臺灣博碩士論文加值系統

無電鍍鎳(EN)膜具有許多優異特性，因而在工業界常廣泛應用於表面改質。經適當之熱處理後，無電鍍鎳磷膜層會因鎳磷化合物的析出而強化。然而，過度的熱處理會使膜層中晶粒成長過大而導致硬度下降。因之，提高鎳磷膜層的結晶溫度使其能在更高溫的環使用境中具有足夠、甚至更高的強度，將是一關鍵的技術發展。本研究利用第三元添加於二元鎳磷膜層中使其成為三元鎳磷基膜，藉此探討第三元之添加對鎳磷基薄膜的熱穩定性、機械性質及表面特性之影響。
利用磁控濺鍍技術，成功地鍍製出三元鎳磷鎢薄膜，經由適當的熱處理，最高硬度可由二元鎳磷薄膜的1240HK提高到達1790HK。同時，此最高硬度的生成溫度也由二元鎳磷膜的350°C提升為550°C，熱穩定性的提升亦由此得證。經過微觀結構及相鑑定分析，顯示三元鎳磷基膜經熱處理後會相轉變為Ni3P析出及Ni(W)合金基地兩相。由此，實驗中建構一鎳磷基膜的強化理論：Ni-P化合物析出強化以及Ni基地受W添加而固溶強化兩個效果。再配合定量的理論計算，驗證不同成分的鎳磷基膜析出強化及固溶強化所造成硬度表現上的變化。無電鍍Ni78.4P18.3W3.3膜的Ni3P析出量較濺鍍Ni80.0P15.3W4.7膜多(18.3>15.3 mole%)，但兩者基地都具有相同的固溶強化比例(12at.%)，且Ni80.0P15.3W4.7膜的基地量較Ni78.4P18.3W3.3膜大(38.8>26.8mole%)，故所表現出的硬度皆在1600HK左右。經由濺鍍技術的控制及熱處理，可將Ni基地的W固溶量增加至20at.%，也因此將Ni-P-W膜的最大硬度明顯地提升到達1790HK。透過鍍覆參數的控制及靶材的設計，可以精準的控制三元鎳磷鎢合金膜的成分，也由此控制Ni3P析出及Ni(W)基地量，使Ni-P-W膜獲致最高硬度。
經由表面分析，無電鍍二元及三元鎳磷基膜具有結瘤狀表面型態，由濺鍍方法所鍍製之鎳磷基膜則具有與基材相同之平坦表面型態，其平均表面粗糙度約在2-4奈米，較無電鍍膜為佳。經熱處理後，無電鍍與濺鍍鎳磷基膜層的表面型態與粗糙度皆無明顯變化，顯示熱處理對鎳磷基薄膜表面性質無顯著影響。以濺鍍方法所製作之二元鎳磷膜，在未經熱處理前膜層便有Ni-P化合物析出，加入鎢同時濺鍍後，有效抑制Ni-P化合物的析出，此亦證明第三元鎢的添加對鎳磷薄膜熱穩定性的提升。

