ab ele E METALLURGY PRINCIPLES AND PRACTICERe. 195.00 PHYSICAL METALLURGY: Principles and Practice, Second Edition V. Raghavan (© 2006 ty Prentice-Hall of India Private Limited, New Delhi. Allrights reserved No part of this book may be reproduced in any form, by mineogiaph er any other means, without pemisson in writng from the publisher 1SBN-978-81-203-3012.2 “The export rights of this book ar vosted solely withthe publisher. ‘Twenty-third Printing (Second Ealition) une, 2012 Published by Asoke K. Ghosh, Prenice-Hall ol India Private Limted, M97, ‘Commaugm Cicus, New Delh-1¥000% and Printed by Mohan Makhijan ai Rekha Printers Private Limited New Debhi-110020.Contents Preface Preface to the First Edition Physical Constants Conversion Factors STRUCTURE OF METALS AND ALLOYS. i 12 13 La Ls References 2 Nature of Metallic Bonding 1 Crystal Structures of Meals 2 Structure of Alloys 10 Imperfections in Crystals 14 Experimenial Sudy of Suucture 22 Questions 27 PHASE DIAGRAMS 24 23 24 25 26 27 28 29 2.10 Experimental Determination of Phase Diagrams The Phase Rule 29 Binary Phase Diagrams 30 Free Energy Composition Curves for Binaty Systems Microstructural Changes during Cooling 40 ‘The Iron Carbon Equilibrium Diagram 42 Effect of Allo ments on the Fe-C Diagram ‘The CopperZine Phase Diagram — 5/ Ternary Phase Diagrams 52 Quaternary Phase Diagrams 57 References 63 Questions 64 PHASE CHANGES 3.1 32 33 34 35 ‘Types of Phase Changes 65 Diffusion in Solids 66 Nucleation and Growth Kineties 67 Solidification 71 Pearlitic Transformations 79 xl xiii 1.28 29-64 a7 6 58 65-99ME Contents 3.6 Bainitic Transformations 83 3.7. Martensitic Transformations 84 3.8 Precipitation and Age Hardening 92 3.9. Recovery, Recrystallization and Grain Growth 96 References "99 Questions 99 HEAT TREATMENT OF STEELS 100-126 4.1 The'ET Diagrams 100 42° The C.C-TDiagrams 104 4.3. Function of Alloying Elements 106 4.4 Formation of Austenite 107 4.5. Typical Heat Treatment Processes 100 4.6 Hardenability 112 4.7 Quench Cracks 1/9 48 Case Hardening 122 References 125 Questions 126 MECHANICAL PROPERTIES 127-160 S.L The Tensile Test. 127 5.2 Plastic Deformation Mechanisms 134 5.3. Methods of Strengthening Metals against Yield 137 SA Creep Resistance 143 5.5 Fracture 147 5.6 Fatigue Failures 153 References 159 Questions 159 6 CORROSION AND ITS PREVENTION 161-184 6.1 ‘The Galvanie Cell 167 6.2. ‘The Electrode Potentials 164 63. Polarization 167 6.4 Passivation 169 6.5 General Methods of Corrosion Prevention 172 6.6 Cathodic Protection 173 6.7 Coatings 175 6.8 Corrosion Prevention by Alloying 6.9 Stress Corrosion Cracking 179 References 183 Questions 183Conents vit ENGINEERING ALLOYS. 188-225, 7.1 Steel Specifications 185 7.2 Low Carbon Steels 188 73. Mild Steels 191 74 Medium Carbon Steels 195 7.3. High Strength Structural Steels 197 7.6 Tool Materials 199 7.7 Stainless Steels 203 7.8 High Temperature Alloys 205 7.9 Cast irons 207 7.10 The Light Alloys 2/3, 7.11 Copperand Its Alloys 218 7.12 Bearing Alloys 223 References 224 Questions 225 INDEX 227-232,PREFACE In the Second Edition of this book, several new sections such as thermoelastic martensite, shape memory alloys, rapid solidification processing and quaternary phase diagrams have been included at appropriate places. The text has been updated and rewritten for greater clarity. The quality of diagrams has been improved and their numbers increased. The list of references at the end of each chapter has been updated. | wish to thank Ms R. Malar for her assistance in preparing the diagrams. ‘Thanks are due to the editorial and production team of the Publishers, Prentice-Hall of India, for their assistance and support.PREFACE TO THE First EDITION Physical Metallurgy deals with the relationship between structure and properties of metals and alloys. It forms a vital link in the processes of making, shaping and heat treating of metals. It thus interfaces with the other areas of metallurgy such as process metallurgy, mechanical metallurgy and engineering metallurgy. Voluminous books are available which deal with the fundamentals of this subject in a detailed and rigorous manner. In addition, there are books dealing with specific topies such as the structural aspect at an advanced level. At the other end, some books present just factual data on the properties and uses of various grades of steels and nonferrous alloys. There is thusa clear need for a book that gives @ broad introduction to the subject dealing with the principles at a reasonable depth and at the same time discussing their relationship to practice. This book aims to do that. ‘All undergraduate students of engineering and metallurgy study phase diagrams, heat treatment principles, mechanical behaviour of alloys, corrosion phenomena, and properties and uses of specific engineering alloys. Undergraduate students of metallurgy have an introductory course on physical metallurgy in their early years. Students of engineering, specially mechanical and chemical engineering, study these topies in one course of the othet—whether it be metallurgy, engineering materials or materials science and metallurgy. This book is intended for such students. In addition, the book is designed to be used by students doing self-study and preparing for the associate membership examinations of the Indian Institute of Metals (AMIIM), the Institution of Mechanical Engineers, the Institution of Engineers, etc. The simple style of the book should make it attractive to them. The opening chapter covers the structural aspects with a discussion of the unit cells of metallic crystals, solid solutions, intermediate phases and structural imperfections. Equilibrium diagrams are introduced in the second chapier, with emphasis on the binary diagrams. Short sections on ternary systems and on experimental methods of determining phase diagrams are included. The major topics under phase changes are solidification, steel transformations and precipitation processes in nonferrous alloys. A separate chapter is devoted to the heat treatment of steels, with a detailed discussion of the concept of hardenabilty The chapter on mechanical properties not only covers the basic concepts on deformation and strengthening mechanisms, but also deals with applicstions to creep, fatigue and fracture. Even though corrosion is a peripheral topic in physical metallurgy, in view of its importance, it is discussed in a separatePreface to the First Esition chapter. The last chapter is totally devoted to practice, giving information on He, treatment, properties and uses of individual alloys with their ns, covering mast types of steels and common nonferrous alloys. The author wishes to thank his colleagues in the metallurgy group of the Department of Applied Mechanics for their assistance. Support received from IIT Dethi for preparing the manuscript and the diagrams is acknowledged. Encouragement from Dr. D.P. Antia, Shri C.V, Sundaram and Professor A.K. Seal of the Indian Institute of Metals is appreciated. New Delhi V. RAGHAVAN July 20. 1983PuysicAL CONSTANTS Avogadro's number Boltzmann’s constant Gas constant Planck’s constant Electronic charge Electron rest mass, Velocity of light Bohr magneton (magnetic moment) Pemittivity of free space Permeability of free space Faraday’s constant Atomic mass unit (amu) Acceleration due to gravity N= 6.023 x 10? mol! = 1380 x 107 Kt 8614 x 105 eV Kt R= 8314) mol KT hh = 6.626 K 1043's e = 1.602 x 10 C my = 9.109 x 10°" kg c= 2.998 x 10° m My = 9.273 x 102° A mi? 6) = 8854 x 10° Foot My = An x 107 Hm! = 1.287 10-6 Hom F = 9649 KC mol"! (of electrons) 1/(10°N) = 1.660 x 1027 ke g= 981 ms?CONVERSION Factors 1 inch I nm 1A ° 786 TF per °F kef Ib dyne dynefem atmosphere bar psi ksi (108 psi) ton/sq.in. kgfiem? kgtimm dynefem? tom (mm of Hg) kgtimm’? ksi Vin ev ere calorie eVientity ergiem erglem? erg/em? Ibsindin® Ibicu.in em/em? 254 mm 10° m 10 m = 0.1 nm 1/573 rad (P+ 273.15) K 5/97 + 459.67) K 9/5 0.101 325 MN m2 10! MPa 6.89 KN m2 6.89 MN mm 15.46 MN m? 98.1 KN m? 9.81 MN m? OINN 133.3 Nm? 0.310 MN m3? 