Preface...xv List of Contributors...xvii CHAPTER 1 Nanotechnology to Nanomanufacturing... 1 1.1 Introduction...1 1.2 Approaches to Nanotechnology...2 1.3 Transition from Nanotechnology to Nanomanufacturing...3 1.3.1 Top-Down Approach...4 1.3.2 Bottom-Up Approach...5 1.4 Conclusions...10 References...13 CHAPTER 2 Gas Phase Nanofication: A Strategy to Impart Fast Response in Sensors... 14 2.1 Introduction...15 2.2 Proposed Rationale...16 2.3 Methods of Establishing the Desired Redox Po 2...17 2.4 Sample Preparation...20 2.4.1 Materials and Processing...20 2.4.2 Characterization...22 2.4.3 High Temperature Reductive Etching Process...22 2.4.4 Gas Sensing Experiments...23 2.5 Results and Discussion...23 2.5.1 Mo- and MoO 3 -Based Studies...23 2.5.2 W- and WO 3 -Based Studies...30 2.5.3 TiO 2 -Based Studies...41 2.6 Conclusions...50 References...51 CHAPTER 3 Advanced Characterization Techniques for Nanostructures... 53 3.1 Measurement of the Topology of Nanostructures...54 3.1.1 Field Emission Scanning Electron Microscope...54 3.1.2 Scanning Probe Microscopy...55 3.1.3 Optical Microscopes...61 3.2 Measurement of Internal Geometries of Nanostructures...66 3.2.1 Transmission Electron Microscope...66 3.2.2 Focused Ion Beam...67 v
vi Contents 3.2.3 X-Ray Diffraction...69 3.2.4 Mercury Porosimetry...70 3.3 Measurement of Composition of Nanostructures...73 3.3.1 Energy Dispersive X-Ray Spectroscopy...73 3.3.2 X-Ray Photoelectron Spectroscopy...75 3.3.3 Secondary Ion Mass Spectroscopy...77 3.3.4 Auger Electron Spectroscopy...78 3.4 Conclusion...80 References...81 CHAPTER 4 Non-Lithographic Techniques for Nanostructuring of Thin Films and Bulk Surfaces... 86 4.1 Introduction...86 4.2 Template-Assisted Nanostructuring...88 4.3 Electric Field Induced Nanostructuring...101 4.4 Laser-Induced Nanostructuring...107 4.5 Vapour Liquid Solid Technique...113 4.6 Summary and Outlook...118 Acknowledgements...119 References...119 CHAPTER 5 Engineered Carbon Nanotube Field Emission Devices... 125 5.1 Introduction...126 5.1.1 Synthesis...128 5.1.2 Positional Control...139 5.1.3 Alignment Control...142 5.2 Field Emission...144 5.2.1 Electron Microscopy...155 5.2.2 Parallel Electron Beam Lithography...157 5.2.3 X-Ray Sources...159 5.2.4 Microwave Sources...162 5.2.5 Displays...163 5.2.6 Gas Ionization Sensors and Gauges...166 5.2.7 Interstellar Propulsion...169 5.3 Conclusion...169 Acknowledgments...170 References...170 CHAPTER 6 Upconverting Fluorescent Nanoparticles for Biological Applications... 187 6.1 Introduction...187 6.2 The Mechanism of Fluorescent UC...189
vii 6.3 Upconverting Nanoparticles...189 6.4 Conjugation of Biomolecules to UCN...190 6.5 UCN for Biological Applications...193 6.5.1 UCN in Immunoassays...193 6.5.2 UCN in Bioimaging...194 6.5.3 UCN for Photodynamic Therapy...195 6.6 Conclusion...197 Acknowledgements...197 References...197 CHAPTER 7 Micro- and Nanomachining... 