v

Contents

Preface ......................................................................................................................xvList of Contributors ................................................................................................xvii

CHAPTER 1 Nanotechnology to Nanomanufacturing �������������������� 11�1 Introduction .....................................................................................11�2 Approaches to Nanotechnology ......................................................21�3 Transition from Nanotechnology to Nanomanufacturing ...............3

1.3.1 Top-Down Approach .............................................................41.3.2 Bottom-Up Approach ............................................................5

1�4 Conclusions ...................................................................................10References ............................................................................................13

CHAPTER 2 Gas Phase Nanofication: A Strategy to Impart Fast Response in Sensors ��������������������������� 14

2�1 Introduction ...................................................................................152�2 Proposed Rationale........................................................................162�3 Methods of Establishing the Desired Redox Po2 ..........................172�4 Sample Preparation .......................................................................20

2.4.1 Materials and Processing.....................................................202.4.2 Characterization ..................................................................222.4.3 High Temperature Reductive Etching Process ....................222.4.4 Gas Sensing Experiments ....................................................23

2�5 Results and Discussion ..................................................................232.5.1 Mo- and MoO3-Based Studies ............................................232.5.2 W- and WO3-Based Studies ................................................302.5.3 TiO2-Based Studies .............................................................41

2�6 Conclusions ...................................................................................50References ............................................................................................51

CHAPTER 3 Advanced Characterization Techniques for Nanostructures ������������������������������������������������ 53

3�1 Measurement of the Topology of Nanostructures .........................543.1.1 Field Emission Scanning Electron Microscope ..................543.1.2 Scanning Probe Microscopy ...............................................553.1.3 Optical Microscopes............................................................61

3�2 Measurement of Internal Geometries of Nanostructures ..............663.2.1 Transmission Electron Microscope .....................................663.2.2 Focused Ion Beam ...............................................................67

vi Contents

3.2.3 X-Ray Diffraction ...............................................................693.2.4 Mercury Porosimetry ..........................................................70

3�3 Measurement of Composition of Nanostructures .........................733.3.1 Energy Dispersive X-Ray Spectroscopy .............................733.3.2 X-Ray Photoelectron Spectroscopy ....................................753.3.3 Secondary Ion Mass Spectroscopy ......................................773.3.4 Auger Electron Spectroscopy ..............................................78

3�4 Conclusion.....................................................................................80References ............................................................................................81

CHAPTER 4 Non-Lithographic Techniques for Nanostructuring of Thin Films and Bulk Surfaces ���������������������������� 86

4�1 Introduction ...................................................................................864�2 Template-Assisted Nanostructuring ..............................................884�3 Electric Field Induced Nanostructuring ......................................1014�4 Laser-Induced Nanostructuring ...................................................1074�5 Vapour–Liquid–Solid Technique .................................................1134�6 Summary and Outlook ................................................................118Acknowledgements ............................................................................119References ..........................................................................................119

CHAPTER  5 Engineered Carbon Nanotube Field Emission Devices ������������������������������������������������ 125

5�1 Introduction .................................................................................1265.1.1 Synthesis ...........................................................................1285.1.2 Positional Control..............................................................1395.1.3 Alignment Control .............................................................142

5�2 Field Emission .............................................................................1445.2.1 Electron Microscopy .........................................................1555.2.2 Parallel Electron Beam Lithography .................................1575.2.3 X-Ray Sources ..................................................................1595.2.4 Microwave Sources ...........................................................1625.2.5 Displays .............................................................................1635.2.6 Gas Ionization Sensors and Gauges ..................................1665.2.7 Interstellar Propulsion .......................................................169

5�3 Conclusion...................................................................................169Acknowledgments ..............................................................................170References ..........................................................................................170

CHAPTER 6 Upconverting Fluorescent Nanoparticles for Biological Applications ���������������������������������� 187

6�1 Introduction .................................................................................1876�2 The Mechanism of Fluorescent UC ............................................189

viiContents

6�3 Upconverting Nanoparticles ........................................................1896�4 Conjugation of Biomolecules to UCN ........................................1906�5 UCN for Biological Applications ................................................193

6.5.1 UCN in Immunoassays .....................................................1936.5.2 UCN in Bioimaging ..........................................................1946.5.3 UCN for Photodynamic Therapy ......................................195

6�6 Conclusion...................................................................................197Acknowledgements ............................................................................197References ..........................................................................................197

CHAPTER 7 Micro- and Nanomachining ��������������������������������� 2027�1 Introduction .................................................................................2037�2 Machining Effects at the Microscale ...........................................203

