本研究主要針對耐火高熵合金(Refractory High Entropy Alloy, RHEA)之高溫氧化行為進行分析與探討，並且共分為四部分：第一部分為含鋁、鉻、矽之複雜型耐火高熵合金於攝氏1200度之氧化行為探討、第二部分為以四方體型(tetragonal)氧化物為保護性氧化層的新型耐火高熵合金之氧化與氮化現象、第三部分為NV1耐火高熵合金於攝氏1200度以上之氧化及氮化現象、第四部份為耐火高熵合金氧化物預測之初探。
在第一部分中，2款新設計的耐火高熵合金在攝氏1200度被恆溫氧化10小時。掃描式電子顯微鏡分析顯示這些合金表面具有鋁矽氧化物層，且氧化層結構明顯受到鋁及釩含量的影響：隨著鋁含量提升及釩含量降低，內氧化區的孔洞尺寸有所下降。
在第二部分中，本研究以熱重分析法及恆溫氧化法對於一款新型耐火高熵合金(NV1)於攝氏1000及1100度進行最多200小時的實驗。實驗結果顯示外氧化層對於氧化增重行為影響顯著，且其由包含氧化鋁及氧化鉻分散顆粒之四方體型氧化物組成。於攝氏1000度，此合金由於缺乏生成緻密四方體型氧化物的能力，導致其氧化增重於200小時的實驗時間內均呈現指數成長的趨勢；於攝氏1100度，氧化增重曲線中出現2個導因於保護性四方體型氧化物層生成的拋物線型氧化增重。此合金於攝氏1100度恆溫氧化200小時後的總氧化增重量為4.03 mg/cm2，顯示其為目前文獻中此溫度最具抗氧化能力的耐火高熵合金。本研究結果亦指出未來進一步設計足以長時間於高溫抵抗氧化的耐火高熵合金之見解。
在第三部分中，本研究著重於NV1耐火高熵合金於攝氏1200、1300及1400度之超高溫恆溫氧化行為，並且實驗時間長達100小時。此實驗條件是目前耐火高熵合金之氧化行為研究中前所未見的。於攝氏1200度，由於包含氧化鋁及氧化鉻分散顆粒之四方體型氧化物層之生成，氧化增重曲線趨向於拋物線型；於攝氏1300度，氧化鉻揮發導致氧化增重爆發性的增加；於攝氏1400度，氧化增重曲線主要呈現單一的冪定律(power-law)，並且有莫來石(Mullite)被觀測到出現於氧化層內。此研究揭示耐火高熵合金在超高溫環境下出現的氧化行為以及其發生機制，並為未來設計抗氧化行耐火高熵合金提供新的設計概念。
於第四部份中，作者試圖以鋁、鉻兩種主要生成保護性氧化層的元素之活性(activity)對耐火高熵合金的生成氧化物進行初步的分類與預測。實驗結果顯示鋁、鉻的活性並無法作為耐火高熵合金是否可以生成保護性氧化鋁、氧化鉻層的單一依據，且合金成分對於氧化產物的影響十分顯著。然而鋁、鉻活性、合金成分與氧化產物及行為之間的關係，尚需要進一步的實驗才能夠更加釐清。此部分的研究預期有助於理解耐火高熵合金的氧化行為，以及未來耐火高熵合金的設計。

This study emphasizes the analysis and discussion on the high temperature oxidation behaviors of the RHEA. It is divided into four parts: The first part is the investigation on the oxidation behaviors of (Al, Cr, Si)-bearing complex RHEAs at 1200 °C; the second part is the oxidation and nitridation of a novel RHEA protected by tetragonal oxide at 1000 and 1100 °C; the third part is the oxidation and nitridation of NV1 alloy at 1200 °C and above; the fourth part is the preliminary study on predicting the oxides of the RHEA.
In the first part, the microstructure of two newly developed RHEAs was examined after isothermal oxidation at 1200 °C for 10 hours. Scanning electron microscope (SEM) analysis showed the formation of aluminosilicate layer on the sample surface, and the structure of oxide layers appears to be greatly affected by the content of Al and V. With increased Al content and decreased V content, the size of pores within the internal oxidation zone was decreased.
In the second part, this study examines the oxidation a novel oxidation-resistant RHEA (NV1) by means of thermogravimetric method and isothermal oxidation at 1000 and 1100 °C for up to 200 hours. The external oxide layer strongly influenced the mass gain behaviors, and it consisted of tetragonal oxide with some dispersion of Al2O3 and Cr2O3. At 1000 °C, the inability to form dense tetragonal oxide layer resulted an exponential dependence of mass gain throughout 200 hours. At 1100 °C, mass gain curve showed two parabolic dependences associated with the formation of protective tetragonal oxide layer, the mass gain after 200 hours was 4.03 mg/cm2, which indicates that it is one of the most oxidation resistant RHEAs comparing to literature data to-date. This study can also provide insights on how to further develop RHEA to withstand long term oxidation at elevated temperatures.
In the third part, this study focuses on the isothermal oxidation behaviors of the RHEA used in the second part at 1200, 1300, and 1400 °C for up to 100 hours. Such experimental conditions are unprecedented in the literature regarding to the oxidation behaviors of the RHEAs. At 1200 °C, the oxidation mass gain curve yielded toward parabolic behavior owing to the formation of a tetragonal complex oxide layer with Al2O3 and Cr2O3 dispersions; breakaway oxidation contributed by Cr2O3 evaporation occurred at 1300 °C; a single power-law behavior governed the oxidation mass gain curve at 1400 °C, and mullite was identified within the oxide scale. This study revealed the oxidation behaviors of the RHEA and their mechanisms at extremely high temperature, as well as the guidelines for the future design of oxidation-resistant RHEA.
In the fourth part, the author attempts to preliminarily classify and predict the oxide formation of the RHEAs with the activity of Al and Cr, which are the elements that form the protective oxide layer on the alloy surface. The results indicated the Al and Cr activity could not be taken as sole factor for determining whether a protective Al2O3 and Cr2O3 layer would form for a RHEA. In addition, it appeared that the chemical composition strongly affected the oxidation products for RHEAs. However, the relationships among the Al and Cr activity, chemical composition, and the oxidation products and behaviors for RHEAs requires more studies to be further clarified. This study is expected to improve the understanding on the oxidation behaviors and alloy design of the RHEAs in the future.

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