利用急冷旋鑄及真空熱壓製備Zn4Sb3奈米/微米晶塊材之熱電性質與機械性質研究

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姓名

陳漢文(Han-Wen Chen) 查詢紙本館藏

畢業系所

材料科學與工程研究所

論文名稱

利用急冷旋鑄及真空熱壓製備Zn4Sb3奈米/微米晶塊材之熱電性質與機械性質研究
(The study of thermoelectric and mechanical properties for the nano-/micro-grain Zn4Sb3 fabricated by melt spinning and vacuum hot pressing)

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摘要(中)

β-Zn4Sb3為熱電性能表現最佳的中溫熱電材料，為提升其熱電優值，本研究中混和具有奈米晶與微米晶結構的Zn4Sb3粉末，藉由增加塊材內部晶界面來降低塊材導熱度，進而提高熱電轉換效率。首先將急冷旋鑄法製備具有奈米晶的Zn4Sb3薄帶研磨成粉末後，再與熔融法製備的微米晶粉末互相混合，其Zn4Sb3粉末混合比例以奈米晶/微米晶：95/5 vol.%、90/10 vol.%、85/15 vol.%與80/20 vol.%為基準預製混和粉末，再利用真空熱壓法燒結成相對密度約為99.5%以上之Zn4Sb3塊材，使其具有高的破裂韌性可達1.46 MPa．m1/2。藉由奈米晶的晶粒細化來增加Zn4Sb3材料Seebeck係數與降低熱傳導率，同時利用添加微米晶的來增加載子的移動進而提升電導率，由於奈米/微米複合結構不但降低了材料的晶格熱導率並同時提升了電導率，進而提高整體之ZT值。研究結果顯示80 vol.%奈米晶/20 vol.%微米晶複合結構熱壓塊材在325℃表現出最高ZT值為1.22。

摘要(英)

The β-Zn4Sb3 thermoelectric(TE) material β-Zn4Sb3 has the best performance during 350~400℃. Its advantages include low cost and simple fabricate process. Some researches indicated that its ZT value can reach 1.37 at 400℃
In this study, we select two methods to fabricate nano- and micro- grained Zn4Sb3 process. One is melt spinning process (30 m/s) for Zn4Sb3 ribbon and the other one is a traditional manufacture method by using melt diffusion and quenching for bulk sample. The melt spun ribbons and melt diffused bulk material were both grinded into powders, then mix these two powders with nano/micro-grain sized powder ratio of 95/5 vol.%、90/10 vol.%、85/15 vol.% and 80/20 vol.%. Then these mixed powders were fabricated into bulk samples via vacuum hot pressing (HP) method. The fracture toughness can reach as high as 1.46 MPa．m1/2 because of its high relative density above 99.5%. We propose that with nano- and micro- grained composite structure can increase the phonon scattering and decrease the lattice thermal conductivity at the same time and so as to enhance ZT value. The results show that the optima thermoelectric property occurs at the bulk sample with nano/micro-grain grained vol.ume ratio of 80/20, the measurement of the Seebeck coefficient, electric conductivity, and thermal conductivity are 213 μV/K, 337 S/cm and 7.53 mW/cmK2 ,respectively, which presented a ZT value as high as 1.22 at 598 K.

關鍵字(中)

★ Zn4Sb3
★ 真空熱壓法
★ ZT值

關鍵字(英)

