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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