Physical Metallurgy Principles Second Edition niversity Series in Basic Engineerin: Robert E.Reed-Hill ® D. VAN NOSTRAND COMPANY Roa OSAMA NORONIG LONGON MELBOURNE. Van Nostrand Compony Regional Offices: New York Ciacinnati Millbrae London Toronto Melbourne Copyright @ 1973 by Litton Educational Poblising, I. Library of Congress Catalog Card Number: 79-181094 ISDN: 0-402-26868-8, ‘At eights reserved. Certain portions ofthis work copyright @ 1984 by Litton fEdueational Publishing, Ins. No part of this work covered by the copyrights hereon may be reproduced or used in any fozm or by soy means ~ graphic, lectronc, or mechanies, inchading photocopying, recording, taping, oF Information storage snd tezieval systems ~ without written permission of the publisher. ‘Manufactored inthe United States of America ‘Published by D. Van Nostrand Company 450 Wert 33rd Street, New York, N.Y. 10001 ‘Published simultaneously In Canada by Van Nostrand Reinhold Le i bom mo 9 8 7 6 5 4 Preface ‘The basic plan and. philosophy of the oxginal edition are continued in this volume, The major changes in the new edition are largely the result of constructive suggestions and advice by Professor Richard W, Heckel, of Drexel University, Dean Walter $. Owen, of Northwestern University, and Professor Marvin Metzger, of the University of linois. One result of these suggestions is the inclusion of a chapter on nucleation and growth kinetics. The outline ofthis ‘chapter was also lsplted by a set of clss notes Kindly loaned to the author by Professor Heckel. The considerable assistance of Dr. John Kronsbein in revising and expanding Chapter 3, Elementary Theory of Metals is also gratefully acknowledged. 'As 4 consequence of requests for the inclusion of topies either missing or too lightly covered in the fist edition, the new book has been increased in size by about ten percent. In a broad sense, the additional material fits into two tlssifications. First are the topics that have recently become significant in the field of metallurgy. The second group consists of wellestablished subjects not covered in the frst edition, but which, from use of the text, were found to be needed for a more unified presentation, Among the former subject areas are flectron microscopy, fracture mechanics, supetrconductivity, superplaticity, dynamic recovery, dynamic strain aging, electrotransport, thermal migration, ‘and emissary dislocations. In the latier category belong the new chapter on rucleation and growth Kinetics and such topics as magnetism, the zone theory of alloy phases, the five degrees of freedom of « grain boundary, the phase rule, tric stess and trie strain, coring and homogenization of castings, work hardening, and diffusion in nonisomorphic systems. “The number of problems is substantially increased over thet in the original book, in conformity with the current trend in engineering to place more ‘emphasis on problem solving. Problems have been written with the aim of both ilustrating points covered in the text and exposing the student to material and ccancopts not covered directly inthe book. ‘The helpful assistance of Dr. John Hren, Dr. Robert T. DeHiolf, Dr. Derele Dove, Dr. Ellis Verink, and Dr. F. N. Rhines, all of the University of Florida, ‘who either reviewed sections of the book or gave suggestions, is acknowledged with thanks, Robert E. Reed Hill| | Contents ‘THE STRUCTURE OF METALS . 0K 1 1.1 ‘The Structure of Metals, 1 1.2 Metallographic Specimen Prep- aration, 2 1.3 The Crystal Structure of Metals, $1.4 Unit Cells, 5 1.5 The Body-Centored Cubic Structure, 6 1.6 Coordination Num- ber of the Body-Centered Cubic Lattice, 71-7 The Face-Centere Cubie Lattice, 7 1.8 Comparison of the Face-Centered Cubic and Close-Packed Hexagonal Structures, 91.9 Coordination Number of the Systems of Closest Packing, 11 | 1.10 The Unit Coll of the Close Packed Hexagonal Lattice, Il 1.11 Anisotropy, 12_ 1.12 Textures to Preferred Orientations, 13 1.13 Miller Indices, 15 1.14 Crystal | Structures of the Metallic Elements, 21 1.15 The Stereographie | jection, 22 1.16 Directions That Lie in a Plane, 24 1.17 of a Zone, 24 1.18 The Wulff Not, 25 1.19 Standard | Projections, 31 1.20 The Standard Stereographic Triangle for Cubic | Crystals, 33. Problems, 34 2. DIFFRACTION METHODS 38 2.1 The Bragg Law, 39 2.2 Lave Techniques, 43 2.3 The Ro- tating Crystal Method, 4524 The Debye-Seherrer or, Powder Method, 46.25 The X-Ray Spectrometer, 50.2.6 The Trans gfe mission Electron Microscope, St "Problem, 58 & : -Y'S3. ELEMENTARY THEORY OF METALS .OK 60 BH The Ioternat Energy of a Crystal, 60 GB Tonic Crystals, 61 G3) The Born, Theory of Tonic Crysis, 62 GD Van der Waals Crystals, 67 (3.3 Dipoles, 67 3.6 Inert Gases, 68 3.7 Induced Dipole, 69 38 The Latico Energy of an InertGas Solid, 71 39 The Debye Frequency, 71 310 The Zero Point Energy, 73 43.11 Dipole-Quadrupole and Quadrupole Quadrupole Terms, 75 wtwi contents Contents/ix 51B)Molceular Cosas, 75. 3.9 Refinements to the Born Theory fh 5:18 The Grin Size, 226 5.19 ‘The Bieet of Grain Boundaries on Sine crystals: 76, 3.18 Covalent and Metal Bonding, 77 SS Mechasial Properties, 228 Problems, 230 SA5 The Uncertainty Principle, 81 3.16-The Dusl Nature of & Jiatcs es S17 FrecBlectron ‘Theory, 88 3.18 The Density of Sas VACANCIES .Ox 208 States, 98 3.19'The Effect of Temy Electrons in the Energy Levels, 99 ature on the Distribution of 30 excctonie Specie Heat, 6.1 Thermal Behavior of Metals, 238 62 tniernal Energy, 240 100 3.21 The Zone Theory, 101 3.22\The Dependence of the 63 Entropy, 240 6.4 Spontaneous Reactions, 241 6.5 Gibbs Energy on the Wave Number, 107 3.25 The Deny of States go Fes Baar, 202, 6.6 Sasi ‘Mechanical Definition of Entropy, Cue 111 3.24 Application of the Zone Theory to Alloy Phases, Gi, ito acini, 230,68 Vaeney Maton, 257-69 Ine 112. '3.93)Cotductors. and Tasulators, 116 (3.26 Semiconductors, Ysa Atoms and Divacancies, 260 Problems, 263 {Uno 39? Impurity Semiconductor, 121 328 Magnetism. 124 8 329 Ferromagnetism, 130 3.30 Anfiferromagnetism and Festi “——-T ANNEALING -O' 27 a Flcctrical Resistivity Function of XD magnetism, 133, 3.51 The Electrical Rest os 1a 7.1 Stored Energy of Cold Work, 267 7.2. The Relationship of Free ee Za Temperature, 134 3.32 Superconducivity, 135 Problems 141 Energy to Strain Energy, 268 7.3 The Release of Stored er a | 269.74 Recovery, 271 7 Recovery in Single. Crystals, 54 DISLOCATIONS AND SLIP PHENOMENA -OK 144 7.6 Polygonization, 274 7.7 Dislocation Movements in Polygoniza- tion, 277 7.8 Recovery Processes at High and Low Temperatures, 282 7.9 Dynamie Recovery, 282 7.10 Recrystallization, 284 7.11 The Effect of Time and Temperature on Recrystallization, 286 7.42 Recrystalization Temperature, 288 7.13 The Effect of Strain fon Recrystallization, 288 7.14 The Rate of Nucleation and the Rate fof Nucicus Growth, 290 7.15 Formation of Nuclei, 291 7.16 Driving Force for Reerystalization, 294 7.17 The Reerystallized Grain Size, 294 7.18 Othor Variables in Recrystallization, 297 4.1 The Discrepancy Between the Theoretical and Observed Yield ‘Stresses of Crystals, 144 4.2. Dislocations, 146 4.3 The Burgers Veetor, 15644 The Frank-Read Sovree, 158_ 4.5 Nucleation of Dislocations, 159 4.6 Bend Gliding, 163 4.7 Rotational Slip, 166 4.8 Climb of Edge Dislocations, 169 4.9 Slip Planes and Slip Di- rections, 171 4.10 Slip Systems, 1734.11 Critical Resolved Shear gf Sess, 173 4.12 Slip on Equivalent Slip Syems 177 4.13 The Dabeation Density, 177 4-14 Slip Systems in Different Crystal 719 fh oe sanity of the Metal, 297 7.20 Tail Grim Size, 298 "7.21 Fe Forms, 178 Problems, 184 Grain Growth, 298 7.22 Geometrical Coalescence, 302 7.23 2 “hree-Dimensional Changes in Grain Geometry, 303. 7.24 The Grain DISLOCATIONS AND GRAIN BOUNDARIES O% 190 Growth Law, 304 7.25 Impurity Atoms in Soli Solution, 310 gv 126 Impurities in the Form of Inchsions, 311° 7.27 The Fee a2 Surface Effects, 315 7.28 The Limiting Grain Size, 316 7.29 Preferred Orientation, 318 7.30 Secondary Recrystallization, 318 731 Strain-Induced Boundary Migration, 319 Problems, 321 51 CrossSlip, 190 52 Slip Bands, 192. 5.3 Double Cros-Sp, 133 oe erp Suetre Rotation Duvig Tense and Compresie Deformation 195 5.5 The Notation for the Slip Systems in the Fo ‘Deformation of F.C.C. Crystals, 197 5.6 Vector Notation for Dis- | a raed 5:1 Dislocations inthe Fce-Centerd Cubic Lats, A Mor Si Intrase and Extnsie slacking Fauls in Face-Contered = SOLID SOLUTIONS -oK 2s Cubic Metals, 206 5.9 Extended Dislocations in Hexagonal Metals, ff 8.1 Intermediate Phases, 327 8.2 Interstitial Solid Solutions, 327 207 5.10 Extended Dislocations and CrossSlip, 207 5.11 Dis 83 Solubility of Carbon in Body-Centered Cubic Iron, 328 8.4 focation Interzetions, 2095.12 Grain Boundaries, 213 5.13 Dis eS _ Substitutional Solid Solutions and the Hume-Rothery Rules, 332 Jeaton Intersections, Ange Grain Boundary, 214 5.14 The | @ IF 8 lateracion of Distvatons and Solute Atoms, 333. 8.6 The (eaten Mosel aetom of «Grin Boundary, 216 5.19 Grain |“ gg Strss Fld of a Ser Dislocation, 233, 8.7 The Sess Filo 09 Boundary Energy, 219 5.16 Surface Tension of the Grain Bound, [EEZ Lege Disocation, 334 8.8 Dislocation Atmospheres, 33689 The ary, 219" 5.17 Boundaries Between Crystals of Different Phases, 222, | rowan Equation, 338 8.10 ‘The Drag of Atmospheres on Movingx/Contents Dislocations, 339 8.11 The Sharp Yield Point and Liders Bands, Ba BLD The Theory of the Sharp Yield Point, 344 8.13 Stain veG@aning 346814 Dysamnic Stsin-Aging, XG te Bogan ame Sire 351 ews ‘B15 The Role of Problems, 353 PRECIPITATION HARDENING - 0% 358 9.1 The Significance of the Solvus Curve, 359 9.2 The Solution Treatment, 360 9.3 The Aging Treatment, 361 9.4 Nucleation of Precipitates, 365 9.5 Heterogeneous Versus Homogeneous Nuclea- tion, 368 9.6 Theories of Hardening, 370 9.7 Additional Factors in Precipitation Hardening, 374 Problems, 375 -0k DIFFUSION IN SUBSTITUTIONAL SOLID SOLUTIONS.OK 378 10.2. Nonideal Solutions, 379 10.3 Dif 10.4 The Kirkendall Bflect, 386 10.5 Porosity, 390 10.6 Darken's Equations, 392 10.7 Fick's Second Law, 397 10.8 The Matano Method, 400 10.9 Deter- rnination of the Intrinsic Difusivities, 404 10.10 SeltDiffusion in Pure Metals, 406 10.11 Temperature Dependence of the Diffusion Covffcient, 409 10.12 Chemical Diffusion at Low-Solute Concen- ration, 412 10.13 The Study of Chemical Ditfusion Using Radio- tative Tracers, 414 10.14 Diffusion Along Grain Boundaries and Pree Surfaces, 418 10.15 Fick’s First Law in Terms of a Mobility ‘and an Effective Force, 422 10.16 Blectrotransport and Thermo {Pamiaration, 425 Problems, 428 . 10.1. Tdeal Solutions, 378 fusion in an Ideal Solution, 381 INTERSTITIAL DIFFUSION OK 43 Lid Measurement of Interstitial Difusivities, 432 11,2 The Snoek (gf Bieeu 33" 113 Experimental Detaminaan of the, Nelaraten ee Time, 441 11.4 Experimental Data, 450 11.5 Anelasic Measure- ments at Constant Strain, 450 Problems, 451 PHASES .OK aan 12.1 Basic Definitions, 454 12.2 The Physical Nature of Phase Mix tures, 456 12.3 Thermodynamics of Solutions, 457 12.4 Equilib- hum Between Two Phases, 460 12.5 The Number of Phases in on ‘Alloy System, 461 12.6 Two-Component Systems Containing Two Phases, 470 "12.7 Graphical Determinations of Partisl-Molal Free Energies, 471 12.8 Two-Component Systems with Three Phases in Contents /xi Equilibrium, 474 12.9 The Phase Rul 475. 12.10 Ternary Sys- tems, 478 Problems, 478, NUCLEATION AND GROWTH KINETICS .OK 480 13.1 Nucleation of a Liquid from the Vapor, 480 Dering Theory, 488 13.3 Freezing, 490 13.4 Solid State Resc~ tions, 493 13.5 Heterogeneous Nucleation, 496 13.6 Growth _ Kinetics, $01 13.7 Diffusion Controlled Growth, 504 13.8 Inter ference of Growing Precipitate Particles, 510 13.9 Interface Con- trolled Growth, S11 13.10 Transformations That Occur on Heating, 514 13,11 Dissolution of a Precipitate, 515 Problems, 518 13.2 The Becker- BINARY PHASE DIAGRAMS - OK 522 4.1 Isomorphous Alloy Systoms, $22 14.2 The Lever Rule, 524 14.3 Equilibrium Healing or Cooling of an Isomorphous Alloy, 527 14.4 ‘The Isomorphous Alloy System from the Point of View of Free Energy, 530 14,5 Maxima and Minima, 532 14.6 Superlattices, 534 14.7 Miscibility Gaps, 539 14.8 Butectic Systems, 541 149 The Equilibrium Microstructures of Eutectic Sysiems, 542 14.10 The Peritectic Transformation, $49 14.11 Monotectics, $52 14.12 Other Three-Phase Reactions, 552 14.13 Intermediate Phases, 553. 14.14 The Copper-Zine Phase Diagram, 556 14.15 Diflusion in Non-Isomorphie Alloy Systems, 559 Problems, 565 18 SOLIDIFICATION OF METALS 568 15.1 The Liquid Phase, 568 15.2 Nucleation, 572 15.3 Crystal Growth from the Liguid Phase, 575 15.4 Stable Toterface Freczing, QELS ISS Denke Groh 579 13.6 Dene ring in Cpls 583 15.7 Fresrng of tno, 588, 15.8 The Grain Sie of PL castings, 593 15.9 Segregation, 394 15.10 Homogenization, 586 15.11 Inverse Segregation, 602. 15.12 Porosity, 603, Problems, 608, SL “S16 DEFORMATION TWINNING AND MARTENSITE . ok >) REACTIONS et "4 16.1 Deformation Twinning, 611 S Theory of Twinning, 614 16:3 Identification of Deformation Twins, > 622. 16.4 Nucleation of Twins, 624 16.5 Twin Boundaries, 62: © 16.6 Twin Growth, 627 16.7 Accommodation of the Twinning EY shear, 629. 168 Martensite, 635. 16,9 The Bain Distortion, 638 S© 16.10 The Martensite Transformation in an Indium-Thallium Alloy, 5 pa 16.2 Formal Crystallographic cm fo Trans}sii/Contents < é fo we me 17 19 © tion of Martensite Plates, 654 640 16.11 Reversibility of the Martensite Transformation, 642 16.12 Athermal Transformation, 642 16.13 Wechsler, Lieberman, ‘and Read Theory, 643 16.14 Irrational Nature of the Habit Plane, 650 ty of Habit Planes, 651 16.16 The Tron- Nickel Martensitie Transformation, 651 16.17 Isothermal Forma tion of Martensite, 653 16.18 Stabilization, 653 16.19 Nuclea- 16,20 Growth of Martensite Plates, 655 16.21 The Efect of Stress, 655 16.22 The fect of Plastic Deformation, 656 Problems, 657 ‘THE IRON-CARBON SYSTEM . OK 661 17.1 The Transformation of Austenite to Pearlite, 663 17.2 Peatlite, 665 17,3 The Effect of Temperature on the Pearlite Trans- formation, 670 17.4 Time-Temperature-Transtormation Curves, 679 17.5 The Bainite Reaction, 681 17.6 The Complete T-1-T Diae gram of an Eutectoid Steel, 687 17.7 Slowly Cooled Hypoeutectoid Stecls, 690 17.8 Slowly Cooled Hypereutectoid Steels, 693 17.9 Tsothermal Transformation Diagrams for Noncutectoid Steels, 695 Problems, 698 THE HARDENING OF STEEL -OK 701 18.1 Continuous Cooling Transformations, 701 18.2 Herdenabitity, 704 18.3 ‘The Variables that Determine the Hardenability of a Stee), 710 18.4 Austenitic Grain Size, 711 18,5 The Effect of Austenitic Grain Size on Hardenability, 712 18.6 The Infiuence of Carbon Content on Hardenability, 713 18.7 ‘The Influence of Alloying Ele ments on Hardenability, 714 18.8 The Significance of Hardenability, 719. 18.9 ‘The Martensite Transformation in Steel, 720 18.10 The Hardness of Iron-Carbon Mattensite, 725 18.11 Dimensional ‘Changes Associated with the Formation of Martensite, 729 18.12 ‘Quench Cracks, 730 18.13 Tempering, 733 18.14 Sphereidized Comentite, 739° 18.15 The Eflect of Tempering on Physical Prop- erties, 742 18.16 The Interrelation Between Time and Temperature in Tempering, 744 18.17 Secondary Hardening and the Fifth Stage ‘of Tempering, 743 Problems, 747 FRACTURE 19.1 Failure by Easy Glide, 749 tiple Gide), 751 age, 753 19.5 Fracture in Glass, 755 749 19.2 Rupture by Necking (Mul- 40.3 The Eflect of Twinning, 752 19.6 Cleav- 19.6 The Grifith Theory, l fe ee 20 CREEP . OK opto Ellect of Nonmetallic Inelusons, 821 Cs Contents 759° 19.7 Grifith Cracks in Glass, 760 19.9 The Grifith Equation, 762 19.10 The Nucleation of Cleavage Cracks, 763 19.11 Crack Nucleation in Iron, 765 19.12 Crack Nucleation in Zinc, 768 19.13 Propagation of Cleavage Cracks, 769 19.14 The Effect of Grain Boundavies 774 19.15 The Effect of the State of Stress, 777 19.16 The Impact Test, 780 19.17 The Sig- niffcance of the Impact Test, 782 19.18 Ductile Fractures, 786 19,19 Intererystalline Brittle Fracture, 794, 19.20 Temper Brittle ness, 795 19.21 Blue Brittleness, 796 19.22 Fracture Mechanics, 797 19.23 The Stress Intensity Factor, 800 19.24 Fracture ‘Toughness Measurements, 801 19.25 Fatigue Failures, 809 19.26 ‘The Macroscopic Character of Fatigue Failure, 810 19.27 The _ Rotating-Beam Fatigue Test, 811 19.28 The Microscopie Aspects Wot Fatigue Failure, 814 19.29 Fatigue Crack Growth, 818 19.30 19.31 The Effect of Steet ‘Microstructure on Fatigue, 822 19.32 Low-Cycle Fatigue, 823 19.33 Certain Practical Aspects of Fatigue, 824 Problems, 824 19.8 Crack Velocities, 761 “8 827 20.1 Work Hardening, 827 20.2 Considére Criterion, 829 20.3 ‘The Relation Between Dislocation Density and the Stress, 830 20.4 Taylor's Relation, 832 20.5 The Nature of the Flow-Stress Com- ponents, 834 20.6 The Effect of Alloying on the Flow-Stress Components, 835 20.7 ‘The Relative Roies of the Flow-Suress Com ponents in Face-Centered Cubie and Body-Centered Cubic Metals, 837 20.8 Superplasticity, 840 20.9 The Nature of the Tims Dependent Strain, 841 20,10 Creep Mechanisms, 847 20.11 ‘Creep When More than Ono Mechanism is Operating, 859 20.12 Grain-Boundary Shear, 865 20.13 Intercrystalline Fracture, 867 20.14 The Creep Curve, 871 20.15 Practical Applications of Creep Data, 877 20.16 Creep-Resistant Alloys, 880 20.17 Alloy Sys- toms, 882 Problems, 884 Appendices 888, List of Important Symbols 901 List of Greck Letter Symbols 903 Index 9041 The Structure of Metals ‘The most important expect of any engineering material i its structuce, because its propecties are closely related to thie feature. To be successful a materials ‘engineer must have» good understanding of this relationship between structure and properties. By way of illustration, wood Is @ very easy material in whic 10 see the close interaction between structure and properties. Atypical structural ‘wood, such as southern yellow pine, is essentially an aray of long hollow cells or ‘bers! These fess, which ar formed largely from elilose, are aligned with the 4 gain of the wood and ace cemented together by another weaker oxpanic mate PO called lignin. The structure of woo roughly analogous to that of a ‘bundle of drinking saws. [fcan bo split easily along its pra, that, parallel fo ot the cells. Wood is also much stronger in compression (or tension) parallel to its grainr than itis in compression (or tension) perpendicular to the grain, It makes fxcellent columss and bgims, but i snot really suitable fr tension members requited to carry lace Tas, because the low resistance af wood to shear parallel to its grain makes i difficult to attach end fastenings that will not pull out. As a APL seule, wooden bridges and other lange wooden struetues are often constructed containing see He rds to support the tensile loads. 