Table of Contents

Cover

Title Page

List of Contributors

Preface

Editor in Chief

Chapter 1: Overview: Affirmation of Nanotechnology between 2000 and 2030

1.1 Introduction
1.2 Nanotechnology – A Foundational Megatrend in Science and Engineering
1.3 Three Stages for Establishing the New General Purpose Technology
1.4 Several Challenges for Nanotechnology Development
1.5 About the Return on Investment
1.6 Closing Remarks
Acknowledgments
References

Chapter 2: Nanocarbon Materials in Catalysis

2.1 Introduction to Nanocarbon Materials
2.2 Synthesis and Functionalization of Nanocarbon Materials
2.3 Applications of Nanocarbon Materials in Electrocatalysis
2.4 Applications of Nanocarbon Materials in Photocatalysis
2.5 Summary
Acknowledgments
References

Chapter 3: Controlling and Characterizing Anisotropic Nanomaterial Dispersion

3.1 Introduction
3.2 What Is Dispersion and Why Is It Important?
3.3 Characterizing Dispersion State in Fluids
3.4 Characterization of Dispersion State in Solidified Materials
3.5 Conclusion
Acknowledgments
References

Chapter 4: High-Throughput Nanomanufacturing via Spray Processes

4.1 Introduction
4.2 Flash Nanoprecipitation
4.3 Electrospray
4.4 Liquid-in-Liquid Electrospray
4.5 Spray-Assisted Layer-by-Layer Assembly
4.6 Conclusion and Future Directions
References

Chapter 5: Overview of Nanotechnology in Military and Aerospace Applications

5.1 Introduction
5.2 Implications of Nanotechnology in Military and Aerospace Systems Applications
5.3 Nano-Based Microsensor Technology for the Detection of Chemical Agents
5.4 Nanotechnology for Missile Health Monitoring
5.5 Nanoenergetics – Missile Propellants
5.6 Nanocomposites for Missile Motor Casings and Structural Components
5.7 Nanoplasmonics
5.8 Nanothermal Batteries and Supercapacitors
5.9 Conclusion
References

Chapter 6: Novel Polymer Nanocomposite Ablative Technologies for Thermal Protection of Propulsion and Reentry Systems for Space Applications

6.1 Introduction
6.2 Motor Nozzle and Insulation Materials
6.3 Advanced Polymer Nanocomposite Ablatives
6.4 New Sensing Technology
6.5 Technologies Needed to Advance Polymer Nanocomposite Ablative Research
6.6 Summary and Conclusion
Nomenclature
Acronyms
Acknowledgments
References

Chapter 7: Manufacture of Multiscale Composites

7.1 Introduction
7.2 Nanoconstituents Preparation Processes
7.3 Liquid Composites Molding (LCM) Processes for Multiscale Composites Manufacturing
7.4 Continuous Manufacturing Processes for Multiscale Composites
7.5 Challenges and Advances in Multiscale Composites Manufacturing – Environmental, Health, and Safety (E, H, & S)
7.6 Modeling and Simulation Tools for Multiscale Composites Manufacture
7.7 Conclusion
References

Chapter 8: Bioinspired Systems

8.1 Introduction and Literature Overview
8.2 Electrical Properties of a Single Palladium-Coated Biotemplate
8.3 Materials and Methods
8.4 Results and Discussion
8.5 Conclusion and Outlook
Acknowledgments
References

Chapter 9: Prediction of Carbon Nanotube Buckypaper Mechanical Properties with Integrated Physics-Based and Statistical Models

9.1 Introduction
9.2 Manufacturing Process of Buckypaper
9.3 Finite Element-Based Computational Models for Buckypaper Mechanical Property Prediction
9.4 Calibration and Adjustment of FE Models with Statistical Methods
9.5 Summary
References

Chapter 10: Fabrication and Fatigue of Fiber-Reinforced Polymer Nanocomposites – A Tool for Quality Control

10.1 Introduction
10.2 Materials
10.3 Composite Fabrication
10.4 Discussion – Fatigue and Fracture
10.5 Summary and Conclusion
Acknowledgments
References

Chapter 11: Nanoclays: A Review of Their Toxicological Profiles and Risk Assessment Implementation Strategies

11.1 Introduction
11.2 Nanoclay Structure and Resulting Applications
11.3 Nanoclays in Food Packaging Applications
11.4 Possible Toxicity upon Implementation of Nanoclay in Consumer Applications
11.5 Conclusion and Outlook
Acknowledgments
References

Chapter 12: Nanotechnology EHS: Manufacturing and Colloidal Aspects

12.1 Introduction
12.2 Colloidal Properties and Environmental Transformations
12.3 Assessing Nano EHS
Summary
Acknowledgments
References

Index

End User License Agreement

List of Illustrations

Chapter 1: Overview: Affirmation of Nanotechnology between 2000 and 2030

Figure 1.1 Converging foundational technologies, and their interdisciplinary and spin-offs subfields.
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).
Figure 1.4 S-curves for two science and technology megatrends: past and envisioned conceptualization of “Nanomanufacturing” and “Digital Technology” [6].
Figure 1.5 2000–2030 convergence–divergence cycle for global nanotechnology development.
Figure 1.6 Thirty-year vision to establish nanotechnology: changing the research and education focus and priorities in three stages from scientific curiosity to immersion in socioeconomic projects [1–4]. The reports are available on www.wtec.org/nano2/ and www.wtec.org/NBIC2-report/.
Figure 1.7 Creating a general purpose technology in three stages between 2000 and 2030. Each stage includes two generations of nanotechnology products.
Figure 1.8 The flow of nanotechnology R&D investments and outcomes in the United States in 2014.

