本研究主要探討聚偏二氟乙烯(PVDF)多孔型薄膜之製備及改質。首先利用浸漬-沈澱法製備聚偏二氟乙烯薄膜，溶劑為磷酸三乙酯(TEP)，非溶劑為水；藉由改變製膜液與沈澱槽之組成，製作出一系列不同孔隙結構之薄膜，並以SEM、DSC、XRD、Contact Angle等來作膜材物性分析。其次，利用電漿聚合法將聚甲基丙烯酯環氧丙烷(PGMA)接枝在各薄膜上，並探討電漿處理時間、電漿功率、薄膜孔隙結構、反應溫度、反應濃度等參數對接枝量的影響；再利用PGMA的環氧基分別與離胺酸及己二胺上的胺基反應形成共價鍵，而將此二者固定於薄膜表面，同樣地對各反應參數(例如反應溫度、反應濃度、pH值等)加以探討，預計本研究所製備之各種不同孔隙結構或化學組成的薄膜將可應用於神經細胞的培養，成為有用的生醫材料。

This research will focus on the investigations of the formation and modification of porous poly(vinylidene fluoride) (PVDF) membranes, and their applications in biomedical technology. First of all, immersion-precipitation method will be adopted to prepare PVDF membranes, for which process triethylphosphate (TEP) and water will be used as the solvent and nonsolvent, respectively. By varying the compositions of the casting dope and the precipitation bath, it is expect that a series of membranes with different porous structures will be formed. SEM, DSC, XRD, and Contact Angle measurement will be employed to characterize these membranes. Then, they will be grafted, on their top surfaces, with a certain amount of poly(glycidyl methacrylate) (PGMA) using the plasma-induced polymerization method. Process parameters, such as plasma treatment time, plasma power, membrane structure, reaction temperature, reactant concentrations, etc., will be investigated to see their effects on the grafting yield. Subsequently, lysine and 1,6-hexanediamine will be immobilize on various membranes by reaction of them with epoxy group of previously grafted PGMA. Similarly, various reaction conditions (e.g., reaction temperature, reactant concentrations, pH, etc.) will be the subjects of studies.

目錄
論文提要內容	I
ABSTRACT	II
目    錄	III
圖  目  錄	IX
表  目  錄	XII
第一章  序  論	1
1-1 前  言	1
1-2 薄膜程序	2
1-3 PVDF薄膜	3
1-4 研究動機與實驗目的	7
第二章  基礎理論	10
2-1 高分子薄膜	10
2-1.1 薄膜之定義	10
2-1.2 薄膜之孔隙結構	12
2-1.3 薄膜製備	15
2-1.3.1 熱誘導式相轉換法(THERMAL INDUCED PHASE SEPARATION; TIPS)	15
2-1.3.2 乾式相轉換法(PRECIPITATION BY SOLVENT EVAPORATION)	15
2-1.3.3 濕式相轉換法(WET-PHASE INVERSION)	16
2-1.3.4 乾/濕式混合製程(DRY/WET PROCESS)	16
2-1.3.5 蒸氣相沉澱法(PRECIPITATION FROM THE VAPOR PHASE)	17
2-1.4 成膜理論	17
2-1.4.1 成膜理論-熱力學	18
2-1.4.2 成膜理論-質傳動力學	21
2-2 電漿基本原理	23
2-2.1 電漿產生方式	25
2-2.2 電漿誘導接枝聚合反應	26
第三章  PVDF薄膜之合成與物性分析	27
3-1 前言	27
3-2 實驗	27
3-2.1 實驗材料	27
3-2.2 實驗儀器	29
3-2.3 實驗方法與步驟	30
3-2.3.1 薄膜的製備	30
3-2.3.2 相圖的製作	31
3-2.3.3 薄膜結構與物性分析	32
3-3 結果與討論	33
3-3.1 WATER-TEP-PVDF三成分系統之相圖	33
3-3.2 薄膜SEM結構分析	34
3-3.3 薄膜成膜速率與孔隙度之量測	42
3-3.4 抗張強度檢測	45
3-3.5 滲透性與水通量檢測	47
3-3.6 接觸角分析	50
3-3.7 DSC測試	51
3-3.8 XRD測試	52
3-4 結論	55
第四章  PGMA/PVDF複合薄膜之合成	56
4-1 前言	56
4-2 實驗	56
4-2.1 實驗材料	56
4-2.2 實驗儀器	58
4-2.3 實驗方法與步驟	59
4-2.3.1 GMA單體除抑制劑	59
4-2.3.2 除氧	59
4-2.3.3 薄膜表面活化	60
4-2.3.4 接枝反應	60
4-2.3.5 定量分析	60
4-2.3.6 複合薄膜之化性分析	61
4-3 結果與討論	62
4-3.1 AR電漿處理後薄膜之整體重量分析	62
4-3.2 AR電漿處理PVDF表面接觸角及自由能變化	64
4-3.3 接枝PGMA薄膜之FTIR-ATR分析	66
4-3.4 接枝PGMA薄膜之1H-NMR分析	68
4-3.5 接枝PGMA薄膜之ESCA分析	69
4-3.6接枝PGMA薄膜之EDS分析	73
4-3.7 接枝PGMA薄膜之SEM結構分析	77
4-3.8 電漿處理條件對薄膜接枝PGMA之影響	80
4-3.8.1 電漿功率對接枝PGMA之影響	80
4-3.8.2 電漿處理時間對接枝PGMA之影響	82
4-3.8.3 單體濃度對接枝PGMA之影響	84
4-3.8.4 反應溫度對接枝PGMA之影響	85
4-3.8.5 薄膜結構對PGMA接枝量之影響	86
4-4 結論	87
第五章  PVDF-G-PGMA薄膜固定離胺酸與己二胺	88
5-1 前言	88
5-2 實驗	89
5-2.1 實驗材料	89
5-2.2 實驗儀器	90
5-2.3 實驗方法與步驟	90
5-2.3.1 固定離胺酸與己二胺	90
5-2.3.2 離胺酸與己二胺定量分析	91
5-3 結果與討論	93
5-3.1 PH值變化對固定離胺酸與己二胺之影響	93
5-3.2 單體濃度對固定離胺酸與己二胺之影響	97
5-3.3 反應溫度對固定離胺酸與己二胺之影響	102
5-3.4 固定離胺酸與己二胺於複合薄膜之FTIR-ATR分析	105
5-3.5 固定離胺酸與己二胺於複合薄膜之接觸角分析	109
5-4 結論	111
第六章  總  結	112
第七章  參考文獻	114

