Essentials in Nanoscience and Nanotechnology

Narendra Kumar, Ph.D., is Former Director, DRDO, of MoD, India; carried out pioneering research in the development of advanced materials including nanomaterials and products based on them for various defense applications; and has over 100 research papers, 12 patents, and a book, Nanotechnology and Nanomaterials in the Treatment of Life-Threatening Diseases, to his credit. He is recipient of several national awards including Best Scientist DRDO Award and MRSI- Annual Award, 2010. Dr. Kumar is associated with American Chemical Society and Materials Research Society of India. Sunita Kumbhat, Ph.D., is Professor of Chemistry at J. N. V. University, Jodhpur, India, teaching graduate and postgraduate courses on Analytical Chemistry; research fields include electrochemistry, sensor/biosensor, SPR technology, and nanomaterials. She has been Commonwealth Academic Staff Fellow 1994–1995, Oxford University; UGC-National Associate 1995–1997, BARC, Mumbai; and INSA-JSPS Fellow 2005, Kyushu University, Japan. Dr. Kumbhat is associated with International Society Electrochemistry, Bioelectrochemical Society, Chemical Research Society of India, and National Assessment and Accreditation Council, India.

• Preface xiiiAcknowledgments xvAbout the Authors xvii1 Introduction 11.1 Definitions of Nanoscience and Nanotechnologies 11.2 Uniqueness of the Nanoscale 31.3 Nanoscience in Nature 41.3.1 Naturally Occurring Nanomaterials 71.3.2 Nanoscience in Action in Biological World 81.4 Historical Perspective 101.5 Nanomaterials 131.5.1 Nanoparticles 161.5.2 Nanowires and Nanotubes 171.5.3 Nanolayers/Nanocoatings 171.5.4 Nanoporous Materials 171.6 Strategies for Synthesis of Nanomaterials 181.7 Properties of Nanomaterials 181.8 Significance of Nanoscience 191.9 Commercial Applications 201.9.1 Food Industry 221.9.2 Cosmetics 221.9.3 Textile 221.9.4 Medicine 221.9.5 Electrical and Electronic Goods 231.10 Potential Health Hazards and Environmental Risks 241.11 Futuristic Outlook 25Review Questions 26References 272 Nanomaterials: General Synthetic Approaches 292.1 Introduction 292.2 Top-Down Approach 302.2.1 Mechanical Milling 312.2.2 Mechanochemical Processing (MCP) 322.2.3 Electro-Explosion 332.2.4 Sputtering 342.2.5 Etching 342.2.6 Laser Ablation 362.2.7 Lithography 372.2.8 Aerosol-Based Techniques 432.2.9 Electrospinning 472.3 Bottom-Up Approaches 492.3.1 Chemical Vapor Deposition 492.3.2 Chemical Vapor Condensation (CVC) 542.3.3 Plasma Arcing 552.3.4 Wet Chemical Methods 552.3.5 Hydrothermal/Solvothermal 602.3.6 Reverse Micelle Method 602.3.7 Sol–Gel Method 612.3.8 Sonochemical Method 642.3.9 Biomimetic Approaches 662.3.10 Molecular Self-Assembly 702.3.11 Langmuir–Blodgett (LB) Film Formation 712.3.12 Stabilization and Functionalization of Nanoparticles 72Review Questions 73References 743 Characterization Tools for Nanomaterials 773.1 Introduction 773.2 Imaging Through Electron Microscopy 793.2.1 Scanning Electron Microscope (SEM) 853.2.2 Transmission Electron Microscope (TEM) 913.3 Scanning Probe Microscopy (SPM) 973.3.1 Scanning Tunneling Microscope (STM) 973.3.2 Atomic Force Microscope (AFM) 1023.4 Characterization Through Spectroscopy 1073.4.1 UV–Visible Plasmon Absorption and Emission 1083.4.2 Vibrational Spectroscopies: FTIR and Raman Spectroscopy 1093.4.3 Raman Spectroscopy Based Imaging 1163.4.4 X-Ray Photoelectron Spectroscopy (XPS) 1193.4.5 Auger Electron Spectroscopy 1263.4.6 Secondary Ion Mass Spectrometry (SIMS) 1303.5 Scattering Techniques 1333.5.1 X-Ray Diffraction Methods 1343.5.2 Dynamic Light Scattering (DLS) 1403.5.3 Zeta Potential Analysis 142Review Questions 145References 1464 Nanomaterials 1494.1 Introduction 1494.2 Inorganic Nanomaterials 1504.2.1 Metals and Alloys 1504.2.2 Metal Oxides of