202 7.1 Introduction...203 7.2 Machining Effects at the Microscale...203 7.2.1 Shear Angle Prediction...206 7.2.2 Plastic Behavior at Large Strains...210 7.2.3 Langford and Cohen s Model...210 7.2.4 Walker and Shaw s Model...211 7.2.5 Usui s Model...212 7.2.6 Sawtooth Chip Formation in Hard Turning...212 7.2.7 Fluid-Like Flow in Chip Formation...213 7.3 Size Effects in Micromachining...214 7.4 Nanomachining...214 7.4.1 Nanometric Machining...215 7.4.2 Theoretical Basis of Nanomachining...216 7.4.3 Comparison of Nanometric Machining and Conventional Machining...227 Acknowledgments...227 References...227 CHAPTER 8 Design of Experiments: A Key to Innovation in Nanotechnology... 230 8.1 Introduction to DoE...231 8.2 OFAT: The Predominant Method Used in Practice...232 8.3 Traditional Methods Used in Research and Development...234 8.3.1 Completely Randomized Design...235 8.3.2 Two-Level Factorial Design...236 8.3.3 RSM...237 8.3.4 Taguchi s Method...238 8.3.5 Opportunities for Improvement in Experimentation...239 8.4 Modern DoE Methods Appropriate for Nanotechnology and Nanomanufacturing...240 8.4.1 Split Plot Design and Its Variants...240
viii Contents 8.4.2 MSSP Design...242 8.4.3 Repeated Measures...243 8.4.4 Saturated and Supersaturated Design...243 8.4.5 Mixture Design...244 8.4.6 Computer Deterministic Experiments...244 8.4.7 Computer-Generated Design: Alphabetical Optimal Design...245 8.5 Summary of Nanotechnology Articles That Use Statistical Experimentation...245 8.6 Final Remarks...250 References...250 CHAPTER 9 Environmental and Occupational Health Issues with Nanoparticles... 255 9.1 Introduction...255 9.2 Potential Health Effects...256 9.3 Current State of the Literature...257 9.4 Characterization of Airborne Nanoparticles...263 9.5 Conclusions...268 References...268 CHAPTER 10 Commercialization of Nanotechnologies: Technology Transfer from University Research Laboratories... 270 10.1 Introduction...271 10.1.1 Venture Capitalists...271 10.1.2 Start-Up Companies in Nanotechnology...272 10.2 Role of Government in Commercialization...272 10.3 Role of Academic Research in Commercializing Nanotechnology Products...273 10.4 Technology Transfer for Nanotechnology Products...275 10.5 IP Impact and Ownership...276 10.5.1 Patents...276 10.5.2 Trade Secrets...276 10.5.3 Copyright...276 10.6 Role of the Entrepreneur, Major Corporations, and National Laboratories in Commercialization...277 10.7 Concluding Remarks...277 Acknowledgments...278 References...278 Internet Resources...278
ix CHAPTER 11 Fabrication of Hydrogel Micropatterns by Soft Photolithography... 279 11.1 Introduction...279 11.2 Microfabrication...280 11.2.1 Microfabrication Techniques...281 11.3 Lithography...282 11.4 Hydrogel as a Biomaterial...282 11.5 Soft Photolithography of Hydrogel Micropatterns...283 11.5.1 Fabrication of PDMS Stamp...283 11.5.2 Surface Functionalization of Silicon Substrates by Silanization...286 11.5.3 Soft Photolithography...287 11.6 Conclusion...290 References...291 CHAPTER 12 Nanocrystalline Diamond for RF-MEMS Applications... 294 12.1 Introduction...294 12.2 Diamond Crystal Structure and Properties...295 12.3 Chemical Vapour Deposition of Diamond Films...296 12.4 Growth Mechanism of NCD Films...298 12.5 Techniques for the Characterization of NCD Films...299 12.6 Mechanical Resonators...304 12.7 Electrostatic and Thermal Switches...305 12.8 Design of the Thermally Actuated NCD Actuator...306 12.9 Fabrication and Integration...307 12.10 Measurement and Analysis...310 Acknowledgements...315 References...316 CHAPTER 13 Analysis of the Effects of Micromachining Using Nanostructured Cutting Tools... 319 13.1 Introduction...319 13.2 Computational Analyses...320 13.2.1 Computational Analysis of Temperature in Micromachining...320 13.2.2 Finite Element Analysis...329 13.3 Computational Results...330 13.3.1 Uncoated Microtools...330 13.3.2 Coated Cutting Tools...331 13.4 Discussion...337
