Engineering Materials and Processes Springer-Verlag Berlin Heidelberg GmbH ONUNE UBRARY Engineering springeronline.com Series Editor Professor Brian Derby, Professor of Materials Science Manchester Science Centre,Grosvenor Street, Manchester, MI 7HS, UK Madeleine Durand-Charre Microstructure of Steels and Cast Irons Translated by James H. Davidson B.Met. Ph.D. C.Eng. M.I.M. With 289 illustrations , Springer Prof. Dr es Sciences Madeleine Durand-Charre Institut National Polytechnique de Grenoble e-mail: [email protected] Originally published in French as La microstructure des aciers et des fontes. Genese et interpretation, Ed. SIRPE, Paris 2003 ISBN 978-3-642-05897-4 ISBN 978-3-662-08729-9 (eBook) DOI 10.1007/978-3-662-08729-9 Cataloging-in-Publieation Data applied for Bibliographie information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographie data is available in the Internet at <http://dnb.ddb.de>. This work is subject to copyright. All rights are reserved, whether the whole or part of the material is coneerned, specifica1lythe rights of translation, reprinting, reuse ofillustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplieation of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag Berlin Heidelberg GmbH. 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Coverdesign: Erich Kirchner, Heidelberg 6213020 uw Printed on acid-free paper - 5 4 3 2 1 0 - Preface How many times ha ve 1 heard the question MIs there stIll anything to discover in steels ?~ often with the conclusive comment '~know everything about steels - they've been studied lor years !" On the contrary, in recent decades, the development 01 new grades, extended lunctions and novel applications has continued at an accelerating pace. More than hali the steels used today did not even exist live years ago. This simply demonstrates the vast potential 01 these materials. Starting Irom an iron base, numerous alloying elements can be added to modi/y the microstructure, the mechanical and physicalp roperties and the surlace characteristics 01 steels. A wide variety 01 metallurgical mechanisms, includi ng solidilication, solid state phase translormations, recrystallisation and precipitation can be used in steels to obtain a whole range 01 uselul properties, by appropriate thermomechanical and heat treatments. More reliable and simpler manulactu ring processes, together with modern on line non destructive inspection systems, enable increasingly closer control 01 microstructures, and consequently the attainment 01 higher and more reproducible perlormance levels. The melting and processing 01 steels and cast irons therelore continue to challenge metallurgists and remain an essential driving lorce lor research and development. This can be illustrated by two noteworthy examples, which are mentioned in the present book. The lirst concerns packaging steels, particular/y tllOse used lor beverage cans. The increased strength 01 today's steels has enabled the strip thickness employed to be reduced to less than 150 pm. This has placed extreme demands on cleanness requirements, with the need to guarantee no more than one inclusion larger than a micron in size per kllometre 01 strip. The second example is related to solid state phase translormations. Depending on the steel composition and the thermomechanicalp rocessing cycles employed, the equilibrium condi tions at the interlace can vary tremendously, leading to translormation rates that diller by severalorders 01 magnitude. This can generate high/y localised concentration peaks at the interlace. The mechanisms involved can be understood and verilied only by the use 01 highly sophisticated modern experimental techniques, such as high resolution transmission electron microscopy and the tomographic atom probe. The large number 01 dillerent microstructures observed in steels and cast irons intrigued ear/y metallurgists. The properties 01 metals in general are close/y related to their micros tructures. For example, the attractive appearance 01 many old Damascus steel swords was also a sign 01 their quality. The scientilic study 01 the nature, composition and geometry 01 the blade patterns provided modern metallurgists with valuable clues to the processes employedb Y ancient smiths to manulacture these swords. TZis historical example, discussed in detail by way 01 introduction, illustrates the underlying theme 01 the book, name/y, the central role 01 microstructures in steels and cast irons. The numerous structural translormations that can occur in steels during solidilication and cooling complicate the identilication and interpretation 01 the linal microstructures obtai- LA MICROSTRUCTURE DES ACIERS ET DES FONTES ned However, their analysis has been signi/icantly clarified by extensive research studies