1.1 The Structure of Metals, The structure in metals of similar importance to that in wood, although often in a more subtle manner, Metals are crystalline when in the solid form. While very large single erystls_ can prepared, the normal metallic object consists of an aggregate of many very enjstals, Ms therefore polverysaline. The crystal jn these mate Inocmally referred to as is grains, Because of thelr very small sizes, an optical microscope, operating al magnifications between about 100 and 1000 times, is ‘sutlly required in order to examine the structural features associated with the gains in a metal, Structures sequicing tis range of magnification for thir examination fall into the clas Known as microstructures, Occasionally, metalic objects, such a castings, may have very large crystal that are discernible to the naked eye or are easily resolved under a low-power microscope. Structure in this catagory is called macrowracture. Finally, ther jx the basi truce side the sea sn anions ee Ths m macroest t 5 tnveqoest at suabedtut 1 erotora ortuLs by mer op ede,_2rPoysiat Metatusy Priniees aso (Of the various forms of structure, microstructure (that visible under the optical microscope) has been historically of the greatest usp’ and interest to the fmetallurgist. Because the metallurgical microscope is pormally operated at magnifications where its depth of field is extremely shalldw, the metallie surface fo be observed must be very flat, AC the same time, it must reveal accurately the nature of the strocture inside the metal. One is therefore presented with the problem of preparing « very smooth flat and undistorted surface, which is by ro cans an edgy taak. The procedures required to obtain the desired goal fll under the general heading of metallographic specimen preparation. (N60) 12 Metallographie Specimen Preparation, To a large extent, metallographic specimen preparation is an art. The techniques tend to vary Somewhat from one luborstory to another. Variations in the procedures may also be required depending on the nature of the metal to be examined, because Thelals vary widely in hardness and texture. Nevertheless, the basic operations Tend to be similar: for the purpose of illstrating the nature of metallographic specimen preparation, et us consider @ technique suitable for iron and steels, What follows is only x simple outline, and for further details « suitable teference * should be consulted. “Lot us suppose that @ small specimen has been cut out of a steel object and that a suitable fet surface has been prepared on one side of this specimen by sawing and grinding, The normal procedure is to mount the specimen ina small piasie dise (about 1 in, in diameter and %’n. thick) with the surface of the {pecimen to be polished exposed on one side ofthe disc as shown in Fig, 1-1 Gne technique to form this disc consists of frst plscing the specimen inside @ La Fig. 1.1. A metallographic specimen. 1. Polishing the Micro Section, Part Lav 2. The AB Metal Diget, 11, Nos. and 3, (965), Bacher, Lie, Eraston lino. “Te Strgtura of Metals simple ting mold, and then pouring liquid epoxy resin into the mold to Ol it. ‘The epoxy hardens in a matter of hours to yield a sirong, convenient handle for holding the specimen during the subsequent steps in surface preparation. These stops involve four basic types of operations: (1) fine grinding, (2) rough polishing (3) final polishing, and (8) etching, fo the fist three stoges, te basic Ebjectve is to reduce the thickness of the deformed layer ying below the Specimen surface. All cutting and grinding operations badly deform the metal feat to the surface, The true structure of the metal will become visible only Wien ‘ene has completely removed the deformed layer, Since each stage in the Jrepertion of the specimen itself tends to deform the surface, iis necessary to evra suevession of finer and finer abrasives. Each abrasive acts 10 remove the deformed layer lett Grom the coarser stage preceding it, hile iin turn Leaves a distorted layer of reduced depth. ‘Fine grinding. In this stage, the specimen surface is ground using silicon ceaibide powder bonded onto specially prepared papers. The specimen may be hand-ubbed azainst the abcasive paper, which i aid over a fat surface, such as 8 dice of plate glass. Alteratively, the abrasive paper may be mounted on the Livface of a flat, horizontally rotating wheel and the metallographic specinen hele against it In ether case, the surface is usually lubricated with water, which provides 2 oshing ation to carry away the particles cut from the surface, Thee Trades of abrasive re used: 320 git, 400 grit, and 600 galt. Te conesponding Bistcle ser of the slicon cabide are about 33, 25, and 17 microns respec: Trely, where one micron is 10 cm. In each of these fne grinding stages the Specimen is moved over tho surface so thatthe scratches ae formed in only one Guectfon, In prooceding from one paper to the next, the specimen is rotated hough an angle of about 43°, so that the new serach are placed on the surface aon angle to thoge formed during the preceding stage. Grinding thea ontinved antil-well past the point at which the seatches from the preceding stage have disappeared. "Rough polshiyg. This is probably the critical stage. At the present time the slvasve extensively used forthe rough polishing operation is powdered diamond dust, with paticl size of about 6 microns. The diamond pow desis crtiod in a paste that is oilsoluble. A very small quantity ofthis paste is needed, and this is Placed on the nylon clourcovered surface of rotating polishing, wnel. The fubicant used during the polishing operation isa specially prepared oll. The specimen is peesod against the cloth of the rotating whee! with considerable Tress. In the polishing stags, the specimen is tot held ina fxed position on the polishing whcl, but is moved around the wheel inthe dcection opposite to the rotation of the whee! itself. This insures a more uniform polishing action. ‘Tne diamond parteles have astcong cutting actlon and can be very effective in Temoving the deep layer of deformation remaining from the fine grinding Sporation. The fat that 6 miezon diamond powder sable to remove the effectsAlpiysiet Matalurgy Princo resulting fom the 17 micron silicon cabide abrasive in the last stage of fine finding speaks for self. ‘Final polishing. Here the fine scratches and very thin distorted layer remaining from the rough polishing stage are removed. The polishing compound tually used is alumna (Al,O,) powder (gama form), with a particle sizeof 1.05 microns, This is placed on & dath-covered wheel, and distilled water Is used f5 4 lubricant, In contrast to the napess nylon cloth used in rough polishing, the loth used in this step normally contains @ nap. If tis and the preceding sages hhve been carefully erred outa seratel-fee surface, with almost no detectable layer of distorted meta, wil be obtained. ‘Fiching, ‘The. granular structure ina metallographic specimen usually cannot be seen under the microscope after the final polishing operating has been Completed. The grain boundaries in a metal have a thickness of the order of fear atom diameters at best, andthe resolving power ofa microscope Is much too Tow to reveal thee presence. Only i'a metal contains several crystals of different colors that touch each othe wil boundaries be visible. Ina pure metal this is, of oure, imporibe. In order to make the boundaries visible, metallographic Specimens sre ususlyeteted. fn most eases this involves immersing the polished furfice in a weak acidic or allalne etching solution. The most commonly used folutin for tel is called rita! and consists of «2 perent solution of nite ald in alcohol, Tn some cases the etching solution is applied to the surface by rubbing lt gently with a cotton svab wetted with the agen. Tn either cae, the resultant effet Isto dissolve metal away fom te specimen surface, With a good ttching solution, the removal of metal ftom the surface will not occur uniformly, Sometimes the etching agent wil attack the grain boundaries more rapidly thag the surface of he gains. Other etching solutions wall disse the ‘arlous grains accoeding to the orientation of the surface that they present tothe Uiching solution. The nature of this effect is shown schematialy in Fig. 12. Here the boundaries are made visible because they appear as shallow stepson the fufice of the spesimen, These neadly vertical surfaces do not sefect fight into te objective lens of a microscope In the seme fashion as the smooth horizontal Caystal surfaces that lie Detween them, and, es x result, the locations of the trstal boundaries shouldbe observed under & microscope, ee bn Fig.1.2 The etching solution reveals the erystal boundaries, “The Struct of Matt Electvo-polishng and electro-etching. ‘There axe a number of metals, such as stainless steel, titanium, and zirconium, from which itis very difficult to remove the distorted surface layers. Mechanical polishing is not very successful with these materials. As a result, they are often polished by an electro-polishing technique in the final polishing stage. In this case, the specimen is made the Anode in a suitable alectolytc bath, while the cathode isan insoluble material. If ‘the proper current density is used, i is possible to dissolve away the specimen surface in a manner that produces 2 fine surface polish. In electro-polishing, the bath and current are deliberately contrlled so as to produce 2 surface that is smooth and without relief. On the other hand, itis also possible to alter the ‘composition of the bath and the current density conditions so as to produce the surface elie required in etching. The corresponding procedure is called electroetching. a 1.3. ‘The Crystal Structure of Metals, A crystal is defined ss an orderly artay of atoms in space. Thore are many different types of crystal structures, same of which are quite complicated, Fortunately, most metals crystallize in one of throe relatively simple structures: the face-centered cubic, ‘the body-centered cubic, and the close-packed hexagonal. 14 Unit Cells, The unis cell of a crystal structure is sip fons joes smn lh eb Ah, ven. pal ar diction wl Gelop te eal ce, Figure 13A shown the at col Ife boujconced cubic tice. is evident ta ls nae dvd om the shape of he uit cel Eight unit cell are combined in Fig, 3Bin ode o show ow the unit el fs into the complete tc, Note that atom of Fig 133 dont not blog ulguly toon unl cl but ia prt of al eight nicl that Srround i Therefor, fcan be sad at only onecighth of tis corner stom .ccc. 2ab/ctnbe ad. 8 -divegib + compacta : 4 fone diai p face, ow AOCOEE Fig. 1.3. (A) Body-centered cubie unit cell, (8) Eight unit cells of the ‘body-centored cubic atic. ~ plano + compacto : 6 (110) & fro} Seq enpilhamete fiPhyseat Metalloray Prine ‘belongs to any one unit cell. This fict may be used to compute the number of toms per unit cell in a body-centered cubie crystal. Even a small crystal will tontait billions of unit cells, and the calls in the interior of the erystal must greatly exceed in number those lying on the surface. Therefore surface cells may Be neglected in our computations. In the interior of a crystal, each comet atom Of a unit cell is equivalent to atom a of Fig. 1.3B and contributes one-eighth of fin atom to a unit cell In addition, each cell also possesses an atom located at its enter that is not shared with other unit cells. The bady-centered_cubje lattice thus has two atoms per unit cel; one cantsbuted by the corer atoms, and one Tocated at the center of the eel, ovo uni coujecto: 4 cre tsb /eélala (ALL) 28 inp Me coord. 12 plrucs oclaédnens + Duperia: © a worl MBC Fig. 1.4 Face-centered cubte unit cel The unit cell of the face-centered cubic lattice is shown in Fig. 14. In this case, the unit cell hasan ators in the center of each face. ‘The number of atoms per unit call in the face-entered cubic lattice can be ‘computed in the same manner as inthe body centered cubic lattice. The eight Gomer atoms again contribute one atom to the cell. There are also six Facc-centered atoms to be considered, each 2 part of two unit cells. These ‘contribute six times one-half an atom, or Uuee atoms. The fece-centered cubic lattice basa total_of four atoms per unit cel, or twice a_many_2s_the bbody-centered cubic lattice. - ~ 1.5 The Body Centred Cubic Structure, tis frequenily con venient to consider metal ental ag structures formed by staking together hark Shere, Ths lade to the soled hardball mode ofa exystlie lattice, where the radius of the sphere is taken af al the distance between the centers ofthe most elesely spaced atoms. igue 1s shows the hardball model of the body centered cubic unit ell A studs of the figure shows thatthe atom atthe center ofthe ce fe cliear with SEEN comer atom; thats, the atoms connecting dagonlly opposite comers of She cabe Toon strait Hes, cach atom touching the next in sequence, These nea arya do not end atthe comers ofthe unt cell, but continue on through the coal rae ke a row of beads strung on wie Goo Pig. 1.38). These four tube dingoals conttte te close picked dections ofthe Bodycontered cubic ‘The Suuetuce of Metals? cesta, dctions tht un continuously through te tice. on which the sons as closely spaced as possible. — 7 ther consideration of Figs 1.5 and.1.3B eval hat all atoms in the snd eae kee ct hs he a a ee of fonions, Exc of the ec cold hae been chown ste enter of te taking al covnet atoms of Fig 130 seats of el, and all enters of eas Fig. 1.5. Hord-ball model of the body-centered cubie unit cell. 1.6 Coordination Number of the Body-Centered Cubic Lattice, ‘The coordination number of a crystal structure equals the number of nearest neighbors that an atom possesses inthe lattice. In due body-centered cubic unit cell, the center atom has eight neighbors touching it (we Fig. 1.5). We have ready sen that al atoms in this lattice are equivalent. Therefore, every atom ‘of the body-centered cubic structure not Iying at the exterior surface posesses tight nearest neighbors, and the coordination number ofthe attice is eight. 1.7 The Foce-Centered Cubic Lattice, ‘The hard-balt_ model assumes special significance in the face-centered cubic crystal, for in this structure the atoms or spheres are packed together as closely es possible. Figute 1.6A shows a complete facecentered cubic cell, and Fig. 1.68 shows th sara plane) in which the atom are spaced a tightly as possb. fone of these close packed planes is shown in Fig. 1.7. ‘Thee le inthe octahedra plane (the directions aa, Bande). spheres toc and are colines/Physis Moratoray Principles o Fig. 1.6 (A) Face-centered cuble unit eal! {hard-ball model). (8) Same cell With @ corner atom removed to show an octahedral plane. (C) The sixface agonal directions urning to Fig. 1.64, we_see that the close packed directions of Fig. 1.7 correspond to diagonals that cross the faces of the cube. There are six of these ad deections in the face-ceniexed cubic lattice, as shown in Fig. 1.6C. Face diagonals lying on the reverse faces of the cube are not counted in this total because each is parallel to a direction lying on a visible face, end, in considering ccystallographically significant directions, parallel directions ave the same. It jointed out that the face-centered cubic structure has four \tahedral planes. This can be verified as follows. If an atom is ‘of the comers of a unit cell ia'a manner similar to that of Fig. LSB, an octahedral plane will be evealed in each instance. There act eight of these planes, but since diagonally opposite planes are parallel, they are ceystallographieally equal, This reduces the number of different octahedral planes to four. The fase-centered cubic lattice, however, is unique in that it contains as many_as four planes of closest packing, each containing three ‘Tha Structure of Meta Fig. 1.7. Atomic arrangement in the octahedral plane of a faca-cantared cubic metal. Notice thst the atoms have the closest possible packing, This same configuration of atoms is also observed in the basal plane of close-packed hexagonal crystals. The close-packed directions are aa, band ce se-packed directions. No other lattice possesses such a large number of tlose-pucked pl cloted-packed directions, This fact is important, since it ives face-centered cubic metals physical properties different from those of other ‘metals, among which is the ability to undergo severe plastic deformation 1.8 Comparison of the Face-Centered Cubic end ClosePecked Hoxagonal Structures. The faco-centered cubic lattice can be constructed by frst arranging atoms into numberof close-packed plans, similar to that shown in Fig. 1.7, and then by stacking there planes over each other in the proper sequence. Thers are s numberof ways in which planes of closest packing ean be 6 slose-packed hexagons tice, another the ice. That there ie more than one vay” of stacking jane can bast dowa on a previous one consider the close-packed plane of atoms in Fig. 18. The canter of each atom in the figure i indicated by the symbol A, Now, if single stom i placed on top ofthe configuration of Fig 1.8, it will be attracted by interatomic forces into one of the nstural pockets that occur between any three contiguous atoms. Suppose that it falls into the pocket marked By at the upper let of the Aigue; then a second atom cannot be Aropped into either Cy or Cy because the atom at By overlaps the pocket at these two points. However, the second atom can fall into By of and start the formation of a second close-packed plane consisting of atoms occupying all B‘ovPhysiat Metaturgy Princes Fig. 1.8 Stacking sequences In close-packed erystal structures. postions. Altemativly, the second plane could ave been set down in such « aaenseo il ony C postions. Ts i the fest close-packed lane cecple A ease secon plane ey Setpy HC poston, Lat us asume that te see lan tas the B contgration. Tne the pockets ofthe sozond plane fl inf over ING centers ofthe afoms in the fst plane (4 postions) and half over the C pockets in the first plane, The dtd plane nay now beset down ovr the Second plane fato oither Aor C postions. IF set down into A positions, the Sams inthe tid layer fall cree over ator i the fis ayer. This isnot the facecentred eubic order, but that of the close-packed hexagonal structure. The facecentored cubic stacking order is: A forthe frst plana, for the second plane, and C forthe third plane, which may be weitten as ABC. The fourth plane In the fucecentered cubic latice, however, does fall on the A position, the ith fon B, and the sixth on C, s0 thot the stacking order for faceeentezed cubic cxystals is ABCABCABC ete. [athe lse-packed hexagonal steucture, the atoms in every other plane fall directly ov ther, corresponding to the stacking order ABABAB. “Theres no bask difference in the packing obtained by the stacking of spheres in the face-centered cobic or the close-packed hexagonal arangement, Since both give an ideal close packed structure, There is, however,» marked the physical properties of hexagonal elote-packed metals Taguesium) and the face-centered exbic metals in ne structure, The most Stsking differenn od planes, In the face centered ubielatice there are four planes of closest packing the octahedral planes; but fn the close-packed hexagonal lattice only one plane, the Basal plane) is fcivalent to” the octahedral plane, The single closepacked plane_of the hexagonal lattice ergunders, mong other tags, liste deformation properties iat are much more diteotional than those Found in eubie crystals. “Tho Structure of Matas 4.9 Coordination Number of the Systoms of Closest Packing. “The ooordination number of an ator in a crystal has been defined as the number (of nearest neighbors that it possesses. This number Is 12 for both face-centered ccuble and close-packed hexagonal crystals, as may be verified with the aid of TS. Thus, consider atom Ay lying in the plane of atoms shown as circles wn with continuous lines. Six other atoms lying in the same close-packed plane as Ag are in nearest neighbor positions. Atom 4 also touches thees atoms ‘in the plane directly above. These three atoms could occupy B positions, as indicated by the dashed lines around pockets By, B2, and By, of they could ‘occupy positions C;, Cy, and C,_In ether ease, the number of nearest neighbors in the plane just above Ag is limited to three. In the same manner, it may be shown that Ay has three nearest neighbors in the next’ plane below the close-packed plane containing Ao. The number of nearest neighbors of atom Aa are thus twelve in gumber: six in its own plane, three in the plane above it, and tluree in the plane below it, Since the argument is valid no matter whether the atoms in the close-packed planes just above or below atom ag are in B or C positions, it holds for both face-centered cubfe and close-packed hexagonal stacking sequences. We conclude, therefore, that the coordination number in ‘these lattices is 12 1.10. The Unit Cell of the Close-Packed Hexagonal Lattice. The configuration of atoms most frequently used to represent the close-packed Ihexagonel structure is shown in Fig. 1.9. This group of atoms contains more than the minimum number of atoms needed to form an elementary building block for the lattice; therefore itis not a true unit cell. However, because the arrangement of Fig, 1.9 brings out important crystallographic features, including, - ACA ie silava wri compee (o00!) , (Lof0) -plano basal Need 12 -diecdo + compacta Bf{is2o] a 2 tipo: plano frismetico Tipe 2 -2¢q embilha ments AGAR Fig. 1.9 The close-packed hexagonal unit cell the sixfold symmetry of the lattice, i ix commonly used asthe unit cel of the close-packed hexagonal structure. A comparison of Fig. 19 with Fig. 17 shows that the atoms in the planes at the top, bottom, and center of the unit esl belong toa plane of closest packing, the(basalplanslof the crystal. The figure ako shows that the atoms in these basal planes have the proper stacking2ppoysiea Metallurgy Prineltos sequence for the hexagonal close-packed lattice (ABA ...); atoms atthe top of the cell are directly over those at the bottom, while atoms in the central plane hhave a different set of positions. "The basal plane of a hexagonal metal, like the octahedral plane of a face-centered cubic metal, has Unree close-packed directions. These directions ‘correspond to the lines aa, Bb, cc of Fig. 17. 