本研究以報廢彈藥中的黃銅金屬為研究對象，主要目的為提出一對環境較友善且能將報廢彈藥有效處理之方法，並將彈藥中可用之資源(如銅、鉛)加以回收，以電化學方法研究其中反應之原理。首先嘗試以硫酸侵蝕黃銅，使用線性極化電阻法(LPR，Linear Polarization Resistance)，改變硫酸濃度、樣品表面清潔程度及溶液中氯離子濃度等條件，測定.22 LR、9 mm、.38 SPL及.45AUTO等彈藥中之黃銅在不同條件下之腐蝕速率，最終測得最快之腐蝕速率為14.45 mpy，經換算後得知至少需1.24年才能將該彈藥外殼完全溶解，除時間成本過長外，僅依靠腐蝕速率進行推估並無法保證實際處理效果。為減少處理時間，導入法拉第電解定律，使黃銅電解溶於電解液中，改變通過電流、硫酸濃度及氯離子濃度等操作參數，實驗結果指出實際主導電解反應速率之參數為操作電流。然而在樣品表面上之電流密度過高時，可能使得金屬表面生成金屬氧化物附著，出現陽極鈍化現象干擾電解反應。陽極鈍化為常用的防腐蝕技術，但對於本研究之電解處理方法具有負面影響，於是使用計時電位法(CP，Chronopotentiometry)，測試90分鐘內，200 mA/cm2的高電流密度下，0.25M、0.5M、1M硫酸靜止與攪拌溶液中，黃銅的鈍化情形，實驗後發現加入磁石攪拌電解液幾乎可避免黃銅電解時陽極鈍化發生，且於1M的靜止硫酸液中，樣品黃銅的鈍化情形最為嚴重，故以次條件進行加入氯離子之實驗，加入0 ppm、30 ppm、60 ppm、90 ppm氯離子之鈍化時間分別5.4、4.2、6.3、9.0分鐘，可小幅延遲鈍化發生的時間。

Brass metal exists in waste ammunitions is the target of this study. The main purpose is to propose a environmentally friendly and effective process for scrapping waste ammunitions, recycling the available resources (copper and lead) from these ammunitions, and studying principles of the reactions with electrochemical process. First, try to corrode brass with sulfuric acid. Use linear polarization resistance (LPR) method to determine the corrosion rate of brass from four models of ammunition (.22 LR, 9 mm, .38 SPL and .45AUTO) under different condition (concentration of sulfuric acid, concentration of chloride ions in solution and the surface of samples was clean or not) . The fastest measured corrosion rate was 14.45 mpy. After calculating with this result, it takes at least 1.24 years to completely dissolve the ammunition shell. Except for the high time costs, only relying on the corrosion rate to estimate cannot guarantee the actual treatment effect. In order to reduce the processing time, Faraday's laws of electrolysis is led, let brass be electrolytic dissolved in the electrolyte (sulfuric acid). The operating parameters are operating current, concentration of sulfuric acid and the chloride ions concentration. The experimental results indicate that the parameter which actually leads electrolysis reaction's rate is the operating current. However, when the current density on the surface of the sample is increased to a degree, the metal surface may be attached metal oxides to passivate, anode passivation may interfere with the electrolysis reaction. Anode passivation is a commonly used anticorrosive technology, but it has a negative impact on the electrolytic treatment process of this study. Therefore, using chronopotentiometry (CP) method to observe the anode passivation situation with a high current density of 200 mA/cm2 in 90 minutes. The operating parameter of this part are concentration of sulfuric acid, the chloride ions concentration and electrolyte condition (mixed or stable). The experimental result show that stirring electrolyte with magnet can almost avoid the anode passivation during brass electrolysis, and in the 1M sulfuric acid without stirring had the most obvious passivation situation. Therefore, add chloride ions in 1M stable sulfuric acid to delay the passivation time. The passivation time of 0 ppm, 30 ppm, 60 ppm, 90 ppm are 5.4, 4.2, 6.3, 9.0 minutes, can slightly delay the occurrence of passivation.

