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Unformatted text preview: Materials Chemistry Materials Chemistry by Bradley D. Fahlman Central Michigan University, Mount Pleasant, MI, USA A C.I.P. Catalogue record for this book is available from the Library of Congress. ISBN 978-1-4020-6119-6 (HB) ISBN 978-1-4020-6120-2 (e-book) Published by Springer, P.O. Box 17, 3300 AA Dordrecht, The Netherlands. www.springer.com Printed on acid-free paper First published 2007 Reprinted 2008 All Rights Reserved 2008 Springer Science + Business Media B.V. No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission from the Publisher, with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. TABLE OF CONTENTS Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chapter 1. WHAT IS MATERIALS CHEMISTRY? . . . . . . . . . . . . . . . . . . . . 1.1 HISTORICAL PERSPECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 CONSIDERATIONS IN THE DESIGN OF NEW MATERIALS . . . 1.3 DESIGN OF NEW MATERIALS THROUGH A "CRITICAL THINKING" APPROACH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chapter 2. SOLID-STATE CHEMISTRY . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 AMORPHOUS VS. CRYSTALLINE SOLIDS . . . . . . . . . . . . . . . . . . 2.2 TYPES OF BONDING IN SOLIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1 Ionic Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2 Metallic Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3 Molecular Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4 Covalent Network Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 THE CRYSTALLINE STATE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.1 Crystal Growth Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.2 The Unit Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.3 Crystal Lattices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.4 Crystal Imperfections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.5 Phase-Transformation Diagrams . . . . . . . . . . . . . . . . . . . . . . . . 2.3.6 Crystal Symmetry and Space Groups . . . . . . . . . . . . . . . . . . . . 2.3.7 Physical Properties of Crystals . . . . . . . . . . . . . . . . . . . . . . . . . 2.4 THE AMORPHOUS STATE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1 SolGel Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.2 Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.3 Cementitious Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chapter 3. METALS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 MINING AND PROCESSING OF METALS . . . . . . . . . . . . . . . . . . . 3.1.1 Powder Metallurgy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v ix 1 2 5 6 13 13 14 14 16 19 21 21 23 25 28 41 47 49 53 63 63 71 77 87 87 92 vi 3.2 Table of Contents METALLIC STRUCTURES AND PROPERTIES . . . . . . . . . . . . . . . 3.2.1 Phase Behavior of IronCarbon Alloys . . . . . . . . . . . . . . . . . . 3.2.2 Hardening Mechanisms of Steels . . . . . . . . . . . . . . . . . . . . . . . 3.2.3 Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.4 Nonferrous Metals and Alloys . . . . . . . . . . . . . . . . . . . . . . . . . METAL SURFACE TREATMENTS FOR CORROSION RESISTANCE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . MAGNETISM IN METALS AND ALLOYS . . . . . . . . . . . . . . . . . . . REVERSIBLE HYDROGEN STORAGE . . . . . . . . . . . . . . . . . . . . . . 99 99 106 118 122 135 138 143 153 153 158 159 162 202 207 221 223 227 250 256 264 275 278 280 282 319 342 357 357 360 368 390 399 404 412 418 3.3 3.4 3.5 Chapter 4. SEMICONDUCTING MATERIALS . . . . . . . . . . . . . . . . . . . . . . 4.1 PROPERTIES AND TYPES OF SEMICONDUCTORS . . . . . . . . . . 4.2 SILICON-BASED APPLICATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.1 Silicon Wafer Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.2 Integrated Circuits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3 LIGHT-EMITTING DIODES: THERE IS LIFE OUTSIDE OF SILICON! . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4 THERMOELECTRIC (TE) MATERIALS . . . . . . . . . . . . . . . . . . . . . . Chapter 5. ORGANIC "SOFT" MATERIALS . . . . . . . . . . . . . . . . . . . . . . . . 5.1 POLYMER CLASSIFICATIONS AND NOMENCLATURE . . . . . . 5.1.1 Polymerization Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2 "SOFT MATERIALS" APPLICATIONS: STRUCTURE VS. PROPERTIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1 Molecular Magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.2 Polymer Additives: Plasticizers and Flame Retardants . . . . . Chapter 6. NANOMATERIALS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1 WHAT IS "NANOTECHNOLOGY"? . . . . . . . . . . . . . . . . . . . . . . . . . 6.2 NANOSCALE BUILDING BLOCKS AND APPLICATIONS . . . . . 6.2.1 Zero-Dimensional Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . 6.2.2 One-Dimensional Nanostructures . . . . . . . . . . . . . . . . . . . . . . . 6.3 TOP-DOWN NANOTECHNOLOGY: "SOFT LITHOGRAPHY" . . Chapter 7. MATERIALS CHARACTERIZATION . . . . . . . . . . . . . . . . . . . . 