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研究生:吳婉君
論文名稱:以A.B.S.為底材進行次磷酸氫鈉為還原劑之無電鍍銅研究
論文名稱(外文):A study on the Electroless Copper Plating on ABS by Using Sodium Hypophosphite as the Reducing Agent
指導教授:鄧嬿娥
指導教授(外文):Dang Yeng Eare
學位類別:碩士
校院名稱:逢甲大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2001
畢業學年度:89
語文別:中文
論文頁數:80
中文關鍵詞:無電鍍還原劑
外文關鍵詞:electrolesscopperreducing agent
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電鍍銅的應用已經有四十年之久,然而鍍液中廣泛使用的還原劑仍以甲醛(HCHO)為主,不僅溶液不安定,且甲醛容易揮發,又有毒性。本研究擬在硫酸銅溶液中,加入檸檬酸鉀、硼酸和少量鎳鹽,以次磷酸氫鈉為還原劑,進行無電鍍銅於塑膠(A.B.S.)底材上。銅離子不易直接被次磷酸氫鈉還原,可以先使鎳離子與次磷酸氫鈉於適當條件下作用,而產生一有利於銅離子還原的環境,以達成銅析鍍的目的。

Electroless copper had been applied in the industries for more than forty years , the main reduction component is formaldehyde(HCHO), which is not only unstable in the solution , but also volatile easily and toxic. In this investigation , the sodium hypophosphite is choose as the new substance to substitute of formaldehyde , and the plating bath contains sodium citrate , boric acid , and small amount of Ni salt. A.B.S. plastic is used as the substrate. Since copper ion is not easily reduced by sodium hypophosphite , so Ni are added and react with sodium hypophosphite at first , followed by chemical deposition of copper.

