臺灣博碩士論文加值系統

本研究將所製備之雙親性嵌段共聚高分子PS-b-PEGMA添加於聚偏氟乙烯鑄膜液中，並使用濕式誘導相分離(LIPS)程序與蒸氣誘導相分離(VIPS)程序成形超過濾與微過濾聚偏二氟乙烯高分子薄膜，並系統性探討其抗生物沾黏特性。第一部分，使用LIPS與VIPS程序所製備之薄膜將以傅里葉轉換紅外光譜、X-射線光電子光譜、電子顯微鏡、原子力顯微鏡進行鑒定與比較。接著先評估以LIPS程序所製備之超過濾薄膜的血液相容性，來確認其是否可適用於血液接觸之相關應用。所製備之薄膜在單一成分之蛋白質溶液(含纖維蛋白原、免疫血清球蛋白、人血清白蛋白)與寡含血小板血漿溶液中，透過酵素免疫分析法來量測其蛋白質吸附量，並以電子顯微鏡與鐳射掃瞄共軛聚焦顯微鏡來觀察各式血球(血小板、紅血球與白血球)於膜面之貼附情形。此外，溶血實驗與凝血時間也被分析與觀察。最後評估以VIPS程序所製備之微過濾薄膜於微藻培養回收之應用，除了同時測試薄膜系統的靜態抗蛋白吸附能力外，在動態條件下的防污能力也是本研究的主要挑戰的討論焦點。結果顯示，可使用LIPS程序成功製備出PEGylated PVDF薄膜系統，在較高的PS-b-PEGMA添加含量可有效改善其血液相容性質，特別是優越於未改質之PVDF薄膜的抗凝血性質。另一方面，以VIPS程序製備之PS-b-PEGMA-4薄膜顯示非常高的通透量與超過97.7%的微藻截留率，指出其具高效率之微藻培養回收能力。最重要的是，以LIPS與VIPS製程所製備之薄膜系統皆呈現優秀的抗污能力，其不可逆污染性質被明顯最小化，且透過去離子水即可簡單將薄膜進行物理清洗來恢復其通量損失。
因此，本研究所製備之PS-b-PEGMA/PVDF薄膜系統同時具有抗污、血液相容性與高液體通透量，可廣泛地提供具有潛力的特定應用，如血液透析和微藻回收。

The present work deals with the preparation of ultrafiltration (UF) and microfiltration (MF) membranes with enhanced fouling resistant ability by using two different methods, liquid- induced phase separation (LIPS) and vapor-induced phase separation (VIPS), after in-situ modification of the PVDF solution using amphiphilic PS-b-PEGMA block copolymers as additive. In the first section, using FT-IR, XPS, SEM, AFM, and contact angle meter, the surface chemistry, morphology, and hydrophilic properties of LIPS along with VIPS membranes were characterized and compared. The next part dealt with the evaluation of the hemocompatibility of UF-LIPS membranes as it was intended for blood-contacting uses. The so called ELISA test was used to assess protein adsorption from single protein solution (FN, γ-globulin, HSA) and PPP solution. Also, blood cells (thrombocytes, erythrocytes, and leukocytes) attachment was investigated by means of SEM and confocal microscopy. Additionally, hemolysis experiments and measurements of plasma-clotting time were carried out. The final portion was dedicated to the assessment of MF-VIPS membranes’ efficiency when applied in microalgae harvesting. Apart from testing the static protein resistance of both membrane systems, the antifouling ability in dynamic conditions which is the primary focus of this study were also challenged. Results demonstrate that PVDF membranes were successfully prepared with a facile approach. PEGylated membranes prepared by LIPS process containing the highest copolymer content showed improved blood compatibility; particularly the anticoagulant property was evidently enhanced compared to the virgin PVDF membranes. On the other hand, PS-b-PEGMA-4 VIPS membranes, exhibited exceptionally high permeate flux and rejection ratio of more than 97.7% that suggests efficient harvesting of microalgae. Most importantly, both LIPS and VIPS membranes exhibited outstanding antifouling capability as irreversible fouling was notably minimized and simple physical cleaning by DI water was able to recover flux loss.
