非晶形二氧化鈦微米球應用於選擇性阻隔近紅外光之研究

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研究生：	朱昭武 Chu, Chao-Wu
論文名稱：	非晶形二氧化鈦微米球應用於選擇性阻隔近紅外光之研究 Amorphous TiO2 Microspheres as Near-infrared Radiation Selective Blocking Material
指導教授：	李紫原 Lee, Chi-Young
口試委員:	徐文光 Hsu, Wen-Kuang 裘性天 Chiu, Hsin-Tien
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2018
畢業學年度：	106
語文別：	中文
論文頁數：	71
中文關鍵詞：	非晶形二氧化鈦、微米球、米氏散射、溶膠凝膠法、近紅外光阻隔
外文關鍵詞：	amorphous TiO2, microsphere, Mie scattering, sol-gel process, infrared radiation blocking
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本研究利用溶膠凝膠法，以四異丙基鈦為前驅物，並加入辛酸形成鈦的錯合物，合成出均勻且圓的非晶形之二氧化鈦實心球，粒徑從亞微米級至微米級。基於米氏散射理論，粒徑約1 μm之微米球能對近紅外光產生散射，阻隔近紅外線之熱輻射，進而降低溫度，使二氧化鈦微米球具備隔熱性質。本研究合成非晶形之二氧化鈦實心球，並將其應用於隔熱鍍層之材料。
實驗上，將粒徑1300 nm非晶形之二氧化鈦微米球及市售二氧化鈦(P25)鍍在玻璃基板上，並以UV-Vis-NIR光譜圖及溫度量測曲線，分析材料對近紅外光阻隔與隔熱能力的表現。根據結果顯示，鍍在玻璃基板的二氧化鈦微米球，在近紅外光與可見光波段之穿透率分別約為45% 及60%，而P25則約為75% 及60%。然而，溫度量測是從25°C持續照光加熱1小時，二氧化鈦微米球與P25溫度上升的幅度有著明顯的差異，最終溫度分別約為43°C及52°C。綜合這些結果，本研究合成之二氧化鈦微米球在隔熱材料的應用上，具有相當大的發展潛力，能夠有效抑制室內溫度的提升，達成節能的功效。

Amorphous TiO2 spheres with sizes ranging from submicroscale to microscale were synthesized by sol-gel process of titanium isopropoxide (TTIP) with octanoic acids. Based on Mie scattering theory, microspheres with diameter about 1 μm scatter near-infrared (NIR) selectively, resulting in thermo-temperature reduction, which leads to significantly improved insulation properties. In this work, amorphous TiO2 spheres were fabricated and applied to thermal insulation coating materials.
With spreading amorphous TiO2 microspheres (diameter of ~1.3 μm) and commercial TiO2 P25 on glass, the heat insulation performance was examined by UV-Vis-NIR spectrum. The results show that the optical transmittances in near-infrared and visible light region are 45% and 60% respectively for TiO2 microsphere coated glass, whereas, for commercial TiO2 P25 coated glass are 75% and 60% respectively, which indicate the heat insulation performance of TiO2 microsphere is better than that of commercial TiO2 P25. Furthermore, heat shielding test revealed different temperature between amorphous TiO2 microspheres and P25 (~43°C and ~52°C) after heating from ~25°C for 1 hour continuously. According to these results, amorphous TiO2 microspheres could be a promising thermal insulation material to improve indoor thermal environment effectively.

目錄

摘要    I
Abstract    II
誌謝    III
第一章 緒論    1
1.1 前言    1
1.2 研究動機    3
第二章 文獻回顧    4
2.1 二氧化鈦基本性質    4
2.2 二氧化鈦合成方法    6
2.2.1 溶膠凝膠法 (Sol-gel process)    6
2.2.2 水熱法 (Hydrothermal synthesis)    9
2.3 鍍膜方法    11
2.3.1 旋轉塗佈法 (Spin coating)    11
2.3.2 Langmuir–Blodgett 薄膜沉積法    12
2.4 散射效應 (Scattering)    14
2.4.1 散射性質簡介    14
2.4.2 米氏散射 (Mie scattering)    16
2.5 紅外光 (Infrared)    17
2.5.1 紅外光簡介    17
2.5.2 近紅外光熱效應    19
第三章 實驗    20
3.1 實驗材料與內容    20
3.2 實驗分析設備    22
3.3 Micron-sized TiO2 spheres之合成    25
3.4 Micron-sized TiO2 spheres應用於隔熱塗料之研究    27
3.4.1 鍍膜方法    27
3.4.2 光穿透測試    30
3.4.3 溫度測量系統之設置    31
3.4.4 隔熱效果測試    38
第四章 結果與討論    39
4.1 材料形貌與性質之鑑定    39
4.2 鍍膜性質之分析    44
4.3 Micron-sized TiO2 spheres 近紅外光阻隔能力之分析    48
4.3.1 不同粒徑實心球及市售TiO2(P25)之比較    48
4.3.2 不同TiO2晶型之比較    51
4.3.3 鍍膜單層與多層之比較    57
4.3.4 不同鍍膜覆蓋率之比較    59
4.4 Micron-sized TiO2 spheres 隔熱能力之量測分析    62
第五章 結論與未來展望    64
5.1 結論    64
5.2 未來展望    66
第六章 參考文獻    67