Chapter 2: Nanocarbon Materials in Catalysis

Figure 2.1 Schematic illustration for the construction of inorganic nanoparticle/nanocarbon hybrids. The cases of hybridizing with (a) GO and (b) CNT. (c) Transmission electron microscopy (TEM) images to show an example of TiO₂/GO hybrid.
Figure 2.2 (a) TEM image of the ordered carbon molecular sieve CMK-1. (b) Evolution of X-ray diffraction (XRD) patterns during the synthesis of CMK-1 with the silica template MCM-48. A: The silica template MCM-48, B: the carbonized composite, and C: CMK-1 after removal of the template.
Figure 2.3 Schematic illustration of modifying SWCNTs with FePc via (a) π–π interactions and (b) axial ligands.
Figure 2.4 (a) Scanning electron microscopy (SEM) image and (b) and (c) TEM images of the CoO/NCNT hybrid. (d) XRD patterns of the CoO/NCNT hybrid. (e) ORR polarization curves of the hybrid and Pt/C. (f) Chronoamperometric curves of the hybrid and Pt/C for ORR at 200 mA/cm².
Figure 2.5 Catalytic cycle showing the redox mechanism involved in ORR on pyrolyzed Fe-N_x/C active sites in dilute alkaline medium.
Figure 2.6 (a) Schematic diagram of the preparation of NiFe-LDH nanosheets/graphene for water splitting. (b) XRD pattern of NiFe-LDH nanosheets/graphene. (c) Polarization curves of Ni_2/3Fe_1/3-RGO, Ni_2/3Fe_1/3-NS, and GO in 1 M KOH solution.
Figure 2.7 (a) Detection of O₂ evolution from the echo-MWCNTs catalysts using rotating ring disk electrode measurements. (b) Schematic diagram for showing the O₂ evolution reactions occurred at the oxygen-containing groups on the surface of MWCNTs.
Figure 2.8 (a) Schematic diagram of the preparation of MoS₂/RGO hybrid. (b) SEM and TEM (inset) images of the MoS₂/RGO hybrid. (c) Schematic illustration for the growth of large, free MoS₂ particles without any GO sheets. (d) SEM and TEM (inset) images of the free MoS₂ particles.
Figure 2.9 (a) Projected density of states (DOS) of H (1 s) and its bonded C (2p) when H is adsorbed on the surface of pristine CNTs, Fe@CNTs, and Fe@NCNTs. The dashed lines present the center of the occupied band. (b) The free energy profiles of Tafel and Heyrovsky routes for Fe@CNTs. (c) The free energy profiles of the Heyrovsky route for pristine CNTs, Fe@CNTs, and Fe@NCNTs. (d) A schematic representation of the HER process on the surface of Fe@NCNTs.
Figure 2.10 (a) Schematic illustration of the synthesis of the CoN_x/C electrocatalysts. (b) HER polarization plots, (c) RRDE measurements, and (d) Tafel plots of the CoN_x/C, N/C, Co/N, and Pt/C catalysts in 0.5 M H₂SO₄. (e) Initial and postpotential cyclic voltammograms of CoN_x/C and Co/N in 0.5 M H₂SO₄. (f) HER polarization plots and (g) Tafel plots of CoN_x/C, N/C, Co/N, and Pt/C catalysts in 1 M KOH.
Figure 2.11 (a) Schematic diagram of the electrochemical reduction of CO₂ coupled to renewable electricity sources in carbon cycle. (b) Several incidental reactions related to carbon dioxide reduction and water reduction with relative reduction potentials.
Figure 2.12 Calculated free energy diagram for CO₂ electroreduction to CO on pristine CNTs and NCNTs at 0 V and 0.3 V versus RHE, respectively.
Figure 2.13 Proposed mechanisms for the CO₂ reduction reaction on Mn−N−C and Fe−N−C.
Figure 2.14 Various applications of graphene-based photocatalysts.
Figure 2.15 (a) Schematic illustration for the charge transfer and separation in the Zn_0.8Cd_0.2S/RGO hybrid photocatalyst; (b) proposed mechanism for photocatalytic H₂-production under simulated solar irradiation.
Figure 2.16 Schematic diagrams for a Z-scheme photocatalysis system operating without (a) and with (b) GO as electron shuttle mediator at the interfaces between the n- and p-type semiconductors.
Figure 2.17 Schematic energy level diagrams of the as-prepared GO and irradiated GO and the mechanism for photocatalytic water reduction and oxidation on irradiated GO.

Chapter 3: Controlling and Characterizing Anisotropic Nanomaterial Dispersion

Figure 3.1 An example process flow diagram is shown for nanomaterial exfoliation in liquid, drying, and incorporation into a polymer nanocomposite process. There are clear parallels between these steps and classical chemical engineering technology.
Figure 3.2 Schematic distinguishing degrees of dispersion and distribution.
Figure 3.3 Logarithmic isolines of interfacial (surface) area per volume of particles (µm⁻¹ = m²/ml with respect to aspect ratio α = H/R, where H is the height or length and R is the radius based on approximating particles as cylinders (area/volume = 1/H + 1/R).
Figure 3.4 Distribution of micro- and nanoscale fillers at the same 0.1 vol% in a reference volume (a): alumina (Al₂O₃) particle; (b): carbon fiber; (c): graphene nanoplatelet (GNP); (d): carbon nanotubes (CNT).
Figure 3.5 Optical microscopy images of melt extruded nanocomposites (a) and (b) PP/SWNT and PP/C12SWNT by dry mixing, (c) and (d) PP/SWNT and PP/C12SWNT by rotary evaporation, and (e) and (f) PP/SWNT and PP/C12SWNT by hot coagulation.
Figure 3.6 Raman maps of melt extruded nanocomposites (a) and (b) PP/SWNT and PP/C12SWNT by dry mixing, (c) and (d) PP/SWNT and PP/C12SWNT by rotary evaporation, and (e) and (f) PP/SWNT and PP/C12SWNT by hot coagulation.

