本研究工作主要是探討中空陰極放電式離子鍍著系統（HCD ion-plating system，簡稱HCDIP）的基本操作參數例如溫度、偏壓、鍍膜功率等對TiN薄膜的優選方向、孔隙度、晶粒尺寸等微結構特性與表面鍍TiN的304不鏽鋼其耐腐蝕性的影響。
在實驗測試範圍內，TiN薄膜的優選方向、孔隙度、晶粒尺寸等微結構特性主要是受到溫度與離子撞擊強度的影響。TiN薄膜的優選方向隨著溫度與離子撞擊強度的不同而在(200)、(111)與(220)之間變化。高溫與低撞擊強度有助於(200)優選方向的形成，低溫與高撞擊強度則產生(220)優選方向，在這兩種較極端之間的鍍膜條件則形成(111)優選方向。提高鍍膜溫度或離子撞擊強度都可減低TiN薄膜的孔隙度。TiN薄膜的晶粒大體而言隨溫度增加而變大; 低溫下離子撞擊強度的影響不大; 高溫下隨撞擊強度的增加，晶粒尺寸會增大到一最大值，進一步提高離子撞擊強度反而使晶粒尺寸減小。鍍膜過程中離子撞擊與溫度的交互影響會形成具有特定微結構的TiN薄膜。大略而言，緻密的TiN薄膜其特徵是晶粒大，或是具有強烈(111)優選方向的小晶粒。

在腐蝕的研究上，電化學測試的結果顯示高溫與高偏壓有助於形成保護性較佳的TiN薄膜。大體而言，孔隙度較高的TiN薄膜其保護性較差，然而相同孔隙度的TiN薄膜其對304不鏽鋼基材的保護程度也可能有一個數量級的差異。表面鍍TiN的304不鏽鋼其腐蝕狀況，在不同階段可觀察到TiN薄膜上微裂縫的生成、微裂縫的延伸擴展與TiN薄膜的碎裂。

本論文也以整合性指標來呈現溫度、偏壓、鍍膜功率等主要鍍膜參數與TiN薄膜的優選方向與孔隙度之間的關聯。在測試條件範圍內，TiN薄膜的優選方向隨著溫度與離子撞擊強度的不同而在(200)、(111)與(220)之間變化的現象，可藉SE / T(K) 此一整合指標簡單而清楚的呈現。隨著SE / T(K) 指標的增加，TiN薄膜的優選方向由(200)轉變成(111)至(220)。孔隙度因鍍膜溫度或離子撞擊強度提高而減低的現象，可藉SE ×T指標呈現。隨著SE ×T 指標的增加，TiN孔隙度隨之減低。

在薄膜孔隙度與腐蝕的研究上，本論文由推導與實驗驗證提出新的孔隙度測量概念，此概念主要是以電化學測試的外加腐蝕電量來評估孔隙度測量的準確性。減低外加腐蝕電量可避免電化學測試過程造成TiN薄膜下的304不鏽鋼基材的過度腐蝕，而得到正確的孔隙度測量值; 在此情形下，本研究中所使用的各種電化學孔隙度測量方法都能得到一致的結果。電化學腐蝕測試中，TiN鍍膜試片其腐蝕量隨外加腐蝕電量的增加而變化的情形，可反應出TiN鍍膜試片其腐蝕的演變過程。

This work investigated the influence of the main process parameters on the preferred orientation, porosity, grain size and corrosion behavior of TiN films deposited by Hollow Cathode Discharge Ion-Plating system (HCDIP).
Within the investigated ranges, the preferred orientation, porosity, grain size of TiN films vary mainly with the change of deposition temperature and the ion bombardment, which is expressed with an index of SE. High deposition temperature together with low ion bombardment helps to deposition a (200)-oriented TiN coating. On the contrary, low deposition temperature and high ion bombardment lead to a TiN film with (220) preferred orientation. Between these two extreme deposition conditions, (111) is the preferred orientation of deposited TiN films. Increasing deposition temperature or the degree of ion bombardment can reduce the porosity of TiN films. The grain size of TiN films generally increases with increasing temperature. The influence of ion bombardment is more evident at high temperature. Grain size initially increases with ion bombardment but decreases at later stage. The relative importance of the effects induced by the temperature and the ion bombardment determines the specific microstructure characteristics of TiN coatings. Roughly speaking, the denser TiN coatings either have a large grain size or a highly (111)-preferred texture with smaller grain.

The electrochemical corrosion studies reveal that high deposition temperature and high negative bias voltage are beneficial to deposit TiN coatings with better corrosion resistance. Generally, TiN-coated stainless steels with high porosity have lower corrosion resistance. However, the variation of corrosion extent may be more than one order of magnitude for TiN coatings with the same level of porosity, especially at low level of porosity. At early stage of corrosion, micro-cracks appear on the TiN coating. The corrosion of substrate will be accelerated after the extension of the micro-cracks on TiN film.

In this study, two combined indexes were used to describe the correlation between the preferred orientation, the porosity of TiN films and the deposition temperature, bias voltage and deposition power. Within the investigated ranges, the preferred orientation of TiN films changes from (200) to (111) and then to (220) with the increasing SE / T(K) index. And the porosity of TiN coatings decreases with increasing SE ×T index.

This work also proposed a methodology, which is based on the corrosiveness of electrochemical test process, to measure the porosity of TiN coatings. By decreasing the corrosiveness of test process the problem of pinhole enlargement can be avoided and accurate measurement can be achieved. Based on this methodology, different electrochemical porosity test techniques can achieve a similar result of porosity measurements.

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