1.10 MN m2 1.602 x 10°" J 1075 4.18) 96.49 kJ mol! 105 J mt 10-3 J m2 od? 175 1m? 27 680 kg m> Jo m msavi Conversion Factors 1 1 1 1 1 mole/em*/see molefem? cm/sec mA/em? Abr 10* mol m 10° mol mChapter Structure of Metats AND ALLoys Physical metallurgy deals wit he relationship betwee structure and properties ‘of metals and alloys The strucure lnflycrced significantly bythe proces ‘adopted Jor metal extraction from the ores and subsequent faseation. The Properties of ecrestare mainly those demanded by engineers suchas enge, ‘icity touginess and corosion resistance. This physical metallurgy intr aces wit areas of processor chemical meaurey, mechaneal metallrey aod ‘engineering metallurgy, I prvies vital link in making, shaping eating and Using meals and albys. In this inteductery textbook, the prinples and the comesponding practise of physical netalligy are olned in simple toms, ‘without pong ito rigorous mathematica eatment ofthe strvcture-sropery relaionsips. LL NATURE OF METALLIC BONDING “Th lon in + met! are held ioglter by chsmical bonds known ax metic buds, The malic onding has cern unique eharacerists a sted elo 1. A netalc etal can be visualized ss an array of pestve fons, with a common pool af clecrans a wich ll he metal atoms have coi thei outemostelectons. The ctor in this pool have freedom ib move theegh the ext any part and virally in any diwtion. They ae known a5 ree leas. The atetve force between the postive ins and the ngatvely-changel fee elections is what binds the meal ome ogee in he ental2c! Meat 2. The re electrons cary bath electric curret and heat trough the ext ‘Thay are responsible fr the excellent electrical and thermal comdctivy of metals 2. The bonds formed hy the fae slectrns a onde Tete a 40 comsizans about bond angles. Anatom ina metalic esta is bended 19 ‘Sins mitosis spore penn, Th provides corel Fei inthe diectioss along wih the metal atoms can te displaced during plastic deformation. This manly reponsible for he unique properties DF high duet and mallabiliy tha metals posses. For exams. g0d Sambo dawn into xcromol thin wires aluminium ean be role iat Fos less than 0.1 im thick, 1.2 CRYSTAL STRUCTURES OF METALS Approximately thee fours ofthe elemerts in the periods table are meta ‘More than twothirds of them (more than 50) possess relatively simple crystal structures, Understanding these structures and ther charactsstiesis a frst tep ine stay of physeal metal. ody centred cubic (BCC) crystal The reference uni (called thexpac ais) for his crystal isa cube, wih atice points at the eight comers and atthe body ‘ene ahrwn in Fig, Ila inthe uit al of the erie, atoms ar polioned ‘one a each ltice point, i. atthe elght comers and tthe body centre of the Unis: As eh ants met st any corner, he share ofthe unit under consideration fora comer alom is one-sighth ave Fig. 1.te- The tom atthe body cenke holngs entirely 1 te un. ger L1 The bay cv eens) he ACC pace ie, th it ello the BCC ey an) he ra of ere ams the ai el So, the etitive number f atoms in te ut cel 8 (corner atoms) 1/8 + 1 hod canted ators) ‘The body centred atom is uching al the comer stom. Each comer atom in tam i touching eight body conteed atoms of the neighbouring cell. TheSic of Wetland loyy 3 number of nearest neighbours toa given som is elle the co-ndination number Z 2= Sor the BCC crs ‘The distance benween nearst atoms is wed to dstne the radius r of the ton. For the BCC crystal the cenir-to-cntre distance of nearest neighbours is clearly half of the body diagonal, «3/2. whereas the length of the cube Cees koma the tice purameter Noting fom Fig, {tb tht the nearest eighbous tush each oer We have reais forthe BCC ers The packing efciency (PE) of atoms in the unit cells defined as ol of toms he unite FE oll of he wnt ell x14/3)8 (aN 14)* 068 ‘The density p of the cyst can be eaeulted as follows mass toms the uit el Plume of the unit ell For example, for BCC ion at rom temperature, latice parameter a ~ 2.87 A (287 = 10" my ‘mass of the Fe stom = $5.5 atomie mass units (amu) 66 x 1077 kg 39.89 5 100 9 ast <0" 7840 kg w= 7.84 glen! ‘Typical examples of metals which form BCC enstals a given below. Pr. Lace 28h 27 525 351 41S 429330 530 305 36 Face centred cubie (FEC) erystal_ The face centres cubic spce later is shown inFig. 2a. Inthe FCC crystal there are eight atlomsat the eight comers ‘of the cube, with sis mare atoms located a the six face centres, Fig. 126. A face eented atom is shared by two neighbouring unit els, for which that Tae is common, as can be see from Fig. 12e, The effective umber of atoms in the FOC nit cll i 8 (Comer aoms) x 1/8 + 6 (face cented atoms) « 1/2 =4 Posie! Meat Inthe FCC ert, each som is in contact with Wwelte neighbours, For ‘example the face centred atom ofthe fron face in Fi, 1.26 sin eontet with ‘the four comer atoms on fat fce al the fur face-centred atoms jst Behind item the top, the botlom and thet side faces of the unk ell) In aliton, ital in contact with four fce-cetred atoms ofthe unt ell in Tent of {ot sen in Fi. 1.2, So the econdination number ofthe FCC ental The distance harwoon nenest mighhoure is half of the fice diagonal «2/2. The ais ofthe atom is 7= av2/4 forthe FCC ens The packing etfiiency canbe shown te be 074, Examples of metas form ing the FCC exstal ae listed teow. Mout AON Nom Om temperatures, changes over to the FCC at 912°C ané back again to BCC at BOC. This phenomenon is ealed pobmarphin Hexagonal close packed (HCP) erysial The hexagonal space latce i shown in Fig. 13a. The alom arangenens within the HF unt eel are shown it Fig, 1.38 There are six atoms al the ix comer ef the hwo hexagonal faces aed ‘one cach a her face centes. There are Ue atoms inte mide ayer (wbere ther are no late points) Each comer of he hevagoral pam i share by $x ‘other prams andthe top and the Poston hexagonal laces ae shared by two cell, Fig, 13e. The eflectve number of atoms in the HF uit cell i 12 (comer atoms) > 16 + 2 (fae cere stoms) « 172+ 3 (middle layer atoms within the zo) = 6 “Tn sles of ease mia il aside the ul, bt tseSiracare of Metaland lays § [Asin the FCC crys, each atom here is ia contact with twelve nears hoighbous. For example, refering 1 Fig. 136, the central atom on the top hexagonal face touches the six surrounding atoms on te sae face, thre inthe middle layer and thre inthe pane above (not shows), yielding Z~ 12. iu “The neagoa es ps esta te exam spc aes, 1b) te HCP ante. at () he shang of mms hy te it ‘The distance between nearest neighbours is he site ofthe hexagon a So, 1 alt forthe HEP crt ‘The height of the prism gives the second katie parameter e. The ideal packing «ficiency cen be shows to be the same as fr the FCC esta (0.7) ‘Typical examples of HCP expt and thelr ace parameters ar listed belos6 osc! Meat Other less-commonly occuring mealc ental suc inclade the tet- rageal te othorhambic andthe rheebohedal crystals. Inthe tetragonal eel, two sides of the unit ell are gual but the thied side is of a iflerent Leng, Inthe orhorhombic unit cell all the thre sides are of different lengths. The angles tweet the axes in these 180 unit cals ae the same as inthe cubic ‘erystal (90) In he ehombshedn ell. the toe axes ae ofthe sane length and the angles between axes are equal te one another, bur not 90° Geometry of dose packing For fll understanding ofthe FCC and 1ICP ‘enyaline arangements, we need to examine the geometry of close packing (Gearing clover pacing). Figure 1a shoma a lose pack plane of equal Sized spheres. The sphere cant be put ary cleser than they are in Fi 14. 