Therefore, PS-b-PEGMA/PVDF membranes with integrated antifouling property, blood compatibility, high permeate flux provided wide variety of specific applications for instance hemodialysis and microalgae recovery.

Table of Contents
摘要 I
Abstract II
Acknowledgements III
Table of Contents IV
Figures Caption VII
Chapter I 1
Chapter II 3
II-1.Fouling in membrane filtration systems 3
II-1.1.Classifications of membrane fouling 3
II-1.2.Classification of antifouling materials 4
II-2.Various approaches in preparing antifouling membranes 6
II-2.1.Grafting 8
II-2.2.Coating methods 9
II-2.3.Polymer blending together with phase inversion process or in situ modification process 11
II-3.Amphiphilic polymer additives for anti-biofouling membranes 12
II-4.Industrial relevance of membranes 15
II-4.1.Membranes for applications in water and waste water 17
II-4.2.Membranes for medical applications 21
II-4.3.Membranes in microalgae harvesting 25
II-5.Conclusions and importance of the study 29
Chapter III 31
III-1.Materials 31
III-2.Preparation and Purification of PS-b-PEGMA Copolymer 32
III-3.Characterization of PS-b-PEGMA Copolymer 33
III-4.Preparation of casting solutions 35
III-4.1.Preparation of solutions for membranes prepared by LIPS process 35
III-4.2.Preparation of solutions for membranes prepared by VIPS process 35
III-5.Preparation of PEGylated PVDF membranes 36
III-5.1.Preparation of PEGylated PVDF membranes by LIPS process 36
III-5.2.Preparation of PEGylated PVDF membranes by VIPS process 37
III-6.Physico-chemical characterization of PEGylated membranes 38
III-6.1.Chemical characterization of modified membranes 38
III-6.2.Physical characterization of modified membranes 39
III-6.3.Mechanical properties of modified membranes 40
III-7.Anti-biofouling capability of PEGylated PVDF membranes in relation to its hydrophilic properties 40
III-7.1.Hydrophilic properties of PEGylated PVDF membranes 40
III-7.2.Resistance to protein adhesion 41
III-7.3.Resistance to bacterial attachment 42
III-8.Hemocompatibility of PS-b-PEGMA/PVDF membranes 42
III-8.1.Adsorption of fibrinogen γ-globulin and human serum albumin onto virgin and PEGylated PVDF membranes 42
III-8.2.Adsorption of platelet poor plasma onto virgin and PEGylated PVDF membranes 43
III-8.3.Attachment of blood cells onto virgin and PEGylated PVDF membranes 44
III-8.4.Evaluation of hemolytic activity after blood contact with virgin and PEGylated PVDF membranes 45
III.8.5.Evaluation of blood clotting time after blood contact with virgin and PEGylated PVDF membranes 46
III-9.Anti-biofouling properties of PEGylated PVDF membranes in dynamic conditions 47
III-9.1.Assessment of the resistance to plasma protein fouling during filtration of membranes prepared by LIPS 47
III-9.2.Assessment of the resistance to fouling during protein filtration of membranes prepared by LIPS 49
III-9.3.Assessment of the resistance to fouling during microalgae filtration of membranes prepared by VIPS 49
Chapter IV 51
IV-1.Physico-chemical characterization of virgin and PEGylated membranes as prepared by LIPS and VIPS process 51
IV-1.1.Characterization of chemical properties 51
IV-1.2.Characterization of physical properties 54
IV-2.Anti-biofouling capability of PEGylated PVDF membranes in relation to its hydrophilic properties 58
IV-2.1.Evaluation of hydrophilic properties of membranes 58
IV-2.2.Evaluation on the resistance of membranes to protein attachment 59
IV-2.3.Evaluation on the resistance of membranes to bacterial attachment 61
IV-3.Evaluation of hemocompatibility of virgin and PEGylated membranes as prepared by LIPS method 62
IV-3.1.Analysis of results from single protein tests and protein-in-PPP tests 62
