臺灣博碩士論文加值系統

本研究主旨為研究「聚矽氮烷液態高分子前驅物」作為保護性鍍層之性能提升開發。「聚矽氮烷液態高分子前驅物 (Polysilazane preceramic precursor, PSZP)」為聚合物衍生陶瓷(Polymer Derived Ceramics, PDC)眾多種類之一，可藉由在惰性氣氛下不同的熱解溫度，使液態高分子前驅物轉化為具不同特性之結晶或非晶矽基陶瓷，且由於其前驅物為液相聚合物，可透過聚合物成型方法作為陶瓷薄膜成型方式，故製程難度低且成本低，熱解後之SiCNO矽基陶瓷具有高硬度、高溫穩定性、高化學穩定性、耐磨耗性、高抗腐蝕性及生物惰性，而本研究透過量測不同熱解溫度下，SiCNO矽基陶瓷薄膜之機械性質及化學性質，並且藉由摻雜不同粉末填料及合成陶瓷材料於聚矽氮烷中以提升SiCNO矽基陶瓷薄膜機械性質。首先透過旋轉塗佈方式將聚矽氮烷液態高分子前驅物塗佈於矽晶圓表面，並分別進行700℃、800℃、900℃、1000℃、1100℃及1200℃溫度之熱解，使聚矽氮烷轉化為結晶或非晶之SiCNO矽基陶瓷，再藉由奈米壓痕量測系統比較出最優異之機械性質為1100℃的熱解溫度，硬度可以達到9.22 GPa，彈性模數則為77.7 GPa，以H/E代表破壞彈性應變(Elastic strain to failure)，其值可達到0.118，而H3/E2代表斷裂韌性(Fracture thoughness)，其值則可達0.129 GPa。接著透過摻雜氮化鋁及二氧化鈦陶瓷粉末於聚矽氮烷中，進行1100℃的熱解程序，並透過奈米壓痕量測系統測得當氮化鋁及二氧化鈦粉末摻雜比例為3wt %時，平均硬度表現分別可達到9.39 GPa及10.88 GPa，彈性模數分別為76.7 GPa及79.6 GPa，而破壞彈性應變H/E值分別為0.122及0.137，斷裂韌性H3/E2值則分別為0.141 GPa及0.203 GPa，說明摻雜氮化鋁及二氧化鈦粉末作為填料可以有效地提升複合矽基陶瓷薄膜硬度及耐磨耗性。而為了更進一步提升複合矽基陶瓷薄膜機械性質，選擇透過硼氫化鈉以溶膠-凝膠法還原正丙醇鋯及異丙醇鈦於聚矽氮烷液態高分子前驅物中，通過1100℃的熱解程序使聚矽氮烷得以完全相變化形成氧化鋯及氧化鈦複合矽基陶瓷薄膜，最後由奈米壓痕量測系統測得當5wt %的異丙醇鈦還原液混和於聚矽氮烷液態高分子前驅物中，經由1100℃之熱處理後，形成的氧化鈦複合矽基陶瓷薄膜平均硬度為10.67 GPa，彈性模數為84.5 GPa，破壞彈性應變H/E值達到0.126，斷裂韌性H3/E2值為0.170 GPa，而摻雜比例10wt %之氧化鋯複合矽基陶瓷薄膜平均硬度大幅提升至11.54 GPa，彈性模數達到101.2 GPa，破壞彈性應變H/E值為0.114，斷裂韌性H3/E2值為0.150 GPa，此研究結果說明透過還原填料於聚矽氮烷液態高分子前驅物所形成之複合矽基陶瓷薄膜可以有效提升機械性質。本研究亦透過電化學分析儀量測SiCNO矽基陶瓷薄膜於銅泡棉之抗腐蝕性能，研究結果顯示未具有SiCNO矽基陶瓷薄膜之銅泡棉腐蝕電位為0.022V，腐蝕速率為1510.2μm/year，而具有SiCNO矽基陶瓷薄膜之銅泡棉腐蝕電位提升至0.52V，提升了23倍，而最佳腐蝕速率則降低至7.56μm/year，腐蝕速率降低近200倍，證明SiCNO矽基陶瓷薄膜作為保護性鍍層，可以大幅提升抗腐蝕性能。

The purpose of this research is to study the mechanical and electrochemical properties of liquidic polysilazane preceramic precursor as a protective surface coating. Polysilazane is one of Polymer Derived Ceramics (PDC) systems, that can be transformed from liquid polymer precursors into crystalline or amorphous silicon-based ceramics with different properties by heat treating at pyrolytic temperatures. Due to the preceramic precursors are liquid-phase polymers, ceramic films can be molded by polymer molding methods, making the process simpler and cheaper. The pyrolyzed SiCNO silicon-based ceramics have high hardness, high temperature stability, high chemical stability, wear resistance, high corrosion resistance and biological inertness. In this study, the mechanical and chemical properties of SiCNO silicon-based ceramic films are measured at different pyrolytic temperatures, and the mechanical properties of SiCNO silicon-based ceramic films are enhanced by doping different nano ceramic powders and synthetic ceramic materials as fillers in liquidic polysilazane preceramic precursor. Firstly, we coat the liquidic polysilazane preceramic precursor on the surface of silicon wafers by spin-coating, and then pyrolyze it at 700°C-1200°C in inert atmosphere to trigger the transformation of polymer-to-ceramic (SiCNO). The nanoindentation