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研究生： 葉宗凱
Yeh, Tsung-Kai
論文名稱： Sn-Zn-xAg-Al-Ga無鉛銲錫氧化行為之研究
Investigations on the Oxidation Behavior of Sn-Zn-xAg-Al-Ga Lead-Free Solders
指導教授： 林光隆
Lin, Kwang-Lung
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2007
畢業學年度： 95
語文別： 中文
論文頁數： 86
中文關鍵詞： 無鉛銲錫 、鬚晶 、熱重分析 、氧化 、恆溫恆濕
外文關鍵詞： solder, oxidation, whisker, TGA
相關次數： 點閱：76  下載：3 
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    • 錫鋅系無鉛銲錫一直以來有抗氧化性不良的缺點，無論在製程或應用環境中，均容易受到氧化所造成的影響，使得產品壽命降低。本研究係探討本實驗室所開發的Sn-8.5Zn-xAg-0.01Al-0.1Ga(x = 0~1.0wt％)無鉛銲錫合金在高溫中與恆溫恆濕環境中的氧化行為，恆溫恆濕實驗過程中，銲錫表面出現鬚晶，因此本研究也進一步觀察錫鬚晶的成長行為。
    顯微結構分析結果顯示，Sn-8.5Zn-xAg-0.01Al-0.1Ga(x = 0~1.0wt％)銲錫合金添加銀之後，會於合金中形成AgZn3介金屬化合物，且使原本銲錫基地內之富鋅相逐漸減少。熱重分析(Thermal Gravimetric Analysis, TGA)的結果顯示，Sn- 8.5Zn-xAg-0.01Al-0.1Ga(x = 0~0.5wt％)銲錫合金隨著銀含量增加，氧化速率及氧化量都會減少，氧化物的主要成份是ZnO，因為氧化層阻擋鋅原子與氧原子之間的互相擴散與反應，氧化反應約到25分鐘達到平衡。
    銲錫合金經恆溫恆濕試驗(85℃/85％RH)後，所產生的氧化物大部份為ZnO，也有少量SnO2，氧化層的厚度隨銀含量增加而增加。錫鬚晶主要是因為銲錫合金內部的壓縮應力所產生，壓縮應力的來源是由於鋅於錫之晶界氧化生成ZnO，造成體積膨脹，擠壓錫之晶粒。

    The Sn-Zn based solder exhibits unsatisfactory oxidation resistance. It is very prone to oxidation that decreases the life of products. This study investigated the oxidation behavior of Sn-8.5Zn-xAg-0.01Al-0.1Ga(x= 0~1.0wt％) solders at high temperatures and during heat/humidity exposure. During the experiment, some whiskers formed on the surface of the solder. Therefore, the observation of Sn whisker growth behavior was also investigated in this study.
    The microstructure of Sn-8.5Zn-xAg-0.01Al-0.1Ga(x=0~1.0wt％) shows that the AgZn3 compound was formed after the addition of Ag to the solder. The results of thermal gravimetric analysis(TGA) showed that the oxidation rate and oxide decreased as the Ag content of Sn-8.5Zn-xAg- 0.01Al-0.1Ga(x=0~0.5wt％) increase. The major composition of the oxide was ZnO. Because the oxidation layer blocked the reaction and diffusion between Zn and O2, the oxidation reaction reaches saturation after 25 minutes.
    The content of Zn-rich phase decreased in the matrix. After heat/humidity exposure at 85℃/85％RH(relative humidity), the major oxide formed are ZnO and a few SnO2. The thickness of oxidation layer increases with increasing Ag content. Sn whisker growth was driven by the compressive stress in the solder. The compressive stress is introduced due to the volume expansion when ZnO formed at the grain boundary of Sn.

    中文摘要..................................................I 英文摘要.................................................II 致謝....................................................III 總目錄...................................................IV 表目錄...................................................VI 圖目錄..................................................VII 第壹章 簡介............................................1 1-1　電子構裝技術.........................................1 1-2　無鉛銲錫材料的應用...................................5 1-2-1　Sn-Ag-Cu系合金.....................................6 1-2-2　Sn-Zn系合金........................................6 1-3　銲錫材料的氧化行為...................................6 1-3-1　製程環境中的氧化...................................6 1-3-2　應用環境中的氧化..................................10 1-3-3　氧化熱力學........................................10 1-3-4　氧化動力學........................................12 1-3-5　氧化機構..........................................15 1-3-6　純錫的氧化行為....................................15 1-3-7　Sn-Pb合金的氧化行為...............................16 1-3-8　Sn-Zn-X合金的氧化行為.............................16 1-4　錫鬚晶的影響........................................16 1-4-1　錫鬚晶的成因......................................19 1-5　研究目的............................................19 第貳章　實驗方法與步驟...................................20 2-1　實驗構想與設計......................................20 2-2　銲錫合金的配製......................................20 2-3　高溫氧化行為分析....................................20 2-3-1　熱重分析..........................................20 2-3-2　比重量測..........................................24 2-3-3　表面氧化層的分析..................................24 2-3-4　分析氧化行為模式..................................26 2-4　恆溫恆濕試驗........................................26 2-4-1　試片製備..........................................26 2-4-2　恆溫恆濕試驗條件..................................26 2-4-3　表面及橫截面分析..................................26 第參章　結果與討論.......................................28 3-1　微觀組織觀察........................................28 3-2　高溫氧化行為........................................33 3-2-1　不同銲錫材料的氧化行為比較........................33 3-2-2　氧化速率計算......................................39 3-2-3　氧化活化能比較....................................39 3-2-4　表面氧化物分析....................................42 3-2-5　綜合討論..........................................53 3-3　錫鬚晶成長行為......................................58 3-3-1　不同銲錫材料在恆溫恆濕下的氧化行為................58 3-3-2　錫鬚晶成長比較....................................67 3-3-3　綜合討論..........................................67 第肆章　結論.............................................79 參考文獻.................................................80 自述.....................................................86

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