By
Franzesca Michelle 11604006
BACHELOR’S DEGREE in
CHEMICAL ENGINEERING - PHARMACEUTICAL ENGINEERING FACULTY OF LIFE SCIENCES AND TECHNOLOGY
SWISS GERMAN UNIVERSITY The Prominence Tower
Jalan Jalur Sutera Barat No. 15, Alam Sutera Tangerang, Banten 15143 - Indonesia
June 2020
Revision after the Thesis Defense on Friday, 17th July 2020
Franzesca Michelle STATEMENT BY THE AUTHOR
I hereby declare that this submission is my own work and to the best of my knowledge, it contains no material previously published or written by another person, nor material which to a substantial extent has been accepted for the award of any other degree or diploma at any educational institution, except where due acknowledgement is made in the thesis.
Franzesca Michelle
_____________________________________________
Student Date
Approved by:
Dr. Dipl. -Ing. Samuel P. Kusumocahyo
_____________________________________________
Thesis Advisor Date
Dr. Dipl. -Ing. Samuel P. Kusumocahyo
_____________________________________________
Dean Date
ABSTRACT
REVIEW ON MODIFIED ULTRAFILTRATION MEMBRANES WITH ANTIBACTERIAL PROPERTIES
By
Franzesca Michelle
Dr. Dipl. -Ing. Samuel P. Kusumocahyo, Advisor
SWISS GERMAN UNIVERSITY
Ultrafiltration technology has long been utilized and largely applied in the pharmaceutical industry, in food and beverage processing, and in treating water because of its excellent performance. Although, a common limitation to a membrane’s performance is fouling, which is the permeate flux decline due to concentration polarization of foulants from the feed on the membrane’s surface. A new fouling problem emerges when the feed contains microorganisms (bacteria). The bacteria can cause biofouling, where adhered bacteria on the membrane’s surface are more difficult to remove due to their adhesive secretions. A way to reduce biofouling is the incorporation of antibacterial additives to the membrane, through surface modification or embedding the additives into the membrane matrix. The modified membranes are proven to have increased hydrophilicity and gained an antibacterial property, thus having an increased permeability and an amount reduction in adhered bacteria. The chances of biofouling were significantly lowered, and the overall membrane performance was enhanced. Despite the positive results, commercial antibacterial ultrafiltration membranes are not yet available as research on this topic is still new and ongoing. This review will discuss and summarize the effects of antibacterial additives on ultrafiltration membranes, using data from collected articles.
Keywords: Ultrafiltration membrane, biofouling, modification, antibacterial, hydrophilicity.
Franzesca Michelle
© Copyright 2020 by Franzesca Michelle
All rights reserved
DEDICATION
I dedicate this work to my parents and brother who have always supported me.
Franzesca Michelle ACKNOWLEDGEMENTS
First and foremost, my utmost gratitude to the Almighty God for all His mercy and blessings that enabled me to complete my thesis work successfully.
I wish to thank my advisor, Mr. Samuel Kusumocahyo, who is also the dean of Life Sciences faculty, for guidance, advice, and continuous support throughout the making of this thesis.
Many thanks to my friends in the pharmaceutical engineering department for the company and the times we spent together. Special thanks to Jessica, who has been a close friend of mine; Elena, for the memes and laughs; and Shelly, who can relate to my thesis work. I also want to extend my gratitude to Syarifa, my senior, who has been very helpful.
Finally, my sincerest gratitude to my parents for the unconditional support. This thesis would not be completed without it.
TABLE OF CONTENTS
Page
STATEMENT BY THE AUTHOR ... 2
ABSTRACT ... 3
DEDICATION ... 5
ACKNOWLEDGEMENTS ... 6
TABLE OF CONTENTS ... 7
LIST OF FIGURES ... 9
LIST OF TABLES ... 13
CHAPTER 1 - INTRODUCTION ... 14
1.1Background ... 14
1.2Review Objective ... 16
1.3Significance of Study ... 16
CHAPTER 2 - LITERATURE REVIEW ... 17
2.1Membrane ... 17
2.1.1Membrane Based on Morphology ... 18
2.1.2Ultrafiltration Membrane ... 18
2.2Biofouling ... 20
2.3Membrane Modification ... 21
2.3.1Hydrophilicity and Contact Angle ... 21
2.3.2Surface Grafting, Surface Coating, and Polymer Blending ... 22
2.3.3Antibacterial Modifications ... 23
CHAPTER 3 – RESEARCH METHODS ... 26
3.1 Venue and Time ... 26
3.2 Materials and Equipment for the Lab Experiment ... 26
3.2.1 Materials ... 26
3.2.2 Equipment ... 26
3.3 Experimental Procedure ... 27
