edited byCarlos R. Cabrera Félix A. Miranda

Advanced Nanomaterials for Aerospace Applications

Advanced Nanomaterials

for Aerospace

Applications

for the WorldWind PowerThe Rise of Modern Wind Energy

Preben MaegaardAnna KrenzWolfgang Palz

editors

Advanced Nanomaterials

for Aerospace

Applications

edited byCarlos R. Cabrera Félix A. Miranda

Published by

Pan Stanford Publishing Pte. Ltd.Penthouse Level, Suntec Tower 3 8 Temasek Boulevard Singapore 038988 Email: editorial@panstanford.com Web: www.panstanford.com

British Library Cataloguing-in-Publication DataA catalogue record for this book is available from the British Library.

Advanced Nanomaterials for Aerospace Applications

Copyright © 2014 Pan Stanford Publishing Pte. Ltd.All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the publisher.

For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from the publisher.

Cover image courtesy of NASA (modified).

ISBN 978-981-4463-18-8 (Hardcover)ISBN 978-981-4463-19-5 (eBook)

Printed in the USA

Contents

Preface xiii

1. AdvancedSensorNanomaterialsforAerospaceApplications 1

Gary W. Hunter, Jennifer C. Xu, Laura J. Evans, Luis F. Fonseca, Ram Katiyar, María M. Martínez-Iñesta, Wilfredo Otaño, Neeraj Panwar, and Randy L. Vander Wal

1.1 Introduction 2 1.2 Overview of Aerospace Applications 3 1.2.1 Leak Detection 3 1.2.2 High-Temperature Physical Parameters 4 1.2.3 Emissions Monitoring 5 1.2.4 Fire Safety and Environmental Monitoring 6 1.2.5 Radiation Detection 7 1.3 Sensor Examples 8 1.3.1 Palladium Nanoshells for Hydrogen Sensing 9 1.3.2 Pd Ultrathin Films and Nanowires Using

Solid State Reduction and Zeolite Templates 12 1.3.3 Transition Metal Silicide Nanowires for

Temperature Sensors 16 1.3.4 Combustion Product Sensors Based on

Nanostructures 20 1.3.5 ZnO Bandgap Modulation for Solar Blind

UV Detectors 23 1.3.5.1 ZnBeMgO films by spin coating 24 1.3.5.2 ZnBeMgO films by pulsed laser

deposition 25 1.3.6 Long-Term Implementation/Further

Necessary Steps 27

vi Contents

2. ChallengesandPossibilitiesinNanosensorTechnology 39

Gary W. Hunter, Laura Evans, Jennifer Xu, Azlin Biaggi-Labiosa, Randy L. Vander Wal, Luis F. Fonseca, Gordon M. Berger, and Mike J. Kulis

2.1 Overview of Challenges in Nanosensor Technology 40 2.2 Fabrication of Sensors Based on Nanostructures 44 2.3 Characterization of the Sensor Nanostructures 51 2.4 Sensing Mechanisms 55 2.5 Smart Nanosensor Systems 59 2.6 Summary and Future Possibilities 63

3. NanoporousMaterialsinAtmosphereRevitalization 71

Arturo J. Hernández-Maldonado, Yasuyuki Ishikawa, Raphael G. Raptis, Bernadette Luna, Lila Mulloth, Christian Junaedi, Subir Roychoudhury, and Jay L. Perry

3.1 Introduction 71 3.1.1 Development History of Atmosphere

Revitalization Systems for Space 72 3.1.2 Design Challenges and Considerations 74 3.2 Microporous Materials 78 3.2.1 Zeolitic Adsorbents 78 3.2.2 Amine-Based Adsorbents 84 3.2.3 Metal Organic Frameworks 85 3.3 Microlith®-Based Structured Adsorbents 88 3.4 Closing Remarks 91