Electroless nickel (EN) deposit is frequently employed for many industrial applications due to its various excellent properties. The electroless Ni-P deposit can be strengthened by the precipitation of Ni-P compounds after heat treatment. Nevertheless, the hardness of Ni-P films degrades with excessive annealing. It is thus critical to increase the crystallization temperature so that the Ni-P deposit can withstand sufficient or even superior hardness at elevated temperatures. To enhance the thermal stability, the addition of a third element in the Ni-P coating to form a ternary Ni-P-based coating is put into practice. It is found that thermal stability of electroless Ni-P-W deposit can be enhanced by the co-deposition of W as compared to binary electroless Ni-P films. The ternary Ni-P-W alloy coating is also fabricated by rf magnetron sputtering technique with dual targets of Ni-P/Cu and pure W. A fixed P/Ni ratio and linear W content dependence on input power is revealed in the ternary Ni-P-W coating, indicating a well control in composition of the coating through sputtering technique. Thermal stability analysis shows that the introduction of W in the Ni-P coating by co-sputtering retards the Ni3P precipitation and retains the strengthening effect to a higher temperature of 550°C. Microstructure evolution indicates that all coatings in the as-deposited state show amorphous structure. The precipitation of Ni3P accompanied with W dissoluted Ni matrix is revealed to be the final product of the phase transformation in Ni-P-W coatings after thermal treatment.
Results in microhardness test show that the surface hardness can be engineered by the controlling the composition and microstructure in the Ni-P-W coating. After heat treatment, the coating is strengthened by the precipitation of Ni-P compounds and solutioning of W in the crystallized Ni matrix. Quantitative analysis for the strengthening effect of the Ni-P-W coatings is performed based on Ni-P compound precipitation and Ni(W) matrix ratio. Both electroless Ni78.4P18.3W3.3 and sputtered Ni80.0P15.3W4.7 coatings exhibit a hardness around 1600 HK due to Ni3P precipitation and W solutioning hardening in Ni matrix to a W/Ni(W) ratio of approximately 12at.% after heat treatment. A higher microhardness of 1790 HK is measured in the sputtered Ni76.7P15.9W7.4 coating. Through quantitative analysis, the effect of strengthening in Ni-P-W ternary coatings under heat treatment can be clearly demonstrated.
From surface analysis, the nodular nature of the electroless coatings is responsible for the rougher surface profile as compared to the sputtered coatings. With the co-sputtering of W, the early stage Ni-P compounds is suppressed, according to X-ray and surface morphology analysis. After heat treatment, the surface morphology and roughness of both electroless and sputtered Ni-P-W films remain identical to those in the as-deposited state, indicating a stable surface characteristic under thermal treatment.

Table List III
Figure Caption IV
Abstract VII
Chapter I Introduction 1
1.1 Background 1
1.2 Material System 2
1.4 Critical Issues 3
1.5 Motivations and Goals 4
Chapter II Literature Review 9
2.1 Surface Engineering 9
2.2 Sputtering Technique 11
2.2.1 Sputtering 11
2.2.2 Magnetron Sputtering 12
2.2.3 RF Sputtering 13
2.3 Electroless Plating 13
2.4 Ni-P-Based Coating 14
2.4.1 Ni-W Coating 14
2.4.2 Electroless Ni-P Coating 16
2.4.2.1 Application, Advantage and Limitation of Electroless Nickel 16
2.4.2.2 Structure and Properties of Electroless Ni-P Coating 18
2.4.3 Electroless Ni-P-based Coating 20
2.4.4 Sputtered Ni-P-based Coating 23
2.5 Surface Characterization 24
2.5.1 Morphology Investigation 24
2.5.2 Surface Roughness Measurement 25
Chapter III Experimental Procedure 45
3.1 Substrate Preparation 45
3.2 Deposition Techniques 46
3.2.1 Electroless Plating 46
3.2.1.1 Electroless Ni-P Plating 46
3.2.1.2 Electroless Ni-P-W Plating 46
3.2.2 Magnetron Sputtering 47
3.2.2.1 Target Preparation 47
3.2.2.2 Sputtering Conditions 47
3.3 Heat Treatment and Thermal Property Measurement 48
3.4 Measurements and Analysis 48
3.4.1 Composition Analysis 48
3.4.2 Phase Identification 49
3.4.3 Microstructure Investigation 49
3.4.4 Microhardness Evaluation 49
3.4.5 Scratch Testing 50
3.4.6 Surface Characterization 50
3.4.6.1 Morphology Observation 50
3.4.6.2 Surface Roughness Measurement 51
Chapter IV Results & Discussion 60
4.1 Thermal Stability and Mechanical Properties of Ni-W-P Electroless Deposits 60
4.2 Fabrication, Thermal Stability, and Microhardness of Sputtered Ni-P-W Coating 66
4.3 Surface Characteristics of Electroless and Sputtered Ni-P-W Alloy Coatings 72
4.4 Surface Morphology and Roughness Evaluation of Ni-P-W Coatings 79
4.5 Microstructure, Microhardness, and Strengthening Mechanisms of Ni-P-W Ternary Coatings 83
4.6 Mechanical Characterization of Ni-P-based Ternary Coatings by RF Magnetron Sputtering 93
Chapter V Conclusions 142
References 145
Appendixes 151

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