Nanocoatings and ultra-thin films © Woodhead Publishing Limited, 2011 Related titles: Nanostructured metals and alloys (ISBN 978-1-84569-670-2) Nanostructured metals and alloys have enhanced tensile strength, fatigue strength and ductility and are suitable for use in applications where strength or strength-toweight ratios are important Part I of this important book reviews processing techniques for bulk nanostructured metals and alloys Parts II and III discuss microstructure and mechanical properties, whilst part IV outlines applications of this new class of material Electroless copper and nickel-phosphorus plating (ISBN 978-1-84569-808-9) Compared with electroplating, electroless plating allows uniform deposits over different surfaces Electroless copper and nickel-phosphorus deposits provide protective and functional coatings in industries as diverse as electronics, automotive, aerospace and chemical engineering Written by leading experts in the field, this important book reviews the deposition process and the key properties of electroless copper and nickel-phosphorus deposits as well as their practical applications Thermal barrier coatings (ISBN 978-1-84569-658-0) Thermal barrier coatings are used to counteract the effects of high temperature corrosion and degradation of materials exposed to environments with high operating temperatures The book covers both ceramic and metallic thermal barrier coatings as well as the latest advances in physical vapour deposition and plasma spraying techniques Advances in nanostructured thermal barrier coatings are also discussed The book reviews potential failure mechanisms in thermal barrier coatings as well as ways of testing performance and predicting service life A final chapter reviews emerging materials, processes and technologies in the field Details of these and other Woodhead Publishing materials books can be obtained by: • • • visiting our website at www.woodheadpublishing.com contacting Customer Services (e-mail: sales@woodheadpublishing.com; fax: +44 (0) 1223 832819; tel.: +44 (0) 1223 499140 ext 130; address: Woodhead Publishing Limited, 80 High Street, Sawston, Cambridge CB22 3HJ, UK) contacting our US office (e-mail: usmarketing@woodheadpublishing.com; tel (215) 928 9112; address: Woodhead Publishing, 1518 Walnut Street, Suite 1100, Philadelphia, PA 19102-3406, USA) If you would like to receive information on forthcoming titles, please send your address details to: Francis Dodds (address, tel and fax as above; e-mail: francis dodds@woodheadpublishing.com) Please confirm which subject areas you are interested in © Woodhead Publishing Limited, 2011 Nanocoatings and ultra-thin films Technologies and applications Edited by Abdel Salam Hamdy Makhlouf and Ion Tiginyanu Oxford Cambridge Philadelphia New Delhi © Woodhead Publishing Limited, 2011 Published by Woodhead Publishing Limited, 80 High Street, Sawston, Cambridge CB22 3HJ, UK www.woodheadpublishing.com Woodhead Publishing, 1518 Walnut Street, Suite 1100, Philadelphia, PA 191023406, USA Woodhead Publishing India Private Limited, G-2, Vardaan House, 7/28 Ansari Road, Daryaganj, New Delhi – 110002, India www.woodheadpublishingindia.com First published 2011, Woodhead Publishing Limited © Woodhead Publishing Limited, 2011 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 Reasonable efforts have been made to publish reliable data and information, but the authors and the publishers cannot assume responsibility for the validity of all materials Neither the authors nor the publishers, nor anyone else associated with this publication, shall be liable for any loss, damage or liability directly or indirectly caused or alleged to be caused by this book Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming and recording, or by any information storage or retrieval system, without permission in writing from Woodhead Publishing Limited The consent of Woodhead Publishing Limited does not extend to copying for general distribution, for promotion, for creating new works, or for resale Specific permission must be obtained in writing from Woodhead Publishing Limited for such copying Trademark notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation, without intent to infringe British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Control Number: 2011934932 ISBN 978-1-84569-812-6 (print) ISBN 978-0-85709-490-2 (online) The publisher’s policy is to use permanent paper from mills that operate a sustainable forestry policy, and which has been manufactured from pulp which is processed using acid-free and elemental chlorine-free practices Furthermore, the publisher ensures that the text paper and cover board used have met acceptable environmental accreditation standards Typeset by Toppan Best-set Premedia Limited, Hong Kong Printed by TJI Digital, Padstow, Cornwall, UK © Woodhead Publishing Limited, 2011 Contents Contributor contact details Introduction Part I Technologies Current and advanced coating technologies for industrial applications A S H Makhlouf, Max Planck Institute of Colloids and Interfaces, Germany Introduction Electro- and electroless chemical plating Conversion coatings Chemical and physical vapor deposition (CVD and PVD) Spray coating Other coating techniques New lightweight materials Trends in environmentally friendly coatings, self-assembling and self-cleaning coatings Trends in nanocoatings New composite and powder coatings Advanced polymers and fillers Developments in coating processes Acknowledgements References 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 1.11 1.12 1.13 1.14 2.1 2.2 