Microwave Engineering of Materials - Pan Stanford presents recent improvements in microwave...

The use of microwaves has gradually democratized itself in several scientific areas and is now a common methodology in domains as different as chemistry, protein digestion, mining, and metallurgy. Materials chemistry is one field where microwave irradiation technologies are being studied. In recent years, development of nanotechnologies has increased the interest of materials scientists in these new technologies. Microwave methodologies are now routinely used in several areas of materials science, and new advances are ongoing. This book presents recent improvements in microwave engineering of materials and nanomaterials, interactions of microwave chemistry with materials, and advances in microwave technologies in several domains such as polymer synthesis and modification, processing of various materials (ceramics, glasses, metallic alloys, zeolites), and synthesis and functionalization of diverse nanomaterials (carbon nanotubes, MOF semiconductors, inorganic nanoparticles). The book will be of interest to all students and researchers in materials science and nanosciences who want to discover or increase their knowledge of microwave technology.

Dr. Erwann Guénin is an assistant professor at Université Paris 13 since 2002. He is now in the Laboratory of Vascular Translational Science Inserm U1148 (previously he was in the Laboratory of Chemistry, Properties and Structure of Biomaterials and Therapeutic Agents UMR CNRS 7244). He teaches chemistry for various courses in life science licence, master biomaterials and master therapies, and life technologies. Dr. Guénin initially studied organic chemistry at Université de Bretagne Occidentale, Brittany (France), where he got his PhD in 1999 in the synthesis of new cationic lipids and their applications in DNA transfection. For 20 months, as a postdoctoral researcher in the group of Dr. A. B. Tabor at University College London (UK), he worked on peptide synthesis for DNA transfection applications. He then worked for a year in Centre de Neurochimie, Université de Strasbourg, with Dr. E. Trifilieff on the development of peptide vaccines. At Université Paris 13, Dr. Guénin first worked on the synthesis, characterization, and vectorization of phosphorous therapeutic agents. He later joined the nanomaterials group of the CSPBAT laboratory in 2010 and has been developing, with Pr. L. Motte, new methodologies for the synthesis and functionalization of nanomaterials with applications in biomedical and environmental sciences. He has also done notable work on the development of several grafting methodologies involving click chemistry and microwave irradiation.

Guénin

Erwann Guéninedited by

Microw

ave Engineering of Materials

Microwave Engineering of MaterialsFrom Mesoscale to Nanoscale

ISBN 978-981-4669-42-9V496

Microwave Engineering of Materials

Erwann Guéninedited by

Microwave Engineering of MaterialsFrom Mesoscale to Nanoscale

February 2, 2016 12:25 PSP Book - 9in x 6in 00-Erwann-Guenin-prelims

Published by

Pan Stanford Publishing Pte. Ltd.

Penthouse Level, Suntec Tower 3

8 Temasek Boulevard

Singapore 038988

Email: [email protected]

Web: www.panstanford.com

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

Microwave Engineering of Materials: From Mesoscale to Nanoscale

Copyright c© 2016 Pan Stanford Publishing Pte. Ltd.

All rights reserved. This book, or parts thereof, may not be reproduced in anyform or by any means, electronic or mechanical, including photocopying,recording or any information storage and retrieval system now known or tobe invented, without written permission from the publisher.

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ISBN 978-981-4669-42-9 (Hardcover)

ISBN 978-981-4669-43-6 (eBook)

Printed in the USA


Contents

Foreword xiii

1 Introduction to Microwave Chemistry 1Dariusz Bogdal and Mateusz Galica1.1 Nature of Microwave Irradiation 1

1.2 Microwave Thermal Effect vs. Nonthermal Effect 8

1.2.1 Nonthermal Effects 10

1.2.2 Thermal Effects 14

1.2.3 Thermal Gradients 15

1.3 Conclusion 25

2 General Features of MW Interaction with Materials 31S. Takayama, M. Sato, and J. Fukushima2.1 Introduction to General Features of MW Interaction

