表面改質乃工業中關鍵的技術，目的係修飾工件表面，增加其應
用價值與延長使用壽命。其中，多元合金氮化物保護性鍍膜因其優異
機械性質，電化學與磨耗性質而備受矚目。本研究之目標為開發奈米
複合晶鉻鉬矽氮薄膜，由調變矽含量，探討其高溫磨耗性質。
鉻鉬矽氮薄膜由射頻磁控濺鍍系統鍍附於選定基材，藉由調變鉻
鉬與矽的靶槍功率，通入氮氣反應形成不同矽含量之氮化物薄膜。薄
膜隨著矽含量增加，由鉻鉬氮柱狀晶結構漸漸轉變為奈米複合晶鉻鉬
矽氮。高溫磨擦實驗中，矽的添加使摩擦係數微幅增加，但潤滑相氧
化鉬的形成仍使系統整體之高溫摩擦係數維持在較低數值。在磨耗率
方面，加入矽7.5 原子百分比之鉻鉬矽氮因機械強化作用主導而使磨
耗率大幅降低。同時矽的添加亦能使原本高溫容易揮發之氧化鉬降低
其揮發速度。
最後由田口法優化製程參數，針對四個參數:矽靶功率、基板偏
壓、製程溫度與Ar/N2氣體比例進行最佳化，大幅提升鉻鉬矽氮薄膜
機械性質，同時達到更低磨耗率。

Surface modification engineering is a key technology in industry.
The goal is to deposit the coatings or to administer treatment to the
surface of interest. This study aims to develop a new multi-component
nitride material as a protective coating applied to wear condition at
elevated temperature.
Phase I: Creating and investigating a new coating system
CrMoN coatings has been found to have superior mechanical and
tribological properties, such as high hardness, low friction due to the solid
solution strengthening and the formation of lubricating molybdenum
oxide. In this study, the mechanical and tribological properties of CrMoN
with various Si contents were investigated. The quaternary CrMoSixN
coatings were deposited on silicon wafer and Inconel 718 by RF
magnetron sputter with Si contents ranged from 0 at. % to 11.1 at. %.
Through nanoindentation, the hardness and the H3/E*2 ratio of CrMoSixN
coatings were obtained. The results showed that mechanical
characteristics in CrMoSixN coatings were strongly influenced by Si
contents. The CrMoSixN coating exhibited highest values in H3/E*2 ratio
with 7.5 at. % Si doped, in which columnar grains turned into
nanocomposite structure. The strengthening mechanism of
nanocomposite structure was attributed to grain refinement and
prevention of direct penetration of cracks. Furthermore, tribological
behavior of CrMoSixN coatings was investigated by ball-on-disc
tribometer in atmosphere at 750 oC. The results indicated that the
tribological properties of CrMoSixN coatings at 750 oC could be
significantly improved with the Si addition due to protective oxide
formation on wear tracks and the cooperation of MoO3 as solid lubricant.
Although not the best in wear behavior, CrMoN coating still showed
good performance owing to the presence of molybdenum content, which
is thought to be beneficial to tribological properties at high temperature as
well. With 7.5 at. % Si doping, the CrMoSixN coatings showed superior
mechanical and tribological characteristics, leading to potential
applications for wearproof and self-lubricating dry cutting tools at
elevated temperature.
Phase II : Process Optimization of CrMoSiN by DOE-Taguchi
With further investigation of mechanical properties enhancement in
CrMoSiN coatings by deposition parameter control, Taguchi method in
design of experiment was introduced into this study. The method has long
been recognized as an powerful way to optimize the complicated process
over decades. The aim is to enhance the reliability of CrMoSixN coatings
under high temperature tribological properties in comparison of related
research in literature. Four controlling parameters: Silicon target power,
substrate bias, substrate temperature and Ar/N2 flow rate were chosen.
With three levels of each variable parameter, nine experiments were
determined based on Taguchi Orthogonal Array. The results showed that
the nanocomposite CrMoSixN fabricated through DOE Taguchi method
exhibited much better mechanical properties and tribological behaviors
than previous study. Furthermore, the contribution of each controlling
parameter on micro-hardness of thin films was quantitatively evaluated
through ANOM and ANOVA. This method provides a mighty tool in
optimizing the parameter controlled process in coating area.
In summary, the development of CrMoSiN coatings through phase I
and phase II reveals tribological mechanism at high temperature,
indicating a promising system in protective coating at extreme condition