Chapter 4: High-Throughput Nanomanufacturing via Spray Processes

Figure 4.1 Block copolymers can adopt several phases depending on their concentration and temperature.
Figure 4.2 Schematics of the (a) cosolvent addition and (b) interfacial instability processes.
Figure 4.3 Schematic of flash nanoprecipitation process (four inlet stream multi-inlet vortex mixer shown).
Figure 4.4 Force and stress diagram for an electrospray in cone-jet mode. The variables indicated can impact the size and shape of the liquid cone.
Figure 4.5 Modes of electrospray.
Figure 4.6 Schematic of coaxial electrospray for immiscible fluids.
Figure 4.7 (a) Schematic of a liquid–liquid electrohydrodynamic atomization system. (b) Cone-jet mode spraying of glycerin in hexane. Barrero et al. 2004 [74]. Reproduced with permission of Elsevier. (c) Spraying carbon tetrachloride in distilled water at various voltages applied using high-voltage power supply. Sato et al. 1993 [73]. Reproduced with permission of Elsevier.
Figure 4.8 (a) Electrospray-incorporated microfluidic device, showing emulsification of water in oil. Yeh et al. 2012 [77]. Reproduced with permission of Springer. (b) Schematic of membrane filter-incorporated liquid-in-liquid electrospray.
Figure 4.9 (a) Rapid spray-assisted LbL assembly. The completion of each cycle indicates of deposition of a layer pair. (b) A substrate is sprayed with a solution (or dispersion) containing the adsorbing species. (c) The result is a liquid film that wets the substrate, and species diffuse and adsorb to the substrate's surface. (d) Dip-assisted LbL assembly.
Figure 4.10 (a) Cross-sectional scanning electron microscopy (SEM) of polyaniline nanofiber/graphene oxide sheet spray-assisted LbL films. Kwon et al. 2015 [88]. Reproduced with permission from The Royal Society of Chemistry. (b) SEM of spray-assisted LbL deposition of positively and negatively charged silica nanoparticles on fabrics. Carosio et al. 2013 [89]. Reproduced with permission of American Chemical Society. (c) Cross-sectional transmission electron microscope image of an alternating layers of TiO₂ (dark gray) and SiO₂ (light gray) nanoparticles assembled via spray-assisted LbL assembly. Nogueira et al. 2011 [84]. Reproduced with permission of American Chemical Society. (d) SEM of conformal coatings made by spray-assisted LbL assembly on Tyvek®. Krogman et al. 2007 [85]. Reproduced with permission of American Chemical Society.

Chapter 5: Overview of Nanotechnology in Military and Aerospace Applications

Figure 5.1 (a) Plasmons become reflected heat loss; (b) plasmons enhanced via roughed surface; (c) plasmons greater enhancement via nano-roughed surfaces.
Figure 5.2 Commercial gold-coated substrate with an array of resonant cavities for SERS effect.
Figure 5.3 Experimental setup of SERS instrumentation system.
Figure 5.4 Experimental Raman spectrum for TNT (1 pg).
Figure 5.5 Experimental Raman spectrum for RDX (1 pg).
Figure 5.6 Prototype of triple element thick-film sensor.
Figure 5.7 Schematic of sensor describing the test electrolyte deposition.
Figure 5.8 Schematic of triple element thin-film sensor.
Figure 5.9 Voltammetry test setup.
Figure 5.10 Raw data of sensor response to ammonia.
Figure 5.11 Graph of thick-film gas sensor sensitivities to rocket outgassing chemicals.
Figure 5.12 CAD illustration of the ZnO nanowire array device on sapphire substrate. Flat S-shaped electrodes consist of silver to form ohmic contact on ZnO nanowires (tube shaped).
Figure 5.13 Actual prototype ZnO nanowire array device.
Figure 5.14 Amperometric detection of p-nitrophenol vapor using ZnO nanowire device.
Figure 5.15 (a) Design concept schematic for the nanowire sensor. (b) Photo images of the nanowire sensor-fabricated devices.
Figure 5.16 Image of the wireless sensing system, (a) wireless module and (b) data acquisition board.
Figure 5.17 Full data collection run recorded with a tin oxide sensor and the wireless system.
Figure 5.18 Plot of production of gas from degrading propellant shown in relationship to depletion of a stabilizer (MNA); time frame is on the order of years. After the graphical crossover point, gas generation increases exponentially (because stabilizer is near depletion).
Figure 5.19 SEM image of nanoporous alumina membrane; the average pore size is ∼250 nm.
Figure 5.20 (a) The experimental setup for testing the nanoporous alumina membrane; (b) the prototype nanoporous membrane.
Figure 5.21 (a) IR absorption spectrum of CO₂ and N₂O collected by nanoporous membrane; (b) IR absorption spectrum of 1 ppm of N₂O.
Figure 5.22 Multichannel sensor array (NASA-AMES).
Figure 5.23 Single sensor element with carbon nanotubes across gold electrodes.
Figure 5.24 Conceptual sketch of fiber optic backscattering spectroscopic system used for measuring the concentration level of propellant stabilizer (MNA) and other ingredients inside a rocket motor.
Figure 5.25 Photos of sample propellant that is fresh/un-aged (sample #0) and accelerated aged for up to 25 years. (a) Propellant un-aged with 2% MNA. (b) Propellant aged 4.2 years, MNA depleting MNA. (c) Propellant aged 8.2 years, MNA depleting. (d) Propellant aged 12.6 years, MNA depleting. (e) Propellant aged 16.8 years, MNA depleting. (f) Propellant aged 21.0 years, MNA depleting. (g) Propellant aged 25.0 years, MNA depleting.
Figure 5.26 Measured results showing absorption spectrums for samples of fresh propellant (un-aged, sample #0) and sample propellants accelerated aged up to 25 years.
Figure 5.27 SEMs showing the structure of CNTs, multiwalled (a); and single-walled (b).
Figure 5.28 SEM of multiwall carbon nanotube array used as a thermal interface.
Figure 5.29 Carbon nanotube doped epoxy specimens from RPI.
Figure 5.30 RPI samples loss factor as a function of frequency.
Figure 5.31 Diagram of thermal batteries.
Figure 5.32 Aluminum on CNT.

