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Synthesis of bioactive NaHTi3O7 films on Ti-coated Si by a low temperature hydrothermal-galvanic couple method
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經由X光繞射（XRD）、拉曼光譜（Raman）及X光光電子能譜儀（XPS）分析結果確認，利用水熱-化學電池法及水熱法均可在Ti/Si基材上，在小於100°C的低溫環境下製備出NaHTi3O7膜。以場發射掃描式電子顯微鏡（FE-SEM）觀察試片反應前後橫截面及表面微結構形貌。在本研究中顯示利用Ti/Si以水熱-化學電池法和水熱法於4M NaOH溶液中，在80°C下反應2小時均可製備出非晶(少量結晶)NaHTi3O7膜，以水熱-化學電池法形成NaHTi3O7膜厚約350 nm，但以水熱法製備生成NaHTi3O7膜厚僅約200 nm，顯示水熱-化學電池法反應較為快速。在4M NaOH溶液中，當反應溫度於50-80°C時則形成非晶NaHTi3O7膜。而Ti/Si以水熱-學電池法於6M NaOH溶液中，在60°C下反應2小時即可生成非晶(少量結晶)NaHTi3O7膜。本實驗以水熱-化學電池法及水熱法所製備NaHTi3O7膜表面皆為奈米網狀結構，NaHTi3O7膜生成厚度及表面網狀孔洞尺寸皆隨NaOH濃度、水熱溫度及反應時間增加而增加。分析NaHTi3O7膜生成量與Ti基材消耗量之化學計量關係，發現實際膜厚較理論膜厚高出許多，可能是所生成之NaHTi3O7膜為奈米網狀結構，使密度大幅降低所致。綜合以上結果可得知水熱-化學電池製程反應速率比水熱法快速，此原因為水熱-化學電池法是由於兩極間所產生電位差加速離子遷移驅動力，促進氧化還原反應加速進行，使得在相同條件製程下，水熱-化學電池法膜厚成長較水熱法快速之原因。
The objective of this research is to synthesize bioactive NaHTi3O7 films on Ti-coated Si (Ti/Si) by the hydrothermal-galvanic couple method at low temperatures (<100C). No research concerning the preparation of NaHTi3O7 films by using such a method or substrates has been reported in the literatures. In this work, the NaHTi3O7 films were synthesized over Ti/Si substrates in NaOH alkaline solutions using a hydrothermal-galvanic couple method. The influences of the NaOH concentration, the reaction temperature, and the time on the growth of NaHTi3O7 are discussed. In addition, the hydrothermal method also employed for comparison. The obtained NaHTi3O7 films were soaked in simulated body fluid (SBF) to evaluate the biological activity by growing the apatite on the NaHTi3O7 surface. The NaHTi3O7 films prepared on Ti/Si below 100C by both the hydrothermal-galvanic couple and the hydrothermal methods were confirmed by X-ray diffraction, Raman spectrometer, and X-ray photoelectron spectroscopy. The surface morphology and thickness of obtained NaHTi3O7 films was investigated by field-emission scanning electron microscopy. The NaHTi3O7 films which low crystallinity could be obtained in 4M NaOH solutions at 80C for 2h by both the hydrothermal-galvanic couple and the hydrothermal methods. The thickness of obtained NaHTi3O7 films was about 350 nm by the hydrothermal-galvanic couple method, while the films thickness was merely about 200 nm by the hydrothermal method. The results indicate that the hydrothermal-galvanic couple technique could enhance the growth rate of the films. The amorphous NaHTi3O7 films were obtained in the 4M NaOH solution as the reaction temperature was 50-80C. NaHTi3O7 films with low crystallinity could be prepared in 6M NaOH solution at 60C for 2h by using a hydrothermal-galvanic couple method. Nano-network structured NaHTi3O7 films could be synthesized by both the hydrothermal-galvanic couple and the hydrothermal methods. The pore size and the thickness of nano-structured NaHTi3O7 films increased with increasing of the NaOH concentration and the hydrothermal temperature, as well as the reaction time. Because the porous NaHTi3O7 films exhibited lower density, the actual thickness of the films was much higher than the calculated value. It has been found that growth rate of the film synthesized by the hydrothermal-galvanic couple technique was much faster than that prepared by the hydrothermal method, which is due to the voltage drop existing between two electrodes. The voltage drop apparently improves the migration of ions in solutions to enhance the reaction rate. The NaHTi3O7 films with low crystallinity favored for the growth of apatite on the NaHTi3O7 film surface with satisfactory adhesion. Similar results could be observed on the amorphous NaHTi3O7 films favorably after annealed at 600C. This indicates that apatite could grow on the NaHTi3O7 films without any post-treatment, suggesting that the films may have great potentials in biomaterials.
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