DECONTAMINATION OF CHEMICAL WARFARE SIMULANTS USING ELECTROSPUN MEDIA

DECONTAMINATION OF CHEMICAL WARFARE SIMULANTS USING ELECTROSPUN MEDIA RAMAKRISHNAN RAMASESHAN NATIONAL UNIVERSITY OF SINGAPORE 2011 DECONTAMINATION OF CHEMICAL WARFARE SIMULANTS USING ELECTROSPUN MEDIA RAMAKRISHNAN RAMASESHAN (M. Sc Molecular Engineering, Singapore-MIT Alliance, NUS) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF MECHANICAL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2011 ACKNOWLEDGEMENT First of all, I would like to sincerely thank Prof. Seeram Ramakrishna for his confidence in me and providing me an opportunity to enroll in his research group; for his constant encouragement and supervision during the course of my research at NUS. His positive attitude and enthusiasm has always been a great source of motivation. I would also like to thank all my colleagues at NUSNNI, in particular Dr. Subramaniam Sundarrajan, Dr. Barhate Rajendrakumar, Dr. Neeta Lala, Mr. Teo Wee Eong and Mr Liu Yingjun for providing many valuable suggestions and guidance throughout this research project. A special word of gratitude goes to Dr. Subramaniam Sundarrajan for having patiently and painstakingly corrected this document. I would like to show my sincere appreciation to the administrative staff of NUSNNI and NUS Mechanical Engineering department for their excellent support throughout my candidature at NUS. This research would not have been possible without the financial support provided by DSTA under the project grant POD0412402 and I am grateful for the funding support received from NUS and DSTA for my candidature and research. I would like to thank all my teachers from my school and undergraduate days who had enormous faith in me; it is the faith and the goodwill that has helped me come this far. I would also like to thank my parents for their constant motivation in the little things that I and for having shaped my career. I am indeed fortunate to have been blessed with such wonderful parents. A special word of gratitude goes to my wife, for her patient support and encouragement throughout drafting this thesis. i TABLE OF CONTENTS ACKNOWLEDGEMENT . i TABLE OF CONTENTS ii LIST OF TABLES . v LIST OF FIGURES vi EXECUTIVE SUMMARY . x RESEARCH DELIVERABLES . xii CHAPTER I Introduction 1.1 Chemical warfare and protection . 1.2 Need for Better Protective Wear – Use of non-wovens 1.3 Nanofibers for Protection 1.4 Objective of study 1.5 Significance of this research CHAPTER – Background and Literature Review 2.1 Chemical Warfare Agents . 2.2 History of Chemical Warfare 11 2.3 Protection from CWA 13 2.4 Use of electrospun nanofibers for chemical warfare protection 15 2.5 Motivation for the research 16 2.6 Electrospinning 16 2.7 Electrospinning applied to ceramic systems: . 18 2.8 Unique properties of electrospun nanofibers over other structures . 21 CHAPTER – Polymer Nanofibers Functionalized with Catalyst for Detoxification of Nerve Agents 22 3.1 Organophosphorus Nerve Agents 22 3.2 Methods of Detoxification of Nerve Agents . 23 3.3 Materials and Experiments 26 3.4 Synthesis 28 3.5 Characterization and Analysis . 28 3.6 Testing the OP hydrolytic activity . 29 ii 3.7 Results and Discussion 30 3.8 Summary 36 CHAPTER – Ceramic Nanofibers for Detoxification of Chemical Warfare Agents38 4.1 Background and Introduction 38 4.2 Experimental 39 4.3 Testing the detoxification ability . 41 4.4 Results and discussion . 42 4.5 Summary 53 CHAPTER – Carbon Nanofibers Functionalized with Non-specific Catalyst . 54 5.1 Background and Introduction 54 5.2 Experimental Procedures . 55 5.3 Results . 60 5.4 Discussion and interpretation of results . 66 5.5 Summary 72 CHAPTER – Nanofiber-Carbon Nanoparticle (nanodiamonds) Nanocomposite Materials for Decontamination of Nerve Agents 74 6.1 Introduction . 