with Materials: Microwave, Heat, and Materials 31

2.1.1 Maxwell’s Equations 32

2.1.2 Waves in Materials and the Dispersion Relation 34

2.1.3 Energy Transfers from Microwaves to Materials 36

2.1.4 Effect on Magnetization 37

2.1.5 Internal Heating, Volumetric Heating, and

Rapid Heating 38

2.1.6 Selective Heating 39

2.2 Nonthermal Microwave Effects 39

2.2.1 Decrystallization and Formation of

Nanodomain Structures 39

2.2.2 Enhancement of Nonthermal Reduction of CuO

and TiO2−x during Microwave Heating 43

2.2.3 Sintering Behavior of Metal Powders Involving

Microwave-Enhanced Chemical Reaction 48


vi Contents

2.3 Energy Transfer Mechanism on Microwave Processing 55

2.3.1 Introduction 55

2.3.2 Chemical Reactions and Phase Transitions

under Microwave Irradiation 57

2.3.3 Excitation of Ultrasound Waves by External

Microwaves 58

2.3.4 Collisionless Energy Transfers from

Electrokinetic Waves to Materials 61

2.3.5 Rate Equations with Perturbations by

Microwave in Velocity Space 63

2.3.6 Energy Balance Estimations 65

2.3.7 Magnetic Effects 69

2.4 Conclusion 70

3 Microwave-Assisted Synthesis and Modification ofPolymers 73Martin Fimberger and Frank Wiesbrock3.1 Introduction 73

3.2 Controlled Radical Polymerization 74

3.2.1 Reversible Addition–Fragmentation Chain

Transfer 75

3.2.2 Atom Transfer Radical Polymerization 78

3.2.3 Emulsion Polymerization 79

3.3 Step-Growth Polymerizations 81

3.4 Ring-Opening Polymerizations 84

3.4.1 Poly(ε-Caprolactone)s, Poly(Glycolic Acid), and

Polylactides 84

3.4.1.1 Homopolymers of ε-caprolactone 85

3.4.1.2 Copolymers of ε-caprolactone 87

3.4.1.3 Copolymers of poly(glycolic acid) 88

3.4.1.4 Homopolymers of lactic acid 89

3.4.2 Poly(2-oxazoline)s and Poly(2-oxazine)s 91

3.5 Highlights 98

3.5.1 Ionic Liquids and Solvent-Free Polymerizations 98

3.5.2 Click Chemistry 102

3.6 Scale-Up 104

3.7 Conclusion 105

3.7.1 Safety Rules 106


Contents vii

4 Microwave Processing of Ceramics and Glasses 115D. C. Folz, D. E. Clark, and R. L. Schulz4.1 Introduction 116

4.1.1 The Ceramics Industry 116

4.1.2 Brief Review of Microwave–Ceramic

Interactions 117

4.1.2.1 Methods of heating 121

4.1.2.2 Benefits of microwave processing 123

4.2 Low-Temperature Microwave Applications: Drying 124

4.3 Moderate-Temperature Applications: Glass Nucleation

and Crystallization 127

4.4 High-Temperature Applications: Sintering 130

4.5 Summary 135

5 Microwave Processing of Composites, Glass-CeramicCoatings and Metallic Alloys: An Overview 141Sumana Ghosh5.1 Introduction 141

5.2 Microwave Processing of Composites 142

5.2.1 Microwave Processing of Glass-Ceramic

Coatings 149

5.3 Microwave Processing of Metallic Alloys 151

5.4 Conclusion 156

6 Microwave Engineering for Synthesizing Clays and ModifyingProperties in Zeolites 163Olga Bergada, Fiseha B. Gebretsadik, M. Dolores Gonzalez,Judith Granados-Reyes, Elena Perez, Tatiana Sanchez,Isabel Vicente, Pilar Salagre, and Yolanda Cesteros6.1 Introduction 164