1 hulling a sreetimensional strutre,anater cese puke plane can Be plod ovr the ist, such that is spheres fico he angular eaves Hetween the spheres ofthe tit layer, There ae two ses of such eats, designated 2 and in Fig. 1a, The second plane of atoms, Fig 14 oe. can rest verialy ‘ver either the B postions o the C postions. If we asume that fey rest over B postions, then the hit close packed plane ea he stacked on the second in two ways The atom of Be thi plane can be verily over the C positions ‘or alemativels over the firstplane atoms, ie over postions. These two fvrangements ce designated AAC and ABA stackings respetivel, ‘The FCC crystal a staking of close packed planes inthe sequence ABCABC...InFig. 15, the comespondence between the BCABC...stacking land the atoms ofthe unit cll shown, This figure son be compar with Fig, 1.2b, ther the atoms are drawn to tei correct sizes. The slose packed planes are inlined an angle the cube fas and sre Krovi $6 setohedhal planes. “The HEP ental is « stacking of close poked planes inthe sequence ABABA.... Refering 40 Fig, 13b, if we call the close packed plane ‘onesponding othe bore hexagonal fase, is easily seen thatthe ators ‘ofthe top hexagonal ayer are vertically over those ofthe bttom layer end ar,Siracare of Metal and lays 7 therfore, to be designated also as The three toms in the middle nto the ‘wingula evies batween the tp and the bottom ayes and are Bplane stows. The C positions are not wsed ie this stacking gore LS The conesponlecehevest ABC. schitg an he FUE wt el The toy dagoal 1) is pep te cls pc planes ‘The ideal sla raio of HCP stacking i 1.633. The ratos in teal ena, however, vary’ signicanly Tom the ideal vale, se fable on page s. “Miler indies ‘The method devised by Miler i widely used to denote die: tions and planes in crystal, Let the vector in Fig. 16a represent a dection in arya (not cubis in his ea), To find the Miller ndivs of tis diction, ‘the component of ke vector along the thee axes ae determined multiples ‘of the unit yesor ertesponding to cach deetion, The vector thas a component of aloeg the a-axis 1 along b and | alone ‘Note at the absciute magniudes ofthe componetts along b and e ate mt the same, but they are ani, when expressed a multiples ofthe corresponding unit vectors, The Miller indices of ths direction is given by [21], where the squire backets stand for a diction I there is @ negative component, i is denoted by afar placed on top of the appropriate number. Im eabic ental its convenient to have a aotation to spect family of directions. The family is denoted by pointed brackets, eg, <21>> stands for 210, GIT}, 1211, (131 (121), ee. giving all combinations of the indices both postive and negative. The cube edges in the unix cell are represented by p>, te face diagonls by =110> and e body diagonds by <111>8 Posi! Meat 4 oo For determining the Miller indies ofa plane ina enstal, the following Procedure is wed, Referring to Fig. 1.6, the steps ae 1 Find the intercepts of the plane onthe thee coordinate axes 201% 2. Take reciprocals “1d 3. Comert into sinaestintepes in the same ratio 124 44 close in paretheses 3) A fanily of panes i denoted by curly brackets {For example he faces ‘oF «cube are denote! by {100}, The actakedral pines in Fig, 13 are 11) Example 1. Dra a ese packed plane within the unit ell ofan FCC ental and give ite Miller ines 2. Maik the close packed directions tha lie on this pine and give their 3 Draw a (10) plane within the same unit cll and ind the line of iatersee- tion of the 90 planes, Sottion 1. Refering 1 Fig. 1.5, the close packed planes inthe FCC crystal are of the {111} type. Using 2 as the origin in Fig. 1.7, the Miller nies ofthe plate sketched is (TT1) 2 The atoms are touching one anaher along the fice diagonals of an FCC lxysial Thee ae mice face diagonals that ie ox the above plane, cous sponding to the three clos packed directions. Ther Mille indies are Taking oigin a4, AB = [011] wR, BC = {Toi acca TgSiracore of Metaland lays 9 a i) 0) Figwre 17 Pas and dros within the cable wt el 3. Taking Cas the origin, the (17 0) plne is drawn. Thelneofintesecton OF tae to planes is BE: “aking ofsn a 8, BR wT Nate: AS the choice of origin is abit, iis ehsen such hat the ‘iretions start om ihe org and he planes make itereeps on the hese ‘net within the unit cel Miler-Bravais indices For hexagonal crys, fourpitmotatin hi known 1s MillerRravais indices, is used. The use of sich a notation enables exyallogaphivally equivalent planes or dtetons ins hexagonal crystal t be ‘devoid by the tame set of indices. Thve of the axes ty, 0: and 0, tre «coplanar and fe onthe basal plane of the hexagonal prism, Fg. 1.3 witha 120" ange beincen them. The four ans is thee ass perpencul fo the basal pane The determination ofthe Milr-travais nies usted fn Fig, 1.8 for the two examples given bolo, The indices ofa prismatic plane (one of the vertical ices ofthe prism) is of the sype (100). Hrmakes an intercept of and I slong a) anda, tee rapectvely and ie parallel tothe Not thatthe use of thre coplnar vectors resus inthe condi thet hk10 Pst allen /\/ \J\ a ‘The indices oF adtecon tat along one ofthe toe a axes (ple 0 4 sile of the hoxagonal fce) te of the type [2T TO}. For this example, the 0 (postive devstion from Healiy), th formation of ike bonds (A.A and BB bonds) is prefered. For small postive values of Ala there tendency fo like lon cuser tether inthe slid olin ‘Onan average, an A atom has more A neighbours than iste eave fora perce random sold soliton. Atlas temperatures efor Inge posve ‘values oF Aff te clustering tendeney increases. Eventual immrciilty resus. Te sold solution spits nto two separge piss, one nich In A tnd the other rch in B 3. WM <0 (sezative deviation from ideality, the formation of unlte bores (AR bonds) i prefered: Mere thee ic 8 endency fr shor mage ‘ordering, ig. & and B. atoms show a preference 19 bocome nearest neighbour At low tomperature, lag range order may tin and an ordered slid soutien may form. If A/7qy 5 only slightly negative, the ‘ordring tendency may br so wet that lng range ordaing dove not foccar af any temperature If fa, fas @ large negative value, the alley ‘nay remain in the fuly erred ste rit pt the eli pit behaving Tike a chemical compound On mixing two wetas a a constant temperature, + Lage number of dstin- ‘uishablecontguraonsw of equal potential ener resul. The cenfgwatonal ent &.is given by Shine aay \whae is Botumann’s constant. The entopy of mixing, mole facion oF A wih Ay ole tacten OF 8 [1, + -Xy= 1) ltd Fandom solé Soon tums ou 10 be AS —R Oly In 34 + iy IX) a3) 2X4 ad Xs being faction. the entropy of mixing is always poste, I wends 0 lower the fs energy according 49. (Il). ‘An dal slid slution is random: For small evitons from ideality (ether postive or negative, the solid solution eap sil be ahem to be random foe the purpose of computing the entropy of mixing. This i alld regular solution Spprosination. The tee encrey oF mining is then sien by Ging Man + RING bn Ny + Xe bX) aaySacre of Malton Aliya 13 The variation in the fee energy ofa sold solution as funtion of com- postion sketched schematiesly in Fig, 1.10. Figure 