以急冷旋鑄法及機械冶金法製備Zn4Sb3熱電塊材及其熱電性質之研究

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劉昆明(Kun-ming Liu) 查詢紙本館藏

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以急冷旋鑄法及機械冶金法製備Zn4Sb3熱電塊材及其熱電性質之研究
(Study of the thermoelectric material Zn4Sb3 synthesized by the process of rapidly-quenched melt spinning and mechanical metallurgy and the thermoelectric property)

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摘要(中)

能源短缺以及環境污染問題越來越嚴重，尋找替代性能源方案是刻不容緩。熱電發電原理根據某些材料特有的熱電(Thermoelectric)特性，材料在無做功的情形下，可以將熱能和電能做互相轉換。半導體熱電材料發電模組係根據 Seebeck 熱電原理，只要在材料兩端建立溫度差，發電模組的線路即可獲得電位差，此現象不須外加做功即可將熱能轉換電能，具有體積小、無做動部件、無噪音、無汙染、維修成本低廉等優點。熱電材料的優劣取決於材料的 ZT 值，Z是熱電優值(Figure of merit)，定義為 α2σ/κ，其中α=ΔV/ΔT，為材料的Seebeck 係數；σ 是材料的導電率；κ 是材料的導熱率，T 是絕對溫度。因此可以看出一個優良的熱電材料需要高Seebeck 係數、高導電率、低熱傳導率。現階段而言，熱電值大多在 1以下，無法有更出色的應用，本研究將利用急冷旋鑄法製備具有奈米晶粒 Zn4Sb3 中溫型熱電材料粉末，並以熱壓燒結製作具有奈米結構的熱電塊材，以求增進功率因數(α2σ)和降低熱導性，最後探討熱電材料在不同急冷旋鑄條件下之晶粒尺度、微結構的不同以及利用不同熱壓粉末燒結條件對熱電塊材特性之影響。

摘要(英)

The problems of energy shortage and environment pollution are going seriously. It is important to find alternative energy source project. Thermoelectric materials have thermoelectric properties that can transport heat energy to electric energy without external work. Semiconductor thermoelectric materials power generator is working under Seebeck thermoelectric Law. By establishment of the temperature difference across the materials circuit, we can get voltage across power generator. The advantage of this technology is small volume, quiet, no vibration, no pollution and low maintenance cost. Thermoelectric materials properties can be defined as the figure of merit. The figure of merit is defined as ZT = α2σ/κ, where α is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity and T is the temperature in Kelvin. Therefore, a good material should possess high electrical conductivity, large Seebeck coefficient and low thermal conductivity to retain the heat at the junction and to reduce the heat transfer losses. Most of thermoelectric materials’ ZT value are lower than 1. They do not have potential for commercial application.
The purpose of this program will prepare high performance medium-temperature thermoelectric alloy powder, Zn4Sb3 with nano-structure by means of rapidly-quenched melt-spinning (MS) technique. Then, these rapidly quenched nano-structured alloy ribbons will be ball milled into fine powder and pressed by hot pressing under vacuum to form the bulk samples. The final product fabricated via this new process is expected to increase its power factor ( α2σ ) and reduce thermal conductivity in comparison with the conventional process. In addition, the relationship between the microstructure (grain size) of alloy and its process condition as well as the effect of microstructure on the thermoelectric performance will be investigated.

關鍵字(中)

★ 熱電材料
★ 急冷旋鑄法
★ Seebeck 係數
★ 導電度

關鍵字(英)