Transition and Non-transition Elements 1564.2.3 Non-oxide Inorganic Nanomaterials 1614.3 Organic Nanomaterials 1614.3.1 Polymeric Nanoparticles 1614.3.2 Polymeric Nanofilms 1624.3.3 Nanocellulose 1624.3.4 Biodegradable Polymer Nanoparticles 1654.3.5 Dendrimers 1654.4 Biological Nanomaterials 1664.4.1 Categories 1674.4.2 Potential Applications 1694.5 Nanoporous Materials 1704.6 Quantum Dots 1734.7 Nanoclusters 1754.8 Nanomaterials in Different Configurations 1784.8.1 Nanofibers 1794.8.2 Nanowires 1794.8.3 Nanotubes 1804.8.4 Nanobelts 1834.8.5 Nanorods 184Review Questions 185References 1865 Carbon-Based Nanomaterials 1895.1 General Introduction 1895.1.1 Carbon Nanomaterials: Synthetic Carbon Allotropes (SCAs) 1905.2 Fullerene 1925.2.1 Properties of Fullerene 1935.2.2 Application Potentials of Fullerene 1955.3 Carbon Nanotubes (CNTs) 1965.3.1 Classification of CNTs 1965.3.2 Synthesis of CNTs 1985.3.3 Functionalization of CNTs 2035.3.4 Purification of CNTs 2055.3.5 Special Properties of Carbon Nanotubes 2075.3.6 Applications 2085.4 Graphene 2085.4.1 Electronic Structure of Graphene 2105.4.2 Unique Properties of Graphene 2115.4.3 Synthesis 2125.4.4 Characterization of Graphene 2195.4.5 Applications 2215.5 Carbon Nano-Onions 2225.6 Carbon Nanofibers 2245.7 Carbon Black 2255.7.1 Crystallinity 2275.7.2 Homogeneity and Uniformity 2275.8 Nanodiamond 2275.8.1 Synthesis of Nanodiamond 2285.8.2 Properties 2305.8.3 Applications 232Review Questions 233References 2346 Self-Assembled and Supramolecular Nanomaterials 2376.1 Introduction: Self-Assembly 2376.1.1 Supramolecular Chemistry 2386.2 Historical Perspective of Supramolecular and Self-Assembled Structures 2396.3 Fundamental Aspects of Supramolecular Chemistry 2406.3.1 Molecular Self-Assembly 2416.3.2 Molecular Recognition and Complexation 2426.3.3 Mechanically Interlocked Molecular Architectures 2426.3.4 Supramolecular Organic Frameworks (SOFs) 2426.3.5 Biomimetic 2436.3.6 Imprinting 2436.3.7 Molecular Machines 2436.4 Self-Assembly Via Non-Covalent Interaction 2446.4.1 Long-Range Forces in Self-Assembly 2446.4.2 Short-Range Forces in Self-Assembly 2476.4.3 Self-Assembly in Soft Materials 2506.4.4 Advantages of Self-Assembly 2516.4.5 Challenges in Self-Assembly 2526.5 Synthetic Strategies for Molecular Self-Assembly 2526.5.1 Physiosorption (Patterned Organic Monolayers) 2536.5.2 Chemisorption 2546.5.3 Metal Ion–Ligand Interactions 2546.6 Biological Self-Assembly 2556.7 Templated (Non-Molecular) Self-Assembly 2566.7.1 Self-Assembly Through Capillary Interactions 2576.7.2 Self Assembly Through Lego Chemistry 2586.8 Self-Assembled Supramolecular Nanostructures 2606.8.1 Inorganic Colloidal Systems 2616.8.2 Liquid-Crystalline Structures 2626.8.3 Self-Assembled Structured Nano-Objects in Unusual Shapes 2636.9 Self-Folding Nanostructures 2636.10 Applications 2646.10.1 Supramolecular Chemistry 2646.10.2 Self-Assembled Nanomaterials 2656.10.3 Nanomotors 266Review Questions 267References 2687 Nanocomposites 2717.1 Introduction 2717.1.1 Man-Made Ancient Composites 2727.1.2 Modern Examples of Composites 2737.1.3 Nanocomposites 2737.1.4 Structure and Composition of Nanocomposites 2747.1.5 Properties of Composite Materials 2767.1.6 Classification of Nanocomposites 2777.2 Ceramic–Matrix Nanocomposites 2797.2.1 Structural Ceramic Nanocomposites 2797.2.2 Functional Ceramic Nanocomposites 2837.3 Metal–Matrix Nanocomposites 2847.3.1 Metal–Ceramic Nanocomposites 2857.3.2 Carbon Nanotubes–Metal Matrix Composites 2867.4 Polymer–Matrix Nanocomposites 2897.4.1 Polymer–Inorganic Nanocomposites (PINCs) 2917.4.2 Polymer–Clay Nanocomposites (PCNs) 2997.4.3 Polymer–Carbon Nanocomposites 3067.4.4 Polymer–Polysaccharide Nanocomposites 3107.5 Nanocoatings 3137.5.1 Functional Nanocoating 3147.5.2 Smart (Responsive) Nanocoatings 321Review