74 6.2 Introduction of nanodiamonds . 75 6.3 Scope of work 77 6.4 Chemistry of Nanodiamonds . 77 6.5 Use of Electrospun polymer nanofibers as functional supports 78 6.6 Effect of adding nanoparticles to polymer nanofibers . 79 6.7 Experimental Methods . 80 6.8 Results and Discussion 84 6.9 Summary 98 CHAPTER - Fabrication of Nanocomposite Filter Media, and Modeling the Filtration Aspects . 99 7.1 Introduction . 99 7.2 Experimental Details . 100 7.3 Results and Discussion: . 105 7.4 Modeling the Filtration Properties . 111 iii 7.5 Optimization of Parameters and Loading 113 7.6 Modeling of Parameters based on the results obtained . 124 7.7 Summary 127 CHAPTER – Conclusion and Recommendation for Future Work . 128 8.1 Summary of Research and Conclusion 128 8.2 Future Direction - Improve Survivability 131 8.3 Future Direction - Application in Sensors . 133 Appendix-1 . 149 List of Companies Producing Electrospun Nanofibers . 149 Appendix-II 151 Electrospun Ceramic Nanofibers produced (by way of this research) and Decontamination efficiencies against Nerve and Mustard agent simulants 151 iv LIST OF TABLES Table 3.1 Properties of Nanofiber Membranes 30 Table 3.2 Relative rates of OP hydrolysis by different functionalized 35 nanofiber membranes Table 4.1 List of products detected for CEES degradation using Zinc 50 titanate Table 4.2 Zinc titanate ceramic fiber characteristics and their 52 detoxification efficiency Table 5.1 Mean Fiber Diameter for each sample and Percentage Yield 61 Table 5.2 Specific Surface Area, Average Pore Diameter, Micropore 63 Volume Table 5.3 Paraoxon Absorption Efficiency and Specific Surface Area 70 Table 6.1 The assignments of the bands of β-CD 88 Table 6.2 Specific surface area studies using BET 98 Table 7.1 Reactivity of nanocomposite membranes towards chemical 108 warfare simulants Table 7.2 Properties of the nanocomposite layer (electrospun media) 109 Table 7.3 Porometer measurements 112 Table 7.4 Pressure Drop and Paraoxon Decontamination efficiency 116 Table 7.5 Table of results for Composite Fiber Characteristics (PSU- 118 ZnTiO3) Table 8.1 Summary of the research on Decontamination of Chemical 129 Warfare Simulants using Electrospun media v LIST OF FIGURES Figure 1.1 Research Roadmap Figure 2.1 A brief history of Chemical Warfare 12 Figure 2.2 Protection through Adsorption – Activated Carbon Lined Garments Figure 2.3 13 a) Model of the JSLIST developed fabric and b) Activated carbon in spherical form which is used in the SARATOGA fabric c) Mesopores in a single carbon 15 sphere/granule Figure 2.4 Model of the electrospinning set-up 18 Figure 3.1 Types of Organophosphorus Nerve Agents 22 Figure 3.2 Degradation routes of OP Compounds 23 Figure 3.3 Paraoxon - OP agent simulant 29 Figure 3.4 SEM image of (A) PVC-β-CD, (B) PVC-IBA, (C) PVCβ-CD and IBA and (D) PVC and (3-carboxy-4- 31 iodosobenzyl) oxy-β-CD nanofibers Figure 3.5 Change in absorbance (410±10 nm) for 15 hours Figure 3.6 Change in the absorbance (at 410±10 nm) for the first 100 minutes Figure 3.7 SEM Image of granular activated Carbon Figure 4.1 SEM micrographs of electrospun 40% zinc titanate nanofibers 34 35 36 43 Figure 4.2 TEM images and SAED of 40% Zinc Titanate nanofibers 44 Figure 4.3 Stages of annealing and formation of the ZnTiO3 phase 45 Figure 4.4 XRD of ZnTiO3 nanofibers annealed at 700oC 45 Figure 4.5 FT-IR of the fabricated 40% ZnTiO3 nanofibers 48 Figure 4.6 Decrease in uv absorbance of paraoxon using 40% ZnTiO3 nanofibers Figure 5.1 Transformation of PAN to Ladder Polymer in stabilization Figure 5.2 From left to right a) Polymer fibers before HT b) 49 58 60 vi Polymer fibers after HT 600°C Figure 5.3 From Left to right a) Polymer fibers after HT 700°C b) Polymer fibers after HT 1000°C Figure 