The properties of Engineering materials

Second Edition Raymond A. Higgins BSc (Birm), CEng,

Formerly Senior Lecturer in Materials Science, West Bromwich College of Commerce and Technology; former Chief Metallurgist, Messrs Aston Chain and Hoo Co! Ltd!, Birmingham; and "#aminer in Metallurgy to the $nstitution of %roduction "ngineers, The City and &uilds of London $nstitute, The 'nion of Lancashire and Cheshire $nstitutes and The 'nion of "ducational $nstitutes!

Viva Books Private Limited

New Delhi. M m!ai .Chennai

" R A Higgins #irst So th Asian Edition $%%& '(' A B))*S +R('A,E -(M(,ED
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PREFACE To the First Edition

,his !oo8 was written 5rimarily as an introd ction to Materials Science :or those engineering st dents who !ecome in9ol9ed with the s !3ect at ad9anced technical college le9el or, as :irst=year ndergrad ates, :eel the need o: an introd ction to its !asic 5rinci5les, (t may also 5ro9e se: l to those st dents o: metall rgy who :ind it necessary to e<tend their 8nowledge to incl de the 5ro5erties o: non=metallic materials ,he treatment o: materials science in this !oo8 is o: a descri5ti9e and ? alitati9e nat re. ,he a thor has little regard :or those writers who, shir8ing the tas8 o: setting down a l cid e<5lanation o: some 5rinci5le or dogma, 5roclaim that .@..,his is go9erned !y the :ollowing mathematical e<5ression....@. Similarly the tem5tation to write a te<t!oo8 which claims to !e an Aintrod ction@ to the s !3ect yet lam!astes the l c8less reader with di::erential e? ations on 5age 0, has also !een resisted. Some years ago the a thor was lect ring on #ic8Bs -aw o: Di:: sion to a class o: engineering st dents and, ha9ing gi9en a descri5tion and e<5lanation o: the 5rinci5les in9ol9ed, remar8ed that :or the !ene:it o: de9otees o: the di::erential calc l s, these -aws co ld !e e<5ressed mathematically as :ollowsC..At this 5oint one 5artic lar st dent 9isage !ecame ill minated with the light o: nderstanding and, in res5onse to a do !tlessly acrid remar8 :rom the lect rer, its owner admittedD A(B9e 3 st realised Bwhat calc l s is all a!o t.@ ,he st dent in ? estion had !een

e<5osed to the calc l s in a 5res ma!ly sterile 5 re=mathematical :orm :or at least three years 5re9io sly. ;hen the a thor !egan to teach metall rgy to engineers he ? ic8ly disco9ered that their conce5tion o: the nat re o: solids was one in which min te !illiard !alls=called BatomsB=were st c8 together with some mysterio s Bcelestial gl eB. ;e now a55reciate that e9en a mildly academic st dy o: the mechanical 5ro5erties o: engineering materials is meaningless i: it does not see8 to relate the strengths o: these materials to the :orces which o5erate !etween the : ndamental 5articles contained in them. Most modem sylla! ses ha9e there:ore !een written along these lines. Ne9ertheless many st dents still enter engineering co rses witho t ha9ing o::ered chemistry e9en as an B)=(e9elB s !3ect. ;ith this 5ro!lem in mind the relationshi5 !etween atomic str ct re and chemical !onding is disc ssed in sim5le terms in the :irst three cha5ters. Similarly an elementary 8nowledge o: 9an der ;aals :orces has !een deemed necessary in order that the reader can com5are and contrast the mechanical 5ro5erties o: metals with those o: 5lastics materials. (t is ho5ed that the treatment o: these to5ics nder the headings o: B,he AtomB, B,he Molec leB and B,he CrystalB will hel5 the reader to clari:y his ideas s ::iciently so that he can em!ar8 on the st dy o: materials science which :ollows. No do !t in an e::ort to Bget into the mar8etB ? ic8ly many a thors o: otherwise e<cellent te<t!oo8s o: metall rgy ha9e, in recent years, added to their !oo8s an e<tra cha5ter on B+lasticsB and ha9e then considered that they were 3 sti:ied in descri!ing their wor8s as dealing with BMaterials ScienceB. S ch a co rse o: action is rarely :r it: l in that the non=metallics cha5ter remains totally di9orced :rom the rest and this a thor resisted the tem5tation to 5roceed in this way with his BEngineering Metall rgyB which will contin e as a se5arate 5 !lication dealing solely with metals. #inally the a thor wishes to than8 his :riend and colleag e o: many years standing, E. A. Boyce Es?., #.R.(.C., o: the ;est

Bromwich College, :or reading the :irst three cha5ters o: this !oo8 and :or ma8ing hel5: l s ggestions relating to the !asic chemistry they contain.

R. A. H(EE(NS *i+ision of Materials Technology, West Bromwich College of Commerce and Technology, Wednes,ury, West Midlands!

PREFACE To the Second Edition

,he Swedish scientist S9ante A g st Arrheni s died at a!o t the time ( was recei9ing my :irst school lessons in 5hysics ! t it is only ? ite recently that his BE? ationB has :o nd its way into college sylla! ses :or Materials Science. )ther : ndamental scienti:ic BlawsB, Bhy5othesesB and Brelationshi5sB ha9e !een similarly assimilated. ,he science o: materials has ceased to deal with s !stances on a mainly descri5ti9e !asis and now :ollows a more B? antitati9eB a55roach so that the st dent, in addition to retaining a !asic 8nowledge o: 5hysics and chemistryB, m st !e 5re5ared to se e<5ertise ac? ired in his accom5anying maths co rse. ,his change in the a55roach to the st dy o: materials Science d ring recent decades has ena!led the e<aminer to 5ose ? estions re? iring a n merical answer and, in t rn, this has hel5ed him to a55ease e<aminations assessors, re:erees, committees and the li8e who were contin ally clamo ring :or more ? estions o: a Bsearching nat reB whilst re3ecting those which, they claimed, merely called :or Aa reg rgitation o: class notes@. Conse? ently in this edition ( ha9e introd ced a :ew ty5ical e<amination ? estions, along with s ggested answers, on s ch to5ics as are s ita!le. Ne9ertheless the reader sho ld regard any 5ractical

a55lication o: some o: these 5ro!lems with ca tion. ,h s, whilst the di::erential e? ations associated with #ic8Bs -aws indicate to s that di:: sion in metallic solid sol tions is not a sim5le Alinear@ 5rocess and also e<5lain to s why coring is ne9er com5letely remo9ed e9en a:ter 5rolonged annealing, these -aws are o: limited se in 5ractical calc lations (see :ootnote to section %.%.$). Since this !oo8 was :irst written there has !een considera!le 5rogress in some !ranches o: Materials Science. whilst the 5ro5erties o: metals and alloys had !een :airly e<tensi9ely e<5lored d ring the :irst hal: o: the twentieth cent ry, ceramics and com5osite materials had recei9ed only limited attention. ,he closing decades o: the twentieth cent ry, howe9er, saw !oth ceramics and a wide range o: com5osites !ecoming :irmly esta!lished as engineering materials. Conse? ently cha5ters dealing with these to5ics ha9e !een almost com5letely rewritten. My than8s are d e to Dr R ssell ;. H. +arry, Senior Editor with Messrs Edward Arnold, who, as a res lt o: his tra9els aro nd Britain, is a!le to 8ee5 me in:ormed o: many o: the de9elo5ments ta8ing 5lace in ni9ersity and college co rse sylla! ses

Mention at the !eginning o: this 5re:ace o: early science lessons ( recei9ed as a !oy !ro ght to mind one introd cing s to BlightB. ,his 5henomenon was e<5lained as !eing 5ro5agated !y Bwa9emotion tra9elling thro gh the aether (or ether), a fluid which 5er9ades the whole Fni9erseB. Similarly one o:ten heard the 5hrase, B(B9e 3 st heard it o9er the aetherGB (a re:erence to some momento s BBC anno ncement s ch as the marriage or di9orce== o: one o: their star BcroonersB). M ch later in my school days the ne tron was disco9ered= ntil then it had disg ised itsel: as a 5roton cl tching to its !osom a ca5ti9e electron. Ah well, things ha9e mo9ed on since those :ar=o:: days and itBs !een ? ite a tas8

8ee5ing 5 with it all. (n the words o: the +reacher some three tho sand years ago= B. !!of ma ing many ,oo s there is no end,! and much study is a weariness of the flesh! B (Ecclesiastes, H((, $0) R. A. H(EE(NS Walsall, West Midlands!

,o ,HE ;)MEN )# MI -(#E= My ;i:e, Helen and o r Da ghter, Alice.

A;hate9er ha55ens, ha55ens as it sho ld. )!ser9e care: lly and yo will :ind this to !e tr e.B Marc s A reli s (AD $0$=$&4), BMeditationsB ((', $4) or, 5 t another way B;hen the tree :alls, how can the shadow standJB Mary -a9in, B(n the Middle o: the #ieldsB.

1 The Atom
1 1 Fntil a :ew h ndred years ago==a mere !lin8 o: the eye in the time scale o: the Fni9erse=ed cated Man !elie9ed that o r Earth was the :i<ed h ! a!o t which the whole o: Creation re9ol9ed. ,he modern astronomer, howe9er, 9is alises this 5lanet as ! t a s5ec8 o: d st in a gala<y, one o: !illions o: other gala<ies, that go to ma8e 5 an e9er=e<5anding Fni9erse, the 9isi!le edge o: which is some $40/ 8m distant. Meanwhile the atomic scientist concerns himsel: with the architect re o: the atom itsel: and in so doing is dealing with min te 5articles o: the order o: $4=/$ 8g in mass. Somewhere !etween these two e<tremes in si7e ordinary Man ga7es o t into the a55arently limitless 9oid and tries to ma8e sense o: it all 1 1 1 +ossi!ly the most im5ortant hy5othesis le:t to s !y the Eree8s was Democrit sB idea o: the atom. He s ggested that all matter was com5osed o: small ! t indi9isi!le 5articles which he calls BatomsB. ) r modern word is in :act deri9ed :rom the Eree8 alomos, meaning Bindi9isi!leB, and tho gh we now 8now that these atoms can !e s !di9ided into a series o: e9en smaller 5articles, !y this : ndamental conce5t Man had laid the cornerstone o: modern chemistry. ,he ideas o: Democrit s and his :riends a55ear to ha9e !een neglected !oth d ring the Dar8 Ages and the Renaissance which :ollowed and it was not ntil $&4/ that the English chemist Kohn Dalton en nciated his Atomic ,heory. #rom then onwards 5rogress in the :ield o: 5 re chemistry was ra5id and !y $&6& the R ssian chemist Dimitri Mendelee: 5rod ced his :irst great classi:ication o:

the 8nown elements, a system !y which he was a!le to 5redict the 5ro5erties o: other elements at that time still n8nown. Science deals largely with systems o: classi:ication. ,h s, the !iologist classi:ies li9ing things :irst as either animal or 9egeta!le. ,he :ormer he s !di9ides into 9erte!rate and in9erte!rate=and so on. Chemistry is, a!o9e all, a science o: classi:ication. Both elements and their com5o nds are 5laced into gro 5s de5ending 5on their chemical and 5hysical 5ro5erties. (n this !oo8 we shall !e classi:ying s !stances mainly !eca se, as engineers, we are interested in their mechanical 5ro5erties, ! t :irst it will !e necessary to see8 reasons which e<5lain why some materials are strong whilst others are wea8, and, in 5artic lar, what sort o: s !=atomic Bgl eB ma8es atoms Bstic8B together at all.

#ig. $.$ AristotleBs idea o: the nat re o: the Fni9erse. E9en m ch later men were still o!sessed with ideas o: sim5le geometrical 5atterns as go9erning nat ral laws. St dents o: the occ lt still 5lay aro nd with B5entaclesB and the li8e.

The !at"re of F"ndamental Particles

1 # As long ago as $&// Michael #araday reached the concl sion that a :low o: electricity was d e to the mo9ement o: se5arate

5articles thro gh a cond ctor whilst, later, Sir ;illiam Croo8e showed that cathode rays co ld !e !ent !y an electromagnetic :ield th s s ggesting that these rays consisted o: electrically=charged 5articles o: some 8ind. ,hese 5articles ltimately !ecame 8nown as BelectronsB and were in :act the :irst o: the s !=atomic 5articles to !e disco9ered. ,oday we ma8e considera!le se o: the electromagnetic de:lection o: electrons, as :or e<am5le, in the cathode= ray t !e o: a tele9ision set. 1 # 1 ,he Electron is a 9ery small 5article carrying a charge o: what we ar!itrarily re:er to as Bnegati9e electricityB, it was e<amined ? antitati9ely in $&%> !y Sir K. K. ,homson. He assigned the :irst 9al e :or the ratio Bcharge2massB (e2m) to the electron !y o!ser9ing the de:lections o: cathode rays in magnetic and electrical :ields o: 8nown strengths. His early res lts were inacc rate=as are those o: any e<5lorer with :ew Bstars to g ideB and the c rrently acce5ted 9al es areD ChargeD $.6 < $4=$% co lom!s (negati9e electricity) MassD %.$46 < $4=/$ 8g (4.4441.&& a.m. .) (Since the masses o: these 5articles o: atomic and s !=atomic si7e are incon9eniently small when related to the 8ilogram, the atomic mass scale is generally sed to e<5ress the masses o: : ndamental 5articles and atoms. ,he atom o: the car!on isoto5e $06C is ta8en as the standard at $0.44444 atomic mass nits (a.m. .). D ring the co rse o: its history the electron has ac? ired other names s ch as the BnegatronB and the BL=5articleB and is re5resented !y 9ario s sym!ols s ch as L, e- and -e! ,he electron has another s5ecial 5ro5erty which in:l ences its e::ect on atomic 5ro5erties. Besides ha9ing mass and electrical charge it !eha9es as tho gh it were s5inning on an a<is. ,his Bs5inB ca ses the electron to act as tho gh it were a min te magnet and so esta!lished the close relationshi5 !etween magnetism and

electricity. (t also means that the electron 5ossesses ang lar moment m and this m st !e ta8en into acco nt in s5ectrogra5hic meas rements. 1 # # The Proton (n $&&6 E gene Eoldstein noticed l mino s rays emerging :rom holes in a 5er:orated cathode which he had sed in a cathode=ray t !e. ,hese rays were tra9eling in a direction o..osite to that o: the cathode rays. -ater it was shown that they were de:lected !y !oth magnetic and electrical :ields ! t in the o55osite direction to that o: a stream o: electrons (cathode rays). Conse? ently it was realised that the 5articles o: which these new rays consisted were 5ositi9ely charged. (nitially they were 8nown as Bcanal raysB since they 5assed thro gh channels in the cathode ! t in $%4> K. K. ,homson s ggested the name B5ositi9e raysB and when a determination o: the 9al e charge2mass (e2m) was made it showed them to consist o: 5articles which were m ch hea9ier than electrons. Fltimately it was :o nd that the mass o: the lightest o: these new 5articles was ro ghly that o: the ordinaryB hydrogen atom ($./.0) when stri55ed o: its lone electron. ,he name .roton, deri9ed :rom the Eree8 word meaning B:irstB, was s ggested !y R ther:ord in $%04. ,he 5roton carries an e? al ! t o55osite (hence 5ositi9e) charge to that o: the electron. (ts mass is $.6>01 < $4=0> 8g ($.44>06/ a.m. .) ma8ing it some $&/6 times hea9ier than the electron, (t is re5resented !y a n m!er o: sym!ols s ch as ., $H and $$HM the latter !eing the most commonly sed and indicating that it is the n cle s o: the hydrogen atom with a mass o: one and a 5ositi9e charge o: one. 1 # $ The !e"tron D ring my school days chemists got along ? ite well with 3 st two 5articles with which to e<5lain the 5ro5erties o: atoms=the negati9e electron and the 5ositi9e 5roton. +hiloso5hically the conce5t o: these two 5articles seemed to :it in with the e<istence o: two se<es in the !iological worldG (t was

realised, howe9er, that all atoms with the e<ce5tion o: hydrogen were more massi9e than they sho ld !e when ta8ing into acco nt the n m!ers o: 5ositi9ely charged 5rotons (n their n clei. ,he di::ic lty was o9ercome !y ass ming that also 5resent in the n cle s were a n m!er o: 5rotons which were B5airedB with electrons on a one :or one !asis th s rendering the com5osite nit electrically ne tral. ,h s we classi:ied electrons as !eing either Bn clear electronsB or B5lanetary electronsB. So N. '. Sidgwic8Bs The "lectronic Theory of /alency, 5 !lished in $%0> was an er dite treatise on chemical com!ination, the ! l8 o: which is still 9alid today, yet it ma8es no mention o: the neutron since this 5article was not disco9ered ntil $%/0 !y Sir Kames Chadwic8. (Ne9ertheless d ring the year $%/.2/1 when ( st died inorganic chemistry at ni9ersity the lect rer still disregarded the e<istence o: the ne tron and in :act o r recommended te<t !oo8 was Sidgwic8==$ still ha9e my co5yG) ,he ne tron is so called !eca se it has no res ltant electrical charge. (t has a mass o: $.6>1 < $4 =0> 8g ($.44&661 a.m. .) ma8ing it 9ery slightly more massi9e than the 5roton so that earlier chemists can !e :orgi9en :or ass ming that these nits o: Bdead massB in the atomic n cle s were 5rotons Bne trali7edB !y the 5resence o: com5arati9ely light electrons. ) r 8nowledge o: the role o: the ne tron in n clear science is still :ar :rom com5lete. (t is a relati9ely sta!le 5article within the n cle s o: most atoms ! t in a n m!er o: atoms with 9ery large n clei it tends to !e nsta!le gi9ing rise to radioacti9ity and other :orms o: ind ced n clear reaction. Eenerally the 5resence o: the ne tron has little e::ect on ordinary chemical and 5hysical 5ro5erties (other than atomic mass). Chemical 5ro5erties are go9erned !y the dis5osition o: electrons 5resent in the atom.

1 # % Since Chadwic8Bs disco9ery o: the ne tron the n m!er o: elementary 5articles has 5roli:erated. ,hese can !e 9ery ro ghly classi:ied into three main gro 5sD (i) ,aryons 5rotons and other 5articles o: mass greater than that o: the 5rotonM (ii) mesons any o: a gro 5 o: 5articles ha9ing a rest mass !etween those o: the electron and the 5roton and ha9ing an integral Bs5inBM (iii) le.tons which incl de electron, m on, 5ositron (5ositi9e electron) and ne trino (which 5ossesses neither mass nor charge= ! t only s5inG) ,he term B? ar8B has !een ado5ted to descri!e anyone o: a n m!er o: hy5othetical elementary 5articles with charges o: 0e- or 10e(where e- is the charge on the electron) and considered to !e the : ndamental nits o: all !aryons and mesons. (ncidentally the word B? ar8B was coined !y Kames Koyce in Finnegan2s Wa e3 Howe9er, the reader need not !e disco raged !y the com5le<ity o: atomic str ct re. )nly three 5articles= the electron, the 5roton and the ne tron=ha9e any direct e::ect on the distincti9e 5ro5erties o: each element so no consideration o: other !aryons, mesons, le5tons=or ? ar8s=need !e gi9en and will not !e mentioned : rther in this !oo8. #or, in tr th, it seems thatD 2We are such stuff as dreams are made of! B Be:ore we lea9e the intrig ing s !3ect o: : ndamental 5articles (or sho ld we re:er to them as BentitiesBJ) 5erha5s a !rie: mention sho ld !e made o: the a55arent d al nat re o: the electron. (n a st dy o: 5article 5hysics the electron can !e e? ally well considered as a discrete 5article or as a :orm o: wa9e motion in which the electron constit tes a wa+e .ac et! (-ight which is s ally descri!ed as a :orm o: electromagnetic radiation may also

!e considered as a !eam o: B5articlesB or B5hotonsB.) Howe9er, in st dying the str ct res o: atoms it will !e more con9enient to regard the electron as a 5article e9en tho gh this gi9es a restricted 9ision o: the s !3ect.

The Str"ct"re of the Atom

1 $ E9erything is ! ilt 5 o: atoms. ,hey are 9ery tiny 5articles and the co55er=nic8el alloy British 15 coin in yo r 5oc8et contains some /4>44444444444444444444 atoms=gi9e or ta8e a :ew trillions whilst, in America, the dime will contain ro ghly 0$ %44 444 444 444 444 444 444 atoms=gi9e or ta8e a :ew ? intillions. Each atom has at its centre a n cle s consisting o: a gro 5 o: 5rotons and ne trons whilst Bin or!itB aro nd the n cle s are electrons. An indi9id al atom consists almost entirely o: em5ty s5ace. Altho gh most o: the mass is concentrated in the n cle s !oth the n cle s and the indi9id al electrons in Bor!italsB aro nd it are o: a55ro<imately the same diameter. (: we imagine the n cle s o: an atom as consisting o: a s5here the si7e o: a gol: !all then the o termost electron will !e re5resented !y a gol: !all in an or!it o: some $44 meters radi s :rom the n cle s. ;e m st !e care: l, howe9er, not to acce5t too literally the ideas which diagrams re5resenting atoms 5resent. ,hese diagrams (#ig. $.0) are merely a con9enient way o: s mmarising the general ma8e= 5 o: an atom rather than gi9ing an act al 5ict re o: what the atom wo ld loo8 li8e were it 5ossi!le :or it to !e made 9isi!le.

,h s, s ch diagrams !ear the same relationshi5 to the act al nat re o: an atom as does a 5a5er street g ide to the 5ictorial 9iew o: a town=it shows the locality o: the ACoc8 and Mag5ie@ ! t gi9es no hint o: the act al a55earance o: that e<cellent hostelry.

1 $ 1 Altho gh the original 5ict re o: the atom as 9is alised !y the Danish 5hysicist Niels Bohr in $%$/ is now 8nown to gi9e an incom5lete 5ict re o: the str ct re o: the atom it is still o: considera!le se in showing, s !3ect to the sort o: limitations 3 st mentioned, the general 5article ma8e= 5 o: the atom. Brie:ly, Bohr s ggested that electrons or!ited the n cle s in :i<ed BshellsB ! t that when an electron recei9ed energy it mo9ed :rom a lower to a higher le9el within the shell. Con9ersely when it ga9e 5 that energy it :ell !ac8 again to its :ormer le9el (#ig. $./). ,h s Bohr a55lied a ? ant m theory to electron or!its in ro ghly the way in which Ma< +lanc8 and Al!ert Einstein had ? antised light. *nowledge o: the gro 5ing o: electrons was deri9ed originally :rom s5ectromagnetic st dies where!y the wa9elength (N) o: light emitted was meas red. #rom these st dies it was concl ded that a small B5ac8etB or 4uantum o: energy is re? ired to ma8e an electron mo9e :rom one energy le9el to the ne<t=higher energy le9el. Con9ersely a ? ant m o: energy, 8nown as a .hoton, was emitted when an electron :ell !ac8 :rom a higher

to the ne<t=lower le9el. ,he energy " o: the 5hoton can !e calc lated :rom its wa9elength N sing the e? ationD "5 h!c ======= N

where h is +lanc8Bs constant, c is the 9elocity o: light and c2 N !ecomes the wa9e :re? ency. (n 5ractical terms +lanc8Bs constant is 6.60 < $4=/. 3o le. seconds. 1 $ # ,he somewhat ten o s nat re o: the electron has already !een to ched 5on. (n :act 5hysicists no longer thin8 o: an electron or!it as consisting o: a s5eci:ic 5ath. ,he de:inite Bor!itB has !een re5laced !y the term or,ital which re:ers to a mathematical : nction re5resenting the distri! tion o: the electron within the s5ace occ 5ied !y the atom. ,he electron can !e 9is alised as a sort o: BmistB o: electricity rather than as a single 5articleM the or!ital 5rescri!ing the density o: that BmistB at any 5oint within the atom. Alternati9ely the electron may !e regarded

almost in the nat re o: a Bres ltant 5articleB (here the term Bres ltantB is sed in the mechanical sense) and the or!ital inter5reted as denoting the statistical 5ro!a!ility o: :inding that 5article at any gi9en 5oint aro nd the n cle s. Conse? ently it m st !e stressed again that 5ict res showing an atom as consisting o: a central n cle s a!o t which a n m!er o: electrons are mo9ing in de:inite or!its m st not !e inter5reted too literally. ,hey are 5 rely sym!olic and o::er a sim5le diagrammatic means o: showing the electron com5lement o: the 9ario s ? ant m shells. S ch diagrams will !e sed in the 5ages which :ollow in order to e<5lain in sim5le terms the methods o: chemical !onding. ,he modern idea o: the str ct re o: the atom, as a55lied to that o: hydrogen, is indicated in #ig. $... (nstead o: an electron occ 5ying a single :i<ed or!it the 5ro!a!ility o: it e<isting at any location is indicated !y the gra5h (ii) and res ltant diagram (iii). Mendelee: had o!ser9ed the 5eriodicity o: chemical 5ro5erties o: the then=8nown elements and this 8nowledge ltimately ga9e rise to the +eriodic ,a!le as we 8now it today (,a!le $./). Not only is there a

re5eating 5attern with regard to chemical 5ro5erties o: the elements in the same gro 5 ! t also 5eriodicity in connection with their electrical, magnetic and mechanical 5ro5erties. Modem

atomic theory s ccess: lly e<5lains why the arrangement o: elements within the +eriodic ,a!le is go9erned !y the manner in which additional electrons are sit ated in elements o: ascendingB O n m!erB. 1 $ $ Electrons s rro nding the atomic n cle s are not all at the same energy le9el. Conse? ently it is con9enient to gro 5 electrons into shells with di::erent characteristics. ,he :irst 4uantum shell contains only two electrons, whilst the second shell contains a ma<im m o: eight, the third eighteen, and the :o rth thirty=two. ,he greatest n m!er o: electrons in a gi9en shell is 6n6 where n is 8nown as the 4uantum num,er o: the shell. As already s ggested this electron shell conce5t is somewhat o9er=sim5li:ied. Amongst other things it s ggests that all electrons within a shell are e? al whereas in 5ractice they are not. ,he a55lication o: what is 8nown as %auli2s e#clusion .rinci.le is o: hel5 here. ,his 5rinci5le states that there are de:inite r les go9erning the energy le9els and 5ro!a!le 5ositions o: electrons which are in or!it aro nd a n cle s. ,h s the single electron o: a hydrogen atom is normally at the lowest 5ossi!le energy le9el so that the most 5ro!a!le 5osition o: this electron is that indicated in #ig. $..(ii). No more than two interacting electrons can ha9e the same or!ital ? ant m n m!ers. E9en these two are not entirely identical since they e<hi!it in9erted magnetic !eha9io rs or Bs5insB. #ig re $.1 shows the electron com5lement=de5icted in the manner o: the Bohr atom=:or the :irst ele9en elements o: ascending atomic n m!er (7)! An atom o: the :irst element, hydrogen, contains a single 5roton in the n cle s and a single electron in or!it aro nd it. ,he atom is o: co rse electrically ne tral Heli m contains two 5rotons in the n cle s and two electrons in the :irst shell. ,hese two electrons :ill the :irst shell ma8ing heli m a 9ery sta!le element which does not react with other elements. -ithi m has three 5rotons (O P /), and since the :irst ? ant m shell is

already :illed (with the heli m atom) the third electron in the lithi m atom m st go into the second ? ant m shell. (n atoms o: each o: the elements which :ollow=!erylli m, !oron, car!on, nitrogen, o<ygen, :l orine and neon=one more electron is added to the second ? ant m shell. Howe9er, as indicated !y %auli2s e#clusion .rinci.le no more than two electrons can ha9e the same energy le9els and, hence, the same 5ro!a!ility o: 5osition. Additional location 5ro!a!ilities are there:ore introd ced and su,shells esta!lished in the manner indicated in #ig. $.0 showing a sim5le B5article diagramB o: the o<ygen atom. ,he :act that s5ectrometric methods were sed in early wor8 on atomic str ct res led to the ado5tion o: s5ectrogra5hic nomenclat re. ,h s, since the most de:inite s5ectral lines are o!tained :rom those electrons which :all to the lowest energy le9el within a gi9en shell, the notation s has !een sed :or those electrons in each ? ant m shell which ha9e the lowest energy le9els. Hence 8s6 indicates that two electrons (o: o55osite magnetic s5ins) are 5resent in the low=energy :irst ? ant m shell (:ormerly re:erred to as theB 9 shellB). Similarly 0s0 indicates that two electrons are 5resent in the lowest energy le9el o: the second ? ant m shell (:ormerly theB L shellB). Since two is the ma<im m n m!er o: electrons which can e<ist in this s=s !shell, : rther

s !shells are created to hold the other si< electrons which are mem!ers o: this second 5rinci5al shell. Each o: the s cceeding shells contains two or more s !shells which are designated ., d and f! ,he greatest n m!er o: electrons in these s !shells is si<, ten and :o rteen res5ecti9ely. ;e will consider again the e<am5le o: o<ygen (#ig. $.0) which has si< electrons in its second ? ant m (or L) shell. (t has the electron notation 8S6; 6s6, 6.: which indicates that two electrons are in the :irst (or 9) shell and si< electrons in the second (or L) shell (two in the lower s !shell and :o r in the ne<t=higher s !shell). ,he com5lete electron notation system :or the chemical elements in the :irst :o r 5eriods o: the 5eriodic ta!le is gi9en in ,a!le $.0. 1 $ % A st dy o: ,a!le $.0 will show that in se9eral instances ? ant m shells o: higher n m!er !egin to acce5t electrons in their le9els !e:ore the 5receding shells o: lower ? ant m n m!er ha9e !een :illed. ,his is d e : ndamentally to o9erla55ing o: energy le9els o: s cceeding s !shells and also o: s cceeding 5rinci5al shells. Since electrons are most sta!le when they are in a 5osition o: least energy they nat rally see8 o t s ita!le s5aces in shells or s !shells where 9acancies o: lowest energy le9el occ r. #or these reasons there are gro 5s o: BtransitionB elements in the 5eriodic classi:ication in which an o ter=or 9alency=s !shell !egins to :ill !e:ore a : ll ? ota o: electrons is 5resent in the 5re9io s s !shell. #or e<am5le in the scandi m=nic8el series the :s s !shell !egins to :ill !e:ore the ;d s !shell has recei9ed its : ll com5lement o: ten electrons. Similar sit ations occ r with other transition series s ch as yttri m=5alladi m and in the lanthanide (Brare earthB) and actinide (trans= ranic) elements.

The Atomic !"cle"s

1 % ,he n cle s o: an atom consists o: an association o: 5rotons and ne trons. Since these are 5articles some $&/6 times hea9ier

than the electron it :ollows that the mass o: an atom tends to !e concentrated in its n cle s. ,he n m!er o: 5rotons in the n cle s o: a sta!le atom is always e? al to the total n m!er o: electrons in the 9ario s shells aro nd the n cle s. Since the charge on a 5roton is e? al ! t o55osite to that on an electron it :ollows that a sta!le atom is electrically ne tral. ,he n m!er o: 5rotons in the n cle s o: an atom is called the Atomic N m!er (7) o: the element.

,he ne trons, also 5resent in the n cle s, ha9e little e::ect on the chemical 5ro5erties o: the element since they carry no res ltant electrical charge. ,hey !eha9e as a :orm o: Bn clear !allastB increasing the total mass o: the atom. ,he n m!er o: ne trons 5resent in the n cle s may 9ary e9en :rom one atom to another of the same element! Conse? ently when we meas re the relati+e atomic mass o: an element we :ind that it is rarely a whole n m!er since we are in :act meas ring the a9erage mass o: a large n m!er o: atoms o: se9eral di::erent masses. )riginally the relati9e atomic massQ o: an element was the a9erage s5eci:ic mass o: an atom o: that element as com5ared with the mass o: an atom o: hydrogen. #or 9ario s reasons a car!on atom o: atomic mass $0.4444 is now sed as the standard. Howe9er, in an nderstanding o: the 5ro5erties o: the elements the atomic n m!er (7) is o: m ch greater signi:icance than the relati9e atomic mass. 1 % 1 (soto5es whilst the n m!er o: 5rotons in the n cle s o: any atom o: a single element is :i<ed, the n m!er o: ne trons can 9ary :rom one atom to another. ,h s the n cle s o: any chlorine atom will always contain $> 5rotons, ! t a!o t >1R o: all chlorine atoms contain $& ne trons whilst ro ghly 01R contain 04 ne trons. ,hese two di::erent chlorine atoms are 8nown as isoto.es and chlorine is said to !e isoto.ic! ,he relati9e atomic masses o: these two chlorine isoto5es will !e /1 and /> res5ecti9ely (#ig. $.6) ! t since the lighter isoto5e is the more 5lenti: l this e<5lains why the a9erage relati9e atomic mass o: chlorine is /1..6. (t is im5ortant to remem!er that these two isoto5es will ha9e e<actly similar chemical 5ro5erties since !oth ha9e the same atomic n m!er and conse? ently the same electron con:ig ration. Hydrogen too is isoto5ic and occ rs as three isoto5es (#ig. $.>). ,he BordinaryB hydrogen atom (sometimes called .rotium)S contains a single 5roton in its n cle s, whilst the n cle s o: isoto5e 0 (generally called deuterium)S contains a ne tron in

addition to the 5roton. ,he n cle s o: isoto5e / (8nown as tritium) S consists o: two ne trons in addition to the
Q +re9io sly 8nown as Batomic weightB. S,his naming o: isoto5es is to !e disco raged=it may gi9e the im5ression that se5arate elements are !eing descri!ed rather than isoto5es o: a single element, in this case hydrogen.

#ig. $.> ,he str ct ral ma8e= 5 o: the three isoto5es o: hydrogen. ,he isoto5e o: heli m, T0He, has a similar atomic mass to triti m ! t is o: a 9ery di::erent nat re !eca se o: its B:illedB electron shell.

5roton. Altho gh the relati9e atomic masses o: the three isoto5es are $, 0 and / res5ecti9ely the a9erage relati9e atomic mass o: hydrogen is no more than $.44>%> !eca se isoto5es 0 and / are e<tremely rare.

1 % # !"clear Binding Forces ,he n cle s o: an atom consists o: a collection o: 5rotons and ne trons. Now li8e=charged !odies re5el each other with a :orce which is in9ersely 5ro5ortional to the s? are o: their distance a5art (the Co lom! -aw). Since 5rotons are 5ositi9ely charged 5articles why does not the n cle s disintegrate d e to re5 lsion !etween these 5rotonsJ ,he answer to this ? estion is that :orces which !ind together the 5articles o: the n cle s are not in :act o: an electrostatic nat re. Neither are they magnetic or gra9itational in character ! t a55ear to !e se5arate :orces entirely and a!o t which little is yet 8nown. ,hese :orces act not only !etween the 5rotons ! t also !etween the ne trons and are 8nown as n clear !inding :orces. An atomic n cle s may contain a large n m!er o: nucleons (i.e. 5rotons and ne trons) !o nd together as a coherent nit. N cleons in the core are s !3ected to their s5ecial :orces o: attraction !y all neigh!o ring n cleons ! t those on the s r:ace are attracted inwards towards the core !y the ! l8 o: the n cleons sit ated there. ,his 5rod ces something in the nat re o: a
#ig. $.& N cleons (i.e. 5rotons U and ne trons V) at the s r:ace are attracted inwards !y those at the core.

Bs r:ace tensionB e::ect at the o ter limits o: the n cle s so that n clei can !e regarded as !eing constit ted a:ter the :ashion o: dro5lets o: moist re.

;hilst m ch remains to !e disco9ered a!o t these n clear !inding :orces it is clear that they are e::ecti9e o9er an e<tremely limited range, o:ten less than the radi s o: the n cle s. #ig re $.% is a gra5h in which the 5otential energy 5ossessed !y a 5roton, d e to :orces acting !etween it and a near!y n cle s, is 5lotted as a : nction o: the distance se5arating them. ;hen the 5roton is at A sim5le electrostatic re5 lsion tends to 5 sh it away :rom the n cle s which has its centre at ). ,h s the 5roton can !e considered to 5ossess 5otential energy in the same way that a com5ressed s5ring 5ossesses 5otential energy and i: released it wo ld recoil :rom the n cle s. As the 5roton gets closer to 4 the electrostatic :orce=and hence the 5otential energy o: the 5roton= increase 5redicta!ly according to the Co lom! -aw, and 5otential energy wo ld !e e<5ected to go on increasing in the direction o: H ntil contact was achie9ed !etween 5roton and

n cle s. At B, howe9er, the c r9e :lattens o:: at some 5otential energy 9al e, ", !eca se the 5roton now comes close eno gh to !e nder the in:l ence o: the n clear !inding :orce. Beyond C the n clear !inding :orce is m ch greater than the electrostatic :orce o: re5 lsion and so the 5roton is now attracted to the n cle s instead o: !eing re5elled !y it. Relati9e to its 5re9io s condition it can now !e considered to 5ossess Bnegati9e 5otential energyB. ,he ca5t red 5roton is said to !e in a B5otential wellB o: de5th " W ; and this energy wo ld !e re? ired to remo9e it :rom the n cle s. 1 % $ An im5ortant 5oint to a55reciate is that whilst electrostatic re.ulsion acts o+er fairly large distances, the nuclear ,inding force o.erates o+er +ery small distances! ,here:ore a small n m!er o: n cleons can hold together !eca se it is geometrically 5ossi!le :or the n clear !inding :orce to o9ercome the electrostatic re5 lsion !etween 5rotons, ! t there is a limit to this n m!er. A 9ery large n cle s is certain to 5ossess many n cleons which are o tside the in:l ence o: the short=range n clear !inding :orce ! t any 5rotons will still !e in:l enced !y the m t al re5 lsion !etween each otherBs long= range electrostatic :ields. ,here:ore as a n cle s !ecomes large the total electrostatic re5 lsion !etween 5rotons increases whilst !eyond a certain si7e the total n clear !inding :orce !etween n cleons does not. ,h s in a hea9y n cle s the total !inding :orce is not strong eno gh to hold the n cle s together against the total re5 lsion :orces !etween all o: the 5rotons. ,his is one reason why Be<traB ne trons are 5resent in these hea9y n clei o: rani m and radi m to 5ro9ide e<tra !inding :orce to the total whilst adding nothing to the electrostatic :orces o: re5 lsion, since ne trons

ha9e no charge. Howe9er, these e<tra ne trons ma8e the n cle s more massi9e still and the total !inding :orce still wea8er so that in s5ite o: its e<tra ne trons a massi9e n cle s tends to !rea8 5. #or a n cle s to !e sta!le it needs to !e less than a certain ma<im m si7e, determined !y the relati9e magnit de o: the o55osing :orces o: attraction and re5 lsion and containing an o5tim m ratio o: charged 5articles (5rotons) to ncharged 5articles (ne trons). All nat rally occ rring n clei (with the e<ce5tion o: hydrogen $$H) are a mi<t re o: 5rotons and ne trons and the ratio o: ne trons to 5rotons increases :rom $D$ :or the lightest n clei to ro ghly $.1D$ :or the most massi9e n clei. ,hose n clei with atomic mass n m!ers greater than 04% are nsta!le to some degree and no atom with a mass n m!er greater than 0/& occ rs nat rally. ,hose massi9e n clei there:ore ndergo radioacti9e decay. 1 % % !"clear Binding Energ& By sing an a55arat s 8nown as the mass s5ectrogra5h it is 5ossi!le to determine atomic masses with a 5recision o: a!o t $ in $44444. (n this way the mass o: the 5roton has !een determined as $.44>06/ a.m. . and the mass o: the ne tron as $.44&661 a.m. . Since the n m!ers o: 5rotons and ne trons in any atomic n cle s are 8nown and since the masses o: the elementary constit ents ha9e !een acc rately determined it wo ld seem 5ossi!le to clac late the mass o: a n cle s with 5recision :rom these 9al es. #or e<am5le the heli m n cle s .0He contains two 5rotons and two ne trons. Hence (ts mass sho ld !eD 0 5rotons P 0 < $.44>06/ P 0.4$.106 a.m. . 0 ne trons P 0 < $.44&661 P 0.4$>//4 a.m. . ,otal P ..4/$&16 a.m. .

B t in :act the mass o: the heli m n cle s is ..440>6. a.m. . ,he di::erence !etween the e<5ected mass and the act al mass isD ..4/$&16 = ..440>6. a.m. . P 4.40%4%0 a.m. . ,his di::erence is 8nown as the mass defect! (t :ollows that in the :ormation o: the heli m n cle s :rom its constit ent 5rotons and ne trons a 5ortion o: matter amo nting to 4.40%4%0 a.m. .is con9erted into energy. ,his energy is 5resent in the :orm o: the !inding :orce which holds the 5articles together as s ggested in the 5re9io s section. ,he amo nt o: energy released !y the con9ersion o: this amo nt o: matter may !e deri9ed :rom EinsteinBs mass= energy e? ationD " P mc 0 where c is the 9elocity o: light (/ < $4& ms=l)M m is the mass in9ol9ed and " the energy 5rod ced. Hence the s !stit tion o: a!o9e 9al es in this e? ation indicates the energy releasedD " P 4.40%4%0 < $.66$ < $4=0> < (/ H $4&)0 K P ../1 H $4=$0 K (;here $ atomic mass nit P $.66$ < $4=0> 8g).

States o: Matter
1 ' All elements can e<ist as either gases, li? ids or solids. ,he state in which an element e<ists de5ends 5on the com!ination o: tem5erat re and 5ress re which 5re9ails at that time.

#ig. $.$4 ,he n cle s o: the heli m isoto5e .0He weighs less than the :o r n cleons (0 5rotons and 0 ne trons) ta8en se5arately.

#ig $.$$ #orces o5erating !etween single atoms. (i) Here the atoms are so :ar a5art that only wea8 :orces o: attraction o5erate !etween them. (ii) Now the atoms are close together and strong :orces tend to 5 ll them closer together. (iii) ;hen the electron or!itals are close or o9erla55ing a strong :orce o: re5 lsion ! ilds 5.

#orces o: attraction and re5 lsion o5erate !etween atoms and the total :orce in9ol9ed may !e the res ltant o: a n m!er o: :orces. #irst, :orces o: re5 lsion will o5erate !etween the n clei o: two atoms since !oth n clei are 5ositi9ely charged. Similarly the electrons o: one atom will re5el those o: another atom since electrons are negati9ely charged. )55osing these :orces o: re5 lsion are :orces o: attraction in which the 5ositi9ely charged n cle s o: one atom is attracted !y the negati9ely charged electrons o: the other atom. At the same time there will !e a gra9itational :orce o: attraction o5erating !etween the massi9e n clei o: !oth atoms. ;hether the res ltant :orce !etween the two atoms is o: attraction or re5 lsion de5ends 5on the distance a5art o: their centres.

(: the two atoms are an in:inite distance a5art then their .otential energy of interaction can !e ass med to !e 7ero. As the atoms mo9e closer together a :orce o: attraction !etween them increases and 5otential energy falls !eca se wor8 is !eing done !y the atoms as they mo9e closer together nder the :orce o: attraction. As they get 9ery close a short=range :orce o: re5 lsion ! ilds 5 and ltimately tends to !alance the :orce o: attraction. At this stage the 5otential energy rises !eca se the atoms are now !eing 5 lled together. ,his state o: a::airs is indicated in #ig. $.$0 where the 5otential energy d e to :orces o: attraction (c r9e a), re5 lsion (c r9e !) and the res ltant (c r9e c) is shown in relation to the interatomic distance !etween the atom centres. +otential energy is at a minim m (+o) at the e? ili!ri m 5osition (ro) and 9o re5resents the wor8 re? ired to se5arate the atoms com5letely. (n a gas at relati9ely high tem5erat res the a9erage energy o: the atoms is s ::icient :or the :orces o: attraction !etween them to !e rendered negligi!le. ,hey a55roach each other on a collision 5ath and only at short distances will strong :orces o: re5 lsion lead to se5aration. As the tem5erat re o: the gas is decreased so is the 8inetic energy o: each atom. #ig $.$0

Conse? ently :orces o: attraction !etween atoms !ecome more signi:icant. At some tem5erat re a stage is reached where large gro 5s o: atoms are held together since their thermal acti9ation is ins ::icient to 5 ll them a5art, i.e. the gas condenses to :orm a li? id. At a lower tem5erat re still the :orce o: attraction 5redominates to the e<tent that atoms :all into a :i<ed 5attern and so :orm a solid.

A9agadro@s Constant
1 ( (n ordinary chemical reactions, i.e. where the release o: n clear energy is not in9ol9ed, the Law of Conser+ation of Matter a55lies. ,his states that d ring s ch a chemical reaction matter is neither created nor destroyed. ,h s o r early school chemistry ta ght s how to B!alanceB chemical e? ations and, !y re:erence to the a55ro5riate atomic mass n m!ers o: the elements in9ol9ed, calc late reacting masses o: chemical reagents, th sD C W)0 XC)0 $0 0Y$6QP/0 $0W(0Y$6)P.. A5arts !y weight@A5arts !y weight@A5arts !y weight@ (n the a!o9e e? ation :or B5arts !y weightB (or more 5ro5erly BmassB) we can s !stit te any nit o: mass=grams, 8ilograms, tonnes or e9en the old (m5erial h ndredweights=i: we wish. ,he e? ation then tells s that !y ! rning $0 tonnes o: car!on (in the :orm o: coal or co8e) we are sing /0 tonnes o: atmos5heric o<ygen and 5rod cing no less than .. tonnes o: car!on dio<ide= which goes towards aggra9ating the Ereenho se E::ect. (: the coal also contains $ R s l5h r o r $0 tonnes o: car!on will in9ol9e the ! rning also o: 4.$0 tonnes o: s l5h r. ,his :orms the gas s l5h r dio<ide, S40, which enters the atmos5here and is ltimately washed down

Q Re:erence to A55endi< (( will show the acc

rate 9al e :or the atomic mass o: the o<ygen atom as $1.%%%. ! t :or most 5 r5oses a55ro<imate 9al es are sed.

as Bacid rainB (dil te s l5h ric acid) on o r northern :orests and those o: o r l c8less Scandina9ian neigh!o rsD S /0 4.$0t W)0 0Y$6P/0 4.$0t XS)0 /0W(0Y$6)6. 4.0.t

,his 4.0. tonnes o: S)0 5rod ces 4./6>1 tonnes o: s l5h ric acid. Altho gh there may !e a moral in9ol9ed here o r o!3ect is to show how sim5le Bchemical arithmeticB can !e sed to calc late reacting ? antities o: materials on an ind strial scale. (n materials science, howe9er, we o:ten wish to st dy s !stances at atomic le9el. ,hen we need to 8now the act al masses and dimensions o: these tiny 5articles. 1 ( 1 ,he $%th cent ry (talian 5hysicist, Amedeo A9ogadro, s ggested that e? al 9ol mes o: all gases at the same tem5erat re and 5ress re contain e? al n m!ers o: molec les. D ring my school days this was 8nown as A9ogadroBs Hy.othesis ! t in more recent years has generally !een acce5ted as his Law! )!9io sly the molec les in ? estion may 9ary in mass :rom one gas to another. #or e<am5le one molec le o: car!on dio<ide (C) 0 P $0 W (0<$6) P ..) is 00 times more massi9e than one molec le o: hydrogen (H 0 P 0<$ P 0). #rom the Hy5othesis was de9elo5ed the se: l in:ormation thatD ,he gram=molec lar mass o: any gas occ 5ies a 9ol me o: 00..litres (dm/) at standard tem5erat re and 5ress re. Here the term Bgram=molec leB re:ers to the relati9e molec lar mass o: a gas e<5ressed in grams. ,h s a gram=molec le o: car!on

dio<ide contains .. g o: the gas. ,his ? antity the Bgram=molec lar massB (o:ten still called the Bgram=molec lar weightB=a hango9er :rom 5re=S( days) is im5ortant in many chemical calc lations and is now 8nown as a BmoleB (or BmolB) o: the s !stance !eing considered. 1 ( # A9ogadroBs original Hy5othesis dealt with the relationshi5 !etween n m!ers o: molec les and the 9ol me they occ 5ied in common gases. Since all elements (and many com5o nds) can e<ist in the gaseo s state it :ollows that a mole o: any 5 re s !stance will contain the same n m!er o: elementary 5articles in which :orm the s !stance normally e<ists. ,h s the mole is de:ined in S( terms as the amount of su,stance that contains as many elementary entities as there are atoms in <!<86 g of car,on $0 6C. ,he BentityB may !e an atom, a molec le, an ion, a radical, etc. ,his n m!er o: entities is 8nown as A9ogadroBs Constant or N m!er, =A and =A P 6.40010 H $40/ atoms (etc.)2mole.

# The )olec"le

# 1 (n the 5re9io s cha5ter we considered some o: the 5ro5erties o: the atom as a single :ree 5article. Ne9ertheless, a5art :rom those o: the Bno!le gasesB, atoms rarely occ r as single 5articles ! t are generally attached to other atoms :orming small or large gro 5s. ;hich is 3 st as well otherwise o r Earth=i: it e<isted at all=wo ld 5res ma!ly consist o: a mass o: rare:ied gas. ;hat is the nat re o: the :orce o: cohesion which a55arently !inds atoms togetherJ (n this cha5ter and the ne<t we shall attem5t a sim5li:ied answer to this ? estion. ;e ha9e seen ($././) that in the second and third 5eriods o: the +eriodic ,a!le the o ter electron shell o: an atom is generally com5lete when the n m!er o: electrons in it reaches eight. Q Conse? ently as the res lt o: a chemical reaction !etween two atoms in these 5eriods there is a general tendency :or the o ter shells o: electrons in each atom to :inish with eight electrons. Most metallic atoms contain one, two or three electrons in their o termost shells (or s !shells in the case o: metals in 5eriod :o r onwards) whilst in the o ter shells o: atoms o: non=metallic elements the n m!er o: electrons is nearer to eight. ,h s, when

one atom is strongly metallic (the element occ 5ies a 5osition on the le:t=hand side o: the +eriodic ,a!le) and the other strongly non=metallic (the element is sit ated on the e<treme right o: the ,a!le), chemical !onding is achie9ed !y the metallic atom donating its o ter=shell electrons to :ill the o ter shell o: the non= metallic atom. ,his 5rod ces what is 9ario sly termed an ionic, .olar or electro+alent !ond. (ts :ormation gi9es rise to the 5rod ction o: ions, the ! ilding !loc8s o: some crystal str ct res which will !e dealt with in the ne<t cha5ter.
>$n the first .eriod, i,e! HHe, the num,er of electrons in+ol+ed is of course only two! whilst in the case of .eriods four and onwards the outer shells increase in si?e, i!e, 8@, 8@,;6, etcA each terminating with the a..ro.riate !no,le gas2 structure.

(: the atoms concerned are o: elements near to each other in the centre o: the +eriodic ,a!le they can com!ine most easily !y sharing electrons :rom their o ter shells :orming common or!itals which are the !asis o: the co+alent !ond. # 1 1 By whate9er means chemical com!ination ta8es 5lace it :ollows that as we are dealing with small n m!ers o: Bacti9eB electrons, atoms will com!ine in sim5le ratios, one ty5e with the other. ,he +alency (or +alence) o: an element is s ally descri!ed as Bthe n m!er o: atoms o: hydrogen with which an atom o: that element can com!ineB. Since one atom o: o<ygen is a!le to com!ine with two atoms o: hydrogen (#ig. 0..) the 9alency o: o<ygen is said to !e two.

The Covalent Bond

# # ,wo atoms o: the gas :l orine will com!ine !y sharing a 5air o: electrons (#ig. 0.$). (n this way the o ter shell o: each atom now

has a com5lete Bneon octetB and the two atoms are held together !y the electrical :orces in9ol9ed !y sharing electrons !elonging to the o ter or!itals o: !oth atoms. #or this reason the co9alent !ond is a strong and sta!le chemical !ond.

,wo hydrogen atoms com!ine in a similar way e<ce5t that the Bheli m d 5letB o: each is com5leted !y sharing the 5air o: electrons th s !ro ght together (#ig. 0.0).

):ten more than two electrons are in9ol9ed in the :ormation o: the co9alent !ond. ,h s, the o ter shell o: the nitrogen atom contains :i9e electrons and two nitrogen atoms will com!ine !y sharing si< electrons=three donated to the !ond !y each atom(#ig.0./) (n each case the 5article :ormed !y the com!ination o: two atoms in this

manner is called a molecule! Molec les can contain more than two atoms=in :act some molec les o: the more com5le< car!on com5o nds contain many tho sands o: atoms. Most o: the common non=metallic gases, howe9er, e<ist as molec les which are diatomic=that is, the molec le contains two atoms. ,he Bno!le gasesB (heli m, neon, argon, etc.) are e<ce5tions to this general r le. Since the o ter electron shells o: their atoms are already com5lete they will not normally com!ine with other atoms, either o: their own ty5e or o: other elements. Hence, they are monatomic, that is they e<ist as single atoms and do not :orm molec les. # # 1 Atoms o: nli8e elements com!ine to :orm molec les in a similar manner. ,h s two hydrogen atoms are co9alently !onded to an o<ygen atom to 5rod ce a molec le o: the com5o nd we call water. A 5air o: electrons is shared !etween the o<ygen atom and each o: the two hydrogen atoms (#ig.0..) so that the neon octet o: the o<ygen atom is com5leted, as are the heli m d 5lets o: each o: the hydrogen atoms.

,he str ct re o: the water molec le is s ch that the ,ond angle !etween the two hydrogen atoms is $41Z (#ig. 0.1). As we shall see later (0....), this 5artic lar sha5e o: the water molec le o::ers an

e<5lanation o: many o: the 5ro5erties o: water. # # # )olec"lar )ass ,he molec lar mass==still commonly 8nown as the Bmolec lar weightB==o: a com5o nd which e<ists in the :orm o: sta!le molec les is 9irt ally the s m o: the atomic masses o: all atoms within the molec le. ,h sD Molecular mass of water (H2O) = (2 1.008) + 16
P $&.4$6

where the atomic masses o: hydrogen and o<ygen are $.44& and $6.444 res5ecti9ely. Molec lar mass (or more 5ro5erly relati+e

molec lar mass) has no nits since, li8e atomic mass, it is relati9e to the mass o: the car!on atom $06C ($0.4444) ($..).

Car*on and its Compo"nds

# $ ,he element car!on occ 5ies a 5osition in the centre o: the +eriodic ,a!le. ,h s it may !e e<5ected to :orm co9alently !onded com5o nds more readily than most elements. ,his it does, 5artic larly with hydrogen, o<ygen, nitrogen and the halogens and so 5rod ces a 9ast range o: tho sands o: s !stances we call Aorganic com5o nds@. ,hese incl de many com5le< s !stances :o nd in li9ing organisms, !oth animal and 9egeta!le, as well as many materials e<tracted :rom coal and 5etrole m (which are deri9ed :rom li9ing organisms). ,he gro 5s o: organic com5o nds o: 5artic lar interest to the materials scientist are those 8nown as Bs 5er= 5olymersB or, more commonly, as B5lastics materialsB. # $ 1 +ossi!ly the sim5lest o: the organic com5o nds is the gas methane, the main constit ent o: Bnat ral gasB. A molec le o: methane consists o: an atom o: car!on co9alently !onded to :o r hydrogen atoms. #ig re 0.6 indicates diagrammatically the electron distri! tion within the molec le. ,he tr e three=dimensional sha5e o: the molec le will !e something li8e that shown in #ig. 0.>. Methane is in :act the sim5lest com5o nd in a series o: com5o nds 8nown collecti9ely as al8anes (:ormerly the B5ara::insB). ,his

:rom one com5o nd to the ne<t. As molec lar si7e increases so do :orces o: intermolec lar attraction (0..). Hence, whilst the com5o nds methane, ethane and 5ro5ane are gases at normal tem5erat res and 5ress res, ! tane is a gas which is readily com5ressed to :orm a li? id (BCam5ing Ea7B). S ccessi9e mem!ers o: the series are 9olatile li? ids :ollowed !y less 9olatile li? ids s ch as 5ara::in oil (B8eroseneB in the FSA)M whilst at the 55er end o: the series are solids s ch as 5ara::in wa< with a :orm la o: the order C14H(40 (,a!le 0.$). (ncidentally all o: these com5o nds in the series are deri9ed :rom cr de 5etrole m.

# $ # ,here is only one !asic 5attern in which the car!on atoms can !e arranged in the :irst three com5o nds in the series, namely, methane, ethane and 5ro5ane. ;ith the com5o nd ! tane, howe9er, car!on atoms can !e arranged in two di::erent 5atterns as indicated in #ig. 0.%. (n :act two di::erent s !stances do e<ist with di::erent 5hysical 5ro5erties (,a!le 0.0) e9en tho gh a molec le o: each com5o nd contains the same n m!ers o: atoms o: car!on and hydrogen. ,hese two s !stances, each ha9ing the same molec lar :orm lae, yet di::erent molec lar structures are 8nown as isomers! (n the case o: 5entane C1H$0 there will !e three isomersM the n m!er o: isomers increasing as the molec lar :orm la increases. (n :act the molec le ,etracontane, C.4H&0.will !e re5resented !y no less than 60.%$$>&&41&/$ 5ossi!le isomers.

,a!le 0.0 ============================================================================================================ (somer Melting 5oint(oC) Boiling +oint(oC) ============================================================================================================ n=B tane iso=B tane =$/& =$1% =4.1 =4.0

============================================================================================================

# $ $ ,he al8ane series descri!ed a!o9e consists o: hydrocar!ons ;hich are said to !e Bsat ratedB. Brie:ly, this means that car!on atoms are 3oined to their neigh!ors !y means o: single !onds. Another series e<ists in which the com5o nds are B nsat rated.. that is. do !le 9alency !onds connect certain o: the car!on atoms. ,hese com5o nds are o: the general :orm la CnH0n and the :irst mem!er o: the series is ethylene (#ig. 0.$4). Collecti9ely 8nown as the al8enes (:ormerly the Bole:ins.), these hydrocar!ons tend to !e less chemically sta!le than do the al8anes and the do !le !ond can !e A!ro8en@ relati9ely easily !y chemical means.

Ethylene is a !y=5rod ct o: the 5etrole m re:inery since, d ring the Bcrac8ingB o: some o: the hea9ier oils to 5rod ce light and more 9olatile hydrocar!ons (s ch as octane), an nsat rated hydrocar!on gro 5 is le:t o9er=in this case ethylene, C0H.. (: ethylene is s ita!ly treated the. do !le !ond !etween the car!on atoms is !ro8en and sim ltaneo sly large n m!ers o: these nits are :ormed. ,hese immediately lin8 5=or .olymerise-to :orm long chain=li8e molec les o: the s !stance B5olyethyleneB, or

5olythene as it is commonly 8nown. ,he se? ence in this 5rocess is indicated in #ig. 0.$$.

#ig. 0.$$ ,he 5olymeri7ation o: ethylene to :orm 5oly(ethylene) or +olythene +olythene is one o: a large n m!er o: these s 5er=5olymers (commonly called B5lasticsB), which are :inding increasing se as engineering materials. ,hey will !e disc ssed in more detail in Cha5ter ,wel9e.

+ntermolec"lar Forces
# % ,he atoms in a molec le are, as we ha9e seen, held together !y co9alent !onds. ,hese are strong 5rimary !onds, which are de5endent 5on relati9ely 5ower: l electrostatic :orces. At the same time wea8er electrostatic :orces o: a secondary nat re gi9e rise to attractions !etween any one molecule and its neigh!ors. )nly in this way can we e<5lain the :act that a gas condenses to :orm a li? id and that the li? id s !se? ently crystallises to :orm a solid. ,he secondary electrostatic :orces o5erating !etween molec les in:l ences s ch im5ortant 5ro5erties as melting 5oint, sol !ility and, in 5lastics, tensile strength. +ower: l modern adhesi9es o: the Bim5actB 9ariety rely on these secondary intermolec lar :orces and ill strate the collecti9e e::ect o: large n m!ers o: s ch secondary !onds o5erating sim ltaneo sly.

As early as $&>/ Kohannes Dideri8 9an der ;aals a D tch 5hysicist, so ght to e<5lain de9iations :rom the Eas E? ation (%/ P BT)! As readers may 8now, this relationshi5 is tr e only :or a .erfect gas. No gas is B5er:ectB in this sense and 9an der ;aals introd ced corrections into the Eas E? ation s ch thatD (+Wa2'0)('=!) PR, ;here ! is a constant related to the act al 9ol me o: the molec les o: the gasM a is also a constant and a2'0 re5resents the loss o: 5ress re d e to forces of attraction- ,etween the molecules of the gas . A sta!le molec le or a sta!le atom (e.g. an atom o: a no!le gas) is, ta8en as a whole, electrically ne tral since the n m!er o: 5rotons 5resent is !alanced !y an e? al n m!er o: electrons. Howe9er the res ltant BcentreB o: the electro5ositi9e charges does not necessarily coincide with the centre o: the negati9e charges. ,hen the 5article=whether molec le or single ncom!ined atom== can !e ass med to 5ossess a res ltant [di5ole momentB

Fig 2.12 I (i) t!e ce ters of "ositi#e a $ egati#e c!arges coi ci$e %&ut i (ii) t!e' are se"arate$ so t!at t!e molecule (or si gle atom i t!e case of t!e o&le gases) will !a#e a resulta t ($i"ole mome t(

(#ig. 0.$0). ,hese intermolec lar :orces. o:ten re:erred to as 9an der ;aals :orces, are o: :o r main ty5esD # % 1 Attraction Bet,een Permanent -ipoles .A Molec le o: the gas hydrogen chloride contains one atom o: hydrogen and one o: chlorine, co9alently !onded (H=C(). Howe9er. ,he electrons

tend to !e concentrated rather more densely in the region o: the chlorine n cle s (which contains a larger 5ositi9e charge) than aro nd the hydrogen n cle s (which contains only a single 5ositi9e charge d e to the 5resence o: one 5roton). ,he ne9en distri! tion o: electrons in the molec lar or!ital is e? i9alent to a se5aration o: charges. #or this reason the hydrogen n cle s tends to !e rather Be<5osedB so that that 5art o: the molec le has a res ltant small 5ositi9e charge (\W). Con9ersely the 5an o: the molec le containing the chlorine n cle s will carry an e? al negati9e charge (4=) (#ig. 0.$/). ,h s the hydrogen chloride molec le will 5ossess a res ltant di5ole moment. S ch a molec le is said to !e 5olar whereas a hydrogen molec le, in which the charges were e? ally distri! ted wo ld !e non=5olar since it 5ossessed no res ltant di=5ole moment. !eca se o: its relati9e symmetry.

Fig 2.1) t!e molecular or&ital of !'$roge formatio of a $i"ole mome t

c!lori$e it s!owi g (ii) t!e

Fig.2.1* +ttractio a $ re"ulsio &etwee "erma e t $i"oles follows t!e well, - ow laws of electrostatic attractio a $ re"ulsio .

+olar molec les will re5el each other or attract each other according to the way in which they are orientated (#ig. 0.$.). ,he degree o: m t al di5ole alignment will go9ern the e<tent o: intermolec lar attraction. Since= this alignment is o55osed !y thermal motion, di5ole :orces are de5endent largely 5on tem5erat re. ,h s, as tem5erat re rises these :orces decrease. #or e<am5le, the 5lasticity o: thermo5lastic 5olymers increases with the tem5erat re. # % # Attraction Bet,een Permanent -ipoles and +nd"ced -ipoles (n some cases the or!ital o: a non=5olar atom or molec le may !e a::ected !y the close 5ro<imity o: a strongly 5olar molec le.

fig 2.15 .!e formatio of a i $uce$ $i"ole

(n #ig. 0.$1 it is ass med that the B5ositi9e endB o: a 5ermanent di5ole has a55roached a non=5olar atom or molec le in which the electron clo d is large, di:: sed and ca5a!le o: easy distortion. ,he electron clo d o: the non=5olar 5article will !e attracted towards the 5ositi9e end o: the 5ermanent di5ole. ,his distorts the electron clo d o: the non=5olar 5article to the e<tent that a tem5orary di5ole is :ormed. S ch a distortion o: an electron clo d is re:erred to as 5olarisation. ,he 5ositi9e 5ole o: the 5ermanent di5ole attracts the electrons o: the non=5olar atom or molec le and so ! ilds 5 a negati9e charge :acing it. Hence the 5ermanent di5ole and the ind ced di5ole are in a 5osition in which they will attract each other.

# % $ -ispersion Forces Altho gh. there are many molec les which a55ear to !e non=5olar, that is the centres o: 5ositi9e and negati9e charges wo ld seem to !e coincident, all molec les=and the single atoms o: no!le gases=ha9e time=9arying di5ole moments the nat re o: which will de5end 5on the 5osition o: the electrons at any 5artic lar instant. Consider the case o: two atoms o: the no!le gas, argon, in close 5ro<imity to each other (#ig. 0.$6). (: the electron clo ds are e9enly distri! ted as in (i) then there will !e no res ltant di5ole moment in either atom and they will neither attract nor re5el each other. (t, howe9er, an ne9en distri! tion o: the electron clo ds is 5resent as in (ii) then the atoms will re5el each otherM ! t i: the electron clo ds are distri! ted as in (iii) then the electron clo d o: .atom A [ill !e attracted !y the B n5rotectedB n cle s o: atom B.

Fig 2.16 .!e formatio of $is"ersio forces &etwee two atoms of +rgo

,he dis5lacement o: electrical charges necessary to 5rod ce a di5ole is tem5orary and random so that a molec le , as a whole, o9er a 5eriod o: time has no res ltant di5ole. Howe9er i: it has a di5ole moment at anyone instant it will ind ce another in a near neigh!o r and a :orce o: attraction will !e set 5 !etween the two. (t is tho ght that s ch interactions m st !e largely res5onsi!le :or 9an der ;aals !onding !etween non=5olar atoms and molec les. ,he : nctioning o: these dis5ersion :orces was 5ost lated !y -ondon as long ago as $%/4 and. e<ce5t in a :ew cases where 9ery strong di5ole moments e<ist, these :orces e<ceed in magnit de all other intermolec lar :orces, when considered collecti9ely.

,he dis5ersion e::ect is e9ident when considering the relationshi5 !etween molec lar mass and !oiling 5oint. Massi9e molec les contain more electrons than do light ones and so the attraction d e to dis5ersion e::ects is greater in the massi9e molec les. Heat o: e9a5oration is a meas re o: the energy re? ired to o9ercome :orces o: attraction !etween molec les so that they can se5arate. Since the !oiling 5oint is 5ro5ortional to the heat o: e9a5oration it is a con9enient criterion in assessing these intermolec lar :orces. ,h s normal co9alently !onded com5o nds with massi9e molec les ha9e higher !oiling 5oints than those with small. molec les. An e<cellent e<am5le o: this 5rinci5le is gi9en !y the homologo s series, the al8anes, mentioned earlier in this cha5ter. ,he lower mem!ers are gases at ordinary tem5erat res and 5ress res, then, as the series is ascended, li? ids o: increasing !oiling 5oint are :ollowed !y higher mem!ers which are wa<y solids (,a!le 0.$). Dis5ersion :orces, along with 5ermanent di5oles :ig re largely in the intermolec lar :orces which 5re9ail !etween the chain=li8e molec les in s 5er=5olymers. # % % The .&drogen Bond ;hen a hydrogen atom is co9alently !onded to a relati9ely large atom s ch as nitrogen. o<ygen or :l orine, a 5ower: l 5ermanent di5ole is set= 5. ,his is !eca se the electron clo d tends to !ecome concentrated aro nd that 5an o: the molec le containing the nitrogen, o<ygen or :l orine n cle s. th s lea9ing the 5ositi9ely charged hydrogen n cle s relati9ely B n5rotected., (n this way 5artic larly strong di5ole=di5ole :orces o: attraction can !e set 5. ,hese are : ndamentally similar in nat re to the 5ermanent di5ole=di5ole :orces descri!ed earlier ! t are o: m ch greater magnit de.

Fig. 2.1/ .!e &asis of t!e (!'$roge &o $( (or (&ri$ge() i t!e water molecule

,his e::ect is a55arent in the case o: the water molec le. Here the o<ygen 5art o: the molec le, carrying the n=5aired electrons, will !e negati9ely charged whilst the hydrogen 5ortions will !e corres5ondingly 5ositi9ely charged. ,he hydrogen atoms :orm B!ridgesB (shown th s in #ig. 0.$&) !etween themsel9es and o<ygen atoms o: other molec les th s lin8ing the molec les together. (t m st !e remem!ered that #ig. 0.$& shows a two=dimensional diagram whereas in 5ractice a three=dimensional s5atial 5attern e<ists.

Fig.2.18 .!e formatio of !'$roge &o $s &etwee molecules i water.

A55ro<imately two=thirds o: the heat o: 9a5orisation o: water at its !oiling 5oint is sed 5 in disr 5ting these hydrogen !onds or B!ridges@. S ::icient hydrogen !onds are :ormed to acco nt :or the a!normally high !oiling 5oint o: water. #or e<am5le, since the s l5h r atom is more massi9e than that o: o<ygen the com5o nd hydrogen s l5hide, H0S, might !e e<5ected to ha9e a higher !oiling 5oint than that o: water, H0). (n :act the !oiling 5oint o: hydrogen s l5hide is =64ZC, some $64ZC lower than that o: water. ,his is a55arently d e to the relati9ely large si7e o: the s l5h r

atom ca sing a lesser concentration o: the electrons so that a wea8er di5ole moment is 5rod ced in the molec le. (n the same way the molec le o: hydrogen chloride, HC(, does not e<hi!it a strong hydrogen !ond !eca se o: the large si7e o: the chlorine atom, whereas the hydrogen :l oride, H#, molec le does 5ossess a 5ower: l hydrogen !ond !eca se o: Dhe smaller si7e o: the :l orine atom and also its 9ery strong electronegati9e character. ,he hydrogen B!ridgeB associated with the hydro<yl (=)H) and other gro 5s in many organic 5olymers contri! tes considera!ly to their o9erall cohesion. ;hilst it is m ch stronger than other 9an der ;aals :orces it is ne9ertheless wea8er than the ordinary co9alent !ond. (n terms o: !ond energy a co9alent !ond may re5resent as m ch as $>448K2mole whilst the hydrogen !ond wo ld !e e? i9alent to some .1 8K2mole. Bond energies o:. he wea8er 9an der ;aals :orces 9ary !etween 4.$ 8K and 04 8K2mole D/.0.6).

$ The Cr&stal
$ 1 ;hen sed in a non=scienti:ic sense the term crystal , con9eys an im5ression o: a material which is geometrically reg lar in sha5e and which is !oth l stro s and trans5arent=as the e<5ression [as clear as crystalB s ggests. (n :act crystals o: many materials ha9e an irreg lar e<ternal sha5e tho gh the 5articles within these crystals are arranged in some reg lar 5attern. Many crystalline materials are o5a? e and do not ha9e a l stro s a55earance, (n general terms a s !stance can !e descri!ed as crystalline when the 5articles :rom which it is ! ilt are arranged in a de:inite three=dimensional 5attern which re5eats o9er a long range. Metals and indeed all tr ly solid s !stances are crystalline in str ct re. Non=crystalline BsolidsB s ch as glass, 5itch and many 5olymers can o:ten more con9eniently !e considered as e<tremely 9isco s li? ids in so :ar as their 5hysical and mechanical 5ro5erties are concerned. Again the ? estion arises=what is the nat re o: the :orces which !ind together the nits :rom which a crystal is ! ilt (n some ty5es o: crystal the !inding :orces consist o: co9alent !onds. in others hydrogen [!ridgesB (0....)M whilst in mineral crystals and those o: inorganic salts generally, the :orce o: attraction is d e to what is descri!ed 9ario sly as an ionic, 5olar or electro9alent !ond.

The Electrovalent Bond

$ # (n the 5re9io s cha5ter we saw that a co9alent !ond is :ormed when electrons :rom the o ter shell o: two (or more]

atoms are shared in s ch a way that the a55ro5riate no!le=gas str ct res are attained in the o ter electron shells concerned. Howe9er chemical com!ination can also ta8e 5lace !y the trans:er o: electrons :rom one atom to another s ch that a no!le=gas str ct re is attained in the 9alency shells o: each res ltant 5article. ,h s, a metallic atom which contains only one or two 9alency electrons tends to gi9e 5 these electrons to a non=metallic atom which already has a 9alency shell o: si< or se9en electrons. (n this way the o ter electron shell o: each res ltant 5article attains a no!le=gas str ct re. $ # 1 ,he metal sodi m reacts 9igoro sly with the 5oisono s gas chlorine to 5rod ce a 9ery sta!le s !stance, sodi m chloride (common salt). (n this instance the sodi m atom which carries a single electron in its o ter shell donates this electron to a chlorine atom which 5re9io sly had se9en electrons in its o ter shell. By means o: this trans:er the sodi m 5article is le:t with a com5lete o ter shell (the Bneon shellB) and the chlorine 5article also has a com5leted shell (the Bargon shellB). Since an electron trans:er has ta8en 5lace :rom one atom to another we can no longer re:er to the res ltant 5articles as BatomsB. ,he sodi m 5article is o!9io sly something less than a sodi m atom whilst the chlorine 5article is something more than a chlorine atom. +articles 5rod ced !y electron trans:er in this manner are 8nown as ions. +rior to the chemical reaction d ring which the electron trans:er too8 5lace, the atoms were electrically ne tral !eca se in each case the n m!er o: 5ositi9ely charged 5rotons in the n cle s was !alanced !y an e? al n m!er o: negati9ely charged electrons in or!itals aro nd the n cle s. D ring the reaction the sodi m atom lost an electron and the ion so :ormed m st there:ore carry a res ltant 5ositi9e charge. Similarly, since the chlorine atom recei9ed this electron the chlorine ion 5rod ced m st carry a res ltant negati9e charge (#ig. /.$).

Since the two ions :ormed as a res lt o: this chemical reaction carry e? al ! t o55osite charges they will attract each other and it is this :orce o: co lom!ic attraction which constit tes the electro9alent !ond. Altho gh generally wea8er than a co9alent !ond, this electro9alent !ond is m ch stronger than any o: the relati9ely :ee!le 9an der ;aals :orces.

Fig 3.1 .!e formatio of a electro#ale t , or ,io ic , &o $ &etwee a so$ium atom a $ a c!lori e atom

Fig.3.2 0ac! 1a+ io is surrou $e$ &' si2 3l, io s

$ # # ;hen sodi m and chlorine react with each other e9en on the la!oratory scale many ,millions o: atoms are in9ol9ed and an e? ally large n m!er o: ions is 5rod ced. ;hilst there is m t al attraction o: sodi m ions :or chlorine ions, :orces o: re5 lsion o5erate !etween all li8e ions. ,hat is, each sodi m ion is re5elled !y all other sodi m ions whilst each chlorine ion is re5elled !y all other chlorine ions. As a res lt the system attains e? ili!ri m when each chlorine ion is s rro nded !y si< sodi m ions and, con9ersely, when each ion o: sodi m is at the same time s rro nded !y si< chlorine ions (#ig. /.0)= (n this instance the relati9e si7es o: the chlorine ions and sodi m ions are s ch that a c !ic ty5e o: 5attern is :ormed. Since each sodi m ion is s rro nded !y si< chlorine ions it is said to ha9e a co=ordination n m!er o: Si<. #or a similar reason chlorine also has a co= ordination n m!er o: si< Diagrams re5resenting crystal str ct res are somewhat clearer i: the centre o: each ion is re5resented !y a small circle (#ig. /.0(ii) and #ig. /./(ii)). (n this c !ic ty5e o: str ct re the three a<es o: symmetry are at right angles to each other. ,he chlorine ions ta8e 5 5ositions as :ar as 5ossi!le :rom other chlorine ions and since they are e? ally charged they are also e? ally s5aced. Each chlorine ion has Si< sodi m ions e? ally s5aced aro nd it and in contact with it. Since there is an electrostatic :ield e<tending into the s5ace o tside this nit other sodi m ions and chlorine ions will !e attracted so that the str ct re de5icted in #ig. /./ ! ilds 5 and e<tends as long as ions are a9aila!le.. ,he :ramewor8 on which the nits o: a crystal arrange themsel9es according to some :i<ed 5attern is 8nown as a s5ace lattice. $ # $ ,he ions arrange themsel9es in 5ositions dictated 5rinci5ally !y the :orces o: attraction !etween the 5ositi9e sodi m ions and the negati9e chlorine ions. (n addition to this :orce o: attraction !etween o55ositely charged ions other :orces o5erate !etween ions. ,h s there is the gra9itational :orce o: attraction which will always act !etween ad3acent massi9e n clei. Also

when ions come into close 5ro<imity to each other their o ter com5letely :illed electron shells !egin to o9erla5 and a :orce o: electrostatic re5 lsion is set 5 !etween the li8e negati9e charges.

Fig. 3.3 .!e cr'stal structure of so$ium c!lori$e. (i) a $ (ii) s!ow t!e u it cell of so$ium c!lori$e% w!ilst (iii) i $icates t!e co ti uous structure of t!e cr'stal suc! t!at eac! face of a u it cell is s!are$ &' t!e e2t cell. I fact we !a#e two i ter"e etrati g face,ce tre$ cu&ic structures. o e of 1a+ a $ o e of 3l, ().6.2).

At some s5eci:ic se5aration distance these :orces o: attraction and re5 lsion will !e in e? ili!ri m. (n this condition the 5otential energy o: the system will !e at a minim m and o: negati9e sign since an in5 t o: energy wo ld !e re? ired to dis5lace ions :rom their e? ili!ri m 5ositions. ,he 5otential energies associated with attraction and re5 lsion are in9ersely 5ro5ortional to some 5ower o: the distance o: se5aration, r,!etween n clei. ,he energy d e to attraction is o: negati9e sign

and is e? al to ^A2rm whilst the 5otential energy (+E) d e to re5 lsion is e? al to B2rn. A and B are constants de5endent on the nat res o: the ions, i.e. s ch :actors as n clear mass and magnit de o: charge. m and n are 5owers (to !e determined) where n is greater than m. ,he res ltant 5otential energy, ', is gi9en !yD =A 'P B

===== W ==== rm rn

,he relationshi5 !etween 5otential energy and interatomic distance is indicated in #ig. $.$0 where c r9e ! re5resents the +E associated with :orces o: re5 lsion, c r9e a the +E associated with :orces o: attraction whilst c r9e c re5resents the +E associated with the res ltant :orce, each as a : nction o: the distance !etween n clei. ,he 5otential=energy BwellB is dee5est at the e? ili!ri m s5acing, ,), and its de5th, ' 4, the energy re_ ired to se5arate ions com5letely. $ # % ,he distances !etween the centre o: any chlorine ion and the centre o: the si< nearest sodi m ions is less than the distances !etween the centre o: that same chlorine ion and the centre o: the si< nearest chlorine ions. Conse? ently the :orces o: attraction !etween any ion and its neigh!o rs are greater than the :orces o: re5 lsion, and the crystal is there:ore a sta!le str ct re. ,he n3it str ct re in the case o: the s !stance sodi m chloride is the crystal. Sodi m chloride does not e<ist in the :orm o: molec lesQ and it is there:ore not a55ro5riate to write the :orm la ANaCl@ since this wo ld im5ly the e<istence o: one molec le o: sodi m chloride. Ne9ertheless ! sy chemists are in the ha!it o: re5resenting sodi m chloride !y the em5irical :orm la, NaCl, as a ty5e o: Bchemical shorthandB.

$ # ' Sodi m chloride will dissol9e readily in water, ,his is d e to two im5ortant 5ro5erties o: waterD (i) it :orms a 5olar molec le (0....)D (ii) it has a high dielectric constant, ,he hydrogen BendB o: the water molec le is attracted to the negati9ely. charged chlorine ions and the o<ygen [endB o: the molec le to the 5ositi9ely

charged sodi m ions. ,his ca ses water molec les to cl ster ro nd ions at the s r:ace o: a sodi m chloride Crystal ntil their :orces o: attraction are s ::icient to o9ercome the electro9alent !ond !etween sodi m ions and chlorine ions. ,he ions then mi< :reely with water molec les in sol tion. ,his 5rocess o: se5aration o: sodi m ions :rom chlorine ions on sol tion is termed dissociation! (t is sometimes incorrectly called ionisation. ,he latter 5rocess in :act too8 5lace d ring the original reaction !etween sodi m and chlorine when atoms o: each element !ecame ions. $ # ( Bond strength is most easily meas red in terms o: the energy re? ired to !rea8 a chemical !ond. that is the ? antity o: heat

which is necessary to 9a5orise the solid 5hase and so com5letely se5arate the
4

.!oug! I - ow of at least o e te2t &oo- o material scie se i w!ic! t!e aut!or $escri&es a 5so$ium c!lori$e molecule67

constit ent atoms. (n each case the heat o: 9a5orisation o: one gram=mole is meas red so that we shall always !e dealing with the same n m!er o: !onds, i.e. =A A9ogadroBs N m!er. As wo ld !e e<5ected 9an der ;aals !onds are wea8est and re? ire !etween 4.$ and 04.4 8K2mole whilst the co9alent !ond re? ires .44=$>44 8K2mole de5ending 5on the material (#ig. /.1). Between these two e<tremes come metallic and ionic !onds, those o5erating in sodi m chloride !eing an e<am5le o: the latter.

(n any solid at tem5erat res a!o9e 4 * the atoms are in a state o: constant 9i!ration and when a solid is heated these 9i!rations increase ntil a 5oint is reached where the !onds 3oining these atoms are r 5t red. Atoms then mo9e a5art, that is, melting occ rs. ,h s there is a relationshi5 !etween !ond strength and melting 5oint. (: we com5are a series o: Bli8e elementsB e.g. the Al8ali Metals o: Ero 5 (, we note that melting 5oint (as a : nction o:

!ond strength) decreases as the atomic n m!er, O, (ncreasesD ,here:ore one can ass me that electrons o: higher 5rinci5al ? ant m, :orm wea8er !onds so that smaller 9i!rational energies at lower tem5erat res are s ::icient to disr 5t these !onds.

Space Lattices
$ $ A s5ace lattice can !e de:ined as a distri! tion o: 5articles in three dimensions s ch that e9ery 5article has identical

s rro ndings. (t is generally con9enient to imagine a s5ace lattice as contin ing to in:inity in all directions, :or altho gh crystals themsel9es are o: :inite si7e the nits :rom which they are ! ilt are e<ceedingly small. ,h s a small crystal o: co55er some 4.$ mm in diameter will ne9ertheless contain ro ghly /<$4$6 atoms o: co55er. A section o: a s5ace lattice o: general :orm is ill strated in #ig. /.6. Since the 5oints at which 5articles are considered to e<ist are reg larly distri! ted, the : ndamental geometry o: the s5ace lattice can !e descri!ed !y three lattice 9ectors A, B and C. ,he 9ectors de:ine the nit cell and the geometry o: the s5ace lattice is s5eci:ied satis:actorily !y the lattice constants (9ector lengths) a, !and c and the inter=a<ial angles , and . $ $ 1 ,here are only :o rteen di::erent 5atterns in which 5oints can !e arranged in order to satis:y the de:inition or a s5ace lattice. ,hese are the Bra+ais s.ace lattices (#ig. /.>). ): these not more than si< are met with in metallic str ct res and in :act only three are really common. $ $ # #re? ently in a st dy o: Crystals it !ecomes necessary to identi:y a 5artic lar 5lane o: atoms r nning thro gh the str ct re. S ch 5lanes and directions are !est descri!ed !y a set o: n m!ers 8nown as miller indices!

Fig. )./ .!e fourtee 8ra#ais s"ace lattices. (9 = "rimiti#e: 3 = ce tre$ o ;a&( face: I = &o$' ce tre$ a $ F =face ce tre$).

,hese are widely sed in H=ray analyses and other methods sed in deri9ing crystal str ct res. Miller indices are 5ro5ortional to the reci5rocals o: the interce5ts which the 5lane ma8es with the three 5rinci5al a<es (<. y and ?) o: the system. ,hey are deri9ed as :ollowsD (i) determine the interce5ts which the 5lane ma8es with the three crystal a<es. ,hese interce5ts are e<5ressed as the n m!er o: a<ial lengths (a, , or c) :rom the origin. (n #ig. /.& these interce5ts areD < P /M y P $M 7 P 0 (ii) ta8e reci5rocals o: these interce5t 9al es. i.e. l2/M $M $20M (iii) con9ert these reci5rocals to the smallest integers which are in the same ratio, i.e. 0M 6M /. ,his is written in the :orm (06/). ,h s 5lane ABC in #ig. /.& is re5resented !y the Miller indices (06/). ,hese indices re5resent not only the 5lane ABC ! t all 5lanes 5arallel to it. #or e<am5le a 5lane with the interce5ts 6. 0. . will !e

5arallel to 5lane ABC and will !e re5resented !y the same miller indices. A 5lane on the o55osite side o: the )rigin wo ld ha9e negati9e interce5ts on the a<es and wo ld !e denoted (0 6 /). ,he a!o9e deri9ation o: Miller indices re5resents the general case (a triclinic str ct re in which a !c and). ;e will now consider some ty5ical 5lanes :or a sim5le c !ic system. (n #ig. /.%(i) the 5lane indicated has the :ollowing interce5tsD <P$M yP M 7P Conse? ently the Miller indices ;ill !e (l44)`the reci5rocals o: $, ,, ,he 5lane indicated in #ig. /.%(9) has interce5tsD HP$MyP$M7P and hence Miller indices ($$4).

#ig re /. %(9i) ha9ing e? al interce5ts on all a<es is re5resented !y Miller indices ($$$). (n the case o: the sim5le c !ic str ct re, 5lanes which :orm 5arallel gro 5s are enclosed in !rac8ets, e.g. ah8l]. ,h s the :ollowing are e? i9alent 5arallel 5lanesD $$$ P ($$$)M ($$$)M ($$$)M ($$$)M ($$$)M ($$$)M ($$$)M ($$$)M ($$$)M

$ $ $ Directions thro gh a crystal can !e s5eci:ied in terms o: the indices which gi9e the integral co=ordinates o: a 5oint on a line drawn !etween the 5oint and the origin. Direction indices are written in s? are !rac8ets b c to disting ish them :rom Miller indices written in 5arentheses ( ) which re5resent a 5lane. (n the case o: the sim5le c !ic cell the direction normal to the .lane (h8l)

is bh8lc. #ig re ;!8< indicates some o: the im5ortant directions :or a sim5le c !ic cell. A general family o: directions is written dh8le.

E/perimental -erivation of Cr&stallographic Planes

$ % (nter5lanar distances :or crystalline materials are generally determined !y H=ray methods. ,he H=rays sed are o: short wa9elength and hence great 5enetrating 5ower. ,hey are also as nearly as 5ossi!le BmonochromaticB, that is, o: a single wa9elength. ,he method sed de5ends 5on the :act that in a crystal, 5lanes occ r which are occ 5ied !y atoms according to a reg lar 5attern and that H=rays will !e either re:lected or transmitted at these 5lanes. #ig re /.$$ re5resents diagrammatically two layers o: atoms in a crystal str ct re. ,he layers are distance d a5art. (t is ass med that two incident wa9es stri8e the crystal at H and I. ,he wa9e which stri8es the :irst layer at H will either !e re:lected or transmitted to a 5oint I$ in the second layer. Here the 5rocess is re5eated. ,he wa9e re:lected :rom I inter:eres constr cti9ely at ++$ with the wa9e which is transmitted :rom H to I$ and s !se? ently re:lected 5ro9iding that H$I$O$ is an integral m lti5le o: the wa9elength o: the incident H=rays. sing sim5le geometry it can !e seen thatD H$I $ P I $ O $ P d! sin $ % 1 Bragg0s La, #or constr cti9e inter:erence o: H=rays, BraggBs -aw states thatD n P 0d.sin where is the incident angle o: H=radiation. #or the 5rinci5al di::raction, n P $ and so d can !e calc latedD d5 20 sin (nter5lanar s5acings are 9ery small and since the ma<im m 9al e o: sin is one, short wa9elength monochromatic H=rays m st !e

sed so that is o: the same order as the inter5lanar s5acings, i.e. a55ro<imately $4=$4 m.

(n 5ractice i: a !eam o: H=rays :alls on a crystal re:lection :rom a gi9en 5lane can only ta8e 5lace i: that 5lane is inclined to the B5encilB o: H=rays at the necessary angle, . ,his condition is nli8ely to !e satis:ied and a 5owdered sam5le o: the crystalline material is sed so that, ine9ita!ly, a :ew 5articles will !e s ita!ly orientated to ma8e re:lection 5ossi!le. ,he 5owdered sam5le is 5laced at the geometric centre o: a circ lar stri5 o: 5hotogra5hic :ilm and s !3ected to a 5encil o: H=rays (#ig. /.$0). Di::raction occ rs :rom 5lanes that are more or less randomly orientated with res5ect to the so rce. Hence the di::raction 5attern will !e s5herically distri! ted s ch that the circ lar arrangement o: the :ilm interce5ts also the !ac8=di::raction 5atterns. ,his is a 9ery sensiti9e method :or the determination o: inter5lanar s5acings, gi9ing errors o: no more than 4.41R in meas rements o: the order o: 0 < $4=$4 m.

The )etallic Bond

$ ' A!o t three=? arters o: the elements are metals, only a!o t one= eighth are non=metals, whilst the remainder, the metalloids, ha9e 5ro5erties which are intermediate !etween metals and non= metals. ,he non= metals are characterised !y relati9ely high electro negati9ities, !y !eing 5oor cond ctors o: heat and electricity and !y ha9ing melting 5oints and !oiling 5oints which are generally low. Metals, howe9er, ha9e relati9ely high melting 5oints and !oiling 5oints and are good cond ctors o: heat and electricity. Moreo9er they 5ossess 5lasticity, the 5ro5erty which 5ermits

5ermanent de:ormation witho t accom5anying :ract re. All o: these 5ro5erties are related to the nat re o: the metallic !ond, and are connected with the :act that metallic atoms ha9e only one or two electrons in their ,he atoms o: a metal are arranged s ch that their ions con:orm to some reg lar crystal 5attern (#ig. /.$/) whilst their 9alency electrons !eha9e as tho gh they are mo!ile, :orming a common Aclo d@. s rro nding the ions. ,hese electrons can !e descri!ed as delocalised and no 5artic lar electron B!elongsB to any 5artic lar atom. Altho gh the indi9id al electrons are !o nd to metallic atoms m ch less strongly than are those in non=metallic elements, the shared electrons !ind metallic ions 9ery tightly into the lattice since there is attraction !etween the 5ositi9ely charged n clear 5rotons and the delocalised electrons o: the common Aclo d@. ,his res lts in the high melting 5oints and !oiling 5oints o: metals, whilst the mo!ility o: the electrons con:ers high cond cti9ity o: !oth heat and electricity.