4. NanotechnologyinAdvancedLifeSupport:WaterRecycling 101

Michael Flynn, Eduardo Nicolau, and Carlos R. Cabrera

4.1 Introduction 101 4.2 Membranes 102 4.2.1 Pervaporation Membranes 102 4.2.2 Reverse Osmosis Membranes 103 4.2.3 Forward Osmosis Membranes 104

viiContents

4.2.4 Future Directions in Membrane Development 105

4.2.4.1 Zeolite ceramic membranes 105 4.2.4.2 Catalytic nanoparticle membranes 106 4.2.4.3 Mixed matrix membranes 106 4.2.4.4 Nanoparticle membranes 106 4.2.4.5 Block copolymer membranes 107 4.2.4.6 Bio-inspired membranes 107 4.2.4.7 Aquaporin membranes 108 4.3 Catalysts 108 4.3.1 Catalytic Materials 109 4.3.1.1 Thermal 109 4.3.1.2 Electrocatalysts 109 4.3.1.3 Photocatalyst 110 4.3.2 Catalyst Supports 110 4.3.2.1 Thermal 110 4.3.3 Catalytic Processes Developed for Flight

Applications 111 4.3.3.1 Volatile removal assembly 111 4.3.3.2 Aqueous phase catalytic oxidation 111 4.3.3.3 Electrochemical 112 4.3.3.4 Bioelectrochemical cells 114 4.3.3.5 Adsorption process 115 4.4 Scale Formation and Precipitation 117 4.4.1 Molecular Scale Control 118 4.4.2 Electrodialysis 118 4.4.3 Nucleation Devices 120 4.5 Effects of Microgravity on the Nanoscale 120 4.5.1 Concentration Polarization 120 4.5.2 Electrochemical 122 4.5.3 Biology—Gas Diffusion 124 4.6 Current Integrated Strategies for Water

Reclamation 125

viii Contents

5. NanomaterialsforAdvancedLithium-IonBatteryAnodes 131

Richard S. Baldwin, James J. Wu, and William R. Bennett

5.1 Introduction 131 5.2 Promising Nanomaterials as Alternative Anodes 134 5.2.1 Carbon-Based Anodes 134 5.2.2 Silicon-Based Anodes 135 5.2.2.1 Si nanoparticles 137 5.2.2.2 Si nanowires 137 5.2.2.3 Si nanorods 137 5.2.2.4 Silicon nanowhiskers 138 5.2.2.5 Nanoscale silicon films 138 5.2.2.6 Silicon/carbon composite 138 5.2.3 Tin-Based Anodes 139 5.2.4 Transition Metal Oxide–Based Anodes 140 5.3 Practical Considerations 140 5.3.1 Value of Anode Specific Capacity 140 5.3.2 Advantages and Disadvantages of

High-Surface-Area Electrodes 141 5.3.3 Importance of Electrode Loading 142 5.3.4 Importance of Electrode Potential 143

6. AdvancesinDesigningHigh-EnergyCathodeMaterialsforLi-IonRechargeableBatteries 149

Ram S. Katiyar and Gurpreet Singh

6.1 Introduction 150 6.2 High Voltage Spinel Electrode Materials 152 6.3 Layered Cathode Materials 160 6.4 Carbon-Coated LiFePO4 167 6.5 Conclusions 170

7. NanomaterialsinRegenerativeFuelCells 179

Thomas I. Valdez, Ileana González-González, and Carlos R. Cabrera

7.1 Introduction 179 7.2 The Regenerative Fuel Cell System 180

ixContents

7.3 Space-Rated Regenerative Fuel Cell Systems 182 7.4 Fuel Cell and Electrolyzer Reactions 183 7.5 Fuel Cell, Hydrogen Oxidation Reaction 183 7.6 Fuel Cell, Oxygen Reduction Reaction 184 7.7 Electrolysis, Oxygen Evolution Reaction 185 7.8 Electrolysis, Hydrogen Evolution Reaction 187 7.9 Fabrication of Nanomaterials for Regenerative

Fuel Cells 187 7.10 Materials Development for Proton Exchange

Membrane-Based Hydrogen/Oxygen Fuel Cells 188 7.11 Oxygen Evolution Catalysts 190 7.12 MEA Development for NASA Non-Flow-Through