7.1 OPTICAL MICROSCOPY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2 ELECTRON MICROSCOPY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2.1 Transmission Electron Microscopy . . . . . . . . . . . . . . . . . . . . . 7.2.2 Scanning Electron Microscopy (SEM) . . . . . . . . . . . . . . . . . . . 7.2.3 Photoelectron Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3 SURFACE CHARACTERIZATION TECHNIQUES BASED ON ION BOMBARDMENT . . . . . . . . . . . . . . . . . . . . . . . . . . 7.4 SCANNING PROBE MICROSCOPY . . . . . . . . . . . . . . . . . . . . . . . . . 7.5 BULK CHARACTERIZATION TECHNIQUES . . . . . . . . . . . . . . . . Table of Contents vii Appendix A. TIMELINE OF MATERIALS AND TECHNOLOGICAL DISCOVERIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433 Appendix B. "THERE'S PLENTY OF ROOM AT THE BOTTOM" . . . . 441 Appendix C. MATERIALS-RELATED LABORATORY EXPERIMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.1 CHEMICAL VAPOR DEPOSITION OF CARBON NANOTUBES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.1.1 Background Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.1.2 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.2 SUPERCRITICAL FLUID FACILITATED GROWTH OF COPPER AND ALUMINUM OXIDE NANOPARTICLES . . . . . . . C.2.1 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.3 SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTALS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.3.1 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.4 TEMPLATE SYNTHESIS AND MAGNETIC MANIPULATION OF NICKEL NANOWIRES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.4.1 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.5 INTRODUCTION TO PHOTOLITHOGRAPHY . . . . . . . . . . . . . . . C.5.1 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C.6 SYNTHESIS OF GOLD NANOCLUSTERS . . . . . . . . . . . . . . . . . . . C.6.1 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453 453 453 455 457 458 460 463 465 465 469 469 472 472 Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475 Preface Though most colleges and universities now have courses and degree programs related to materials chemistry, there is a need for a textbook that addresses inorganic-, organic-, and nano-based materials from a structure vs. property treatment. As I quickly discovered, trying to fill this void represented a daunting task of providing a suitable breadth and depth coverage of the rapidly evolving field of materials all in a concise format. The material contained herein is most appropriate for junior/senior undergraduate students, as well as first-year graduate students in chemistry, physics, and engineering fields. In addition, this textbook will be extremely useful for researchers in industry as an initial source to learn about materials/techniques, with references provided for more detailed investigation. After providing a historical perspective for the field of materials in the first chapter, the first concentration of the textbook focuses on solid-state chemistry. Though there are many popular textbooks that deal with this topic, my approach contains some unique perspectives. In addition to colored illustrations of archetypical crystalline unit cells, digital photos of models are also provided to add clarity to their structures. Further, a large section on amorphous solids including solgel techniques and cementitious materials is provided largely left out of most solid-state textbooks. The next chapter on metals contains a thorough treatment of traditional and powder metallurgical techniques, with a focus on the complex phase behavior exhibited by the FeC system and steels. However, also left out of most metallurgy textbooks, I cover topics such as corrosion inhibition, magnetism, hydrogen storage, and the structure/properties of other metallic classes, such as the coinage metals and other alloys, such as those exhibiting shape-memory properties. The next chapter deals with semiconducting materials, which consists of a discussion of band theory and semiconductor physics. Unique among other texts, I also describe in great detail the evolution of the transistor, with a discussion of current limitations and solutions currently being investigated by researchers in the field. Also described in this chapter is IC fabrication, including vapor deposition techniques, photolithography, and ion implantation. The current trends in applications such as LEDs/OLEDs, thermoelectric devices, and photovoltaics (including emerging technologies such as dye-sensitized solar cells) are also provided in this chapter. ix x Preface Polymers and organic-based "soft" materials represent one of the largest materials classes; however, these materials are often left out of solid-state textbooks. Herein, I cover the chemistry of the five classes of polymers, from simple chains to complex branched dendritic architectures. Again, the approach is unique in that it covers traditional mechanisms and structure/property relationships for polymers, in addition to advanced