臺灣博碩士論文加值系統

摘要
本研究主要是探討在加熱過程中，不同元素對於鎂合金發生燃燒反應的溫度的影響。使用的實驗材料為商用鎂鋁合金（純鎂、AZ61A、AZ80A和AZ91D）以及自行熔煉的鎂鈣與鎂鋁錳合金。另外，利用自行設計的加熱測溫裝置，比較鋁、鈣、錳等三種元素，對於抑制鎂合金燃燒的效果。
實驗結果發現鎂鋁合金發生燃燒反應的溫度，會隨著合金中鋁含量的增加而降低，主要是因為合金基地中的鎂鋁低熔點共晶物的含量會隨著鋁的添加量增加而增加，使合金容易發生局部熔解的情形，進而破壞合金表面原本的保護層，導致燃燒。
而添加鈣到鎂合金中，則是添加量愈多，發生燃燒反應的溫度愈高，主要原因是鈣會形成一層緻密的氧化層，阻止合金中的鎂元素與空氣中的氧做進一步的接觸。
鎂鋁錳合金中，錳含量增加也會提高合金發生燃燒反應的溫度，因為錳含量提高會消耗合金基地中更多的鋁元素，以形成Al6Mn析出物，所以合金中的低熔點鎂鋁共晶物的量會因此而減少，導致合金發生燃燒反應的溫度有提高的現象。

Abstract
The purpose of this study is aimed at investigating the difference of the ignition temperatures affected by adding elements, Al、Ca、Mn, into magnesium alloys. The alloys used in this experiment are commercial Mg-Al alloys ( pure magnesium, AZ61A, AZ80A, AZ91D ) and Mg-Ca、Mg-Al-Mn alloys melted by designed apparatus.
Experimental results show that adding more aluminum into magnesium alloys would lower the ignition temperature of the alloys. Inversely, adding more calcium and manganese into magnesium alloys would raise the ignition temperatures. Aluminum added into magnesium alloys would form low melting point eutectics, leading to local melt and therefore lowering the ignition temperature. Eventually, the specimens would burn out during experiment.
However, adding calcium into magnesium alloys would retard the ignition process by forming thin and dense CaO films on the surface of the alloys.
In the Mg-Al-Mn alloys, increasing manganese content increase the ignition temperature due to a great percent of precipitate, Al6Mn, formed leading to decrease amount of low melting point eutectics. So adding manganese would increase the ignition temperature of the magnesium alloys.

總目錄
中文摘要
英文摘要
總目錄-------------------------------------------------------------------------i
表目錄-----------------------------------------------------------------------iii
圖目錄------------------------------------------------------------------------iv
第一章 前言--------------------------------------------------------------------1
第二章 文獻回顧----------------------------------------------------------------2
2-1 鎂與鎂合金的基本特性-------------------------------------------------------2
2-1-1 鎂-----------------------------------------------------------------------2
2-2-2 鎂合金-------------------------------------------------------------------2
2-2 鎂合金的熔煉與安全防護-----------------------------------------------------5
2-2-1 熔煉流程-----------------------------------------------------------------6
2-2-2 熔煉設備-----------------------------------------------------------------6
2-2-3 助熔劑及保護氣體---------------------------------------------------------7
2-2-4 其他注意事項------------------------------------------------------------12
2-3 鎂與鎂合金的燃燒特性與機制------------------------------------------------13
2-3-1 純鎂--------------------------------------------------------------------14
2-3-2 鎂鋁鋅合金--------------------------------------------------------------16
2-3-3 鎂鈣合金----------------------------------------------------------------17
2-4 鎂合金的回收概況----------------------------------------------------------19
第三章 實驗步驟---------------------------------------------------------------22
3-1 實驗目的------------------------------------------------------------------22
3-2 實驗材料------------------------------------------------------------------22
3-2-1 商用鎂鋁鋅合金----------------------------------------------------------22