x Contents 13.5 Conclusions...341 Acknowledgments...341 References...341 CHAPTER 14 Metal Oxide Nanopowder... 343 14.1 Introduction...344 14.2 Use of Nanopowders Since the Year 2000...348 14.3 The Chemistry of Metal Oxide Nanopowder...352 14.3.1 Important Behaviour of Metal Oxide Nanopowder...354 14.3.2 Criteria for the Synthesis of Metal Oxide...354 14.3.3 Requirements for the Synthesis of Nanoparticles...357 14.3.4 Controlling Factors for the Growth of Nanopowder...357 14.4 Different Methods Used for the Synthesis of Metal Oxide Nanopowder...359 14.4.1 High Temperature Synthesis...359 14.4.2 Low Temperature Synthesis...360 14.4.3 Replication Method...360 14.4.4 Mechanical Attrition...360 14.4.5 Hydrothermal Synthesis...360 14.4.6 Inverse Micelle Method...361 14.4.7 Sol Gel Process...362 14.4.8 General Mechanism for Sol Gel Process...364 14.4.9 Acid-Catalysed Mechanism...364 14.4.10 Pechini Method...367 14.5 Characterization of Metal Oxide Nanopowder...370 14.5.1 Infrared Spectroscopy...370 14.5.2 Ultraviolet Spectroscopy...371 14.5.3 Thermal Analysis...371 14.5.4 Raman Spectroscopy...371 14.5.5 Atomic Force Microscopy...372 14.5.6 X-Ray Diffraction Studies...373 14.5.7 Wide Angle X-Ray Scattering...373 14.5.8 Small Angle X-Ray Scattering...373 14.5.9 Electron Microscopy...374 14.5.10 Transmission Electron Microscopy...374 14.5.11 Scanning Electron Microscopy...374 14.5.12 Characterization of Porosity...375 14.6 Application Based on Phase Transfer...376 14.6.1 The Synthesis of Monometal-Based Nanopowder...376 14.6.2 Use of Titania Film in Car...384
xi 14.7 Synthesis of Bimetallic Alkoxide for the Preparation of Bimetallic Oxide Nanopowder...384 14.7.1 Physico-Chemical Properties of Bimetallic Alkoxides...385 14.7.2 Preparation of Bimetallic Oxide Nanopowder Via Sol Gel Process...388 14.7.3 Some SEM Data of Bimetallic Oxide...389 14.8 Applications of Metal Oxide for Photoluminescence...392 14.9 Conclusions...397 14.10 Future Prospects...397 Acknowledgement...398 Dedication...398 References...398 CHAPTER 15 Some Approaches to Large-Scale Manufacturing of Liposomes... 402 15.1 Introduction...403 15.2 Structure and Self-Assembly of Phospholipids...404 15.3 Biological Functionality of Liposomes...405 15.3.1 Conventional Liposomes...405 15.3.2 Cationic Liposomes...405 15.3.3 Thermosensitive (Temperature-Sensitive) Liposomes...405 15.3.4 ph-sensitive Liposomes...406 15.3.5 Long-Circulating (Sterically Stabilized) Liposomes...406 15.3.6 Ultradeformable Liposomes (Transferosomes)...406 15.4 Methods of Liposome Preparation...407 15.4.1 Thin Film Hydration Method...407 15.4.2 Reverse Phase Evaporation Vesicles...407 15.4.3 Freeze-Drying Method...408 15.4.4 Proliposome Methods...408 15.5 Large-Scale Manufacture of Particulate-Based Proliposomes...411 15.5.1 Proliposomes Manufactured Using Fluidized-Bed Coating...412 15.5.2 Proliposomes Produced Using Air-Jet (Fluid Energy) Milling...412 15.5.3 Proliposomes Produced Using Spray Drying...413 15.6 Large-Scale Manufacture of Ethanol-Based Proliposomes...413 15.7 Conclusions...413 References...413