圖目錄
Fig.1-1 Common material for making membranes	4
Fig.1-2 Immobilization of lysine on PVDF membranes	8
Fig.1-3 Immobilization of 1,6-hexanediamine on PVDF membranes	8
Fig.1-4 Epoxy groups hydrolyze to two alcohol groups	8
Fig.2-1 Schematic representation of the cross-sections of various types of membranes	11
Fig.2-2 Cellular sponge like structure in a membrane	13
Fig.2-3 Membrane consisting of spherical particles	13
Fig.2-4 Coexistence of cellular pores and crystalline particles in a membrane	14
Fig.2-5 Macrovoids in a membrane	14
Fig.2-6 Nodule structure in a membrane	14
Fig.2-7 Schematic representation of the isothermal phase behavion of a nonsolvent-solvent-polymer system consisting of a one-phase region (I), a two-phase region (II) and a gel region (III)	20
Fig.2-8 Schematic representation of mass transfer occurring at the membrane/coagulant interface, J1：Flux of coagulant, J2：Flux of solvent	22
Fig.2-9 Schematic representation of coagulation paths correspoing to the cases J2>>J1 (A) and J2<<J1 (B)	22
Fig.2-10 The reaction scheme of plasma-induced polymerization	26
Fig.3-1 Phase diagram of the Water-TEP-PVDF system	34
Fig.3-2 SEM micrographs of a PVDF membrane prepared from the Water/TEP/PVDF system, Bath : Pure water	37
Fig.3-3 SEM micrographs of a PVDF membrane, Bath : 40% TEP	38
Fig.3-4 SEM micrographs of a PVDF membrane, Bath : 50% TEP	39
Fig.3-5 SEM micrographs of a PVDF membrane, Bath : 60% TEP	40
Fig.3-6 SEM micrographs of a PVDF membrane, Bath : 70% TEP	41
Fig.3-7 Precipitation time for PVDF membrane formation	42
Fig.3-8 Thickness of membranes precipitated from with different TEP contents	44
Fig.3-9 Porosity of membranes precipitated from different baths	44
Fig.3-10 Average tensile strength of membranes precipitated from different baths	46
Fig.3-11 Average elongation at break of membranes precipitated from different baths	46
Fig.3-12 Water flux of membranes precipitated from different baths at different pressure	49
Fig.3-13 The contact angles of membranes precipitated from different baths	50
Fig.3-14 DSC themograms of PVDF membranes precipitated from different baths	51
Fig.3-15 XRD diffractograms of PVDF membranes precipitated from different baths	53
Fig.3-16 Deconvolation of XRD patterns of PVDF membranes precipitated from different baths	54
Fig.4-1 Weight loss of RF power at different plasma exposure time	63
Fig.4-2 Weight loss of plasma exposure time at different RF power	63
Fig.4-3 Contact angle of water on plasma treated PVDF surfaces as a function of plasma exposure time and RF power	65
Fig.4-4 Wetting tension of water on plasma treated PVDF surfaces as a function of plasma exposure time and RF power	65
Fig.4-5 FTIR-ATR spectra of GMA monomer, PVDF membrane, and PGMA/PVDF composite membrane	66
Fig.4-6 FTIR-ATR spectra of PGMA/PVDF composite membranes at different grafiting times	67
Fig.4-7 1H-NMR spectra of PVDF membranes	68
Fig.4-8 ESCA spectrum of a PVDF membrane	70
Fig.4-9 ESCA spectrum of PVDF membrane grafted with PGMA	71
Fig.4-10 ESCA spectrum of PVDF membrane grafted with PGMA	72
Fig.4-11 EDS spectrum of a PVDF membrane	74