論文目次

摘要 I
Abstract II
致謝 IV
目錄 VI
圖目錄 IX
表目錄 XI
第一章、緒論 1
1-1 前言 1
1-2 研究目的 2
第二章、文獻回顧 5
2-1 熱電效應 5
2-1-1 Seebeck 效應 6
2-1-2 Peltier係應 7
2-1-3 Thomson效應 7
2-2 電導率 8
2-3 熱傳導率 9
2-4 Wiedemann-Franz定律 10
2-5 Zn4Sb3簡介 11
2-5-1 Zn4Sb3之原子組成比 12
2-5-2 Zn4Sb3之晶體結構 12
2-6 熔融法製備Zn4Sb3 13
2-7奈米晶Zn4Sb3製備 14
2-7-1 機械合金法 14
2-7-2急冷旋鑄法(Melt spinning) 14
2-8 Zn4Sb3塊材成型方法 15
2-8-1 熱壓法(Hot pressing) 15
2-8-2 火花電漿法燒結(Spark plasma sintering) 16
第三章、實驗方法與設備 21
3-1 起始原料 21
3-2 粉體及燒結體製備 22
3-2-1急冷旋鑄法製備具奈米晶的Zn4Sb3薄帶 22
3-2-2熔融法製備Zn4Sb3塊材 22
3-2-3粉體研磨及混合 23
3-2-4真空熱壓成形 23
3-3 材料性質分析 24
3-3-1 X光繞射分析(XRD) 24
3-3-2 示差掃描分析(DSC) 24
3-3-3 掃描式電子顯微鏡分析(SEM) 25
3-3-4 穿透式電子顯微鏡分析(TEM) 25
3-3-5 粉體粒徑量測 25
3-4 材料性質量測 26
3-4-1 Zn4Sb3熱電材料分析樣品準備 26
3-4-2 Seebeck係數量測 26
3-4-3 電導率量測 27
3-4-4 熱傳導率量測 27
3-4-4-1 比熱量測 28
3-4-4-2 密度量測 29
3-4-4-3 熱擴散係數量測 29
3-4-5 機械性質量測 30
3-4-5-1 硬度量測分析 30
3-4-5-2 奈米壓痕量測 30
3-4-5-3 破裂韌性 30
第四章、結果與討論 41
4-1 熔融法製備之Zn4Sb3之基本性質 41
4-1-1熔融法製備之Zn4Sb3之XRD分析 41
4-1-2熔融法製備之Zn4Sb3之DSC熱分析 41
4-1-3熔融法製備之Zn4Sb3之粒徑分佈分析 42
4-2 急冷旋鑄法製備之Zn4Sb3之基本性質 42
4-2-1急冷旋鑄法製備之Zn4Sb3之XRD分析 42
4-2-2 急冷旋鑄法製備之Zn4Sb3之DSC熱分析 43
4-2-3 急冷旋鑄法製備之Zn4Sb3之粒徑分佈分析 43
4-2-4 急冷旋鑄法製備之Zn4Sb3之TEM分析 44
4-3熔融法與急冷旋鑄法製備之Zn4Sb3混合熱壓塊材之性質量測 45
4-3-1熔融法與急冷旋鑄法製備之Zn4Sb3混合熱壓塊材之XRD分析 45
4-3-2熔融法與急冷旋鑄法製備之Zn4Sb3混合熱壓塊材之DSC熱分析 45
4-3-3 熔融法與急冷旋鑄法製備之Zn4Sb3混合熱壓塊材之密度量測 45
4-3-4熔融法與急冷旋鑄法製備之Zn4Sb3混合熱壓塊材之顯微結構觀察 46
4-3-5 熔融法與急冷旋鑄法製備之Zn4Sb3混合熱壓塊材之熱電性質量測 47
4-3-5-1 熱壓塊材之Seebeck係數 47
4-3-5-2 熱壓塊材之電導率 47
4-3-5-3 熱壓塊材之功率因子 48
4-3-5-4熱壓塊材之比熱量測 49
4-3-5-5 熱壓塊材之熱擴散係數量測 49
4-3-5-6 熱壓塊材之熱傳導率 50
4-3-5-7 熱壓塊材之ZT值 51
4-3-6 熱壓塊材之機械性質 52
第五章、結論 65
參考文獻 66

參考文獻

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指導教授

鄭憲清(Shian-Ching Jang)

審核日期

2015-7-13

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