IV-3.2. Analysis of the resistance of PEGylated membranes to blood cells adhesion 65
IV-3.3. Analysis of the effect of PS-b-PEGMA copolymer to PVDF membranes hemolysis and anti-coagulant activity 69
IV-3.4.Analysis of the effect of PS-b-PEGMA copolymer in the dynamic anti-fouling behavior of membranes 71
IV-4.Evaluation of antifouling properties in dynamic conditions of virgin and PEGylated membranes as prepared by VIPS method 75
IV.4.1.Assessment of the resistance of membranes to biofouling during BSA filtration 75
IV.4.2.Assessment of the resistance of membranes to biofouling during microalgae filtration 79
Chapter V 84
References 87
Figures Caption
Figure 1.Stages of biofilm formation as redrawn from [16] 4
Figure 2.Schematic representation of various methods in preparing antifouling membranes as redrawn from [20] and [24] 7
Figure 3.Schematic illustrations of bare and coated membranes [29] 11
Figure 4.Chemical structures of amphiphilic copolymers used in various studies. (a) Synthetic route of MF-g-PEGn [31] (b) Transitions of the PDMAEMA into zwitterion by using 1,3-propane sultone and 3-bromopropionic used as reaction agent [32] (c) Chemical structure of poly(VC-co-PEGMA) [34] 13
Figure 5.Schematic representing basic principles involved in membrane separation [45] 17
Figure 6.Main historic developments of membrane oxygenators [60] 24
Figure 7.Schematic presentation of an overall microalgae production, 26
Figure 8.a) 1H NMR spectra and b) chromatogram of PS30-b-PEGMA60 copolymer 34
Figure 9.Schematic of PEGylated PVDF formation 37
Figure 10.Chemical characterization of virgin and modified PVDF membranes. 52
Figure 11.Atom content at the surface of membranes as a function of 54
Figure 12.Summary of SEM and AFM images of virgin and PEGylated PVDF membranes 55
Figure 13.Stress-strain characteristic plots of virgin and PEGylated PVDF membranes as prepared by LIPS and VIPS method 57
Figure 14.Influence of PS-b-PEGMA content on hydration properties of membranes 58
Figure 15.Influence of copolymer content on the resistance of membranes to protein adsorption 59
Figure 16.FT-IR spectra of modified membranes by LIPS 60
Figure 17.Qualitative and quantitative analysis of bacterial attachment using Escherichia coli 62
Figure 18.Evaluation of the resistance of virgin and PEGylated membranes by LIPS method to the adsorption of single proteins including FN, -globulin, and HSA (left panel) and 63
Figure 19.Evaluation of the resistance of PEGylated membranes by LIPS method to platelets, red blood cells, and white blood cells adhesion 66
Figure 20.Quantitative analysis of red blood cells (erythrocytes) [left panel] and white blood cells (leukocytes) [right panel] attachment onto virgin PVDF and PEGylated PVDF membranes 68
Figure 21.Hemolysis of RBC solution (left panel) and plasma clotting time (right panel) in the presence of virgin PVDF and PEGylated PVDF membranes 70
Figure 22.Pure water fluxes and dimensionless fluxes of commercial hydrophobic, commercial hydrophilic and PEGylated PVDF membranes before and after immersion to PPP 72
Figure 23.SEM images of commercial and PEGylated PVDF membranes 75
Figure 24.Pure water fluxes and dimensionless fluxes of commercial hydrophilic, virgin and PEGylated PVDF membranes using BSA solution 76
Figure 25.Summary of the corresponding FRR, DRr, DRir values during 78
Figure 26.Pure water fluxes and dimensionless fluxes of commercial hydrophilic, virgin and PEGylated PVDF membranes using microalgae solution 80
Figure 27.(a) SEM micrographs of virgin and PEGylated PVDF membranes before and after filtration of BSA and microalgae solution.(b) Rejection ratio of commercial, virgin, and PEGylated PVDF membranes 82

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