7.2.1 Shear Angle Prediction ......................................................2067.2.2 Plastic Behavior at Large Strains ......................................2107.2.3 Langford and Cohen’s Model............................................2107.2.4 Walker and Shaw’s Model .................................................2117.2.5 Usui’s Model .....................................................................2127.2.6 Sawtooth Chip Formation in Hard Turning .......................2127.2.7 Fluid-Like Flow in Chip Formation ..................................213

7�3 Size Effects in Micromachining ..................................................2147�4 Nanomachining ...........................................................................214

7.4.1 Nanometric Machining......................................................2157.4.2 Theoretical Basis of Nanomachining ................................2167.4.3 Comparison of Nanometric Machining

and Conventional Machining ............................................227Acknowledgments ..............................................................................227References ..........................................................................................227

CHAPTER 8 Design of Experiments: A Key to Innovation in Nanotechnology ���������������������������������������������� 230

8�1 Introduction to DoE.....................................................................2318�2 OFAT: The Predominant Method Used in Practice .....................2328�3 Traditional Methods Used in Research and Development ..........234

8.3.1 Completely Randomized Design.......................................2358.3.2 Two-Level Factorial Design ..............................................2368.3.3 RSM ..................................................................................2378.3.4 Taguchi’s Method ..............................................................2388.3.5 Opportunities for Improvement in Experimentation .........239

8�4 Modern DoE Methods Appropriate for Nanotechnology and Nanomanufacturing ..............................................................2408.4.1 Split Plot Design and Its Variants ......................................240

viii Contents

8.4.2 MSSP Design ....................................................................2428.4.3 Repeated Measures............................................................2438.4.4 Saturated and Supersaturated Design ................................2438.4.5 Mixture Design..................................................................2448.4.6 Computer Deterministic Experiments ...............................2448.4.7 Computer-Generated Design: Alphabetical

Optimal Design .................................................................2458�5 Summary of Nanotechnology Articles That Use

Statistical Experimentation .........................................................2458�6 Final Remarks .............................................................................250References ..........................................................................................250

CHAPTER 9 Environmental and Occupational Health Issues with Nanoparticles ����������������������������������� 255

9�1 Introduction .................................................................................2559�2 Potential Health Effects ...............................................................2569�3 Current State of the Literature.....................................................2579�4 Characterization of Airborne Nanoparticles................................2639�5 Conclusions .................................................................................268References ..........................................................................................268

CHAPTER 10 Commercialization of Nanotechnologies: Technology Transfer from University Research Laboratories �������������������������������������� 270

10�1 Introduction ..............................................................................27110.1.1 Venture Capitalists .......................................................27110.1.2 Start-Up Companies in Nanotechnology .....................272

10�2 Role of Government in Commercialization .............................27210�3 Role of Academic Research in Commercializing

Nanotechnology Products ........................................................27310�4 Technology Transfer for Nanotechnology Products ................27510�5 IP—Impact and Ownership ......................................................276

10.5.1 Patents ..........................................................................27610.5.2 Trade Secrets ................................................................27610.5.3 Copyright .....................................................................276

10�6 Role of the Entrepreneur, Major Corporations, and National Laboratories in Commercialization ....................277

10�7 Concluding Remarks ................................................................277Acknowledgments ..............................................................................278References ..........................................................................................278Internet Resources ..............................................................................278

ixContents

CHAPTER 11 Fabrication of Hydrogel Micropatterns by Soft Photolithography ���������������������������������������������� 279

11�1 Introduction ..............................................................................27911�2 Microfabrication ......................................................................280

11.2.1 Microfabrication Techniques .......................................28111�3 Lithography ..............................................................................28211�4 Hydrogel as a Biomaterial .......................................................28211�5 Soft Photolithography of Hydrogel Micropatterns ..................283

11.5.1 Fabrication of PDMS Stamp ........................................28311.5.2 Surface Functionalization of Silicon Substrates

by Silanization .............................................................28611.5.3 Soft Photolithography ..................................................287

11�6 Conclusion ...............................................................................290References ..........................................................................................291

CHAPTER 12 Nanocrystalline Diamond for RF-MEMS Applications ����������������������������������������������������� 294

12�1 Introduction ..............................................................................29412�2 Diamond Crystal Structure and Properties ..............................29512�3 Chemical Vapour Deposition of Diamond Films .....................29612�4 Growth Mechanism of NCD Films ..........................................29812�5 Techniques for the Characterization of NCD Films.................29912�6 Mechanical Resonators ............................................................30412�7 Electrostatic and Thermal Switches .........................................30512�8 Design of the Thermally Actuated NCD Actuator ...................30612�9 Fabrication and Integration ......................................................307