$ ' 1 (t m st !e admitted that the a!o9e inter5retation o: the metallic !ond is o9ersim5li:ied and :ails nder more detailed ? antitati9e e<amination. Ne9ertheless this sim5li:ied 5ict re is se: l at this stage in considering some o: the mechanical 5ro5erties or metals, and a slightly more detailed e<amination o: the nat re o: the metallic !ond will !e 5resented[ later in this !oo8 ($&./.$). $ ' # Electrical Properties Electrons in the electron Bclo dB are not !o nd to :i<ed or!itals ! t are a!le to mo9e :reely thro gho t the !ody o: metal, that is their mo9ement is random. (: a relati9ely small electrical 5otential di::erence is a55lied to a 5iece o: metal the random electron mo9ements are con9erted into an orderly electron stream towards the higher 5otential. ,h s metals are e<cellent cond ctors o: electricity and this :low o: electrons 5rod ced !y the a55lication o: a 5otential di::erence ( is what we call a Bc rrentB o: electricity. (n non=metallic elements the o ter=shell electrons o: atoms are con:ined in co9alent !onds. ,hey are there:ore na::ected !y the a55lications o: an electrical 5otential di::erence nless it is 9ery great. Conse? ently most non=metallic elements and com5o nds are !ad cond ctors, 5artic larly those o: the organic 5olymer ty5e where co9alent !onding e<ists thro gho t large molec les (0././). Many s ch s !stances are in :act sed as ins lators. Some elements, o:ten re:erred to as Ametalloids@, 5ossess 5ro5erties which are intermediate !etween those o: metals and non=metals. ,his is re:lected in their electrical 5ro5erties. (n silicon and germani m :or e<am5le the energy necessary to detach electrons :rom their co9alent !onds and mo9e them thro gh the str ct re o: the solid is m ch less than with most non=metals. ,hese elements are termed semi=cond ctors.

Cr&stal Str"ct"res in )etals

$ ( As we ha9e seen, the :orces !inding the atoms in a metal are non=directional, and since in a 5 re metal all atoms are o: the same 8ind and si7e, they will arrange themsel9es in the closest 5ossi!le 5ac8ing 5atterns which are associated with 5ositions o: minim m 5otential energy. Most o: the metals o: engineering im5ortance crystallise in one o: three 5rinci5al ty5es o: str ct re in all o: which the atoms are held together solely !y the metallic !ond. ,he s5heres sed in the ill strations which :ollow re5resent atomic cores !etween which the electron clo d will !e distri! ted. $ ( 1 The Close1packed .e/agonal Str"ct"re 2CP.3 ;hen we 5lace the snoo8er !alls in the triang lar :rame at the !eginning o: a game we are in :act 5ac8ing them in the closest 5ossi!le arrangement in a single 5lane. ,he arrangement is that indicated in #ig. /.$.(() and it will !e seen that any s5here, H, is to ched !y si< immediate neigh!o rs. -ines 3oining the centres o: these s5heres :orm a reg lar he<agon. (: we consider any three s5heres, lines 3oining their centres :orm an e? ilateral triangle and at the centre o: this triangle is a small s5ace !etween the s5heres. Now consider a s5here 5 t on to5 o: these :irst three so that it rests in the hollow :ormed !y them. ,he s5ace so enclosed !y the :o r s5heres is termed a tetrahedral site since it is enclosed !y :o r s5heres whose centres lie on the 5oints o: a reg lar tetrahedron. ,his ty5e o: site is o: great im5ortance in a st dy o: crystallogra5hy. (: a second layer o: s5heres is now 5laced on to5 o: the :irst layer and allowed to :ind its own le9el, each s5here in this second layer will come to rest in one o: the hollows :ormed !y the :irst layer as indicated in #ig./.$.(ii).

,here are two +ossi!le 5ositions in which s5heres o: a third layer can !e 5laced either in those 5ositions mar8ed H or in those mar8ed I. (: we 5lace them in 5ositions mar8ed H, the centre o: each s5here in the third layer will !e 9ertically a!o9e the centre o: a s5here in the :irst layer. ,his is the close=5ac8ed he<agonal (C+H) str ct re and i: the arrangement in the :irst layer is re5resented !y A and that in the second layer !y B, the ! ilding order in9ol9ed here is ABABABAB... etc. Any atom in the system is to ched !y si< atoms in its own 5lane (#ig. /.$.(i)) and !y three atoms in the 5lane !eneath. ,he C+H str ct re is so called !eca se it has an a<is o: si<:old symmetry 5er5endic lar to the layers o: closest 5ac8ing, that is, 5er5endic lar to the 5lane o: the 5a5er in #ig. /.$.(i). A nit cell o: this str ct re is shown in #igs /. $.(iii) and (i9)M #ig. /.$.(iii) indicating the atomic cores in contact and #ig. /. $.(i9) the s5ace lattice. +lastic de:ormation in metals ta8es 5lace !y a 5rocess 8nown as Bsli5B, that is !y layers o: atoms gliding o9er each other. ,his occ rs most :re? ently !y the close=5ac8ed 5lanes sli55ing in close=5ac8ed directions. (n the C+H str ct re s ch sli5 is limited since it will occ r mainly along !asal 5lanes o: the he<agon. ,h s,

most metals with a C+H str ct re are m ch less d ctile than those with a :ace=centred c !ic str ct re. $ ( # The Face1centred C"*ic Str"ct"re 2FCC3 (n this str ct re the !asic 5ositions o: s5heres in the first two layers are the same as those indicated in #ig. / .$.(ii). #or the third layer, howe9er, the s5heres are 5laced in the hollows mar8ed I (#ig. /.$.(ii)). ,h s in this third layer the s5heres are in di::erent 5ositions :rom those in the :irst layer (th s di::ering :rom the C+H str ct re). (: we re5resent this third layer !y C then the ! ilding order will !e ABCABCABCABC... etc. ,his is the closest 5ossi!le 5ac8ing in a c !ic :orm (#ig. /.$1(i)). (: the nit cell o: this str ct re is e<amined it will !e :o nd that there is a s5here in the centre o: each o: si< :aces o: the c !e. ,he str ct re is there:ore 8nown as face-centred cu,ic! (t will also !e noted that the s5heres :orming the :aces o: the nit cell are not closely 5ac8ed, and i: the ! ilding 5 o: the crystal is contin ed (#ig. /.$1(iii)) it will !e o!ser9ed that the s5aces in this crystal :ace are !o nded in each case !y :o r s5heres. (: a s5here is now 5laced at the :ront o: one o: these s5aces and another at the rear, the ga5 so enclosed is called an octahedral site since it is !o nded !y si< to ching s5heres with their centres at the 5oints o: a reg lar octahedron. )ctahedral sites, li8e tetrahedral sites, are im5ortant in a st dy o: crystallogra5hy. (: the s5here mar8ed S in #ig. /.$1(i) is now remo9ed the e<5osed layer, which is along the ($$$) 5lanes, has si< s5heres (#ig. /.$1(i9)) which re9eal the close=5ac8ed arrangement :ormed in the ! ilding 5 o: the str ct re. ,hese close=5ac8ed layers are in ($$$) 5lanes which are at right angles to the !ody=diagonal o: the c !e and the se? ence o: layers along that. diagonal is ABCABCABCABC... etc.

#ig re /. $1(i9) re9eals that the ($$$) 5lane is one o: close= 5ac8ing. ,he direction o: closest 5ac8ed rows o: atoms is b$$4c. Altogether there are :o r sets o: closely 5ac8ed ($$$) 5lanes in the :ace=centred c !ic str ct re and twel9e sets o: close=5ac8ed directions. As already mentioned, 5lastic de:ormation o: metallic crystals generally occ rs !y the sli55ing o: close=5ac8ed 5lanes o9er each other and in the close=5ac8ed directions. #or this reason the :ace=centred c !ic str ct re wo ld !e e<5ected to show a considera!le ca5acity :or 5lastic de:ormation. ,his is indeed s 55orted !y the :act that all o: the more d ctile and mallea!le metals ha9e :ace=centred c !ic str ct res. ,hey incl de gold, sil9er, co55er, al mini m, 5latin m, lead and nic8el. $ ( $ The Bod&1centred C"*ic Str"ct"re 2BCC3 ,he nit cell :or this str ct re consists o: a s5here at the centre o: a c !e with eight other s5heres at the corners o: the c !e and to ching the central

s5here (#ig. /.$6). ,h s 5ac8ing is not so close as in the other two systems. So when iron, which is an allotro5ic (/.6..) metal, changes :rom a BCC str ct re to one which is #CC on heating to %$4ZC, a meas ra!le contraction occ rs s5ontaneo sly

,he most closely 5ac8ed 5lanes are ($$4) o: which there are si<. ,he closest 5ac8ed direction is that o: ($$$) o: which there are :o r. Since the closest 5ac8ed 5lanes are still more o5en than those o: #CC and there are less close=5ac8ed directions, it :ollows that the BCC str ct re is less d ctile than the #CC str ct re. #or e<am5le, iron in its #CC :orm is more mallea!le than in its BCC :orm. $ ( % Allotrop& is de:ined as the a!ility o: a single s !stance to e<ist in more than one 5hysical :orm. ,hese allotro5es are generally sta!le o9er di::erent tem5erat re ranges. ,h s iron (= iron) is !ody=centred c !ic at am!ient tem5erat res ! t on heating it loses its :erromagnetism at >&4ZC (the Curie .oint) tho gh retaining its BCC str ct re. ,his 5hase is 3 dged to !e a di::erent allotro5e==iron. # rther heating to %$4ZC leads to recrystallisation to a :ace=centred c !ic str ct re (=iron) which at $.44ZC re9erts to a !ody=centred c !ic :orm (termed =iron to disting ish it :rom the BCC :orm e<isting !elow %$4ZC). ,hese allotro5ic changes are re9ersi!leD

>&4ZC

%$4ZC

l.))ZC

=iron =iron =iron =iron (BCC) (BCC) (#CC) (BCC)

,he allotro5y o: solids which relies soley on di::erence in crystal str ct re. is 8nown as .olymor.hism! Many metals are 5olymor5hic and sometimes two 5olymor5hs will !e :ace=centred c !ic and close=5ac8ed he<agonal (C+H) res5ecti9ely. ,his is :easi!le since the change #CCfC+H ta8es 5lace with relati9e ease. $ ( ' Coordination !"m*er and Packing Fraction An e<amination o: #ig. /.$. shows that the central atom H in the 55er 5lane o: the C+H str ct re has si< other atoms on the same 5lane as nearest neigh!o rs. (;hen re5resented !y s5heres in these diagrams atoms are shown as to ching the central atom.) ,his central atom is also to ched !y three atoms on the 5lane !elow and similarly !y three atoms on the 5lane directly a!o9e (not shown in the diagram). ,h s, in a$$, twel9e atoms are in contact with the central atom as nearest neigh!o rs. ,his total, $0, is the coordination num,er o: the C+H str ct re. (n the #CC str ct re (#ig. /.$1) the central atom in the 55er 5lane has :o r atoms to ching it as nearest neigh!o rs, :o r atoms in the 5lane !elow and similarly :o r atoms in the 5lane a!o9e (not shown). Again the total, $0, is the coordination n m!er o: the #CC str ct re and is characteristic o: all metallic str ct res with the closest 5ossi!le 5ac8ing o: atoms. (n the BCC str ct re, howe9er, any atom=:or e<am5le the central atom in the single nit shown in #ig. /. $6(i)=is to ched !y only eight other atoms, that is, :o r in the 5lane a!o9e and :o r in the 5lane !elow, gi9ing a coordination n m!er o: eight.

all metallic str ct res with the closest 5ossi!le 5ac8ing o: atoms. (n theB

)nly one metal, radioacti9e 5oloni m, is 8nown to crystallise in sim5le c !ic :orm, that is with one atom at each corner o: a c !e. Here any atom is to ched !y si< nearest neigh!o rs so that this 9ery loose 5ac8ing o: atoms has a coordination n m!er o: si<. ,h s it will !e seen that the coordination n m!er is generally an indication o: how closely atoms (or ions) are 5ac8ed in a crystal str ct re. ;e can calc late the density o: 5ac8ing more 5recisely in terms o: a .ac ing fraction which is the 5ro5ortion o: s5ace in a nit cell act ally occ 5ied !y the atoms. (n the BCC system (#ig. /.$>(i)) a nit cell contains one com5lete atom at its centre and one=eighth o: an atom at each o: the eight corners o: the nit c !e gi9ing a total o: two atoms 5er nit cell. Hence the total 9ol me o: these atoms in terms o: their diameter * isD 0< b.2/(D20)/cPD/2/ ,he internal diagonal AC (#ig. /.$>(iig o: the nit cell o: 5arameter, a, is o: length e? al to two diameters o: the atoms concerned.

,he diagonal AB o: a :ace o: the c !e is e? al to (a0Wa0) Hence the internal diagonal AC is gi9en !y (a0Wa0) P (/a0) P0D a P0D2/ and the 9ol me o: the nit cell !y a; P b0D2/c/ 'ol me o: 0 atoms +ac8ing :raction P P P P 'ol me o: nit cell D/2/ 4b0D2/c/ /2& 4.46&4

(n the #CC system (#ig. /.$>(iii)) each o: the eight comers o: a nit cell contains one=eighth o: an atom, whilst each o: the si< :aces o: the nit cell contains hal: an atom, gi9ing a total o: :o r atoms 5er nit cell. ,he length o: a diagonal o: a :ace o: the nit cell (#ig. /.$>(i9)) is e? al to two atom diameters (6*) so thatD 0D P (a0Wa0) a P D 0 'ol me o: 0 atoms +ac8ing :raction P 'ol me o: nit cell P P . < b.2/ (D20)/c4(D0)/ (02/) 400

or HenceD

P 4.>.4 ,his ill strates the magnit de o: the contraction which occ rs when BCC () iron trans:orms to #CC() iron at %$4oC and the 5ac8ing :raction increases :rom 4.6& to 4.>.. (n a nit cell o: the C+H system (#ig. /.$>(9)) hal: an atom at the centre o: the 55er :ace is s rro nded !y si<, one=si<th atoms gi9ing a total :or that 5lane o: one=and=a=hal: atoms. Similarly a : rther one=and=a=hal: atoms are contri! ted !y the !ottom 5lane o: the nit cell. ): the three atoms in the central 5lane o: the nit cell segments A, Band C (#ig. /.$>(9)) are Alost@ to neigh!o ring cells ! t those Alosses@ are !alanced !y Agains@ o: similar segments H, I and O :rom atoms e<ternal to the cell. Hence three atoms are contri! ted !y this 5lane ma8ing a total o: si< atoms 5er nit cell. ,he 9ol me o: those si< atoms isD 6< b.2/ (D20)/c P D/ As is indicated in #ig. /.$>(9) and (9i) side a o: the reg lar he<agon is e? i9alent to one atom diameter *! ,he height c o: the he<agonal 5rism is e? al to 0h where h is the height o: the reg lar tetrahedron o: edge, a! B t h Pa 02/ so that c P 6h P 6a(02/). ,he area o: the he<agonal !ase o: the nit cell (o: side a) b(//)20ca0 so that the 9ol me o: the he<agonal 5rism(height 0a(02/) P /a/0 which, since a P *, (S ;*/0! HenceD 'ol me o: 6 atoms +ac8ing :raction P 'ol me o: nit cell P ( D/)2 (/D/0) P 2(/0) P 4.>.4 (n the sim5le c !ic system a nit cell contains only one atom in total (one ^ eighth o: an atom at each o: the eight corners o: the

c !e). ,he 9ol me o: the nit cell is D/ since each side is e? al in length to one atom diameter, HenceD +ac8ing :raction P b.2/ (D20)/c4D/

P P

26 4.10/

,his con:irms the 9ery o5en 5ac8ing o: atoms in this system.

[Q] The atomic radius of aluminium is 1.43 x 10 10 m and its atomic mass num!er is 26."#. $i%en that &%ogadro's (um!er) (&) is 6.022 x 1023 * mole calculate the densit+ of aluminium. .!e atomic ra$ius of alumi ium is 1.*) 2 10 ,10 m. He ce t!e $iameter is gi#e &'= > = 2.86 < 10,10 m For t!e F33 structure (alumi ium) t!e le gt! of o e si$e of t!e u it cell is e?ual to= D2= 2 < 2.86 2 10,10 m He ce t!e #olume of a u it cell of alumi ium is e?ual to= (2 2 2.86 2 10,10)) = 6.61/ < 10,2@ m) + u it cell of F33 alumi ium co tai s four atoms. 1 -Amole of alumi ium (atomic mass 26.@8) co tai s 1 + atoms. .!erefore% mass of four alumi ium atoms is= * 2 26.@8 = 1+ He ce% $e sit' of alumi ium is= Mass of * alumi ium atoms Bolume occu"ie$ &' * 2 26.@8 = 6.022 2 102)2 6.61/ 2 10,2@ 6.022 2 1026 * 2 26.@8

* alumi ium atoms = 2./08 2 10) -gAm) i.e. relati#e $e sit' = 2./08 .!is #alue is slig!tl' !ig!er t!a t!at $etermi e$ e2"erime tall' (2.6@@) $ue to t!e "rese ce of #arious small ca#ities i la&orator' (or factor') "ro$uce$ metals. .!is will &e $iscusse$ later i t!is a $ su&se?ue t c!a"ters ()./.2: C.)).

,he Crystallisation o: Metals $ 4 All 5 re elements e<ist either as gases. li? ids or solids and the state in which an elementQ e<ists de5ends 5on the 5re9ailing com!ination o: tem5erat re and 5ress re. ): the metallic elements, only merc ry is a li? id at ordinary tem5erat res, tho gh a n m!er o: metals melt !elow red heat. A :ew, li8e 7inc, cadmi m and merc ry !oil at relati9ely low tem5erat res and can !e 5 ri:ied !y distillation. (n $&0> !otanist Ro!ert Brown was sing a microsco5e to e<amine some min te 5ollen 5articles :loating on the s r:ace o: water. He was s r5rised to o!ser9e that these 5articles were in a state o: contin o s motion which was agitated and irreg lar. At the time he was com5letely !a::led !y the 5henomenon ! t later it was realised that the motion 5rod ced in the 5articles was the res lt o: im5act !y mo9ing in9isi!le water molec les at the s r:ace o: the water. ,he same 8ind or motion, 8nown as BBrownian motionB, can !e seen in the solid 5articles com5rising smo8e. ;hen these 5articles, s s5ended in air, are 9iewed thro gh a microsco5e they are seen to 5 rs e irreg lar 3er8y 5aths d e to !om!ardment !y :ast=mo9ing o<ygen and nitrogen molec les. )!ser9ations o: this 8ind showed that molec les in gases and li? ids were in a state or contin o s motion and this led ltimately to the :orm lation o: the inetic theory of matter! $ 4 1 Metals :orm monatomic gases, that is the 9a5o r consists o: single atoms o: the metal. ,hese atoms are in constant motion and

are colliding contin ally with the walls o: their container. ,he collisions gi9e rise to the 5ress re e<erted !y the gas. (: tem5erat re is increased atoms mo9e more ? ic8ly as heat energy is trans:ormed into 8inetic energy. Hence collisions with the sides o: the container will increase and so 5ress re will increase,
4 .!e same is ot ecessaril' true of com"ou $s si ce ma ' of t!ese $ecom"ose at a tem"erature &elow t!eir &oili g "oi t. a $ some &elow t!eir melti g "oi t.

ass ming that the 9ol me o: the gas is 8e5t constant !y restraining e<5ansion. (: the tem5erat re is allowed to :all the a9erage 8inetic energy o: the atoms decreases and is lost as heat energy (s5eci:ic heat). E9ent ally an a a9erage energy content is reached where 9an der ;aals :orces acting !etween atoms are a!le to o9ercome the 8inetic mo9ement o: many o: the atoms. Hence those with less than the a9erage 8inetic energy are attracted to each other so that they stic8 to each other, that is they condense to :orm dro5lets o: li? id which :all nder gra9ity. At this 5oint the remainder o: the 8inetic energy is gi9en 5 as heat (latent heat o: 9a5orisation). No orderly arrangement o: atoms e<ists in the li? id metal and atoms are still :ree to mo9e with res5ect to each other, that. is, a li? id 5ossesses mo,ility! At a lower tem5erat re still the li? id !egins to solidi:y. ,his is a 5rocess where atoms change :rom a disordered or amor.hous state to an ordered crystalline state. As this occ rs 5otential energy is lost (#ig. /. $&)=this time as latent heat o: : sion=and since the atoms arrange themsel9es according to some orderly 5attern, shrin8age generally accom5anies solidi:ication. #or this reason the 55er 5ortion o: a metal ingot is B5i5edB (#ig. /.06). $ 4 # + re metals, li8e other 5 re s !stances, solidi:y at a :i<ed single tem5erat re. (deally this will occ r in accordance with the

ty5e o: cooling c r9e shown in #ig. /.$%(i). Howe9er, in most cases there is some degree o:

Fig. ).1@ .'"ical cooli g cur#es for cr'stalli e a $ amor"!ous soli$s. I (iii) t!ere was i sufficie t molte metal to "ro#i$e late t !eat w!ic! woul$ ot!erwise !a#e cause$ a retur to e?uili&rium as i (ii).

nder cooling o: the li? id !e:ore the onset o: crystallisation. ,his is d e to a lac8 o: n cleation o: the system (#ig. /.$%(ii) and (iii)). )nce a crystal n cle s :orms it 5ro9ides a solid2li? id inter:ace where crystallisation can 5roceed (#ig. /.04). Fnder ind strial conditions n cleation may occ r on a 5article o: slag or dross, ! t with 9ery 5 re li? id metal some degree o: nder cooling will occ r. ;hen n cleation ltimately ta8es 5lace the

greater the e<tent o: nder cooling the greater wi$l !e the rate o: crystalli7ation and, conse? ently, the rate at which latent heat is li!erated. As a res lt the tem5erat re o: the melt will rise to reach e? ili!ri m at the :ree7ing 5oint o: the metal (#ig. /.$%(ii)). (: only small amo nts o: molten metal are in9ol9ed ins ::icient

latent heat may !e a9aila!le to allow the :ree7ing 5oint to !e regained (#ig. /.$%(iii)). ,he n clei which :orm, will !e sim5le nits o: the crystal 5attern in which the metal solidi:ies, generally C+H, #CC or BCC. Crystal growth will tend to occ r in the o55osite direction

to that in which heat is !eing cond cted :rom the melt. ,h s a Bs5i8eB !egins to grow :rom the n cle s into a region o: nder= cooled li? id, ! t as this occ rs, latent heat is li!erated and this warms 5 the li? id in :ront o: the growing s5i8e. Hence growth o: the s5i8e is retarded and as a res lt secondary s5i8es !egin to grow :rom the 5rimary one and these are :ollowed !y tertiary s5i8es (#ig. /.0$). ,hese 5rimary, secondary and tertiary !ranches :ollow crystallogra5hic 5lanes and gi9e rise to the general reg larity o: the str ct re. ,he crystal s8eleton which de9elo5s is called a dendrite, a re:erence to its tree=li8e growth (E8. dendron, Ba treeB), in which the 5rimary, secondary and tertiary arms resem!le the tr n8, !ranches and twigs o: a tree.

,he main !ranches o: the dendrite contin e to grow ntil the o ter :ringes ma8e contact with those o: neigh!o ring dendrites (#ig. /.0/). Since they are th s restrained :rom : rther o tward growth these e<isting arms thic8en as heat :lows o twards :rom the region. Each dendrite de9elo5s inde5endently so that the o ter !ranches o: neigh!o ring dendrites ma8e contact at irreg lar angles. Moreo9er heat :low is not necessarily ni:orm and so the

:inal crystals are o: irreg lar sha5e tho gh

Fig. 3.23 .!e $e $ritic soli$ificatio of a metal. (i) >e $rites &egi to $e#elo" from ewl' forme$ uclei &' "utti g out "rimar' a $ seco $ar' arms. (ii) .ertiar' arms form a $ meet ot!ers growi g i t!e o""osite $irectio . (iii) >e $rites co ti ue to grow u til t!eir outer arms touc! t!ose from eig!&ouri g $e $rites. 02isti g arms t!e t!ic-e . (i#) D!e t!e metal is com"letel' soli$ t!ere is little

e#i$e ce of t!e $e $ritic met!o$ of growt! si ce i a "ure metal all atoms are similar. .!e o l' grai &ou $aries are #isi&le.

the atoms within anyone crystal are reg larly s5aced with res5ect to each other in a crystal lattice. (: the metal nder consideration is 5 re only crystal !o ndaries will !e 9isi!le when a section o: the metal is e<amined nder the microsco5e since all atoms 5resent in the str ct re are similar. ,he 5resence o: im5 rities, howe9er, may re9eal the dendritic 5attern to some e<tent as these im5 rities tend to congregate in that metal which solidi:ies last, that is, !etween the dendrite !ranches and 5artic larly towards the crystal !o ndaries. Shrin8age ca9ities, :ormed d e to lac8 o: li? id as solidi:ication contraction occ rs, may also o tline the dendrite sha5e to a limited e<tent (#ig. /.0.).

$ 4 $ Altho gh the dendrites in #ig. /.0/ are shown as !eing geometrically 5er:ect in res5ect o: the directionality o: their !ranches, in 5ractice there is o:ten misorientation !etween neigh!o ring arms with res5ect to each other within the same crystal! ,his may !e as m ch as .o in some cases. (t is d e to the 5ress re o: growing arms 5on each other as they com5ete :or s5ace, rather li8e the !ranches o: 5ine trees in a dense #orestry Commission 5lantation. # rther misorientation o: indi9id al atoms occ rs at crystal !o ndaries. Here is a :ringe o: metal a!o t three atoms thic8 where the atoms are mis:its with res5ect to !oth

crystals. Iears ago this was 8nown as Bgrain !o ndary cementB ! r :ort nately this misleading term

has :allen into dis se. ,he e<istence o: this :ringe o: mis:it atoms e<5lains some o: the mechanical 5ro5erties .o: metals. Since it is o: an amor5ho s nat re (#ig. /.01) it !eha9es rather li8e an e<tremely 9isco s li? id. ;hilst at low tem5erat res metals generally :ail !y the 5ro5agation o: transcrystalline crac8s, at high tem5erat re :ail re in9aria!ly :ollows intercrystalline 5aths, 5res ma!ly !eca se the amor5ho s :ilm has !ecome less 9isco s at the higher tem5erat re. #ine=grained metals, which will contain more grain !o ndary and, hence, more mis:it atoms 5er nit 9ol me, cree5 more readily than coarse=grained metals o: similar com5osition. (t is reasona!le to s 55ose that cree5 ($6..) is a 5ro5erty closely associated with the amor5ho s state. $ 4 % ,he o9erall si7e and, to some degree, the sha5e o: crystals in a metal ingot 9aries with the rate o: cooling. Ra5id cooling gi9es rise to considera!le nder cooling and the 5resence o: a mo ld s r:ace hel5s to n cleate the li? id. As a res lt a dense shower o: n clei will :orm instantaneo sly and so a layer o: 9ery small or

BchillB crystals will res lt (#ig. /.06(ii)). As the mo ld warms 5 5rogressi9ely and the rate o:

cooling is red ced a stage is reached when crystal growth inwards is !alanced !y heat :low o twards. #resh n clei are not :ormed and so the e<isting crystalsB grow in col mnar sha5e. ;ith large ingots the rate o: cooling at the centre may !e so low that :ew n clei :orm

since there is little ndercooling. Conse? ently the res ltant crystals tend to !e large and @e? i=a<ed@, that is, o: e? al a<es. An im5ortant e::ect which the 5rocess o: solidi:ication has 5on an ind strially cast metal is in the segregation o: dissol9ed im5 rities at the !o ndaries o: crystals. + re metal tends to crystallise o t :irst so that the metal in the region o: the crystal !o ndaries may !ecome so rich in im5 rities that the limit o: sol !ility o: the latter is e<ceeded ca sing it to se5arate o t as :ilms o: im5 rity in the crystal !o ndary region. ,his may gi9e rise to e<cessi9e !rittleness in that region so that intercrystalline :ract re res lts. /.>.1 Rapid Solidification Processes 2RSP3 ,hese ha9e !een in9estigated in recent decades 5artly with the aim o: 5rod cing smaller crystals and so limiting the e::ects o: segregation=the smaller the crystals the greater the amo nt o: crystal !o ndary 5er nit 9ol me o: the metal and conse? ently the more Bdil teB the im5 rity. Howe9er, !y sing 9ery high rates o: cooling at the onset o: solidi:ication, :or e<am5le in e<cess o: $46 ZC 5er second, it is :o nd that with some metals and alloys a com5letely amor5ho s str ct re can !e retained=the onset o: crystallisation has !een halted. Hence there will !e no serio s segregation since crystal !o ndaries ha9e !een eliminated. # rther im5lications o: RS+ are mentioned in $/.6.&.

Cr&stal Str"ct"res of !on1metallic )aterials

$ 5 So :ar we ha9e dealt with crystal str ct res which are de5endent 5on the :ormation o: the ionic !ond or the 5resence o: the metallic !ond !etween cores. ,he co9alent !ond and relati9ely wea8 9an der ;aals :orces also 5lay their 5arts in crystal :ormation. ,he co9alent !ond which is the !asis o: molec le :ormation may lead to the 5rod ction o: molec les so large that within these molec les e<ists a re5etiti9e 5attern common to crystalline str ct res. Similarly, the :ormation o: crystals in which

molec les are nits relies on 9an der ;aals :orces o5erating !etween the molec les. ,h s water crystallises to :orm ice. Here the :orces o: attraction are s 55lied !y the hydrogen !ond (0....).

6iant )olec"les
$ 5 1 Three1dimensional Cr&stals Altho gh in a geometrical sense all crystals will !e three=dimensional, the term is sed here as a re:erence to a<ial directions. ,he !est=8nown e<am5le o: this ty5e o: str ct re is that o: diamond. ,he crystal 5attern is determined !y the :act that in this allotro5e car!on e<hi!its its normal 9alency o: :o r, s ch that each car!on atom is 3oined to :o r o: its immediate neigh!o rs !y co9alent !onds. (n order that this shall occ r symmetrically each car!on atom is s rro nded !y :o r others whose centres lie at the corners o: a reg lar tetrahedron. ,he central atom is in contact with the other :o r (in #ig. /.0& only the centres o: the atomic cores are indicated). (: the str ct re is e<tended to incl de more car!on atoms (#ig. /.0&(ii)) it will !e noticed that the whole :ig re is tetrahedral and will contin e to e<tend BdownwardsB s ch that each car!on atom is 3oined to :o r others !y co9alent !onds. ,he str ct re can also !e regarded as !eing !asically c !ic (#ig. /.0&(iii)) and it can !e shown that as s ch the str ct re is m ch less closely 5ac8ed than a !ody=centred c !ic

Fig 3.2# .!e cr'stal structure of $iamo $. (i) .!e u it cell% i $icati g t!at !ere car&o !as a coor$i atio um&er of four: (iii) a $ (i#) s!ow !ow $iamo $ ca &e co si$ere$ as a cubic structure. 1ote t!at i (ii) ot all #ale cies are use$ u" i t!e (fri ge( atoms of t!e cr'stal% w!ic! will of course &e co ti uous i "ractice. (< re"rese ts t!e same atom i t!e s'stem i eac! case.)

str ct re. ,h s, in #ig. /.0&(i9), only :o r o t o: the eight c !ic nits has a car!on atom at its centre whilst many o: the Bcorner sitesB are n sed. Diamond can there:ore !e regarded as a three=dimensional giant molec le (or macromolec le), Cn! (n the Crystal so 5rod ced the car!on atom has a coordination n m!er o: :o r. Diamond is mechanically strong and is the hardest s !stance 8nown. Moreo9er it has an e<tremely high melting 5oint=in :act at ordinary 5ress res it does not melt, ! t at a!o t /144 oC thermal 9i!rations o: the atoms are strong eno gh to o9ercome the 5ower: l co9alent !onds and 9a5orisation !egins. Both o: these :actors ill strate the 9ery great strength o: the co9alent !ond. Since in diamond all car!on atoms are co9alently !onded s ch that all a9aila!le electrons are sed 5, diamond is not a cond ctor o: electricity ($&./.0). )ther elements o: similar 9alency (with car!on they constit te Ero 5 (' o: the 5eriodic classi:ication), e.g. silicon. germani m and the BgreyB allotro5e o: tin, also crystallise in the diamond=ty5e o: str ct re. $ 5 # La&er Str"ct"res Each car!on atom in a diamond crystal achie9es a sta!le octet o: electrons !y :orming :o r co9alent !onds with neigh!o ring car!on atoms. Another allotro5e o: car!on. Era5hite, also e<ists. (n gra5hite the atoms are !onded in the :orm o: a ring str ct re so that :lat layers are 5rod ced in a reg lar he<agonal networ8 (#ig. /.0%). Each

car!on atom is s rro nded !y three other car!on atoms (#ig. /.0%(i)) so that the coordination n m!er o: car!on in this instance is three. As #ig. /.0%(ii) indicates each car!on atom ses only three o: its o ter shell electrons to :orm co9alent !onds. ,he :o rth electron in each case can !e regarded as !eing BsharedB to some e<tent in the nat re o: the electrons in the metallic !ond. ,h s. whilst diamond does not cond ct electricity, gra5hite does. ;hilst the car!on atoms within these layers or sheets are !onded co9alently the layers themsel9es are held together only !y wea8 9an der ;aals :orces. #or this reason whilst the sheets themsel9es are strong they slide o9er each other

9ery easily so that gra5hite is a good l !ricant. Materials li8e clay ( n=:ired) and talc are also o: this ty5e (n the molec les o: thermo5lastic materials e.g. 5olythene, car!on atoms are co9alently !onded to :orm long=chain molec les (0././). ;hilst these BchainsB are strong in themsel9es they are only !onded to neigh!o rng molec les !y wea8 9an der ;aals :orces so that nder com5arati9ely low stress these molec les will mo9e relati9e to each other with ease, rendering 5olythene a so:t :le<i!le material.

$ 5 $ )olec"lar Cr&stals Molec les are se5arate sel:=contained nits as are atoms so that it is 5ossi!le :or them to arrange themsel9es in a crystalline :orm. ;hilst the atoms within a molec le are held together !y co9alent !onding, the molec les themsel9es are !onded !y 9an der ;aals :orces. ,he element tell ri m :orms long=chain molec les and these in t rn arrange themsel9es in a 5attern with li8e molec les to 5rod ce crystals. Many 5olymers are regarded as !eing amor5ho s, that is, noncrystalline, yet many do 5ossess some crystalline regions 8nown as fringed micelles! ,hese are o:ten lin8ed together !y a chain molec le which [ e<tends :rom one micelle to another (#ig. /./4). Since intermolec lar

:orces are only o: the wea8 9an der ;aals ty5e, crystallisation is not as 5er:ect o9er a long range with these c m!ersome chain molec les as it is when crystals grow :rom single atoms $ 5 % F"llerenes -am5!lac8=or soot= sed to !e classed as a third allotro5e o: car!on (amor5ho s car!on) ! t it was later :o nd to consist o: 9ery small gra5hite 5latelets. A short while ago, howe9er, a third allotro5ic :orm o: car!on was disco9ered=the fullerene! ,his allotro5ic :orm consists o: a series o: large molec les each containing an e9en n m!er o: car!on atoms arranged in the :orm o: a closed hollow cage (#ig. /./$(ig. ;hen car!on atoms :orm a 5 rely he<agonal networ8 (#ig. /.0%) the str ct re consists o: a :lat sheet as in gra5hite ! t i: .entagons are

incl ded at s ita!le sites then the str ct re can no longer remain :lat ! t is Bdrawn 5B into glo! lar :orm (#ig. /./$(ii)).

,his is similar to the ty5e o: constr ction sed architect rally in geodesic domes s ch as that ho sing BScience ;orldB in 'anco 9er. (n :act the name A: llerene@ is deri9ed :rom that o: the, FS engineer and architect Richard B c8minster # ller who de9elo5ed geodesic design. Nearer to home, the 5anels o: a modern soccer !all :ollow a similar 5attern. # llerenes contain e9en n m!ers o: car!on atoms :rom 04 5 to as many as 644 ! t the more symmetrical and sta!le molec les are those with !etween 0& and >4 car!on atoms . ,he :irst : llerene to !e 5rod ced and isolated in any ? antity was C64, 8nown as ! c8minster : llerene. ,his can !e man :act red !y stri8ing a car!on arc in a low=5ress re argon atmos5here. ,he car!on 9a5o r so :ormed condenses as a d st which contains a 5ro5ortion o: C64 molec les. ,his can !e dissol9ed o t o: the resid e with !en7ene in which it :orms a magenta colo red sol tion. ,he : llerene will crystallise o t :rom the !en7ene in the :orm o: magenta :ace=centred c !ic crystals. (n the : llerene molec le the e9en n m!er o: car!on atoms is arranged o9er the s r:ace o: a closed hollow cage. Each atom is !onded trigonally to its three neigh!o rs (#ig. /./$(i)) !y !onds

con:orming to a 5olyhedral networ8 consisting o: $0 5entagons and n he<agons (where n is any n m!er e<ce5t nity). (n C64 the $0 5entagons are isolated :rom each other and inters5ersed symmetrically among the 04 lin8ed he<agons (#ig. /./$(ii)). ,he C64 molec le is a!le to interact with some other atoms or gro 5s, acce5ting 5 to three electrons in the 5rocess. Radicals and large atoms tend to !e attached to the o tside o: the cage (:orming e<ohedral com5le<es) whilst smaller atoms s ch as those o: the al8ali metals are held inside the cage (:orming endohedral com5le<es). (nteresting amongst these is C64*/ which is s 5ercond cti9e ($&...0) 5 to /4 * s ggesting that research might !e worthwhile in this direction # llerenes are s ch new materials that as yet their technology is in its in:ancy and large amo nts o: research remain to !e done to assess their 9al e in s ch wide :ields as 5lastics materials, 5harmace tics, str ct ral materials and electronics ind stries. )ne wonders what the sci=:i writers will ma8e o: themG

!on1cr&stalline S"*stances
$ 7 All tr e solids are crystalline in nat re. Howe9er, a n m!er o: a55arently solid materials are amor5ho s, that is, their atoms or molec les do not con:orm to any reg lar geometrical 5atterns. Solids s ch as glass and 5itch are com5arati9ely rigid and are !ro8en !y s dden im5act, ! t i: a steady load is a55lied o9er a long 5eriod o: time the material will :low. A 5iece o: 5itch will :low 9ery grad ally, o9er a 5eriod o: months, to ta8e the sha5e o: a 9essel into which it has !een 5laced. A glass rod, s 55orted at each end, will sag nder its own weight i: le:t in this 5osition :or a long time. ,he de:ormation 5rod ced will !e .ermanent and nli8e the tem5orary elastic de:ormation 5rod ced when an elastic solid is lightly stressed within its elastic limit. ,hese amor5ho s BsolidsB do not melt at a de:inite tem5erat re as do 5 re crystalline materials. (nstead they so:ten grad ally and !ecome more mo!ile th s resem!ling li? ids o: 9ery high 9iscosity. ,he 9iscosity of a li? id increases as its tem5erat re :alls and i: it is cooled !elow its :ree7ing 5oint witho t crystallisation ta8ing 5lace its 9iscosity may reach a 9al e as m ch as $4$4 times that o: water. 'iscosity is related to 9an der ;aals :orces. As tem5erat re :alls thermal 9i!rations o: the molec les are red ced and so 9iscosity increases, since 9an der ;aals :orces will also increase.

,he low mo!ility o: large molec les in relation to their thermal acti9ation was :irst in9estigated in glasses and so terms s ch as BglassB and BglassinessB are sed to descri!e the 5ro5erties and !eha9io r o: amor5ho s BsolidsB in general. At high tem5erat res glasses :orm normal li? ids which :low nder the a55lication o: shear stresses As the glass cools normal contraction in 9ol me ta8es 5lace and, altho gh crystallisation does not set in, a 5oint is achie9ed where a change in the rate o: contraction occ rs (#ig. /.//). Below this tem5erat re, called the glass transition tem.erature ($/.6), there is no : rther rearrangement o: atom 5ac8ing and any contraction as does ta8e 5lace is d e only to a red ction in 9i!rations o: the atoms as thermal energy is lost.

% )echanical Properties
% 1 Str ct ral materials sed in mechanical and ci9il engineering 5ractice m st generally ha9e strength! ,his 9al e is a meas re o:

the e<ternally a55lied :orces which are necessary to o9ercome internal :orces o: attraction !etween : ndamental 5articles within the material s ch as we ha9e !een disc ssing in the :irst three cha5ters o: this !oo8. Brie:ly, strength is d e to the s m o: :orces o: attraction !etween negati9ely charged electrons and 5ositi9ely charged 5rotons within the material. ;hen co9alent !onds 3oin large n m!ers o: atoms to 5rod ce giant molec les is the case o: the car!on atoms in diamond or car!on :i!re, the strength o: the res ltant material is great. Similarly the metallic !ond, which in some res5ects can !e regarded as a m lti5le co9alent !ond, ens res that :or most metals strength is high. Some materials s ch as 5olymers consist o: long :i!re=li8e molec les in which the strength within the :i!res is high de5ending as it does on co9alent !onds acting !etween the constit ent atoms. Howe9er, only wea8 9an der ;aals :orces hold one molec le to its neigh!o rs and it is the s m o: many s ch indi9id ally wea8 !onds which ens res that 5olymers are reasona!ly strong. Small molec les howe9er ha9e :ew 9an der ;aals :orces acting !etween them so s !stances s ch as H0S, C)0 and S)0 remain as gases at ordinary tem5erat res and 5ress res where the thermal acti9ity o: s ch molec les o9ercomes the wea8 9an der ;aals :orces acting !etween them % 1 1 Constr ctional materials generally m st !e a!le to withstand the action o: considera!le :orces witho t ndergoing other than 9ery small amo nts o: distortion. (n the :ield o: what is loosely termed 5rod ction engineering, howe9er, 9ery di::erent 5ro5erties may !e desira!le. Here a material m st !e ca5a!le o: 5ermanent de:ormation at the e<5ense o: as little energy as 5ossi!le. ,hat is, it m st !e mallea,le and ductile! (n the case o: metals a :orming 5rocess ca ses the metal to lost its so:tness and !ecome harder and stronger, that is, it wor hardens! ,h s the 5rod ction engineer designs his :orming 5rocess to tilise the mallea!ility or d ctility o: the material and at the same time generate in it s ::icient strength :or s !se? ent ser9ice. )ther mechanical 5ro5erties

incl de elasticity, hardness, toughness and also cree. and fatigue 5ro5erties ($6..M $6.1). (n each case the 5ro5erty is associated with the !eha9io r o: the material towards the a55lication o: :orce and the engineer is generally interested in the Adensity o: :orce@ which is necessary to 5rod ce some de:inite amo nt o: de:ormation, either tem5orary or 5ermanent in the material % 1 # Stress Aa meas rement o: density o: :orces@M de:ined as :orce 5er nit area o: cross section. ,he S( nit o: stress is the +ascal (+a) which is e? i9alent to a :orce o: one Newton acting on an area o: one s? are metre, i.e. N2m0 or Nm=0. Since the Newton is a small nit o: :orce relati9e to the s? are metre we shall generally !e dealing with stresses meas red in the region o: millions o: +ascals and the :orce re? ired to !rea8 in tension a steel mem!er one s? are metre in cross section is di::ic lt to 9is alise. Howe9er, since M9a = M1Am2 = 1Amm2 we can thin8 in terms o: the latter nit (=Cmm6) since it will !e e? i9alent to the n m!er o: nits re? ired to !rea8 in tension a wire or :i!re slightly o9er $ mm in diameter. N umerically o: co rse it will !e the same as that e<5ressed in M+a. 89: A steel rod ( mm in diameter is "nder the action or a tensile force (P) of %;; !e,tons Calc"late the tensile stress 2 3 acting in the *ar 8A: P +2A

P +2r0 P .44 2(4.44/)0 N2m0 P $.$.>4>0 N2m0 P $..$1 M+a % 1 $ Strain re:ers to the 5ro5ortional derormation 5rod ced in a material nder the in:l ence o: stress. (t is meas red as the

n m!er o: metres o: de:ormation s ::ered 5er metre o: original length and is a n merical ratio. 89: The original ga"ge length 2Lo3 marked on an al"mini"m test piece is %; mm The test piece is strained in tension so that the ga"ge length *ecomes %# $ mm Calc"late the strain 2 3 8A: P (ncrease in length2-o P (.0./ ^ .4)2 .4 P 4.41>1 P (mm ^mm)2mm P i.e. mm2mm Strain is s ally ? oted as a 5ercentage, P 4.41>1 < $44R P 1.>1R

Fnits

Strain may !e either elastic or .lastic! Elastic strain is re9ersi!le and disa55ears when the stress is remo9ed. Atoms are dis5laced :rom their initial 5ositions !y the a55lication o: stress ! t when this stress is remo9ed they ret rn to their initial 5ositions relati9e to their neigh!o rs 5ro9ided that the strain has !een o: an elastic nat re. Strain is ro ghly 5ro5ortional to the a55lied stress (#ig. ..$(i)), and, :or 5ractical 5 r5oses, the material o!eys Hoo8eBs

-aw. ,his states that, :or an elastic !ody, strain 5rod ced is directly 5ro5ortional to stress a55lied.

% 1 % <o"ng0s )od"l"s of Elasticit& (E) is the ratio !etween the stress a55lied and the elastic strain it 5rod ces. ,hat is, it is the stress re? ired to 5rod ce a nit ? antity o: elastic strain. (t is related to the rigidity o: the material and is a 9al e o: s 5reme im5ortance to the constr ctional engineer. ,he mod l s o: elasticity is e<5ressed in terms o: either tensile or com5ressi9e stresses and its nits are the same as those :or stress, sinceD E P Stress2 Strain P N2m0 = m2m PN2m0 P +a Beca se o: the n merical magnit de o: the 9al e o: " it is commonly e<5ressed as E+a (or EN2m0).

89: A steel ,ire ; ''mm# in cross1sectional area (A) and 1; m long is e/tended i elasticall& 1 (5mmmm *& a force of 14 #%! Calc"late the mod"l"s of elasticit& (E) for the steel 8A: P +2A P $>.0.24.11 N2mm0 P /$./. MN2m0

P $.6& < $4=/ m 2$4m P 4.444$6& EP 2 P /$./. MN2m0 2 4.444$6& P $&61.> MN2m0 2 P $&6.1 E5a Alternati9ely " can !e deri9ed :rom the slo5e o: the linear 5ortion o: the stress2strain diagram :or the material, i.e. Slo5e < ga ge length "5 Cross=sectional area ,he so5histicated technology o: these closing years o: the twentieth cent ry o:ten in9ol9es consideration o: the mass o: material re? ired to 5ro9ide the necessary strength and rigidity in a str ct re. ,his is 5artic larly so in the aero=s5ace and other trans5ort ind stries and in :act in any sit ation where wor8 done against gra9ity m st !e 5aid :or in terms o: increasingly e<5ensi9e : el. ,h s the mod l s o: elasticity is commonly e<5ressed as a s.ecific modulus of elasticity in which " is related to the relati9e density o: the materialD E S5eci:ic mod l s o: elasticity P relati9e density N2m0 Fnits P

*g2m/ *g2m/ P N2m0

% 1 ' Plastic Strain ,his res lts when a material is stressed to the e<tent where its elastic limit is e<ceeded. (t coincides with a mo9ement o: the atoms within the str ct re o: the material into 5ermanent new 5ositions with res5ect to neigh!o ring atoms. ;hen the stress is remo9ed only elastic strain disa55ears and any 5lastic strain 5rod ced is retained (#ig. ..$ (ii)). Mallea,ility re:ers to the e<tent to which a material can ndergo de:ormation in com5ression !e:ore :ail re occ rs. whilst ductility re:ers to the degree o: e<tension which ta8es 5lace !e:ore :ail re o: a material in tension. All d ctile materials are mallea!le ! t mallea!le materials are not necessarily always d ctile since a so:t material may lac8 strength and th s tear a5art 9ery easily in tension. D ctility is commonly e<5ressed in 5ractical terms as the 5ercentage elongation in ga ge length a standard test 5iece s ::ers d ring a tensile test to :ail re. #ig re ../ ill strates the necessary :or a standard relationshi5 !etween ga ge length and cross=

sectional area of the test 5iece i: res lts are to !e com5ara!le. Since the ! l8 o: 5lastic de:ormation occ rs at the Bnec8B (!etween O and I) it is clear that a 5ercentage elongation !ased on OI as the ga ge length wo ld gi9e di::erent res lts :rom that !ased on HI as the ga ge length. Conse? ently tensile test 5ieces sho ld !e geometrically similar and are 8nown as .ro.ortional test .ieces! ,hey are s ally circ lar in cross=section and BS+ lays down (B.S.$&D +art $ and 0Q) that :or 5ro5ortional test 5iecesD Lo P 1.61 S4 where L< is the ga ge length and S< the original area o: cross= section. ,his :orm la was ado5ted internationally and S( nits are sed. #or test 5ieces o: circ lar cross=section it gi9es a relationshi5D where d is the diameter at the ga ge length. ,h s a test 5iece o: cross=sectional area 044 mm0 will ha9e a diameter o: $1.%6 mm (i.e. $6 mm) and a ga ge length o: &4 mm. ,his is in :act in accordance with Bar,a2s Law which states that the 5ercentage elongation o: a material at :ract re is constant irres5ecti9e o: s5ecimen dimensions 5ro9ided thatD L<CS< P a constant. #rom this an em5irical e? ation can !e deri9edD

where a and , are constants :or the material. Also related to d ctility is reduction in cross-sectional area meas red at the 5oint o: :ract re. 'ery d ctile materials are considera!ly red ced in cross=section !e:ore they !rea8.
Q S 5erceded !y British and E ro5ean Standards bBSENc $440.

% 1 ( Stress=strain -iagrams ;hen corres5onding 9al es o: stress and strain deri9ed d ring a tensile test are 5laned gra5hically it is :o nd that each ty5e o: material is re5resented !y a characteristic c r9e. Materials o: negligi!le d ctility, s ch as : lly hardened steels,cast iron and concrete, ndergo little or no 5lastic de:ormation !e:ore :ract re (#ig. ...(i)). ,hat is, there is no yield 5oint and only elastic e<tension occ rs. A d ctile material, on the other hand, e<hi!its an elastic limit (or limit of .ro- .ortionality) !eyond which 5lastic de:ormation occ rs. ,he ma<im m stress which a material can withstand !e:ore 5lastic :low sets in is 8nown as its yield strength! (n so:ter :erro s materials (wro ght=iron and low=car!on steels) and some 5lastics materials the onset o: 5lastic :low is mar8ed !y a 9ery de:inite yield 5oint (#ig. ...(iii)) and it is there:ore a sim5le matter to calc late the yield stress. (n other materials. com5rising 5ractically all d ctile metals and alloys the elastic limit is not well de:ined (#ig. ...(i9)). (n most res5ects the yield stress o: a material is o: greater im5ortance to the design= engineer than is the ma<im m strength is deri9ed :or those materials which show no o!i9io s yield 5oint .this is 8nown as the 5roo: stress and is that stress which will 5rod ce a 5ermanent (5lastic) e<tension o: 4.$R Q in the ga ge length o: the test 5iece. (t is deri9ed as indicated in #igs ...(ii) and (i9) Materials which ha9e recei9ed some treatment s ch as wor8 hardening or, in the case o: some alloys, s ita!le heat=treatment, are generally stronger ! t less d ctile than those in the : lly so:t condition. ,his is indicated in the stress2strain c r9e #ig. ...(ii).

% 1 ( 1 Secant modulus Many so:t materials 5artic larly thermo5lastics ($0.1..) do not o!ey Hoo8eBs -aw and the stress= strain diagram shows no region where a linear relationshi5 a55lies so that it is not 5ossi!le to ma8e a sim5le meas rement o: Io ngBs Mod l s, "! As a re5resentati9e alternati9e we can calc late the secant modulus o: the material. ,his is the ratio o: nominal stress to the corres5onding strain at some s5eci:ic 5oint on the :orce2e<tension diagram. #ig re ..1 shows that the secant mod l s is in :act the slo5e o: the line )S. (: a :orce % is re? ired to 5rod ce 4.0R strain in the ga ge length, thenD

Fig. *.* Ee"rese tati#e stressAstrai $iagrams for #arious t'"es of material. (i) 1o ,$uctile material. (ii) Femi,$uctile material. (iii) a $ (i#) >uctile materials. T = te sile stre gt!: B = &rea-i g stre gt!: Y = 'iel$ stress a $ P = "roof stress.

;here A is the initial cross=sectional area o: the test 5iece. #or most materials the secant mod l s associated with a strain o: 4.0R is meas red, tho gh in some cases a strain o: 4.l R is s5eci:ied. ..$.6.0 Tangent modulus Sometimes the tangent modulus is called :or. ,his is determined !y drawing a tangent to the :orce2e<tension diagram at a 5oint corres5onding to the s5eci:ied strain (see e<ercise !elow). ,henD Ea ge length (L<) tangent mod l s P Slo5e o: tangent H Cross=sectional area(A) 89: A tensile test on a plastics material gave the res"lts sho,n *elo, d"ring the initial stages of the test> E/tension 2mm3 ; ; ;$ ; ;'' ; ;7 ; 1% ; #; ; $4 ; (1
Force 2!3 ; 1;; 1'; #;; #'; $;; %;; ';;

The test piece had a cross1sectional area of '; mm # and a ga"ge length of '; mm Plot the force=e/tension diagram for the material over the range of readings given and determine> 2i3 the tangent mod"l"s at ; # ? strain> 2ii3 2ii3 the secant mod"l"s at ; '? strain bAc (i) Tangent modulus at <!6D strain 4.0R strain on a ga ge length o: 14mm P 4.$ mm. Hence tangent,AT, is drawn at an e<tension e? t9alant to 4.$. mm. ,he slo5e o: tangent AT is gi9en !yD ,B (..4=%1)N P AB 4./ mm P$$14N2mm

Hence mod l s at 4.0R strain is e? al toD $$14 < 14 mm P $$14 N2mm# 14 mm# P $.$1 E+a

ii) Secant modulus at <!ED strain 4.1R strain on a ga ge length o: 14 mm P 4.01 mm. #orce re? ired to 5rod ce this strain (:rom #ig. ..6) is //. N. Hence draw )SD //. N Slo5e o: )S P 4.01 mm P $//6 N2mm HenceD Slo5e o: )S < ga ge length Secant mod l s P Cross=sectional area $//6 < 14 mm P 14 mm0 P $//6 N2mm0 P $.//6 E +a % 1 4 The tensile strength o: a material is deri9ed !y di9iding the ma<im m :orce s stained d ring the test !y the original cross=sectional area o: the test 5iece. ,he nits in9ol9ed are those o: stress and generally MN2m0 or N2mm0 are the most con9enient to se tho gh M+a will !e the a55ro5riate deri9ed 1$ nit. ,hey will o: co rse !e n merically the same, (t is im5ortant to note that at all stages d ring a tensile test stress is calculated on the ,asis of the original area of cross-section! ,hat is, it does not ta8e into acco nt the diminishing cross=sectional area at the narrowest 5oint in the Bnec8B d ring the :inal stages o: 5lastic de:ormation. #or this reason these so=called Bstress2strainB diagrams are really modi:ied :orce2e<tension diagrams and to 5lot a true stress2strain diagram it

wo ld !e necessary to ta8e into acco nt the diminishing cross= section !y meas ring the minim m diameter at the nec8 with each reading o: the :orce sed (#ig...>)

Eenerally meas rement o: tr e stress in this manner is im5ractica!le and the 9al e re:erred to as the engineering stress is o: more se in 5ractice. Force Engineering stress P )riginal area o: cross=section Howe9er, it sho ld !e a55reciated that the ordinate s ally la!eled BstressB in the ma3ority o: 5 !lished diagrams nearly always re:ers to this Bengineering stressB rather than to tr e stress. ,he red ction in cross= section o: d ctile materials d ring 5lastic :low leads to the a55arent anomaly that the !rea8ing strength is less than the tensile strength. (n :act o: co rse the true !rea8ing stress is the greater as indicated in #ig. ..>.

89: The follo,ing res"lts ,ere o*tained d"ring the tensile testing of a heat1treated nickel1chromi"m1mol&*den"m steel> #orce (*N)
E/tension 2mm3 ##' #'; #4' ; %4 ; '7 1 1;

$14

$44

$14

$>1

044

; ;;7 ; 17 ; #5 ; $$ ; $7 $;; $1; $1; #7; $ %; ' ;; ( %; 4 %; 2Break3

The original diameter of the test piece ,as 1( mm and the ga"ge length 5; mm The diameter at fract"re ,as 1# % mm -etermine 2i3 Tensile strength@ 2ii3 <o"ng0s )od"l"s@ 2iii3 ; #? proof stress@ 2iv3 ? Elongation@ 2v3 ? Red"ction in area at fract"re 8A:

%ma# (8N) (i) T5 Ao (mm0) P/$$204$ 8N2mm P $.1.> 8N2mm0 P $.1.> E5a (ii) P
0

5ma<P/$$ *N Ao P d02. b(/.$.0) < ($6)0c2. P 04$ (mm0)

EPSlo5e o: )E 3 -2A $14 (8N) < &4 (mm) 4.0& (mm) 3 04$ (mm0)
Slo5e o: BlinearB section )E in #ig. ..&(ii) is $14 8N24.0& mm

P 0$/.00 8N2mm0 P0$/.00E+a

(iii)

<!6D .roof stress 4.0R o: &4 mm P 4.$6 mm. Hence draw a line 5arallel to the BlinearB 5ortion o: the :orce2e<tension diagram :rom a 5oint re5resenting a 5ermanent e<tension o: 4.$6 mm. ,his meets the diagram at + indicating that a :orce o: 01> 8N wo ld 5rod ce this amo nt o: 5ermanent e<tension. % (8N) 4.0R 5 P A (mm0) 01> P 04$

P $.0>% 8N2mm0 P $.0>% E+a

E<tension at :ract re < $44R (i9) R Elongation P -o P >..4mm < $44R &4mm P %.01R AR (9) R AR P Ao P (04$ = 3 ($0..)0 ) . P 04$ mm0 /%.%$R mm0 3 $44 < $44R

% 1 5 ,he 5henomenon descri!ed a!o9e may !e e<5lained as :ollows. D ring a tensile test the elongation 5rod ced in the test 5iece is at :irst elastic and the :orce sed m st increase as it 5 lls atoms : rther :rom their 5ositions o: e? ili!ri m. ;hen the yield stress is reached elongation ta8es 5lace more ra5idly as 5lastic :low ta8es o9er and atoms mo9e into new 5ositions and a ret rn to the original sha5e o: the test 5iece is im5ossi!le. Ne9ertheless as 5lastic :low 5roceeds the :orce necessary to 5rod ce it increases as

wor -hardening, the nat re o: which is disc ssed later (1.>), sets in. ,he stress=strain c r9e :ollows an a55ro<imately 5ara!olic :orm according to the em5irical relationshi5D t P C tn where t is the tr e stress and t the tr e strain and C and n are constants :or the metal. n is termed the Bstrain=hardening e<5onentB ( s ally !etween 4.$ and 4.. :or most metals). As the test 5iece e<tends so its strength increases d e to wor8=hardening according to the a!o9e e<5ression ! t a Stage is reached where the uniform red ction in cross=sectional area, which has accom5anied the uniform increase in ga ge length, ceases and a degree o: 5lastic insta!ility is introd ced !y the red ction in cross=sectional area. At this 5oint, coinciding with ma<im m :orce on the nominal stress2nominal strain diagram, t P n! ,he 5lastic de:ormation then !ecomes concentrated o9er a small 5art o: the ga ge length and Bnec8ingB occ rs. Since the cross=sectional area decreases ra5idly the stress at the nec8 increases and with old=ty5e mechanically loaded testing machines this led to the ra5id stretch and !rea8 o: the test 5iece at the nec8. ;ith modern hydra lically or s5ring=loaded machines :orce is a tomatically rela<ed and the test can 5roceed to a meas red !rea8ing :orce ! t o: co rse d ring this :inal stage o: the test, tho gh the a55lied :orce decreases the true stress at the nec8 is contin ally increasing as the diameter at the nec8 decreases. % 1 7 ;hen a nominal stress2nominal strain diagram is 5lotted the nominal stress (n P %CA< where % is the :orce and A< the original area o: cross section, whilst the nominal strain, n P (L-L<)CL< where L is the length o: the original ga ge length nder :orce %, and L< is the original ga ge length. ,his can !e writtenD

nP

=$ or L<

n W$P

L<

,he tr e stress ((t P %CAt where At is the tr e cross=sectional area at the instant when :orce % is o5erating. ,he tr e strain is gi9en !yD
-

d-

P ln -4 Since P $W n

-4 t P ln ($W n)
(: we ass me that the 9ol me change d ring 5lastic de:ormation can !e neglected and

-At P -4A4 or -4A4 AtP then t P +-4A4

B t -4 there:ore t P + A4 .ardness % # (n general terms hardness is de:ined as the a!ility o: a material to resist s r:ace a!rasion. ,he relati9e harnesses o: minerals ha9e in :act long !een assessed !y re:erence to MohrBs Scale (,a!le ..$). ,his consists o: a list o: materials arranged in order s ch that any mineral in the list will scratch anyone !elow it. ,h s diamond, the hardest s !stance 8nown, heads the list with a hardness inde< o: $4 whilst talc is at the :oot with a hardness inde< o: $. ,he s r:ace hardness o: any s !stance can !e related to MohrBs Scale !y determining which o: these standard s !stances will 3 st scratch it. ($W n) P ($W n)

)!9io sly MohBs Scale wo ld !e inade? ate in the accurate determination o: the hardness o: s ch materials as metallic alloys, and rather di::erent Bty5es o: hardness test ha9e !een de9elo5ed :or s ch s !stances. S ch instr ments as the , rner Sclerometer (which attem5ted to meas re s r:ace Bscratcha!ilityB) were soon a!andoned in :a9o r o: machines, which meas re the resistance o: the s r:ace layers o: a material to 5enetration, !y some :orm o: indenter rather than s r:ace hardness de:ined in terms o: a!rasion resistance. ;hilst these c rrent methods are less re5resentati9e o: tr e s r:ace hardness they o::er means !y which s r:ace 5ro5erties can !e com5ared m ch more acc rately. % # 1 ,he Brinell test was de9ised !y a Swede. D, Kohann Brinell in $%44. (n this test a hardened steel !all is :orced into the s r:ace o: the test 5iece sing an a55ro5riate s5eci:ied :orce. ,he diameter o: the im5ression 5rod ced is meas red and the Brinell Hardness (nde<. HB deri9ed :rom + HBP S r:ace area o: im5ression ,he s r:ace area o: the im5ression can !e shown to !eD D (D=(D0=d0) 0 where D is the diameter o: the indenter sed and d the diameter 4$ the im5ression 5rod ced, soD 0+ HB P D(D=(D0=d0)

,he nits are 8g:2mm0 ! t hardness 9al es are always ? oted as a sim5le inde<. ((n the real world o: co rse this :orm la is little sed, HB !eing deri9ed :rom ta!les relating HB with * and d; or in modern testing machines, direct reading !y electronic means.) (n this test it is im5ortant that % shall !ear a correct relationshi5 to the diameter o: the indenter, *, :or reasons indicated in #ig. ..%.

)!9io sly as d a55roaches D in 9al e ( #ig. ..%(i)), d !ecomes insensiti9e to 9ariations in + and the res lt is meaningless. (n #ig. ..%(ii) 9ariations in d will !e erratic. ,h s :or di::erent materials the ratio +2d0 is standardised in order to o!tain com5ara!le res lts D

,h s in testing steel a $4 mm !all wo ld !e sed in con3 nction with a /444 8g: :orceM or a $ mm !all with a /4 8g: :orce. ,he diameter o: the !all sed will !e go9erned !y the width and thic8ness o: the test 5iece (#ig. ..$4) always !earing in mind that the larger the diameter o: !all which can !e sed the more acc rate the res lt is li8ely to !e.

% # # )e&er +nde/ ,his is related to the s sce5ti!ility o: a material to wor8 harden, in this case d ring the a55lication o: the hardness test. (t can !e determined !y 5lotting a series o: s ita!le :orces. %, against the diameter, d, o: the indentation 5rod ced :rom a single !all indenter and determining the Meyer (nde<, n! :romD % P dn or log% P log W n log d where % is the :orce (8g:), d is the diameter o: the im5ression (mm) and is a constant. #or most metals n 9aries !etween 0 and 0.1. Since n re5resents the ca5acity o: a metal :or a!sor!ing cold wor8 !e:ore !ecoming wor8=hardened, it gi9es insight into the mechanical 5ro5erties o: the material. 89: Test pieces of 0fire1refined0 copper in *oth the soft 2annealed3 and cold1,orked conditions ,ere Brinell tested "sing a 1 mm diameter *all and a series of different loads as sho,n> MateriaI Force, P (kgf) Diameter of impression Annealed copper ' 1; 1' 1; #; $; 2i3 2ii3 ; '1% ; '7( ; $(7 ; '1% ; (1% ; $('

Cold1,orked copper

Calc"late the average Brinell .ardness +nde/ for each specimen Carr& o"t a )e&er Anal&sis to determine the )e&er constants for each specimen

(i) Fse the :orm laD HB

ii iii

0+ P D(D=(D0=d0)

#or annealed co55erD i9 with 1 8g: :orce, HB P .1.$ 9 $4 8g: :orce, HB P ...& 9i $1 8g: :orce, HB P .1./ 9ii A9erage 9al e o: HB P .1.$ %0./ 04 8g: :orce, HB P &%.1 <i /4 8g: :orce, HB P %6.% A9erage 9al e o: HB P %0.%

9iii i< #or cold=wor8ed co55erD < with $4 8g: :orce, HB P

<ii

(iii) MeyerBs (nde<, n, is deri9ed :rom % P dn where n and are the constants to !e determined. ,he Meyer e? ation can !e writtenD <iii Log% 5 logWn log d <i9 ,he most con9enient way o: deri9ing the constants n and is to 5lot gra5hs o: log % against log d :or each s5ecimen.
<9 <9i Material <9ii Annealed

+( gf) co55er 1 $4 4.0&% <i< $1

<9iii

Log + d(mm) Logd 4.6%% 4./6% = $.444 $.$>6 $.444 $./4$ 4.6$. 4./61 4.1$6 4.1$. = =4.0$0 =4../> =4.0&>

4..//

<< <<i Aork1hardened copper$4 <<ii 04

<<iii <<i9

/4

$..>>

4.1%6

=4.001

Slo5e at gra5h is gi9en !y which is e? al to log +2log d! #or annealed co55erD $.61 nP 4.>/>1 #or ;or8 hardened co55erD $.%& nP P 0./ 4.&>1 #or annealed co55erD log P $.61 (interce5t with coordinate at a) HenceD P 0.0

 P ...> #or ;or8 hardened co55erD log P $.%& (interce5t with coordinate at !) HenceD P %1.1 % # $ ,he /ic er2s *iamond %yramid Test (or Diamond +yramid Hardness ,est) ses a diamond 5yramid indenter o: geometrical sha5e indicated in #ig. ..$0. ,his has the :ollowing ad9antages o9er methods which se a s5herical steel indenterD (i) the 5yramid is o: constant angle ma8ing the choice o: a s ita!le %C*6 ratio nnecessaryM ii) the diamond 5yramid is less li8ely to distort nder high :orces than is a steel !all. ,he 'ic8erBs Hardness, H+, is related to the a55lied :orce, %, and the s r:ace area o: im5ression in the same manner as is Brinell Hardness, 9i7D #orce (% H+ P S r:ace area o: im5ression 6% sin 20 P d0 $.&1.. + P 8g:2mm0 d0 where is the angle ($/6Z) !etween o55osite :aces in the diamond 5yramid and d is the mean length o: diagonals (d$ and d6) o: the im5ression (mm). Hardness indices, H+, 9ary !etween a55ro<imately &444 :or diamond and 1 :or lead.

A n m!er o: other hardness tests s ch as Roc8well (which ses either a diamond cone or a steel !all) are also in se.
#or most metallic alloys tensile strength is a55ro<imately 5ro5ortional to hardness tho gh there is no : ndamental connection !etween them other than in the general sti::ness o: the material.

To"ghness
% $ ,o ghness is meas red in terms o: the amo nt o: energy re? ired to :ract re a standard test 5iece. #or this reason it m st not !e con: sed with strength which is meas red in terms o: stress re? ired to !rea8 a standard test 5iece. Since energy is the 5rod ct o: a9erage :orce and the distance thro gh which it acts, the area

nder the stress2strain diagram is related directly to the energy necessary to !rea8 a material . (n :act some materials, when hardened and strengthened !y a s ita!le 5rocess, lac8 to ghness whereas in their so:test and most d ctile state they are e<tremely to gh. ,his relationshi5 is

Fig % 1% Stress2strain diagrams :or (i) an alloy which has !een treated to increase its strength, (ii) the same alloy in the so:t, d ctile condition. ,he energy, indicated !y the area nder the c r9e, re? ired to !rea8 the test 5iece, is greater in the case o: the less strong ! t more d ctile material. indicated !y the area nder the stress2strain c r9e (#ig. ..$.) in each case. % $ 1 ,he 5ractical methods sed :or meas ring to ghness di::er :rom those associated with the stress2strain diagram in that they em5loy shoc8 loading. A 5ortion o: the 8inetic energy o: a swinging 5end l m is a!sor!ed in :ract ring a standard, s ita!ly notched, test 5iece. (n !oth the (7od and Char5y methods o: meas ring im5act to ghness the nit o: energy is the Ko le. ,hese tests o::er a se: l 5ractical indication o: how a material will react to conditions o: shoc8 loading. and in many circ mstances to ghness will !e more im5ortant than tensile strength as a criterion o: s ita!ility o: a material.

Bther )echanical Tests

% % Many other tests ha9e !een de9ised in order to assess s5eci:ic mechanical 5ro5erties o: interest in 5ractical engineering. #or e<am5le the Erichsen test gi9es a rather !etter estimation o: a materials s ita!ility :or dee5 drawing than does a :ormal R elongation. 'ario s !end tests and com5ression tests are also se: l in some circ mstances. Sim5le descri5tions o: some o: these tests will !e :o nd in Materials for the "ngineering Technician !y this a thor.

(t may ha9e !een noticed that no mention has !een made here o: cree5 or :atig e=testing. ,hese to5ics are associated with metal :ail re and will !e dealt with later in this !oo8 ($6.. and $6.1).

' The -eformation of )aterials

' 1 A well=worn cliche o: yesteryear, m ch too old to ha9e originated :rom any o: today@s 5se do=scienti:ic 3o rnalists, s5ec lated 5on the 5ossi!le e::ect o: Aan irresisti!le :orce meeting an immo9a!le o!3ectB. (n :act any :orce may !e regarded as irresisti!le in so :ar that no o!3ect is com5letely immo9a!le, since all s !stances when s !3ected to mechanical stress s ::er some change in sha5e. Many ret rn to their original :orm when the stress is rela<ed, 5ro9iding the stress has not !een too greatM s ch s !stances 5ossess elasticity! ;hen :orce is a55lied the ions or molec les o: which the material is com5osed are mo9ed small distances :rom their 5ositions o: e? ili!ri m and when the dis5lacing :orce is remo9ed they ret rn to their original 5ositions (#ig. 1.$(i)). (: the dis5lacing :orce is increased steadily the s !stance ltimately reaches its elastic limit. (ncrease o: stress !eyond this limit leads to one o: two alternati9e res ltsD (i) the material may shatter into :ragments (#ig. 1.$(iii))M (ii) it may remain as a coherent whole ! t :ail to ret rn to its original :orm when the dis5lacing :orces ha9e !een remo9ed. (t has s ::ered .lastic deformaation (#ig. 1.$(ii)). 1.$.$ (n general non=metallic elements and most ionically !onded com5o nds !elong to the :irst gro 5, that is, they 5ossess elasticity ! t no 5lasticity. Metals and many organc 5olymers, howe9er,

5ossess high degrees o: !oth elasticity and 5lasticity. ,hey can !e sha5ed !y com5ression and tension and a:ter s ch treatment their str ct res are s !stantially na::ected since they ha9e s ::ered de:ormation ! t ha9e retained their contin ity. A sim5li:ied e<5lanation o: the di::erences in !eha9io r !etween metals and ionic crystals can !e made in terms o: their res5ecti9e str ct res when stressed !eyond their elastic limits. A metallic crystal consists o: 5ositi9ely

Fig ' 1 .!e &e!a#iour of materials i stress.(i) + material stresse$ &elow its elastic limit,remo#al of stress lea$s to $isa""eara ce of strai .(ii) + $uctile material% suc! as a metal% u $ergoes elastic a $ "lastic strai . .!e latter $oes ot $isa""ear w!e stress is remo#e$. (iii) 3om"letel' &rittle materials $o ot strai "lasticall'.

charged ions s rro nded !y an Belectron clo dB (/.1). ;hilst the 5ositi9e ions will re5el each other they are held in e? ili!ri m 5ositions !y :orces o: m t al attraction !etween each ion and the negati9ely charged Bclo dB. ;hen a dis5lacing :orce is a55lied to a 5lane o: ions (#ig. 1 .0(i)) this tends to mo9e 5ositi9e ions in one 5lane nearer to those in the ne<t ad3acent 5lane. ,he :orces o: re5 lsion !etween ions will increase to a ma<im m at the elastic limit ! t are then o9ercome so that )ne layer o: ions mo9es with

res5ect to its neigh!o r. ,here is no disr 5tion, howe9er, at this stage !eca se o: the m t al attraction !etween 5ositi9e ions and the s rro nding electron clo d. ,he 5lane along which mo9ement occ rs is called a sli. .lane! A crystal o: a s !stance s ch as sodi m chloride consists o: 5ositi9ely charged sodi m ions and negati9ely charged chlorine ions arranged so that each ion is s rro nded !y those o: o55osite charge. Any attem5t to 5rod ce sli5 in the b$44c direction (#ig.

1.0(ii)) will :ail since this wo ld !ring li8e ions into closer contact. -i8e ions wo ld immediately re5el each other so that the two hal9es o: the crystal se5arate. ,h s the crystal shatters along a clea+age 5lane. Beca se o: this se9ere restriction in the a9aila!ility o: sli5 systems in ionically !onded materials, s ch materials tend to :ract re at :airly low stresses=lower than those at which sli5 wo ld otherwise occ r. (n ceramics !oth ionic and strong co9alent !onds are 5resent. Conse? ently one might e<5ect them to ha9e high strengths and high elastic mod li. ;hilst mod li are reasona!ly high and com5ressi9e strengths demonstrate the !ond strengths,

tensile strengths tend to !e low. ,his is d e 5rinci5ally to the 5ro5agation o: micro=crac8s which act as stress raisers.

Plastic -eformation in )etals

' # ,he :act that a metal can ndergo !oth elastic and 5lastic de:ormation is demonstrated d ring a tensile test in which the test 5iece is tested to destr ction. ,hat 5lastic de:ormation ta8es 5lace !y some :orm o: sli5 is o!ser9a!le sing an ordinary metall rgical microsco5e (#igs 1./ and 1..).

#ig. 1./ ,he :ormation o: sli5 !ands in a metal stressed !eyond its yield 5oint. (i) Be:ore stressing. (ii) A:ter stressing=!loc8s o: sli55ed atoms some .4 atoms wide and 5 to .44 atoms high cast shadows on the s r:ace o: the metal gi9ing an a55earance as in (iii). (: a d ctile metal or alloy is 5olished and etched to re9eal its crystal str ct re and is then s? ee7ed laterally in a 9ice, ta8ing care not to damage the etched s r:ace, the shadows cast !y the ridges :ormed as sli5 occ rs can !e seen as hair=li8e lines (#ig. 1./(iii)) at a magni:ication o: $44 < or so.
Sli5 ta8es 5lace on s5eci:ic crystallogra5hic 5lanes in a gi9en metal. Eenerally these sli5 5lanes are the atom 5lanes o: greatest inter=5lanar s5acing since then :orces !etween the sliding 5lanes will !e at a minim m. ;ithin the 5lanes the greatest density o: atom 5ac8ing is 5resent. ,h s sli5 occ rs in the direction o: the greatest density o: atom 5ac8ing.

' # 1 (n #CC metals li8e co55er sli5 s ally occ rs along the a$$$] 5lanes (#ig. /.$1(i9)) since the 5er5endic lar distance !etween these 5lanes is greater than that :or any other set o: 5lanes in the crystal and the atomic 5o5 lation in these 5lanes is denser than in any other :amily o: 5lanes. ,h s the 5lanes o: easiest sli5 are also those o: densest 5ac8ing.

,he sli5 directions in the #CC str ct re are the d$$4e :amily (:ace diagonals). ,here are :o r e::ecti9e sets o: 5lanes ! t each 5lane has three 5ossi!le sli5 directions, gi9ing a total o: twel9e directions in which sli5 co ld ta8e 5lace with e? al ease in a #CC crystal.(n #ig. 1.1(i) only two o: the :o r 5lanes are shown :or the sa8e o: clarity. ' # # (n the C+H str ct re the (444$) or !asal 5lanes are o: similar arrangement to the ($$$) 5lanes in the #CC str ct re. Howe9er, in C+H there is ! t one s ch set o: !asal 5lanes instead o: :o r ($$$) 5lanes in #CC. Hence there are only three easy sli5 systems in C+H (#ig. 1.1(ii)). ,his is re:lected in the di::erences in mechanical 5ro5erties !etween the mallea!le and d ctile #CC metals li8e al mini m and co55er, and the relati9ely !rittle C+H metals li8e 7inc where sli5 is restricted. As indicated in #ig. /.$6 the BCC str ct re does not contain any 5lanes o: closest 5ac8ing as are 5resent in the #CC or C+H str ct res. Howe9er, sli5 occ rs along those 5lanes where the density o: 5ac8ing is greatest. ,here are si< s ch 5lanes ($$4) where sli5 can ta8e 5lace with two directions b$$$c in each, gi9ing a total o: $0 sli5 systems.

' # $ Normally we are dealing with 5olycrystalline metals ! t m ch : ndamental in:ormation on the nat re o: sli5 has !een o!tained !y st dying the !eha9io r o: single crystals o: metals in stress ,hese single crystals can !e grown nder care: lly controlled la!oratory conditions and then machined as test 5ieces.

D ring a tensile test sli5 occ rs along 5arallel sli5 5lanes (#ig. 1.6) the 5recise direction o: which can !e o!ser9ed. By determining the yield stress o: s ch a crystal e<5erimentally we can then calc late the critical resol9ed shear stress acting along a sli5 5lane which will 3 st 5rod ce sli5. (: & is the yield stress and CR the critical resol9ed stress acting along )S on the sli5 5lane then, Com5onent o: y along )S P y .cos ,he area o: 5ro3ection on o: nit P cos Hence,

area

o:

CRP y.cos . cos (n di::erent single crystals o: the same material 9al es o: and will 9ary, that is crystallogra5hic 5lanes will !e di::erently orientated with res5ect to the a<is o: the test 5iece :rom one s5ecimen to the ne<t. ,h s single crystals o: the same material will sli5 at di::erent angles to the a<is and conse? ently at di::erent 9al es o: &, ! t when the stress is resol9ed along the sli5 5lane all crystals o: the same material sli5 at the same critical resol9ed shear stress. (t is 5ossi!le to calc late theoretically this critical resol9ed shear stress :rom a 8nowledge o: the :orces which act !etween : ndamental 5articles within the metallic !ond.(: we do this we :ind that the Atheoretical strength@o: a metal is generally one thousand times or more the 9al e o!tained e<5erimentally as o tlined a!o9e. )!9io sly, there:ore, sli5 is not a sim5le 5rocess in which all o: the atoms in a com5lete 5lane mo9e simultaneously with re:erence to the atoms in an ad3oining 5lane. rather li8e one 5enny in a 5ile sliding o9er its neigh!o r. Moreo9er. ,he ass m5tion that sli5 ta8es 5lace in this sim5le manner does not e<5lain why metals wor8 harden 5rogressi9ely d ring a cold= wor8ing o5eration. )nly in recent decades has the low strength o: a metal relati9e to its Btheoretical strengthB !een s ccess: lly e<5lained.

+mperfections in Cr&stals
' $ D ring the early days o: the twentieth cent ry a great deal o: in9estigation into the crystal str ct res o: metals too8 5lace and there was a tendency :or metall rgists to regard metallic crystals as !eing relati9ely 5er:ect in :orm. S ch a conce5t, howe9er made it di::ic lt to e<5lain some o: the 5ro5erties o: metals and alloys, 5artic larly s ch 5henomena as di:: sion in solid sol tions (>..) and the :act mentioned a!o9e, namely, that the 5ractical 9al e o!tained :or the critical shear stress o: a metal is se9eral orders o:

magnit de less than that ded ced :rom theoretical considerations !ased on instantaneo s [!loc8B sli5. ,he s ggestion that atoms in a metallic Crystal are arranged in a rigid 5attern :rom which there is no de9iation has long since !een re3ected as e9idence to the contrary has acc m lated o9er the years. C rrently the metall rgist thin8s o: a metallic crystal as ha9ing atoms arranged according to some general o9erall 5attern ! t in which all manner o: local :a lts and de:iciencies can e<ist ca sing distortions and irreg larities in the s rro nding crystal lattice (#igs 1,> and 1,&), whilst H=ray= in9estigations (/..) will

Fig. 5.# Furt!er cr'stal $efects. (i) + Frenkel defect is a #aca a atom mo#es (as a result of a i crease i t!ermal #i&ratio ) i to "ositio within t!e cr'stal. (ii) + Schottky defect is a #aca c' ma er &ut t!e $is"lace$ atom ta-es u" a lattice "ositio o cr'stal.

c' "ro$uce$ w!e a self interstitial forme$ i a similar t!e surface of t!e

re9eal the general crystal 5attern o: a metal they cannot detect single lattice :a lts and the e<istence o: many o: .these is still largely a matter o: hy5othesis.

' $ 1 )ne o: the most im5ortant o: these lattice :a lts was 5ost lated more or less inde5endently in $%/. !y ,aylor, +olanyi and )rowan. (n its sim5lest :orm it consists o: a region containing an e<tra hal:=5lane o: atoms (#ig. 1.%). ,his is termed an edge

dislocation and it 5lays a 9ery im5ortant role in determining the mechanical 5ro5erties o: metals. (n the early days o: the Dislocation ,heory there was no direct 5roo: that s ch :a lts did in :act e<ist in crystals ! t o9er the years more and more s 55orting e9idence acc m lated so that d ring the 5ost=war years the theory !lossomed and !ecame widely acce5ted. More recently the e<istence o: dislocations was 9eri:ied metallogra5hically sing 9ery high=5ower modi:ications o: the electron microsco5e.

,he arrangement o: atoms in the region o: an edge dislocation is shown in #igs 1.% and 1.$4. ,he 5resence o: dislocations in s ch

diagrams is generally indicated !y the sign. Fnder the action o: ade? ate stress the dislocation will mo9e 5rogressi9ely thro gh the crystal to the right (#ig. 1.$$) ntil it ltimately :orms a sli. ste. as indicated. (n 5ractice the mo9ement may !e halted !y some other :a lt or discontin ity within the crystal or, alternati9ely, !y the crystal !o ndary. ' $ # +ossi!ly +ro:. N. MottBs classical analogy o: the methods a9aila!le :or smoothing wrin8les :orm a hea9y car5et e<5lains most clearly the relationshi5 !etween sli5 and the :orce necessary to 5rod ce it. (magine that on laying a wall=to=wall car5et a small wrin8le remains in the car5et near to an edge, which is to ching a wall (:ig. 1.$0(ig. Attem5ts to remo9e the wrin8le !y 5 lling on the o55osite edge o: the car5et will achie9e little=sa9e the 5ossi!ility o: !ro8en :inger nails=!eca se o: the necessity o: o9ercoming :riction !etween the whole o: the car5et and the :loor. (n a similar way instantaneo s !loc8 sli5 in a metallic crystal o9er a com5lete 5lane wo ld necessitate o9ercoming inter=atomic :orces o9er the whole o: the 5lane at the same instant.

Ret rning to o r car5et, one can with 9ery little e::ort coa< the wrin8le along with oneBs toe so that it mo9es, ste5 !y ste5, across the :loor (#ig. 1.$0(ii) to (i9). )nly local :riction in the immediate 9icinity o: the wrin8le then needs to !e o9ercome. ,his is analogo s to the 5rogressi9e mo9ement o: an edge dislocation where the only inter=atomic :orces !eing o9ercome at any instant are those acting in the locality o: the dislocation. (n this way

Fig.5.11 .!e mo#eme t of a e$ge $islocatio u $er t!e i flue ce of stress. .!e u it sli"% &% is - ow as t!e 8urgers #ector of sli".

;e can e<5lain why the yield stress o: a metal is so small in com5arison with that calc lated on the ass m5tion o: !loc8 sli5.

' $ $ Sli5 may also occ r !y the mo9ement o: a screw dislocation, the 5rinci5le o: which is shown in #ig. 1.$/. Fnder the in:l ence o: shear stress this ty5e o: dislocation also mo9es in the sli5 5lane. Howe9er, dislocations are generally o: a more com5le< nat re, which can ne9ertheless !e resol9ed into a com!ination o: the edge and screw ty5es (#ig. 1.$.).

The 6eneration of -islocations

' % ;e ha9e seen that when a metal is 5lastically de:ormed sli5 ta8es 5lace on a n m!er o: 5lanes within any crystal (#ig. 1./). ,he :act that these sli5 5lanes are 9isi!le nder the microsco5e at :airly low magni:ication indicates that not only are the 5lanes ? ite :ar a5art ! t that the Bste5sB are o: considera!le thic8ness. Q Howe9er. a dislocation mo9ing along a sli5 5lane and r nning o t at the o!ser9ed s r:ace o: the metal can only 5rod ce a s r:ace ste5 o: one atomic s5acing inD de5th (#ig. 1.$$) and it wo ld re? ire a large n m!er o: dislocations. all on the same 5lane, to 5rod ce the res ltant large ste5 o: .44 atoms o!ser9ed e<5erimentally. (t seems, there:ore, that an initial dislocation m st in some way !e a!le to re5rod ce itsel: and so lead to a contin ation o: the 5rocess o: sli5. ,he #ran8=Read so rce o::ers

a 5la si!le e<5lanation o: this 5ossi!ility. ,he original so rce is 9is alised as a dislocation line anchored at its ends, 5ossi!le !y other :a lts. ,he a55lication o: shear stress ca ses the line to !ow o twards, t rning in +%n itsel: (#ig. 1.$1) and e9ent ally :orming a com5lete dislocation loo5. Since the original dislocation line still remains the 5rocess can re5eat 5rod cing a series o: dislocation loo5s or ri55les radiating :rom the original so rce. ' % 1 So :ar we ha9e !een dea$ing on$y with the mo9ement o: e<isting dislocations and their 5ermitting o: e<tensi9e sli5 !y means o: #ran8=Read so rces. (t has !een ass med that s ch dislocations were [! ilt intoB the str ct re d ring the solidi:ication 5rocess. (t is reasona!le to s 55ose that this will occ r as dendrite arms inter:ere with each others growth d ring the com5etition :or diminishing inter=dendritic s5ace. ,he :ormation o: dislocations along grain !o ndaries where there is a small angle o: mis:it (1.1) arises in a similar manner. ,he mo9ement o: dislocations will e9ent ally !e halted !y s ch o!stacles as grain !o ndaries, other gro 5s o: dislocations and im5er:ections along the sli5 5lane. (: the acting stress is incresed new dislocations will !e initiated in the str ct re and sli5 will contin e ntil all a9aila!le sli5 5lanes ha9e !een sed 5 so that the mo9ement or dislocations is no longer 5ossi!le. # rther increase o: stress will ltimately lead to :ract re.

Fig.5.15 .!e o"eratio of a Fra -,Eea$ source;

,he stress necessary to 5rod ce new dislocations is m ch greater than that re? ired to mo9e those already 5resent. ,his relationshi5 is ill strated !y the tensile 5ro5erties o: metallic whis8ers. ,hese are 9ery small hair=li8e single crystals grown nder care : lly controlled conditions and generally containing only a single dislocation which r ns along the central a<is. A tensile stress along this a<is will ca se no mo9ement o: the dislocation. As no other dislocations are a9aila!le sli5 cannot ta8e 5lace ntil a new dislocation is initiated at E (:ig 1.$6). (mmediately, the stress :alls to that necessary to mo9e this new dislocation (I) and : rther dislocations are 5ro5agated !y the #ran8=Read mechanism so 5ermitting 5lastic :low to 5roceed. ' % # (n $%16 D. Marsh de9elo5ed an e<tremely sensiti9e micro testing machine ca5a!le o: determining the tensile 5ro5erties o: s5ecimens o: s ch small dimensions as $4=> mm0 cross=sectional area and 4.01 mm long. ,his machine co ld detect e<tensions o: the order o: 4.1 nm. (n addition to

Fig. 5.1, Gsi g a se siti#e (micro( testi g mac!i e o a #er' small s"ecime

co tai i g a fi ite um&er of $islocatio ce tres re#eals t!e i creme tal ature of sli" (i). I a ormal te sile test o a large s"ecime (ii) sli" is ta-i g "lace co ti uall' at a #er' large um&er of ce tres so t!at a regular cur#e is o&tai e$.

!eing se: l :or determinations on single whis8ers other small diameter s5ecimens containing a limited n m!er o: dislocation centres co ld also !e tested. #ig re 1.$>(i) shows the. stress2strain diagram :or a small thin s5ecimen tested in a Marsh machine. Here the stress2strain c r9e is in the :orm o: a series o: ste5s since the machine is s ::iciently sensiti9e to detect the generation o: dislocations :rom an indi9id al so rce. ;hilst single dislocations,

co ld not !e detected e9en !y the sensiti9e Marsh machine the 5rod ction o: a dislocation so rce releases a n m!er o: dislocations sim ltaneo sly so that the total amo nt o: sli5 associated with one so rce is meas ra!le. ;ith : rther increases o: stress there are 5otential dislocation so rces ready to generate dislocations and these are 5res ma!ly triggered !y the in:low o: thermal energy. So rces are triggered ? ite erratically and the sli5 5rod ced is 9irt ally instantaneo s gi9ing a series o: irreg lar ste5s ill strated. (n the case o: a large test 5iece (#ig. 1.$>(ii)) so many centres o: dislocation are !eing triggered contin o sly thro gho t the s5ecimen that the ty5ical smooth c r9e o: a stress2strain diagram is 5rod ced. ' % $ (nteraction !etween dislocations mo9ing on the same or on near!y 5lanes m st !e considered 5artic larly in so :ar as they a::ect the distri! tion o: strain energy. ,he 5resence o: the e<tra

hal: 5lane o: atoms in a sim5le edge dislocation gi9es rise to an increase in strain energy in that region. (magine an a<e !lade (re5resenting the e<tra hal: 5lane o: atoms) dri9en into a log o: wood (#ig. 1.$&). ,his will 5rod ce loc8ed= 5 strain

fig.C.1@ >islocatio s of t!e same sig will re"el eac! ot!er.

