本研究已探討鈉鈣玻璃表面之鍍鋅薄膜及鋅塊在CuSO4/NaCl混合溶液中化成處理之異同。對鋅塊之化成處理而言，化成反應過程如下：首先形成黑色皮膜(Zn、Cu及Cu(OH)2)，銅在黑色皮膜與鋅塊之間析出，脫落的黑色皮膜轉變成黃色粉末(Cu2O)，黃色粉末轉變成綠色粉末(CuCl2複合物)，鋅塊表面覆蓋白色的ZnO。對鍍鋅薄膜而言，首先形成黑色皮膜(Zn、Cu及Cu(OH)2)，紅色皮膜(Cu)，黃色皮膜(Cu2O)及綠色皮膜(CuCl2)。鍍鋅薄膜在重量百分濃度為0.6％、1.2％及2.3％化成溶液之活化能分別為33.60(J/mol)、28.21(J/ mol)及14.87(J/mol)。

The conversion coatings of zinc film on the soda-lime silicate surface comparing with bulk zinc in CuSO4/NaCl aqueous solution were investigated. For bulk zinc, first, the black coatings (Zn, Cu and Cu (OH) 2) formed on the surface. Next, copper was precipitated between the black coatings and bulk zinc. Then, part of black coatings fell off and formed the yellow powder (Cu2O). After that, yellow powder turned into green powder (CuCl2 complexes). At last, the surface of bulk zinc was covered by zinc oxide. For zinc film, the change of color was as follows: black coatings (Zn, Cu and Cu (OH) 2), red coatings (Cu), yellow coatings (Cu2O) and green coatings (CuCl2). The activation energy of zinc film for the conversion coatings in 0.6wt%, 1.2wt% and 2.3wt% CuSO4/NaCl aqueous solution are 33.60(J/mol), 28.21(J/mol) and 14.87(J/mol), respectively.

總目錄
中文摘要....................................................................................................I
英文摘要...................................................................................................II
總目錄......................................................................................................III
圖目錄......................................................................................................VI
表目錄.......................................................................................................X
	導論..................................................................................................1
1-1前言............................................................................................1
1-2文獻回顧....................................................................................2
1-2.1化成處理介紹........................................................2
1-2.2化成處理的方式....................................................3
				1-2.3化成處理的種類....................................................3
	1-2.4鋅的化成處理.......................................................4
		1-2.4.1鉻酸鹽處理..................................................4
		1-2.4.2鉬酸鹽處理..................................................7
	1-2.5 Cl-與S042-對鋅的影響...........................................9
	1-2.6 影響塊材化成處理之因子................................10
	1-2.7活化能..................................................................11
	1-2.8成核反應..............................................................11
		1-2.8.1均質成核....................................................12
		1-2.8.2異質成核....................................................13
	1-2.9薄膜的製備方式..................................................14
1-3研究動機與研究目的..............................................................16
			1-3.1研究動機..............................................................16
			1-3.2研究目的..............................................................16
	實驗設計........................................................................................20
2-1實驗材料與設備......................................................................20
			2-1.1實驗材料..............................................................20
			2-1.2實驗設備..............................................................20
2-2實驗步驟..................................................................................21
			2-2.1前置作業..............................................................21
2-2.2實驗流程..............................................................22
2-3實驗分析..................................................................................24
参、結果與討論........................................................................................26
3-1鋅塊化成處理..........................................................................26
3-2鋅薄膜化成處理......................................................................27
			3-2.1鋅薄膜化成處理及其化成反應機制..................27
			3-2.2反應時間與溶液濃度/鋅薄膜厚度之關係.........31
3-2.3反應活化能..........................................................32
3-2.4光學性質..............................................................33
3-2.5皮膜應用..............................................................36
肆、結論....................................................................................................70
伍、參考文獻............................................................................................72
 