10a i foray eat Soltion, where Alo, ~ 0. The fee energy decreases with incresing coneet- tration of either clement reaching a minimum atthe mt-composton. where the ‘entopy of mixing isa maximum. Figie 1.10) iva ease where Any <0, The fiee ener curve has the same shapo asin Fig. 10a, bat mere U-shape Figre 1.10 i for a solution wiere Aff, > 0. The fee enewgy curve decreases inal at theo pure ends de to the deminance of the enroy term. With increasing eoneenteaion, however, the postive 4g. tem dominates and the few energy cue hac two minina anda maximum, Thor eno compte sod solbilty in ths case. The manimum solid solublites are obtained by drain the common tangent othe fee nora curve Fi. 110e. The compositions ‘omesponding 6 the poins of tngensy cand c, give the limit of solubility at {be fo edo specvely. Tn between cel ey Ue ll fs sabe eal co mince of two solid solutons of composition cy and c With increasing ten- Petture, however, the ettopy frm may dominate over the enthalpy term or ll composition, the free energy curve may become U-shaped anda singe sod Solaion may tecome stale over the enife composition range rr BAG GB a b . awe 1.0 Poesy of sd soto) meg Aj 200, (eu Stun Aig 1 Hea. Abd 6} Ail sie Intermediate phases Ioermediate phases fete alloy erysal tts which are diferent ffm citer of the paren exysas, Some merediate phases hare ‘4 xed compostion and arecallelintermetalc compounds, Quite oe, however, the intermediate phases have a signieant composition range. Only a few intemetalic compounds obey the normal rules of valene: Many of these are based on the cubic sutures of sodium chloride (NaC) oF ‘alum fuorie (Ca) the NaCl structere the chlrine ions ave atthe FCC postions ofthe cubic unit cell andthe sodium ions are atthe octaedal vos. Examples of sich imermetite phases are MgSe PbS and CT. Inthe CaF ‘str, the calcium ions are a the FCC postions ant the Muorne ions are at ‘the toahadral void postions Examples are MgSi, MgiSn, Cu8 and BoC ‘The nickel arsenide (NiAS) structure is fen ormel by the traxsiton metals ‘alloyed with the meullods of te V and Vi columns such ass, Bl, Sb, Se and14. Physical Maas ‘Te. The sructure has the HCP sacking sequence with atemate layers of metal and metalloid atoms. These phases have a faily wide range of scubiiy Examples are CrSb, CuSn and MnSe Elecron pases (alo calle electron compwunds oF Hume Rothery com pounds) have 2 ide range of solubility. They oxeur ut cerain definite values Typical exampies are Cuzn (3:2), CuzZn (21:13) and Cuzny (7), Laver pen pssess one of the tes elted stivetures withthe gene! formula AB., Examples ofthe thee protonype structures based ox magnesium fare: MgCu; able}, Maz; (hexagonal) and MEN hexagonal) ‘The sigma phate has a complex erysl siectre and is very brite. The unit cells tragonal wih 30 atoms in the eel, THs phase isa source of cembritlment in stainless steels, “lo carbles ad nies form very bard and brite compounds They sre ‘often cubic with the formula MX. wih the metal toms (M) in FCC postions ‘andthe erbon or nitrogen (X) in iets position (ocahedral of vetrao- da, Exsmples ate TiC. VC. NBC, TIN, VN and NBN. Example of carbides ‘wih oer stmtures are CrsCu CryCy, MOC and WC. Tike vther solid soluton,inerediats phases ty remain disordered high temperate and become dered at low terperatures. The BIBCC) phase ‘oe CZ alloy stems peal example, The canpostion of is around SOCUSOZa. At temperatures above 445°C, the copper and zinc atoms ae an only diseibued onthe BCC ses. At lower temperatures, sn ordered stuctre forms withthe zine stoms atthe body comers and the copper atoms athe body ‘ezmes (or vee vest) When this occurs, extra ines appear in the difaction pater, =the ordre shueture corresponds to a sinple cubie space latice (ith latice points athe eight corners ofthe cube ony) rather than the BCC 1 aldtcnal diracton ines general, intemecale compounds and ordered sold soluions poses line ductility and are relatively brite phases. They are usefl for inereasng the strength of ¢ tle mais, bur athe cox of reduced duc. 1.4 IMPERFECTIONS IN CRYSTALS Inperfectons in crystals en be classed according to her geometry as pois, lineand sirface imperectis, The characteristic of iferent imperfect ave briefly censideed below, Polat imperfections Thee a point-like regions of distortion in the ems The common ‘pes ae (@) vacancy (6) inerstialeySrctr of Meals ond he 18 (6) inestialimporiy, and (4) substations impurity [A vacancy isan atomic sit from which the atom is missing, on Fig. 1.1 An interaey rors tan atoms dnplce fom regular te too ite sit site, in Fig. 111, An inertial impurity is sal stom occupsing Ines votd space Berween pare atoms ofthe eysta © Hn Fg. I.E A subsitsional impurayis an impurity atom that as substituted for one ofthe Parent atoms ona regular atom sited i the Sure (ier! pa, td (2) ssbtionel pry Point mperecrins ineease signfcanty the connguraonal entropy of the ‘ryt and thereby lower is ee energy. So, a cerain umber n of point imperteccons isin thermodynamic eqilibrum inthe esta at given temper ture For example the faction cF vacances n/N ina esta at temperature Tis Ben by 2 wixo( Ate Wy geon(-] as) whe thet mr of somes and Ys ety of farmation Beaten ent Kaylee mentite uch oe at peo trngng i tn fom eh ental othe sre Dibeatons Line mpeecr ae own a dso. The yoy of ‘cation ca be ndenood wih efereace othe to ning sat Be wpe 1. the edge dileatin, and 2 the Seren disbcationaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.18 Physical Maan ‘tides a (11) plane causing slip over the hatched region. then exes-lips ‘on a nonpanllel Ty plane. Inthe double crosstip process illstated. it ‘again cxes-slps ack fo 3 (111) plat, veh is parallel to the ‘ital plane. age dislocations canotceoss-slip. When they move on a ple be than the slip plan, the mation hnvolhes ation or subtraction of atoms to te ede. ‘Ta ete El sthcoiservaiv wd sald clio: Aci ein ‘of stoms geneally occurs at a atemie sep eiled jog en the edge ofthe incomplete pare, Fig. 14 Edgedskcatins clin upc lint dv, depernling ‘on whether the incamplet: plane shinks or increase in extent Addition of ‘om Is roqired for chiming down, whereas subiracion of atoms (or ‘equivalently addition of vacances) i aquired fr clnbing up. In Fig. 1-8, roving of he to the Ie s equivalent climbing down; moverert to the ‘oh i climbing up. Clinb can clearly occur only when there i sufficient thera energy for the difsion of atom to or avy from the edge of the incamplew plan. 1, threfre, an important process in high temperanre deformation known as erp, discussed under Seo. 58 igure 14 og sa sp on te edge of te iconpete pln oa ee dost. Patil dislocations and stacking faults Full dislocations described above have an integra ate translation as the Burgers vector. Fox paral (or impr fect dslcatons, the Burger vector a ction ofan interatomic distance. As the elastic enewy of dislocations is proportional othe square of their Burgers ‘eet, th spliting of a fll location by into wo partial dislocations by and yi favoured enerztca, whenaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.22 Pistal Malley Figere LI7_ The sais sranganent a oe sie af in bundy ‘A lame substiuional atom can ieteraet witha vacancy in the same esl to wor the distortona exergy. The Wo defects stay together in close poxin= ity. Point imperfections imtract with the ditortonal peomery asiocint wth dlislocatins. For exemple, a large substitutional stom can lower is distrtional ‘nergy hy staying in the toil region jst below the edge of the incomplte plane ofan edge dislocation, An inet atom, tht i