Energy in the s rro nding wood in a manner similar to the e<tra hal:=5lane o: atoms in an edge dislocation. Conse? ently two edge dislocations o: the same sign (#ig. 1.$%), mo9ing on the same or near!y 5lanes, will tend to re5el each other in order to red ce the concentration o: elastic strain energy in the region. (ncreased stress will !e re? ired to mo9e them closer together so that, nder s ch circ mstances, not only does the total strain energy increase ! t also the tensile strength which is a meas re o: the stress re? ired to 5rod ce sli5. Normally dislocations o: the same sign will 5ile 5 against o!stacles s ch as grain !o ndaries when the a55lied stress is great eno gh. Con9ersely, i: edge dislocations o: o..osite sign (#ig. 1.04) mo9e into

Fig. 5.20 >islocatio s of o""osite sig will te $ to attract (i) a $ so a eac! ot!er.

i!ilate

close 5ro<imity they will tend to attract each other. Ass ming that they are on the same sli5 5lane they will annihilate each other with a conse? ent red ction in strain energy. (: their sli5 5lanes are se5arated !y a :ew atomic s5acings a row o: 9acancies will remain

(#ig. 1.0$) ! t the total strain energy will !e red ced d e to the annihilation o: the dislocations

Fig. 5.22 + grai &ou $ar' w!ere t!e a gle of misfit is small. (i) I $icati g t!e "ositio of t!e cr'stal &ou $ar'. (ii) 3r'stals Hoi e$ wit! e$ge $islocatio s "rese t. (+fter Eea$% (>islocatio s i 3r'stals(.)

-islocations .ithin /r+stal 0oundaries

' ' ,hat grain !o ndaries are a region o: some disorder has already !een s ggested (/.>./). Howe9er, when the angle o: Bmis:itB !etween ad3acent crystals is small an atomic arrangement similar to that in #ig. 1.00 may !e 5rod ced. Here the two crystals are a!le to 3oin more or less contin o sly along most o: their common !o ndary with, o: co rse, a certain amo nt o: elastic strain. Since ad3acent 5lanes in the two crystals are not 5arallel some o: these 5lanes m st terminate at the !o ndary gi9ing rise to line im5er:ections 5assing thro gh the crystal normal to the 5lane o: the 5a5er. ,hese :a lts mani:est themsel9es as sim5le edge dislocations. (: * is the s5acing !etween these dislocations, , the interatomic s5acing and % the angle o: mis:it, thenD ,C6 Sin == P ===== 0 * , =-6* ,h s B *5---------------0 sin (20)

since e is small ! DP=====

as increases the 9al e o: * decreases, i.e. the dislocations mo9e closer together ntil their indi9id al identity is lost and the !o ndary !ecomes a general disordered region (#ig. /.01). ' ' 1 ,he 5assage o: a dislocation across a grain !o ndary m st !e e<tremely rare since it wo ld re? ire a high degree o: BcoherencyB !etween the ad3acent crystal lattices. Normally, grain !o ndaries o: what e9er sort will act as !arriers to the mo9ement o: dislocations and, d ring 5lastic de:ormation, will !ecome regions o: 9ery high strain energy as dislocations 5ile 5 :rom there to :orm a com5le< intercrystalline Btra::ic 3amB. ,his high concentration o: strain energy at the grain !o ndaries o: cold= wor8ed metal gi9es rise to the 5re:erred intercrystalline corrosion 5re9alent in hea9ily cold=wor8ed metals ($%.1). ' ' # Since a grain !o ndary im5edes the mo9ement o: dislocations !y ca sing them to B5ile 5B there, it :ollows that :ine=grained metals are stronger than coarse=grained metals o: similar com5osition since they contain more grain !o ndary 5er nit 9ol me o: metal. ,he yield strength, hy, is related to grain si7e !y the Hall-%etch e4uationF hy P hGH yd-8C6 where d is the a9erage grain diameter, hi and y !eing constants :or the metal at a gi9en tem5erat re. (hi is related to the=intrinsic resistance o: the metal to the mo9ement o: dislocations whilst y is associated with the generation o: dislocations.)

DE#)RMA,()N BI ,;(NN(NE

' ( Altho gh sli5 is the more signi:icant 5rocess !y which 5lastic de= :ormation occ rs in metals !rie: mention m st !e made o: the 5henomenon 8nown as twinning! ;hilst sli5 is a 5rocess associated with a line de:ect (the dislocation), twinning is related to a .lane de:ect (the twin !o ndary). (n sli5 all atoms in a !loc8 ha9e mo9ed the same distance when sli55ing is com5lete (#ig. 1.0.Bi)) ! t in de:ormation !y twinning (#ig. 1.0.(ii))

atoms within each s ccessi9e 5lane in a !loc8 will ha9e mo9ed di::erent distances. ;hen twinning is com5lete the lattice direction will ha9e altered s ch that one hal: o: the twin is a mirror image o: the other hal:, the twinning line corres5onding to the 5osition o: a mirror. ,winning, li8e sli5, also 5roceeds !y the mo9ement o: dislocations. ,he net res lt o: a twinning 5rocess on the lattice o: a crystal is

de5icted in #ig. 1.01.

,he stress re? ired to 5rod ce de:ormation !y twinning tends to De higher than that necessary to 5rod ce de:ormation !y sli5. ,winning is more li8ely to occ r in metals which are shoc8 loaded at low tem5erat res. ,h s in BCC iron s dden loading at low ,tem5erat res 5rod ces thin lamellar twins which are generally 8nown as Ne mann !ands. ,winning is commonly enco ntered in C+H metals li8e 7inc, whilst when a !ar o: tin is !ent s ddenly the :ormation o: twins can !e heard ta8ing 5lace. ,he Ancients 8new this as Bthe cry o: tinB. ' ( 1 ,win=:ormation ta8es 5lace d ring the annealing o: some cold= wor8ed metals. (n this case recrystallisation is initiated at a 5lane instead o: at a 5oint so rce and twin !ands are o!ser9ed within the new crystals as a res lt. ,hese Bannealing twinsB are common in co55er, !rasses, !ron7es and a stenitic steels==alloys with low stac8ing :a lt energies=and are di::erent in this res5ect :rom the mechanical niins nder consideration here. ,hey are :ormed not !y mechanical shear ! t as 5art o: the 5rocess o: grain growth.

Aork .ardening
' 4 As de:ormation 5roceeds==whether !y sli5 or !y twinning=the metal !ecomes harder and stronger and a stage is reached when : rther de:ormation is im5ossi!le. Any increase in stress lead only to :ract re. At this stage, when tensile strength and hardness are at a ma<im m and d ctility is at a minim m, the material is said to !e wor8=hardened. ;e can s mmarise the e::ects o: 5lastic de:ormation !rie:ly as :ollows i: s ::icient stress is a55lied to a metal sli5 (or twinning) will ta8e 5lace in indi9id al crystals. As de:ormation 5roceeds the ca5acity :or : rther cold wor8 diminishes as dislocations :ind themsel9es in 5ositions :rom which : rther mo9ement is im5ossi!le. an increase in stress is then necessary to initiate new dislocations and mo9e these ntil they too !ecome !loc8ed. Fltimately a 5oint is reached when no more mo!ile dislocations are a9aila!le. ,his coincides with the 5oint o: ma<im m resistance to sli5 (the ma<im m strength and hardness) where no more de:om$ation is 5ossi!le and :ract re will ta8e 5lace i: an increase in stress is attem5ted. # rther 5lastic de:om$ation can only !e carried o t i: the material is annealed. ' 4 1 D ring a cold=wor8ed 5rocess some %4R o: the mechanical energy em5loyed is con9erted to heat whilst the remaining $4R is retained in the material as 5otential energy in the :om$ o: elasticallyB !alanced strains in the lattice str ct re. ,he introd ction o: hear energy to the system d ring an annealing 5rocess 5ermits s ::icient mo!ility o: the atoms so that dissi5ation o: strain energy. Can ta8e 5lace. ,he initial relie: o: stress is :ollowed !y recrystallisation o: the metal. . ' 4 # Strengthening mechanisms ,here are three 5rinci5al strengthening mechanisms in metals. ,hey are strain hardening (1.>) solution hardening (>.1) and dis.ersion hardening (8:!8!E and $../). (n solid sol tions the mo9ement o: dislocations is

im5eded !y irreg larities in the lattice str ct re ca sed !y the 5resence o: sol te atoms (#ig. 1.>), whilst the 5resence o: small ! t strong 5articles dis5ersed as se5arate 5hases thro gh the metal will also halt the mo9ement or a dislocation j:rontB.

Stress1relief and Recr&stallisation

' 5 As we ha9e seen a cold=wor8ed metal is in a state o: considera!le mechanical stress res lting :rom elastic strains internally !alanced. M ch o: the Bloc8ed 5B strain energy is associated with the 5resence o: dislocations. (n the region o: +

(#ig. 1.06) the lattice is in tension and since atoms there are dis5laced : rther a5art the region will 5ossess 5otential energy. ,he high energy associated with the congregation o: dislocations at grain !o ndaries has !een mentioned as a reason why corrosion occ rs more readily there than elsewhere in the Str ct re. ,hese high=energy regions also initiate recrystallisation d ring an annealing 5rocess so that new BseedB crystals a55ear :irst at the old grain !o ndaries o: the original distorted str ct re (#ig. 1./4). (n the early stages o: an annealing 5rocess some degree o: stress relie: occ rs as atoms mo9e o9er limited distances into 5ositions nearer to e? ili!ri m. At this stage, howe9er, there is no alteration in the distorted a55earance o: the str ct re and in :act hardness and tensile strength remain at the high 9al e 5rod ced !y cold wor8. At low tem5erat res the mo9ement o: dislocations is restricted to glide along sli5 5lanes, ! t at higher tem5erat resD in edge dislocation is a!le to mo9e o t o: its sli5 5lane !y a 5rocess

8nown as clim,! (: the terminal row o: atoms (normal to the 5lane o: the 5a5er) in the e<tra hal:=5lane is remo9ed this constit tes .ositi+e clim, and the strain energy o: the immediate 9icinity will !e red ced. (: an e<tra row is added to the hal:=5lane this res lts in negati+e clim, and the strain energy o: the region will !e increased.

' 5 1 ,he di:: sion o: interstitial atoms towards an edge dislocation (#ig. 1.0&(i)) can gi9e rise to negati+e clim, whilst the di:: sion o: atoms away

(n this instance we are interested mainly in 5ositi9e clim! and the red ction o: strain associated with it. (t can ta8e 5lace most easily !y the di:: sion (>..) o: 9acancies towards the dislocation as s ggested in #ig. 1.0>. Here atoms migrate :rom the end o: the hal:=5lane to :ill 9acancies which a55roach them !y means o: the di:: sion mechanism.

:rom the hal:=5lane to !ecome interstitials will ca se .ositi+e clim, (#ig. 1.0&(ii)). All o: these 5rocesses necessitate the mass migration o: atoms !y di:: sion and clim! is there:ore 5ossi!le only !y thermal acti9ation. ,he red ction o: strain energy d ring annealing

will most li8ely in9ol9e 5ositi9e clim! !y the di:: sion o: 9acancies. ,he reader may 5ossi!ly !e worried !y the :act that in the a!o9e descri5tion o: the mechanism o: clim! the ass m5tion has !een made that a whole row o: atoms is remo9ed (or added) sim ltaneo sly, whereas in 5ractice, indi9id al 9acancies or small gro 5s o: 9acancies di:: se to (or :rom) the dislocation. #ig re 1.0% ill strates clim! in9ol9ing a short section

o: a dislocation line, res lting in the :ormation o: two ste5s generally descri!ed as Gogs! D ring an annealing 5rocess elastic strains are :irst dissi5ated !y limited mo9ements o: atoms in the manner of those mentioned a!o9e. ,hen, at a higher tem5erat re, wholesale recrystallisation o: the distorted str ct re occ rs and is accom5anied !y a :all in tensile strength and hardness to a55ro<imately their original 9al es. whilst the ca5acity to acce5t cold=wor8 ret rns. ,his ty5e o: annealing 5rocess. which is sed 5rinci5ally when a metal is to ndergo : rther cold de:ormation. ta8es 5lace in three stagesD ' 5 # The Relief of Stress ,his o:ten ta8es 5lace at relati9ely low tem5erat res at which atoms ne9ertheless are a!le to mo9e small distances into 5ositions where they will inc r less strain. -ocal mo9ement o: interstitial atoms or 9acancies may !e in9ol9ed as o tlined a!o9e. ,here is, howe9er,
No o!ser9a!le alteration in the distorted str ct re which was 5rod ced !y mechanical wor8 and !oth tensile strength and hardness will remain at a high le9el.

-ow=tem5erat re annealing which does not ca se recrystallisation and which conse? ently does not lead to a :all in strength and sti::ness engendered !y cold=wor8, is se: l in

dissi5ating local strain which might otherwise gi9e rise to stress corrosion ($%.1). ' 5 $ Recr&stallisation Altho gh low=tem5erat re annealing is o:ten sed to relie9e internal stresses o tlined a!o9e, most annealing 5rocesses in9ol9e com5lete recrystallisation o: the distorted cold=wor8ed str ct re. As the annealing tem5erat re is increased a 5oint is reached where new crystals !egin to grow :rom n clei initiated within the most hea9ily de:ormed regions. ,hese n clei :orm at 5oints o: high energy s ch as crystal !o ndaries and other localities rich in 5iled= 5 and entangled dislocations. ,he new crystals so :ormed are 9ery small at :irst ! t grow steadily ntil they ha9e a!sor!ed .the whole o: the distorted str ct re 5rod ced originally !y mechanical wor8 (#ig. 1./4). ,he new crystals are e? i=a<ed in sha5e, that is they do not show any directionality as did the distorted crystals which they re5lace.

,he minim m tem5erat re at which recrystallisation will ta8e 5lace is called the recrystallisation tem.erature! ,his tem5erat re is lowest :or 5 re metals and is raised signi:icantly !y e9en small amo nts o: im5 rities. ,h s, whilst commercial=grade al mini m recrystallises at a!o t $14C :ollowing mechanical wor8, that o: Bsi< ninesB 5 rity (%%.%%%%R 5 re) a55arently recrystallises !elow room tem5erat re and conse? ently does not cold=wor8 when de:ormed at am!ient tem5erat res.

,in and lead normally recrystallise !elow room tem5erat re so that it is im5ossi!le to wor8=harden them since they recrystallise whilst the wor8ing 5rocess is ta8ing 5lace. Hot=wor8ing is, o: co rse, a 5rocess which is carried o t a!o9e the recrystallisation tem5erat re. Normally the wor8ing tem5erat re m st !e well a!o9e the recrystallisation tem5erat re so that reco9ery is ra5id eno gh to 8ee5 5ace with the rate o: de:ormation. (t is not 5ossi!le to assign a 5recise recrystallisation tem5erat re to any metal since the tem5erat re at which recrystallisation !egins is go9erned largely !y the amo nt o: cold= wor8 which the metal has ndergone. ,he greater the amo nt o: cold=wor8, the greater will !e the amo nt o: strain energy loc8ed 5 in the str ct re and so the lower the tem5erat re at which recrystallisation may !egin when heat energy is s 55lied. #or most metals the recrystallisation tem5erat re is !etween one third and one hal: of the melting 5oint (*el9in scale). ,hat is the mo!ilities of all metallic atoms are ro ghly e? al at the same :raction of their melting 5oints (*) ' 5 % 6rain 6ro,th At tem5erat res a!o9e that of recrystallisation of the metal, the newly :ormed crystals will tend to grow !y a!sor!ing each other in canni!al :ashion. ,his will res lt in the :ormation of a relati9ely coarse=grained str ct re, the ltimate grain si?e de5ending 3ointly 5on the time of treatment and the tem5erat re em5loyed (#ig.`1./$)

Since !o ndaries ha9e higher energies than any other region o: the crystal, a 5olycrystalline mass will !e a!le to red ce its energy i: some o: the grain !o ndaries disa55ear. ,h s at tem5erat res in e<cess o: that o: recrystallisation large crystals grow !y a!sor!ing small ones. A crystal !o ndary tends to mo9e towards its centre o: c r9at re (#ig. 1./0) in order

to shorten its length. ,o accommodate this atoms mo9e across the !o ndary to 5ositions of greater sta!ility where they will !e s rro nded !y more neigh!o rs in the conca9e :ace of the growing crystal ' 5 ' The )eas"rement of 6rain SiCe Crystal si7e=or BgrainB si7e= has a direct in:l ence on the d ctility o: many metals and alloys

and is o: great im5ortance in selecting a material :or dee5 drawing (6.../) and similar 5rocesses. A method o: assessing grain si7e is there:ore necessary. (n all methods some :orm o: microe<amination is in9ol9ed. ,he most direct method is to co nt the n m!er o: crystals o!ser9ed in a 8nown area o: :ield o: 9iew so that grain si7e can !e e<5ressed as the n m!er o: grains2mm0. ,he AS,M grain si7e inde< n m!er is deri9ed :rom the n m!er o: grains2in0 when co nted at a magni:ication o: < $44. ,he AS,MQ inde<, =, is gi9en !yD n56(=-8) where n is the n m!er o:grains2in0 at a magni:ication o: < $44. ,his can !e writtenD -ogn P (=-8) log0 -ogn or N P =================== Q $ 4./4$4 #or d ctile non=:erro s metals sed in dee5 drawing o5erations grain si7e is o:ten e<5ressed in terms o: BA9erage Erain DiameterB (AED) (in mm). ,his is more easily and ? ic8ly assessed sing the gro nd glass screen o: a microsco5e e? i55ed :or 5hotomicrogra5hy. A line $44 mm long is drawn on the screen and an image o: the test s5ecimen 5ro3ected on the screen at a magni:ication o: < $44. (,he $44 mm line there:ore re5resents a length o: $ mm on the s r:ace o: the test s5ecimen.) ,he n m!er o: crystals c t !y the line is then co nted so thatD $mm AEDP N m!er o: crystals c t
(,his ass mes that on a9erage crystals will !e reg lar 5olygons in sha5e, or, 9ery ro ghly, circ lar.)

#or most metals destined :or dee5 drawing o5tim m AED is generally !etween 4.4. and 4.46 mm. ' 5 ( Arrheni"s La, ,his is an e? ation o: a semi=em5irical ty5e which relates to many rate=controlled 5rocesses s ch as are met in 5hysical and chemical reactions. (n materials science thermally=acti9ated 5henomena li8e recrystallisation, cree5 and di:: sion are go9erned !y this -aw which states that the rate, 9, at which a 5rocess occ rs 9aries e<5onentially with the tem5erat re, T (*). 9 P Ae-ICBT where _ is the acti9ation energy o: the reaction (K 8 mol=()M B is the ni9ersal gas constant (&./$./ K mol=l *=$)M A is a constant :or the reaction. Q American Society :or ,esting Materials. ,he e? ation is s ally e<5ressed asD ' P A e<5 (=_2R,) ;hich can !e written in logarithmic :orm asD

ln 9 P ln A =(_2R,)

The -eformation of Pol&meric )aterials

' 7 ,he arrangement o: atoms in the crystal str ct re o: a metal :ollows a reg lar threedimensional5eriodicity ! t the atoms in a 5olymer are generally arranged in a :ar more com5le< and less= reg lar manner, 5artic larly since the molec les themsel9es are o:ten not geometrically aligned. #or this reason it has !een less easy to e<5lain the de:ormation o: 5olymers in terms o: their str ct res Single !onds in a 5olymer chain are ca5a!le o: rotation. ,his is ill strated in #ig. 1.//, which re5resents the last twel9e atoms o: a linear 5olymer molec le. S 55ose a rotation o: $&44 too8 5lace

a!o t Aa@ only, the rest o: the molec le, containing 5ossi!ly tho sands o: car!on atoms, wo ld=!e dis5laced relati9e to the !ond Aa@ and it is nli8ely that s ::icient s5ace wo ld !e a9aila!le :or

this e9en i: eno gh molec lar energy were a9aila!le.

Fig. C.)) .!e effect of two &o $ rotatio s 0 car&o c!ai t!e relati#e s"aci g of atoms i a

(: howe9er the rotation at Aa@ were accom5anied !y a sim ltaneo s $&4 rotation at A!@, only a short section o: the chain wo ld !e dis5laced. Not only wo ld less s5ace !e needed ! t also less molec lar energy wo ld !e re? ired. Ne9ertheless the 5osition o: a short section o: the molec le wo ld !e changed with res5ect to its neigh!ors. (: s ::icient rotational energy is s 55lied the::i$a$$y this ty5e o: rotational transition will !e ta8ing 5lace contin o sly in all molec les thro gho t the material and the molec lar chains will !e in constant motion relati9e to each other. ,he system co ld !e 9is ali7ed as something li8e a t ! : ll o: intertwined wriggling eels ,he acti9ity o: the molec lar chain will de5end 5on tem5erat re ! t also 5on the si7e and nat re o: the intermolec lar :orces o55osing rotation. (t will also de5end 5on the com5le<ity o: the chain nits. So, whilst molec les o: sim5le BsectionB li8e 5olythene can rotate easily, molec les with large com5le< nits wo ld re? ire e<tra s5ace in which to rotate, th s ma8ing rotation corres5ondingly di::ic lt. ' 7 1 (n materials o: low molec lar eight atoms are held in :i<ed 5ositions either !y chemical !onds or !y inter=molec lar :orces acting within the crystal str ct re. ;hen stress is a55lied the atoms are dis5laced :rom their e? ili!ri m 5ositions and distances !etween them alter ntil the new :orces, which are set 5, !alance

the a55lied stress. Ass ming that distortion is within the elastic range, atoms till ret rn to their original 5ositions when stress is rela<ed. Ereater stresses ca se 5ermanent distortion. (n metals the mo9ement o: dislocations whilst inother materials, s ch as ceramics, s dden r 5t re occ rs with little or no 5lastic de:ormation. ;hen stress is a55lied to a 5olymer material elastic de:ormation will occ r where9er two atoms are held in :i<ed +ositions relati9e to one another !y chemical !onds or inter=molec lar :orces. ,h s in cross=lin8ed 5olymers ($0./) and in thermo 5lastics at tem5erat res !elow their glass=transition 5oints ($0.../) all atoms can !e regarded as !eing :i<ed in this way so that only elastic de:ormation is 5ossi!le. Some elastic de:ormations also 5ossi!le in thermo5lastics at tem5erat res a!o9e their glass=transition 5oints as the atoms within the molec les are held !y co9alent !onds, whilst i: crystallites are 5resent inter=Molec lar :orces will hold atoms also. Elastic de:o::i$ation o: this ty5e occ rs instantaneo sly. (n amor5ho s regions o: the 5olymer material the molec les are held only !y the relati9ely wea8 9an ^der= ;aals :orces o5erating !etween them. Hence they can mo9e relati9e to each other witho t di::ic lty. ,his Molec lar sli5=or 5lastic de:ormation=does not occ r instantaneo sly ! t is time de5endent since it is related to the 9iscosity. Conse? ently the com!ined elastic and 5lastic distortion is said to !e 9isco elastic ($0.1.$). ' 7 # (n a linear 5olymer a large n m!er o: di::erent chain arrangements are 5ossi!le 9arying :rom the tightly coiled to the : lly e<tended :orm. Since rotational transitions are ta8ing 5lace contin o sly the chain sha5es will !e constantly changing. #or each molec le which tends to c rl 5 another will straighten so that the a9erage e<tension o: the chains remains constant. Howe9er, when stress is a55lied the e<tensions are no longer random ! t occ r in the direction in which the stress is acting. ,h s tensile stress 5rod ces e<tension in the material (#ig. 1./.).

Fig ' $% The effect of stress on molec"lar shape and arrangement in a linear pol&mer ;hen stress is remo9ed the changes in sha5e o: the molec les contin e ! t those changes, which in9ol9e c rling 5, are now in the 5re5onderance and the original a9erage e<tension is regained so that the material ret rns to its original si7e. ,h s chain straightening is an elastic 5rocess ! t it is 9iscoelastic !eca se the changes in sha5e are time de5endent in so :ar as the time de5endence is determined !y the magnit de o: those intermolec lar :orces o55osing the rotational transitions. ,he a55lication o: stress also ca ses molec lar sli5 (#ig. 1./.) as the relati9ely wea8 9an der ;aals :orces o5erating !etween the linear mole=c le=1 are o9ercome. ,his is a non=re9ersi!le 5rocess so that the e<tension 5rod ced is non=elastic. (t is also a time= de5endent 5rocess !eing in:l enced !y the rotational transitions. ,he e<tent o: rotational transitions to accommodate sli5 m st !e greater than that to allow :or the ty5e o: segment shi:t, which :acilitates chain straightening. Straightening is there:ore ? ic8er than sli55ing. ,he 5henomenon is disc ssed : rther in Cha5ter ,wel9e ($0.1).

6 Sha5ing +rocesses
( 1 ,he arts and cra:ts o: early Man were in9ol9ed mainly with the Sha5ing o: wood and stone, and metals s ch as gold, co55er and later iron. ,he se o: 5rimiti9e hand tools ga9e way o9er the cent ries to man :act re !y relati9ely so5histicated 5rocesses which ta8e into acco nt the acc m lated 8nowledge o: 5hysical and chemical 5ro5erties o: the s !stances !eing sha5ed, #om$ing 5rocess are now !ased on the se o: mo lds and dies==o:ten o: com5le< sha5e=:or sha5ing a wide range o: materials, ,he de9elo5ment o: s ch 5rocesses made 5ossi!le the mass 5rod ction o: large n m!ers o: identical articles with a conse? ent red ction in the real costs o: man :act red goods generally. Many solid s !stances 5ossess s ::icient 5lasticity to allow them to !e sha5ed !y either tensile or com5ressi9e :orces. Eenerally 5lasticity in=creases with tem5erat re and, so, many s ch 5rocesses are hot=wor8ing o5erations, some solid materials, howe9er. +ossess negligi!le 5lasticity and are relati9ely !rittle at all tem5erat res. ,hese materials, nota!ly concrete, cast iron and others, can most easily !e sha5ed !y allowing them to solidi:y :rom the li? id state in a s ita!ly sha5ed mo ld or !y sing some machining 5rocess in which 5articles o: the material are chi55ed away !y a lathe or e9en a masonBs chisel. Ne9ertheless, recent wor8 on 5rocesses s ch as hydrostatic e<tr sion has sho ld that the red ction o: s r:ace :riction !etween wor8 5iece and die, leading to the ma<im m tili7ation o: what 5lasticity a material does 5ossess, allows relati9ely !rittle materials li8e cast iron to !e de:ormed mechanically witho t :ract re.

Methods o: sha5ing materials are there:ore 9aried and o:ten 9ery ingenio s and a single cha5ter in a !oo8 o: this ty5e can do little more than catalog e the more im5ortant methods sed.

Sha5ing !y Solidi:ication :rom the -i? id State

( # ;hat are commonly called Bcasting 5rocessesB are sed to sha5e a n m!er o: materials ! t more es5ecially metals. (n :act well o9er %%R o: the total mass o: metals sed are melted and cast at some stage in the man :act ring 5rocess. A considera!le ? antity o: !oth :erro s and non=:erro s alloys are o: co rse cast as ingots which are then :orged, rolled or e<tr ded, whilst large amo nts o: iron, steel and light alloys are cast into some :orm o: sha5ed mo ld to 5rod ce a com5onent which ;ill !e sed in s !stantially this :orm. Metallic alloys are strongly crystalline and 5ass :rom a mo!ile li? id to a rigid solid o9er a tem5erat re range, which is generally small. ,he res ltant solid is strong !eca se o: its crystalline nat re and the o5eration o: the metallic !ond within crystals. . )rganic 5olymers are generally ns ita!le :or casting !eca se many o: them decom5ose at tem5erat res well !elow those necessary to 5rod ce ade? ate li? id mo!ility. 'an der ;aals :orces o5erating !etween long chain molec les o55ose mo!ility. S ch 5lastics materials as are cast there:ore de5end 5on a chemical rather than a 5hysical change ta8ing 5lace to e::ect solidi:ication. Cold=setting 5lastics o: the ty5e sed with glass= :i!re or car!on=:i!re rein:orcement, consist o: two mo!ile li? ids ;hich are mi<ed and which will then 5roceed to 5olymeri7e ($0.0.$ and$0./.0) and so, harden. ,he same 5rinci5les a55ly in many res5ects to cement, concrete, 5laster and other ceramic 5rod cts, which are cast into mo lds. Crystalli7ation, accom5anying chemical change, 5rod ces rigidity in these cases.

( # 1 Casting )etals
Since the ! l8 o: metallic materials is cast as ingots or :inished sha5es, a melting 5rocess is an integral stage in most metal= :orming o5erations. # rnaces sed 9ary considera!ly in design ! t those ! rning : el can !e classi:ied !roadly into three gro 5s. (i) # rnaces, li8e the :o ndry c 5ola, in which the charge is in intimate contact with the ! rning : el. Altho gh thermal e::iciency is high !eca se o: the contin o s o5eration o: the : rnace and the intimate contact !etween ! rning : el and charge, direct trans:er o: im5 rities :rom : el to charge can ta8e 5lace. (ii) # rnaces in which the charge is o t o: contact with the : el ! t is in contact with its 5rod cts o: com! stion. ,rans:er o: im5 rities will !e limited to those o: a gaseo s nat re and thermal e::iciency will still !e reasona!ly high. Re9er!eratory : rnaces (#ig. 6.$(ii)) o: many indi9id al designs==incl ding the o5en=hearth : rnace are widely sed in steel ma8ing that :all into this category. (iii) # rnaces in which the charge is isolated !oth :rom the : el and it@s +rod cts o: com! stion. Cr ci!le : rnaces constit te this gro 5. Ma<im m 5 rity o: charge is maintained !eca se contact !etween Charge and : el is at a minim m. Ne9ertheless thermal e::iciency will !e 9ery low since most o: the heat !y5asses the charge and lea9es with the :l e gases.

Fig. 6.2 The structure of steel ingots. 123 & t+4ical 5!ig end do.n' ingot mould sho.ing ho. the '4i4e' can !e restricted. 1ii3 The de%elo4ment of the '4i4e' !+ successi%e solidification of elemental shells. 1iii3 6a7or segregation of im4urities in the central 4i4e.

)!9io sly electricity is a chemically clean : el whether sed :or resistance heating, ind ction heating or in an arc : rnace, ! t it is relati9ely e<5ensi9e. (t is there:ore a55arent that in any melting 5rocess where 5 rity o: charge is im5ortant melting costs will !e high. 6 # 1 1 +ngot Casting Steel ingots o: se9eral tonnes in mass are commonly cast into cast=iron mo lds. ,hese are s ally cast B!ig= end=downB. (#ig. 6.0(i)), ,o :acilitate the stri55ing o: the mo ld. ,his can !e li:ted o:: the solidi:ied ingot with a minim m dist r!ance o: the latter (#ig. 6.0(ii)), an im5ortant :actor since crac8ing when in the hot Atender@ state 9ery easily damages the ingot. As a metal solidi:ies it shrin8s and so the le9el o: the remaining li? id :alls 5rogressi9ely leading to the :ormation o: a 5i5e in the to5 o: the ingot (#ig. 6.0(ii)). ,his is minimised !y the se o: a hot to5=a re:ractory collar at the to5 o: the ingot mo ld, which retains a reser9oir o: molten metal ;hich :eeds into the ingot as it solidi:ies and shrin8s. ,he 5i5e, as it :orms, is :illed :rom the molten

reser9oir. ,he a!sence o: any :eeding arrangement (#ig. 6.0(ii)) wo ld lead to e<cessi9e 5i5ing. Segregation o: im5 rities is also tro !lesome in steel ingots. D ring the initial stages o: solidi:ication relati9ely 5 re metal crystalli7es :irst so that any dissol9ed im5 rities tend to acc m late in that metal which solidi:ies last. Hence the metal in the central 5i5e will !e more im5 re than that which crystalli7es initially at the s r:ace o: the ingot (#ig. 6.0(iii)). ,his is generally termed ma3or segregation. Minor segregation on the other hand re:ers to the acc m lation=!y the coring mechanism (>././)=o: im5 rities at crystal !o ndaries thro gho t the ingot. ): the two, minor Segregation is the more deleterio s in its e::ects since it ca ses o9erall intercrystalline wea8ness. Non=:erro s alloys may !e cast as :lat sla!s :or rolling to sheet, or as cylinders :), e<tr sion o: rod, t !e and other sections o: 9arying com5le<ity (6././). ( # 1 # contin"o"s casting it will !e o!9io s that the casting o: steel !y the ingot 5rocess is ine::icient. Ma3or segregation in the B5i5edB region means that some o: the ingot Bto5B (#ig. 6.0(iii)) m st !e cro55ed d ring the early stages o: rolling (and s !se? ently remelted). ;ith the elimination o: this waste in mind the de9elo5ment o: contin o s casting 5rocesses has !een going on :or many years and=aided !y the e<5ansion o: modern electronic remote control=has reached the stage where the ! l8 o: ordinary steel 5rod ced in the de9elo5ed world comes :rom contin o s= Casting 5lants. ,he elements o: contin o s casting are ill strated in #ig. 6./.

Molten metal is :ed into a short assistance=cooled mo ld at a controlled rate and as soon as solidi:ication is s ::iciently ad9anced the !ase o: the mo ld is withdrawn ta8ing with it the em!ryo ingot. ,his is engaged !y a series o: s 55ort and withdrawal rolls, which con9ey the contin o s ingot to the red ction mill 5ro5er. S ch segregation o: im5 rities as ta8es 5lace will !e ni:orm and will !e : rther dis5ersed !y the rolling 5rocess. Metal loss is e<tremely small. ,he 5rod ction o: castings to some :inished and o:ten intricate sha5e may !e achie9ed !y one o: a n m!er o: di::erent 5rocesses. ,he 5artic lar 5rocess sed will !e go9erned !y s ch criteria asD (i) ,he si7e o: the casting=large castings will !e most economically made in sand mo lds.

(ii) ,he s r:ace :inish desired=a !etter s r:ace :inish is o!tained sing metal, Bsynthetic sandB or 5laster mo lds, ! t these 5rocesses are more e<5ensi9e than sand casting. (iii) ,he dimensional acc racy re? ired=again greater acc racy is 5ossi!le sing methods mentioned in (ii) as against sand casting. (i9) Com5le<ity o: design, e.g. the 5resence o: re=entrant sections and internal ca9ities. (n many instances sand casting will !e the only +rocess 5ossi!le. (9) ,he mechanical 5ro5erties s5eci:ied=generally the se o: metal Mo lds gi9e :iner grain d e to ra5id cooling so that 5ro5erties are rather !etter. (9i) ,he total n m!er o: castings re? ired=generally it will !e neconomical to 5rod ce a metal mo ld nless se9eral tho sands o: castings are re? ired. ( # 1 $ Sand Casting Most readers will !e :amiliar with the 5rinci5les o: this 5rocess. A wooden 5attern is made s ch that when sand is rammed ro nd it in a mo lding !o< (#ig. 6..) the mo ld can !e s5lit and the 5attern

;ithdrawn lea9ing a ca9ity into which metal is 5o red. Castings o: great com5le<ity can !e 5rod ced !y this 5rocess sing m lti= 5art !o<es and, where necessary, sand cores to :orm holes and other internal ca9ities in the com5onent. Moreo9er the 5rocess is chea5 to o5erate 5artic larly when only small n m!ers o: castings are re? ired, since the wooden 5attern is relati9ely ine<5ensi9e to 5rod ce. As against these ad9antages dimensional acc racy is in:erior to that attaina!le !y other 5rocesses whilst s r:ace :inish is sometimes 5oor. ,he slow rate o: solidi:ication which 5re9ails in a Sand mo ld gi9es raise to coarse=grain and this in t rn res lts in a relati9ely wea8 !rittle str ct re. ( # 1 % Shell )o"lding (n ordinary sand casting the Mo lding sand Contains s ::icient nat ral clay to act as a !inding material :or the silica 5articles. (n shell=Mo lding 5rocesses this nat ral clay !ond is re5laced !y a synthetic !onding material o: the thermosetting=resin (5henol :ormal=dehyde) ty5e. ,he Mo lding mi<t re there:ore consists o: clean, clay=:ree silica sand mi<ed with 1R o: the 5lastic !onding agent. Each hal: o: the shell mo ld is made on a metal 5attern 5late, which is heated to a!o t 014ZC !e:ore !eing 5laced on to5 o: a

Bd m5 !o<B. ,he !o< is then in9erted (#ig. 6.1(i) so that the 5late is co9ered with the sand2resin mi<t re. ,he resin melts and in a!o t thirty seconds the hot 5attern 5late !ecomes coated with a shell o: resin=!onded sand. ,his shell hardens as the resin sets and the !o< is t rned to its original 5osition (#ig. 6.1(ii)) so that s r5l s sand2resin mi< :alls !ac8 into the !o<. ,he shell is then stri55ed :rom the 5attern 5late with the hel5 o: e3ector 5ins. ,he two hal9es o: the mo ld th s 5rod ced are then clam5ed or cemented together to recei9e their molten charge. ,he main ad9antage o: this 5rocess lies in the high degree o: dimensional acc racy o!tained. S r:ace :inish is also :ar s 5erior to that associated with an ordinary sand casting. Shell mo lds store well and are ? ite rigid so that they can !e trans5orted as necessary. ,he 5rinci5al disad9antage o: the 5rocess arises :rom the high cost o: metal 5atterns tho gh this is some what o::set !y the :act that relati9ely ns8illed la!o r can !e tili7ed so that la!o r costs are m ch less than those associated with. Ereensand mo lding. ( # 1 ' +nvestment Casting ;hilst shell mo lding was de9elo5ed in Eer=many d ring the Second ;orld ;ar, the origins o: in9estment casting lie in 5re=history when ancient cra:tsmen 5rod ced mo lds !y 5ressing clay aro nd a 5attern car9ed :rom !eeswa<. S !se? ent !a8ing o: the clay mo ld melted o t the wa< lea9ing a ca9ity to recei9e the metal charge. #or modem in9estment casting wa< 5atterns are 5rod ced in 5recision metal mo lds and then a::i<ed to a BtreeB (#ig. 6.6). ,he

wa< assem!ly is then Bin9estedB with a mi<t re o: :inely 5owdered sillimanite and ethyl silicate. ,he action o: water and heat on the latter ca se it to :orm a strong silica !ond !etween the sillimanite 5articles. ,he heating 5rocess also melts o t the wa< 5attern lea9ing a mo ld ca9ity, which will recei9e the charge o: metal. ,o im5ro9e the acc racy o: the mo ld im5ression metal is cast into the mo ld nder 5ne matic 5ress re or !y centri: ging.

)ne ad9antage o: the 5rocess is that e<tremely com5le< sha5es can !e cast since the 5attern is not withdrawn m ch o: the intricate wor8 in gold. ornamentation carried o t in the si<teenth cent ry !y Ben9en to Cellini was !y this 5rocess. #rom the aesthetic 5oint o: 9iew there is no dis:ig ring B5arting lineB on the :inished casting as is a55arent with other casting 5rocesses. E<treme 5recision in dimensions is 5ossi!le and the 5rocess is o: engineering im5ortance :or ma8ing small com5onents :rom 9ery hard, strong materials which cannot !e sha5ed !y :orging or machining. ,his 5rocess can cast !lades :or gas t r!ines and 3et engines. ,he 5rinci5al disad9antage o: in9estment casting is@ its high o5erational cost. ( # 1 ( -ie1casting ,his 5rocess in9ol9es the se o: a metal mo ld. Since the cost o: machining the mo ld ca9ity is high, die= casting is economical only when large n m!ers o: castings= generally se9eral tho sands=are re? ired. (n gra9ity die=casting,

now termed 5ermanent=mo ld casting, molten metal is 5o red into the metal mo ld in a similar manner to ordinary sand casting. (n 5ress re die=casting, o:ten called 3 st Bdie=castingB, the molten metal is in3ected into the mo ld ca9ity nder 5ress re (#ig. 6,>) so that a m ch more acc rate im5ression o: the mo ld ca9ity is o!tained. +ress re die=casting is the more common 5rocess and BcyclingB is ra5id. As soon as the casting is solid the die is 5arted. Eenerally it is so designed that the casting mo9es away with the mo9ing 5art o: the die :rom which it is detached !y a system o: e3ector 5ins.

,he main ad9antages o: die=casting are acc racy o: dimensions, good s r:ace :inish and im5ro9ed mechanical 5ro5erties arising :rom the :ine grain 5rod ced !y ra5id solidi:ication. Altho gh the cost o: the mo ld is high, la!o r costs in o5eration are low relati9e to sand casting, so that the 5rocess is economical :or the man :act re o: large n m!ers o: 7inc=!ase and al mini m=!ase com5onents in the a tomo!ile and other ind stries. ( # 1 4 The Lost1foam Casting Process ,his was 5receded !y what was called the : ll=mo ld 5rocess. (n this a 5attern was car9ed :rom a !loc8 o:@ e<5andedB 5olystyrene (E+S) ($0.&). ,his 5attern was then 5laced in a :las8 and co9ered with dry resin= !onded silica sand. ;hen molten metal was 5o red directly on to the E+S 5attern the latter e9a5orated and the metal occ 5ied the

s5ace so 5ro9ided. ,he thermosetting=resin !onding material 5re9ented colla5se o: the sand mo ld. (t was :o nd that i: n!o nded dry silica sand was sed to s rro nd the E+S 5attern in a steel :las8 and the :las8 then 9i!rated or ta55ed to consolidate the sand, !onding agents co ld !e dis5ensed with. ,his was named the lost=:oam 5rocess. A;hilst@ the original : ll=mo ld 5rocess was essentially a Bone=o::B o5eration sed :or ma8ing single castings, e.g. ornamental 5 r5oses. ,he lost=:oam 5rocess has !een ada5ted :or mass 5rod ction. ,he 5atterns are made !y= in3ecting E+S A!eadsB into a heated s5lit al mini m die which is : rther heated so that the [!eadsB e<5and and : se together. ,he 5rocess is sed in the man :act re o: al mini m alloy and iron castings. ( # # Casting !on1metallic )aterials Not many non=metallic materials are s ita!le :or casting !eca se most o: them lac8 a ;ell=de:ined 5oint where a mo!ile li? id trans:orms to a rigid solid as is the case ;ith metals. ( # # 1 Brganic Pol&mers ,he disorder=Worder change that occ rs in metals on crystalli7ation res lts in a com5lete and s dden change in 5ro5erties :rom a mo!ile li? id to a 9ery rigid solid. No s ch well=de:ined change occ rs in 5lastics materials since only 9ery limited crystalli7ation may occ r. Beca se o: the 5resence o: large chain molec les in a 5olymer considera!le 9an ^der =;aals :orces o5erate !etween them so that mo!ility in 5lastics is ne9er 9ery high and most o: them in :act decom5ose on heating to tem5erat res well !elow those at which any signi:icant mo!ility is attained. . S ch 5olymer materials as are cast areD in :actD those o: the cold= setting ty5e ($0./.0). Here two s !stances o: relati9ely small molec lar si7e are mi<ed and allowed to 5olymeri7e so that long= chain molec les s !=se? ently :orm and the 9iscosity o: the material increases 5rogressi9ely ntil a rigid str ct re is o!tained (#ig. $.0..). ,his change is chemical rather than 5hysical since 9alency lin8s :orm !etween small molec les to 5rod ce large ones. Casting 5rocesses in9ol9ing s ch changes are sed :or 5otting.

Small s5ecimens in a trans5arent 5lastic case and also :or encasing electronics e? i5ment in a 5rotecti9e ins lating ca5s le. ,he 5rocess is also sed to 5rod ce str ct res in which cold=setting resins are strengthened with glass= or car!on=:i!re. ( # # # Ceramics +laster o: +aris and sillimanite=ethyl silicate mi<t res (6.0.$.1) are o:ten cast :or 9ario s 5 r5oses. Some cement mi<t res are also cast, generally mi<ed with some :orm o: aggregate. (n all o: these instances hardening is accom5anied !y a chemical reaction tho gh in a :ew cases crystalli7ation may also occ r. Again, the change 5rod cing rigidity is chemical rather than 5hysical. Concrete ($..6.>) is cast into sim5le sha5es in ! ilding constr ction. ,he mo ld is generally constr cted o: sim5le wooden Ash ttering@, which is remo9ed when the concrete has set. S ch casting is carried o t in sit ation. 'ario s concrete mi<t res may also !e cast in s ch :orms as 5a9ing :lags, +i5es or garden B: rnit reB (gnomes, toads or A5hrodites). ,his is termed +re=cast concrete in the sense that it is not cast in sit , ! t is trans5orted a:ter it has set. ,he more com5le< sha5es and ornamental wor8 are o:ten cast into +laster o: +aris or gelatine mo lds. M ch o: the cast concrete sed in ! ilding constr ction is either o: the rein:orced or the 5re=stressed 'ariety ($1.$4.$20).

.ot1forming of Solids
( $ As might !e e<5ected, these 5rocesses are a55lied to those materials the 5lasticity o: which increases a55recia!ly as the tem5erat re rises. Many metals and all thermo5lastic 5olymers :all into this class. Howe9er, whilst increase in tem5erat re gi9es rise to an increase in mallea!ility, this is s ally accom5anied= 5artic larly in metals=!y a decrease in d ctility, !eca se tensile

strength is red ced and the material tears a5art more readily. Conse? ently most hot=:orming 5rocesses in9ol9e the se o: com5ressi9e :orces so that the material is rolled, :orged in a die or :orced thro gh a sha5ed ori:ice. A metal is hot=wor8ed a!o9e its re crystalli7ation tem5erat re (1.&./) so that re crystalli7ation occ rs sim ltaneo sly with de:ormation and the material does not wor8 harden. (n metals the as=cast str ct re is relati9ely wea8 and !rittle !eca se o: the coarse crystal str ct re 5resent and also the Segregation o: im5 rities at the crystal !o ndaries. Mechanical wor8ing redistri! tes these im5 rities more ni:ormly thro gho t the metal so that the em!rittling e::ect is less mar8ed. At the same time re crystalli7ation +rod ces m ch :iner grain, which : rther leads to !etter mechanical +ro5erties. (m5 rities tend to !e elongated in a :i!ro s manner along the main direction o: wor8ing. ( $ 1 Forging Blac8smiths ha9e !een sha5ing heated 5ieces o: metal d ring the last 6444 years or so sing sim5le tools s ch as a hammer and an an9il. Altho gh some handwor8 is still carried o t !y smiths 5artic larly in re5airs to agric lt ral machinery and the li8e, most engineering :orgings are 5rod ced in some :orm o: Bclosed dieB.

;hich is :i<ed to a massi9e an9il, whilst the other hal: is attached to the@ 5B o: a g ided hammer (#ig. 6.&). A heated wor8 5iece is inter5osed 1( $ 1 1 -rop Forging ,his in9ol9es the se o: a closed die, one hal: o: !etween the die :aces as they come together. (n order that the die ca9ity shall !e :illed a small e<cess o: metal m st !e a9aila!le and this is s? ee7ed o twards to :orm a :lash, which is easily trimmed away :rom the res ltant :orging. ( $ 1 # .ot Pressing is a de9elo5ment o: dro5 :orging which is generally sed :or 5rod cing sim5le sha5es. Here hydra lically dri9en ram re5laces the hammer so that the wor8 5iece is sha5ed !y steady 5ress re rather than !y a s ccession o: hammer !lows. De:ormation is then more ni:orm thro gho t the wor8 5iece. -arge :orgings can !e made direct :rom ingots o: s ita!le si7e. D ring :orging re:inement o: grain and redistri! tion o: im5 rities lead to a !ig im5ro9ement in mechanical 5ro5erties. ,h s a :orging is always stronger and to gher than a casting o: similar sha5e and com5osition. Nat rally a :orging is :ar more e<5ensi9e to 5rod ce than an e? i9alent casting. Moreo9er relati9ely sim5le sha5es )nly can !e 5rod ced !y :orging since solid metal, e9en nder high +ress res, :lows to the sha5e o: a die m ch less easily than does a li? id metal. Smaller :orgings are generally 5rod ced :rom stoc8 in the :orm o: Hot=rolled !ar. (n s ch stoc8 im5 rities will already ha9e !een distri! ted directionally !y the rolling 5rocess 5rod cing :i!re as indicated in #ig. 6.%(i). D ring :orging this :i!re will :ollow the conto rs o: the die and so strength will !e maintained. (: :or some

reason o: !ad die design, :i!re Bo tcro5sB to the s r:ace 5rod cing a sit ation similar to that indicated :or the machined com5onent in #ig. 6.%(iii), this may gi9e rise to 5lanes o: wea8ness along which :ract re can occ r. #i!re distri! tion in a :orging can !e e<amined ? ite easily. A re5resentati9e section is :irst c t=this is the most tiresome 5art o: the 3o! i: no mechanical aid is a9aila!le=and then gro nd :lat to a reasona!ly smooth :inish (a!o t B0&4B grade emery 5a5er). ,he section is then etched :or a!o t$1 min tes in hot 14R hydrochloric acid when the :i!re will !e clearly re9ealed (#ig. 6.$4).

( $ # .ot Rolling Metal 5late, sheet. Hot=rolling 5rocesses 5rod ce all stri5 and rod. (n most cases a sim5le two=high[ re9ersing mill (#ig. 6.$$) is sed in the initial stages to [!rea8 down the ingot. ,he res ltant sla! or !loom is then s ccessi9ely= red ced in cross=section in a s ita!le train o: :inishing rolls. M ch hot rollino7 is now integral with a contin o s=casting nit (6.0.$.0). +late, sheet and other :lat material may !e 5rod ced in 5lain rolls ! t rod and other sections s ch as rails and RSK m st !e 5assed thro gh rolls man :act red !y hot rolling since the #CC str ct re (5resent a!o9e a!o t %)4ZC in mild steel) is m ch more mallea!le than is the BCC str ct re. Howe9er, most metals and alloys are signi:icant more mallea!le at high tem5erat res and are there:ore hot rolled in the initial stages :rom the ingot. Cold wor8ing is only a55lied as a :inishing 5rocess in the interest o: s r:ace :inish, acc racy o: dimensions and the control o: mechanical 5ro5erties. ( $ $ E/tr"sion ,he e<tr sion o: !oth sim5le and com5le< sections is achie9ed !y :orcing the solid material thro gh a s ita!le sha5ed die rather in the manner in which tooth5aste is :orced :rom a r !e. Both :erro s and non=:erro s metals are e<tr ded :rom heated !illets tho gh in many cases cold e<tr sion is 5ossi!le. A :ew metals are e<tr ded :rom hot or cold 5owders whilst thermo5lastic 5olymers are e<tr ded as heated 5owders, sometimes aro nd a steel rein:orcement stri5 0S in the case o: 5lastic c rtain rail.

,he cast !illet is heated to the re? ired tem5erat re (/144=144ZC :or al mini m alloysM $$444=$014ZC :or steelsD) and trans:erred to the container o: the e<tr sion 5ress.,he ram is dri9en hydra lically with s ::icient :orce to e<tr de the metal thro gh an alloy steel die (#ig. 6.$0).

,he 5rinci5al ad9antage o: the 5rocess is that, in a single o5eration :rom a cast ingot, ? ite com5le< sections with reasona!ly acc rate dimensions can !e o!tained. ,y5ical 5rod cts incl de ro nd rodM he<agonal !rass rod (:or 5arting o:: as n ts)M stress=!earing sections in al mini m alloys (:or aircra:t constr ction)M car!on and alloy=steel t !es as well as small diameter rod :or drawing down to wire. ( $ % Blo,1mo"lding of Plastics ,his 5rocess is sed to man :act re hollow articles s ch as 5olythene !ottles. E<tr ded t !e (5arison) is heated and then !lown !y air 5ress re against the walls o: a steel mo ld. ,he two hal9es o: the mo ld then 5art to release the mo lding. ( $ % 1 Film1*lo,ing of Plastics #ilm can !e !lown contin o sly :rom e<tr ded thermo5lastics as indicated in #ig. 6.$/. S ch material has a nominal thic8ness o: not more than 4.01 mm and the 5rocess is widely sed in the man :act re o: 5olythene :ilm and t !e :or 5arting o:: as !ags and other :orms o: 5ac8aging. . ( $ ' Calendering ,his 5rocess is sed to 5rod ce thermo5lastic sheet, 5artic larly o: +'C and 5olythene. ,he calendering machine

consists o: two or more heated rolls into which the 5lastics material is :ed as heated do gh. ,he :ormed sheet is cooled on a chill roll (#ig. 6.$.). Calendering machines are also sed to coat 5a5er, :a!ric and :oil with a :ilm o: 5lastics material.

( $ ( Vac""m1forming of Plastics ,his 5rocess is sed to 5rod ce sim5le 3 sha5es :rom thermo5lastic sheet stoc8. ,he heated sheet is held at its edges and then stretched !y the ad9ancing mo ld section (#ig. 6.$1). ,he :inal sha5e is 5rod ced !y a55lying a 9ac m so

that the wor8 5iece is mo lded to the sha5e o: the die !y e<ternal atmos5heric 5ress re.

Cold1forming of Solids
( % Most solid materials can !e sha5ed more easily at high tem5erat res. ,he cost o: the heating 5rocess is more than o::set !y a !ig sa9ing !oth in time and mechanical energy re? ired :or the s !se? ent sha5ing o: the wor8 5iece. Ne9ertheless a large n m!er o: cold=wor8ing 5rocesses are sed in the :orming o: d ctile metals and alloys. ,hese are generally :inishing 5rocesses e<ce5t in the case o: drawing and dee5=drawing ( o5erations where the a55lied :orces are tensile in nat re and hot=wor8ing D cannot there:ore !e sed !eca se o: the low tensile strength o: most metals at high tem5erat res. Cold=wor8ing is a terminal o5eration in many metal=sha5ing 5rocesses :or one or more o: the :ollowing reasonsD (i) a clean, smooth or 5olished :inish can !e o!tainedM (ii) closer dimensional tolerances are 5ossi!leM (iii) the mechanical 5ro5erties o: many alloys can !e ad3 sted only !y the amo nt o: cold=wor8 a55lied to them. Strength, hardness and rigidity increase with the amo nt o: cold=wor8. ( % 1 Cold1rolling Most sheet and stri5 metal is cold=rolled in the :inal stage :or one or all o: the reasons 3 st noted. Sim5le two= high mills with ( highly 5olished rolls are o:ten sed to 5rod ce a smooth dense :inish. ;hen rolling wide sheets o: thin :oil considera!le roll 5ress res are re? ired. Since small diameter rolls are necessary in order to 5re9ent sli5 !etween rolls and wor8 5iece, the rolls tend to !end nder s ch 5ress res th s :r strating the attem5t to 5rod ce 9ery thin hard :oil. ,he sit ation is resol9ed !y the se o: !ac8ing rolls (#ig. 6.$6).

( % # -ra,ing ;ire, rod and t !es are cold=drawn :rom stoc8, which was initially either e<tr ded or rolled :rom the ingot. (n wire man :act re this o:ten in9ol9es a series o: drawing stages inter5osed with annealing o5erations to so:ten the material as it !ecomes wor8=hardened.

Fig ( 1( Cold=rolling with a :o r=high mill (!y rolling the stri5 whilst in tension, ,$ and , 0, roll 5ress res can !e red ced).

,he dies sed (#ig. 6.$>) are o: hardened tool steel or t ngsten car!ide .,he drawing :orce in wire man :act re is 5ro9ided !y winding the wire on to a rotating dr m or B!loc8B (#ig. 6.$>(ig) whilst :or the 5rod ction o: rods or t !es some :orm o: draw !ench is re? ired (#ig. 6.$>(ii)). (n t !e drawing it is generally necessary to s 55ort the internal !ore o: t !e. ,his is o:ten done !y drawing the t !e on to a steel rod=or mandrel, which 5asses thro gh the die along with the t !e :rom which it is s !se? ently e<tracted. . ( % $ -eep1dra,ing ,his 5rocess di::ers :rom sim5le metal 5resswor8 in that some degree o: wall=thinning always ta8es 5lace. Eenerally some :orm o: c 5 is :irst 5rod ced :rom a :lat !lan8 and this c 5 is then drawn so that its walls !ecome 5rogressi9ely thinner. ,he tools sed com5rise some :orm o: 5 nch and die system. Dee5=drawn com5onents range in si7e :rom small !rass cartridge cases to al mini m mil8 ch rns. Eenerally the more d ctile

materials s ch as >E=/4 !rass, c 5ro=nic8el, co55er, al mini m and mild steel are sed. ,he :orces o5erating in dee5=drawing are largely tensile so that it is

.#ig. 6.$& Stages= in a dee5=drawing 5rocess. ine9ita!ly a cold=wor8ing 5rocess. (nter=stage annealing is there:ore sed when the wor8 5iece !ecomes wor8=hardened. As a res lt o: annealing, regions o: wea8ness are o:ten enco ntered in a

dee5=drawn com5onent. ,hese are d e to 9ariations in grain si7e arising d ring the recrystallisation 5rocess which accom5anies annealing. ,h s in the drawn c 5 (#ig. 6.$%),

Fig ( 17 'ariations in grain=si7e coincident with di::erent amo nts o: cold wor8 in a dee5=drawn c 5 which was s !se? ently annealed

,he grain si7e at A is satis:actory since the material has recei9ed no cold=wor8 and the grain si7e is more or less that o: the original stoc8. No recrystallisation ha9ing ta8en 5lace. At B the grain si7e is satis:actory !eca se hea9y cold=wor8 :ollowed !y annealing has ind ced com5lete recrystallisation :rom many n clei. ,he metal at C, howe9er recei9ed only the critical amo nt o: cold=wor8 necessary 3 st to initiate recrystallisation. Hence 9ery :ew n clei :ormed in this region o: 9ery little de:ormation so that the grain si7e was large and d ctility corres5ondingly low.

( % % Cold1forging ,his incl des a n m!er o: 5rocesses where a cold wor8 5iece is :orged in some :orm o: closed die. 6.....$ Coining (#ig. 6.04) is a 5rocess o: this ty5e in which 9ariation in

Fig ( #; the di::erence !etween coining and em!ossing. (n em!ossing no 9ariation in thic8ness o: the wor8=5iece occ rs

thic8ness occ rs in the com5onent d ring :orging and hence some degree o: metal :low relati9e to the die. ,his cons mes energy as :riction and wear on dies is considera!le. Ne9ertheless a hard, wear=resistant com5onent res lts. ( % ' +mpact E/tr"sion ,his is a cold=wor8ing 5rocess sed in a n m!er o: 9ariations. +ossi!ly the !est 8nown o: these is the method sed to 5rod ce colla5si!le t !es :or tooth5aste, sha9ing cream and the li8e (#ig. 6.0$). ,hese may !e in lead, tin or al mini m, tho gh !low=mo lded thermo5lastics materials are now the most widely sed :or toiletries.

Fig ( #1 (m5act e<tr sion o: a dis5osa!le t !e.

A small nheated !lan8 is :ed into the die ca9ity and as the 5 nch descends 9ery ra5idly metal is s? ee7ed 5wards into the ga5 !etween 5 nch and die to :orm a cylindrical shell. ,he threaded no77le may !e :ormed d ring im5act or it may !e 5rod ced in a se5arate 5rocess. )ther articles made !y im5act e<tr sion incl de

al mini m canisters and ca5s les :or :ood, medical 5rod cts and 5hotogra5hic :ilmsM and shielding cans :or radio com5onents. ( % ( Cold1forming from Sheet > Metal (n these 5rocesses little or no 9ariation in the thic8ness o: the wor8 5iece occ rs d ring :orming tho gh di9erse methods are sed to achie9e the re? ired sha5e. 6...6.$ Em!ossing (#ig. 6.04) di::ers :rom coining in that the thic8ness o: the original stoc8 is more or less maintained. Since little :low o: metal occ rs m ch less energy is lost as :riction as com5ared withB the coining 5rocess. Em!ossing is there:ore sed in the man :act re o: hollow ! ttons, !adges and the li8e. 6...6.0 R !!er +ressing (#ig. 6.00) sed :or the :orming o: car= !ody 5anels, h ! ca5s and other re=entrant sha5es, stainless=steel ta!leware aircra:t 5anels and 5ots and 5ans. A r !!er 5ress s ally consists o: a stationary 55er container which holds the r !!er 5ad and a lower 5laten which carries the die and wor8 5iece. ,his lower 5laten is :orced 5wards (nto the r !!er !y means o: hydra lic cylinders, the :le<i!le r !!er :orcing the wor8 5iece into the die ca9ity and th s acting as a ni9ersal 5 nch.

Fig ( ## R !!er 5ressing.

#or 5ressing so:t al mini m alloys dies can !e made relati9ely chea5ly :rom 5a5er=rein:orced synthetic resin. tho gh 7inc alloys

and im5ro9ed 5ly=woods are also se: l die materials. Some materials s ch as titani m sheet and magnesi m alloy sheet are hot 5ressed. ,hen mild=steel or cast=iron dies are sed together with heat=resisting r !!er 5ads (generally 5rotected !y a Bsla9eB mat). ( % ( $ Stretch Forming (#ig. 6.0/) o: 5anels !oth in the aircra:t ind stry and in coach ! ilding is carried o t 5rinci5al)D[ on d ctile heat=treata!le al mini m alloys, tho gh some stainless steel and titani m alloys are also stretch :ormed. ,he earliest ty5e o: machine was o: the rising=ta!le model as shown. Here the wor8 5iece is gri55ed !etween 3aws and the :orming !loc8 is mo nted on a rising ta!le act ated !y a hydra lic ram As with the other cold=:orming 5rocesses stresses sed m st e<ceed the elastic limit so that the wor8 5iece is de:ormed within its 5lastic range. Stretch !loc8s are generally o: wood or com5ressed resin=!onded 5ly=woods. ( % ( % Spinning a 5rocess sed to 5rod ce a hollow sha5e !y a55lying lateral 5ress re to a re9ol9ing !lan8 so that it is :orced on to a s ita!le :ormer which rotates with it (#ig. 6.0.,). (n its sim5lest :orm the e? i5ment consists o: a lathe in which the !lan8 is held !etween a ch c8 and a tail lathe, and sim5le :orming tools which are generally !ars with ro nded ends. #or e<ternal s5inning a :ormer is s ally attached to the ch c8. ,he e? i5ment re? ired is sim5le and hardwood :ormers are chea5 to

Fig ( #$ strech :orming

Fig ( #% Hand=o5erated s5inning.

5rod ce. Small n m!ers=o: com5onents can there:ore !e 5rod ced m ch more chea5ly than !y an e? i9alent dee5=drawing o5eration. Moreo9er com5le< com5onents o: re=entrant sha5e can !e made easily !y s5inning, the :ormer (as in #ig. 6.0.) then !eing segmented to :acilitate withdrawal. Conical sha5es, di::ic lt to ma8e !y dee5 drawing, can also !e s5 n ,y5ical 5rod cts are ornaments in co55er and !rass, m sical instr ments (incl ding Banti? eB 5osthorns c rrently !eing 5rod ced in large n m!ers in BQrmQngQamG), coo8ing tensils and stainless= steel dairy tensils. Mechanised s5inning has !een de9elo5ed in recent years nder the name o: B:low t rningB. ( % ( ' E/plosion Forming D ring recent years a n m!er o: techni? es ha9e !een de9elo5ed :or the :orming o: metals in which the energy sed :or :orming is released o9er a 9ery short time inter9al. ,hese are loosely called high=energy=rate :orming=M=or HER#=5rocesses. (n these HER# 5rocesses energy is released at s ch a rate that local de:ormation occ rs !e:ore energy can !e

dissi5ated !y B5lastic wa9esB thro gh the material. Mechanical e::iciency is th s im5ro9ed. Energy can !e released ? ic8ly either !y a s dden change in 5ne matic 5ress reM !y the se o: high=9oltage electrical dischargeM or !y the se o: high e<5losi9es. ,h s !y detonating no more than 4.$ 8g o: a s ita!le high e<5losi9e, energy can !e dissi5ated at a rate e? i9alent to 6 < $46 8;. A method o: e<5losion :orming in which water is sed to transmit the shoc8 wa9es is ill strated in #ig. 6.01. ,his is generally termed the Bstand=o::B method, the charge !eing s s5ended a!o9e the !lan8=die assem!ly. Dies can !e o: clay or 5laster :or one=o:: 3o!s or o: concrete, wood, resin or metal :or longer Br nsB. ,he 5rocess is sed e<tensi9ely at 5resent :or 5rototy5e 5rod ction or :or 9ery short r ns. )!9io sly la!o r costs o: the 5rocess are relati9ely high since s8illed and res5onsi!le

Fig ( #1 E<5losion :orming.

o5erati9es m st !e em5loyed to handle and 5re9ent the loss o: s ch dangero s e<5losi9es to terrorist organisations.

Forming from Po,ders

( ' All :inished sha5es in thermosetting 5olymers and many o: those in thermo5lastic 5olymers are 5rod ced !y com5ressing heated 5owders or gran les. (n thermosetting 5olymers cross= lin8ing !onds :ormed d ring the setting 5rocess render the change irre9ersi!le and the com5onent once :ormed, cannot s !se? ently !e so:tened. ;ith thermo5lastic 5olymers 9an der ;aals :orces o5erating !etween molec les gi9e rise to 5lasticity which 9aries with tem5erat re. ;hilst most metals are cast either as ingots or as sha5ed castings, increasing se is made o: 5owder=metall rgy 5rocesses. (nitially these 5rocesses were sed to deal with those metals with 9ery high melting 5oints and which co ld not !e melted satis:actorily on an ind strial scale :or lac8 o: a s ita!le high=tem5erat re re:ractory. +owder metall rgy was : rther, de9elo5ed to introd ce s ch se: l :eat res as controlled 5orosity and the :ormation o: alloys :rom metals which are not misci!le in the li? id state.,he ! l8 o: engineering ceramic 5rod cts are sha5ed !y similar 5rocesses. ( ' 1 Po,der )etall"rg& ,he 5rinci5les o: 5owder metall rgy are mentioned elsewhere (>.&) and here the technical details will !e !rie:lydescri!ed. A ty5ical 5rocess may !e di9ided into :o r stagesD (i) 5rod ction o: a s ita!le 5owder and mi<ing it with necessary additi9esM (ii) com5acting the 5owder in a sha5ed dieM (iii) sintering the res lting com5act at a tem5erat re high eno gh to e::ect contin ity !etween the 5articlesM (i9) si7ing and :inishing. +owders may !e 5rod ced !y a n m!er o: 5rocesses. #or e<am5le, t ngsten 5owder is o!tained !y the chemical red ction o: 5owdered t ngsten o<ide, whilst co55er 5owder can !e electro= de5osited :rom sol tion. Some hard, !rittle metals are 5owdered !y grinding or 5 l9erisation

,he 5owder is then com5acted in a die o: s ita!le sha5e (#ig. 6.06).

...
Fig ( #( Stages in the com5acting o: a !ron7e=!earing ! sh, :rom a mi<t re o: co55er and tin 5owders

+ress res sed may 9ary !etween a!o t 1 N2mm0 :or so:t metals li8e tin and $144 N2mm0 :or 9ery hard metals li8e t ngsten. Dies o: tool steel or t ngsten car!ide are generally sed ! t e9en so wear on dies is se9ere. ,o red ce this wear some l !ricant s ch as gra5hite, oil, 7inc stearate or 5ara::in wa< (in a sol9ent) is s ally mi<ed with the 5owder 5rior to com5acting it. ,he com5acts are then sintered !y heating them to a tem5erat re which is generally a!o9e that o: recrystallisation. Di:: sion and recrystallisation across ad3acent 5article !o ndaries 8nit the 5articles :irmly together so that a strongly contin o s str ct re is 5rod ced. (n some cases, as in the man :act re o: oil= less !earings :rom mi<ed co55er and tin 5owders, one o: the metals melts and is drawn !y ca5illary action into the s5aces !etween the 5articles o: the other metal 9irt ally BsolderingB them together .Sintering is carried o t in some :orm o: 5rotecti9e atmos5here which will limit s r:ace o<idation to a minim m. Some re:ractory metals li8e 5latin m and t ngsten are gi9en treatments in the region o: $014o=0144ZC in an atmos5here o: hydrogen.

Sintering ine9ita!ly 5rod ces some distortion and alteration in si7e. A si7ing o5eration is there:ore sed to achie9e dimensional 5recision and im5ro9e s r:ace :inish o: the com5onent. Si7ing is carried o t on mechanically or hydra lically o5erated 5resses, sing tools which are !asicallysimilar to the original com5acting tools. ( ' # Forming Pol&mers from Po,ders (n most o: these 5rocesses the 5owdered or gran lated 5olymer is com5ressed in a heated mo ld or die, tho gh in in3ection mo lding the 5olymer 5owder is heated in an e<ternal com5ression cham!er and trans:erred to a cold mo ld. ,his has the ad9antage that the mo lding hardens ? ic8ly th s shortening the 5rod ction cycle. 6.1.0.$ E<tr sion +lastics are generally e<tr ded !y means o: a Bscrew 5 m5B (#ig. 6.0>). ,he 5owder is carried :orward !y the screw mechanism

Fig ( #4 ,he e<tr sion o: 5lastics materials= sing a Bscrew 5 m5B.

into the heated 7one where it !ecomes so:t eno gh to !e :orced thro gh the die, the a5ert re o: which is sha5ed in accordance with the re? ired cross=section. Man=made :i!res are e<tr ded sing a m lti=hole die, or s5inneret. ;ire can !e coated with 5lastics !y e<tr sion, the wire !eing 5assed into the die a5ert re in the manner o: a mandrel. +lastics c rtain rail is similarlye<tr ded on to a steel stri5 which 5ro9ides added strength.

6.1.0.0 (n3ection Mo lding (#ig. 6.0&) ,his is a ra5id 5rocess widely sed :or mo lding in 5olythene and 5olystyrene. ,he 5owder is heated in the in3ection no77le so that it so:tens and is trans:erred to the mo ld nder 5ress re. Since the mo ld itsel: is cold the 5lastics material soon hardens and can !e ? ic8ly e3ected. A Bs5rayB o: com5onents is mo lded at one BshotB. (ndi9id al com5onents are then !ro8en away :rom the system o: r nners. .

Fig ( #7 Com5ression mo lding.

6.1.0./ Com5ression Mo lding (#ig. 6.0%)is 9ery sed :or !oth thermo5lastic and thermosetting 5olymers, ! t is 5artic larly s ita!le :or the latter. ,he mo ld m st !e heated in either case ! t m st !e cooled again :or thermo5lastic mo ldings !e:ore they can !e e3ected. A care: lly meas red ? antity o: 5owder is sed and 5ro9isions made to s? ee7e o t the slight e<cess necessary to ens re :illing o: the mo ld ca9ity.

6.1.0.. ,rans:er Mo lding (#ig. 6./4) is sed :or thermosetting 5olymers.!oth 5owder cham!er and die are heated and the res ltant mo lding allowed to remain in the mo ld long eno gh to set. ,his 5rocess is ca5a!le o: 5rod cing rather more intricate sha5es than is com5ression mo lding.

4 ALLB<S

4 1 ,he :irst metals to !e sed !y li:an were those :o nd Bnati9eB, namely gold and co55er, and it was not ntil the ad,=ent o: the Bron7e Age that the widescale se o: a metallic alloy !eganD (t is tho ght that !ron7e was disco9ered accidentally !y some 5rimitii=e h nter iiBho inad9ertently smelted a mi<ed co55er=tin ore in his cam5 :ire. Ne9ertheless it was soon realised that this new material co ld !e m ch harder and stronger than 5 re co55er and there:ore se: l :or man)B more 5 r5oses. (n the modern world se 5 re metals only when 5ro5erties s ch as high electrical or thermal cond cti9ity or high d ctility are re? ired .By allowing we are e<tend the range o: se: l metallic 5ro5erties and o:ten to introd ce entirely new ones. 4 1 1 An alloy can !e de:ined as a metallic solid or li? id consisting o: an intimate association o: two or more elements. ,he elements concerned mingle together on the atomic scale and ii=hiGst the 5rinci5al constit ents are generally metals some non=metallic elements are also im5ortant constit ents o: engineering alloys. ,h s C/r!4n as the alloying addition to ircn :orms o r most im5ortant alloy steel. Normally a se: l alloy can only !e 5rod ced i: the elements concerned are sol !le in each other in the molten state k that is they :orm a single homogeneo s sol tion in the cr ci!le. Some molten metals do not dissol9e in each other ! t instead :orm two

se5arate layers = as do oil and water when an attem5t is made to mi< them. ,h s molten lead and molten 7inc will not dissol9e in each other com5leteGD[ ( nless the tem5erat re is in e<cess o: >%&ZC (&.6.$)). ,he lead atoms are too large relati9e to those o: 7inc to allow m ch sol !ility. (nstead a layer o: molten 7inc (containing some dissol9ed lead) will :loat on to5 o: a layer o: molten lead (which will contain some dissol9ed 7inc). S ch a sit ation cannot !e e<5ected to gi9e rise to the :ormation o: a se: l alloy. Clearly, when cast the lighter metal will tend to :loat to the s r:ace !e:ore solidi:ication is com5lete tho gh there may !e limited Bentanglementk o: the ti$K[4 com5onent metals. ):ten a se: l material wo ld res lt :rom a ni:orm conglomerate o: 5articles o: two insol !le metals, :or e<am5le iron and co55er, as a chea5 !earing metal=then 5owder metall rgy (>.&.0 and 6.1.$) comes to o r aid. 4 1 # Eenerally, then, a 5rere? isite to the :ormation o: a se: l alloy is that all o: the com5onents o: the alloy shall !e mingled intimately together (#ig. > .$(ii)) in the li? id state. ;hilst an alloy

:re? ently contains more than two elements we shall !e dealing in the main with a !inary mi<t re, that is one containing two com5onents. ,he term com5onent re:ers in this case to a metallic element tho gh it co ld e? ally im5ly a chemical com5o nd as wo ld !e the case i: we were dealing with the sol tion o: some s !stance in water.

,he metal which is 5resent in the larger 5ro5ortion is o:ten re:erred to as the 5arent metal or sol9ent, whilst the metal (or non= metal) 5resent in the smaller 5ro5ortion is 8nown as the sol te. ,his nomenclat re is sed in a st dy o: sol tions generally, :or e<am5le, sol tions o: s !stances in water or in organic sol9ents. . ;hen the molten sol tion !egins to solidi:y the a::inities which di::erent ty5es o: atoms ha9e :or each other go9ern the ty5e o: arrangement which res lts in the s !se? ent solid str ct re. ,h s i: two di::erent metals are similar in chemical 5ro5erties so that they ha9e little chemical a::inity :or each other, they will, 5ro9ided their atoms are o: similar order o: si7e, Bcoe<ist 5eace: llyB :orming mi<ed crystals, or what is termed a solid sol tion. (:, on the other hand, they are rather di::erent in res5ect o: chemical characteristics they may attract each other to the e<tent that they :orm a ty5e o: chemical com5o nd=o:ten re:erred to as an intermetallic=com5o nd. (n a sit ation where nli8e atoms attract each other less than li8e atoms, the two ty5es tend to se5arate into di::erent crystals,which meet at a m t al grain !o ndary. A heterogeneo s mi<t re o: this ty5e is termed a 5hase mi<t re. ,he e tectic str ct re :o nd in many alloys is s ch a mi<t re. 4 1 $ )n the :ace o: it the way two metals !eha9e when we attem5t to alloy them seems to res lt in a 9ery hit=or=miss sit ation. (n :act nothing co ld !e : rther :rom the tr th and the ty5e o: str ct re 5rod ced is a : nction o:D (i) the relati9e 5ositions o: the two metals in the 5eriodic classi:ication (,a!le $./]=that is the n m!er o: 9alency electrons in their res5ec= ti9e o ter shellsM (ii) the si7es o: the two atoms relati9e to each other. ,hese in:l ences will !ecome a55arent in this cha5ter and the one which :ollows.

Solid Sol"tions
4 # A : ndamental characteristic o: all solid sol tions is that the com5lete intermingling o: the atoms o: !oth metals ii[hich 5re9ail in the li? id sol tion is retained in the solid state. ,he range o: com5ositions can 9ary in !oth li? id and solid sol tions. Some materials are sol !le in each other in all 5ro5ortions, others only 5artially sol !le one in the other. 4 # 1 Alcohol and water : rnish an e<am5le o: two li? ids which show com5lete m t al sol !ility in all 5ro5ortions. ,h s !eer is, alas, a relati9ely wea8 sol tion o: alcohol in water whilst whis8y and 9od8a are relati9ely strong sol tions o: alcohol and water. (n all alcoholic !e9erages a

single 5hase is 5resent in the !ottle. ,he 5arallel case in metallic solid sol tions is ill strated !y the metals co55er and nic8el. ,hey are said to !e com5letely misci!le as solids since they :orm single= 5hase alloys in all 5ro5ortions. ,hat is, whate9er the com5osition o: a co55er=nic8el alloy, its microstr ct re will consist o: crystals o: one ty5e only, containing co55er and nic8el atoms intimately mingled. )nly a limited n m!er o: 5airs o: metals are com5letely m t ally sol !le in this way. ,hey incl de, in addition to co55er and nic8el, gold=sil9erM gold=5latin m and antimony= !ism th (>./.$). 4 # # Some li? ids are 5artially sol !le in each other. ,h s water will dissol9e a small amo nt o: acetone gi9ing a single li? id sol tion rich in water, whilst acetone will similarly dissol9e a small amo nt o: water gi9ing a single li? id sol tion rich in acetoneM ! t i: a55ro<imately e? al 9ol mes o: water and acetone are sha8en together, two se5arate layers will remain. ,he 55er layer will !e acetone sat rated with water and the lower layer will !e water sat rated with acetone. ,he com5ositions o: these two layers will !e di::erent, the 55er !eing= acetone=rich and the lower water= rich. A great many 5airs o: metals show limited solid sol !ility in 5arallel manner. ,hey are said to !e 5artially misci!le. 4 # $ A 9ery :ew 5airs o: metals m t ally sol !le as li? ids, !ecome com5letely insol !le as solids. E9en then it is 5ossi!le that some 9ery slight solid sol !ility e<ists ! t is so small as to !e di::ic lt to meas re. Q ,h s cadmi m and !ism th which :orm a single homogeneo s li? id sol tion in all 5ro5ortions, se5arate o t, to all intents and 5 r5oses, com5letely on solidi:ication so that the microstr ct re contains two 5hases==crystals o: 5 re cadmi m and crystals o: 5 re !ism th. 4 # % Solid sol tions are either s !stit tional or interstitial (#ig. >./).;hilst atomic si7e is not the only criterion go9erning the ty5e o: solid

sol tion to !e :ormed it is clear that interstitial solid sol tions are generally 5rod ced only when the sol te atom is small com5ared with the sol9ent atom. ,he sol te ion is then a!le to :it into the interstices, or ga5s, !etween the sites occ 5ied !y the sol9ent ions. ;hilst an interstitial solid sol tion
Q (n a similar manner we o:ten loosely re:er to s !stances as !eing insol !le in water, whereas in :act they are 9ery s5aringly sol !le. Most s !stances ha9e some degree o: sol !ility in water

may !e :ormed d ring the solidi:ication o: an alloy it will !e a55arent that s ch a sol tion can also :orm in a 5arent metal which is already solid, !y Bin:iltrationB o: the s5aces !etween its ions. Non=metallic elements o: small atomic si7e are a!le to dissol9e in this wa9 in a n m!er o: metals. ,h s K steel can !e car! rised !y 5ermitting car!on atoms to di:: se into the s r:ace o: #CC iron (%.%.$), whilst it can !e nitrided !y allowing nitrogen atoms to !e a!sor!ed !y BCC iron .(%.%.0)[. )n the de!it side, hydrogen em!rittlement is s ::ered !y a n m!er o: metals since the 9ery small hydrogen atom can !e a!sor!ed interstitially !y the lattices o: many solid metals. (n s !stit tional solid sol tions atoms o: the sol te metal ta8e 5 sites in the lattice str ct re o: the sol9ent metalk ,his s !stit tion can !e either ordered or disordered. (n the :ormer k atoms o: the sol te metal ta8e 5 certain :i<ed 5ositions (#ig. > . /(iig. S ch solid sol rions tend to !e hard and !rittle, whilst those o: the disordered ty5e are to gh and d ctile and there:ore more se: l as constit ent 5hases o: engineering alloys. #ort nately the greater 5ro5ortion o: s !stit tional solid sol tions are o: the

disordered ty5e. 4 # ' ,he :ormation o: solid sol tions in metallic alloys is to !e e<5ected since atoms in metals are held together 5rinci5ally !y the m t al attraction !etween their 5ositi9e ions and the common [electron clo dB (/.1) 5ermeating them. S ch a !ond is relati9ely indi::erent !oth to the e<act 5ro5ortions o: the di::erent ty5es o: com5onent ions and also their 5recise distri! tion in the crystalline 5attern.'aria!le solid sol tions o: wide ranges o: com5arison are there:ore common. 4 $ ;e are inde!ted to +ro:. ;. H me=Rothery o: )<:ord more than to any other metall rgist :or o r : ndamental 8nowledge o: the str ct re o: alloys. He concl ded that the :olloiiing :actors ha9e the greatest in:l ence on the :ormation o: s !stit tional solid sol tionsD (i) atomic si?e the greater the di::erence in si7e !etween the atoms o: the two metals in9ol9ed the smaller kill !e the range o9er which they are sol !le. (: atom diameters di::er !y more than $1R o: that o: the sol9ent metal then solid sol !ility, is generally e<tremely small ! t i: diameters di::er !y less than >R then, other things !eing e? al, they will !e li8ely to :orm solid sol tions in all 5ro5ortions. Any di::erence in atomic si7e will o: co rse 5rod ce some strain in the res ltant crystal str ct reM

(ii) electrochemical .ro.erties the ions o: all metals are electro5ositi9e ! t some are more electro5osit9e than others. Eenerally, the greater the di::erence in electro5ositi9ities the greater will !e the chemical a::inity o: one ion :or another so that they will tend to :orm a com5o nd rather than a solid sol tion. (: on the other hand their electro5ositi9ities are similar then. other things !eing e? al, they will 9ery 5ro!a!ly :orm a solid sol tionM

(iii) +alency a metal o: lower 9alency is more li8ely to dissol9e one o: higher 9alency than 9ice 9ersa always ass ming that other conditions are :a9o ra!le. ,his holds tr e 5artic larly :or alloys o: the mono9alent metals co55er, sil9er and gold with many metals o: higher 9alency. 4 $ 1 #rom the a!o9e it can !e concl ded= that two metals are most li8ely to :orm s !stit tional solid sol tions o9er a wide range o: com5ositions i: their atomic si7es are a!o t e? al and i: their electrochemical 5ro5erties are similar. ,hese conditions are : l:illed when two metals are 9ery close together in the 5eriodic classi:ication o: the elements= s ally side !y side in the same 5eriod (nic8el and co55er) or one a!o9e the other in the same gro 5 (sil9er and gold). Also i: singly they crystallise in the same 5attern this will assist sim5le disordered s !stit tion. +airs o: metals which : l:ill these conditions and dissol9e in each other in all 5ro5ortions in the solid state incl deD C =NiM Ni=+dM Mo=;M (r= +tM =#e=CrM #e=NiM A =AgM A =+tM Ag=+dM Mo=,iM Se=,eM Re=R M N!=,iM *=R!M Cr=;M Co=+d Bi=S!M As=S! and ,i=Or. Many o:. these=! t not all=are #CC 5airs o: elements. 4 $ # ,he 9alency e::ect is related to the a!ility o: the metallic !ond to acce5t changes in the electron concentration as com5ared with the rigid 9alency laws associated with co9alent com5o nds. (:, say, al mini m is dissol9ed in co55er the electron concentration is increased since, whilst each co55er atom contri! tes one electron to the common Bclo dB each al mini m atom will contri! te three electrons. Sol !ility o: al mini m in co55er reaches a limit with a!o t 04R atoms o: al mini m=that is, a!o t $.. 9alency electrons 5er atom. Q ,his ratio holds good :or the sol !ility o: many other metals (o: di::erent 9alencies) in co55er.
Q (n e9ery $44 atoms, &4 9alency electrons will !e 5ro9ided !y &4 atoms o: co55er and 64 9alency electrons !y 04 atoms o: al mini m

4 $ $ ,he atomic si7e :actor 5lays a signi:icant 5art in the :ormation o: many alloys o: ind strial im5ortance. ,h s !oth co55er and iron are ro ghly in the middle o: the metals as :ar as si7e :actor is concerned. Conse? ently they will dissol9e many metals in :airly large ? antities, so that co55er is the !asis o: !rasses, !ron7es and c 5ro=nic8elsM whilst iron will dissol9e large amo nts o: nic8el, chromi m, manganese, t ngsten,9anadi m. and co!alt gi9ing a wide range o: alloy steels. +rimary s !stit tional solid sol tions !ased on #CC metals are 9ery s ita!le :or se as wro ght alloys since they can !e sha5ed !y 5lastic de:ormation !eca se o: their high d ctilities. ,he 5rocess also increases strength and hardness. ;hen sol !ility decreases with :all in tem5erat re to a 9ery low 9al e this may :orm the !asis :or 5reci5itation hardening treatment (>.1.0). 4 $ % ;hilst a 5 re metal solidi:ies at a single :i<ed tem5erat re a solid sol tion solidi:ies o9er a range o: tem5erat res (&.6./.$). As crystalli7ation commences there is a tendency :or the metal with the higher melting 5oint to solidi:y more ? ic8ly than that o: lower melting 5oint. Conse? ently the core o: the res ltant crystal will contain rather more atoms o: the metal o: higher melting 5oint whilst the o ter :ringes and !o ndary regions o: the crystal will contain a larger 5ro5ortion o: atoms o: the metal o: lower melting 5oint. ,his change in com5osition :rom core to o ter :ringes re9eals the dendritic str ct re o: s ch an alloy when a 5re5ared section is e<amined nder the microsco5e. ,he di::erence in com5osition !etween the core o: the crystal and its !o ndary regions is re:erred to as coring (#ig. >..), and is most 5rono nced in solid sol tions which ha9e solidi:ied ra5idly and cooled ? ic8ly to room tem5erat re. Slow cooling on the other hand 5ermits di:: sion to occ r so that coring is totally or 5artially lost. 4 $ ' ,he 5resence o: sol te atoms in a lattice str ct re im5oses strain ,his strain will !e at a minim m i: the sol te atoms are

e9enly dis5ersed thro gho t the crystal. Hence there is a tendency :or di:: sion to occ r ntil the concentration gradient o: sol te atoms within the crystal is 7ero. (: ra5id cooling o: the alloy has res lted in e<tensi9e coring then 5rolonged annealing at a tem5erat re 3 st !elow the :ree7ing range will generally s 55ly s ::icient thermal acti9ation to 5ermit di:: sion and the dis5ersion o: coring.

-iff"sion in Solid Sol"tions

4 % (t is a :easi!le ass m5tion. that di:: si_n o: interstitial sol te atoms will ta8e 5lace with ease since the relati9ely sma(l atoms in9ol9ed can mo9e easily thro gh the str ct re o: the 5arent metal. Car! rising and nitriding ha9e already !een mentioned in this conte<t. ;e can only attem5t to e<5lain di:: sion in s !stit tional solid sol tions, howe9er, i: we 5ost late the 5resence o: 9acant sites (or 9acancies) (1./) in the str ct re. ;e ha9e already seen that the e<istence o: dislocations e<5lains some o: the mechanical 5ro5erties o: metals and this is a : rther instance where an otherwise ne<5lained 5hysical 5ro5erty relies on the s5ec lation that metallic crystals contain many im5er:ections (1./). 4 % 1 Since the 5resence o: a sol te atom im5oses strain it is reasona!le to s 55ose that a sol te atom and a 9acancy wo ld migrate to each other and so red ce strain to a minim m. ,he associated sol te atom and 9acant site co ld then migrate thro gh the str ct re, each mo9ement o: one site s5acing !eing achie9ed !y a series o: Bmo9esB as indicated in #ig. >.1. ,he rate at which di:: sion ta8es 5lace de5ends 5res ma!ly 5on the a9aila!ility o: 9acant sites. (t also de5ends 5on the concentration gradient o: the sol te atoms within the str ct re o: the 5arent metal and 5on the tem5erat re at which di:: sion is ta8ing 5lace. (n $&11 Adol5h #ic8 en nciated laws go9erning the di:: sion o: s !stances generally on a ? antitati9e !asis. Here we

are concerned with the a55lication o: these laws to metallic solid sol tions.

4 % # #ic8Bs #irst -aw states that the amo nt (K) o: material mo9ing across a nit area o: a 5lane in nit time is 5ro5ortional to the concentration gradient (dc2d<) at the same instant ! t o: o55osite sign, i.e. KP =D. (dc2d<) (,his ass mes that the <=a<is is 5arallel to the direction in which the concentration gradient is o5erating.)