Chapter 6: Novel Polymer Nanocomposite Ablative Technologies for Thermal Protection of Propulsion and Reentry Systems for Space Applications

Figure 6.1 Schematic diagram illustrating the different ablation mechanisms and different zones of an ablator under thermal attack, as adapted from the NASA-JSC charring ablation model. Diagram courtesy of NASA.
Figure 6.2 (a) Ablation rate, (b) residual mass, (c) backside temperature, and (d) surface temperature of MX-4926 and NRAMs with different types of nanoparticles [(HE)₂ MT-Cloisite® 30B, PR-24-PS CNF, and SO-1458 POSS®] at various loading levels.
Figure 6.3 Average peak temperatures at two in-depth locations of the control sample and different phenolic-MWCNT nanocomposites.
Figure 6.4 TEM images of (a) 2.5%, (b) 5%, and (c) 10% Cloisite 30B in TPUN.
Figure 6.5 TEM images of (a) 2.5%, (b) 5%, and (c) 10% MWNT in TPUN.
Figure 6.6 Representative temperature profiles of EPDM/Kevlar profile and PNCs tested using the OTB.
Figure 6.7 Peak in-depth temperatures of EPDM/Kevlar and PNCs.
Figure 6.8 (a) Kevlar/EPDM, (b) 10% Clay, (b) 10% MWNT, and (c) 20% CNF PNC post oxyacetylene torch burn.
Figure 6.9 SEM of Kevlar/EPDM char post oxyacetylene torch burn (unit bar at left is 200 µm and at right is 2 µm).
Figure 6.10 SEM of 10% nanoclay PNC char post oxyacetylene torch burn in progressive magnification (unit bar at left is 100 µm and at right is 10 µm).
Figure 6.11 SEM of 10% MWNT PNC char post oxyacetylene torch burn in progressive magnification (unit bar at left is 100 µm and at right is 200 nm).
Figure 6.12 SEM of 20% CNF PNC char post oxyacetylene torch burn in progressive magnification (unit bar of left is 20 µm and right is 2 µm).
Figure 6.13 Scheme of a breakwire-like ablation recession sensor (plug).
Figure 6.14 Scheme of the proposed thermocouple-based recession sensor.
Figure 6.15 Drilling layout for the 4- (a) and 4-level (b) plugs. SEM analysis of the surface of the 4- (c) and 8-level (d) CCC plugs.
Figure 6.16 Fully assembled 4-level plug (a). CCC plug inserted in the oxyacetylene test bed (b).
Figure 6.17 Temperature profiles for the 4-level plug LDCC4L1 acquired during the test with the OTB.
Figure 6.18 Time at which the TCs experienced the first break versus position of each TC head for the 4-level LDCC plugs: interpolation based on the first (a) and second (b) method.
Figure 6.19 Time at which the TCs experienced the first break versus position of each TC head for the 4-level HDCC plugs: interpolation based on the first (a) and second (b) method.
Figure 6.20 Temperature profiles acquired during the test of the 8-level CCC plug with the OTB: sample HDCC8L1 (a). Detail of the temperature profiles over the range of time at which all TCs of sample HDCC8L1 experienced the first break (b).
Figure 6.21 Time at which the TCs experienced the first break versus position of each TC head for the 8-level HDCC plugs: interpolation based on the first (a) and second (b) method.
Figure 6.22 Recession data for all C/Ph sensors.
Figure 6.23 Char compressor schematic diagram.
Figure 6.24 Sensor force versus voltage using several duty cycles with a linear fit for a correlation.
Figure 6.25 Char force data of 5 wt% CNF thermoplastic elastomer nanocomposite.
Figure 6.27 Char force data of 5 wt% MMT thermoplastic elastomer nanocomposite.
Figure 6.28 Average maximum force of each type of thermoplastic elastomer nanocomposites.
Figure 6.29 Average energy dissipated of each type of thermoplastic elastomer nanocomposites.
Figure 6.30 SEM results of the charred materials (in-depth). MMT (a, b), MWNT (c, d), and CNF (e, f)-based TPUNs.
Figure 6.31 Schematization of the different types of porous char: CNF (a) and CNT (b) based char. The carbonaceous interface plays a vital role on the mechanical properties of the resulting char. Moreover, increasing the char compactness, the capability of the oxidizing species to diffuse into the inner layers of the char tends to decrease.
Figure 6.32 Char force data of neat and charred Kevlar-filled EPDM.
Figure 6.34 Char force data of neat and charred 10 wt% MWNT thermoplastic elastomer nanocomposite.
Figure 6.35 Average maximum force of Kevlar EPDM, 7.5 wt% MWNT, and 10 wt% MWNT.
Figure 6.36 Average energy dissipated of Kevlar EPDM, 7.5 wt% MWNT, and 10 wt% MWNT.
Figure 6.37 Models of material erosion: (a) non-decomposing, (b) decomposition of noncharring material, and (c) decomposition plus chemical reaction of charring material [87]. T_aw is the adiabatic wall temperature.