2.3 Nanostructured thin films from amphiphilic molecules J Y Park and R C Advincula, University of Houston, USA Langmuir monolayer Amphiphilic polymers Dendrons and dendrimers xi xv 3 10 12 13 14 16 17 18 20 20 24 24 28 36 v © Woodhead Publishing Limited, 2011 vi Contents 2.4 2.5 2.6 2.7 2.8 Metal/semiconductor nanoparticles 2-D arrays of colloidal spheres Conclusions Acknowledgements References Chemical and physical vapor deposition methods for nanocoatings I V Shishkovsky, P N Lebedev Physics Institute of the Russian Academy of Sciences, Russia Substrate preparation for ultra-thin films and functional graded nanocoatings Paradigm of functional graded layer-by-layer coating fabrication Nanocoating fabrication methods Physical vapor deposition-based technologies Chemical vapor deposition-based technologies Conclusion and future trends References 3.1 3.2 3.3 3.4 3.5 3.6 3.7 4.1 4.2 4.3 4.4 4.5 4.6 5.1 5.2 5.3 5.4 Surface-initiated polymerisation for nanocoatings V Harabagiu, L Sacarescu, A Farcas, M Pinteala and M Butnaru, ‘Petru Poni’ Institute of Macromolecular Chemistry, Romania Introduction Physisorption and chemisorption, equilibrium and irreversible adsorption Preparation of surface-bound polymer layers Properties and applications Acknowledgement References Methods for analysing nanocoatings and ultra-thin films D M Bastidas, M Criado and J.-M Bastidas, National Centre for Metallurgical Research (CENIM), CSIC, Spain Introduction Electrochemical methods Surface-sensitive analytical methods for ultra-thin film coatings Spectroscopic, microscopic and acoustic techniques for ultra-thin film coatings © Woodhead Publishing Limited, 2011 41 44 48 48 48 57 57 60 61 63 71 74 75 78 78 79 87 110 112 112 131 131 132 140 145 Contents 5.5 5.6 5.7 Conclusions Acknowledgements References Part II Applications 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 7.1 7.2 7.3 7.4 7.5 7.6 7.7 8.1 8.2 8.3 8.4 8.5 8.6 8.7 Conventional and advanced coatings for industrial applications: an overview A S H Makhlouf, Max Planck Institute of Colloids and Interfaces, Germany Introduction Conventional coating technologies for the automotive and aerospace industries Advanced coating technologies for the automotive and aerospace industries Packaging applications Coatings for the electronics and sensors industry Paints and enamels industry Biomedical implants industry Acknowledgements References Nanocoatings for architectural glass J Mohelnikova, Brno University of Technology, Czech Republic Introduction Spectrally selective glass Dynamic smart glazings Glass surface protections Conclusion Acknowledgements References Nanocoatings and ultra-thin films for packaging applications A Sorrentino, University of Salerno, Italy Introduction Nanomaterials in packaging High barrier packaging Anti-microbial packaging Nanosensors in packaging Packaging as a drug carrier and for drug delivery Nanotechnology solutions for the packaging waste problem © Woodhead Publishing Limited, 2011 vii 153 153 153 157 159 159 159 162 170 171 173 174 175 177 182 182 183 188 194 195 196 196 203 203 208 209 215 216 218 219 viii Contents 8.8 8.9 8.10 8.11 Anti-static packaging applications Regulation and ethical issues in the new packaging industry Future trends References Advanced protective coatings for aeronautical applications M G S Ferreira, M L Zheludkevich and J Tedim, University of Aveiro, Portugal Introduction: corrosion in aeronautical structures Types of corrosion in aircraft Factors influencing corrosion Corrosion of aluminum and its alloys Corrosion of magnesium alloys Protective coatings in aerospace engineering Pre-treatments Anodizing coatings Functional nanocoatings in aerospace engineering Nanocoatings for detection of corrosion and mechanical damage Self-healing coatings: nanostructured coatings with triggered responses for corrosion protection Application of nanomaterials for protection of aeronautical structures Conclusion and future trends References 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.10 9.11 9.12 9.13 9.14 10 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 10.10 10.11 Nanoimprint lithographic (NIL) techniques for electronics applications I Tiginyanu, V Ursaki and V Popa, Academy of Sciences of Moldova, Republic of Moldova Lithography techniques and nanoimprint lithography (NIL) fundamentals Thermoplastic and laser-assisted NIL Photo-assisted nanoimprinting Soft NIL Extensions of soft NIL Scanning probe lithography (SPL) Edge lithography NIL for three-dimensional (3D) patterning Combined nanoimprint approaches Applications Conclusions © Woodhead Publishing Limited, 2011 220 221 222 223 235 235 236 241 243 244 246 247 253 258 259 261 266 270 270 280 280 286 291 297 301 307 309 311 315 317 320 Contents ix 10.12 10.13 Acknowledgement References 322 322 11 Ultra-thin membranes for sensor applications I Tiginyanu, V Ursaki and V Popa, Academy of Sciences of Moldova, Republic of Moldova Introduction Graphene and related two-dimensional (2D) structures Nanometer-thick membranes of layered semiconductor compounds Ultra-thin membranes of gallium nitride Conclusion Acknowledgement References 330 Nanocoatings for tribological applications S Achanta and D Drees, Falex Tribology NV, Belgium and J.