臺灣博碩士論文加值系統

鈦合金發展至今已有200餘年的歷史，其中以粉末冶金製作鈦及鈦基合金的研究，更已經超過50年，相較於其它金屬，鈦及鈦合金，提供了比強度高、密度低及良好的疲勞強度。以鈦合金取代鐵基合金重量時，可減少並提升機械特性，鈦合金也有良好耐腐蝕性，且與人類骨骼具有高度生物相容性，這些特性使得鈦合金成為人體植入物的最佳選擇。此外，金屬基複合材料(MMCs)已知具有相當優越的機械性質，許多相關的研究會在鈦基材料上添加MC型碳化物，來作為鈦基合金之強化介質以提升其性質。
本實驗利用三種金屬粉末進行混合，分別為鈦、鉬及鉻粉，配置成三種不同合金，其三種配比分別為：Ti-8Mo-4Cr、Ti-8Mo-6Cr與Ti-8Mo-8Cr，並將鈦鉬鉻合金於1200°C、1250°C、1275°C與1300°C四種溫度下，持溫一小時進行真空燒結。為了要評估鈦鉬鉻合金經過真空燒結後的微觀結構與機械性質，本研究利用測量視孔隙率、硬度、橫向破裂強度(TRS)以及X光繞射儀(XRD)、掃描式電子顯微鏡(SEM)與光學顯微鏡(OM)等，來檢測鈦鉬鉻合金之性質。最後，進一步選擇Ti-Mo-Cr合金最佳的燒結參數，並添加碳化鈮(NbC)及碳化鋯(ZrC)等碳化物作為強化相來改善其機械性質。
實驗結果顯示，Ti-8Mo-6Cr合金於1300°C燒結一小時下，可獲得最高的硬度(66.5 HRA)、良好的視孔隙率(0.10 %)與橫向破裂強度(1152.9 MPa)，因此本研究將選用Ti-8Mo-6Cr添加碳化鈮與碳化鋯，做進一步的改善與分析。研究結果則顯示，添加1 wt% NbC碳化物的Ti-8Mo-6Cr合金，於1250°C燒結一小時後，具有最佳的性質，其硬度可以達到64.0 HRA，且橫向破裂強度明顯地增加至1522.0 MPa，同時極化阻抗高達3602.83 Ω·cm2，可以有效地改善其耐腐蝕性。添加5 wt%碳化鋯於1275°C燒結後，有較佳的視孔隙率(0.09%)、較高的硬度(66.4 HRA)，以及最高之極化阻抗值(11815.0 Ω·cm2)。

Titanium alloys have been developed over 200 years, whereas the powder metallurgy of titanium and Ti-based alloys has only been researched the last 50 years. Actually, titanium and its alloys offer high strength-to-weight ratios, low density and good fatigue strength compared with other materials. Moreover, they provide a potential for weight reduction and performance improvements when substituting ferrous-based alloys. The chemical properties of titanium alloys include good resistance to corrosion, good antiseptic properties and high biocompatibility with humans. These properties make titanium alloys a common choice for biomaterial implanted in the human body. In addition, the metal matrix composites (MMC) are well known for their excellent mechanical properties. Many investigations have depended on the characteristic of carbide as a reinforcing medium in a Ti-based alloy in order to enhance performance.
In this study, three different powders (titanium, molybdenum and chromium) were mixed and used to produce Ti-Mo-Cr alloys of three different proportions: Ti-8Mo-4Cr, Ti-8Mo-6Cr and Ti-8Mo-8Cr. The Ti-Mo-Cr alloys underwent a vacuum sintering process at various sintering temperatures of 1200°C, 1250°C, 1275°C and 1300°C for 1 h, respectively. To assess the microstructural and mechanical properties of the Ti-Mo-Cr alloys through the vacuum sintering processes, tests on the apparent porosity, hardness and transverse rupture strength (TRS) and microstructure inspections were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical microscopy (OM), with the purpose of improving the microstructure and properties of sintered Ti-Mo-Cr alloys. Finally, the optimal sintered parameters were subjected to the addition of various carbides (NbC and ZrC) as a strengthening phase after the sintering process.
The experimental results show that the highest hardness (66.45 HRA), good apparent porosity (0.10%) and transverse rupture strength (1112.87 MPa) of Ti-8Mo-6Cr alloys were obtained after sintering at 1300°C for 1 h. As a result, this study utilized the Ti-8Mo-6Cr alloys with the addition of niobium carbide and zirconium carbide for further improvement and analysis. The test results also indicated that when 1 wt% NbC carbide was added to Ti-8Mo-6Cr alloys, the possessed optimal properties after sintering at 1250°C for 1 h. The hardness was approached to 64.01 HRA, and the transverse rupture strength obviously increased to 1521.98 MPa, respectively. Meanwhile, the polarization resistance achieved 3602.83 Ω·cm2 which led to effectively improving corrosion resistance. When 5 wt% ZrC carbide was added to Ti-8Mo-6Cr alloys, the possessed optimal properties after sintering at 1275°C for 1 h. The preferable apparent porosity 0.09%, The hardness was enhanced to 66.40 HRA, and the polarization resistance achieved 11815.00 Ω·cm2.

