以電漿電解氧化法於空氣濺鍍之ZrN/Si基材上製備氧化鋯膜及其特性分析

Abstract

Abstract This research is to make ZrO2 films on air-based sputtering deposited ZrN/Si substrates by plasma electrolytic oxidation. The films have porous characteristics which were formed by plasma electrolytic oxidation. The ZrN is conductive and biocompatibility and also zirconia is biocompatibility. This research was combined with those properties. The influences of reaction voltage on the growth of ZrO2 films were discussed. The formation mechanism and biocorrosion resistance of ZrO2 films on ZrN/Si by plasma electrolytic oxidation were also investigated. The ZrO2 formed on nitrogen-based sputtering deposition ZrN/Si substrates by plasma electrolytic oxidation and the references synthesized ZrO2 films on Zr bulk by plasma electrolytic oxidation were also compared. A potentiostatic mode was used to synthesize the ZrO2 films with the different voltages for 30 sec. The spark discharge, X-ray diffraction, and scanning electron microscope were used to recognize plasma electrolytic oxidation and electrochemical. The X-ray diffraction showed that tetragonal is major crystalline phase and included some monoclinic crystalline phases. The plasma was benefited to the ZrO2 films growth when spark discharge was observed by reaction process. That affection made the relatively intensity of ZrO2 films increased. Scanning electron microscope showed that the surface of ZrO2 content pores which were the main characteristics of plasma electrolytic oxidation. Spark discharge was observed during the synthesis at voltages 49-55 V, which could aide the formation crystalline phases and the surface display porous. On the other hand, electrochemical oxidation occurred at voltages below 45 V. There have no spark been observed and the surface have been displayed cracks. Voltages 46-48 V were defined the transition region from electrochemical oxidation to plasma electrolytic oxidation. Spark discharge was observed at local specimen surface by reaction process. With voltage raise the partial spark discharge increase. The contrast experiment form zirconia films on nitrogen-based sputtering deposition ZrN/Si by plasma electrolytic oxidation. The voltage 42 V spark discharge was observed and 55 V was occurred partial spark discharge. All of them were existed cracks and porous structure. The references made ZrO2 films on Zr bulk substrate were compared. We can know that reaction energy, substrate, electrolyte, power supply also can affect the reaction mechanism of plasma electrolytic oxidation.

The biocorrosion of as-deposited ZrN films and the ZrO2 films with plasma electrolytic oxidation were analyzed by Tafel test. According to the results, we know that the corrosion potential increased with raised voltage. The ZrO2 films formation at 52 V have best corrosion resistance. The ZrO2 films formed on highest 55 V content more defects for example crack and pores. The corrosion resistance was decrease with defects increase. The ZrO2 films formed on ZrN/Si substrates by plasma electrolytic oxidation have best corrosion resistance than the references reported that meant the research had development potentialities on biomaterial.

摘要 本研究是以電漿電解氧化法於空氣濺鍍之導電氮化鋯薄膜上製備功能性氧化鋯膜。電漿電解氧化法製備之薄膜具有多孔之特點，氮化鋯具有導電性及生醫相容性，氧化鋯亦具有生醫相容性，結合三者之特點，並探討不同反應電壓對於氧化鋯膜生成之影響，進而判別氧化鋯膜於氮化鋯膜上之生成機制，探討所生成氧化鋯膜之抗生物腐蝕特性。以氮氣濺鍍之氮化鋯薄膜為底材作為對照組，探討兩者製備氧化鋯之差異，再與文獻中以鋯塊材進行電漿電解氧化法製備氧化鋯膜相比較，探討氧化鋯生成差異。 不同定電壓模式反應時間30秒下製備氧化鋯膜，由反應過程中有無火花放電現象、X光繞射分析、場發式掃描電子顯微鏡分析實驗結果判斷，已成功利用電漿電解氧化法於空氣濺鍍之氮化鋯膜上製備出主要為正方相並含有少量單斜相之兩相混和氧化鋯膜，且實驗過程中有火花放電發生，電漿有利於輔助氧化膜成長，氧化鋯之相對強度會有大幅增加的趨勢，場發式掃描電子顯微鏡分析得知試片呈現多孔形貌為電漿電解氧化特徵。在反應電壓49?55 V實驗過程中有火花產生，試片表面形貌呈多孔狀，由此判斷49?55 V為電漿電解氧化反應。電壓45 V以下無火花放電產生，試片表面呈現微裂縫形貌，判斷為電化學氧化反應。反應電壓46?48 V反應過程中試片只有出現局部火花放電，隨著反應電壓提高火花放電區域亦增加，微裂縫及多孔結構兩者並存於試片表面形貌，為電化學轉變為電漿電解氧化反應機制之過渡區。利用氮氣所濺鍍之氮化鋯製備氧化鋯，電壓42 V時並未有火花放電出現，電壓55 V時有局部火花放電產生，兩者試片表面皆存在微裂縫及孔洞結構，以此判斷42?55 V應為電化學氧化轉變為電漿電解氧化反應之過渡區。與文獻以鋯塊材為反應基材比較得知，反應能量(電壓或電流密度)、基材、電解液、電源供應模式皆影響電漿電解氧化反應機制之原因。 抗生物腐蝕方面，將原始氮化鋯試片及反應生成ZrO2膜後之試片進行腐蝕分析，由抗腐蝕實驗結果得知隨著反應電壓的增加腐蝕電位提高，當反應電壓52 V時所製備之ZrO2膜之抗生物腐蝕能力最佳，最高反應電壓55 V試片內含有較多缺陷比如隙縫或者孔洞，造成抗腐蝕能力下降；與搜尋之文獻相比較，本研究利用電漿電解氧化法於氮化鋯膜上製備之氧化鋯膜，抗生物腐蝕性較佳，表示在生醫領域之應用有其發展之潛力。?