臺灣博碩士論文加值系統

本研究目的在探討不同基材表面型態對電漿聚合層結構之影響，實驗以濕式相轉換法，藉由調整成膜路徑，製備出具有三種不同表面型態(緻密皮層、多孔皮層及無皮層)之聚苯醚碸(Poly(ether sulfone), PES)基材膜。並以高週波電漿輔助化學氣相沈積反應系統(Radio Frequency-Plasma Enhanced Chemical Vapor Deposition, RF-PECVD)，進行乙炔氣體電漿聚合反應，沈積具有高均勻性及良好基板附著性之電漿披覆層，以製備出具高透過量之非對稱膜材。同時利用掃描式電子顯微鏡(Scanning Electron Microscopy, SEM)觀測薄膜經電漿聚合之結構型態變化，並結合正子湮滅光譜(Positron Annihilation Spectroscopy, PAS)量測技術，探討電漿複合膜不同層間奈米結構之變化，釐清基材膜表面型態對電漿聚合層物理結構之影響。
由水蒸氣透過測試結果可發現，在相似厚度之聚合層條件下，不同表面型態之基材膜會影響電漿複合膜的透過性質。當基材膜表面為蕾絲狀無皮層結構(T3)時，可製得具低透過阻力之電漿沈積層。在電漿參數(電漿功率、沈積時間、乙炔進料流量及氬氣添加)對不同表面型態基材膜之電漿聚合層結構型態影響之探討中，具不同表面型態之基材膜，經相同電漿聚合反應後，可製得具相似厚度之聚合層；並且隨電漿功率、進料氣體流量、沈積時間之改變，其聚合層沈積速率亦具有相似之變化趨勢。並且發現當基材膜表面型態為不連續面，有機會製備出類似柱狀結構之沈積層，但隨著沈積層厚度之增加，結構呈現類似柱狀之情形會漸漸轉為不明顯。
藉由正子湮滅光譜技術探討複合膜微結構，並經由VEPFIT軟體分析不同層間S parameter值之變化。由最佳之擬合結果顯示，當PES基材膜表面為緻密皮層(T1)或多孔皮層(T2)，可於三層結構區分得最佳吻合結果；當PES基材膜表面為蕾絲狀結構(T3)，則以四層結構區分得最佳吻合結果。T1及T2基材膜製得具三層結構之電漿複合膜分別為(I)乙炔電漿聚合層、(III)過渡層及(IV)PES基材膜；然而，對於T3基材膜，因電漿聚合反應中，基材膜面孔洞受電漿聚合物填充之效應，造成過渡層前期產生另一層由乙炔電漿聚合物與PES基材高分子共存之混合層(II)。因此更明確地說明基材膜表面型態對電漿沈積層內部結構之影響，特別在過渡層區。

The purpose of this study is to investigate the effect of the substrate surface morphology on the physical structure of plasma-polymerized films. The wet-phase inversion method was used in fabricating the substrate, and by means of changing the membrane formation path, poly(ether sulfone) (PES) substrates with three different surface types (dense skin layer, porous skin layer, and skin-free layer) were formed. Radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD) was the technique applied to conduct the acetylene gas plasma polymerization to deposit plasma-polymerized layer on a substrate with a high homogeneity and good adhesion properties, resulting in the preparation of an asymmetric membrane with a high flux. Scanning electron microscopy (SEM) was used to observe the change in the structure of the plasma-polymerized membrane, and it was combined with the positron annihilation spectroscopy (PAS) technique to investigate the change in the nano-structure of the different layers of the plasma-polymerized composite membrane and to clarify the effect of the substrate surface morphology on the plasma-polymerized layer physical composition.
It can be found from the water vapor permeation results that at similar deposited layer thicknesses, different substrate surface morphologies influenced the characteristic permeation rate in the plasma-polymerized composite membrane. With a substrate surface with a lacy-like skin-free structure, a plasma-polymerized layer with a low permeation resistance could be obtained. On investigating the effect of plasma parameters (plasma power, deposition time, acetylene gas feed flow rate, and argon gas amount) on the plasma-polymerized layer structure of different substrate surface morphologies, substrates with different surface morphologies underwent the same change after the plasma polymerization reaction and their polymerized layer deposits had similar thicknesses; changes in the plasma power, feed gas flow rate, and deposition time produced similar trends of changes in polymer layer deposition rates. When the substrate surface morphology was discontinuous, there was a probability to produce a deposited layer with a pillar-like structure; however, with increasing deposited layer thickness, the pillar-like structure would gradually become not obvious.