5.4 FT-IR Spectrum of Non Heat Treated functionalized nanofibers Figure 5.5 FT-IR Spectrum of functionalized carbon fibers at 600°C Figure 5.6 Decrease in UV absorbance of Paraoxon for FeTiO3 nanofibers Figure 5.7 XRD for sample Heat treated at 1000°C Figure5.8 Porous and Pop-corn like bead formation on nanofibers prior to HT 61 62 62 64 65 66 Figure5.9 FT-IR spectra at various temperatures of carbonization 68 Figure 5.10 Chemisorption of Paraoxon on Iron Titanate 71 Figure 6.1 Different diamond materials 75 Figure6.2 Cluster structure of detonation diamond and surface functional groups Figure6.3 Initial surface functionalization by oxidative treatment or solid-phase reaction with gaseous reactants Figure 6.4 FTIR spectra of as received nanodiamonds and acidtreated nanodiamonds Figure 6.5 FTIR spectra of pure β-CD and β-CD-functionalized nanodiamonds Figure 6.6 Diagram of β-CD-functionalized nanodiamonds Figure 6.7 MALDI-TOF MS graph of β-CD-functionalized nanodiamonds Figure 6.8 SEM images of electrospun PSU nanofiber membranes of about 1000nm Figure 6.9 76 78 85 86 87 88 89 TEM images of (a) nanocomposites from electrospinning a blend of acid-treated nanodiamonds in PSU solution. (b) & (c) nanocomposites from electrospraying acid- 90 treated nanodiamonds onto PSU nanofibers. Figure 6.10 TEM images of acid-treated nanodiamonds 91 vii electrosprayed onto PSU nanofibers before stirring in heptane, (b) after stirring in heptane. Figure 6.11 Model of electrospraying set-up Figure 6.12 UV absorption graphs – to show relative binding capacity for paraoxon (a simulant of nerve agent) by as- 93 95 received nanodiamonds and activated carbon. Figure 6.13 UV absorption graphs – to study binding capacity and detoxification capability for paraoxon (a simulant of 95 nerve agent) by different materials. Figure 6.14 (a) From left to right - paraoxon in heptane solution, pure white b-CD powder, white b-CD turned yellow in paraoxon solution, yellow solution due to the formation of p-nitrophenol when NaOH was added to paraoxon 95 solution. (b) Zoom-in picture of white b-CD turning yellow in paraoxon solution (left of picture) when compared to pure white b-CD powder Figure 6.15 (a) & (b) SEM and TEM of b-CD functionalized nanodiamonds electrosprayed onto PSU nanofibers before extraction of paraoxon. (c) Selected area electron diffraction (SAED) image of the b-CD nanodiamond 97 particle on the surface of the nanofibers which shows its polycrystalline nature Figure 6.16 SEM and TEM of β-CD-functionalized nanodiamonds electrosprayed onto PSU nanofibers after extraction of 97 paraoxon Figure 7. Schematic depicting the production of nanocomposite fibers Figure 7.2 103 (a) SEM image of the synthesized ZnTiO3 nanoparticle clusters; mean diameter 150±80nm (b) XRD spectrum of 105 ZnTiO3 nanoparticles Figure 7. (a) SEM image of the melt blown glass fiber mat; mean fiber diameter 20±4 μm (b) SEM image of the 106 viii References 10. 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(2006) 3651-3659 148 Appendices Appendix-1 List of Companies Producing Electrospun Nanofibers 1. Applied Sciences Inc. (development of advanced materials and their applications) 2. Catalytic Materials LLC (manufacture of high purity multiwalled carbon nanotubes and graphite nanofibers) 3. CSIRO (offer world–leading skills in the formation of complex fibrous structures and product development) 4. Donaldson (filtration systems and replacement parts) 5. Elmarco (a world leader in the nanofiber industry is the first and still the only company in the world that offers its customers machines for industrial production of nanofibers) 6. eSpin Technologies (polymeric nanofiber manufacturing) 7. Fibertex (needlepunch and spunmelt nonwovens) 8. Finetex Technology (filtration media) 