12�10 Measurement and Analysis ......................................................310Acknowledgements ...............................................................................315References .............................................................................................316

CHAPTER 13 Analysis of the Effects of Micromachining Using Nanostructured Cutting Tools ������������������� 319

13�1 Introduction ..............................................................................31913�2 Computational Analyses ..........................................................320

13.2.1 Computational Analysis of Temperature in Micromachining .......................................................320

13.2.2 Finite Element Analysis ...............................................32913�3 Computational Results .............................................................330

13.3.1 Uncoated Microtools ....................................................33013.3.2 Coated Cutting Tools ...................................................331

13�4 Discussion ................................................................................337

x Contents

13�5 Conclusions ..............................................................................341Acknowledgments ..............................................................................341References ..........................................................................................341

CHAPTER 14 Metal Oxide Nanopowder ���������������������������������� 34314�1 Introduction ..............................................................................34414�2 Use of Nanopowders Since the Year 2000 ...............................34814�3 The Chemistry of Metal Oxide Nanopowder ...........................352

14.3.1 Important Behaviour of Metal Oxide Nanopowder .....35414.3.2 Criteria for the Synthesis of Metal Oxide ....................35414.3.3 Requirements for the Synthesis of Nanoparticles ........35714.3.4 Controlling Factors for the Growth of Nanopowder ....357

14�4 Different Methods Used for the Synthesis of Metal Oxide Nanopowder ..................................................................35914.4.1 High Temperature Synthesis ........................................35914.4.2 Low Temperature Synthesis .........................................36014.4.3 Replication Method ......................................................36014.4.4 Mechanical Attrition ....................................................36014.4.5 Hydrothermal Synthesis ...............................................36014.4.6 Inverse Micelle Method ...............................................36114.4.7 Sol–Gel Process ...........................................................36214.4.8 General Mechanism for Sol–Gel Process ....................36414.4.9 Acid-Catalysed Mechanism .........................................364

14.4.10 Pechini Method ............................................................36714�5 Characterization of Metal Oxide Nanopowder ........................370

14.5.1 Infrared Spectroscopy ..................................................37014.5.2 Ultraviolet Spectroscopy ..............................................37114.5.3 Thermal Analysis .........................................................37114.5.4 Raman Spectroscopy ....................................................37114.5.5 Atomic Force Microscopy ............................................37214.5.6 X-Ray Diffraction Studies ...........................................37314.5.7 Wide Angle X-Ray Scattering ......................................37314.5.8 Small Angle X-Ray Scattering .....................................37314.5.9 Electron Microscopy ....................................................374

14.5.10 Transmission Electron Microscopy ..............................37414.5.11 Scanning Electron Microscopy ....................................37414.5.12 Characterization of Porosity ........................................375

14�6 Application Based on Phase Transfer ......................................37614.6.1 The Synthesis of Monometal-Based Nanopowder .......37614.6.2 Use of Titania Film in Car ...........................................384

xiContents

14�7 Synthesis of Bimetallic Alkoxide for the Preparation of Bimetallic Oxide Nanopowder ............................................38414.7.1 Physico-Chemical Properties of Bimetallic

Alkoxides .....................................................................38514.7.2 Preparation of Bimetallic Oxide Nanopowder

Via Sol–Gel Process .....................................................38814.7.3 Some SEM Data of Bimetallic Oxide ..........................389

14�8 Applications of Metal Oxide for Photoluminescence ..............39214�9 Conclusions ..............................................................................397

14�10 Future Prospects .......................................................................397Acknowledgement ................................................................................398Dedication ............................................................................................398References ............................................................................................398

CHAPTER 15 Some Approaches to Large-Scale Manufacturing of Liposomes ����������������������������� 402

15�1 Introduction ..............................................................................40315�2 Structure and Self-Assembly of Phospholipids .......................40415�3 Biological Functionality of Liposomes ....................................405

15.3.1 Conventional Liposomes ..............................................40515.3.2 Cationic Liposomes .....................................................40515.3.3 Thermosensitive (Temperature-Sensitive)

Liposomes ....................................................................40515.3.4 pH-Sensitive Liposomes ..............................................40615.3.5 Long-Circulating (Sterically Stabilized)

Liposomes ....................................................................40615.3.6 Ultradeformable Liposomes (Transferosomes) ...........406

15�4 Methods of Liposome Preparation ...........................................40715.4.1 Thin Film Hydration Method .......................................40715.4.2 Reverse Phase Evaporation Vesicles ............................40715.4.3 Freeze-Drying Method .................................................40815.4.4 Proliposome Methods ..................................................408