★ Seebeck coefficient
★ Melt-spinning method
★ thermoelectric materials

論文目次

中文摘要…………………………………………………………………… i
英文摘要…………………………………………………………………… ii
誌謝………………………………………………………………………… iv
目錄………………………………………………………………………… v
圖目錄……………………………………………………………………… viii
表目錄……………………………………………………………………… xi
一、緒論…………………………………………………………………… 1
1.1 研究背景……………………………………………………… 1
1.2. 研究方向以及動機…………………………………………… 2
二、文獻回顧與整理……………………………………………………… 4
2.1. 熱電效應基本原理…………………………………………… 4
2.1.1. Seebeck 效應………………………………………………… 5
2.1.2. Peltier 效應…………………………………………………… 6
2.1.3. Thomson效應………………………………………………… 6
2.2. 熱電材料性能的物理參數…………………………………… 7
2.2.1. Seebeck 係數 α ……………………………………………… 7
2.2.2. 導電率 σ ……………………………………………………… 8
2.2.3. 導熱率 κ ……………………………………………………… 9
2.3. 熱電材料分類及研究進展…………………………………… 11
2.4. β-Zn4Sb3 熱電材料現今概況………………………………… 15
2.4.1. β-Zn4Sb3 化合物的結構特點……………………………… 15
2.4.2. β-Zn4Sb3 化合物的熱電性能……………………………… 16
2.4.3. β-Zn4Sb3 化合物的相變化…………………………………… 17
2.5. 奈米塊材於熱電之應用……………………………………… 19
2.5.1 奈米塊材對熱傳導係數之影響……………………………… 20
2.5.2. 奈米塊材對 Seebeck 係數之影響…………………………… 20
三、實驗方法及實驗設備………………………………………………… 23
3.1. 實驗流程圖…………………………………………………… 23
3.2. 實驗設備介紹………………………………………………… 25
3.3. 熱電材料基礎性質分析……………………………………… 27
3.3.1. XRD - X射線繞射分析 ……………………………………… 27
3.3.2. 顯微結構觀察與分析………………………………………… 27
3.3.3. 熱電塊體材料密度量測……………………………………… 27
3.3. 熱電材料熱電性質分析 ……………………………………… 28
3.3.1 Seebeck 係數量測 …………………………………………… 28
3.3.1 導電率量測…………………………………………………… 28
四、實驗結果與討論……………………………………………………… 30
4.1. X-ray 繞射結果分析………………………………………… 30
4.1.1. 融熔擴散製程與急冷旋鑄製程的合金相組成……………… 30
4.1.2. 各製程 Zn4Sb3 熱電塊材之相組成………………………… 31
4.1.3. Zn4Sb3 熱電塊材之元素組成………………………………… 32
4.2. 微結構分析…………………………………………………… 33
4.2.1. Zn4Sb3 速凝粉末穿透式電子顯微鏡分析 ………………… 33
4.2.2. 掃描式電子顯微鏡分析……………………………………… 33
4.3. 速凝粉末之 DSC 分析……………………………………… 35
4.4. 塊體材料之熱電性能………………………………………… 36
4.4.1 Seebeck 係數………………………………………………… 36
4.4.2. 導電率………………………………………………………… 37
五、結論 ………………………………………………………………… 38
參考文獻…………………………………………………………………… 74
圖 1-1 Seebeck 效應示意圖…………………………………………… 39
圖 1-2 電子電洞運行模擬圖…………………………………………… 39
圖 1-3 熱電發電模組原理圖…………………………………………… 40
圖 1-4 Peltier 效應示意圖……………………………………………… 40
圖 1-5 熱電致冷器原理圖……………………………………………… 41
圖 2-1 Zn4Sb3 晶體結構模擬圖………………………………………… 41
圖 2-2 β-Zn4Sb3 與其他熱電材料之 ZT 值與溫度的比較…………… 42
圖 2-3 為 Zn-Sb 二元相圖……………………………………………… 42
圖 2-4 熱電材料性能演進圖……………………………………………… 43
圖 2-5 Schematic of energy distribution of carriers before and after filtered by energy barrier……………………………………………………… 43
圖 2-6 Relationship between power factor and energy barrier height……………………………………………………………… 44
圖 3-1 急冷旋鑄法設備………………………………………………… 44
圖 3-2 粉末冶金熱壓設備……………………………………………… 45
圖 3-3 Bruker, KAPPA Apex II…………………………………………… 45
圖 3-4 掃描式電子顯微鏡……………………………………………… 46
圖 3-5 Seebeck 係數和導電度量測示意圖…………………………… 46
圖 3-6 DSC 機台………………………………………………………… 47
圖 3-7 熱擴散係數量測機台…………………………………………… 47
圖 4-1 速凝粉體與母合金之 XRD 圖…………………………………… 48
圖 4-2 Zn4Sb3 母合金熱電塊材之 XRD 圖…………………………… 48
圖 4-3 Zn4Sb3 銅輪轉速 7.6 m/s 之塊材 XRD 圖……………………… 49
圖 4-4 Zn4Sb3 銅輪轉速 11.2 m/s之塊材 XRD 圖……………………… 49
圖 4-5 Zn4Sb3 銅輪轉速 19 m/s 之塊材 XRD 圖……………………… 50
圖 4-6 Zn4Sb3 粉末(銅輪線速度 7.6 m/s) 之 TEM 圖………………… 51
圖 4-7 Zn4Sb3 (銅輪線速度 7.6 m/s) 之 TEM 圖……………………… 52
圖 4-8 Zn4Sb3 粉末(銅輪線速度 11.2 m/s) 之 TEM 圖…………………53
圖 4-9 Zn4Sb3 粉末(銅輪線速度 11.2 m/s) 之 TEM 圖…………………54
圖 4-10 Zn4Sb3 粉末(銅輪線速度 19 m/s) 之 TEM 圖……………… 55
圖 4-11 Zn4Sb3 粉末(銅輪線速度 19 m/s) 之 TEM 圖……………… 56
圖 4-12 (a) Zn4Sb3 速凝薄帶之自由面 SEM 圖……………………… 57
圖 4-12 (b) Zn4Sb3 速凝薄帶之自由面 SEM 圖……………………… 58
圖 4-13 Zn4Sb3 母合金粉末冶金塊材…………………………………… 59
圖 4-14 Zn4Sb3 銅輪線速度(7.6m/s)粉末冶金塊材 …………………… 60
圖 4-15 Zn4Sb3 銅輪線速度(11.2m/s)粉末冶金塊材 …………………… 61
圖 4-16 Zn4Sb3 銅輪線速度(19m/s)粉末冶金塊材……………………… 62
圖 4-17 Zn4Sb3 母合金與速凝薄帶 DSC 圖…………………………… 63
圖 4-18 300℃ 熱壓試塊之 Seebeck 係數 α …………………………… 64
圖 4-19 400℃ 熱壓試塊之 Seebeck 係數 α …………………………… 65
圖 4-20 300℃ 熱壓試塊之導電度 σ …………………………………… 66
圖 4-21 400℃ 熱壓試塊之導電度 σ …………………………………… 67
圖 4-22 300℃ 熱壓試塊之功率因子………………………………………68
圖 4-23 400℃ 熱壓試塊之功率因子………………………………………69
表 1 β−Zn4Sb3 晶體結構理論模型比較表……………………………… 70
表 2 β-Zn4Sb3 室溫下的物理參數………………………………………… 71
表 3 β-Zn4Sb3 銅輪速率與晶粒尺寸對照表……………………………… 72
表 4 300℃ 下各試塊密度值……………………………………………… 72
表 5 400℃ 下各試塊密度值……………………………………………… 72
表 6 各試塊之 EDS 分析………………………………………………… 73

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指導教授

鄭憲清(Shian-Ching Jang)

審核日期

2012-7-24

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