摘 要 i
ABSTRACT iii
誌 謝 v
目 錄 vi
表目錄 x
圖目錄 xii
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
第二章 文獻回顧與基礎理論 3
2.1 鈦合金的由來與發展 3
2.1.1 鈦的由來 3
2.1.2 鈦及鈦合金的物理性質 4
2.1.3 鈦及鈦合金的應用 6
2.2 鈦合金的性質 8
2.2.1 α鈦合金與近α鈦合金 11
2.2.2 α+β鈦合金 12
2.2.3 β鈦合金與近β鈦合金 12
2.3 強化機制 15
2.3.1 固溶強化 15
2.3.2 散佈強化 18
2.4 破斷面分析 21
2.4.1 鈦合金破斷面理論 22
2.5 鈦合金的腐蝕行為 24
2.5.1 腐蝕形態 24
2.6 腐蝕特性 25
2.7 粉末冶金簡介 26
2.7.1 基本製成 26
2.7.2 粉末冶金產品之特點[33] 26
2.7.3 燒結原理 27
第三章 實驗流程、設備與分析方法 29
3.1 實驗流程 29
3.1.1 原料粉末 30
3.1.2 粉末混合 31
3.1.3 成形 32
3.1.4 真空燒結 33
3.2 分析方法 34
3.2.1 雷射粒徑 35
3.2.2 X-ray繞射 35
3.2.3 光學顯微鏡 36
3.2.4 掃描式電子顯微鏡 36
3.2.5 收縮率與視孔隙率 37
3.2.6 硬度 39
3.2.7 橫向破裂強度 39
3.2.8 動態電位極化試驗 41
第四章 結果與討論 42
4.1 粉末粒徑分析 42
4.1.1 原始基材粉末 43
4.1.2 強化相粉末 43
4.2 混合後粉末分析 44
4.2.1 混合後粉末之成份分析 45
4.2.2 強化相添加後粉末之成份分析 46
4.3 鈦鉬鉻合金性質 49
4.3.1 X-ray繞射分析 49
4.3.2 金相以及顯微組織 53
4.3.3 燒結緻密度檢測 61
4.4 機械性質 63
4.4.1 硬度 63
4.4.2 橫向破裂強度 64
4.4.3 破斷面分析 66
4.4.4 Ti-8Mo-xCr在不同燒結溫度下之小結 68
4.5 碳化物添加後之合金性質 70
4.5.1 碳化物添加後X-ray繞射分析 70
4.5.2 碳化物添加後金相以及顯微組織 75
4.5.3 碳化物添加後燒結緻密度檢測 84
4.6 碳化物添加後之機械性質 88
4.6.1 碳化物添加後之硬度 89
4.6.2 碳化物添加後之橫向破裂強度 91
4.6.3 碳化物添加後之破斷面分析 93
4.7 碳化物添加後之極化腐蝕特性 98
第五章 結論 100
參考文獻 101

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