臺灣博碩士論文加值系統

以磁控濺鍍技術搭配純鎳與純鋁濺鍍靶材所鍍製之二元鎳鋁合金薄膜，經由改變濺鍍時靶材輸出功率與基板溫度，可分別控制與改變薄膜之成份。鎳鋁合金薄膜之鋁含量可由製程參數精準地控制在2.7至62.9 at.%之間。經相鑑定分析，初鍍態的鎳鋁合金薄膜會因濺鍍靶材輸出功率、基板溫度與製程壓力的變化而生成結晶或奈米晶之微結構。在結晶度良好的鎳鋁合金薄膜中，可於不同製程參數所鍍製的微結構中鑑定出非序化Ni(Al) (γ)、序化AlNi3 (γ′)、Al3Ni (ε)以及Al3Ni2 (δ)等相。經退火處理後，可以發現大部份鎳鋁合金薄膜不再經歷相變化過程，此可說明其初鍍時便已達到熱力學之準平衡態。同時，透過薄膜表面形貌與晶粒大小之觀察，可發現改變製程參數造成之影響，進一步可由表面形貌推測鎳鋁合金薄膜所處的不同微結構平衡。經由奈米壓痕試驗測試其機械性質，可發現當高能量的濺鍍功率於薄膜中生成Ni(Al)與AlNi3強化相時，薄膜可得最高的硬度值。鎳鋁合金薄膜硬度之改變取決於其微結構與相的變化，以及晶粒尺寸效應的影響。為了研究與建立Ni-P、Ni-P-Al與Ni-Al系統間之差異，將Ni-P與Ni-P-Al薄膜系統一同引入作為成份與微結構不同之比較。Ni-P、Ni-P-Al與Ni-Al系統間不同的微結構與相變化機制也在本研究作一深入的討論。

Binary Ni-Al alloy coatings were fabricated by magnetron co-sputtering technique with multi targets of pure Ni and Al metals. The chemical composition variation of the coatings in terms of sputtering input power modulation and substrate deposition temperature variation was investigated. The Ni-Al coatings with Al contents ranged from approximately 2.7 to 62.9 at.% could be manipulated through multi-gun sputtering. The as-deposited Ni-Al coatings possessed crystalline and nano-crystalline microstructures with respect to deposition input powers, substrate temperatures, and working pressures. Significant crystallization feature of disordered Ni(Al) (γ) and ordered AlNi3 (γ′) , Al3Ni (ε), and Al3Ni2 (δ) phases were observed for the Ni-Al coatings with the variation in sputtering input powers and substrate deposition temperatures. The phase evolution analysis of Ni-Al coatings indicated the good thermal stabilities for the coatings under both as-deposited and post annealed states. A thermodynamic quasi-equilibrium state formed at as-deposited state for the Ni-Al coating was confirmed. The dependency of surface morphologies and grain sizes on the variation of input powers, substrate deposition temperatures was intensively discussed. Through nano-indentation analysis, the coatings with Ni(Al) and AlNi3 microstructure feature exhibited a higher hardness. The formation of Ni(Al) and AlNi3 phases was the strengthening mechanism for Ni-Al coatings under high energy input during sputtering. The variation in hardness was attributed to the crystallite size and microstructure evolution. In order to figure out the effect of Al in properties for Ni-based coatings, the Ni-P and Ni-P-Al coating systems were compared with Ni-Al binary coating. The microstructure, phase evolution, and related properties of the Ni-P, Ni-P-Al, and Ni-Al coatings were discussed.

