Nanotechnology Commercialization
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List of Contributors xv
Preface xix
Editor in Chief xxi
1 Overview: Affirmation of Nanotechnology between 2000 and 2030 1
Mihail C. Roco
1.1 Introduction 1
1.2 Nanotechnology - A FoundationalMegatrend in Science and Engineering 2
1.3 Three Stages for Establishing the New General Purpose Technology 9
1.4 Several Challenges for Nanotechnology Development 15
1.5 About the Return on Investment 16
1.6 Closing Remarks 21
Acknowledgments 22
References 22
2 Nanocarbon Materials in Catalysis 25
Xing Zhang, Xiao Zhang, and Yongye Liang
2.1 Introduction to Nanocarbon Materials 25
2.2 Synthesis and Functionalization of Nanocarbon Materials 26
2.2.1 Synthesis and Functionalization of Carbon Nanotubes 26
2.2.2 Synthesis and Functionalization of Graphene and Graphene Oxide 27
2.2.3 Synthesis and Functionalization of Carbon Nanodots 29
2.2.4 Synthesis and Functionalization of Mesoporous Carbon 29
2.3 Applications of Nanocarbon Materials in Electrocatalysis 31
2.3.1 Oxygen Reduction Reaction 32
2.3.2 Oxygen Evolution Reaction 36
2.3.3 Hydrogen Evolution Reaction 39
2.3.4 Roles of Nanocarbon Materials in Catalytic CO2 Reduction Reaction 43
2.4 Applications of Nanocarbon Materials in Photocatalysis 47
2.4.1 Application of Nanocarbon Materials as Photogenerated Charge Acceptors 48
2.4.2 Application of Nanocarbon Materials as Electron Shuttle Mediator 48
2.4.3 Application of Nanocarbon Materials as Cocatalyst for Photocatalysts 50
2.4.4 Application of Nanocarbon Materials as Active Photocatalyst 51
2.5 Summary 51
Acknowledgments 52
References 52
3 Controlling and Characterizing Anisotropic Nanomaterial Dispersion 65
Virginia A. Davis andMicah J. Green
3.1 Introduction 65
3.2 What Is Dispersion andWhy Is It Important? 66
3.2.1 Factors Affecting Dispersion 73
3.2.2 Thermodynamic Dissolution of Pristine Nanomaterials 73
3.2.3 Intermolecular Potential in Dispersions 74
3.2.4 Functionalization of Nanomaterials 75
3.2.5 Physical Mixing 77
3.2.5.1 Sonication 77
3.2.5.2 Solvent IntercalationMethods 78
3.2.5.3 Shear Mixing Methods 78
3.3 Characterizing Dispersion State in Fluids 81
3.3.1 Visualization 81
3.3.2 Spectroscopy 83
3.3.3 TEM 85
3.3.4 AFM 85
3.3.5 Light Scattering 85
3.3.6 Rheology 86
3.4 Characterization of Dispersion State in Solidified Materials 88
3.4.1 Microscopy 89
3.4.2 Electrical Percolation 89
3.4.3 Mechanical Property Enhancement 89
3.4.4 Thermal Property Changes 90
3.5 Conclusion 90
Acknowledgments 90
References 91
4 High-Throughput Nanomanufacturing via Spray Processes 101
Gauri Nabar,Matthew Souva, Kil Ho Lee, Souvik De, Jodie Lutkenhaus, Barbara Wyslouzil, and Jessica O.Winter
4.1 Introduction 101
4.2 Flash Nanoprecipitation 104
4.2.1 Overview 104
4.2.2 Importance of Rapid Mixing 105
4.2.3 Mixers Employed in FNP 106
4.2.3.1 Confined Impinging Jet Mixers (CIJMs) 106
4.2.3.2 Multi-Inlet Vortex Mixers (MIVMs) 107
4.2.3.3 Mixer Selection 107
4.2.4 FNP Product Structure 107
4.2.5 Applications of FNP Nanocomposites 108
4.3 Electrospray 108
4.3.1 Overview 108
4.3.2 Single Nozzle Electrospray 109
4.3.2.1 Forces and Modes of Electrospray 109
4.3.2.2 Applications of Single Nozzle Electrospray 110
4.3.3 Coaxial Electrospray 111
4.3.3.1 Configuration 111
4.3.3.2 Applications 112
4.3.4 Future Directions 113
