Woodhead Publishing Ltd Abington Hall Abington Cambridge CB1 6AH England www.woodheadpublishing.com ISBN-13: 978-1-85573-933-8 ISBN-10: 1-85573-933-X CRC Press LLC 6000 Broken Sound Parkway, NW Suite 300 Boca Raton FL 33487 USA CRC order number WP3449 ISBN-10: 0-8493-3449-7 Nanostructure control of materials Edited by R. H. J. Hannink and A. J. Hill The ability to measure and manipulate matter at the nanometer level is making possible a new generation of materials with enhanced mechanical, optical, transport and magnetic properties. This important book summarises key developments in nanotechnology and their impact on the processing of metals, polymers, composites and ceramics. After a brief introduction, a number of chapters discuss the practical issues involved in the commercial production and use of nanomaterials. Other chapters review ways of nanoengineering steel, aluminium and titanium alloys. The book discusses the use of nanoengineered metal hydrides to store hydrogen as an energy source, and the development of nanopolymers for batteries and other energy storage devices. It also covers the use of nanotechnology to enhance the mechanical properties of ceramics, the production of synthetic versions of natural materials such as bone, and the development of nanocomposites. Nanostructure control of materials is an ideal introduction to the ways in which nanotechnology is being used to create new materials for industry. It will be welcomed by R&D managers in sectors such as automotive engineering as well as academics working in this exciting area. Dr Richard Hannink is an Honorary Fellow and Dr Anita Hill is a Research Scientist at CSIRO Manufacturing and Infrastructure Technology, Australia. Nanostructure control of materials Hannink and Hill Woodhead Publishing and Maney Publishing on behalf of The Institute of Materials, Minerals & Mining 240 x 159 /Pantone 4995 & 262 3 m I The Institute of Materials, Minerals & Mining 24mm Nanostructure control of materials Related titles: Nanolithography and patterning techniques in microelectronics (ISBN-13: 978-1-85573-931-4; ISBN-10: 1-85573-931-3) Currently, surface patterning is achieved by means of optical lithographic techniques but with industry moving towards the fabrication of devices with size features of 100 nm less, the technological community is looking for alternative approaches to materials fabrication at the nanoscale. By using nanolithography, scientists can drive patterning currents through surfaces while building a 3D structure from a series of patterned layers. Electron induced chemical lithography can create ultra-high resolution templates for the site-selective immobilisation of molecules, to form functional, hierarchically organised structures. This new book will concentrate on state-of-the-art nanolithographic methods with a particular emphasis on polymer research. Polymer nanocomposites (ISBN-13: 978-1-85573-969-7; ISBN-10: 1-85573-969-0) This new book concentrates specifically on the four main groups of polymer nanocomposites: layered silicates, nanotube, nanoparticle and block co-polymer systems. There is also a section on inorganic/organic hybrid systems. Each chapter gives comprehensive coverage of the dynamic properties of these materials and the various processing methods used in their production, design, performance and applications. The book is the first to give a comprehensive treatment of the subject. Materials for energy conversion devices (ISBN-13: 978-1-85573-932-1; ISBN-10: 1-85573-932-1) The term electroceramic is used to describe ceramic materials that have been specially formulated with specific electrical, magnetic or optical properties. Electroceramics are of increasing importance in many key technologies including microelectronics, communications and energy conversion. This innovative book is the first comprehensive survey on major new developments in electroceramics for energy conversion devices. It presents current research from leading innovators in the field. Details of these and other Woodhead Publishing materials books and journals, as well as materials books