本研究目的採用非平衡磁控濺鍍法添加鈦介層鍍覆氮化鈦鋯之薄膜在AISI D2 鋼上，其厚度超過3微米並保持著良好機械性質，同時，探討添加鈦介層對於氮化鈦鋯薄膜之機械性質影響。主要控制實驗參數為鍍膜的薄膜厚度和鈦介層的添加。實驗中共分成三系列，分別為:氮化鈦薄膜、氮化鈦鋯薄膜以及添加鈦介層之氮化鈦鋯薄膜。由於氮化鈦鋯薄膜的鈦鋯比為3:1 時和其他鈦鋯成份比例相比較下，此成分具有最低的殘留應力，故在本實驗中被採用。研究中薄膜的氮和金屬比例介於1.0-1.2 之間，且氮化鈦鋯中的鈦鋯比也約為3:1，氮化鈦薄膜硬度在25 GPa且氮化鈦鋯薄膜硬度皆大於30 GPa，不受介層之影響。在氮化鈦鋯薄膜厚度小於1微米下，添加鈦介層可以明顯增加氮化鈦鋯薄膜之(111)織構係數的增加並同時幫助了氮化鈦鋯薄膜的應力釋放。在添加鈦介層的氮化鈦鋯薄膜系統中的殘留應力變化，在膜厚度小於1微米下之殘留應力保持固定，但當厚度由1.5微米增加到3微米時，殘留應力是隨著薄膜厚度上升而增加，表示著鈦介層在釋放應力的效果中有一定的限制在存在。刮痕試驗結果中，添加了鈦介層對氮化鈦鋯薄膜的附著力只稍微增加，在磨耗試驗結果中發現當薄膜有較大的破裂韌性之值，薄膜的抗磨耗性質較佳，同時，薄膜中的儲存能越小，薄膜的抗磨耗性也越佳。表示薄膜之破裂韌性和其本身的儲存能是主導該薄膜的抗磨耗性之重要因素。

The objective of this study was to deposit thick TiZrN coatings with Ti interlayer above 3 μm on AISI D2 steel by dc unbalanced magnetron sputtering and investigated the effect of Ti interlayer on mechanical properties, simultaneously. The controlling deposition parameters were the adding of Ti interlayer and thickness of the coating. The Ti0.75Zr0.25N coating was selected due to the lowest residual stress comparing with Ti0.45Zr0.55N and Ti0.15Zr0.85N. There were three experimental conditions, namely, TiN(t) coating, TiZrN(tz) coating, and TiZrN/Ti(tzt) coating. The results showed that TiZrN coating with Ti interlayer, which thickness up to 3 μm were successfully deposited on D2 steel substrate. The N/Ti ratio for TiN coatings and N/(Ti+Zr) ratio for TiZrN coatings were nearly constant ranging from 1.0 to 1.2 and Zr/(Zr+Ti) ratio for TiZrN coatings were about 0.25. The hardness of TiN coatings was 24.2 and 26.2 GPa and the hardness of TiZrN coatings higher than 30 GPa. The texture of TiZrN coatings were with strong (111) by adding the Ti interlayer when the thickness of TiZrN coating smaller than 1 μm. The residual stress of TiZrN coatings was higher than TiN coatings and the residual stress were released by adding Ti interlayer. The residual stress of tzt-series was about constant until the TiZrN coating thickness reached 1 μm, then the residual stress increased with increasing TiZrN coating thickness. This pointed out the limitation of stress relief by adding Ti interlayer. From the results of scratch test, the adhesion of TiZrN/Ti coating slight increased. In the wear test, the coating with higher toughness possessed better wear resistance; meanwhile, the coating with smaller store energy possessed better wear resistance. The effect of store energy and toughness were the dominate factors on the wear resistance of coatings.

致謝............ I
摘要............ III
Abstract....... IV
Contents....... V
List of Figures....... VIII
List of Tables....... XII
Chapter 1 Introduction.......1
Chapter 2 Literature Review.......2
2.1 Characteristics of Transition Metal Nitride (TiN and ZrN).......2
2.2 Characteristics of TiZrN.......5
2.2.1 Structure of TiZrN.......5
2.2.2 Property of TiZrN .......8
2.3 Effect of Ti Interlayer.......9
2.4 Tribological Behavior.......12
2.4.1 Adhesion Strength.......12
2.4.2 Wear Resistance.......13
Chapter 3 Experimental details.......15
3.1 Substrate Preparation.......15
3.2 Deposition procedures.......15
3.3 Characterization Methods for structure and compositions.......19
3.3.1 Auger electron spectroscopy (AES).......19
3.3.2 X-ray Photoelectron Spectroscopy (XPS).......19
3.3.3 X-Ray Diffraction (XRD) and Grazing Incidence XRD (GIXRD).......20
3.3.4 Field-Emission Gun Scanning Electron Microscopy (FEG-SEM).......22
3.3.5 Dual Beam Focused Ion Beam (FIB).......22
3.3.6 Atomic Force Microscopy (AFM).......23
3.4 Characterization Properties measurement method .......24
3.4.1 Hardness and Young’s Modulus.......24
3.4.2 Residual Stress measured cos2αsin2Ψ method and Layer-by-layer method.......25
3.4.3 Scratch test.......28
3.4.4 Wear test.......30
Chapter 4 Results.......33
4.1 Structure.......36
4.1.1 Chemical composition.......36
4.1.2 Crystal Structure.......37
4.1.3 Microstructure.......41
4.2 Property.......47
4.2.1 Residual stress.......47
4.2.2 Stress gradient.......47
4.2.3 Hardness and Young’s modulus.......52
4.2.4 Scratch Test.......53
4.2.5 Wear test.......57
Chapter 5 Discussion.......67
5.1 Comparison performance between TiN and TiZrN coating .......67
5.2 Effect of Ti interlayer.......68
5.2.1 Variation of texture.......68
5.2.2 Harness of TiZrN coating.......69
5.2.3 Variation of residual stress.......70
5.3 Wear test.......74
5.3.1 Mechanism of failure mode.......74
5.3.2 Wear rate.......75
5.3.3 On the significance of both H/E and Store energy .......81
Chapter 6 Conclusions.......82
Future work.......83
Reference.......84
Appendix A.......89
Appendix B.......94
Appendix C.......96
Appendix D.......97
Appendix E.......98

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