Chapter 7: Manufacture of Multiscale Composites

Figure 7.1 Nanoparticle reinforcement of the matrix in a unidirectional fiber composite. Vlasveld et al. 2005 [3]. Reproduced with permission of Elsevier.
Figure 7.2 Multiwalled carbon nanotubes grown on the surface of carbon fibers.
Figure 7.3 Concept of multiscale reinforcement composites.
Figure 7.4 Use of aligned CNT forests to strengthen interlaminar region in composite laminates.
Figure 7.5 Common particle reinforcements/geometries and their respective surface area-to-volume ratios.
Figure 7.6 Strategies for covalent functionalization of CNTs (a: direct sidewall functionalization; b: defect functionalization).
Figure 7.7 Schematics of CNT functionalization using noncovalent methods (a: polymer wrapping; b: surfactant adsorption; c: endohedral method) [29, 30].
Figure 7.8 Electronic microscope images of different CNTs: (a) TEM image of SWCNT bundle. Thess et al. 1996 [40]. Reproduced with permission of The American Association for the Advancement of Science. (b) SEM image of entangled MWCNT agglomerates. Ma et al. 2010 [15]. Reproduced with the permission of Elsevier.
Figure 7.9 Sonicators with different modes for CNT dispersion (a) water bath sonicator; (b) probe/horn sonicator), and the effect of sonication on the structure of CNTs.
Figure 7.10 (a) Calendering (or three roll mills) machine used for particle dispersion into a polymer matrix and (b) corresponding schematic showing the general configuration and its working mechanism.
Figure 7.11 (a) Schematics of ball milling technique and (b) container.
Figure 7.12 (a) Shear mixer and (b) extruder used for CNT dispersion.
Figure 7.13 Schematic of preparing well-aligned PANI/MWCNT composites.
Figure 7.14 Schematic of the electrospinning process.
Figure 7.15 TEM images of PAN/SWCNT nanocomposite fibrils (the average diameter of SWCNTs is 1.3 nm) Ko et al. 2003 [59]. Reproduced with permission of JohnWiley & Sons.
Figure 7.16 AFM image of LC/MWCNTs under 1.8 V/µm electric field (5 µm × 5 µm).
Figure 7.17 Overview of multiscale composite manufacturing process.
Figure 7.18 Blocking phenomenon in a VARTM experiment.
Figure 7.19 Resin transfer molding (RTM).
Figure 7.20 Vacuum-assisted resin transfer molding (VARTM) layup illustration.
Figure 7.21 VARTM: (a) longitudinal flow and (b) transverse flow illustrating flow front through the thickness of preform laminates.
Figure 7.22 Resin film infusion diagram.
Figure 7.23 The marco method of RIFT (ca. 1950) [77].
Figure 7.24 Resin infusion between double flexible tooling.
Figure 7.25 Bagging setup for autoclave.
Figure 7.26 Quickstep schematic.
Figure 7.27 Pultrusion process.
Figure 7.28 Filament winding diagram [91].

