臺灣博碩士論文加值系統

本實驗研究是以自持傳遞高溫合成法（Self-propagating High temperature Synthesis, SHS）探討在不同之反應模式下，所合成之金屬氮化物與碳化物。由於反應物反應形式之不同，所得之產物與結果則有所差異，因此本實驗中所探討之反應模式，乃以反應物進行反應之形式區分，主要為固相-氣相之燃燒反應、固相-固相之燃燒反應，以及同時進行固相-固相與固相-氣相之燃燒反應，並於此三種反應模式中特別針對其火焰鋒面傳遞模式、火焰鋒面傳遞速度及燃燒溫度變化等燃燒特性加以觀察，並於固相-氣相反應模式中研究試片密度、預熱溫度、稀釋劑含量及氮氣壓力對於火焰傳遞速度與產物轉換率之影響；在固相-固相反應模式中則探討試片密度、預熱溫度、稀釋劑含量對於產物組成之影響；而同時進行固相-固相與固相-氣相反應模式中，則是改變金屬粉末與碳粉末之混合比以合成不同[C]/([C]+[N])函數比之金屬碳氮化物，最後再將實驗所得之產物進行產物顯微結構之觀察與成份分析。在固相-氣相之燃燒反應中，分別以鉭及鋁為反應物，於0.274～4.238MPa之氮氣環境下燃燒合成金屬氮化物，由於鉭之熔點甚高，因此利用低熔點之鋁作為反應物，以探討反應物熔點對於固相-氣相燃燒反應之影響，實驗結果顯示，在固相-氣相燃燒反應過程中，均有出現二次燃燒現象，而由於鋁之熔點較低，因此在反應過程中明顯熔化變形，由於反應需外部氮氣滲透參與反應，因此試片密度與氮氣壓力則為固相-氣相反應中之重要參數，降低試片密度與提高氮氣壓力均可有效提升產物之氮化率，而氮-鋁反應時易因高溫熔化，故需添加稀釋劑來加以改善，當稀釋劑含量為50wt%時，則可有效防止試片熔化而使產物氮化率提升。而固相-固相之反應模式則是將鉭與碳於氬氣中形成碳化鉭，實驗結果顯示可合成出TaC與Ta2C兩種產物，藉由熱電偶所量測之反應溫度約介於1700～1800oC之間，而產物TaC外觀上則明顯膨脹且有明顯裂痕，經成分分析後可知產物中會有少許鉭殘留，而產物Ta2C中則有生成少許TaC，只需提高產物密度即可改善，而藉由火焰鋒面傳遞速度與反應溫度，可計算出碳-鉭反應之活化能分別為TaC：187.42及Ta2C：298.97 kJ/mole。而將鉭與碳置於氮氣中燃燒，即可同時進行固相-固相與固相-氣相反應而生成碳氮化鉭，而碳含量與氮氣壓力則為影響反應之最主要參數，增加氮氣壓力則可使產物氮化率提升，含碳量越高時越不容易發生二次燃燒，而產物分析中發現，所得之產物均有鉭殘留，且含碳量較低之產物易有中間產物Ta2N生成。

An experimental study on different reaction modes of self-propagating high temperature synthesis (SHS) was investigated to prepare metal nitrides, carbides, and carbonitrides. Three different modes of SHS reactions were studied, including solid/gas, solid/solid, and simultaneous solid/solid/gas synthesis reactions. In this study, the propagation of the self-sustained flame front was observed and the flame front velocity and combustion temperature were measured. Different experimental variables were examined and discussed for different SHS reactions.
In the solid/gas combustion reactions, tantalum nitride (TaN) was prepared from tantalum (Ta) powder compacts in gaseous nitrogen, and the result showed that sample density and nitrogen pressure were important parameters. Lower density and higher pressure can increase the degree of conversion. Besides, the melting point of reactant was also important to solid/gas combustion reactions. In order to demonstrate the influence of melting point on the reaction, aluminum (Al) powder compacts was used to synthesize aluminum nitride in nitrogen to compare with the case of tantalum which has a high melting point of 2996 oC. Because the melting point of aluminum (660oC) was lower than combustion temperature (1600~1800 oC), the addition of diluent was required in order to prevent the melting of samples and to achieve a high extent of conversion.
In the solid/solid combustion reactions, tantalum carbides were prepared from tantalum/carbon powder compacts in argon. Results indicated that the different molar ratios of Ta:C = 1:1 and 2:1 produced two kinds of carbides TaC and Ta2C, and an increase in the sample density enhanced the degree of conversion of the product. The activation energies of SHS processes associated with TaC and Ta2C systems were determined to be 187.42 and 298.97 kJ/mole, respectively, based upon the measurement of flame-front velocity and combustion temperature.
Simultaneous solid/solid/gas combustion reactions conducted in this study produced tantalum carbonitrides Ta(C,N) from the compacts of tantalum and carbon powder mixtures under nitrogen pressures. Results indicated that the carbon content and nitrogen pressure were important parameters. Higher nitrogen pressure can increase the degree of conversion. X-ray diffraction (XRD) analysis indicated the existence of a small amount of unreacted Ta in the final products, and the presence of negligible Ta2N under the condition with a low content of carbon.

目錄

授權書 iii
中文摘要 iv
英文摘要 vi
誌謝 viii
目錄 ix
圖目錄 xii
符號說明 xvii
第一章 緒論 1
1.1 研究背景 1
1.2 文獻回顧 2
1.2.1固相燃燒合成之相關文獻 2
1.2.2氮化鉭之相關文獻 3
1.2.3碳氮化鉭之相關文獻 3
1.2.4碳化鉭之相關文獻 4
1.2.5氮化鋁之相關文獻 5
1.3 研究目的 6
第二章 實驗方法 8
2.1 試片 8
2.2 燃燒室主體 9
2.3 資料擷取系統 10
2.4 影像擷取系統 10
2.5 產物分析 11
第三章 固相-氣相反應模式 12
3.1 氮化鉭 12
3.1.1火焰傳遞模式之觀察 12
3.1.2 火焰鋒面傳遞速度 13
3.1.3 溫度量測 14
3.1.4 產物分析 14
3.2 氮化鋁 16
3.2.1火焰傳遞模式之觀察 16
3.2.2 火焰傳遞速度 17
3.2.3 溫度量測 17
3.2.4 產物分析 18
第四章 固相-固相反應模式 21
4.1 碳化鉭 21
4.1.1 火焰傳遞模式之觀察 21
4.1.2 火焰傳遞速度 22
4.1.3 溫度量測與活化能計算 23
4.1.4 產物分析 24
第五章 固相-固相/固相-氣相反應模式 25
5.1 碳氮化鉭 25
5.1.1 火焰傳遞模式之觀察 25
5.1.2 火焰傳遞速度 26
5.1.3 溫度量測 27
5.1.4 產物分析 28
第六章 結論 30
參考文獻 34

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