圖目錄

圖1    二氧化鈦anatase晶體結構    5
圖2    二氧化鈦rutile晶體結構    5
圖3    鈦的烷氧化合物與有機酸的螯合形式    7
圖4    四異丙基鈦與有機酸的反應機制    8
圖5    與碳鏈長度不同的有機酸反應    8
圖6    水熱法所用之高壓反應釜    10
圖7    水熱法合成過程    10
圖8    旋轉塗佈法    11
圖9    在壓縮過程中，兩性分子於液面的狀態變化    13
圖10    以Langmuir–Blodgett沉積法鍍膜過程    13
圖11    瑞利散射與米氏散射    15
圖12    粒子大小與入射光波長比值對瑞利散射與米氏散射的影響    15
圖13    紅外光的分類    18
圖14    實驗內容    21
圖15    合成二氧化鈦微米球之實驗步驟    26
圖16    旋轉塗佈法之實驗步驟    27
圖17    二氧化鈦實心球分佈於液面上之情形    28
圖18    Langmuir–Blodgett薄膜沉積法之實驗步驟    29
圖19    自製的浸漬提拉鍍膜機之設計    29
圖20    自製四通道溫度自動記錄器之電路設計    33
圖21    自製四通道溫度自動記錄器之指令程式設計    33
圖22    RTD電生熱產生誤差與電壓量測限制之探討    34
圖23    冰水共存校正法找出最佳化輸出電流    34
圖24    自製四通道溫度自動記錄器與LabVIEW量測間隔設定    35
圖25    標準模型屋之設計與製作    36
圖26    燈源之設計與製作    37
圖27    自製溫度測量系統之實際量測    37
圖28    隔熱效果測試前之溫度量測校正    38
圖29    不同粒徑之二氧化鈦微米球    41
圖30    二氧化鈦實心球之XRD繞射圖    42
圖31    二氧化鈦實心球之IR光譜圖    42
圖32    二氧化鈦實心球之EDS元素分析    43
圖33    不同粒徑之二氧化鈦實心球AFM分析    45
圖34    粒徑1300 nm二氧化鈦實心球之Alpha Step分析    46
圖35    以Langmuir–Blodgett薄膜沉積法進行鍍膜後之SEM    47
圖36    不同鍍膜方法之比較    47
圖37    非球狀二氧化鈦之SEM形貌分析    49
圖38    不同粒徑的二氧化鈦實心球，以及市售P25、非球狀二氧化鈦之UV/Vis/NIR穿透光譜圖    49
圖39    鍍膜後各樣品之實照(樣品為不同粒徑的二氧化鈦實心球，以及市售P25、非球狀二氧化鈦)    50
圖40    以不同條件鍛燒二氧化鈦微米球    53
圖41    鍛燒後二氧化鈦微米球之XRD繞射圖    54
圖42    (a)(b)非晶形(未鍛燒), (c)(d) Anatase/rutile混相, (e)(f) Rutile相之形貌    55
圖43    不同晶相之UV/Vis/NIR穿透光譜圖    56
圖44    單層與多層鍍膜之比較    58
圖45    單層與多層鍍膜樣品之UV/Vis/NIR穿透光譜圖    58
圖46    不同鍍膜覆蓋率樣品之UV/Vis/NIR穿透光譜圖    60
圖47    不同鍍膜覆蓋率樣品之實照    61
圖48    隔熱能力測試之溫度曲線    63


表目錄

表1 實驗藥品    20
表2 二氧化鈦微米球之圓度與粒徑分布計算    41
表3 鍍膜後，各樣品之覆蓋率計算    50
表4 不同晶相鍍膜後，樣品之覆蓋率計算    56
表5 不同鍍膜覆蓋率樣品之覆蓋率計算    61
                                

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