tov large forte vad occupies, can simlrly lower it eneray by staying inthe cor of am edge Alsloctin. Such an effets paticuly marked in low carbon and mild tee. wher the sverized inter) carbon stows tnd 10 segregate in voids around the tensile region of edge dislocations. Such slate atmospheres around dis ‘atons ate Known as Cone! aumospieres. Pole imperfections aso sezrezate ‘at grain boundaties ss the steucture a the boundary is more ape th ‘he imerior of the esta. Such segregatien resus In Several me important effects sich as the solute dag effect on a migrating and inerganuareracking Disleatons fie on slip planes win th crystal. As the crystal orientation scrss a grain tounduy (4 twin boundary) changes drupt. a Gsloeation on ‘sip plane in any one grin cannot cross the boundary aad move oF to the Same slip plane oF the next pain. Because of this, movi ilocations get pled up against grain boundaries. This ess in an importa inlanee of pan sire fon the sield stength of metals and loys. LS. EXPERIMENTAL STUDY OF STRUCTURE, ‘The structure seen with the naked eye or under ow magniition by acid etching of ste! bars, bills, castings and fygngs i called macrosracur. teaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.26 Physical Masons ledropolshing. in the window tetnigue, pointed decides ae used. The met dietly in froat ofthe pointed eleecode sdisolved more rapilly asd perforate. The metal adjacent tthe perforations thin enough tans the lectons, Difficton patens can he obsined over any selected ares of the ratix oof panicles embedded init “The scasning electron meroscope 10 the scanning electron mieraseope, Fig, 1196, beam ofelecwons is moved ove the specien surface in a sequense ‘of closely spaced ies. The eletons inert wih the surge wom ahd the ‘output depends on th: compesition ard topoeraphy. The output signal is picked tp end ws to modate the brightnes of aca ray bea, whch is movie synchronously with be seaning search bea. The depth of feus ofthe scanning «lecron microscope i 0 high fata rate surface can be directly examined Without ay polishing. In metallagies! studies, Factopephic examination and, to allesser extent, examination of polished and etched srfaes ate cared cut ‘The electron probe microaralyzer The composition of alloys can be determined by convention chemical analysis and other modern instrumental rmetnds such as spectroscopy or x-ray Nuorescence These give only the average ‘commposiion. The eleston probe micreanayzer (EPMA is a ol for determining ‘the composition ona mcton scale relevant to metallica problems such as iteration of very small incusons and preciptes and eomposiion raierts fn tibre ovl, fa his trun bei of eects about yim Samer strikes the spesimen surface, interacting with the atoms ef the specinen 19 Produce ‘rays. By measuring the wavelength and intensity of the x7a"s Produced, iti possible © determine which ekmens are present and thir respective concentrations. X-ray difraction The eystlstrucure of metals ané alloys is determined by sera difation. The Bragg law describes the effect produced bya eam of x rays of wavelength J inclent st an snale of @ (alld the Bragg angle) on 0 41 et of ara! atomic plnes wih an interplararspucing ofc: eam tain as) wre i an integer, ‘There ares numberof metods or determining the ysl tet, Inthe rowder method, a monochrome beam of xr is incident on the powder sample ofthe anknown metal. The diffracted beam is recoded in dfiracto- rete as a funtion of 28 Figure 1.20 shows a wacing from a dict, where the intensity peaks correspond to postions, where the Breey eendtion given in Eg. (1.8) i satisfied. Computer software packages are ow avilable for analyzing tv draetion daa and ascertaining the ery stictueaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.30 Physical Metallurgy Components Components refer to the independent chemical species that eon stitute an alloy. For plain carbon steel, iron and carbon are the chemical specie so, the components are Fe and C (graphite). However, carbon almost always isin the combined form as cementite (Fe,C) in steels, even though cement- ite is metastable and has a higher free energy as compared to graphite. So, it is common to show the phase relationships in the Fe-C system on a metastable phase diagram with Fe and Fe,C as the components. The choice of all the three (Fe, C and Fe,C) as components does not constitute a set of independent chem cal species. Degrees of freedom ‘The degrces of freedom refer to the number of indepen dent variables associated with the system. The total number of variables is the external variables (temperature and pressure) plus the composition variables. The number of composition variables required to express the concentration of C components in a phase is (C — 1)* . For a system with P phases, total variables = P(C - 1) +2 (22) The degree of freedom F is equal to or less than the total number of variables F2C-P+2 1, Fis less than the total number. The minimum value for the degree of freedom is zero and this sets an upper limit on the number of phases that can coexist in a system under equilibrium, 2.2 BINARY PHASE DIAGRAMS The most commonly used phase diagrams are those that depict the equilibrium between two components. These are known as binary phase diagrams. Many engineering alloys contain more than two components, Nevertheless, the binary diagram between the two major components is still useful in interpreting the phase relationships, For exemple, the Fe-Fe,C phase diagram is used in the study of carbon steels, which usually contain small quantities of S, P, Si and Mn, in addition to Fe and C. In other cases, more complex phase relationships have to be studied. For equilibrium in a system containing three components, temary phase diagrams are used, Further, it is possible to depict the more ‘complicated phase relationships between 4 number of components oa a pseudo- binary diagram, For graphical representation of the binary phase relationships, we need a map with three axes corresponding to temperature, pressure and composition. ‘As three-dimensional diagrams are difficult to draw on paper, for binary phase diagrams it is customary to ignore the pressure variable and the vapour phase. Note that every phase in equilibrium ina system will haveall the components init, however small may’ be the congentration of a component.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.34 Physical Metallurgy 10 oT 10 er 7 | fw oa ¢ i” be 5 [ft nestor bo E * wo Ye Blas so 400 a a Copper, wt. % Figure 22. “The silver-copper phase diagram isa simple eutectic system, cool —> reaction é L ne @ + B structure Fee Fee composition > & a ope wee Cu 281 88 2 Plate-like crystals (or rod-like erystals) of cand fi arranged in an altemating, parallel fashion are the characteristic structure of the eutectic mixture as shown in Fig. 2.32, Sometimes, an abnormal or divorced eutectic structure is observed. Here, the eutectic is present in so small a volume fraction that the plate-like structure des not form. Instead the minor phase of the eutectic forms and ‘grows as islands that appear unconnected on a polished surface. The other phase forms the continuous matrix. Abnormal eutectic structures are observed, when one of the phases forms strong covalent bonds, e.g. the ALSi and Fe graphite systems. Chinese soript is a structure between the lamellar (normal) ‘eutectic and the abnormal eutectic, Here, the lamellar morphology has degenerated into a pattern that looks like a Chinese seript, Fig. 236. An alloy to the left of the eutectic is known as a /ypoeuectic