xii Contents CHAPTER 16 Nanocoatings in Medicine: Antiquity and Modern Times... 418 16.1 Introduction...418 16.2 What is a Nanocoating?...419 16.3 Common Nanocoating Methods...421 16.4 Nonmedical Applications of Nanocoating Technologies... 424 16.4.1 Nanoprotection...424 16.4.2 Mechanical Properties...425 16.4.3 New Functionality...426 16.5 Nanocoating of Medical Devices...428 16.5.1 Dentistry...428 16.5.2 Implants...429 16.5.3 Stents...431 16.5.4 Cells...432 16.5.5 Miscellaneous...433 16.6 Nanocoating of Pharmaceutical Dosage Forms...435 16.7 Conclusions...439 References...439 CHAPTER 17 Smart Precursors for Smart Nanoparticles... 444 17.1 Introduction...447 17.2 Type of Nanoparticles...452 17.2.1 Novel Properties of Materials at the Nanoscale...452 17.3 Structure of Nanoparticles...453 17.4 Conductive Properties...454 17.5 Metal Oxide...456 17.6 Shape of the Particles...459 17.6.1 Particle Size and Its Distributions...459 17.7 Surface Charge Density and their Colloidal Stability...459 17.7.1 Interfacial Polarity...460 17.7.2 Cross-Linking...460 17.7.3 Functionality...460 17.8 Chemistry of Metal Alkoxides Used as Single-Source Molecular Precursors for the Synthesis of Nanomaterials...460 17.8.1 Geometrical Concept in the Design of Molecular Structure...461 17.8.2 Schematic Representation of the Major Experimental Steps Involved in the Synthesis of Mixed Metal Oxide Nanopowder...464 17.8.3 Reactivity of Metal Substitution Reactions...465 17.9 Molecular Structure Plays the Decisive Role...465
xiii 17.9.1 Synthesis of Nanomaterials...468 17.9.2 Capping Agents...472 17.9.3 Liquid-Phase Synthesis...472 17.9.4 Advantages of Vapor-Phase Synthesis...480 17.9.5 Methods Used for Liquid or Vapor Precursor Process...482 17.9.6 Processing for the Synthesis of Nanostructure Materials in the Nanoparticle...482 17.9.7 Vacuum Thermal Evaporation Technique for Deposition...482 17.10 Experimental Techniques...484 17.10.1 FTIR Spectra...485 17.10.2 Difference in Energy States = Energy of Light Absorbed...486 17.10.3 Calcination at 450 C for 4 h in Dry Air...486 17.10.4 Ultraviolet and Visible Spectroscopy...487 17.10.5 Thermal Gravimetric Analysis and Differential Thermal Analysis...493 17.10.6 Specific Surface Area...494 17.10.7 Scanning Electron Microscopy...498 17.10.8 Probe Microscopy...500 17.11 Diffraction Techniques...500 17.11.1 Neutron Diffraction...501 17.12 Miscellaneous Techniques...504 17.12.1 Confocal Laser Scanning Microscopy...504 17.12.2 Extended X-Ray Absorption Fine Structure (EXAFS)...504 17.12.3 X-Ray Fluorescence Spectroscopy...505 17.12.4 Mass Spectroscopy...505 17.12.5 Photoelectron Spectroscopy...505 17.12.6 X-Ray Photoelectron Spectroscopy...505 17.12.7 Brunauer, Emmett and Teller (BET)...506 17.13 Applications of Nanomaterials...506 17.14 Uses of Nanomaterials for Various Applications...507 17.14.1 Thin Coatings...508 17.15 Conclusion...521 Dedication...521 References...521 Index...539