-P Celis, Katholieke Universiteit Leuven, Belgium Introduction Use of nanostructured coatings in tribology Review of nanostructured coatings for friction and wear applications Advanced techniques for characterizing tribological properties of nanostructured coatings Conclusions and future trends Acknowledgements References 355 Self-cleaning smart nanocoatings J O Carneiro, V Teixeira, P Carvalho, S Azevedo and N Manninen, University of Minho, Portugal Introduction: TiO2 photocatalysis Photocatalysis processes The photocatalytic cleaning effect of TiO2-coated materials New and smart applications of TiO2 coatings Conclusions References 397 Index 414 11.1 11.2 11.3 11.4 11.5 11.6 11.7 12 12.1 12.2 12.3 12.4 12.5 12.6 12.7 13 13.1 13.2 13.3 13.4 13.5 13.6 © Woodhead Publishing Limited, 2011 330 331 341 344 351 351 351 355 356 367 382 391 391 392 397 399 402 406 410 411 Index adhesion, 59 aerospace engineering conventional coating technologies and smart nanocoatings for corrosion protection, 235–70 aluminium and its alloys, 243–4 anodising coatings, 253–7 applications of nanomaterials, 266–70 corrosion in aeronautical structures, 235–6 corrosion of magnesium alloys, 244–5 detection of corrosion and mechanical damage, 259–61 factors influencing corrosion, 241–3 functional nanocoatings, 258–9 future trends, 270 pretreatments, 247–53 protective coatings in aerospace engineering, 246–7 self-healing coatings, 261–6 types of corrosion in aircraft, 236–41 air/knife coating, 11 Alclad, 244 aluminium see also Alclad corrosion, 243–4 Amontons-Coulomb law, 357 Amontons’ law, 388 AMS2488, 382 analytical methods electrochemical methods, 132–40 cathodic stripping for mechanically polished copper specimens, 133 dependence of current density peak and potential peak on potential scan rate for copper specimens, 134 electrical equivalent circuit used to model the impedance data, 136 electrochemical impedance spectroscopy, 133–9 experimental data vs impedance calculated using KK relationships, 137 Nyquist plot for AISI 316L stainless steel, 135 organic coatings porosity, 140 parameters used in the simulation of impedance data, 136 potentiodynamic potential/current measurements, 132–3 water absorption in organic coatings, 139–40 nanocoatings and ultra-thin films, 131–53 spectroscopic, microscopic and acoustic techniques, 145–53 glow discharge optical emission spectroscopy, 150–1 414 © Woodhead Publishing Limited, 2011 Index infrared, Raman and Mössbauer spectroscopies, 145–7 ion scattering, Rutherford backscattering and secondaryion mass spectroscopy, 148–50 scanning acoustic microscopy and Kevin probe force microscopy, 152–3 scanning electron microscopy and transmission electron microscopy, 151–2 x-ray diffraction, 147–8 surface-sensitive analytical methods, 140–5 characterisation by AFM, 141 specular reflectance infrared spectroscopy characterisation, 143–5 XPS study of corrosion protection, 142–3 anodic aluminum oxide, 292 anodisation, 63 anodising, 6, 253–7 electrochemical chracterisation, 255–6 fatigue properties, 256–7 S-N plots for Al 2024-T3, 257 film structures, 254–5 micrograph of anodised Al 2024, 256 TEM micrographs of aluminium, 255 anti-microbial packaging, 215–16 anti-Stokes scattering, 146 antistatic packaging, 220–1 architectural glass, 182–95 dynamic smart glazings, 188–94 activated photoelectrochromic device, 192 composition of electrochromic glazing, 189 composition of glass laminate with liquid crystals or suspended particles, 192 electrochromic glazings, 188–9 415 gasochromic electrochromic device composition, 191 gasochromic-electrochromic glazings, 190–1 glazing composition with two complementary electrochromic layers, 189 light control and thermal imaging glazings, 193–4 liquid crystal and suspended particle glazings, 192–3 photochromic-electrochromic glazing devices, 191–2 photovoltaic-powered electrochromic device, 190 photovoltaic-powered electrochromic glazings, 190 thermally-activated glazings, 193 glass surface protections, 194–5 water droplet contact angle on hydrophilic and hydrophobic surface, 195 spectral transmittance and reflectance clear float and low iron and low-e glass, 186 low-e glass with single and double Ag layer, 187 low-e glass with single and triple Ag layer, 187 spectrally selective glass, 183–8 glass with low-emissivity coatings, 184–8 low-e coating layer, 185 optical properties and emissivity of glass, 183–4 ASTM 2625, 382 ASTM B449-93, 247 atmospheric pressure CVD, 72–3 atom transfer radical polymerisation, 102–3, 105 atomic force microscopy, 32, 308–9 atomic layer deposition, 71 automotive, 363–4 piston skirt damage due to severe scuffing, 364 © Woodhead Publishing Limited, 2011 416 Index Bayresit, 210 benzophenone, 102 biomaterials, 366 biomedical implants industry, 174–5 most common techniques for hydroxyapatite coatings formation, 176 bismuth telluride, 344 bit patterned media, 318 Boegel, 252 ‘bond coat,’ 138 bottom-up method, 106 Bragg’s law, 147 Brasher–Kingsbury empirical relationship, 140 Brewster angle microscopy (BAM), 27 capillary force lithography, 301 carbon nanotubes, 217, 221 catalysed photoexcitation, 400 cationic polymerisation, 295 cerium, 248–9 chalcogenide, 343 chemical conversion coatings, 159–61 chromate and chromate-free conversion coatings, 160–1 conversion coatings by hydrothermal treatment, 160 chemical liquid deposition, 63 chemical shift, 142, 147 chemical solid growth, 63 chemical vapour deposition, 6–7, 71–4, 336, 373–5 chemisorption, 82 chromate conversion coating, 5–6, 152–3, 247–8 chrome-free conversion coatings, chromic acid anodising, 254 chromium-free inhibitors, 248–50 chromogenic glazings, 183 cluster-beam PVD, 68 CMOS image sensors, 318–19 coating capacitance, 139 coating technologies advanced polymers and fillers, 17–18 conductive polymers, 17–18 fillers, 18 hyperbranched polymers, 17 organic–inorganic hybrid polymers, 17 water-soluble paint, 18 chemical and physical