alloy. An alloy to the right is called a iypereuaectic alloy. In both these cases, on cooling below the liquidus boundary, the procutectic phase (cor ) separaics out frst. ‘On further cooling, the fiaction of the proeutectic phase increases til the eutectic temperature is reached, Just above the eutectic temperature 7,, the tie-line indicates that the composition of the proeutectic phase is cq (or eq.) and the liquid is ofaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.38 Physical Metallurgy ower temperature 7, cuts across the two phase region in Fig. 2.Sa. The corresponding free energy curves intersect each other, Fig. 2.5e. There is a certain range of composition over which the free energy of a mixture of the liguid and ihe solid phases is lower than either of the phases. This composition range is obtained by drawing @ common tangent xy to the two curves, see Fig, 2.5c. The compositions at points x and y' are ¢; and c, respectively. Over the range of composition to the left of c;, the free energy of the liquid is lowe 50, itis the stable phase. For compositions that lie between x and yy, two-phase equilibrium prevails. The mixture of the two phases in the proportion given by the lever rule has the lowest free energy, For compositions to the right of ,, the solid phase is the stable phase, At temperature 75, Fig. 2.5d, the solid phase has lower fice energy and is stable over the entite composition range, fh z L 4 o KS m a g 5 Me : 5 7 : i a i an +S é ! 1 ‘I a b s s 5 ? ; S| i i eT A a G B A B ¢ a Figure 2.5 Pree energy-composition relationships for an isomorphous system at three temperatures For a eutectic system, three free energy-composition curves are drawn, one for each of the phases: q, and liquid. The sketches in Fig, 2.6a-d illustrate the relationships. At 7), Fig. 2.6a, the liquid phase is stable over the entire ‘composition range, as it has a lower free energy, At Ts, the liquid free energy curve intersects both the cand f free energy curves, Fig. 2.6h. Two commonaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.42_ Physical Metallurgy Deviation from equilibrium is a serious problem in alloy systems in which a peritectic reaction occurs. Recall that this reaction is between a liquid and a solid. The product of the reaction is a solid, which forms at the boundary between the two parent phases. As soon as some solid product (@) forms, the parent phases (Z and f) get separated and are no longer in contact. This phenomenon is known as surrounding or enveloping, Fig, 2.9. Further reaction Figure 2.9 In the peritectic reaction + b> a surrounding or enveloping cceurs, shen the product ce phase surrounds the unreacted B phase can occur only through solid state diffusion through the intervening product, layer. Solid state diffusion being very slow, peritectic alloys solidify with large deviations from the equilibrium composition and structure, ‘A homogerizing treatment is required to remove the compositional variations that aezompany coring or surrounding. The alloy is heated toa high temperature and held there for a prolonged period, during which diffusion levels out the compositional gradients and yields @ homogeneous solid solution. Extreme care is required during heating not to cross the solidus. Note that, for a cored structure, the effective solidus is lower than the equilibrium solidus. If this solidus is crossed, melting occurs near the grain boundaries. Liquation is often accompanied by grain boundary oxidation and the phenomenon is ealled burning. A bumt alloy is permanently damaged, as the oxidized grain boundaries cannot be restored to the initial unoxidized condition by means of a heat treatment or by mechanical working. Overheating refers to heating close to the solidus, but without causing, liquation. Overheating impairs the properties of steels through loss of ductility and toughness. It is associated with the segregation of impurities and subsequent precipitation along grain boundaries. The effects of overheating are not permanent and can be removed by a subsequent heat treatment. 2.5 THE IRON CARBON EQUILIBRIUM DIAGRAM In Fe-C alloys. carbon may be present either in the form of fiee carbon (graphite) ras iron carbide (FesC). The most frequently oceurring form in steels is FesC, known as cementite. As already pointed out, cementite is metastable with respectaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.46 Physical Metallurgy As the two boundaries of a cementite plate are close together. they may not be resolved as separate lines. Cementite often appears as a single dark line. At higher magnifications or in a coarse distribution in peerlite, the cementite boundaries show up as separate lines. Hypoeutectoid steels The composition of hypoeutectoid steels is less than 0.77% C. In aldition to pearlite, the proeutectoid ferrite (pro cd) is present, Fig. 2.12, The fraction of the pro a can be estimated from lever rule. For example, in mild steel of 0.2% C. Sean = OIT=02 Pea 077-002 Satie = 1 = 0.76 = 0.24 ‘The proeutectoid ferrite forms at the austenite grain boundaries between 4; and Ay temperatures. Hypereutectoid steels Here, the proeutectoid phase is cementite. It separates between Acq, and 4, temperatures as a thin network along the austenite grain boundaries: In a 1.2% C steel, applying lever rule, we have f 12-077 Pe 6.67 -0.77 Ipcnite = 1 - 0.07 = 0.93 0.76 Figure 2.12 Scanning Electron Micrograph f mill otek, showing procuteciid ferite and pearite 2.6 EFFECT OF ALLOYING ELEMENTS ON THE Fe-C DIAGRAM The effect of alloying elements on the Fe-C phase relationships is best under- stood by first considering the two types of phase diagrams obtained, when iron is alloyed with a substitutional element.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.50_ Physical Metallurgy move closer, thus restricting the extent of the austenite phase. To the left of the field are austenite and ferrite and to the right austenite and carbide. The eutectoid temperature moves up. The eutectoid composition shifts to lower carbon contents, With Cr> 19%, the austenite phase field disappears altogether, The critical composition at which this happens are given below for a few typical cases. Ferrite aabiizer cr 3 Mo OW v Criical compositon, vite 195 Lot 1200, 2 1000] g 5 2 wo & oo RO 08 4316 Carbon, we. Figare 2.16 The shifting of the fy and Ay phase boundaries in the preseace of mangancse. Carbon being an austerite stabilizer, «higher eoncentraon of a fenite stabilizing element (19.5% Cr for FeCCr as compared to 12.7% Cr for Fe-Ct) is required inthe presence of carbon to eliminate the austenite il For low ally sels containing C between 0.08 and 14 wi, 4 and As erica temperatures ae given by the following cepiial equation Ag (°C) = 723 = 10.7Mn = 16.7Ni + 29.1Si SP 6.9Cer + 200k8 + 6-38 des CC) = 910 ~ 203 JE ~30NIn — 20€4 ~ 15.2 —Ner— 7H0P + 44.781 + 31.5Mo + OAV + 460AL-+ 13.1W + 120Aaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.54. Physical Metallurgy Fa prlar avlar IF three phases coexist, their relative proportion is determined from a tie- triangle, For example, if the overall composition o in Fig. 2.19b exists as a mixture of 7% Sand ¢, the respective compositions being s,/ and u, the relative proportions of the three phases are given by (see Fig, 2.19b): fy= ollsl f= omltm fe= onlun ‘An example of an isothermal section of the Fe-Cr-Ni system at 650°C shown in Fig. 2.20. Two tie-triangles are seen in this section, Three phases are present in each of the tie-triangles. FS > e = Ni Weight Percemt Nickel Figure 2.20, FeCreNi ternary isothermal section at 650°C Another common way of presenting the ternary phase relationships is to draw vertical sections (called isoplechs), keeping the concentration ef one com= ponent constant. The xaxis then gives the variation of one of the other two components. Temperature is plotied on the y-axis, Figure 2.21 shows a vertical section of the Fe-Cr-Ni system at a constant Fe content of 74 wi%.