6.2 Synthesis of Clays Using Microwaves 167

6.2.1 Cationic Clays: Hectorites and Saponites 168

6.2.1.1 Hectorites 168

6.2.1.2 Saponites 171

6.2.2 Anionic Clays: Hydrotalcites and

Hydrocalumites 174

6.3 Microwave-Assisted Modification of Zeolites 175


viii Contents

6.3.1 Effect of Microwaves on the Acidic Properties

of Ni-Exchanged Mordenites 176

6.3.2 Modification of Surface and Acidic Properties

during Dealumination of Zeolites by Acid

Treatment With Microwaves 179

6.3.3 Microwave-Assisted Sulfonic Acid

Functionalization of Zeolites by Postsynthesis 182

6.4 Future Prospects 186

7 Microwave Engineering of Carbon Nanotubes 195Madhulika Sinha and Yong-Chien Ling7.1 Introduction 195

7.2 Microwave Chemistry 197

7.3 General Synthesis of CNTs 199

7.3.1 Properties of CNTs 199

7.3.2 Arc Discharge Method 200

7.3.3 Laser Ablation Method 201

7.3.4 Chemical Vapor Deposition Method 202

7.4 Microwave-Assisted Synthesis of CNTs 202

7.4.1 CNT Applications 202

7.4.2 Interaction Mechanisms between CNTs and

MW 203

7.4.3 Effect of Modifiers 204

7.4.4 MW-Assisted Purification of CNTs 205

7.5 Covalent and Noncovalent Functionalization of CNTs 210

7.5.1 MW-Assisted Synthesis of CNTs-Based

Nanocomposites 210

7.5.2 MW-Assisted Synthesis of CNTs-Based Hybrids 212

7.6 Summary and Future Scope of Microwave-Assisted

Synthesis of CNTs 217

8 Microwave Synthesis Porous Zeolitic Metal–OrganicFramework Materials 229Hossein Kazemian and Sohrab Rohani8.1 Introduction 229

8.2 Metal–Organic Frameworks 230

8.3 Applications of MOFs 236

8.4 Microwaves for Chemical Synthesis 239


Contents ix

8.5 MOF Synthetic Approaches 244

8.6 MOF Synthesis Using the Microwave and Ultrasonic

Hybrid Technique 249

8.7 Conclusions 257

9 Microwave-Assisted Synthesis of Metallic Nanoparticles 263Stephany Garcıa, Graham W. Piburn, and Simon M. Humphrey9.1 Introduction 263

9.2 Equipment 267

9.3 Common Reagents and Their Compatibility with

Microwave Heating 270

9.4 Direct Microwave-Assisted Synthesis of Unsupported

MNPs 273

9.4.1 Monometallic MNPs 273

9.4.2 Heterobimetallic MNPs 278

9.4.2.1 Core–shell MNPs 279

9.4.2.2 Alloy MNPs 281

9.4.3 Ex situ Supported MNP Catalysts 285

9.4.4 In situ Microwave-Assisted Synthesis of MNPs

Inside Support Media 286

10 Microwave-Assisted Synthesis of SemiconductorNanomaterials for Energy Conversion 305Xinjuan Liu, Likun Pan, and Chang Q. Sun10.1 Introduction 305

