臺灣博碩士論文加值系統

奈米纖維由於其高比表面積與表面官能基之修飾等優點，因此有利於進行廣泛的實驗研究與探討。而於本論文中，主要利用溶膠凝膠法與靜電紡絲技術以製備二氧化鈦(TiO2)奈米纖維，並利用L-929老鼠成纖細胞進行細胞貼附實驗以對於TiO2纖維進行生物相容性之研究。
由於前驅物叔丁醇鈦(Titanium butoxide; TBT)之物理性質不利於以靜電紡絲技術製備奈米纖維，因此實驗中以聚(2-乙基-2-唑?) (Poly(2-ethyl-2-oxazoline); PEOXA)做為高分子載體與TBT均勻混合後以靜電紡絲製備Ti(OR)n-PEOXA複合纖維，分別以改變混合比例 (15:1、10:1、7.5:1、6:1)、工作電壓 (10、15、20、27 kV)、以及工作距離 (5、10、15 cm)等實驗參數下，分析纖維之結構特性與直徑分布，並以鍛燒技術於300至700度之條件下製備TiO2纖維。其纖維直徑分布為112至173 nm之間，實驗結果中顯示，纖維結構、直徑大小以及結晶狀態均受到鍛燒溫度的影響而有所改變。
由於TiO2纖維之結構脆弱，因此於本實驗以聚己內酯(polycarpolactone; PCL)以旋轉塗佈技術增加該纖維之機械強度，分別以傅立葉紅外線光譜儀(FT-IR)、電子顯微鏡(SEM)、熱重分析儀(TGA)、拉曼光譜儀、X-射線繞射分析(XRD)、表面積(BET)以及細胞貼附對於(15:1)-Ti(OR)n-PEOXA、TiO2以及PCL-c-TiO2 纖維進行分析實驗。

Nano-architecture materials such as nanofibers are extensively studied due to their unique characteristics such as large surface area to volume ratio and flexibility in surface functionalization. In this study, a facile and versatile technique for the fabrication of TiO2 nanofibers by the combination of sol-gel and electrospinning techniques was proposed. The biocompatibility study of TiO2 fibers were also evaluated by culturing L-929 fibroblast cells.
Due to the physical properties of the used precursor, titanium (IV) butoxide (TBT), that was not able to be electrospun directly to generate TiO2 fibers. Poly(2-ethyl-2-oxazoline) was used as a template, followed by mixing with TBT, to proceed the sol-gel process through electrospinning for the preparation of Ti(OR)n-PEOXA fibers. The electrospinning parameters included the ratio between TBT and polymer (15:1, 10:1, 7.5:1 and 6:1), applied voltages (10, 15, 20 and 27 kV), and tip-to-collector distances (5, 10, and 15 cm) were investigated in relation with morphological characteristics and the mean diameter of the fibers. Subsequently, the remitted fibers were calcinated at 300 to 700 C in order to obtain pure TiO2 fibers (TiO2).
The as-prepared TiO2 fibers revealed average diameter ranging from 112 to 173 nm with random orientation. The results indicated that the calcination temperature significantly affected the fibers morphology, diameter size and crystalline phases. However, calcinated TiO2 fibers were fragile therefore PCL (polycarpolactone) was spin-coated on one side of TiO2 fibers in order to improve the mechanical strength. The (15:1)-Ti(OR)n-PEOXA, TiO2, and PCL-c-TiO2 fibers were characterized by fourier transformed infrared (FTIR), field emission scanning electron micrsocopy (FE-SEM), thermo-gravimetric analysis (TGA), Raman spectroscopy, and X-ray diffraction (XRD), BET surface area and interactions with mammalian cells.

Abstract i
摘要 ii
Acknowledgement iii
Content ii
List of figures iv
List of tables vii
Equation list viii
Chapter 1. Introduction 1
1.1. Overview 1
1.2. Motivation 3
Chapter 2. Literature Review 4
2.1 Nanofibers 4
2.2 Electrospinning 8
2.2.1. Solution parameter 9
2.2.2. Process parameter 12
2.2.3. Ambient parameter 14
2.3 Polymeric fibers 14
2.4 Inorganic fibers 16
2.4.1 Titanium dioxide fibers (TiO2 fibers) 18
2.4.2 Physical and chemical properties of TiO2 25
2.4.3 Potential TiO2 as biomaterials 28
Chapter 3. Experimental 31
3.1. Chemicals 31
3.1.1. Electrospinning solution 31
3.1.2. Cell culture solution 32
3.2. Instruments 34
3.3. Preparation of Ti(OR)n-PEOXA and TiO2 fibers 34
3.4. Preparation of TiO2 fibers coated polymer 35
3.5. Cell experiment 36
3.5.1. Cell line 36
3.5.2. Preparation of -MEM medium 36
3.5.3. Preparation of phosphate buffered saline (PBS) 36
3.5.4. Harvesting of L-929 fibroblast cells 36
3.5.5. In vitro cell culture 37
3.5.6. Cell counting 37
3.5.7. Cell viability assays 38
3.5.8. Cell morphology 39
3.6. Characterization techniques 39
3.6.1. Electrospinning unit 39
3.6.2. Fourier Transform Infrared Spectrometer – Attenuated Total Reflectance (FTIR-ATR) 39
3.6.3. Field Emission Scanning Electron Microscopy (FE-SEM) 40
3.6.4. Thermogravimetric Analysis (TG-DTA) 40
3.6.5. X-ray Diffraction (XRD) 40
3.6.6. Raman Spectrometry 40
3.6.7. ELISA reader 41
3.6.8. Determination of average diameter of fibers by Image J software 42
3.6.9. Statistical analysis 42
Chapter 4. Results and Discussion 43
4.1. Preparation of Ti(OR)n-PEOXA and TiO2 fibers 43
4.2. Electrospinning Ti(OR)n-PEOXA fibers 44
4.2.1. Effects of solution concentration 44
4.2.2. Effects of applied voltages 46
4.2.3. Effects of tip to collector distance 48
4.2.4. Optimized parameters for electrospinning Ti(OR)n-PEOXA fibers 48
4.3. Characterizations of Ti(OR)n-PEOXA fibers 49
4.4. Characterizations of TiO2 fibers 51
4.4.1. Surface morphology of TiO2 fibers by FESEM 51
4.4.2. Surface functionality of TiO2 by FTIR-ATR 54
4.4.3. Crystals orientation of Ti(OR)n-PEOXA and TiO2 by Raman Spectroscopy 55
4.4.4. Crystallinity of TiO2 by XRD 56
4.4.5. Determination of specific surface area by BET 59
4.5. Modification of TiO2 fibers with polymer 60
4.5.1. Optimization of polymer film/TiO2 (polymer-c-TiO2) 60
4.6. Cell responses on TiO2 and PCL-c-TiO2 62
4.7. Cell morphology 66
Chapter 5. Conclusions 69
Appendix 71
References 74
Questions and answer (Q&A) 81

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