1.11 Anisotropy. When_the properties independent of direction, the material sad to be isotropic. Thu, itu aerial, ove should expect to find that it has the same strengt ‘Oecif its eleticl resistivity were to be measured, the same value of {his property would be obtained irrespective of how 2 resistivity specimen was tut from a quantity ofthe mater. The physiesl properties of crystals normally depend strongly on the direction along which they are measured. Thismeans that, bastally, erystals are aot irotropi, but anisotropic. To this regard, consider body-contered cubic crystal of iron, The three most important directions inthis ciysal ae the ditections labeled a, 2, and in Fig 1.10. That these directions Sre not equivalent canbe recognized from the fact thatthe spacings of the atoms slong the tives ditection ar different, boing equal respectively, i terms ofthe Inteice parameter a (the length of one edge of the nit cel), a, 2a, and ‘Va. The physical properties of roa, measured along these three directions, aso tend to be eifferent, As an example, consider the B-#f curve for the Fig. 1.10 The most important directions in a body-centared cubic crystal. ‘Tha Structure of Mataa/12 25,000 20.000 15,000] 10,000) 5,009} Fig. 1.11 An iron exystal is much easier to magnetize along an a direction of Fig. 1.10 than along ab or e direction, (Atter Barrett, C. S,, Structure of Metals, .453, New York: McGraw Hill Book Co., 1943, Used by permission.) ‘magnetization of iron crystals. As may be seen in Fig. 1.12, the magnetic induction & rises mest rapidly with the magnetic field intensity H along the direction a, at an intermediate rate slong 6, and last rapidly along c.Intorpreted ‘in_another way, we may say thet ¢ is the direction of easiest magnetization, hile ¢ is correspondingly the most difficult. Tdealy, a polycrystalline specimen might be expected to be isotropie I its crystals were randomly oriented, for then, from a macroscopic point of view, the anisotropy of the crystals should be averaged out. However, a truly random arrangement of the crystals seldom achieved, because manufacturing procsses tend to align the grains in a metal so that thei orientations are not uniformly distbuted, The reel is what Is known a a texture or a preferred orienta Because most polyenytaliine metile have #prefcred ofentation, they tend to ‘be anisotropic, the degree of ding on the depree of exysal alignment. 1.12 Textures or Proferred Orientations. Wires are formed by pulling rods through successively smaller and smaller des. In the case of iron, this kind of deformation tends to align a B direction of each crystal parallel to the wire axis. About this direction the exystals are normally considered to be‘a/eyseat Metatlrgy Princes ww a Fig. 1.12 Two basic crystalline orientations that can be obtained in rolled plates of body-centered cubic metals. randomly ange Thi typeof preted arangeient ofthe yas na eon aa rere spore ven i the malls ge heat testa that oe A atthe op srr, he et tnd fo Kxp ab dietion sare fe wes, Browse the dfoaton use in orig sheets ane air Saealy svodersionl in starter, te prefered onan ound aan ture rete than that obseed in wis. AB indted in wea ot aly dos ne fon to nda deton peal 1 the ong ae ana te lt, but there alo 9 stong tendency for a cube ae ce atthe uni cay fo be lige orl tothe rong ane oc Sova ofthe ses or plat. hoe are number of esons why an understanding of e-ytlproperte impetnt tote meat Gre of tize that tho basic ansekopy of inthe nto reected nthe poe objects of comme, I Rola be tote ake tet tos not aways undesieble, Pref onetatons 2. Receystaliatnn olowlae cole Work I discussed in Chapa 7. ‘The Swuctuce of Metls1S can offen cesult in materials with superior properties. An interesting example of this sort is found in the alloy of iron with 4 percent of silicon, used for making transformer coils. In this case, by a complicated combination of rolling procedures and heat treatments, itis possible to obtain a very strong preferred ‘orientation in which an a direction of the crystals is aligned parallel to the rolling izection, while a cube plane, or face of the unit ell, remains parllel to the rolling plane. This average orientation is shown schematically in Fig, 1.12B, The significant featule of this texture i that it places the disection of easy ‘magnetization parallel to the length of the sheet. In manufacturing transformers, it is then a rather simple matter to align the plates in the core so that this diveetion is parallel to the direction along, which the magnetic ux runs. When ‘this occurs, the resultant hysteresis loss can be made very small 1.13 Miller Indices. As one becomes more and more involved in the study of erystals, the need for symbols to describe the orientation in space fof important crystallographic directions and planes becomes evident. Tiaus, while the directions of closest packing in the body-centered e may be dsscbed as the diagonals that tavéee the unit ell, and the conesponding “Girections in the face-centered cubic lat igonals that eross the faces {CS thuch easier to define these dizections in terms of several simple integers. The Miller system of designating indices for crystallographic planes and directions is universally accepted for tis purpose. In the discussion that fellows, the Biller indies for eubie and hexagonal crystals wil be consigered. ‘The indices for other eystal structures are not difelt to develop, but space considerations prechue their dcision of a cube, t Die Saeeoae ane eee ee ene system with axes parallel to the edge of the unit cal of a cubic costal (See Cubic Fig. 1.13.) In this coordinate system, the unit of measurement along all three Fig, 113 _The [111] and [101] directions in 9 cubic crystal directions m and 1, respectively.A ee 16/Physica eratlurgy Principles $ ) “ Fig. 1.14 (A) The four cube diagonals of @ cubic lattice, m, n, u, and v {8) The components of the veetor q zhatparaliels the cube diagonal p area, ~2, and a. Therefore, the indices of q are (141) axes is the length of the edge of a unit cell, designated by the symbol ain the Figure. The Miller indices of sections are introduced with the aid of several simple examples. Thus the cube diagonal m of Fig, 1.13 has the same direction fas.a vector £ with a length that equals the diagonal distance across the cell. The component of the veetor # en each of the three coordinate axes is equal to a. Since the unit of measurement along cach axis equals a, the vector has ‘components 1, 1, and 1 on the x, and 2 axes respectively. The Miller indices of the direction mm ate now written (111). In the same manner, the direction », which crosses a face of the unit cll diagonally, has the same direction as a vector 's the length of which i the face diagonal of the unit cell. The x, y, and = components of this vector are 1, 0, and 1 respectively; the corresponding Miler indices are [101]. The indices of the x axis are [100], the y axis [010] , nd the axis [ppt] ‘A general rule for finding the Miler indices of a crystallographic direction'can now be stated, Draw a vector from the origin parallel to the direetion whose indices are desired, Make the magnitude of the vector such that its components ‘on the thtce coordinate axes have lengths that are simple integers. These integers ‘must be the smallest numbers that will give the desired direction. Thus, the fntegers 1, 1, and 1, aid 2, 2, and 2 represent the same direction in space, but, by convention, the Miller indices are [L11} and not [222] Let us apply the above rule to the determination of the Miller indices of a second cube diagonal; that indicated by the symbol p in Fig, 1.14. The veetor @ (witich starts at the origin in Fig. .14B) is parallel to the direction p. The components of q ae 1, —I, and 1, and, by the sbove definition, the “The Severe of Matas 17 2. ple Chat) fawihic: {hh Co.e.wl 1 Chet) ush Us wee Fig. 1.18 The intercepts of the (623) plene with the coordinate axes. corresponding Miller indices of p ate [111] where the negative sign of the y index is indicated by a bar over the coresponding integer. The indices of the diogonal min Fig. 1148 have already been shown tobe [111], and itray also be shown that the indices of the diagonals w and v are (111] and [111]. The Tour cube diagonals thus have indies (111), [111], (111, and (117). When specific erystallographie erection i refered to, the Miler indies are enclosed in square brackets as above. However, itis sometimes desable to refer to al ofthe directions of the same frm, Ia this cate, the indices of one of these directions ate enclosed in caret (1), and the symbols read to signify all four directions ({111], [111], [111], and. (L11]), which are considered as a class ‘Thus, one might say thatthe clore packed dictions in the body-centered eabie lattice are 11 directions, whereas a specific crystal might be stresed in tension along its (111) direction and simultaneously compressed along its (1T1] alieztion. ‘Cuble Indices for lanes. Ceystallopraph planes are als identified by sets of integers. These ace obtained from the itorcepts tha the planes make withthe coordinate axes. Ths, in Fig. 1-15 the indieated plane intercepts the x y, and z Plano: | ee gon hd ¢ i d im Bice es | : PS oro)” Le 270 : # o 1 © Fig. 1.16 (A) Cube planes of a cubic crys (8) The (011) plane, (C) The (111) plane.regia do Plano: iver ° eteted Ky sat fee. Chee) o/s tale Prince axes at 1, 3, and 2 unit-cell distances respectiely. The Miller indices are proportional aot to these intercepts, but to their eeciprocals Y's and, by Aetnition, the Miller indices are the smallest integers having the same ratios 63 these rexiprocals. The desied integers are, therefore, 6,2, 3. The Miler indies fof a plane are enclosed in perenthees, for example (623), insted of brackets, ths making it posible to differentiate between plants and direction. “Lat us now determine the Miller indices of several important planes of cubic crystals. The plane ofthe face @ of the eube shown in Fig. 1.16A is parall to both the yr and z axes and, therefore, may be said to intercept these axes at infinity. ‘The x intercept, however, equals 1, and the reciprocals of the three intercepts are 1, Yur Yo» The corresponding Miller indices are (100). The indices of the face b are (10), while those of ¢ are (001). The indicated plane of Fig. 1168 has indices (011), and that of Fig. 1.16C (111). The later plane i an octahedral plane, as siay be seen by refering to Fig 1.7. Other octahedral planes have the indices (11), (171), and (LID, where the bar over a sit represents a negative intercept, BY way of illustration, the (111) plane s shows in Fig 17, where it mey be seen thatthe x intercept is negative, whereas they and 2 intercepts are positive, This figure also shows that the (171) plane parallel to the (I11) plane and is, therefore, the same crystallographic plane. Binal, the indices (11) nd CT) represent the same plans as (11) and (uy “The set of planes of a given form, such a the four octahedral planes (11), (111), (111), and (111), are represented as a group with the aid of braces tncising one of the inlee, that is, (111). Thus, if one wishes to refer to a Specific plane in a crystal of known orientation, parentheses are used, but if the class of planes eto ba rferred to, braces are used. Fig, 1.17 The (111) and (171) planes are peraliel to each other represent the same crystallographic plan “The Structure of Metals ‘An important feature of the Miler indices of cubic erystls is thatthe integers of the indices of a plane and of the dieet ‘to the plane are identical Ths, face a of perpendicular to this plane, has indices [100]. In the same manner, Detahedral plane of Fig 1.16C and its normal, the cube diagonal, have i (111) and [111] respectively. Noncubie crystals do not, in general, possess this ‘equivalence between the indices of planes and normals to the planes. Miller Indices for Hexagonal Crystals. Planes and directions in hexagonal metals are defined almost universally in terms of Miller indices containing four digits instead of three. The use of a four-digit system gives planes of the same form similar indices, Thus, in a fosradigit system, the planes (1120) and (1210) ‘are equivalent planes, The three-digit system, on the other hand, gives equivalent planes indices that are not similar. Thus, the above two planes would have indices (110) and (120) in the three-digit system. Fourdigit hexagonal indices are based on a coordinate system containing Four ‘axes, Three axes correspond to close-packed directions and lie in the basal plane ff the crystal, making 120” angles with each other. The fourth axis is normal to the basal plane and is alled the ¢ axis, wheteas the thee axes that jie in the basal plane are designated the a1, a2, and a3 axes. Figure 1.18 shows the hexagonal unit cell superimposed upon the fouraxis coordinate system. It is ‘customary to take the unit of measurement along the ay, a3 andl ay axtsas the Gistance between atoms in a close-packed direction. The magnitude of this unit js indicated by the symbol a, The unit of measurement for the ¢ axis is the height ofthe unit cell that is designated a Let us now determine the Miller indices of several iniportant close-packed hexagonal lattice planes. The uppermost surface of the unit cell in Fig, 1.19 the cube in Fig. 1.1GA has indices (100), and the x axis, the pS Fig. 1.18 The four coordinate axes of a hexagonal erystbaw srewshie Situated 48 ordem. (LOE ae ordern (1132) (rego: eres etary Princes : Tire To To) st direcots ‘po T (lolol [tijo Z- (4120) 4. 4 directs figo T [ello] " (ooo1) ' oe oH ieteat is 1g Fig. 1.19 The (1072) plane of a hexagonal metal. corresponds to the basal plane of the crystal. Since it is paalel to the axes. a, 4, and ay; it mst intercept them at infinity. Its c wes intercept, however, IS ‘equal to 1. The reciprocals of these intercepts are Vo Yo, You and ‘A. The Miller indices of the basal plane are, therefore, (0001). The six vertical surfaces ofthe ‘unit ell are known as prism planes of Type I. Consider now the prism plane that forms the front face ofthe cell, which has intercepts as follows: a: at 1,3 at, dy at —1, and ¢ at is Miller indices are, therefore, (1010). Another important type of plane in the hexagoral lattice i showa in Fig. 1.19. The intercepts are as, at I, a3 at,a, at 1, and cat 14, and the Milles indices are accordingly (1012). Miler indices of directions are also expressed in terms of four digits. In “writing direction indices, the thd digit must always equal the negative suon of the first two digits. Thus, if the frst two digits are 3 and 1, the thd must be =A, that i [3140]. ‘Let us investigate directions lying only in the basal plane, since this will simplify the presentation, If» dzection les in the besal plane, then it has no component along the © axis, and the fourth digit of the Miler indices will be 'As our first example, lt us find the Miller indices ofthe a, axis. This axis hat fhe same dicection a the vector sum of three vectors (Pig. 1.20), one of length 42 along the a, axis, another of length —t parallel to the ay axis, and the tied of Jength ~1 parallel to the a, axis. The indices ofthis direction are, accordingly {2110}. This unvisldy method of obtaining the direction indices fs necessary in order thatthe relationship mentioned above be maintained between the frst tO digits and the third, The corresponding indices ofthe ds and ay axes are (1210] and [1120]. These * digonal axes of Type f. ‘Another impor rections lying in the basal plane are the digoal axes ‘of Type Uz a set of axes perpendicular to the digonal axes of Type I. Fig. 1.21 shows of of the axes of Type II and indicates how its direction indices are ‘The Structure of Metas/24 liners Tye L 4 = Bed) Fig, 1.20. Determination of indices ofa digonal axis of Type t — 12110) duces Ty fe z 4 ota Fig. 1.21 Determination of dices of a digonal axis of Type 1! — [1010] determined. The vector 5 in the figure determines the desired direction and fequale the vector sum of a unit vector lying on aj, snd another parallel to 03, but measured in a negative sense, The indices of the digonal axis of Type Il are thus [1070]. In this eae, the second digit is zero because the projection of the vector son the as axis is 2er0. 1.4 Grystal Structures of the Morac Elements. Some of the snost important metais ae classified according to their crystal structures in Table 1 ‘A.ruember of metals are(FOIVRORpHTG) that is, they crystallize fn mersage wc _22pevysia tallrgy Preis ‘Table 1.1 Crystal Structure of Some of the More Important Metallic Elements. Faceccncred cubic ——_‘Cosepacked hesaponal Hodcentred cuble Tron 10°C 10 1400") apres Copper Zine silver Titer Geld Zieoniase ‘barium Berlin Molybienam Nickel Cadi Chromium asd ‘Akal Metals (C1,Na, Ky Platine b,c) Patinwm Iron (alow TaM0"C 10 1539°C) “Tungsten Vanadium ~ one sicustuse, The most important of these Is irom, which crystallizes os either Dody-cenlered cubic or face-centered cubic, with each structure stable in ‘separate temperature ranges, Thus, at all temperatures below 910°C and above 1490°C to the melting point, the preferred crystal structure is body-centered ‘cubic, whercas between 910°C and 140°C the metal is stable in the face-contered cubic structure. 