Carbon Nanofibers

Madhuri Sharon, (Retd. Director at Reliance Industries), PhD from Leicester University UK, postdoctoral research from Bolton Institute of Technology U.K., is currently the Director of NSN Research Centre for Nanotechnology & Bionanotechnology and Managing Director of Monad Nanotech as well as Adjunct-Professor University of Mumbai & Professor-Emeritus JJT University, India. She has published more than 130 papers, 4 books and 11 patents. Her research focuses on the synthesis, biosynthesis and application of various nanomaterials (graphene oxide, carbon dots, carbon nanomaterials and nanometals) in drug-delivery. Maheshwar Sharon, (Retd. Professor IIT Bombay) PhD from Leicester University, U.K, and postdoctoral research from Bolton Institute of Technology, U.K., is Director of NSN Research Centre for Nanotechnology & Bionanotechnology and Technical Director of Monad Nanotech as well as Adjunct-Professor at the University of Mumbai, India. His specializations are electrochemistry (photoelectrochemistry & battery), solid state chemistry (diffusion & electrical properties), superconductivity, carbon (fullerenes, nanocarbon, low band gap semiconductor, etc.) and energy: photovoltaic wet & dry solar cells. For his contribution to carbon he was awarded the 'Bangur Award'. He has five patents, five books and 173 publications to his credit.