Chapter 8: Bioinspired Systems

Figure 8.1 TEM images of palladium-deposited TMV1Cys at 25 °C with different molar ratio of palladium-ion to TMV1Cys. This ratio is (a) 3.4 × 10⁻⁶ mol/mg of palladium-ion to TMV1Cys and (b) 10.8 × 10⁻⁶ mol/mg of palladium-ion to TMV1Cys. The scale bars represent 100 nm.
Figure 8.2 Palladium biomineralization on the TMV by (a) self-mineralization process and by (b) adding an external reducing agent (DMAB).
Figure 8.3 TEM image of a large number of tobacco mosaic virus-templated nanostructures formed through electroless deposition of palladium onto the viral surface in the absence of external reducing agents. The Pd-coated TMV nanowires are 350 nm in length and 50 nm in diameter. In some instances the nanowires are on top of one another, which causes a cross-like pattern to be seen, and in other instances the nanowires are aligned end to end. These instances can cause two well-aligned rods to appear as a single rod with twice the rod length.
Figure 8.4 Summary of electrical device fabrication characterization procedure. (1) The process starts with a thin film of gold on a glass substrate. (2) The FIB is used to mill a 100 µm × 100 nm gap in the gold. (3) A solution containing TMV-Pd particles is deposited onto the substrate. (4) TMV-Pd is deposited across the nanogap through evaporation of the solvent. (5) The FIB assists Pt deposition on the edges of the TMV-Pd and ensures no other particles are crossing the gap. (6) Microprobes are used to apply a voltage and measure the current between the two electrodes.
Figure 8.5 SEM image of the two nanogap electrodes electrically separated from each other and the rest of the gold substrate by gold milling with a FIB. (1) indicates the nanogap and (2) shows one of the ∼100 µm² gold electrodes.
Figure 8.6 SEM image of TMV-Pd particles spanning the nanogap between the gold electrodes. Platinum is deposited onto the edges of one TMV-Pd nanorod. The other TMV-Pd particles spanning the gap are later removed with the FIB. The TMV-Pd in the upper left corner of the image show the degradation from FIB exposure as they are no longer uniform nanowires and instead appear as discrete particles.
Figure 8.7 (a) I–V profiles for the TMV-Pd nanowire across the gold nanoscale channel (light gray) and across the bare (i.e., in the absence of the TMV-Pd nanorod) nanoscale channel (dark gray) with an applied bias of –0.1 V ≤ V ≤ 0.1 V. (b) A linear plot of the experimentally determined resistance values of TMV-Pd particles spanning nanoscale gaps between gold electrodes of varying channel lengths. The resistivity equation, RA = ρL + R_contact, describes the linear behavior where ρ is the resistivity, and a vertical axis intercept (R_contact) greater than zero relates to the contact resistance of the system.
Figure 8.8 TEM image of a TMV-Pd nanowire displaying the individual grain size of the Pd particles that form on the surface of the TMV during the aqueous coating and reduction process. The gray (∼5 nm) line indicates the width of a single Pd nanoparticle on the outer surface of the uniform palladium coating.
Figure 8.9 (a) The normalized absorption spectra of the XAS experimental data (light gray line) compared to palladium foil (black line). The overlap indicates presence of Pd–Pd bonds. (b) The Fourier transform of k²-weighted normalized absorption data in R-space for TMV-Pd compared to Pd foil indicates a Pd coordination number of 11, which corresponds to a particle diameter of ∼7 nm, which is in good agreement with the TEM image of Figure 8.8.

Chapter 9: Prediction of Carbon Nanotube Buckypaper Mechanical Properties with Integrated Physics-Based and Statistical Models

Figure 9.1 A sample of BP and its nanostructure with a scale factor of ×10,000.
Figure 9.2 An example of cracked BP.
Figure 9.3 MD simulation result of PVA wrapping around a CNT.
Figure 9.4 The multistage manufacturing process of PVA-treated BP.
Figure 9.5 The comparison of SEM images of pristine BP (a) and PVA-treated BP (b).
Figure 9.6 Cross-sectional images of PVA-treated BP.
Figure 9.7 Typical SEM image of CNT sheet.
Figure 9.8 A comparison between original image (a) and processed image (b). The brightness and sharpness of top layer CNTs are enhanced, providing a more distinguishable input for the analysis software.
Figure 9.9 The comparison of diameter measurement results. The results from the processed image not only reduced the discrepancy between manual measurement and software analysis but also better captured the trend.
Figure 9.10 (a) Length measurements and (b) orientation measurements of a random BP.
Figure 9.11 The parameters for generating individual CNTs (a) and a generated CNT network sample with a control cell size of 5 µm × 5 µm and a CNT volume fraction of 0.3 (b).
Figure 9.12 The randomly generated CNT network (a) and the corresponding truss structure (b).
Figure 9.13 CNT networks before (light gray) and after (dark gray) the 1% strain is applied.
Figure 9.14 The comparison of three sets of 500 computer simulations under different settings.
Figure 9.15 The response surface of the Kriging model.
Figure 9.16 The comparison between experimental data and physical model.
Figure 9.17 LOO cross-validation results of the GP model at PVA level of (a) 0.6, (b) 0.7, (c) 0.8, and (d) 0.9.
Figure 9.18 The procedure of two-step algorithm for Young's modulus prediction.
Figure 9.19 The comparison of experimental data and different prediction methods.

Chapter 10: Fabrication and Fatigue of Fiber-Reinforced Polymer Nanocomposites – A Tool for Quality Control

Figure 10.1 XD commercial grade CNTs.
Figure 10.2 CNT functionalization routes. (a) Fluorination – amino route, (b) oxidation route.
Figure 10.3 Scheme for Cloisite 30B (Southern Clay Products).
Figure 10.4 Spraying technology schematic.
Figure 10.5 Fluorinated functionalized CNT bundles and ropes deposits on (a) carbon fabric and (b) carbon fiber surfaces.
Figure 10.6 Heated vacuum assisted resin transfer molding fabrication (H-VARTM) setup.
Figure 10.7 (a) Schematic of tension–tension fatigue loading cycle for a fiber reinforced. (b) Schematic plots of the stress (σ) – number of cycles to failure (N), or S–N plots.
Figure 10.8 Four stages between matrix crack initiation and failure in fiber reinforced polymer composites.
Figure 10.9 (a) Composite normal matrix cracking, fiber–matrix cracking. (b) Fiber/fabric delamination, overloaded fibers and rupture. (c) Composite cross-section failure. (Loading direction – horizontal).
Figure 10.10 (a) Schematic of functionalized CNT reinforced fabric–matrix interface, CNTs strengthen matrix. (b) Raman spectrometry scan of CNTs reinforcing fabric–matrix interface.
Figure 10.11 Epoxy-CNF, neat epoxy resin fatigue tests.
Figure 10.12 Well-dispersed f-CNFs in PU matrix. f-CNF measured diameters, 78.05, 105.2 nm. f-CNF bonding with PU matrix weak.
Figure 10.13 Composite failure surfaces. (a) PU-glass fiber composite, (b) CNF reinforced PU-glass fiber composite.
Figure 10.14 Composite failure surfaces. (a) Epoxy-glass fiber composite, (b) nanoclay reinforced epoxy-glass fiber composite.
Figure 10.15 Raman images. (a) SEM image of crack propagating in matrix and seemingly deviated and blunted at fabric–matrix interface. (b) Raman spectrometry scan of CNT-reinforced fabric–matrix interface. Crack deviated and blunted due to CNTs.