and modelling work, providing a scienti/ic understanding of the mechanisms involved Variations in microstructure then become local markersH of the composition and thermo mechanical history, conserving the memory ofs uccessive metallurgical changes and ena bling evaluation of transformation rates. Equilibrium phase diagrams form an essential basis for the interpretation ofm icrostructu res. Their experimental determination is refined by the precise analysis of equilibrium constituents. Recent progress in modelling now enables experimental ch:agrams to be com pleted and enriched by calculating phase equilibria. The great originality of the present book is a constant and rewarding confrontation between equilibrium aspects, microstructu ralobservations and modelling predictions. This approach also enables the vast variety of steels to be treated by considering a series oft ypical examples, illustrating the major catego ries ofm etallurgical phenomena. A new angle is thus provided for interpreting certain phase diagrams that appear difficult to understand for the non specialist. Moreover, empha sis is placed in this way on the limitations associated with the experimental interpretation ofm icrostructures, on the possibility ofm isleading artelacts, and on the risk ofd rawing too hasty conclusions without giving due consideration to kinetic factors. The exhaustive treatment ofm etallurgical changes in steels and cast irons prepares the rea der for the last part of tbe book, which describes the major lamilies ofs teels in a deductive manner. Emphasis is placed on the scienti/ic procedure underlying the design ofn ew steel grades, enabling more rapid development, together with breakthrough innovations that would be impossible by a purely empirical approach. The book shouJdp rove useful for a wide range ofr eaders and should -bnd a prominent place on of/ice bookshelves and those ofm any microscope rooms. It will remind investigation and quality control specialists of the imperative need to base the interpretation ofm icros tructures on a rigorous scienti/ic understanding. It will help R iii D englneers to design new steels to meet increasingly challenging user requirements. For metallurgy teachers, it will provide a large collection ofp ractical examples to illustrate their lectures, based on the authors wide experience accumulated during numerous case studies. Finally, it will reveal to students the lascinating worJd ofs teels and cast irons, at the same time didactically guiding them through a vast -b'eJd ofm etallurgical knowledge. While satis/ying the curiosity and thirst for knowledge ofa wide range ofr eaders, the book also provides food for thought andp roves that, despite the excellent level ofc urrent unders tanding concerning steels and cast irons, much still remalns to be achieved, by pushing metallurgical science to its furthermost limits. Jean-Hubert SCHMITT Director, Isbergues Research Centre Ugine iii ALZ -ARCELOR Group VI Acknowledgements Research metallurgists 01 my generation have witnessed prolound changes due ta the pro gress achieved in the last lew decades in the b:eld 01 metallography. Thanks ta the immense contribution 01 electron microscopy, microstructures can now be explored in their lin est details. HoweveI, the task 01 the metallurgist is stIll that 01 analysing and interpreting the observations in order ta understand the origins 01 the microstructure. The interpretation 01 a micrograph requires an extensive metallurgical culture, since numerous translormations have olten leit traces an dillerent scales olobservation. The present book aims ta provide the lundamental concepts necessary lor this purpose. Emphasis is placed throughout an micrographic leatures, which are discussed and interpreted in detaij The microstructural characteristics are also used as a guideline lor classilying the major lamilies ollerrous alloys, enabling beginners ta steer their way through the labyrinth 01 commercial grades. The objective 01 the book is ta comprise a uselul tool that is sul/iciently compact ta bndi ts place neri ta a microscope. An important aspect throughout the book is the role 01 phase eqUllibria. The latter part 01 the 20th century saw the development 01 the theoretical calculation 01 phase diagrams based an thermodynamic data lor the constituent phases, backed by direct experimental determinations 01 phase boundaries and characteristic temperatures. The models now available are extremely powerlu!, quite representative, and lncreaslngly easy ta use. Howe veI, the excessive simplib·cation 01 these tools and their use as simple "black boxes" can lead ta a loss 01 scienti/ic inlormation, a sort 01 "data laundering'; that must be avoided by a thorough understanding 01 the underlying principles. It is lor this reason that Irequent relerence is made ta ternary diagrams, using examples chosen among the iron base systems, which undoubtedly represent an excellent basis lor reasoning. The project 01 the present book was ambitious and 1 am extremely gratelul lor the support and encouragement received Iram numerous sources. First 01 al!, Bernard Baroux is ta be thanked lor welcoming the idea and obtaining the backing 01 the Arcelor company. He pro vided the con/idence necessary at a stage when the outlines 01 the book were stIll hazy, and proved a staunch ally in promoting the project. 