topics such as homogeneous catalysis, polymer additives, and selfhealing polymers. A detailed discussion of "molecular magnets" is also provided in this chapter, due to their relatively mild syntheses and "soft" properties relative to traditional inorganic-based magnets. I devoted a significant effort in the next chapter to nanomaterials, due to their increasing popularity and relevance for current/future applications. In addition to structure/property descriptions and applications, essential topics such as nomenclature, synthetic techniques, and mechanistic theories are described in detail. The last chapter is also of paramount importance for the materials community characterization. From electron microscopy to surface analysis techniques, and everything in between, this chapter provides a thorough description of modern techniques used to characterize materials. A flowchart is provided at the end of the chapter that will assist the materials scientist in choosing the most suitable technique(s) to characterize a particular material. At the end of each chapter, a section entitled "Important Materials Applications" is provided, along with open-ended questions and detailed references/bibliography. Appendices are also provided that contain an interesting timeline of major materials developments, the complete Feynman speech "There's Plenty of Room at the Bottom," and a preliminary collection of materials-related laboratory modules. These additions were provided to promote student engagement through effective student instructor interactions. Though I attempted to hit all of the "high notes" in the materials world, an obvious omission would be a detailed discussion of biomaterials of increasing importance throughout the world. Applications such as biomimetics and drug delivery are presented in this edition; however, a detailed discussion of this topic was beyond the scope of providing a concise first edition a separate chapter on this topic will appear in future editions. The realization of a major milestone such as the completion of a textbook would not have been possible without the influence of many people in my life. First and foremost, I wish to thank my precious wife Diyonn for her patience and support during the many months of seclusion, as I crouched behind the laptop monitor. I am eternally grateful to my parents Frank and Pearl for their continuing support and godly wisdom, to whom I attribute all of my many blessings and successes. I must also acknowledge my Ph.D. advisor Andy Barron (Rice University) for his guidance and advice. I truly have never met anyone with as much drive and excitement for both materials research and teaching (as well as professional autoracing!). I thank him for being such an effective role model for the challenging and rewarding life of academia. Of course, this textbook is the compilation of input from a number of my professional colleagues. I wish to thank Profs. Anja Mueller, Bob Howell (at CMU), Richard Finke (Colorado State University), and Jean-Claude Thomassian (at Georgia Preface xi Southern University) for their input and suggestions regarding various sections of this textbook. I am also very appreciative for the input provided by the first students to have access to evolving versions of the textbook Nick Bedford, Jesse Thompson, Brandon Rohde, Brian Smith, Dan Denomme, Jason MacDonald, Laura Slusher, David Moyses, Michael Todd, Leontios Nezeritis, and Megan McCallum. The administration at CMU has also been a constant source of support. In particular, I wish to thank President Michael Rao, Dean Bob Kohrman, chemistry Chairman David Ash, and my faculty/staff colleagues from the chemistry department. I cannot express in words what their support has meant to me. The close proximity to Midland, MI, a leading center of the chemical industry, has also provided much inspiration for this textbook and my research projects. In particular, Petar Dvornic (Michigan Molecular Institute) is a constant source of inspiration and also provided much feedback for this textbook. I also gratefully acknowledge Don Tomalia (Dendritic Nanotechnologies, Inc. at CMU) for his support since my arrival at CMU in 2002. Thanks for putting CMU on the map in the dendrimer field! I would also like to acknowledge the funding agencies of the Dreyfus Foundation, Research Corporation, and the Army Research Laboratory who provided support for my research interests during my first years at CMU. Last, but certainly not least, I thank every reader of this book, and solicit your comments to my email fahlm1b@cmich.edu. Please let me know what you think of this edition; I will earnestly try to incorporate your suggestions to strengthen future editions. Bradley D. Fahlman, Ph.D. Mount Pleasant, Michigan March 2007 ...
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This note was uploaded on 08/21/2008 for the course EMA 3010 taught by Professor Unknown during the Fall '08 term at University of Florida.

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