,he constant D is the di:: sion coe::icient and 9aries with di::erent solid sol tion systems and other 5re9ailing conditions s ch as tem5erat re. (t is e<5ressed in nits m0=s, i.e. Atoms P =D. ( atoms2m/) b K P = D. (dc2d<)c 0 m 2s m or =D P m02s ,he negati9e sign indicates that mo9ement is in a down=gradient direction. ;hen dc2d< P 4, K P 4 which means that when the Bdri9ing :orceB 5ro9ided !y the concentration gradient reaches 7ero (CD in #ig. >.6 is hori7ontal)mo9ement o: atoms will cease. #ic8Bs -aw is o: the same general ty5e which go9erns :or e<am5le, the :low o: heat along a metal !ar. (n :act #ic8Bs -aw was really an e<tension o: o!ser9ations made !y #o rier in $&00. )hmBs -aw is also o: this ty5e and deals with the :low o: electrons :rom a region o: high concentration to one o: lower concentration

where the dri9ing :orce is 5ro9ided !y the m t al re5 lsion !etween li8e=charged electrons which can tra9el easily thro gh the lattice str ct re o: a metal. ,he :low o: ions as go9erned !y #ic8Bs -aw generally re? ires thermal acti9ation since lattice distortion ca sed !y the 5resence o: sol te atoms does not gi9e rise to s ::icient energy to 5ermit di:: sion naided. Moreo9er, as we ha9e seen (>...$), ions (atoms) are not a!le to mo9e easily thro gh the lattice o: the sol9ent metal. ,he sit ation dealt with !y #ic8Bs -aw is one where the concentration gradient remains constant th s 5ro9iding a steady dri9ing :orce and conse? ently steady-state di:: sion. (n 5ractice this sit ation rarely o!tains and generally the concentration gradient at a 5lane alters as soon as di:: sion !egins so that !oth concentration gradient and atom :low change with time so that transient-state di:: sion 5re9ails. 4 % $ Fick's Second Law (also 8nown as the *iffusion Trans.ort "4uation) deals with transient=state di:: sion. (t deri9es :rom #ic8Bs #irst -aw and :rom the :act that matter is conser9ed within the system. (t relates the change in concentration with time ( c2t). (t can !e e<5ressedD

cP (DQ c) t <
which will delight the hearts o: a:icionados o: the di::erential calc l s. ,he a!o9e e<5ression deals with the general case ! t i: D re:ers to a s5eci:ic case and is constant thenD

cP DQ 0c t <0
#rom this it can !e seen why the :inal stages o: di:: sion d ring a

homogeni7ation annealing 5rocess are 9ery slow indeed. ,he rate o: di:: sion decreases as the concentration gradient diminishes and e9en a:ter 5rolonged annealing a trace o: coring may !e 9isi!le in the microstr ct re o: the alloy. ;e can write #ic8Bs Second -aw in the :ormD 0

C<P DQ C< t <0

where C< is the concentration o: a di:: sing s5ecies o: atom at some distance < :rom a s r:ace whilst t is the time (seconds). ,he s al mathematical sol tions to di::erential e? ations o: this :orm may !e sedQ ! t ass ming that the concentration o: Cs o: the di:: sing s5ecies at the s r:ace remains constant=and this is common when dealing with the 5enetration !y gases or sma$$ atoms li8e those o: car!on into a solid metal s r:ace as in car! rising (%.%.$]=then the :ollowing sol tion can !e sedD
Q

,his is the Er !e sol tion to the Di:: sion ,rans5ort E? ation in which Co is the initial concentration o: the di:: sion s5ecies (when t P 4). BEr:B re:ers to the Berror : nctionB in9ol9ed in s ch a sol tion and is ta! lated in some mathematical ta!les (a limited range o: 9al es o: the error : nction is gi9en in A55endi< ( :or corres5onding 9al es o: the inde5endent 9aria!le, y). ;hen 9al es are s ch thatD er:y Py ,henD Cs=C< < Cs=C4 0(Dt)$20

Cs=C< Der:( <) Cs=C4 0(Dt)$20

Da! hands with the calc l s may wish to 5 rs e this : rther !y re:erring to ,he Mathematics o: Di:: sion !y K. Cran8 ()<:ord Fni9ersity +ress, $%>1). ,his !oo8 deals with mathematical sol tions to di::erential e? ations.

and this e<5ression o:ten 5ro9ides 9al es which are s ::iciently acc rate :or many 5 r5oses _, A steel 5late o: ni:orm car!on content 4.6R was inad9ertently e<5osed to a strongly o<idi7ing atmos5here :or $4 min tes at $444 C (i) ;hat will now !e the car!on content at a de5th or 4.01 mm !elow the s r:aceJ (ii) At what de5th will the car!on content ha9e :allen to 4./1RJ (,he di:: sion coe::icient (D) is /.$4 < $4=$$ m02s at $4444C.) Ans, $. ,he 5resence o: the strongly o<idi7ing atmos5here at the s r:ace means that the car!on content tl$ere is ). Fsing the Er !e sol tion o: the e? ationD

;hen y P 4.%$>, er: y P 4.&411 (e<tra5olating 9al es :rom A55endi< (). HenceD

A : rther e<ercise in9ol9ing the Di:: sion ,rans5ort E? ation will !e :o nd in Cha5ter % (%.%.$). >.... Di:: sion in a mi<t re o: gases ta8es 5lace witho t any signi:icant energy in5 t to the system since all atoms (or molec les) are in a state o: motion. ;ith solid metals, howe9er, an in5 t o: thermal energy is re? ired to ca se an atom to B3 m5B o t o: its lattice 5osition and mo9e to a new 5osition. (: Ed is the energy re? ired to 5rod ce that B3 m5B then it can !e shown thatD D P Doe= Ed2R, )r D P Do e<5 (= Ed2R,) where Do is a constant. ,his Arrheni s ty5e e? ation indicates that in solids di:: sion rates are in:l enced considera!ly !y tem5erat re whilst in gases, where there is 9irt ally no energy !arrier (Ed P 4),

di:: sion coe::icients are generally inde5endent o: tem5erat re, i.e. D P Do.

Strengthening )echanisms -ependent on Solid Sol"*ilit&

4 ' ,he most common reason :or alloying is to increase the strength o: a metal and generallyB the re? ired 5ro5erties res lt :rom the :ormation o: a solid sol tion. ,he 5resence o: sol te atoms will im5ede the mo9ement o: dislocations and so increase the yield stress o: the material. 4 ' 1 0Sol"te Atmospheres0 (n any metal the 5resence o: a dislocation ca ses distortion o: the lattice str ct re near it. (n a solid sol tion this distortion=and the strain energy associated with it=can !e red ced !y the 5resence o: sol te atoms. ,h s, i: the sol te atoms are larger than those o: the 5arent metal they will red ce strain in the lattice i: they ta8e 5 sites ;here the lattices is in tension(#ig.>.>(i)) (: on the other hand the sol te

atoms are smaller than those o: the 5arent metal they will red ce strain i: they occ 5y sites where the lattice is in com5ression (#ig. >. >(ii)). ,he necessary migration o: sol te atoms to s ita!le sites to 5rod ce this sit ation will occ r d ring solidi:ication or d ring an annealing 5rocess, which will 5ermit di:: sion. S ch an array o: sol te atoms in the region o: a dislocation is o:ten re:erred to as a sol te atmos5here or Cottrell atmos5here a:ter Sir Alan Cottrell the

eminent scientist who in his chosen disci5line o: metall rgy did so m ch to esta!lish dislocation theories. >.1.$.$ Ha9ing th s migrated to these 5ositions the sol te atoms, whether large or small, will e::ecti9ely B5in downB the dislocation and o55ose its mo9ement since any attem5t to mo9e the dislocation away :rom the sol te atmos5here will increase considera!ly the distortion and strain energy o: that region o: the lattice. ,his e::ect is indicated in #ig. >.& which

shows the distortion remaining when the dislocation has mo9ed away :rom the sol te atmos5here in each case. (n this way sol te atmos5heres increase the yield stress o: an alloy. Annealing, :ollowing a cold= de:ormation 5rocess, will 5ermit sol te atoms to align themsel9es once more near to a dislocation and so 5rod ce a new sol te atmos5here. >.1.$.0 (n interstitial solid sol tions the small sol te atoms will occ 5y 5ositions where the lattice is in tension (#ig. >.%) since interstitial ga5s will

!e larger in these regions. ,his hy5othesis a::ords a con9incing e<5lanation o: the yield=5oint e::ect in mild steel and did m ch to hel5 esta!lish the dislocation theory at a time when 9ery limited e9idence was a9aila!le. (n #ig. >.$4 the yield 5oint A corres5onds to the stress re? ired to mo9e dislocations away :rom their associated sol te atmos5heres o: interstitial

car!on atoms !y which they were 5egged down. ,he stress B is that necessary to 8ee5 the dislocations mo9ing once they ha9e !een se5arated :rom their sol te atmos5heres. (,he stress re? ired :or sli5 to contin e s !se? ently increases as the steel wor8=hardens, that is, dislocations !ecome 3ammed against each other or against other o!stacles.) 4 ' # Coherent Precipitates (: salt is dissol9ed in water in increasing amo nts a sat rated sol tion is ltimately :ormed and no more salt will dissol9e at that tem5erat re. As the tem5erat re is raised the sol tion !ecomes nsat rated and so more salt will dissol9e ntil sat ration is again reached. ;hen the tem5erat re is allowed to :all the sol tion tends to !ecome s 5er=sat rated so that solid salt is 5reci5itated :rom the sol tion as small crystals.

>.1.0.$ A similar relationshi5 s ally 5re9ails in metallic solid sol tions in cases where sol !ility is limited. ,hat is, the solid sol !ility o: one metal in the other increases as the tem5erat re rises (#ig. >.$$). (:, howe9er, the tem5erat re is allowed to :all ? ic8ly, 5reci5itation cannot occ r as easily as in the case o: li? id sol tions since di:: sion in solids is 9ery slow as com5ared with li? ids. Conse? ently a s 5ersat rated solid sol tion may !e retained at room tem5erat re. ,his s 5ersat rated solid sol tion will not !e in a state o: e? ili!ri m and the tendency :or the sol te to 5reci5itate will remain. ;hether or not 5reci5itation does occ r will de5end 5on the degree o: thermo dynamical im!alance in the system. (n many cases the s 5ersat rated solid sol tion will !e retained com5letely and inde:initely whilst in others the sol te will se5arate o t as isolated 5articles 9isi!le at high magni:ications nder the microsco5e. ,here is, howe9er, an intermediate stage, where, !y means o: di:: sion, sol te atoms !egin to congregate into gro 5s so that their concentration in some regions is greater than it was initially (#ig. >.$0). Ne9ertheless they still occ 5y 5ositions within the lattice o: the 5arent metal and the lattice is still contin o s or coherent, al!eit distorted !y the 5resence o: the high

concentration o: sol te atoms. S ch an arrangement o: sol te atoms is termed a coherent 5reci5itate and is 8nown to ha9e a considera!le strengthening e::ect on the str ct re 5res ma!ly !eca se it will o55ose the mo9ement o: dislocations. >.1.0.0 (: 5reci5itation contin es the sol te atoms ltimately lea9e the lattice o: the 5arent metal to :orm their own 5artic lar lattice 5attern. Since this lattice does not BmatchB that o: the 5arent metal the str ct res are no longer coherent so that a grain !o ndary :orms !etween the 5reci5itated 5article and the BmotherB solid sol tion (#ig. >.$0(i9)). ,h s a non=coherent 5reci5itate( Some writers descri!e these as Bincoherent 5reci5itatesB.) is 5rod ced and will !e o!ser9ed as se5arate .

small crystals, e9en tho gh they are so small as to re? ire an electron microsco5e to render them 9isi!le. ;hen non=coherent 5reci5itates ha9e !een :ormed the strength o: the alloy :alls

considera!ly since large n m!ers o: sol te atoms ha9e !een lost :rom the initial solid sol tion. Dislocations will there:ore !e a!le to mo9e more easily. (n #ig. >.$0(i9) the non=coherent 5reci5itate has !een de5icted, :or the sa8e o: sim5licity , as !eing o: a 5 re element. (n 5ractice it is m ch more li8ely to !e either an intermetallic com5o nd or another solid sol tion. ,hat is, it will ta8e with it some atoms o: the 5arent metal to 5rod ce a crystal str ct re which is not coherent with that o: the original solid sol tion.

Solid Sol"tions in !on1metallic )aterials

4 ( Solid sol tions are :ormed in many ionic com5o nds. ,h s mi<ed crystals can !e grown in9ol9ing those inorganic salts which ha9e geometrically similar crystal :orms. S ch salts are said to !e isomor.hous and are ty5i:ied !y the gro 5 8nown as Bal msB. ,hese are do !le s l5hates o: sodi m, 5otassi m, al mini m and ammoni m. Howe9er, not all ionic solid sol tions are deri9ed :rom isomor5ho s salts. ,h s nic8el o<ide, Ni), and magnesi m o<ide, Mg), dissol9e in each other in all 5ro5ortions in the solid state whilst sil9er !romide and sil9er iodide, tho gh o: 9ery di::erent crystal str ct res will ne9ertheless :orm solid sol tions. +artial solid sol !ility is common with ionic com5o nds as it is with metallic solid sol tions. 4 ( 1 Altho gh organic 5olymers are not necessarily crystalline in :orm an analogy can !e drawn !etween co=5olymers ($0.0.$) and metallic solid sol tions. (n these co=5olymers di::erent BmersB ($0.$./) are lin8ed together !y co9alent !onds which corres5ond to the :ree electron !onds in metallic solid sol tions. By sing di::erent mers to ! ild 5 a 5olymer chain materials o: modi:ied mechanical 5ro5erties can !e 5rod ced. ,he e<tremely to gh 5lastics material ABS=a co=5olymer o: acrylonitrile, ! tadiene and styrene mers=is s ch a s !stance. ;hilst these co=5olymers are not

solid sol tionsB the se o: di::erent mers in the 5olymer chain modi:ies the 5ro5erties as does the introd ction o: sol te atoms into a d ctile metal.

+ntermediate Phases
4 4 ,hese are 5hases which in general ha9e di::erent lattice str ct res :rom those o: the 5arent metals and are :ormed in the intermediate ranges o: com5osition. Se9eral di::erent :orms o: intermediate 5hase occ r. 4 4 1 Secondar& Solid Sol"tions Sometimes solid sol tions are :ormed in intermediate ranges o: com5osition which do not incl de the 5 re metals as com5onents. Eenerally they ha9e crystal 5atterns which are di::erent :rom those o: the com5onent metals and are termed secondary solid sol tions. E<ce5t that the range o: com5ositions does not incl de one o: the 5 re metals, the secondary solid sol tion is not otherwise 9ery di::erent in 5ro5erties :rom ordinary 5rimary solid sol tions. (n some secondary solid sol tions the distri! tion o: atoms amongst the a9aila!le sites :ollows a disordered arrangement with a :airly wide range o: sol !ility. (n others, the atoms are in an ordered 5attern and in some res5ects resem!le intermetallic com5o nds more than disordered secondary solid sol tions. 4 4 # SiCe1factor Compo"nds are those in which com5osition and crystal str ct re ad3 st themsel9es in order to 5ermit com5onent atoms to 5ac8 themsel9es together in a coherent 5attern. ,his state o: a::airs is ty5i:ied !y the -a9es 5hases in which the general com5osition is !ased on the :orm la AB0, e.g. MgCF0 (c !ic)M MgOn0 and MgNi0 (!oth he<agonal). ,hese com5o nds :orm mainly !eca se o: a s !stantial di::erence in si7e !etween the com5onent atoms. ,his si7e di::erence is o: the order o: /4R and allows the com5onent atoms to 5ac8 together in a crystal 5attern o: higher coordination n m!er (/.6.1) than the ma<im m (twel9e) which is 5ossi!le in lattices o: close=5ac8ed e? al s5heres. (n thi,M :orm la AB0 eachB A B atom has si<teen

neigh!ors (.A W $0B) whilst each BBB atom has twel9e neigh!ors (6A W 6B), gi9ing an a9erage coordination n m!er o: $/.//. ,hese high coordination n m!ers are made 5ossi!le !y the 5resence o: the :ree=electron !ond in metallic str ct res. 4 4 $ +ntermetallic Compo"nds ,hese :all into two se5arate gro 5s. >.>./.$ /alency Com.ounds ;hen one metal is 9ery strongly electro= 5ositi9e and the other only wea8ly electro5ositi9e they may com!ine to :orm a com5o nd in which the ordinary r les o: chemical 9alency a55ly. ,h s, the strongly electro5ositi9e metals, towards the le:t=hand side o: the +eriodic ,a!le, :orm com5o nds s ch as these with the 9ery wea8ly electro5ositi9e metals ad3acent to the non=metals on the right=hand side o: the ,a!le, e.g. Mg /S!0, Mg0Sn and Mg0+!. (n these com5o nds the range o: sol !ility o: any e<cess metal is generally 9ery small and o:ten they ha9e sim5le lattice str ct res li8e ionic crystals (/.0.0). Sometimes s ch a com5o nd is so sta!le that it will ha9e a higher melting 5oint than either o: its 5arent metals. ,h s Mg0Sn melts at >&4ZC whereas the 5 re 5arent metals magnesi m and tin melt at 614ZC and 0/0ZC res5ecti9ely. ,hese a55ear to !e tr e chemical com5o nds whereas the other intermediate 5hases mentioned here are 9irt ally transitional !etween these com5o nds and 5rimary solid sol tions since in all other cases atoms are held in 5osition !y the :ree electrons o: the metallic !ond. >.>./.0 2"lectron Com.ounds2 or H me=Rothery com5o nds=in which the normal 9alency laws are not o!ser9ed ! t in which there is o:ten a :i<ed ratio !etween the total n m!er o: 9alency electrons o: all the atoms in9ol9ed and the total n m!er o: atoms in the Bmolec lar :orm laB o: the intermetallic com5o nd in ? estion. ,here are three s ch ratiosD

,h s in the com5o nd C On the co55er atom 5ro9ides one 9alency electron whilst the 7inc atom 5ro9ides two, gi9ing a total o: three 9alency electrons to two atoms, i.e. a ratio o: /20. Similarly in the com5o nd C /$Sn&, each co55er atom contri! tes one electron and each tin atom :o r electrons. Hence /$ electrons are contri! ted !y co55er and /0 (. < &)!y tin ma8ing a total o: 6/ electrons. Altogether /% atoms are in9ol9ed in the molec lar :orm la C KlSn&. Hence the ratio is 6/2/% or 0$2$/. ,hese H me=Rothery ratios ha9e !een se: l in relating str ct res which a55arently had little else in common. 4 4 % (n general intermetallic com5o nds are less se: l as a !asis :or engineering alloys than are solid sol tions. (n 5artic lar intermetallic com5o nds are s ally 9ery hard and !rittle, ha9ing negligi!le strength or d ctility. ):ten the com5o nd has none o: the 5hysical characteristics o: its 5arent metals. ,h s C KlSn& is a 5ale !l e 5hase as seen nder the microsco5e, and a small ingot o: it will cr m!le to 5owder nder ? ite gentle 5ress re in the 3aws o: a 9ice. ,he ne<5ected colo r is d e to the di::erent lattice characteristics as com5ared with those o: the 5arent metals. Since intermetallic com5o nds are o: :i<ed com5ositions, and will generally dissol9e only small amo nts o: their 5arent metals, they do not e<hi!it coring when 9iewed nder the microsco5e. ,his :act=and, o:ten, n s al colo r=hel5s to identi:y them microsco5ically. Moreo9er the lac8 o: 9aria!ility in com5osition im5osed !y the :ormation o: com5o nds gi9es a 5ossi!le e<5lanation o: the !rittleness o: these materials. Beca se crystals o: :i<ed com5osition are :ormed there are no amor5ho s regions at the grain !o ndaries and hence a lac8 o: grain=!o ndary cohesion (/.>./). ,h s the com5o nd Ni/A( has an ordered #CC str ct re so

that whilst a single crystal o: Ni/A( is e<tremely d ctile a 5olycrystalline mass o: Ni/Al is 9ery !rittle and :ails along the grain !o ndaries. ,his can !e o9ercome !y adding 4.41R !oron which raises the R elongation :rom 4 to o9er 14R. ,his is 5ossi!ly d e to the o!ser9ed segregation o: !oron at the grain !o ndaries ca sing disorder there and allowing the 5ile= 5 o: dislocations to !e relie9ed !y sli5 across !o ndaries rather than !y crac8ingM 4 4 ' 'ery o:ten, small amo nts o: these intermetallic com5o nds are 5resent as essential 5hases in engineering alloys. #or e<am5le, a !earing metal m st !e hard and wear=resistant whilst at the same time !e to gh and d ctile. ,hese are di9erse 5ro5erties not to !e enco ntered in a single= 5hase alloy since, whilst 5rimary solid sol tions are to gh and d ctile they are relati9ely so:t and do not resist wear and, on the other hand, whilst intermetallic com5o nds are hard and wear=resistant with a low coe::icient o: :riction, they are wea8 and !rittle. ,he metall rgist, howe9er, :orm lates an alloy which will contain small isolated 5articles o: intermetallic com5o nd held :irmly in a to gh d ctile matri< o: solid sol tion. ,he latter wears lea9ing the 5articles o: intermetallic com5o nd standing 5ro d so that they carry the load at a 9ery low coe::icient o: :riction. ,h s !earing !ron7es ($4=$1R Sn) contain 5articles o: C K$Sng em!edded in a matri< o: 5rimary solid sol tion a. ($$.>.0). Similarly BwhiteB !earing metals (Ba!!itts) contain crystals o: the intermetallic com5o nd S!Sn em!edded in a matri< o: antimony=tin solid sol tion ($$.>.$). (t was mentioned earlier that some o: these com5o nds ha9e higher melting 5oints than their 5arent metals. ,h s NiA( melts at $6.4ZC and is !eing sed as a coating :or t r!ine !lades since, in addition to this high melting 5oint, the :ilm o: A(0)/ which :orms on the s r:ace acts as a !arrier ($%.0.$) to : rther o<idation. >.>.6 +nterstitial Compo"nds :ormed when the sol !ility o: an interstitially dissol9ed element (>.0..) is e<ceeded. ,hen, an intermediate 5hase is 5reci5itated in which the :ormer sol te atoms

are again held in interstitial 5ositions, ! t now in a com5o nd o:ten o: more com5le< crystal str ct re. ,h s, nder normal conditions, BCC iron will hold no more than 4.40R car!on in interstitial solid sol tion and when this amo nt is e<ceeded the interstitial com5o nd #e/C (Cementite) is 5reci5itated. ,hese interstitial com5o nds are generally the car!ides, nitrides, hydrides and !orides o: the transition metals, e.g. ,aC, ,iN, ,iH 0, ;0C and .;C. Most o: them ha9e metallic 5ro5erties. ,hey incl de the hardest and most re:ractory o: s !stances with melting 5oints as high as /144ZC (N!C) and /&44ZC (,aC). Some o: the car!ides are e<tremely im5ortant and :orm the !asis o: high=s5eed c tting tools (;C, ;0C, ,iC, MoC and ,aC) ($4...$). Since many o: these interstitial com5o nds are strong at high tem5erat res they are sed in a :inely=dis5ersed :orm to strengthen many heat= resisting steels ($4.1.0) and alloys ($$.1.0).

Po,der )etall"rg&
4 5 (t is sometimes desira!le to ma8e an BalloyB o: two metals which are either com5letely or 5artially insol !le in each other (n !oth the solid and li? id states. ,his is the oil=water conce5t mentioned earlier. )!9io sly any attem5t to ma8e an alloy !y the s al 5roced re o: melting and casting will :ail since the two metals will :orm se5arate layers d ring the : sion 5rocess. A wide dis5ersion o: the two metals can !e 5rod ced howe9er !y mi<ing them thoro ghly as e<tremely :ine 5owders. ,he 5owder mi<t re is then Bcom5actedB in a closed die sing a 5ress re which 9aries !etween ..4 and &44 N2mm0 de5ending 5on the strength and d ctility o: the materials !eing sed. A:ter s ch treatment the com5acted sha5e is strong eno gh to 5ermit handling since some adhesion will ha9e ta8en 5lace !etween indi9id al 5articles 5ro9iding that their s r:aces are clean and no<idised. Metal=to= metal contact nder high 5ress re a55arently leads to some degree o: Bcold=weldingB !etween sliding ad3acent s r:aces.

4 5 1 ,he com5act is then BsinteredB, that is, heated to some tem5erat re generally !elow the melting 5oints o: !oth metals (! t sometimes a!o9e that o: one o: them as in the case o: sintered= !ron7e !earings where the tin 5owder melts and in:iltrates the co55er 5articles). ,his treatment 5rod ces a mechanically strong material as the 5articles !ond together across the inter:ace where only limited adhesion was e::ected !y com5acting. (n some cases this !onding is 5ro!a!ly d e to grain=growth across the cold= wor8ed inter:aces ! t it is more generally agreed that di:: sion is the 5rinci5al mechanism !y which s r:aces 8nit together. 4 5 # (nitially, 5owder metall rgy was sed to 5rod ce ingots o: re:ractory metals li8e 5latin m and t ngsten which ha9e s ch high melting 5oints that they cannot !e melted con9eniently. -ater the 5rocess was sed as a means o: BalloyingB metals, which, as mentioned a!o9e, do not dissol9e in each other in the li? id state. ,he controlled degree o: 5orosity 5ossi!le with com5acted 5owders is also tili7ed in s ch com5onents as stainless steel :ilters :or corrosi9e li? ids, and, o: co rse, oil=less !ron7e !earings.Fse: l low=cost oil=less !earings can also !e made :rom mi<t res o: co55er and iron 5owders since these two metals are only 5artially sol !le in each other in either the li? id or solid states.As the relati9e costs o: metallic 5owders contin e to :all, 5owdermetall rgy will !e sed more and more as a standard 5rod ction method. ,he negligi!le amo nt o: 5rocess scra5 as com5ared with casting o5erations will ma8e the method com5etiti9e :or ses other than the rather s5eciali7ed ones o tlined a!o9e.

5 +hase E? ili!ri m
&.$ (n a st dy o: metallic alloys, or indeed other materials which contain more than one com5onent, a most im5ortant conce5t is that concerning the term B5haseB. A 5hase can !e de:ined as a homogeneo s !ody o: matter e<isting in some 5rescri!ed 5hysical :orm. ,h s the chemical s !stance water, H0), can e<ist in three di::erent 5hase :orms=solid, li? id and 9a5o rM whilst 5 re iron can e<ist as :o r di::erent 5hases (,a!le &.$). (Note that there are only two di::erent solid 5hases in iron since l and m are identical. ,he terms l and m are only sed to di::erentiate !etween. ,he tem5erat re ranges o9er which BCC iron can e<ist.)

&.$.$ Many solid s !stances are m lti5hase in character. #or e<am5le, ordinary concrete contains cement, sand and aggregate as identi:ia!le 5hases in the str ct re whilst, on the microsco5ical scale, the str ct re o: steel consists o: two 5hases=a solid sol tion we call :errite, and iron car!ide, #e/C. ,he 9ario s ty5es o: 5hase li8ely to !e enco ntered in metallic alloys were disc ssed in Cha5ter Se9en. ,hese 5hases can !e either 5 re metals, intermetallic com5o nds or solid sol tions :or, des5ite the e::ects o: coring, a solid sol tion is a single contin o s 5hase which will

!ecome homogeneo s i: it is allowed to reach thermodynamic e? ili!ri m !y a 5rocess o: di:: sion. (n any m lti5hase str ct re two 5hases ha9e a common !o ndary se5arating them. ,h s, a dro5 o: oil 5laced in water shares a common 5hase !o ndary with the water which s rro nds it.

The Thermod&namic Basis of Phase EE"ili*ri"m

5 # ,he entire st dy o: 5hase e? ili!ri m is de5endent 5on the : ndamental laws o: thermodynamics. ;hilst a com5rehensi9e treatment o: the disci5line cannot !e nderta8en here an nderstanding o: some o: the terms in9ol9ed will !e se: l. *nowledge o: the energy content o: a 5hase is necessary to a st dy o: 5hase relationshi5s. Altho gh this energy content may !e e<5ressed in a n m!er o: ways it is 5erha5s most easily de:ined in terms o: the internal energy, E. ,his com5rises the thermal energy o: the !ody together with 9i!rational energy, electronic energy and other :orms which may !e internally stored in the str ct re o: the !ody 5 # 1 ,he 8inetic theory o: gases 5roclaims that the constit ent 5articles( Either atoms or molec les de5ending 5on the nat re or= the gas,) are in a state o: constant motion and that the 5ress re e<erted !y a gas is d e to the res ltant changes in moment m arising :rom the s m o: im5acts which these 5articles ma8e with the walls o: the container. (: heat energy is s 55lied to the system this is stored. since energy is conser9ed, as an increase in the 8inetic energy o: the 5articles. Ne9ertheless the 8inetic energy o: the 5articles is not the only energy 5ossessed !y the gas. Consider a ? antity o: gas enclosed in a container !y means o: a mass=less, :riction=less 5iston (#ig. &.$). (: e<ternal heat energy is s 55lied to the gas then it will e<5and and the 5iston will !e raised so that the 5ress re !oth inside and o tside the container remains constant. Since the 9ol me o: the gas increases and mo9es the 5iston against atmos5heric 5ress re, wor8 will !e done ,his wor8 will !e e? al to

the 5rod ct o: the total :orce acting on the end o: the 5iston and the distance thro gh which it mo9es, i.e. ;or8 done !y e<5anding gas P +.A. P +. 'B (where the 9ol me, ' P A. -)

,h s the heat s 55lied to the gas nor only raises its tem5erat re ! t also does wor8 e? i9alent to +'. Hence the total energy s 55lied is E W +' where E is the increase in internal energy. (: we now consider the 5rocess o5erating in re9erse so that energy is stored in the gas this energy will !e a9aila!le s !se? ently. # rther i: we imagine that this re9erse 5rocess ends when !oth 9ol me and internal energy a55roach 7ero then the total stored energy is gi9en !yD HPEW+' ,his total stored energy is called the enthal5y (H). 5 # # ,he #irst -aw o: ,hermodynamics deals essentially with the conser9ation o: either internal energy or o: enthal5y de5ending 5on how the -aw is a55lied. ;hen we consider an isolated ? antity o: a s !stance in a closed system only internal energy is in9ol9ed ! t when the mass o: the s !stance we are dealing with is allowed to 9ary, that is, enter or lea9e the system then enthal5y is in9ol9ed.

. 5 # $ ,he Second -aw o: ,hermodynamics deals with the conser9ation o: another thermodynamically ? antity 8nown as entro5y, S. Entro5y is associated with the degree o: BrandomnessB or disorder o: the 5articles constit ting mass o: matter. ,he greater the degree o: disorder the greater the entro5y, the more 5recise the order the lower the entro5y. ,h s when a metal melts its atoms 5ass :rom a state o: order to one o: relati9e disorder and the entro5y increases. ;hilst most materials e<5and slightly as they melt a :ew, s ch as antimony, !ism th and ice, shrin8 slightly. ,h s entro5y is not connected with 9ol me change and the term +' is not in9ol9ed. ;e can concl de there:ore that latent heat s 55lied in melting a solid is stored in the degree o: disorder which is 5rod ced. ,his stored energy howe9er is not a9aila!le :or doing wor8 and is re:erred to as Btrans:ormation energyB or Bentro5y energyB. (t can !e e<5ressed as the 5rod ct o: tem5erat re (,) and the entro5y (S). Beca se the li? id 5hase which is 5rod ced contains non=a9aila!le energy this m st !e s !tracted :rom the total energy=or enthal5y (H)=in order to deri9e the amo nt o: energy a9aila!le :or doing wor8. ,h s the :ree energy (E) can !e deri9ed :romD EPH=,.S PEW+'=,S ,he ? antity ,S re5resents the energy which is B!o nd 5B in the solid. ,he :ree energy (E) is at a minim m when the system is in e? ili!ri m. (t is this thermodynamic ? antity, which !ecomes im5ortant in st dying 5hase relationshi5s. Since :ree energy incor5orates !oth the thermal energy content o: a material thro gh H and the degree o: order (or disorder) o: the material thro gh S it de:ines the nat re o: the material a!sol tely.

Phase EE"ili*ri"m of Single S"*stances

5 $ ,he 5henomenon o: 9a5o r condensation has already !een mentioned in terms o: the relationshi5 !etween the 8inetic energy

o: 5articles and 9an der ;aals :orces o5erating !etween them. As a 9a5o r is cooled the a9erage 8inetic energy o: its 5articles decreases. Fltimately a tem5erat re is reached where the 8inetic energy o: most o: the 5articles is ins ::icient to resist the 9an der ;aals :orces acting !etween them. ,hose 5articles with less than a9erage 8inetic energy stic8 together, that is, condense to :orm dro5lets o: the li? id 5hase. ,he tem5erat re at which this condensation !egins is o:ten re:erred to as the dew 5oint o: the 9a5o r. 5 $ 1 As : rther 8inetic energy is dissi5ated 5articles condense in increasing n m!ers. ,his occ rs at a constant tem5erat re, the 8inetic energy !eing gi9en 5 in the :orm o: heat energy (the latent heat o: 9a5ori7ation). Some o: the 5articles with 8inetic energy greater than the a9erage do not condense ! t are a!le to remain in the 9a5o r 5hase, this state o: a::airs o!taining when these remaining 5articles e<ert a 5ress re e? al to that o: the 5re9ailing am!ient 5ress re. )nce the ma3ority o: the 5articles ha9e condensed the tem5erat re !egins to :all again as : rther heat is withdrawn :rom the system and : rther condensation o: some o: the remaining 9a5o r 5articles occ rs. ,he 5rocess is ill strated !y the cooling c r9e :or water (#ig. &.0) in which the condensing 5articles will !e molec les o: H0).

,his 5rocess is o: co rse re9ersi!le. (: the li? id is heated the :irst

! !!les o: 9a5o r wo ld a55ear at the tem5erat re , c. # rther addition o: heat the latent heat o: 9a5orisation=wo (d ca se the li? id to contin e to 9a5orise isothermally. ntil all o: the li? id had !een 9a5orised. (: heat contin es to !e 5assed into the system the 9a5o r tem5erat re will rise and the 8inetic energy o: its molec les will increase. ,he tem5erat re at which ! !!les !egin to a55ear is 8nown as the ! !!le 5oint. #or a 5 re s !stance !oth dew 5oint and ! !!le 5oint are at the same tem5erat re which is re:erred to generally as the !oiling 5oint. 5 $ # At the tem5erat re , c !oth water and water 9a5o r can e<ist together and i: the :low o: heat to or :rom the system is sto55ed then the relati9e amo nts o: the two 5hases will remain constant. ,his is o!9io s since heat m st :low into the system in order to 5ro9ide energy to o9ercome the 9an der ;aals :orces and to se5arate one molec le :rom another. Con9ersely, to condense more 9a5o r the 8inetic energy o: molec les m st !e red ced, !y e<tracting heat energy, in order that 9an der ;aals :orces can o9ercome the red ced 8inetic energy and so o5erate !etween molec les to !ind them together. Altho gh the relati9e amo nts o: the two 5hases remain constant as long as energy neither enters nor lea9es the system, a state o: dynamic e? ili!ri m e<ists. ,hose 9a5o r molec les o: higher energy gi9e 5 their 8inetic energy and condense i: they stri8e the s r:ace o: the li? id. Since this energy cannot esca5e :rom the system it increases the energy le9el o: the neigh!oring molec les in thek li? id 5hase so that they are li8ely to o9ercome the 9an der ;aals :orces o5erating !etween them. Hence as they ac? ire s ::icient 8inetic energy they 3oin the 9a5o r 5hase. ,h s a small=scale dynamic e? ili!ri m e<ists !etween the condensing molec les :rom the 9a5o r and the 9a5ori7ing molec les :rom the li? id. Since the 5ro5ortions o: the 5hases remain constant the rates o: condensation and 9a5ori7ation m st remain e? al. ,his state o: a::airs constit tes the !asis o: 5hase e? ili!ri m. ,he 9a5o r 5hase is in e? ili!ri m with the li? id 5hase so that thermodynamically the :ree energies o: the two 5hases are e? al.

,he dynamic !alance corres5onds to a !alance !etween changes in enthal5y and entro5y. (n the a!o9e it has !een ass med that 5ress re remained constant (at>64 mmHg) and that only tem5erat re was altered. (: the 5ress re also were altered then the e? ili!ri m o: the system wo ld !e 5set. Since enthal5y wo ld change the relati9e ? antities o: the two 5hases 5resent wo ld also change ntil e? ili!ri m was once more esta!lished. 5 $ $ A state o: e? ili!ri m will e<ist !etween the li? id and 9a5o r 5hases at tem5erat res other than the normalQ(,he !oiling 5oint at Batmos5heric 5ress reB (>64 mmHg)). !oiling 5oint. At a tem5erat re !elow the !oiling 5oint the li? id e<erts a 9a5o r 5ress re in the s5ace a!o9e it !eca se the 9a5o r molec les are in dynamic e? ili!ri m with it. (: the o9erall 5ress re to which the li? id 5hase is s !3ected is red ced to the 9a5o r 5ress re at any gi9en tem5erat re, the li? id will !egin to !oil. #or this reason it is im5ossi!le to ma8e a decent c 5 o: tea on Mo nt E9erest. At high altit des the atmos5heric 5ress re is so low that water !oils at tem5erat res well !elow $44ZC and cannot o: co rse !e raised to a higher tem5erat re.

Phase -iagrams

5 %. ,he relationshi5 !etween tem5erat re, 5ress re and the 5hases in which 5 re water e<ists is shown in the sim5le 5hase diagram, #ig. &./. Q ,he !oiling 5oint at Batmos5heric 5ress reB (>64 mmHg).

Fig 5 $ ,he +2, 5hase diagram :or 5 re water. Fsing this diagram we can, :or any gi9en com!ination o: tem5erat re and 5ress re, :ind in what 5hase state BH 0)B e<ists, and also determine what e::ect any alterations o: tem5erat re and 5ress re will ha9e on the sta!ility o: a gi9en 5hase. #or e<am5le the B: sion c r9eB is an almost 9ertical line indicating that 5ress re 9ariations ha9e little e::ect on the :ree7ing tem5erat re o: water. ,he same is tr e o: the :ree7ing 5oints o: metals, :or which reason we can generally neglect the e::ects o: 5ress re in o r st dies o: alloy 5hase e? ili!ri m. 5 % 1 ,he B9a5orisation c r9eB, howe9er, indicates that the !oiling 5oint o: water is 9ery de5endent 5on 5ress re, ;ater !oils at $44ZC at a 5ress re o: >64 mmHg (5oint B), (ncrease in 5ress re a!o9e >64 mmHg will raise the !oiling 5oint, whilst red ction !elow >64 mmHg will considera!ly lower it, ,he Bs !limation c r9eB indicates that at low 5ress res solid ice can 9a5orise=or

su,lime-witho t 5assing thro gh the li? id 5hase, A n m!er o: s !stances, nota!ly car!on dio<ide (Bdry iceB) and solid iodine, s !lime at ordinary atmos5heric 5ress res. b9c Ahat ,ill *e the appro/imate *oiling point of ,ater at the
Mo nt E9erest Base Cam5 i: the !arometric 5ress re there is e? i9alent to /&4 mm o:, merc ryJ

bAc

By re:erence to the Bwater 9a5orisationB c r9e (#ig. &./) we see that at a 5ress re o: /&4 mmHg the corres5onding water 9a5orisation tem5erat re (i.e, the !oiling 5oint) is a55ro<imately 6/ 4c.

5 % # +ossi!ly the most interesting :eat re o: this sim5le 5hase diagram is the tri.le .oint, ,, at which water can e<ist in the solid, li? id and 9a5o r :orms sim ltaneo sly. ,his 5oint , re5resents a 5ress re o: ..1>% mmHg and a tem5erat re o: ).))%&ZC and only nder these 5recise conditions o: tem5erat re and 5ress re can the three 5hases co=e<ist. Any 9ariation in either tem5erat re or 5ress re will ca se at least one o: the 5hases to disa55ear. ,he tri5le 5oint in 5hase e? ili!ri m is o: co rse not con:ined to water only. #or e<am5le, solid li? id and gaseo s hydrogen can co=e<ist at =01%.0ZC and 1..$ mmHg.

The Phase R"le

5 ' #irst it will !e necessary to de:ine more 5recisely some o: the terms sed in connection with 5hase e? ili!ri m. ,h s the whole aggregate o: di::erent !odies with which we are dealing is

descri!ed as a system! (: this system is com5letely ni:orm thro gho t, ha9ing the same com5osition and 5ro5erties at any 5oint, it is said to !e homogeneous! Either ice, water or water 9a5o r e<isting se5arately wo ld re5resent s ch a system. (:, howe9er, the system consists o: two or more di::erent 5arts, each o: which is homogeneo s in itsel: ! t whose 5ro5erties di::er :rom those o: the other 5arts, then the system is said to !e heterogeneous! Hence, at the tri5le 5oint, , (#ig. &./), ice, water and water 9a5o r e<isting together constit te a heterogeneous three-.hase system! At any 5oint on the c r9e ,B two 5hases can co=e<ist, 9i7. water and water 9a5o r, so that the com5lete system is heterogeneo s and two 5hase. +oint A re5resents a single homogeneo s 5hase, water 9a5o r. 5 ' 1 A general law dealing with 5hase e? ili!ri m was de9elo5ed in $&>6=>& !y Kosiah ;illard Ei!!s, 5ro:essor o: mathematical 5hysics at Iale. *nown as the %hase Bule it can !e o: considera!le se in sol9ing some o: the more di::ic lt 5ro!lems o: 5hase e? ili!ri m. S 55ose we again consider 5oint A in #ig. &./. ,his indicates that at a tem5erat re o: a55ro<imately $$4ZC and a 5ress re o: .14 mmHg the chemical com5o nd, H0), e<ists as a homogeneo s single 5hase, water 9a5o r. ;e can alter ,oth tem.erature and .ressure 4uite inde.endently (within limits) witho t altering the nat re o: the system which will remain a homogeneo s single 5hase. ,h s a system o: this ty5e can !e said to 5ossess two degrees of freedom or to !e ,i+ariant! ,he same conditions o: co rse a55ly to ice and water when they e<ist as single 5hases !y themsel9es. ,he term Bdegree o: :reedomB (or +ariance) descri!es any 9aria!le 5ro5erty s ch as tem5erat re, 5ress re, 9ol me or other 9al es which are interrelated in the system. +oint B on #ig. &./ re5resents the tem5erat re ($44ZC) at which water !oils nder normal atmos5heric 5ress re (>64 mmHg).

,h s at that 5oint two 5hases can co=e<ist, 9i7. water and water 9a5o r. Howe9er, the n m!er o: degrees o: :reedom ha9e now !een red ced to one since we can only 9ary either tem5erat re or 5ress re. ,hat is, the new tem5erat re (or 5ress re) m st !e re5resented !y a 5oint on the 9a5orisation c r9e otherwise one o: the 5hases will disa55ear (either the 9a5o r 5hase will condense i: we mo9e to a 5oint on the le:t o: the c r9eM or the li? id 5hase will 9a5orise i: we mo9e to a 5oint on the right o: the c r9e). Conse? ently i:, :or the sa8e o: arg ment, we raise or lower the tem5erat re then the 5ress re m st !e raised or lowered in sym.athy with it. Hence we ha9e only one degree o: :reedom since in this case 5ress re is tied to tem5erat re and cannot !e 9aried inde5endently witho t the disa55earance o: one or other o: the two 5hases. S ch a system is uni+ariant! At 5oint , on #ig. &./ all three 5hases, ice, water and water 9a5o r, can e<ist together ! t clearly i: we alter either tem5erat re or 5ress re then at least one o: the 5hases will disa55ear. Conse? ently in this three=5hase system there are no degrees o: :reedom and it is said to !e non+ariant! 5 ' # (: the n m!er o: degrees o: :reedom are re5resented !y f and the n m!er o: 5hases !y ., then the 5henomena descri!e a!o9e can !e related !y a single r leD fH. P / ($) ,h s in a single=5hase system s ch as a solid 5 re metal, f5 0, i.e. there are two degrees o: :reedom whilst at the melting 5oint (where . P 0) then f5 $, and the system is ni9ariant. (: three 5hases=solid, li? id and 9a5o r=are 5resent at the same time then no degrees o: :reedom remain and at least one o: the 5hases will disa55ear i: either tem5erat re or 5ress re are altered. (n an alloy containing two metals, melting occ rs. o9er a range o: tem5erat res rather than at a single, :i<ed tem5erat re. ,h s, two 5hases (li? id and solid) can !e 5resent o9er a range o: tem5erat res instead o: at a single tem5erat re. Altho gh two

5hases are 5resent we are a!le to 9ary tem5erat re and 5ress re inde.endently witho t a loss o: e? ili!ri m so that there are two degrees o: :reedom. ;e can now ma8e a55ro5riate alterations to e? ation ($)D fH. P . (0) ,his e? ation can !e written in the general :ormD fH.5nH6 (/) where n is the n m!er o: com.onents in the system. As :ar as metallic alloy systems are concerned the term Bcom5onentB signi:ies a 5 re metal. ,h s an alloy containing two metals is a two=com5onent system. (n 5ractice we o:ten deal with com5onents which are not elements. #or e<am5le, in the system, ice=salt=sol tion, the com5onents are, e::ecti9ely, salt and water !oth o: which are chemical com5o nds. 5 ' $ Altho gh Ei!!Bs +hase R le as re5resented a!o9e !y (/) deals with the general case in which 5ress re constit tes one o: the degrees o: :reedom, a st dy o: metallic alloys does not normally in9ol9e a consideration o: the e::ects o: 5ress re. ;e are normally dealing only with li? id and solid 5hases and 5ress re 9ariation then has a negligi!le e::ect on their e? ili!ri m tem5erat re, generally e9en less in :act than it has on the slo5e o: the B: sion c r9eB in the ice=water=9a5o r system (#ig. &./). (: 5ress re is ass med to !e 8e5t constant the n m!er o: degrees o: :reedom :alls to one since one 5ossi!ility o: 9ariance has !een remo9ed :rom the system. At constant .ressure, there:ore, the +hase R le can !e e<5ressedD $H.5nHl (.)

5 ' % ,his modi:ication o: the +hase R le will !e generally se: l to s when we are st dying alloy systems at a constant atmos5heric 5ress re. A single=5hase molten alloy containing two metals=that is, two com5onents =in a ni:orm li? id sol tion in each other, can now !e e<amined sing the modi:ied R leD

fW$P0W$ .B. f 56 ,h s there are two degrees o: :reedom=one !eing tem5erat re and the other com5osition=so that, within certain limits, !oth tem5erat re and com5osition can !e 9aried inde5endently witho t introd cing a second 5hase into the system.

Phase EE"ili*ri"m in T,o1component S&stems

5 ( ,his constit tes !y :ar the most im5ortant gro 5 o: systems to !e st died since it incl des all !inary metallic alloys. ;e shall !egin, howe9er, !y considering a system in9ol9ing two li? ids which are only 5artially misci,le> in each other since a n m!er o: im5ortant :eat res can !e disc ssed in terms o: this system.
Q-iterally Bmi<a!le B==or in this case Bsol !leB.

5 ( 1 ,wo -i? ids which are (ncom5letely Misci!le in Each )ther #ig re &.. re5resents the 5hase=e? ili!ri m conditions :or the system lead=7inc in the li? id state a!o9e 144ZC. Diagrams o: this ty5e are commonly 8nown as thermal e4uili,rium diagrams, and indicate the relationshi5s which e<ist !etween tem5erat re, com5osition and 5hase constit tion in a two=com5onent system. ,he !ase line=or a,scissa-of the diagram always shows the com5osition 9arying !etween $44R o: one com5onent at one side o: the diagram and $44R o: the other com5onent at the o55osite end. (n most diagrams the 5ercentages are !y mass ! t in some cases it is more rele9ant to show the 5ercentages in terms o: the n m!ers o: atoms. ,he ordinate re5resents tem5erat re. ,h s, 5oint +

Fig 5 % ,he e? ili!ri m diagram :or lead and 7inc a!o9e 144ZC. (#ig. &..) re5resents a mi<t re consisting o: .1R !y mass o: lead and 11R !y mass o: 7inc at a tem5erat re o: 6)))C. At 144ZC molten 7inc will dissol9e a!o t 0R lead (5oint A) gi9ing a single sol tion which !ecomes sat rated at this amo nt o: 0R lead. At the same tem5erat re molten lead will dissol9e 5 to a!o t 1R 7inc (5oint B). Between these two limits gi9en !y A and B two se5arate molten layers will co=e<ist in the container. ,he 55er layer will consist o: molten 7inc saturated with lead (com5osition A) and the lower layer will consist o: molten lead sat rated with 7inc (com5osition B). ,he slo5e o: the line ADKC indicates that, as the tem5erat re rises, the sol !ility o: lead in molten 7inc increases. Similarly the slo5e o: BEC indicates that the sol !ility o: 7inc in molten lead also increases nder similar conditions. ,he two sol !ility c r9es meet in C at a tem5erat re o: >%&ZC indicating that a!o9e that tem5erat re the two com5onents, lead and 7inc,

!ecome com5letely sol !le in each other so that only one layer (5hase) will !e 5resent whate9er the com5osition o: the mi<t re as long as the tem5erat re remains a!o9e >%&ZC. S 55ose we ha9e a molten mi<t re consisting o: /4R lead and >4R 7inc (com5osition H). At, say, 144ZC this will consist o: a sat rated sol tion o: lead in 7inc (com5osition A=0R lead2%&R 7inc) together with a sat rated sol tion o: 7inc in lead (com5osition B=%1R lead21R 7inc). ,h s the mi<t re will consist o: two 5hases, i.e. two se5arate sat rated sol tions. (: the tem5erat re is now raised the amo nt o: lead which dissol9es in molten 7inc will increase (as will the amo nt o: 7inc which dissol9es in molten lead), ntil at K (>10ZC) the molten 7inc will ha9e a!sor!ed the whole /4R lead 5resent and so one 5hase disa55ears and a single homogeneo s sol tion remains. Now let s consider a mi<t re containing .1R lead 211R 7inc at 6))ZC, re5resented !y 5oint + (#ig. &..). Ass ming that the molten mi<t re has had time to reach e? ili!ri m at this tem5erat re=stirring will ha9e assisted this 5rocess=then !y drawing a Btem5erat re hori7ontalB thro gh 5 we are a!le to o!tain in:ormation :rom the diagram. ,his tem5erat re hori7ontal #D+EE, c ts the !o ndaries !etween the single= and do !le= 5hase :ields at D and E res5ecti9ely. Since the tem5erat res o: the 5hases in e? ili!ri m m st !e the same, then D and E m st re5resent the com5ositions o: the two 5hases in e? ili!ri m at that tem5erat re (644ZC). ,h s at 644ZC the li? id 5hase, D, contains &.1R lead2%$.1R 7inc (:rom (Dig. &..) whilst the other li? id 5hase, E, contains &&.1R lead $$.1R 7inc. #rom #ig. &.. we can also determine the 5recise 5ro5ortions in which each 5hase (com5ositions D and E res5ecti9ely) is 5resentD -et d, e and . !e the 5ro5ortions o: lead in the mi<t res o: com5ositions D, E and + res5ecti9ely.

,henD

,his is commonly 8nown as the Le+er Bule :or :airly o!9io s reasons (#ig. &.1). (: we imagine the tie line> DE (#ig. &..) to !e a le9er with its : lcr m at + (which is the com5osition o: the mi<t re as a whole), :rom e? ation ($)D (;eight o: 5hase o: com5osition D). D+ P (;eight o: 5hase o: com5osition E) .+E (0)

which is e? i9alent to Bta8ing momentsB o: the weights o: the two 5hases a!o t a : lcr m re5resenting the o9erall com5osition o: the mi<t re. 5 ( # Some 6eneral R"les For +nterpreting EE"ili*ri"m -iagrams #or the general inter5retation o: thermal e? ili!ri m diagrams, 5artic larly those dealing with metallic alloy systems, a n m!er o: r les were deri9ed :rom Ei!!Bs +hase R le !y the #rench metall rgist. A. +orte9in. Some o: these r les and de:initions may !e :o nd hel5: l. (i) ,he areas o: the diagram are s ally re:erred to as B5hase :ieldsB and on crossing any slo.ing !o ndary line :rom one :ield to the ne<t the n m!er o: 5hases will always change !y one. ,h s in #ig. &.6

two single=5hase :ields are se5arated !y a two=5hase :ield containing each o: the 5hases. (ii) (n a !inary system no 5hase :ield can contain more than two 5hases.,hree 5hases can co=e<ist only at a single 5oint s ch as a e tectic 5oint (#igs &.$0 and &.$/) (iii) At 5oint + (#ig. &.6) two 5hases can e<ist together. (: a tem5erat re hori7ontal is drawn thro gh + the com5osition o: one 5hase (in this instance a li? id) is gi9en !y - and the com5osition o: the other 5hase (in this case a solid) which is in e? ili!ri m with it, !y S. + re5resents the com5osition o: the alloy mi<t re as a whole.
(i9) ,he relati9e amo nts o: the two 5hases 5resent at the tem5erat re and com5osition re5resented !y + are gi9en !y the lengths -+ and +S res5ecti9elyD

,his is o: co rse the -e9er R le deri9ed a!o9e.

(9) A 5hase which does not occ 5y a :ield !y itsel: ! t a55ears only in a two=5hase :ield is either a 5 re metal (#ig. &.$/) or an intermetallic com5o nd o: in9aria!le com5osition (#ig. &.$&). ((n each case the B5hase :ieldB is in :act in:initely narrow, !eing a 9ertical line re5resenting the a55ro5riate :i<ed com5osition.) (9i) (: a 9ertical line re5resenting the o9erall com5osition, C, o: some alloy (#ig. &.>) crosses a slo5ing line o: the diagram it means that a

#ig . &.> change (n the n m!er o: 5hases will occ r at that 5oint ()), i.e. a 5hase will !e 5reci5itated or a!sor!ed. ,h s in #ig. &.> on raising the tem5erat re :rom ,$ to ,0 the 5hase H will !e a!sor!ed, whilst on cooling :rom ,0 to ,$ the 5hase H wo ld !e 5reci5itated. 5 ( $ T,o Components ,hich are Sol"*le in Each Bther in All Proportions in Both the LiE"id and Solid States Since this case is o: 5artic lar im5ortance in a st dy o: metallic alloys we shall deal here with a system in which !oth com5onents are metals and which :orm a series o: disordered s !stit tional solid sol tions in all 5ro5ortions (>.0..). Many 5airs o: metals :orm solid sol tions which are !asically o: this ty5e (>./.$). Since the co55er=nic8el alloys are o: commercial interest this system is sed as the e<am5le.

Fig 5 5 Cooling c r9es :or 5 re co55er, 5 re nic8el and a series o: intermediate alloys o: the two metals.

5 ( $ 1 ;hilst a 5 re metal :ree7es and melts at a constant single tem5erat re an alloy, with certain e<ce5tions (&.6...$), :ree7es and melts o9er a range o: tem5erat res. S 55ose we ma8e 5 a n m!er o: co55er2nic8el alloys o: di::erent com5ositions. ;e shall :ind that they solidi:y o9er di::erent tem5erat re ranges and !y 5lotting the cooling c r9es (#ig. &.&) we can determine the tem5erat res at which :ree7ing !egins and ends :or each alloy. ,his in:ormation can then !e sed to 5lot the 5hase e? ili!ri m diagram :or the com5lete system (#ig. &.%), ass ming, o: co rse, that each

#ig. &.% ,he 5hase e? ili!ri m diagram :or co55er and nic8el sing the salient 5oints o: the cooling c r9es :rom #ig. &.&.

alloy cooled slowly eno gh :or it to attain something a55roaching e? ili!ri m at each stage o: the cooling 5rocess. ,he res ltant 5hase diagram is one o: the most sim5le we enco nter in a st dy o: the e? ili!ri m systems o: metals. (t consists o: two lines only, the 55er=or li4uidus=a!o9e which any 5oint will re5resent in tem5erat re and com5osition a com5letely li? id 5hase, and the lower=or solidus= !elow which any 5oint will re5resent in tem5erat re and com5osition a com5letely solid 5hase. Between these two lines is a 5hase :ield in which !oth li? id and solid 5hases co=e<ist. A55lying the +hase R le (f W . P n W $) to the single=5hase :ields, !oth a!o9e the li? id s and !elow the solid s, we ha9eD or fH856H8 fP0

so that the system, !eing !i9ariant, !oth tem5erat re and com5osition can !e 9aried inde5endently within limits witho t any alteration in the str ct re ta8ing 5lace. (n the two=5hase :ield, !etween li? id s and solid sD or fH656H8 fP$

so that the system is ni9ariant and tem5erat re and com5osition can no longer !e altered inde5endently witho t a loss o: e? ili!ri m. Any change in tem5erat re m st !e accom5anied !y an a55ro5riate change in com5osition (and 9ice 9ersa) or !alance !etween the 5ro5ortions o: the 5hases 5resent will !e 5set. S 55ose we ha9e made 5 an alloy containing >4R nic8el and /4R co55er (H in #ig. &.$4). At tem5erat res a!o9e , this will e<ist as a homogeneo s li? id ! t as the tem5erat re :alls to ,, the li? id s tem5erat re o: this alloy, solidi:ication will !egin. (: we draw a tem5erat re hori7ontal thro gh H and , it c ts the solid s at I. I is there:ore the com5osition o: the solid 5hase which can e<ist in e? ili!ri m with the li? id 5hase o:

com5osition H at the tem5erat re ,. Conse? ently dendrites o: com5osition I !egin to solidi:y. Since these dendrites are m ch richer in nic8el (a55ro<imately %$R Ni as read :rom the diagram) than was the original li? id, the remaining li? id will ha9e !ecome de5leted in nic8el and corres5ondingly richer in co55er as a res lt. ,h s the com5osition o: the remaining li? id mo9es to the le:t o: the diagram=say, to H l. No : rther solidi:ication occ rs ntil the tem5erat re has :allen to ,$ and at this tem5erat re we :ind that the solid 5hase which is in e? ili!ri m with the li? id Hl is now o: com5osition I$, i.e. rather less rich in nic8el than was the original dendrite. Solid o: com5osition I$ there:ore :orms a coating o9er the original dendrite. Howe9er, we will ass me that the system is cooling e#tremely slowly so that .hase e4uili,rium is attained at e+ery stage of solidification! Clearly, (at ,$), crystals o: solid o: uniform com5osition I$ thro gho t constit te the e? ili!ri m 5hase nder these conditions and this ni:ormity is achie9ed !y di:: sion which 5roceeds according to #ic8Bs -aws (>...0), nic8el atoms mo9ing o twards :rom the cores o: the dendrites, to !e re5laced !y co55er atoms which mo9e inwards. Ass ming that a state o: e? ili!ri m has !een th s achie9ed at the tem5erat re ,$ we can se the Ble9er r leB to o!tain com5lete in:ormation a!o t the system at this tem5erat reD ;eight o: li? id(com5ositionHl) .Hl 4 P ;eight o: solid (com5osition I$) .)I$ or

(n the case o: the alloy chosen=>4R Ni2/4R C =we ha9e (reading :rom #ig. &.$4)D ;eight o: li? id (1%R Ni) P ;eight o: solid (&1R Ni) (>4 =1%) (&1 =>4) P $$ $1

;e ha9e there:ore !een a!le to determine the 5recise com5ositions o: each 5hase and the 5ro5ortions in which they co= e<ist in e? ili!ri m at $/61ZC (,$). Solidi:ication contin es in this way as the tem5erat re :alls slowly, the com5osition o: the li? id changing (d e to mi<ing ca sed !y con9ection) along H$ H0 H/ whilst the com5osition o: the solid changes (d e to di:: sion) along I $ I0 I/. ,h s at tem5erat re ,0 the com5osition o: the growing dendrites will ha9e changed to I0 whilst the com5osition o: the ni:orm li? id in e? ili!ri m with them will !e H0. Meanwhile the 5ro5ortion o: li? id to solid will also ha9e changed to )I 02)H0. #inally, at tem5erat re ,/ the last trace o: li? id (o: com5osition H/) solidi:ies at the crystal !o ndaries and is immediately a!sor!ed !y di:: sion so that the solid !ecomes ni:orm and o: com5osition I/ thro gh= o t=which is, o: co rse, the same as that o: the original li? id (H). (t co ld not !e otherwise since matter has !een conser9ed and the initial li? id 5hase and the :inal solid 5hase are o: ni:orm com5osition. 5 ( $ # (n the a!o9e e<5osition we ass med that the rate o: cooling was Bin:initely slowB so that com5lete e? ili!ri m !y means o: con9ection (in the li? id) and di:: sion (in the solid) co ld !e achie9ed at each stage o:

the 5rocess. Fnder 5re9ailing conditions o: ind strial casting, howe9er, the rate o: solidi:ication o tstri5s the rate o: di:: sion and the solid str ct re is na!le to attain ni:ormity and e? ili!ri m. ,h s the com5osition o: the core o: each dendrite is in the region o: I, that is it contains more nic8el than the e? ili!ri m amo nt, so that the o ter :ringes m st contain corres5ondingly more co55er than the e? ili!ri m amo nt. ,his is the mechanism o: coring and, clearly, the greater the rates o: solidi:ication and cooling the greater will !e the e<tent o: coring in the :inal str ct re since there will !e less chance :or di:: sion to ta8e 5lace (#ig. &.$$). (: the cored str ct re is heated to a s ::iciently high tem5erat re di:: sion will ta8e 5lace according to #ic8Bs -aws and a:ter an ade? ate 5eriod o: time the concentration gradient will a55roach

7ero as nic8el atoms di:: se o twards :rom the core and are re5laced !y co55er atoms mo9ing inwards towards the core. Di:: sion ceases when a ni:orm com5osition 5re9ails. As the degree o: coring a55roaches 7ero d ring annealing, the rate o: any : rther di:: sion !ecomes e<tremely slow so that detecta!le coring is still 5resent in most ind strially annealed materials. 89: A copper1nickel allo& contains 5;? C"=#;? !i B& reference to Fig 5 1; detemine as acc"ratel& as is possi*le> 2i3 the temperat"re at ,hich s"ch a molten allo& *egins to solidif&@

2ii3 the composition of the initial dendrites ,hich form@ 2iii3 the temperat"re at ,hich solidification ,ill *e complete Ass"me an e/tremel& slo, rate of cooling 8A: (i) Draw a 9ertical line on the diagram re5resenting the com5osition (04R Ni2&4R C ). ,his c ts the li? id s line at a 5oint re5resenting a tem5erat re o: $041oC (a55ro<imately). ,his is the tem5erat re at which :ree7ing !egins. (ii) ,he tem5erat re Bhori7ontalB :rom $041ZC c ts the solid s line at a 5oint which re5resents an alloy com5osition, .>R Ni21/R C , which will !e the com5osition o: the :irst dendrites to :orm. (iii) ,he 9ertical line re5resenting the o9erall com5osition o: the alloy (04R Ni2&4R C ) c ts the solid s line at $$01ZC (a55ro<imately). ,his is the tem5erat re at which solidi:ication o: the 04R Ni2&4R C alloy is com5lete=ass ming that solidi:ication ta8es 5lace 9ery slowly so that e? ili!ri m is reached at e9ery stage o: solidi:ication.

5 ( % T,o S"*stancesF Completel& )isci*le as LiE"idsF Become Totall& +nsol"*le in Each Bther as Solids Most readers will 8now that the easiest way to remo9e a coating o: ice :rom the garden 5ath is to s5rin8le a small amo nt o: Bcommon saltB (sodi m chloride) on it. ,he ice soon !egins to melt and a glance at the rele9ant 5art o: the 5hase diagram (#ig. &.$0) e<5lains why this ha55ens. Altho gh we may se only a small 5ro5ortion o: salt (say C) we see that !oth ice and sol tion are in e? ili!ri m at tem5erat res !etween a!o t =.ZC and =0/ZC. ,here:ore Bsl shB will soon

Fig 5 1# +art o: the ice=sodi m chloride 5hase e? ili!ri m diagram. :orm and the sli55eriness o: the ice !e eliminated d e to the :ormation o: some li? id. (n the nli8ely e9ent o: the tem5erat re !eing !elow =0/ZC scattering salt wo ld !e n:r it: l since solid ice and solid salt are then the 5hases in e? ili!ri m with each other and ice wo ld not melt. ;hen salting o r roads the -ocal A thority ses s !stances which are chea5er than sodi m chloride ! t e? ally e::ecti9e !oth in de=:rosting the tarmac and in ca sing corrosion o: o r motor cars. Q

QCalci m chloride is sed 5rinci5ally. (t. is a low=9al e !y=5rod ct o: soda man :act re. ,he e tectic mi<t re (with water) :ree7es at =1$ZC ma8ing it e::ecti9e at 9ery low tem5erat res.

5 ( % 1 ,he diagram is a ty5ical e<am5le o: what is commonly called a eutectiferous series! ,he term eutectic is deri9ed :rom the Eree8, Be te8tosB or Bca5a!le o: !eing melted easilyB, a re:erence to the :act that a mi<t re o: 5recisely e tectic com5osition (0/.6R sodi m chloride2>6..R water in the a!o9e e<am5le) has the lowest :ree7ing tem5erat re range in the series. (n a system o: this ty5e the com5onents are m t ally sol !le as li? ids ! t d ring solidi:ication se5arate o t either 5artially or com5letely. (n this section we are dealing with cases o: com5lete insol !ility in the solid state. ,he 5henomenon o: de.ression of free?ing .oint is in9ol9ed here. ,h s the addition o: sodi m chloride to water 5rogressi9ely de5resses its :ree7ing 5oint. Con9ersely the addition o: water to sodi m chloride will 5rogressi9ely de5ress its :ree7ing 5oint. QQ ,he two c r9es meet in a minim m=or e tectic=5oint at =0/ZC and 0/.6R (!y mass) o: sodi m chloride. ;hiche9er com5onent is 5resent in e<cess, o: this e tectic com5osition will crystallise o t :irst as the mi<t re cools so that the :inal li? id will always !e o: e tectic com5osition. #or this reason any mi<t re in the series=other than one o: e tectic com5osition=will solidi:y o9er a range o: tem5erat re. A mi<t re o: e<actly e tectic com5osition, howe9er, will solidi:y at a single tem5erat re in the same manner as 5 re water. QQ,he melting 5oint o: sodi m chloride (&4$ZC) is o: co rse a!o9e the !oiling 5oint o: water ! t the relationshi5 holds tr e :or water= rich mi<t res !elow l)))C

5 ( % # (t is do !t: l whether two s !stances can e9er !e classed as !eing com.letely insol !le in each other. #or e<am5le, we normally s5ea8 o:, say, sil9er chloride as !eing Binsol !le in waterB whereas in :act it has a meas ra!le slight sol !ility. ,he same is tr e o: solids, and in 5artic lar, metals. ,otal insol !ility in the solid state is e<tremely rare and 5ro!a!ly non=e<istent when those two metals were initially com5letely sol !le in each other as li? ids. ,h s, altho gh we shall disc ss the !ism th2cadmi m system here as an e<am5le o: com.lete insolu,ility in the solid state we now !elie9e that a small degree o: solid sol !ility e<ists !etween the metals. Ne9ertheless we shall ignore this slight solid sol !ility :or the sa8e o: o r arg ment. Bism th, one o: the Bless=metallic metalsB in a chemical sense, :orms a :airly com5le< ty5e o: crystal str ct re. ;hilst this is !asically rhom!ic the metallic !ond is 5artly re5laced !y co9alent !onding with the res lt that atoms arrange themsel9es in layers with 9an der ;aals :orces o5erating !etween these layers. (t is not s r5rising there:ore that !ism th is e<tremely !rittle and that it is rel ctant to :orm mi<ed crystals with cadmi m which crystallises in a normal C+H 5attern. Again the 5hase diagram is o: sim5le :orm consisting o: two lines only, the li? id s AEB and the solid s CED, or, more 5ro5erly ACEDB. 5 ( % $ ;e will consider the solidi:ication o: a !ism th2cadmi m alloy o: com5osition H (#ig. &.$/) that is, containing 01R !ism th2>1R cadmi m. At any 5oint a!o9e the li? id s line AEB this will consist o: a com5letely homogeneo s li? id and solidi:ication will commence when the tem5erat re :alls to ,. At this tem5erat re the solid in e? ili!ri m with the li? id H is 5 re cadmi m since the rele9ant solid s 5hase !o ndary in this case is the $44R cadmi m ordinate. Hence dendrites o: 5 re cadmi m !egin to :orm. ,his ca ses the remaining li? id to !ecome corres5ondingly richer in !ism th so that its com5osition mo9es to the le:t, say to Hl, # rther solidi:ication occ rs as the

tem5erat re :alls to ,$ when more 5 re cadmi m will crystallise. ,his 5rocess contin es ntil the tem5erat re has :allen to $..ZC !y which time the remaining li? id contains 64R !ism th2 .4R cadmi m, that is, the tem5erat re and com5osition are re5resented !y the 5oint E=the e tectic 5oint. A55lying the Ble9er r leBD ;eight o: li? id (com5osition ")! E+ P ;eight o: 5 re cadmi m. D+
or

;eight o: li? id (com5osition E) P ;eight o: 5 re cadmi m (S !stit ting 9al es :rom #ig. &.$/) P

D+ E+

$44=>1 P >1=.4

01 P /1

1 >

,h s there are se9en 5arts !y mass o: solid cadmi m to :i9e 5arts !y mass o: li? id. At this stage the two metals are in e? ili!ri m with each other in the remaining li? id. (t is reasona!le to s 55ose, howe9er, that d e to the moment m o: crystallisation o: the 5rimary cadmi m , a little too m ch cadmi m de5osits throwing the com5osition o: the li? id slightly to the le:t o: E. E? ili!ri m is almost immediately restored as a :ilm o: !ism th de5osits and in this manner the remaining li? id solidi:ies !y de5ositing alternate layers o: cadmi m and !ism th as the li? id com5osition swings to and :ro a!o t E. ,he tem5erat re remains constant at $..ZC ntil the solidi:ication 5rocess is com5lete.

,he :inal str ct re there:ore consists of .rimary crystals o: cadmi m in a matri< o: e tectic which in t rn consists o: alternate layers o: 5 re cadmi m and 5 re !ism th in a laminated str ct re which is ty5ical o: metallic e tectics. ,he 5ro5ortion o: 5rimary cadmi m to e tectic will o!9io sly !e the same as indicated a!o9e since the li? id re:erred to then has now solidi:ied as e tectic. ,h s there will !e > 5arts !y mass o: solid cadmi m to 1 5arts !y mass o: e tectic which in t rn contains 64R !ism th and .4R cadmi m. &.6.... A homogeneo s li? id containing. say &4R !ism th204R cadmi m will !egin to solidi:y !y de5ositing 5rimary dendrites o: !ism th. ,hese do not resem!le the dendrites o: other metals ! t are ro ghly c !ic in sha5e (#ig. &.$/). Since !ism th has !een re3ected :rom sol tion the latter has !ecome corres5ondingly richer in cadmi m so that its com5osition mo9es to the right towards the e tectic 5oint. Fltimately the li? id will contain 64R !ism th and .4R cadmi m at l..oc when it will solidi:y as e tectic as in the case o: the 01R !ism th2>1R cadmi m alloy. (n :act any !ism th2cadmi m alloy will contain e tectic which will always !e o: :i<ed com5osition, namely, 64R !ism th2.4R cadmi m. Any li? id sol tion o: com5osition either side o: the e tectic amo nt will :irst de5osit which e9er metal is in e<cess o: the e tectic com5osition in the :orm o: 5rimary crystals ntil the :inal li? id is o: the e tectic com5osition at $..ZC (#ig. &.$.). (t m st !e em5hasised that in the :inal str ct re there is no ? estion o: solid sol !ility since e9en in the e tectic 5ortion the alternate layers o: the two 5 re metals are readily resol9a!le sing ? ite a low=5ower microsco5e. At the e tectic 5oint three 5hases can co=e<ist in e? ili!ri m, i.e. li? id, solid cadmi m and solid !ism th. ,he solid cadmi m and solid !ism th o: co rse constit te the e tectic. Hence there are two com5onents (cadmi m and !ism th) and three 5hases. A55lying the modi:ied +hase R leD fH.5nH8

fH;56H8 Therefore

f5<

,his means that the system is in9ariant so that i: either com5osition or tem5erat re are altered at least one o: the 5hases will disa55ear.

5 ( % ' ;e can s mmarise the general 5ro5erties o: the e tectic as :ollowsD (i) in a !inary system it consists o: a heterogeneo s mi#ture o: two 5hases, i.e. it m st not !e regarded as a single 5hase itsel:M (ii) it solidi:ies at a single :i<ed tem5erat re=the lowest tem5erat re in the seriesM (iii) it will !e o: :i<ed com5osition ,whate9er the o9erall com5osition o: the alloy in which it e<ists. (i9) it solidi:ies in ty5ical lamellar manner, tho gh in some cases the lamellae o: one o: the 5hases degenerate to glo! lar :orm d e to s r:ace=tension e::ects.

5 ( ' T,o S"*stances Completel& )isci*le as LiE"ids *"t Bnl& Partiall& Sol"*le in Each Bther as Solids (n the two 5receding sections we ha9e considered
cases !oth o: com5lete solid sol !ility (C 2Ni) and total insol !ility (Bi2Cd) in the solid state. ,hese were, in a sense, s5ecial cases o: which this one is the general, since here we shall deal with the case o: 5artial sol !ility. Since the two s5ecial cases re:erred to 5ermit o: sim5ler inter5retation they were considered :irst, so that the reader clo d 5rogress :rom the sim5le to the more com5le<.

@!J!E!8 ,he sil9er=co55er system is a ty5ical e<am5le o: 5artial solid sol !ility. ,he 5rinci5al :eat res not enco ntered d ring o r st dy o: 5re9io s 5hase systems are the 5hase !o ndaries CRC $Rl# and DFDlFlE in #ig. &.$6. ,hese !o ndaries occ r !elow the solid s line and conse? ently se5arate 5hase :ields containing only solid 5hases. ,his means that 5hase changes can ta8e 5lace in an alloy a:ter solidi:ication is com5lete. A line s ch as C# or DE is generally termed a sol+us! As the diagram indicates we ha9e in the system two solid sol tions and Q res5ecti9ely sinceD (i) sil9er will dissol9e 5 to a ma<im m o: &.&R co55er at the e tectic, tem5erat re :orming the solid sol tion M (ii) co55er will dissol9e 5 to a ma<im m o: &.4R sil9er at the e tectic rk tem5erat re :orming the solid sol tion . ,he slo5e o: these !o ndary lines C# and DE indicates that !oth the sol !ility o: co55er in sil9er () and the sol !ility o: sil9er in co55er ().
Q (n 5hase diagrams o: metallic alloys it is c stom to la!el 5hases :rom le:t to right sing letter o: Eree8 al5ha!et as a55ro5riate.

decrease with :all in tem5erat re. ,his is a 5henomenon mentioned earlier (>.1.0) and is also a common :eat re o: 5artial sol !ility in the li? id state as instanced !y the 7inc2lead system (&.6.$). @!J!E!6 ;e will now e<amine the solidi:ication o: two re5resentati9e alloys in the series. #irst, we will consider an alloy o: com5osition H (#ig. &.$6) that is, containing /1R Ag261R C . ,his will !egin to solidi:y as the li? id s is reached at tem5erat re ,, when dendrites o: the solid sol tion o: com5osition I will commence to :orm. Since the dendrites are relati9ely rich in co55er then the remaining li? id will !e le:t corres5ondingly rich in sil9er and its com5osition will mo9e to the le:t, say to H l. # rther de5osition o: , this time o: com5osition I$ will occ r as the tem5erat re :alls to ,$ and, i: we ass me slow cooling, then the original dendrites will also ha9e changed to this com5osition (I $) !y means o: di:: sion. ,h s, at tem5erat re ,$. we ha9eD ;eight o: ni:orm li? id (com5osition Hl) .H$) P ;eight o: ni:orm solid sol tion (com5osition I$) .)I$ As the tem5erat re contin es to :all slowly, contin es to de5osit and at the same time change in com5osition along I lD whilst the remaining li? id changes in com5osition along H$E. .At >>%4C, the e tectic tem5erat re, we ltimately ha9e li? id o: com5osition E and solid sol tion o: com5osition D in the ratioD ;eight o: ni:orm li? id (com5osition E) .E)$ P ;eight o: ni:orm solid sol tion (com5osition D). )lD As the tem5erat re !egins to :all !elow >>%4C the remaining li? id solidi:ies as a e tectic !y de5ositing alternate layers o: (com5osition C) and (com5osition D) ntil the li? id is sed 5. )!9io sly the ratioD

;eight o: 5rimary ========================== will !e the same as that indicated a!o9e, i.e. ;eight o: e tectic E)$2)$D

(: we ass me a 9ery slow rate o: cooling then : rther changes will occ r in the str ct re o: the solid alloy as the tem5erat re :alls and the solid sol !ilities o: each metal in the other decrease along C# and DE res5ecti9ely. ,h s co55er will !e re3ected :rom the . layers o: the e tectic in the :orm o: 5articles o: the other solid sol tion . ,hese 5articles will 3oin the layers o: ad3acent to those o: . Similarly sil9er will !e 5reci5itated :rom the layers in the :orm o: a small amo nt o: a which will 3oin the layers. ,he crystals o: 5rimary will also re3ect some sil9er in the :orm o: and this will sometimes !e seen as a :ilm s rro nding the 5rimary crystals (#ig. &.$6) in cases li8e this. At, say, .44 4C the com5osition o: will !e gi9en !y C$ and the com5osition o: (!oth e tectic and 5rimary) !y D$. Beca se o: the e<tremely slow rate o: ionic di:: sion at low tem5erat res little change in str ct re can !e e<5ected in this case !elow a55ro<imately /44ZC. @!J!E!; ;e will now consider the cooling o: an alloy o: com5osition +, that is, containing %1R Ag21R C . ,his will, o: co rse, !egin to solidi:y at tem5erat re S (#ig. &.$6) !y de5ositing dendrites o: o: com5osition _. Solidi:ication will !e com5lete at tem5erat re S$ when the :inal traces o: li? id will !e o: com5osition +$ ! t i: we ass me slow cooling s ch that e? ili!ri m is maintained thro gho t, then li? id +$ will !e a!sor!ed !y di:: sion so that the o9erall com5osition o: the solid sol tion a is _$ (which, o: co rse, is the same as that o: the original li? id +).

No : rther changes ta8e 5lace in the ni:orm a. crystals as they cool slowly towards R. )n reaching R, howe9er, the solid sol tion !ecomes : lly sat rated with co55er and as the tem5erat re :alls !elow that corres5onding to R, co55er will !e re3ected :rom sol tion, not o: co rse as 5 re co55er ! t as solid sol tion o: com5osition F, which is the 5hase in e? ili!ri m with at that tem5erat re. As the tem5erat re :alls slowly contin es to 5reci5itate :rom and !oth solid sol tions in :act change in com5ositions along R# and 'E res5ecti9ely ntil at, say /44ZC, contains little more than 4.1R co55er (R$).and no more than 4.0R sil9er (F$). ,he relati9e amo nts o: and at this tem5erat re will !e gi9en !yD ;eight o: (com5osition R$) .R$' P ;eight o: (com5osition F$) .'F$ F5 to this 5oint we ha9e !een dealing with the solidi:ication and cooling o: alloys on the ass m5tion that cooling has !een slow eno gh :or e? ili!ri m to ha9e !een maintained at each stage. (n 5ractice this is rarely so and in a system s ch as this, ra5id cooling is li8ely to ha9e the :ollowing 5rinci5al e::ectsD (i) 5rimary crystals, whether o: or , will !e hea9ily coredM (ii) is li8ely to !e s 5ersat rated with co55er, and with sil9er since cooling will ha9e !een too ra5id to 5ermit di:: sion and 5reci5itation. ,his a55lies !oth to 5rimary and and also to e tectic and .

2i3 -ra, the thermal eE"ili*ri"m diagram for the s&stem on sE"ared paper as acc"ratel& as the a*ove fig"res allo, and la*el all phase fields 2ii3 -escri*e step *& step the solidification and cooling "nder eE"ili*ri"m conditions from lBBBGC to BGC of an allo& containing 4;? Fa=$;? .i Sketch the e/pected str"ct"res at each stage 2ill3 Calc"late the proportions of phases in this 4;? Fa=$;? .i allo& at temperat"res of 2a3 5;;GC@ 2*3 %;;GC 2iv3 -escri*e step *& step the solidification and cooling "nder eE"ili*ri"m conditions from 11';GC to BGC of an allo& containing 5'? Fa=1'? .i Sketch str"ct"res at each stage 2v3 Sketch and descri*e the str"ct"re ,hich ,o"ld most pro*a*l& *e o*tained if the 5'? Fa=1'? .i allo& ,ere cooled slo,l& to 4;;GC and then E"enched in cold ,ater

(ii) ,he >4R #a2/4R Hi alloy !egins to solidi:y at A (%/1ZC) !y de5ositing n clei o: . o: com5osition B (&&.0R #a2$$.&R Hi) ca sing the com5osition o: the remaining li? id to change along AE as the alloy cools slowly. Di:: sion occ rs and !y the time the tem5erat re has :allen to 604ZC the com5osition o: the growing dendrites has changed along BD so that they are ni:orm and o: com5osition D (>6R #a20.R Hi). ,he remaining li? id (com5osition E) now crystalli7es as a e tectic !y de5ositing alternate layers o: . (com5osition D) and (com5osition E). As the alloy cools slowly to 44C the com5osition o: . Changes along DD$ whilst will change in com5osition along EE $ , i.e. 5articles o: will 5reci5itate :rom (!oth 5rimary and e tectic) whilst 5articles o: will 5reci5itate :rom the e tectic . ,he 5reci5itated 5articles will : se into the a55ro5riate layers o: the

e tectic, i.e. 5articles will 3oin the a layers whilst 5articles 3oin the layers.

(i9) An alloy containing &1R #a2$1R Hi will !egin to solidi:y at H ($4%4ZC) !y de5ositing o: com5osition I (%.R #a26R Hi). As solidi:ication 5roceeds nder e? ili!ri m conditions it will !e com5lete at &14ZC (O) when the com5osition o: will !e &1R #a2$1R Hi (and the last trace o: li? id was o: com5osition 6$.1R #a2/&.1R Hi=a!sor!ed !y di:: sion into the ni:orm ). Fni:orm contin es to cool ntil at .60ZC (O$) it !ecomes sat rated with Hi so that : rther cooling !elow .60ZC ca ses 5rogressi9e 5reci5itation o: 5articles o: as the com5osition o: changes along DD$ (at the same time the 5reci5itated will change in com5osition along EE$ as the tem5erat re contin es to :all, i.e. migration o: !oth #a and Hi atoms !etween and is contin o s).

(9) ,he e<5ected str ct re o!tained !y ? enching an &1R #a2$1R Hi alloy :rom >44ZC will !e similar to (!) in the diagram. _ enching (ra5id cooling) will s 55ress any 5reci5itation o: :rom the so that a metasta!le solid sol tion o: will ens e. (t will !e s 5ersat rated with Hi at )ZC and there:ore nsta!le. (n some alloy systems 5reci5itation o: min te 5articles o: wo ld indeed ta8e 5lace with 5assage o: time de5ending 5on the relati9e thermal acti9ation at am!ient tem5erat re.

8 ! ! A S&stem in Ahich a Peritectic Reaction Bcc"rs So :ar we ha9e !een dealing with alloy systems in which
solidi:ication is either o: the solid sol tion or e tectic ty5e. A : rther mode o: solidi:ication in9ol9es the 5eritectic reaction. Here two 5hases which are already 5resent together in a heterogeneo s mi<t re react to 5rod ce a third 5hase, one or !oth o: the original 5hases disa55earing in the 5rocess. #re? ently one o: the reacting 5hases is a li? id tho gh this is not a 5re=condition and ? ite o:ten two solids will ta8e 5art=al!eit 9ery slowly=in a 5eritectic reaction. ;hen a li? id reacts with a solid in this way it in9aria!ly coats it with an en9elo5e o: the new 5hase. ,his :ilm or en9elo5e e::ecti9ely ins lates the initial solid 5hase :rom : rther reaction, e<ce5t !y the 9ery slow 5rocess o: di:: sion. ,he term B5eritecticB is deri9ed :rom the Eree8, B5eriB which means Baro ndB (as in B5erimeterB), a re:erence here to this s rro ndirig en9elo5e o: the new 5hase. @!J!J!8 ;e will consider the 5latin m2sil9er system which is one o: the :ew !ased almost solely on a 5eritectic reaction. (n this system any alloy containing !etween $0R and 6%R sil9er will !egin to solidi:y !y :orming dendrites o: the solid sol tion a ! t, when the tem5erat re :alls to $$&1ZC (the 5eritectic tem5erat re), reacts with the remaining li? id to 5rod ce a new solid sol tion , i.e.

 W li? id

#irst let s consider the solidi:ication o: an alloy o: com5osition H (>1R +t201R Ag) (#ig. &.$>). ,his !egins to solidi:y in the normal manner o: a solid sol tion as the tem5erat re :alls to , !y de5ositing dendrites o: o: com5osition A. Ass ming that cooling is ta8ing 5lace 9ery slowly so that e? ili!ri m is attained at each stage o: the 5rocess, then !y the time the 5eritectic tem5erat re o: $$&1ZC has !een reached the str ct re consists o: ni:orm o: com5osition + and li? id o: com5osition R in the ratioD ;eight o: solid sol tion (com5osition +) .+H$ P ;eight o: li? id (com5osition R) .Hl R K st !elow $$&1ZC the 5eritectic reaction ta8es 5lace !etween the solid sol tion and the remaining li? idD $$&1ZC W li? id P ,he com5osition o: the new solid sol tion at this tem5erat re is gi9en !y _, i.e. 11R +t2.1R Ag. Howe9er the o9erall com5osition o: the alloy is H, i.e. >1R +t201R Ag and it :ollows that not all o: the a will !e sed 5 since it was o!9io sly in e<cess o: that re? ired to 5rod ce a str ct re solely o: . ,here:ore when the reaction is com5lete some will remain. (n :act the com5osition o: the alloy, when solidi:ication is 3 st com5lete is gi9en !yD ;eight o: solid sol tion (com5osition +). +H$ P ;eight o: solid sol tion (com5osition _) .H$_ S !stit ting a55ro5riate 9al es in the a!o9e e? ationD ;eight o: solid sol tion (&&R +t2$0R Ag)(01 =$0) P ;eight o: solid sol tion (11R +t2.1R Ag)( .1 =01) or ;eight o: solid sol tion . (&&R +t2$0R Ag) .1 =01 04 ========================================================= ======== P ====

;eight o: solid sol tion (11R +t2.1R Ag)

01 =$0

$/

As the alloy contin es to cool slowly will change in com5osition along ++$ and along __$, An alloy o: com5osition I (.4R +t264R Ag) will also !egin to solidi:y !y de5ositing solid sol tion . (n this case solidi:ication !egins at tem5erat re S as dendrites o: o: com5osition B :orm. Again ass ming 9ery slow cooling we shall ha9e a solid sol tion . o: com5osition + and remaining li? id o: com5osition R !y the time the tem5erat re has :allen to $$&1ZC. Howe9er, the 5ro5ortions o: . and li? id are di::erent :rom what they were in the 5re9io s case since this alloy is richer in sil9er. ,h sD ;eight o: solid sol tion (com5osition +).+I$ P ;eight o: li? id (com5osition R). IlR Conse? ently the li? id is 5resent in s ch e<cess that when the 5eritectic reaction ta8es 5lace all o: the is sed 5 and some li? id remains. K st !elow the 5eritectic tem5erat re we ha9eD ;eight o: solid sol tion (com5osition _). _I$ P ;eight o: li? id (com5osition R) .I$ R As the tem5erat re contin es to :all the remaining li? id solidi:ies as , the crystals o: which change in com5osition along )I 0. Solidi:ication is com5lete at I0 when ni:orm crystals o: o: this com5osition (which o: co rse is the same as I) remain. @!J!J!6 Mention has already !een made o: the tendency :or a 5hase 5rod ced as a res lt o: a 5eritectic reaction to coat a solid reactant. ,his will most certainly ha55en d ring any ! t e<tremely slow rates o: cooling. ,he e::ect is ill strated in #ig. &.$>. Here the dendrites (shown in !lac8), on reacting with the remaining li? id, ha9e !ecome coated with the new solid sol tion (light) (ii). ,his

will ine9ita!ly Bseal o::B the :rom the remaining li? id and so sto5 : rther direct reaction !etween the two. As the tem5erat re :alls the remaining li? id solidi:ies as . Howe9er, d e to di:: sion, 5latin m atoms will migrate o twards :rom the cores so that these regions will change 5rogressi9ely in com5osition to that o: (iii). (: cooling is slow eno gh, or i: the solid alloy is s !se? ently annealed at a high tem5erat re, di:: sion will 5roceed to com5letion and ni:orm ltimately remain (i9).

@!J!J!; A 5eritectic reaction may also res lt in the :ormation o: an intermetallic com5o nd o: :i<ed com5osition. S ch a sit ation is ill strated in #ig. &.$& which consists o: the rele9ant section o: the gold2lead 5hase diagram. Here an alloy o: com5osition H (&4R A 204R +!) will !egin to solidi:y at tem5erat re , !y de5ositing dendrites o: 5 re gold. ,his 5rocess contin es ntil at .$&ZC, the 5eritectic tem5erat re, we ha9e crystals o: 5 re gold along with the remaining li? id o: com5osition - (11R A 2.1R +!). A 5eritectic

reaction then occ rs !etween the gold dendrites and the remaining li? id to 5rod ce the new 5hase A 0+!, an intermetallic com5o nd o: :i<ed com5osition as is indicated !y the :act that its 5hase B:ieldB is the ordinate thro gh= 61.6R A 2/...R +!. ;hen the alloy is com5letely solid its 5hase ma8e= 5 will !e gi9en !yD ;eight o: gold. SH$ P ;eight o: A 0+!. H$+ or ;eight o: gold ======================= ;eight o: A 0+! H$ + ======== P SH$ /... =04 ============= P 04 $... ========= 04

An alloy containing, say, 64R A 2.4R +! (I) will !egin to solidi:y !y de5ositing dendrites o: gold as !e:ore ! t when the 5eritectic reaction occ rs (at I $) all o: the solid gold will !e sed 5 in :orming A 0+!. (Some li? id will remain and as the tem5erat re :alls the str ct re will ndergo : rther changes not indicated in this limited section o: the gold2lead 5hase diagram.)

8 ! " A S&stem Ahich Contains Bne or )ore +ntermediate Phases So :ar we ha9e !een dealing with alloy
systems in which the metals ha9e had little chemical a::inity :or each other. Conse? ently, a5art :rom the gold2lead system 3 st mentioned, no intermetallic com5o nds ha9e !een :ormed in these alloy series and the res ltant 5hase diagrams ha9e !een o: a relati9ely sim5le nat re. (: the reader re:ers to Dr Ma< HansenBs com5rehensi9e wor8 Constit tion o: Binary Alloys,Q he will :ind that many 5hase diagrams are o: com5le< constr ction and o:ten contain twenty or more 5hase :ields. ,his state o: a::airs is d e to the :ormation o: a n m!er o: intermediate 5hases in the series. (ndeed the com5lete gold2lead system re:erred to a!o9e is o: this ty5e since it incl des other intermetallic com5o nds as well as A 0+!.

Q Since Dr HansenBs 9ery se: l !oo8 was 5 !lished many years ago and has not recently !een re9ised many o: the 5hase diagrams are now o t o: date in the light o: more recent in9estigational wor8.

@!J!K!8 ,he magnesi m2tin system (#ig. &=.$%) is one which incl des a single intermediate 5hase. ,his 5hase is an intermetallic com5o nd o: the B9alencyB ty5e, Mg0Sn, and its 5hase B:ield[ is re5resented !y the ordinate thro gh >4.%R tinD ,his indicates that the 5hase is o: in9aria!le com5osition and that Mg 0Sn dissol9es neither magnesi m nor tin. (t will also !e noted that this sta!le intermetallic com5o nd has a melting 5oint (>>&ZC) which is higher than that o: either magnesi m or tin. ,he system can !e inter5reted as tho gh we were dealing with two se5arate e tectic series 3oined together at the Mg 0Sn ordinate. #or e<am5le a 1)214 alloy will !egin to solidi:y at H !y de5ositing crystals o: 5 re Mg0Sn (the tem5erat re hori7ontal thro gh H c ts the other !o ndary o: the 5hase :ield at the ordinate re5resenting 5 re Mg0Sn). Mg0Sn contin es to crystallise o t ntil at 16$ZC, the e tectic tem5erat re o: the Mg2Mg0Sn section o: the diagram, the remaining li? id is o: com5osition E. ,his li? id then solidi:ies as a e tectic consisting o: alternate layers o: (com5osition A) and

Mg0Sn. )n : rther slow cooling, changes in com5osition along AB !y re3ecting 5articles o: Mg0Sn (which will 3oin the Mg0Sn layers in the e tectic). Since Mg0Sn is o: :i<ed com5osition no change will ta8e 5lace either in its 5rimary crystals or in its e tectic layers. (t will !e noted that whilst inter5reting the solidi:ication o: this alloy H we ha9e not crossed the Mg 0Sn ordinate to the other hal: o: the diagram. @!J!K!6 _ ite o:ten an intermetallic com5o nd ;ill ta8e into sol tion a limited amo nt o: one or !oth o: its constit ent com5onents. ,hen the intermediate 5hase :ield occ 5ies Bwidth[ on the diagram instead o: !eing re5resented !y an ordinate thro gh the com5osition o: the intermetallic com5o nd. +art o: the nic8el2tantal m 5hase diagram (#ig. &.04) is sed here to ill strate this case. ,he intermetallic com5o nd ,aNi/ contains 14.6>R ,a2.%.//R Ni when 5 re. Howe9er, the diagram indicates that ,aNi/ will ta8e into solid sol tion !oth tantal m and nic8el gi9ing rise to the 5hase :ield la!eled BB.

