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研究生:施經瑋
論文名稱:多元合金之熱電性能研究
論文名稱(外文):A study of thermoelectric properties of multi-element alloys
指導教授:廖建能
學位類別:碩士
校院名稱:國立清華大學
系所名稱:材料科學工程學系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
論文頁數:64
中文關鍵詞:熱電多元
相關次數:
  • 被引用被引用:4
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  • 下載下載:54
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通常一個好的熱電材料必須具備良好的電導係數及Seebeck係數,以及低熱導係數,這是一般傳統合金所無法具備的。相對於單一主元素之傳統合金,具多主元素之高熵合金係一嶄新的冶金概念。在目前已開發之部分高熵合金系統業已展現出極優異之機械性質與化學性質,然而高熵合金之電性質與熱電性質則尚未有詳盡之探討。本研究以half-heusler三元合金當作出發點,利用真空電弧熔煉製作合金,經由熱處理後,量測其熱電性質,找到兩個具有發展潛力的系統:ZrTiSnSiNi2、ZrTiSnGeNi2,室溫下熱電優值ZT分別為0.02與0.045。當在中高溫的範圍(250~300℃)時功率因子(S2/ρ)約可增加3~4倍,將成份改質為Zr0.9Ti0.9Nb0.2SnSiNi2,結果顯示室溫下的熱電優值ZT約為0.078。利用X光結晶繞射(XRD)、掃瞄式電子顯微鏡(SEM)與能量散佈光譜儀(EDS)鑑定出此二多元合金系統為具有半導體與金屬組成相的複合材料。
A good thermoelectric material requires high Seebeck coefficient (S) and electrical conductivity (σ) but low thermal conductivity (κ), which are not common found in traditional metallic alloys. As compound with traditional metallic alloy, high entropy alloy of multi constituent element is a newly developed metallurgical concept. A variety of different forms of the multi-element alloys have been demonstrated to possess superior mechanical and chemical properties. However, the electrical and thermoelectric properties of the multi-element alloys have not been thoroughly explored yet. In this study, multi-element alloys were prepared by arc-melting and thermal annealing. Their thermoelectric properties were characterized after appropriate sample preparation. We find two multi-element alloy systems based on half-Heusler structure:ZrTiSnSiNi2 and ZrTiSnGeNi2. The thermoelectric figure of merits (ZT , Z= S2/(ρ×κ)) of these multi-element alloys were equal to be 0.02 and 0.045, respectively, at room temperature. These multi-element alloys showed 3 times increase in power factor (S2/ρ) in the middle temperature range (250℃ to 300℃). By adding Nb element into the alloy forming Zr0.9Ti0.9Nb0.2SnSiNi2, the thermoelectric figure of merit was found to be 0.078 at room temperature. The multi- element alloys were identified to be a composite material containing semiconductor-like phase and metallic-like phase by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDS).
目錄………………………………………………………………..……Ⅰ
圖目錄…………………………………………...…………………….. Ⅳ
表目錄………………………………...……………………….………. Ⅴ
摘要……………………………………………………………….…...VII
英文摘要……………………………………………………..………VIII
第一章、簡介…………………………………………………..…………1
1.1研究動機………………………………………..…………………….1
1.2實驗目的……………………………………………..……………….2
第二章、文獻回顧………………………………………………..………3
2.1熱電簡介……………….……………………………..………………2
2.1.1熱電現象………………………….…………….………….3
2.1.2 Seebeck效應………………………………………………3
2.1.3 Peltier效應……………………………………………...…4
2.1.4 Thomson效應…………………….…………………..……5
2.1.5 Seebeck效應、Peltier效應與Thomson效應之關聯性….6
2.1.6熱電性質…………………….…………………….……….7
2.2高熵合金簡介………………………………………………..……...10