The composite membrane microstructure was investigated further by means of the positron annihilation spectroscopy technique. Based on the VEPFIT software analysis, the change in S parameter values for different layers was shown from best fittings, and with a PES substrate surface with a dense skin layer (T1) or a porous skin layer, a three-layer model produced best fitting results; with a PES substrate surface with a lacy-like structure (T3), a four-layer model gave best fitting results. The structures of T1 and T2 plasma-polymerized composite membranes had three layers: (I) acetylene plasma-polymerized layer, (III) transition layer, and (IV) PES substrate; however, the T3 substrate whose pores were filled with a polymer due to the plasma polymerization reaction had additional pre-transition layer formed by acetylene plasma polymer and PES polymer coexisting in a mixed layer (II). These results explicitly explain the substrate surface morphology influence on the internal structure of the plasma-polymerized deposited layer, especially in the transition layer region.

目錄
中文摘要 I
英文摘要 III
致謝 V
圖目錄 X
表目錄 XX
第一章 緒論 1
1-1研究緣起 1
1-2 研究動機與目的 3
第二章 原理與文獻回顧 8
2-1 薄膜製備方法 8
2-1-1 濕式相分離法(Wet phase separation) 8
2-1-2 水蒸氣誘導式相分離(Vapor induced phase separation, VIPS) 9
2-1-3 乾式相分離法(Precipitation by solvent evaporation) 9
2-1-4 乾/濕式製程(Dry/wet process) 10
2-2 非溶劑誘導相分離成膜 10
2-2-1 熱力學 10
2-2-2 動力學 12
2-2-2.1 質傳動力學 12
2-2-2.2 合併成長動力學 15
2-3 電漿簡介 17
2-3-1 電漿原理 17
2-3-2 電漿基本氣相反應 18
2-3-3 電漿聚合理論 22
2-3-4 高分子材料表面之電漿改質 24
2-4 正子湮滅光譜 (Positron annihilation spectroscopy, PAS) 分析技術 26
2-4-1 正子湮滅時間(Positron annihilation lifetime, PAL)分析儀 27
2-4-2 可變單一能量慢束正子束(Variable monoenergy slow positron beam, VMSPB)分析儀 28
2-4-2.1 都卜勒展寬能量光譜(Doppler-broadened energy spectrum, DBES) 28
2-4-2.2 正子湮滅時間光譜（Positron annihilation lifetime spectroscopy, PALS） 31
2-4-3 文獻回顧 31
第三章 實驗 34
3-1實驗藥品 34
3-2實驗儀器 35
3-3實驗方法 36
3-3-1高分子溶液配製 36
3-3-2 鑄膜液黏度量測 36
3-3-3光穿透實驗 36
3-3-4薄膜製備 38
3-3-5電漿聚合法製備複合膜 39
3-3-6 蒸氣透過測試 40
3-4 儀器原理 42
3-4-1掃描式電子顯微鏡 42
3-4-2 可變單一能量慢速正子束 (Variable monoenergy slow positron beam, VMSPB)分析儀 43
第四章 結果與討論 44
4-1 PES基材膜之製備 44
4-1-1 高分子濃度對薄膜結構之影響 44
4-1-2 凝聚劑對薄膜結構之影響 46
4-1-3 溶劑對薄膜結構之影響 49
4-2 複合膜結構型態對其水蒸氣透過測試之影響 55
4-3 複合膜微結構之探討 58
4-3-1 電漿功率對乙炔電漿聚合層沈積速率及複合膜結構型態之影響 59
4-3-2 沈積時間對乙炔電漿聚合層沈積速率及複合膜結構型態之影響 63
4-3-3 乙炔進料氣體組成對聚合層沈積速率及複合膜結構型態之影響 69
4-3-4 氬氣電漿蝕刻效應對電漿聚合層沈積速率與複合膜結構型態之影響 74
4-4 正子煙滅光譜技術探討複合膜微結構 83
4-4-1 電漿功率對複合膜內部微結構之影響 83
4-4-2 沈積時間對複合膜內部微結構之影響 92
4-5 基材膜表面型態對電漿沈積層成長機制影響之探討 98
第五章 結論 100
參考文獻 101
作者自述 106

圖目錄
第一章
Fig. 1-1 Schematic representation of various membrane cross-sectional morphologies. 2
Fig. 1-2 Schematic representation of the composite membrane and the corresponding electrical circuit analogue.[3] 3
Fig. 1-3 Schematic representation of the different type composite membrane: (A)with skin layer, (B)skin-free. 3
Fig. 1-4 SEM images of the CA support structures with (A) skin-layer and (B) skin-free layer. 5
Fig. 1-5 The cross-section SEM morphologies (x10 k)of polyamide thin-film composite membranes prepared with different surface morphologies of CA support membrane. (A) PA/Skin CA composite membrane and (B) PA/Skin-free CA composite membrane. 5
Fig. 1-6 Schematic drawing of the plasma-polymerized SiOxCyHz/MCE composite membranes.[4] 7

第二章
Fig. 2-1 Schematic representation of a ternary phase diagram of polymer/solvent/ nonsolvent. 11
Fig. 2-2 Polymer rich phase (black) and polymer lean phase (white).[1] (І, VI)Dense structure; (II)Sponge structure; (III)Bi-continuous or lacy structure; (IV)Nodules. 12