3-2-2 鎂鈣合金----------------------------------------------------------------22
3-2-3 鎂鋁錳合金--------------------------------------------------------------24
3-3 試片規格------------------------------------------------------------------24
3-4 實驗設備------------------------------------------------------------------24
3-5 實驗步驟與方法------------------------------------------------------------25
第四章 結果與討論-------------------------------------------------------------27
4-1 實驗設備理論基礎----------------------------------------------------------27
4-2 鎂鋁鋅合金的分析結果------------------------------------------------------27
4-2-1 實驗現象觀察------------------------------------------------------------27
4-2-2 由熱量分析來討論燃燒結果------------------------------------------------29
4-3 鎂鈣合金的分析結果--------------------------------------------------------32
4-3-1實驗現象觀察-------------------------------------------------------------32
4-3-2由熱量分析來討論燃燒結果-------------------------------------------------33
4-4鎂鋁錳合金的分析結果-------------------------------------------------------36
4-4-1 實驗現象觀察------------------------------------------------------------36
4-4-2 由熱量分析來討論燃燒結果------------------------------------------------36
4-5 綜合討論------------------------------------------------------------------39
第五章 結論-------------------------------------------------------------------40
參考文獻----------------------------------------------------------------------41
附錄1 實驗設備吸收的熱量------------------------------------------------------94
附錄2 未經固溶處理的鎂鋁合金之氧化過程示意圖----------------------------------95
附錄3 經固溶處理後的鎂鋁合金之氧化過程示意圖----------------------------------96
附錄4 鈣含量較高的鎂鈣合金之氧化過程示意圖------------------------------------97
附錄5 鈣含量較低的鎂鈣合金之氧化過程示意圖------------------------------------98
附錄6 鎂鋁錳合金之氧化過程示意圖----------------------------------------------99
表目錄
Chap. 2
Table 2-1 鎂元素來自礦物中的比例[1]-------------------------------------------45
Table 2-2 鎂的物理特性[2]-----------------------------------------------------45
Table 2-3 鎂合金的成份比例[3]-------------------------------------------------46
Table 2-4 鎂合金助熔劑之比較[25]----------------------------------------------46
Table 2-5 IMA建議的保護氣氛組成[24]-------------------------------------------47
Table 2-6 鎂合金加工用礦物性切削液基本性質[24]--------------------------------47
Table 2-7 鎂燃燒時的滅火劑種類[24]--------------------------------------------47
Chap. 3
Table 3-1 商用鎂鋁鋅合金之成份------------------------------------------------48
Table 3-2 鎂鈣合金之成份------------------------------------------------------48
Table 3-3 鎂鋁錳合金之成份----------------------------------------------------48
Chap. 4
Table 4-1 AZ80A和AZ91D的固溶處理條件[36] -------------------------------------49
Table 4-2 參與反應的鋁元素佔試片中鋁含量的重量比率----------------------------49
Table 4-3 鎂鋁錳合金中共晶物與析出物所佔之面積率------------------------------49
圖目錄
Chap. 2
Fig. 2-1 Scheme of a production line with a protective atmosphere containing SF6 and a turbulent filling of the shot chamber[28]---------------------------50
Fig. 2-2 Scheme of the total encapsulated melting and casting process with a SF6-free argon-atmosphere and laminar filling of the shot-chamber up to 100％[28] -------------------------------------------------------------------------50
Fig. 2-3 Conductive melting and dosing furnace for magnesium alloys with a controlled gas pressure dosing system[28]-------------------------------------51