9. HILLS Inc. (manufacture of machinery and technology for the synthetic fiber industry) 10. Hyperion Catalysis (carbon nanotube development and commercialization) 11. IME Technologies (consultancy, prototyping, contract research) 12. Koch Industries, Inc. (premium fibers, polymers and intermediates) 13. Nano FMG (nanofiber production processes to convert the polymer nanofibers to commercial products) 14. NanoAmor - Nanostructured & Amorphous Materials Inc. 15. Nanostatics, LLC (development of high performance materials) 16. Neotherix (novel bioresorbable scaffolds for tissue regeneration and repair) 17. Nicast (possessing unique electrospinning capabilities applicable to a variety of medical applications) 18. Physics Instruments Co. (Manufacturers of Electrospinning Appartus for making nano-fibres from Polymers). 19. Physical Sciences Inc. (Providing contract research and development services) 20. SNS Nano Fiber Technology, LLC (a producer of specialized nanofiber matrices) 149 Appendices 21. SurModics (providing a nanofibrillar matrix for in vivo-like cell culture performance) 22. Zeus, Inc. (Zeus biomaterials platform is targeted for the development of a wide variety of medical products for both preventive care and the treatment of disease) 150 Appendices Appendix-II Electrospun Ceramic Nanofibers produced (by way of this research) and Decontamination efficiencies against Nerve and Mustard agent simulants Nanofiber sample name Diameter range (nm) BET Surface area (m /g) Paraoxon (Nerve agent simulant) decomposition efficacy for first 50 CEES (Mustard agent) decomposition efficacy for first 60 20 % ZnTiO3 40 – 550 122±30 68 - 77% 60 - 66% 40 % ZnTiO3 40 – 600 128±10 88 - 91% 62 - 69% 50 % ZnTiO3 60 – 600 102±12 80 - 87% 65 - 67% 60 % ZnTiO3 110 – 700 94±30 74 - 79% 60 - 64% AlTiO3 130-300 98±10 72 - 74% 50 - 52% FeTiO3 40-200 88±17 60 - 64% (CEPS) 40 - 43% MgTiO3 70-300 N/A 80 - 86% (CEPS) 55 - 70% NiFe2O4 30-150 N/A 77 - 84% (CEPS) 45 - 58% CuMoO4 60-170 N/A 65 - 78% (CEPS) 62 - 67% Fe2MnO4 70-250 N/A 74 – 85% (CEPS) 57 - 63% NiMn3O4 40-200 N/A 67-73% (CEPS) 45 – 57% Ceramic System Phase identified from XRD Nanofiber Diameter (nm) Average BET Surface area (m2/g) Paraoxon decomposition efficacy for first 50 CEES decomposition efficacy for first 60 Nickel ferrite (ferromagnetic) NiFe2O4 60-130 86 77-84 45-58 Cerium Oxide CeO2 40-170 73 40-52 30-33 Iron Manganese oxide (Ferromagnetic) Fe2MnO4, Fe2O3 and MnO 30-80 91 74-85 57-63 Copper chromate (electrochromic) CuO, Cr2O3 and CuCrO4 60-200 54 56-61 23-34 Copper chromate (electrochromic) CuCrO4 55-140 74 64-67 19-27 Tin Oxide (Chemisistor) SnO2 40-100 - 75-79 63-65 Cobalt Chromate CoCrO4 60-90 - 38-43 45-49 Cobalt Molybdate CoMoO4 45-140 - 65-77 62-68 (LBMO – CMR) La0.3Ba0.7MnO3 35-70 - 58-66 34-48 (LSMO – CMR) La0.3Sr0.7MnO3 30-80 - 60-65 40-46 Copper Molybdate (Piezochromic) -- 15-80 - 65-78 83-86 151 [...]... Objective of study The objective of this study is to demonstrate that electrospun nanofibers could be used for detoxification of chemical warfare agents This is based on the following approaches: - Using electrospun polymer membranes that are loaded with catalyst - Using electrospun ceramic nanofibers - Using electrospun carbon nanofibers functionalized with non-specific catalysts - Using electrospun. .. motivation for this study The objective of this research is to understand and to evaluate the detoxification abilities of electrospun nanofibers against chemical warfare agents and assess the possibility of using the electrospun nanofibers as protective membranes in face masks and warfare clothing Electrospinning was chosen as the method of fabricating the nanofibers as it is a simple and versatile... polymer nanofiber-carbon nanoparticle nanocomposite and - Using