Foreword xix


Preface xxi


1 An Introduction to Carbon Nanofiber 1
Maheshwar Sharon


1.1 Introduction 1


1.1.1 History of Carbon Fiber 2


1.1.2 What is a Carbon Fiber? 3


1.1.3 Structures of Carbon Fibers 5


1.1.4 Synthesis of Carbon Fibers 6


1.1.4.1 Carbon Fibers from PAN 6


1.1.5 Properties of Carbon Fibers 6


1.2 Properties of Carbon Nanofiber and How It Differs from Carbon Nanotube 7


1.2.1 History of CNF 8


1.2.2 Role of Surface States in Controlling the Properties of CNFs 9


1.3 Synthesis of Carbon Nanofiber (CNF) 11


1.3.1 Chemical Vapor Deposition (CVD) Method 11


1.3.2 Precursors for CNF 12


1.3.3 Use of Catalyst in the Synthesis of CNF 12


1.3.4 Selection of Variable Parameters for Growth of CNF 13


1.3.5 Epitaxial Growth of Aligned CNF 14


1.3.6 Mechanism of CNF Synthesis 14


1.4 Properties of CNF and Its Composites 15


1.5 Applications of CNF 15


1.6 Health Hazards of CNF 18


1.7 Summary 19


References 19


2 Biogenic Carbon Nanofibers 21
Madhuri Sharon


2.1 Introduction 21


2.2 Plants as Source of Precursor for CNF Synthesis 22


2.2.1 Plant Parts 26


2.2.1.1 Fibrous Plant Material Used for Synthesizing CNF 26


2.2.1.2 Characterization of CNF Obtained by Pyrolysis of Plant Seeds 29


2.2.2 Plant Metabolites 34


2.2.2.1 Characterization of CNF Obtained by Pyrolysis of Plant Metabolites 36


2.3 CNF Derived from Parts of Different Plants and Their Applications 37


2.3.1 Hydrogen Storage in CNF 37


2.3.2 Removal of Heavy Metals by CNF 38


2.3.3 Microwave Absorption Capacity of CNF 39


2.3.4 CNF as Electrocatalysts for Microbial Energy Harvesting 40


2.3.5 CNF as Regenerative Medicine 40


2.3.6 CNF as Deodorizer 41


2.3.7 CNF Composites for Strong and Lightweight Material 41


2.3.8 Biogenic CNF as Supercapacitor 42


2.3.9 Plant-Derived CNM for Use in Coatings 43


2.4 Comparative Structure of Chemically and Biogenically Synthesized CNF 43


2.4.1 CNF Synthesized from Chemical Precursors 43


2.4.2 CNF Synthesized from Plant Parts or Plant Metabolites as Precursors 44


2.5 Concluding Remarks 45


References 45


3 Role of Nanocatalysts in Synthesis of Carbon Nanofiber 49
Suman Tripathi


3.1 Introduction 49


3.2 Nanocatalysts 50


3.2.1 Concept of Nanocatalysis 51


3.2.2 Metallic Nanoparticles (NP) as Catalyst 52


3.2.3 Types of Nanometals as Catalyst 53


3.2.3.1 Nanometal Colloids as Catalysts 54


3.2.3.2 Nanoclusters as Catalysts 54


3.2.3.3 Nanoparticles as Catalysts 54


3.2.3.4 Nanopowder as Catalysts 54


3.3 Methods for the Preparation of Nanoparticles 54


3.3.1 Hydrothermal Method of Metal Nanoparticles 55


3.3.2 Microwave-Irradiated Synthesis of Metal Nanoparticles 55


3.3.3 Dendrimer-Assisted Synthesis of Metal Nanoparticles 55


3.3.4 Reverse Micelle Method of Metal Nanoparticles 56


3.3.5 Co-Precipitation Method of Metal Nanoparticles 57


3.3.6 Biogenic Synthesis (Green Synthesis) Method of Metal Nanoparticles 58


3.4 Role of Nanocatalyst in the Production of CNF 60


3.5 Different Types of CNF 61


3.6 Synthesis of Carbon Nanofiber (CNF) Using Nanocatalysts 64


3.6.1 Laser Ablation Method 65


3.6.2 Chemical Vapor Deposition (CVD) 65


3.6.3 Self-Propagating High-Temperature Synthesis (SHS) or Combustion Synthesis (CS) 67


3.6.4 Floating Catalyst Method 68


3.6.5 Electrospinning Method 68


3.6.5.1 Polyacrylonitrile (PAN) 70


3.6.5.2 Pitch 70


3.6.5.3 Cellulose 70


3.7 Summary 71


References 71


4 Carbon Nanofiber and Polymer Conjugate 75
Anuradha Pandey Dubey


4.1 Introduction 75


4.2 What is a Composite? 76


4.3 Polymers Used for Conjugating CNF 79


4.3.1 Starch 79


4.3.2 Cellulose 81


4.3.3 Collagen 81


4.3.4 Chitosan 82


4.3.5 Gelatin 83


4.3.6 Fibrin 83


4.3.7 Alginate 84


4.3.8 Poly Vinyl Alcohol (PVA) 84


4.3.9 Poly Ethylene Glycol (PEG) 84


4.3.10 Poly Caprolactone (PCL) 85