1.15 The Stereogaphie Projection. The steeographic projection in soful metilurgial too, for t permits the mapping in two dimensions of crystallographic. planes and directions ina convenient and straightforward runner, The real value of the method & attained when i is posible to visualize Cryttallogaphicfeetues éiretly in terms oftheir stereographic projections. The Durpore of this section is to concentrate on the geometrical correspondence between erysalographe planes and geetons and their streographic prolec- tions, In each cae, a sketch ofa certain crystallographic Feature, in terms ofits location inthe unit ell, i compared with its coresponding sterographle projection. ‘Sever simple examples will be considered, but before this is doe, attention wi be called to several pertinent facts. The slereographic projection is a {wodimensional drawing. of three-dimensionsl data. The geometry of ll Crystallographic planes and directions are accordingly reduced by one dimension. Planes are platted a great cele line, 2 sare plotted as points. Als, {he normal to a plane completely deerbes the oventation ofa plane “Ae our first example, consider several of the more important planes ofa cubic lattice: specifically the (100), (110), and (211) planes. All three planes are treated inthe thee pats of Fig, 1.22. Notice that ographle projetion ‘teach plane can be represented lier by a peat circle or by a point showing {he direction in space that s nonma to the pane. Misay crystallogrephic problems can be solved by considering the stereo- “The Sructre of Mate 23 oro {0c oreen {ie} orc Tope Fig, 1.22. Stereographic projections of several important planes of a cubic “tal, (A) Cubie system, the (100) plane, ine oF right along the {100} diretion. {E) Cubic aystem, the (110) plane, tine of sight along the [100] ree: TC) Cuble system, the (171) plane, line of sight along the [100] direction. ection. graphic projections of planes and ditections in a single hemisphere, that i, fhotmally the one in front of the plane of the paper. The thee examples given in Fig. 122 have all been plotted in this manner. If the need arises, the steeographie projections in the rear hemisphere can also be plotted in the same diagram. However, itis necsssary that the projetions inthe two hemispheres be distinguishable [rom each other. This may be accomplished ifthe streographic50) ros nZowa 2AiPeysicat Metallargy Principles orren : j A c7 NY 8) Sra 1 inn pe ane Fig. 1,23 Cubic systam, the (120) plane, showing the stereogrephic projections ‘from beth hemispheres Hine of sight the [100} diceetion.. projections of planes and directions inthe Forward hemisphere are drawn ax solid lines and dots respectively, while those in the rear hemisphere are plotted as dotted lnes and ctled dots respectively, Asan iustraton, considee Pig 123, in Which the projections in both hemispheres of a single plane are shown. The (120) plane ofa cubic lattice is used inthis example 1.16 Directions That Lie in a Plane. Frequently one desires to show the positions of certain important crystallographic directions that lie in a particular plane of 2 crystal. Thus, in a body-centered cubie exystal one of the ‘more important planes is (110) and in each of these planes one finds two close-packed (111) directions. The two that lie in the (101) plane are shown in Fig. 1.24, where they appear as dots lying on the great circle representing the (101) plane. ate ee ee lee etna ie we 2 compen deco fom he aes ye ( (oh ep od a) Pane (0 on Fig. 1.24 Cubic system, the (101) plane and the two (111) directions thet lie in this plane, line of sight [100]. “The Structure of Mtae/25 “ apo free Wm 5 Hoy fo St e hleat Fig. 1.25 _Cubie system, zone of planes the zone axis of wihich is the (111] direction. The three {110} planes thet bolong to this zone are illustrated in the ‘above figures. FFiguee 1.25 shows that there are thyee (110) ection. There are slso three (112) planes, and six (123) planes, es well as a ‘number of higher indice pla have the same zone axis. The pertinent (112) and (123) planes are shown in Fig. 1.26, whereas the stereographie projection of these and the sbove-mentioned (130) planes are shown in Fig. 1.27. Notice that nth nies Ogre oly the poe of he pan ed. nd goat Socal-ore ie es fall reat clecle representing the stereographic aoe of the (111) plane. 1.18 The Wulff Net. ‘The Wulff ner is astereographic projection ‘of latitude and longitude lines in which the north-south axis is parllet to the plane of the paper. The latitude and longitude lines of the Wulff net serve the sume function #8 the corresponding lines on a geographical map or projection; that is, they make possible graphical messurements. However, in the st ple json we pinay Inserted ensign wee i distarice that is usually more important, A typical Walt menlona nt drown to Inert eshove in Fig, 128, Attention is now called to several fects cbout the Wulff net. Fest, all meridians Clongitude lines), Je basic ceclo, are great cicles. Sssond, it nes that passthrough the [11 ‘the equator is nde lines are small_cteles. Third, angular distances between poinfs representing directions in gpace can_be a) 20 302o(Physicl Metlaray Pringles i oe “The Structure of Mota/27 ‘rae thvae (012) type planes fg (12) Plane ype planes ar | Ben ! Grey ‘ ea 4 Gen oda ba fas} Pole Gra (23) ona a1) 7432) ond 230) oy Grejons en lanes Plows Pines ean. Fig, 1.28 Wolf, or meridional, stereographic net dravn with 2° intervals measured on the Wulff net only if she points dire of then. Tee odlng of many crystallographic problems, tis frequently necessary to satus #storenpepale projection cortesponding ta gven crystal rzntaion {nova diferent enlentaion. This i done fora number of reasons. One of the eC portant Bs to being experimentally measured data ito. a standard Projection where the base ce Is simple lox-packed plane sch as (100) oF Fig, 1.27. Stereographic projection of the zone containing the 12 planes shown (111). Deformation markings, or other experimentally observed crystallographic in Figs. 1.25 and 1.26. Only the poles of the planes are plotted. Notice thar all phenomena, usually can be more readily interpeeted when stadied in texms of ‘of the planar poles fein the (111) plane. standard projections._20/P sical Natllury Princip BA. Fig. 1.29 Rotation about the canter of the Wutff net, (A} The effect of the Aisired rocation on the cuible unit eel. Line of sight [100]. (B) Perspective view ‘of the (111) plane before and after the rotation (C) Steraographic projection of the (171) plane and its pole before and after rotation. Rotation clockwise 45° about the [100] direction. In solving problems with the aid of the Wulff net, itis eustomary to cover it With a piece of tracing paper. A common pin is then driven through the paper and into the exact center of the net, The popes, thus mounted, serves asa work sheet on which erystallographic data are plotted. The following two types of rotation of the plotied data are possible. Rotation about an Axis in ihe Line of Sight. This cotation is exsily performed by merely rotating the acing paper, relative to the net, about the pin. As an example, let us rotate a cubic lattice 45° WX divection at an axis” Tit. colation as the effet of placing the pole of the (111) ue dives plane, as olated in Fig.1 22C, oa the equator of the Wolff net. Figure 129A x08 shows the effect of the desired rotation on the orientation of Use cubic unit cell “The Structure of Mot/29 (os), oa ee seen Tee ent Fig. 1.20 ‘Rotation about the north-south axis of the Wulff net. (AD Perspective viows of tho unit cell before and after the rotation showing the frientation af the (710) plane. (B) Stereographic projection showing the above rotation. For the sake of clarity of presentation, only the (710) plane is shown. ‘The rotation of the pole is not shown. Also, the meridians of tha Wulff net are omitted. witen the cell i viewed slong the [100] dcection. Note that because the basi circle represents the (100) plane, a simple rotation of the paper by 45° about the pin produces the desired rotation in he stereographic projection. . Rotation about the North-South Axis of the Wulff Net. This rotation isnot 3°) & ss simple 1o perform as tat given above, which canbe ceconpisted by merely stage rotating the work sheet bout the oin. Rotations of this seeond pe a hy accomplished by a graphical method, The data are first plotted stereographically * fnd then rotated along atiude lines and veplotted in such manner that each 210 NS Point undergoes the sae change in longitude, The method wil be quite evident 42e tone considers the drawings of Fig 1-30 In the pres that the forward face (100) 0 Hectian an axl Cone ‘cientation and steréographic projection of the (110) plane. In Fig. 130A, the tights and lefehand drawings represen the cubic unit cll before and after the Totation respectively. Te eect ofthe rotation on the stereographe projection of the (110) plane is shown in Fig. 1.30B. Each of the curved arrows shown in this drawing epreents a change in ongtede of O°, In there drawings, the pole of the (110) plane is not shown in order to simplify the presentation. The rotation that the (110) pole undergoes is shown, however, in Fig. 131. ‘By usig sim examples, che two bese rotations that can be made when the ‘Wulff net bused have been pointed out above. All porbl rotations of «esta In three dimension ean be duplistd by ving these rotations on a streographie rojection,(Physical Matalteray Principe Fig. 1.31 The rotation of the pole of the (110) plane is given above. The iagram on the left shows the rotation in a perspective figure, whereas that on the right shows the motion of the pole along a latitude line of a stereogrephic projection which, in this ease, isthe equator. Fig. 1.32 A 100 standard stereographic projection of « cubic ervstal. “Tho Structure of mera 1.19 Standard Projections. A stereographic projection, ia which «4 prominent crystallographic direction or pole of an important plane Ties at the ‘center of the projection, is known asa standard stereographic projection. Such « projection for a cubic cxystal is shown In Fig. 1.32, where the (100) pole i ‘assumed to be normal to the plane of the paper. This figure is properly called standard 100 projection of a eubic crystal. In this diagram, note that the poles of| all the {100}, (110), and (111) planes have been plotted at their proper orientations. Each of these basic crystallographic directions is represented by = characteristic symbol. For the (100) poles, this is a square, signifying that these poles correspond to fourfold symmetry axes. I the crystal is votated 90° about ‘any one of these directions, it will Be retumed to an orientation exactly ‘equivalent to its origital orientation. In a 360° rotation about a (100? pole, the ‘crystal reproduces js original orientation four times. tn the same fashion,» (11D sponds to a three-fold symmetry axis, and these ditections ae Fig. 1.83 A 100 stondard stereographic projection of a cubic erystal showing adgitional poles._2nysio! Mataturgy Princo Fig. 1.34 A111 standard projection ofa cubic crystal indieated_in the steeographic projection by triangles. Finally, the two-fold ty_af the (10) directions is indicated by the use of small ellipses to designate thei postions inthe st tion. fore complete TOD slandrd projection of «cable cyt shown in ig, 133, This includes the poles of other planes of somewhat higher Miller indices, Fig, 133 can be considered to be. elther 2 projection showing the “icections ina eubie crystal ar the-poles of i plans. This is because ina cubic ‘aytal, a plane is always normal tothe direction with the same Miler indices. Ia ‘Fenaponal close pecked erystal, however, the projection showing the pols of the planes isnot the same as one showing crystallographic direction. "AIL standard projection is shown tn Fig. 1.34 that contains the sume poles a the 100 projection in Fig. 1.33. The threefold symmetry of the crystal Structure about the pole of a (111 plane i clearly evident in this figure. At the Same time, attention i called to the fact chat the 100 projection of Fig. 1.33 also plainly eevee te four-fold symmetry sbout« 100% pole. ‘The Suucture of ews/33 Fig. 1.36 The orystellographie directions ay, 23, and ay shown in this standart projection are equivalent because they lie in similar positions inside thelr Fespective standard stereagraphie triangles. 1.20 The Standard Stercosraphie Triangle for Cubie Crystals ‘The great circles comesponding tothe {100) and (110) planes of a cubic erystal axe also shown in the standard projections of Figs. 133 and 134. These great ‘decles pass through all of the poles shown on the dsgram except those of the G2) planes. At the same time, they divide spherical tangles. These spherical tangles alle in the forvard hemi ‘the projection. There are, of course, 24 similar teangle in the rea Hemisphere ‘An examination of the triangles ouilined,in Figs. 133 and 134 shows an interesting fa x an onmed by 1) divetion, “« 1105 diestion, and a WOO) direction, This is a hishly _signffeant obssraation, see it meats that each triangle corresponds, to a region of the crystal tht is equiv 5 that the thre lntice dections, marked ay, az, and ay, and shown in Fig. 1.35, re erystallograph. ically equivalent, beceuse they are located atthe same relative postions inside three stereogaphlc tolangles. To illustrate this point, let us asume that it is24/ehysieal Metallurgy Princilae Fig. 1.38 When itis necessary to compare the orientations of # number of crystals, this often ean be done conveniently by plotting the erystal axes in a single storaograpic triangle, as inicated inthis figure possible to eut throe tensile specimens, with axes parallel to ‘of a very large single crystal. If now tensile tests were t ‘ee smaller erystals, one would expect to get identical the three specime if some other physical property, sich as the electrical zesstivity, were to be measured along these three icections. The plotting of crystallographic dais is often simplified because ofthe tequivalence of the stereographic tangles. For example, if one should have a lange number of long, cylindrical crystals and wishes 10 plot the orientations of the individual crystal axes, this can be done conveniently in a single stereographic triangle, 28 shown in Fig. 1:36. and a3, out Problems 1, Moke 4 drawing of the cubic unit cell in which are shown the close-packed directions of the body-contered cubic crystal. Label all of these directions with theie proper direetion indices. 2, In the same manner as in Problem 1, draw a unit call om which are superimposed the close-packed directions of the face-centered cubie orystal structure, Identify each direction with its proper direction indices. 3. Fig. 1.25 shows three planes of the form (110) How many planes of this type are there in all? In sketches similar to those of Fig. 1.25 show the remaining (110) planes and label esch with its Miller indices. 4, There are 12 planes of the form (112). Three of these are shown inside a ‘cubic unit cell in Fig, 1.26. Draw similar sketches showing the other nine, Label etch with its proper Miller indices. 1 Note that the (1120) direction i |. The (1121) and (1132) planes are important with sega “Tho Structure of Metae35 ‘This diagram shows the Thompson Tetrahedron, a geometrical figure formed by the four cubic (L11 planes. Identify each plane by its proper Miller indices. Would this figure be of more significance in regard 10 showing important crystallographic features in the body-zentered cubic crystal structure or the face-centered cubic rystal structure? Explain, considering both the surfaces and the edges af the tetrahedron, ‘The hexagonal close-packed planes of the type (1010) are called prism planes of Type J. How many of them are there and what are their indices? ‘What is the significance of these planes relative to the hexagonal unit cell shown in Fig. 1.19? - Draw a hexagonal unit cell and show the orientation in this cll of the plane {110}. This a prism plane of Type I. How many prism planes of Type Tl are thore ad what are thet indices? Show that» sbsided prism ean alo be formed using prism planes of Type I ormal to the (1130) plane. However, (O72? isnot perpendicular to (1012). Show that this is eve geometrically Jn a hexagonal unit ce, draw in the (1012) and the (1OT1) planes. Aso draw in the {1012} and {10TTI dicetions. How are these planes and dlveotions selatea? oformation mechanisms in certain hexogonal close-packed met titanium and citconium, Show the orientation in the unit cell of one plane ‘of each type.oc (Physical meta an Identity the dicestion indices of the line ¢—b shown in this unit cell. This Sine lies in three important planes. Identify them Stereagraphie Projection “The following problems involve the plotting of stereographic projections and require the use of the Wulff net, shown in Fig. 1.28, and e sheet of tracing psper. Tn each case frst place the tracing paper over the Wulff net and then mark the ‘center of the net on the tracing paper with adot, Next, trace the outline of the ‘basic circle and place a small vertical mark at the top of the cile to serve as an 7 | 12, Place the tracing paper so that the basic citee is aligned with the perimeter of the Wulff net and the index mark falls over the north pole of the net. Now assume that a cubic crystal is viewed from ebove slong the = axis, as indicated in the figure. Plot the position of the poles ofall the (100) planes and label thems properly on the diagram, 13, The basic circle in Problem 12 carresponds to what (100) plane? Draw in the great circles corrosponding to the other to (100) planes and label them ‘with their Miler indices 14, Plot the poles of all six (110) planes and label them, Now draw on the 15, 16. 17. 