from Maney Publishing, can be obtained by: • visiting www.woodheadpublishing.com • contacting Customer Services (e-mail: sales@woodhead-publishing.com; fax: +44 (0) 1223 893694; tel.: +44 (0) 1223 891358 ext. 30; address: Woodhead Publishing Ltd, Abington Hall, Abington, Cambridge CB1 6AH, England) If you would like to receive information on forthcoming titles, please send your address details to: Francis Dodds (address, tel. and fax as above; email: francisd@woodhead- publishing.com). Please confirm which subject areas you are interested in. Maney currently publishes 16 peer-reviewed materials science and engineering journals. For further information visit www.maney.co.uk/journals. Nanostructure control of materials Woodhead Publishing and Maney Publishing on behalf of The Institute of Materials, Minerals & Mining CRC Press Boca Raton Boston New York Washington, DC W OODHEAD PUBLISHING LIMITED Cambridge England Edited by R. H. J. Hannink and A. J. Hill Woodhead Publishing Limited and Maney Publishing Limited on behalf of The Institute of Materials, Minerals & Mining Published by Woodhead Publishing Limited, Abington Hall, Abington, Cambridge CB1 6AH, England www.woodheadpublishing.com Published in North America by CRC Press LLC, 6000 Broken Sound Parkway, NW, Suite 300, Boca Raton, FL 33487, USA First published 2006, Woodhead Publishing Limited and CRC Press LLC © Woodhead Publishing Limited, 2006 The authors have asserted their moral rights. This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. 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Project managed by Macfarlane Production Services, Dunstable, Bedfordshire (macfarl@aol.com) Typeset by Replika Press Limited, India Printed by T J International Limited, Padstow, Cornwall, England Contents Contributor contact details ix Foreword by T W Turney xiii Acknowledgements xv Introduction: special properties resulting from nanodimensionality xvii A J HILL and R HANNINK, CSIRO, Australia 1 Nanoparticle technologies and applications 1 P CASEY, CSIRO, Australia 1.1 Introduction 1 1.2 Commercial production of nanoparticles 4 1.3 Synthesis and production processes 7 1.4 Examples of commercial production 19 1.5 Applications 24 1.6 Future challenge of nanoparticle production 27 1.7 Useful websites 27 1.8 References 27 2 Nanometric architectures: emergence of efficient non-crystalline atomic organization in nanostructures 32 T ASTE and T DI Matteo, The Australian National University, Australia 2.1 Introduction 32 2.2 Equal spheres packings 34 2.3 Searching for structure: the radial distribution function 35 2.4 Local motifs and orientation symmetry 37 2.5 Understanding the structure: local geometrial organization 39 2.6 A packing of tetrahedra 42 2.7 Structural organization and packing fraction 44 2.8 Packing hierarchy: the topological structure beyond first neighbors 48 2.9 Can disorder be more efficient? 50 2.10 Conclusions 54 2.11 Acknowledgments 54 2.12 References 54 3 Nanostructure characterisation using electron-beam techniques 57 J RICHES and J DRENNAN, University of Queensland, Australia 3.1 Introduction 57 3.2 Sample preparation 59 3.3 Nanoanalysis 62 3.4 Imaging 67 3.5 Future trends 69 3.6 Acknowledgments 72 3.7 References 72 4 Organic–inorganic nanocomposite membranes for molecular separation processes 76 T C MERKEL and I PINNAU, MembraneTechnology and Research Inc., USA 4.1 Introduction 76 4.2 Transport in dense membranes 77 4.3 Transport in composite materials 77 4.4 Nanocomposite membrane research 78 4.5 Conclusions and future trends 92 4.6 References 94 5 Developing fast ion conductors from nanostructured polymers 97 M FORSYTH, J ADEBAHR, N BYRNE and D MACFARLANE, Monash University, Australia 5.1 Introduction 97 5.2 Polymer electrolytes 97 5.3 Composite electrolytes 100 5.4 Conclusions 110 5.5 References 111 6 Nanostructures in biological materials 115 H GAO and H YAO, Max Planck Institute for Metals Research, Germany and B JI, Tsinghua University, China 6.1 Introduction 115 6.2 Nanostructures of biological materials 116 Contentsvi 6.3 Mechanics of bulk nanostructures of bone-like