Fig. 2-4 Time variation of sample temperature and continuous emission intensity. Magnesium sample[29]-----------------------------------------------51
Fig. 2-5 Direct photograph of sample appearance. Magnesium sample[29]---------52
Fig. 2-6 Emission spectrum of magnesium flame with identified characteristic lines and bandheads[29]-------------------------------------------------------52
Fig. 2-7 Schematic representation of four stages in surface oxidation.[29]----53
Fig. 2-8 Schematic representation of transition to homogeneous reaction in open space.[29]--------------------------------------------------------------------54
Fig. 2-9 Section of an underburned magnesium sample.[32]----------------------55
Fig. 2-10 Atmospheric exposure testing of the molten Mg-5Ca alloy.[13]--------55
Fig. 2-11 (a) Temperature vs. thickness of the oxide film of the molten Mg-5Ca alloy exposed for 20 hours in air, (b) thickness of the oxide film vs. holding time of the molten Mg-5Ca alloy at 1273 K in air.[13]-------------------------56
Fig. 2-12 Scanning electron micrographs of the cross sections of the oxide film formed on the molten Mg-5Ca alloy exposed for 20 hrs in air at (a) 1123 K, (b) 1173 K, and (c) 1273 K. Capital “U” denotes the most upper zone of the oxide film.[13]---------------------------------------------------------------------57
Fig. 2-13 Surface morphologies of pure magnesium(a, b) and Mg-1.5Ca(c, d) alloy oxidized at 500℃ (a, c: low magnification, b, d: high magnification).[10]----58
Fig. 2-14 X-ray diffraction patterns of the oxide film formed on the molten Mg-5Ca alloy held for 1 hr at 1073 K in the air.[13]-----------------------------58
Fig. 2-15 AES depth profiles sputtered from the surface of pure Mg and Mg-Ca alloys oxidized at 440(a), 480(b) and 500℃(c) for 1 hr.[10]------------------59
Fig. 2-16 Model of the oxide film formed on the molten Ca-bearing Mg alloy[13] -------------------------------------------------------------------------------59
Fig. 2-17 坩堝爐精煉示意圖[34]------------------------------------------------60
Fig. 2-18 鹽床精煉法示意圖[34]------------------------------------------------60
Fig. 2-19 雙槽過濾法示意圖[34]------------------------------------------------61
Fig. 2-20 氣泡除渣法示意圖[34]------------------------------------------------61
Fig. 2-21 減壓過濾法示意圖[34]------------------------------------------------62
Fig. 2-22 真空蒸餾法示意圖[34]------------------------------------------------62
Chap. 3
Fig. 3-1 坩堝示意圖-----------------------------------------------------------63
Fig. 3-2 真空熔解爐實體圖-----------------------------------------------------64
Fig. 3-3 真空熔解爐示意圖-----------------------------------------------------64
Fig. 3-4 鑄塊外形-------------------------------------------------------------65
Fig. 3-5 燃燒測溫裝置實體圖---------------------------------------------------65
Fig. 3-6 燃燒測溫裝置示意圖---------------------------------------------------66
Chap. 4
Fig. 4-1 AZ61A試片在空氣中加熱的溫度曲線--------------------------------------67
Fig. 4-2 AZ61A試片加熱後的外觀------------------------------------------------67
Fig. 4-3 鎂鋁合金燃燒後的殘留物之X光繞射分析圖--------------------------------68
Fig. 4-4 純鎂試片在空氣中加熱的溫度曲線---------------------------------------68
Fig. 4-5 純鎂試片加熱後的外觀-------------------------------------------------69
Fig. 4-6 純鎂試片實驗後的殘留物-----------------------------------------------69