18 “The Structure of Motah37 projection the great cies orzesponding to these planes. A¢ this point you will have plotted a figure similar to that of Fig, 1.32, whichis standard 100 projection of the euble erysal. What standard projection have you plotted? How can you rotate the exystal shown inthe projection obtained atthe end of Problem 14 so that it wil be in a standatd 100 orientation? Show the paths that each {100 and #110} poe wl follow during this rotation. Plot a standard (0001) sereogrphic projection of a hexagonal close-packed czystal showing the poles of al prism planes of Type (IOTO!, ané Type 1, (0120), a well s the baal plane pole (0001). In the drawing of Problem 16, connect the baal plane pole to the prism plane. poles with great circles (straight ins). This will divide the Stcreographic projection into a set of speccal siagles. Examine those teangles and note if there is any similarity to thote shown in Fig. 1.31 for bie crystal Reconstruct the standard projestion of Problem 16, bul add onto thie Giagram the poles of all the (10TH, 11072), (1013), WOT), (1131, 0172), 411173), and (1124), using the data (or magnesium given in Appendit B. Tis will produce e pole figure for a hexagonal metal that shows most of te Important planes of this eysalstruetuce2 Diffraction Methods Because crystals are symmetrical arrays of atoms containing rows and planes of hhigh atomic density, they are able to act as three-dimensional diffraction ‘ee ratings. If light rays are to be efficiently diffracted by a grating, then the spacing of the grating (distance between ruled tines on & gating) must be approximately qual to the wavelength of the light waves. In the case of wile Tight, gratings with line separations between 10,000 and 20,000 A are used to aiffract wavelengilis in He rage from 4000 to 8000 A. In erystals, however, the Feparation between equally spaced parallel rows of atoms or atomic planes is much smaller and of the order of afew A units, Fortunately, low-voltage Xeays have wavelengths of the proper magnitudes to be clffracted by crystals, that, X-rays produced by tubes operated in the range between 20,000 end 50,000 volts, a8 contrasted to those used in medical applications, where velages exceed 100.000 wots When Kays of a given frequency strike an atom, they interact with its clectrons, causing them to vibrate with the ftequensy of the X-ray beam. Sines the electrons become vibeating electrical charges, they reradiate the X-rays with no change in frequency. These reflected rays come off the aloms in any Gitection, in other words, the electrons of an atom “scatter” the X-ray beam in all dictions. ‘When atoms spaced at regular intervals are radiated by a beam of X-ays, the seatlered_radiation undergoes, werference. In certain directions constructive directions. destructive interferes is struck by a parallel beam of X-rays, the beam undergoes constructive interference when the angle of incidence equals the angle of reflection. Thus, in Fig.2.L, the rays marked ay to ay represent 2 parallel ‘beam of X-rays. A wave front of this beam, whee all rays are in phase, is shown by the line 44. The line BB is drawn perpendicular to rays reflected by the atoms in a ditection such that the angle of incidence equals the angle of Teflection. Since BB lies at the same distance from the wave front AA_when ‘measured along any ray, all points on BB must be in phase. It is, therefore, a ‘wave front, and the direction of the reflected rays isa direction of constructive {nterference, 2 Diffraction Rathoo/38 Fig. 2.1 An X-ray beam is rellected with constructive interference when the tangle of incidence equals the engle of raflection. 24 The Bragg Law. The above discussion does not depend on ‘the frequency of the radiation. Howover, when the X-mays are reflected, not fiom an array of atoms arranged in a solitary plane, but from atoms on a number of equally spaced parallel planes, such as exist in crystals, then constructive Interference can occur only under highly restricted conditions. The luw that ‘governs the latter case is known as Bragg’s law. Let us now derive an expression for this important relationship. For this purpose, let us consider each plane of atoms in a erystal af a semitransparent mirror; that is, that each plane reflects 3 purt of the Xray beam and also permits part of it to passthrough. When X-rays strike a crystal, the bean is reflected not only from the surface layer of atoms, but from atoms underneath the surface to a considerable depth. Figure 2.2 shows an Xray beam that is being reflected simuttaneously from two parallel lattice planes, In an actual exse, the beam would be reflected not from just two lattice planes, but from a lazge umber of parallel planes. The lattice spacing, or istance between planes, is represented by the symbol d In Fig, 2.2, The line (04; is drawn perpendicular to the incident rays and is therefore » wave Front Points o and m, which lie on this wave front, must be in phase. The line oA, is drawn perpendicular to the reflected rays a, and a3, and the condition for 04,, to be a wave front is that the reflected cays must be in phase at points o snd r.40/Physical Mattar Prncpes ‘This condition can only be satisfied if the distance mpa equals a multiple of ‘complete wavelength, that is, it must equal 2 or 2A or 34 or mA where 2 is the ‘wavelength of X-rays and an arbitraty integer. ‘An examination of Fig, 2.2 shows that both the distances mp and pr equal sind. The distance mpm is, accordingly, 24 sin 0. IF this quantity is equated to toh, we have Bragg" law’ —— [d= 2d sing | where n= 1,2,3, A= wavelength in A = interplasar distance in A {6 angle of incidence or reflection of X-ray bear When the above relationship is satisfied, the reflected rays ay and.a3_will be in will result, Furthermore, the angles at which ‘onion, even avery sal deviation f 0's ie above relationship caves destructive inaoyance of the-refesibd ys, AE consequence, the selected boum leaves tie cyl ay capable of proding sary age of 0c on a photomapis TEC us how consider a simple example of an application of the Bragg ‘equation, Let us assume that the {110} planes of a body-centered cubic crystal fnve# separation of 1181 A. I these planes are iadiated wits Xeays from a {ube with a copper tage, te strongest ine of which, the Kay basa wavelength 1540 Ay fist ondee (n= 1) reflection wl our a as seg of 1 L { utof-detterh ay Culkin) as bene () [A second-order reflection from these {110} planes is not possibie with radiation of this wavelength because the argument of the are sin (h/2d) is, QyLs4o zien “°* 21.540) Wey 130 a number greater than unity, and therefore the solution is impossible. On the fer hand, a tungsten target ia an Xray gives a Kay line with a wavelength of 02090 A. ‘Eleven. orders of reflections are now possible. The angle 8, ‘corresponding, to several of these reflections, is shown in Table 2.1, and Fig. 23 shows a schematic representation ofthe same reflections Ditrsetion Mathods/ Table 21 ‘Onder of reflection 0 angle of eence or reflection 1 ss 2 wo 20" 5 26 40" n ow ne Order 11th order cient beams dn eran fio} rrenes Fig. 2.3 Certain angles at which Bragg reflections occur using a crystal with an interplanar spacing of 1.181 A and X-rays of wavelength 0.2090 A (WK, b. Jdering the above example, it is important to notice that, although oa eich cess ornare 05000 K ail bsseheced ‘wilt constrain interference fram the (10) planes, only a ey light eit le ane 8 away fiom any ofthese eleven values causes dasrstive inerference ana canellstion of the selected bean. Whether a beam of Xays reflected Troma set of cystllogzphic plies ths a seniveFunedon of te angle of the Xeey not be expected to occu cei 7 Cay Suppose hata cfstl i maintained ina Sxed erfeniation with respect tox beam of Xraye and thst ths beam 6 not mongchromaie bul_con ais all seovelengts longer than a given minimum rae hy This ype of Tony beam called a white Xray bean, since ts analogous to waite li ins all the wavelongis in the vile spectcum Although the angle ‘i ceed oa ges of plane in he ct ad hea Sonsan,refeetions from all pl cult tthe Xray’ beam iypc Mettargy Princes Let the X-ray beam have a minimum wavelength of 0.5 A, and let it make a {60° angle with the surface ofthe crystal, which, in tur, is assumed to be paralel toa set of {100} planes. In addition, let the {100} planes have a spacing of 1 A. Substituting these values in the Bragg equation gives m= 2d sind X= 2(1) sin 60" = 1.732 “Thus, the rays reflected from {100} planes will contsin the wavelengths L.732.A for fistorder reflection 0.866. for second-order reflection 0.546. for third-order reflection {Ail other wavelengths wil effer destructive interference in the above examples, the reflecting planes were assumed parallel to the ceytal surface. This is nota necesary requirement for reflection; it quite posible to abtain selections fiom planes hat make all anges with the surface, “Thos in Fig. 2, the incident beam is shown normal to the surface and a (001) plane, whit making aa ange 9 with two (210) planes ~ (O12) and (072). The Feflecions from these two planes are shown schematically in Fig. 24. Itmay be concluded thet when a beam of white Xays strikes » oystal, many rllecied Seams wil emerge from Ue crystal, each reflected beam coresponding to. Taflectign fom a different estalographic plane. Furthermore, in contrast io the incident beam thai & continuous in wavelength, cach reflected beam wil aly diperei wavelengths as prescribed by the Brag equ ornat locldent Norra teor eee ce Fig, 24 Xray reflections from planes not paraliel to the surface of the specimen. oer (or) | Diffraction Mathods/43 22. Lave Techniques. The Laue X-ray diffaetion methods make use of a crystal with en orientation that Is Axed with respect to a beam of continuous X-rays, as described in the proceding seotion. There ate two basic “Laue techniques: in one, the beams r n" r fe incident Xeuy beam afo sti; inthe other, the feflected beams that pass ‘through the crystal are studi ihe latter method cannot be applied to ‘estals of appreciabio thickness (1 mm or more) because ofthe losin intensity ofthe X-rays by thelr absorption in the metal. The first method is known as the Dackeflection Lave technique; te lattes asthe nansmision Love technique “The back-eflection Laue method is especially valuable for determining the ovientation of the lative inside crystals when the erystals are large and therefore bpaque to X-ays. Many physical and mechanical properties vary with direction inside crystals. The study of these anisotropic proportes of erystals requires @ knowledge of the lattice orientation in the erysal Figure 2.5 shows the arrangement of a typical Lave back-efletion camera, Xrays from the target of an Xeray tube ao collimated into 2 narzow bearn by a tube several inches long with an interaal diameter of sbout 1 mm. The narrow ‘beam of Xrays impinges on the crystal at the right of the figure, where itis diifzeted into a number of reflected bears that stike the cassette containing photographic film, The front of the cassette is covered with a thin shect of rnaterial, for example, back paper, opaoque to visible light, Dut tcansparent to the reflected Xray beams. n this way, the postions of the reflected beams are recorded on the photographie fn as an array of small dark spots. Figure 2.6A shows the backreflection Xay pattern of a magnesium crystal oriented so tat the incident Xcay beam was perpendicular tothe bas pane of the crystal. Each spot cortesponde to 2 zeflection from a single erystllographic fe sixfold symmetry of the lattice, wien viewed in a direct ir to the basal plane, is quite apparent. If the crysial is rotated ina. Floment Alected beoms target timated X-ray beam sssete for holding tmayenystet Maatury Pineioes ry Fig, 2.6 Laue back-reflection photooraphs. (A) Photogreph with Xray beam perpendicular to the basal plane (0001). (6) Photograph with X-ray beam perpendicular to a prism plane (1120). Dashed lines on the photograph are drawn to show that the back: reflection spots lie on hyporbolas. Girection away from the one that glves the pattern of Fig. 2.6A, the pattern of spots changes (Fig.2.6B); novertheles it still defines the orientation of the lattice in space. Therefore the orientation of the erystal ean be determined in terms of a Lave photograph. ‘Transmission Lave patterns can be obtained with an experimental rrange- iment similar to that for back-zeflection patterns, but the film is placed on the ‘opposite side of the specimen from the X-ray tube. Specimens may have the shape of small rods or plates, but must be small in their dimension parallel to the \ Reflected ‘eon eested pines Som Restecting lonae ww @ Fig, 2.7 (A) Laue backreflection photographs record the reflections from planes nearly perpenciculer to the incident X-ray beam. (8) Laue transmission photographs record the reflections from planes nearly parallel to the incident Xray beam. i Dithaetion termed Xray beam. Wheres the back-eflection techlque reflects the X-ay beam from planes nearly perpendicular tothe beam itself, the transmission technique records ‘the reflections from planes nearly pail to the beam, as ean be seen in ig. 27. Lave transmission photographs, like back-reflection photographs, consist of arrays of spots. However, the arrangements of the spots differ in the two methods: transmission patterns usally have spots aranged on elipes, bacle reflection on hyperbola. (See Fig. 2.6) ‘The Lave transmission technique, lke the baclerflection technique is also sd fo find the orientation of crystal lates. Both methods can be used to study a phenomenon ciled diieram. A-crsta that hs been bent, o otherwise ‘istoried, will have eurvedlatice planes that act in tie manner of curved isto ‘and form distorted or elongated spots instead of imal ciicular images of the ‘Xray Beam. A typleal Laue pattem ofa distorted crystals shown in ig, 28. In ‘any’ cases, analysis of the asterism, or distortion, of the spols in Lave Photographs leads to valuable information concerning the mechanisms of paste deformation In the above examples (Lave methods), a erystal Is maintained in a fxed ‘orientation with respect to the Kay beam. Reflections are beam is continuous, that is, the wevelongh is the variable ay difraction techniques tat use Xrays ofa single frequency of wavelength will now be considered. In these methods, since is no longer a variable, its necessary to vary the angle @ in order to obtain reflections. 23 The Rotating Crystal Method. In the rotatingerystal ‘method, crystallographic planes are brought into reflecting positions by rotating Fig. 2.8 Astersm in a Laue back-reflection photograph. The reflections from istorted- or curved:crystal planes form elongated spot.Ac/Physiel Mattergy Princo etn gone = —astreted 8am \ptrastes beom tal camara. (8) Sulematic representation of the diffraction pattern obtained from rotating eoftal comers, Reflected beams make spots ying in horizontal rows Fig, 29 (A) Schematic diagram of @ rotating sinaleervs mot scot shout oe of ia whe nancy radiating wi eam 2 seers we nly tcrdt ono photopapie monceuame Tyson De rpesan-See i 29 fora ssematc ewe te method) 2.4 The DebyeScherrer or Powder Method. In this method c {is taken to see thatthe specimen contains not one crystal, but more thar sever undied randomly oriented crystals. The specimen may be either 2 small polycrystalline metal wire, oF a finely ground powder of the metal contained in Trastc elulose, or last tube. In either caso, the crystalline aggregate consis PMoylinder about 0.5 mm in diameter with crystals approximately 0.1 mm in fdismetor or smaller. In the DebyeScherrer method, es in the rotating Single-crystal method, the angle © i the variable; the wavelength X remains constant. In the powder method, a variation of & is obtained, not by rotating & Sinale crystal sbout one of its axes, but through the presence of many small -f02-0707% Se8-0, Fig. 210 Simple cubic late. Relative interplanar spacing for (100) ad (110) planes. | Dittxction Methods/47 crystals randomly oriented in space inthe specimen. The prineples involved in the Debye-Scherrer method canbe explained wit the ad ofan example For the sake of simplicity, let us assume a crystalline structure with the simple cubic laice shown in Fig.2.10, and thatthe spacing between {100} planes equals 1 A. Ie can easly be shown that che interplanar spacing for planes Of the {110} type equals that of (100) planes divided by the square root af two, and i, therefore, 0.707 A. (Soe Fig, 2.10.) The {110} spacing is, therefore, smaller than the (100) spacing In fact al ther planes inthe simple cuble tate have a smaller spacing than that of the cube, or {100}, planes, a is shown by the following equation for the spacing of crystallographic planes in a euble atic, where h, & and Lace the three Miler indiess of a plane in the crystal, day the interplanar spacing of the plane, and e the length of the unital edge ton” TERRE In the simple cubic structure, the distance between cubie planes, dy 99, equals. ‘Therefore the abowe expression is written yy = Now, acorn to the Brage equation id= 2dsin 8 and for Firsonder reflections, wha equals one, we have () Naa, ‘This equation tells us that planes with the largest spacing will weflect at the smallest angle 0. If now it is arbitrarily assured that the wavelength of the X-ray beam is 04 A, firtordor reflections will oceur from {100} planes (with the assumed 1 A spacing) when ° ‘On the other hand, {100} planes with a spacing 0.707 A reflect when 04 goog’‘ayPnysial meralury Paps ean Teerarcant Fig. 2.11 Firstorder reflections from (100} planes of a hypothetical simple ‘ubic latte. Powdered erystal specimen. All other planes with larger indices (that is, (111), (234), ete) reflect at still larger angles. Figure 2.11 shows how the DebyeSchesrer reflections are found. A parallel beam of monochromatic Xeays coming from the left of the figure is shown striking the crystalline aggregate. Since the specimen contains hundreds of randomly oriented crystals in the region illuminated by the incident X-ray beam, many of these will have {100} planes at the correct Bragg angle of 11°30'. Each of these crystals will therefore reflect part of the Incident radiation in a direction that makes an angle twice 11°30' with the original beam. However, ‘because the eryatals ae randomly oriented in space, all the reflections will not le ix the seme direction, but, instead, along the surface of a cone that makes an sigle of 23° with the original direction of the X-ray beam. In the same manner, it can be shown that first-order reflections ftom {110} planes form a cone the Fig. 2.12 Schematic representation of the Debye or powder camera. Specimen assumed to be simple cubic. Not all reflections are shown. } | | i DirsetionRsthod/A surface of which makes an angle of twice 16°28', or 32°56" with the original direction of the bear, and that the planes of sil higher indices form cones of reflected rays making lager and larger angles with the original direction of the ‘eam, ‘The most commonly used powder cameras employ a long strip film that is curved into the form of a circular eylinder surrounding the specimen, 8 shown in Fig.2.12. A schematic view of a Debye-Scherrer film after exposure and development is shown in Fig. 2.13. On a DebyeScherrer film, the distance 25 between the two cicular segments ‘of the {100} cone is related to the angular opening of the cone and therefore to the Bragg angle @ betweon the reflecting plane and the incident beam, Thus, the tangle in radians between the surface ofthe cone and the X-ray beam equals 9/R, where R is the radius of the circle formed by the film. However, this same angle also equals 26, and, therefore, mR “This last relationship. is important because itis possible to measure the Bragg je 0 with it. In the above example, the spacing between parallel lattice planes was assumed to be known. This assumption was made in order to explain the principles of the Debye-Scherrer method. In many cases, however, one may not ‘know the interplanar spacings ofa crystal, and measurements of the Bragg angles can then be used to determine these quantities. The powder method is, accordingly, a powerful tool for determining the crystal strveture of a metal In ‘complicated crystals, other methods may have to be used in conjunction with the powder method in order to complete an identification. In any case, the Debye-Scherrer method is probably the most important of all methods used in ie fi Lite ss iO {lod} ana aed Unit racted beam Fig. 2.13 Powder camera photograph. Diffraction lines correspond to the reflections shown in Fig. 2.12.‘soyPhysic! Metallurgy Principles the determination of crystal structures. Another very important application of the powder method is based upon the fact that each erystalline material has its fown characteristic set of interplanar spicings. Thus, while copper, silver, and gold all have the same crystal structure (face-entered cubic), the unit eels of these three metals are different in size, and, asa result, the interplanar spacings and Bragg angles are different in each case. Sines each crystalline material has its fown characteristic Bragg angles, it is possible to identify unknown crystalline phases in metals with the aid of their Bragg releetfons, For this purpose, a card file system (Xsay Diffraction Dsta Index) has been published listing for approximately a thousand elements and crystalline compounds, not only the Bragg angle of each important DebyeScherrer diffraction line, but also its relative srength or intensity. The identification of an unknown crystalline phose in a metal can be made by matching powder pattern Bragg angles and reflected Intensities of the unknown substance with the proper card of the index. The method is analogous to a fingerprint identification system and constitutes an important method of qualitative chemical analysis. 