Here we :ollow the r les that a single=5hase :ield (in this case the 9ertical lines re5resent intermetallic com5o nds o: non=9ariant

com5osition) always se5arates two=5hase :ields and that on crossing a slo5ing 5hase !o ndary the n m!er o: 5hases always changes !y one. ,his 5hase diagram indicates that gold and lanthan m are com5letely sol !le in all 5ro5ortions in the li? id state ! t are com5letely insol !le in each other in the solid state. ,he :o r intermetallic com5o nds :orm a series o: e tectic systems, o9er a55ro5riate ranges o: com5osition, with gold, lanthan m and with each other. At 661ZC and 6>R -a a 5eritectic reaction ta8es 5lace so that with alloys containing more then 6>R -a a e tectic series A -a02-a is 5resent.

Ternar& Allo& S&stems

5 4 So :ar we ha9e !een dealing only with two com5onent systems. Since, in st dying metallic systems in 5artic lar, we ha9e neglected the e::ects o: 5ress re 9ariation, only two 9aria!les ha9e re? ired consideration. )ne o: these has !een tem5erat re and the other, 9ariation o: the amo nt o: one com5onent with res5ect to the other. Q Hence only two gra5hical dimensions are re? ired to re5resent s ch a system and :lat 5a5er s ::ices :or this 5 r5ose. (n the case o: a ternary alloy, howe9er, the amo nts o: any two o: the three metals can !e 9aried inde5endently and the e<tra 9aria!le in9ol9ed re? ires an e<tra dimension :or its re5resentation, i.e. we m st se a three=dimensional 5hase diagram. ,he !ase o: this will !e in the :orm o: an e? ilateral triangle, each a5e< o: which re5resents $44R o: one o: the metals (#ig. &.0$). ,h s an alloy containing /4R Bi264R Sn2$4R +! will !e re5resented !y 5oint +. (,his can !e demonstrated mathematically.)
Q Clearly, in a !inary system the 5ro5ortions o: each metal m st add 5 to $44R. ,h s i: the amo nt o: one is changed the amo nt o: the other changes in sym5athy and there is only one inde5endent 9aria!le in9ol9ed.

,em5erat re will !e re5resented !y ordinates normal to the triang lar !ase. 5 4 1 #ig re &.00 ill strates (within its limitations) the ternary alloy system :or !ism th2tin2lead. ,he !inary systems tin2lead. -ead2!ism th and !ism th2tin are : ndamentally o: the e tectic ty5e and are re5resented !y

Fig 5 ## ,he !ism th=tin=lead 5hase system. (i) this is a 5ro3ection o: the li? id s s r:aces on to a hori7ontal 5lane in the manner o: a conto red ordnance s r9ey ma5. (ii) (s a s5ace model showing the li? id s s r:aces. E $ is the e tectic 5oint o: the Sn=+! system ($&/ZC)M E0 the e tectic 5oint o: the +!=Bi system at $0.ZC and E / the e tectic 5oint o: the Bi=Sn system at $/1ZC. ,he ternary e tectic 5oint Et is at $444C.

the B9erticalB= end :aces o: the s5ace model (#ig.&.00(ii)). ,he !inary li? id s lines de9elo5 to li? id s s r:aces in the three= dimensional model and these s r:aces intersect in three B9alleysB which drain down to a 5oint o: minim m tem5erat re 9ertically a!o9e Et. ,his is the ternary e tectic 5oint o: the system, its tem5erat re !eing lower than that o: either o: the !inary e tectic 5oints E$, E0, E/. #or this system the ternary e tectic contains 14R Bi20&R +!200R Sn and :ree7es at $44ZC. At this ternary e tectic 5oint :o r 5hases can co=e<ist, i.e. solid !ism th, solid tin, solid lead and li? id. ,he com5onents o: the system are !ism th, tin and lead. A55lying the modi:ied +hase R leD fH.5nH8 fH:5;H8 f5< ,h s at this e tectic 5oint, as at a !inary e tectic 5oint, the system is in9ariant.

5 4 # (n considering this ternary system we ha9e dealt only with the li? id s Bs r:aceB. Eenerally we shall !e more in9ol9ed with changes which ta8e 5lace in solid alloys at lower tem5erat res, i.e. BinsideB the s5ace model. Clearly s ch three=dimensional 5hase B9ol mesB are rather incon9enient to ill strate, tho gh :or demonstration 5 r5oses three=dimensional s5ace models may !e constr cted sing !its o: di::erently colo red electrical wire to indicate 5hase !o ndaries. Many years ago s ch a 5ro3ect sed to !e a :a9o rite e<ercise leading to the award o: a +h.D. in many ni9ersity metall rgy de5artments. M ch 5ainsta8ing wor8 was in9ol9ed incl ding the casting o: alloys o: di::erent com5ositions within the series,

:ollowed !y care: l chemical analysis, 5rolonged annealing o: sam5les at di::erent tem5erat res and then ? enching. ,he 5hase str ct re was then e<amined, generally sing the microsco5e. (t is generally more se: l to se either hori7ontal BslicesB (that is, isothermal sections) at the re? ired tem5erat resM or 9ertical slices at a :i<ed amo nt o: one o: the com5onents. #ig re &.0/ re5resents a 9ertical slice :rom the ternary iron2chromi m2car!on system. ,his has !een ta8en at the $/ R Cr !ase line and the section shown will !e 5arallel to the iron2car!on end :ace o: the s5ace model. ,he same sort o: arrangement can !e sed :or m lti= com5onent alloys. ,hen, all ! t one o: the com5onents are :i<ed and a two=dimensional diagram drawn showing tem5erat re and one com5onent as 9aria!les. ,hese diagrams= s ally called B5se do=!inaryB diagrams=are 9ery se: l :or st dying alloy steels which may contain 5 to si< com5onent elements.

7 Steel and its heat treatment

7 1 (ron was 8nown to the Ancients as BMetal :rom Hea9enB or BMetal :rom the StarsB :rom which we may concl de that s ch iron as was sed in those times was o: meteoric origin. ,he deli!erate smelting o: iron ores seems to ha9e originated some /144 years ago and !y that time the (ron Age can !e said to ha9e arri9ed. +res ma!ly historians wo ld agree that we are still in the (ron Age :or, des5ite the de9elo5ments o: al mini m alloys and 5lastics materials d ring the twentieth cent ry, steel ndo !tedly remains o r most im5ortant engineering material. (t is nli8ely that the 5resent state o: technological de9elo5ment co ld ha9e !een achie9ed in any :ield witho t the hel5 o: steel as o r main str ct ral, constr ctional and tool material = and all this at a relati9ely low :inancial o tlay. Almost all :erro s materials = car!on steels, alloy steels and cast irons are deri9ed :rom 5ig iron 5rod ced in the !last : rnace. +ig iron is a relati9ely im5 re material containing 5 to a total $4R o: car!on, silicon, manganese, 5hos5hor s and s l5h r. ,he man :act re o: steel :rom 5ig iron in9ol9es the 5rogressi9e o<idation o: these im5 rities which are lost as slag or gas. S ch 5rocesses were, ntil the latter hal: o: the twentieth cent ry, carried o t either in a Bessemer con9erter or an o5en=hearth : rnace which, whilst remo9ing the ! l8 o: the im5 rities 5resent in the original 5ig iron, le:t !ehind a signi:icant amo nt o: these im5 rities in the metal and, in the case o: the now o!solete Bessemer 5rocess, introd ced a new im5 rity, atmos5heric nitrogen. ;hilst amo nts o: these resid al im5 rities were small they were s ::iciently 9aria!le in ? antity to ma8e 5recise alterations in 5ro5erties (!y alloying) di::ic lt. (n the years :ollowing the Second ;orld ;ar, howe9er, new steel=ma8ing

5rocesses were de9elo5ed=the new !asic o<ygen 5rocesses where low 5riced BtonnageB o<ygen re5laces air and so eliminates nitrogen contamination=and electric 5rocesses where totally controlled and chemically clean conditions lead to a high=5 rity 5rod ct o: 5redicta!le 5ro5erties. ,he high d ctility o: s ch a material has allowed steel = or more 5ro5erly, iron = to re5lace many o: the more e<5ensi9e non=:erro s metals :or dee5=drawing and other :orming 5rocesses. %.$.$ Steel is essentially an alloy o: iron and car!on containing 5 to ro ghly 0.4R car!on. By 9arying this car!on content and the heat treatment o: the res ltant alloy we can o!tain an enormo s range o: mechanical 5ro5erties, whilst the addition o: alloying elements s ch as nic8el, chromi m and moly!den m e<tends the 5ro5erties still : rther. Ne9ertheless it is a so!ering tho ght that, ! t :or the 5olymor5hic changes which occ r in iron (/.6..), the heat treatment o: steel as we 5ractise it wo ld !e im5ossi!le and that iron2car!on alloys wo ld then ha9e e<tremely limited 5ro5erties. Certainly tool steels and high=strength constr ctional steels wo ld not !e a9aila!le to the engineer. (t is 5ossi!le that we wo ld still !e in the Bron7e Age. 7 1 # ,he relati9ely small car!on atoms dissol9e interstitially in iron. Howe9er, whilst the #CC :orm o: iron will dissol9e 5 to 0.4R C, the ma<im m sol !ility o: car!on in BCC iron is only 4.40R at >0/ZC and this :alls almost to 7ero (5ro!a!ly o: the order o: 0.4 < $4=>R) at )ZC. ,his is !eca se the interatomic s5aces in BCC iron are 9ery small so that car!on atoms cannot readily !e accommodated. (n :act car!on atoms are too large :or e<tensi9e interstitial solid sol tion ! t too small to :orm a sta!le s !stit tional solid sol tion with iron. ;hilst the interatomic s5aces are larger in #CC iron they are not large eno gh to accommodate car!on atoms :reely. Some crowding there:ore

occ rs 5rod cing strain in the str ct re so that not all s5aces can !e occ 5ied. ,he ma<im m sol !ility o: car!on in the #CC :orm o: iron is 0.4R and this sets the limit o: the car!on content o: a steel. As the #CC :orm changes to BCC any car!on in sol tion in e<cess o: 4.40R will !e 5reci5itated :rom solid sol tion ass ming that it is cooling slowly eno gh to 5ermit this. Fnder the slowest rate o: cooling which is 5ossi!le car!on does not 5reci5itate as gra5hite ! t as iron car!ide, #e/C, -i8e most metallic car!ides this is a hard s !stance. Conse? ently as the car!on content o: a steel increases so does its hardness e9en tho gh it has not !een heat treated ! t is only in the slowly cooled condition. %.$./ Since steel is s ch, an im5ortant alloy and has !een st died since the 9ery early days o: metallogra5hyQ names ha9e !een ado5ted :or the three 5hases mentioned a!o9e. ,he interstitial solid sol tion o: car!on in #CC iron is 8nown as A stenite. (t can contain 5 to 0.4R C and is a sta!le 5hase !etween >0/ and $.%/ZC. ,he interstitial solid sol tion o: car!on in BCC iron is 8nown as #errite. ,his is sta!le !elow %$4ZC and can contain a ma<im m o: only 4.40R C (at >0/ZC). Ne9ertheless altho gh :errite contains so little dissol9ed car!on this car!on e<erts considera!le in:l ence on the mechanical 5ro5erties o: :errite !y o55osing the mo9ement o: dislocations (>.1.$.0). #or this reason 9ery high 5 rity iron (%%.%%%%R) is e<tremely so:t and d ctile as com5ared with the low=car!on :errite o: dead=mild steel. (ron car!ide, #e/C, is generally 8nown as Cementite. )ther 5hases, and mi<t res o: 5hases, are also gi9en s5ecial names as we shall see s !se? ently
Q +ro:essor Henry Sor!y (o: She::ield) was cond cting the systematic microsco5ical metallogra5hy o: steels in the early $&64s.

%.$.. ;hat is 5o5 larly 8nown as the Biron2car!on diagramB is strictly s5ea8ing not a tr e e? ili!ri m diagram since cementite (iron car!ide) is not a com5letely sta!le 5hase. Era5hite is in :act

more sta!le than cementite ! t n cleation o: cementite ta8es 5lace in ad9ance o: 5reci5itation o: gra5hite mainly !eca se at that stage the #CC iron is sat rated with car!on. )nce cementite has :ormed it is ? ite sta!le and :or most 5ractical considerations can !e treated as an e? ili!ri m 5hase. Howe9er, whilst #ig. %.$ re5resents what is generally 8nown as the Biron2car!on e? ili!ri m diagramB we sho ld !ear in mind that it is more 5ro5erly la!eled the Biron2iron car!ide metasta!le systemB. 71' +hase changes within the str ct res o: solid alloys are o:ten sl ggish :or reasons s ch as those descri!ed in >...$. )nce an alloy has solidi:ied atoms mo9e with greater di::ic lty into 5ositions o: e? ili!ri m and o:ten re? ire considera!le thermal acti9ation to e::ect this state. ,his also a55lies to the 5olymor5hic trans:ormation () which ta8es 5lace in iron = and conse? ently in car!on steels. #ig re %./ indicates that :or a 4..R car!on steel the trans:ormation, a stenite:errite, !egins at F$ (a55ro<imately &04ZC). (n :act on heating s ch a steel the :errite a stenite change wo ld 5ro!a!ly not !e com5lete ntil &14ZC whilst on cooling the re9erse trans:ormation wo ld not !e com5lete ntil a!o t >%4ZC. ,h s the (a stenite a stenite W :errite) change 5oint :or this 4..R car!on steel is ta8en as &04ZC = the e? ili!ri m tem5erat re midway !etween >%4ZC and &14ZC. Similarly the a stenite 5earlite trans:ormation may not occ r ntil a!o t >14ZC on heating whilst it may !e delayed ntil 6%4ZC on cooling= >0/ZC is an a9erage 9al e in this case :or the Be? ili!ri mB tem5erat re. ,hese meas red tem5erat res de5end largely on the rates o: heating (or cooling) which 5re9ail d ring the 5lotting o: the cooling c r9es. ,he tem5erat res meas red on heating were designated A c( and Ac/ whilst those meas red d ring cooling were designated Arl and Ar/ when these trans:ormation 5oints were in9estigated more

than a cent ry ago !y the #rench scientist #. )smond. His nomenclat re is still sed, i.e. BcB stands :or Bcha ::ageB (heating) whilst BrB stands :or Bre:roidissementB (cooling). BAB re5resents BarretB (arrest) since these tem5erat res were meas red as arrest 5oints on corres5onding heating or cooling c r9es. (ncidentally the A0 tem5erat re re:ers to the C rie 5oint (>6&ZC :or 5 re iron) a!o9e which iron loses its :erromagnetism. ,he tem5erat re does not a55ear on the 5hase diagram since no crystal change is in9ol9ed and sol !ilities o: added elements are not a::ected. 71( ;hilst methods :or determining the 5ositions o: 5hase !o ndaries !ecome more so5histicated metall rgists ne9ertheless rely to a great e<tent on 9is al analysis o: microstr ct res sing sim5le o5tical microsco5es. #or reasons s ch as this it is di::ic lt :or e<am5le, to determine whether or not a steel is o: 5recise e tectoid str ct re when 9iewed thro gh the microsco5e and that the o!ser9ed str ct re does not contain a 9ery small e<cess o: either :errite or cementite

Fig 7 1 ,he iron=car!on 5hase e? ili!ri m diagram (more 5ro5er$y the Biron=iron car!ide metasta!le systemB).

D ring my li:etime as a metall rgist the e tectoid com5osition o: car!on steel has s ccessi9ely !een esta!lished !etween 4.&%R and 4.>>R car!on, 9al es o: 4.&$M 4.&/M 4.&1 and 4.&4R !eing in :ashion d ring di::erent 5eriods the while. #or this reason ( ha9e ado5ted the 9al e 4.&R car!on and ha9e retained this o9er the years. )ther 9al es in the iron2car!on system show similar 9ariations ! t are o: little conse? ence in 5ractice. ( ma8e these 5oints since readers may !e 5 77led !y 9ariations in 5hase diagrams as !etween di::erent te<t !oo8s. 714 (: iron did not ndergo 5olymor5hic changes at $.44 and %$4ZC ! t retained its #CC str ct re at all tem5erat res it wo ld

5res ma!ly :orm a sim5le e tectic system with a e tectic 5oint at ../R C and $$.>C, and the solid sol !ility o: car!on in a stenite :alling :rom 0.4R at $$.>C to a 9ery low 9al e at )ZC. ,he res ltant alloy wo ld ha9e limited se and wo ld not !e amena!le to the e<tensi9e heat=treatments a55lied to car!on steels as we 8now them, tho gh some limited 5reci5itation=hardening treatment might !e 5ossi!le. ,he 9ery limited solid sol !ility o: car!on in the BCC :orms ( and ) introd ces modi:ications to the diagram as indicated. ,h s a steel containing less than 4.1$R C will !egin to solidi:y as dendrites o: which, at $.%/ZC will ndergo a 5eritectic reaction with the remaining li? id to 5rod ce (a stenite). As the steel cools the #CC str ct re will ltimately !egin to trans:orm to one which is BCC and car!on will !e thrown o t o: solid sol tion as cementite. Since car!on dissol9es interstitially in iron the di:: sion o: car!on atoms is relati9ely ra5id and normally there is no coring o: car!on with res5ect to iron. )ther alloying elements, and 5artic larly im5 rities, may, howe9er, !e cored es5ecially i: they dissol9e s !stit tionally in iron. ,he ,rans:ormation o: A stenite Fnder Near E? ili!ri m Conditions 7# ;e will now st dy the solidi:ication and trans:ormations which occ r as a 4..R C steel cools slowly :rom the li? id state to room tem5erat re S ch a steel will !egin to solidi:y when its tem5erat re :alls to , (#ig. %.0)

Fig 7 # ,he 5eritectic region o: the iron=car!on diagram.

and dendrites o: BCC (o: com5osition D) !egin to :orm. ,his 5hase, , contin es to crystallise and at the same time change in com5osition along DD$ ntil, at $.%/ZC, its com5osition is gi9en !y Dl (4.$R C). ,he remaining li? id in e? ili!ri m with at this tem5erat re is o: com5osition C (4.1$R C). A 5eritectic reaction then occ rs !etween and this remaining li? id 5rod cing a new 5hase=the solid sol tion (a stenite).Since the o9erall com5osition o: the steel lies !etween + and C all o: the will !e sed 5 in the reaction and the s r5l s li? id will then solidi:y o t as whilst the tem5erat re :alls to S and the changes in com5osition along +S !y di:: sion o: car!on. No : rther 5hase change ta8es 5lace ntil the tem5erat re has :allen to ,$ (#ig. %./). ,his is 8nown as the 55er critical=or A /= tem5erat re :or this 5artic lar steel. Q
Q,he 55er critical tem5erat re o: steel is gi9en !y the a55ro5riate 5oint corres5onding with its com5osition on the line FE' (#ig. %./).

As the tem5erat re :alls 3 st !elow , $ crystals o: BCC (:errite) o: com5osition H !egin to grow within the a stenite which o: co rse they grad ally re5lace. Since the :errite contains less than 4.40R C it :ollows that the remaining a stenite !ecomes richer in car!on so that its com5osition mo9es to the right towards E. By the time the tem5erat re has :allen to >0/ZC we shall ha9e :errite o: com5osition - (4.40R C) and remnant a stenite o: com5osition E (4.&4R C) in the ratioD ;eight o: :errite (4.40R C) P -$E ;eight o: a stenite (4.&R C) --$ i.e. there are a55ro<imately e? al masses o: each 5hase 5resent at this instant. 7#1 ,he lower Bcritical = or A $= tem5erat re is gi9en !y the line -) (#ig. %./) and is o: co rse constant at >0/ZC :or all car!on steels. ,he 5oint E will !e recognised as !eing associated with a e tectic ty5e o: trans:ormation. +re9io sly we ha9e !een dealing with the :ormation o: e tectics :rom li? id sol tions. Here, howe9er, the trans:ormation o: a solid sol tion (a stenite) is in9ol9ed and so the res ltant str ct re in this case is termed a e tectoid. As the tem5erat re :alls 3 st !elow >0/ZC the remaining a stenite, now o: com5osition E, trans:orms to e tectoid !y 5reci5itating alternate layers o: :errite (com5osition -) and cementite (#e/C). ,his 5artic lar e tectoid is 8nown as 5earlite, a re:erence to the :act that, li8e mother=o:=5earl, it !eha9es as a di::raction grating in dis5ersing white light. (t is im5ortant to realise that 5earlite is not a 5hase ! t a mi<t re o: two 5hases, :errite and cementite. Since the a stenite 5resent in the str ct re at 3 st a!o9e >0/ZC has now trans:ormed to 5earlite the ratioD

;eight o: 5rimary :errite P -$E ;eight o: 5earlite --( i.e. as in ($) a!o9e. All hy5o=e tectoid steels, that is, those containing less than 4.&R C consist o: 9arying ? antities o: 5earlite and 5rimary :errite, ass ming that they are in an e? ili!ri m state. # rther :all in tem5erat re will ha9e no signi:icant e::ects on the microstr ct re. ,he car!on contents o: !oth 5rimary and e tectoid :errite will decrease :rom the already low 9al e o: 4.40R to 9irt ally 7ero. ,his car!on will 5reci5itate as tiny 5articles o: cementite mainly at the :errite grain !o ndaries. 7## A steel containing e<actly 4.&R C will solidi:y directly as a stenite (!etween _ and R=#ig. %.0) and will ndergo no : rther changes ntil it reaches the e tectoid 5oint E when the whole o: the str ct re will trans:orm :rom a stenite to 5earlite. Hy5er= e tectoid steels, i.e. those containing more than 4.&R C, will also solidi:y directly as a stenite. )n reaching the 55er critical tem5erat re (a 5oint on E'), 5rimary cementite will !egin to se5arate o t generally as em!rittling :ilms at the a stenite grain !o ndaries so that the com5osition o: the remaining a stenite mo9es to the le:t towards E. At >0/ZC this remaining a stenite contains e<actly 4.&R C and will trans:orm to 5earlite as !e:ore.

The Formation of Pearlite

7 $ ;hen a stenite trans:orms isothermally 3 st !elow >0/ZC the reaction 5rod ct is 5earlite, the e tectoid o: :errite and cementite indicated !y the iron2car!on diagram. As em5hasised already 5earlite is not a 5hase ! t a mi<t re o: two 5hases. ,hese two 5hases, :errite and cementite, are 5resent in a de:inite ratio as indicated !y the le9er r leD ;eight o: :errite. (4.&) P ;eight o: cementite. (6.6> =4.&) Since cementite, #e/C, contains 6.6>R !y weight o: car!on.

,here:oreD ;eight o: :errite ;eight o: cementite

P (6.6> =4.&) 4.&

P 1.&> P >./ 4.& $

As the relati9e densities o: :errite and cementite are ro ghly e? al the lamellae o: :errite are a55ro<imately se9en times the width o: those o: cementite. As a res lt :errite :orms a contin o s 5hase with the 5lates o: cementite s rro nded !y this :errite matri<. Since :errite is to gh and d ctile this ma8es 5earlite to gher and stronger than it wo ld !e i: the !rittle cementite were contin o s. 7$1 ,he mechanism o: the a stenite 5earlite trans:ormation is ty5ical o: many reactions within solid alloys in that it !egins at grain !o ndaries in the main and contin es into the e<isting grains. ,his is 5redicta!le since the atoms at grain !o ndaries ha9e higher energy states than atoms within the grains. Hence these atoms at grain !o ndaries re? ire less e<tra energy in order to !rea8 away :rom their neigh!o rs to :orm a new str ct re. (t is tho ght that car!on atoms collect together and so :orm a cementite n cle s (#ig. % ..(ii)). As this n cle s grows inwards :rom the !o ndary the s rro nding a stenite !ecomes s ccessi9ely de5leted in car!on and, since its com5osition mo9es to the le:t o: the e tectoid 5oint, so layers o: :errite se5arate on either side o: the cementite n cle s (iii). Beyond these :errite layers an increase o: car!on occ rs so that more cementite n cleates (i9) and so on, the str ct re ! ilding 5 as alternate layers o: cementite and :errite (9i).

Hses of Steel
7 % )rdinary car!on steels can !e classi:ied con9eniently into :o r main gro 5s in terms o: their s5eci:ic sesD 7 % 1 0-ead1mild0 Steels containing 5 to ).$1R C, which are sed :or

Fig 7 % ,he n cleation and growth o: 5earlite (rt is ass med that the steel in this instance contains 4.&R car!on).

general 5resswor8 and other a55lications where high d ctility is necessary in :orming. e.g. motor=car !odies, tin cans, nails and wire. Since $%14 there has !een a considera!le im5ro9ement in the chemical 5 rity o: mild steel generally. ,his has res lted in im5ro9ed d ctility so that dead=mild steel has re5laced some o: the more e<5ensi9e dee5=drawing alloys s ch as >4=/4 (BcartridgeB) !rass :or many traditional ses. 7 % # )ild Steels containing 4.$1=4./R C. ;ro ght :orms are sed as RSK and other str ct ral mem!ers, sha:ting, le9ers and 9ario s :orgings. Steels sed :or sand castings s ally contain 4./= 4./1R C. 7 % $ )edi"m1car*on Constr"ctional Steels containing 4..= 4.6R C, which are widely sed :or com5onents in the engineering ind stries, e.g. a<les, connecting rods, gears, wire ro5es, rails, etc. 7 % % Tool Steels. containing 4.6=$.1R C. 7 % ' Steels in the :irst two o: these gro 5s, i.e. containing less than 4./R C, do not harden s ::iciently when heat treated to ma8e this generally worth while. ,his is not d e s5eci:ically to lac8 o: car!on as we shall see later (%.6.6). S ch steels are there:ore sed

in the cast, hot=rolled, cold=wor8ed or normalised :orms. ,he third and :o rth gro 5s contain steels with more than 4..R C and can !e hardened or strengthened !y an a55ro5riate heat treatment 5rogramme. (n Britain the motor=car ind stry is the largest single ser o: steel,:ollowed !y 9ario s !ranches o: the ! ilding and 5lant constr ction ind stries. ,h s, des5ite the attracti9e 5ro5erties o::ered !y steel in its heat=treated :orms we m st not :orget that the ! l8 o: :erro s material is o: the low=car!on ty5e which is not heat=treated. Some o: the many ses o: car!on steels related to car!on content and mechanical 5ro5erties are ill strated in #ig. %.1.

Fig 7 ' ,he relationshi5 !etween R car!on, ses and mechanical 5ro5erties o: car!on steels in the hot=rolled condition.

.eat1treatment Processes ,hich EE"ili*ri"m Str"ct"res in Steels

Prod"ce

7' Se9eral heat=treatment 5rocesses a55lied to steels res lt in the :ormation o: 5earliticQ str ct res. (n the :irst two o: these 5rocesses mentioned here no 5hase change occ rs since the

treatment is carried o t !elow the A $==or lower critical= tem5erat re. Process Annealing ,his is an inter=stage annealing o5eration s ch as might !e a55lied to any hea9ily cold=wor8ed metal or alloy in order to achie9e recrystallisation (1.&./) and lead to the reco9ery o: mallea!ility and d ctility so that : rther cold=wor8 may !e a55lied. (n this conte<t it is sed mainly to so:ten mild sed mainly to so:ten mild and dead=mild steels which ha9e !ecome
Q (n this sense the term B5earliticB means that the steel has cooled slowly eno gh :or 5earlite to :orm, not that the str ct re will necessarily !e wholly 5earlitic, which o: co rse it will not !e i: less==or more=than 4.&R C is 5resent.

wor8=hardened !y cold=rolling or drawing and which m st ndergo : rther cold=:orming. A ty5ical e<am5le is the drawing o: low= car!on steel wire. ,he 5resence o: small amo nts o: car!on in the :orm o: scattered 5atches o: 5earlite is not signi:icant here. ;e are in9ol9ed mainly with the wor8=hardening o: :errite. ,he recrystallisation tem5erat re o: :errite is o: the order o: 144ZC ! t on an ind strial scale annealing at a!o t 614ZC is generally em5loyed so that recrystallisation will 5roceed more ? ic8ly and a treatment time o: a!o t one ho r !e am5le. ,he str ct re remains one o: :errite25earlite thro gho t and since no 5hase change occ rs the e? ili!ri m diagram is not in9ol9ed here. 7'# Spheroidising Anneals ,he machining o: high=car!on steels e9en in the normalised condition is di::ic lt since the layers o: 5earlitic cementite 5ro9ide hard !arriers to c tting. ,he str ct re can !e s ita!ly modi:ied !y a 5rolonged annealing treatment= 5wards o: twel9e ho rs=at a tem5erat re !etween 614ZC and >44ZC, that is, 3 st !elow A$. Again, no 5hase change will occ r ! t, d e to s r:ace energy e::ects, the cementite layers o: the 5earlite grad ally !rea8 5 and ass me a glo! lar :orm (#ig. %.6).

Fig 7 ( ,he s5heroidisation o: 5earlitic cementite on 5rolonged annealing 3 st !elow A$.

Not only is machina!ility im5ro9ed ! t cold=:orming 5rocesses are 5ossi!le when the steel is in this condition. A:ter sha5ing is com5leted the steel can !e hardened or the original 5earlitic str ct re restored !y normalising. 7 ' $ !ormalising ,he general aim o: this 5rocess is to re:ine the grain o: a steel which, :or some reason, has !ecome coarse= grained. S ch re:inement o: grain im5ro9es the mechanical 5ro5erties 5artic larly in res5ect o: d ctility and to ghness. Normalising is a55lied to hy5oe tectoid steels and in9ol9es heating the material to a tem5erat re not more than 14ZC a!o9e the A/ 55er critical tem5erat re. Between A l and A/ the initial str ct re recrystallises to a stenite ! t, and this is the im5ortant 5oint, to a stenite o: 9ery :ine grain. A:ter a short 5eriod o: Bsoa8ingB the steel is remo9ed :rom the : rnace and cooled in still air when the :ine=grained a stenite will trans:orm to :ine=grained :errite and 5earlite. (t is im5ortant that neither the tem5erat re nor the time o: treatment !e e<ceeded or grain growth o: the newly :ormed a stenite will ta8e 5lace and gi9e rise to coarse=grained :errite and 5earlite. Normalising also im5ro9es the machina!ility o: hy5o= e tectoid steels. ,he res ltant s r:ace :inish is also s 5erior to that o!tained !y machining an annealed com5onent, since high d ctility in the latter leads to a tendency to local tearing o: the s r:ace. 7 ' % Annealing of Castings Sand castings in steel commonly contain a!o t 4./1R C and, !eca se o: the slow rate o:

solidi:ication and cooling in the sand mo ld, considera!le grain growth ta8es 5lace in the a stenite whilst it is at tem5erat res a!o9e $444ZC. Conse? ently s ch a steel is 9ery coarse grained !y the time the tem5erat re has :allen to A/and the 5rimary :errite tends to se5arate o t as elongated 5lates at the a stenite grain !o ndaries and also along the close=5ac8ed a$$$] 5lanes within the coarse a stenite grains (#ig. %.$4). ,his is termed a ;idmanstattenQ str ct re and is characterised !y !rittleness since :ract re can 5ro5agate easily along the !o ndaries o: the coarse 5rimary :errite 5lates. ,he str ct re can !e re:ined !y heat treatment in a 5rocess closely resem!ling normalising. ,he casting is heated to some 14ZC a!o9e the A/ tem5erat re, soa8ed :or a 5eriod de5ending 5on the section o: the casting

Fig 7 4. ,he re5lacement o: the coarse ;idmans8tten 5attern !y a :ine=grained str ct re d ring the annealing o: a casting

and then cooled, s ally in the : rnace. Air cooling wo ld !e more li8ely to lead to the :ormation o: internal stresses 5artic larly in castings o: 9aria!le section which wo ld there:ore cool ne9enly. As the casting is heated to the Al tem5erat re small a stenite grains
QA str ct re o: this ty5e was :irst o!ser9ed on the s r:ace o: a meteorite !y Aloys Bec8 9on;idmanstatten in $&4.=5ossi!ly one o: the :irst e<c rsions into 5ractical metallogra5hy.

re5lace the coarse 5earlite and as the tem5erat re rises to A /, the coarse ;idmanstatten :errite 5lates grad ally trans:orm to :ine= grained a stenite also. )n cooling again this :ine=grained a stenite is re5laced !y :ine= grained :errite25earlite. ;hilst the tensile

strength is little a::ected !y this treatment, d ctility is almost do !led and im5act to ghness increased considera!ly. 7 ' ' 0F"ll Annealing0 is sometimes sed :or car!on steels o: all com5ositions. Hy5o=e tectoid steels are heated to a55ro<imately 14ZC a!o9e the A/ tem5erat re :ollowed !y slow cooling, generally in the : rnace. S ch a treatment a55lied to hy5er= e tectoid steels wo ld gi9e rise to the 5reci5itation o: coarse !rittle intercrystalline networ8s o: 5rimary cementite (%.0.0) d ring the s !se? ent cooling 5rocess !etween A/ and A$. ,his co ld only !e dis5ersed !y hot :orging im5ractica!le i: the wor8 5iece is already Bto si7eB. Hence hy5er=e tectoid steels are heated to /4ZC a!o9e A $ :ollowed !y slow cooling. Fnder these conditions glo! lar 5rimary cementite (:ormed !y the original rolling (or :orging) 5rocess 3 st a!o9e A$) is not dissol9ed and so cannot 5reci5itate as needles on cooling. (n either case a so:t coarse=grained str ct re :ree o: stress and easily machina!le is :ormed. S !se? ently the :inished 5rod ct may !e normalised or hardened (and tem5ered) as re? ired.

The !on1eE"ili*ri"m Transformation of A"stenite

7 ' +hase trans:ormations in solid alloys do not occ r instantaneo sly ! t are 9ery time=de5endent. Many s ch trans:ormations rely on di:: sion which in s !stit tional solid sol tions is ine9ita!ly a slow 5rocess (>..). #or this reason, 5artic larly in many ind strial 5rocesses, the rate o: tem5erat re :all :ar o tstri5s the a!ility o: the alloy to maintain 5hase e? ili!ri m d ring cooling. ):ten when am!ient tem5erat re is reached the thermal energy o: the system is too low to allow : rther trans:ormation, and a non=e? ili!ri m str ct re is tra55ed, sometimes 5ermanently nless : rther heat=treatment is a55lied. 7(1 Since car!on dissol9es interstitially in =iron it is a!le to di:: se com5arati9ely ? ic8ly so that, :or e<am5le, the res ltant

coring o: car!on with res5ect to iron is negligi!le. Ne9ertheless when a stenite is cooled ra5idly !elow the Al tem5erat re=to a!o t 044ZC or so=the dri9ing :orce tending to ca se trans:ormation :rom #CC to BCC is so great that it occ rs !e:ore car!on has an o55ort nity to :orm se5arate crystals o: car!ide. Conse? ently s 5er sat ration o: the new BCC str ct re with car!on is !o nd to res lt. ,his ca ses considera!le distortion o: the str ct re which in t rn ma8es sli5 9irt ally im5ossi!le, a :act which mani:ests itsel: in the great hardness 5rod ced !y ? enching a steel in cold water. S ch ? enching o: steel :rom the a stenitic condition gi9es rise to a solid sol tion o: car!on in BCC iron which is o: the order o: at least one

#ig. %.& (ll strates the e::ect o: increase in car!on content on the str ct res o: normalised 5lain car!on steels. #errite (light) with increasing amo nts o: 5earlite (dar8). ,he 5earlite is not generally resol9ed at this magni:ication. (Etched in 0R Nital.) < $14.

#ig. %.% $.0R car!on tool steel, annealed. +earlite and 5rimary cementite (#e/C), Here the high magni:ication is s ::icient to resol9e the 5earlite showing lamellae o: cementite in a :errite matri<. (Etched in 0R Nital.) < $444.

tho sand times s 5ersat rated. (t a55ears nder the microsco5e as acic lar (needle=sha5ed) crystals tho gh what is !eing o!ser9e a is in reality a cross=section thro gh ro ghly disc s=sha5ed 5lates. ,his str ct re, 8nown as martensite, is single=5hased since all o: the car!on has !een retained in solid sol tion. (: the degree o: nder cooling is less se9ere allowing trans:ormation to 5roceed isothermally at some tem5erat re !etween 014ZC and 114ZC then car!ide will 5reci5iate tho gh not in the lamellar :orm :o nd in 5earlite. (n this case the car!ide tends

to :orm as small 5articles too small to !e 9isi!le e<ce5t at high magni:ications, and the str ct re is 8nown as Bainite. ;hereas 5earlite :ormation is initiated !y the n cleation o: car!ide, !ainite :ormation a55ears to !e initiated !y :errite growth which in t rn is :ollowed !y the 5reci5itation o: car!ide 5articles ad3acent to the :errite. ,rans:ormation which occ rs at the lower end o: the range (aro nd 014ZC) gi9es rise to 9ery small car!ide 5articles and the str ct re, 8nown as lower !ainite, resem!les most closely that o: martensite in sha5e. ,rans:ormations occ rring in the region o: 144ZC on the other hand, allow m ch larger car!ide 5articles to :orm and the str ct re, which has a di::erent a55earance to that :ormed aro nd 014ZC, is s ally 8nown as 55er !ainite. ,rans:ormations which occ r at tem5erat res 3 st !elow >0/ZC and down to a!o t 114ZC will gi9e rise to 5earlite. ,he lower the trans:ormation tem5erat re within these limits the :iner the str ct re o: 5earlite 5rod ced.

Fig 7 1' ,he thermal treatment se? ence :or the ceri9atioo o: a ,rr diagram. ,he s5ecimens are o: ro ghly the dimensions o: a British $ 5 5iece or an American dime coin.

7(# ,he relationshi5 !etween the tem5erat re at which trans:ormation o: a stenite occ rs and the str ct re and 5ro5erties 5rod ced can !e st died !y re:erence to a time=tem5erat re= trans:ormation (,,,) diagram. S ch a diagram (#ig. %.$>) relates the tem5erat re at which the trans:ormation o: a stenite is ta8ing 5lace with the time necessary :or this to occ r and the ty5e o: str ct re 5rod ced as o tlined a!o9e. ,his :orm o: diagram is 5rod ced :or a steel o: single com5osition and we shall consider one o: e tectoid (4.&R C) com5osition. As #ig. %./ indicates this steel !ecomes com5letely a stenitic when heated 3 st a!o9e >0/ZC so a s ::icient n m!er o: s5ecimens, all identical in si7e and com5osition (4.&R C) are heated in a !ath o: molten salt at >/4ZC so that they attain this state. A!o t ten o: these s5ecimens are then remo9ed sim ltaneo sly :rom the a stenitising !ath and ? ic8ly trans:erred to another salt !ath which will !e maintained at some

5redetermineded

tem5erat re !elow >0/ZC. (ndi9id al s5ecimens are then remo9ed :rom this second=or inc !ation=!ath a:ter increasing time inter9als and immediately ? enched in cold water. ,his :inal ? ench e::ecti9ely halts any trans:ormation which was ta8ing 5lace at the inc !ation tem5erat re in the second !ath and any a stenite which remained will !e con9erted to martensite !y the :inal ? ench. Microsco5ical e<amination will re9eal the e<tent to which trans:ormation had occ rred d ring inc !ation in the second salt

!ath (#ig. %.$6). ,h s a s5ecimen which was almost com5letely martensitic (A) had only 3 st !eg n to trans:orm a:ter !eing held :or one second at the inc !ation tem5erat re (144ZC in this case)M whilst one which contained no martensite ! t which was almost com5letely !ainite (B) had already trans:ormed to !ainite a:ter ten seconds at the inc !ation tem5erat re. ,he :inal water ? ench co ld then ha9e no : rther e::ect on the str ct re since the trans:ormation o: a stenite was already com5lete. Any s5ecimen inc !ated at 144ZC :or a time intermediate !etween these two e<tremes wo ld,on ? enching in the :inal water !ath, contain a mi<t re o: !ainite and martensite (C) indicating that trans:ormation was incom5lete a:ter that holding time (in this case :i9e seconds). ,he same se? ence o: o5erations is then re5eated with other !atches o: the same a stenitised steel ! t sing di::erent inc !ation tem5erat res. At each inc !ation tem5erat re the time :or trans:ormation to !egin and to !e com5leted can then !e ascertained and the com5lete ,(, c r9es 5lotted. (n 5ractice small thin s5ecimens o: a55ro<imately the dimensions o: a British $5 5iece or an American dime coin are sed in order that they shall attain 9ery ? ic8ly the tem5erat re o: the inc !ation !ath to which they are trans:erred. A length o: tem5erat re=resistant wire is generally :i<ed to the s5ecimen to :acilitate ra5id trans:er and ? enching. 7 ( $ ,he res ltant ,,, c r9es 5lotted :rom in:ormation o!tained !y st dying the isothermal trans:ormations o: a 4.&R C steel are shown in #ig. %.$>. ,he hori7ontal !ro8en line re5resenting the tem5erat re o:>0/ZC is o: co rse the Al tem5erat re a!o9e which the str ct re o: the4M&R C steel in ? estion consists entirely o: sta!le a stenite. At tem5erat res !elow this line a stenite !ecomes increasingly nsta!le and the two a55ro<imately C=sha5ed c r9es indicate the time inter9als necessary :or the a stenite :errite W car!ide trans:ormation to !egin and to reach com5letion when a s5ecimen is cooled ra5idly to the inc !ation tem5erat re.

As might !e e<5ected trans:ormation is sl ggish at tem5erat res immediately !elow >0/ZC since a stenite is then only slightly short o: its lowest e? ili!ri m tem5erat re, ! t as the tem5erat re :alls towards 114ZC !oth the delay in starting and the time re? ired :or com5letion o: trans:ormation decrease ra5idly. Again this is to !e e<5ected since the greater the degree o: ndercooling o: the a stenite the greater will !e its rge to trans:orm. Both the inter9al !e:ore trans:ormation !egins and the 5eriod o: trans:ormation itsel: are at a minim m at a!o t 114ZC. Q Any trans:ormation which ta8es 5lace !etween >0/ZC and 1144C is initiated !y cementite 5reci5itation since in this range the di:: sion o: car!on in #CC iron is ra5id and the trans:ormation 5rod ct is 5earlite (%./)=coarse 5earlite 3 st !elow >0/ZC where trans:ormation is sl ggish and !road lamellae ha9e time to :ormM ! t :ine 5earlite when ra5id trans:ormation occ rs near 114ZC. At tem5erat res !etween 114ZC and 0044C trans:ormation !ecomes increasingly sl ggish with decrease in tem5erat re, :or, altho gh the #CC str ct re !ecomes increasingly nsta!le the : rther the tem5erat re :alls !elow >0/ZC, the thermal di:: sion o: car!on at lower tem5erat res !ecomes m ch slower and in:l ences trans:ormation. (n this tem5erat re range trans:ormation is initiated !y :errite 5reci5itation (instead o: cementite as in 5earlite :ormation) and the 5rod ct !ainite, 9aries in a55earance :rom a dar8 :eathery mass :or that :ormed in the region o: 114ZC ( 55er !ainite) to an acic lar str ct re resem!ling martensite :or that :ormed in the region o: 004ZC (lower !ainite).
Note that a logarithmic scale is sed.

7 ( % ,he hori7ontal lines at the :oot o: the diagram are, strictly s5ea8ing, not 5art o: the ,,, diagram ! t re5resent the tem5erat re range o9er which the trans:ormationD a stenite=W martensite !egins (Ms) and is a!o t %4R com5lete (M%4). ,he M: line at which trans:ormation is $44R com5lete is at a55ro<imately =14ZC so that most steels ? enched toroom tem5erat re e<hi!it some Bretained a steniteB in the microstr ct re.

(t m st !e em5hasised that these ,,, c r9es re5resent isothermal trans:ormations, that is, trans:ormations which ha9e ta8en 5lace at a series o: single inc !ation tem5erat res, and it wo ld !e inadmissi!le to s 5erim5ose on them cooling c r9es which re5resent more or less contin o s rates o: cooling. Howe9er, it is 5ossi!le to deri9e modi:ied ,(, c r9es which are related to contin o s rates o: cooling. ,hese are similar in sha5e to tr e ,,, c r9es ! t are dis5laced somewhat to the right as indicated in #ig. %.$&.

7 ( ' )n this diagram c r9es H, I and O, re5resenting di::erent contin o s cooling rates, are s 5erim5osed. C r9e H indicates a rate o: cooling s ch as might 5re9ail d ring a normalising 5rocess. ,rans:ormation o: the nsta!le a stenite !egins at * and is com5lete at N and the 5rod ct is o: co rse :ine 5earlite. A 9ery

ra5id :all in tem5erat re is re5resented !y c r9e I. Here the BnoseB o: the modi:ied trans:ormation=!egins c r9e is missed so that nsta!le a stenite 5ersists ntil at 4 (on the Ms line) trans:ormation direct to martensite !egins. ,he ra5id cooling necessary in order to a9oid the nose o: the trans:ormation=!egins c r9e e<5lains why it is not 5ossi!le to harden ni:ormly 9ery hea9y sections in ordinary car!on steel. ;hilst the surface o: a thic8 !ar might cool s ::iciently ra5idly to !e re5resented !y c r9e I and so !ecome martensitic, the core o: the same !ar will cool more slowly and !e re5resented, say, !y c r9e O. ,h s, in the core, trans:ormation to !ainite will !egin at _, !e arrested again some where in the region o: R and the a stenite which remains will !egin to trans:orm to martensite at S. Conse? ently whilst the o ter s8in o: the !ar will !e totally martensitic the core will contain a mi<t re o: martensite and so:ter !ainite. 7 ( ( ,he ,,, c r9es we ha9e !een considering are those :or a 4.&R C steel. (: the car!on content is either a!o9e or !elow this amo nt the c r9es are dis5laced to the le:t so that the critical cooling rateQ re? ired to 5rod ce a totally martensitic str ct re will !e e9en greater. Hence the need :or drastic water ? enches in order to harden 5lain car!on steels !ecomes a55arent. ;ith a steel o: less than 4./R C the trans:ormation=!egins c r9e has mo9ed so :ar to the le:t (#ig. %.$%(i)) that it is im5ossi!le to cool a steel s ch that the :ormation o: considera!le amo nts o: :errite in the 55er tem5erat re ranges is a9oided. ,he res ltant str ct re there:ore contains martensite inters5ersed with so:t :errite. 7 ( 4 An n:ort nate res lt o: this need to cool 5lain car!on steels so ra5idly, i: they are to !e com5letely hardened, is that internal ? enching strains are set 5. ,hese strains lead to distortion and, 5artic larly with com5onents o: com5le< sha5e, to ? ench crac8ing. ;ith ra5id cooling it is ine9ita!le that the o ter s8in and the inner core o: a 5iece o: steel will 5ass thro gh the #CC BCC

trans:ormation a:ter different time inter+als. Since a 9ol me change accom5anies this trans:ormation (/.6./) it :ollows that the s8in, as it changes to BCC, will tend to e<5and away :rom the core which at that instant is still #CC in str ct re. (nternal strain is set 5 and this is 9ery li8ely to ca se crac8ing o: the s8in which has 3 st trans:ormed to hard, !rittle martensite. #ort nately the addition o: alloying elements li8e nic8el, chromi m or moly!den m to a steel red ces considera!ly the rate o: cooling necessary to 5rod ce a martensitic str ct re. ,h s the ,,, c r9es are dis5laced to the right (#ig. %.$%(ii)). ,his ma8es it 5ossi!le to oil ? ench=or e9en air harden=a s ita!le steel and still o!tain a hard martensitic str ct re thro gho t. (t will !e noted (#ig. % .$%(ii)) that :or a low=alloy steel se5arateC=sha5ed ,,, c r9es re5resent the a stenite :errite W 5earlite and a stenite !ainite trans:ormations. A similar sit ation arises with the ,,, diagram :or a e tectoid 5lain=car!on steel ! t the two sets o: c r9es
QRe5resented !y a cooling c r9e which 3 st gra7es the nose o: the rele9ant trans:ormation= !egins c r9e.

o9erla5 to the e<tent that single contin o s c r9es (#ig. %.$>) can !e sed to re5resent the trans:ormation 5henomena.

)ass Effects and .ardena*ilit&

7 4 (t will ha9e !ecome o!9io s :rom the :oregoing acco nt that there is a ma<im m cross=section :or car!on steels which, i: e<ceeded, will not !e ni:ormly martensitic e9en when ? enched at the greatest 5ossi!le rate :rom the a stenitic state. ,h s whilst a small=section !ar (#ig. %.04) will ha9e cooled ra5idly eno gh :or martensite to ha9e !een :ormed thro gho t, thic8er !ars will contain !ainite or e9en :ine 5earlite in those regions where a stenite did not cool :ast eno gh to a9oid c tting into the nose o:

the a55ro5riate trans:ormation=!egins c r9e. ,he dis5lacement o: ,,, c r9es to the right d e to the addition o: alloying elements to a car!on steel ma8es it 5ossi!le to oil= or air=harden ? ite hea9y

sections o: s ita!ly alloyed steels. Howe9er, to 5re9ent the mis se o: their steels !y o9er o5timistic c stomer.s who may ass me incorrectly that any alloy steel can !e oil=hardened in hea9y sections, man :act rers generally s5eci:y a ruling section :or a 5artic lar alloy steel. ,his r ling section is the ma<im m diameter which can !e hardened ( sing the recommended heat=treatment 5rogramme) i: the stated mechanical 5ro5erties are to !e o!tained. (: this diameter is e<ceeded then the mechanical 5ro5erties may 9ary across the section since the core will not ha9e cooled ra5idly eno gh to ha9e trans:ormed to martensite d ring ? enching. Any s !se? ent tem5ering will not 5rod ce the desired str ct re or 5ro5erties. 741 ,he Kominy end=? ench test is o: 5ractical 9al e in assessing the Bde5th o: hardeningB o: a steel. Here a standard test 5iece (#ig. %.0$) is

heated to its a stenitic range, dro55ed into 5osition in a s ita!le holding 3ig as shown and then ? enched at its end !y a 3et o: water at standard tem5erat re and 5ress re. (n this way di::erent rates o: cooling are achie9ed along the length o: the test 5iece. ;hen it is cool, a B:latB a!o t 4.. mm dee5 is gro nd along the side o: the test

5iece and hardness determinations made e9ery millimetre along the length :rom the ? enched end. ,he res lts are then 5lotted (#ig. %.00). ;hilst there is no sim5le relationshi5 !etween the res lts o: this test and the r ling section o: a steel, it is o: 9al e in ma8ing a 5reliminary estimation o: the latter.

.eat1treatments Based on the !on IeE"ili*ri"m transformation of A"stenite

75 Heat=treatments most 5o5 larly associated with steels are those which lead to the de9elo5ment o: great hardness or strength. All o: these 5rocesses res lt in the :ormation o: str ct res which are not in e? ili!ri m at room tem5erat re and in9ol9e cooling :rom the range o: sta!le a stenite at s ch a rate that 5earlite :ormation is 5re9ented. 751 .ardening A hardening 5rocess see8s to 5rod ce a ni:orm martensitic str ct re thro gho t the steel and i: this is to !e achie9ed the whole o: the com5onent m st !e cooled at a rate

which e<ceeds the critical cooling rate :or the steel. ,hat is, the cooling c r9e :or the core m st 5ass to the le:t o: the trans:ormation=!egins c r9e (#ig. %.04). ,o attain this o!3ecti9e a 5lain car!on steel m st generally !e ? enched in cold water and hea9ier sections may need to !e ? enched in !rine or ca stic soda sol tion which will 5romote e9en ? ic8er rates o: cooling. 'ery hea9y sections in car!on steel cannot !e com5letely hardened and then alloy steels m st !e sed instead. A ma3or di::ic lty associated with water ? enching 5lain car!on steels is that distortion and crac8ing are always li8ely to occ r (%.6.>). -ess drastic ? enching in oil can !e sed :or thin sections in car!on steel and :or hea9ier sections in low=alloy steels and a martensitic str ct re still o!tained. (n all ? enched steels 9arying amo nts o: a stenite may !e retained since the M : line is at s !=7ero tem5erat res. S ch retained a stenite will gi9e rise to so:t s5ots ! t can !e made to trans:orm to martensite !y : rther treatment in solid car!on dio<ide or li? id o<ygen as re? ired. _ enching oils are o: animal, 9egeta!le or mineral origin ! t traditionally whale oil was the most commonly sed. ,his has now !een re5laced !y mineral oils and 9ario s synthetic organic com5o nds !ased on 5olyal8ane glycols (in water sol tion). Most will agree this was e<cellent news :or the whale which is now only h nted to satis:y the de5ra9ed a55etites o: a :ew go rmands who a55arently wish to eat these no!le docile creat res. A hy5o=e tectoid steel is generally hardened !y heating it to a tem5erat re 3 st a!o9e A/ so that it !ecomes com5letely a stenitic, and then ? enching it in the a55ro5riate medi m. Symmetrical com5onents li8e a<les sho ld !e ? enched Bend=onB and agitated 9igoro sly so that they cool as ni:ormly as is 5ossi!le th s minimising distortion. Hy5er=e tectoid steels are s ally hardened !y ? enching :rom 3 st a!o9e the A $ tem5erat re to gi9e a str ct re o: 5rimary car!ides in martensite. (n :act the hot=rolling o: hy5er=e tectoid steels is :inished 3 st a!o9e the A $ tem5era= t re so that the 5rimary cementite is rendered glo! lar in :orm !y the wor8ing 5rocess which is ta8ing 5lace sim ltaneo sly with the

5reci5itation o: 5rimary cementite. (: wor8ing were :inished a!o9e the Acm tem5erat reQ 9ery !rittle networ8s o: 5rimary cementite wo ld :orm aro nd the a stenite grains as the steel cooled !etween the Acm and A $ tem5erat res. #or a similar reason a hy5ere tectoid steel (s 55lied as hot=rolled !ar) sho ld ne9er !e heated 9ery :ar a!o9e Al as once the glo! lar 5rimary cementite has !een re= a!sor!ed !y the a stenite it is li8ely to !e de5osited as !rittle :ilnis along the a stenite grain !o ndaries on cooling. 7 5 # Tempering Martensite is a non=e? ili!ri m 5hase :or which reason its name does not a55ear on the iron=car!on diagram. (:, there:ore, martensite is heated the str ct re is ena!led to 5roceed in some degree towards e? ili!ri m de5ending 5on the tem5erat re sed. Essentially tem5ering ca ses the dis5ersed dissol9ed car!on atoms to 5reci5itate as car!ide 5articles which increase in si7e as the tem5erat re increases.

At low tem5erat res (!etween $44 oC to 044oC) e<tremely thin 5latelets o: =car!ide, which is o: di::erent com5osition to #e/C, are :ormed and the car!on content o: the remaining martensite :alls to a!o t 4./R as a res lt. At :irst the hardness increases slightly (#ig. %.0/) as car!ide 5reci5itation
Q,he tem5erat re at which 5rimary cementite !egins to se5arate :rom the a stenite, in a hy5er=e tectoid steel.

!egins ! t then !egins to :all again as the amo nt o: 5reci5itated car!ide increases. At a!o t .44ZC the =car!ide.!egins to change to ordinary #e/C and low=car!on martensite starts to re9ert to :errite. ,hese changes are accom5anied !y a :all in hardness ! t a corres5onding increase in d ctilityand to ghness. D ring low=tem5erat re tem5ering the original martensite !ecomes dar8 in a55earance d e to the 5reci5itation o: the E= car!ide 5articles. ,hese 5articles are too small to !e 9isi!le sing an o5tical microsco5e. ;hen higher tem5ering tem5erat res are sed the str ct re loses its original martensitic a55earance and glo! lar car!ide 5articles in a :errite matri< can !e seen at high magni:ications sing an o5tical instr ment. ,he :ormer terms o: BtroostiteB and Bsor!iteB to descri!e these res5ecti9e str ct res are now generally o!solete and metall rgists 5re:er to s5ea8 in terms o: Btem5ered martensiteB. At tem5ering tem5erat res a55roaching A l 5reci5itation o: #e/C is s ch that the str ct re resem!les that 5rod ced !y a s5heroidising anneal (%.1.0). (n :act this treatment is o:ten sed to s5heroidise a steel :ollowing a s ita!le ? enching o5eration since i: is ? ic8er and gi9es a more reg lar dis5ersion o: cementite. +lain=car!on (and also low=alloy) steels are s ally tem5ered !elow 014ZC where hardness and wear=resistance are o: 5aramo nt im5ortance. ;hen greater d ctility is re? ired, as in stress=!earing 5arts in aircra:t and A tomo!ile engineering, then higher tem5ering tem5erat res 5 to 614ZC are em5loyed. 7 5 $ +sothermal Treatments ,hese treatments are !ased on in:ormation o!tained a!o t the isothermal trans:ormations o: steels as em!odied in the ,,, c r9es (%.6.0), tho gh it m st !e admitted that many old ind strial 5rocesses s ch as the B5atentingB o: steel wire 5redated the theoretical consideration o: s ch matters !y many years. ,he 5rinci5al ad9antage o: isothermal trans:ormation is that it red ces the 5ossi!ility o: internal stresses !eing generated d e to ra5id cooling thro gh the Ms=M: (or more 5ro5erly Ms=M%4) range.

%.&./.$ Martem5ering ,his is rather an n:ort nate title :or this treatment since it is, in no sense, a tem5ering 5rocess. #or that matter it is not an isothermal treatment either since trans:ormation to martensite occ rs on a :alling tem5erat re gradient. ,he o!3ect o: the treatment is o: co rse to minimise war5ing, distortion and crac8ing which are li8ely to occ r d ring c stomary ? ench= hardening which might otherwise !e em5loyed. ,he treatment in9ol9es heating the steel to its a stenitising tem5erat re and then ? enching it as ra.idly as .ossi,le in a molten salt !ath which is maintained 3 st a!o9e the M s tem5erat re. ,he steel is held in the salt !ath :or long eno gh to 5ermit its str ct re to attain the same tem5erat re thro gho t (#ig. %.0.(i). (t is then withdrawn :rom the salt !ath and allowed to cool 4uite slowly to room tem5erat re (remem!er the ,,, diagram em5loys a logarithmic time a<is). As the diagram indicates !oth the s8in and the core o: the com5onent will then 5ass thro gh the Ms=M%4 M

range more or less sim ltaneo sly so that distortion arising :rom the generation o: internal stresses will !e minimised. A ni:orm martensitic str ct re will ha9e !een 5rod ced. L!@!;!6 Austem.ering ,he o!3ect o: this treatment is again to eliminate the need :or a drastic water ? ench and the Bthermal shoc8B associated with it. (n this case a tr e isothermal trans:ormation to !ainite is in9ol9ed. (n so :ar as mechanical 5ro5erties are concerned !ainite 5rod ced !y isothermal trans:ormation is as satis:actory as the 5arallel str ct re 5rod ced !y tem5ering martensite (%.&.0). ,he :ormer is initiated !y :errite se5aration, the latter !y car!ide 5reci5itation. ,h s, !y sing isothermal trans:ormation the need :or an e<tra tem5ering 5rocess is eliminated ! t, more im5ortant still, the c stomary se9ere ? ench needed to 5reci5itate the !irth o: martensite !ecomes nnecessary. Moreo9er the to ghness and d ctility o: a stem5ered steels is o:ten greater than that o: similar steels hardened and tem5ered in the orthodo< ways to similar hardness 9al es. Again as #ig. %.0.(ii) shows, it is necessary to cool the steel ra5idly 5ast the nose o: the trans:ormation=!egins c r9e. Howe9er, the ? enching=!ath tem5erat re, which is always o: co rse a!o9e Ms, is ad3 sted to gi9e !ainite o: the desired :orm. ,he steel is allowed to remain in the ? enching !ath long eno gh :or trans:ormation to !ainite to !e com5lete, when it can !e cooled to room tem5erat re at any con9enient rate. (n 9iew o: the o!9io s ad9antages o: these isothermal treatments the reader may well as8D B;hy are the old methods o: ? enching2tem5ering still sedJB ,he answer lies in the :act that s ccess: l isothermal treatments are de5endent 5on cooling the steel ra5idly eno gh to miss the BnoseB o: the trans:ormation=!egins c r9e, other wise :ine 5earlite will :orm in the range 144Z=644ZC. ,h s, as :ar as .lain-car,on steels are concerned these 5rocesses are limited to the treatment o: materials not more than $4 mm thic8 which can !e cooled s ::iciently ra5idly. #or e<am5le, a stem5ering is a se: l treatment :or s5rings, 5ins, needles,

screws, garden s5ades and similar thin com5onents. High=car!on steel wire too is similarly treated. ;ith alloy steels the sco5e is greater !eca se o: the dis5lacement o: the ,,, c r9es which indicate the lower critical cooling rates 5re9ailing. (n s ch cases an oil ? ench will !e 9ery ro ghly e? i9alent to martem5ering since the cooling c r9e re5resenting an oil ? ench le9els o t near to the M s line !eca se o: the higher !oiling 5oint o: oil as com5ared with that o: water.

S"rface .ardening of Steels

7 7 #re? ently com5onents li8e gears and a<les need to !e to gh and d ctile ! t, at the same time, ha9e a hard, wear=resistant s r:ace. D ctile materials are s ally so:t whilst hard materials are generally !rittle, so the most e::ecti9e way to achie9e this di::ic lt com!ination o: 5ro5erties is to se a steel which has a s r:ace o: di::erent com5osition :rom that o: the coreM as is contri9ed !y car! rising or nitriding. Alternati9ely a steel o: ni:orm car!on content can !e sed and its s r:ace heat=treated in a di::erent manner :rom the core. 7 7 1 Case1hardening ,his is a title generally gi9en to those 5rocesses which in9ol9e car! rising the s r:ace o: a to gh, d ctile low=car!on steel. Since car!on dissol9es interstitially in #CC iron it :ollows that the low=car!on steel em5loyed m st !e heated to a!o9e A/ (a!o t %44Z=%14ZC) in an atmos5here which will release :ree car!on atoms. ,reatment time m st !e s ::icient to 5rod ce a BcaseB o: the re? ired de5th. Solid, li? id and gaseo s car! rising media are sed. Solid media contain some :orm o: car!on s ch as charcoal along with an acti9ator li8e !ari m car!onate. ,he com5onents are 5ac8ed into

steel !o<es with this medi m and heated :or 5 to :i9e ho rs. -i? id media are !ased on molten sodi m cyanide2sodi m car!onate mi<t res. ,he 5oisono s nat re o: these mi<t res and the dis5osal o: 5rocess waste 5oses 5ro!lems in the modern world. Most large=scale ind strial car! rising now em5loys gaseo s media, s ch as town gas, nat ral gas or other hydrocar!ons li8e 5ro5ane. Easeo s methods are clean, ra5id and e::icient. D ring car! rising a concentration gradient o: car!on in iron is set 5 as indicated in #ig. %.01. ):ten s5eci:ications ? ote a hardness 9al e as determining the limit o: the useful case. (n #ig. %.01 a hardness o: 114 H9 is 3 dged to coincide with this limit which in this instance is at a de5th o: $.0 mm where the car!on content will 5ro!a!ly !e a!o t 4./R. #ollowing car! rising heat=treatment o: the com5onent is necessary. (n many instances ? enching direct :rom the car! rising medi m is em5loyed ! t the co nsel o: 5er:ection is to se a do !le heat=treatment 5rocess. ,he core str ct re is :irst re:ined !y normalising the com5onent 3 st a!o9e the

A/ tem5erat re for the core! ,he com5onent is then reheated to a!o t >64ZC which is a!o9e the A/ tem5erat re :or the case, and then ? enched.

77# !itriding ,his 5rocess in9ol9es the interstitial solid sol tion o: nitrogen atoms to :orm a 9ery hard s8in on the s r:ace o: the com5onent. S5ecial steels containing either $.4R al mini m

or small amo nts o: chromi m, moly!den m and 9anadi m are sed so that hard nitrides o: these metals will :orm in the s r:ace layers. ,he charge is heated at 144ZC :or 5wards o: :orty ho rs in an atmos5here o: ammonia. ,his dissociatesD NH/k/H W N and the atomic nitrogen released dissol9es interstitially in the s r:ace o: the BCC iron. ,he main ad9antages o: nitriding as com5ared with car! rising areD (i) Since no ? enching is re? ired a:ter nitriding, crac8ing and distortion are nli8ely. (ii) High s r:ace hardness 5 to $$14 /%= is o!taina!le with some o: the s5ecial BNitralloyB steels. (iii) Resistance to corrosion and resistance to :atig e are good. (i9) Hardness is retained 5 to 144ZC whereas a hardened car! rised com5onent !egins to so:ten at 044ZC d e to normal e::ects o: tem5ering. ,he 5rinci5al disad9antage o: nitriding is that the 5lant o tlay is high whereas com5onents can !e car! rised in solid media ? ite chea5ly. As with many 5rocesses the ? estion o: nit cost is de5endent largely 5on the scale o: Bthro gh5 tB. 7 7 $ +nd"ction and Flame .ardening (n these 5rocesses a steel o: ni:orm car!on content= s ally a!o t 4..R C=is sed. ,he com5onent is :irst normalised to gi9e a to gh, d ctile, 5earlitic core. (ts s r:ace is then heated, either !y a gas torch or !y high= :re? ency ind ction methods, and, almost immediately, ? enched !y means o: water 3ets. ,his 5rod ces a hard martensitic s8in on to5 o: the to gh 5earlitic core. ,he two 7ones are generally se5arated !y a layer o: !ainite which red ces the 5ro!a!ility that

the case will :la8e away. Symmetrical com5onents s ch as gears and a<les can !e s5 n !etween centres d ring heating and ? enching, th s ens ring a more ni:orm str ct re.
Q (t is e<tremely nli8ely that s ch in:ormation wo ld !e o!tained in the real world o: ind stry !y calc lations o: this ty5e=which are de9ised mainly to terrorise st dents d ring e<aminations. (nstead a series o: 5ieces o: the a<le material in ? estion wo ld !e car! rised :or di::erent 5eriods o: time (all at the same 5redetermined tem5erat re). ,he case de5th, meas red !y sim5le metallogra5hic ins5ection, wo ld then !e 5lotted +s car! rising time. (n any e9ent an e<5eriment o: this ty5e wo ld need to !e 5er:ormed to deri9e D :or the car! rising conditions i: the mathematical a55roach were to !e sed=a Bchic8en=and=eggB sit ation G

1; Allo& Steels and Engineering Cast +rons

1; 1 ManBs early :erro s im5lements were o: wro ght origin, :orged :rom meteoric iron and, later, :rom the s5ongy mass 5rod ced !y the low=tem5erat re red ction o: iron ore. De9elo5ment o: : rnaces which co ld red ce and melt iron and so 5rod ce cast iron !egan in a!o t $444 B.C. in China whence the technology s5read to (ndia !e:ore the start o: the Christian era. ,he 5rocess was inde5endently, i: somewhat !elatedly, disco9ered in E ro5e in the :o rteenth cent ry A.D. ,he ;orldBs :irst metal !ridge=that at (ron!ridge in Shro5shire=was ! ilt o: cast iron in $>>%. ,he se o: cast iron was wides5read in 'ictorian times :or ornamental (J) as well as :or engineering 5 r5oses, whereas it is now sed solely as a so5histicated engineering material with a highly de9elo5ed technology. 1; 1 1 ,ho gh the :irst alloy steel was a high=manganese alloy originated !y Had:ield in $&&0, commercial alloy steels are o: the twentieth cent ry. ,h s, high=s5eed steel was :irst 5rod ced in the FSA !y ,aylor and ;hite in $%44 and the :irst stainless steel !y Brearley o: England in $%$/, tho gh it did not attain commercial stat s ntil m ch later. (n the :oregoing cha5ter the str ct res, 5ro5erties and heat= treatments o: ordinary car!on steels were o tlined. Here we shall deal with some o: the more com5le< iron=!ase alloys which

de5end :or their s5eci:ic 5ro5erties on the 5resence o: other elements in addition to car!on.

Allo& Steels
1; # Alloying elements are added to car!on steels to im5ro9e their e<isting 5ro5erties ! t, in some cases, also to introd ce new 5ro5erties s ch as corrosion resistance. Small amo nts o: manganese (4./=4.&R) are always 5resent in so=called 5lain=car!on steels as a resid e :rom deo<idation and des l5h risation. S ch manganese has a meas ra!le e::ect in red cing the critical cooling rate :or a steel. Howe9er, it is not regarded as an alloying element nless it e<ceeds 0.4R, whilst it has !een traditional to regard 4.$R Mo or 'M 4./R ;, Co or. CrM or 4..R Ni as !eing the minim m ? antities o: these elements to ? ali:y :or Balloy stat sB. ,he introd ction o: the modem generation o: micro-alloyed steels ($4./..) has rendered s ch a de:inition s5 rio s since amo nts as small as 4.4441R o: some elements made to a high=5 rity mild steel e::ecti9ely im5ro9e 5ro5erties. ,he 5rinci5al e::ects which the main alloying elements ha9e on the str ct re and 5ro5erties o: steels can !e classi:ied as :ollowsD 1; # 1 +ncrease in Tensile Strength Most o: the elements sed in alloy steels dissol9e s !stit tionally to some e<tent and 5redicta!ly, increase the tensile strength as a res lt. ,his o: co rse is a general e::ect o: alloying (>.1). (n low=alloy steels the :errite is strengthened in this way whilst high d ctility and to ghness are maintained. ,ho gh metall rgically ns5ectac lar, this is one o: the most im5ortant :eat res o: alloying in steels. 1; # # Changes in the Pol&morphic Transformation Temperat"res ,he 5olymor5hic trans:ormation tem5erat res in9ol9ed here are the A/, at %$4ZC in 5 re iron, where the

trans:ormation occ rs, and the A., at $.44ZC, where the change occ rs. Some elements, nota!ly nic8el, manganese, co55er and co!alt, raise the A. tem5erat re and de5ress the A/ as indicated in #ig. $4.$(i). Conse? ently, when added to a car!on steel these elements will tend to sta!ilise a stenite () !y increasing the tem5erat re range o9er which it can 5ersist as a sta!le 5hase. Many o: these elements are #CC in str ct re at room tem5erat re th s :a9o ring the retention o: the #CC a stenite in which

they are s !stit tionally dissol9ed and retarding its trans:ormation to BCC :errite. Moreo9er since most o: these elements do not :orm car!ides, the car!on tends to remain in solid sol tion in the a stenite. ;hen a stenite is sta!ilised at room tem5erat re !y amo nts o: the alloying element in e<cess o: H (#ig. $4.((i)) then the steel will also lose its :erromagnetism. )ther elements, the most im5ortant o: which are chromi m, moly!den m, t ngsten, 9anadi m, al mini m and silicon, ha9e the o55osite e::ect in that they sta!ilise :errite ( ) !y raising the A/ tem5erat re and de5ressing the A.. ,hese elements restrict the :ield o9er which a stenite e<ists, :orming what is generally termed a B =

loo5B (#ig. $4.$(ii)) in the a55ro5riate diagram. Most o: these elements are BCC in str ct re at room tem5erat re so it is not s r5rising that they Sta!ilise BCC :errite. Since some o: them (the Cr=Mo= ; gro 5 o: the transition metals) :orm 9ery sta!le car!ides they :a9o r the 5reci5itation o: car!on in this :orm and : rther aid the trans:ormation. 1; # $ Relative Sta*ilit& of Car*ides Some elements :orm 9ery sta!le car!ides when added to a car!on steel. Many o: these car!ides are harder than iron car!ide. Since these elements will increase the hardness o: a steel they are generally sed in tool steels o: s 5erior ? ality. S ch elements incl de chromi m, moly!den m, t ngsten, 9anadi m and manganeseM whilst titani m and nio!i m also ha9e 9ery strong car!ide=:orming tendencies (#ig. $4.0). Com5le< car!ides are o:ten 5resent when one or more o: these elements are added to a steel.

Not all o: the alloying elements sed in steel ha9e a chemical a::inity :or car!on when in the 5resence o: iron. ,h s nic8el, al mini m and silicon do not :orm car!ides in the 5resence o: iron and in :act ca se insta!ility o: #e/C so that car!on is 5reci5itated in the :orm o: gra5hite. ,here:ore i: it is necessary to add a55recia!le amo nts o: these elements to steel it can only !e done in the 5resence o: one or more o: the car!ide=sta!ilising elements already

mentioned. #or this reason there are no high=car!on steels containing nic8el as the sole alloying element. +nfl"ence on 6rain 6ro,th D ring heat=treatment, 5artic larly at high tem5erat res, grain growth o: a stenite will ine9ita!ly ta8e 5lace. ,he 5resence o: some elements will accelerate this grain growth and so increase the res ltant !rittleness o: the com5onent. ,he most im5ortant element which 5rod ces this nwelcome e::ect is chromi m. Conse? ently care m st !e ta8en in heat=treating chromi m steels to a9oid nd e o9er= heating or sing e<cessi9e treatment times. #ort nately grain growth is rendered more sl ggish !y the 5resence o: some elements, nota!ly nic8el and 9anadi m. Hence these elements are generally classed as Bgrain re:inersB. 1; # ' -isplacement of the E"tectoid Point ,he addition o: any o: the im5ortant alloying elements to a car!on steel will ca se dis5lacement o: the ,e tectoid 5oint s ch that the str ct re will !e totally 5earlitic e9en tho gh the steel contains less than 4.&R car!on. #or e<am5le, the addition o: 0.1R manganese to a steel containing 4.61R car!on will 5rod ce a com5letely e tectoid str ct re (#ig. $4./), whilst a stainless c tlery steelcontaining $/R chromi m and 4./1R car!on is also e tectoid. ,he e tectoid tem5erat re may !e raised or lowered (#ig. $4./), the A l tem5erat re !eing dis5laced in sym5athy with A/ as mentioned a!o9e ($4.0.0). Hence alloy steels generally contain less car!on than 5lain car!onsteels sed :or similar 5 r5oses

1; # ( Retardation of Transformation Rates ;e ha9e seen (%.6.>) that the addition o: alloying elements tends to red ce the critical cooling rates necessary to o!tain a com5letely martensitic str ct re in steels. ,his is indicated !y the dis5lacement o: the ,,, c r9es to the right in #ig. %.$%(ii). All alloying elements, with the e<ce5tion o: co!alt, ha9e this e::ect and it is one o: the most se: l :eat res im5arted !y alloying since it renders 5ossi!le oil ? enching or e9en air hardening as alternati9es to a drastic water ? ench. #or e<am5le, a steel containing ..01R nic8el and $.01R chromi m can !e air hardened in thin sections or oil hardened in sections 5 to $14 mm diameter. Atoms o: these elements which are dissol9ed s !stit tionally im5ede the trans:ormation. E<tremely small amo nts o: !oron ( 5 to 4.441R) may !e added to low=car!on2low=alloy steels in order to im5ro9e de5th o: hardening. ,he atomic si7e o: !oron renders it too large :or easy interstitial solid sol tion ! t too small :or ready s !stit tional solid sol tion. (t is tho ght that the !oron atoms there:ore migrate to lattice im5er:ections which e<ist at grain !o ndaries th s decreasing strain energy in these regions. ,his in t rn delays the incidence o: n cleation o: :errite and so retards the trans:ormation o: a stenite.

1; # 4 +mprovements in Corrosion Resistance ,hose metals which !ecome coated with a thin ! t dense and adherent :ilm o: o<ide ($%.0) are o:ten 5rotected :rom : rther corrosion !y this se: l !arrier. ,h s al mini m, a relati9ely reacti9e metal, is sta!le as an engineering material !eca se o: the 5rotection a::orded !y the dense and closely adherent :ilm o: Al0)/. Al mini m, together with silicon and chromi m, im5art this 5ro5erty to steel when sed as alloying elements, ! t when res ltant mechanical 5ro5erties ha9e to !e considered, only chromi m o: the elements mentioned can !e sed. Chromi m :orms a dense ! t adherent :ilm on steel and 5rotects it e::ecti9ely when a minim m o: $/R chromi m is sed.

Constr"ctional Allo& Steels >

1; $ ,he addition o: alloying elements to medi m=car!on constr ctional steels has the :ollowing ad9antageo s res ltsD (i) mechanical 5ro5erties, ! t in 5artic lar yield strength, tensile strength, to ghness and d ctility are im5ro9edM (ii) critical trans:ormation rates are considera!ly red ced so that a steel can !e hardened !y oil ? enching or air cooling. 1; $ 1 Nic8el is se: l in 5romoting these 5ro5erties since it strengthens :errite !y solid sol tion and im5ro9es to ghness !y its tendency to im5ede grain growth. Fn:ort nately nic8el also :a9o rs gra5hitisation o: any cementite 5resent so that, in a medi m=car!on steel, it is generally accom5anied !y a car!ide sta!iliser s ch as chromi m, which will also assist it in strengthening :errite and red cing trans:ormation rates. S ch steels contain rather more than two 5arts o: nic8el to one o: chromi m,ma<im m ? antities !eing ..01R Ni and $.01R Cr, gi9ing an air=hardening steel. ,hese nic8el=chromi m steels regretta!ly s ::er a :a lt 8nown as Btem5er !rittlenessB. ,his

mani:ests itsel: as a 9ery low im5act to ghness 9al e in a nic8el= chromi m steel which has !een tem5ered in the range 014=.44ZC. ,ensile 5ro5erties, howe9er, are not s !stantially im5aired. #ort nately this de:ect can !e minimised !y adding a!o t 4./R moly!den m, th s gi9ing rise to the 5o5 lar range o: Bnic8el= chrome=molyB steels. Constr ctional steels o: this ty5e are sed :or the man :act re o: a<les, sha:ts, gears, connecting rods, !olts, !rac8ets, etc. 1; $ # ): recent years greater se has !een made o: small additions o: the relati9ely chea5 alloying element manganese to re5lace some nic8el and chromi m in the chea5er grades o: low=alloy steels. ,hese steels are sed ? ite widely in the a tomo!ile ind stry. Manganese 5romotes increased de5th o: hardening !y red cing critical cooling rates. (n low=car!on steels it e::ecti9ely red ces the tem5erat re at which !rittle :ract re ($6./) will ta8e 5lace. Com5ositions, heat=treatments, 5ro5erties and ses o: some 5o5 lar low=alloy constr ctional steels are gi9en in ,a!le $4.0. 1; $ $ Altho gh most o: the constr ctional alloy steels are in the low=alloy class, a :ew high=strength2high=alloy steels are 5rod ced. ,hese are the BmarageingB steels, ty5ical o: which is one containing $&R Ni, &R Co, .R Mo and 5 to 4.&R ,i. Since s ch a high nic8el content will ha9e a considera!le gra5hitising in:l ence car!on m st !e 8e5t low=a!o t 4.4/R. S ch a steel is :irst sol tion treated ($$./.0) to a!sor! 5reci5itated com5o nds. )n air=cooling the str ct re will !ecome martensitic !eca se o: the red ction in the trans:ormation rates inc rred !y the high=alloy content. Fnli8e ordinary tetragonal martensite this is o: BCC :orm and hence m ch so:ter and to gher. Howe9er, the steel can now !e .reci.itation hardened ($$./.0) at 144ZC :or two ho rs so that coherent 5reci5itates o: com5o nds s ch as ,iNi / are :ormed and tensile strengths o: o9er 0444 M+a0 de9elo5ed. ,he term BmarageingB re:ers o: co rse to the Bage=hardeningB= or BageingB =o: martensite.

S ch steels are nat rally 9ery e<5ensi9e and their se is generally limited to so5histicated technology s ch as roc8etry.

1; $ % .igh1strength Lo,1allo& 2.SLA3 Steels )ne o: the most signi:icant de9elo5ments in the steel ind stry in recent decades has !een the steady im5ro9ement in the chemical 5 rity o: dead=mild steels. ,his has meant that BmicroB additions o: s ita!le alloying elements can !e made to 5rod ce e::ecti9e and consistent increases in yield strength whilst retaining high d ctility and to ghness. S ch consistency o: 5ro5erties co ld not !e attained sing a dead mild steel o: irreg lar ? ality. _ ite small ? antities o: N!, ', ,i and Al are now sed in these .SLA and other micro-alloyed steels. .SLA steels are c rrently em5loyed in the str ct ral wor8 o: ! ildings, !ridges and 5i5elines. ,he 5rinci5al : nction o: the added elements is to com!ine with the small amo nts o: car!on and nitrogen 5resent to :orm 9ery small car!o=nitride 5reci5itates (TiC@ Ti! or !*C!) which se9erely restrict crystal growth d ring hot=:orming and annealing 5rocesses. Strength o: HS-A steels increases as grain= si7e decreases seemingly d e to dis5ersion hardening ($..$.1) associated with these 5reci5itates. Nio!i m in amo nts !etween 4.46 and 4.$R will 5rod ce yield strengths 5 to /14 M+a in cold= wor8ed annealed :orms and 114 M+a in some hot=rolled HS-A steels. A ty5ical o::=shore 5i5eline material may contain C=).4%M Si=)./M Al=).4/M Mn=$./1M N!=).4/1 and '=).4>R. S ch an alloy cannot !e re:erred to as a BsteelB in the normal sense ! t rather as a Bdis5ersion=strengthened ironB. Ne9ertheless the term BsteelB is generally sed ind strially. (n the a tomoti9e ind stries cold=:ormed annealed micro= alloyed steels Bare not con:ined to high=strength materials. ,h s a to=!ody 5ressings in Bdi::ic ltB sha5es re? ire a low-strength steel with high ductility. 'ac m degassed steel with small amo nts o: titani m and2or nio!i m contain min te se5arate 5reci5itates o: ,i or N! car!ides and nitrides ! t no car!on or nitrogen in interstitial solid sol tion. S ch a BsteelB has a 9ery low yield stress ! t a 9ery high d ctility=ideal :or cold :orming.

Allo& Tool Steels

1; % Alloying elements are added to tool steelsD (i) (ii) to increase hardness and wear=resistance !y the :ormation o: car!ides which are m ch harder than #e/CM to im5art resistance to the tem5ering e::ects associated with high tem5erat re wor8ing. ,his a55lies not only to e<5os re to high tem5erat res when these steels are sed in hot= wor8ing dies, ! t also to :rictional heat generated in c tting tools d ring high=s5eed machining 5rocesses. Correctly hardened high=s5eed steel will resist tem5ering 5 to d ll=red heat.

,he alloying elements in9ol9ed here are the re:ractory metals chromi m, t ngsten, moly!den m and 9anadi m, all o: which :orm 9ery hard sta!le car!ides. Moreo9er since they are all BCC metals they limit the range o9er which a stenite may e<ist (as indicated !y the =loo5 :ormed in the !inary diagram when each is added to iron) and so sta!ilise :errite and martensite. 1; % 1 -ow=alloy tool steels generally contain small amo nts o: chromi m and are oil=hardened :rom tem5erat res slightly a!o9e those sed :or e? i9alent 5lain car!on steels. S ch steels are sed :or !all=!earings, chisels and hot=wor8ing dies. ,he high=alloy tool steels, howe9er, contain considera!le amo nts o: t ngsten, moly!den m and 9anadi m as well as chromi m (,a!le $4./). ): recent years the relati9e scarcity o: t ngsten has led to the wider se o: moly!den m and 9anadi m, 5artic larly in high=s5eed steels. (n order that these steels shall not lose their hardness at high wor8ing tem5erat res the ma<im m amo nt o: t ngsten (or moly!den m) m st !e 5resent in solid solution in the original a stenite !e:ore it is ? enched. #ig re $4.. = a 5se do=!inary

diagram (&.>.0) re5resenting a high=s5eedsteel=indicates that at a tem5erat re o: say %44Z C, little more than 4.0R C along with its associated tungsten is in solid sol tion in the a stenite and that e9en at the solid s tem5erat re o: a!o t $/44Z C only an amo nt, S, is in solid sol tion. #or this reason, in order to retain as m ch car!on and t ngsten in solid sol tion in the ? enched str ct re as is 5ossi!le and so o!tain !oth hardness and tem.er-resistance, 9ery high ? enching tem5erat res are necessary. At these high tem5erat res decar! risation and grain growth are ra5id nless s5ecial 5reca tions are ado5ted. ,h s a two=cham!er : rnace ena!les 5reliminary 5re=heating to !e sed and so limit grain growth !y red cing the time o: contact with the high ? enching tem5erat reM whilst the se o: inert : rnace atmos5heres 5re9ents decar! risation o: the tool s r:ace.

1; % # ,he large amo nts o: alloying elements 5resent slow down trans:ormation considera!ly and so air=hardening (or oil=? enching o: hea9y sections) can generally !e sed. Considera!le amo nts o: a stenite are retained on ? enching and a Bsecondary hardeningB treatment is necessary. ,his in9ol9es heating the tool to a!o t 114ZC to 5romote the trans:ormation o: retained a stenite to martensite. ,wo or three s ch treatments are o:ten necessary !e:ore the a stenitemartensite trans:ormation a55roaches com5letion. )nce :ormed, the martensite is similarly 9ery sl ggish to tem5ering at tem5erat res 5 to >44ZC, wherein lies the most im5ortant :eat re o: high=s5eed steels.

Stainless and .eat1resisting Steels 1%

1; ' ,he role o: chromi m in im5arting corrosion resistance to steel has !een mentioned ($4.0.>) and amo nts !etween $/R and 0$R are commonly sed :or this 5 r5ose. ,hose steels containing only chromi m as an alloying element are o: co rse :erritic since chromi m sta!ilises BCC iron and ? enching those chromi m steels which contain s ::icient car!on will 5rod ce a hard martensitic str ct re. ,h s, high=chromi m steels containing 4./R C are sed :or the man :act re o: ta!le 8ni9es and other r st= resistant edged toolsM whilst those containing little or no car!on are sed :or 5ress=wor8 and dee5=drawing since they can !e hardened only !y cold=wor8. 1; ' 1 Chromi m steels tend to !ecome !rittle d ring heat treatment !eca se chromi m 5romotes grain growth. Stainless steels containing !oth nic8el and chromi m are there:ore less li8ely to s ::er :rom !rittleness !eca se o: the grain=re:ining in:l ence o: nic8el. ,he well=8nown B$&=&B stainless steels are in this class. ,hese are non=hardening alloys in which the car!on content is normally less than 4.$ R. E9en so the :inal treatment is s ally a ? ench :rom $414ZC in order that car!on is retained in solid sol tion and to 5re9ent it :rom 5reci5itating as 5articles o: chromi m car!ide which wo ld im5air the corrosion resistance o: the alloy ($%.>.$).Alternati9ely the addition o: 5 to $.4R o: either nio!i m or titani m (which ha9e high a::inities :or car!on) e::ecti9ely Bties 5B any car!on 5resent so that it is no longer a9aila!le to 5reci5itate as chromi m car!ides. ,his is necessary :or stainless steels which are to !e welded and wo ld !e 5rone to Bweld decayB ($>.6.0) nless so B5roo:edB. 1; ' # Heat=resisting steels m st resist o<idation at high tem5erat res and, in some cases, attac8 !y s l5h ro s gases

($%.0.0). #or this reason they may contain as m ch as /4R chromi m together with small amo nts o: silicon. ,he general tendency :or chromi m to ind ce grain growth, with its attendant !rittleness, is o::set !y adding nic8el. ,hese steels m st !e reasona!ly strong at high tem5erat res so they are Bsti::enedB !y adding small amo nts o: two or more o: the :ollowingD car!on, t ngsten, moly!den m, titani m and al mini m, so that small 5articles o: car!ides or intermetallic com5o nds are :ormed. (n this manner the limiting cree5 stress is raised d e to .article hardening ($..$.1). Metall rgical 5rinci5les in9ol9ed in the heat=resisting steels also a55ly to the BNimonicB series o: alloys. ,hese are not steels ! t contain !asically >1R nic8el=04R chromi m, sti::ened with small amo nts o: car!on, titani m, al mini m, co!alt, moly!den m or nio!i m.

Engineering Cast +rons

1; ( (n terms o: cost 5er nit mass cast iron is the chea5est metall rgical material a9aila!le to the engineer. (t is in :act re= melted 5ig iron, the com5osition o: which has ndergone some ad3 stments d ring the melting 5rocess. A5art :rom its low cost other commenda!le 5ro5erties o: cast iron incl de good rigidity and com.ressi+e strengthM e<cellent :l idity so that it ma8es good casting im5ressionsM and good machina!ility. ;hilst the d ctility and tensile strength o: ordinary= grey cast iron are not 9ery high !oth o: these 5ro5erties can !e considera!ly im5ro9ed !y treatments which modi:y ,the microstr ct res o: s ita!le irons. D ring the nineteenth cent ry cast iron was sed !oth :or engineering and domestic 5 r5oses. ,oday the 'ictorian :ire5laces, lam5 standards and water :o ntains ha9e largely disa55eared= e<ce5t as collectorBs items=

and cast iron is now sed solely as a reasona!ly so5histicated engineering material. Alloy=and other s5ecial cast irons are now sed :or the man :act re o: s ch com5onents as cran8sha:ts, a<les and connecting rods, hitherto the 5ro9ince o: :orged steels.

1; ( 1 The Relationship Bet,een Composition and Str"ct"re of Cast +ron Most engineering cast irons contain 0.4=/.1R C. Re:erence to the right=hand hal: o: the iron=car!on e? ili!ri m diagram (#ig. %.$) indicates that an alloy in this range !egins to solidi:y !y de5ositing dendrites o: a stenite and that !y the time that the e tectic=tem5erat re ($$.>ZC) has !een reached the str ct re will consist o: a stenite () crystals containing 0.4R C and a remaining li? id containing ../R C. ,his li? id then solidi:ies at $$.>ZC !y :orming a e tectic, 8nown at one time as lede,urite, consisting o: a stenite (0.4R C) and cementite (6.6&R C). )n : rther cooling !oth 5rimary and e tectic a stenite will change in com5osition along 'E (#ig. %./) !y de5ositing 5articles o: cementite ntil at >0/ZC the remaining a stenite contains 4.&R C where it trans:orms to 5earlite. Conse? ently a :inal str ct re o: cementite and 5earlite wo ld res lt (#ig. $4.%). (n 5ractice o: co rse we are not dealing with sim5le iron=car!on alloys since cast iron contains, in addition to car!on, 5 to 0.1R SiM 4.&R MnM 4.&R + and 4.$ R S and the :orm in which car!on e<ists de5ends to some e<tent on the amo nts o: these other elements 5resent. ;e ha9e seen ($4.0./) that the 5resence o: some elements in steel renders car!ides nsta!le so that they tend to decom5ose :orming gra5hite. Silicon is one o: these elements and its 5resence in 9arying amo nts in cast iron has a similar in:l ence on the state in which car!on e<ists. ,h s a high=silicon iron==containing as m ch as 0.1R Si=will !e almost com5letely gra5hitic and will contain little or no cementite. ,he 5resence o: large amo nts o: gra5hite in the str ct re will lead to a :ract red s r:ace ha9ing a grey a55earance. ,hat is, it will !e a Bgrey ironB. (:, on the other hand, the silicon content is low=in the region o: 4.1R=then cementite will tend to !e sta!le and little or no gra5hite will :orm. Since cementite is e<tremely !rittle s ch an iron will !e mechanically wea8 and a :ract red s r:ace will !e sil9ery white since cementite is a white com5o nd. #or this reason it is termed a Bwhite ironB.