4.4 Liquid-in-Liquid Electrospray 113
4.4.1 Overview 113
4.4.2 Importance of Relative Conductivities of the Dispersed and Continuous Phases 114
4.4.3 Modified Liquid-in-Liquid Electrospray Designs 115
4.4.4 Applications and Future Directions 117
4.5 Spray-Assisted Layer-by-Layer Assembly 117
4.5.1 Overview 117
4.5.2 Influence of Processing Parameters on Film Quality 119
4.5.2.1 Effect of Concentration 120
4.5.2.2 Effect of Spraying Time 120
4.5.2.3 Effect of Spraying Distance 120
4.5.2.4 Effect of Air Pressure 121
4.5.2.5 Effect of Charge Density 121
4.5.2.6 Effect of Rinsing and Blow-Drying 122
4.5.2.7 Effect of Rinsing Solution 122
4.5.3 Applications 122
4.5.4 Future Directions 123
4.6 Conclusion and Future Directions 123
References 123
5 Overview of Nanotechnology in Military and Aerospace Applications 133
Eugene Edwards, Christina Brantley, and Paul B. Ruffin
5.1 Introduction 133
5.2 Implications of Nanotechnology in Military and Aerospace Systems Applications 134
5.3 Nano-Based Microsensor Technology for the Detection of Chemical Agents 135
5.3.1 Surface-Enhanced Raman Spectroscopy 135
5.3.1.1 Design Approach 136
5.3.1.2 Experiment 137
5.3.1.3 Results 138
5.3.2 Voltammetric Techniques 139
5.3.2.1 Design Approach 140
5.3.2.2 Experimental/Test Setup 142
5.3.2.3 Results 143
5.3.3 Functionalized Nanowires - Zinc Oxide 145
5.3.3.1 Design Approach 145
5.3.3.2 Experimental/Test Setup 146
5.3.3.3 Results 146
5.3.4 Functionalized Nanowires - Tin Oxide 147
5.3.4.1 Design Approach 148
5.3.4.2 Prototype Configuration/Testing 148
5.3.4.3 Results 148
5.4 Nanotechnology for Missile Health Monitoring 149
5.4.1 Nanoporous Membrane Sensors 150
5.4.1.1 Design Approach 150
5.4.1.2 Experimental Setup and Prototype Configuration 150
5.4.1.3 Results 152
5.4.2 Multichannel Chip with Single-Walled Carbon Nanotubes Sensor Arrays 154
5.4.2.1 Design Concept 154
5.4.2.2 Experimental Configuration 154
5.4.2.3 Results 155
5.4.3 Optical Spectroscopic Configured Sensing Techniques - Fiber Optics 155
5.4.3.1 Design Concept Spectroscopic Sensing 156
5.4.3.2 Experimental Approach/Aged Propellant Samples 156
5.4.3.3 Results from Absorption Measurements 157
5.5 Nanoenergetics - Missile Propellants 158
5.5.1 Multiwall Carbon Nanotubes 158
5.5.1.1 Design Approach 158
5.5.1.2 Experiment 159
5.5.1.3 Results 160
5.5.2 Single-Wall Carbon Nanotubes 160
5.5.2.1 Design Approach 160
5.5.2.2 Experiment 161
5.5.2.3 Results 162
5.6 Nanocomposites for Missile Motor Casings and Structural Components 162
5.6.1 Thermal Methods 162
5.6.2 VibrationalMethods 164
5.6.2.1 Design Approach 164
5.6.2.2 Experiment 164
5.6.2.3 Results 165
5.7 Nanoplasmonics 167
5.7.1 Metallic Nanostructures 168
5.7.2 Gallium-Based UV Plasmonics 169
5.8 Nanothermal Batteries and Supercapacitors 169
5.9 Conclusion 172
References 173
6 Novel Polymer Nanocomposite Ablative Technologies for Thermal Protection of Propulsion and Reentry Systems for Space Applications 177
Joseph H. Koo and Thomas O. Mensah
6.1 Introduction 177
6.2 Motor Nozzle and Insulation Materials 179
6.2.1 Behavior of Ablative Materials 182
6.3 Advanced Polymer Nanocomposite Ablatives 184
6.3.1 Polymer Nanocomposites for Motor Nozzle 185
6.3.1.1 Phenolic Nanocomposites Studies byThe University of Texas at Austin 185
6.3.1.2 Phenolic-MWNT Nanocomposites Studies by Texas State University-San Marcos 188