Hydrogen/Oxygen Fuel Cell Stack 193 7.13 MEA Development for NASA High-Pressure

Electrolyzers 194 7.14 Conclusion 196

8. NanotechnologyforNanoelectronicDevices 201

Félix A. Miranda and Harish M. Manohara

8.1 Introduction 201 8.2 What Makes Nanotechnology So Attractive for

Nanoelectronics Applications? 202 8.3 Examples of Nanoelectronic Devices 203 8.4 Characterization Techniques for Nanoelectronics

Applications 207 8.5 Nanotechnology/Nanoelectronics in Future NASA

Communications Systems 212 8.5.1 Logic Devices 212 8.5.2 Nano Field-Effect Transistors 213 8.5.3 Graphene-Based Nanocircuits 216 8.5.4 Nanoantennas 219 8.5.5 Nanoionics 220 8.5.6 CNT Vacuum Microelectronics 222 8.6 Conclusions 222

x Contents

9. BriefIntroductiontoNanocompositesforElectromagneticShielding 227

Stefano Bellucci and Federico Micciulla

9.1 Introduction 227 9.2 Nanocomposites 228 9.3 Dielectric and Magnetic Materials 237 9.4 Electromagnetic Compatibility 250 9.5 Electromagnetic Interference Shielding

Properties 254

10. EpoxyNanocompositeBasedonCarbonNanotubesforElectromagneticInterfaceShielding 267

Stefano Bellucci and Federico Micciulla

10.1 Introduction 267 10.2 Carbon Nanotubes 269 10.3 Epoxy Nanocomposite Filled with Carbon

Nanotubes: DC Measurements 279 10.4 AC Conductivity Measurements 304 10.5 Epoxy Nanocomposite Filled with Carbon

Nanotubes: Shielding Effectiveness Measurements 323 10.6 Conclusions 327

11. BringingNASA-RelevantNanotechnologyResearchintotheClassroom 341

Ana-Rita Mayol, Christian L. Menéndez, Melissa Dávila, and Liz M. Díaz-Vázquez

11.1 Introduction 341 11.2 Bringing Research into the Classroom: Rationale 342 11.3 Methodology: Conceptualization and Designing

the Appropriate Hands-On Activities 343 11.4 Implementation of Developed Lessons:

Implementing Electrochemical Concepts in the Curriculum 348

11.5 Demistifying NASA Technology: Water Quality 349 11.6 Conclusion: What Are We Really Teaching:

Concepts, Skills, or Both? 350

xiContents

12. FutureDirectionsinNanotechnologyR&DatNASA 355

Michael A. Meador

12.1 Introduction 355 12.2 Discussion 357 12.2.1 Grand Challenge: 50% Lighter Composites 357 12.2.2 Structures with Integrated Energy

Generation and Storage 359 12.2.3 Graphene: From Molecules to Devices 362 12.2.4 Nanopropellants 364 12.2.5 Hierarchical Integration 365 12.3 Conclusions 366

Index 371

Preface

The book titled Advanced Nanomaterials for Aerospace Applications has been developed for a community interested in aerospace science and nanotechnology. Scientists and engineers of the NASA-University Research Center for Advanced Nanoscale Materials (CANM) at the University of Puerto Rico and from the NASA John H. Glenn and Ames Research Centers, the George C. Marshall Space Flight Center, the Jet Propulsion Laboratory, Pennsylvania State University, and INFN-Laboratori Nazionali di Frascati, Italy, have joined efforts to present the applications of nanomaterials in sensors, life support systems, regenerative fuel cells, Li-ion batteries, robust lightweight materials, nanoelectronics, and electromagnetic shielding. The CANM at the University of Puerto Rico has been involved in the development of these exciting research areas in collaboration with NASA centers for more than 10 years. Most of the scientists and engineers who have been part of the CANM are authors or co-authors of the chapters in this Book. Their efforts and collaborations on the research, development, and applications of nanomaterials have advanced some of the technology to higher NASA Technology Readiness Levels. The outcome of some of these collaborations and interactions is summarized in the chapters of this book to be shared with the aerospace and nanotechnology communities. Chapters 1 and 2 are devoted to sensor technology. Chapter 1 offers a thorough overview of a variety of sensors being developed in support of NASA’s mission. Among these are sensors for leak detection, high-temperature physical state monitoring, emis-sions monitoring, fire and environmental detection, and radiation detection, among others. Chapter 2 focuses on the challenges as-sociated with the fabrication and reproducibility of nanostructures into microsensors and microsensor systems. It also discusses the characterization of the basic properties of nanowires, and the