Fig. 2-3 Schematic representation of a casting file/coagulation interface. 13
Fig. 2-4 Schematic representation of different coagulation paths. 13
Fig. 2-5 Ternary phase diagram nonsolvent/solvent/polymer system.[16] 14
Fig. 2-6 Schematic diagrams showing the evolution of local morphologies for two phase-separation mechanisms.[17] 16
Fig. 2-7 Schematic diagram of reactions occurred in a plasma reactor. 22
Fig. 2-8 Schematic of structures possible by plasma treatment.[23] 24
Fig. 2-9 Mean stopping distance (a) as a function of positron incident energy and stopping profiles and (b) for positron as a function of mean depth.[35] 27
Fig. 2-10 Normalized positron annihilation lifetime (PAL). 28
Fig. 2-11 A Doppler broadening energy spectrum (DBES) (a) definition of R (3r/2rarea ratio) parameters from DBES and (b) definitions of S &W parameter, S is ratio of total counts from central region, W is the ratio of wing region, to the total 511 keV annihilation counts. 30

第三章
Fig. 3-1 Schematic representation of the light transmission experiment. 37
Fig. 3-2 Sketch of membranes prepared by nonsolvent induced phase separation process. 38
Fig. 3-3 The schematic diagram of the plasma reactor system. 39
Fig. 3-4 (a) Schematic diagram of permeation cell；(b) Tentative mechanism of vapor permeation. 40
Fig. 3-5 The schematic diagram of vapor permeation apparatus. 41
Fig. 3-6 Variable monoenergy slow positron beam. A: 50 mCi 22Na positron source, B: W-mesh moderator, C: magnetic field (70 G) coils, D: ExB filter, E: positron accelerator, F: correcting magnets, G: gas inlet, H: positron lifetime detector (MCP) for PAL, I: turbo molecular pump, J: samples, K: sample manipulator, L: ion pump, M: Ge solid state detector, N: lifetime detector (BaF2). 43
第四章
Fig. 4-1 The surface morphologies (x20k) of the PES membranes formed by directly immersing different concentration PES/NMP casting films in water: (A) 15 wt% (B) 20 wt% (C) 25 wt %. 45
Fig. 4-2 The cross-section morphologies of the PES membranes formed by directly immersing different concentration PES/NMP casting films in water: (A), (a) 15 wt%; (B), (b) 20 wt%; (C), (c) 25 wt %. (A)~(C) total, x500; (a)~(c) top region, x50k. 45
Fig. 4-3 The SEM images of the PES membranes formed by directly immersing 20 wt% PES/NMP casting films in (A), (a) water; (B), (b) ethanol; (C), (c) n-propanol. (A)~(C) surface, x10k; (a)~(c) cross-section, x500. 47
Fig. 4-4 Light transmission curves of 20 wt% PES/NMP casting film immersed into various coagulations. 49
Fig. 4-5 The SEM images of the PES membranes formed by directly immersing (A), (a) 20 wt% PES/NMP; (B), (b) 20 wt% PES/2P casting films in ethanol bath. (A), (B) surface, x20k; (a), (B) cross-section, x500. 51
Fig. 4-6 Light transmission curves of 20 wt% PES/NMP and 20 wt% PES/2P casting films immersed into ethanol. 52
Fig. 4-7 The SEM images of the PES membranes formed by directly immersing different concentration PES/2P casting films in ethanol: (A), (a) 10 wt%; (B), (b) 15 wt%; (C), (c) 20 wt %. (A)~(C)surface, x20k; (a)~(c) cross-section, x500. 54
Fig. 4-8 The SEM morphologies of the different PES surface morphologies support membrane; PES support membrane with dense skin-layer (T1): (A), (a), porous skin-layer (T2): (B), (b), and skin-free layer(T3): (C), (c). (A)~(C) surface, x20k; (a)~(c) cross-section, x50k. 55
