (W) with a indice spacing of 0.223 nm is (110), which is the maximum peak of tungsten (W) X-ray diffraction. The tungsten oxide hydrate (WO3•H2O) has a 0.375 nm indice spacing when the Miller index is (120) and a 0.347 nm indice spacing when the Miller index is (111), which is the maximum peak of tungsten oxide hydrate (WO3•H2O) X-ray diffraction.
The results of the composition analysis of the zinc oxide colloid and tungsten oxide colloid prepared with electric spark discharge method are as the followings: Zinc oxide (ZnO) colloid contains zinc (Zn) and zinc oxide (ZnO). Tungsten oxide WO3) colloid contains tungsten (W) and tungsten oxide hydrate (WO3•H2O). In the Raman spectroscopy of zinc oxide (ZnO), E1(LO) characteristic peak and E2(H) characteristic peak are produced on the positions of 412 cm-1 and 570cm-1 respectively. In the analysis of Photoluminescence (PL), the nano zinc oxide (ZnO) illuminates as the wavelength reaches 366nm and 498m. This indicates that both the structural quality and crystallinity of the zinc oxide (ZnO) prepared in this experiment are high and there is no condition of unfavorable Miller index. In the analysis of the Raman spectroscopy of tungsten (W) and tungsten oxide hydrate (WO3•H2O), obvious characteristic peaks can be found on four positons including 247.5 cm-1、313.1 cm-1、706.8 cm-1 and 807.5 cm-1. In the study of Photoluminescence (PL), there are five obvious characteristic peaks found on the PL spectroscopy, which are 446nm, 470nm, 489nm, 520nm and 570nm respectively. This shows that the structural quality of tungsten oxide hydrate is high.

摘要 i
Abstract iii
誌謝 vi
Contents vii
List of Table x
List of Figure xi
Chapter 1 INTRODUCTION 1
1.1 Research Background 1
1.2 Research motivation and purpose 3
1.3 Research methods and procedures 7
1.4 Architecture of dissertation 11
Chapter 2 LITERATURE REVIEW 13
2.1 Introduction of Electrical Discharge Machining 13
2.1.1 Principle of electric discharge machine 15
2.1.2 Introduction to the system structure of the electric discharge machine 22
2.2 Introduction of nano zinc oxide (ZnO) 26
2.2.1 Metal Zinc（Zn） 26
2.2.2 Introduction of nano ZnO. 27
2.2.3 Common method for producing nano ZnO. 31
2.3 Introduction of nano tungsten oxide (WO3) 33
2.3.1 Metal Tungsten（W） 33
2.3.2 Nano tungsten oxide (WO3) 34
2.3.3 Common preparation of nano tungsten oxide (WO3) 35
2.4 Introduction of nano metal colloidal properties 38
2.4.1 Suspension stability of nano metal colloid 38
2.4.2 Optical properties 39
2.4.3 Brownian motion 40
2.4.4 Quantum Size Effect 43
2.4.5 DLVO Theory 45
2.4.6 Tyndall effect 50
2.4.7 Sedimentation 51
2.4.8 Zeta potential 51
2.4.9 Surface effect 55
Chapter 3 RESEARCH METHODS AND EQUIPMENT DESCRIPTION 57
3.1 Research methods and research processes 57
3.1.1 Research Methods 57
3.1.2 Research Procedure 59
3.2 Zinc oxide and tungsten oxide colloid prepared by Electrical Discharge Machine 60
3.2.1 Process and Parameter Control of Zinc Oxide Prepared by Electrical Discharge Machine 60
3.2.2 Preparation of Tungsten Oxide Process and Number Control by EDM 66
3.3 Introduction to Nano Colloid Analyzer 68
3.3.1 UV-Visible Spectrophotometer 69
3.3.2 Zetasizer Nano System 70
3.3.3 Scanning Electron Microscope 71
3.3.4 Through-type Scanning Electron Microscope 72
3.3.5 Energy Dispersive Spectrometer（EDS) 74
3.3.6 X-ray diffraction analyzer (XRD) 75
3.3.7 Photoluminescence spectrum analyzer 77
Chapter 4 EXPERIMENTAL RESULTS AND DISCUSSION. 79
4.1 Analysis of the characteristics of nano zinc oxide 79
4.1.1 Analysis of Particle Size and Suspension of Nano ZnO. 79
4.1.2 Analysis of the Characteristics of ZnO on Light. 81
4.1.3 Analysis of Colloidal Composition of ZnO 88
4.1.4 ZnO colloidal X-ray diffraction analysis (XRD) 90
4.1.5 Crystal Structure Analysis of Transparent Electron Microscopy (TEM) Zinc Oxide (ZnO) 93
4.1.6 Raman spectroscopy analysis 98
4.1.7 Photoluminescence Spectroscopy (PL) analysis 100
4.2 Characteristic Analysis of WO3•H2O Nano Colloid 104
4.2.1 Analysis of Nanoparticle Size and Suspension of WO3•H2O Nano Colloid 104
4.2.2 Optical Properties Analysis of WO3•H2O 106
4.2.3 Analysis of Colloidal Composition of WO3•H2O. 114
4.2.4 X-ray diffraction analysis of prepared WO3•H2O colloid 115
4.2.5 Analysis of crystal structure of WO3•H2O by TEM. 117
4.2.6 Raman spectroscopy analysis of WO3•H2O 126
4.2.7 WO3•H2O with Photoluminescence (PL) Spectral Analysis 128
4.3 Results and discussion 131
4.2.1 Analysis results of nano zinc oxide characteristics 131
4.3.2 Analysis results of WO3•H2O 136
Chapter 5 CONCLUSIONS AND FUTURE PROSPECTS 143
5.1 Conclusion 143
5.2 Contribution of the paper 146
5.3 Directions of future research 147
REFERENCES 149
Publication List 163

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