6.3.2 Polymer Nanocomposites for Internal Insulation 189
6.3.2.1 Thermoplastic Polyurethane Nanocomposite (TPUN) Studies by The University of Texas at Austin 190
6.4 New Sensing Technology 195
6.4.1 In situ Ablation Recession and Thermal Sensors 196
6.4.1.1 Production of the C/C Sensor Plugs 198
6.4.1.2 Ablation Test Results of Carbon/Carbon Sensors 200
6.4.1.3 Ablation Test Results of Carbon/Phenolic Carbon Sensors 209
6.4.1.4 Other Ablation Sensors Results 211
6.4.1.5 Summary and Conclusions 212
6.4.2 Char Strength Sensor 213
6.4.2.1 Setup and Calibration of Compression Sensor 214
6.4.2.2 Analysis Method 215
6.4.2.3 Char Compressive Strength Results 216
6.4.2.4 Additional Considerations on the Interpretation of the Data 223
6.4.2.5 Concluding Remarks 226
6.5 Technologies Needed to Advance Polymer Nanocomposite Ablative Research 227
6.5.1 Thermophysical Properties Characterization 227
6.5.1.1 Thermal Conductivity 227
6.5.1.2 Thermal Expansion 228
6.5.1.3 Density and Composition 228
6.5.1.4 Microstructure 229
6.5.1.5 Elemental Composition 229
6.5.1.6 Char Yield 229
6.5.1.7 Specific Heat 229
6.5.1.8 Heat of Combustion 230
6.5.1.9 Optical Properties 230
6.5.1.10 Porosity 230
6.5.1.11 Permeability 230
6.5.2 Ablation Modeling 231
6.6 Summary and Conclusion 236 Nomenclature 236
Acronyms 237
Acknowledgments 237
References 238
7 Manufacture of Multiscale Composites 245
David O. Olawale,Micah C. McCrary-Dennis, and Okenwa O. Okoli
7.1 Introduction 245
7.1.1 Multifunctionality of Multiscale Composites 245
7.1.2 Nanomaterials 247
7.2 Nanoconstituents Preparation Processes 249
7.2.1 Functionalization of CNTs 249
7.2.1.1 Chemical Functionalization 249
7.2.1.2 Physical (Noncovalent) Functionalization 250
7.2.2 Dispersion of Carbon Nanotubes 252
7.2.2.1 Ultrasonication 254
7.2.2.2 Calendering Process 255
7.2.2.3 Ball Milling 256
7.2.2.4 Stir and Extrusion 256
7.2.3 Alignment of CNTS 258
7.2.3.1 Ex situ Alignment 258
7.2.3.2 Force Field-Induced Alignment of CNTs 259
7.2.3.3 Magnetic Field-Induced Alignment of CNTs 259
7.2.3.4 Electrospinning-Induced Alignment of CNTs 260
7.2.3.5 Liquid Crystalline Phase-induced Alignment of CNTs 261
7.3 Liquid Composites Molding (LCM) Processes for Multiscale Composites Manufacturing 261
7.3.1 Resin Transfer Molding (RTM) 262
7.3.2 Vacuum-Assisted Resin Transfer Molding (VARTM) 263
7.3.3 Resin Film Infusion (RFI) 265
7.3.4 The Resin Infusion under Flexible Tooling (RIFT) and Resin Infusion between Double Flexible Tooling (RIDFT) 266
7.3.5 Autoclave Manufacturing 267
7.3.6 Out-of-Autoclave Manufacturing: Quickset 268
7.3.6.1 Quickstep 268
7.4 Continuous Manufacturing Processes for Multiscale Composites 269
7.4.1 Pultrusion 269
7.4.2 FilamentWinding 270
7.5 Challenges and Advances in Multiscale Composites Manufacturing - Environmental, Health, and Safety (E, H, & S) 271
7.5.1 Nanoconstituents Processing Hazards 271
7.5.2 Composite Production and Processing 272
7.5.3 Life Cycle Assessment - Use and Disposal 273
7.6 Modeling and Simulation Tools for Multiscale Composites Manufacture 273
7.6.1 Nanoparticle Modeling 274
7.6.2 Molecular Modeling 274
7.6.3 Simulation 274
7.7 Conclusion 275
References 276
8 Bioinspired Systems 285
Oluwamayowa Adigun, Alexander S. Freer, LaurieMueller, Christopher Gilpin, BryanW. Boudouris, and Michael T. Harris
8.1 Introduction and Literature Overview 285