measurement system has shown when pyrolytic temperature reaches 1100℃, the maximum hardness and reduced modulus achieves 9.22 GPa, and 77.7GPa, respectively. The value of H/E for elastic strain to failure and H3/E2 for fracture toughness achieves 0.118 and 0.129 GPa. To enhance the mechanical properties of SiCNO silicon-based ceramic films, we use aluminium nitride and titanium dioxide ceramic powders as fillers. The average hardness of aluminium nitride and titanium dioxide powders as the fillers of polysilazane at a doping ratio of 3wt% achieve 9.39 GPa and 10.88 GPa, the reduced modulus achieve 76.7 GPa and 79.6 GPa, the H/E values of elastic strain to failure achieve 0.122 and 0.137, and the H3/E2 for fracture toughness achieve 0.118 and 0.129 GPa, respectively. Addition of aluminum nitride and titanium dioxide powders as fillers can effectively improve the hardness and wear resistance of the composite silicon-based ceramic films. In order to further improve the mechanical properties of the composite silicon-based ceramic film, sodium borohydride is used to reduce n-propanol zirconium and isopropanol titanium as fillers in liquidic polysilazane preceramic precursor by sol-gel method. As measured by a nanoindentation measurement system, the average hardness and reduced modulus of the titanium dioxide composite silicon-based ceramic film with 5wt% isopropanol titanium reduction solution pyrolyzed at 1100°C can achieve 10.67 GPa and 84.5 GPa, respectively. Those H/E values for elastic strain to failure and H3/E2 values for fracture toughness achieves 0.126 and 0.170 GPa, respectively. The average hardness and reduced modulus of the 10wt% zirconium oxide composite silicon-based ceramic films are increased significantly to 11.54 GPa and 101.2 GPa, respectively. Those H/E values for elastic strain to failure and H3/E2 values for fracture toughness achieve 0.114 and 0.150 GPa. The results show that the mechanical properties of composite silicon-based ceramic films can be effectively enhanced by reducing titanium and zirconium as silicon-based ceramic fillers.
Anti-corrosion test is to impregnate the copper foam in different concentrations of liquidic polysilazane preceramic precursor in acetone, and then it is pyrolyzed at 700 °C. The experimental results show that the corrosion potential of copper foam without SiCNO silicon-based ceramic film is 0.022V and the corrosion rate is 1510.2μm/year, while the corrosion potential of copper foam with SiCNO silicon-based ceramic film is increased to 0.52V, which is 23 times higher, and the best corrosion rate is reduced to 7.56μm/year, which is nearly 200 times lower. This demonstrates that SiCNO silicon-based ceramic films can significantly improve corrosion resistance as a protective surface coating.

