臺灣博碩士論文加值系統

　　本研究量測Sn-9Zn-xX (X=Ag、Cu)不同無鉛銲錫合金系統的熱物性質，並探討不同添加元素及其添加量對合金系統的固液相溫度、兩相區範圍、潛熱釋放模式、熔解熱與熱膨脹係數等的影響。
　　使用電腦輔助冷卻曲線分析的方法來量測與計算不同合金系統之固液相溫度、兩相區溫度及潛熱釋放模式，並以黃提出的凝固模式將解析結果定量呈現。使用示差掃描測定儀量測合金的固液相溫度並計算合金的熔解熱。利用掃描式電子顯微鏡及電子探針微區分析儀觀察合金生成相的微組織，其化學組成與元素分布情形則以能量散佈光譜儀及波長散佈光譜儀分析。另外，使用熱膨脹儀量測Sn-9Zn-xAg合金系統的熱膨脹係數。
　　研究結果發現不論在升溫或冷卻的過程，Sn-9Zn-xAg三元合金的液相溫度及兩相區範圍，皆會隨著銀含量的增加，且銀含量到1.5wt%後，曲線開使出現第二個峰，。以潛熱釋放模式來看，Sn-9Zn-0.5Ag合金類似共晶合金的釋放模式，而1.5Ag、2.5Ag以及3.5Ag等合金的模式為生成兩條垂直線，一條代表β-Sn的生成，一條代表Sn-9Zn共晶相的析出。而且銀含量愈高，初晶β-Sn的生成量愈多，共晶相的析出量則愈少。由電腦輔助冷卻曲線分析及微結構分析顯示Sn-9Zn-xAg三元合金的凝固機構為先析出鋅-銀介金屬化合物、接著β-Sn相凝固、最後為生成層狀Sn-Zn共晶結構。且隨著銀含量增加，鋅-銀介金屬化合物析出量增加，β-Sn相相對增加，層狀共晶結構相對減少。而凝固模式中的參數fp數值會隨之增加。而隨著冷卻速率增快，初晶相固相率fp及非線性因子ne、np數值皆會隨之降低。Sn-9Zn-xAg合金的熱膨脹係數會隨著溫度增加而增加，溫度到達90℃時，即不再有明顯的變化。隨著銀含量的增加，平均熱膨脹係數會線性上升。當銀含量超過1.5wt%時，無鉛銲錫合金的熱膨脹係數會明顯的大於傳統鉛-錫合金。根據上述結果，Sn-9Zn-xAg無鉛銲錫合金從熱物性質的觀點來看，銀的含量不應超過1.5wt%。
Sn-9Zn-xCu三元合金方面，在不論在升溫或冷卻的過程，合金的液相溫度及兩相區範圍，也會隨著銅含量的增加而升高，只是在0.6Cu時會有類似共晶的現象。Sn-9Zn-xCu三元合金的凝固機構為先析出Cu-Zn介金屬化合物、接著為β-Sn相、最後為生成層狀Sn-Zn共晶結構。隨著銅含量增加，Cu-Zn介金屬化合物增加，β-Sn相跟著增加，層狀共晶結構相則相對減少。Sn-9Zn-xCu中0.1Cu與0.6Cu的潛熱釋放模式類似共晶合金的釋放模式。而0.5Cu、1.5Cu、2.5Cu以及3.5Cu等合金的潛熱釋放模式為生成兩條垂直線，一條代表β-Sn的生成，一條代表Sn-9Zn共晶相的析出。且Cu含量愈高，初晶β-Sn的生成量愈多，共晶相的析出量則愈少，因為Cu含量增加改變了生成相的比例，使得潛熱釋放模式也隨之變化。
　　Sn-9Zn-xAg與Sn-9Zn-xCu兩種三元合金系統的熱物行為相當類似。實驗量測三種錫-鋅系無鉛銲錫合金系統的熔解熱皆高於傳統錫-鉛銲錫合金。

