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Solid State Chemistry

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Solid State Chemistry

byR.C. Ropp WarrenNew Jersey USA

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ELSEVIER AMSTERDAM - BOSTON- HEIDELBERG- LONDON- NEW YORK- OXFORD PA R IS - S A N D I E G O - S A N F R A N C I S C O - S I N G A P O R E - S Y D N E Y - T O K Y O

ELSEVIER SCIENCE B.V. Sara Burgerhartstraat 25 P.O. Box 211, 1000 AE Amsterdam, The Netherlands

9 2003 Elsevier Science B.V. All rights reserved.

This work is protected under copyright by Elsevier Science, and the following terms and conditions apply to its use: Photocopying Single photocopies of single chapters may be made for personal use as allowed by national copyright laws. Permission of the Publisher and payment of a fee is required for all other photocopying, including multiple or systematic copying, copying for advertising or promotional purposes, resale, and all forms of document delivery. Special rates are available for educational institutions that wish to make photocopies for non-profit educational classroom use. Permissions may be sought directly from Elsevier's Science & Technology Rights Department in Oxford, UK: phone: (+44) 1865 843830, fax: (+44) 1865 853333, e-maih permissions@elsevier.com. You may also complete your request on-line via the Elsevier Science homepage (http://www.elsevier.com), by selecting 'Customer Support' and then 'Obtaining Permissions'. In the USA, users may clear permissions and make payments through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA; phone: (+1) (978) 7508400, fax: (+1) (978) 7504744, and in the UK through the Copyright Licensing Agency Rapid Clearance Service (CLARCS), 90 Tottenham Court Road, London W1P 0LP, UK; phone: (+44) 207 631 5555; fax: (+44) 207 631 5500. Other countries may have a local reprographic rights agency for payments. Derivative Works Tables of contents may be reproduced for internal circulation, but permission of Elsevier Science is required for external resale or distribution of such material. Permission of the Publisher is required for all other derivative works, including compilations and translations. Electronic Storage or Usage Permission of the Publisher is required to store or use electronically any material contained in this work, including any chapter or part of a chapter. Except as outlined above, 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, recording or otherwise, without prior written permission of the Publisher. Address permissions requests to: Elsevier's Science & Technology Rights Department, at the phone, fax and email addresses noted above. Notice No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made. First edition 2003 Library of Congress Cataloging in Publication Data A catalog record from the Library of Congress has been applied for.

British Library Cataloguing in Publication Data A catalogue record from the British Library has been applied for. ISBN: 0 444 51436 8

The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper). Printed in The Netherlands.

Preface

Most of the

books

concerning

"Solid

State

Chemistry"

that

I have

e xamin ed have been w r i t t e n for the specialist or for the advanced s t u d e n t . I have c o m p o s e d this book with the novice in mind. That is, those w h o have little b a c k g r o u n d but w i s h to begin to learn about the solid state and w h a t it entails can start at the be gi nn i ng and build u p o n their knowledge and experience. This includes those working in biotechnology, p h a r m a c e u t i c a l a n d p r o t e o m i c s own the

fields. At this point in

time, they have s e q u e n c e d the h u m a n g e n o m e and are trying to define t h e s t r u c t u r e of proteins. It is m y opinion t h a t the material in this book will be helpful to t h e m as well. With this in mind, I have p r e s e n t e d the information in this book in a f o r m t h at can be easily u n d e r s t o o d . I t h i n k that it is quite i m p o r t a n t t hat any s t u d e n t of the body of knowledge t h a t we call "science" needs to be cognizant of the history a nd effort t hat has been m a d e by those w h o p r e c e d e d us. It was Newton who said: "If I have seen further, it is because I have stood on the s h o u l d e r s of giants". Thus, I have tried to give a s h o r t history of each particular s e g m e n t of solid state theory and technology. I have enjoyed c o m p o s i n g the material in this book and t r u s t t h a t t h e reader can use it as a self-study to build u p o n his (her) knowledge. I t h a n k m y wife, Francisca Margarita, profusely for her s u p p o r t during t h e time t h a t it has t a k e n to finish this c o m p o s i t i o n . R.C. R o p p March 2 0 0 3 store of usable