xiv

sensing mechanisms of nanostructures of different crystal struc-tures. New sensor systems that can be enabled by nanotechnology are also discussed. Chapters 3 and 4 present the use of nanomaterials for life support system applications. The chapters summarize the challenges faced by the environmental control and life support system engineers and scientists in improving the atmospheric revitalization and water reclamation subsystems currently used in space platforms such as the International Space Station. In this context, the chapters discuss the promising materials developments that may enable solutions to address these challenges for human space exploration missions beyond low earth orbit. These include water-recycling systems in space platforms and the effects of reduced gravity environment on the performance of life support systems (Chapter 4). Chapter 5 discusses the performance advantages of different nanostructured electroactive materials, as compared to microstructured materials, for the negative electrodes (i.e., anodes) of lithium-ion batteries. Chapter 6 complements Chapter 5 by discussing the advances in the design of high-energy cathode materials for rechargeable lithium-ion batteries. Chapter 7 provides insights on the use of nanomaterials for renewable energy applications, in particular the development of nanomaterials used as catalysts for fuel cells and electrolyzers in regenerative fuel cell systems for NASA applications. Chapters 8, 9, and 10 present other areas of nanotechnology relevant for aerospace applications. Chapter 8 addresses the use of nanotechnology for the development of nanoelectronic devices and applications. The chapter provides some examples of nanoelectronic devices and characterization techniques, as well as an assessment of the use of nanoelectronics in future NASA communication systems. Chapters 9 and 10 discuss the use of advanced nanomaterials for electromagnetic shielding, a topic of utmost relevance for long-duration human presence in space. Since one of the roles of the CANM initiative was the development of approaches and mechanisms to foster nanotechnology outreach and education, it seems appropriate to include in this book a chapter on this most relevant subject matter. Accordingly, Chapter 11 discusses nanotechnology educational components based on advanced nanomaterials for aerospace applications and the

Preface

xv

initiative implemented in this area as part of the CANM educational and outreach efforts. Finally, Chapter 12 provides an overall NASA perspective on the future trends in nanotechnology and discusses initiatives and mechanisms currently in place to facilitate the advancement of research and technology development delineated by such trends. There are many people and organizations that have made this book possible. In particular, the editors would like to thank each of the authors of the chapters featured in this book for their hard work and outstanding contributions. We wish to express our gratitude to the students, colleagues, and officers of the University of Puerto Rico, who in many ways contributed to the work featured in this book. We would like to extend our gratitude to Ms. Katrina Emery, former project director of the NASA University Research Centers Program, for her support and encouragement throughout the years. We are grateful to Ms. Kaprice L. Harris and Ms. Deborah A. Szczepinski (Stinger Ghaffarian Technologies, Inc.) of NASA Glenn Research Center’s Office of the Chief Counsel, for their help regarding compliance with government regulations and policies. It is our hope that this book will fill the expectations of the reader and presents an opportunity to learn more about advanced nanomaterials for aerospace applications.

Dr.CarlosR.CabreraNASA-URC Center for Advanced Nanoscale Materials

The University of Puerto Rico, Rio Piedras CampusSan Juan, Puerto Rico

Dr.FélixA.Miranda NASA John H. Glenn Research Center at Lewis Field, Cleveland, OH

May 2014

Preface