4.3.11 Poly Lactic-co-Glycolic Acid (PLGA) 85


4.3.12 Poly Glycerol Sebacate (PGS) 86


4.4 Approaches Involved in Synthesizing Polymer/CNF Nanocomposites 86


4.5 Various CNF Composites 87


4.5.1 CNF/Epoxy Composites 88


4.5.2 CNF/Phenolic Resin Composites 89


4.5.3 CNF/Polyaniline (PANI) Composites 89


4.5.4 CNF/Poly (Ether Ether Ketone) Nanocomposite 90


4.5.5 CNF/Biopolymers Nanocomposites 90


4.5.6 CNT/CNF-Epoxy Nanocomposites 91


4.6 Possible Futuristic Applications of CNF/Polymer Composites 91


4.6.1 Sensors 92


4.6.2 Batteries 93


4.6.3 Food Packaging 94


4.7 Summary 95


References 95


5 Characterization of Carbon Nanofiber 99
Sundeep Deulkar


5.1 Introduction 99


5.2 Microscopic Characterization Techniques 99


5.2.1 Atomic Force Microscopy (AFM) 100


5.2.2 Scanning Tunneling Microscopy (STM) 103


5.2.3 Electron Microscopy for Morphology and Surface Characterization 104


5.2.3.1 Scanning Electron Microscopy (SEM) 104


5.2.3.2 Transmission Electron Microscopy (TEM) and Scanning Transmission Electron Microscopy (STEM) 108


5.3 Spectroscopic Characterization 112


5.3.1 Raman Spectroscopic Studies of Carbon Nanofibers 113


5.4 Spectroscopic Analysis of CNF by XRD 117


5.5 Measurement of Mechanical Properties of CNF 122


5.5.1 Tensile Strength Testing/Tension Testing 122


5.5.2 Young's Modulus 123


5.6 Optical Property Analysis of CNF 127


5.6.1 Ellipsometric Method for CNF and MCNF 128


5.6.2 UV-Vis-NIR Spectrophotometric Method for ACNF Analysis 129


5.6.3 Measuring Optical Band Gap 131


5.7 Thermal Properties and Thermal Effect Analysis 132


5.7.1 Thermogravimetric Analysis (TGA) 132


5.7.2 Differential Scanning Calorimetry (DSC) 134


5.7.3 Differential Thermal Analysis (DTA) 135


5.7.4 Thermal Conductivity 135


5.8 Specific Surface Area (SSA) Determination of CNF 139


5.8.1 Methylene Blue (MB) Test 140


5.8.2 Brunauer-Emmett-Teller (BET) Specific Surface Areas 142


5.9 Characterization of Electrical Properties 145


5.9.1 Two-Probe and Four-Probe Methods for Resistivity Measurement 148


5.9.2 Four-Probe Methods for Resistivity Measurement 149


5.9.3 Tunneling Atomic Force Microscopy (TUNA) Analysis 150


5.9.4 Hall Effect Measurement 152


References 154


6 Carbon Nanofiber - A Potential Superconductor 159
Harish K. Dubey


6.1 Introduction 159


6.2 Superconductors 161


6.2.1 Theory of Superconductors 161


6.2.2 Measurement Technique of Superconductivity 163


6.2.3 Types of Superconductors 163


6.3 History of Existing Superconductors 165


6.4 Superconductivity in Organic Materials 168


6.5 Can Carbon Nanofiber Also Be a Possible Superconductor? 169


6.6 Summary 173


References 173


7 Carbon Nanofiber for Hydrogen Storage 175
Bholanath Mukherjee


7.1 Introduction 175


7.2 Hydrogen - Its Advantages and Disadvantages as Source of Energy 176


7.2.1 Advantages 177


7.2.2 Disadvantages 177


7.3 Methods of Hydrogen Storage 178


7.3.1 Storage of Liquid Hydrogen 178


7.3.2 Storage of Gaseous Hydrogen 178


7.3.2.1 In Metal Hydride Storage Tanks 178


7.3.2.2 Storage of Compressed Hydrogen in High-Pressure Tank 179


7.3.2.3 Hydrogen Storage in Glass Microspheres 179


7.3.2.4 Storage in Array of Glass Micro Tubules/Capillaries 180


7.3.2.5 Storage of Hydrogen in Chemicals 180


7.3.2.6 Storage of Hydrogen in Metal Amidoboranes 180


7.3.2.7 Storage of Hydrogen in Metal Organic Framework System 181


7.4 Different Forms of Carbon and Nanocarbon for Storage of Hydrogen 181


7.4.1 Activated Carbon 182


7.4.2 Single-Walled Carbon Nanotubes (SWCNTs) 184


7.4.3 Multi-Walled Carbon Nanotubes (MWCNTs) 187


7.4.4 Metal-Doped Carbon Nanotubes 188


7.4.5 Graphene and the Like 189


7.5 Carbon Fibers for Storage of Hydrogen 191


7.6 Pyrolyzed Natural Fibers from Plant/Animals to Store Hydrogen 192


7.6.1 Carbonization/Pyrolysis 192


7.7 Summary 201


References 201