8.2 Electrical Properties of a Single Palladium-Coated Biotemplate 289
8.3 Materials and Methods 290
8.4 Results and Discussion 293
8.5 Conclusion and Outlook 297
Acknowledgments 300
References 300
9 Prediction of Carbon Nanotube Buckypaper Mechanical Properties with Integrated Physics-Based and Statistical Models 307
KanWang, Arda Vanli, Chuck Zhang, and BenWang
9.1 Introduction 307
9.2 Manufacturing Process of Buckypaper 310
9.3 Finite Element-Based ComputationalModels for Buckypaper Mechanical Property Prediction 313
9.4 Calibration and Adjustment of FE Models with Statistical Methods 322
9.5 Summary 331
References 332
10 Fabrication and Fatigue of Fiber-Reinforced Polymer Nanocomposites - A Tool for Quality Control 335
Daniel C. Davis and Thomas O. Mensah
10.1 Introduction 335
10.2 Materials 336
10.2.1 Carbon Fabric and Fiber 337
10.2.2 Glass Fabric and Fibers 337
10.2.3 Polymer Resin 337
10.2.4 Carbon Nanotubes 338
10.2.5 Carbon Nanofibers 339
10.2.6 Nanoclays 340
10.3 Composite Fabrication 341
10.3.1 Hand Layup 341
10.3.2 Resin Transfer Molding 342
10.4 Discussion - Fatigue and Fracture 344
10.4.1 Fatigue and Durability 344
10.4.2 Carbon Nanotube - Polymer Matrix Composites 347
10.4.3 Carbon Nanofiber - Polymer Matrix Composites 349
10.4.4 Nanoclay - PolymerMatrix Composites 354
10.5 Summary and Conclusion 359
Acknowledgments 360
References 360
11 Nanoclays: A Review of Their Toxicological Profiles and Risk Assessment Implementation Strategies 369
Alixandra Wagner, Rakesh Gupta, and Cerasela Z. Dinu
11.1 Introduction 369
11.2 Nanoclay Structure and Resulting Applications 369
11.3 Nanoclays in Food Packaging Applications 370
11.4 Possible Toxicity upon Implementation of Nanoclay in Consumer Applications 375
11.4.1 In Vitro Studies Reveal the Potential of Nanoclay to Induce Changes in Cellular Viability 376
11.4.2 Proposed Mechanisms of Toxicity for the In Vitro Cellular Studies 380
11.4.3 In Vivo Evaluation of Nanoclay Toxicity 383
11.5 Conclusion and Outlook 385
Acknowledgments 387
References 388
12 Nanotechnology EHS: Manufacturing and Colloidal Aspects 395
Geoffrey D. Bothun and Vinka Oyanedel-Craver
12.1 Introduction 395
12.1.1 Challenges 397
12.1.2 Recent Initiatives and Reviews 399
12.2 Colloidal Properties and Environmental Transformations 400
12.3 Assessing Nano EHS 402
12.3.1 Example: Silver Nanoparticles (AgNPs) 407
12.3.2 Role of Manufacturing 407
Summary 409
Acknowledgments 409
References 409
Index 417
Chapter 1
Overview: Affirmation of Nanotechnology between 2000 and 2030
Mihail C. Roco1,2
1National Science Foundation, Arlington, VA, USA
2National Nanotechnology Initiative, U.S. National Science and Technology Council, Washington,, DC, USA
1.1 Introduction
In the nanoscale domain, nature transitions from the fixed physical behavior of a finite number of atoms to an almost infinite range of physical-chemical-biological behaviors of collections of atoms and molecules. The fundamental properties and functions of all natural and man-made materials are defined and can be modified efficiently at that scale. The unifying definition of nanotechnology, based on specific behavior at the nanoscale and the long-term nanotechnology research and education vision, was formulated in 1997-1999, and its implementation begun with National Nanotechnology Initiative (NNI) in 2000. We have estimated that it would take about three decades to advance from a scientific curiosity in 2000 to a science-based general purpose technology with broad societal benefits toward 2030 [1-3] (see www.wtec.org/nano2/).