25 The X-Ray Spectrometur. The Xray spectrometer is a device that measures the intensity of the Xray reflections from a eystl with an tlecivonie device, such asa Geiger countertobe or ionization chamber, instead of| {photographie film. Figure 2.14 shows the elementary parts of a spoctro- meter —a crystalline specimen, a parallel beam of Xeays, and a Geiger ountertube, The apparsus iso arranged that both the crystal andthe intensity i we couniertbe, however, avays ‘up each Brapy reflecion 2 intensify measiring device i conriee‘ed through a suitable amplification system to a chart recorder, where the intensity of the reflection is recorded on a chart bby a pen. In this manner one obtains an accurate plot of intensity agsnst Brag, ‘angles. A typical X-ray spectrometer plot is shown in Fig. 2.15. "The X-ray spectrometer is most commonly used with a powder specimen in Fig. 2.14 Xray spectrometer. Ditrstion Mathod/S1 easy celtic, Brags ooo 5 Fig. 2.15 The X-ray spectrometer records on a chart the reflected intensity as 2 function of Bragg angle. Each intensity peak corresponds toa erystallegraphic plane ina reflecting position. the form of e rectangular plate with dimensions about 1 in. Long and ¥ in. wide, ‘The specimen may be a sample ofa polycrystalline metal, and it should be noted that, in contrast to the Debye Schorrer method where the specimen isa fine wi (approximately 0.5 mm dimeter), the spectrometer sample has a finite size, ‘which makes the specimen much easier to prepare and is therefore advantageous. Because the X-ray spectrometer is capable of measuring the intensities of Bragg, rellections with great accuracy, both qualitative and quantitative chemical analyses can be made by this method. 26 The Transmission Electron Microscope. Within the past few ‘years a very powerful technique has become availabe to metallurgists, It involves the use of the electrom microscope to study the internal structure of this cexystlline films ot foils. These foils, which can be removed from bulk samples, fare normally only several thousand A thick. The thickness is dictated by the Voltage at which the microscope is operated. The normal instrument is rated at bout 100,000 volts, and electrons accelerated Ly this woltsge can give an acceptable image ifthe Foil isnot made thicker than the indicated value. Thinner foils, on the other hand, tend co be less useful in revealing the nature of the structure in the metal, Some instruments have been developed that operate at ‘much higher voltages (of the order of a milion volts) and in them the fois ean bbe proportionally thicker. However, equipment costs are also much greater, and relatively ew of these instruments are available. In the transmission electron microscope, the detail in the image is Formed by the diffraction of electrons from the crystallographic planes of the object being investigated. The electron microscope is, in many respects, analogous to an ‘optical microscope, The source is an electron gua instead ofa light filament. The Tenses are magnetic, being composed normlly of a current-carrying cotl ‘surrounded by a soft iron case. The lenses are energized by direct current. An excellent, easy to read description of the electron microscope & given in the‘52/Pysis! Metallurgy Pines so ssacinen a oneere tens moge of source er oft Fig. 2.16 Schematic drawing of a transmission electron microscope. ‘book by Simaliman and Ashe! . For our present purposes we shall concentrate on thet part of the microscope containing the specimen and the objective lens ‘This region is indicated schematically in Fig. 2.16. In this diagram, the electron beam #8 shown entering the specimen fom above. This beam originated in the electron gun and has passed rough a set of condensing lenses before it reaches the specimen. On emerging from the specimen, the beam passes through the rear element of the instruments objective lens. Shortly beyond this lens element, the rays converge to form a spot at point in plane. Ths spot is equivalent to an mage of the souree. Somewhat beyond this point, the image ofthe specimen i formed at plane £s. Similar double imoge effects are obserabe in sirnle optical instruments where it is posable to form images of the light source at ane position and images ofa lantern side or other abject at other positions. Because the image formation inthe transmission electron microscope depends ‘om the difraction of electron, its necessary to consider some elementary facts about this typo of diffraction. As éomonstaied in Chapter 3, electrons not only hve many of the attributes of parties, but they also possess waveite properties. 1 wil also be shown that the wavelongth of an electron i related to its velocity » by the elation A 1, Smaliman, RE, and Ashboe, K. HL G. Modern Metalography. Pargron Pres, oxford, 1966 i i i | | Ditrsetion Matnods/S2 where 2 is the wavelength of the electron, m is its mass, and itis Planck's ‘constant equal to 6.63 x 10"?7 erg. sec. "This expression shows that the ‘wavelongth of an electron varies inversely a its velocity. The higher the velocity, the shorter its wavelength. "Now let us assume that an eloetron is accelerated by a potential of 100,000 volts. It ean easly be shown that this wil give the electron a velocity of about 2x10! cm/sec and, by the above equation, a wavelength of about 4x 1071 em, or about 410" A. This is about two orders of magnitude somal than the average wavelength used in X-ay diffraction studies of metalic crystals, This causes a corresponding difference in the nature ofthe diffraction, as can be deduced by considering Bragy’s law. Suppose that we are coneermed with first order diffraction, where a= 1. Then, by Brage’s law, we have A= 2d sind I @, the spacing of the parallel planes frorn which the electrons ase ceflected, sumed t0 be about 2 A, we have O=sind = 0.01 The angle of incidence or reflection of a diftacted beam is thus only ofthe order of 10°? radians, or about 30. This means that wien & beam of electrons is pasted through a thin layer of ciystalline material only those planes nesrly piralle the beam can be expected to contbute to the resting difintion patter — “Let us now consider how the Image is formed inthe elsetron microscope as the result of diffraction. fn this regard, consider Fig. 2.17. Here iti assumed that some of the electroas, ia passing through the specimen, are diffracted by one of the sets of plane inthe specimen. In general, only part ofthe electrons wil be diffracted, and the remainder will pass directly through the specimen ‘without being difiacted These latter electrons wil form a spot at positon a and tan image of the specimen (O; ~ 0) atthe plane J as indicated in Fig. 2.16 On the other hand, the diffracted electrons wil enter the objective lens at slightly deferent angle and wil converge to form a spot at point b. These rays that pass through point & wil also form an image ofthe specimen at fa that i supetimpored over that fom the direct beam. Inthe sbove, it as been assumed that the crystal isso oriented thatthe electrons re reflect primarily from a single crystallographic plane. This should cause the formation of a. single pronounced spot at point b as a result of the diffraction, It is also posible to have simultaneous elections fiom a number of planes. In this eas, instead ofa single spot appeating in f, at point b atypical aay of spots ora difraction atten wil form on plane [. A characteristic diction patter wil be Aeserbed presently "The eleclzon microscope s0 constructed that either the image of the~oge ot spacinen Fig. 2.17 images oan be formed In the transmission electron microscope corresponding to the direct bear o* to a diffracted beam. (Images from more ‘then one diffracted beam are also posible). diffraction pattern (formed at 1,) or the image of the detail in the specimen (Gormed at J2) can be viewed on the fluorescent screen of the insteument, Alternatively, both of these images can be photogeaphed on a plate or film. This ‘is possible because» projection lens system (not shown) is located in the ‘microscope below that part of the instrument shown in Fig. 2.16. This lens system can bo adjusted to project either the image of the diffraction pattern at plane Jy, or that of the specimen st plane Jz, onto the fluorescent screen oF photographic emulsion In operating the instrument as 2 microscope, one has the choice of using cither the image formed by the direct beam or the imago formed by diffraction from a particular set of planes. The elimination of the beam causing ether of these two types of images is made possible by the insertion of an aperture diaphragm at plane J, that allows only one of the corresponding beams to pss ‘through it, as shown in Fig, 2.18. In this diagram, the diffracted beam is shown intercepted by the diaphragm, while the direct beam is allowed to pass through the aperture. When the specimen is viewed in this manner, a bright-ield image {s formed. Imperfections in the erystal will normally appear as dark areas inthis image. These imperfections could be small inclusions of different transpazency fom the matrix crystal, and therefore visible in the image as a result of a oss in Intensity of the beam where it pastes through the more opaque particles. OF ‘more general interest, however, is tho case where the imperfections are fault in Dittesion Method/SS cs Specimen Ditractee bao Fig. 2.18 The use of a diapheagin to select the d eed image. the crystal lattice itself, A very important defect of this type, that will be of considerable concern to us in subsequent chapters, is dislocation, Without delving too deeply into the nature of dislocations at this time, itis necessary to point out that dislocations involve distortions in the arrangement ofthe crystal planes. Such local distortions will have effects on the diffraction of electronsy because the angle of incidence between the electron beam and the lattice planes around the dislocation are altered. In some cases this may cause an increase {0 the number of diffiacted electrons, and in others a decrease. Since the direct ‘beam can be considered to be the difference between the incident beam an the diffracted beam, a local change inthe diffracting conditions in the specimen wil bbe reflected by a corresponding alteration in the intensity recorded in the specimen image. Dislocations are thus visible in the image becnuse they affect the diffraction of electrons. Ina bright-feld image, dislocations normally appear as dark lines. A typical bright-field photograph is shown in Fig. 4.9. ‘The alternate method of using the electron microscope is to place the aperture so that a diffracted ray allowed to pass, while the direct beam is cut Off. The image of the specimen formed in this case it of the dark-field type. ‘Here, dislocations appear as white lines lying on a dark background. Bright-field illumination is normally used, because darkfield images are usually more subject to distortion. This is because (as may be seen in Fig. 2.17) the diffracted beam, after leaving the specimen, does nat travel down the microscope exis. "An important feature of the transmission electron microscope is the stage ‘that holds the specimen, As indicated above, diffraction plays 2 very important‘Se/Physle! Matlurgy Prnepios Fig. 2.19 This stersographic projection of a cubie erystal shows the principle planes whose zone axis s [100] role in making the defects in the crystal structure visible In the image. In order ‘that the specimen may be capable of being allged so that a. suitable crystallographic plane can be brought into 2 rellecting condition, it is usually necessary for the specimen to be tilted with respect to the electron beam. The stage of an electron microscope used for metallurgical investigations is normally constructed so that the specimen may be rotated or tilted. With regard to the diffraction patterns observable in the microscope, an interesting diffraction pattern is obtained when the specimen is tilted in its stage so that an important zone axis is placed parallel to the microscope axis. When, this is done, a pattern is obtained whose spots correspond to the planes of zane whose axis paralels the electron beam. By way of illustration, let us assume that the specimen i so oriented that a <100> direction is parallel to the instrument axis, Pigure 2.19 shows a stereographie projection in which the zone axis is located at the center of the projection. The poles of the planes belonging to this zone should therefore lie on the basic circle of the stereographic projection, In the figure, only the planes of low indices are shown. The liffraction pattern corresponding to this zone is shown in Fig. 2.20. The Miller indices of the planes responsible for each spot are indicated alongside the corresponding spots. ‘The most significant feature of the diffraction pattern in Fig. 2.20 is that all spots correspond to planes parallel to the electron beam, Furthermore, as may Ditrason tathoes67 ont wo Bom es oi00 ig O910 oo (On or Fig. 2.20. The diffraction pattorn corresponding to 2 beam directed slong 1100}, in a cubic erysta be seen in Fig. 220, spots are indexed at both 100 and 100. This implies that the lecirons are sefleted from both sides ofthe same planes. Obviously, the simple Breas picture shown in Fg, 22, where dhe angle of incidence equals the ange of reflection, does not apply in this case. The reasons for this are not easy t0 Undersiand. However, several factors are undoubtedly involved. Of some Jmportaice isthe small value of the Bragg angle 0, whichis about 10°? radians. ‘Another isthe fact that the tzansmision sposimen is very thin, s0 that he flectron beam, in traversing the specimen, sees a lattice that is nearly twodimensionei. Tals tends to relax the diffizetion conditions. Pinay, the ‘Seetron microscope, with the specimen located inside a system of Inst, nota Simple diffracting device. For our present purposes, however, it is more important to note the aatuce ofthe diffraction pattern than the causes for it ‘Attention is now ealled to the spacing of the spots in the diffraction pattem in Fig, 2.20. In this igure, the distance from the spot corresponding to the Aiect beam to that of a reflection froma {100} plane is indicated asl 9, while the corresponding distance to 2 {110} flection oy. As can be deduced from the figure, loo, =-V2lo 6. Atention is now called to Fig. 2.10, where it jt shown thatthe spacing between th tvo respective planes varies inveraly a8 V2. This indicates thatthe spacing ofthe spots inthe diffaction pattem isinversly proportional to the interplanar spacing. This result, unlke the relationship of the Incident beam tothe planes fror which it is reflected, iin good agreement with the Bragg law. In the present caso, where the angle # i small, sin 0=9 and Braga’ law sedees to m= 2d0‘8/Physioa Mealury Princes Since the angle @ is smal, tan @ is also approximately equal to @ and we should expect the diffracted spots to be deviated through distances that gre inversely proportional to the interplanar spacing d. It is clear from the above that with the electron microscope itis possible both to investigate the internal defect structure of a crystalline specimen using the {instrument as a microscope, and to determine a considerable degree of informa- tion about the crystallographic Features of the specimen using it asa diffraction Instrument, With regard to the latter application, the diffraction pattems can yield information about the nature of the crystal structure and about the orientation of the crystals in a specimen, Furthermore, the electron microscope ‘has a diaphragm in its optical path that controls the size ofthe area that i able to contribute to the diffraction pattern. As a result, itis possible to obtain information about an area ofthe specimen thet has a radius es small as 0.5u. The liffraction pattems are therefore called selected arer diffraction patterns. Problems 1. The interplanar spacing of the (110) planes in an irom crystal is 2.024 A. AL ‘what Bragg angle, 6, will silver, Kg, radiation (0.558 A) suffer first order reflection from these planes? How many orders of reflection are possible when Cu Ky, radiation is Sitfracted from the (110) planes of an iron erystal? 3. At what angles wll the reflections of Problem 2 occur? 4. Given that the interplanar spacing of the (110) planes in iron is 2.024 A, ‘compute the lutice parameter efor this erystalsttucture 5. Suppose that 2 silver single crystal has been propazed £0 that one of its surfaces is parallel to a (U1) plane. At what angle to the axis of the collimator tube should this surface be inclined if « second order reflection is desired using copper X, radiation, given that the lattice parameter @ for AB 4.078 AD 6. Make a sketch of a face-centered cuble unit cell, Show that there exists @ (010) plane that lies midway between the outside (010) faces ofthis eel In terms of the lattice parameter, what is therefore the true interplanar spacing between the (1001 planes in this crystal structure? Now consider the relation WEE What values of f, &, and ¢ wil give the (010) interplanar spacing that you hhave deduced? 7. Tur to Appendix C. This table lists the indices of hk! values for the most Important reflecting. planes. in the simple cubic, body-centered cubic, and face-contered cubic structures, Note that indices of the form {220} conespond to a second order reflection fom (110) planes. On the basis of your answer to Problem 6, why is no reflection listed for (100) in the face-centered eubie structure? | | | 10. a 2. 13. 