1 am also indebted ta my colleagues in Gre noble lor the laith accorded ta the success 01 this work, particularly Colette Allibert at the Institut National Polytechnique de Grenoble (INPG) and Claude Bernard at the Labora toire de Thermodynamique et Physico-Chimie Metallurgique (LTPCM). From a scienti/ic standpoint, it appeared a daring and somewhat loolhardy idea ta adven ture into /ields outside my own research areas. 1 was able ta take up the challenge thanks ta the kindness and availabiJity 01 numerous lndustrial and university scientists, and the help 01 coJJeagues ln my own lahoratory. For exampJe, incursions have been made lnto territories as dangerous as the bainite translormation, thanks ta salety nets provided by Yves Brechet andh is team. In the lield 01p hase equiJibria, my environment in the LTPCM was extremely heJplu!, and my thanks are due particuJarJy ta Annie Antoni-Zdziobek who satislied my unquenchabJe thirst lor calculated phase diagram sections. My teaching and research coJ- LA MlCROSTRUCTURE DES ACIERS ET DES FONTES leagues, Claude Bernard, Yves Brechet, Catherine Colinet, Patricia Donnadieu, Franfois Louchet, Catherine Tassin-Arques, Muriel Veron {and Francis Durand, my husband} ior med an exceptionally constructive reading committee. In industrial circles, 1 am particu larly grateiul to Laurent Antoni, Pierre Chemelle, James Davidson, Andre Grellier, Philippe Maugis, Daniel Nesa, Andre Pineau, David Quidort, Pierre-Emmanuel Richy, Sophie Roure, and Zinedine Zermout, ior much precious iniormation and advice. Special thanks are also due to the technical team at my laboratory, particularly Alain Domeyne, who helped to prepare the expenments used as a source oie xamples. 1 am especially grateiul to my translator, Dr. James Davidson, ior his rigorous translation, combining his linguistic sk11ls with his competence as an industrial research metallurgist. Indeed, his contribution went beyond a simple translation, since the detailed critical analy sis necessary to reiormulate the text in English proved an extremely eilicient means oic la ri!ying the original French version whenever it appeared inexact or not suiiicient1y explicit. Finally, James Davidson frequently provided precious complementary indications based on his experience oii ndustrialp roblems. Over the years, 1 have built up a library oih igh quality electron micrographs, thanks to the help and competence oit he members oit he Consortium des Moyens Technologiques Com muns (CMTC) within the INP in Grenoble. lam particularly grateiul to Jacques Garden, Laurent Maniguet, Rene Molins, Florence Robaut and Nicole Valignat. In addition, numerous photographs have been kindly supplied by outside laboratories and museums. 1 always iound a warm welcome and a positive response to my severe demands concerning the quality oip hotographs. These people and organisations are mentioned in the ligure captions and 1 am extremely grateful to all those concerned ior their invaluable contribution. Madeleine Durand-Charre viii Table of contents First Part The history of iron and steel of swords and ~ ploughshares 1 From lron to steel 1-1 The long history of iron .............................................. 3 1-2 The three sources ofiron .............................................. 4 1-3 Early ironmaking technology .......................................... 6 1-4 The spread of ironmaking technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 8 2 Of swords and swordmaklng 2-1 Swordmaking, the cuning edge of metallurgical history ..................... 13 2-2 The Celtic swordmaking tradition ..................................... 14 2-3 Merovingian and Carolingian swords ................................... 16 2-4 True or oriental Damascus steel swords produced using wootz steel ............ 20 2-5 Mechanical or pattern welded damascene swords .......................... 20 2-6 In search of a lost art . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 21 2-7 Asiatic swords ..................................................... 