圖目錄
圖1-1 活化能之反應位能示意圖..........................................................17
圖1-2 自由能與溫度之關係圖..............................................................17
圖1-3 液體-固體之界面示意圖.............................................................18
圖1-4 粒徑大小與自由能之關係圖......................................................18
圖1-5 異質成核之晶體與壁面或外來粒子之接觸角示意圖..............19
圖2-1實驗流程圖....................................................................................25
圖3-1 鋅塊化成處理之流程圖：(a)未反應之鋅塊；(b)浸泡於0.6％的NaCl和0.6％的CuSO4‧5H2O混合溶液後，表面形成黑色皮膜；(c)由於內部銅不斷析出以及溶液吸收引起膨潤，造成黑色皮膜產生體積膨脹；(d)脫落的黑色皮膜粉末(受到氣泡浮力或晃動)與溶液反應形成黃色Cu2O粉末；(e)黃色粉末最後轉變成綠色CuCl2粉末；(f)塊材最後覆蓋滿白色的ZnO皮膜.............37
圖3-2 鋅塊經化成處理後，黑色皮膜之EDAX圖譜............................38
圖3-3 鋅塊化成處理氧化還原反應之示意圖......................................39
圖3-4 鋅塊經化成處理後，紅色析出物之XRD圖譜...........................39
圖3-5 氣泡的浮力或晃動造成黑色皮膜脫落，而脫落的黑色皮膜變成黃色的氧化亞銅..........................................................................40
圖3-6 鋅塊經化成處理後，黃色粉末之EDAX圖譜............................40
圖3-7 鋅塊經化成處理後，黃色粉末之XRD圖譜...............................41
圖3-8 鋅塊經化成處理後，綠色粉末之XRD圖譜...............................41
圖3-9 鋅塊經化成處理後，綠色粉末之EDAX圖譜............................42
圖3-10 鍍鋅薄膜之鈉鈣玻璃浸泡於化成裡溶液後，其反應變化過程：形成(a)黑色皮膜；(b)紅色皮膜；(c)紅色皮膜變成黃色皮膜時，中間存在灰色邊界；(d)黃色皮膜及(e)綠色皮膜.....................43
圖3-11  Na2O-CaO-SiO2基材表面鍍鋅薄膜之SEM照片...................44
圖3-12 鍍鋅薄膜表面經化成處理反應2秒鐘後之EDAX圖譜.........45
圖3-13 鍍鋅薄膜表面經化成處理反應後，反應2秒鐘之SEM照片，箭頭A為Cu析出物，箭頭B為經過腐蝕顆粒之鋅表面腐蝕型態............................................................................................46
圖3-14 鍍鋅薄膜表面經化成處理後，黑色皮膜之EDAX圖譜..........47
圖3-15 銅與鋅形成置換反應後，鋅表面形成黑色物質，其物質為Cu、Zn及Cu(OH)2之示意圖............................................................48
圖3-16 鍍鋅薄膜表面經過化成處理後，黑色皮膜之SEM照片.........49
圖3-17 鍍鋅薄膜表面經化成處理後，紅色皮膜之EDAX圖譜..........50
圖3-18 鍍鋅薄膜表面經化成處理後，紅色皮膜之XRD圖譜.............51
圖3-19鍍鋅薄膜表面經過化成處理後，紅色皮膜之SEM照片，倍率(a)3萬倍；(b)20萬倍..................................................................52
圖3-20鍍鋅薄膜表面經過化成處理後，紅色皮膜由周圍開始向內形成黃色皮膜，(a)紅色皮膜外圍形成黃色皮膜之示意圖(b)紅色皮膜；(c)黃色皮膜與紅色皮膜之灰色邊界；(d)外圍黃色皮膜................................................................................................53
圖3-21鍍鋅薄膜表面經化成處理後，黃色皮膜之EDAX圖譜............54
圖3-22 鍍鋅薄膜表面經化成處理後，黃色皮膜XRD圖譜.................55
圖3-23鍍鋅薄膜表面經過化成處理後，黃色皮膜之SEM照片...........56
圖3-24鍍鋅薄膜表面經化成處理後，綠色皮膜之EDAX圖譜............57
圖3-25 鍍鋅薄膜表面經化成處理後，綠色皮膜XRD圖譜.................58
圖3-26 鍍鋅薄膜表面經化成處理後，綠色皮膜之SEM照片.............58
圖3-27 溶液濃度與反應時間之趨勢圖................................................60
圖3-28 鍍鋅薄膜厚度與反應時間之趨勢圖........................................60
圖3-29 鋅薄膜以高濃度進行化成處理後，ZnO沉積之情形..............61
圖3-30 鋅薄膜以高濃度進行化成處理示意圖：(a)Zn溶解迅速，
Cu2＋無法附著及成長；(b)Zn溶解後形成Zn(OH)2的沉積，經脫水後再形成ZnO.....................................................................61
圖3-31  lnV與1000/T作圖，斜率m=－ Q/R................................................63
圖3-32各種顏色皮膜經煆燒400OC(持溫4小時)後，其XRD圖譜......64
圖3-33黑色皮膜：(a)未煆燒、(b1)煆燒400OC及(b2)煆燒400OC(煆燒
前表面被破壞區域)之SEM照片；(c)未煆燒及(d)煆燒400OC之吸收光譜；(e)未煆燒及(f) 煆燒400OC之穿透光譜............65
圖3-34紅色皮膜：(a)未煆燒及(b)煆燒400OC之SEM照片；(c)未煆
燒及(d)煆燒400OC之吸收光譜；(e)未煆燒及(f)煆燒400OC之穿透光譜....................................................................................66
圖3-35黃色皮膜：(a)未煆燒及(b)煆燒400OC之SEM照片；(c)未煆
燒及(d)煆燒400OC之吸收光譜；(e)未煆燒及(f)煆燒400OC之穿透光譜...................................................................................67
圖3-36綠色皮膜：(a)未煆燒及(b)煆燒400OC之SEM照片；(c)未煆
燒及(d)煆燒400OC之吸收光譜；(e)未煆燒及(f)煆燒400OC之穿透光譜...................................................................................68
圖3-37 Cu2O在太陽光下照射4小時後，水分解照片...........................69
 