Fig. 4-9 The SEM morphologies of the plasma-polymerized films with different PES surface morphologies support membrane; PES support membrane with dense skin-layer (T1): (A), (a), porous skin-layer (T2): (B), (b), and skin-free layer(T3): (C), (c). (A)~(C) surface, x20k; (a)~(c) cross-section, x50k. (Plasma polymerization conditions: power of 200 W; system pressure of 0.2 torr; C2H2 flow rate of 20 sccm; deposition time of 6 min) 56
Fig. 4-10 Effect of plasma power on the deposition rate of the C2H2 plasma-polymerized film on three kinds of PES surface morphologies, dense skin-layer(T1), porous skin-layer(T2) and skin-free layer(T3). (Plasma polymerization conditions: system pressure of 0.2 torr; C2H2 flow rate of 20 sccm; deposition time of 15 min) 59
Fig. 4-11 The surface morphologies (x20k) of (a) PES and the plasma-polymerized films prepared at plasma power of (b) 60 W, (c) 120 W, (d) 200 W, and (e) 300 W. T1, T2, and T3 represent PES membrane with dense skin-layer, porous skin-layer, and skin-free layer, respectively. (Plasma polymerization conditions: system pressure of 0.2 torr; C2H2 flow rate of 20 sccm; deposition time of 15 min) 61
Fig. 4-12 The cross-section morphologies (x50k) of (a) PES and the plasma-polymerized films prepared at plasma power of (b) 60 W (c) 120 W (d) 200 W (e) 300 W. T1, T2, and T3 represent PES membrane with dense skin-layer, porous skin-layer, and skin-free layer, respectively. (Plasma polymerization conditions: system pressure of 0.2 torr; C2H2 flow rate of 20 sccm; deposition time of 15 min) 62
Fig. 4-13 Relationship between deposition time and deposition rate of the C2H2 plasma-polymerized film on three kinds of PES surface morphologies, dense skin-layer(T1), porous skin-layer(T2) and skin-free layer(T3). (Plasma polymerization conditions: system pressure of 0.2 torr; C2H2 flow rate of 20 sccm; power of 200 W) 63
Fig. 4-14 The surface morphologies (x20k) of (a) PES and the plasma-polymerized films prepared by the deposition time of (b) 1 min, (c) 3 min, (d) 6 min, (e) 10 min, and (f) 15 min. T1, T2, and T3 represent PES membrane with dense skin-layer, porous skin-layer, and skin-free layer, respectively. (Plasma polymerization conditions: system pressure of 0.2 torr; C2H2 flow rate of 20 sccm; power of 200 W) 65
Fig. 4-15 The cross-section morphologies (x50k) of (a) PES and the plasma-polymerized films prepared by the deposition time of (b) 1 min, (c) 3 min, (d) 6 min, (e) 10 min, and (f) 15 min. T1, T2, and T3 represent PES membrane with dense skin-layer, porous skin-layer, and skin-free layer, respectively. (Plasma polymerization conditions: system pressure of 0.2 torr; C2H2 flow rate of 20 sccm; power of 200 W) 67
Fig. 4-16 Effect of C2H2 flow rate on the deposition rate of the C2H2 plasma-polymerized film on three kinds of PES surface morphologies, dense skin-layer (T1), porous skin-layer(T2), and skin-free layer(T3). (Plasma polymerization conditions: system pressure of 0.2 torr; power of 200W; deposition time of 15min) 69
Fig. 4-17 The surface morphologies of (a) PES and the plasma-polymerized films prepared in the C2H2 flow rate of (b) 3 sccm, (c) 5 sccm, (d) 10 sccm, (e) 15 sccm, and (f) 20 sccm. T1, T2, and T3 represent PES membrane with dense skin-layer, porous skin-layer, and skin-free layer, respectively. (x20k) (Plasma polymerization conditions: system pressure of 0.2 torr; power of 200 W; deposition time of 15 min) 70