A long-term strategic view is needed because nanotechnology is a foundational general purpose field. Three development stages of nanotechnology, corresponding to the level of complexity of typical outcomes, have been envisioned: passive and active nanostructures in the first stage of development (Nano 1), nanosystems and molecular nanosystems in the second stage (Nano 2), and converging technology platforms and distributed interconnected nanosystems in the last stage (Nano 3).
We use the definition of nanotechnology as set out in Nanotechnology Research Directions [2]. Nanotechnology is the ability to control and restructure matter at the atomic and molecular levels in the range of approximately 1-100 nm, and exploiting the distinct properties and phenomena at that scale as compared to those associated with single atoms or bulk behavior. The aim is to create materials, devices, and systems with fundamentally new properties and functions for novel applications by engineering their small structure. This is the ultimate frontier to economically change materials and systems properties, and the most efficient length scale for manufacturing and molecular medicine. The same principles and tools are applicable to different areas of relevance and may help establish a unifying platform for science, engineering, and technology at the nanoscale. The transition from the behavior of single atoms or molecules to collective behavior of atomic and molecular assemblies is encountered in nature, and nanotechnology exploits this natural threshold.
This chapter describes the timeline and affirmation of nanotechnology, its three stages, key challenges, and discusses nanotechnology return on investment.
1.2 Nanotechnology - A Foundational Megatrend in Science and Engineering
Nanotechnology is a foundational, general purpose technology for all sectors of the economy dealing with matter and biosystems, as information technology is a general purpose technology for communication and computation. Biotechnology and cognitive technologies are two other foundational technologies growing at the beginning of the twenty-first century (Figure 1.1). Table 1.1 shows several category levels of science and technology (S&T) platforms according to their level of generality and societal impact: foundational S&T, topical S&T, application domain, and product/service platform. While there are only five foundational S&T platforms most dynamic at this moment (Figure 1.1), the number of topical S&T platforms increases with the number of spin-offs, interplatform and further recombination growth. Each topical S&T platform has several application domains, which at their turn each have a series of products and related services. The importance of foundational platforms - and in particular its most exploratory component part at this moment, nanotechnology - is underlined by the cumulative investment amplification factor by developing the respective S&T platform that is a product of the foundational platform investment amplification factor, with the topical, application area and product amplification factors.