Chapter 11: Nanoclays: A Review of Their Toxicological Profiles and Risk Assessment Implementation Strategies

Figure 11.1 Cellular uptake of nanoclays by A549 cells. A549 cells grown onto eight-well chamber slides were (a) fixed (control) or (b) incubated with rhodamine (light gray) labeled Cloisite Na⁺ (25 µg/ mL) for 4 h, (c) or 24 h. Cells were also counterstained with Alexa Fluor 488 phalloidin (gray) for their cytoskeletal organization identification and Hoechst (dark gray) for their nuclear localization. Intracellular accumulation of the nanoclays was detected by confocal microscopy; the representative images show the nanoclays localization mostly concurrent with the nuclear regions. Verma et al. 2012 [32]. Reproduced with permission of Springer. HepG2 cells uptake (d) 0–62.5 µg/ml Cloisite Na⁺ labeled with Neutral red uptake (NR) or (e) 0–500 µg/ml Cloisite 30B labeled with NR. All values are expressed as mean ± SD. *Significantly different from control (p ≤ 0.05). Maisanaba et al. 2013 [44]. Reproduced with permission of Elsevier. Comet assay results of (f) Caco-2 cells after 24 and 48 h of exposure to 8.5, 17, or 34 µg/ml Clay 2; (g) HepG2 cells after 24 and 48 h of exposure to 22, 44, and 88 µg/ml Clay 2. Results from three independent experiments with two replicates/experiment. All values are expressed as mean ± S.D. *Significantly different from control (p < 0.05). **Significantly different from control (p ≤ 0.01). Houtman et al. 2014 [43]. Reproduced with permission of Elsevier.
Figure 11.2 (a) Comet assay performed on Wistar rats (n = 6) exposed to Cloisite 30B suspended in water (being administered at 250, 500, and 1000 mg/kg body weight of rat) or cell-culture medium (being administered at 1000 mg/kg body weight of rat). Ethylmethane sulfonate (EMS) suspended in water was the positive control. For the experiments, six rats were exposed to 250 mg/kg body weight. Data from liver, kidney, and colon cells of the EMS-exposed group were statistically significantly different (p < 0.001, p < 0.001: *** and p < 0.05: *), respectively, from the values in the corresponding control group (two-tailed, unpaired t-test). Internal standards: positive controls (Caco-2 cells exposed to 0.05% ethylmethane sulfonate):16 slides, % tail DNA, mean ± S.D., 21.6 ± 6.6; negative controls (untreated Caco-2 cells): 16 slides, % tail DNA, mean ± S.D., 1.8 ± 0.6. Sharma et al. 2014 [56]. Reproduced with permission of Elsevier. (b) Catalase (CAT) and (c) superoxide dismutase (SOD) activities (nKat/mg protein) in kidney of rat exposed to Clay 1. The values are expressed as mean ± SD (n = 10). The levels observed are significant at *p < 0.05 in comparison to control group values. Maisanaba et al. 2014 [59]. Reproduced with permission of Taylor & Francis.
Figure 11.3 Histopathological evaluations of liver of Wistar rats exposed to a PLA-Clay1 extract as beverage for 90 days. (a) He-stained liver section and (b) He-stained kidney sections. Bars, 100 µm. (a,b) Control rats. (a) Liver parenchyma with hepatocytes with normal morphology, central nuclei, and light cytoplasm (He), organized in hepatic cords (circle). (b) Normal structure of kidney parenchyma with glomerulus (circle), proximal convoluted tubules (Pct), and distal convoluted tubules (Dct). (c,d) Exposed rats. (c) Liver parenchyma with hepatocytes with normal morphology, central nuclei, and light cytoplasm (He), organized in hepatic cords (circle). (d) Normal structure of kidney parenchyma with glomerulus (circle), proximal convoluted tubules (Pct), and distal convoluted tubules (Dct). Maisanaba et al. 2014 [59]. Reproduced with permission of Taylor & Francis.
Scheme 11.1 Schematic representation of the proposed mechanisms of toxicity induced by cellular exposure to nanoclays. In vitro exposure of cells to nanoclays with different physicochemical properties undergo changes in their structure and functions, with such changes being directly correlated with cellular morphology or proliferation rates controlled at the genetic level.