Fig. 4-18 The cross-section morphologies of (a) PES and the plasma-polymerized films prepared in the C2H2 flow rate of (b) 3 sccm, (c) 5 sccm, (d) 10 sccm, (e) 15 sccm, and (f) 20 sccm.T1, T2, and T3 represent PES membrane with dense skin-layer, porous skin-layer, and skin-free layer, respectively. (x50k) (Plasma polymerization conditions: system pressure of 0.2 torr; power of 200 W; deposition time of 15 min) 72
Fig. 4-19 Effect of Ar content in the feed gas on the deposition rate of the C2H2/Ar plasma polymerized film on three kinds of PES surface morphologies, dense skin-layer (T1), porous skin-layer(T2), and skin-free layer(T3). (Plasma polymerization conditions: system pressure of 0.2 torr; power of 200W; total flow rate of 20 sccm; deposition time of 15min) 74
Fig. 4-20 The deposition mechanical model for a-C:H films.[42] 75
Fig. 4-21 The surface morphologies (x20k) of (a) PES and the plasma-polymerized films prepared in Ar content of (b) 90 vol%, (c) 85 vol%, (d) 75 vol%, (e) 50 vol%, (f) 25 vol%, (g) 10 vol%, and (h) 0 vol%. T1, T2, and T3 represent PES membrane with dense skin-layer, porous skin-layer, and skin-free layer, respectively. (C2H2/Ar plasma polymerization conditions: system pressure of 0.2 torr; power of 200W; total flow rate of 20 sccm; deposition time of 15 min) 77
Fig. 4-22 The cross-section morphologies (x50k) of (a) PES and the plasma-polymerized films prepared in Ar content of (b) 90 vol%, (c) 85 vol%, (d) 75 vol%, (e) 50 vol%, (f) 25 vol%, (g) 10 vol%, and (h) 0 vol%. T1, T2, and T3 represent PES membrane with dense skin-layer, porous skin-layer, and skin-free layer, respectively. (C2H2/Ar plasma polymerization conditions: system pressure of 0.2 torr; power of 200W; total gas flow rate of 20 sccm; deposition time of 15 min) 79
Fig. 4-23 The SEM morphologies of (A), (a) Pristine PES(T1) membrane with dense skin-layer; (B), (b) After Ar-plasma treated PES(T1) membrane; and (C),(c) Pristine PES(T3) membrane with skin-free layer. (A)~(C) surface, x20k; (a)~(c) cross-section, x50k. 81
Fig. 4-24 The SEM morphologies of the plasma-polymerized composite membranes with different morphological substrates: (A), (a) Pristine PES(T1) membrane with dense skin-layer; (B), (b) After Ar-plasma treated PES(T1) membrane; and (C),(c) Pristine PES(T3) membrane with skin-free layer. (A)~(C) surface, x20k; (a)~(c) cross-section, x50k.(C2H2-plasma polymerization conditions: system pressure of 0.2 torr; power of 200W; gas flow rate of 20 sccm; deposition time of 15 min) 82
Fig. 4-25 The SEM images of the plasma-polymerized films with different PES surface morphologies support membrane; PES support membrane with dense skin-layer (T1): (A), (a), porous skin-layer (T2): (B), (b), and skin-free layer (T3): (C), (c). (A)~(C) surface, x20k; (a)~(c) cross-section, x50k. (C2H2-plasma polymerization conditions: power of 60 W; system pressure of 0.2 torr; gas flow rate of 20 sccm; deposition time of 15 min) 84
Fig. 4-26 The SEM images of the plasma polymerized films with different PES surface morphologies support membrane; PES support membrane with dense skin-layer (T1): (A), (a), porous skin-layer (T2): (B), (b), and skin-free layer (T3): (C), (c). (A)~(C) surface, x20k; (a)~(c) cross-section, x50k. (C2H2- plasma polymerization conditions: power of 200 W; system pressure of 0.2 torr; gas flow rate of 20 sccm; deposition time of 15 min) 84
Fig. 4-27 S parameter vs. positron energy (depth) in the plasma polymerized film on different surface morphologies PES membrane at different plasma power. (Plasma polymerization conditions: deposition time of 15 min; C2H2 flow rate of 20 sccm; system pressure of 0.2 torr) 85
