磁控濺鍍三元鎳磷鉻合金薄膜之微觀結構、微硬度及熱行為分析

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研究生：	陳威有 Wei-Yu Chen
論文名稱：	磁控濺鍍三元鎳磷鉻合金薄膜之微觀結構、微硬度及熱行為分析 Thermal Behavior, Microstructure and Microhardness of Ternary Ni-P-Cr Coating by RF Magnetron Sputtering Process
指導教授：	杜正恭 Jenq-Gong Duh
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2003
畢業學年度：	91
語文別：	英文
論文頁數：	86
中文關鍵詞：	磁控濺鍍、鎳磷鉻薄膜、微硬度、熱穩定性、熱循環測試
外文關鍵詞：	magnetron sputter, Ni-P-Cr coating, microhardness, thermal stability, thermal cycle test
相關次數：	點閱：3 下載：0
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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鉻薄膜，經過適當的熱處理，其最高硬度可以達到1500HK，相較於一般傳統的二元Ni-P系統有明顯的提升。為了更精確的探討鉻在鎳磷基三元薄膜的結晶行為影響，可以藉由DSC的分析得知NiP的析出溫度會因為第三元的添加，而由原本的380C（Ni-P）往高延緩到450C。同時，對於最高硬度的生成溫度也由原本沒有添加鉻的380°C提升為500°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，顯示三元鎳磷鉻薄膜經處理後會相轉變為Ni3P析出以及Ni-Cr固溶合金基地兩相。由此實驗中建構出一鎳磷基薄膜的強化理論：Ni本身的微小尺寸的強化效果以及Ni-P化合物析出強化，最後再加上第三元元素（鉻）會在Ni基地中行程固溶強化。除了長時間的熱處理評估，本實驗亦設計了在400°C以及450°C的短時間的熱循環測試其硬度值分別為1200 HK 和1300HK，其析出強化相Ni3P都尚未達到完全結晶狀態。

以磁控濺鍍所製備之三元鎳磷基薄膜其結晶行為以及機械性質表現會受到第三元元素的的種類以及含量影響。而本實驗所選用的鉻添加定二元鎳磷系統中，不管在熱穩定以及機械性質都有顯著的提升。

Binary Ni-P and ternary Ni-P-Cr alloy coatings were fabricated by the RF magnetron sputtering technique with dual targets of electroless nickel alloy as well as an additional element metal. The as-deposited Ni-P and Ni-P-Cr coating exhibited amorphous structure. The thermal property of coating was investigated by the annealing test for 4 hours and also by cycling test for 30 minutes in N2 atmosphere at 400 and 450C. The related mechanical properties were evaluated by Knoop microhardness test, and the measured microhardness was employed to evaluate the thermal stability of the binary and ternary alloy. The microhardness was 1250HK and 1380HK for Ni-P alloys at 400C and ternary Ni-P-Cr at 450C, respectively, after 4 hours annealing. For cycling test over 8 times cycles at 400 □C, the microhardness of Ni-P-Cr deposit was 1200 HK, in which full recrystallization of Ni3P precipitation was not yet completed. To evaluate the influence of Cr doping in Ni-P deposit, the differential scanning calorimeter (DSC) analysis was employed to characterize the temperature of phase transformation in the Ni-P-based coatings, including binary Ni-P, ternary Ni-P-Cr and Ni-P-W. Crystallization behavior in binary and ternary Ni-P-based coatings was quite distinct due to the addition of Cr and W. Microhardness test indicated that the sputtered Ni-P-Cr and Ni-P-W coatings exhibited superior hardness and excellent thermal stability than the Ni-P coating. In addition, chromium exhibited compatible thermal characteristic with the tungsten for the ternary Ni-P-based system. Strengthening mechanism in sputtered Ni-P-Cr and Ni-P-W deposits would also be discussed.

Table List   III
Figure Caption IV

Abstract   VI

Chapter I Introduction 1

1 Background 1

2 Material System of Ni-P-X 1

3 Importance and Application of Ni-P Based Coating 2

4 Critical Issues 3

5 Objective of This Study 3

Chapter II Literature Review 5

1 Sputtering Technique 5

1.1 Sputtering 5

1.2 Magnetron Sputtering 6

1.3 RF Sputtering 7

2 Binary Ni-P Deposits 7

2.1 Fabrication 7

2.2 Microstructure and Phase 9

2.3 Annealing Behavior 10

2.4 Mechanical Properties 10

3 Ternary Ni-P-X Deposits 11

3.1 Ni-P-Cu 12

3.1.1 Electroless Ni-P-Cu 12

3.1.2 Sputtered Ni-P-Cu 14

3.2 Ni-P-W 15

3.2.1 Electroless Ni-P-W 15

3.2.2 Sputtered Ni-P-W 16

3.3 Ni-P-Cr 17

Chapter III Experimental Procedure 36

1 Substrate Preparation 36

2 Deposition Technique ~ RF Magnetron Sputtering 37

2.1 Target Preparation 37

2.2 Deposition of Ni-P and Ni-P-Cr Films 37

3 Heat Treatment and Thermal Property Measurement 38

3.1 DSC analysis 38

3.2 Procedure of Annealing 38

4 Measurements and Analysis 39

4.1 Composition Analysis 39

4.2 Phase Identification and Microstructure Investigation   39

4.3 Hardness Evaluation 40

4.3.1 MHT ~ Knoop 40

4.3.2 NHT ~ Berkovich 40

Chapter IV Results & Discussion 50

1 Compound Target Design and Composition Control of P/Ni and Cr    50

2 Thermal stability of sputtered Ni-P and Ni-P-Cr coatings during cycling test and annealing treatment                               52

2.1 Composition 52

2.2 Phase Identification 52

2.3 Microhardness 54

2.3.1 Annealing Test 54

2.3.2 Cycling Thermal Test 55

3 Compared with NiP, NiPCr and NiPW  57

3.1 Composition of NiP-based Deposit 57

3.2 Crystallization behavior of sputtered Ni-P, Ni-P-Cr and Ni-P-W deposits        58

3.2.1 DSC Profile 58

3.2.2 XRD Pattern 58

3.3 Thermal stability evaluated by microhardness         61

Chapter V Conclusions 81

References   83

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