10.2 Microwave-Assisted Synthesis of Semiconductor

Nanomaterials for Photocatalysis 307

10.2.1 Photocatalysts 309

10.2.1.1 Semiconductor oxide 309

10.2.1.2 Metal tungstate 316

10.2.1.3 Metal vanadates 320

10.2.1.4 Metal molybdates 324

10.2.1.5 Perovskite-type materials 325

10.2.1.6 Hydroxy salts 328

10.2.1.7 Bismuth oxyhalides 331

10.2.1.8 Other semiconductors 334

10.2.2 Summary 336


x Contents

10.3 Microwave-Assisted Synthesis of Semiconductor

Nanomaterials for Sensitized Solar Cells 337

10.3.1 QD-Sensitized Solar Cells 337

10.3.1.1 Semiconductor sulfides 339

10.3.1.2 Semiconductor selenide 340

10.3.2 Dye-Sensitized Solar Cells 342

10.3.2.1 Semiconductor oxide 342

10.3.3 Summary 347

10.4 Summary and Outlook 347

11 Microwave Nanosurface Engineering 369S. Richard, R. Aufaure, E. Nehlig, L. Motte, and E. Guenin11.1 Introduction 369

11.2 Microwave Fundamentals 371

11.3 Microwave Surface Modification of Nanomaterials 372

11.3.1 MW Modification of Porous Silicon-Based

Nanomaterials 373

11.3.1.1 MW functionalization of porous

silicon surfaces 374

11.3.1.2 MW functionalization of

nanosilica surfaces 377

11.3.2 MW Functionalization of Carbon-Based

Nanomaterials 382

11.3.2.1 MW functionalization of

single-walled and multiwalled

carbon nanotubes 382

11.3.2.2 MW synthesis of composites with

CNT and formation of

inorganic/organic nanohybrids 387

11.3.2.3 MW functionalization of other

carbon nanomaterials 388

11.3.3 MW Functionalization of Inorganic

Nanoparticles 389

11.3.3.1 MW formation of SiO2 or TiO2

shell on inorganic nanoparticles 389

11.3.3.2 MW formation of a metallic shell

on inorganic nanoparticles 393


Contents xi

11.3.3.3 MW formation of an organic

polymer shell on inorganic

nanoparticles 396

11.3.3.4 MW functionalization of small

molecules at the inorganic

nanoparticle surface 398

11.3.4 MW Functionalization of the Plasmonic

Nanostructure 402

11.4 Conclusion 403

Index 421


Foreword

I first came upon reports of microwave-assisted reactions while I

was doing my PhD in the 1990s. At that time microwaves were not

developed as they are now in chemistry laboratories. I remember

well the reaction of most of the senior researchers to my questioning

on microwave synthesis. I am not ashamed to say that at that time

in France scientists using this methodology were not considered as

pioneers but more as charlatans. Hopefully and in great part due

to the priceless work of people such as Andre Loupy, the scientific

community vision evolved rapidly. Nevertheless there are still

unbelievers, often among the older researchers, and I remember that

a few years ago, while defending my project “Habilitation a Diriger

les Recherches” (a French diploma needed to supervise my PhD),

I had an animated discussion over microwaves. I was told by one

member of my jury that studying reactions done under microwave

irradiation was not a proper research project as microwaves were

only a different heating methodology. My response was simple: “Yes,

it is a different source of heating methodology as horse riding and

high-speed trains are two different transportation methodologies,

but to travel from one point of the planet to another would you

really ride a horse? And was the development of high-speed trains

not due to scientific research?” Note that having unbelievers among

the scientific community is important because it obliges us to be

more rigorous to describe phenomena and improve the quality of

our research.

Since I am a senior scientist working first in organic chemistry

and more recently in surface science, I have tried to test microwave

solutions for my projects, whenever it was possible, and it was

often conclusive. It rapidly became for me an essential tool, and

I even managed to convert some colleagues to microwaves. More


xiv Foreword

recently, when I started to work in nanosciences, I discovered that

microwaves were was used in various areas of materials science,

not only for the synthesis of materials and nanomaterials, but

also for their structure and surface modifications. This is what

prompted me to edit this book. The idea was to describe the

use of microwave irradiation for the engineering of materials and

nanomaterials. This covers an area of science at the crossroads of

many disciplines: organic chemistry, polymer chemistry, materials

science, surface science, nanoscience, etc. That is why I tried to

gather the best scientists in their areas for them to explain the

improvement brought by microwaves in their disciplines. The first

two chapters consist of an introduction to microwaves from two

different points of view. In Chapter 1, Bogdal and Galica introduce

microwave chemistry from the organic chemistry point of view.

Then Takayama, Sato, and Fukushima, in Chapter 2, give the general

features of microwave interaction with materials. In the following

chapters the authors show the application of microwaves for

engineering of various materials and nanomaterials. In Chapter 3,

Fimberger and Wiesbrock review the proceedings of microwave-

supported polymerizations and modifications of polymers. In

Chapter 4, Folz, Clark, and Schulz present microwave processing

of ceramics and glasses. Ghosh then gives further insight into the

microwave processing of composites, glass-ceramic coatings, and

metallic alloys in Chapter 5. Continuing with the processing of

materials Salagre and Cesteros’s group reviews microwave-assisted

synthesis of clay and the microwave modifications of zeolites. In

Chapter 7 Sinha and Ling propose a literature survey of microwave-

based methods for synthesis of carbon nanotubes. In Chapter 8

Rohani and Kazemian focus on another nanomaterial—metallic

organic frameworks—and describe the use of microwaves for their

synthesis and functionalization. The next two chapters describe

the use of microwaves for nanoparticle synthesis. Garcıa, Piburn,

and Humphrey treat the synthesis of metallic nanoparticles in

Chapter 9. Liu, Pan, and Sun present the synthesis of semiconductor

nanomaterials in Chapter 10. Finally in the last chapter Motte, our

students, and I describe the use of microwaves for the surface

modification of various types of nanomaterials.


Foreword xv

I hope that this book will be of some help for young chemists and

other scientists wanting to learn more about microwave engineering

of materials and nanomaterials. And I finally hope that some of the

unbelievers will be converted after reading this cooperative work.

Erwann Guenin

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