vapour deposition, 6–7 chemical vapour deposition, 6–7 physical vapour deposition, coating processes developments, 18–20 conversion coatings, 5–6 anodising, chromate conversion coating, 5–6 chrome-free conversion coatings, current and advanced for industrial applications, 3–20 electro- and electroless chemical plating, 4–5 electrochemical plating, 4–5 electroless chemical plating, new composite and powder coatings, 16–17 composite coatings, 16 powder coatings, 16–17 new lightweight materials, 12–13 other coating techniques, 10–12 air/knife coating, 11 curtain coating, 12 dip coating, 12 gravure coating, 10–11 knife over roll coating, 11 Meyer rod coating, 11 roll-to-roll coating, 11 slot/die and slot/extrusion coating, 12 sol–gel coatings, 10 spin coating, 10 spray coating, 7–10 cold spraying, high-velocity oxygen fuel spraying, plasma spraying, 8–9 thermal spraying, vacuum plasma spraying, warm spraying, 9–10 © Woodhead Publishing Limited, 2011 Index trends in coatings, 13–16 environmentally friendly coatings, 13 micro- and nanocapsule-based coatings, 14–15 nanocomposite coatings, 15–16 self-assembling molecules, 13 self-cleaning coatings, 14 coatings see also nanocoatings advanced technologies for automotive and aerospace industries, 162–70 modelling and computer simulations, 169–70 powder coating, 168 self-cleaning coatings, 167–8 ‘smart’ multifunctional coatings, 163 ‘super’-hard coatings, 164–7 thermal barrier coatings, 169 transparent coatings, 168 biomedical implants industry, 174–5, 176 conventional and advanced for industrial applications, 159–76 conventional technologies for automotive and aerospace industries, 159–62 chemical conversion coatings, 159–61 organic and inorganic coatings, 161–2 thermal-sprayed coatings, 162 electronics and sensor industry, 171–3 electronic nanodevices, 172–3 photovoltaic surfaces, 173 sensors, 171–1 most common techniques for hydroxyapatite coatings formation, 176 packaging applications, 170–1 coatings for food and pharmaceutical industries, 170 coatings in the paper industry, 170–1 417 paints and enamels industry, 173–4 coefficient of friction, 388 cold spraying, ‘colloid probe,’ 141 combustion chemical vapour deposition, 73 complex non linear least squares (CNLLS) procedure, 135 compliance packaging, 206 composite coatings, 16 conductive polymers, 17–18 conductors, 58 controlled radical polymerisation, 102–6 conventional radical polymerisation, 92, 93–4, 102 conversion coatings, 5–6 anodising, chromate conversion coating, 5–6 chrome-free conversion coatings, conversion electron Mössbauer spectra, 147 corrosion, 236 aeronautical structures, 235–6 aluminium and its alloys, 243–4 anodising coatings, 253–7 electrochemical chracterisation, 255–6 fatigue properties, 256–7 film structures, 254–5 applications of nanomaterials, 266–70 deicing process, 268 XTEM bright field images of TaSi2–Si3N4 nanocomposite coating, 269 coating technologies and smart nanocoatings, 235–70 future trends, 270 factors, 241–3 susceptibility of metallic materials, 243 functional nanocoatings, 258–9 self-healing effect, 258 magnesium alloys, 244–5 nanocoatings for detection and mechanical damage, 259–61 © Woodhead Publishing Limited, 2011 418 Index pH sensing coatings on aluminium alloys, 260 pretreatments, 247–53 chromate conversion coatings, 247–8 chromium-free inhibitors, 248–50 magnesium-rich primers, 252–3 sol–gel coatings, 250–2 protective coatings in aerospace engineering, 246–7 schematic of aerospace coating system, 246 self-healing coatings, 261–6 electrochemical impedance spectra of AA2024substrates, 262 scanning vibrating electrochemical technique, 265 types of corrosion in aircraft, 236–41 CFRP in Boeing 777 design, 240 fastener joint, 238 optical micrograph of scribe and filament, 237 corrosion fatigue, 241 crevice corrosion, 238 ‘critical brush density,’ 30 critical nucleus, 108 curtain coating, 12 deep drilling tools, 365–6 rock drill with cemented carbide buttons, 366 deformation, 360 Derjaguin–Muller–Toporov theory, 358 diamond-like carbon, 293–4 1,2-dichloroethane, 333 dielectric layers, 58 diffuse reflectance technique, 144 dip coating, 12 dip-pen nanolithography, 308 discrete track recording, 318 doping, 342 ‘double-pass transmission,’ 144 DS4 tester, 387 Durethan, 214 dynamic smart glazings, 188–94 edge lithography, 309–11 edible packaging, 220 electret, 303 electrochemical impedance spectroscopy, 133–9, 255–6 Bode diagrams for aluminium, 257 electrochemical liquid growth (ECLG) method, 63 electrochemical plating, 4–5 electrochromic glazings, 188–9 electroless chemical plating, electron acoustic images, 152 electron-beam evaporation, 65 electron-beam evaporation PVD, 65–6 electron beam lithography, 283 electron spectroscopy for chemical analysis, 161 electronic packaging, 206–8 electronics nanoimprint lithography, 280–321 applications, 317–20 combined nanoimprint approaches, 315–17 edge lithography, 309–11 extension of soft NIL, 301–7 lithography techniques and fundamentals, 280–6 NIL for 3D patterning, 311–14 photo-assisted nanoimprinting, 291–6 scanning probe lithography, 307–9 soft NIL, 297–301 thermoplastic and laser-assisted nanoimprint lithography, 286–91 electroplating, 375 Elektron, 245 encapsulation, 218–19 ‘end-grafted polymers’ see ‘polymer brush’ energy dispersive x-ray spectroscopy (EDS), 148 environmentally friendly coatings, 13 equilibrium adsorption, 80 ethylene tetrafluoroethylene, 287 EVG, 318 exfoliation, 239 © Woodhead Publishing Limited, 2011 Index extreme UV lithography, 282–3 extrusion, 12 F-NAD, 161–2 fatigue tests, 256–7 field-effect transistor, 311, 