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vii

Table off contentsPreface Table of Contents CHAPTER 1 - The Phase Chemistry of Solids 1 . 1 . - Phase Changes of Solids, Liquids and Gases 1.2.- Differences Between the Three States of Matter a. The Gaseous State b. The Liquid State c. The Solid State 1.3.- The Close-Packed Solid 1.4. Phase Relations Between Individual Solids References Cited Problems for Chapter 1 CHAPTER 2- Determining the Structure of Solids 2.1.- Scientific Basis for Determining the Structure of Solids 2.2.- Solid State Structure Conventions and Protocols 2.3.- How to Determine the Structure of Compounds 2.4.- Symmetry Distribution of Crystals 2.5.- Phase Relationships Among Two or More Solids SUGGESTED READING Problems for Chapter 2 CHAPTER 3- Defects in Solids 3.1.- The Defect Solid a. The Point Defect in Homogeneous Solids b. The Point Defect in Heterogeneous Solids c. The Line Defect d. The Volume Defect 3.2.- Mathematics and Equations of the Point Defect a. The Plane Net 3.3.- Non-Stoichiometric Solids 3.4.- Defect Equation Symbolism

PaBei iii

2 9 12 15 17 23 27 28 31 31 45 55 61 64 69 69 71 73 74 72 82 85 88 88 95 98

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3.5.- S o m e Applications For Defect C h e m i s t r y a. P h o s p h o r s 3.6.- Defect Equilibria a n d Their E n e r g y 3.7. Defect Equilibria in Various Types of C o m p o u n d s a. S t o i c h i o m e t r i c Binary C o m p o u n d s of MXs b. Defect C o n c e n t r a t i o n s in MXs C o m p o u n d s 3.8.- The Effects of Purity (And I m p u r i t i e s ) Suggested Reading P r o b l e m s for C h a p t e r 3 A p p e n d i x 1. C o n c e n t r a t i o n s of Defects in Non-Ionized a n d Non-Stoichiometric Compounds A. Defects in N o n - S t o i c h i o m e t r i c MXs + d C o m p o u n d s A p p e n d i x I I. Analysis of a Real Crystal Using the Thermodynamic Method A. The AgBr Crystal with a Divalent Impurity, Cd 2+ B. Defect Disorder in AgBr- A T h e r m o d y n a m i c A p p r o a c h AoDendix III. Statistical M e c h a n i c s a n d the Point Defect CHAIrI'ER 4- M e c h a n i s m s a n d Reactions in the Solid S t a t e 4. I.- P h a s e C h a n g e s 4.2.- The Role of P h a s e B o u n d a r i e s in Solid State R e a c t i o n s 4.3.- Reaction Rate P r o c e s s e s in Solids 4.4.- Defining H e t e r o g e n e o u s Nucleation P r o c e s s e s 4.5.- The T a r n i s h i n g R e a c t i o n 4.6.- Fick's Laws of Diffusion 4.7.- Diffusion M e c h a n i s m s 4.8. - Analysis of Diffusion R e a c t i o n s 4.9. - Diffusion in Silicates 4. I0.- Diffusion M e c h a n i s m s W h e n the Cation C h a n g e s V a l e n c e P r o b l e m s for C h a p t e r 4 A p p e n d i x I- Math Associated with Nucleation Models of 4 . 4 . 1 . A p p e n d i x II- Math Associated w i t h Incipient Nuclei G r o w t h A p p e n d i x III- H o m o g e n o u s Nucleation P r o c e s s e s A p p e n d i x IV- Diffusion E q u a t i o n s Relating to F u n d a m e n t a l Vibrations of the Lattice

99 100 101 103 104 107 110 112 113 115 115 118 118 120 124 129 130 132 138 140 146 148 151 156 161 171 175 177 182 184 188

CHAPTER 5- Particles and Particle Technology 5.1.- Sequences in Particle Growth 5.2.- Sintering, Sintering Processes and Grain Growth 5.3.- Particle Size 5.4.5.5.5.6.5.7.Particle Distributions Particle Distributions and the Binomial T h e o r e m Measuring Particle Distributions Analysis of Particle Distribution P a r a m e t e r s A. The Histogram B. Frequency Plots C. Cumulative F r e q u e n c y D. Log Normal Probability M e t h o d 5.8.- Types of Log Normal Particle Distributions A. Unlimited Particle Distributions B. Limited Particle Distributions C. Particle Distributions with Discontinuous Limits D. Multiple Particle Distributions Case I: Fluorescent Lamp Phosphor Particles Case II: T u n g s t e n Metal Povcder 5.9.- A Typical PSD Calculation 5.10.- Methods of Measuring Particle Distributions A. The Microscope- Visual Counting of Particles B. Sedimentation Methods C. Electrical Resistivity-The Coulter Counter D. Other Methods of Measuring Particle Size Permeability Gas adsorption Particle size by laser r e f r a c t o m e t r y Suggested Reading Problems for Chapter 5 Chapter 6. - Growth of Crystals 6. I.- Methods of Growth of Crystals 6.2.- Furnace Construction 6.3.- Steps in Growing a Single Crystal

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Czochralski Growth of Single Crystals

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