electrospun polymer nanofiber-metal oxide nanoparticle nanocomposite The performance of the nanofibers will be evaluated using chemical warfare simulants of the nerve and mustard agents Their performance will be compared to existing technology and their applicability in fabrication of a protective ensemble will be discussed A roadmap of the... Introduction 1.1 Chemical warfare and protection Chemical warfare is the oldest form of warfare known to mankind [1], where the destructive action is brought about by the toxic nature of the agents as compared to explosive forces or heat that is commonly found in conventional warfare Even in modern times, the prospect of a chemical warfare is as threatening as compared to a nuclear war since the chemical weapons... technology of attaching the carbon spheres to a textile carrier fabric, the majority of the outer surface of the spheres is freely accessible to harmful gases Since 1997, JSLIST’s SARATOGA has been the only chemical and biological protective overgarment approved for use by all branches of the U.S Military [7] 2.4 Use of electrospun nanofibers for chemical warfare protection The first report on electrospun. .. Yingjun, Barhate R.S., Neeta L Lala and Seeram Ramakrishna Functionalized Polymer Nanofiber Membranes for Protection from Chemical Warfare Agents, Nanotechnology, (17), 2006, 2947-53 (2) Ramakrishnan Ramaseshan and Seeram Ramakrishna, Zinc Titanate Nanofibers for the Detoxification of Chemical Warfare Simulants, Journal of the American Ceramics Society, 90 (6), 2007, 1836-42 (3) Neeta lala, Li Bojun,... close attention to the many different applications of the electrospun nanofibers Thus several industries across the World are engaged in the fabrication of electrospun nanofibers for various applications Appendix-1 shows a listing of industries around the globe that are engaged in the nanofiber fabrication business 17 Chapter –II Figure 2.4: Model of the electrospinning set-up (adapted from [11]) Electrospinning... variety of climatic conditions and can remain effective for many weeks These "dusty" agents are difficult to detect unless wetted Once detected, they may be decontaminated with a 5 percent chlorine bleach solution 2.2 History of Chemical Warfare Historically mankind has used poisonous chemicals for the purpose of defense, i.e to disable, incapacitate or kill insects and other animals The concept of chemical. .. prohibition of use in war of asphyxiating, 11 Chapter –II poisonous or other gas, and of bacteriological methods of warfare also known as the Chemical Weapons Convention (CWC, 1925, Geneva) However, in World War II, nerve agents such as tabun and sarin were developed and stockpiled by the Germans and used to kill thousands of concentration camp victims The Japanese imperial army also used chemical weapons... a) Functionalized polymer nanofibers, b) Ceramic nanofibers c) Functionalized Carbon nanofibers, d) Polymer nanocomposites with carbon nanoparticles (nanodiamonds) and e) Polymer nanocomposites with metal oxide nanoparticles To compare the effect of decontamination, simulants of nerve and mustard agents were used It is also shown that among these 5 different categories of materials, the polymer nanocomposites . Summary of the research on Decontamination of Chemical Warfare Simulants using Electrospun media 129 LIST OF FIGURES Figure 1.1 Research Roadmap 5 Figure 2.1 A brief history of Chemical Warfare. DECONTAMINATION OF CHEMICAL WARFARE SIMULANTS USING ELECTROSPUN MEDIA RAMAKRISHNAN RAMASESHAN NATIONAL UNIVERSITY OF SINGAPORE 2011 DECONTAMINATION. objective of this research is to understand and to evaluate the detoxification abilities of electrospun nanofibers against chemical warfare agents and assess the possibility of using the electrospun