　　The thermal physical properties of the Sn-9Zn-xX (X = Ag, Cu) lead-free solder alloy systems are examined in this study. The effects of alloy composition and cooling rate on the liquidus temperature, solidus temperature, pasty ranges, latent heat release modes, fusion heats and coefficient of thermal expansion were investigated.
　　A Computer Aided-Cooling Curve Analysis (CA-CCA) technique was used to determine the pasty ranges and latent heat release modes for the alloys. The solidification model proposed by Hwang was used to quantity the results. The Differential scanning calorimetry was also used to measure the liquidus temperature and solidus temperature of alloys. The fusion heat of the alloys was also calculated. The morphology of alloys and intermetallic compounds were observed with Scanning electron microscope and Electron probe microanalyzer. Energy dispersive spectrometer and Wave dispersive spectrometer were used to analyze the chemical compositions and elemental dispersion of intermetallic compounds. The CTE of Sn-Zn-xAg alloys is measured by using a dilatometer with a heating rate of 5 �aC/min from 40 �aC to 120 �aC.
　　The experimental results show that as the silver content of the Sn-9Zn-xAg alloy increases, the liquidus temperature rises and the pasty range broadens. However, when the silver content exceeds 1.5%, a second peak can be observed from the heating and cooling curves. As long as the silver content is below 0.5 wt%, silver has little effect on the microstructure because it is basically the eutectic Sn-9Zn and the fs-T relationship is nearly a vertical line. However, as the silver content exceeds 1.5 wt%, the formation of the Ag-Zn intermetallic compounds becomes obvious. This causes the alloy composition to deviate from the eutectic and to lean towards the tin-rich side of the Sn-Zn phase diagram. This in turn causes the proportion of the primary tin phase to increase and that of the zinc-tin eutectic phase to decrease. This is reflected on the plot of the fs-T relationship by two distinct vertical regions. One corresponds to the primary tin phase and the other to the eutectic phase. As the silver content further increases, the effects of intermetallic compound formation become even more obvious. As an alternative to CA-CCA, Huang’s model can be used to obtain a quantitative fs-T function. As the silver content increases, the primary solid fraction for Huang’s model increases. As the cooling rate increases, the primary solid fraction and the nonlinearity factors ne and np decrease. The CTE is increased with increasing temperature. When the temperature reaches 90 ℃, the increase becomes less obvious. Furthermore, CTE increases linearly with increasing silver content. As the silver contents are over 1.5%, the values of CTE are greater than the conventional Sn-37Pb alloy. Based on the above observations, silver content should not exceed a maximum of 1.5% in order to develop a lead free solder with proper thermo-physical properties.
　　The results also show that as the copper content of the Sn-9Zn-xCu alloy increases, the liquidus temperature rises and the pasty range broadens. However, when the copper content is 0.6 wt%, the eutectic like situation can be observed from the heating and cooling curves. As long as the copper content is below 0.1 wt%, copper has little effect on the microstructure, which is basically the eutectic Sn-9Zn and the fs-T relationship is nearly a vertical line. However, as the copper content exceeds 0.6 wt%, the formation of Cu-Zn intermetallic compounds becomes obvious. This is reflected on the plot of the fs-T relationship by two distinct vertical regions. One corresponds to the primary tin phase and the other to the eutectic phase. As the copper content further increases, the effects of intermetallic compound formation become even more obvious. As an alternative to CA-CCA, Huang’s model can be used to obtain a quantitative fs-T function.
Sn-9Zn-xAg and Sn-9Zn-xCu ternary alloy systems have similar thermal physical behavior. The fusion heat of three Sn-Zn based lead free solder alloy experimental measured in this study are all higher than lead-tin solder alloy.

中文摘要 Ⅰ
英文摘要 Ⅲ
目錄 Ⅵ
表目錄 Ⅸ
圖目錄 Ⅹ
符號對照表 ⅩⅢ
英漢名詞對照表 ⅩⅣ
第一章 緒論 1
1-1 研究動機 1
1-2 研究目的 4
第二章 文獻回顧 5
2-1 傳統鉛錫合金與無鉛銲錫 5
2-2 無鉛銲錫之重要基本性質 6
2-2-1 熔點 6
2-2-2 熔解熱釋放與固相率變化 7
2-2-3 熱膨脹係數 7
2-2-4 表面張力 8
2-2-5 電阻係數 8
2-2-6 微結構 8
2-2-7 銲錫與基材之界面反應 9
2-2-8 剪切強度 9
2-2-9 伸長率 10
2-2-10 抗潛變性 10
2-2-11 氧化行為 10
2-2-12 抗腐蝕性 11
2-3 常見無鉛銲錫合金系統 11
2-3-1 Sn-Ag合金系統 11
2-3-2 Sn-Au合金系統 12
2-3-3 Sn-Bi合金系統 13
2-3-4 Sn-Cu合金系統 14
2-3-5 Sn-In合金系統 14
2-3-6 Sn-Sb合金系統 15
2-3-7 Sn-Zn合金系統 16
第三章 數學分析 26
3-1 潛熱總量與凝固潛熱釋放模式 26
3-2 電腦輔助冷卻曲線分析理論 29
3-3 固相率與溫度關係的理論分析 32
第四章 實驗方法與步驟 36
4-1 本研究之實驗材料 36
4-2 示差掃描熱量測定 36
4-3 電腦輔助冷卻曲線分析 37
4-3-1 實驗裝置 37
4-3-2 實驗步驟 38
4-4 熱膨脹係數量測 38
4-5 微觀組織觀察 39
第五章 結果與討論 43
5-1 電腦輔助冷卻曲線分析驗證與零曲線之決定 44
5-2 錫-鋅-銀無鉛銲錫合金之熱物性質量測 49
5-2-1 錫-鋅-銀合金的固液相溫度 49
5-2-2 錫-鋅-銀合金的顯微組織觀察與分析 51
5-2-3 錫-鋅-銀合金的熔解熱 53
5-2-4 錫-鋅-銀合金潛熱釋放模式 55
5-2-5 錫-鋅-銀合金的熱膨脹係數 57
5-3 錫-鋅-銅無鉛銲錫合金之熱物性質量測 86
5-3-1 錫-鋅-銅合金固液相溫度與熔解熱 86
5-3-2 介金屬化合物熱力學之解析 87
5-3-2 錫-鋅-銅合金的潛熱釋放模式與微觀組織 87
第六章 結論 101
參考文獻 103

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