3.4 Literature Review Procedure ... 29
3.5 Analytical Procedure ... 30
CHAPTER 4 – RESULTS AND DISCUSSION ... 31
Franzesca Michelle 4.2 General Overview on Membrane Modification and Antibacterial Additives
... 36
4.3 Membrane Modification with Metal Additives ... 41
4.3.1 Silver Additives ... 41
4.3.2 Copper Additives ... 52
4.3.3 Combination of Metal Additives and Other Metals ... 56
4.4 Membrane Modification with Organic Additives ... 62
4.5 Membrane Modification with Carbon-Based Additives ... 73
4.5.1 Graphene Oxide as an Additive ... 73
4.5.2 Carbon Nanotube as an Additive ... 79
4.6 Other Additives for Antibacterial Property ... 84
4.7 Summary of Discussion ... 91
4.8 Future Commercialization of Antibacterial Ultrafiltration Membrane ... 99
CHAPTER 5 – CONCLUSION AND RECOMMENDATIONS ... 101
5.1 Conclusion ... 101
5.2 Recommendations ... 101
REFERENCES ... 103
Appendix A. Short Summary of Membrane Performances from Collected Articles 114 Appendix B. More Pictures Taken During Lab Experiments ... 123
Appendix C. Permeate Flux Data of Membrane 400-3 ... 124
CURRICULUM VITAE ... 126
LIST OF FIGURES
Figures Page
Figure 2. 1. Diagram of Membrane Process. ... 17
Figure 2. 2. Cross sections of various membranes. ... 18
Figure 2. 3. Cross-flow diagram. ... 19
Figure 2. 4. Comparison between ultrafiltration and other membrane technologies. .. 19
Figure 2. 5. Schematic diagram of flux decline due to fouling caused by concentration polarization layer of foulants above the cake layer... 20
Figure 2. 6. Surface wetting types (left) and contact angle (right). ... 22
Figure 2. 7. Appearance of a microtiter plate. ... 25
Figure 2. 8. Schematic diagram of flow cytometry... 25
Figure 3. 1. Experimental procedure diagram... 27
Figure 3. 2. Illustration of the ultrafiltration experiment. ... 29
Figure 3. 3. Research procedure for selecting papers for literature review. ... 29
Figure 3. 4. Schematic flow of how the literature review was done. ... 30
Figure 3. 5. Diagram of Analytical Procedure. ... 30
Figure 4. 1. Polymer solution preparation diagram. ... 32
Figure 4. 2. The casting solution (left) of 4000-1.25 membrane and the resulting membrane appearance after coagulation bath and rinsing (right). ... 33
Figure 4. 3. Thicker 4000-1.25 membrane still showed imperfections. ... 34
Figure 4. 4. The casting solution (left) and the resulting 400-1.25 membrane (right) was observed to not have holes but appeared to be thinner than other samples. ... 34
Figure 4. 5. The casting solution of 400-2 membrane was more prone to form a dry layer at the top (left) and the appearance of the resulting membrane was not very appealing (right). ... 35
Figure 4. 6. Top (left) and side (right) view of membrane 400-3 casting solution. ... 35
Figure 4. 7. The two 400-3 membranes appeared to have no visible holes and thicker than other PEG 400 membranes. ... 36
Figure 4. 8. Graph of pure water permeate flux of membrane 400-3. ... 36
Franzesca Michelle oxidative stress from metal or carbon-based additive (middle), and physical damage by sharp edges usually from graphene material (right)... 38 Figure 4.10. Schematic diagram of antibacterial mechanism of silver nanoparticles, which can also be applied to other metal nanoparticles. ... 38 Figure 4.11. Simple illustration of blending in an additive into the membrane polymer solution. ... 39 Figure 4.12. Simple illustration of coating a membrane by immersion or dipping it into additive solution. ... 40 Figure 4.13. Simple illustration of etching and grafting on a membrane. ... 40 Figure 4.14. Surface modification process illustration of etching by plasma and
PMMA deposition on membrane. ... 42 Figure 4.15. Polyurethane nanofiber with silver nanoparticles. ... 43 Figure 4.16. a) Fluxes of virgin PES and modified PES membranes (JBF: water flux before fouling, JF: flux with fouling, JAF: flux after fouling). b) Flux recovery and BSA rejection of virgin PES and modified PES membranes. ... 45 Figure 4.17. Surface modification by dopamine and in situ immobilization of silver nanoparticles. ... 45 Figure 4.18. Illustration of silver nanoparticles loading on a polydopamine sphere. .. 46 Figure 4.19. Surface modification steps to immobilize silver nanoparticles on a PVDF membrane. ... 47 Figure 4.20. Release of silver ions induces bacterial lysis... 48 Figure 4.21. Fabrication process of GO-Ag composite membrane. ... 49 Figure 4.22. The wet spinning method (left) to create hollow fiber membrane (right).