論文審定書 i
誌謝 ii
摘要 iii
Abstract v
目錄 viii
圖目錄 xi
表目錄 xvi
第一章 緒論 1
1.1前言 1
1.2研究動機 3
第二章 文獻回顧 4
2.1聚合物衍生性陶瓷介紹 4
2.1.1聚合物衍生性陶瓷熱解 5
2.1.2 聚合物衍生性陶瓷填料摻雜 9
2.1.3 聚合物衍生性陶瓷應用 10
2.1.4 聚矽氮烷介紹 12
2.2金屬與陶瓷填料介紹 15
2.2.1氮化鋁 15
2.2.2二氧化鈦 17
2.2.3氧化鋯 20
第三章 實驗方法與設備分析 23
3.1實驗材料 23
3.2實驗設備 24
3.3實驗流程 25
3.3.1矽晶圓塗佈聚矽氮烷液態高分子前驅物 26
3.3.2矽晶圓塗佈含陶瓷填料之聚矽氮烷液態高分子前驅物 27
3.3.3摻雜氮化鋁及二氧化鈦陶瓷粉末作為聚矽氮烷液態高分子前驅物填料 28
3.3.4利用硼氫化鈉還原氧化鋯及氧化鈦作為聚矽氮烷液態高分子前驅物填料 29
3.3.5聚矽氮烷液態高分子前驅物塗層熱處理 31
3.3.6 抗腐蝕性能量測 32
3.4分析設備 33
3.4.1陶瓷薄膜表面分析 33
3.4.2陶瓷薄膜結晶成分及結構分析 37
3.4.3奈米壓痕量測系統 (Nano-indenter System) 41
3.4.4電化學分析儀 (Electrochemical analyzer) 48
第四章 結果與討論 52
4.1陶瓷薄膜表面型態分析 52
4.1.1聚矽氮烷液態高分子前驅物轉化矽基陶瓷薄膜表面型態分析 52
4.1.2摻雜氮化鋁粉末作為填料之複合矽基陶瓷薄膜表面型態 55
4.1.3摻雜二氧化鈦粉末作為填料之複合矽基陶瓷薄膜表面型態 57
4.1.4還原鋯複合矽基陶瓷薄膜表面型態 59
4.1.5還原鈦複合矽基陶瓷薄膜表面型態 62
4.1.6摻雜不同填料之複合矽基陶瓷薄膜與SiCNO矽基陶瓷薄膜表面粗糙度量測 64
4.2陶瓷薄膜奈米壓痕量測及機械性質分析 67
4.2.1聚矽氮烷液態高分子前驅物轉化矽基陶瓷薄膜奈米壓痕量測 67
4.2.2摻雜氮化鋁及二氧化鈦粉末填料之複合矽基陶瓷薄膜奈米壓痕量測 72
4.2.3以溶膠凝膠法還原氧化鋯及氧化鈦填料之複合矽基陶瓷薄膜奈米壓痕量測 81
4.2.4複合矽基陶瓷及SiCNO矽基陶瓷薄膜機械性質比較 84
4.3陶瓷薄膜結晶結構及成分分析 86
4.3.1聚矽氮烷液態高分子前驅物轉化矽基陶瓷薄膜能量色散X射線元素分析 86
4.3.2聚矽氮烷液態高分子前驅物轉化矽基陶瓷薄膜X光繞射分析 89
4.3.3摻雜氮化鋁粉末作為填料之複合矽基陶瓷薄膜X光繞射分析 91
4.3.4摻雜二氧化鈦粉末作為填料之複合矽基陶瓷粉末X光繞射分析 94
4.3.5還原鋯及還原鈦複合矽基陶瓷薄膜X光繞射分析 95
4.3.6摻雜二氧化鈦、氧化鋯及氮化鋁之聚矽氮烷液態高分子前驅物轉化陶瓷薄膜拉曼光譜儀量測 98
4.4陶瓷薄膜電化學腐蝕性能量測及分析 100
4.4.1聚矽氮烷液態高分子前驅物轉化矽基陶瓷薄膜電化學腐蝕性能量測 100
第五章 結論與未來展望 104
5.1結論 104
5.2未來展望 107
參考文獻 108

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