表目錄
表2-1 不同濃度與不同鍍鋅薄膜厚度示意圖......................................23
表3-1 鋅塊經化成處理後，黑色皮膜之EDAX成份含量....................38
表3-2 鋅塊經化成處理後，黃色粉末之EDAX成分含量....................40
表3-3鋅塊經化成處理後，綠色粉末之EDAX成份含量......................42
表3-4 鍍鋅薄膜表面經化成處理反應2秒鐘後，EDAX之成分含量..45
表3-5 鍍鋅薄膜表面經化成處理後，黑色皮膜之EDAX成分含量....47
表3-6 鍍鋅薄膜表面經化成處理後，黑色皮膜之EPMA成分莫耳數
比................................................................................................48
表3-7 鍍鋅薄膜表面經化成處理後，紅色皮膜之EDAX成分含量....50
表3-8鍍鋅薄膜表面經化成處理後，紅色皮膜之EPMA成分莫數
比................................................................................................51
表3-9 鍍鋅薄膜表面經化成處理後，黃色皮膜之EDAX成分含量....54
表3-10 鍍鋅薄膜表面經化成處理後，黃色皮膜之EPMA成分莫耳數比................................................................................................55
表3-11鍍鋅薄膜表面經化成處理後，綠色皮膜之EDAX成分含量....57
表3-12不同厚度之鋅薄膜在不同濃度條件下，經化成處理後，反應
	 不在變化所需時間....................................................................59
表3-13 鋅薄膜化成反應完畢所需的反應時間(黃色皮膜出現的時間，C4T1、C5T1、C6T1及C6T2無法看見黃色皮膜，由白色出現為判斷)...........................................................................................62
表3-14鋅薄膜化成反應之反應速率(nm/s) ..........................................62
表3-15 以鋅薄膜厚度(1414nm)在不同濃度與溫度條件下進行化成處理後，鋅置換反應完畢所需時間(秒) ....................................63
表3-16 鋅薄膜化成反應速率(nm/s) .....................................................63

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