332 filiform corrosion, 237–8 fillers, 18 fluorine-modified polymers, 161 focused ion beam, 283 food packaging, 205–6 fourier transform infrared Raman spectroscopy, 146 Fresnel equations, 145 fretting, 365 fretting corrosion, 241 friction, 356–8 functional graded nanocoatings, 57–60 gallium nitride, 344–51 AFM images, 347 CL spectra from dislocation cluster, 350 SEM images, 346, 348 SEM vs monochromatic μ-CL images, 349 galvanic corrosion, 239 gasochromic-electrochromic glazings, 190–1 GENOCURE, 296 geometric hindered factor, 213 glass surface protections, 194–5 glass transition temperature, 290 glow discharge optical emission spectroscopy (GDOES), 150–1 grafting density, 83–4 ‘grafting from’ approach, 92 ‘grafting through’ method, 106 ‘grafting to’ approach, 89–91 graphene 2D structures, 331–41 graphene FETs in the electrolyte solution, 341 HRTEM images of graphene membrane, 335 microfabrication steps, 333 419 morphological and structural analyses of the ZnO–G HAs, 338 optoelectronics, 339 graphene nanoribbons, 333 graphene oxide, 336 graphene sheets, 221 graphene transparent conducting films, 339–40 graphite fibres, 239–40 graphite particles, 221 gravure coating, 10–11 Greenwood–Williamson theory, 357–8 Hall–Petch relationship, 367–8 heterogenous nucleation, 108 hexagonal boron nitride phase, 342 high barrier packaging, 209–15 models of aligned mono-disperse flakes in periodic arrangement, 212 oxygen permeability as function of water vapour barrier properties, 210 oxygen scavenging materials, 214–15 samples of oxygen scavenging materials, 215 high ordered pyrolytic graphite, 47 high velocity oxy-fuel spraying, 8, 148, 162 holographic patterning, 312 homogenous nucleation, 108 hot embossing see thermal nanoimprint lithography Hydrotect, 398–9 8-hydroxiquinoline, 266 hydroxyapatite, 174, 175 hyperbranched polymers, 17 hyperfine splitting, 147 immersion lithography, 282 Imprio, 318 ‘in situ polymerisation,’ 209 in-situ tribometry, 387 indium tin oxide, 339 infrared spectroscopy, 145–6 InMat Nanocoatings, 211 © Woodhead Publishing Limited, 2011 420 Index inorganic coatings, 161–2 interfacial shear strength, 358–9 intergranular corrosion, 239 International Technology Roadmap for Semiconductors, 282 intimate contact area, 359–60 ion beam milling, 194 ion implantation process, 68 ion-plating PVD, 68 ion scattering spectroscopy, 148–9 irreversible adsorption, 80 isomer shift see chemical shift Johnson–Kendall–Roberts contact theory, 358 Kevin probe force microscopy (KPFM), 152–3 Kirchhoff’s law, 184 knife over roll coating, 11 Kramers–Kronig test, 137, 145 Langmuir monolayer, 24 Langmuir–Blodgett assembly, 334 Langmuir–Blodgett film, 383 Langmuir–Blodgett technique, 87, 92 Langmuir–Blodgett–Kuhn multilayers, 32 Langmuir–Schaefer method, 27 Langmuir–Schaefer monolayers, 32 laser ablation PVD, 66 laser-assisted direct imprint, 290–1 laser-induced chemical vapour deposition, 308 lasercarb coating, 380 lateral force microscopy, 383 laws of friction, 357 layer-by-layer deposition, 87, 264 layered double hydroxides, 211, 262–4 light control and thermal imaging glazings, 193–4 light-emitting diodes, 193 linear potential sweep, 132 ‘liquid condensed phase,’ 27 liquid crystal and suspended particle glazings, 192–3 ‘liquid expanded phase,’ 26 ‘liquid glass,’ 194 lithography techniques, 280–6 nomenclature of methods, 281 process steps, 285 lotus effect, 14 low energy ion scattering, 149 low pressure CVD, 72–3 magnesium alloys, 244–5 magnesium-rich primers, 252–3 matrix-assisted laser desorption/ ionisation, 66 matrix-assisted pulsed-laser evaporation, 66 mean surface roughness, 141 melt mixing process, 209 2-mercaptobenzothiazole, 266 metal corrosion, 235 metal-organic chemical vapour deposition, 365 Meyer rod, 11 Meyer rod coating, 11 micro-based coatings, 14–15 microcontact printing, 297, 298 microelectromechanical systems, 359 micromachining, 307 micromolding in capillaries, 300 microtribometers, 363 sample, 364 MIL-DTL-5541, 247 molecular beam epitaxy, 311 molecular-beam epitaxy PVD, 67–8 molybdates, 249 montmorillonite, 211 Mössbauer absorption spectrometry, 147 Mott–Schottky plots, 139 nanocapsule-based coatings, 14–15 nanoclay particles, 220 nanocoatings and ultra-thin films analytical methods, 131–53 electrochemical methods, 132–40 spectroscopic, microscopic and acoustic techniques, 145–53 © Woodhead Publishing Limited, 2011 Index surface-sensitive analytical methods, 140–5 architectural glass, 182–95 dynamic smart glazings, 188–94 glass surface protections, 194–5 spectrally selective glass, 183–8 chemical and physical vapour deposition methods, 57–75 chemical vapour deposition based technologies, 71–4 D-gun spray deposition of functional gradient coating from titanium and hydroxyapatite, 70 future trends, 74–5 paradigm of functional graded layer-by-layer coating fabrication, 60–1 physical vapour deposition based technologies, 63–71 substrate preparation for ultrathin films and functional graded nanocoatings, 57–60 typical installation diagram for PVD and CVD coating, 64 corrosion protection in aerospace engineering, 235–70 aluminium and its alloys, 243–4 anodising coatings, 253–7 applications of nanomaterials, 266–70 corrosion in aeronautical structures, 235–6 corrosion of magnesium alloys, 244–5 detection of corrosion and mechanical damage, 259–61 factors influencing corrosion, 241–3 functional nanocoatings, 258–9 future trends, 270 pretreatments, 247–53 protective coatings in aerospace engineering, 246–7 self-healing coatings, 261–6 types of corrosion in aircraft, 236–41 fabrication methods, 61–3 421 approximate