18 19. |. Compute the velocity of an Dittraction Muthode/SS Why is no reflection listed in Appendix C for the indices (110)? What may bbe deduced in general about the missing reflections in the table of Appendix e Assume that two face-centered cubic crystals, copper and aluminum respectively, are identically oriented with a {111} face normal to the X-ray ‘beam in a Laue back-reflection camera. Would there be any difference in the azrangement or positions of the spots in the respective photographs? Assume that the distance between the specimen ond the film in a Law back-reflection camera is $ em, and that 2 copper crystal is photographed with the (111) plane normal to the X-ray beam. For simplicity, also assume that the film is circular in shape, with a diameter of 20 cm, On this film, ‘would it be possible to see reflections from any of the [100} planes? Th the diffraction pattern of Problem 10, would it be possible to see any. reflections from {110} planes? If 50, make a sketch to scale showing the pattern of the spots, In a powder camera photograph of a faceventered cubic nickel specimen the separation between the {wo lines lying closest to the position of the ‘undiffracted beam is 7.80 om. What planes of the crystal structure are responsible for these lines? If the camera radius i 5 em and the radiation is Cu Kay, what is the lattice parameter of nickel? With the aid of Appendix C determine the data in order to make a sketch like Fig, 2.13 that will show the first four pairs of lines in a powder pattera pliotograph of an iron specimen. Assume a comera radivs of 5 em, Cu Ke, wiation (1.537 A), and ope = 2.861 A. cron. after has been aceclerated by a potential of 100,000 volts, Determine the wavelength of the electron corresponding to Problem 14, 16. Determine the wavelength corresponding to the electrons in a millionvolt electron microscope. [Assuring that the wavelength of the electrons in an electcon microscope i 3.9 107 A, compute the Bragg angle for the reflection ofthese electrons {rom the {100} planes of an iron erystal ; Examine Fig. 34 showing a {111 stendard projection of a cubic erystl ‘What can you deduce from this pole figure about the indices ofthe planes ‘whose spats should appear nearest the center of the selected area diffraction, pattom ofa crystal with its (111) plane normal to the electron beam? Make a sketch to scale similar to Pig, 2.21 showing the diffraction pattern of Problem 183 Elementary Theory of Metals CRYSTAL BINDING ‘Ceystlline solids are empirically grouped into four classifications: (a) ionic, (6) ‘van der Waals, (¢) covalent, and (2) metallic. This fs nota rigid classification, for ‘many solids ere ofan intermediate character and not capable of being plseed in = specific clas, Nevertheless, this grouping is very convenient and greatly used in practice to indicate the general nature of the various solids. 3.1 The Internal Energy of 3 Crystal. The internal energy of a crystal is considered 10 be composed of two parts. Fis, thre is the lattice enerey U that is defined as the potential energy due to the eleerortatic attractions and repulsions that atoms exzrt on one another. Socond, there the thermal energy of the crystal, associated with the rations ofthe etoms about their equilibria lati positions. It consists of the sum of all the individual vibrational energies (kinetic and potential) of the etoms. In order to ‘most conveniently study the nature of the binding forees that hold crystals together (the lattice energy U), it is desiable to eliminate from our considerations, as far as possible, complicating considerations of the thermal energy. This can be done most conveniently by assuming that all cohesive Calculations eter to nero degrees absolute, Quantum theory tells vs that st this temperature the atoms will bein their lowest vibrational energy states and that the zero-point energy asociated with these states i sal. For the present, it will be assumed that the zero-point energy can be neglected and that all calculations refer 10 0° K. In setting up quantitative relationships to express the cohesion of soi, tis customary to worle with cohesive enoeies rather than cohesive forces, The fenerpy concept is prefered because itis more conveniently compared with experimental data. Thus, the heat of sublimation andjor the heat of formation fof 2 compound are both related to cohesive energies. In fact, the heat of Sublimation at 0° K, which is the eneray required to dissociate « mole of a Substance into free ators at absolute 220, Ia particularly convenient measure ofthe cohesive energy of simple slid such as 2 metal Elomentary Theory of Metas61 Fig. 31 Tho sodium ehioride lattes. 32 Ionic Crystals, ‘The sodium ctiloride crystal serves as a gaod example of an ionic solid. Figure 3.1 shows the lattice structure of this set, ‘whieh is simple cubic with alternating lattice positions occupied by positive and negative ions, This lattice can algo be pictured of two interpenetrating ace-contered cubic structures made ‘up of positive and negative ions respectively. Figure 3.2 shows another form of ionic lattice, that of cosium chloride. Here each ion of a given sign is surcounded by eight neighbors ofthe opposite sign. In the sodium chloride lattice, the comesponding coordination number is 6. An ‘example in which this number is 4 is shown in Fig. 33. In genera, all theee of the above structures are characteristic of twosatom ionic crystals in which the positive and negative ions both carry charges of the same size. This is equivalent to saying that the atoms that make up the crystal have the sime valence. fonie crystals can also be formed from atoms that have different valences, for ‘example, CaF; and TiO>. These, of course, form sil different types of erystal Jattices! that will not be discussed Ideally, ionic crystals are formed by combining © highly electropositive ‘metallic clement with a highly electronegative element such as one of the halogens, oxygen, or sulfur. Certain of these solids have very interesting physical properties that are of considerable importance to the metallurgist. In particular, ‘he study of plastic deformation mechanisms in ionic crystals, for example, LiF, AgCl, and MgO, has greatly added to our understanding of similar processes in metals, S006 Fo Modo Thor of Sait, MeCre Book Co I. New You, 940 pas.‘s2/Psia!Matalary Principles Fig. 2 The cesium chloride lattice, Fig. 33 The zincblende lattice, 2nS. 33. The Born Theory of lonie Crystals. The classical theory developed by Born? and Madelung? gives a simple and rather understandable picture of the nature of the cohesive forces in ionte crystals. [tis first assumed that the ions are electrical charges with spherical symmetry and that they interact with each other according to simple central-force laws. In ionic crystals, these interactions take two basic forms, one long range and the other short range. The fxs is the well-known electrostatic, or coulomb, force that varies inversely with the square of the distance between 2 pair of ions, or Where ¢; and ey are the charges on the ions, and riz is the center-to-center distance between the ions, The corresponding coulomb potential energy for @ pair of ions is ‘The other type of interaction isa short-range eepulsion that occurs when ions are ‘brought so close together that their outer electron shells begin to overlap. When. this happens, very large forces are brought into play that force the fons away from each other. In a typical ionic erystel, such 25 NaCl, Both the positive and negative ions have filled electron sholls characteristic of inert gases. Sodium, in 2. M. Borns work i surmaized in the Handbucs der Phys, XXIV. 3. Madelung, = 2et. fr Pyik, 11 898 (1910), aiving up an electron, becomes a positive ion with the electron configuration of neon (1s?, 2s, 2p°), while chlorine, in gaining an electron, assumes that of argon (1s*, 25°, 2p*, 3s, 3p*). On a timeverage basis, am atom with an inert-gas arrangement of electrons may be considered as # positively charged nucleus surrounded by a spherical volume of negative charge (corresponding to the electrons), Inside the outer limits of this negatively charged region all the available electronic energy states are filed. It is not possible to introduce into this volume another electron without drastically changing the energy of the stom, When two closed-shell fons are brought together so that their electron shells begin to overlap, the energy of the system ({he two ions taken together) rises very rapidly, or, as it might otherwise be stated, the atoms begin to repel cach other with large Forces. ‘According to the Born theory, the total potential energy ofa single fon in an ionic crystal of the NaCl type, due to the presence of all the other ions, may be expressed in the form OF bur + Oe In this expression, 6 is the total potential energy ofthe on, ys its energy due to coulomb interactions with all te other one In the ert, and dis the fepulie energy. This expresion may algo be Willen i 7 c= Here ¢ is the electron charge, ris the distance between centers of an adjacent pair of negative and positive ions (Fig. 3.4), mia large exponent, usualy of the order of 9, and A and B aze constants. If we now think in terms ofthe potential fenotgy of a crystal containing one mole of NaCl, rather than in texms ofa single jon, the above equation becomes NECA , NB where AV is Avogadro's number and (isthe total lattice potential energy. The first term on the cighthand side of this equation represents the electrostatic fenerey due to simple coulomb forces between ions, whereas the second term is ‘that due to the repulsive intersctions that arise whea ions closely approach each ‘other, It is basic assumption of the Born theory that the repulsive energy can ‘be expressed as a simple inverse power ofthe interionic distance. While quantum thoory tells us that a repulsive term of the type Be? /r is not rigorously correct,58 /Physiat Metallurgy Principles er 7 Fig. 3.4 Interionic distances in the sodium chloride lattice. itis still « good approximation® for small variations ofr from the equilibrium separation between atoms rg ‘We shall presently consider in more deta the Individual terms of the Born ‘equation, but before doing this lot us look at the variation of the lattice energy with respect to the interionic distance r. This ean be done conveniently by plotting each of te two terms on the right of the equation separately. The cohesive energy Wis then obtained 2s a function of rby summing the curves of the individual terms. This is done in Fig. 2.$ for an assumed value of 9 for the exponent , Note that the repulsive term, because of the large value of the ‘exponent, determines the shape of the total energy curve at small distances, ‘whereas the coulomb energy, with its smaller dependence on , isthe controlling factor at large values of 7. The important factor in this addition is that the cohesive energy shows a minimum, Up, at the interione distance ry, where rg is the equilibrium ssparation between ions at O° K. IF the separation between ions Js cithor increased or decreased from ro, the (otal energy of the crystal rises. Corresponding to this increase in enezay Is the development of restoring forces acting to return the ions to their equilibrium separation ra. [Let us now consider the coulomb energy term of the Bom equation, which fora single ion is ou Seitz, F, The Modern Theary of Solids, MeGraw il Book Co,, Ine, New York, Elementary Theory of Metas/65 otenl energy Fig. 3.5 Variation of the lettice energy of an ionic crystal with the spacing between fons ‘assuming that we are specifically interested in a sodium chloride exystal where there isa unit charge on each ion and 2" = 1. Because the coulomb energy varies inversely as the frst power of the distance between charged ions, coulomb interactions act over large distances, and it is aot sufficient to consider only the coulomb energy between a given ion and its immediate neighbors. That this is true may be seen in the following. Around each negative chlorine ion there are 6 positive sodium atoms at a distance of r. This may be confirmed by studying Fig. 3.4. There is an attractive energy between exch of the six sodium ions and the chlorine fons equal to ~e/r, of in total ~6e*/r. The next closest fons to & sven chlocine ion are 12 other negatively charged chlorine fons at a distance ‘Vir. The interaction energy between these ions and the given fon is aesordingly 122! Vr. Following this there are 8 sodium ions at a distance of Vir, 6 cilorine fons at Vr, 24 sodium atoms at Vr, ete. Its evident, therefore, that the coulomb energy ofa single fon equals a series of terms of the form. wie Re ae ee 0 ir ar ir * Je ore/Pnysie! Mataargy Pineipes € jg sas4sn 3.004107. The constant 4 of the coulomb energy, of course, equals the sum of the terms inside the brackets in the sbove expression. This sris, as expressed above, des not converge because the terms do not dectease in size as the distance between fons is made larger. There are other mathematical methods of summing the ionic interactions* and it is quite possible to evaluate the constant A, which is called the Madelung number. For sodium chloride, the Madelung number is 1.7476 and the coulomb, or Madelung energy, for one fon inthe crystal is, accordingly, 1.7476 —— For asingle ion, the repulsive energy text is In this term the twa quantities, B and n, must be evaluated. This can be sceomplished with the aid of two experimentally determined quantities: rp, the equilibrium interonic separation at O° K; and Ko, the compressibility of the solid at 0° K. At ry the nat force on an jon due to the other ions is zero, so that the first derivative of the total potential energy with respect to the distance, which equals the force on the ion is also zero or (8), eC) Since the quanity is already known, the above expression produces an ‘equation relating x and B. A second equation is obisined from the fact that the compressibility is a function of the second derivative of the cohesive energy (@6/ar),,, at r=re. In making these computations, the equilibrium separation of ions ro can be experimentally obtained from X-ay diffraction resguremtents of the lattice constant extrapolated to 0° K, In the NaCl crystal, ‘his quantity equals 2.81 A, The compressibility is dotined by the expression Ler a vy 5, Sher, J.C. Introduction to Chemical Physics. MeGrow Ki Bet ine, New vod it i FHL Book Co, Ine, i | Elementary Theory of Metal/67 i the compressibility, is the volume of the crystal, and (O//p)r is the rate of change of the volume of the crystal with respect to pressure at constant temperature. The compressibility is thus the relative rate of change of volume with pressure at constant temperature, and is a quantity capeble of experimental evaluation and extrapolation to 0° K. ‘When the calculations outlined above are made,*7 itis found that the Born ‘exponent for the sodium chloside lattice is 8.0. In terms of this exponent, the Computed cohesive energy is 180.4 keal per mole. The latter is actually the ‘energy of Formation of a mole of solid NaCl from a mole of Na* ions, in the Spor form, and a mole of gaseous CI” ions. tis not possible experimentally to measure this quantity directly, but it can be evaluated from measured values of the heat of formation af NaCl from metalic sodium and gaseous Cy in ‘combination with measured values of the energy to sublime sodium, the enexey to ionize sodium, the energy to disociate molecular chlorine to atontic chlorine, ‘and the energy t0 ionize chlorine. When all of these values are considered, the fexperimental value of U for the NaCl lattice turns out to be 182 Keal per mole. "The rather good correspondence between the measured value of the cohesive nergy for NaCl and the value computed with the Born equation shows that the latter gives a good first approximation of the cohesive energy for a typical ionic solid, 3.4 Van der Waats Crystals. [nthe final analysis, the cohesion of ‘an fonie erystal is the result of its being composed of fons; atoms carrying ‘loctreal charges. In forming the crystal, the atoms arrange themselves in such a ‘way that the attractive eNergies betwoen ions with unlike charges greater than All ofthe repulsive energies between fons with charges of the same signs. We shall how consider another type of bonding that makes possible the formation of ccystils from atoms or even molecules that are electrically neutral and possess flectron configurstions characteristic of inert gases. The forces tat hold this type of solid together are usually quite small and of short range. They ate called van det Waals forces and arise from nonsymmetrieal charge distributions. The ost important component of these forces can be ascribed to the imeractions of electrical dipoles. 35 Dipotes. An lect! dipole i formed by a pair of ‘oppositely charged particles (#e and —e,) separated by a small distance. ‘Let us Gall ths distance a. Because the charges ate not eoncentrc,shey produce an Slectietaie field that i capable of exerting a Force on other eoctzia charges ‘Tous in Fig. 36, let and fy e the respective distances from the two charges 6 Slater, J.C. Pes Reviow, 23 488 (1924), 5. Seite F, Aladern Theory of Solids. MeGraw p86, Book Co, te, New York, 1940,‘58/Pnysicl mettaray Princes bol Fig.9.6 An electrical ciple. of the dipole to another charge ¢ lying at a distance r from the center of the dipole. This lator will experience a force It can be shown that, ifthe distance ris large relative tothe dipole separation , the above expression is equivalent to 2.005 0 re Mesgeee In this latter, ris the distance ftom the dipole to the position of the single charge ce, and 6 is the angle between the axis of the dipole and the direction r. It is ‘customary to call eya the product of one of the dipote charges and the distance between the dipole charges the dipole moment. Let us designate it as. The clectical field intensity (Foree on a unit charge) due to a dipole can now be written as cos a ‘which shows that the field of a dipole varies as the Inverse cube ofthe distance, ‘whereas the fleld of single charge varies asthe inverse square of the distance 3.6 Inert Gases, Let us turn to a consideration of the inertges atoms such a5 neon or argon, The soliés formed by these elements serve as the prototype for the van der Wanls crystals, just as crystals of the alkali halides (NaCl, ete.) are the prototype for ionle solids. It is interesting that they Elementary Theory oF Meta crystallize (at low tomporatures) in the fucecentered cubic system. In these atoms, as in all others, there is 2 positively charged nucleus surrounded by electrons traveling in orbits. Bocause of their closed shell structures, we can comsider that over a period of time the negative charges of the electrons are distributed about the nucleus with complete spherical syminetsy. The eenter of gravity of the negative charge on a timeaverage basis therefore coincides with the center of the positive charge on the nucleus, which means that the inert gas atoms have no average dipole moment. They do, however, bave an instantaneous dipole moment beeause their electrons, in moving around the nuclei, do not have ‘enters of gravity that instantaneously eoincide with the nuclet. 3.7 Induced Dipoles. When an atom is placed in an external electrical field, ts electrons are, in general, displaced from their normal postions relative to the nucleus. This charge redistribution may be considered equivalent to the formation of a dipole inside the atom. Within limits, the size of the induced dipole is proportional to the applied field, so that we write y= 08 where yy isthe induced dipole moment, E isthe electrical fielé intensity, anal a isa constant known as the polarizability When two inertgas aloms are brought close together, the instantaneous dipole in one atom (due to its electron movements) is able to induce a dipole in the other. This mutual interaction betwoon the atoms results in a net attractive force between the atoms. Figure 3.7 repracents twa inertges atoms of the same kind (pethaps argon atoms) separated by the distance 7. Now let it be asumed that the atom on the left possesses an instantaneous dipole moment jz due to the ‘movement Bf the electrons around the nucleus. This moment will produce a field Eat the positon of the second atom, which, in tur, induces a dipole moment in the latter equal to p= 0k where uy isthe induced dipole moment, a is the polarizability, and Es the feld at the right-hand atom due to the dipole moment in the left-hand atom. ‘ple ose! ‘Spore manent Fig. 3.7 Dipole-dipote interaction ina pair of inert-gas atoms.