_ ite small amo nts o: s l5h r will ha9e the o55osite e::ect to that o: silicon, that is, s l5h r will tend to sta!ilise cementite and so :a9o r the :ormation o: a white iron. Howe9er, the direct e::ect o: s l5h r in iron, as in steel, is to increase the !rittleness e<cessi9ely so the :o ndryman does not se s l5h r as a means o: controlling the str ct re o: cast iron. Eenerally he will attem5t to 8ee5 the s l5h r content to a minim m, and instead se a 9arying silicon content as a means o: controlling the state o: the car!on 5resent. 1; ( # The +nfl"ence of Cooling Rates on the Str"ct"re of Cast +ron E9en tho gh silicon is 5resent in a cast iron in s ::icient ? antities to gra5hitise any cementite 5resent s ch decom5osition does not occ r instantaneo sly ! t is time de5endent.

Conse? ently i: a cast iron solidi:ies ra5idly its :ract re may well !e white !eca se cementite has had ins ::icient o55ort nity to decom5ose, nder the in:l ence o: silicon. to :orm gra5hite. Clearly the sectional thic8ness o: a casting in:l ences its rate o: solidi:ication and cooling and this, in t rn, will control the condition o: the car!on. An iron which, in hea9y sections, will 5rod ce a grey iron may, when BchilledB !y casting it as a thin section, gi9e a !rittle white str ct re. ,he e<tent to which a 5artic lar iron will Achill@ in this way is generally e<amined !y casting a sam5le in the :orm o: a ste55ed !ar (#ig. $4.>).

The Str"ct"re and Properties of Cast +ron

1; 4 A white cast iron contains !oth .rimary and .earlitic cementite. ,he addition o: silicon to the com5osition ca ses :irst the 5rimary cementite and then the 5earlitic cementite to decom5ose to gra5hite and :errite. ,he !est com!ination o: mechanical 5ro5erties in an ordinary grey iron is o!tained when the str ct re consists o: small :la8es o: gra5hite in a 5earlitic matri<. S ch a str ct re will !e achie9ed !y the :o ndryman !y ad3 sting the silicon content o: the iron to s it the sectional thic8ness o: the casting and hence the rate o: cooling which will 5re9ail d ring its solidi:ication.

Fnder the microsco5e gra5hite :la8es in cast iron a55ear as irreg lar strands with 5ointed ends. (n :act what we see are sections thro gh gra5hite :la8es which, in reality, are sha5ed something li8e the corn :la8es sold as a !rea8:ast cereal. Ne9ertheless the shar5 rims, which a55ear in cross=section as 5ointed ends, act as stress=raisers in the str ct re and are res5onsi!le :or considera!le red ctions in strength and to ghness o: the res ltant casting. (n the design o: stress=!earing com5onents generally, the engineer ma8es e9ery attem5t to a9oid in=c t shar5 corners which can act as stress=raisers. Similarly, on the microsco5ic scale, the metall rgist can 5ro9ide an iron in which

the stress=raising :la8es o: gra5hite are re5laced !y ro nded glo! les o: car!on.

Special Cast +rons

1; 5 ,hese are cast irons in which the mechanical 5ro5erties ha9e !een im5ro9ed either !y alloying or !y some treatment which has ca sed gra5hite to 5reci5itate in a s5heroidal :orm and so eliminate the wea8ening gra5hite :la8es. 1; 5 1 Spheroidal1graphite 2S 6 3 Cast +ron> Also 8nown as Bd ctile ironB in the FSA, this is one s ch iron where :la8e gra5hite is re5laced !y s5herical 5articles o: gra5hite. ,his is achie9ed !y adding small amo nts o: magnesi m= s ally as a magnesi m2nic8el alloy=to gi9e a res ltant magnesi m content o: no more than 4.$ R in the iron. ,his is s ::icient to Bn cleateB the gra5hite so that it :orms as s5herical glo! les (#ig. $4.$0). S ch an iron may ha9e a tensile strength o: >>1 M+a. ,ensile strengths o: the order o: $644 M+a (elongation $.4R) can !e attained !y a stem5ering s ch an iron at 014ZC (:ollowing initial a stenitising at %44ZC). 1; 5 # Compacted1graphite 2C 6 3 +rons> ,hese are intermediate in str ct re and hence in mechanical 5ro5erties=!etween ordinary grey :la8e gra5hite irons and SE irons. Molten iron o: near=e tectic com5osition is treated with a single alloy addition containing small amo nts o: Mg, ,i and Ce. ,his ca ses short gra5hite :la8es with rounded edges to !e :ormed, leading to the term B9ermic lar ironB !eing ado5ted in the FSA. ,hese ro nded edges are less hostile as stress raisers than the ac te edges o: ordinary gra5hite :la8es. 1; 5 $ )allea*le Cast +rons> ,hese are cast to sha5e in the normal way sing a low=silicon iron which will 5rod ce a !rittle white str ct re. Both 5rimary and 5earlitic cementite are s !se? ently eliminated !y s ita!le heat treatment. (n the

Blac8heart +rocess the castings are heated :or 5wards o: :orty ho rs at a!o t %44ZC so that cementite decom5oses to :orm s5herical BrosettesB o: Btem5er car!onB in a to gh :erritic matri<. Blac8heart mallea!le iron is sed widely in the motor=car ind stry :or s ch com5onents as rear=a<le ho sings, wheel h !s, !ra8e shoes and door hinges.

(n the Whiteheart +rocess the heating 5rocess is =carried o t nder o<idising conditions so that car!on is 5rogressi9ely eliminated :rom the str ct re. As car!on in the s r:ace layers o<idises and is lost as car!ondio<ide, more car!on di:: ses o twards :rom the core and is in t rn eliminated lea9ing a totally :erritic str ct re tho gh a central core o: 5earlite in9aria!ly remains. ,he s r:ace o:ten e<hi!its o<ide 5enetration and mallea!le iron 5rod ced !y this method is widely sed in :ittings :or gas, water and steam 5i5esM !icycle and motor=cycle :rame :ittings and switch=gear e? i5ment. (n %earlitic Mallea,le (ron heat treatment is a55lied to ca se decom5osition o: all 5rimary cementite. ,he wor8 is then heated to %444C so that some o: the tem5er car!on is dissol9ed in the a stenite then 5resent. S !se? ent cooling leads to the :ormation o: a strong, to gh 5earlitic matri<. 1; 5 % Allo& Cast +rons> ,hese ma8e se o: the same elements as are em5loyed in alloy steels. =ic el is the most common element sed. (t 5romotes gra5hitisation and has a se: l grain= re:ining=and hence, to ghening=e::ect. Chromium on the other hand increases hardness and wear=resistance !y sta!ilising car!ides. /anadium 5romotes heat= resistance in cast iron !y rendering car!ides 9ery sta!le so that they are less li8ely to decom5ose at high tem5erat res. Co..er, which is only 9ery s5aringly sol !le, im5ro9es the resistance to atmos5heric corrosion.

11 !on1ferro"s )etals and Allo&s

11 1 -imited amo nts o: co55er li8e gold. )cc r ncom!ined in the, EarthBs cr st and it was :or this reason that !oth metals were sed in Ancient times. (t is tho ght that a short BCo55er AgeB 5receded the ;ell=doc mented BBron7e AgeB. ,he Romans sed lead==one can still see the remnants o: their 5l m!ing in +om5eii= whilst +hoenicians came :rom the East to trade :or tin with the Ancient Britons o: Cornwall .,he 5rod ction o: other im5ortant metals li8e al min m, 7inc, nic8el and Magnesi m is o: more recent origin and the ind strial history o: others s ch as titani m s5ans decades rather than cent ries.

Copper and its Allo&s

,he ! l8 o: the world o t5 t o: co55er is sed nalloyed mainly in the electrical ind stries. ,ho gh it is second to sil9er in terms o: cond cti9ity relati9e costs are o: co rse m ch in :a9or o: co55er. Since the 5resence o: im5 rities serio sly im5airs electrical Cond cti9ity ($&..) either electrolytically re:ined ()#HC=Bo<ygen= :ree high=cond cti9ityB) co55er or :ire=re:ined (Bto gh 5itchB) co55er is se% :or electrical 5 r5oses.

11 # 1 + re co55er is a 9ery d ctile metal. Being #CC in str ct re. (n the Bso:tB condition it has a R elongation o: 64 ! t is relati9ely wea8 with tensile strength o: no more than 0$1 M+a. Cold=drawn co55er has a strength o: only /.4 M+a and :or se as tele5hone ;ires the addition o: $RCadmi m will increase the strength to .64 M+a whilst red cing s5eci:ic cond cti9ity !y only 1R (#ig. $&.1). Beca se o: its high d ctility and good corrosion resistance m ch co55er is also sed in domestic 5l m!ing, 5artic larly since the a9aila!ility o: standard 5i5e connectors (containing 5re=set solder) has made 3oining a sim5le 5roced re.

11 # # =5hase alloys in the C =OnM C =Sn and C =A( systems are all d ctile. ,hey were there:ore sed widely :or dee5 drawing and 5resswor8 ! t 9ast im5ro9ements in the d ctility o: Bmild steel in

recent decades co 5led with de9elo5ments in :orming techni? es ha9e meant that m ch chea5er mild steel has largely re5laced !rasses and !ron7es e<ce5t where the higher corrosion resistance o: the latter is a 5riority. 11 # $ Brasses are C =On alloys containing 5 to .1R On (#ig. $$.$). ,he a=5hase !rasses containing 5 to a55ro<imately />R On are noted mainly :or high d ctility which reaches a ma<im m at /4R On. >4=/4 !rass is sed :or the dee5=drawing o: com5onents re? iring good resistance to corrosion. Cold=wor8ing 5rocesses sha5e this gro 5 o: !rasses almost entirely in the :inishing stages. An alloy containing /44M 4 On !egins to solidi:y at H (a!o t %64ZC) !y de5ositing dendrites o: com5osition I. Since these dendrites are Co55er=rich (a55ro<. 0/R On) the remaining li? id !ecomes less rich in co55er. (: we ass me solidi:ication to 5roceed slowly then the li? id changes in com5osition along HH$ whilst the dendrites change in com5osition along II$ as the tem5erat re :alls. At I$ solidi:ication is com5lete and ni:orm (>4R C =/4R On) is the res lt. Ra5id cooling nder ind strial conditions wo ld not allow di:: sion to 5roceed to com5letion so that some coring wo ld !e retained in the growing crystals. Hence the shrin8ing 9ol me o: li? id wo ld !ecome so enriched with On that at %40ZC a 5eritectic reaction wo ld occ r res lting in the :ormation o: o: com5osition C (/6.&R On) along the grain

!o ndaries. #ort nately this is generally ? ic8ly a!sor!ed d ring the early stages o: hot wor8ing and the str ct re attains e? ili!ri m showing a ni:orm str ct re as indicated !y the e? ili!ri m diagram (see #igs $$./and $$..). A 64=.4 !rass !egins to solidi:y at O as the 5hase and solidi:ication is com5lete at O$.Since the range !etween li? id s and solid s is small there will !e little coring in the crystals. As the tem5erat re :alls to a!o t >>4ZC (O0) dendrites o: a. (com5osition ;) !egin to se5arate o t along certain 5lanes within the str ct re 5rod cing a ty5ical ;idmanstatten str ct re (#ig. $$.1). ,his 5rocess contin es as the tem5erat re :alls, changing in com5osition along ;E whilst :/ changes along O 0H. Hence at .1.ZCD

;hereas B is hard and rather !rittle is so:t and mallea!le. Hence 64=.4 ( W B) !rasses are sha5ed !y hot=wor8ing (rolling, :orging or e<tr sion) a!o9e >>4ZC ! t on a falling tem.erature gradient so that the 5rocess

:inishes !elow >>4ZC. ,h s as 5reci5itates it is 5re9ented :rom :orming a !rittle ;idmanstatten str ct re ! t is !ro8en 5 into a gran lar 5attern instead (#ig. $$.6). Additions o: 5 to 0R +! which is insol !le in !oth li? id and solid !rass, im5ro9es the machina!ility o: !rass !y initiating chi5= crac8s in ad9ance o: the c tting toolM whilst $.4R Sn will increase corrosion resistance. 11 # % Tin BronCes these also :all into two gro 5s. ,he single= 5hase =alloys are to gh, d ctile, strong and corrosion resistant. ,hey are more hea9ily cored in the cast Condition than are the !rasses and this is indicated !y the wide range !etween the li? id s AD and the solid s AB in the C =Sn system (#ig. $$.0) as com5ared with the narrow li? id s=solid s range in the C =On system (#ig. $$.$). Moreo9er di:: sion o: tin in co55er is slow so that cast C =Sn alloys with as little as 6R Sn may contain some o: ,he !rittle intermetallic com5o nd (C /$Sn&). (n ind strial 5ractice cooling is ne9er slow eno gh to 5ermit trans:ormation to (C /Sn) to occ rM :or which reason the lower (!ro8en=line) 5art o: the diagram is o: theoretical rather than 5ractical interest. ,h s a 1R Sn !ron7e, which has cooled ra5idly, will !e hea9ily cored (#ig. $$.>) and will contain small B(slands@ o: s8y !l e (C /$Sn& inters5ersed !etween the dendrites. A similar alloy slowly cooled wilt e<hi!it a com5letely a str ct re with 9ery light coring ! t it will !e most nli8ely to contain any o: the 5hase which can only occ r nder strictly controlled la!oratory conditions. ,hese (H !ron7es are cold=rolled (#igs $$.% and $$.$4) to sheet and drawn to wire and other sections. Bron7es containing in e<cess o: $4R Sn will show considera!le amo nts o: d e to e<cessi9e coring o: the .S ch an alloy will ndergo a n m!er o: 5hase changes as it cools. At >%&ZC the a dendrites will react 5eritectically with the remnant li? id to

5rod ce the solid sol tion (com5ositionC=00R Sn). ,his changes in com5osition along CE and in t rn ndergoes a e tectoid trans:ormation at 1&6ZC to gi9e a e tectoid (E) containing 0..6R SnM i.e. W in which is another solid sol tion. At 104ZC yet another e tectoid ,rans:ormation occ rs :orming a e tectoid o: com5osition # (0>R Sn) containing the 5hases l and & (C /$Sn&). At each stage o: this series o: 5hase changes some a will remain in e<cess o: the e tectoid com5osition so that the :inal str ct re will consist o: cored dendrites o: the solid sol tion a with an in:illing o: W e tectoid (#ig. $$.&). As mentioned a!o9e it is nli8ely that with normal cooling rates the e tectoid trans:ormation at a55ro<imately /14ZC (K) will occ r, m ch less the 5reci5itation o: (C /Sng) :rom as is indicated !y the stee5ly slo5ing !o ndary EH. D e to the 5resence o: considera!le ? antities o: the e<tremely (!rittle intermetallic com5o nd (C /$Sn&) in !ron7es containing more than $4RSn these alloys are too !rittle to 5ermit cold= wor8ing sing normal ind strial 5rocesses. (n :act d ring the Second ;orld ;ar one o: my tas8s was to 5rod ce sla!s o: coldrolled $0R Sn !ron7e in connection with early 5rototy5es o: ;hittleBs 3et engine. ,his entailed sol tion annealing o: the Cast ingots :or $0 ho rs at >.4ZC, i.e. 3 st !elow the solid s tem5erat re, to a!sor! the !rittle . E9en so the ni:orm so o!tained wor8=hardened 9ery ? ic8ly and many inter=stage anneals were in9ol9ed in rolling to si7e.My team :inally 5rod ced a cold= wor8ed $0R Sn !ron7e with a tensile strength in e<cess o: $444 M+a ! t it was 9ery e<5ensi9e to 5rod ceG Bron7es containing more than $4R Sn are sed :or the man :act re o: corrosion=resistant castings and !earings in which the 5resence o: 5articles o: the hard 5hase, c shioned in a to ch

matri< o: 5ro9ides a hard=wearing, low=:riction s r:ace. ,in Bron7es are generally deo<idi7ed with small amo nts o: 5hos5hor s. -ea9ing a resid e o: no more than 4.4.R 5hos5hor s in the alloy. ,he addition o: 5hos5hor s in e<cess o: this amo nt and 5 to $.4R is made when increased strength, corrosion Resistance and casting :l idity are necessary. ,hese alloys are 8nown as .hos.hor ,ron?es. (n Bg nmetalsB some o: the e<5ensi9e tin is re5laced !y 7inc. ,his not only red ces cost ! t ma8es deo<idi7ation with 5hos5hor s nnecessary since 7inc itsel: has a high a::inity :or o<ygen :orming insol !le 7inc o<ide which 3oins the dross on the s r:ace o: the molten alloy. 11 # ' Al"min"m BronCe As in the two 5re9io s alloy systems co55er :orms a d ctile solid sol tion, here containing a ma<im m o: %..R A(. ,hese a alloys are also 9ery corrosion resistant. Since the 1R Al alloy is o: the colo r o: $& ct gold it was sed largely in the man :act re o: B;oolworthBs wedding ringsB. Eood resistance to corrosion ens red that it was nli8ely to lea9e !ehind an em!arrassing green stain on the wearerBs :inger d ring its wee8end o: se. Now that 5roo: o: marriage is no longer a Social re? irement these =al min m !ron7es ha9e la5sed into o!solescenceG As the 5hase diagram (#ig. $$.$$) indicates alloys containing !etween %.1R and $..%1R Al solidi:y as a solid sol tion and as the tem5erat re :alls either 5rimary or 5rimary $20 will 5reci5itate within the crystals ntil at 161ZC the remaining trans:orms to a e tectoid o: (W0). ,his e tectoid trans:ormation (W0) is similar to that which occ rs in Steels at >0/ZC (A stenite ()+earlite(W#e/C)) ,he similarity does not end there as the 5rod cts o: the trans:ormation o: L are also in:l enced !y cooling rates as are those in steel

,h s an $$R A( alloy (#ig. $$.$$) o: com5osition which is cooling e#tremely slowly !egins to de5osit 5rimary as the tem5erat re :alls !elow H and at 161ZC, the e tectoid tem5erat re. the str ct re consists o: 5rimary (com5osition _) and remaining (com5osition R) in the ratioD

K st !elow 161ZC remaining trans:orms to a e tectoid consisting o: alternate lamellae o: (%..R A() and 0 ($1.6R A() (#ig. &.$1). # ndamentally 0 is a !rittle com5o nd C %Al. and occ 5ies a similar 5osition here to that o: #e/C in steel. ;ater ? enching o: the $$R Al alloy :rom &44ZC 5rod ces a 9ery hard martensitic ty5e o: str ct re which res5onds to tem5ering as does marten=site in steel, whilst air cooling :rom &44ZC gi9es a str ct re which is analogo s to !ainite in steels. ,he res5onse to cooling rates !y an al mini m !ron7e is there:ore similar to that o: a low=alloy (oil=? enching air ? enching) steel. Des5ite these a55arently attracti9e 5ro5erties little se is now made o: s ch alloys and most W 0 al mini m !ron7es now sed are as corrosion resistant castings. ,his limited 5o5 larity is d e largely to di::ic lties arising d ring casting. High casting tem5erat res in9ol9e e<cessi9e o<idation o: the al mini m, the entra55ed o<ides

o: which ca se nso ndness o: the castings. Methods alle9iate this are e<5ensi9e.

sed to

11 # ( C"pro1nickels Since !oth co55er and nic8el are #CC metals with similar atomic dimensions and chemical 5ro5erties it is not s r5rising that they :orm s !stit tional solid sol tions in all 5ro5ortions (#ig. &.$4). ,hey are to gh, d ctile and reasona!ly strong when cold=wor8ed. Beca se o: their high cost they are sed mainly where high d ctility co 5led with good corrosion resistance are re? ired s ch as in the man :act re o: o r c rrent Bsil9erB coinage. Nic8el=sil9ers are co55er=nic8el=7inc alloys sed (in the sil9er= 5lated :orm) :or c tlery man :act re, tho gh now largely re5laced !y stainless steels :or s ch 5 r5oses. 11 # 4 Ber&lli"m BronCe contains 5 to 0R Be and can !e strengthened !y 5reci5itation treatment to gi9e tensile strengths in the region o: $.44 M+a. (t is sed as a tool material in the gas ind stries and e<5losi9es :actories where s5ar8s, generated :rom steel tools, might ha9e disastro s res lts. Details o: some o: the more im5ortant co55er=!ase alloys are gi9en in ,a!le $$.$.

Al"mini"m and its Allo&s

11 $ Beca se o: its high a::inity :or o<ygen, al mini m co ld not !e e<tracted on a commercial scale ntil the electrolytic decom5osition o: al mini m o<ide was introd ced in $&&6. Hence the technology o: al mini m has !een de9elo5ed almost entirely in the twentieth cent ry. Des5ite its great a::inity :or o<ygen the corrosion=resistance o: al mini m is high. ,his is !eca se a thin ! t im5er9io s :ilm o: o<ide :orms on the s r:ace o: the metal and 5rotects it :rom : rther o<idation. ,he :ilm can !e : rther thic8ened !y BanodisingB and since al mini m o<ide is e<tremely

hard, wear=resistance is also increased !y the 5rocess. ,he high a::inity o: al mini m :or o<ygen ma8es it se: l as a de=o<idant in steels. ;hilst the electrical cond cti9ity o: al mini m is less than a hal: that o: co55er, weight for weight it 5ro9ides a !etter cond ctor, and, where s5ace is a9aila!le as in 5ower=grid ca!les, it is widely sed. Howe9er, 5 re al mini m is relati9ely so:t and wea8=it has a tensile strength o: no more than %4 M+a in the annealed condition= and :or most engineering 5 r5oses is sed in the alloyed :orm. ,he strengths o: many al mini m=!ase alloys can !e : rther increased !y .reci.itation hardening (>.1.0) to5rod ce a strength2mass ratio =or s.ecific strength =o: the same order as :or high=tensile steels. ,he greater relati9e 9ol me o: al mini m alloy in9ol9ed :or a s5eci:ic :orce=!earing ca5acity means that greater :le<i!ility in design is 5ossi!le. Al mini m alloys sed in !oth cast and wro ght :orms may !e 5reci5itation hardened i: o: s ita!le com5osition. 11 $ 1 Al"mini"m Allo&s Ahich are not .eat1treated Altho gh these alloys are not metall rgically e<otic as are those which can !e 5reci5itation hardened, they none the less acco nt :or the greater 5ro5ortion or the ind strial o t5 t. ,he most widely sed casting alloys are those containing $4=$/ R Si which im5arts ka considera!le increase in casting :l idity. ,hese alloys are o: a55ro<imately e tectic com5osition (#ig. $$.$0) so that their :ree7ing range is 9ery small ma8ing them 5artic larly s ita!le :or die casting where ra5id e3ection :rom the die is desira!le in the interests o: o t5 t. ,he rather coarse e tectic str ct re can !e re:ined !y a 5rocess

8nown as modification. ,his in9ol9es adding a small amo nt o: sodi m (a!o t 4.4$ R o: the mass o: the charge) to the melt 3 st !e:ore casting. ,his delays 5reci5itation o: silicon when the normal e tectic tem5erat re is reached so that when n cleation !egins a :ine grain res lts :rom ra5id crystallisation d e to nder=cooling. A shi:t o: the e tectic com5osition to the right is also ca sed. Hence a $0R Si alloy when modi:ied will contain an e<cess o: 5rimary a. instead o: em!rittling 5rimary silicon, which a55ears in the str ct re o: the nmodi:ied $0R alloy (#ig. $$.$0). Modi:ication raises the tensile strength :rom $04 to 044 M+a and the R elongation :rom 1 to $1. ,he cast al mini m=magnesi m alloys are nota!le mainly :or good com!ination o: corrosion resistance and rigidity, ma8ing them 5artic larly s ita!le :or moderately stressed 5arts wor8ing in marine atmos5heres. ,hose wro ght alloys which are not heat= treated rely :or their strength on the :ormation o: solid sol tions which are s !se? ently wor8=hardened !y cold=wor8ing 5rocesses. A mere $ R Mn is all that is necessary to strengthen al mini m s ::iciently to ma8e it s ita!le :or the man :act re o: mil8=!ottle ca5s and 9ehicle 5anelling, ! t where good corrosion resistance is also necessary then 5 to 1R Mg may !e added.

11 $ # Al"mini"m Allo&s Ahich are .eat1treated Altho gh 5reci5itation hardening can !e a55lied to many alloys, !oth :erro s and non=:erro s, it is most commonly sed to strengthen s ita!le al mini m=!ase alloys. BAge= hardeningB, as it was then called, was in :act disco9ered in some al mini m=!ase alloys at the !eginning o: the twentieth cent ry and s !se? ently de9elo5ed :or se in military aircra:t d ring the #irst ;orld ;ar. A n m!er o: wro ght Bd ral min=ty5eB alloys are in se ! t 5ossi!ly the !est 8nown is that !ased on . R C . At tem5erat res a!o9e that indicated !y A (#ig. $$.$/) the str ct re will consist entirely o: l=solid sol tion. (:

the alloy is allowed to cool slowly to room tem5erat re then the 5hase n(C A(0) will !e re3ected as a non=coherent 5reci5itate in accordance with the e? ili!ri m diagram which indicates that the solid sol !ility o: co55er in al mini m :alls :rom 1.>R at 1.&ZC to

4.0R at )ZC. ,he res ltant str ct re lac8s strength !eca se the l matri< contains so little co55er in solid sol tion, whilst it will !e !rittle !eca se o: the 5resence o: !rittle 5articles o: n. (: the alloy is slowly reheated n is grad ally re=dissol9ed ntil at A the str ct re once more consists entirely o: the ni:orm solid sol tion l. (n ind strial 5ractice a sol tion=treatment tem5erat re gi9en !y B will !e sed to ens re ma<im m sol tion o: n. Care m st o: C or else !e ta8en that the tem5erat re does not e<ceed that gi9en !y C or the alloy will !egin to melt

,he alloy is ? enched :rom B so that co55er is retained in s 5er= sat rated solid sol tion at room tem5erat re. ,his increases strength !eca se the whole o: the .R C is now in solid sol tion and !rittleness decreases !eca se the !rittle 5articles o: (C A(0)

are now a!sent. Howe9er, since the str ct re is not in e? ili!ri m s !se? ent migration o: co55er atoms occ rs to the e<tent that they :orm coherent 5reci5itates (>.1.0.$) within the latticeD C W Al X nB

(A( lattice) (A( lattice) ((ntermediate coherent 5reci5itate) Since the coherent 5reci5itates im5ede the mo9ement o: dislocations the strength o: the alloy increases. 11 $ $ ,he e<tent o: the :ormation o: coherent 5reci5itates at ordinary tem5erat res is limited so that strength attains a :airly low ma<im m 9al e in a :ew days and this 5rocess sed to !e called Bage=hardeningB. At higher tem5erat res the :ormation o: coherent 5reci5itates 5roceeds : rther and so the strength contin es to increase (#ig. $$.$1). Howe9er, a 5oint is reached where the thermal acti9ation is s ch that tiny non=coherent 5articles o: (C A(0) !egin to :orm in accordance with 5hase e? ili!ri mD nB X n(C A(0) (Coherent) (non=coherent)

At this 5oint strength and hardness !egin to :all ra5idly. ,h s o5tim m strength, :or the alloy rele9ant to #ig. $$.$1, wo ld !e o!tained !y 5reci5itation treatment at $61ZC :or $4 ho rs. ,reatment at 044ZC (c r9e D) wo ld lead to the :ormation o: non= coherent 9irt ally Bo9erta8ingB that o: the :ormation o: coherent n o. 11 $ % (n addition to the .R C d ral min=ty5e o: alloy, other ;ro ght al mini m alloys which can !e 5reci5itation hardened are those containing small amo nts o: magnesi m and silicon. ,hese :orm the com5o nd Mg0Si the sol !ility o: which, li8e that o: C Al0, increases considera!ly with tem5erat re. A:ter many years o: de9elo5ment wor8 5reci5itation=hardening alloys containing 5 to 0.1R lithi m are !eing sed in military aircra:t. Since lithi m has a relati9e density o: only 4.1/. alloys containing, it ha9e a relati9e density as low as 0.1., o::ering an increase in s.ecific modulus o: 5 to 01R. +reci5itation hardening is d e mainly to a 5hase mB (A(/-i), a 5reci5itate coherent with the matri<. A n m!er o: al mini m=!ased casting alloys can also !e 5reci5itation hardened with ad9antage. +ossi!ly the !est=8nown o: these is the aircra:t 5iston alloy 8nown as I alloyB. Q ,his contains small amo nts o: co55er, nic8el, manganese and titani m and is nota!le :or its tolerance o: relati9ely high wor8ing tem5erat res. Com5ositions and 5ro5erties o: some o: the more im5ortant al mini m= !ase alloys are descri!ed in ,a!le $$.0.
89: An al"mini"m allo& 2#? C"@B $? )g3 in the form of rivets is sol"tion treated at %7'GC and "sed ,hilst +t remains +n this soft s"persat"rated solid1sol"tion condition +t s"*seE"entl& precipitation hardens at am*ient temperat"re after the riveting operation is complete -"ring tests it ,as fo"nd that the sol"tion1treated allo& *egan to harden in %1=# ho"rs at am*ient temperat"re 2#;GC3 ,hilst if placed in *oiling ,ater 21;;GC3 the precipitation hardening process *egan in onl& $1=# min"tes J The reference code "sed d"ring the development of this allo& at the !PL d"ring the First Aorld Aar

+t is reE"ired to refrigerate a *atch of sol"tion1treated rivets so that the onset of precipitation hardening is dela&ed in order that the rivets ma& *e stored and "sed over a period of fo"r da&s after sol"tion treatment Ahat refrigeration temperat"re m"st *e "sed so that the rivets ,ill not fail d"ring the riveting processK

)agnesi"m1*ase Allo&s
11 % Des5ite its high a::inity :or o<ygen magnesi m, li8e al mini m, is a sta!le metal with a high resistance to corrosion at ordinary tem5erat res. (ts chie: attri! te is its 9ery low relati9e density ($.>), which ma8es it se: l in the aircra:t and aeros5ace ind stries. (t has a low tensile strength ! t its alloys containing s ita!le amo nts o: al mini m, 7inc or thori m can !e strengthened !y 5reci5itation hardening. ,he solid sol !ility o: each o: these elements decreases as the tem5erat re :alls (#ig. $$.$6) th s ma8ing

the 5reci5itation treatment 5ossi!le. Both cast and wro ght alloys are sed, 5artic larly as castings and :orgings in the aircra:t ind stries=landing wheels, cran8 cases, 5etrol tan8s and many engine 5arts in !oth 5iston and 3et engines. A ty5ical general 5 r5ose casting alloy may contain % A(=).1 On=).0 Mn=!al. Mg,

de9elo5ing a tensile strength o: 5 to014 M+a in the heat=treated conditionM whilst a wro ght magnesi m=!ase alloy containing 1 On=).6 Or=!al. Mg may reach a tensile strength o: /$1 M+a when 5reci5itation hardened.

!ickel1*ase Allo&s
11 ' Nic8el is a 9al a!le constit ent !oth in corrosion=resistant alloys and, since it restrains grain=growth at high tem5erat res, in high=tem5erat re alloys. 11 ' 1 Corrosion1resistant Allo&s Nic8el is a 5rinci5al constit ent o: many corrosion=resistant alloys sed in. the chemical ind stries. Many o: these alloys are to gh and d ctile as well as !eing corrosion resistant. ,h s, BCorronel BB (66 NiM 0& MoM 6 #e) is 5artic larly resistant to mineral acids and acid chloride sol tions and can !e 5rod ced in the :orm o: t !es and other sections :or se in the chemical and 5etro=chemical ind stries.BHastelloy DB (&1 NiM $4 SiM / C M $ A() on the other hand is a to gh, 9ery hard casting alloy which is 5artic larly resistant to hot concentrated
s l5h ric acid.

11 ' # .igh1temperat"re Allo&s Nic8el=chromi m alloys are 5artic larly s ita!le :or high=tem5erat re wor8ing. Chromi m im5arts a low rate o: o<idation ($%.0) at all tem5erat res whilst nic8el limits grain growth and the !rittleness arising there:rom at high tem5erat res. Since these alloys also ha9e a high s5eci:ic resistance they are 5artic larly s ita!le :or resistance wire sed in heater elements o: electric :ires, immersion heaters, toasters, etc. A grade o: BBrightrayB containing &4 Ni=04 Cr has a ma<im m wor8ing tem5erat re o: $$14ZC. ,he !est=8nown o: the nic8el=chromi m !ase high=tem5erat re alloys are those o: the BNimonicB series which 5layed a leading 5art in the de9elo5ment o: the 3et engine, ! t are now sed :or a $arge n m!er o: a55lications where a high cree5 strength at ele9ated

tem5erat res is re? ired. Most BNimonicB alloys contain a55ro<imately >1 Ni and 04 Cr to :orm a to gh o<idation=resistant matri< at tem5erat res sometimes in e<cess o: l)))ZC. ,he alloy is sti::ened :or se at high tem5erat res !y small additions o: titani m, co!alt, 7irconi m, al mini m and car!on in s ita!le associations. ,hese elements hel5 to raise the limiting cree5 stress at high tem5erat res !y the :ormation o: dis5ersed 5articles o: car!ides or com5o nds s ch as NiA(/.

Linc1*ase Allo&s
.

11 ( ,hese are e<cl si9ely die=casting alloys which contain .R Al and 5 to 0.>R C , the !alance !eing 7inc, and are sed :or the man :act re o: a large n m!er o: domestic and engineering com5onents. Door handles :or motor cars, !odies :or windscreen wi5er motors, :rames :or electric :ires, acc rately scaled childrenBs toys and 5arts :or washing machines and re:rigerators are ty5ical e<am5les. S ch alloys ha9e ? ite good strength (/04 M+a) and rigidity, ! t are sensiti9e to the 5resence o: small amo nts o: im5 rities li8e cadmi m, lead and tin which ca se intercrystalline !rittleness and some dimensional insta!ility which mani:ests itsel: as swelling o: the casting d ring se. ,hese :a lts are largely d e to intercrystalline corrosion :or which reason good ? ality 7inc=!ase die=casting alloys are generally made :rom B:o r ninesB 7inc, i.e. 7inc which is %%.%%R 5 re. Another series o: 7inc=!ase alloys contains &, $$ and 0>R Al res5ecti9ely along with small amo nts o: C and Mg. ,he &R alloy is sed :or 5ress re die=casting whilst the others are more s ita!le :or gra9ity die casting. -i8e the .R Al alloys they m st !e 8e5t :ree o: im5 rities i: intercrystalline !rittleness is to !e a9oided. A:ter casting they age=harden nat rally, ra5id cooling d ring casting ha9ing s 55ressed the attainment o: e? ili!ri m.

Bearing )etals
11 4 ,he mechanical re? irements o: a !earing metal can only !e met !y the intelligent se o: alloying. A !earing m st !e hard and wear=resistant with a low coe::icient o: :riction ! t at the same time !e to gh, shoc8 resistant and s ::iciently d ctile to allow :or Br nning inB. ,hese 5ro5erties o: hardness, to ghness and d ctility cannot !e :o nd to the re? ired degree in a single=5hase alloy. ,h s, intermetallic com5o nds are hard and ha9e a low coe::icient o: :riction ! t are e<tremely !rittle, whilst 5 re metals and solid sol tions tho gh d ctile are s ally so:t and with a relati9ely high coe::icient o: :riction. A s ita!le com!ination o: mechanical 5ro5erties can, howe9er, !e o!tained !y sing an alloy in which 5articles o: a hard intermetallic com5o nd are em!edded in a matri< o: d ctile solid sol tion=or, in some cases, a e tectic o: two solid sol tions. D ring the Br nning inB 5rocess the so:t matri< tends to wear lea9ing the hard 5articles standing 5ro d. ,his not only red ces the o9erall coe::icient o: :riction o: the !earing s r:ace ! t also 5ro9ides channels thro gh which l !ricant can :low. 11 4 1 0Ahite01*earing )etal ,hese are either tin=!ase or lead= !ase.,he :ormer, the high=? ality Ba!!itt metals, contain as m ch as %4R Sn and 5 to $4R S!. ,hese two metals :orm Bc !oidB crystals o: the intermetallic com5o nd S!Sn which are easily identi:ied in the microstr c=t re and which constit te the hard, low=:riction 5hase. (n lead=:ree white metals the c !oids are held in a matri< o: the solid sol tion a (#ig. $$.$&) whilst in white metals to which lead has !een added in amo nts 5 to &4R in order to red ce cost, the S!Sn c !oids will !e in a matri< consisting o: a e tectic o: two solid sol tions=one tin=rich and the other lead=rich.

C !oids o: S!Sn se5arate :rom the li? id 5hase !etween H and 0.6ZC and since the relati9e density o: S!Sn is less than that o: the li? id, the c !oids :loat to the s r:ace as they :orm. ,o 5re9ent this ty5e o: segregation 5 to /R C is added to white=!earing metals. ,his :orms the intermetallic com5o nd C (Sn' which se5arates o t as a networ8 !e:ore the :ormation o: S!Sn c !oids. ;hen these latter s !se? ently !egin to :orm they !ecome tra55ed !y the networ8 o: CF(Sn' crystals and so 5re9ented :rom segregating at the s r:ace o: the casting.

11 4 # Copper1*ase1*earing Allo&s ,hese incl de the 5lain tin !ron7es ($4=$1R Sn) and 5hos5hor !ron7es ($4=$/R SnM 4./=$.4R +). As the 5hase diagram (#ig. $$.0) indicates these alloys will !e o: l W m str ct re, and tho gh nominally the hard com5o nd m (CF$1 Sn5) will !e 5resent as a e tectoid with l, in 5ractice the layers o: m coag late to :orm hard 5articles in a to gh matri< o: the solid sol tion l th s : l:illing the general re? irements o: a !earing metal.

retain s ::icient 5orosity to allow them to !e im5regnated with l !ricating oil. ,hese Boil=lessB !earings are widely sed in 9ac m cleaners, washing machines, gramo5hone motors and other a55lications where l !rication might !e either ncertain or a l !rication system n3 sti:ia!ly e<5ensi9e.

Titani"m Allo&s
11 5 (n terms o: its occ rrence in the EarthBs cr st titani m is a relati9ely a! ndant metal and, o: the engineering metals, only al mini m, iron and magnesi m are more 5lenti: l. ,he amo nt o: titani m ore within the range o: mining o5erations is a!o t one h ndred times greater than that o: co55er. Howe9er, the 9ery high a::inity o: titani m :or !oth o<ygen and nitrogen ma8es it di::ic lt to e<tract whilst the molten metal itsel: reacts with all 8nown re:ractories. ,h s titani m is an e<5ensi9e metal !eca se o: its cost o: e<traction and :orming rather than any scarcity o: its ores. C rrently titani m !illets cost a!o t p1.44 5er 8g. High=5 rity titani m has a relati9ely low tensile strength (0$6 M+a) and a high d ctility (14R) ! t the strength can !e raised considera!ly !y alloying. (t is a 5olymor5hic element. ,he l 5hase (C+H) trans:orms on heating to &&0.1ZC to L (BBC) (#ig. $$.$%(i)) and this change=5oint is

a::ected !y alloying as is the A/ 5oint in iron. ,h s alloying elements which ha9e a greater sol !ility in l than in L tend to sta!ilise a o9er a wider range o: tem5erat res (#ig. $$.$%(ii).,hese elements incl de al mini m, which dissol9es s !stit tionally, and o<ygen, nitrogen and car!on all o: which dissol9e interstitially. Elements which dissol9e more readily in L sta!ilise it in 5re:erence to l (#ig. $$.$%(iii) and (i9). ,hey incl de the transition metals

iron, chromi m, moly!den m etc. Alloys re5resented !y a 5hase diagram o: the ty5e (i9) can !e 5reci5itation hardened as might !e e<5ected with a diagram o: this :orm (>.1.0.$). A ty5ical titani m= !ase alloy, (M( >44 (6 A(M 1 OrM / MoM $ C ) attains a tensile strength o: $1.4 M+a. 11 5 1 ,he relati9e density o: titani m is only ..1 and s ita!le alloys !ased on it ha9e a high s5eci:ic strength. Moreo9er cree5 5ro5erties 5 to 144ZC are 9ery satis:actory whilst the :atig e limit is also high. ,itani m alloys there:ore :ind a55lication in the com5ressors o: 3et engines. (n t r!ine engineering generally titani m alloys, !eing o: low relati9e density, im5ose m ch lower centri: gal stresses on rotors and discs :or a gi9en !lade si7e. ,itani m alloys are also 9ery resistant to erosion !y wet steam and other media so that steam t r!o=generators, gas t r!ines and condenser t !ing all ma8e se o: these alloys. Beca se o: the high s5eci:ic strength, high tem5erat re resistance and good erosion resistance generally, many titani m alloys :ind se in s 5ersonic aircra:t=incl ding BConcordeB=as str ct ral :orgings. S ch an alloy is (M( ,i6&4 ($$ SnM 0.01 A(M . MoM 4.0 Si) which de9elo5s a strength o: $/44 M+a. An interesting de9elo5ment in the se o: titani m is c rrently ta8ing 5lace in Ka5an=as a roo:ing materialD ;hilst titani m is o: co rse e<5ensi9e its high s5eci:ic strength allows greater :le<i!ility in design and its low relati9e density means that a m ch smaller load=!earing ca5acity is re? ired o: the roo: mem!ers. Moreo9er it is o: attracti9e a55earance and re? ires minim m maintenance=== im5ortant in a co ntry li8e Ka5an where marine corrosion ca ses considera!le 5ro!lems with the more traditional metals sed in architect re. 11 5 # ,itani m has a 9ery high resistance to corrosion. -i8e al mini m it coats itsel: with an im5er9io s closely adherent :ilm o: o<ide which 5rotects it :rom : rther corrosion so that, des5ite its relati9ely high cost, titani m is now sed increasingly where high

corrosion resistance in 9ery hostile conditions is o: 5rimary im5ortance. ;hen atmos5heric 5oll tion control is ta8en serio sly and gen ine attem5ts are made to red ce the 9ast amo nts o: s l5h r dio<ide reaching the atmos5here :rom 5ower stations ! rning coal, some :orm o: washing or Bscr !!ingB o: the :l e gases is necessary. ;et lime or limestone is generally sed :or this 5 r5ose with the o!3ect o: ne tralising the s l5h ric acid :ormed when S) 0 in the :l e gas com!ines with water. +rior to ne tralisation s l5h ric acid will condense on some s r:aces within the :l e=gas des l5h risation (#ED) 5lant. #ED 5lants in the FSA and more recently here at National +owerBs Dra< Station ha9e !een :itted with titani m sheet linings. Altho gh the initial cost is higher than the alternati9e BglassB or !orosilicate linings, ann al maintenance costs are m ch lower and lining li:e m ch longer in the case o: titani m, res lting in a lower o9erall ann al cost when it is sed. Since titani m is s 5erior to most other non=:erro s engineering alloys and stainless steels in terms o: resistance to all :orms o: salt water corrosion it is 5otentially se: l in e? i5ment sed on o::= shore 5lat:orms.

1# Plastics )aterials and R"**ers

1# 1 ,he townshi5s o: mid=nineteenth=cent ry Colorado attracted a mostley assortment o: ad9ent rers, gam!lers, saloon ladies and others !enton the ac? isition o: easy wealth. Amongst the more res5ecta!le esta!lishments o: these towns were !illiard saloons which !ecame increasingly 5o5 lar. So m ch so that the ? est :or i9ory led to the !r tal sla ghter o: the A:rican ele5hant to s ch an e<tent that i9ory !ecame scarce and hence 9ery e<5ensi9e. (n an attem5t to 5ro9ide !illiard !alls Kohn Hyatt so ght a s !stit te. His early 5rod cts consisted o: a core o: i9ory d st !onded with shellac and an e<terior coating o: the somewhat nsta!le com5o nd collodion. Fn:ort nately 9iolent im5act o: the !a(ls o:ten ca sed the collodion to e<5lode so that e9ery g nman in the saloon instincti9ely B5 lled a g nB. Q Howe9er, in $&6& Hyatt s ccess: lly ado5ted a s !stance de9elo5ed some :o rteen years earlier !y Ale<ander +ar8es o: Birnlingham, England (t consisted o: a mi<t re o: cell lose nitrate and cam5hor and had !een 8nown as B+ar8eseneB. ,his, the :irst o: the man=made 5lastics, was renamed Bcell loidB and was sed widely ntil a :ew years ago :or the man :act re o: many articles, in 5artic lar toys s ch as dolls. (ts dangero s in:lamma!ility :inally led to its o!solescence so that com5arati9ely little o: it is now sed. ;hen in $%4> Bae8eland 5atented his 5rocess :or the man :act re o: B!a8eliteB the 5lastics ind stry co ld !e said to ha9e Barri9edB, :or this material was ? ic8ly ado5ted !y the ra5idly e<5anding electrical trades as an ins lation material. Now 5lastics materials o: some thirty di::erent com5ositions are sed in o r

e9eryday arte:acts=the modern motor car contains a!o t 01R !y weight o: them. 1# 1 1 A,he term 0plastics0 is not one which is easy to de:ine 5recisely.Many :amiliar B5lasticB articles li8e ! ttons, switchgear 5arts and egg=c 5s are in :act no longer 5lastic a:ter !eing mo lded to sha5e since they !ecome hard and !rittle and can no longer !e de:ormed on heating. ,here was little theoretical nderstanding o: the nat re o: these materials ntil a!o t $%04 when Herman Sta dinger descri!ed them as Bmacro=molec lesB and 9is alised their long thread=li8e :orm. He s ggested thatthey co ld !e seen sing an ordinary o5tical microsco5e ! t :or the :act that an indi9id al molec le is so thin (i: the a9erage 5olythene molec le were magni:ied so that it a55eared as a :i!re $ mm in diameter then it wo ld !e 1 m in length). +lastics can !e de:ined as organic materials containing molec les o: high molec lar weight (i.e. !etween $4. and $4>) and which can !e mo lded to sha5e !y the a55lication o: 5ress re at moderately high tem5erat res. )nce mo lded they may retain their 5lasticity in the manner o: 5olythene or nylon or they may !ecome 5ermanently hard and !rittle li8e !a8elite. Some 5lastics, howe9er, are com5o ndyd as li? ids and 5roceed to BsetB witho t the a55lication o: either heat or 5ress re.

1# 1 # Amongst the elements car!on and hydrogen, !oth with hal:= :illed shells, are Bs5ecial casesB in that together they :orm 5ro!a!ly 04 times as many com5o nds as there are com5o nds o: all other chemical elements. Since car!on com5o nds are so n mero s and their chemical 5ro5erties so distincti9e they are dealt with in a se5arate !ranch o: chemistry=organic chemistryM so=called !eca se many o: these com5o nds were originally associated with li9ing things. By :orming :o r co9alencies the car!on atom has a : lly=shared octet and there:ore no Blone=5airB o: electrons. Beca se o: this it cannot act as an electron donor (as do metallic atoms). At the same time it cannot !e an electron acce5tor (as do most non=metallic atoms) !eca se there are no a9aila!le or!itals. #or these reasons car!on com5o nds tend to !e 9ery sta!le and car!on atoms can :orm 9ery sta!le !onds with other car!on atoms. (n :act car!on can :orm :airly sta!le m lti5le co9alent !onds !oth with itsel: and with some other elements. ,he :ollowing three com5o nds with hydrogen e<hi!it single, do !le and tri5le !onds in9ol9ing car!on Atoms.

All three com5o nds are gases. Ethane is e<tremely sta!le chemically since a single !ond co9alently 3oins the car!on atoms to each other. Con9ersely the tri5le !ond 3oining the two car!on atoms in the acetylene molec le is m ch less sta!le and is :airly easily r 5t red. D ring my schooldays rather long ago (Bm a:raid= the cyclist :o nd his way at night !y the dim light o: an acetylene lam5 inside which water dri55ed slowly on to calci m car!ide to yield acetylene. ,his ! rned with an e<tremely sooty :lame since with an inade? ate air s 55ly the wea8 tri5le !ond !ro8e to yield a large e<cess o: n! rnt car!on. (,he released car!on 5anicles were ill minated !y that 5art o: the gas which did ! rn. to greater l mino s :lame des5ite the 9ast e<cess o: soot.) (n the gas ethylene the do !le !ond,tho gh stronger than the tri5le !ond o: acetylene, can ne9ertheless !e made to !rea8 (!y heating the gas at a 5ress re o: some $444 atmos5heres) yielding :ree 9alencies which will instantaneo sly lin8 5 with :ree 9alencies :rom other li8e molec les to gi9e a long=chain molec le 5 to $044 car!on atoms in length. A55lied heat is only re? ired to initiate the reaction as, once started, it !ecomes strongly e<othermic. ,he 5rod ct is o: co rse 5oly=ethylene or B5olytheneB as it is commonly called. 1# 1 $ (t is thermodynamically more di::ic lt to ! ild 5 than to !rea8 down ! t in the 5resent technological age the organic chemist has learned to reassem!le some o: the !its 5rod ced !y these destr cti9e 5rocesses.More im5ortant still he has ! ilt 5 com5le< com5o nds :rom these sim5le nits to 5rod ce s !stances s ch as ha9e ne9er !een 8nown in Nat re. #oremost amongst these s !stances are the su.er-.olymers or .lastics so m ch a 5art o: li:e in modem times.
.

,he synthesis o: 5olythene :rom ethylene=a !y=5rod ct o: 5etrole m Bcrac8ingB=has already !een mentioned (0././ and a!o9e). (n this instance ethylene, C0H. is 8nown as the monomer whilst 5oly=ethylene (C0H.)n is the 5olymer. ,he single re5eating nit, in this case =C0H. = is o:ten termed the mer. S ch a 5rocess is 8nown as addition 5olymerisation since a long s ccession o: mers 3oin together in this way :orming a long chain=li8e molec le. 1# 1 % ,he n m!er o: mers which lin8 5 is s ally re:erred to as the degree o: 5olymerisation, An@. As the degree o: 5olymerisation increases and the si7e o: the molec le increases in conse? ence so does the melting 5oint o: the 5olymer so 5rod ced. ;hen 5olythene has a molec ler mass o: only 044, n P a55ro<. > (since the re5eating nit =C0H.= has a molec lar mass o: b0 < $0 W . < $c P 0&) and the 5olymer (=C0H.=)> is a 9isco s li? id at am!ient tem5erat re. As the molec lar mass is increased to .44 (n P 55ro<. $.) the 5olymer now has a melting 5oint, ,m, o: 60ZC. ,m contin es to rise with the degree o: 5olymerisation ntil, when the molec lar mass is in the region o: $4444an P a55ro<. >$1), , m has reached $/4ZC. ,h s the degree o: 5olymerisation in a 5lastics material is a Meas re o: the a9erage si7e o: the molec le in terms o: the n m!er o: monomer nits=or mers=contained in the molec le. As indicated in #ig. $0./ molec lar si7e in a 5lastics material 9aries according to a Ea ssian=ty5e distri! tion.

Thermoplastic Pol&mers 1# # Com5o nds !ased on ethylene in which one or more o: the hydrogen atoms ha9e !een re5laced !y a di::erent atom or gro 5 o: atoms are 8nown collecti9ely as 9inyl com5o nds (,a!le $0.$). Some o: these 9inyl com5o nds will 5olymerise s5ontaneo sly at ordinary tem5erat res (#ig. $0..) whilst others 5olymerise when heated in the 5resence o: a catalyst. A ty5ical 9inyl com5o nd may e<ist as a 9ery mo!ile li? id (#ig. $0..(i). ,he li? id :lows as easily as water !eca se only wea8 9an der ;aals :orces o5erate !etween the relati9ely[ small molec les. As 5olymerisation 5roceeds (#ig. $0..(ii) the molec les reach a si7e where the 9an der ;aals :orces !ecome. e::ecti9e so that the li? id !ecomes relati9ely 9isco s. As 5olymerisation nears com5letion (#ig. $0..(iii) the molec les !ecome 9ery long so that the s m o: wan der ;aals :orces acting !etween ad3acent molec les !ecomes considera!le and the material so 9isco s as to !e regarded as a solid. (t no longer :lows nless it is heated. ,his increases the energy o: the molec les so that they are a!le to o9ercome the 9an der ;aals :orces acting !etween them. S ch a s !stance is said to !e thermo5lastic since it can !e so:tened re5eatedly !y the a55lication o: heat. 1# # 1 +olymers deri9ed :rom a single monomer s ch as are listed in ,a!le $0.$ are descri!ed as homo5olymers. Sometimes two di::erent monomers are sed in the synthesis o: the large molec le. ,he latter is then 8nown as a co5olymer. #or e<am5le a mi<t re o: 9inyl chloride and 9inyl acetate can !e 5olymerised to 5rod ce the co5olymer, 5oly9inyl chloride= acetateD

Thermosetting Pol&mers
1# $ ,he 5olymers mentioned so :ar ha9e all !een o: the thermo5lastic ty5e. ,hat is they can !e so:tened and remo lded re5eatedly !y the a55lication o: heat. A n m!er o: 5olymeric s !stances, howe9er, are o: the thermosetting 9ariety. ,hese are 5lastic in the 5rimary stages o: man :act re ! t once mo lded to sha5e they BsetB and cannot s !se? ently !e so:tened !y re=heating. ,hermosetting is d e to the :ormation o: co9alent !onds !etween chain molec les. 1# $ 1 (n $%4> a Belgian chemist Dr -eo Bae8eland de9elo5ed the :irst synthetic 5lastics material. Recognising the im5ortance o: his disco9ery he 5atented it and named the 5rod ct B!a8eliteB. ,his is a thermosetting material made :rom the two organic chemicals 5henol, C6H1. )H, and :ormaldehyde, H. CH) Fnder s ita!le conditions these two s !stances can !e made to react with each other (#ig. $0.1). As a res lt o: this reaction a chain=ty5e o:

molec le is 5rod ced. Howe9er, this method o: 5olymerisation di::ers :rom that in9ol9ed in addition 5olymerisation as ty5y:ied

!y the 5oly=9inyls. Here 5arts o: the reacting molec les are eliminated (in this 5artic lar instance as molec les o: water, H0)) and this ty5e o: reaction is termed condensation 5oilymerisation.

(n the a!o9e reaction only s ::icient :ormaldehyde is sed to lin8 the 5henol molec les in a sim5le linear manner (#ig. $0.6). Conse? ently at this stage the material, 8nown in the trade as a B:irst=stage resinB or Bno9ola8B, is still thermo5lastic. (t is allowed to cool and is then 5owdered and mi<ed with he<amethylene tetramme. D ring the s !se? ent mo lding 5rocesses the he<amethylene tetramine decom5oses. releasing more :ormaldehyde which :orms cross lin8s !etween the chain= molec les o: the no9ola8 (#ig. $0.>). ,he :omation o: these cross lin8s means that the chain=molec les are now 3oined !y co9alent !onds which are 9ery strong when com5ared with the relati9ely wea8 9ander waals :orces which hold together the chain molec les

in a thermo5lastic material, #or this reason thermosetting materials are generally stronger at ele9ated tem5erat res than are thermo5lastic materials in which 9ander waals :orces are readily o9ercome !y thermal 9i!rations within the molec les. ,hermo5lastic 5olymers are there:ore o:ten descri!ed as linear .olymers whilst the more rigid thermosetting materials are 8nown as networ .olymers! ,he Bnet=wor8B is o: co rse three dimensional and not two dimensional as diagrams drawn on :lat 5a5er may s ggest

1# $ # Cold1setting Plastics Similar in 5rinci5le to the thermosetting materials are the cold=setting 5lastics. ,hese are :ormed !y reagents which will ndergo 5olymerisation when they are mi<ed at ordinary tem5erat res. (n addition to mo lding materials some 9arnishes and adhesi9es are o: this ty5e.

The Ph&sical !at"re of Solid Pol&mers

1# % So :ar we ha9e !een considering the :orm o: single 5olymer molec les. ;ith the e<ce5tion o: Bthree=dimensionalB condensation 5olymers o: the thermosetting ty5e these molec les can !e 9is alised as thread=li8e entities !onded to their neigh!o rs !y 9an der ;aals :orces. Some molec les=li8e those o: 5olyethylene. are symmetrical@ in section whilst others may carry relati9ely ! l8y side gro 5s. non=symmetrically 5laced, ,h s, in 5olystyrene these a55endages consist o: 5henyl gro 5s 4, and in 5oly5ro5ylene the gro 5. =CH/. Moreo9er, any sam5le o: a 5 re 5olymer will contain molec les o: 9arying length. ,h s, whilst a 5olyethylene molec le consists on a+erage o: a chain some $044 car!on atoms in length, indi9id al molec les may contain many more=or less= than the a9erage n m!er. -i8ewise 9arying degrees o: Bside=!ranchingB can occ r in 5olyethylene molec les (#ig. $0.&), 5rod cing !ranches o: 9arying lengths. ,he 5resence

Fig 1# 5 Side !ranching in 5olyethylene (5olythene) molec les o: these side !ranches has considera!le e::ect on the mechanical 5ro5erties, generally increasing the strength and hardness. ,he :orces acting !etween indi9id al atoms within a 5olymer molec le are o: the 5rimary 9alency ty5e=strong co9alent !onds (0.0) =whilst :orces acting !etween ad3acent molec les are o: a secondary nat re 8nown collecti9ely as 9an der ;aals :orces (0..).

Nat rally the magnit de o: these relati9ely wea8 secondary !onding :orces go9ern the ease with which molec les may !e se5arated and so a::ect s ch 5ro5erties as sol !ility, 9iscosity and :rictional 5ro5erties. ;hilst strength de5ends largely 5on the co9alent !onding within the molec le chains it is also a::ected !y 9an der ;aals :orces o5erating !etween ad3acent chains.

1# % 1 Many solid s !stances e<ist in 5 rely crystalline :orm. ,his is s ally so when the 5articles o: which they are com5osed, whether ions or molec les, are small and are a!le to :all easily into a 5redetermined reg lar 5attern. ,he long 5olymer chains in 5lastics materials, howe9er, are li8ely to !ecome entangled, 5artic larly i: large side a55endages are 5resent. Conse? ently only a limited degree o: crystalline arrangement is generally 5ossi!le in the case o: these s !stances and limited regions occ r in which the linear chains are arranged in an ordered 5attern (#ig. $0.%). ,hese

Fig 1# 7 ,he e<istence o: BcrystallitesB in a solid 5olymer. ordered regions are 8nown as crystallites! ,hey can !e detected !y the se o: H=ray analysis (/..) which 5rod ces a55ro5riate di::raction 5atterns. ,hose 5olymers which are com5letely amor5ho s o: co rse 5rod ce no s ch clear 5atterns. (n the solid state, there:ore, 5olymers can !e regarded as consisting o: !oth crystalline and amor5ho s regions in relati9e amo nts which 9ary :rom one 5olymer to another and which de5end 5on the molec lar str ct re as well as 5on the 5re9io s thermal history. ,hose 5olymers in which the molec lar str ct re is reg lar and the section highly sym= metrical, show a high 5ro5ortion o: Crystallites. S ch 5olymers incl de

Re5etiti9e Fnits o: high symmetry allow chains to align themsel9es. B l8y side chains, s ch as are 5resent in 5oly9inyl acetate, on the other hand, im5ede the :ormation o: crystalline regions and s ch s !stances are largely amor5ho s. Crystalline regions 9ary in length :rom as m ch as 14 nm :or strongly crystalline materials li8e 5olythene to as little as 0 nm :or 5oorly crystalline 5olymers li8e 5oly9inyl chloride. Highly crystalline 5olymers ha9e a crystallinity o: &4=%4R . ;hen a 5olymer crystallises :reely in the a!sence o: any e<ternal :orces the crystallites so :ormed are randomly orientated, ! t i: an e<ternal stress is a55lied in a single direction the crystallites orientate themsel9es so that their longit dinal a<es are 5arallel to the direction o: the a55lied stress. D ring the 5rocess o: cold stretching the degree o: crystallinity o: a 5artially crystalline 5olymer does not increase a55recia!ly ! t in the case o: amor5ho s 5olymers or those o: 9ery low crystallinity, some increase in crystallinity may occ r. As the degree o: crystallinity and the e<tent o: orientation increase so do the tensile strength and sti::ness. 1# % # )elting Points of Cr&stalline Pol&mers A 5 re and com5letely crystalline solid, :or e<am5le a metal or an inorganic salt, melts at a single de:inite tem5erat re called the melting 5oint. An amor5ho s solid, howe9er, merely !ecomes 5rogressi9ely less rigid as it is heated ! t shows no shar5 transition :rom solid to li? id. ,his is ro ghly what one wo ld e<5ect since, as with a li? id (which is amor5ho s), 9iscosity decreases 5rogressi9ely as 9an der ;aals :orces decrease. with rise in tem5erat re. #or those

5olymers which are 5artic larly crystalline, howe9er, a melting c r9e similar to that shown in #ig. $0.$4 is o!tained. Here the change in

Fig 1# 1; ,he melting c r9e :or a 5artially crystalline 5olymer.

s5eci:ic 9ol me is sed as an indication o: the change in str ct re. Melting !egins as the smaller, less 5er:ect, crystallites change to an amor5ho s str ct re and this is indicated !y the grad al change in the sha5e o: the c r9e. At a high tem5erat re there is a :airly s dden change in the s5eci:ic 9ol me with tem5erat re, and this is regarded as the melting 5oint. ,he melting 5oint, , m, o: a crystalline 5olymer is de:ined as the tem5erat re at which the crystallinity disa55ears and the str ct re !ecomes com5letely amor5ho s. Melting 5oint is, to some e<tent, a meas re o: the 9an der ;aals :orces acting !etween molec les. ,h s, increase in crystallinity o: 5olythene leads to an increase in melting 5oint 5res ma!ly !eca se .inter=molec lar :orces are greater in the crystalline regions where chains are more closely aligned. 1# % $ 6lass Transition Temperat"re Fnder normal conditions 5olymers may !e either so:t, :le<i!le s !stances or hard !rittle glassy materials. (: a so:t, :le<i!le 5olymer is cooled s ::iciently a tem5erat re is reached where it !ecomes hard and glassy. ,h s, a so:t r !!er !all when cooled in li? id air !ecomes hard and !rittle

and will shatter to :ragments i: an attem5t is made to !o nce it whilst it is still at a low tem5erat re. ,he tem5erat re at which this change in 5ro5erties ta8es 5lace is 8nown as the glass transition tem5erat re. #or some 5olymers the glass transition tem5erat re is a!o9e room tem5erat re so that these materials are normally hard ! t will !ecome so:t and 5lia!le when heated. +olystyrene (,a!le $0.0) is a 5olymer o: this ty5e. ,he glass transition tem5erat re, ,g, can !e assessed !y meas ring the change in some 5ro5erty s ch as s5eci:ic 9ol me or s5eci:ic heat with change in tem5erat re and is indicated !y a change in slo5e o: the c r9e 5rod ced (#ig. $0.$$). ,he glass transition tem5erat re is less well de:ined than is the crystalline melting 5oint, ,m.

Fig 1# 11 Deri9ation o: the glass transition tem5erat re. ,g.

1# % % ,he glass transition tem5erat re is a 5ro5erty associated with the amor5ho s regions in a 5olymer and is s ally descri!ed as the tem5erat re at which, on heating, the 5olymer chains ac? ire s ::icient thermal energy to 9i!rate in a co=ordinated manner. Below ,g the atoms, a5art :rom restricted 9i!rations a!o t e? ili!ri m 5ositions, are in a rigid :ro7en state and the 5olymer is hard and glassy as a res lt.

A!o9e ,g the co=ordinated 9i!rations re:erred to a!o9e im5art to the 5olymer its r !!er=li8e 5ro5erties. ,he 5resence o: 5lasticisers and other additi9es which decrease the magnit de o: the 9an der ;aals :orces gi9e rise to a red ction in , g. Con9ersely the 5resence o: ! l8y radical gro 5s attached to the chain, ma8ing the molec le non=symmetrical, increase , signi:icantly. ,h s +'C (&>ZC) and, more 5artic larly, 5olystyrene ($44ZC) ha9e higher 9al es o: , g than 5olyethylene (=%4ZC).

Fig 1# 1# ,he 9ol me=tem5erat re relationshi5 o: a high 5olymer. ,he 55er c r9e is :or a com5letely amor5ho s 5olymer while the lower is :or a 5artly crystalline one.

The )echanical Properties of Pol&mers

1# ' Engineers are :amiliar with the elastic 5ro5erties o: metals and with the e<tent to which they are reasona!ly constant nder normal conditions. E9en with metals, o: co rse, large de9iations

occ r when high tem5erat res or large de:ormations are in9ol9ed, whilst the e::ects o: cree5 o9er long 5eriods o: time are also well 8nown. ;ith 5lastics, howe9er, s ch de9iations occ r when relati9ely normal conditions 5re9ail ma8ing it im5ossi!le to relate de:ormation in 5lastics in terms o: sim5le elastic constants. As one might e<5ect :rom a st dy o: the str ct re o: a 5olymer, de:ormation is 9ery de5endent 5on time. Molec lar res5onse is slow to reach e? ili!ri m with the e<ternal :orces and so the material contin es to de:orm, or cree5, almost inde:initely. ;hen the a55lied :orces are remo9ed some reco9ery may occ r ! t a degree o: 5ermanent de:ormation may also 5ersist. 1# ' 1 De:ormation in 5lastics is also 9ery de5endent 5on tem5erat re and this m st !e 9ery serio sly considered in design to a :ar greater e<tent than is necessary with metals. As tem5erat re increases the wea8 9an der ;aals :orces are : rther diminished and sli5 occ rs more easily !etween ad3acent chains. ;hen a crystalline material, s ch as a metal, is stressed atoms are 5rogressi9ely dis5laced :rom their e? ili!ri m 5ositions ntil new internal :orces set 5 !alance the e<ternally a55lied :orces. Ass ming that the distortion 5rod ced is not too great, the atoms will ret rn to their original 5ositions when the stress is remo9ed. -arger stresses will 5rod ce 5ermanent de:ormation ! t 5ro9ided that the stress does not reach these 9al es the change in sha5e o: the material is instantaneo s and elastic. ,his mode o: de:ormation may also occ r in a 5lastic 5on the a55lication o: stress. ;hen two atoms within a chain are held in :i<ed 5ositions relati9e to each other !y strong co9alent !onds, some dis5lacement o: the atoms relati9e to each other occ rs instantaneo sly on the a55lication o: stress (#ig. $0.$/). )n the remo9al o: stress the atoms immediately ret rn to their original 5ositions. (n highly cross=lin8ed 5olymers and in thermo5lastics !elowB their glass=transition 5oint, atoms can !e regarded as !eing

:i<ed in this manner so that this is the only ty5e o: de:ormation 5ossi!le.

Fig 1# 1$ + rely elastic de:ormation in chain molec les,

(n thermo5lastics a!o9e ,g this ty5e o: elastic de:ormation will !e d e not only to !onds !etween indi9id al atoms in chains ! t also, i: crystallites are 5resent, to inter=molec lar :orces as well. (n the amor5ho s regions o: s ch thermo5lastics, howe9er, the molec les are only attracted to each other !y relati9ely wea8 9an der ;aals :orces. so that they are a!le to Bsli5B

Fig 1# 1% ,he sli5 o: chain molec les into new 5ositions into new 5ermanent 5ositions relati9e to each other (#ig. $0.$.). ,his ty5e o: mo9ement is not instantaneo s ! t is de5endent 5on the 9iscosity o: the material. 'iscoelastic de:ormation th s occ rs. 1# ' # (n addition to elastic de:ormation which is de5endent 5on small mo9ements o: atoms relati9e to each other[ and 5lastic de:ormation ca sed !y wholesale sli55ing o: chain molec les 5ast one another into 5ermanent new 5ositions, : rther de:ormation occ rs d e to straightening o: coiled and :olded chain molec les themsel9es in the direction o: the a55lied stress (#ig. $0.$1).

Fig 1# 1' De:ormation in chain 5olymers d e to chain straightening

Essentially this ty5e o: distortion is elastic since it is d e to chain= straightening which will !e a re9ersi!le 5rocess when stress is rela<ed. (t is also a time=de5endent change so that the res ltant de:ormation is 9iscoelastic. Straightening o: molec les tends to ta8e 5lace more ? ic8ly than sli55ing so that m ch o: the initial de:ormation is elastic. 1# ' $ BS5ring and dash5ot@ models are widely sed to re5resent the 9iscoelastic modes o: de:ormation o: a com5letely amor5ho s thermo5lastic material a!o9e ,g (#ig. $0.$6). Here it is ass med that the s5rings o!ey Hoo8eBs -aw, i.e. strain (q) is 5ro5ortional to stress (h) orD qPh2E

Fig 1# 1( BS5ring and dash5otB modelsD (i) a MaHwell elementM (ii) a 'oigt=*el9in elementM (iii) a com!ination model to ill strate the method o: de:ormation in a stressed thermo5lastic 5olymer. where E is Io ngBs Mod l sM whilst the dash5ots contain a Newtonian :l id in which the de:ormation2time relationshi5, de2dr, is linear :or a gi9en stress, i.e. dq2dt P h2r where r is the 9iscosity o: the :l id. ,he element o: the model in which the s5ring and dash 5ot are in series (#ig. $0.$6 (i) is s ally called a Ma<well element whilst the element in which the s5ring and dash5ot are in 5arallel (#ig. $0.$6(ii)) is termed a 'oigt=*el9in element. ,he s5ring Sl re5resents the instantaneo s elastic de:ormation o: the atomic !onds !etween indi9id al atoms, whilst the s5ring S0 re5resents the elastic de:ormation arising :rom chain straightening, the dash5ot D$ introd cing the time=de5endence o: that de:ormation. Dash5ot D0 sim lates the non=elastic, non=re9ersi!le time=de5endent de:ormation d e to molec les sli55ing relati9e to each other into new 5ositions.

Fnder the action o: a :orce the 9ario s com5onents o: the system shown in #ig. $0.$6 will gi9e strain2time diagrams as indicated in #ig. $0.$>. (: we now consider the s dden a55lications o: a :orce, #, to the system as a whole we o!tain a strain2time relationshi5 li8e that indicated in #ig. $0.$&. ,he s dden a55lication o: :orce res lts in an elastic de:ormation S l (ii) which is :ollowed !y a 9iscoelastic res5onse S0 in the S02D$ nit co 5led with 9isco s :low in the dash5ot D0 (iii) in time, t $. ;hen the dis5lacing :orce is remo9ed the elastic element (S l) rela<es immediately (i9) and the 9iscoelastic element slowly (9) d ring time (t0 =t$), ! t the 9isco s :low D0is ne9er reco9ered (9). (t sho ld !e a55reciated that these models only e<hi!it the general characteristics o: the 9iscoelastic !eha9io r o: 5olymers and are necessarily o9ersim5li:ied, ,here is considera!le de9iation !oth :rom the Hoo8ean elastic res5onse and :rom Newtonian :low.

FigF 1# 14 Strain=time c r9es :or the 9ario s com5onents o: the system shown in #ig. $0.$6.

1# ' % Stress1strain )eas"rements ,he :orce=e<tension ty5e o: test already well esta!lished with metals was soon a55lied as a matter o: co rse to 5olymer materials. Fn:ort nately tests carried o t at a single tem5erat re and a single rate o: :orce a55lication are relati9ely meaningless when a55lied to 5olymers and in order to o!tain reasona!le se: l data a series o: tensile tests carried o t o9er a range o: tem5erat res and a55lication rates are necessary. ,he most s ccess: l method o: testing is to stretch the test 5iece at a constant rate and meas re the tensile :orce 5rod ced in it !y means o: strain ga ges or !y some electronic de9ice.

Fig 1# 15 Strain=time relationshi5 :or s5ring and dash5ot@ model shown in #ig $0.$6.

Stress=strain c r9es :or di::erent ty5es o: 5olymer were classi:ied some years ago !y Carswell and Nason into :i9e main gro 5s (#ig. $0.$%). ;ea8, so:t 5olymers s ch as wo ld !e o: little se 5ractically ha9e not only a low tensile strength and mod l s o:

elasticity ! t also a relati9ely low elongation (#ig. $0.$%(i)). #or many o: the 9ery so:t thermo5lastics the stress strain diagram does not show any signi:icant linear 5ortion and it is c stomary to meas re E !y re:erence to the secant mod l s (..$.6.$) at a strain o:, ty5ically, 4.0R. Hard and !rittle materials, s ch as 5olystyrene, 5olymethyl methacrylate and some o: the 5henolic resins at room tem5erat re, ha9e :airly high tensile strengths and ? ite high mod li o: elasticity, ! t they o:ten !rea8 with an elongation o: no more than $ R (#ig.$0.$%(ii)).

Fig 1# 17 ,y5e o: stress=strain diagram :or di::erent 5olymer gro 5s (a:ter Carswell and Nason).

Hard and strong 5olymers (#ig. $0.$%(iii))=some rigid 5oly9inyl chlorides and modi:ied 5olystyrene=ha9e a relati9ely high tensile strength and mod l s o: elasticity co 5led with a moderate elongation o: 5 to $4RM whilst many so:t, to gh materials s ch as

5lasticised 5oly9inyl chlorides and some r !!ers ha9e low yield 9al es and elastic mod li ! t high elongations o: 5 to 144R or more, co 5led with moderately high tensile strengths (#ig. $0.$%(i9)). ,o gh, hard 5olymers incl ding nylons and cell losics are characterised !y high yields, high tensile strengths and high elastic mod li. ,hey also elongate considera!ly, generally !y Bnec8ingB (#ig. $0.$%(9)).
Fig 1# #; ,ensile stress=strain c r9es :or low=density 5olythene at 9ario s tem5erat res.

1# ' ' ,ensile 5ro5erties are highly de5endent 5on tem5erat re (#ig. $0.04) and a series o: tests is necessary in order to gi9e worthwhile in:ormation a!o t the material. #or rigid 5olymers elongation s ally increases as tem5erat re increases tho gh :or r !!ers elongation may increase as the tem5erat re :alls within certain limits.

Fig 1# #1 ,he e::ect o: rate o: de:ormation on the stress=strain characteristics o: 5olymethyl methacrylate.

,he rate at which de:ormation is 5rod ced also has a considera!le e::ect on the tensile 5ro5erties o: a 5olymer as indicated in #ig. $0.0$. As the rate, o: elongation is increased so the tensile strength increases. ,h s an increase in the rate o: de:ormation has a similar e::ect to a decrease in tem5erat re.

1# ' ( Cree5, or grad al e<tension nder a constant :orce, is a 5henomenon which m st !e considered in the case o: metals, 5artic larly i: they are destined to wor8 at high tem5erat res ($6..). +olymers, howe9er, are m ch more 5rone to this ty5e o: de:ormation as has !een s ggested in the :oregoing section. (n the :ormB o: an engineering com5onent a rigid

Fig 1# ## Cree5 c r9es :or cell lose acetate at 01ZC.

5olymer m st !e a!le to withstand reasona!le tensile or com5ressi9e :orces o9er long 5eriods o: time witho t alteration in sha5e. E9en a so:t 5lastic raincoat m st !e ca5a!le o: s 55orting its own weight so that it can hang in the wardro!e :or long 5eriods witho t grad ally :lowing on to the :loor. ,he series o: cree5 c r9es shown in #ig. $0.00 are ty5ical o: most thermo5lastic 5olymers. ,he test 5iece ndergoes an initial elongation as soon as the s5eci:ied :orce is a55lied and this is :ollowed !y a 5eriod d ring which there is a ra5id rate o: cree5. ,his cree5 rate then decreases to a constant 9al e, which a55roaches 7ero :or small 9al es o: stress. As wo ld !e e<5ected the greater the a55lied :orce the greater the cree5 rate and elongation. Cree5 5ro5erties o: a 5olymer are 9ery de5endent 5on tem5erat re. At tem5erat res well !elow the glass=transition tem5erat re, , g, a 5olymer tends to !e rigid and ha9e a low cree5

rate :or a gi9en stress. As the tem5erat re is increased the cree5 rate and the amo nt o: elongation increase. At ,g a gi9en load gi9es a m ch greater elongation than the same load at lower tem5erat res. E9en more signi:icant is the great increase in the rate o: elongation :or, whilst at tem5erat res well a!o9e , g greater elongations will !e o!tained, the act al cree5 rate decreases. Fnder these circ mstances the cree5 rate o: a 5olymer can !e estimated sing the 'oigt=*el9in model (#ig.$0.$6(iii)). #rom ($) and (0) ($0.1./)D

:rom which it can !e shown thatD

(

,his is an Arrheni s ty5e relationshi5 (1.&.6) which, in addition to cree5, go9erns many time= and tem5erat re=related 5rocesses s ch as di:: sion (>...0), o<idation ($%.0.$) and corrosion. (t states that the rate o: cree5 (or di:: sion, etc.) increases e<5onentially with tem5erat re, or, that the time :or a gi9en amo nt o: cree5 (or di:: sion, etc.) decreases e<5onentially with tem5erat re.

Plasticisation
1# ( +lasticisers are s !stances which are added to 5lastics materials in order to im5ro9e their :low 5ro5erties and in some cases to red ce the !rittleness o: the 5rod ct. ,wo 5rinci5al gro 5s o: 5lasticisers are in se. Some s !stances=called B5rimary 5lasticisersB==contain 5olar gro 5s which ne tralise the :ields o: :orce o: the 5olymer gro 5s, th s red cing the 9an der ;aals :orces !etween ad3acent 5olymer chains. (n many cases, howe9er, the 5lastlciser is a com5ati!le and inert material witho t 5olar gro 5s ! t which e<ists dis5ersed thro gho t the 5olymer 5ro9iding mechanical Bs5acersB which se5arate the 5olymer chains and so red ce the 9an der ;aals :orces o: attraction !etween them. ,hese are termed Bsecondary 5lasticisersB(#ig.$0.0/(ii)).

#ig. $0.0/ ,he : nction o: a secondary 5lasticiser in se5arating 5olymer chains (ii) and so red cing intermolec lar attraction (9an der ;aals :orces) (i).

1# ( 1 +nternal Plasticisation ,his in9ol9es the 5olymer chain !y introd cing small amo nts o: another monomer nit d ring 5olymerisation. ,his second monomer re? ires long and :le<i!le side gro 5s. ,h s +'C can !e 5lasticised !y adding $1R o: 9inyl acetate d ring 5olymerisation. ,he 5resence o: the occasional ! l8y acetate gro 5s in the 5olymer so :ormed act as s5acers and so red ce the inter=molec lar :orces !etween ad3acent chains. ,his in t rn increases the amo nt o: 9isco s mo9ement 5ossi!le. (n this case increase in 5lasticity de5ends 5on the :ormation o: a new co5olymer rather than 5on the se o: a 5lasticiser and is less o:ten em5loyed.

1# ( # E<ternal +lasticisation ,his 5rocess is more commonly sed. Here the 5lasticiser is added to the 5olymer a:ter 5olymerisation is com5lete. (t is o:ten a com5ati!le non=9olatile sol9ent li? id which will dis5erse in molec lar :orm thro gho t the 5olymer 9irt ally :orming a 9ery 9isco s sol tion with the latter. )nly the amor5ho s regions are so a::ected and a highly crystalline 5olymer cannot s ccess: lly !e 5lasticised in this way since ins ::icient sol9ent will !e a!sor!ed. An alternati9e :orm o: e<ternal 5lasticisation in9ol9es the se o: a non=sol9ent oil. ,his dis5erses as tiny dro5lets thro gho t the 5lastics material. ,hese dro5lets act as s5acers !etween the 5olymer chains decreasing the 9an der ;aals :orces in the s al way. )

Fillers and other Additives

1# 4 ,o a large e<tent :illers are sed in 5lastics materials in the interests o: economy. ):ten 5 to &4R o: the additi9e is sed. (n general :illers are :inely 5owdered nat rally occ rring non=5olymic materials which are readily a9aila!le at low cost. +henolic (!a8elite) ty5e resins are nearly always com5o nded, or :illed with s !stances s ch as wood :lo r, short cell lose :i!res :rom wood 5 l5, cotton :loc8, mica and as!estos. (n addition to the economic ad9antages o!tained :rom the increase in ! l8 so 5rod ced, these materials greatly im5ro9e the strength, to ghness and dimensional sta!ility o: the 5rod ct. Mica im5ro9es electrical resistance whilst gra5hite red ces :riction. As!estos, o: co rse, im5ro9es tem5erat re resistance. Some so:t thermo5lastics are !lended with 5 to &4R mineral solids s ch as cr shed ? art7, clay or limestone. (n materials o: this ty5e the 5lastics material : nctions as an inter=5article adhesi9e in m ch the same way as cement in concrete. )n the whole, howe9er, :illers are more o:ten sed with the thermosetting mo lding com5o nds o: the 5henol=:ormaldehyde ty5e.

(n some cases the 5olymer is the 9ehicle :or a :illing material with s5ecial 5ro5erties. ,h s, some magnetic materials can !e !onded in 5article :orm with a s ita!le 5olymer so that !etter control o: eddy c rrents is 5ossi!le and more com5le< sha5es more easily 5rod ced. (n addition to s ch materials as colo rants, other additions may also !e made to 5lastics materials. ,h s antio<idants are sometimes sed to 5re9ent or inhi!it the o<idation o: 5olymers. ,he antio<idants are them sel9es s !stances which readily o<idise and in this way 5rotect the 5olymer itsel:. Sta!ilisers are also sometimes sed, :or e<am5le, to 5re9ent damage to a 5olymer !y long e<5os re to ltra=9iolet light which o:ten ca ses 5hoto= decom5osition as e9idenced !y a yellowish tinge and a red ction in trans5arency as well as a serio s deterioration in mechanical 5ro5erties. ,he addition o: car!on !lac8 to the 5olymer renders it o5a? e to light and in this way 5rotects it.

Foamed or 0E/panded0 Plastics )aterials

1# 5 #oamed r !!er has !een in se :or many years ! t more recently a n m!er o: 5olymers ha9e !ecome a9aila!le in this :orm. ): the thermo5lastic 5olymers Be<5andedB 5olystyrene is well= 8nown as an e<tremely lightweight 5ac8ing material, also as a thermal ins lator and :or the man :act re o: ceiling tiles :or the enth siastic home decorator. F5 to %>R o: its 9ol me consists o: air ! !!les ma8ing it an e<cellent :lotation material, since it has only a!o t one=tenth the relati9e density o: cor8 and does not !ecome waterlogged. Chie: o: the thermosetting 5olymers a9aila!le as :oams are the 5oly rethanes. ,hese are a9aila!le in the :le<i!le :orm :or the man :act re o: 5holstery and s5onges whilst rigid 5oly rethane :oams are sed :or the internal rein:orcement o: aircra:t wings.

,wo 9arieties o: :oamed 5olymers are man :act red=o5en (interconnecting) or closed cell lar str ct res=tho gh in 5ractice :oams are li8ely to contain some o: each ty5e o: str ct re with one 5redominating. As s ggested a!o9e, thermo5lastics, thermosetting 5olymers and elastomers can all !e :oam e<5anded and a n m!er o: methods are a9aila!le :or introd cing the gas 5oc8ets into the 5olymerD (i) By mechanically mi<ing air with the 5olymer whilst it is still in the molten state or dissol9ed in some sol9ent which wil$ e9a5orate. (ii) By dissol9ing a gas s ch as car!on dio<ide in the mi< !y the se o: 5ress re. D ring the hardening 5rocess 5ress re is red ced so that the gas is released :rom sol tion=rather li8e the ! !!les o: car!on dio<ide in mineral waters. Since hardening is in 5rogress the gas ! !!les are tra55ed 5rod cing a :oam. (iii) Similar in 5rinci5le is the addition o: a 9olatile com5onent to the mi<. D ring the hardening 5rocess this 9a5orises :orming ! !!les. (i9) Alternati9ely a gas may !e e9ol9ed d ring a cross=lin8ing 5rocess, e.g. as a res lt o: condensation 5olymerisation ($0./.$). ,his gas or 9a5o r can !e tilised to 5rod ce the :oaming 5rocess d ring hardening. (9) A B!lowing agentB may !e added which wil$ release gas in the mi< d ring heating. ,his is se: l :or :oaming thermo5lastics. A common reagent is sodi m !icar!onate which reacts in the same way as it does in !a8ing 5owder, that is. !y releasing ! !!les o: car!on dio<ide on heating th s ca sing the ca8e to rise.

R"**ers

1# 7 R !!er is a 9ery im5ortant material sed in a wide 9ariety o: 5rod cts ranging :rom tyres :or hea9y goods 9ehicles and motor cars to condoms and chewing g m. (t is an elastomer, ,his is a s !stance in which the arrangement o: the 5olymer molec les allows considera!le re9ersi!le e<tension to ta8e 5lace at normal tem5erat res. Elastomers e<ist as long chain molec les which are irreg larly coiled. !ent and generally entangled. when in the nstressed state. Since the coils are not arranged in a reg lar 5attern the str ct re is amor5ho s. ;hen a tensile :orce s ::icient to stretch the material is a55lied, the molec les 5artially disentangle and straighten o t so that they !ecome orientated in the general direction in which stretching occ rs. Since the molec les !ecome more closely aligned along the direction o: stretching, the :orces o: attraction !etween ad3acent molec les also increase so that the material !ecomes stronger and sti::er. As tem5erat re is red ced 5olymers !ecome less elastic and 5ass into a glassy state. ,his occ rs at the glass transition tem5erat re, ,g, and this 9aries :rom one 5olymer to another. , g :or most se: l elastomers is well !elow room tem5erat re. ,his can !e demonstrated !y cooling a r !!er !all to a 9ery low tem5erat re in li? id air. ;hen an attem5t is made to !o nce the !all it shatters in a manner similar to glass. Fnder normal conditions the molec les o: an elastomer are in constant motion with ad3acent sections 9i!rating relati9e to each other. As ,g is reached the molec lar str ct re !ecomes rigid so that mo9ement is restricted. (n crystalline 5olymers the 5resence o: m lti5le and hence :airly strong 9ander ;aals :orces acting !etween ad3acent molec les will raise ,g to 9ery near the so:tening tem5erat re o: the 5olymer. Conse? ently s ch materials are not elastomeric. 1# 7 1 Nat ral r !!er is a 5olymer deri9ed :rom the sa5 o: the r !!er tree, He+ea ,rasiliensis. Since this tree is nati9e to So th America it is !elie9ed that Christo5her Col m! s was the :irst E ro5ean to handle a 5iece o: r !!er. (t seems that some tri!es o: So th American (ndians 5layed !all games :rom 9ery early times.

,he monomer :rom which r !!er 5olymerises is iso5rene, C 1H&. D ring the nat ral 5olymerisation 5rocess, do !le !ond 5ositions in the molec le are rearranged (#ig. $0.0.(i)) so that iso5rene nits lin8 5 in the s al manner o: 5olymers to :orm a

chain molec le some 04444 car!on atoms=or a55ro<imately 4.4401 mm=in length. ,his ty5e o: chain molec le can dis5lay the 5ro5erty o: stereoisomerism! #or o r 5 r5oses this can !e e<5lained in a sim5li:ied manner as indicated in #ig. $0.0.(ii) and (iii). .Here it will !e noticed that the CH/ gro 5s can !e arranged on di::erent BsidesB o: the chain. ,he arrangement indicated in #ig. $0.0.(ii) is termed the BcisB=con:ig ration and is the str ct re 5resent in r !!er, whilst that shown in #ig. $0.0.(iii) is 8nown as the BtransB= con:ig ration and is the molec lar 5attern o: gutta-.ercha!

R !!er is an elastomer whilst g tta= 5ercha is in:le<i!le and hard !y com5arison. ,his co ld well !e d e to the :act that a chain molec le o: the [cisB ty5e (r !!er) is a!le to !end and coil easily in one direction, i.e. BawayB :rom the CH/ gro 5s (#ig= $0.01) whilst the relati9ely e9en distri! tion o: CH/ gro 5s on !oth BsidesB o: the molec le in the BtransB con:ig ration (g tta=5ercha) limits :le<i!ility

o: the molec le in either direction. Since the do !le !ond cannot rotate, the CH/ gro 5s are in :i<ed 5ositions. Hence !oth the cis= and trans=con:ig rations are sta!le and one :orm cannot con9ert to the other. 1# 7 # (n its nat ral state r !!er is !oth elastomeric and thermo5lastic.Being thermo5lastic it !ecomes 5ermanently de:ormed when it is stretched since 9an der ;aals :orces o5erate !etween the chain molec les only at a limited n m!er o: 5oints. (n this state r !!er is seless as an engineering material, ! t when r !!er is B9 lcanisedB these 9an der ;aals :orces are re5laced !y strong 5ermanent co9alent !onds and the material !ecomes thermosetting (#ig= $0.06).

$0.%./ ,he 5rocess o: 9 lcanisation was introd ced !y Eoodyear in $&/% and in9ol9es the se o: s l5h r to 5ro9ide cross lin8s

!etween the 5olyiso5rene molec les. ,he raw r !!er is :irst BmasticatedB or 8neaded !etween rolls so that a degree o: de5olymerisation occ rs and the material !ecomes more 5lastic as a res lt. (t can then !e mi<ed with s ::icient s l5h r=or other 9 lcanising agents=!e:ore !eing heated to 044ZC to ca se cross= lin8ing !etween the 5olyiso5rene molec les (#ig. $0.0>).

As the relati9ely nsta!le do !le !onds in the 5olyiso5rene chain are !ro8en, s l5h r atoms :orm co9alent !onds with ad3acent chains. ,he greater the amo nt o: s l5h r sed the higher the degree o: cross=lin8ing !etween ad3acent chains and the harder and more rigid the 9 lcani7ed r !!er !ecomes since mo9ement o: one chain relati9e to its neigh!o rs !ecomes more di::ic lt. ;hen an e<cess o: s l5h r is sed so that all a9aila!le !ond sites are sed 5 a hard rigid solid is 5rod ced and elastomeric 5ro5erties disa55ear. S ch a material was 5rod ced in the early years o: the twentieth cent ry nder s ch trade names as B' lcaniteB and BE!oniteB and sed in the man :act re o: B:o ntain 5ensB and coil :ormers sed !y amate r radio constr ctors. S ch 5 r5oses ha9e long !een re5laced !y modern rigid 5lastics materials ! t BE!oniteB sheet is still sed as a lining :or tan8s carrying corrosi9e li? ids, 5artic larly those containing the Cl= ion, since it has a higher resistance to Cl= !eca se o: its : lly cross=lin8ed str ct re and the conse? ent a!sence o: a9aila!le reacti9e sites.