Chapter 12: Nanotechnology EHS: Manufacturing and Colloidal Aspects

Figure 12.1 Engineered nanomaterials entering the environment. Links are shown between production, consumer use and disposal, wastewater treatment plants (WWTPs), and waste incineration plants (WIPs).
Figure 12.2 Nanoparticle complexity using gold (Au) and silver (Ag) as examples. The Figure depicts differences in particle shape, size, crystallinity, and surface coating composition and charge (bottom half). Also shown are different transformations that take place in aqueous media and different toxicity mechanisms.
Figure 12.3 Corona formation (biological and/or environmental) around nanoparticles and nanoparticle aggregation.
Figure 12.4 Life cycle of nano-enabled products from the raw materials to disposal.
Figure 12.5 Compositional and combinatorial engineered nanomaterials (ENMs) libraries, including metals, metal oxides, carbon nanotubes, and silica-based nanomaterials, to perform mechanism-based EHS and toxicity analyses.
Figure 12.6 Agglomeration and nanoparticle “delivery” to cells in vitro. (a) In cell culture media, primary particles form agglomerates with media contained within the agglomerates and protein coronas formed on the particle surfaces. (b) Agglomerates administered to cells settle over time and form a concentrated layer near or deposited onto the cell surface. As a result, the administered dose is less than the delivered dose. (c) The effective density or delivered dose can be estimated by centrifuging the agglomerates and evaluating their packing factor (referred to also as a stacking factor).
Figure 12.7 Adaptation mechanisms of microorganisms to metals and antibiotics. These can include (i) reduced uptake of metal ions via transporter downregulation; (ii) efflux of metal ions via transporter upregulation; (iii) upregulation of extracellular biomolecular expression, which can in turn influence metal–cell surface binding, uptake, and efflux; (iv) intracellular sequestration through the formation of metal precipitates or metal–protein aggregates; (v) repair in response to ROS; (vi) metabolic bypass via enzymatic disruption; and (vii) chemical modification that reduce metal toxicity (e.g., via precipitation).

List of Tables

Chapter 1: Overview: Affirmation of Nanotechnology between 2000 and 2030

Table 1.1 Proposed classification of science and technology platforms
Table 1.2 Global and US revenues from products incorporating nanotechnology
Table 1.3 Generations of nanotechnology products and productive processes, and the corresponding interval for beginning commercial prototypes
Table 1.4 Examples of main NNI R&D centers, user facilities, and networks sponsored by NSF

Chapter 3: Controlling and Characterizing Anisotropic Nanomaterial Dispersion

Table 3.1 Summary of analytical techniques for dispersion characterization
Table 3.2 Standard deviation of G band intensities over the entire map for melt extruded samples obtained by Raman mapping, giving a quantitative measure of distribution and uniformity

Chapter 5: Overview of Nanotechnology in Military and Aerospace Applications

Table 5.1 Resulting CNT sensors and supplementary characteristics
Table 5.2 Evaluation of multiwalled CNT results
Table 5.3 Evaluation of single-walled CNT results
Table 5.4 Initial comparison of mechanical properties of CNTs in propellant with the baseline

Chapter 6: Novel Polymer Nanocomposite Ablative Technologies for Thermal Protection of Propulsion and Reentry Systems for Space Applications

Table 6.1 Specimen configuration for composition laminates fabrication
Table 6.2 Recession rate (RR) for the different materials and configurations using 0.25-mm TCs
Table 6.3 Recession rate (RR) for the CCC materials and different configurations using 0.5-mm TCs
Table 6.4 Recession rate (RR) for the C/Ph and configurations using 0.5-mm TCs
Table 6.5 Summary of ablation recession rate of different ablatives for 4-level TC sensors based on combined linear regression of experimental data
Table 6.6 The currently available simulation tools for ablation modeling [97]

Chapter 7: Manufacture of Multiscale Composites

Table 7.1 Advantages and disadvantages of various CNT functionalization methods
Table 7.2 Dimension and corresponding number of particles in composites for different fillers
Table 7.3 Comparison of various techniques for CNT dispersion in polymer composites

Chapter 8: Bioinspired Systems

Table 8.1 Summary of comparable biotemplate-metal systems suiTable for applications in nanocircuits

Chapter 9: Prediction of Carbon Nanotube Buckypaper Mechanical Properties with Integrated Physics-Based and Statistical Models

Table 9.1 Simulation results of Young's modulus under different combinations of average CNT length and PVA amount
Table 9.2 The source of variations in computer simulation results
Table 9.3 Experimental measurements of Young's modulus of random BP
Table 9.4 Comparison of SRMSE (statistical adjusted physical models versus regression model)
Table 9.5 Comparison of SRMSE (latent variable versus other methods)

Chapter 11: Nanoclays: A Review of Their Toxicological Profiles and Risk Assessment Implementation Strategies

Table 11.1 Examples of nanoclays researched along with their organic modifiers, applications, and associated References

Chapter 12: Nanotechnology EHS: Manufacturing and Colloidal Aspects

Table 12.1 Commonly used nanomanufacturing techniques

Nanotechnology Commercialization

Manufacturing Processes and Products

Edited by

Dr. Thomas O. Mensah, Editor in Chief

Georgia Aerospace Systems, Nano technology Division, Georgia Aerospace,
Inc., Atlanta, GA

Dr. Ben Wang, Editor

School of Industrial and Systems Engineering, Georgia Tech Manufacturing
Institute, Georgia Institute of Technology, Atlanta, GA

Dr. Geoffrey Bothun, Editor

Department of Chemical Engineering, University of Rhode Island, Kingston, RI

Dr. Jessica Winter, Editor

William G. Lowrie Department of Chemical and Biomolecular Engineering, The
Ohio State University Columbus, OH

Dr. Virginia Davis, Editor

Department of Chemical Engineering, Auburn University, Auburn, AL

A Joint Publication of the American Institute of Chemical Engineers and John Wiley & Sons, Inc.

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