8 Carbon Nanofiber for Microwave Absorption 211
Dattatray E. Kshirsagar


8.1 The Need to Develop a Microwave Absorber 211


8.2 Types of Microwave Absorbers 212


8.2.1 Resonant Absorber 213


8.2.2 Broadband Absorbers 215


8.2.3 Magnetic Absorbers 217


8.2.4 Dielectric Absorber 218


8.2.5 Metal Absorber 220


8.3 Considerations for Nano Absorbers 221


8.3.1 Nanoferrite Absorber 222


8.3.1.1 Limitations of Ferrites 222


8.4 The Radars 223


8.4.1 Detection and Ranging 223


8.4.2 Multi-Band 3D Radar 223


8.4.3 Quantum Radar 224


8.4.4 LIDAR (Light Imaging Detection & Ranging) 225


8.5 Role of CNF in Microwave Absorption 226


8.6 Need for Fabricating a CNF and Polymer Composite 228


8.7 Summary 230


References 232


9 Carbon Nanofiber for Removal of Dye from Aqueous Medium 235
Sanjukta Bhowmik


9.1 Introduction 235


9.2 Morphology of Biogenic and Chemically Synthesized CNFs from Different Precursors 236


9.2.1 Chemical Vapor Deposition Method (CVD) 237


9.2.2 Plasma-Enhanced Chemical Vapor Deposition (PECVD) 240


9.2.3 Electrospinning of Polymer Fibers 241


9.3 Novel Dye Removal Properties of CNF 243


9.4 Absorption of Different Dyes 245


9.5 Summary 248


References 249


10 Carbon Nanofiber to Remove Heavy Metals from Aqueous Medium 251
Jayashri Shukla


10.1 Introduction 251


10.1.1 What Are Heavy Metals? 251


10.1.2 List of Heavy Metals 252


10.1.3 Sources of Heavy Metals 252


10.2 Are Heavy Metals Essential for Living Beings? 253


10.2.1 Damaging Effect of Heavy Metals on Biosystem 253


10.2.1.1 Arsenic 254


10.2.1.2 Cadmium 254


10.2.1.3 Chromium 255


10.2.1.4 Lead 256


10.2.1.5 Mercury 256


10.2.2 Heavy Metal and Soil Toxicity 257


10.2.3 Heavy Metal and Plant Toxicity 258


10.2.4 Toxic Effects of Heavy Metals on Aquatic Environment 258


10.3 Methods Used for Removal of Heavy Metals 258


10.3.1 Adsorption 259


10.3.1.1 Adsorption on New Adsorbents 259


10.3.1.2 Adsorption on Modified Natural Materials 259


10.3.1.3 Adsorption on Industrial By-Products 260


10.3.1.4 Adsorption on Modified Agricultural and Biological Wastes (Biosorption) 263


10.3.1.5 Adsorption on Modified Biopolymers and Hydrogels 263


10.3.2 Membrane Separation/Filtration 265


10.3.3 Electrodialysis and Photocatalysis 269


10.3.4 Chemical Oxidation and Advanced Oxidation 269


10.3.5 Chemical Precipitation 269


10.3.6 Chemical Coagulation 270


10.3.7 Chemical Stabilization 271


10.3.8 Ion Exchange 271


10.3.9 Waste LCD Panel Glass 271


10.3.10 Electrolytic Recovery or Electrowinning 272


10.3.11 Electrodialysis 272


10.3.12 Photocatalysis 272


10.4 Evaluation of Heavy Metals Removal Processes 274


10.5 Role of CNF in Removing Heavy Metals 275


10.5.1 Suitability of Chemically Synthesized CNF for Heavy Metal Removal 277


10.5.2 Suitability of Biogenic CNF 277


10.6 CNF to Remove Heavy Metals 279


10.7 Summary 284


References 284


11 Carbon Nanofiber as Electrode in Li-Ion Battery 291
Manisha Khemani


11.1 Introduction 291


11.1.1 Why Lithium? 292


11.2 Types of Lithium-Ion Batteries 294


11.2.1 Lithium Nickel Manganese Cobalt Oxide Battery 294


11.2.2 Lithium Cobalt Oxide Battery 294


11.2.3 Lithium Manganese Oxide Battery 294


11.2.4 Lithium-Titanate Battery 295


11.2.5 Lithium Iron Phosphate Battery 295


11.3 Theory of Generation of Power in Lithium Battery 295


11.3.1 Positive Electrode or Cathode 295


11.3.2 Negative Electrode Anode 296


11.3.3 Electrolyte 296


11.4 Role of Carbon, Lithium and Cobalt in Li-Battery 297


11.4.1 Advantages of LIB 300


11.4.2 Disadvantages of LIB 302


11.5 Role of CNF in Lithium Battery and Possibility of Increasing Its Efficiency 303


11.6 Recent Advances in Lithium Battery Utilizing Carbon Nanomaterial and CNF 305


11.6.1 Polyacrylonitrile (PAN) 306


11.6.2 Walnut Shell 306


11.6.3 FeOx-CNT/CNF Composite 306