materials 122 6.4 Mechanics of surface nanostructure of gecko-like materials 131 6.5 Conclusions 139 6.6 Future trends 141 6.7 Acknowledgement 142 6.8 References 142 7 Mechanical behavior of metallic nanolaminates 146 A MISRA, Los Alamos National Laboratory, USA 7.1 Introduction 146 7.2 Methods of synthesizing metallic nanolaminates 147 7.3 Overview of strengthening mechanisms 150 7.4 Dependence of nanolaminate strength on layer thickness 153 7.5 Modeling of single dislocation behaviour 156 7.6 Plastic stability of nanolaminates 162 7.7 Conclusions 172 7.8 Acknowledgments 174 7.9 References 174 8 Preparation of monolithic nanocrystalline ceramics 177 G RIXECKER, Z BURGHARD and F ALDINGER Max Planck Institute for Metals Research, Germany and L GAO, Chinese Academy of Sciences, China 8.1 Introduction 177 8.2 Synthesis of nonmetallic-inorganic nanoparticles 181 8.3 Green shaping of nanoceramic bodies 186 8.4 Densification 194 8.5 Specific properties and applications 208 8.6 Conclusions and future trends 210 8.7 References 211 9 Nanoengineering of metallic materials 219 R LUMLEY and A MORTON, CSIRO, Australia and I POLMEAR, Monash University, Australia 9.1 Introduction 219 9.2 Nanoengineering of metallic materials 219 9.3 Age hardened alloys 222 9.4 High strength low alloy (HSLA) steels 228 9.5 Mechanical alloying 233 9.6 Amorphous solids and controlled crystallisation through rapid solidification 240 Contents vii 9.7 Future trends 247 9.8 References 247 10 Using magnetic resonance to study nanoprecipitation in light metal alloys 251 K NAIRN and T BASTOW, CSIRO Manufacturing and Infrastructure Technology, Australia 10.1 Introduction to age hardening of light metal alloys 251 10.2 NMR – a novel method for studying precipitation in alloys 254 10.3 NMR spectra of alloys 257 10.4 Conclusions 264 10.5 References 264 11 Nanocrystalline light metal hydrides for hydrogen storage 266 T KLASSEN, GKSS Research Centre Geesthacht GmbH, Germany 11.1 Introduction 266 11.2 Production of nanocrystalline light metal hydrides 267 11.3 Processes of hydrogen absorption and desorption 267 11.4 Nanocrystalline Mg-based hydrides 268 11.5 Nanocrystalline alanates 286 11.6 Evaluation of technical potential of nanocrystalline hydrides 291 11.7 Future trends 298 11.8 References 300 12 Nanofabrication 303 E HARVEY and M GHANTASALA, MiniFAB, Australia 12.1 Introduction 303 12.2 Nanomaterials – top-down and bottom-up approaches 304 12.3 Fabrication technologies – additive/subtractive methods 305 12.4 Lithography-based technologies 306 12.5 Deposition techniques 318 12.6 Fabrication of nanowires – different technologies 323 12.7 Future trends 327 12.8 References 328 Index 331 Contentsviii (* = main contact) Introduction Dr A. J. Hill and Dr Richard Hannink* Commonwealth Scientific and Industrial Research Organisation (CSIRO) Manufacturing and Infrastructure Technology (CMIT) Private Bag 33 Clayton South Victoria 3169 Australia Tel: +613 9545 2665 Fax: +613 9544 1128 E-mail: Anita.Hill@csiro.au Tel: +613 9545664 Fax: +613 9544 1128 E-mail:. Richard.Hannink@csiro.au Contributor contact details Chapter 1 Philip Casey CSIRO (CMIT) Private Bag 33 Clayton South Victoria 3169 Australia Tel: 61 03 9545 2777 Fax: 61 03 9544 1128 E-mail: phil.casey@csiro.au Chapter 2 Tomaso Aste* and Tiziana Di Matteo Department of Applied Mathematics RSPhysSE The Australian National University Canberra ACT 0200 Australia Tel: +61 (0)2 61252846 Fax: +61 (0)2 61250732 E-mail: tomaso.aste@anu.edu.au; tiziana.dimatteo@anu.edu.au [...]