摘要........................................................................................................Ⅰ
ABSTRACT.........................................................................................Ⅱ
目錄........................................................................................................Ⅲ
圖目錄....................................................................................................Ⅶ
表目錄...................................................................................................Ⅹ
符號說明........................................................................................... ⅩⅠ
第一章 緒論..........................................................................................1
1-1前言.................................................................................................1
1-2文獻回顧.........................................................................................2
1-3研究目的.........................................................................................3
第二章 原理..........................................................................................4
2-1無電鍍原理.....................................................................................4
2-1-1 A.B.S.塑膠無電鍍方法............................................................4
2-1-1-1 粗化………..........................................................................4
2-1-1-2 敏化………..........................................................................5
2-1-1-3 活化………..........................................................................5
2-1-2無電鍍銅方法............................................................................6
2-1-2-1以甲醛為還原劑…………………………………………6
2-1-2-2反應電位…………………………..................................6
2-1-2-3以次亞磷酸鈉為還原劑………............…….......................7
2-1-3無電鍍操作變數......................................................................8
2-2動力學研究...................................................................................9
2-2-1反應級數求法..........................................................................10
2-2-2活化能之求法..........................................................................11
2-2-3常數值之求法..........................................................................13
第三章 實驗方法................................................................................14
3-1藥品...............................................................................................14
3-2儀器................................................................................................16
3-3實驗裝置圖...................................................................................17
3-4實驗步驟.......................................................................................18
3-4-1試片規格..................................................................................18
3-4-2 A.B.S.無電鍍之前處理.........................................................18
3-4-3 鍍液組成及析鍍條件.........................................................18
3-4-3-1鍍浴配製.............................................................................18
3-4-3-2試片之析鍍步驟................................................................20
3-4-4試片鍍膜膜厚測試方式………...............................................20
3-5尋求最佳析鍍條件…..................................................................20
3-5-1硫酸銅濃度對析鍍速率之影響.....................................20
3-5-2硫酸鎳濃度對析鍍速率之影響.........................................20
3-5-3硼酸濃度對析鍍速率之影響.........................................22
3-5-4次亞磷酸鈉濃度對析鍍速率之影響.................................22
3-5-5檸檬酸鉀濃度對析鍍速率之影響.....................................22
3-5-6溫度對析鍍速率之影響.....................................................22
3-5-7初始pH值對析鍍速率之影響........................................22
3-6動力學研究步驟…………....................................................……22
3-6-1反應級數求法.....................................................................22
3-6-1-1硫酸銅濃度對起始析鍍速率之影響.......................23
3-6-1-2硫酸鎳濃度對起始析鍍速率之影響...........................23
3-6-1-3硼酸濃度對起始析鍍速率之影響...........................23
3-6-1-4次亞磷酸鈉濃度對起始析鍍速率之影響...................23
3-6-1-5檸檬酸鉀濃度對起始析鍍速率之影響.......................24
3-6-1-6溫度對起始析鍍速率之影響……………………………..24
3-6-2活化能及常數值求法.........................................................24
3-7鍍膜成份分析………………......................................................24
3-7-1銅離子濃度對鍍膜組成影響.............................................24
3-7-2鎳離子濃度對鍍膜組成影響.............................................25
3-7-3鍍膜不同析鍍時間之晶相變化.……......................................25
3-7-4鍍膜不同析鍍時間之表面結構....…......................................25
3-8鍍膜物性測試……………………………...................................25
3-8-1鍍膜再現性及鹽水防腐蝕測試方法.....................................25
3-8-2鍍膜熱振盪附著力試驗.....................................................25
第四章 結果與討論...........................................................................27
4-1各項操作條件對析鍍速率之影響...............................................27
4-1-1硫酸銅濃度對析鍍速率之影響..........................................27
4-1-2硫酸鎳濃度對析鍍速率之影響..............................................27
4-1-3硼酸濃度對析鍍速率之影響..............................................30
4-1-4次亞磷酸鈉濃度對析鍍速率之影響.....................................30
4-1-5檸檬酸鉀濃度對析鍍速率之影響..........................................30
4-1-6溫度對析鍍速率之影響..........................................................34
4-1-7初始pH值對析鍍速率之影響...............................................34
4-2動力學之探討...............................................................................37
4-2-1硫酸銅之反應速率級數......................................................37
4-2-2硫酸鎳之反應速率級數..........................................................37
4-2-3硼酸之反應速率級數..........................................................46
4-2-4次亞磷酸鈉之反應速率級數..................................................46
4-2-5檸檬酸鉀之反應速率級數......................................................46
4-2-6反應活化能及反應速率常數..................................................59
4-2-6-1傳統求法.............................................................................59
4-2-6-2 S.D.求法..............................................................................60
4-3鍍膜成份分析及反應機構之探討................................................67
4-3-1實驗數據分析..........................................................................67
4-3-2反應機構之推測…………......................................................67
4-4 A.B.S.為底材之析鍍時間與膜厚之關係..……...........................69
4-5析鍍時間對鍍膜之影響...........................................................71
4-5-1鍍膜不同析鍍時間之晶相變化..............................................71
4-5-2鍍膜不同析鍍時間之表面結構.............................................71
4-6鍍膜物性測試結果.......................................................................76
4-6-1鹽水防腐蝕測試結果............................................................76
4-6-2鍍膜熱振盪附著力試驗結果................................................81
第五章 結論………..........................................................................82
第六章 參考文獻..............................................................................84
圖 目 錄
Fig.3-1 Apparatus of electroless plating...................................................17
Fig.3-2 thickness measurement…...……….............................................21
Fig.4-1 The thickness of deposition versus [CuSO4] concertration at
various time.................................................................................28
Fig.4-2 The thickness of deposition versus [NiSO4] concertration at
various time.................................................................................29
Fig.4-3 The thickness of deposition versus [H3BO3] concertration at
various time.................................................................................31
Fig.4-4 The thickness of deposition versus [NaH2PO2] concertration at
various time.................................................................................32
Fig.4-5 The thickness of deposition versus [K3C6H5O7] concertration at
various time.................................................................................33
Fig.4-6 The thickness of deposition versus Temperature at various time35
Fig.4-7 The thickness of deposition versus pH at various time.............36
Fig.4-8 The thickness of deposition versus time with various [CuSO4]
concentration............................................................................38
Fig.4-9 Relation between deposition rate and time with various [CuSO4]
concentration............................................................................39
Fig.4-10 The determination of reaction order for [CuSO4]......................41
Fig.4-11 The thickness of deposition versus time with various [NiSO4]
concentration............................................................................42
Fig.4-12 Relation between deposition rate and time with various [NiSO4]
concentration............................................................................43
Fig.4-13 The determination of reaction order for [NiSO4].......................45
Fig.4-14 The thickness of deposition versus time with various [H3BO3]
concentration............................................................................47
Fig.4-15 Relation between deposition rate and time with various [H3BO3]
concentration.............................................................................48
Fig.4-16 The determination of reaction order for [H3BO3]......................50
Fig.4-17 The thickness of deposition versus time with various [NaH2PO2]
concentration............................................................................51
Fig.4-18 Relation between deposition rate and time with various [NaH2PO2] concentration….....................................................52
Fig.4-19 The determination of reaction order for [NaH2PO2]..................54
Fig.4-20 The thickness of deposition versus time with various [K3C6H5O7]
concentration............................................................................55
Fig.4-21 Relation between deposition rate and time with various [K3C6H5O7]
concentration............................................................................56
Fig.4-22 The determination of reaction order for [K3C6H5O7].................58
Fig.4-23 The thickness of deposition versus time with various
temperature...............................................................................61
Fig.4-24 Relation between deposition rate and time with various
temperature...............................................................................62
Fig.4-25 The determination of the activation energy...............................64
Fig.4-26 The determination of the activation energy...............................66
Fig.4-27 The composition of films versus plating time………...............68
Fig.4-28 The thickness of deposition on A.B.S. versus time………......70
Fig.4-29 The analysis of XRD with various plating time........................72
Fig.4-30 The SEM photo of electroless on A.B.S. at 2min.............…….73
Fig.4-31 The SEM photo of electroless on A.B.S. at 3min..............……73
Fig.4-32 The SEM photo of electroless on A.B.S. at 4min..............……74
Fig.4-33 The SEM photo of electroless on A.B.S. at 5min..............……74
Fig.4-34 The SEM photo of electroless on A.B.S. at 6min..............……75
Fig.4-35 The SEM photo of electroless on A.B.S. at 8min..............……75
Fig.4-36 The deposition film weight increase with immersion time...…79
Fig.4-37 The weight of plated film which have been immersed in NaCl
solution for 72 hr versus plated period of this film...............80

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