11.6.4 Carbon Nanobeads (CNB) from Camphor 306


11.6.5 Tea Leaves 307


11.6.6 Various Carbon Materials 308


11.7 Summary 309


References 309


12 Carbon Nanofiber and Photovoltaic Solar Cell 313
Kailash Jagdeo and Maheshwar Sharon


12.1 Introduction 313


12.2 Formation of a Semiconducting Material 314


12.2.1 Introduction to P-N Junction 316


12.3 Semiconductors for Solar Cell 320


12.4 Attempts Made in Making Carbon-Based Solar Cell 320


12.5 Is CNF a Suitable Material for Solar Cell? 321


12.6 Summary 327


References 327


13 Application of Carbon Nanofiber in Antenna 331
Mahesh Partapure


13.1 Introduction 331


13.2 Radiation Types and Characteristics of Antenna 333


13.2.1 Radiation Density 334


13.2.2 Radiation Pattern 334


13.2.3 Directivity 335


13.2.4 Gain 335


13.2.5 Effective Area 336


13.2.6 Input Impedance 336


13.2.7 Impedance Matching 336


13.2.8 Return Loss and Voltage Standing Wave Ratio (VSWR) 336


13.3 Carbon Nanomaterial 337


13.4 Application of Carbon Nanofibers in Antenna 338


13.5 Summary 339


References 340


14 Carbon Nanofiber in Cosmetics 341
Archana Singh


14.1 Introduction 341


14.2 What is a Nanocosmetic 342


14.3 Cosmetics with Nanoparticles in Today's Market 342


14.4 Nanoparticles Used in Cosmetics 344


14.4.1 Titanium Dioxide (TiO2) 344


14.4.2 Zinc Oxide (ZnO) 346


14.4.3 Gold Nanoparticles 348


14.4.4 Silver Nanoparticles 349


14.4.5 Selenium Nanoparticles 350


14.5 Nano-Compositions Used for Loading and Delivery of Nanoparticle 351


14.5.1 Nanoliposomes 352


14.5.2 Solid Liquid Nanoparticles (SLN) 353


14.5.3 Cubosomes 354


14.5.4 Dendrimers 355


14.5.5 Nanocrystals 356


14.6 Cosmetics Containing Carbon Nanomaterials 357


14.6.1 Nanoforms of Carbon for Cosmetics Used in Ancient India that Still Prevail Today: Herbal Kajal/Kohl 357


14.6.2 Carbon-Based Cosmetics 358


14.6.3 Contemporary Cosmetics Using Carbon 358


14.7 Can Activated Carbon, Carbon Black and Carbon Nanotubes Be Replaced with CNF for Use in Cosmetics? 359


14.8 Summary 361


References 362


15 Carbon Nanofiber in Regenerative Medicine 365
Pramod Desai


15.1 Introduction 365


15.1.1 Tissue Engineering - Concept in a Nutshell 365


15.1.2 Why Carbon Nanotubes Are Versatile Scaffolds 367


15.2 Cell Tracking and Labeling 368


15.2.1 Optical Labeling 368


15.2.2 Magnetic Resonance Imaging (MRI) Contrast Agent 369


15.2.3 Radio Labeling 370


15.3 Sensing Cellular Behavior 371


15.4 Augmenting Cellular Behavior 372


15.5 Carbon Nanotubes as Structural Support for Tissue Engineering 374


15.6 Cytotoxicity of Carbon Nanofiber (CNF) 375


15.7 Biocompatibility of Carbon Nanofibers 377


15.7.1 CNTs with Neuronal Cells 378


15.7.2 CNTs with Osteoblast Cell 379


15.7.3 CNTs with Antibody Interactions 380


15.7.4 Ion Channel Interactions with CNTs 380


15.8 Dispersion of Carbon Nanofibers 380


15.8.1 Sonication 380


15.8.2 Stabilization with Surfactant 381


15.8.3 Covalent Functionalization 381


15.9 Summary 381


References 382


16 Carbon Nanofibers and Agro-Technology 389
Manisha Sharan and Madhuri Sharon


16.1 Introduction 389


16.1.1 The Importance of Nanoscale 390


16.1.2 Carbon Nanomaterials 390


16.2 Carbon Nanofibers 391


16.3 Carbon Nanofiber and Agriculture 391


16.3.1 CNF for Plant Growth and Crop Yield 393


16.3.1.1 Seed Germination 394


16.3.1.2 CNF as Fertilizer 395


16.3.1.3 CNF as Plant Growth Stimulator 396


16.3.2 CNF for Plant Protection 396


16.3.2.1 CNF as Antimicrobial and Antifungal for Surface Coating 396


16.3.2.2 CNF as Support for Pesticides, Herbicides and Insecticides 398


16.3.3 CNF for Soil Improvement 398


16.3.4 CNF for Controlled Environment Agriculture 398


16.3.5 CNF for Precision Farming 399


16.3.5.1 CNF and Nanosensors for Diagnostics in Agriculture 400


16.4 Summary 401


References 401


Index 407