R !!er sed in the man :act re o: a tomo!ile tyres is only 9 lcani7ed to the e<tent o: a!o t 1R o: the a9aila!le !ond 5ositions. ,his is s ::icient to red ce the 5lasticity o: the r !!er !y introd cing eno gh s l5h r cross lin8s ! t at the same time retaining most o: the elastomeric 5ro5erties. 1# 7 % (n addition to the 9 lcanising agent raw r !!er is generally com5o nded with other ingredients or B:illersB. Car!on is added to render r !!er tyres o5a? e and so restrict damage !y F' light. Some increase in !oth strength and a!rasion resistance is a::orded !y the addition o: car!on. ,he nsat rated do !le !onds still remaining in r !!er a:ter 9 lcani7ation are s sce5ti!le to o<idation, 5artic larly !y o7one. ,his e::ecti9ely red ces elasticity !y :orming cross lin8s in those remaining 5ositions not already lin8ed !y s l5h r atoms. As a res lt the r !!er !ecomes !rittle or B5erishedB. ,o red ce this tendency 9ario s anti=o<idants are incor5orated in the mi<t re.

The )echanical Properties of R"**er

1# 1; ,he resistance o: r !!er to de:ormation in tension at :irst decreases (as with metals) ! t then increases as indicated in the stress2strain diagram (#ig. $0.0&). R !!er does not o!ey Hoo8eBs -aw when in tension.

,his is d e to the :act that in materials with high elasticity the considera!le e<tension is accom5anied !y a !ig red ction in cross= section whereas in metals, which o!ey Hoo8eBs -aw, this red ction is negligi!le. ,he ratio o: lateral contraction to longit dinal e<tension (+oissonBs Ratio) is there:ore im5ortant in considering the tensile e<tension o: r !!ers. Fnli8e metals generally, 9 lcanised r !!ers do not yield nder stress, that is e<tension is entirely elastic. ,he tensile strength is a!o t 0> M+a with an elongation o: 5 to >44R. As might !e e<5ected Io ngBs Mod l s is relati9ely low since a large amo nt o: strain is 5rod ced !y a small stress and :or nat ral r !!er (NR) the 9al e o: E is a!o t $> M+a. Com5ara!le mechanical 5ro5erties are o!tained :or most synthetic r !!ers so that the choice !etween NR and one o: the synthetic r !!ers is more li8ely to de5end 5on 5ro5erties s ch as wear resistance, heat dissi5ation, ageing and chemical resistance to 5artic lar acids, al8alis and sol9ents. ,he term drift as a55lied to r !!ers is analogo s to cree5 in metals. (t re:ers to 5ermanent distortion o: r !!er nder long=time loading. As with cree5 in metals the rate o: dri:t increases with tem5erat re and li9e loads 5rod ce greater dri:t than do static loads. ,he e::ects o: tem5erat re on r !!ers m st there:ore !e considered care: lly. High tem5erat res accelerate o<idation degradation and whilst antio<idants can hel5 against this, an 55er limit o: $44ZC :or general 5 r5ose r !!ers nder long ser9ice conditions and 014ZC :or s5ecial elastomers is s ally a55lied. All r !!ers !ecome !rittle when the tem5erat re is s ::iciently low ($0.%) so that a minim m wor8ing tem5erat re is a!o t =.4ZC :or most synthetic r !!ers and as low as =61ZC :or NR.

S&nthetic R"**ers
1# 11 ,he Ka5anese in9asion o: BritainBs #ar Eastern r !!er 5lantations in $%.$ led to a serio s crisis in the war 5otential o: the

Allies. ,he sit ation was sa9ed !y the de9elo5ment o: the American synthetic r !!er 8nown as ER=S, a co5olymer o: styrene and ! tadiene. C rrently its 5rod ction e<ceeds that o: NR. Most synthetic r !!ers are 5olymerised :rom organic com5o nds whose names end in -diene (hence they are o:ten called BdienesB). ,hese are o: the general :orm laD

,wo do !le CPC !onds se5arated in this way !y a single !ond are 8nown as conGugated dou,le ,onds. D ring the 5olymerisation 5rocess one o: these do !le !onds disa55ears to 5rod ce the 9alency which 3oins this monomer to another in :orming the 5olymerD

Howe9er, one do !le !ond remains in the BrearrangedB nit and it is this do !le !ond which is a9aila!le :or cross=lin8ing d ring the 9 lcani7ation 5rocess. ,a!le $0.1 indicates the relationshi5s !etween monomers and 5olymers in the more im5ortant r !!ers. ,he chemistry o: some synthetic r !!ers is di::erent. Neither ((R or E+R (,a!le $0.1) are deri9ed :rom BdienesB and when 5olymerisation is com5leted no do !le !onds remain :or 9 lcanisation. Some cross=lin8ing does occ r in E+R, tho ght to !e d e to small crystallites :orming in gro 5s o: 5oly5ro5ylene nits in ad3acent chains, th s Bloc8ingB these chains together. Ne9ertheless a s ita!le diene (e.g. 0R iso5rene) is o:ten sed so that E+R !ecomes E+DR. B tyl r !!er is similarly treated :or 9 lcanisation. 1# 11 1 Styrene-,utadiene ru,,er (SBR) (,a!le $0.1) is 5rod ced !y co5olymerising a!o t >&R ! tadiene with styrene. (t re5resents

the ! l8 o: synthetic r !!ers 5rod ced, its cost !eing relati9ely low ma8ing it se: l :or car tyres. (t is a good general 5 r5ose r !!er with e<cellent a!rasion resistance ! t its :atig e resistance is in:erior to that o: NR. (t di::ers :rom NR in its ageing !eha9io r :or, whereas o<idation ca ses scission ($%.&.0)

in NR leading to so:tening, in SBR cross lin8s tend to :orm ma8ing it harder and more !rittle. (n addition to car tyres SBR is sed :or hose, !elting, :looring, shoe soles and electrical ins lation. (t is less s ita!le than NR :or the tyres o: HE's where heat tends to ! ild 5 more ? ic8ly with SBR. )5erational tem5erat re range is !etween = .44 and &44C.

1# 11 # %oly,utadiene ru,,er (BR) is made :rom the single monomer ! tadiene. (ts strength and tear resistance are generally in:erior to NR ! t it is highly resilient. Hence it is rarely sed alone ! t !lended in amo nts 5to .4R with either NR or SBR to im5ro9e the a!rasion resistance o: tyres in which it is most o:ten sed. ,em5erar re rangeD =.44 to $44ZC. 1# 11 $ Butyl ru,,er ($$B) is 5rod ced !y co=5olymerising iso! tylene with small amo nts o: iso5rene. Since the 5rod ct has a low degree o: B nsat rationB (:ew do !le !onds) it is chemically 9ery sta!le and has a good resistance to heat and to many chemicals ! t not to oils. (t is 9 lcanised in the same way as nat ral r !!er. B tyl r !!er is chea5er than nat ral r !!er and since it is resistant to o7one !eca se o: its $ow nsat ration, it is less lia!le to A5erishB. (t is also im5ermea!le to air and other gases ma8ing it se: l :or inner t !es and t !eless tyres, air !ags, s5orting e? i5ment and mo lded dia5hragms. Being im5er9io s to many chemicals it is also sed :or hoses, tan8 linings and con9eyor !elts Eenerally its 5hysical 5ro5erties are in:erior to NR and SBR. ,em5erat re rangeD =14 to $01ZC. 1# 11 % %olychloro.rene (Bneo5reneB) r !!er (CR) is a 5olymer o: chloro5rene (chloro! tadiene) and is generally in:erior to nitrile r !!er in its resistance to oils ! t !etter than either NR, SBR or ((R. Moreo9er its mechanical 5ro5erties are s 5erior to those o: most synthetic r !!ers and only slightly in:erior to those o: NR. (t is a relati9ely e<5ensi9e material sed :or gas8ets, 5rotecti9e glo9es, adhesi9es, hose, con9eyor !elts and electrical ins lation. A ma3or disad9antage is its 5oor :le<i!ility at low tem5erat res. ,em5erat re rangeD =.4 to $44ZC. 1# 11 ' (so5rene (5olyiso5rene) r !!er ((R) is a synthetic r !!er with 9irt ally the same com5osition and str ct re as NR. (ts 5ro5erties are slightly more ni:orm than NR !eca se o: the

greater BcleanlinessB o: its raw material, iso5rene, ! t it is less easy to 5rocess and is o: lower strength. 1# 11 ( =itrile ru,,er (NBR) is a co5olymer o: acrylonitrile and ! tadiene. (t has e<cellent resistance to grease, oil and sol9ents ! t is attac8ed more easily !y al8alis than is NR. (t is sed e<tensi9ely as an adhesi9e and to im5regnate, or as a coating :or, 5a5er 5rod cts. )ther ses incl de heels :or shoes and as a lining :or hoses and : el tan8s carrying 5etrole m 5rod cts. ,em5erat re rangeD =.4 to $44ZC. 1# 11 4 "thylene-.ro.ylene ru,,er (E+M) is a co5olymer o: the two nsat rated hydrocar!ons (al8enes) ethylene and iso= 5ro5ylene. (t is a non=crystalline 5rod ct with r !!ery 5ro5erties. Beca se o: the chemical sat ration o: its str ct re :ollowing 5olymerisation it is chemically inert and has good resistance to ageing (as does 5olythene). (t is a lightweight r !!er with 5 to 61R o: either monomer. A : rther diene monomer is o:ten added to 5ro9ide sites :or cross=lin8ing (then designated as E+DM) (t has good resistance to weathering and o7one attac8, ! t a rather high cree5 rate and 5oor resistance to sol9ents. ,em5erat re rangeD =14 to $01ZC. 1# 11 5 ): some do7en other synthetic r !!ers a9aila!le Silicone ru,,er (_) is 9ery resistant to weathering and is good :or !oth high and low tem5erat re se. ,em5erat re rangeD =64 to 044ZCM whilst Fluorocar,on ru,,er (#+M) has, li8e +,#E, a high resistance to many aggressi9e chemicals (:l orine !eing the most strongly electronegati9e o: all elements and there:ore :orming 9ery sta!le com5o nds). (t is also se: l at high tem5erat res. ,em5erat re rangeD =/4 to 014ZC.

1$ Ceramics and 6lasses

1$ 1 ,he atoms or molec les o: any crystalline solid are 5ermanently located with res5ect to their neigh!o rs. Atoms 9i!rate contin o sly a!o t e? ili!ri m 5ositions !eca se o: the energy they ha9e recei9ed in the :orm o: heat. ,he total internal energy o: a solid increases as its tem5erat re rises and :or this reason !oth the :re? ency and am5lit de o: atomic 9i!rations increase so that atoms or molec les are :orced : rther away :rom their e? ili!ri m 5ositions. ,his mo9ement away :rom original 5ositions mani:ests itsel: as thermal e#.ansion and also e<5lains the storing o: energy !y a !ody in terms o: its heat ca5acity (s5eci:ic heat). Atomic 9i!rations also : rnish one method !y which heat can tra9el thro gh a s !stance,. that is, !y conduction. Metals are 5artic larly good cond ctors o: heat since their 9alency electrons, constit ting a common Bclo dB, are a!le to mo9e :reely nder the in:l ence o: a tem5erat re gradient 3 st as they will nder the action o: an electrical 5otential di::erence. Materials s ch as glasses, r !!ers, cell lose and many o: the 5lastics materials are s ally considered as solids in the sense that they are o: de:inite and 5ermanent sha5e. )n the other hand they are not crystalline since their molec les are not arranged in a reg lar 5attern. #or this reason, as well as :or others s ch as the lac8 o: a de:inite melting 5oint, they are o:ten regarded as s 5er= cooled li? ids. ;hen heated to a s ::iciently high tem5erat re range they !ecome increasingly 5lastic as the tem5erat re rises. (n

this res5ect they resem!le 9isco s li? ids which !ecome more mo!ile at higher tem5erat res. + re crystalline solids on the other hand 5ass :rom a strictly geometrical lattice str ct re to a li? id state at a single :i<ed tem5erat re. 1$ 1 1 Most ceramics are hard and !rittle and, with the e<ce5tion o: glasses, crystalline in nat re. (n metals the crystalline str ct re is relati9ely sim5le and o5erates thro gh the metallic !ond which renders them d ctile ! t in ceramics chemical !onding is either co9alent (diamond, silicon car!ide, silicon nitride) or ionic (magnesi m o<ide) or in some cases acom!ination o: the two (al mini m o<ide). As the +eriodic Classi:ication (,a!le $./) indicates car!on and silicon are chemically similar elements and each :orms im5ortant ceramic materials. Each has :o r 9alency electrons in its o ter shell and this res lts in their :orming :o r e? i9alent electron or!itals which o: co rse re5el each other strongly so that they are directed tow.ards the corners o: a reg lar tetrahedron (#ig. $0.$). A sta!le BoctetB is then achie9ed !y the :ormation o: :o r co9alencies. ,his tetrahedral :orm is re:lected in the crystalline str ct re o: diamond (#ig. /.0&) and o: many silicon com5o nds (#igs $/./, $/... $/.1 and $/.6). ,he great strength o: co9alent !onds o: this ty5e res lts in the e<treme hardness o: many o: the com5o nds o: car!on and silicon s ch as diamond, silicon car!ide, silica, silicon nitride, t ngsten car!ide, glass, etc. 1$ 1 # ,he term BceramicsB is a55lied to a range o: inorganic materials o: widely 9arying ses. Eenerally these materials are noli=metallic and in most cases ha9e !een treated at a high tem5erat re at some stage d ring man :act re. ,he word BceramicB is deri9ed :rom the Eree8, B8eramosB= or B5otterBs clayB, tho gh the gro 5 o: materials now so descri!ed incl des glass 5rod ctsM cements and 5lastersM some a!rasi9es and c tting tool materialsM ! ilding materials s ch as !ric8s, tiles and drain 5i5esM 9ario s electrical ins lation materialsM re:ractory linings :or : rnacesM

5orcelain and other re:ractory coatings :or metalsM as well as the more traditional ses in 5ottery, croc8ery and sanitary ware. #rom the 5oint o: 9iew o: com5osition and str ct re ceramics can !e classi:ied con9eniently into :o r main gro 5sD (i) Amor5ho s ceramics these are s !stances re:erred to generally as BglassesB. ,hey incl de those s ch as Bo!sidianBQ which occ r nat rally, and man=made glasses sed :or the man :act re o: !ottles, windows and lensesM (ii) Crystalline ceramics these may !e single=5hase materials li8e magnesi m o<ide or al mini m o<ide, or 9ario s mi<t res o: materials s ch as these. (n addition some car!ides and nitrides !elong to this gro 5M (iii) Bonded ceramics materials in which indi9id al crystals are !onded together !y a glassy matri< as in a large n m!er o: 5rod cts deri9ed :rom clayM (i9) Cements a n m!er o: these are crystalline ! t some may contain !oth crystalline and amor5ho s 5hases.

Str"ct"res of Ceramics
1$ # Ceramics are :ar less d ctile than metals and tend to :ract re immediately any attem5t is made to de:orm them !y mechanical wor8 ,hey are o:ten o: com5le< chemical com5osition and their str ct res may also !e relati9ely com5le<. ,hese str ct res :all into two main gro 5sD $/.0.$ Sim5le Crystal Str ct res ,hese incl de str ct res in which the !onding is either ionic or co9alent. ,h s magnesi m o<ide, Mg), is an ionic com5o nd o: c !ic str ct re (#ig. $/.$) similar to that o: sodi m chloride. Magnesi m o<ide is a re:ractory material sed in the linings o: : rnaces :or the man :act re o: steel !y !asic 5rocesses and can withstand tem5erat res in e<cess o: 0444ZC.

Silicon car!ide is also a ceramic material o: sim5le com5osition and str ct re. Here the !onding is co9alent and the str ct re tetrahedral s ch that each silicon atom is s rro nded !y :o r car!on atoms and. con9ersely, each car!on atom !y :o r silicon atoms. As a res lt the str ct re is 9ery . li8e that o: diamond. As mentioned earlier ($/.$.$) !oth car!on and silicon are ? adri9alent mem!ers o: Ero 5 i9.D e to the sta!le co9alent !onds which o5erate and also the symmetry o: the str ct re. silicon car!ide is a 9ery hard material. ,ho gh less hard than diamond which it resem!les in str ct re it is ne9ertheless a well= 8nown a!rasi9e material. Some relati9ely sim5le crystalline ceramics contain a mi<t re o: co9alent and ionic !onds. S ch a material is al mina (al mini m o<ide, A$0)/) (#ig. $/.0). Altho gh the str ct re is !asically close= 5ac8ed he<agonal, one third o: the al mini m ion2atom sites remain 9acant in order to satis:y the 9alency re? irements o: !oth elements. 1$ # # Comple/ Silicate Str"ct"res ,he ma3ority o: ceramic materials, and 5artic lar those deri9ed :rom clay, sand or cement, contain the

element silicon in the :orm o: silicates. ,he similarity !etween silicon and car!on in res5ect o: many chemical 5ro5erties has already !een mentioned. K st as car!on 5olymer molec les are ! ilt 5 :rom a s ccession o: re5eating BmersB ($0.$./) so are many silicates :ormed as chain, sheet or :ramewor8 str ct res. ,he most sim5le silicon==o<ygen BmerB is the BSi).B gro 5 in which a small silicon atom is s rro nded tetrahedrally !y :o r o<ygen atoms (#ig. $/./). (n this way the ? adri9alency o: the silicon is

:ig $/./ the tetrahedral arrangement o: the (Si) .).= ion. iii)indicates the nsatis:ied 9alencies o: the o<ygen atoms.

satis:ied ! t the !i9alency o: the o<ygen atoms is not. Hence to satis:y the 9alency o: the o<ygen atoms, Si) . gro 5s are :re? ently ionically !onded to metallic atoms th s 5rod cing negati9ely charged silicate ions (Si).).= and 5ositi9ely charged metallic ions, e.g. Ca0WM NaWM Mg0W and Al/W. ,he 5ositi9e and negati9e ions then :orm a crystal str ct re. Alternati9ely the electron de:iciency o: the o<ygen can !e made 5 !y com!ination with another silicon atom th s ma8ing it 5art o: an ad3acent tetrahedron (#ig. $/..). ,he res ltant nit (Si 0)> )6= is 5resent in only a :ew minerals. An e<am5le o: a mineral !ased on the (Si). ).= ion is magnesi m silicate=

or forsterite. ,he em5irical :orm la, that is, that :orm la which indicates the ratio o: atoms 5resent in a com5o nd, is Mg 0Si)., ! t it m st !e remem!ered that, as in the case o: sodi m chloride (/.0.0), the nit in9ol9ed here is the crystal and not the molec le ! Forsterite is se: l as a re:ractory material since its melting 5oint is in the region o: $%444C. 1$ # $ ,he str ct re de5icted in #ig. $/.1 is : ndamentally that o: a chain !ased on silicate ions (Si)/ )0=, in which ad3acent chains are ionically !onded !y !ridging metallic ions s ch as Ca0W. Herein lies the di::erence in mechanical 5ro5erties !etween an organic 5olymer and a silicate ceramic. (n the case o: the organic 5olymer ad3acent chain molec les are held together !y wea8 9an der ;aals :orces ! t in the ceramic these :orces are re5laced !y stronger ionic !onds ma8ing ceramics hard and relati9ely strong.

Ne9ertheless the ionic !onds lin8ing the silicate chains to the metallic B!ridgesB are wea8er than the co9alent !onds o5erating within the silicate gro 5. Conse? ently :ract re s ally occ rs thro gh these ionic !onds, that is, 5arallel to the direction o: the silicate chains.

Do !le chains o: silicate tetrahedra are also :ormed, i.e. (Si .)$$ )6= and these are in general more im5ortant than the single=chain com5o nds. Here the o<ygen atoms :orming the !ases o: tetrahedra are shared with ad3acent nits (#ig. $/.6). ,he do !le= chain nits are lin8ed !y metallic ions :orming characteristically rigid crystalline str ct res. (n some cases the chains are held together !y 9an der ;aals :orces as well as !y ionic !onds th s allowing the material to !e se5arated into :i!res. As!estos is an e<am5le o: this class o: mineral which ha9e em5irical :orm lae o: the ty5e /Mg).0Si)0.H0). 1$ # % (n many minerals o: the gro 5 which incl de clays, talc and micas the silicate tetrahedra are lin8ed in sheet :orm instead o: in chain :orm. #ig re $/.> re5resents a B5lanB 9iew o: this system in which the 5ositions o: the o<ygen atoms at the a5ices o: the tetrahedral nits are shown. ,he

em5irical :orm la o: the silicate nit is (Si 0)1 )0=. )n the !asal 5lane o: the sheet all o<ygen 9alencies are satis:ied. i.e. each o<ygen atom has & a9aila!le electrons. ,he mineral aolinite, the sim5lest ty5e o: clay, has al mini m ions (Al/W) which satis:y the 9alencies o: the 55er o<ygen atomsM the remaining two 9alencies o: the A$/W ions then in t rn !eing satis:ied !y ()H)= ions which are also 5resent. Since all 9alencies within the sheet str ct re are now satis:ied ad3acent silicate sheets can attract each other only !y wea8 5olarisation :orces o: the 9an der ;aals ty5e. ,his e<5lains the 5lasticity o: clay and the :act that mica is readily se5ara!le into e<tremely thin sheets. ;hen water is added to clay the H0) molec les are attracted to the s r:ace layers o: the sheets !y 5olarisation :orces (0..) th s 5ro9iding a !o ndary l !ricant !etween ad3acent sheets (#ig. $/.&). ;hen water is

dried o t the 5lasticity o: the clay is corres5ondingly red ced and when the clay is !a8ed cross=lin8ing !etween ad3acent sheets 5rod ces a strong !rittle str ct re. ,his is a non=re9ersi!le reaction com5ara!le with thermosetting o: !a8elite and the clay has now 5ermanently lost its 5lasticity. 1$ # ' ,he de9elo5ment o: the silicate tetrahedral str ct re into three dimensions 5rod ces a :ramewor8 ty5e o: arrangement which is in e::ect a giant molec le (/.&.$) o: em5irical :orm la (Si) 0)n. Each silicon atom is s rro nded !y :o r o<ygen atoms and each o<ygen atom is 3ointly shared !y an ad3acent nit. (n this way all 9alency !onds are sed 5 and a hard,rigid :ramewor8 str ct re is 5rod ced. ,he sim5lest o: these str ct res is that o: cristo!alite whilst another is that o: ? art7. Both o: these materials are hard and :ract re in an irreg lar manner since there is no 5re:erred direction o: clea9age, !onding :orces !eing e? al in all directions. )ther :ramewor8 str ct res incl de 9ario s al minosilicates.

Shaping of Ceramics
1$ $ 'ario s ty5es o: clay are the most widely sed raw materials :or ceramics man :act re. ,hey can generally !e sed in the Bas minedB condition when mi<ed with water which acts as a 5lasticiser ($/.0..). Altho gh clays di::er in com5osition

the main constit ent is an al mino=silicate mineral s ch as aolinite (Al0)/ 0Si)0. 0H0)). ,he 8aolinite, content 9aries according to the ty5e o: clay. English china clay as mined in Cornwall may contain 5 to %1R 8aolinite whilst clays sed in !ric8 man :act re may contain as little as /4R. Most other ceramic materials ha9e to !e man :act red or at least 5 ri:ied !y some chemical 5rocess. ,he 5owders so 5rod ced are then com5acted and sintered to achie9e a coherent solid mass. Elasses howe9er are sha5ed whilst in a li? id state($/.6.$). 1$ $ 1 Shaping Cla& Prod"cts Mention o: the 5otterBs wheel may con3 re 5 9isions o: B!earded weirdiesB wearing sandals, li9ing on a diet o: stewed nettles and 5rod cing 5ottersB 8nic8=8nac8s :or the local to rist trade. Ne9ertheless the 5otterBs wheel still has commercial se tho gh ind stry generally em5loys mechanical o5erations with a standard 5rod ct in 9iew. $/./.$.$ Hydro.lastic forming o: wet clay is most commonly carried o t !y e<tr sion sing a Bscrew 5 m5B similar in design to that in #ig. 6.0>. A:ter !eing e<tr ded the clay is strong eno gh to !e handled 5rior to :iring.Most !ric8s are now made :rom e<tr ded stoc8, i.e. B5arted o::B and em!ossed. $/./.$.0 Sli. casting is sed to 5rod ce a 9ariety o: ho sehold and decorati9e 5ottery :rom china clay, 5artic larly when com5le< or irreg lar sha5es are in9ol9ed. Here the clay is held as a s s5ension, or Bsli5B, o: 5articles in water. ,his is then 5o red into a mo ld made :rom some a!sor!ent material s ch as +laster o: +aris which ta8es 5 water :rom the sli5 lea9ing it ni:orm layer o: clay 5articles on the 0 #orming mo ld walls. ;hen the layer reaches the re? ired thic8ness e<cess sli5 is 5o red away. A:ter the necessary drying 5eriod which allows the article to !ecome strong eno gh it is remo9ed :rom the mo ld (#ig. $/.%) 5rior to :iring.

1$ $ # Forming Ceramics from Po,ders A n m!er o: 9ariants o: a !asic 5ress re=a55lication 5rocess are sed, 5rinci5ally in ma8ing engineering ceramics. $/./.0.$ Cold .ressingCsintering=many engineering ceramics are made !y cold 5ressing the dry or slightly dam5 5owder to 5rod ce a com5act which is strong eno gh to !e handled. ,he com5act is then sintered at a tem5erat re high eno gh to ca se : sion at the 5article !o ndaries as is the case with some 5owder=metall rgy 5rod cts (6.1.$).

$/./.0.0 $sostatic .ressing (#ig. $/.$4) is sed to o!tain a more ni:orm density 5artic larly in com5onents o: intricate sha5e. ,he ceramic 5owder is contained in a r !!er mo ld which is then immersed in a li? id !ath to which a high 5ress re is transmitted. (

$/./.0./ Hot .ressing is sed to 5rod ce a denser 5rod ct in those materials which tend to s ::er :rom high 5orosity, ! t !eca se o: the high tem5erat re and 5ress res in9ol9ed, it is limited to the

man :act re o: sim5le sha5es. Silicon nitride, Si/N., is sha5ed !y hot isostatic 5ressing at tem5erat res in the region o: $&44ZC, sing gra5hite dies and 5ress res o: $44 M+a. 1$ $ $ The .eat1treatment of Ceramics Most clay=!ased ceramics need to !e care: lly dried. As the :ilm o: water which se5arates the ceramic 5articles is remo9ed shrin8age ine9ita!ly occ rs ! t war5ing and crac8ing can !e 5re9ented !y controlling the tem5erat re and h midity o: the en9ironment to constant 9al es. $/././.$ Drying o: the ceramic is :ollowed !y :iring which is carried o t at a tem5erat re which will lead to sintering :ollowed !y 9itri:ication.Sintering in9ol9es the com5acting o: the material !y 5rolonged heat= treatment at a high tem5erat re which is ne9ertheless !elow the melting 5oint o: the main 5hase o: the ceramic. Di:: sion across the 5article !o ndaries occ rs, accom5anied !y some recrystallisation which com5letes the !onding o: the 5articles. Clay=!ased ceramics de5end 5on 9itri:ication occ rring d ring :iring. Here considera!le amo nts o: li? id= 5 to /1R=are :ormed and, on cooling :rom the :iring tem5erat re, this li? id 5hase :orms a glass which is e9ident as a gla7ed :inish on the s r:ace.

Properties of Ceramics
1$ % Fntil recent years most ceramic materials consisted o: crystalline 5articles cemented together !y glass, which, as we shall see later, is an amor5ho s s !stance :ormed when acidic silica =com!ines with a !asic metallic o<ide at high tem5erat res. ,hese materials, mainly al mino=silicates o: 9arying com5ositions, were sed as : rnace liningsM :or the man :act re o: 5ottery and electrical ins lators and :or many ! ilding materials s ch as !ric8s and tiles. Howe9er, modern technologies o: sintering ha9e

5rod ced str ct res which are wholly crystalline. Some o: these materials maintain high strength at ele9ated tem5erat res since low melting 5oint glasses are a!sent. 1$ % 1 Strength ,he high com.ressi+e strength o: ceramics has long !een 8nown to man and was well esta!lished !y the time +heidias constr cted his +arthenon in Athens in a!o t .14 B.C. (n more recent times Messrs Kosiah ;edgwood and Sons -td 5 !lished a 5hotogra5h showing an ele9en=tonne do !le=dec8er ! s s 55orted !y si< o: their :ine !one china co::ee c 5s. Altho gh ceramics are hard and reasona!ly strong they lac8 d ctility and this, in t rn, 5re9ents any stress concentrations which may !e 5resent :rom !eing relie9ed !y the onset o: 5lastic :low. ;hereas metals are mallea!le and d ctile most ceramics, 5artic larly where co9alent !onds are 5resent, are !rittle. ,his is d e largely to the o9erall width o: dislocations 5resent in the str ct re and th s in t rn is de5endent on the nat re o: interatomic :orces. (n a metal the ions are held in 5osition !y their m t al attraction :or the B:le<i!leB electron clo d, whilst in ceramics s ch as diamond the strong co9alent !onds are strictly directional. ,hese :actors in t rn a::ect the e? ili!ri m width o: any dislocations 5resent (#ig. $/.$$). ,he width o: a dislocation is de:ined as the distance o9er which the dis5lacement o: atoms or ions is greater than !2. where ! is the B rgers 9ector o: the material (#ig. 1.$4). $/...$.$ (n #ig. $/.$$ it will !e seen that the width, ;, o: the dislocation in the case o: a metal (i) is m ch greater than in a co9alently !onded material (ii). (n :act it is estimated that with mallea!le metals s ch as gold, co55er and al mini m dislocation widths o: a!o t ten ion s5acings are 5resent (#ig. $/.$$(i)). ;hen the width is great the :orce necessary to

mo9e s ch a dislocation is small !eca se the highly distorted region at the centre o: the dislocation is not critically localised on a single 5artic lar crystal site. (n (ii), howe9er, a large stress will !e necessary to mo9e the dislocation away :rom its strongly localised site. At the same time there is a com5arati9e lac8 o: sli5 systems in a ceramic material and these in:l ences will com!ine to ca se the interatomic :orces o: attraction in the region o: the dislocation to !e e<ceeded so that :ract re occ rs. ,his di::erence in the width o: dislocations as !etween metals and co9alently= or ionically= !onded materials is res5onsi!le :or the high mallea!ility and to ghness o: metals and, conse? ently, their strength and relia!ility as engineering materials. $/...$.0 Since ceramics tend to s ::er :rom the 5resence o: microcrac8s which act as stress raisers it :ollows that tensile stresses m st generally !e 8e5t low i: s dden :ail re is to !e a9oided. Moreo9er the incidence o: s ch :a lts in a ceramic is m ch more 9aria!le than in a metal where the ? ality o: the str ct re is relati9ely easy to control. Conse? ently a !igger BscatterB o: meas red strengths is to !e e<5ected in ceramics. ,heir com.ressi+e strengths, howe9er, are high com5ared with their tensile strengths. Retention o: strength at high tem5erat res is one o: the se: l :eat res o: s ch materials. #or e<am5le, titani m di!oride will maintain a com5ressi9e strength o: 014 M+a at

0444ZC ma8ing it one o: the strongest materials 8nown at that tem5erat re. $/...$./ (n most ceramics d ctility is, :or all 5ractical considerations,7ero. ,his again is !eca se many ceramics are he<agonal in crystal str ct re (#ig. $/.0) in which only two sli5 5lanes are a9aila!le. Moreo9er !onding, !eing co9alent, is strongly directional !etween s5eci:ic atoms ma8ing sli5 9irt ally im5ossi!le. (n 5ractice o: co rse s ch internal im5er:ections as 5orosity : rther red ce strength and d ctility. S ch :a lts are more di::ic lt to control d ring man :act re than they are in metals since most engineering ceramics are com5acted :rom 5owders which s ggest that some 5orosity is ine9ita!le. A :ew ceramics s ch as Mg) in which !onding is 5rimarily ionic e<hi!it limited d ctility when in the :orm o: a single crystal ! t in general ceramics can only !e classed as B!rittle@. 1$ % # Creep ,his ta8es 5lace in ceramic materials at relati9ely high tem5erat res since ceramics are sta!le crystalline solids with high melting 5oints. Elasses on the other hand are non=crystalline and ha9e :airly low so:tening tem5erat res so that considera!le cree5 will occ r at moderate tem5erat res. ;ith these materials steady=state cree5 occ rs according to an Arrheni s=ty5e e<5ression ($6..)D d s2dtPAhn e<5(=_2R,) where A is a constant, _ is the acti9ation energy (also a constant :or the condition), R is the ni9ersal gas constant, , the a!sol te tem5erat re, h the stress and n the time e<5onent which :or many ceramics and glasses is in the region o: $4. 1$ % $ .ardness Ceramic materials generally are hard when com5ared with most other engineering materials. ,his hardness

ma8es certain ceramics se: l as a!rasi9es or, s ita!ly !onded, as c tting tool materials. ,h s, c !ic !oron nitride is almost as hard as diamond whilst materials li8e silicon car!ide, al mina (al mini m o<ide) and !erylli m o<ide are already well 8nown. Some hard ceramics are listed in ,a!le $/.$, hardened tool steel !eing incl ded :or com5arison.
,a!le $/.$ Hardness o: Some Ceramics )aterial knoop hardness n"m*er Diamond >444 C !ic !oron nitride 6%44 ,itani m di!oride //44 Boron car!ide 0%44 Silicon car!ide 0644 Silicon nitride 0644 Al mina 0444 Berylli m o<ide $004 Hardened steel >44

,he hardest o: these s !stances de5end :or their 5ro5erties on the 9ery strong sta!le nat re o: their directional co9alent !onds. 1$ % % Refractoriness generally de:ined as the a!ility o: a material to withstand high tem5erat res witho t a55recia!le de:ormation nder ser9ice conditions. Some re:ractories li8e :ireclay and high= al mina !ric8 so:ten grad ally o9er a range o: tem5erat re and may ltimately colla5se nder load at a tem5erat re well !elow the normal : sion tem5erat re.Materials most widely sed as re:ractories in : rnaces are clays containing 9ario s 5ro5ortions o: silica (Si)0) and al mina (A(0)/). As the thermal e? ili!ri m diagram (#ig. $/.$0) indicates mi<t res containing in the region o: .==&R al mina are !est a9oided :or se at high tem5erat res since they will melt com5letely at a little a!o9e the e tectic tem5erat re o: $1%1ZC. As the amo nt o: al mina increases a!o9e 1.1R the ? antity o: li? id (5rod ced at $1%1ZC) will decrease and so the !ric8s will !e stronger

at that tem5erat re. #or se9ere conditions where tem5erat res reach $&44ZC the al mina content m st e<ceed >$.&R. Certain ceramic materials ha9e 9ery high melting 5oints indeed and :or s5ecial 5 r5oses these may !e sed, ass ming that their relati9e high cost is 3 sti:ied. A :ew o: these high tem5erat re ceramics are incl ded in ,a!le $/.0.
,a!le $/.0 Melting +oints o: Some High=tem5erat re Re:ractory Material Ha:ni m car!ide Tantal"m car*ide ,hori m o<ide Magnesi m o<ide Oirconi m o<ide Berylli m o<ide Al mini m o<ide Silicon nitride # sed silica glass Soda glass Melting 5oint( 4C) /%44 $57; //$1 0&44 0644 0114 0414 $%44 $6&4 (a55ro<.) /.4=./4(a55ro<)

Again ,as with hardness, this 5ro5erty can !e tho ght o: as a : nction o: chemical !ond strength. Strongly !onded materials re? ire a large in5 t o: thermal energy to disr 5t the atomic !onds. 1$ % ' Electrical Properties Fntil a short while ago the se o: ceramics in the electrical ind stries was restricted to ins lation.

,oday ceramic materials incl de many s !stances 9arying in 5ro5erties :rom low=loss high=:re? ency ins lators to semi= cond ctors, cond ctors and :erro=magnets. Conse? ently they are sed as thermistors, thermoelectrics, transistors and storage cells in memory systems. (ndeed the c rrent race to de9elo5 a really high= tem5erat re s 5ercond ctor ($&...0) is !ased at 5resent on so5histicated ceramics.

Some Engineering Ceramics

1$ ' Modern ceramics sed in engineering are eitherD (i) hard materials, s ally o<ides, car!ides, nitrides or !orides o: metals or metalloidsM or (ii) strong materials s ch as car!on or certain glasses in :i!re :orm. ,he hard materials are sed as c tting tools or in the :orm o: wear= resistant or 5enetration=resistant s r:acing s !stances !oth :or military 5 r5oses and in the a to=engineering ind stries. 1$ ' 1 Al"mina (Al0)/) 5rod ced :rom the ore !a <ite which is also the so rce o: metallic al mini m. As mined, !a <ite is a reddish=!rown mineral !eca se o: the 5resence o: im5 rities s ch as iron o<ide and silica. ,he cr shed !a <ite is digested with hot ca stic soda nder 5ress re when the al mini m o<ide dissol9es as sodi m al minate, NaAl)0D Al0)/ W 0Na)H0NaAl)0 W H0) ,he sol tion is :iltered so that solid im5 rities are eliminated. Sodi m al minate is nsta!le so that when C)0 is 5assed thro gh the sol tion al mini m hydro<ide, Al()H)/, is 5reci5itated. ,his is :iltered o::, the remainder o: im5 rities 5assing away in the :iltrate.

,he 5 re Al()H)/ is then dried and calcined at $$44ZC when the hydro<ide decom5oses to gi9e 5 re al minaD
0Al()H)/ Al0)/ W /H0)

(n the man :act re o: armo r 5lating al mina is com5acted as a dry or slightly dam5 5owder at high 5ress re so that a dense 5late, strong eno gh to !e handled, is :ormed. ,his is then densi:ied !y sintering which in9ol9es the consolidi:ication o: the 5owder !y 5rolonged heating at a 9ery high tem5erat re ! t !elow the melting 5oint. + re al mina has a 9ery low thermal cond cti9ity which ma8es it s sce5ti!le to o9er=heating and hence ra5id wear when sed as a c tting tool at high machining s5eeds. ,hermal cond cti9ity is increased !y adding some titani m car!ide which in t rn red ces wear !y o9er=heating. S ch tools ha9e to !e hot=5ressed :rom 5owder with conse? ent limitations on sha5e. An al mina=titani m nitride mi<t re, howe9er, can !e sha5ed !y the orthodo< cold 5ressing2sintering method. (t has a still greater thermal shoc8 resistance than 5 re al mina and is also harder, ma8ing it more s ita!le :or machining harder steels and cast irons nder conditions o: high c tting :orces and high tem5erat res. M ch al mina is sed as military armo r 5lating. (t has the disad9antage o: a high relati9e density o: /.& ! t is relati9ely ine<5ensi9e. S ch armo r in the :orm o: mo lded !reast 5lates is sed !y s5ecialist nits in anti=terrorist, co nter=re9ol tionary o5erations where sni5ers sing high= 5owered ri:les may !e enco ntered. (ts hardness, wear resistance and chemical inertness ha9e led to the increasing se o: al mina in hi5=3oint re5lacements. Since al mina has a low electrical cond cti9ity it is sed :or the ceramic !odies o: s5ar8ing 5l gs. 1$ ' # Silicon !itride and 0Sialons0 Silicon nitride, Si/N., is a sta!le co9alent com5o nd with low thermal e<5ansion which ma8es it se: l :or metal c tting since in addition to great hardness it 5ossesses resistance to thermal shoc8. Silicon nitride itsel:

cannot !e sintered s ccess: lly since a high degree o: 5orosity is retained. Conse? ently re? ired sha5es are 5re:ormed in silicon to 5rod ce 5oro s com5acts which are then heated in a nitrogen atmos5here 3 st !elow the melting 5oint o: silicon ($.$0ZC) to 5rod ce the nitride. 8;!E!6!8 Since Si/N. cannot !e sintered additions o: !asic o<ides s ch as Mg), Al0)/ and I 04/ are made so that, on heating, a li? id 5hase is :ormed !y reaction with acidic Si4 0 which is 5resent on the s r:ace o: the Si/N. grains. )n solidi:ication the res ltant microstr ct re is a two=5hase system consisting o: crystalline = Si/N. em!edded in an intercrystalline !onding 5hase in the :orm o: a glass. ,his glass can !e more or less de9itri:ied !y slow cooling or !y : rther heat=treatment. Silicon nitride tool 5ro5erties are largely de5endent on the amo nt and com5osition o: the intergran lar 5hase, 5artic larly at high tem5erat res. 8;!E!6!6 D ring the $%>4s it was disco9ered that ) 0= co ld !e s !stit ted :or N/= in the str ct re o: the =Si/N. crystal whilst A$/W co ld !e s !stit ted :or Si.W in s ita!le 5ro5ortions which wo ld maintain a !alance o: 9alencies. De5ending 5on the relati9e 5ro5ortions o: the reactants sed the res ltant solid com5o nd. 9irt ally a solid sol tion, can ha9e a str ct re o: either =Si/N. or =Si/N.. ,hese com5o nds are 8nown collecti9ely as BSialonsB (an acronym on the chemical sym!ols o: the 5rinci5al ingredient elementsD Si=Al=)=N). ,he =sialons are o: the general A:orm laBD Si6=7Al7)7N&=7 where O re5resents the degree o: s !stit tion o: silicon and nitrogen !y al mini m and o<ygen res5ecti9ely, andD 4 d O d..0. ,he =sialons are o: com5ositionD MH(Si, Al)$0 (4, N)$6 where Hd0 and M is a metallic ion and can !e -i$W,Be0W,Mg0W, Sc/W,Ca0W, or a lanthanide. ! t I/W is generally sed.

So :ar the =sialons !ased on=Si/N. are those sed in any ? antity=as c tting tool materials :or machining metalsD r !e= and wire=drawing diesM!earingsM welding shieldsD no77lesD roc8=c rring and coal=c tting 5lantM containers :or con9eying li? id metals and in t r!ine !lades. A r 5t re mod l s in the region o: &14 M+a is o!tained. ,he microstr ct re o: a sialon consists o: crystals o: the sialon 5hase held in a glassy or 5artly crystalline matri<. ,he crystals can !e either =sialon

or a mi<t re o: = and =sialons. Eenerally the hardness o: the ceramic increases as the 5ro5ortion o: the =sialon increases ! t the o tstanding 5ro5erty o: sialons is that they retain their hardness at m ch higher tem5erat res than does al mina. ,o ghness is also an im5ortant 5ro5erty tho gh this is less than in a cemented car!ide ($..0) o: similar hardness. (n the :o ndry where a com!ination o: high=tem5erat re and thermal=shoc8 resistance is necessary sialons are sed in the man :act re o: small cr ci!les, im5ellors, thermoco 5le sheaths, radiant heater t !es and the li8e :or se at tem5erat res 5 to $014ZC. 1$ ' $ Lirconia 2LrB#3 a hard re:ractory material which has !een sed :or many years as a high tem5erat re : rnace and cr ci!le re:ractory at tem5erat res 5 to 0144ZC. (t is a 5olymor5hic com5o nd e<isting in three di::erent crystalline 5hases. ,he c !ic :orm, sta!le a!o9e 0/&4ZC changes !elow that tem5erat re= to a

tetragonal :orm and on : rther cooling to !elow $$>4ZC a monoclinic :orm !ecomes sta!leD

Howe9er, the :inal trans:ormation (!elow $$>4ZC) is martensitic in nat re and in :act shares some o: the :eat res o: the a stenite martensite trans:ormation (%.6.$) in steels. (n 5artic lar the 5olymor5hic change is accom5anied !y a s dden 9ol me change o: some / R. Since 7irconia is a !rittle s !stance this s dden e<5ansion ca ses se9ere crac8ing, ma8ing it seless to 5rod ce com5onents :rom 5 re Or)0. Howe9er, additions o: other metallic o<ides will s 55ress the martensitic trans:ormation to !elow am!ient tem5erat resQ and so sta!ilise the tetragonal or e9en c !ic 5hase. 'arying amo nts o: lime and magnesia were added :or this 5 r5ose when 7irconia was sed as a : rnace re:ractory ! t yttria (yttri m o<ide, I 0)/) is now sed as a sta!iliser in modern 7irconia ceramics. 8;!E!;!8 Re:erence to the Or)0= I 0)/ 5hase diagram (#ig. $/.$.) indicates that an addition o: more than a55ro<imately $&R wt I0)/ sta!ilises the c !ic (c) str ct re at am!ient tem5erat res 5rod cing a : lly=sta!ilised 7irconia (#SO). ;hilst the c !ic 5hase. is rather !rittle s ch a str ct re wo ld !e :ree :rom crac8ing

Qthis is com5ara!le with the e::ect o: nic8el in sta!ilising a stenite at am!ient tem5erat re in steels

associated with 9ol me changes (!ro ght a!o t !y tem5erat re 9ariations) s ch as wo ld occ r in nalloyed 7irconia. ;hilst s ch an BalloyB has some electrical ses, e.g. in : el cells, a 5artially sta!ilised 7irconia (+SO) is more se: l as an engineering ceramic. ,h s the addition o: 1R wt I 04/ will sta!ilise the tetragonal (t) 5hase at am!ient tem5erat res as is indicated in #ig. $/.$.. ,he t 5hase so sta!ilised is to gh and reasona!ly shoc8 resistant. 8;!E!;!6 A +SO is 5rod ced !y sintering an ltra :ine Or)0 5owder with 1R wt I 0)/ at $.44=$144ZC and, as #ig. $/.$. indicates, this will 5rod ce a tetragonal str ct re (:ine=grained !eca se o: the ltra:ine 5owder sed).)n cooling a 5ro5ortion o: these t grains trans:orm martensitically to the monoclinic (m) :orm ! t the remainder 5ersist in the metasta,le t :orm.,hose grains remaining in the t state do so !eca se elastic strains internally !alanced in the

matri< o55ose : rther 9ol me increase associated with the t m (martensite) trans:ormation. Fnli8e the martensite trans:ormation in steel which increases !rittleness, the :ormation o: the martensitic 5hase here has a to ghening e::ect.,he 9ol me change associated with the tm trans:ormation res lts in the 5rod ction o: a 5re=stressed material. ,h s any crac8 !eing 5ro5agated thro gh the str ct re is a!le to release the stresses in neigh!oring grains=which immediately ndergo the tm trans:ormation. Beca se the 9ol me o: m is greater than t :rom which it is deri9ed the res ltant 9ol me increase generates com5ressi9e stresses near the ti5 o: the crac8 and e<tra energy is re? ired !e:ore the crac8 can tra9el : rther. (t is !elie9ed, there:ore, that the martensitic=ty5e t m trans:ormation occ rring at the crac8 B:rontB is the 5rinci5al energy=a!sor!ing mechanism, which in t rn increases the to ghness o: the material.

8;!E!;!; +SOs ha9e a low thermal cond cti9ity at all tem5erat res ! t a high coe::icient o: thermal e<5ansion. Both o: these 5ro5erties ma8e +SOs s ita!le as 5rotecti9e coatings on metals wor8ing at high tem5erat res s ch as s 5eralloy rotor !lades in 3et t r!ines. ,he high coe::icient o: thermal e<5ansion red ces the thermal e<5ansion mismatch !etween +SO coating and the metal s !strate. A ty5ical +SO is BCera:ineB containing 1R wt I0)/.

,he Ben9ironmentally :riendlyB 5ro5erties o: 7irconia when sed inside the h man !ody ha9e led to its se in im5lantology. ,his !iocom5ati!ility,com!ined with a !ending strength and to ghness which are do !le that o: the c rrently sed al mina, ha9e led to its ado5tion :or hi5 3oint re5lacements in !oth North America and #rance. An yttria=sta!ilised 7irconia with the trade name +ro7yr is sed. 1$ ' % Some Ver& .ard Engineering Ceramics Among c tting tool materials one m st not :orget the hardest and most e::ecti9e o: all=diamond.,he str ct re o: this allotro5e o: car!on has !een mentioned (/.&.$). (t is strong and hard !eca se o: the 9ery sta!le directional co9alent !onds which !ind each atom to :o r near neigh!o rs. Nat rally occ rring diamonds come mainly :rom A stralia, Oaire, Botswana, C(S, and So th A:rica. ;hilst these nat rally occ rring stones are s 5erior as a tool material :or some a55lications, synthetic diamonds now 5laya ma3or role as an a!rasi9e grit. Diamonds can only crystallise :rom the li? id 5hase, a sit ation only 5ossi!le at e<tremely high tem5erat res and 5ress res. Se9eral claims to ha9e synthesised diamonds were made d ring the nineteenth cent ry ! t it is do !t: l i: any o: these were a thentic. ,he de9elo5ment o: high=tem5erat re 5resses ena!led the Swedish com5any ASEA to s cceed in $%1/. Era5hite ca5s les in the 5resence o: metallic sol9ents were s !3ected to a tem5erat re o: /444ZC and a 5ress re o: o9er %4444 atmos5heres in a hydra lic 5ress. ,echnology has im5ro9ed since then and the man :act re o: this synthetic diamond material a55ears as a ro gh !lac8 grit=which co ld scarcely ? ali:y as Ba girlBs !est :riendB. 8;!E!:!8 BC !icB !oron nitride, BN. is ne<t only to diamond in terms o:hardness. (t is man :act red in a similar way to synthetic diamond and isconse? ently as e<5ensi9e. ,ho gh less reacti9e with :erro s metals at tem5erat res a!o9e $444ZC it will trans:orm to its so:ter he<agonal crystal :orm. Hence it is not sed :or high=

s5eed machining ! t rather :or dealing with hardened alloy steels and chill=cast irons. 8;!E!:!6 Boron car!ide, B.C. is e<tremelKB se: l as a ceramic armo r material where its low relati9e densit), ma8es it iBal a!le in aerona tical a55lications, e.g. !attle:ield helico5ters and 5ersonal armo r :or aircrew. 8;!E!:!; ,itani m di!oride, ,iB0. has !een de9elo5ed :or similar 5 r5oses in gro nd war:are since it has a higher relatiiBe density. (t 5ro9ides 5rotection against hea9y threats s ch as anti=tan8 5ro3ectiles. (t is s ally hot=5ressed and has !oth high hardness and a high elastic mod l s.

6lasses
1$ ( ,he word BglassB will immediately s ggest to the reader the hard !rittle st :: o: which window 5anes and !eer tan8ards are made ! t in scienti:ic terms it has a wider signi:icance. Elass com5rises a range o: s !stances :rom !oiled sweets and to::ee a55les to some so5histicated ind strial materials. )ne 5ro5erty all glasses ha9e in common is that d ring man :act re they m st !e cooled ? ic8ly eno gh to 5re9ent crystallisation :rom ta8ing 5lace so that the glassy (amor5ho s) state is retained at am!ient tem5erat res. ;ith orthodo< glasses this is easy to achie9e. #or e<am5le the B!lan8B :rom which a large o5tical telesco5e mirror is gro nd may !e cooled at a rate o: no more than $ZC 5er day (to a9oid s !se? ent distortion arising :rom internal stress) yet it still retains its amor5ho s state. (n an attem5t to achie9e a glassy state in metals, howe9er, we m st cool them at a rate in the region o: $46oC 5er second. Between these e<tremes are many materials s ch as 5lastics which retain a glassy state d ring managea!le rates o: cooling ! t in many o: which a mi<t re o: !oth glassy and crystalline regions occ rs ($0...$).

,his sit ation e<ists !eca se in !oth glasses (!ased on silica) and 5olymers the chemical B nitB is 9ery large. (n 5olymers we ha9e immense chain molec les in which atoms are held together !y 5ower: l co9alent !onds whilst the molec les themsel9es are attacted to each other !y wea8 9an der ;aals :orces, the total e::ect o: which is ne9ertheless considera!le. (n glasses large silicate networ8s,again co9alently !onded internally, are held together !y ionic !onds 5ro9ided !y metallic ions within the str ct re. (n either case mo9ement o: these h ge Bchemical nitsB with res5ect to their neigh!o rs is di::ic lt e9en when they are thermally acti9ated and so it is easy to cool the material 5ast its normal melting 5oint (, m) witho t crystallisation ta8ing 5lace. (n a metal, howe9er, the Bchemical nitB is 9ery small 9i7. the atom=or more 5ro5erly, the ion, which is strongly attracted to the s rro nding 9ery mo!ile Bclo dB o: electrons. (t there:ore mo9es ? ic8ly and easily into an e? ili!ri m 5osition on reaching , m so that cooling rates o: $46oC2s or more m st !e sed to 5re9ent this :rom ta8ing 5lace. (: silica is melted and then cooled e<tremely slowly it will crystallise at a 5artic lar tem5erat re, , m, the normal melting 5oint o: silica and this 5rocess is accom5anied !y a red ction in 9ol me as atoms ta8e 5 reg lar 5ositions in a crystalline lattice (!ro8en line in #ig. $/.$6.(i)). ,his reg lar crystalline str ct re

is de5icted as a two=dimensional re5resentation in #ig. $/.$%(i). (:, howe9er, molten silica is cooled more ra5idly then it is na!le to attain the long=range order o: a : lly=crystalline str ct re since its atoms are co9alently !onded to neigh!o rs and are there:ore na!le to mo9e as :reely as those in the amor5ho s state o: a molten metal or a molten salt. Ne9ertheless thermal contraction does ta8e 5lace d e to limited rearrangement o: the atoms, leading to their more e::icient 5ac8ing. ,his ty5e o: contraction is common to all li? id glasses (#ig. $/.$6). ;ith : rther red ction in tem5erat re a 5oint is reached where a s dden change in the coe::icient o: e<5ansion occ rs. Below this tem5erat re, called the glass transition tem5erat re (or :icti9e tem5erat re), , g ($0.../), there is no : rther rearrangement o: atom 5ac8ing and s ch small amo nts o: contraction as ta8e 5lace are d e solely to a red ction in the thermal 9i!rations o: the atoms. , g is not a well=de:ined tem5erat re and de5ends 5on the 5re9ailing cooling rate (#ig. $/.$6(ii)). ,he more ra5id the cooling rate, the higher is ,g. Since the slo5e o: the c r9e !etween ,g and ,m is the same as that a!o9e ,m this indicates that, d ring ra5id cooling, there is no change in the str ct re at ,m, i.e. !etween , m and ,g the str ct re is that o: a s 5er=cooled li? id. Moreo9er nli8e the slowly cooled silica at , m there is no e9ol tion o: latent heat at , g. ,h s the glassy state 5re9ailing !elow ,g is 9ery li8e the li? id state. ,his lower coe::icient o: e<5ansion is ro ghly the same as that :or crystals o: similar com5osition to the glass (#ig. $/.$6). (n rigid crystalline materials contraction can only res lt :rom decreased thermal 9i!rations. Hence the term glass co ld well !e de:ined as a s !stance ha9ing e<5ansion characteristics similar to those indicated in #ig. $/.$6. )ther 5hysical 5ro5erties which are a::ected in a similar manner to the coe::icient o: e<5ansion incl de density, electrical resisti9ity, o5tical 5ro5erties and 9iscosity. A glass will sometimes crystallise i: gi9en s ::icient time=5erha5s se9eral h ndred years. ,his 5rocess, 8nown as de9itri:ication, sometimes occ rs with 9ery old stained=glass windows and is

generally mani:ested as a considera!le increase in !rittleness as crystallisation ta8es 5lace. Elass does not always de9itri:y, o: co rse, and some glass at least /444 years old has retained its 9itreo s=or BglassyB =5ro5erties. Howe9er, i: molec lar mo!ility is increased !y raising the tem5erat re the tendency :or de9itri:ication is enco raged. De9itri:ication may also !e 5reci5itated !y the 5resence o: im5 rity 5articles in the glass. S ch n cleation o: crystallisation occ rs in a similar way in molten metals d e to the 5resence o: 5articles o: slag or dross (/.>.0). 1$ ( 1 The )an"fact"re of 6lass Elass was one o: the earliest man=made materials, tho gh 5rior to the 5resent technological age, its com5osition :ell within a limited range. )rdinary commercial glass is 5rod ced :rom 9ario s inorganic o<ides o: which silica in the :orm o: sand is generally the most im5ortant constit ent. ,he 5rinci5al ingredients o: common soda glass are silica sand, lime (:rom limestone) and soda ash (cr de sodi m car!onate). Since glass is one o: the easiest 5rod cts to recycle a large amo nt o: scra5 glass, 8nown as Ac llet@, constit tes the charge to the Btan8B : rnace where !oth raw materials and c llet are heated to $1%4ZC. ,he acidic silica then reacts with !asic lime and soda to :orm the mi<ed silicates we 8now as glass. ,he gas=:ired : rnaces hold 5 to 014 tonnes o: molten glass. ,he : rnace charge can ta8e 5 to %4R c llet, which is deri9ed mainly :rom !ottle !an8s. Fn:ort nately o: the si< !illion glass !ottles 5rod ced in Britain ann ally only one !illion reaches the !ottle !an8=the rest end 5 Bin the !inB. #ew ind stries are a!le to se scra5 so e::iciently and :rom the BgreenB as5ect it is a great 5ity so m ch 5otential c llet is wasted. 8;!J!8!8 Sheet and +late Elass Early sheet glass was man :act red !y !lowing a cylinder which was then c t and, whilst still hot, o5ened o t to :orm a reasona!ly :lat sheet. (n the modem #loat +rocess (#ig. $/.$>) the re? ired mi<t re o: silica and metallic o<ides along with c llet is melted in an o5en=hearth : rnace m ch

li8e that sed ntil recently :or steelma8ing. (n :act the original Siemens !rothers glass=ma8ing : rnace o: $&16 was ada5ted shortly a:ter that date :or steelma8ing. (n the #loat 5rocess a contin o s ri!!on o: molten glass 5 to . m wide :lows :rom the melting : rnace and :loats along the s r:ace o: a !ath o: molten tin. ,he s5eed o: the ri!!on is ad3 sted so that it is held at a high tem5erat re :or long eno gh :or any irreg larities to !e remo9ed so that the s r:ace !ecomes :lat, smooth and 5arallel. ,o 5re9ent o<idation o: the tin and conse? ent contamination o: the glass the B:loat !athB o5erates nder a nitrogen atmos5here.

,he glass=cools s ::iciently !e:ore it lea9es the :loat Btan8B so that it is hard eno gh to !e drawn into the annealing lehr witho t the se o: rollers which might mar8 the s r:ace. ,he main 5 r5ose o: the annealing lehr is to ens re slow, ni:orm cooling, th s limiting internal stresses which wo ld arise :rom ra5id cooling. ;hen allowed to :low nder normal conditions im5osed !y s ch :actors as density and s r:ace tension the thic8ness o: the glass 5rod ced is a!o t 6 mm ! t wor8ing conditions can !e ad3 sted to gi9e thic8nesses !etween 0.1 mm and 01 mm. An im5ortant :eat re o: the #loat +rocess is that modi:ications o: the s r:ace 5ro5erties o: the glass can !e carried o t d ring the 5rocess. Metallic ions s ch as those o: co55er can !e made to re5lace e<isting metallic ions !y 5assing an electric c rrent

!etween the molten tin !ath and an electrode a!o9e the s r:ace o: the glass. ,y5ical 5rod cts o: this electro=:loat 5rocess are anti= glare glass and glass which red ces heat transmission. $/.6.$.0 Elass Blowing ,he de9elo5ment o: modern glass !lowing !egan in 'enice in the twel:th cent ry and !y $0%0 it had !ecome necessary :or the ind stry to see8 secl sion on the near!y (sland o: M rano to a9oid ind strial es5ionage. By the middle o: the nineteenth cent ry #lemish glass !lowers were settling here in the Midlands o: England. At that time my great=grand:ather, as a glass=!lower, was earning a wage some ten times the a9erage :or those days. ,he need :or s8ill and 5ower: l l ngs is now no more and the !lowing o: !ottles, 3ars and other holloware is an a tomated 5rocess sing metal mo lds. Fs ally a mi<t re o:

5ressing and !lowing o5erations is em5loyed (#ig. $/.$&) to sha5e a container :rom the initial Bgo!B o: molten glass. Mo th !lowing is now restricted to the man :act re o: artistic glass and high ? ality ta!leware. The Str"ct"re of 6lass 1$ ( # As we ha9e seen glasses di::er :rom solid crystalline s !stances in res5ect o: a n m!er o: 5ro5erties. ,hey are 5lastic at high tem5erat res and rigid at low tem5erat res ! t nder normal man :act ring conditions they do not crystallise. ,h s glass is in a condition which is contin o s with, and analogo s to, the li? id state o: the s !stance ! t which, as a res lt o: ha9ing !een cooled :rom a : sed state, has ac? ired a high degree o: 9iscosity so as to !e, :or most 5ractical 5 r5oses, rigid. 1$ ( $ ,he str ct re o: crystalline silica, ? art7, is : ndamentally tetrahedral (#ig, $/./) as determined !y H=ray crystallogra5hic methods, (n this three=dimensional str ct re each silicon atom is chemically !onded to :o r o<ygen atoms 5laced at the comers o: the tetrahedron, each o<ygen atom !eing shared with an ad3acent silicon atom :rom another tetrahedron. Howe9er, :or the sa8e o: clarity we will consider a two=dimensional ada5tation o: this str ct re as shown in #ig. $/.$%(i). Here the str ct re is one o: long=range order, that is. a reg lar lattice Str ct re is a55arent. (:, howe9er, : sed silica is cooled at s ch a rare as to ma8e normal crystallisation im5ossi!le. a str ct re s ch as is s ggested in #ig. $/. $%(ii) is o!tained :or silica glass.

Here the long=range order is re5laced !y a short=range one in which indi9id al tetrahedra still 5ersist as they do in crystalline ? art7, ! t the random orientation o: indi9id al tetrahedra, res lting :rom local distortions, destroys the 5eriodicity o: the lattice networ8 and the str ct re is no longer crystalline. ;hen metallic o<ides s ch as soda (Na 0)) and lime (Ca)) are added to the silica the ratio o: o<ygen ions to silicon ions is increased !eca se one Si.W ion m st !e remo9ed :or e9ery :o r NalW ions added i: 9alency !onds are to !e satis:ied. ,he e<tra o<ygen ions cannot !e incor5orated into each o: two tetrahedra and as a conse? ence the networ8 loses its contin ity in regions where these ions are 5resent. ,he str ct re is there:ore less rigid at high tem5erat res and soda glass is more easily wor8ed than 5 re silica glass. Na $W and Ca0W ions ta8e 5 s ita!le 5ositions a9aila!le within the str ct re (#ig. $/.04). Since NalW ions are relati9ely small they are a!le to migrate thro gh the com5arati9ely o5en networ8 with relati9e ease e9en at room tem5erat res. ,his in:l ences some o: the 5ro5erties o: soda glass.

1$ ( % Special 6lasses )rdinary soda glass is o: little se in co5ing with s dden tem5erat re changes. (: !oiling water is 5o red into a cold soda=glass 3ar the latter s ally shatters !eca se soda glass has a relati9ely high coe::icient o: e<5ansion ! t a low thermal cond cti9ity. Di::erential e<5ansion !etween the inner and o ter layers o: the 3ar sets 5 high stresses with which soda glass is na!le to co5e and :ract re occ rs. Fnli8e soda glass, tem5erat re resistant glasses s ch as B+yre<B ha9e only small amo nts o: B:ree ionsB (Na W). (nstead 5 to 04R o: Bglass :ormersB s ch as !oron o<ide, B0)/, are added to the silica. ,hese glass :ormers increase the networ8 :ormation and contin ity within the str ct re. (n t rn this leads to higher 9iscosity, resistance to chemical attac8 and, most im5ortant, a 9ery low coe::icient o: e<5ansion !eca se the networ8 is not disr 5ted. ,he low coe::icient o: e<5ansion ma8es B+yre<B s ita!le :or 8itchen, la!oratory and ind strial ses as the tendency to shatter with s dden tem5erat re change is m ch red ced. (n modem glass=ceramics, controlled de9itri:ication is em5loyed to initiate large n m!ers o: n clei :or crystallisation in glasses o: s ita!le com5osition to 5rod ce 5olycrystalline materials. A:ter sha5ing, the material is gi9en a two=stage heat= treatment. #irst, a low=tem5erat re treatment is gi9en to 5romote the :ormation o: large n m!ers o: crystal n clei within the glass

and this is :ollowed !y a higher tem5erat re treatment at which cryta$ growth rate is at a ma<im m. ,his contin es ntil the crystalline content may reach %4R and only a little glass remains. ,he mechanical 5ro5erties o: s ch a glass=ceramic are intermediate !etween those o: a glass and o: a tr e ceramic s ch as Al 0)/ or Mg). ,hey are sed in coo8ing ware (e.g. B+yroceramB and B+yrosilB), heat e<changers and telesco5e mirror !lan8s. )ther glass=ceramics !ased on magnesia=al mino=silicates and n cleated to gi9e crystals o: cordierite and crysto!alite (#ig. $/.$0) are sed in missile nose cones and heat e<changers. Ceramics o: this ty5e are not only resistant to thermal shoc8 ! t are trans5arent to radar signals. 1$ ( ' The )echanical Properties of 6lass Metals can !e de:ormed !eca se sli5, i.e. the mo9ement o: dislocations, can occ r readily along s ch crystallogra5hic 5lanes as are a9aila!le. Howe9er, glass cannot de:orm in this way !eca se it has no crystal lattice. )nly 9isco s :low can ta8e 5lace in glass and this only !y the thermally assisted mo9ement o: molec les 5ast each other. B t since a glass at am!ient tem5erat re is, !y de:inition, !elow , g, 9ery little thermally assisted mo9ement o: molec les is 5ossi!le. ,h s i: stress is a55lied, molec les are na!le to mo9e signi:icant distances relati9e to one another ma8ing glass !rittle at am!ient tem5erat res. ,he rate o: 9isco s :low is de5endent mainly 5on the 5re9ailing tem5erat re ! t is also de5endent 5on the com5osition and str ct re o: the glass. Small a55lied stresses ca se the more highly strained !onds within the str ct re to !e r 5t red. ,he !ond rearrangement which :ollows this 5rocess leads to a small degree o: 5ermanent strain. As this 5rocess contin es more !onds !ecome strained in t rn to the e<tent where they will !rea8 and so allow 9isco s :low to contin e. As wo ld !e e<5ected the

stresses necessary to ca se a 5rescri!ed degree o: 9isco s :low are less at ele9ated tem5erat res since !ond=strength !ecomes smaller at high tem5erat res. ,he amo nt o: 9isco s :low in glass at am!ient tem5erat res is e<tremely small since it re? ires thermal assistance. Howe9er, glass will :low 9ery slowly nder its own weight and a n m!er o: cases ha9e !een re5orted where large 5late=glass windows ha9e !ecome meas ra!ly thic8er at the lower edge o9er a 5eriod o: years.

,here is little in common !etween the mechanical 5ro5erties o: glasses and metals when nder the action o: a55lied :orces. S ch di::erences can !e classi:ied as :ollowsD (i) nder short=time testing methods, glasses are !rittle at am!ient tem5erat res. ,hey are elastic right 5 to the 5oint o: :ract re and, :ail witho t any 5re9io s yield or 5lastic de:ormation. E9en the most !rittle o: metals show some 5lastic :lowM (ii) altho gh an e<ternal load may !e a55lied in com5ression, :ail re in glass always res lts :rom a tensile com5onent o: the stress. ,he strength o: s ch materials can there:ore !est !e descri!ed in terms o: tensile strengthM (iii) the time :or which a static load is a55lied has a great in:l ence on the strength o: glass in the long term. ,h s the e<tra5olated in:inite=time mod l s o: r 5t re :or glasses is s ally !etween a third and a hal: o: that :or short=time loading. 1$ ( ( The .eat1treatment or 6lass Since glass is a 5oor cond ctor o: heat it :ollows that d ring sha5ing a considera!le tem5erat re gradient may !e set 5 across the section o: the wor8 5iece. Conse? ently its s r:ace, since it cools more ra5idly, will cool to !elow , g and !ecome relati9ely sti:: while the interior, still at a higher tem5erat re, remains in a more mo!ile li? id state a!o9e , g. ,he slower cooling rate is also related to a lower , g 9al e (#ig. $/.$6(ii)) accom5anied !y large 9ol me changes d ring the li? id glass transition,so that d ring cooling the tendency is :or the contraction o: the core to !e greater than that :or the s r:ace. ,his will ine9ita!ly lead to the :ormation o: internal stresses which may res lt in :ail re either d ring :inal stages o: man :act re or in s !se? ent ser9ice. ,here:ore an annealing 5rocess is necessary at a tem5erat re high eno gh to allow s ::icient mo9ement o: molec les into 5ositions a55roaching e? ili!ri m. #ail re to anneal glass lea9es it wea8 and !rittle. 8;!J!J!8 Annealing ,his is s ally carried o t immediately a:ter the sha5ing 5rocess. ,he glass=whether 5late glass, !ottles or 3am

3ars=is 5assed slowly thro gh a con9eyor=hearth ty5e o: : rnace 8nown as a lehr, where the entry tem5erat re is near to , g and the e<it tem5erat re little a!o9e am!ient. ,he small amo nt o: 9isco s :low which ta8es 5lace d ring annealing leads to stress rela<ation within the glass which is th s rendered relati9ely stress=:ree. ,his treatment !ears some similarity to the low= tem5erat re stress= relie: annealing gi9en to some cold=wor8ed metals and alloys s ch as >4=/4 !rass in that atoms more short distances into 5ositions nearer to e? ili!ri m. At the same time it contrasts shar5ly with those annealing 5rocesses which lead to com5lete recrystallisation in metals. 8;!J!J!6 Tem.ering Elass is sometimes to ghened !y a tem5ering 5rocess which see8s to red ce the :ormation o: s r:ace crac8s !y 5 tting the s r:ace in a state o: com5ression. ,he 5rinci5le in9ol9ed is similar to that a55lied in the 5re=stressing o: concrete in order to 5re9ent crac8s :rom de9elo5ing in its s r:ace ($1.$4.0). ,em5ering o: glass is achie9ed !y heating it to m ch the same tem5erat re as that sed :or annealing it, and then cooling the s r:ace ra5idly !y means o: air 3ets. (n common with other s !stances glass contracts as it cools. (nitially the o tside s r:ace cools, contracts and hardens more ? ic8ly than the inside. ,he latter, !eing still so:t, will yield in the early stages o: cooling. D ring the :inal stages o: cooling, howe9er, !oth inside and o tside !eha9e in an elastic manner ! t their contractions are already o t o: ste5. Hence, when the glass has :inished cooling the o ter s r:ace is in a state o: com5ression whilst the inside is in tension. Since the s r:ace layers are in com5ression these com5ressi9e :orces will !alance any moderate tensile :orces to which the glass may !e s !3ected d ring ser9ice. Elass in9aria!ly :ails as a res lt o: tensile com5onents o: :orces e9en when these :orces are, o9erall, com5ressi9e. Elass th s treated has !een sed :or a long time in motor=car windscreens and is li8ely to !e de9elo5ed in the : t re :or many ind strial ses.

Strain 5atterns in trans5arent materials s ch as B5ers5e<B and glass !ecome 9isi!le when 9iewed !y 5olarised light and to a lesser e<tent !y white light which !ecomes 5artly 5olarised when re:lected :rom nonmetallic s r:aces. #or this reason it is o:ten 5ossi!le to see the 5attern o: air=3et im5ingements sed :or cooling the glass when a car windscreen is ins5ected at an o!li? e angle or, 5re:era!ly, !y sing 5olarising s5ectacles. 1$ ( 4 Bptical Fi*res (n recent years the well=8nown electronic systems o: comm nications ha9e !een na!le to deal with the e9er=increasing 9ol me o: in:ormation to !e transmitted. Hence m ch higher transmission :re? encies were re? ired so that comm nications engineering mo9ed into the 9isi!le s5ectr m where the mo9ement o: 5hotons ( nit o: light energy) is sed instead o: the mo9ement o: electrons. ,he act al :i!res consist o: a 5 re silica t !e containing a core o: silica which is Bdo5edB with another o<ide s ch as germani m o<ide, Ee) 0, to gi9e a slightly higher re:racti9e inde<. (Eermani m is a BmetalloidB mem!er o: the car!on=silicon Ero 5 (' so it can !e e<5ected to B:itB into the str ct res o: glasses !ased on silica=Ee o: co rse has a 9alency o: ..) ,he light 5 lses are g ided along the core !y internal re:lection at the inter:ace !etween the core material and the 5 re silica coating. #or light to !e transmitted o9er a signi:icant distance the core material m st ha9e a 9ery high trans5arency and conse? ently !e o: a 9ery high 5 rity so that light 5 lses co ld !e transmitted o9er 8ilometres rather than metresM ! t this was not the only 5ro!lem enco ntered in the early stages o: de9elo5ment o: o5tical :i!res. As #ig. $/.0$ indicates, in a single :i!re system containing a core o: ni:orm re:racti9e inde<, light can tra9el !y a 9ariety o: di::erent 5aths.

,his will lead to distortion o: the signal since the light 5 lses reach their destination at di::erent inter9als. ,his 5ro!lem is o9ercome !y sing a core material in which the re:racti9e inde< 9aries :rom a ma<im m at the centre o: the core to that o: the cladding at the inter:ace in a near=5ara!olic manner. ,hen, those light rays ta8ing a longer 5ath tra9el :aster so that all rays reach their destination sim ltaneo sly. Cores 9ary in diameter !etween 1 and 14 m and :i!res are sed in the :orm o: ca!le systems. Research is directed at red cing the loss o: o5tical signal which, since $%>4,has already recei9ed a twenty=:old red ction. (t is more than $44 years since ,yndall demonstrated to the Royal Society that light co ld !e g ided !y a 3et o: water sing internal re:lections. Now o5tical :i!res sing this 5rinci5le ena!le s to see ro nd corners and conse? ently ha9e many ses. Medical endosco5es are sed to ma8e 9is al e<aminations o: hollow organs s ch as stomach and !owel, whilst in nat ral history st dies similar instr ments are a9aila!le to 5ee5 into==and 5hotogra5h=the nests o: ants and termites. 1$ ( 5 )etallic 6lasses ,he di::ic lty in9ol9ed in 5rod cing cooling rates high eno gh to achie9e the glassy state in metals was to ched on at the !eginning o: this section ($/.6). Ne9ertheless 9ario s ingenio s methods ha9e !een de9elo5ed to attain the high cooling rates o: $46Z_s or so. +erha5s the most s ccess: l has !een some :orm o: the Bmelt s5inner@ (#ig. $/.00). ,his consists essentially o: a co55er wheel rotating at a 5eri5heral s5eed o: 5 to

14 m2s and a 3et o: molten metal 5ro3ected nder 5ress re at the rim. ,his :orms a B5oolB which :ree7es 9ery ? ic8ly and is se5arated :rom the wheel !y centri: gal :orce, :orming a contin o s. Ri!!on which is wo nd onto a s5ool (#ig. /.0/).

,he metallic glasses :ormed !y this 5rocess are s ally alloys which :all into two categoriesD (i) metal=metal alloys in which one or !oth elements is a transition metal, e.g. C (14)=Or(14)M Ni(64)=N!(.4)M (ii) metal=metalloid (or non=metal) alloys where the metal is s ally a transition metal, e.g. +d(&4)=Si(04)M #e(&4)=B(04)M #e( .4)=Ni( .4)=+($.)=B(6). ,he ty5e o: str ct re en9isaged in a metallic glass is o: a dense random 5ac8ing o: s5heres s ch as wo ld !e o!tained !y ti55ing steel !alls into a :le<i!le !ag. Since &4 metal=04 metalloid mi<t res seem to !e most e::ecti9e in 5rod cing metallic glasses, it is s 55osed that in this dense 5ac8ing the smaller metalloid atoms are s rro nded !y larger metallic atoms. Some o: these metallic glasses are strongly :erromagnetic !eing e<tremely Bso:tB magnetically with 9ery high 5ermea!ility. Since they are also 9ery strong mechanically, materials s ch as #e(.4)= Ni(.4)=+($.)=B(6) are sed in the :orm o: :a!ric (wo9en :rom ri!!on) as a magnetic shielding material. Minat re trans:ormers and magnetic cores are also !ased on some o: these glasses. ,ho gh metallic glasses are 9ery strong and sti:: they are ca5a!le o: only 9ery limited 5lastic de:ormation. (n tension this is s ally less than $R at :ract re. +ro!a!ly the !est 8nown is #e(&4)=B(04) ($&.6.&) which is stronger than the !est car!on :i!re and almost as sti::. ,he mechanical 5ro5erties o: these :i!res ha9e yet to !e : lly e<5lored.

1% Composite )aterials
1% 1 New 3argon a55ears :re? ently in the :ield o: technology. ,he 9oca! lary o: the materials scientist was enriched !y the term Bcom5osite materialsB a :ew decades ago. Ne9ertheless the 5rinci5les o: these materials are not new. ,he str ct re o: a massi9e tree, one o: the largest and oldest li9ing things on Earth and which has e9ol9ed o9er a[ 5eriod o: millions o: years, is an e<am5le o: what we now call a A:i!re=rein:orced com5ositeB. As recently as the $%.4s 5lastics material rein:orced with glass :i!re was !ased on the nat ral str ct re o: !am!oo.Com5osite materials= or Bcom5ositesB =can !e di9ided into two main gro 5s. 1% 1 1 Particle Composites in which some matri< material is B:illedB with another material in 5article :orm. S ch a com5osite is designed to : l:il one or more o: the :ollowing : nctionsD (i) to 5ro9ide dis5ersion o: a 9ery hard material in a to gh, shoc8= resistant matri< as in cemented car!ides :or c tting toolsM (ii) to : rnish a material o: increased tensile strength, e.g. the se o: :inely=dis5ersed Al0)/ in metallic al mini mM (iii) to red ce o9erall costs o: some material !y A! l8ing 5@ with a chea5, low=grade B:illerB. ,h s !a8elite mo ldings ha9e long !een B:illedB with sawd st, wood :lo r or minerals s ch as :ine sand or gro nd limestone. 1% 1 # Fi*re1reinforced Composites in which the o!3ect is to 5rod ce a material o: high s5eci:ic strength or mod l s. ,his is the

more im5ortant ty5e o: com5osite :rom an engineering 5oint o: 9iew and will !e disc ssed more : lly in the ne<t cha5ter. 1% 1 $ (: a material contains 5articles these s ::er elastic strains when the material is stressed. (n this way the 5articles contri! te to the load=carrying ca5acity o: the material as well as 5ro9iding o!stacles to the mo9ement o: dislocations, ass ming that the 5articles themsel9es are strong. ,h s i: the 9ol me o: s ch strong 5articles in the com5osite is 5ro5ortionally large they will 5ro9ide a high strength !y 5rod cing a high load=carrying ca5acity. ,he most satis:actory method o: increasing tensile strength is to se the 5articles in the :orm o: long :i!res. ;hen stressed the matri< may !egin to :low ! t in doing so will ca se a :orce to !e set 5 at the s r:ace o: the :i!re. (: the :i!re is long eno gh this transmitted :orce will ltimately lead to its :ract re and the :i!re will there:ore ha9e contri! ted : lly to the strength o: the com5osite material. )!9io sly strength will !e directional, i.e. at a ma<im m 9al e 5arallel to the direction o: the :i!res. 1% 1 % ,he nat re o: the inter:ace !etween the 5articles or :i!res and the matri< has a !earing on the e<tent to which the toad will !e trans:erred :rom the matri< to the strengthening material. Cohesion at the inter:ace may !e achie9ed !y one or more o: the :ollowing methodsD (i) mechanical !onding this in9ol9es a high eno gh coe::icient o: :riction acting !etween the s r:aces. ,his a55lies mainly to some :i!re=rein:orced com5osites e.g. the :i!res in a sim5le hem5 ro5eM (ii) 5hysical !onding de5ending 5on 9an der ;aals :orces acting !etween s r:ace molec lesM . (iii) chemical !onding at the inter:ace=this can, howe9er, gi9e rise to wea8 !rittle com5o nds in some instancesM (i9) m lti5le !onds :ormed !y solid sol tion e::ects.

1% 1 ' Eenerally s5ea8ing so5histicated engineering com5osites :all into three main gro 5sD (i) those in which the matri< is relati9ely wea8 and !rittle ! t is rein:orced !y :i!res or 5latelets o: high tensile strength. S ch materials are se: l when high tensile strength and sti::ness are re? ired as in a :ishing rod or the !lades o: a t r!ine rotorM (ii) materials in which a to gh and d ctile matri< carries the second com5onent in the :orm o: hard s5herical 5articles. ,hese com5osites are characterised !y great hardness and high com5ressi9e strength and are re5resented !y tool and die materialsM (iii) dis5ersion=hardened materials in which the strength o: the matri< is increased !y the action o: microsco5ical 5articles in im5eding the mo9ement o: a Bdislocation :rontB. Since s ch dislocations cannot 5ass thro gh s ch 5articles=ass ming that they are harder and stronger than the matri<=Bloo5sB are :ormed (#ig.$..$). ,hese dislocation loo5s then act as : rther !arriers to the 5rogress o: any dislocation :ronts which may :ollow.

Particle1hardened Composites 1% # ,hese are commonly materials in which the d ctility and to ghness o: a metallic matri< is com!ined with the hardness and strength o: ceramic 5articles. Fs ally 8nown as cermets these

materials are widely sed as c tting=tool ti5s, drilling !its, :riction materials :or !ra8es .,and in the com5o nding o: : el elements :or n clear 5ower 5rod ction. ,he 5rinci5les o: 5article hardening were widely in9estigated in the 5rod ction o: materials :or se in gas t r!ines. S ch materials re? ire a high cree5=resistance at high tem5erat res. Fn:ort nately cermets 5ro9ed to !e generally in:erior to BNimonicB alloys ($$.1.0) in res5ect o: relati9e !rittleness. Cemented car!ides are 5ossi!ly the !est 8nown materials o: this ty5e and ha9e !een sed :or many years. ,hey consist o: hard 5articles o: t ngsten or titani m car!ide in a matri< o: to gh, d ctile co!alt. ,he 5rod ct is man :act red !y com5ressing a mi<t re o: car!ide 5owder and co!alt 5owder to the e<tent where cold=welding occ rs at 5oints !etween the co!alt 5articles. ,his 5rocess is :ollowed !y BsinteringB=that is, heating the com5onent at some tem5erat re a!o9e that o: recrystallisation :or the co!alt so that a contin o s to gh matri< o: co!alt is :ormed (6.1.$). 1% # 1 Cermets are also made !y ca sing a li? id metal to in:iltrate aro nd 5articles o: a solid ceramic. (deally a strong 5ositi9e !ond sho ld !e :ormed at the metal2ceramic inter:ace. ,his may !e achie9ed either !y a chemical reaction !etween metal and ceramic, res lting in the :ormation o: a :ilm o: intermetallic com5o nd !ridging the two 5hases, or !y a sim5le solid sol tion o: the metal and ceramic :orming at the inter:ace. Since intermetallic com5o nds are generally wea8 and !rittle solid sol tion :ormation wo ld seem to !e the more e::ecti9e. (n order that any :orm o: !onding may occ r it is necessary :or the molten metal to wet the s r:ace o: the ceramic. ,his wetting a!ility is related to the s r:ace tension o: the li? id and to the s r:ace energy o: the ceramic, and is a : nction o: the angle o: contact, e, !etween li? id and

solid (#ig. $..0). ,he relation !etween the s r:ace energies is gi9en !y the e? ationD tS' =tS-P t-' cos n ;etta!ility is at a ma<im m in the ideal case, 9i7. when nX 4, ! t this state o: a::airs is ne9er a55roached in 5ractice. ,he ? ality and nat re o: the solid s r:ace is generally the limiting :actor and :ilms o: o<ide or other matter ca se a 5rogressi9e increase o: n and a conse? ent red ction o: adhesion energy !etween the s r:aces. ,y5ical cermets are !ased on hard car!ides, o<ides, !orides or nitrides !onded with a s ita!le to gh strong metal. ,he main gro 5s o: cermets are listed in ,a!le $..$. Cermets may contain 5 to &4R o: the ceramic 5hase with the remainder !onding metal.

-ispersion1hardened )aterials
1% $ Some com5osite materials containing 5articles which are ro ghly s5herical in :orm are de9elo5ed :or tensile strength rather than :or hardness. ): 5rimary im5ortance in dis5ersion strengthening is al mina, A-0)/, in the :orm o: 9ery small 5articles dis5ersed thro gho t a s ita!le matri<. +ossi!ly the easiest material in which to achie9e this state o: a::airs is al mini m itsel:. (: al mini m is 5rod ced in a 5owdered :orm and then gro nd, in the 5resence o: o<ygen= nder 5ress re, m ch o: the s r:ace :ilm o: o<ide so :ormed disintegrates and :orms 9ery :ine 5owder intermingled with the al mini m 5articles. ,he mi<t re is then sintered !y 5owder metall rgy techni? es to gi9e a more or less homogeneo s al mini m matri< containing a!o t 6R

o: al mina 5articles. ,his 5rod ct is 8nown as Bsintered al mini m 5owderB or SA+=and shows a de:inite ad9antage o9er ordinary al mini m in terms o: tensile strength 5artic larly at high tem5erat res. ,he al mina has a dis5ersion=hardening e::ect ($..$.1). ,he high strength attained in some al mini m alloys as a res lt o: 5reci5itation hardening ($$./.0) is n:ort nately lost at high tem5erat resM !eca se o: the :ormation o: large 5articles o: non=coherent 5reci5itates. (n this res5ect SA+ shows an ad9antage in retaining strength at relati9ely high tem5erat res (#ig. $../). Al mina 5articles are tilised :or the dis5ersion strengthening o: other materials, in 5artic lar sil9er and nic8el. 1% $ 1 Con9entional melting2casting techni? es are ns ita!le :or 5rod cing dis5ersion=hardened materials. Since the 5article mineral=or Bdis5ersoid@= is s ally o: low relati9e density it will :loat to the s r:ace o: the molten matri< alloy gi9ing a non= ni:orm com5osite str ct re. A 5rocess 8nown as Bmechanical alloyingB is nder de9elo5ment in which !oth dis5ersoid and matri<, in 5owder :orm, are treated in a high=s5eed !all mill. Here the high=energy im5act o: hard steel !alls 5on the 5owder 5articles ca ses a degree o: Bmechanical alloyingB !etween the 5articles. #inal consolidation and sha5ing is !y orthodo< 5owder metall rgy or e<tr sion.

1% $ # Early dis5ersion=strengthened high=tem5erat re alloys contained thori m o<ide, ,h)0, as the dis5ersoid ! t this mildly radioacti9e s !stance has !een largely re5laced !y yttri m o<ide, I0)/, in modern s 5eralloys sed in aeros5ace. A :eat re o: s ch materials is that high strength is retained at high tem5erat res a55roaching ,m. Both Al0)/ and Al.C/ are sed as dis5ersoids in some al mini m alloys as strength deri9ed :rom mechanical alloyingB is o:ten s 5erior to that o!tained !y heat treatment (5reci5itation hardening). Moreo9er strength is still maintained at tem5erat res at which 5reci5itation=hardened materials wo ld so:ten. +reci5itation=hardened al mini m=lithi m alloys ($$./..) ha9e !een de9elo5ed to red ce the relati9e density o: strong alloys :or the aeros5ace ind stry ! t im5ro9ed 5ro5erties are o!tained !y sing -i0) as a dis5ersion hardener instead since there is always the danger o: introd cing !rittleness d ring 5reci5itation treatment d e to the :ormation o: !rittle :ilms o: intermetallic com5o nd. ,he dis5ersion hardened alloy lnco MA+=A( %410 (,a!le $../) o::ers &R lower relati9e density and $4R greater sti::ness than the e? i9alent con9entional 5reci5itation=hardened alloy. Both alloys in ,a!le $../ are !asically sim5le non=heat=treata!le corrosion=

resistant alloys ($$./.$) which are dis5ersion hardened !y the 5resence o: Al0)/, Al.C/ and, in the second alloy, -i0).

Composite Bearing )aterials

A !earing material re? ires good wear=resistance and a low coe::icient o: :riction com!ined with com5ressi9e strength, to ghness and rigidity. As :ar as metallic !earings are concerned these 5ro5erties do not occ r together in a single=5hase alloy. A solid sol tion, tho gh to gh and strong, has a 5oor wear=resistance and o:ten a high coe::icient o: :riction whilst an intermetallic com5o nd, tho gh hard and rigid and ha9ing a low coe::icient o: :riction, is !rittle and wea8. ,h s a common !earing alloy=s ch as a Ba!!itt metal ($$.> .()=has a d 5le< str ct re consisting o: hard 5articles o: an intermediate 5hase em!edded in a to gh solid sol tion. ,he latter wears, lea9ing the 5articles o: com5o nd standing in relie: and 5ro9iding the low=:riction !earing s r:ace, whilst the wearing o: ,the solid sol tion matri< 5ro9ides channels which assist the :low o: li? id l !ricant traditionally sed in orthodo< engineering 5ractice. #riction !etween s r:aces is d e largely to adhesion and this is at a ma<im m with metals which :orm a solid sol tion in each other. ):ten wear=resistant s r:aces e<hi!it high coe::icients o: [:riction and only a :ew solid materials B gi9e !oth low :riction and resistance to wear. Chie: o: these are gra5hite and some other lamellar solids and some 5olymers.
1% %

1% % 1 A large n m!er o: modern mechanisms 5artic larly in aeros5ace engineering, re? ire solid l !rication in some :orm. ,his may !e d e to the :act that li? id l !ricants are nsta!le at high tem5erat res or that their transmission to the wor8ing s r:aces may !e erratic or, alternati9ely, e<5ensi9e to 5romote. Some materials s ch as gra5hite are intrinsically low=:riction s !stances ! t the most s ccess: l method o: sing the solid l !ricant is to incor5orate it in some :orm o: com5osite so that the l !ricant is in e::ect B! ilt inB. Metallic or 5olymeric matrices containing either lamellar solids (gra5hite or moly!den m dis l5hide) or 5olymers (s ch as +,#E) are the most widely s ggested.

Sintered !ron7e !earings containing small amo nts o: gra5hite ha9e !een sed :or many years as ha9e 9ario s mi<t res o: gra5hite and metals em5loyed as !r sh materials in electrical machinery. ,he : nction o: gra5hite as a l !ricant de5ends 5on its lamellar str ct re (/.&.0). Since only wea8 9an der ;aals :orces o5erate !etween the layered str ct re o: car!on atoms the latter slide o9er each other with ease and 5ro9ide the l !rication e::ect. )ther solids o: lamellar str ct re incl de the s l5hides, selenides and tell rides o: moly!den m, t ngsten, nio!i m and tantal m. ): these the !est=8nown is moly!den m dis l5hide which has !een sed as a high=5ress re l !ricant :or some time. A n m!er o: MoS02metal com5osites ha9e !een sed ! t 5ossi!ly the most s ccess: l so :ar are those containing MoS0 !onded with 5 to $6R iron and .R 5latin m. Mo S0 nic8el com5osites gi9e 5ossi!ly the !est res lts in terms o: low :riction (uP 4.4/ = 4.0) tho gh nic8el is rather a 5oor !inder. Com5osites containing calci m :l oride, Ca#0, as the solid l !ricant in a nic8e2chromi m matri< are also 5romising, ha9ing a coe::icient o: :riction o: a!o t 4.0 and a wor8ing tem5erat re 5 to &44ZC. ,he coe::icient o: :riction o: +,#E (,a!le $0.0) is lower than that o: any other solid material (uP4.4/=4.$) ! t its mechanical 5ro5erties as a single=!earing material are 5oor. #or this reason it is !est sed in a com5osite. Bron7es im5regnated with +R#E are in se tho gh the ma<im m wor8ing tem5erat re o: s ch !earings is limited !y +,#E to a!o t /44ZC. Nylon is also widely sed as a !earing material ! t its main disad9antage is its dimensional insta!ility res lting :rom a!sor5tion o: water.