27 2-8 Contemporary damascene structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 31 PartZ The Genesis of Microstructures 3 The principal phases in steels 3-1 The phases of pure iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 37 3-2 Solid solutions .................................................... 39 3-3 Order-disorder transformations ........................................ 40 3-4 Intermediate phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 42 4 The basie phase dlagrams 4-1 Equilibria between condensed phases ................................... 47 4-2 Theoretically calculated phase diagrams ................................. 53 4-3 Experimentally determined phase diagram ............................... 56 4-4 The Fe-Cr-C system : liquidus surfa ce .................................. 56 4-5 The Fe-Cr-C system : isothermal sections and isopleths ..................... 60 4-6 The Fe-Cr-C system : solidification paths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 62 4-7 The Fe-Cr-C system : the austenite field ................................. 65 4-8 The Fe-Cr-Ni system ............................................... 69 4-9 The Fe-Mn-S system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 71 4-10 The Fe-Cu-Co system .............................................. 75 4-11 The Fe-Mo-Cr system ............................................. 78 LA MICROSTRUCTURE DES ACIERS ET DES FONTES 4-12 The Fe-C-V system ................................................ 84 4-13 Mixed carbides ................................................... 86 5 The formation of solidlficatlon strudures 5-1 Solute partitioning phenomena during solidification ....................... 91 5-2 Local solute partitioning ............................................. 94 5-3 The growing solid interface ........................................... 95 5-4 The evolution of dendritic microstructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 101 5-5 Secondary dendrite arm spacings ..................................... 106 5-6 Eutectic microstructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 108 5-7 Peritectic microstructures ........................................... 116 6 Liquld/solld strudural transformatlons 6-1 Experimental techniques : controlled solidification . . . . . . . . . . . . . . . . . . . . . . .. 121 6-2 Experimental techniques: thermal analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 124 6-3 Solidification paths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 127 6-4 Metastable solidification paths ....................................... 138 6-5 Peritectic transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 141 7 Gralns, graln boundarles and interfaces 7-1 General aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 151 7-2 Characteristics associated with grain boundaries .......................... 157 8 Dlffusion 8-1 Chemical diffusion .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 163 8-2 Zones affected by diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 165 8-3 Case hardening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 168 8-4 DifIUsion couples ................................................. 172 8-5 Galvanising ..................................................... 173 9 The decomposltlon of austenite 9-1 The different types of solid state transformatione ......................... 179 9-2 The representation of solid state phase transformations ................... 180 9-3 Growth mechanisms ............................................... 184 9-4 DifIUsive exchanges at interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 187 9-5 The formation of pro-eutectoid ferrite and cementite ..................... 191 10 The pearllte transformation 10-1 The eutectoid transformation in the Fe-C system . . . . . . . . . . . . . . . . . . . . . . .. 195 10-2 The kinetics of pearlite transformation .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 199 10-3 The influence of alloying elements ................................... 200 10-4 The re-dissolution of pearlite ....................................... 206 11 The martenslte transformatlon 11-1 Displacive transformations in the Fe-C system .......................... 209 11-2 Characteristics of the martensite transformation . . . . . . . . . . . . . . . . . . . . . . . .. 211 11-3 The morphology of martensite ...................................... 215 11-4 Softening and tempering of martensite ................................ 219 12 The bainlte transformation 12-1 Bainite structures ................................................ 223 12-2 Upper bainite ................................................... 225 12-3 Lower bainite ................................................... 232 13 Preclpltatlon 13-1 Continuous precipitation .......................................... 239 13-2 Discontinuous precipitation ........................................ 245 x