‘oVPhysie! Matlary Principles First, consider the force exerted by the left dipole on the right dipole, which may be evalusted as follows. Let us assume, at indicated in Eig. 3.7, that the induced dipole in the right-hand atom is equivalent to the pair of charges ~e" and +e’ separated by the distance a’. According to this, the induced dipole moment is e'a’. Now lot E be the eld intensity due 10 the instantaneous dipole fon the left atom at the negative charge (-e') of the induced dipole. The corresponding field at the position of the postive charge (+e') of the induced dipole is E +-dBjdr + a’. The toca force on the induced dipole due to the field of the other dipole is: However, and therefore but in general the field of a dipole is proportional to the inverse eube of the distance, ot ‘This leads us to the cesult ‘The energy of a pair of inerL-gas atoms due to dipole interactions ean now be evaluated as follows: on [lata ate It can be seen, therefore, that the van der Waals energy between a pair of inert-gas atoms due to dipole interactions varies as the square of the dipole moment and the inverse sixth power of their distance of separation; that the force varies a tho square of the éipole moment is significant. Over a period of time the average dipole moment for an inertgas atom must be zero. The square (Of this quantity does not equal zero, and it ison this basis thet iner-gas atoms can interact. Elamentary Theory of Matal71 3.8 The Lettice Enorgy of an Inert-Gas Solid. When the atoms of a rareas solid have their equilibrium separation, the wa der Waals attraction is countered by a repulsive force. The lettor is of the same nature as that which ‘occurs in ionic crystals and is duc to the interaction that occurs when closed shells of electrons start to overlap. The cohesive energy of an inert-gas solid may ‘therefore be expressed in the form uv. A,B ae where A, B, and m are constants. It has been shown® that ifm equals 12 the hove equation corelates well with the observed propertis of rages sls “The fst corm on the righthand side represonts the total energy for one make of the crystal cused by the dipole dipole interactions betwen all the atoms ofthe sold. It may be obtained by ist computing the energy of a single atom caused ty its interactions with ts neighbors. This quantity then sumed over al the atoms of the erytl. The computations ere Tenthy and will not be dscusse. “The second term in the above eqaton is the mole repulsive energy ‘As might be surmised from the sscond.order nature of the Yam der Wanls interaction, the cohesive energies of the inert ge slide are quite smal, bing of tho order of Yoo of thove ofthe ionic estas. The rae gues have also vey Low rneting and boiling poins, which iz to be expected because of tit smal Cohesive energies. Table 31 gives these properties for the ineraas clements, ‘th the exexption of helium. ‘Fable 3.1 Experimental Cohesive Energies,” Melting Points, and Boiling Points of Inert Gas Elements. Cohesive Melting Boiling Blement Energy Point Point Keal/mal °c °c Ne 0.450 288.6 246.0 A 1.850 1894 1858 Kr 2590 -1sT 152 Xe 3.330 <2 108 3.9 The Debye Frequency. The 2er0-point energy of a crystal its thermal energy when the atoms are vibrating in their lowest energy states. ‘When theoretical and experimental cohesive energies ate compared at an 48, Lenaard Jones 1. Phpsen, #941 (1937) 5, Dobbe, F, Rand Jones, G.O,, Reports on Pog. Phys, 20516 (1957).“721Physiont Maalargy Principles assumed temperature of O° K, this energy, which has previously been neglected, should be included along with other terms. In a crystalline solid there are three vibrational degrees of freedom per atom. To each of these degrees a mode of vibration can be assigned so that there are three modes per atom. A crystal of atom is considered as equivalent to 3W oscillators of various frequencies». ‘The basic reasoning that brought Debye to these conclusions is as follows. First, he astumed that the forces of Interaction between a neighboring pair of atoms were roughly equivalent (0 a linear spring. Pushing the atoms together ‘would have the effect of compressing the spring, and in so doing, a restoring force would be developed that would act to retun the atoms to their rest positions, Pulling the atoms apart would produce an equivalent opposite result. (On this basis, Debye concluded that the entire lattice might be considered to be 1a three-dimensional arcay of masses Interconnected by springs. In effect, ‘assuming a simple cubic crystal, each atom would be held in space by a set of tree pales of spring, as indicated in Fig. 3.84. He next considered how such an array might be able to vibrate, To simplify the presentation, a one-dimensional crystal will be considered, 2s indicated in Fig. 3.88, and following Debye, the existence of longitudinal atte vibrations will be ignored because they are of Jess significance. The vibration modes of such an array are analogous to the standing waves that can be set up ina string. A set of these latter are shown in Fig. 3.17. Ina simple string, the number of possible harmonies is theoretically infinite, and there is no lower limit for the wavelengths that might be obtained. According to Debye, this is not true when a series of masses connected by springs are caused to vibrate, Here, as shown in Fig. 39, the minimum rd ° Fig. 38 (A) Debye model of a simole cubic crystal pictures an atom as a mass joined to its neighbors by sarings. (8) A anedimensional crystal model. | | | | | i i | L Elementary Theory of Matas73 Fig. 3.9 The highest frequency vibration mode for an array of four masses. wavelength or the mode of maximum frequency is obtained when neighboring atoms vibrate against each other. As may be seen in the drawing, the minimum wavelength corresponds to twice the spacing between the atoms, of Amin = 22, where @ is the interatomic spacing.. The (maximum) vibrational frequency associated with this wavelength is where vis the velocity of the shortest sound waves. This latter is normally ofthe coder of 5 x 10? cm/sec. At the same time, the interatomic spacing in metals is about 2.5.A,so that 5x 10° a im = Bee ey” 10"? wibace ‘The valve, vy) =10!? vibjsee, is often used in simple calculations to represent the vibration frequency of an atom in e crystal. Since these exiulations cxdinaily are accurate to only about an order of magnitude (factor of 10), the tse of the maximum vibration frequency for the average vibration frequency oes not exuse serious problems. 3.10 The Zero Point Energy. In standing waves such as those indicated in Fig. 3.17, the order of the harmonic corresponds to the number of, half wavelengths in the standing wave pattern. Observe that in Fig. 3.9, witere there are four atoms, there are four half wavelengths, and this system of four ‘atoms will be able to vibrate in only four modes. Inthe ease ofs linear array of Ng stoms, there will be Ny half wavelengths when the scray vibrates at its maximum frequency. Since this latter frequency corresponds to the 1V,th harmonic, the system will have 4, transverse modes of vibration inthe vertical plane, which is the assumed plane of vibration In the drawing. In a three-dimensional crystal of V atoms, each atom inside the crystal can ‘undergo transvorse vibrations in three independent directions as can be deduced‘TH1Pryien Maatary Picipes by examining Pig, 3.84; and by ceasoning similar to that above, its po show that there are 34 independent transverse modes of vibrations. ‘In Linear crystal, such as that implied in Fig. 3.88, the density of vibrational modes is the same in any frequency interval dv. However, ina three-dimensional frtay or erystal the vibrational modes are three-dimensional, and the multiplicity fof the standing wave patterns increases with increasing frequency. Asa result the three-dimensional case the number of modes possessing frequencies in the range v tov + dis given by soydr= 28 ot ay where /() isa density function, Vis the number of atoms in the crystal,» is the vibrational frequency of an oscillator, and ty i the maximum wbrational frequency, Figure 3.10 is a schematic plot of the Debye density function /(¥) as 2 function of ». The area under this curve from »=0 to 9 =v, equals 31, the total number of oscillators. According to the quantum theory, the zero-point ‘energy of a simple oscillator i hv/2. The total vibrational energy of the exystal at abcolute 200 is, accordingly, meee in eeeS) Bene) Zaee FN ‘This quantity should normally be added to experimentally determined cohesive ‘energies (Table 3.1) in comparing them with computed static lattice energies. "The correction due to the zero-point energy is about 31 percent, or about 0.14 Fig. 3.10 Frequency spectrum of a crystal according to Debye, The maximum lattice frequency is Y,. Etomantary Theory of Metali75 Keal per mol in the case of neon,!® so that the lattice energy Up should be ‘about 0.59 Keal per mol rather than 0.45 Keal per mol, as shown in Table 3.1 ‘The importance of this correction decreases as the atomic number of the rare-gas clement rises, so that for Xe it amounts to about 3 percent. 32.11 Dipole Quadrupote and Quadrupole-Quadrupcle Terms. ‘The van der Waals attractive energy is caused by a synchronization of the ‘motion of the electrons on the various atoms of a solid. Asa first approximation it might be considered that this interaction is equivalent to the development of synchronized dipoles on the atoms. The summation of the dipole interactions throughout the erystal then leads to an attractive energy that varies as the inverse sixth power of the distance. Actually, the complex charge distributions that exist in eeal atoms cannot be accurately represented by picturing them ss simple dipoles. Modem quantum mechanical treatments generally use an texprestion for the van der Waals attractive energy (expressed in tems ofa single ion) of the type tora) whore ci, cx, and cy ate constants. The first term ofthis expression i the Sipoledipoleintraction akeady considered, ‘The second term in the inverse sighth power of tho distance is calle the dipotequadrupol term because the interaction between a dipole on one atom anda quadrupole on another wi ead to an energy that vases as the imerse eighth power of the distonce. A ‘quadruple isa double dipole consisting of four charges. ‘The aster, varying SS the inverse tenth power of the distance, i called the quadrepotequadnpote fevm. it isin general, small und amounts to es than 1.3 percent of the total ven der Waals attractive energy for all of the inert-gas solids.'* The dipole: quadrupole term, on the ater hang, equa approximately 16 percent ofthe {tal attractive energy indicating that, whereas he dipole-dipole teem mek UP Imost of the van der Waals attractive energy, the second tem i lo signfcant 3.12 Molecular Crystals. Many molecules form crystals which are held together by van der Waals forces. Among these are Nz, Hin, and CH typical covalent molecules in which the atoms share valence electrons 10 effectively obtain closed shells for each atom in the molecule, The forces of attraction between such molecules are very small and of the order of those in the inert-gas erystals. 10, ti. 10 fo‘oIPy ict Matury Principe ‘The molecules mentioned in the above paragraph are nonpolar molecules; they do not have permanent dipole moments, Thus, the attractive foree between ‘wo hydrogen molecules comes in laxge measure from the synchronism of lectzon movements in the two molecules, or from instantaneous dipole-dipole interactions. In addition to these, there are also polar molecules, such as water (4,0), which possess permanent dipoles. The interaction between a pair of permanent dipoles is, in general, much stronger than that between induced ‘dipoles. This leads to much stronger binding (van der Waals binding) in their respective crystals with corcespondingly higher melting and boiling points. 3.13 Refinements to the Born Theory of lonie Crystals. In the inert-gas and molecular solids considered in the preceding section, van dex Waals forces are the primary source of the cohesive energy. These forces exist in other solids, but when the binding due to other causes is strong they mey contribute only a small fraction of the total binding enecgy. This is generally true in ionfe ‘aystals, although some types, like the silver halides, may have van der Watls contributions of move than 10 percent. The alkali halides, as may be seen in ‘Table 3.2, have van der Waals energies that amount to only a small percentage of the total’ energy. This table is of particular interest because it lists the contsibution of five terms to the total lattice energy. The frst column gives the Madelung energy, or the frst term in the simple Born equation. The second is the repulsive energy, caused by the overlapping of closed fon shells. The third and fourth columns are van der Waals terms: dipole-tipale and dipote-quadrupole. ‘The fifth column lists zero-point energies; the energy of vibration of the atoms in their lowest energy levels. Finally, the last column is that ‘Table 3.2 Contributions to the Cohesive Energies of Certain of the ‘Allali Hades.” ‘ Dipole Dipole. | Quad. | Zero Madehine \ Repulse | Dipo | — pole | Poine | Tora! vss | a4 33 08 220) ms | 258 | 38 oa | =24 | 2002 wis | ms | 59 ox | 1s | 97 iss | 183 63 ox | -12 | 1762 aos | 255 52 oa | <7 | isa ws2 | 213 1 oi | “18 | srs Rel uss | n99 13 ox | “12 | 627 cc ters | -in7_ | a oi | “10 | iss “lio elon, pe mole, Horn The Modem Taluel given show are exprened ogee ncory of Solin, by Sate, F- Copyright 1940, MGraw-it Book Compa Yor. $8. Ut by persion i i i lesenaty Theory of Metls77 conesponding to the sum of all five terms, which should equal the internal energy of the crystals at zero degrees absolute and at zero pressure, 3.14 Covalent and Metallic Bonding. In both the ionic and the inertgas crystals that have been considered, the crystals ate formed of atoms or ions with closed-shell configurations of electron. In these solids, the electrons axe considered to be tightly bound to thee respective atoms inside the crystal Because of this fact, ionic and rar-as solids are easier to interpret in terms of the lavs of classeat physics, It is only when greater accuracy is needed in computing the physical properties ofthese crystals that one needs to turn tothe more modem quantum mechanical interpretation. Quant however, a essential when it comes to studying Th ‘electrons that are not considered to be permanently bound to specific atoms in the solids. In other words, in both of these solids, the valence electons are of erystal isthe diamond Torin of carbon. Fach carbon atom brings four valence cléctzons info the crystal. The coordination number ofthe diamond structure is aso Tour, as shown in Fig.3.11. Ifa given carbon atom shares one of its four valence electrons with each of its four neighbors, and the neighbors reciprocate in tum, the carbon atom will, a a result of thie sharing of eight electrons, effectively achieve the electron configuration of neon (15°, 2s*, 2p). In this type of crystal it soften convenient ro think ofthe pats of elections which are shared between nearest neighbors as constituting a chemical bond between a pair fof atoms. On the other hand, according to the band theory of solids, the slectrons are not fixed to specific bonds, but can interchange Between bonds. ‘Thus, the vilenee elections in a valenee crystal can alo be thought of as belonging fo the exystal asa whole, ‘The binding asoeated with these covalent, or homopofar, inkages as they are called, is very strong so thatthe cohesive energy ofa solid suc a diamond is very large and, in agreement with this fact, valance solids are usually very hard and have high meting points. “The covilent bond is also responsible for the ohesion of many well-known rlecules, for example, the hydrogen molecue. An idea of how the binding eneegy develops can be obtained by an elementary consideration of the hydrogen molecule, The lowest atomic energy state is associated with the 1s ons ean be accommodated inthis state, but only if they have “Thu, an excited helium atom will have both of is electrons in “he Ls sate, but only ifthe spin vectors of the electrons ate opposed. The fact that two electrons can occupy the same quantum state only if the spins are oppositely irectad is known 38 the Poul exclusion principeNow suppose thatTalenysia Meralargy Prieipes Fig. 3.11 The diamond structure. Each carbon atom is surrounded by four nearest neighbors, Note: ths structure is the same as that of zincblende (ZnS), Fig. 3.3, excopt that thi lattice contzins one instead of two kinds of atoms. {wo hydrogen atoms are mate to approach each other. Then there a to cases Ses) to be considered: wien the spins ofthe electrons onthe two atoms ate parle, and ‘Acuzywhen the spins are oppored. First consider the Isiter case. As the atoms come ‘and close together, the electron on either atom bepins to find tel in the fed of the charge on the nucleus of the other som. Since the splas of the electcons are opposed, each nucleus is capable of containing both electrons in ) the Is ground state, Under these condition, there isa stcong probability thatthe leettons will spend mare time in the neighborhood of one mucteus dhan the © pther, and the hydrogen molecule becomes a pair of charged ions — one postive ‘andthe other negative. This structure is unstable, especially wien the hydrogen ftom afe far apart, as may be estimated feom the energy required to form 2 positive and a negative puir of hydrogen ions (295.6 Keal per mol)? At the normal distance of separation of the atoms in « hydrogen molecu, the tonic structure exists for limited periods of time and contributes about 5 percent of the total binding energy.!? "A much more important type of electron interchange occis when both clectrons simultaneously exchange nuclei. The resulting shifting of the electrons © back and forth between the suck, which occurs at a very rapid cate, i commonly knowa as 4 resonarce effect, nd about 80 percent'* of the binding energy of the hydrogen molecule is atiiouted to i. With the sid of quantum ‘mechanics, the total binding energy of a hydrogen molecule has been computed ~ and, as a result, an insight into the nature of the binding energy associated with this exchange of electrons has been obtained. Quantum mechanics shows that, on the average, the electrons spend more of their time in the region 12, Fasing, L, The ature of the Gremicel Bond. Comell University Pres, then, Nv 1840, p22, _Etemontory Theory of Meta79 between the two protons than they do on the far sides of the protons, From a very elementary point of view, we may consider dhat the binding of the hydrogen molecule results from the attraction of the positively charged hydrogen nucleic the negative charge which exists between them. "Attention is called tothe interrelation between space and time implied in this discussion concerning the timeaverage positon ofthe electrons, These ideas are hormally expresed in terms of a phase space. This is @ coordinate system that includes oth the positions of the particles and their moments (that i, velocities). Thus for a single particle free to move along single direction (the {eanis) there willbe two dimensions in phase space; its position along the axis, tnd its momentum, For 7 partiles capable of moving in single direction, there will be 2 linear dimensions in the phase space associated with these particles ‘These are x1, 2, Sq, the positions of the particles; and py, ps5 ---Pay the momenta ofthe particles. For particles eapzble of moving in three dimensions, there will be 6n degrees of freedom and therefore a corresponding number of

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