Contents ….....................................................................................................I
Table Lists …………………………………………………………………V
Figure Captions …………………………………………………………VII
Abstract ………………………………………………………………….XII
Chapter 1 Introduction ……………………………………………...…….1
1.1 Background ……………………………………………………...…1
1.2 Nitride based hard coatings ………………………………………...3
1.3 Motivation and Objectives ………………………………………....7
1.4 Thesis Overview …………………………………………………..10
Chapter 2 Literature Review ……………………………………………17
2.1 Surface Modification Engineering ………………………………..17
2.2 Sputtering Techniques ……………………………………...……..24
2.2.1 Plasma ……………………………………………………...24
2.2.2 Sputtering …………………………………………………..25
2.2.3 Magnetron Sputtering ………………………………………27
2.2.4 Radio Frequency Reactive Magnetron Sputtering …………29
2.3 Review of Nitride Based Hard Coating …………………………..35
2.3.1 Binary Coating ……………………………………………..35
II
2.3.2 Ternary Nitride Coatings …………………………………...38
2.3.2.1 CrAlN coatings ………………………………………38
2.3.2.2 CrMoN coatings ……………………………………..40
2.3.3 Superhard Nanocomposite …………………………………42
2.3.3.1 Spinodal Phase Segregation of Nanocomposite……...43
2.3.3.2 Requirements for Phase Segregation in Deposition …44
2.3.3.3 Thermal Stability and Oxidation Resistance of
Nanocomposite …………………………………....45
2.4 Characterizations of Material ……………………………………..61
2.4.1 Quantitative Chemical Composition ……………………….61
2.4.2 Nanoindentation Method …………………………………...62
2.4.3 Transmission Electron Microscope ………………………...64
2.5 Taguchi Method in Design of Experiment ………………………..69
2.5.1 Introduction of Design of Experiment (DOE) ……………...69
2.5.2 DOE-Taguchi Method ……………………………………...72
2.5.2.1 Analysis of Mean (ANOM) ………………………….74
2.5.2.2 Analysis of Variance (ANOVA) …………………….77
Chapter 3 Experimental Procedure …………………………………….85
3.1 Sample Preparation ……………………………………………….85
III
3.2 CrMoSiN Thin Film Deposition ………………………………….85
3.3 Measurements and Analysis ………………………………………86
Chapter 4 Experimental Procedure …………………………………….91
4.1 Influence of Silicon-modified Cr-Mo-Si-N Nanocomposite Coatings
on Architecture Transformation and Mechanical Strength …...91
4.1.1 Composition and Microstructure of As-deposited CrMoSixN..
…………………………………………………………………….91
4.1.2 Mechanical Properties of As-deposited CrMoSixN ………...93
4.2 Development of CrMoSixN Nanocomposite Coatings for Anti-Wear
Application at Elevated Temperature ………………………..103
4.2.1 Friction Performance of CrMoSixN at Room Temperature and
High Temperature ………………………………………103
4.2.2 Wear Behavior of CrMoSixN at Elevated Temperature …..106
4.2.3 Microstructure of CrMoSi7.5N after High Temperature Process
…………………………………………………………………...117
4.2.4 Confinement of Volatile MoO3 at Elevated Temperature…119
4.3 Taguchi Method in Design of Experiment of CrMoSixN
Nanocomposite via Process Parameter Control for Further
Improvement in Mechanical Properties ……………………..127
IV
4.3.1 Taguchi Method: L9(34) Orthogonal Array and Hardness of
Samples of CrMoSixN and ANOM Analysis …………...127
4.3.2 ANOVA of Parameter Significance ……............................130
Chapter 5 Conclusions ………………………………………………….143
Reference ………………………………………………………………...147

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