classification scheme of nanocoating technologies, 62 packaging applications, 203–22 anti-microbial packaging, 215–16 antistatic packaging applications, 220–1 future trends, 222 high barrier packaging, 209–15 nanomaterials in packaging, 208–9 nanosensors in packaging, 216–18 nanotechnology solutions for packaging waste problem, 219–20 packaging as a drug carrier and for drug delivery, 218–19 regulation and ethical issues in new packaging industry, 221–2 surface-initiated polymerisation, 78–112 physisorption and chemisorption, equilibrium and irreversible adsorption, 79–87 properties and applications, 110–12 surface-bound polymer layers preparation, 87–110 nanocomposite coatings, 15–16 nanoimprint lithography, 284 3D patterning, 311–14 gold pattern fabrication, 314 electronics, 280–321 applications, 317–20 combined nanoimprint approaches, 315–17 edge lithography, 309–11 extension of soft NIL, 301–7 lithography techniques and fundamentals, 280–6 photo-assisted nanoimprinting, 291–6 scanning probe lithography, 307–9 soft NIL, 297–301 thermoplastic and laser-assisted nanoimprint lithography, 286–91 nanoimprinting in metal/polymer bilayer, 298 nanomaterials, 208–9 © Woodhead Publishing Limited, 2011 422 Index Nanomiser device atomisation, 73 nanomolding in capillaries, 300 nanoreservoirs, 163 nanosensors, 216–18 nanoshaving, 308 nanostructure coatings challenges to establish scale up, 389–91 balance cost/performance ratio, 391 coat different sample sizes and nanostructure retention, 389–90 performance of laboratory tests and reliability analysis, 390–1 friction and wear applications, 367–82 deposition methods, 373–9 engineering materials, 379–82 structure-property relationships, 367–73 tribology, 355–91 friction and wear applications, 367–82 future trends, 391 tribological properties characterisation, 382–91 use of nanostructure coatings, 356–66 nanostructured composite, 209 nanostructured thin films 2-D arrays of colloidal spheres, 44–7 A2-D array fabrication methods at air–liquid interface, 45 amphiphilic molecules, 24–48 amphiphilic polymers, 28–36 block copolymers, 28–32 interfacial behaviour of ionic block copolymers, 31 π-conjugated polymers, 32–6 poly(p-phenylene) derivative chemical structure and π-A isotherm, 33 poly(phenylenevinylene) derivatives possible arrangement at the air–water interface, 34 polythiophene derivatives, 35 PS–b–PEO diblock copolymer surface morphological behaviour, 29 dendrons and dendrimers, 36–41 chemical structure of fourth generation poly(ethyl ether) with hexa(ethylene glycol) tail, 38 poly(amidoamine), 37–40 poly(benzyl ether), 36–7 poly(propylene imine), 40–1 PPI dendrimers, 41 tetra-dendronpoly(amidoamine) dendrimers, 39 Langmuir monolayer, 24–8 isotropic liquid film in trough with movable barrier, 25 Langmuir trough and other experimental techniques, 27 Langmuir–Blodgett rough being compressed, 25 recent researches, 28 surface pressure, 25 surface pressure isotherm, 26–7 surface pressure isotherm for Langmuir monolayer after reference 7, 26 metal/semiconductor nanoparticles, 41–4 TOPO-capped CdSe quantum dot, 43 nanotechnology, 208 solutions for packaging waste problem, 219–20 nanotransfer printing, 298 Nielson equation, 213 nitroxide mediated radical polymerisation, 102, 104–5 1-octadecanethiol, 43 optical proximity correction, 282 organic coatings, 161–2 organic electrochemical transistor, 34 organic thin film transistors, 296 organic–inorganic hybrid polymers, 17 Orowan mechanism, 369 oxalic acid, 254 © Woodhead Publishing Limited, 2011 Index oxide film, 254–5 oxygen scavenging materials, 214–15 packaging anti-microbial packaging, 215–16 antistatic packaging applications, 220–1 multilayer structure and chemical antistatic agent, 221 as a drug carrier and for drug delivery, 218–19 definition, 206 future trends, 222 high barrier packaging, 209–15 models of aligned mono-disperse flakes in periodic arrangement, 212 oxygen permeability as function of water vapour barrier properties, 210 oxygen scavenging materials, 214–15 samples of oxygen scavenging materials, 215 nanocoatings and ultra-thin films applications, 203–22 electronic packaging, 206–8 electronic packaging products, 207 examples of food packaging, 205 food packaging, 205–6 pharmaceutical packaging, 206 pharmaceutical packaging samples, 207 nanomaterials, 208–9 nanosensors, 216–18 radio-frequency identification, 218 nanotechnology solutions for packaging waste problem, 219–20 biodegradable food packaging, 219 principal objectives, 204 regulation and ethical issues in new packaging industry, 221–2 packaging applications, 170–1 food and pharmaceutical industries, 170 paper industry, 170–1 423 barrier-coated papers, 170–1 curtain coating, 171 patina, 132 3-pentadecylphenol, 30 pharmaceutical packaging, 206 phase-change random access memory, 318–19 phase changed materials, 267 photo-assisted nanoimprinting, 291–6 photocatalysis photocatalytic cleaning effect of TiO2-coated materials, 402–6 contact angle of water droplet, 403 UV-vis specta of undoped and Fe-doped TiO2 coatings, 406 processes, 399–402 band-edge energies of semiconductors, 400 photochemical excited TiO2 particle, 399 titanium dioxide, 397–9 photochromic-electrochromic glazing devices, 191–2 photoelectrochromic glazing, 191 photolithography, 282 photoresist patterns, 310 photovoltaic-powered electrochromic device, 190 photovoltaic-powered electrochromic glazings, 190 phyllo silicates, 18 physical liquid deposition, 63 physical solid deposition, 64 physical vapour deposition, 7, 63–71, 373–5 physisorption, 82 pitting corrosion, 238–9 plasma-assisted