Contents I
Table List V
Figure Caption VII
Abstract XVI

Chapter 1 Introduction 1
1.1 Background 1
1.2 Ni-Al Binary Alloy Coatings 1
1.3 Ni-P-X Ternary Alloy Systems 2
1.4 Importance and Applications of Ni-P Based Coating 3
1.5 Development and Investigation of Ni-P-Al Coatings 3
1.6 Critical Issues 4
1.7 Objectives 5

Chapter 2 Literature Review 7
2.1 Surface Engineering 7
2.1.1 Surface treatments 7
2.2.2 Surface coatings 8
2.2 Sputtering Technique 9
2.2.1 Sputtering 9
2.2.2 Magnetron sputtering 11
2.3 Binary Ni-Al Deposits 12
2.3.1 Fabrication methods of Ni-Al deposits 12
2.3.2 Microstructure and phase characteristics 13
2.3.3 Mechanical properties 16
2.3.4 Utilization and applications 17
2.4 Ni-based Alloy Deposits 18
2.4.1 Sputtered Ni-Al coatings 18
2.4.2 Co-sputtering effects on Ni-Al coatings deposition 20
2.4.3 Sputtered Ni-P-Al coatings 24

Chapter 3 Experimental Procedures 53
3.1 Sputtered Deposition of Alloy Thin Films 53
3.1.1 Substrates Preparation 53
3.1.2 Sputtering deposition process via single- and multi-gun sources 54
3.1.2.1 Sputtering source of single-gun deposition process 54
3.1.2.2 Sputtering sources of multi-gun deposition process 54
3.1.3 Sputtering fabrication process control 54
3.2 Ni-based Target Design for Sputtering Deposition 55
3.2.1 Electroplating Ni-P thick film 55
3.2.1.1 Substrate preparation 55
3.2.1.2 Electroplating equipment 55
3.2.1.3 Design of electroplating Ni-P/Cu and Ni-P/Al composite targets for sputtering deposition 56
3.2.2 Sputtering deposition with Ni-P/Cu or Ni-P/Al single-gun source 57
3.2.3 Sputtering deposition with Ni-Al multi-gun sources 57
3.3 Heat Treatment Process 57
3.4 Measurements and Analysis 58
3.4.1 Composition analysis 58
3.4.2 Microstructure observation 58
3.4.3 Phase identification 59
3.4.4 Hardness evaluation 59
3.4.5 Surface morphology evaluation 61
3.4.6 Surface Roughness Measurement 62

Chapter 4 Results and Discussion 74
4.1 Composition Evaluation for Coatings 74
4.1.1 Effect of sputtering target design on composition variation in the Ni-P and Ni-P-Al deposits 74
4.1.2 Effect of process parameters on composition variation in the Ni-Al
deposits 76
4.1.2.1 Effect of input powers on composition variation 76
4.1.2.2 Effect of working pressure and substrate deposition temperature on composition variation of the Ni-Al deposits 78
4.2 Microstructure Evaluation and Phase Identification 80
4.2.1 Effect of input powers on Ni-Al coating structures 80
4.2.2 Effect of substrate deposition temperature 84
4.2.3 Effect of post annealing treatment 88
4.2.4 Effect of Ar gas pressure 91
4.3 Morphological Characteristics of Coatings 92
4.3.1 Morphological characteristics of Ni-Al deposits 92
4.3.1.1 Effect of input powers on the Ni-Al deposits 92
4.3.1.2 Effect of substrate deposition temperatures 94
4.3.1.3 Effect of post annealing treatment 96
4.3.2 Morphological characteristics of Ni-P-Al deposits 97
4.3.2.1 Effect of substrate deposition temperatures 97
4.3.2.2 Effect of post annealing treatment 97
4.4 Mechanical Properties Evaluation 98
4.4.1 Effect of input powers 98
4.4.2 Effect of substrate deposition temperatures 99
4.4.3 Effect of post annealing treatment 101
4.4.4 Effect of the thermal histories variations on the Ni-P-Al deposits 101
4.5 Comparison in Ni-P, Ni-Al and Ni-P-Al Deposits 103
4.5.1 Introduction to Ni-Al and Ni-P-Al deposits 103
4.5.2 Microstructural variations between Ni-Al and Ni-P-Al deposits 104
4.5.3 Effect of P on the Ni/AlNi3 interface cohesion 107
4.5.4 Mechanical properties variations between Ni-Al and Ni-P-Al deposits 109

Chapter 5 Conclusions 181
References 185
Appendixes 193

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