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.58 Physical Metallurgy For two-dimensional representation, the concentration of one of the components and temperature is to be kept constant. Figure 2.25 shows an isothermal section of the Fe-Cr-V-C system at 700°C and at a constant C content of 0.2 wi, MayCy, M,C) and MC are alloy carbides, with M standing for (Fe, Cr, V). ABC is the triangular section of a tietetrahedron, showing a four- phase equilibrium. 20 e+MC G+MC+My,Cy 15 5 5 3 B10 2 a atMC4M C3 a+ My3Cy 2 os +M,CytMa3Cy atMyC; 0 v © v 12 Weight Percent Chromium Figure 2.28 FesCe¥.C quatemary isothermal section a 70KPC and ‘at a constant carbon conten! of 0.2 wt. 2.10 EXPERIMENTAL DETERMINATION OF PHAS! DIAGRAMS ‘A variety of physical techniques are used for the experimental determination of phase diagrams. Among these. the more important are: (i) thermal analysi ii) microscopic examination, and (iii) x-ray diffraction, Other auxiliary techniques are dilatometry, electrical resistivity and mag- measurements,aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.62_Physical Metallurgy CI wo phases DO Xoo — O Single phase o0°0 Initial bracketing ‘Temperature WL%B Figure 2.28 The determination of solvus bourdaries by the metallographic and x-ray methods, Auxiliary techniques Dilatometry is based on the volume change associated ‘with most phase changes. It is common to record the length changes of a specimen as a function of temperature during heating or cooling, Figure 2.29 13000 Fe-0.06C-.92Mn Auto! 000 1000 0200 400-600 800-1000 ‘Temperature, Figure 229 The fractional change is of a low carbon stec! on heating and cooling, The ebrupt changes in slope correspond to phase changes.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.66 Physical Mettturgy in intensity with time, until two diserete phases corresponding to the equilibrium ‘compositions form, Many metallurgical transformations occur by nucleation and growth. We will consider only this mechanism 3.2 DIFFUSION IN SOLID Diffusion is the mass flow process in which atoms change their positions rela- tive to their neighbours in a phase under the influence of thermal energy and a concentration gradient Fiek’s laws Fick's first law describes steady state diffusion and is written as de ae 6.) where J is the diffusional flux in the x-direction (number of atoms transported per unit area per unit time), dc/de is the concentration gradient, and D is the diffusion coefficient Under steady-state conditions, the flux remains independent of position x. Fick's second law is applicable to nonsteady state diffusion. Here, the flux is changing as a funetion of position and time, When the diffusion coefficient not a function of concentration, the second law is of the form: ae S Solutions to the second law for different initial and boundary conditions are available, but will not be covered here. A quick but approximate estimate of the depth of penetration x during nonsteady state diffusion is given by x=VDr G3) Atomic model of diffusion In interstitial diffusion, Fig. 3.la, the diffusing ‘atom jumps from one interstitial site to a neighbouring interstitial site in execut- ing a unit step. The neighbouring site fs usually vacant in dilute solutions. The activation energy for interstitial diffusion is simply the energy barrier along the ppath from one interstitial site to the next. Substitutional diffusion occurs with the aid of vacancies, Fig. 3.1b. A substitutional atom jumps from a regular site into a neighbouring vacent site in executing the unit step. Here considering the probability of an atom crossing the activation barrier along the path, the probability of the neighbouring site being vacant has also to be taken nal diffusion is generally 4-6 orders of J we rand 62) imto account, Because of this, substitut ‘magnitude slower than interstitial diffusion, The unit step in diffusion is executed with the help of thermal energy. So, the diffusion coefficient D is strongly dependent on temperature and is of the formaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.70 _ Physical Mettturgy ‘When both the parent and the product phases are solids, volume or shape changes introduce elastic strains during nucleation. The sirain energy is added as.a positive energy term to the nucleation Eq. (3.5). This has an additional inhibiting effect on the transformation. To minimize the total energy, the particle usually assumes a nonspherical shape such as a disc or a plate The increase in the size of the particle beyond the critical size is called growth, Like nucleation, growth is dependent on thermal fluctuations. The growth rate U is zero at the equilibrium temperature T,, as well as at 0 K. It passes through a maximum at some intermediats temperature, which turns out to be higher than that for the nucleation maximum, as shown in Fig, 3.4. Heterogeneous nucleation Here, there are certain preferred sites in the parent phase, where the probability of nucleation is much greater than that at other sites. The prefered sites are the walls of the container (in the case of a liquid), inclusions, erain boundaries, stacking faults and dislocations (in the case of solids). In Fig, 3.5, he nucleation of the new phase ion the surface of an inclusion Sembedded in the parent a phase is schematically shown. The f particle is in the form of a spherical cap. The contact angle @ is determined by equilibrium between surface tension forces (7) acting at the periphery of the f particle. The energy of the inclusion surface is utilized during nucleation, The barrier for heterogeneous nucleation Af, turns oUt to be L Aftia ~ GaF Fano (2 - 3 603 0 + cos? 0) 68) The Key to the reduction of the nucleation barrier is a small value of @. When the erystal structures of 5 and B are similar and the lattice parameters are nearly equal, a low energy interface forms between them. The contact angle @ is then small and the nucleation bartier is very effectively lowered. Figure 35 The nucleation of a B phase particle on the surfice of a nucleating ‘agent 4, The surface tension forces yg, ste. ast along the indicated diccctions Overall transformation rate ‘The overall transformation rate ddr, where is the fraction of the product formed, is a function of both the nucleation rate and the growth rate. It has the same temperature dependence as nucleation andaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.74 _ Physical Mewatlurgy £ 5 er “ ga er z L 2 le e E 5 «, ‘Compesition a s) s g gr 2 a Tiquidus z 2 Constitutional é eT supercooling & a4 y Distance Distance « é s fou s L Interface Interface e f Figure 3.7 Constitutional superccoing: (a) the phase diagram, (b) the comy Profile inthe liquid abead of the interface, (c) and (d) the temperature profiles ahead of the intrfae, and (e) and (7) the profiles oF the interface Formation of dendrites Under conditions of constitutional supercooling, a cell structure with protrusions forms. If the velocity of the interface (the growth rate of the cells) inereases further, the cells tend to grow along certain preferred directions such as <100> for cubic metals. Then a dendrite structure develops, where the growing crystal is in the form