Fig.4-12 EDS spectrum of PVDF membrane grafted with PGMA	75
Fig.4-13 EDS spectrum of PVDF membrane grafted with PGMA	76
Fig.4-14 SEM of pure PVDF membrane and that grafted with PGMA	78
Fig.4-15 SEM of pure PVDF membrane and that grafted with PGMA	79
Fig.4-16 Effect of plasma power on grafting yield of PGMA	81
Fig.4-17 Effect of reaction time and plasma power on grafting yield of PGMA	81
Fig.4-18 Effect of plasma treatment time on grafting yield of PGMA	83
Fig.4-19 Effect of plasma treatment time on grafting yield of PGMA after reaction for different times	83
Fig.4-20 Effect of GMA concentration on grafting yield of PGMA	84
Fig.4-21 Effect of reaction temperature on grafting yield of PGMA	85
Fig.4-22 Effect of surface morphology on grafting yield of PGMA	86
Fig.5-1 UV spectra of acid orange 7 at different concentrations	92
Fig.5-2 UV absorption calibration curve of acid orange 7	92
Fig.5-3 Reaction between epoxy and amine by nucleophilic substitution	94
Fig.5-4 Titrations of lysine	95
Fig.5-5 Titrations of 1,6-hexanediamine	96
Fig.5-6 Effect of lysine concentration on immobilization yield as determined by weighting method	98
Fig.5-7 Effect of lysine concentration on immobilization yield as determined by UV colorimetry	98
Fig.5-8 FTIR-ATR spectra of lysine/PGMA/PVDF composite membranes immobilized for different times	99
Fig.5-9 FTIR-ATR spectra of lysine/PGMA/PVDF composite membranes immobilized with different lysine concentration	99
Fig.5-10 Effect of 1,6-hexanediamine concentration on immobilization yield as determined by weighting method	100
Fig.5-11 Effect of 1,6-hexanediamine concentration on immobilization yield as determined by UV colorimetry	100
Fig.5-12 FTIR-ATR spectra of 1,6-hexanediamine/PGMA/PVDF composite membranes immobilized for different times	101
Fig.5-13 FTIR-ATR spectra of 1,6-hexanediamine/PGMA/PVDF composite membranes immobilized with different 1,6-hexanediamine concentrations	101
Fig.5-14 Effect of temperature on immobilization yield of lysine	103
Fig.5-15 FTIR-ATR spectra of lysine/PGMA/PVDF composite membranes immobilized at different temperatures	103
Fig.5-16 Effect of temperature on immobilization yield of 1,6-hexanediamine	104
Fig.5-17 FTIR-ATR spectra of 1,6-hexanediamine/PGMA/PVDF composite membranes immobilized at different temperatures	104
Fig.5-18 FTIR-ATR spectra of PVDF membranes	106
Fig.5-19 FTIR-ATR spectra of PVDF membranes	107
Fig.5-20 The contact angles of different composite membranes	110

表目錄
Table 1-1 Membrane processes and the relationship between driving force and phase type	2
Table 1-2 Chemical lesion of PVDF membrane	5
Table 3-1 Porosity of PVDF membranes	43
Table 3-2 Tensile strengths of membranes precipitated from different baths	45
Table 3-3 Wettability of membranes precipitated from different baths	49
Table 3-4 Themal properties and crystallinity of PVDF membranes	52
Table 3-5 Crystal type of PVDF	52
Table 3-6 Crystallinity of PVDF membranes determined by XRD	53
Table 5-1 Typical ranges (v in cm-1)	108
Table 5-2 The contact angles of composite membranes	110

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