15�5 Large-Scale Manufacture of Particulate-Based Proliposomes ............................................................................41115.5.1 Proliposomes Manufactured Using Fluidized-Bed

Coating .........................................................................41215.5.2 Proliposomes Produced Using Air-Jet

(Fluid Energy) Milling .................................................41215.5.3 Proliposomes Produced Using Spray Drying ..............413

15�6 Large-Scale Manufacture of Ethanol-Based Proliposomes .....41315�7 Conclusions ..............................................................................413References ..........................................................................................413

xii Contents

CHAPTER  16 Nanocoatings in Medicine: Antiquity and Modern Times �������������������������������������������������� 418

16�1 Introduction ..............................................................................41816�2 What is a Nanocoating? ...........................................................41916�3 Common Nanocoating Methods ..............................................42116�4 Nonmedical Applications of Nanocoating Technologies .........424

16.4.1 Nanoprotection .............................................................42416.4.2 Mechanical Properties ..................................................42516.4.3 New Functionality ........................................................426

16�5 Nanocoating of Medical Devices .............................................42816.5.1 Dentistry .......................................................................42816.5.2 Implants ........................................................................42916.5.3 Stents ............................................................................43116.5.4 Cells .............................................................................43216.5.5 Miscellaneous ..............................................................433

16�6 Nanocoating of Pharmaceutical Dosage Forms .......................43516�7 Conclusions ..............................................................................439References ..........................................................................................439

CHAPTER  17 Smart Precursors for Smart Nanoparticles ��������� 44417�1 Introduction ..............................................................................44717�2 Type of Nanoparticles ..............................................................452

17.2.1 Novel Properties of Materials at the Nanoscale ...........45217�3 Structure of Nanoparticles .......................................................45317�4 Conductive Properties ..............................................................45417�5 Metal Oxide .............................................................................45617�6 Shape of the Particles ...............................................................459

17.6.1 Particle Size and Its Distributions ................................45917�7 Surface Charge Density and their Colloidal Stability ..............459

17.7.1 Interfacial Polarity .......................................................46017.7.2 Cross-Linking ..............................................................46017.7.3 Functionality ................................................................460

17�8 Chemistry of Metal Alkoxides Used as Single-Source Molecular Precursors for the Synthesis of Nanomaterials .......46017.8.1 Geometrical Concept in the Design of Molecular

Structure .......................................................................46117.8.2 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 .................46517�9 Molecular Structure Plays the Decisive Role ..........................465

xiiiContents

17.9.1 Synthesis of Nanomaterials ..........................................46817.9.2 Capping Agents ............................................................47217.9.3 Liquid-Phase Synthesis ................................................47217.9.4 Advantages of Vapor-Phase Synthesis .........................48017.9.5 Methods Used for Liquid or Vapor Precursor

Process .........................................................................48217.9.6 Processing for the Synthesis of Nanostructure

Materials in the Nanoparticle .......................................48217.9.7 Vacuum Thermal Evaporation Technique for

Deposition ....................................................................48217�10 Experimental Techniques .........................................................484

17.10.1 FTIR Spectra ..............................................................48517.10.2 Difference in Energy States = Energy of Light

Absorbed ....................................................................48617.10.3 Calcination at 450°C for 4 h in Dry Air .....................48617.10.4 Ultraviolet and Visible Spectroscopy .........................48717.10.5 Thermal Gravimetric Analysis and Differential

Thermal Analysis .......................................................49317.10.6 Specific Surface Area .................................................49417.10.7 Scanning Electron Microscopy ..................................49817.10.8 Probe Microscopy ......................................................500

17�11 Diffraction Techniques .............................................................50017.11.1 Neutron Diffraction ....................................................501

17�12 Miscellaneous Techniques .......................................................50417.12.1 Confocal Laser Scanning Microscopy .......................50417.12.2 Extended X-Ray Absorption Fine

Structure (EXAFS) .....................................................50417.12.3 X-Ray Fluorescence Spectroscopy ............................50517.12.4 Mass Spectroscopy .....................................................50517.12.5 Photoelectron Spectroscopy .......................................50517.12.6 X-Ray Photoelectron Spectroscopy ...........................50517.12.7 Brunauer, Emmett and Teller (BET) ..........................506

17�13 Applications of Nanomaterials ................................................50617�14 Uses of Nanomaterials for Various Applications .....................507

17.14.1 Thin Coatings .............................................................50817�15 Conclusion ...............................................................................521Dedication ............................................................................................521References ............................................................................................521

Index ......................................................................................................................539