of a Christmas tree, Fig. 3.8. Recall that the <100> directions are three mutually perpendicular directions. One of them coincides with the growth direction of the central (primary) arm of the dendrite. The other two perpendicular <100> directions correspond to the secondary and tertiary arms of the dendrite. A number of primary dendrites might have branched off from the same nucleus and thus be part of the same grain, see Fig, 38. The spacing between dendrite arms decreases with increasing cooling rateaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.78__ Physical Newallurgy ‘out of the ingot. The left-over CO jis in the form of bubbles or wormholes between columnar grains. The turbulence during gas evolution in a rimmed ingot physically transports the metal to different parts, causing macrosegregation to a greater extent. Capping is a variation of rimming, After the ingot has rimmed for some time, a cast iron cap is placed on top of the mould to freeze the top and stop the rimming action roa roo a b e Figure 310 (a) Killed ingot, showing the shrinkage cavity’ st the top. (b) semikilled ingot, with CO bubbles near the top half, and (©) rimmed ingot with CO bubbles throughout the volume. ‘The upper part containing the exposed pipe in killed steels has to be rejected and this decreases the yield to about 80%. The yield from a rimmed ingot is higher. Continuous casting Continuous casting is now an established method of producing semi-finished steel products like billets, blooms and slabs. In this method, the liquid stee! is first poured from a ladle into a refiactory-lined tundish, which directs the flow into a venical water-cooled copper mould. The strand of steel which comes out of the mould is semi-solid, with a liquid core encased in a thick solidified shell, After solidification is complete, a welding torch cuts the strand into the desired lengths. The structure of the continuously= ‘cast steel is similar to that of an ingot: a chill zone on the surface, followed by columnar grains and a central equiaxed zone, Continuous casting offers several advantages. It yields a semi-finished shape (billet, bloom or slab), in contrast to the unfinished shape obtained in ingot casting. It provides better productivity and yield, reduced energy and man- power, improved product quality and consisiency of quality, as compared to ingot casting. Only’ a killed steel can be continuously cast. The yield here is about 10% more, as there is no rejection in the form of the exposed pipe of an ingot. A rimmed steel cannot be continuously cast, as the rimming action can puncture holes in the solidified shell, with liquid pouring out Rapid solidification processing The cooling rate cessing (RSP) is i in rapid solidification pro- excess of 10° °C per second. In the melt spinning methodaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.82_ Physical Metallurgy ‘The interlameliar spacing If the steel is cooled slowly, the effective transfor- mn temperature is just below the eutectoid temperature. This corresponds to tion of @ high growth rate and a relatively low nucleation rate, see he crystals of ferrite and cementite are relatively coarse. If the steel! is cooled more rapidly, the effective transformation temperature is lower and corresponds to a high nucleation rate and a relatively low growth rate. Note that carbon diffusion is required for growth and that the diffusion rate of carbon decreases with decreasing temperature. The crystals formed are, therefore, finer. The size of the crystals in pearlte is measured by a parameter called the inter lamellar spacing. The interlamellar spacing of a pearlite colony is defined as the distance from the centre of a ferrite (or cementite) plate to the centre of the next ferrite (or cementite) plate. The true spacing is seen under the microscope, when lamellae ofa colony are perpendicular to the plane of observation. When they are inclined at an angle other than 90°, the measured spacing is larger than the true spacing. Experimental is constant for a constant transformation temperature. t decreases with decreas ing reaction temperature. In Fig. 3.15, the logarithm of interlamellar spacing in A is plotted against the degree of supercooling AT below the eutectoid tempera ture. Transformation very near the eutectoid temperature yields coarse pearlite, With the interlamellar spacing of about 1-2 jim. Coarse pearlite is soft, with a hardness of about 5 R, The pearlite formed near the nose of the C-curve (580°C) is very fine, the spacing being less than 0.1 jim. Hardness of very fine pearlite can be as high as 40 R. it is observed that the true interlamellar spacing, 40 2 a6 a ba 28 a a aT=(T,-1).°C igure 31S The variation of the infelamellar spacing with the degree ‘f supercooling AT below the eutectoid temperature 7,aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.86 Physical Mettturgy 600 300 3 3 M, ‘Temperature, °C = s My 4 0 po IN 0 02 04 06 08 19 12 14 Carbon, % Figure 318 ‘The effect of carbon on the Mf, and M; temperatures and ‘on the morphology of martensite in plain carbon steels Other characteristics Two morphologies of martensite are commonly observed: 1. lath martensite, and 2. plate martensite. At low concentrations of carbon and alloying elements and at high tempera- tures, lath martensite forms (see Fig. 3.19). The lath unit has the shape of a strip. A number of laths form in a parallel fashion, more or less completely filling austenite, Fig, 3.194, At higher concentrations of carbon and alloying elements and at lower transformation temperatures, plate martensite forms. The plates are arranged in a non-parallel fashion, partitioning the austenite grains into several smaller pockets, Fig. 3.19b, The hardness of martensite is a fanetion of its carbon content, as shown in Fig, 3.20. The hardness values at 0.1 w1% C intervals are also listed below. Carton wi% Ol 0203S Hardness R38 MOST. To realize the full hardness, the steel should have at least 0.6% C. Alloying elements have no significant effect on the hardness of martensite. Martensite with hardness below 55 R, has some amount of ductility. Those with hardness more than 60 X, are generally brittle,aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.90 _ Physical Mettturgy externally applied stress above /M, (in place of a temperature change) can cause the same cyclic phenomenon, i.e. the plates appear and grow on increasing the applied stress: they shrink on decreasing the stress and disappear when the stress falls to zero, Some of the factors which favour the thermoelastic behaviour are a small hysteresis, a small shear strain associated with the martensiti ‘transformation and accommodation of transformation strains elastically, without the occurrence of the ineversible plastic deformation, 1 1.00 2 |mq | Leet | Bors mF - g M 2050 Sie 4 | feat olf | ° [For 0 100 200 300 400" 500 ‘Temperature, ‘C a Resistance, Ohm 1900 200 400 600, ‘Temperature, °C b Figure 3.22. The reverse transformation of martensite t9 austenite stats a As Shape memory alloys The fact that the martensitic transformation in thermoelastic alloys can be brought about by thermal and/or mechanical means has led to the development of shape memory alloys. A well-known shape memory alloy NiTi (called Nitinol) has nearly equiatomic proportions of Ni and Ti. The stress-strain curve of nitinol at 10°C is compared with the nomal elastic behaviour of stainless steel in Fig. 3.23. The stainless steel exhibits a usial linear elastic region as per Hooke’s law, The elastic strain is less than half of a percent. The