... nanoparticle production, xiv Foreword nanostructured materials, nanostructure characterisation techniques, and nanofabrication All of these topics are presented at the current state of the art in this book Significant progress has also been made by overseas colleagues on many new areas of nanostructure control of materials, and the editors have included chapters of topical interest such as hydrogen... technique, the work of Bastow and Nairn has opened a new area of high throughput atomic and nanoscale metallurgical investigation of alloys Klassen (Chapter 11) has used nanostructure control of metal hydrides to facilitate the transport and storage of large volumes of hydrogen gas One of the major challenges of the forthcoming hydrogen economy is the safe storage of large volumes of hydrogen gas for... super-hydrophobicity These final two examples of nanofabricated structures give some indication of the future direction that manufacturing may take and the benefit that may arise from the nanostructure control of materials The adoption and use of these technologies will help society achieve and maintain a standard of living not possible with our current manufacturing methods and present rate of natural resource consumption... example of the relationship between size and electronic 4 Nanostructure control of materials effects is that of size induced transitions from metal to non-metal in nanocrystals such as Hg, Au, Ag, Pd, Ni and Cu [16] Magnetic: magnetic properties of nanoparticles of transition metals such as Co, Ni show marked variations with size In the nanometric domain, the coercivity (a measure of the strength of a... surface-related rather than bulk controlled, including optical properties of metal oxides,1 gas transport properties of membranes,2 catalytic properties of nanoparticles;3 and the utilisation of these benefits have been some of the drivers for fabrication of structure on the nanoscale The ability to measure and manipulate matter on the nanometer level (nanoscience) has led to the discovery of surprising material... illustrating examples of nanostructure control, fabrication, modelling and utilisation While it cannot be an all-embracing book, it sets the scene for the readers’ further enquiry into this exciting field The chapter topics have been selected to give insight into several aspects of nanostructure control of materials Chapter 1 deals with production technologies and applications of nanoparticles, highlighting... brittle ceramics has become the classic example of nanostructure control of ceramics This approach was first highlighted by the development of a toughened ceramic known as partially stabilised zirconia (PSZ) PSZ was thought to be of little value as an engineering material due to its destructive phase transformation and its brittle behaviour under stress Control of phase form, size and composition at the... describe other alloy systems where the employment of forces under our control, e.g temperature, time, and composition, can be used to tailor the nanostructure of metallic alloys, producing improvements in mechanical properties not previously thought achievable The development of metallic and ceramic materials with superior properties achieved through nanostructure control has been translated to wide ranging... 1.0 µm I.2 (a) Image of nacre platelets (b) Image of the mechanical interlocking of nacre platelets of calcium carbonate (Courtesy Katti et al (10)) – see text for further details xxii Introduction: special properties resulting from nanodimensionality micron scale to make the failure mode one of progressive failure of the individual interlocks (a tough, energy absorbing mode of failure) with an accompanying... An elegant example of nanofabrication of an engineering system is that provided by the work of Zettl and co-workers14,15 on low friction bearings and springs fabricated from multi-wall carbon nanotubes This example is schematically shown in Fig I.4(a) and illustrates the potential of exploiting nanoscale surface features for the manufacture of low-friction devices The production of inner- and outer-roller . rather than bulk controlled, including optical properties of metal oxides, 1 gas transport properties of membranes, 2 catalytic properties of nanoparticles; 3 and the utilisation of these benefits. Commercial production of nanoparticles 4 1.3 Synthesis and production processes 7 1.4 Examples of commercial production 19 1.5 Applications 24 1.6 Future challenge of nanoparticle production. The chapter topics have been selected to give insight into several aspects of nanostructure control of materials. Chapter 1 deals with production technologies and applications of nano- particles,