Fig. 4-28 Schematic diagram of layer depth structure obtained by using VEPFIT program analysis of S parameter data from DBES in plasma-polymerized composite membranes. The plasma-polymerized film on the different PES surface morphologies prepared at different power of (a) 60 W and (b) 200 W. (Plasma polymerization conditions: deposition time of 15 min; C2H2 flow rate of 20 sccm; system pressure of 0.2 torr) 88
Fig. 4-29 The SEM images of the plasma-polymerized films. PES support membrane with dense skin-layer (T1): (A), (a), (B), (b); skin-free layer(T3): (C), (c), (D), (d). (A)~(D) surface, x20k; (a)~(d) cross-section, x50k. (Plasma polymerization conditions: deposition time of 1 min; C2H2 flow rate of 20 sccm; system pressure of 0.2 torr) 89
Fig. 4-30 R parameters vs. positron energy (depth) in the plasma polymerized film on the different surface morphologies PES membrane. (Plasma polymerization conditions: deposition time of 15 min; C2H2 flow rate of 20 sccm; system pressure of 0.2 torr) 90
Fig. 4-31 R parameter vs. positron energy (depth) in the plasma polymerized film on the different surface morphologies PES membrane. (Plasma polymerization conditions: deposition time of 15 min; C2H2 flow rate of 20 sccm; system pressure of 0.2 torr) 91
Fig. 4-32 S parameter vs. positron energy (depth) in the plasma-polymerized film on the different PES surface morphologies prepared by different deposition time of (a) 6 min and (b) 15 min. (Plasma polymerization conditions: power of 200 W; C2H2 flow rate of 20 sccm; system pressure of 0.2 torr) 93
Fig. 4-33 Schematic diagram of layer depth structure obtained by using VEPFIT program analysis of S parameter data from DBES in plasma-polymerized composite membranes. The plasma-polymerized film on the different PES surface morphologies prepared by different deposition time of (a) 6 min and (b) 15 min. (Plasma polymerization conditions: power of 200 W; C2H2 flow rate of 20 sccm; system pressure of 0.2 torr) 94
Fig. 4-34 R parameter vs. positron energy (depth) in the plasma-polymerized film on the different PES surface morphologies prepared by different deposition time. The diagram (b) is the detailed enlargement of diagram (a). (Plasma polymerization conditions: power of 200 W; C2H2 flow rate of 20 sccm; system pressure of 0.2 torr) 97
Fig. 4-35 Schematic representation of different stages of plasma polymer growth on porous PES membrane. 99
Fig. 4-36 Schematic representation of different morphologies of plasma-polymerized films on PES membrane with dense skin-layer(T1), porous skin-layer(T2), and skin-free layer(T3). 99

表目錄
第一章
Table 1-1 Effect of support layer structure on pervaporation performance of PA/CA composite membranes 5

第二章
Table 2-1 Comparison of plasma polymerization with conventional polymerization 23

第四章
Table 4-1 Solubility parameter of each component 48
Table 4-2 Solubility parameter differences between polymer and solvent 51
Table 4-3 Viscosity of different polymer solutiona) 51
Table 4-4 Viscosity of different concentration polymer solutiona) 53
Table 4-5 Effect of the morphology of plasma composite membrane on the water vapor permeation at 25℃ 56
Table 4-6 Effect of plasma power on the thickness of plasma-polymerized films 60
Table 4-7 Effect of C2H2 flow rate on the thickness of plasma-polymerized films 73

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