chemical vapour deposition, 372 plasma energy CVD, 73, 74 plasma spraying, 8–9, 162 poly(1,1-diethylsilacyclobutane)–b– poly(methacrylic acid), 30 poly(3-hexyl-thiophene), 149 polyamide 6, 210 poly(amidoamine), 37–40 poly(benzyl ether), 36–7 © Woodhead Publishing Limited, 2011 424 Index polycarbonate, 288 polyetherimide, 288 polyethylene, 210 poly(ethyleneimine), 317 poly(hydrogenated–isoprene)–b–poly(styrenesulphonate), 30 polylactic acid, 210 polymer-assisted deposition (PAD) method, 69 ‘polymer brush,’ 87 polymer multilayer process, 60 ‘polymerisable complex (PC) route,’ 151 polymethyl glutarimide, 332 poly(methyl methacrylate), 288–9, 332 poly(N-dodecylacrylamide), 34 poly(N-isopropylacrylamide), 111 polypropylene, 210 poly(propylene imine), 40–1 polystyrene, 28 poly(styrene)-b-poly(ethylene oxide) (PS–b–PEO) copolymers, 28 poly(styrene–b–ferrocenyl silane), 30 polystyrene–block–poly(Nisopropylacryamide) (PS–b– PNIPAM) diblock copolymer, 29 polystyrene–b–poly(methyl methacrylate) (PS–b–PMMA) diblock copolymer, 29 poly(styrene)–b– poly(styrenesulphonate), 30 polystyrene–b–poly(vinylpyridine) (PS–b–PVP) copolymers, 30 polystyrene–graft–poly(ethylene oxide) (PS–g–PEO) copolymers, 29 powder coating, 16–17, 168 primary packaging, 204 projection lithography, 282–3 propyltrimethoxysilane, 210 quadruple splitting, 147 quantum dots, 43 quintuple layer, 343–4 radio-frequency identification, 218 Raman spectroscopy, 147 raster, 151 Rayleigh scattering, 146 reactive ion etching, 286–7 regioregular poly(3-hexylthiophene), 34 resistance-heated source evaporation, 66 reverse contact UV-NIL, 314 reversible addition–fragmentation chain transfer polymerisation, 102, 103–4 roll-to-roll coating, 11 Rutherford backscattering spectrometry, 149 ‘sacrificial initiator,’ 105 ‘sacrificial layer,’ 185 scanning acoustic microscopy, 152 scanning beam lithography, 282–3 scanning electron acoustic microscopy, 152 scanning electron microscopy, 151 scanning probe lithography, 307–9 Scheutjens–Fleer self-consistent mean-field theory, 111 secondary-ion mass spectroscopy, 149–50 secondary packaging, 204 self-assembled monolayers, 89 self-assembling molecules, 13 self-cleaning coatings, 14, 167–8 self-healing coatings, 261–6 electrochemical impedance spectra of AA2024substrates, 262 LDHs dual role in corrosion protection, 263 scanning vibrating electrochemical technique, 265 self-switching liquid crystal glazing technology, 193 semiconductor compounds, 341–4 semiconductors, 58 sensitized photoreaction, 400 sensor ultra-thin membranes, 330–51 gallium nitride, 344–51 © Woodhead Publishing Limited, 2011 Index graphene and 2D structures, 331–41 nanometer-thick membranes of semiconductor compounds, 341–4 silicone-modified polymers, 161 silver particles, 215–16 sliding test, 383 slot/die coating, 12 slot/extrusion coating, 12 ‘smart’ multifunctional coatings, 163 smart nanocoatings self-cleaning, 397–411 new and smart applications of TiO2-coated materials, 406–10 photocatalysis processes, 399–402 photocatalytic cleaning effect of TiO2-coated materials, 402–6 TiO2 photocatalysis, 397–9 smart packages, 222 Snell’s law, 144 soft lithography, 286 soft nanoimprint lithography, 297–301 conventional nanoimprint vs electrochemical nanoimprint vs surface charge lithography, 302 GaN-based mesostructures, 305 GaN nanowire merging triangular mesostructures, 306 SEM images from GaN layers subjected to PEC etching, 304 sol–gel coatings, 10, 250–2 sample structure, 252 silane deposition on metallic substrate, 250 solvent-assisted micromolding, 299–300 spectrally selective glass, 183–8 specular component, 144 spin coating, 10 spray coating, 7–10 cold spraying, high-velocity oxygen fuel spraying, plasma spraying, 8–9 thermal spraying, vacuum plasma spraying, warm spraying, 9–10 sputtering PVD, 67 425 Stefan–Boltzmann’s law, 184 step and flash imprint see UV nanoimprint lithography Stokes scattering, 146 stress-corrosion cracking, 241 structure-property relationships, 367–73 graded coatings, 370 historical trends in tribological coatings development, 368 nanocomposites, 370–2 TEM image of nc-TiN/a-C:H, 372 TEM image of WC–12Co coating, 372 smart adaptive coatings, 373 Au/MoS2/DLC/YSZ chameleon coating, 373 strengthening mechanisms, 367–9 hardness as function of grain size, 369 superlattice multilayer, 370 nanomultiayers of TiN/(Ti,Al)N, 371 sulphuric acid anodising, 254 ‘super’-hard coatings, 164–7 conventional coatings, 164–5 composite coating, 165 nitride/carbide.boride coatings, 164–5 nanocoatings, 165–6 nanocomposite coatings, 167 nitride nanocoatings, 166–7 oxide nanocoatings, 166 supersonic free-jet PVD, 69 surface corrosion, 236–7 surface-initiated polymerisation, 78–112 adsorption parameters, 82–5 free energy barrier and the strength of binding interaction, 82–3 grafting density and solvent nature, 83–5 polymer concentration in bulk, 83 nanocoating by ‘reverse grafting,’ 106–10 formation of polymer– nanoparticle complex, 109–10 © Woodhead Publishing Limited, 2011 426 Index nucleation and phase formation, 106 schematic representation, 107 physisorption and chemisorption, equilibrium and irreversible adsorption, 79–87 adsorbed layers topologies, 86 comparative kinetic curves for amino mono-functionalised polystyrene chemisorption, 81 thermodynamics and kinetics, 79–82 topology of surface-bound layers, 86–7 polymer chemisorption processes, 88–106 controlled radical polymerisation, 102–6 conventional radical polymerisation, 92, 102 ‘grafting from’ approach, 92 ‘grafting through’ method, 106, 107 ‘grafting to’ approach, 89–91 properties and applications, 