2.3 half-Heusler結構熱電性質………………………….......................11
第三章、實驗方法與分析………………………………………………14
3.1實驗規劃……………………………………….…………………....14
3.2試片製備…………………………………………………………….17
3.2.1成分計算..…………….…….…………………………….17
3.2.2合金熔煉……………………….…………………………18
3.2.3高溫熱處理…………………………….…………………20
3.2.4研磨拋光…..……………………………………………...20
3.2.5厚膜阻絕層製作………………………………………….20
3.2.6定義熱傳導係數量測用微加熱帶……………………….21
3.3 Seebec係數量測方式…...……………………..…………...………24
3.4 電阻係數量測方式……………………………………….….…….26
3.5 載子濃度量測……………………………………………..….……29
3.6 熱傳導係數量測方式……………………………………………...30
3.6.1 加熱線上的溫度變化……………………………………33
3.6.2 數學推導…………………………………………………35
第四章、實驗結果與討論………………………………………………38
4.1實驗結果….……………………………………………………...….38
4.1.1 ZrTiSnSiNi2之熱電性質……………..…………………..38
4.1.1.1熱處理對Seebeck 係數與電阻係數的影響…….38
4.1.1.2 Seebeck係數與電阻係數隨溫度的變化…………40
4.1.1.3熱處理對ZrTiSnSiNi2晶體結構之影響………….42
4.1.2 ZrTiSnGeNi2之熱電性質…………...…………….……...48
4.1.2.1 Seebeck係數與電阻係數………………………...48
4.1.2.2 Seebeck係數與電阻係數隨溫度的變化………...49
4.1.1.3熱處理對ZrTiSnGeNi2晶體結構之影響…………51
4.3霍爾效應量測…………….…………………………………………54
4.4 熱傳導係數………………………………….……………………..54
4.5 合金定量分析-感應式耦合電漿原子發光光譜儀………………..56
4.6 添加Nb的影響…………………………………………………….58
第五章、結論……………………………………………………..……60
參考文獻……………………………………………………..…..…..…61
附錄.儀器設備………………………………………………………….64





圖目錄

圖2-1、Seebeck效應示意圖…………………………………………….4
圖2-2、Peltier效應示意圖………………………...…………………….5
圖2-3、Thomson效應示意圖…………………………………………...5
圖2-4、熱電線路圖……………………………………………….……..6
圖2-5、各類熱電材料其熱電優值(ZT)隨溫度變化……………………9
圖2-6、Heusler晶體結與half-Heusler晶體結構……………………..13
圖3-1、真空熔煉爐示意圖……………………….……………………15
圖3-2、實驗流程圖…………………………………………….………16
圖3-3、(a)真空電弧熔煉爐設備(b)水冷銅模……………...…………19
圖3-4、厚膜絕緣層製作流程.................................................................21
圖3-5、定義金屬導線流程圖…………………...……………….……23
圖3-6、熱電量測系統示意圖………………………….………………25
圖3-7、電壓差對溫度作圖決定Seebeck係數……..…………………26
圖3-8、直流式四線量測示意圖…………………………………….…27
圖3-9、Van der Pauw四點探針法………………….…………………28
圖3-10、霍爾效應量測裝置圖…..………..……………………………29
圖3-11、3ω方法所需結構示意圖………………….………..…………31
圖3-12、3ω樣本截面圖……………………………………..…………32
圖3-13、3ω樣本俯視圖…………………………..……………………32
圖3-14、ΔT2ω對ln(2ω)做圖…………..…………..……………………37
圖4-1、ZrTiSnSiNi合金Seebeck係數對溫度變化情形……...……..41
圖4-2、ZrTiSnSiNi合金電阻係數隨度溫度變化情形………………41
圖4-3、ZrTiSnSiNi合金功率因子隨溫度變化情形………………..…42
圖4-4、ZrTiSnSiNi合金熱處理前後之微結構……………………….43
圖4-5、ZrTiSnSiNi2合金能量散佈分析光譜儀(EDS)結果比較.……45
圖4-6、Zr0.5Ti0.5SiNi合金電阻係數隨溫度變化…………..……....…46
圖4-7、ZrTiSnSiNi2合金熱處理前後XRD比較…………………….47
圖4-8、ZrTiSnGeNi2合金Seebeck係數隨溫度變化情形…...………50
圖4-9、ZrTiSnGeNi2合金電阻係數隨溫度變化情形….……….……50
圖4-10、ZrTiSnGeNi2合金功率因子隨溫度變化情形..……..…..……51
圖4-11、ZrTiSnGeNi2合金相能量散佈分析光譜儀結果比較……..…52
圖4-12、ZrTiSnGeNi2合金熱處理前後XRD結果比較………..….…53










表目錄


表2-1、Half-Heusler三元合金熱電性質…………………………..…12
表3-1、多元合金之元素相關性質…………………………………….18
表4-1、ZrTiSnSiNi2熱處理前後Seebeck係數與電阻係數…….……39
表4-2、ZrTiSnGeNi2合金熱處理前後Seebeck係數與電阻係數比較..48
表4-3、具Half-Heusler結構之不同合金載子濃度...…………..…...…55
表4-4、具Half-Heusler結構之不同合金熱傳導係數……….……...…55
表4-5、多元合金與具Half-Heusler結構合金之熱電性質比較…..….56
表4-6、ZrTiSnSiNi2合金成分熱處理前後定量分析比較………..…..57
表4-7、ZrTiSnGeNi2合金成分定量分析…………………..……..…..58
表4-8、ZrTiSnSiNi2與Zr0.9Ti0.9Nb0.2SnSiNi2熱電性質比較…………59
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