臺灣博碩士論文加值系統

鍛燒，或稱煅燒，為對金屬礦物或其它固體材料的一種加熱過程，可以使材料內的某些成分產生熱解離、相變化或藉此脫去其中揮發性之成分。通常此加熱過程之最高溫不會超過材料本身的熔融溫度。
本研究是以鍛燒法製備氧化鋅。實驗以醋酸鋅為前驅物，接著加入不同體積的氫氧化鈉進行沉澱反應，並改變pH值，於固定之進料速度、攪拌速度及溫度條件下，初步合成混合氧化鋅與氫氧化鋅之粉體液。以ICP-OES測其殘留鋅離子濃度值，水洗混合氧化鋅與氫氧化鋅之粉體液並檢測電導度值與pH值，最後分析最佳洗滌次數。
將製備好的氧化鋅與氫氧化鋅粉體乾燥後，研磨至所需之粒徑，再以不同的加熱溫度、持溫時間、升溫速度進行鍛燒。將所燒結出之粉體以動態光散射光譜儀測其粒徑大小、X光繞射分析儀測其晶體結晶程度、掃描式電子顯微鏡觀察其表面型態、能量色散型X射線螢光分析儀分析其粉體表徵元素組成。
經由實驗結果得知找到氧化鋅沉澱的最佳條件，醋酸鋅濃度為1.15 M，調整pH值在12.0左右，氫氧化鈉溶液濃度為4 N，入料流速為5 g/min，攪拌速率為200 rpm，反應溫度為25°C。此條件下能製備出球狀的氧化鋅，流動性較佳，應用較為廣泛。
研究結果顯示，粉體中氧化鋅所佔比例隨著鍛燒溫度上升而上升；鍛燒溫度超過300°C以上氧化鋅所占比例皆超過九成以上，直到鍛燒至650°C時氧化鋅比例達到約99%。然而在鍛燒至650°C時，持溫時間只要0.5 h，升溫速度5°C/min的鍛燒條件下能製備出尺寸均一約10奈米的氧化鋅。
本研究提供後續製備氧化鋅奈米微粒時所需要的條件參數，包括外觀的的掌控，提升結晶強度、氧化鋅所佔的比例，以及如何製備出所需的粒徑與分析粒徑之條件，以利欲製備相關條件者參考。

Calcination, also known as calcining, is a heating process of minerals or other solid materials. It can make some ingredients of the material cause thermal dissociation, phase change or getting rid off volatile ingredients. Usually, the highest temperature of the heating process won’t exceed melting point of the material.
In this study, zinc oxide was produced by calcination. The precursor of the experiment is zinc acetate. Then, adding different volume of Sodium hydroxide to cause precipitation reaction, which can change the pH value at the same time. In the condition of constant feed rate, stirring speed and temperature. The powder-liquid of the mixed zinc oxide and zinc hydroxide can be synthesized preliminary. After that, using ICP-OES to measure the residual zinc ion concentration value. Washing the mixed powder-liquid of zinc oxide and zinc hydroxide and measuring the conductivity, pH value of the powder-liquid. Then, analyzing the best number of washing times.
After drying the prepared zinc oxide and zinc hydroxide powder, ground the powder to the required particle size. Then, calcing the powder with conditions, which including： different temperatures, holding time and heating rate. At last, measuring the particle size and the degree of crystallinity by DLS and XRD. Then, observe the exterior and the composition of elemental by SEM and EDS.
Through the experimental results, the best conditions of the precipitation was found when the concentration of zinc acetate was 1.15 M, pH=12.0, 4 N sodium hydroxide solution, feed rate=5 g/min while the stirring speed rpm=200 and reaction temperature was 25°C. Under these conditions, the spherical zinc oxide powder has produced, which has better drillability that can be used widely.
The results show that the ratio of zinc oxide in the powder and the calcining temperature are in direct proportion. When the calcining temperature is above 300°C, the ratio of zinc oxide in the powder would up to 90% and reach 99% while in 650°C. However, when calcining under the temperature of 650°C, the zinc oxide could be produced formally (about 10 nm) with soak time in 0.5 h and heating rate=5°C/min.
The study provides the necessary conditions for the subsequent preparation of zinc oxide nanoparticles for those in need., including the control of the appearance, the increase of the crystal strength, the ratio of zinc oxide, the methods of producing the required particle size and the conditions of analyzing particle size.

摘要 i
Abstract iii
致謝 v
目錄 vi
表目錄 ix
圖目錄 xi
第一章 緒論 1
1.1 前言 1
1.2 研究動機 3
1.3 研究架構 4
第二章 文獻回顧與應用原理 5
2.1 鋅材料簡介 5
2.1.1 鋅原料及鋅化合物基本性質 5
2.1.2 氧化鋅的基本性質 7
2.1.3 氧化鋅的結構 8
2.1.4 氧化鋅的特性及應用 11
2.2 氧化鋅與氫氧化鋅之製備方法與文獻回顧 16
2.2.1 氧化鋅的製備方法 16
2.2.1.1 直接沉澱法 21
2.2.1.2 水溶液法 21
2.2.1.3 水熱法 21
2.2.1.4 化學氣相沉積法 22
2.2.2 氫氧化鋅的製備方法 23
　2.3 奈米材料之理論基礎與文獻回顧 26
2.3.1 奈米尺寸 26
2.3.2 奈米材料之特性 26
2.3.2.1 小尺寸效應（Small size effect） 27
2.3.2.2 表面效應（Surface effect） 28
2.3.2.3 量子侷限效應（Quantum confinement effect） 29
2.3.2.4 宏觀量子穿隧效應（Quantum tunneling effect） 30
2.4 燒結機制 31
2.5 粒徑分析方法 32
第三章 實驗藥品、設備與方法 33
3.1 實驗藥品 33
3.2 實驗設備 35
3.3 實驗方法 39
3.3.1 醋酸鋅純度與濃度之確認 39
3.3.2 醋酸鋅為基底(小量)合成氧化鋅 39
3.3.2.1 水洗氧化鋅 39
3.3.2.2 鍛燒製備氧化鋅 40
3.3.2.3 改變鍛燒溫度 40
3.3.3 改變醋酸鋅濃度 42
3.3.4 醋酸鋅為基底(大量)合成氧化鋅 42
3.3.4.1 水洗次數的選擇 42
3.3.4.2 鍛燒製備氧化鋅 43
3.3.4.3 改變持溫時間與升溫速度 43
第四章 結果與討論 45
4.1 氧化鋅合成(小量)之製備 45
4.2 水洗氧化鋅 47
4.3 鍛燒製備氧化鋅 49
4.3.1 改變鍛燒溫度 50
4.3.2 結晶特性分析 50
4.3.3 結晶尺寸分析 53
4.3.4 結晶表面型貌分析 69
4.4 改變醋酸鋅濃度 86
4.5 最佳製備氧化鋅條件 87
4.6 放大產量後氧化鋅水洗次數之選擇 88
4.7 改變鍛燒持溫時間與升溫速度 91
4.7.1 結晶特性分析 92
4.7.2 結晶尺寸分析 98
4.7.3 結晶表面型貌分析 112
第五章 結論 118
參考文獻 120
附錄 125
符號說明 127

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