... 51 Figure 4.23. Contact angles of membranes over time (left) and flux decline of
membranes during BSA filtration (right). ... 51 Figure 4.24. Attachment process of copper nanoparticles onto halloysite nanotubes. 53 Figure 4.25. The deposition process of copper oxide nanoleaves on cellulose paper (left) and release of copper ions that can damage bacterial cells. ... 53 Figure 4. 26. Interactions of copper ions with a bacterial cell. ... 54 Figure 4. 27. Zinc oxide attachment on a PES-NH2 membrane. ... 56 Figure 4. 28. Modification process a polysulfone membrane with silver nanoparticles- fixed copper(I) oxide nanowires. ... 57
and S. aureus (bottom row). ... 58 Figure 4. 30. Before (left) and after (right) SEM images of E. coli cells after exposure to iron oxide. ... 59 Figure 4. 31. Process illustration of modifying raw HNTs and the resulting modified membrane. ... 60 Figure 4. 32. Pure water flux comparison between membranes and the separation performance of each membrane against 1000 ppm solution of BSA and 100 ppm of HA. ... 61 Figure 4. 33. Fabrication of a modified PES membrane (left) with silica nanoparticles coated with poly(guanidine-hexamethylenediamine-PEI) (right)... 62 Figure 4. 34. Membrane made through one-pot cross-linked copolymerization. ... 65 Figure 4. 35. Flux decline and recovery ratios (left) and the flux decline ratios after an hour of dead-end filtration using BSA solution, and bacterial inhibition rate against S.
aureus (right). ... 66 Figure 4. 36. Illustration of the antibacterial activity of nisin in the membrane. ... 66 Figure 4. 37. Antibacterial mechanism of N-halamine functionalized silica
nanospheres. ... 67 Figure 4. 38. (a) Permeate flux and (b) BSA rejection of the membranes over time.
Each sharp increase of flux indicates a new filtration cycle. ... 68 Figure 4. 39. Illustration of the f-PPTA-modified membrane nanofiber structure and its antibacterial activity. ... 69 Figure 4. 40. Membrane surface modification process with chitosan. ... 69 Figure 4. 41. Introduction of chlorine to the PEK-NH membrane. ... 70 Figure 4. 42. Antibacterial activity of PEK-N-CL membrane and its regenerability. . 71 Figure 4. 43. E. coli on unchlorinated membrane (left) and on chlorinated membrane (right), loss of cellular integrity is evident on the right SEM image. ... 71 Figure 4. 44. Surface modification process to make chlorinated PEO-NH2 membrane and the membrane’s antibacterial activity. ... 72 Figure 4. 45. Functional groups change on the membrane’s surface. ... 72 Figure 4. 46. Antibacterial activity of lysozyme and graphene oxide blended in the membrane. ... 74 Figure 4. 47. Schematic illustration of modification procedure and the antibacterial activity of GO-functionalized zwitterionic polyampholyte hydrogel PES membrane. 74
Franzesca Michelle GO content. ... 76 Figure 4. 49. Fluxes during the pure water filtration and fouling operation with BSA solution. ... 76 Figure 4. 50. Antibacterial activity of the reduced graphene oxide from light-induced photothermal reaction. ... 78 Figure 4. 51. IR images of modified membranes showing a rise in temperature after illumination (left) and the effect on adhered E. coli (right). ... 78 Figure 4. 52. Water fluxes of membranes under 100 psi over time. ... 79 Figure 4. 53. p-CNT positioning in the membrane, hydrophilic polymer brushes faces the water while the hydrophobic CNT is embedded in the matrix. ... 80 Figure 4. 54. Fluxes during filtration cycles (left) and the membranes’ flux recovery percentage (right). ... 81 Figure 4. 55. Antibacterial activity of CNT depends on the presence of an electric field. ... 82 Figure 4. 56. Hollow fiber membrane illustration (left) and SEM image a commercial hollow fiber membrane (right). ... 82 Figure 4. 57. Attachment of hydroxyl groups on MWNTs. ... 82 Figure 4. 58. Illustration of the antifouling resistance comparison between
PVDF/MWNTs membranes (a, b) and PVDF/N-Si-MWNTs membranes (c, d). ... 83 Figure 4. 59. Fluxes of membranes during BSA filtration (JW: initial PWF, JBSA:
BSA aqueous solution permeation flux, JR: cleaned membrane flux) (left) and the time-dependent fluxes with ultrafiltration regeneration cycles (right). ... 84 Figure 4. 60. The presence of HNTs create smooth passage ways for water through the membrane (left) and the addition of lysozyme induced antibacterial property (right). 85 Figure 4. 61. BSA rejection (left) and fluxes (right) of pure and VMT-modified PES membranes. ... 86 Figure 4. 62. Antibacterial activity by T4 phages immobilization on membrane (left) and by direct feed spiking with T4 phages (right). ... 87 Figure 4. 63. Illustration of a spiral-wound membrane module. ... 88 Figure 4. 64. Various spacers and their shapes. ... 88 Figure 4. 65. Possible mechanism of alginate lyase immobilization onto cellulose acetate membrane. ... 90
and c) Alg L-immobilized membranes. ... 90 Figure C. 1. The condition of phenol: pink-coloured (left) and liquified (right)
indicating oxidation. ... 123 Figure C. 2. Pictures of magnified holes in the middle (left) and edge (right) of the 400-3 membrane. Magnification was done using a 40× magnification using the light microscope. ... 123
LIST OF TABLES
Table Page
Table 4. 1. The summary of antibacterial mechanisms as discussed in collected
studies. ... 92 Table 4. 2. Summary of antibacterial additives’ efficiencies and modifiers with their effects on membrane. ... 94 Table 4. 3. List of articles that have desirable experimental results. ... 100