目錄
目錄	I
表目錄	III
圖目錄	IV
第一章、前言	1
1-1研究緣起	1
1-1-1黃銅簡介	1
1-1-2過期彈藥問題	1
1-2研究目的	2
第二章、文獻回顧	3
2-1彈藥的報廢	3
2-2腐蝕	4
2-2-1腐蝕基本原理	4
2-2-2腐蝕種類	5
2-2-3腐蝕速率測定	8
2-3黃銅電解	13
2-4陽極鈍化	14
2-4-1陽極鈍化原理	14
2-4-2陽極鈍化測定	15
2-5氯離子之添加	15
第三章、實驗設備、材料與方法	17
3-1 實驗設備	17
3-2 實驗材料	22
3-3 實驗方法	23
3-3-1 樣品製備	23
3-3-2黃銅腐蝕測定	24
3-3-3 黃銅之電解溶出	27
3-3-4 陽極鈍化	27
3-3-5 電解子彈	28
第四章、結果與討論	29
4-1 黃銅腐蝕測定	29
4-1-1 不同條件下之塔佛常數	29
4-1-2 各條件測得之腐蝕速率	30
4-2 黃銅的電解溶出	32
4-2-1 操作電流對應溶出速率	32
4-2-2 氯離子之影響	33
4-3 陽極鈍化	34
4-3-1 電解液狀態	34
4-3-2 氯離子對鈍化表面之影響	37
4-3-3 鈍化表面觀察	40
4-4 電解子彈	41
4-4-1 實驗過程	41
第五章、結論與建議	45
5-1結論	45
5-2建議	45
參考文獻	46
表目錄
表3-1 樣品處理方法	23
表3-2 常用電化學腐蝕單位	26
表4-1 塔佛常數總表	29
表4-2 各實驗條件下測得之黃銅腐蝕速率	30
表4-3 鈍化時間及情形整理	36
表4-4 氯離子對陽極鈍化影響	40
表4- 5 各分層吸收值比值	44
表4-6 電解實驗結果	44 
圖目錄
圖2-1 傳統彈藥報廢程序	3
圖2-2被腐蝕合金內部示意圖	4
圖2-3合金形成電化學電池	4
圖2-4 各種類腐蝕示意圖	7
圖2-5 極化曲線	11
圖2-6 陽極極化曲線圖	12
圖2-7 Tafol plot	12
圖2-8 循環陽極極化曲線	14
圖3-1 Digi Ivy DY 2300 potentiostat恆電位儀	18
圖3-2 Wavedriver 10 potentiostat恆電位儀及多口瓶電解槽	19
圖3-3 電子天平	19
圖3-4 分光光度計	20
圖3-5 電源供應器	20
圖3-6 電解槽組	21
圖3-7 掃描式電子顯微鏡	21
圖3-8 樣品子彈	22
圖3-9	23
圖3-10	23
圖3-11 LSV線性掃描圖形	25
圖3-12 Tafel plot	25
圖3-13 陽極鈍化示意圖	28
圖4-1將表4-2中之實驗數據結果以折線圖呈現	31
圖4-2 改變操作電流對應電解溶出速率	32
圖4-3 不同濃度氯離子所對應之電解溶出速率	33
圖4-4 硫酸濃度0.25 M 之電壓變化	34
圖4-5 硫酸濃度 0.5 M 之電壓變化	35
圖4-6 硫酸濃度 1 M 之電壓變化	36
圖4-7 氯離子濃度30 ppm，鈍化時間：252秒	37
圖4-8 氯離子濃度 60 ppm，鈍化時間378秒	38
圖4-9 氯離子濃度90 ppm，鈍化時間540秒	39
圖4-10 鈍化時間與氯離子濃度關係	39
圖4-11 於顯微鏡下的陽極鈍化表面	40
圖4-12 磁石攪拌電解實驗過程	41
圖4-13 靜止電解實驗過程	42
圖4-14 各層電解液之波型	43

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