Questions 322References 3238 Unique Properties 3268.1 Introduction 3268.2 Size Effects 3278.2.1 Quantum Confinement 3288.2.2 The Density of States (DOS) 3308.2.3 High Surface Area 3328.3 Physical Properties 3348.3.1 Thermal Properties 3358.3.2 Optical Properties 3368.3.3 Electronic Properties 3418.3.4 Electrical Properties 3428.3.5 Magnetic Properties 3468.3.6 Mechanical Properties 3528.4 Chemical Properties at Nanoscale 3538.4.1 Bonding 3538.4.2 Surface Properties 3548.4.3 Catalysis 3548.4.4 Detection 3558.5 The Concept of Pseudo-Atoms 356Review Questions 356References 3589 Applications of Nanotechnology 3619.1 Introduction 3619.2 Medicine and Healthcare 3639.2.1 Diagnosis 3639.3 Drug Development and Drug Delivery System 3689.3.1 Drug Design and Screening 3689.3.2 Advanced Drug Delivery Systems 3699.3.3 Targeted Drug Delivery 3719.3.4 Remotely Triggered Delivery Systems 3729.3.5 Therapy 3729.3.6 Tissue and Biomaterial Engineering 3739.4 Information and Computer Technologies 3749.4.1 Integrated Circuits 3759.4.2 Data Storage 3769.4.3 Displays 3789.5 Nanoelectromechanical Systems (NEMS) 3809.6 Nanotechnologies in Tags 3819.7 Nanotechnology for Environmental Issues 3829.7.1 Water Purification and Remediation 3839.7.2 Nanotechnology for Air Pollution Control 3849.8 Energy 3859.8.1 Photovoltaic Technologies for Solar-Energy Harvesting 3869.8.2 Artificial Photosynthesis: Production of Solar Fuel 3919.8.3 Thermoelectric Energy 3929.8.4 Piezoelectric Nanomaterials 3949.8.5 Hydrogen Generation and Storage 3949.8.6 Batteries 3979.9 Nanotechnology in Enhancing the Fuel Efficiency 4019.10 Chemical and Biosensors Using Nanomaterials (NMs) 4019.10.1 Artificial Nose as Chemical/Biosensor 4029.11 Nanotechnology in Agro Forestry 4039.11.1 Precision Farming 4039.11.2 Smart Delivery Systems 4049.12 Defense Applications 4049.12.1 Light Military Platforms 4059.12.2 Nanotechnology for Camouflage/Stealth 4059.12.3 Affordable Energy 4079.12.4 Deadly Weapons 4079.13 Nanotechnology in Space 4089.13.1 Space Flight and Nanotechnology: Applications Under Development 4089.14 Consumer Goods 4099.14.1 Nanotextiles 4099.14.2 Self-Cleaning 4109.14.3 Antimicrobial Coatings on Textiles and Other Products 4119.14.4 Cosmetics 4129.15 Sport Goods 413Review Questions 416References 41710 Toxicity and Environmental Issues 41910.1 Introduction 41910.1.1 Toxicity of Nanoparticles 42110.2 Sources of Nanoparticles and Their Health Effects 42210.2.1 Natural Sources of Nanoparticles 42210.2.2 Anthropogenic Nanomaterials 42610.3 Toxicology of Engineered Nanoparticles 43110.3.1 Respiratory Tract Uptake and Clearance 43110.3.2 Cellular Interaction with Nanoparticles 43410.3.3 Nervous System Uptake of Nanoparticles 43710.3.4 Nanoparticles Translocation to the Lymphatic Systems 43810.3.5 Nanoparticles Translocation to the Circulatory System 43810.3.6 Liver Spleen Kidneys Uptake of Nanoparticles 44110.3.7 Gastrointestinal Tract Uptake and Clearance of Nanoparticles 44110.3.8 Dermal Uptake of Nanoparticles 44310.3.9 Nanoparticles Uptake via Injection 44410.3.10 Nanoparticles Generation by Implants 44410.4 Positive Health Effects of Nanoparticles 44510.4.1 Nanoparticles as Antioxidants 44510.4.2 Antimicrobial Activity 44510.5 Environmental Sustainability 44510.6 Safe Working with Nanomaterials 44710.6.1 Safe Laboratory Practices in Handling Nanomaterials 44810.6.2 Exposure Monitoring 44910.7 Nanomaterial Waste Management 44910.8 Gaps in Knowledge about Health Effects of Engineered Nanoparticles 45110.9 Government Standards and Materials Safety Data Sheets 45210.9.1 Control Banding 45310.9.2 Hierarchy of Controls 45310.9.3 Engineering Controls 45310.9.4 Administrative Controls 45410.9.5 Personal Protective Equipment 45510.10 Risk Management 455Review Questions 458References 458Index 463