Figure 1.1 Converging foundational technologies, and their interdisciplinary and spin-offs subfields.
Modified from Roco and Bainbridge [4].
Table 1.1 Proposed classification of science and technology platforms
Category I. Foundational S&T platform (system architecture) II. Topical S&T platform (hierarchical system from I) III. Application field platform (branched, inter- and recombination) IV. Product and service platform (spin-off, inter- and recombination) S&T Platforms- Nanotechnology: (atom architecture)
- Information S&T (bit architecture)
- Modern bio S&T (gene architecture)
- Cognitive S&T (synapsis architecture)
- Artificial Intelligence S&T (system design)
Semiconductors
Genomics
Biomedicine
Contributing: Synthetic biology
Neuromorphic eng
Proteomics
Nanofluidics
Metamaterials .. Cell phone system
Transportation
Medicine
Energy conversion and storage
Agriculture
Space exploration .. Car components
Medical devices
Nano coatings
LEDs
Nano lasers .. Typical timescales 25-50 years 10-25 years 5-10 years 3-5 years One-step investment amplification factor kf(undamental) kt(opical) ka(pplication) kp(product and service) Cumulative investment amplification factor kf kt ka kp kt ka kp ka kp kp Game changer for: Knowledge Technology approach Application field User consumption
Nanotechnology continues exponential growth by vertical science-to-technology transition, horizontal expansion to areas as agriculture/textiles/cement, and spin-off areas (~20) as spintronics/metamaterials/., progressively penetrating in key economic sectors. The number of World of Science publications on nano-extended 20 new terms between 1990 and 2014 that now represent over ¼ of the total publications (Figure 1.2). For this reason, it is increasingly difficult to identify the R&D programs around the word supporting nanotechnology because they are called after an activity that branched out of the foundational field. Figure 1.3 illustrates international government R&D funding the interval 2000-2012 [9].
Figure 1.2 The number of World of Science (WoS) publications on nano-extended 20 new terms between 1990 and 2014.
Figure 1.3 International government R&D funding the interval 2000-2012, after 2013 - increase use of new terms and platforms (using NNI definition, 81 countries, MCR direct contacts).
Most of the larger science and technology initiatives have been justified in the United States and abroad mainly by application-related and societal factors. For example, the Manhattan Project during World War II (with centralized, goal-focused, and simultaneous approaches), the Apollo Space Project (with a centralized, focused goal), and Networking and Information Technology Research and Development (top-down initiated and managed, and established when mass applications justified the return of investment). The initiation of the NNI was motivated primarily by its long-term science and engineering goals and general purpose technology opportunity, and has been managed using a bottom-up approach combined with centralized coordination. A few comments underlying this characteristic are as follows:
Charles Vest, President National Academy of Engineering (PCAST meeting, White House, [8]): "NNI is a new way to run an initiative"
Steve Edwards, "Hall of Fame for Nanoscale Science and Engineering" (Jan. 1, 2006): ".persuading the U.S. government, not to mention the rest of the world, to support nanotechnology. It was a masterful job of engineering the future"
Tim [5], President of the European Nanobusiness Association, and Cientifica Co. (2015): "nanotechnology [is] the first truly global scientific revolution."
Nanotechnology promises to become a general purpose technology with large-scale applications similar to digital technology. It could eventually match or outstrip the digital revolution in terms of economic importance and societal impact once the methods of investigation and manufacturing are developed and the underlying education and infrastructure are established. During about 2020-2030, nanotechnology could equal and even exceed the digital revolution in terms of technology breakthroughs, investments, and societal importance (Figure 1.4) [6].
Figure 1.4 S-curves for...