110–12 modified surfaces properties and applications, 111–12 surface-bound polymer layers physicochemical properties and comparison to bulk properties, 110–11 surface-bound polymer layers preparation, 87–110 ‘grafting from’ of unsaturated and cyclic monomers, 100–1 ‘grafting from’ systems based on controlled radical polymerisation, 95–9 ‘grafting from’ systems based on conventional radical polymerisation, 93–4 methods for preparation of surface linked polymer layers, 88 nitroxide-mediated surface grafting, 104 polymer physisorption techniques, 87–8 RAFT polymerisation, 103 surface ATRP propagation mechanism, 105 surface-bound polymer layers obtained by ‘grafting through’ approach, 107 surface-bound polymer layers obtained through ‘grafting to’ approach, 90–1 surface initiated conventional radical polymerisation, 102 surface polymerisation by ion-assisted deposition, 69 TE67, 387 tertiary packaging, 204 tethered density, 84 ‘tethered polymer layers’ see ‘polymer brush’ tetrabutylammonium hydroxide, 332 tetraisopropyl orthotitanate, 146 thermal barrier coatings, 138, 169 thermal evaporation PVD, 65 thermal expansion coefficient, 286 thermal nanoimprint lithography, 284–5 SEM images, 287 thermal-sprayed coatings, 162 thermal spraying, 8, 375, 377–8 thermally-activated glazings, 193 thermally grown oxide, 138 thermopolymerisation reaction, 290 thermotropic glazing, 193 ‘third body’ friction, 359 titanium, 174–5 titanium diboride, 269 titanium dioxide, 216 efficient energy-saving technology, 409–10 energy-saving system using solar light and stored rainwater, 410 new and smart applications, 406–10 NOx gases applied to construction materials, 407–8 pathways of light and activation of titanium dioxide, 408 schematic illustration, 408 photocatalysis, 397–9 © Woodhead Publishing Limited, 2011 Index photocatalytic cleaning effect, 402–6 soil treatment, 409 purification systems, 409 transmission electron microscopy, 151–2 transparent coatings, 168 tribology, 356 applications, 363–6 aerospace, 363 automotive, 363–4 biomaterials, 366 deep drilling tools, 365–6 mechanical components, 364 repair coatings, 366 turbines, 365 deposition methods, 373–9 coating deposition classification, 374 contact AFM images of WC–12Co, 378 growth pattern in PVD-deposited nc-TiN/a-Si3N4, 376 TEM image of cobalt-hardened gold electrodeposited nanostructured coating, 377 thermal spraying techniques, 378 engineering materials, 379–82 abrasion vs wear resistance of TiN/TaN multilayer coatings, 380 hardness of electrolytic Ni coating versus grain size and abrasion resistance, 379 mechanical and tribological properties of nanostructured coatings, 382 nanostructured HVOF WC–12Co– 2Al-coated vs chromium-plated crankshaft, 381 wear resistance comparison, 381 friction and wear applications, 367–82 structure-property relationships, 367–73 nanostructure coatings, 355–91 future trends, 391 tribological properties characterisation, 382–91 427 challenges in scale up establishment, 389–91 friction loops on etched dual phase steel, 386 friction loops showing topography and phase effects, 385 scale dependence, 387–9 schematic representation of friction mechanisms, 388 techniques for friction and wear characterisation, 382–7 wear track, 385 use of nanostructure coatings, 356–66 friction and wear mechanisms, 356–63 trioctylphosphineoxide, 43 Tupolev TU-134, 245 turbines, 365 ultra-hard materials, 15 ultra-thin films, 57–60 and nanocoatings analytical methods, 131–53 electrochemical methods, 132–40 spectroscopic, microscopic and acoustic techniques, 145–53 surface-sensitive analytical methods, 140–5 packaging applications, 203–22 anti-microbial packaging, 215–16 antistatic packaging applications, 220–1 future trends, 222 high barrier packaging, 209–15 nanomaterials in packaging, 208–9 nanosensors in packaging, 216–18 nanotechnology solutions for packaging waste problem, 219–20 packaging as a drug carrier and for drug delivery, 218–19 regulation and ethical issues in new packaging industry, 221–2 ultra-thin membranes sensor, 330–51 gallium nitride, 344–51 © Woodhead Publishing Limited, 2011 428 Index graphene and 2D structures, 331–41 nanometer-thick membranes of semiconductor compounds, 341–4 ultrananocrystalline diamond , 167 UV nanoimprint lithography, 283–4, 285, 291–6 vacuum deposition methods nanocoatings and functionally graded multilayers, 57–75 vacuum monomer technique, 60 vacuum plasma spraying, vanadates, 249 vapour phase epitaxy (VPE) process, 73 ‘velocity accommodation mode,’ 359 very low-temperature pyrolysis LPCVD, 73 Volta potential map, 153 vortical surface method, 47 warm spraying, 9–10 water-soluble paint, 18 wear, 360–3 mode types and sample case studies, 361 white graphite see hexagonal boron nitride phase Wien’s law, 184 Wilhelmy Plate, 27 X-ray lithography, 316 x-ray Mössbauer spectra, 147 x-ray powder diffraction method, 148 Zenner pinning, 369 zinc dialkyl dithiophosphate, 364 zirconium oxide coatings, 150 © Woodhead Publishing Limited, 2011 ... illumination, etc.) Nanocoatings and ultra-thin films is both a reference and a tutorial for understanding the most common thin-films and coating techniques The book encompasses recent approaches and future... Introduction Ultra-thin films and nanocoatings play a major role in many areas such as micro- and nanoelectronics, machine building, car and aircraft manufacturing, robotics, etc Nanocoatings,... fields of both physics and chemistry The goal of this book is to discuss the basics of ultra-thin films and nanocoatings and their synthesis techniques, surface characterization, and performance for