Fig. 4-7 AZ80A試片在空氣中加熱的溫度曲線--------------------------------------70
Fig. 4-8 AZ80A試片加熱後的外觀------------------------------------------------70
Fig. 4-9 AZ91D試片在空氣中加熱的溫度曲線--------------------------------------71
Fig. 4-10 AZ91D試片加熱後的外觀-----------------------------------------------71
Fig. 4-11 鎂鋁合金的熱焓改變量與溫度關係圖------------------------------------72
Fig. 4-12 鎂鋁二元相圖[35]----------------------------------------------------72
Fig. 4-13 AZ80A試片固溶處理前-------------------------------------------------73
Fig. 4-14 AZ80A試片固溶處理後-------------------------------------------------73
Fig. 4-15 AZ91D試片固溶處理前-------------------------------------------------74
Fig. 4-16 AZ91D試片固溶處理後-------------------------------------------------74
Fig. 4-17 固溶處理後鎂鋁合金的熱焓改變量與溫度關係圖--------------------------75
Fig. 4-18 經固溶處理的AZ91D試片加熱後的外觀-----------------------------------75
Fig. 4-19 Mg0.1Ca試片在空氣中加熱的溫度曲線-----------------------------------76
Fig. 4-20 Mg0.1Ca試片加熱後的外觀---------------------------------------------76
Fig. 4-21 Mg1Ca試片在空氣中加熱的溫度曲線-------------------------------------77
Fig. 4-22 Mg1Ca試片加熱後的外觀-----------------------------------------------77
Fig. 4-23 Mg3Ca試片在空氣中加熱的溫度曲線-------------------------------------78
Fig. 4-24 Mg3Ca試片加熱後的外觀-----------------------------------------------78
Fig. 4-25 Mg5Ca試片在空氣中加熱的溫度曲線-------------------------------------79
Fig. 4-26 Mg5Ca試片加熱後的外觀-----------------------------------------------79
Fig. 4-27 鎂鈣合金的熱焓改變量與溫度關係圖------------------------------------80
Fig. 4-28 鎂-鈣二元合金相圖[35]-----------------------------------------------80
Fig. 4-29 Mg5Ca合金的表面型態（在空氣氣氛下，773 K，7小時）-------------------81
Fig. 4-30 Mg5Ca合金的表面型態（在空氣氣氛下，773 K，7小時）-------------------81
Fig. 4-31 Mg1Ca合金的表面型態（在空氣氣氛下，773 K，7小時）-------------------82
Fig. 4-32 Mg1Ca合金的表面型態（在空氣氣氛下，773 K，7小時）-------------------82
Fig. 4-33 純鎂的表面型態（在空氣氣氛下，773 K，7小時）------------------------83
Fig. 4-34 純鎂的表面型態（在空氣氣氛下，773 K，7小時）------------------------83
Fig. 4-35 Mg6Al試片在空氣中加熱的溫度曲線-------------------------------------84
Fig. 4-36 Mg6Al試片加熱後的外觀-----------------------------------------------84
Fig. 4-37 Mg6Al0.1Mn試片在空氣中加熱的溫度曲線--------------------------------85
Fig. 4-38 Mg6Al0.1Mn試片加熱後的外觀------------------------------------------85
Fig. 4-39 Mg6Al0.5Mn試片在空氣中加熱的溫度曲線--------------------------------86
Fig. 4-40 Mg6Al0.5Mn試片加熱後的外觀------------------------------------------86
Fig. 4-41 Mg6Al1Mn試片在空氣中加熱的溫度曲線----------------------------------87
Fig. 4-42 Mg6Al1Mn試片加熱後的外觀--------------------------------------------87
Fig. 4-43 鎂鋁錳合金的熱焓改變量與溫度關係圖----------------------------------88
Fig. 4-44 Mg6Al1Mn試片鑄態----------------------------------------------------88
Fig. 4-45 Mg6Al0.5Mn試片鑄態--------------------------------------------------89
Fig. 4-46 Mg6Al0.1Mn試片鑄態--------------------------------------------------89
Fig. 4-47 Mg6Al試片鑄態-------------------------------------------------------90
Fig. 4-48 Mg6Al1Mn試片的SEM影像圖---------------------------------------------90
Fig. 4-49 鋁-錳二元合金相圖[35] ----------------------------------------------91
Fig. 4-50 固溶處理後鎂鋁錳合金的熱焓改變量與溫度關係圖------------------------91
Fig. 4-51 Mg6Al0.5Mn試片固溶處理後--------------------------------------------92
Fig. 4-52 Mg6Al0.1Mn試片固溶處理後--------------------------------------------92
Fig. 4-53 合金成份與產生燃燒反應溫度關係圖------------------------------------93

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