CementF )ortar and Concrete

1% ' ,he Ealler s )ratory in the so th=west o: (reland is an e<am5le o: dry stone walling, !eing ! ilt entirely witho t the se o: mortar. A:ter some $144 years it is still 5er:ectly 5reser9ed since there is no mortar to deteriorate. Mortar had, howe9er, !een

sed !y the Egy5tians some .444 years earlier in ! ilding the 5yramids. ,his mortar was !ased on lime containing a little gy5s m. ,hen, as now, these mortars contained a cement which when mi<ed with water to :orm a 5aste, set and 5rogressi9ely hardened with the 5assage o: time. -imestone, CaC)/, is a chea5 5lenti: l material which, when BcalcinedB at a high tem5erat re :orms 4uic limeD CaC)/ X Ca) W C)0
-imestone _ ic8lime

;hen this ? ic8lime is mi<ed with water = or Bsla8edB= calci m hydro<ide or Bsla8ed limeB is 5rod cedD Ca) W H0) X Ca()H)0 W heat
Sla8ed lime

Sla8ing is accom5anied !y a considera!le e9ol tion o: heat and an increase in 9ol me. ,he sla8ed lime s !se? ently hardens slowly as it reacts with car!on dio<ide :rom the atmos5hereD Ca()H) 0 W C )0 XCaC)/ W H0) ,his reaction is accelerated when an e<cess o: water is 5resent in the cement. Since !oth car!on dio<ide and calci m hydro<ide are sol !le in water a ? ic8er reaction res lts than i: a direct gas2solid reaction were in9ol9ed. As CaC) / is m ch less water=sol !le than Ca()H)0 it 5reci5itates in crystalline :orm and the interloc8ing crystals o: CaC)/con9ert the so:t mass to a hard solid. 1% ' 1 Lime )ortar o!tained !y mi<ing sla8ed lime with clean sand and water was the 5rinci5al ! ilding adhesi9e !e:ore the ad9ent o: +ortland cement. (t is still sed in sit ations where a slow hardening 5rocess is admissi!le.

1% ' # Portland Cement -ime=!ased cements were de9elo5ed !y the Romans !y the addition o: 9olcanic ash (5o77 olana) which 5rod ced a ? ic8=hardening, strong hydra lic cement. ,he s ccess o: this cement is e9ident in the Colosse m and the 9ario s a? ed cts still in e<cellent 5reser9ation. ,here was little : rther de9elo5ment in cement technology ntil $>16 when Kohn Smeaton was engaged in ! ilding the Eddystone -ightho se. He re? ired a ? ic8=setting cement which wo ld not !e attac8ed !y sea water. By B! rningB a mi<t re o: limestone and clay he 5rod ced a s ita!le hydra lic cement. ,his material was 5er:ected in $&0. when Kose5h As5din heated the limestone==clay mi<t re so that it :ormed a hard Bclin8erB. ,his was then gro nd to a :ine 5owder gi9ing the 5rod ct we now 8now as B+ortland CementB, so named !y its in9entor as Ba cement o: s 5erior ? ality resem!ling +ortland stoneB (a white limestone o: the island o: +ortland). +ortland cement is the 5rinci5al ! ilding cement in se. (t is essentially a calcined mi<t re o: lime=!earing and clay=!ase materials. ,he lime=!earing material may !e ordinary limestone or e9en dredged marine shells, whilst the clay=!earing material com5rises s ita!le clays or shales. ,hese matenals are 5 l9ensed and then mi<ed in the correct 5ro5ortions 5rior to !eing calcined in rotary 8ilns at a!o t $144ZC. ,he res ltant clin8er is then gro nd with small amo nts o: gy5s m and water and a reenish=grey 5owder=the well=8nown +ortland cement=is the res lt. ;hilst the com5osition o: this cement can 9ary, the most widely sed :orm lation is gi9en in ,a!le $....

1% ' $ ;hen mi<ed with water a wor8a!le 5aste is 5rod ced and the mi<t re remains in this state d ring a dormant 5eriod. .(t then grad ally sti::ens ntil it !ecomes nwor8a!le as an Binitial setB ta8es 5lace. ,his sti::ening 5rocess contin es ntil a state o: B:inal setB is reached. Setting and conse? ent hardening are achie9ed !y a reaction !etween the cement and water. ,his reaction is s ally termed hydration. ,ricalci m al minate, C/A, reacts more ? ic8ly with water than do the other constit ents. ,h s an initial :ast reaction occ rsD C/A W 6H X C/A .H6 W High heat o: hydration (: the a!o9e reaction were allowed to 5roceed witho t restraint the cement wo ld set ra5idly :orming a str ct re o: low strength. Howe9er, the reaction is controlled !y the small ? antity o: gy5s m 5resent. ,his :orms a com5o nd which coats the e<isting C/A grains and so slows down the hydration 5rocess th s reg lating the setting rate. S !se? ently the C0S and C/S constit ents are slowly hydrated so that the strength o: the cement

grad ally ! ilds 5. ,hese chemical reactions are o: a :airly com5le< nat re ! t can !e re5resented !yD 0(C/.S) W 6H X C/.S0.H/W /(C.H) 0(C0.S) W .H X C/.S0.H/ W C.H (0) (n the a!o9e e? ations the :orm la BC .HB re5resents calci m hydro<ide, Ca()H) 0, which may : rther react with atmos5heric car!on dio<ide to :orm calci m car!onate, 5rod cing a : rther grad al increase in strength. ;hilst 5rod cts !ased on cement o: this t)=5e can !e sa:ely BhandledB within a!o t a wee8 they only attain some two=thirds o: their ma<im m strength in a!o t si< months. (n :act concrete !ased on +ortland cement contin es to harden :or years. ($)

The Str"ct"re of Portland Cement

1% ( ;hen the irreg lar 5articles o: cement 5owder are mi<ed with water the reactionD C/.AW6HXC/.A.H6 WHeat (/)

!egins and the dormant 5eriod o: some $1 min tes :ollows. D ring this time the grains !ecome coated with a gelatino s en9elo5e o: C/.A.H6. Since the grains !ecome 3oined at 5oints o: contact (#ig. $...(ii)) !y this gelatino s :ilm there is some loss o: 5lasticity d e to the networ8 o: wea8 chemical !onds :ormed. A:ter a!o t two ho rs the second stage o: hardening sets in as hydration o: !oth C0.S and C/.S ta8e 5lace !y the e? ations ($) and (0) a!o9e. ,hin BneedlesB (act ally, t !es) o: C /.S0 .H/ !egin to 5rotr de :rom the gel coating. ,hese grow and :orm densely=5ac8ed rods

radiating :rom the original cement 5articles which are 5rogressi9ely sed 5. As hydration o: the C0.Sand C/.S contin es the rods !egin to :ill the s5aces !etween the original cement 5articles so that an interloc8ing :ramewor8 o: rods ltimately consolidates into a rigid !ody. S ch a :ramewor8 will 5enetrate into and so adhere to the ro gh 5oro s s r:aces o: stone, !ric8 or other concrete. 1% ( 1 (:, li8e the writer, yo were entertained !y yo r chemistry master d ring the lim!o 5eriod :ollowing Be<amsB yo may recall his demonstration o: a Bsilica gardenB in which crystals o: 9ario s colo red inorganic salts were dro55ed into a sol tion o: sodi m silicate. Almost immediately the crystals were coated with a semi= 5ermea!le mem!rane thro gh which colo red BstemsB ! rst and !egan to grow towards the s r:ace o: the silicate sol tion. ,he growth o: BneedlesB in setting cement :ollows a similar 5rinci5le.

1% ( # ,he gel coating o: C/.A .H6 (e? ation /) which co9ers the cement grains in the initial stages o: setting (#ig. $..1(ii)) is in :act a semi=5ermea!le mem!rane. ,hat is water molec les are drawn thro gh it !y osmosis which see8s to dil te the concentrated sol tion at the internal :ace o: the mem!rane. ,his leads to an increase in 5ress re within the mem!rane coating (#ig. $..1(iii)) ntil, at its wea8est 5oint, it ! rsts (#ig.$..1(i9)) s5o ting a min te 3et o: a concentrated sol tion o: C /. S) and C0.S (dissol9ed :rom the cement 5article) into the s rro nding water. ,he o ter s r:ace o: s ch a 3et hydrates : rther on contact with water to :orm a t !e consisting o: C/.S0 .H/ (#ig. $..1(9) and (9i)) (e? ations ($) and (0)). )smotic 5ress re within the original gel mem!ranes contin es to :orce sol tion thro gh the t !e so that the t !e contin es to grow in the needle=li8e :orm descri!ed, ntil the cement gran le or the water is sed 5. CH i.e. calci m hydro<ide, a !y=5rod ct o: e? ations ($) and (0) remains in sol tion ntil its concentration is s ch that it recrystallises o t (#ig. $...).

1% ( $ (t sho ld !e a55reciated that the :oregoing is a m ch sim5li:ied descri5tion o: cement chemistry. (n :act other reacti9e constit ents s ch as #e0)/ and gy5s m (CaS).) are 5resent in cement the latter also gi9ing rise to a needle=li8e str ct re o: a calci m s l5ho=al minate sometimes called ettringite. ,he setting 5rocess contin es and the :illing o: 5ores in the str ct re increases the sti::ness o: the cement 5aste 5rogressi9ely. Since the hydrated 5rod ct o: the chemical 5rocess occ 5ies a greater 9ol me than did the BdryB +ortland cement it :ollows that e<5ansion accom5anies hydration and setting. Conse? ently cement=and concrete=gi9e an e<cellent im5ression o: the mo ld into which it is cast. ,he setting o: cement is another e<am5le o: a chemical reaction which, li8e di:: sion, is go9erned !y the Arrheni s -aw (1.&.6)D Rate o: setting P A .e=_2R, ,h s the rate o: setting is controlled !y the rate at which water molec les di:: se thro gh the gel mem!rane which in t rn de5ends on tem5erat re, ,. 1( ( % High alumina cement consists o: a 9ery high 5ro5ortion o: a C.A and a relati9ely small amo nt o: C0.S and C/.S and in this res5ect it di::ers considera!ly :rom ordinary +ortland cement. ,he high 5ro5ortion o: C.A con:ers a high hardening rate on this cement so that it reaches in a day the hardness achie9ed !y +ortland cement in a!o t 04 days. Ne9ertheless there is a 5rice to 5ay :or this as the cement is 5artic larly sensiti9e to !oth tem5erat re and ns ita!le en9ironmental conditions. D ring the setting 5rocess in high=al mina cement two metasta!le hydration com5o nds are :ormedD C. A. H$4 and C0. A. H&. ,he cement !egins to harden as soon as these com5o nds !egin to :orm ! t !oth e9ent ally ndergo a : rther change to :orm Ca /. A. H6. ,his reaction is 8nown in the trade as Bcon9ersionB. Since the relati9e

density o: C/. A. H6 is considera!ly higher than that o: either C. A. H$4 or C0. A. H& con9ersion is accom5anied !y a red ction in 9ol me. ,his res lts in 5orosity s ally leading to crac8ing and a !ig loss o: strength. Con9ersion occ rs 9ery slowly in dry, cold conditions (!elow 1ZC) and the de:ects may !e nnoticed :or years ! t in wet, warm conditions catastro5hic :ail re may occ r in a matter o: months. (A!o9e 14ZC con9ersion is almost immediate.) M ch high=al mina cement was sed in the immediate 5ost=war 5eriod !eca se o: its ra5id hardening 5ro5erties, ! t o:ten nder ns ita!le conditions. ;e are still clearing 5 the messG 1% ( ' A ra5id=hardening cement which is in e::ect a :orm o: ordinary +ortland cement achie9es an increased s5eed o: hardening !y raising the 5ro5ortion o: C/. S. ,he cement is also gro nd to a m ch :iner 5owder which increases the area o: cement 5article s r:ace e<5osed to water. ;ith this cement a!o t twice the strength is achie9ed d ring the :irst day as com5ared with ordinary +ortland cement. Ne9ertheless its se :or large str ct res is inad9isa!le since the greater rate o: heat o t5 t d ring the setting 5rocess may lead to the generation o: dangero s resid al stresses in the str ct re. 1% ( ( S l5hate=resistant cements are also necessary nder some irc m= stances and contain no more than 6R C/. A. 1% ( 4 Concrete is 5rod ced :rom a mo lda!le mi<t re o: stone BaggregatesB, sand, +ortland cement and water. ;hen hard it has many o: the attri! tes o: nat ral stone and is e<tensi9ely sed in ci9il engineering and ! ilding. (t is 9ery easy to mo ld in the wet state and is one o: the chea5est constr ctional materials a9aila!le in Britain !eca se o: the a9aila!ility o: the necessary raw materials. A 9ariety o: materials may !e sed as aggregate. Stone and gra9el are the most widely sed and also the most satis:actory. )ther s !stances which may !e a9aila!le chea5ly, e.g. !ro8en !ric8,

!last=: rnace slag, can !e sed where a lower=? ality 5rod ct will s ::ice. Sand is also incl ded in the aggregate and to o!tain a dense 5rod ct a correct stone2sand ratio is essential. By mi<ing 9ario s BgradesB (si7es) o: aggregate in s ita!le 5ro5ortions (#ig. $..6) a relati9ely small ? antity o: cement is all that is necessary to 5ro9ide an adherent :ilm !etween the aggregate 5articles. ,he 5ro5ortion o: cement to aggregate sed is go9erned !y the strength re? ired in the 5rod ct and can 9ary :rom $ D / :or a BrichB mi<t re to $ D $4 :or a BleanB one. ,he ratio commonly s5eci:ied is $D 6 and this 5rod ces 9ery satis:actory concrete i: the aggregate material is so nd, well=graded, 5ro5erly mi<ed with the cement 5aste and, :inally, ade? ately consolidated. )ther things !eing e? al the greater the si7e o: the large aggregate the smaller the cement ratio re? ired to 5rod ce concrete o: a gi9en strength. ,his is to !e e<5ected since a smaller area o: inter:ace will need to !e coated :or a gi9en 9ol me o: aggregate. Concrete made with +ortland cement s ally hardens in a!o t a wee8 ! t ra5id c ring methods can !e sed to shorten this time.

#ormerly the com.ressi+e strength o: concrete sed in ci9il engineering was, ty5ically, no more than .4 M+a. (n recent years, howe9er, serio s attem5ts ha9e !een made to increase this 9al e. ;ith ordinary concrete s ::icient water m st !e

added, o9er and a!o9e that re? ired :or com5lete chemical hydration o: the cement, to render the mi<t re s ::iciently wor8a!le so that it can !e mo lded to sha5e. Fn:ort nately this e<tra water also red ces the ltimate strength o: the concrete. Hence the c rrent tendency is to control the water2cement ratio more acc rately so that a minim m e<cess o: water is 5resent. ,his is also made 5ossi!le !y the addition o: Bs 5er5lasticisersB (5olymer=ty5e l !ricants) which increase the wor8a!ility, that is, allow 5articles to 5ac8 more closely th s red cing 5orosity. Milling the +ortland cement more :inely also red ces 5orosity. As a res lt o: s ch sim5le de9ices concrete with com5ressi9e strengths o: $44 M+a are now 5rod ced in North America whist in E ro5e, Norwegian oil=5rod ction 5lat:orms containing concrete with strengths in e<cess o: &4 M+a are in 5rod ction. 1% ( 5 %lain concrete is s ita!le :or many 5 r5oses s ch as retaining walls, dams and str ct res which rely :or their sta!ility on great mass. Modern motorways, and :o ndations where large e<ca9ations ha9e to !e :illed, are also e<am5les where concrete is cast in sit . At the other end o: the scale small 5re=cast 5arts can !e man :act red !y casting concrete into mo lds, e.g. Are=constit ted stone@ !loc8s and 9ario s items o: garden : rnit re.

Tamacadam and Allied S"*stances

1% 4 Modern methods o: road ma8ing were originated in the early years o: the nineteenth cent ry !y Scots engineer Kohn McAdam. ,he method he originated, that o: coating s ita!le aggregate with tar, is !asically that sed today. ,wo ty5es o: material are now sed as the !it mino s matri<D tars and as5halts. ,ars sed are the resid es deri9ed :rom the destr cti9e distillation o: coal. Some as5halts occ r nat rally, e.g. B,rinidad -a8eB, ! t most are resid es o!tained d ring 5etrole m re:ining 5rocesses .

,he !it mino s material is mi<ed with a s ita!le aggregate s ch as !last=: rnace slag :or coarse :o ndation wor8 and :ine gra9el :or the :inishing layer. Mi<t res are designed to meet s5eci:ic re? irements s ch as sta!ility, d ra!ility, s8id resistance and resistance to 5enetration !y water. ,hose mi<t res sing harder grades o: as5halt are normally 5rocessed in a Bhot=mi<B 5lant at a!o t $/1ZC, whilst those containing the more :l id as5halts may !e mi<ed at am!ient tem5erat res. ,he res ltant mi<t re is to gh and crac8=resistant !eca se o: the !it mino s matri< whilst it is hard=wearing !eca se o: the 5resence o: 5rotr ding 5ieces o: aggregate. (n many ways this resem!les the 5rinci5les 5on which a !earing metal is designed ($...) and is a good e<am5le with which to :inish a cha5ter disc ssing the di9erse 5ro5erties which can !e !ro ght together !y the se o: com5osite materials.

1' Fi*re1reinforced Composite )aterials

1' 1 D ring a recent ram!le thro gh the :orests o: British Col m!ia ( rested :or a while in a gro9e o: mighty ;estern Red Cedars and re:lected that trees are the oldest li9ing things on Earth and that some o: those were si7ea!le sa5lins at the time when, :ar away in England, *ing Kohn was signing Magna CartaQ. 1'.1 1 D ring many millions o: years o: e9ol tion trees ha9e :o nd it necessary to raise a com5le< !iological str ct re high a!o9e the gro nd and to con9ert sim5le elements !y 5hotosynthesis into a material o: high strength. ,h s they ha9e de9elo5ed as tall slender col mns with an array o: s !sidiary mem!ers attached cantile9er :ashion which ha9e to. Carry a55recia!le loads o: lea9es=and o:ten, snow=as well as to resist considera!le wind :orces. ,he materials :rom which these tr n8s and !ranches are constr cted re? ires high strength and sti::ness. (n :act !eca se o: its low relati9e density wood has a s5eci:ic strength higher than many man=made materials (,a!le $1.$). 1' 1 # ,he high s5eci:ic strength=or strength2weight ratio as it was originally termed=o: a wood s ch as 5ine is a res lt o: its internal str ct re (#ig. $1.$), the ma3or 5art o: which consists o: cells, 8nown as tracheids, which are aligned 9ertically in the tr n8 and cemented together !y an amor5ho s matri< com5osed mainly o: the com5le< 5olymer, lignin. ,he tracheids are :i!res a!o t 0 to . mm long and 4.4/ mm thic8 and since their strength is some :i9e

times that o: wood as a whole, wood can !e regarded as a relati9ely wea8 amor5ho s matri< s ccess: lly rein:orced !y the :i!ro s tracheids.
QMy Editor tells me that : rther So th in the arid 5lands o: Eastern Cali:ornia Brisdecone +ines e8e o t an e<istence :or m ch longer ^ 5 to 1444 years in :act.

1' 1 $ ,he internal str ct re o: the tracheids is :airly com5le< ! t consists essentially o: long micro:i!rils o: cell lose molec les arranged in a crystalline 5attern :orming t !es s rro nded !y a layer o: 5olysaccharides ! ilt o: 9ario s s gars. ,hose 5olysaccharides ad3acent to the crystalline cell lose core are themsel9es 5artially crystalline ! t !ecome increasingly amor5ho s towards the s r:ace o: the tracheid. ,his means that !etween the crystalline cell lose core and the amor5ho s mi<t re matri< there is no shar5 !o ndary at which stee5 ste5 stress gradients co ld occ r.(t has !een :o nd that the a9oidance o: a

well=de:ined crystalline ^ amor5ho s inter:ace is im5orant de9elo5ing satis:actory :i!re=rein:orced 5lastics materials

in

As s ggested a!o9e the conce5t o: :i!re=rein:orced com5osites had its origin in nat re. ,h s the rein:orcement o: 5lastics materials !y sing glass :i!re in the $%.4s was !ased on the nat ral str ct re o: !am!oo, whilst the Ancients rein:orced their air=dried !ric8s with straw=a 5ractice one can still o!ser9e in some o: the more remote regions o: the Bal8ans. 1' # #i!re=rein:orced com5osites incl deD (i)matri< materials s ch as thermo5lastic or thermosetting resins, and some metalsM rein:orced with car!on, glass, organic 5olymer and other :i!resM (ii)5lastics materials ( s ally thermosetting) rein:orced with laminations o: wo9en te<tilesM (iii)9ehicle tyres in which 9 lcanised r !!er is rein:orced with wo9en te<tile cords or steel wireM (i9)materials s ch as rein:orced or 5re=stressed concrete. ,he nat re o: the inter:ace !etween :i!re and matri< in:l ences the e<tent to which a :orce is trans:erred :rom the matri< to the :i!re, and cohesion at the inter:ace may !e achie9ed !y either mechanical, 5hysical or chemical !onding ($..0.$).

1' # 1 ;hen there is little or no chemical interaction !etween matri< and rein:orcement material the relati9e density, +c, o: s ch com5osite materials can !e calc lated !y the 9ery sim5le Br le o: mi<t resB. ,henD vc P vr'rW vm($= 'r) where / r is the 9ol me o: the rein:orcement :raction and v r and vm the relati9e densities o: rein:orcement and matri< res5ecti9ely. ;hen a :i!re=rein:orced com5osite is stressed the matri< may !egin to :low ! t in doing so will ca se a :orce to !e set 5 at the inter:ace with the :i!re. (: the :i!re is long eno gh this transmitted :orce will ltimately lead to its :ract re and the :i!re will there:ore ha9e contri! ted : lly to the strength o: the com5osite. )!9io sly strength will !e directional, i.e. at a ma<im m 9al e 5arallel to the direction o: the :i!res. 89: +n a fi*re1reinforced composite the contin"oml&1aligned c&lindrical

fi*res are packed as closel& as is possi*le in a single direction 6iven that the relative densities of fi*re material and matri/ material are # %1 and 1 #5 respectivel& calc"late the ma/im"m relative densit& of the res"ltant composite ass"ming p"re ingredients 8A: ,he closest 5ac8ing o: cylindrical :i!res is achie9ed in a he<agonal 5attern as indicated in the :ollowing cross=sectional diagramD

!eca se o: its low relati9e density, s5eci:ic 5ro5erties, i.e. Mechanical 5ro5erty2Relati9e density are e<cellent. ,he mechanical 5ro5erties o: nidirectional com5osites are o: co rse 9ery anisotro5ic :or the same reason that wood is strong Balong the grainB ! t wea8 Bacross the grainB. S ch di::ic lties can !e largely o9ercome !y sing a m lti=directional :i!re :illing, e.g. wo9en :a!rics and the li8e.

F"nctions of the Constit"ents in a Fi*re Composite

1' $ ,he sim5lest com5osite consists o: contin o s aligned :i!res which ha9e !een com5letely in:iltrated !y a matri< material which has !onded to the :i!res and then hardened. ,he rein:orcing :i!res contri! te the longit dinal mechanical 5ro5erties s ch as strength, sti::ness, cree5 and :atig e 5ro5ertiesM whilst the matri< will generally !e 5hysically wea8er than the :i!re in:illing tho gh its : nctions are 9ital. ,h s the matri< 5rotects the :i!re s r:ace :rom damage and :rom the action o: the en9ironment, whilst 8ee5ing :i!res in the desired 5osition to recei9e stress distri! tion. Eenerally trans9erse 5ro5erties s ch as

shear and com5ress= i9e strength, im5act and to ghness 9al es are largely controlled !y the matri<, tho gh it may also gi9e some 5rotection against crac8 5ro5agation 5er5endic lar to the :i!re direction !y allowing se5aration to occ r !etween :i!re and matri< (#ig. $1.0).

1' $ 1 ,he inter:ace region !etween :i!re and matri< is generally a!o t 4.$ wm or less in thic8ness and can !e considered as a third 5hase in the com5osite. ,he strength o: the :i!re=resin !ond may !e !etween $ and $44 M+a. Bond strength has an im5ortant in:l ence on the o9erall mecha= nical 5ro5erties o: the com5osite. (: too low then the :i!re and matri< trend to o5erate inde5endently leading to 5oor o9erall 5ro5erties, ! t i: too high the com5osite may !e strong and sti:: ! t also e<cessi9ely !rittle. (n 5ractice !ond strength is s ally controlled !y the degree o: treatment gi9en to the s r:ace o: the :i!re material in so :ar as this a::ects the degree o: adhesion.

Reinforcement )echanisms
1' % ;e will consider the :orces acting on a matri< material, the strain at :ail re o: which is greater than that o: the :i!re material (#ig. $1./(i)). ;hen a :orce is a55lied to the ends and

sides o: the com5osite !loc8 di::erent a<ial dis5lacements in !oth :i!re and matri< at either end o: the :i!re initiate shear stresses at the :i!re s r:ace. ,hese stresses are transmitted to the :i!re ca sing an increase in tensile stress within it. Ass ming that a stress 4B # is 5rod ced at a distance # :rom the end o: the :i!re (radi s r), thenD

,ensile :orce in :i!re Pxr0. # AlsoD

#orce acting within the :i!re=matri< inter:ace P 0r. # . where is the shear strength o: the inter:ace material. Since these :orces are in e? ili!ri m in the com5ositeD . xr0. # P 0r. # . # P 0< 2 r As the e<ternal :orce is increased the region o: ma<im m shear stress ad9ances along the :i!re and tensile stress increases. (: a, the total length o: the :i!re is s ch that # ne9er e<ceeds the !rea8ing stress o: the :i!re, then the :i!re will not !rea8 i: the com5osite is stressed : rther, i.e. :ail re will occ r :irst at the inter:ace. Stress distri! tion in the :i!re is indicated in #ig. $1./(ii) and the mean stress is # 20. 1' % 1 ;e will now consider a long :i!re, the length o: which is s ch that :ail re can ltimately ta8e 5lace in it. (: E : is Io ngBs Mod l s :or the :i!re and is the o9erall strain thenD E: P # 2 or # P E: . (0) )!9io sly the strain in the :i!re cannot e<ceed that in the matri< and, !e:ore :ail re, stress in the :i!re will increase with distance :rom either end ntil # P E: . and then ass mes a constant 9al e. #rom e? ations ($) and (0) this occ rs whenD < P E: . . r 2 (0)

As stress in the com5osite increases # reaches the !rea8ing stress ! and :ail re occ rs. ,he 9al e o: < (:rom e? ation ($)) is then gi9en !yD < P -c20 P r .! 2 0 (/) where -c is 8nown as the critical stress trans:er length, i.e. the :i!re length which m st !e e<ceed i: :ail re o: the :i!re is to ta8e

5lace. ,he distri! tion o: stress along the :i!re is as shown in #ig. $1.. and the a9erage stress le9el # is gi9en !yD # 5 # ( $ ^ (-c 20< )) (.) ,he longer the :i!re (0<) the nearer the o9erall stress a55roaches the constant 9al e acting in the centre o: the :i!re and hence the more e::icient is the se o: the rein:orcement. (: the tensile strength and the radi s o: the :i!re are 8nown along with the shear strength, , o: the inter:ace, then e? ations ($) and (0) can !e sed to estimate the :i!re length necessary :or o5tim m se o: the :i!re strength in a short=:i!re com5osite and also the a9erage stress le9el. 1' % # (n the a!o9e it is ass med that the !rea8ing stress o: the :i!re is less than that o: the matri< ! t i: the re9erse o!tains the matri< will :ail :irst. ,he ? estion o: which com5onent o: the com5osite :ails :irst de5ends 5on the 5ro5ortions and the stress2strain characteristics o: the two com5onents. (n 5ractice the :i!re 9ol me o: a com5osite is s ally !etween .4 and >4R=in a BrealB material a !ar say $4 mm < $ mm in cross=section wo ld

contain some $41 indi9id al :i!res, !etween 1 and $4 m in diameter and !etween 4.$ and $ m a5art. #i!re :ail re generally leads to immediate :ail re o: the com5osite ! t here we ha9e !een dealing with the sim5le case o: a single :i!re em!edded in a matri<. (n real m lti=:i!re com5osites the str ct re is m ch more com5le< and s ch 9aria!les as :i!re direction relati9e to the direction in which stresses are acting m st !e considered. (: we ma8e the ass m5tion that the :i!res are long, contin o s and aligned 5arallel in a single direction and that there is com5lete !onding

M ch modern research is aimed at 5rod cing materials o: high s.ecific strength :or the aeros5ace ind stries and since the relati9e density o: a s !stance s ally :ollows the atomic masses o: its constit ent atoms many o: these :i!res are deri9ed :rom com5o nds !ased on the low atomic mass elementsD H, B, C, N, 4, A( and Si. Moreo9er com5o nds !ased on these elements s ally rely :or their strength on the co9alent !ond, the strongest !y :ar o: all chemical !onds. 1' ' 1 Brganic Pol&mer Fi*res +olymers containing long=chain, molec les generally ha9e 5oor sti::ness and strength !eca se these molec les are coiled or :olded in the normal ! l8 material. (:, howe9er, these molec les are stretched and straightened d ring a :i!er man :act ring 5rocess, high strength and sti::ness may !e de9elo5ed. AromaticQ 5olyamide (hence, BAramidB) :i!res are c rrently the most s ccess: l. ,hese are !ased on the :orm laD

and are man :act red commercially nder the name *e92ar. A:ter !eing s5 n, the :i!res are heated nder tension in a nitrogen atmos5here at tem5erat res 5 to 1144C so that the BstretchedB 5ro5erties are retained. ,hese molec lar chains are only held together !y wea8 hydrogen !onds(#ig. $1.1) so that trans9erse and com5ressi9e strengths are low. Howe9er, this in t rn im5arts a high ca5acity :or a!sor!ing energy so
QD ring the early classi:ication o: organic com5o nds s !stances were di9ided into two gro 5s=ali5hatic com5o nds in which car!on atoms are arranged in o5en BchainsB (as in al8ane series, i.e. methane, ethane, etc.) and aromatic com5o nds in which the B!en7ene ring@ or a deri9ati9e s ch as 5henol (#ig. $0.1) is in9ol9ed. Not all BaromaticB com5o nds ha9e 5leasant aroma, while with many ali5hatic com5o nds the scent is 3 st as 5leasant= or malodoro sG

that aramid com5osites are se: l :or resisting im5act damage. Conse? ently they are sed in ! llet=5roo: 9ests and the li8e, whilst their low relati9e density ma8es them 9al a!le in the aeros5ace ind stries. ,hey are sensiti9e to ltra=9iolet light :rom which they m st !e 5rotected. A : rther disad9antage is that they

a!sor! water easily ma8ing them ns ita!le :or se in some chemical ind stries. Strong nylon :i!res ha9e !een sed :or rein:orcement :or a considera!le time and altho gh 5olythene is not normally considered as a 5ossi!le strong material it can !e made strong 5ro9ided 5olythene o: a s ita!le molec lar mass is chosen and i: treatment is a55lied to o!tain molec lar alignment. S ch :i!res wo ld !e se: l only at low tem5erat res since a!o9e $44ZC the molec les ac? ire s ::icient thermal energy to rearrange themsel9es randomly. 1' ' # Car*on Fi*res ;hilst 5olymer :i!res are com5osed o: aligned linear molec les car!on :i!res are made 5 o: twodimensional 5lanes or layers o: car!on atoms arranged as in the gra5hite str ct re (#ig. /.0%). ,he gra5hite crystal is anisotro.icQ in res5ect o: many o: its 5ro5erties and this in t rn is d e to its layer str ct re. #or e<am5le Io ngBs Mod l s meas red in a direction 5arallel to the layers is $4/4 E+a while 5er5endic lar to the layers it is only /1 E+a. ,his is to !e e<5ected since indi9id al car!on atoms in a layer are held to their neigh!o rs !y strong co9alent !onds only 4.$.0 nm long, whereas only wea8 9an der ;aals :orces o5erate !etween ad3acent layers which are com5arati9ely :ar a5art (4.//1 nm). ,h s the !ond energy d e to the co9alent !onds o5erating within the layers is a!o t 644 8K2gram=atom, whereas the interlayer !inding energy is only 1.. 8K2gram=atom. ,he relati9ely high !inding energy within the layers gi9es rise to the high 9al e o: Io ngBs Mod l s since high elasticity is de5endent on a large restoring :orce acting !etween atoms. (n 5ractice car!on :i!res are 5olycrystalline and consist o: a large n m!er o: small crystallites. ,hese are a!o t $4=& m thic8 and 0.1 < $4=& m in diameter and consist o: 5arallel 5lanes o: car!on atoms gro 5ed together. ,he main di::erence !etween the str ct re o: these crystallites and the ideal str ct re shown in #ig. /.0% is that there is no reg larity o: the orientation o: the 5arallel

5lanes and the str ct re is said to !e tur,ostatic. ,he str ct re o: 5er:ect gra5hite has !een li8ened to a 5ac8 o: 5laying cards which has !een ta55ed on a ta!le to s? are 5 indi9id al cards (layer 5lanes) whilst the str ct re in the t r!ostatic gra5hite o: car!on :i!res has !een li8ened to the 5ac8 o: cards collected together into a 5ile ! t not s? ared at the edges so that the orientation o: indi9id al cards (layer 5lanes) is random. E<amination !y the electron microsco5e shows that the Crystallites are gro 5ed together in nits 8nown as :i!rils, which are s != nits o: the :i!re. ,he :i!re itsel: some & < $4=6 m in diameter consists o: a networ8 o: closely 5ac8ed :i!rils each a!o t 0.1 < $4=& m in diameter (#ig. $1.6).

QAnisotro5y is the characteristic o: e<hi!iting di::erent 5hysical 5ro5erties in di::erent directions in a !ody o: material.

,he ! l8 o: car!on :i!re is 5rod cedD[ the 5yrolisis or heat= treatment o: 5olyacrylonitrile :ilament. ,he 5rocess ta8es 5lace in stages in an inert atmos5hereD

(i) a low tem5erat re treatment at 004 C is :irst gi9en. ,his 5romotes cross=lin8ing (thermosetting) !etween molec les rendering the material in: si!le d ring the s !se? ent high=tem5erat re 5rocessM (ii) the tem5erat re is raised to %44 C to Acar!onise@ the :ilament. Decom5osition ta8es 5lace and the 5olymer chains are stri55ed o: all other atoms and gro 5s o: atoms lea9ing a As8eleton@ o: car!on atom in the gra5hitic str ct reD (iii) heat treatment is then a55lied which will 5rod ce the re? ired str ct re and com!ination o: 5ro5erties. -ower tem5erat res ($/44=$144ZC) 5rod ce :i!res o: high strength and low mod l s while higher tem5erat res (0444=/444 C) 5ro9ide :i!res o: low strength ! t high mod l s. D ring the 5rocess the :i!res are 8e5t in tension to 5re9ent c rling and to enco rage good alignment. Car!on :i!res ha9e diameter !etween 1 and $4 m and are a9aila!le in Atows@ containing $, /, 6, $0 or 04 tho sand :ilaments. Car!on :i!re contin es to !e the most 5romising o: com5osite rein:orce= ments in terms o: s5eci:ic strength 5artic $arly since 5rod ction costs are :alling and are li8ely to :all : rther i: c rrent 5ro3ects s cceed in 5rod cing satis:actory :i!re :rom 5itch. 1' ' $ 6lass Fi*res when in the :orn$ o: :i!re glass is considera!ly stronger than it is in any other :orm and as s ch enters the ran8s o: engineering materials. Silica glass :i!re in the :reshly=drawn condition, that is i: tested within ten min tes o: !eing drawn and A nto ched !y h man handB so to s5ea8, may ha9e a tensile strength in the region o: $1 E+a. ,he most min te o: scratches, e9en s ch as wo ld !e 5rod ced !y drawing a :eather across the s r:ace o: the :i!re, will ca se :ract re at considera!ly lower stress. S ch min te crac8s or scratches act as stress=raisers so that at the ti5 o: the crac8 the stress is well a!o9e that necessary to ca se :ract re, whereas the o9erall a9erage stress in the :i!re is

m ch lower than this. Conse? ently, the crac8 will e<tend and, as long as the stress concentration is maintained at the new ti5 o: the crac8, :ract re will contin e (#ig. $1.>(i)). A d ctile material on the other hand can ad3 st to the sit ation !y means o: 5lastic strain so that the high concentration o: stress is a tomatically red ced (#ig. $1. >(ii)).

High ? ality glass :i!re is 5rod ced :rom a melt containing high=5 rity materials. ,his is s5 n at a high tem5erat re and cooled 9ery ra5idly !e:ore !eing gi9en a 5rotecti9e coating termed Bsi7eB. ,his si7e is a mi<t re o: materials which 5rotects the s r:ace :rom damage and acts as a l !ricant. (t also contains a deri9ati9e o: silane (SiH.) which reacts with Sio= lin8s in the glass :i!re and is also com5ati!le with chemical gro 5s in the molec les o: the 5olymer matri<, th s 5romoting :i!re2matri< !onding. Elass :i!re was the :irst o: the modern :i!res to !e sed in com5osites. Now a n m!er o: di::erent ty5es are in 5rod ction the !est 8nown o: which are S=glass, a high=strength magnesia=al minosilicate com5osition and E=glass, a non=al8aline !orosilicate glass which was de9elo5ed :or its electrical ins lation 5ro5erties. Elass :i!res are strong and chea5 tho gh not as sti:: as car!on :i!re. ,heir relati9e densities are also higher than that o: car!on :i!re.

1' ' % Boron Fi*re has a low relati9e density and a 9ery high Io ngBs Mod l s ! t is only moderately strong. Since it is di::ic lt to :a!ricate it is 9ery e<5ensi9e. Ne9ertheless these :i!res are sed in the aeros5ace ind stry !eca se o: their high trans9erse strength which, along with large :i!re diameter, ena!les them to withstand high com5ressi9e :orces. Boron :i!res are grown :rom the 9a5o r 5hase on to t ngsten :ilaments some $1 m in diameter. ,he core :ilament is heated to $/44ZC in a hydrogen atmos5here when 9olatile !oron chloride is admittedD

$44=044 =m in diameter. Boron :i!re may also !e grown on to a car!on :ilament some /4 m in diameter ! t in this case there is no reaction !etween core and coating. 1' ' ' Bther Fi*res Mention m st !e made o: those ceramic :i!res which are now !eing de9elo5ed :or the 5rod ction o: metal

matri< com5osites (MMCs). ,hese are im5ortant :or : t re de9elo5ments in the aeros5ace ind stries where cast and e<tr ded al mini m alloys can !e : rther strengthened !y :i!re rein:orcement. ,he most im5ortant :i!res a9aila!le in this :ield are those o: silicon car!ide and al mina, tho gh the latter ndergoes !oth 5hase changes and grain growth at high tem5erat res. 1' ' ( E<tremely high strengths are attaina!le in materials 5rod ced in the :orm o: Bwhis8ersB. ,hese are hair=li8e single crystals, !etween 4.1 < $4=/ and 0.4 < $4=/ mm in diameter and as m ch as 04 mm long, grown nder controlled conditions and generally ha9ing a single dislocation r nning along the central a<is. ,his relati9e :reedom :rom dislocations means that their yield strength is nearer to the theoretical :or the material (,a!le $1.0). ,h s a gra5hite whis8er may ha9e a strength o: as m ch as 0$ E+a whilst the strength o: car!on :i!re is o: the order o: only / E+a. Fn:ort nately whis8ers are normally 5rod ced only nder la!oratory conditions and their great strength is di::ic lt to tilise nder ordinary 5rod ction 5rocesses. ,h s the high cost o: :orming a whis8er com5osite generally r les o t its se at 5resent and ordinary :i!re com5osites are sed instead.

)atri/ )aterials for Fi*re Composites

1' ( Matri< materials sed in :i!re com5osites may !e o: 5olymer, ceramic or metal tho gh !y :ar the greatest o t5 t to date is o:

com5osites em5loying thermosetting resin matrices. ,o 5rod ce a s ccess: l com5osite the matri< material m st :orm either a :rictional, or more o:ten, a chemical !ond with the :i!re s r:ace. (n the latter case the chemical reaction !etween the two m st not. !e so 9igoro s as to damage the :i!re . ,he matri< material m st !e s ::iciently mo!ile to in:iltrate among indi9id al :i!res at as low as tem5erat re and 5ress re as 5ossi!le d ring mo lding and then solidi:y (or reach ,g) ? ic8ly. #i!res sho ld not !e damaged 5hysically d ring the mo lding 5rocess. A5art :rom com5ati!ility with the :i!re material the choice o: matri< will !e go9erned !y ser9ice re? irements. ,he resistance o: the com5osite to tem5erat re, chemical en9ironment and the e::ects o: moist re are determined !y the matri<, tho gh the :i!re rein:orcement m st !e sta!le to a tem5erat re a!o9e that at which the matri< !egins to deteriorate. 1' ( 1 Thermosetting Resins ,hese are 5olymers which cross= lin8 ($0./) d ring Bc ringB to :orm a glassy hard solid (5olyesters, 9inyl esters and e5o<ies). +olyesters were the :irst thermosetting resins sed (with glass:i!re rein:orcement) to ma8e 5rotecti9e ho sings :or aircra:t radar antenna d ring the Second ;orld ;ar, the res ltant com5osite !eing trans5arent to radio transmissions. ,hese resins still acco nt :or a high 5ro5ortion o: com5osite man :act re since they are chea5, easy to wor8 with and can !e Bc redB at relati9ely low tem5erat res. ,he main disad9antage o: 5olyesters is that they do not !ond well with :i!res so that strength o: the com5osite de5ends largely on relati9ely wea8 9an der ;aals :orces. +olyesters also ha9e a relati9ely high shrin8age coe::icient which : rther im5airs adhesion to the :i!res. #or these reasons 5olyesters are not generally sed :or high=5er:ormance com5osites. E5o<ides are the most e<tensi9ely sed matri< materials :or those com5osites !ased on contin o s car!on or aramid :i!res. ,he resin is mi<ed with a BhardenerB (the reader will !e :amiliar with D(I e5o<ide gl es) and heated :or 5 to eight ho rs at $64=$&4ZC to 5rod ce a hard, insol !le cross=lin8ed str ct reQ with a tensile

strength o: &4=$44 M+a and a Io ngBs Mod l s o: 0=. E+a. Most o: the resins in this class are !ased on molec les ha9ing two or :o r e5o<ide gro 5s. ,his introd ces a greater density o: cross= lin8ing and conse? ently a higher tem5erat re tolerance which is s ally s5eci:ied in terms o: ,g ! t in 5ractice a tem5erat re o: $64ZC is 5ro!a!ly the ma<im m at which s ch a
Q ,he reaction in9ol9ed is o: the ty5e descri!ed in $0./.$ tho gh here we are dealing with cold=setting 5olymers. A m ch stronger harder !ond can s ally !e o!tained with D(I gl es i: the Koint is warmed at $44=$14ZC==a greater degree o: cross=lin8ing is o!tained.

load=!earing com5osite can wor8 contin o sly. A greater degree o: cross=lin8ing will o: co rse mean increased hardness and !rittleness. )ther se: l thermosets incl des well 8nown 5henolics ($0./) which are ine<5ensi9e, :ire=resistant ! t tend to !e !rittle and s ::er :rom high shrin8age. High=5er:ormance resins incl de 5olyimides which may !e either thermo5lastic or thermosetting materials and can withstand tem5erat res o: 0&4=/$1ZC contin o sly. Fn:ort nately they are 9ery e<5ensi9e and re? ire long c ring cycles :ollowing the :i!re=im5regnation stage. 1' ( # Thermoplastic Pol&mers ,hese are generally high= molec lar mass, long=chain molec les which de9elo5 strength at am!ient tem5erat re either !y remaining amor5ho s (! t !ecoming entangled), e.g. 5olycar!onatesM or !y crystallising 5artially. e.g. nylon. #or many a55lications thermo5lastics ha9e the ad9antage o9er thermosets o: greater to ghness and shorter :a!rication cycles, ! t are at a disad9antage in res5ect o: their high 9iscosity at the mo lding tem5erat re, ma8ing :i!re im5regnation di::ic lt. Best 8nown among the many thermo5lastics sed as matrices are Nylon 66, 5olyethylene tere5hthalate (+E,), 5olys l5hone (+SD $14=$>4ZC), 5oly5henylene s l5hide (++SD 044=004oC). 5olyamide imide (+A() and 5olyether ether 8etone (+EE*D 014oC). (#ig res re5resent ma<im m ser9ice tem5erat res.) +EE*=!ased

com5osites ha9e e<cellent resistance to :ail re nder im5act, good strength and a wor8=to=:ract re 9al e 5 to $/ times that o: a com5ara!le e5o<ide com5osite. 1' ( $ )etal )atrices Since the general aim in 5rod cing a com5osite is to de9elo5 a material o: high s5eci:ic strength, s ita!le metals will !e those o: low relati9e density, i.e. al mini m and its alloys, magnesi m and titani m and its alloys. ): the latter the alloyD ,(=6Al=.' is the most sed. Metal matri< com5osites are o: interest !eca se o: the higher tem5erat re (aro nd 144ZC) at which some o: them can o5eratek tho gh other 9al a!le 5ro5erties incl de higher trans9erse and shear 5ro5erties, good im5act resistance and the :act that they can !e 3oined !y orthodo< metall rgical techni? es. ,he main disad9antages are high relati9e density and the general di::ic lty o: :a!rication as com5ared with 5olymer matrices.

The )an"fact"re of Fi*re Composites

1' 4 ,he commercial :orms in which the :i!re materials are s 55lied incl deD (i) ro9ings this is the !asic material, a ro9ing consisting o: a n m!er o: strands or ! ndles o: :ilaments wo nd into a 5ac8age or BcreelB. ,he length o: the ro9ing may !e se9eral 8ilometres and the term is s ally a55lied to glass :i!res whereas ! ndles o: contin o s car!on :i!res are 8nown as BtowsB. A BstrandB o: glass :i!res contains ty5ically some 044 :ilaments each a!o t $4 m in diameterM (ii) wo9en :a!rics in which 9ario s ty5es o: wea9e styles are sedM (iii) cho55ed :i!res :rom a!o t $ mm to 14 mm in length.

Com5osites are man :act red either as indi9id al single com5onents or in the :orm o: sheets or sections in any re? ired length. (n the :ormer case the :i!re material may !e wo9en into a B5re:ormB which ro ghly :its the die ca9ity into which the resin is in3ected. ): a n m!er o: 5rocesses a9aila!le the :ollowing are e<am5les. 1' 4 1 .and and Spra& Placement ,hese 5rocesses acco nt :or the greatest 5ro5ortion o: glass=rein:orced 5lastics (ER+) 5rod ced c rrently in Britain. (n the sim5lest :orm wo9en ro9ings are laid o9er a mo ld s r:ace which has !een coated with a s ita!le non= stic8 agent. ,he li? id resin is then wor8ed into the rein:orcement !y hand sing a !r sh or roller. +olyester resins are most commonly sed with glass :i!re gi9ing a com!ination o: low cost and good chemical resistance. ,his 5rocess=or at least its res lts= will !e :amiliar to those who go Bmessing a!o t in !oatsB since it is the :o ndation o: the man :act re o: many modern 5leas re cra:t, tho gh large 9essels s ch as mine swee5ers 5 to 64 m long ha9e !een Bhand layeredB. 1' 4 # Press )o"lding the most widely sed 5rocess :or mass 5rod cing rein:orced 5lastics com5onents. ,he 5rocess is : ndamentally similar to that in #ig. 6.0%, the charge to the mo ld ca9ity consisting o: :i!re and resin. 1' 4 $ Resin Transfer )o"lding similar in 5rinci5le to the 5rocess shown in #ig. 6./4. ,he :i!re, s ally as a wo9en 5re= :orm, is 5laced in the die ca9ity and the resin then in3ected. 1' 4 % P"ltr"sion a 5rocess where!y 5ro:iles o: :i<ed cross= section are man :act red in contin o s lengths. ,he 5rocess resem!les that sed in the e<tr sion o: metals and 5lastics e<ce5t that in 5 ltr sion the rein:orcing :i!res 5 ll the com5osite thro gh the die system (#ig. $1.%). Most 5 ltr sions are o: glass= :i!re25olyester com5osite gi9ing good corrosion resistance at low

cost. Rod, sheet, t !e and channel 5ro:iles are ty5ical 5rod cts ! t ! ilding 5anels, window :rames, railings and wal8ways in chemical 5lant are also made !y the !asic 5rocess.

1' 4 ' )etal )atri/ Composites 2))Cs3 these are di::ic lt to 5rod ce !eca se relati9ely high tem5erat res and2or 5ress res need to !e sed d ring the 5rocess and this in t rn may ca se damage to the :i!re rein:orcement. Most MMCs are !ased on al mini m alloy matrices which are rein:orced with 5articles or :i!res o: al mina, silicon car!ide, car!on or !oron. -ow melting 5oint metals may !e gra9ity cast to :orm the matri< ! t in order to achie9e ade? ate in:iltration the se o: 5ress re is generally necessary. (n s? ee7e casting mechanical 5ress re is sed to :orce molten metal amongst the rein:orcement material ! t in li? id 5ress re :orming a :i!re B5re=:ormB is :irst 5laced in the die. ,he die is then e9ac ated to red ce the incidence o: 5orosity and assist in:iltration. Molten metal is then :orced in. ,he re? ired 5ress re is lower than with s? ee7e casting and this o::ers greater :le<i!ility in terms o: si7e and sha5e o: the castings 5rod ced. ,wo methods are a9aila!le :or 5rod cing MMCs :rom solid metals. (n the 5owder metall rgy 5rocess a metal 5owder is mi<ed with 5articles or cho55ed :i!res, 5ressed into sha5e and then sintered sing the !asic method descri!ed in 6.1.$. Di:: sion !onding, howe9er, ses metal :oil instead o: 5owder. Alternate layers o: metal :oil and :i!res are 5ressed whilst !eing heated so

that s ::icient di:: sion and grain growth occ rs across the metal= metal inter:aces to !ond the :oils together. )echanical Properties of Fi*re1reinforced Composites 1' 5 A com5osite made !y sim5le 5 ltr sion as descri!ed a!o9e will !e e<tremely anisotro5ic with regard to its mechanical 5ro5erties. (n :act its strength meas red trans9ersely to the direction o: 5 ltr sion may !e only 0 to 1R o: that meas red longit dinally, i.e. along the direction o: the :i!res. (n most cases the trans9erse strength o: the com5osite is less than that o: the matri< resin d e to the 5resence o: 9oids and wea8 inter:acial !onds. Ne9ertheless we m st not :orget that many o: these :i!re= rein:orced com5osites o::er higher 9al es in terms o: s5eci:ic strength and s5eci:ic mod l s than can !e :o nd in any other materials. ,his a!o9e all ma8es them 5re=eminently se: l in the aeros5ace ind stries where engineering design is s ::iciently so5histicated to accommodate the distincti9e characteristics o: these materials. (n mo lding or casting single com5onents it is 5ossi!le to arrange :i!re direction !y the 5lacement o: a :i!re 5re=:orm in the die or mo ld so that e<5ected stresses are catered :or. ,a!le $1./ indicates 9al es :or ni=directional :i!re=rein:orced com5osites and altho gh ? oted strengths and sti::ness o: com5osites are not 9ery di::erent :rom those o: metals, their relati9e densities are m ch lower. Hence these com5osites ha9e greatly im5ro9ed s5eci:ic 5ro5erties. ,he weight sa9ings o!tained in 5ractice are n:et so great as ,a!le $1./ might s ggest !eca se :i!re com5osites are anisotro5ic and this m st !e allowed :or in design. Ne9ertheless sa9ings in weight o: some /4R are achie9ed o9er al mini m alloys.

Hses of Fi*re1reinforced Composites

,he most im5ortant o: these commercially are 5olymer matri< com5osites rein:orced with either glassk car!on or aramid :i!res, and o: these !y :ar the greatest 9ol me consists o: ER+ 5rinci5ally !eca se o: their relati9ely lower cost.

Many commercial airliners :ly with some 5arts o: their 5rimary str ct re and a large 5ro5ortion o: the interior :ittings and trim made :rom s ch com5ositesM whilst s5orting and leis re goods= !oats, gliders, sail!oards, rac? ets and s8is=are made largely :rom :i!re=rein:orced com5osites. Domestically, most 5lastics=!odied a55liances se rein:orcement in the :orm C o: short, cho55ed :i!res incor5orated d ring mo lding o: the 5rod ct. 1' 7 1 ,he :ollowing characteristics o: com5osites dictate their sesD (i) low relati9e density and hence high s5eci:ic strength and mod l s o: elasticityM (ii) good resistance to corrosion in man). en9ironmentsM (iii) good :atig e resistance, 5artic larly along the :i!re directionM (i9) the 5ossi!ility o: economising on material ! l8 !y designing to ma8e se o: the anisotro5ic 5ro5ertiesM (9) the a!ility to red ce 5rod ction costs !y B5arts integrationB, e.g. !y sing a Bone=shotB mo lding instead o: the assem!ly o: se9eral se5arate 5artsM (9i) the generally low thermal e<5ansionk 5artic larly with car!on or aramid :i!res. 1' 7 # ,he ! ilding o: non=magnetic ER+ mine swee5ers was mentioned earlier ! t on a more general scale this low density , corrosion=resistant com5osite has re9ol tionised the leis re and small wor8 !oat=! ilding ind stries !eca se o: its a!ility to mass 5rod ce com5lete h ll and dec8 mo ldings. Similarly in the ! ilding ind stry mo ldings o: decorati9e te<t re and colo r are sed in cladding 5restige ! ildings whilst ER+ :lat and corr gated transl cent sheetings are sed :or roo:ing.

1' 7 $ -arge ? antities o: ER+ are sed in land trans5ort 9ehicles !eca se o: economies in man :act ring where a55ro5riate., and also in the lower : el costs which res lt. (n motor car man :act re the se o: :i!re=rein:orced 5lastics is growing steadily in the :orm o: 5anels, ! m5ers and interior :ittingsM whilst lea: s5rings made in ER+ ha9e e<cellent :atig e 5ro5erties, o::ering a large sa9ing in weight and also a decrease in noise transmitted to the dri9ing seat. E=glass, the most common ty5e o: glass :i!re sed :or rein:orcement wor8, was originally de9elo5ed as an electrical ins lation material. Hence it is not s r5rising that, when com!ined with 5olymer resins, a gro 5 o: com5osites is a9aila!le which can !e mo lded into com5le< sha5es 5ossessing e<cellent ins lating 5ro5erties. Switch casings, ca!le and distri! tion ca!inets, 3 nction !o<es, etc. are 5rod ced in ER+. Similarly in terms o: corrosion resistance these materials are s ita!le :or se in the chemical ind stries :or storing 5otentially aggressi9e chemicals as well as in 9ats, silos, wine 9ats and 5i5elines :or water and sewage. (n more so5histicated a55lications where ma<im m s5eci:ic strength and s5eci:ic mod l s are re? ired then 5lastics material rein:orced with either car!on :i!re or aramid :i!re is sed. Aeros5ace and military aircra:t design s ally em5loy car!on :i!re=rein:orced 5lastics (C#R+), whilst most helico5ter !lades are o: this material. (n the leis re ind stries some o: the ad9anced materials de9elo5ed :or aeros5ace ha9e !een sed to 5rod ce strong rigid h lls in racing yachts, whilst on land many racing cars em5loy a com5osite chassis consisting o: C#R+ s8ins !onded to a honeycom! core.

Concrete Prod"cts Reinforced ,ith Steel

1' 1; ;hilst 5lain concrete ($..6.>) has a reasona!ly high com5ressi9e strength it is wea8 in tension. ,his disad9antage can !e o9ercome :or some 5 r5oses !y rein:orcement with steel rods or

ca!les the 5rod ct then !earing similarity with other :i!re= rein:orced com5osites. 1' 1; 1 Reinforced Concrete Most ceramic materials are relati9ely strong in com5ression ! t relati9ely wea8 in tension and concrete is no e<ce5tion to this r le. #or str ct ral mem!ers s ch as !eams the se o: an ade? ate section o: 5lain concrete wo ld !e neconomic and o:ten ns ita!ly c m!ersome (#ig. $1.$4(ii)). By sing steel rein:orcement rods (#ig. $1.$4(iii)) in that 5art o: the !eam which will !e in tension, : ll ad9antage can !e ta8en o: the high com5ressi9e strength o: the concrete and the cross=section red ced accordingly. ,he ends o: the rods are so sha5ed that they are :irmly gri55ed !y the rigid concrete. 1' 1; # +re=stressed Concrete A so rce o: wea8ness in rein:orced con= crete is indicated in #ig. $1.$4(iii) which shows the :ormation o: small crac8s in the concrete on that side o: the !eam which is in tension. Since steel has a m ch greater elasticity than concrete the steel rods will still !e stretching within their elastic limit when the concrete has already !eg n to crac8. ,he 5resence o: small crac8s which a!sor! moist re wo ld lead to

com5ressi9e :orces on the concrete. Ass ming that the ca!le is in the correct 5osition relati9e to the cross=section o: the !eam these com5ressi9e :orces in the concrete will e<actly !alance the tensile :orces ca sed !y the load a55lied to the !eam d ring ser9ice (#ig. $1.$$(iii)). Since there is no res ltant tension in the concrete crac8s will not de9elo5 in it. ,his method o!9io sly de5ends 5on the :ormation o: a good concrete2steel !ond witho t which the steel mem!ers wo ld tend to sli5 thro gh the concrete when the e<ternal tensioning :orce was released. Bonding !etween steel and concrete is not o: a chemical nat re ! t is more li8ely to !e d e to s r:ace irreg larities in the rein:orcement steel. ,his !onding is im5ro9ed !y a thin layer o: r st on the steel and assisted !y the shrin8age o: the concrete which occ rs d ring hardening.

1( The Fail"re of )aterials in Stress

1( 1 Engineering com5onents m st in most Cases !e designed in s ch a manner that any stresses in9ol9ed d ring ser9ice are ins ::icient to gi9e rise to 5lastic de:ormation. ;hile in tensile or com5ressi!le tests the s5ecimen is s !3ected only to ni=a<rial stress, that is, stress in one direction, in 5ractice a m lti=a<ial stress system m st !e allowed :or. Moreo9er, it is not realistic to se the sim5le yield stress as the criterion in engineering design and 5ractical engineers ha9e long !een in the ha!it o: sing a s ita!le :actor o: sa:ely, ( in order to arri9e at a ma<im m allowa!le stress. Eenerally this ma<im m allowa!le stress is gi9en !y Iield Stress2:, tho gh in some cases the 9al e, Fltimate Stress2:, is sed. Be that as it may, many com5onents which ha9e !een designed s ch that the stresses arising :rom a55lied loads are ins ::icient to lead to 5lastic de:ormation, ne9ertheless :ail in ser9ice. ,here are many ca ses :or s ch :ail re. ,hese are now generally recorded !y designers and are considered, as :ar as is 5ossi!le, in s !se? ent design. Amongst the more im5ortant 5otential ca ses o: :ail re which can !e e<amined ? antitati9ely are !rittleness, cree5, :atig e and the chemical in:l ence o: the en9ironment in which the com5onent is o5erating. ,he :irst three o: these will !e considered

!rie:ly in this cha5ter while the s !3ect o: corrosion is disc ssed in Cha5ter Nineteen. As will !e a55arent :rom a st dy o: Cha5ter #o r. the res lts associated with s ch di::erent tests as the sim5le tensile test and the im5act test are not com5ara!le. ,h s strength m st not !e con: sed with to ghness since the two 9al es are not interrelated. ,he (7od im5act test assesses di::erent 5ro5erties :rom those e<amined in the tensile test which is in any case a relati9ely Blong= timeB method o: loading when com5ared with the im5act test. E9en longer 5eriods o: static loading, 5artic larly at high tem5erat res, may in9ol9e cree5 (or grad al eH$ension) which leads to :ail reM whilst the 5resence o: stresses which are contin ally 9arying in magnit de or direction (tho gh well within the yield stress) may ca se :ail re !y :atig e.

Fract"re
1( # ,he a55lication o: stress to any material will lead to the 5rod ction o: elastic and2or 5lastic strain and i: the stress is increased 5rogressi9ely :ract re will ltimately occ r. ,his :ract re can !e classi:ied as either B!rittleB or Bd ctileB and the mode o: :ract re 5rod ced is go9erned !y the stress at which it occ rs in relation to the elastic25lastic 5ro5erties o: the material (#ig. $6.$). (n the case o: !rittle materials :ail re occ rs ,efore any a55recia!le 5lastic de:ormation can ta8e 5lace !y shear. ,his is ty5i:ied in materials li8e cast iron, glass and concrete. #ract re o: this ty5e=also termed Bclea9age :ract reB=:ollows 5aths !etween ad3acent crystallogra5hic 5lanes which are generally those with the wea8est atomic !onding. (n addition to the materials entioned, clea9age :ract re is 5re9alent in all metals with BCC and C+H str ct res ather than in those which are #CC. Brittle :ract res generally a55ear !right and Bgran larB !eca se o: the re:lection o: light :rom the sections o: indi9id al crystals. D ctile :ract re ta8es 5lace at some stress a!o9e the shear strength o: the material so that some 5lastic :low 5recedes :ract re. As the nec8 !egins to :orm (#ig. $6.$ (ii)) the stress within the nec8ed region o!9io sly increases and reaches a le9el where small ca9ities !egin to 5ro5agate in the central region o: the section. S ch Ca9ities will n cleate more easily i: a second 5hase or 5articles o: some im5 rity, are 5resent :or which reason 9ery 5 re metals are more d ctile than im5 re ones. ,he ca9ities which ha9e :ormed 3oin 5 to :orm a crac8 which is ro ghly normal to the a<is o: stress o: the test 5iece. #inal :ract re then occ rs !y sim5le shear at an angle o: .1Z to the a<is o: stress. shear stress !eing at a ma<im m in this direction. ,he res ltant :ract re is o: the well= 8nown c 5=and=cone 9ariety and occ rs 5artic larly in #CC metals.

,he ty5e o: :ract re 5rod ced is de5endent mainly on the nat re o: the material and in 5artic lar on its lattice str ct re. (t is also a::ected !y other :actors s ch as the condition o: the material in res5ect o: the amo nt o: cold=wor8 it may ha9e recei9edM the ? ality o: its s r:ace :inishM its en9ironment and tem5erat reD and the rate o: a55lication o: stress. ,he latter :actor is ill strated !y the !eha9ior o: a material in a sim5le tensile test as com5ared with its !eha9ior d ring the (7od test where im5act loading allows ins ::icient time :or the ade? ate mo9ement o: dislocations to ta8e 5lace. so that !rittle :ail re tends to res lt nder some circ mstances. 1( # 1 6riffithMs Crack Theor& ,he :act that the real strength o: a metal is ! t a 9ery[ small :raction or the theoretica$ 9al e (deri9ed :rom a 8nowledge o: inter=atomic :orces) has already !een noted

(1.0./). ,his has !een e<5lained in terms o: the mo9ement o: dislocations the theory o: which was de9elo5ed more than hal: a cent ry ago. Ne9ertheless the :ract re o: !rittle materials was st died a decade or so earlier !y A. A. Eri::ith who, in $%04 s ggested that in any !rittle non=metallic s !stance s ch as glass min te crac8s or :iss res, 5artic larly occ rring at the s r:ace, act as stress raisers !y concentrating stresses at their ti5s. ,his is a conce5t 9ery :amiliar to engineers.

,he conce5t o: Bs r:ace energyB is 5erha5s !est nderstood i: we imagine a !loc8 o: 5lastics material c t into two. ,he chemical !onds which :ormerly crossed the !o ndary !etween the two 5ieces o: material will now trans:er their :orces to atoms within each o: the newly created s r:aces. ,he res lt o: these atomic :orces acting amongst themsel9es along the s r:ace constit tes the s r:ace energy. (n :act s r:ace energy is e? i9alent to the wor8 done when !onds are !ro8en d ring the 5rocess o: creating new s r:aces. Another mani:estation o: s r:ace energy is in the s r:ace tension o: li? ids. Elo! les o: B? ic8sil9erB (Hg) are almost 5er:ectly s5herical in :orm, the :orces acting along the s r:ace o:

the metal !eing so great that the ma<im m 9ol me o: metal is contained within the minim m area o: s r:ace=a s5here. ,o s !di9ide a glo! le re? ires some de<terity since to 5rod ce e<tra new s r:aces re? ires an in5 t o: energy. Similarly when a crac8 is 5rod ced in a !rittle solid new :ree s r:aces are generated and energy m st !e s 55lied to achie9e this, :or e<am5le, in the :orm o: strain energy. ,h s as soon as the a55lied stress reaches the 9al e 4[, small crac8s 5resent can !egin to 5ro5agate. As a increases 4[ m st decrease and this can only !e achie9ed !y the ra5id s5read o: crac8s ending in catastro5hic :ail re. Eri::ithBs ,heory has !een 9eri:ied e<5erimentally on glasses and !rittle ceramic materials. (n :act 9ery :ine :i!res :reshly drawn :rom a melt ha9e strengths near to the theoretical 9al e. Howe9er i: these :i!res come into contact with any o!3ect, or e9en with the atmos5here :or short 5eriods, these strengths are considera!ly red ced. ,his s ggests that the strength o: the :i!re is 9ery de5endent on s r:ace 5er:ection and that anything which may initiate e9en the most min te s r:ace irreg larities will wea8en it.

1( # # Factors Leading to Crack Formation (t is reasona!le to s 55ose that crac8 initiation in metals occ rs most :re? ently in the 9icinity o: an incl ded 5article. ;hen sli5 in a metal ta8es 5lace 5ast a rigid incl sion dislocations will 5ile 5 near to the incl sion2metal inter:ace. Ass ming that the incl sion itsel: does not shear, a min te :iss res will !egin to de9elo5 at this inter:ace (#ig. $6..). )!9io sly :iss res can de9elo5 most easily when there is little adhesion !etween the incl sion and the metal containing it. ,h s :iss res can :orm more easily at a co55er2c 5ro s o<ide inter:ace than at an al mini m2al mini m o<ide inter:ace since the degree o: adhesion !etween metal and 5articles o: its o<ide is m ch greater in the latter case.

)ther !arriers to the mo9ement o: dislocations can initiate micro= crac8s in this manner. ,h s a grain !o ndary can act as a !arrier to the 5assage o: dislocations so that a 5ile= 5 occ rs and they !ecome so closely 5ac8ed that a micro=crac8 is n cleated. S ch a crac8 grows !y the addition o: : rther dislocations, which mo9e towards it. Crac8 :ormation also ta8es 5lace !y the mo9ement o: dislocations along close=5ac8ed or other sli5 5lanes within a crystal (#ig. $6.1(i)). ,hese dislocations 5ile 5 at the intersection o: the sli5 5lanes and so initiate a micro=crac8 (#ig. $6.1(ii)).

(n some cases the 5resence o: a discontin ity can arrest the 5ro5agation o: a crac8 !y red cing the stress concentration, which is always 5resent at the ti5 o: a crac8. ,h s the 5ro5agation o: a crac8 in a 5late=glass window can !e sto55ed !y care: lly drilling a hole in :ront o: the ad9ancing crac8. Similarly !rittle :ract re in welded=steel shi5s ($6./) was arrested !y incl ding d mmy ri9et holes to arrest the s5read o: crac8s. Some :i!ro s materials=nota!ly the now=o!solete wro ght iron=are to gh along the direction o: the :i!res !eca se any crac8 :ormed at right angles to the stress will then ha9e to change direction on meeting a :i!re !arrier. (: the inter:ace !etween :i!re and metal is wea8 this can act ally increase the o9erall strength o: the com5osite in the direction of the fi,res. ,he wea8 inter:ace red ces the stress concentration at the crac8 ti5 !eca se the radi s o: the ti5 increases. ,hese e<am5les are go9erned !y the a55ro<imate relationshi5D

i.e. as the crac8=ti5 radi s increases the stress concentration will decrease. 1( # $ Fract"re To"ghness (n all cases o: !rittle :ract re the mechanics o: the 5rocess are similar. Resistance to :ail re is related to the energy which m st !e sed to se5arate 5articles in the region o: the :ract re and here we are 9irt ally descri!ing the s r:ace energy, , o: the material. Catastro5hic :ail re is li8ely to

occ r in metals which contain small crac8s ! t which in other sit ations might de:orm 5lastically !e:ore :ailing. A Bcoarse greyB cast iron consists largely o: d ctile :errite ! t is !rittle !eca se o: the 5resence o: :la8e gra5hite (#ig. $4.$4) which !eha9es as :iss res in so :ar as lac8 o: strength is concerned. ;hen dealing with engineering 5ro!lems it is s al to com!ine with Io ngBs Mod l s in the :ormD

Here *c is 8nown as the fracture toughness or, alternati9ely, as the critical stress intensity factor o: the material and is im5ortant in engineering design. (t is meas red in nits N2ml.1. (: : is the stress necessary to ca se catastro5hic :ail re thenD

where a is one hal: o: the crac8 length (in metres). (n sit ations where a is 9ery small : will !e greater than the yield strength o: the material and some 5lastic de:ormation will occ rs ! t when the crac8 is o: s ch a si7e that :e y then catastro5hic :ail re occ rs, that is, witho t any 5lastic de:ormation. (n hard, !rittle s !stances s ch as ceramics the design strength is determined !y the length o: the micro crac8s 5resent. i.e. i: the longest micro crac8 5resent is o: length 0a then the tensile strength is e? i9alent to ts P ( * a )

-"ctile1*rittle Fract"re and Transition Temperat"re

1( $ Some metals that are to gh and d ctile at am!ient tem5erat res and a!o9e !ecome 9ery !rittle at low tem5erat res.

,he a55earance o: their :ract red s r:aces 9aries accordingly. -ow=car!on steel tends to !ecome increasingly !rittle as s !=7ero tem5erat res are a55roached and it is 5ossi!le that ScottBs $%$0 Antarctic E<5edition wo ld ha9e met a less disastro s end had not !rittle :ail re in the snow tractors in the early stages 5 t the ! rden o: trans5ort solely on horses, dogs and, later, men alone. -ittle serio s attention was 5aid to the 5ro!lems o: !rittle :ract re at low tem5erat res 5rior to the catastro5hic :ail re o: some o: the all= welded B-i!ertyB shi5s d ring the Second ;orld ;ar. Fnder normal circ mstances the stress re? ired to ca se clea9age is higher than that necessary to 5rod ce sli5, ! t i: :or some reason sli5 is s 55ressed, !rittle :ract re will occ r when internal stresses increase to the 9al e necessary to 5rod ce :ail re. ,ri=a<ial stresses acting in the material may !e resid al :rom some 5re9io s treatments and the 5resence o: 5oints o: stress concentration may aggra9ate theB sit ation. ,he B-i!ertyB shi5s, mentioned a!o9e, were :a!ricated !y welding together steel 5lates to :orm a contin o s h ll. Crac8s o:ten, tho gh not always, started at shar5 comers or arc=weld s5ots and 5ro5agated right ro nd the h ll so that the shi5 !ro8e in hal:. A com5letely welded str ct re s ch as a shi5 or a large 5ress re 9essel is in tr th a single contin o s 5iece o: metal and so the ninterr 5ted 5ro5agation o: these crac8s was 9ery ra5id. Similar :ail re does not occ r in ri9eted shi5s !eca se any crac8, which !egins to r n, will terminate in the :irst ri9et hole it reaches. As mentioned a!o9e ($6.0.0.)D Stress concentration at a crac8 P and since the crac8=ti5 radi s has !een re5laced !y the radi s o: the ri9et hole, which is e<tremely large !y com5arison, the stress concentration at the hole decreases almost to 7ero. ,ho gh !rittle :ract re o:ten starts at some o!9io s :a lt, which acts as a stress=raiser this is not always the case and it seems li8ely that one or more o: a n m!er o: 5ossi!le contri! tory ca ses

lead to this ty5e o: :ail re. (t seems li8ely, howe9er, that sl ggishness in the mo9ement o: dislocations at low tem5erat res is common to all cases o: !rittle :ail res. +lastic :low de5ends 5on the mo9ement o: dislocations and this re? ires some :inite time. (: stress increases 9ery ra5idly, it is 5ossi!le that it cannot !e relie9ed ade? ately !y sli5 and a momentary increase in stress to a 9al e a!o9e the shear strength can ca se :ail re. As tem5erat re decreases, the mo9ement o: dislocations !ecomes more di::ic lt so that internal stresses may e<ceed the shear strength at some instant. Brittle :ract re is there:ore more common at low tem5erat res, a :act s 55orted !y the :ail re o: the A-i!erty@ shi5s d ring ser9ice in the cold North Atlantic where high mechanical stresses d e to ro gh weather com!ined with the e::ects o: low tem5erat re. (n some instances, howe9er, these shi5s !ro8e 5 whilst in doc8, the early morning s n ha9ing warmed the dec8 and so generated thermal stress. S ch catastro5hic :ract re mo9ed at a s5eed o: 0 8m2s. 1( $ 1 Metals with #CC str ct res are generally more d ctile than those with either BCC or C+H str ct res !eca se o: the greater n m!er o: a9aila!le sli5 directions associated with the #CC str ct re (1.0.$). At low tem5erat res this !ecomes e9en more a55arent so that BCC metals li8e ;, Mo, Cr, N!, ,a and o: co rse #e all e<hi!it low tem5erat re !rittleness as do C+H metals li8e On and Be. BCC :errite, the 5rinci5al constit ent o: low=car!on steels, is 5artic larly s sce5ti!le to !rittle :ract re, which :ollows a transcrystalline 5ath along the ($44) 5lanes. As indicated in #ig. $6.6 this occ rs at a low tem5erat re and the tem5erat re at which d ctile :ract re is re5laced !y !rittle :ract re is termed the transition tem5erat re. Howe9er, as #ig. $6.6 shows the com5lete d ctileX !rittle trans:ormation ta8es 5lace o9er a range o: tem5erat res rather than at a single tem5erat re and it is more satis:actory to determine some tem5erat re at which, say, 14R o: the :ailed s r:ace e<hi!its a d ctile :ract re with the remaining 14R showing !rittle :ract re. Alternati9ely, the tem5erat re

corres5onding to some ar!itrary 9al e o: K(Char5y) can !e 3 dged as coinciding with the transition tem5erat re. (n #ig. $6.6 a notional 9al e o: 04 K has !een ta8en and this wo ld coincide with a re5resentati9e transition tem5erat re o: y$.4 C. Some elements, nota!ly 5hos5hor s, car!on and nitrogen raise the transition tem5erat re in mild steel :or which reason 5lates sed in the ! ilding o: shi5sB h lls m st !e low in 5hos5hor s. )ther elements, ! t in 5artic lar manganese and nic8el, de5ress the transition tem5erat re o: mild steel. ,h s, the least e<5ensi9e way o: red cing its transition tem5erat re is to increase the manganese2 car!on ratio. S ita!le steel, in which the transition tem5erat re has !een red ced to a sa:e low limit, contains 4.$.R C and $./R Mn. ;hen lower tem5erat res are in9ol9ed low=nic8el steel m st !e sed.

Creep
1( % ACree5@ descri!es the contin ing slow de:ormation with 5assage o: time in materials s !3ected to steady 5ersistent stress. ,his de:ormation is 5lastic and occ rs e9en tho gh the acting stress is !elow the yield stress o: the material. At tem5erat res !elow 4.. ,m (on the *el9in scale) the rate o: cree5 is 9ery small ! t at tem5erat res higher than this it !ecomes increasingly im5ortant. #or this reason cree5 is commonly regarded as !eing a high tem5erat re 5henomenon associated with steam 5lant and gas t r!ine technology. Ne9ertheless with some o: the so:t, low= melting 5oint metals and alloys cree5 will occ r signi:icantly at am!ient tem5erat res. (t has !een re5orted that some ancient lead roo:s are meas ra!ly thic8er at the ea9es than at the a5e<, the lead ha9ing cre5t o9er the cent ries e9en nder its own weight. Cree5 in 5olymer materials !elow ,g :ollows ro ghly the same 5attern as it does in metals ($0.1.6). 1( % 1 ;hen a metal is s ita!ly stressed it ndergoes an instantaneo s elastic de:ormation (#ig. $6.>) ! t this is :ollowed

!y a relati9ely low rate o: 5lastic strain which is !oth time and tem5erat re de5endent as well as !eing de5endent 5on the a55lied stress. ,his 5lastic strain occ rs in three distinct stages (#ig. $6.>)D (i) 5rimary, or transient, cree5, )+, !eginning at a :airly ra5id rate which then decreases with time as strain hardening sets inM (ii) secondary or steady=state cree5, +S, in which the= rate o: strain is ni:orm and at its lowest 9al e. (n this stage the rate o: wor8 hardening is !alanced !y the rate o: reco9ery.

P Ct ($) where t is the time and E the res ltant strain d e to cree5. ,he cree5 rate, d2dt P C, where C is a constant :or a gi9en set o: conditions o: tem5erat re and stress and is e? i9alent to the slo5e o: the section +S o: the cree5 c r9e. C will 9ary with !oth tem5erat re and a55lied stress since reco9ery 5rocesses are !oth tem5erat re and stress de5endent. ,em5erat re de5endence is a conse? ence o: the di:: sion o: dislocations ca sed !y thermal acti9ation and can there:ore !e re5resented !y an Arrheni s=ty5e e? ationD

tertiary cree5, SH, in which the rate o: strain increases ra5idly so that :ract re occ rs at H. ,his stage coincides with the :ormation o: micro crac8s at crystal !o ndaries :ollowed !y nec8ing and ra5id :ail re.

where d2dt is the secondary cree5 rate. H is the acti9ation energy :or cree5, R is the ni9ersal gas constant. , is the a!sol te tem5erat re and A is a constant. ,he secondary cree5 rate also increases with increase o: stress, the relationshi5 !eing generally e<5ressed !yD

where and n are constants, n s ally 9arying !etween / and & :or metals and !etween $ and 0 :or 5olymer materials. E<5ressions (0) and (/) can !e com!ined to gi9eD

(iii) tertiary cree5,SH in which the rate o: strain increases ra5idly so that :ract re occ rs at H. ,his stage coincides with the :ormation o: microcrac8s at crystal !o ndaries :ollowed !y nec8ing and ra5id :ail re

#ig. $6.& 'ariation o: cree5 rates with stress and tem5erat re. (n c r9e A cree5 ltimately !ecomes negligi!le, d e 5res ma!ly to wor8 hardening. (n c r9e C the secondary cree5 rate is higher than in c r9e B !eca se o: the se o: a higher stress and2or a high tem5erat re.

,he relationshi5s !etween stress tem5erat re and the res ltant rate o: cree5 descri!ed a!o9e are ill strated in #ig. $6.&. At a low stress and2 or a low tem5erat re some 5rimary cree5 may occ r ! t this :alls to a negligi!le 9al e in the secondary stage d e 5res ma!ly to strain hardening o: the material. ;ith increased stresses and2or tem5erat res (c r9es B and C) the rate o: secondary cree5 also increases leading to tertiary cree5 and ine9ita!le :ail re. ,his set o: c r9es (#ig. $6.&) relates the increase in strain with timeM whilst tem5erat re and stress are maintained at :i<ed 9al es. Cree5 data may also !e 5resented in other :orms. #or e<am5le, isometric stress2strain diagrams can !e 5lotted (#ig. $6.%(i)) in which stress, strain and time are related :or some single material H at a single :i<ed tem5erat re ,. Alternati9ely 9al es o: time, stress and tem5erat re may !e related to some :i<ed s5eci:ic 9al e o: strain in what are termed isochrono s c r9es (#ig. $6.%(ii)). 1( % # (n cree5 testing a test 5iece in :orm similar to a tensile=test 5iece, is enclosed in a thermostatically controlled electric t !e

: rnace which can !e maintained acc rately o9er long 5eriods at the re? ired tem5erat re.

A s ita!le tensile :orce is a55lied and the e<tension o: the test 5iece determined at s ita!le time inter9als !y means o: some :orm o: sensiti9e e<tensometer. Eenerally a set o: identical test 5ieces will !e tested at the same tem5erat re ! t at di::erent stresses and :rom a st dy o: the res lts it will !e 5ossi!le to arri9e at a ma<im m stress which can !e a55lied and which will res lt in no meas ra!le cree5 ta8ing 5lace. ,his stress is 8nown as the limiting cree5 stress or cree5 limit. )!9io sly this is not a 9ery satis:actory meas rement since it is de5endent largely 5on the sensiti9ity o: the e<tensometer e? i5ment. Moreo9er, :ormal cree5 tests can occ 5y long 5eriods o: time r nning into wee8s or months de5ending 5on the com!ination o: stress and tem5erat re in9ol9ed and s ch tests are conse? ently 9ery e<5ensi9e to carry o t. #or reason s ch as these, it is generally more satis:actory to se some :orm o: short=term test and then deri9e acce5ta!le and sa!le in:ormation !y e<tra5olation. S ch in:ormation may not always 5redict when the tertiary or catastro5hic stage o: cree5 is li8ely to !e reached and to deal with s ch a sit ation some a thorities ha9e 5ro5osed methods which in9ol9e accelerated cree5 tests in which a higher test tem5erat re is sed than will !e e<5erienced in ser9ice,

the material !eing tested to r 5t re at this higher tem5erat re. ;hen :ract re=o:ten re:erred to as cree5 r 5t re=is s5eci:ied then material selection wo ld in9ol9e e<tra5olation o: cree5=r 5t re time with tem5erat re and with stress. ,hese higher tem5erat re res lts are then sed to 5redict the rate o: cree5 o9er a long ser9ice li:e at a lower tem5erat re. )ne o: the !est=8nown methods is that o: -arson and Miller and is !ased on the Arrheni s e? ation, modi:ication o: which gi9esD logl4.trW C P or
m T

,(logl4.tr W C) P m

where tr P cree5 r 5t re time, , P tem5erat re (*) and m P a : nction o: stress which can !e written asD + P :() + !eing the -arson=Miller 5arameter + P ,(logl4.tr W C) C is a constant the 9al e o: which is determined !y 5lotting log $4.tr against l2, and meas ring the interce5t with the a<is. By cond cting a cree5 test sing certain 9al es o: stress and tem5erat re the 9al e o: tr can !e determined. (: this is re5eated with other sets o: 9al es o: stress and tem5erat re the res lts can !e 5lotted on a master c r9e (#ig. $6.$4). ,he 9al e o: 5arameter + holds good :or a wide range o: com!inations o: tr and ,, i.e. !etween short time=high tem5erat re (test conditions) and long time=low tem5erat re (ser9ice conditions). A n m!er o: other 5arameters, de9ised !y other wor8ers ! t similar in methods o: a55lication, are also in se.

1( % $ The )echanism of Creep Early st dy o: the nat re o: cree5 showed that metals o: small grain si7e where more 5rone to cree5 than were those o: coarse grain si7e o: similar com5osition and when tested nder conditions o: similar tem5erat re and stress. E<5eriment show that cree5 rate is 5ro5ortional to $2d0 where d is the a9erage grain diameter o: the metal or alloy. ,his led to the realisation that cree5 is a 5henomenon associated largely with the grain !o ndary regions since :ine=grained metals contain a greater 5ro5ortion o: grain !o ndary material 5er nit 9ol me than do coarse=grained metals. Moreo9er at low tem5erat res the grain= !o ndary material is harder and stronger than the material away :rom the !o ndaries ! t at high tem5erat res the 5osition is re9ersed and the grain !o ndaries !ecome wea8er. At some intermediate tem5erat re=a55ro5riately called the e? i=cohesi9e tem5erat re=!oth grain !o ndary and crystal core are e? ally strong. S ch a tem5erat re is di::ic lt to meas re and is o: little conse? ence in 5ractice. (t is s ggested that cree5 in9ol9es two se5arate modes o: 5lastic de:ormationD (i) that d e to the normal migration o: dislocations which occ rs in crystalline materialsM (ii) that which is o: a 9isco s character and is associated with sliding in the non=crystalline grain !o ndary regions. (n the 5rimary stage o: cree5 dislocation mo9ements are initially ra5id and 9ario s !arriers s ch as sol te atoms are easily o9ercome. New !arriers are introd ced as dislocation 5ile= 5s

occ r at grain !o ndaries and elsewhere ! t thermal acti9ation ena!les dislocations to s rmo nt s ch !arriers, tho gh at a decreasing rate. so that the cree5 rate is red ced. ,h s, as de:ormation contin es. so does wor8=hardening, ! t since the tem5erat re is high, reco9ery 5rocesses are also acti9ely assisted !y dislocation clim! (1.&) and cross=sli5 which is in the motion o: a dislocation :rom one sli5 5lane into another intersecting 5lane. Both o: these dislocation motions will o55ose wor8 hardening. Hence cree5 is essentially a 5rocess in which wor8=hardening is !alanced !y thermal so:tening. At low tem5erat res (c r9e A in #ig. $6.&) reco9ery does not ta8e 5lace and so nrelie9ed wor8= hardening leads to a red ction o: the cree5 rate 9irt ally to 7ero. D ring the secondary cree5 stage the :act that wor8= hardening and reco9ery a55arently !alance each other gi9es rise to a constant rate o: de:ormation !y cree5. (t is generally !elie9ed that the clim! o: edge dislocations is the 5rocess which controls the rate o: cree5 in this stage since it re? ires the higher acti9ation energy. )ther 5henomena s ch as the annihilation o: dislocations (1.../) will also assist the mo9ement o: other dislocations and restore the steady cree5 rate as the second stage 5roceeds. ,he tertiary stage o: cree5 coincides with the initiation o: micro=crac8s at grain !o ndaries. Some o: these may :orm as the res lt o: migration o: 9acancies so that they coalesce at 5oints o: high stress concentration. )ther 9oids may !e generated !y =grain !o ndary sliding (#ig. $6.$0) ! t !y whiche9er method these micro=crac8s are :ormed they will lead to nec8ing and the conse? ent ra5id :ail re o: the mem!er.

( % % Creep Resistance Beca se cree5 rate is low at tem5erat res !elow 4.. , m it :ollows that metals with high melting 5oint are li8ely to !e se: l where high cree5 resistance is re? ired. Fn:ort nately many s ch metals :or e<am5le, t ngsten (, m P //&4ZC)are not only e<5ensi9e ! t, !eca se o: the 9ery Bsti::nessB which contri! tes to their desira!le cree5 resistance, also di::ic lt to :a!ricate. Close 5ac8ing o: the atoms in a metallic str ct re im5edes the mo9ement o: dislocations and in conse? ence #CC and C+H str ct res tend to !e more resistant to cree5 than do BCC str ct res. ,h s nic8el (, m P $.1/ZCM #CC) and co!alt (, m P $.%0ZCM C+H #CC), !oth metals o: intermediate 9al es o: , m, are 9ery se: l in terms o: their cree5 resistant 5ro5erties. Since cree5 ta8es 5lace !y the mo9ement o: dislocations and !y grain=!o ndary sliding, cree5 resistance will !e increased i: ste5s are ta8en to B5egB dislocations in order to limit their mo9ement and also to render grain !o ndary sliding more di::ic lt. Cree5 resistance is there:ore im5ro9ed in the :ollowing waysD (i) !y the addition o: alloying elements which :orm a solid sol tion with the 5arent metal. ,his will only !e e::ecti9e i: the sol te atoms ha9e a low mo!ility. (: on the other hand they di:: se :reely with thermal acti9ation, they will also allow dislocations to tra9el so that reco9eryand hence : rther cree5can 5roceed. Eenerally the greater the di::erence in si7e !etween sol9ent and sol te atoms the greater the resistance to dislocation mo9ement, ! t this is also li8ely to limit the e<tent o: sol !ility. Ne9ertheless the addition o: large amo nts o: alloying elements will 5ro!a!ly lower the melting range o: the alloy to the e<tent that it will !e seless :or high=tem5erat re a55licationsM (ii) !y the incl sion o: alloying elements which will gi9e rise to dis5ersion hardening. Coherent and small non=coherent 5reci5itates are generally 5rod ced !y 5reci5itation treatment and it is essential that at the ser9ice tem5erat re
.44 C

(iii)

s ch 5articles sho ld remain :inely dis5ersed and not coag late. #inely dis5ersed 5reci5itates :orm e::ecti9e !arriers to the mo9ement o: dislocations, as in the Nimonic series o: alloys ($$.1.0) and other alloys containing :inely dis5ersed car!ides and o<ides. Here it is the small=dis5ersed 5articles which act as !arriers to grain= !o ndary sliding and also to the mo9ement o: dislocations ($..$.1). Dislocations can only Bcirc mna9igateB s ch !arriers i: hel5ed !y a degree o: di:: sion assistance, so that metals with a low rate o: sel: di:: sion are s 5erior in cree5 resistanceM !y the 5romotion o: a large grain si7e where this is a55ro5riate. ,his red ces the 5ro5ortion o: grain=!o ndary material 5er nit 9ol me, which, in t rn, limits the :ormation o: 9acancies and the density o: grain=!o ndary slide. Since cree5 is a 5henomenon associated with grain !o ndaries it wo ld seem desira!le to get rid o: them com5letelyG (n :act this has !een achie9ed with the high= tem5erat re cree5=resistant t r!ine !lades o: some 3et engines s ch as the :amo s RB0$$=these com5onents !eing care: lly grown as single crystals.

Fatig"e
1( ' +racticing engineers ha9e long !een aware that Bli9eB loads and alternating stresses o: relati9ely small magnit de can ca se :ail re in a mem!er which co ld carry a m ch greater Adead@ load. Fnder the action o: changing stresses a material may !ecome :atig ed. So, whilst cree5 is a 5henomenon associated with e<tension nder steady :orce acting :or a long 5eriod, :atig e re:ers to the :ail re o: material nder re5eated :l ct ating stresses. 1( ' 1 Early in9estigation into :atig e was carried o t in $&6$ !y Sir ;illiam #air!airn. He :o nd that a wro ght=iron girder which

co ld sa:ely s stain a static mass o: $0 tonnes, ne9ertheless !ro8e i: a mass o: only / tonnes was raised and lowered on to it some / < $46times. #rom : rther in9estigation he concl ded that there was some mass !elow / tonnes which co ld !e raised and lowered an in:inite n m!er o: times on to the girder witho t ca sing :ail re. Some years later the Eerman engineer ; Ihler did : rther wor8 in this direction and de9elo5ed the se: l :atig e=testing machine which !ears his name. 1( ' # Many :ormal :atig e=testing machines are !ased on the original ;zhler design. Here a standard test 5iece is rotated at high s5eed and carries at its end, cantile9er :ashion. a load transmitted !y a !all=race

system (#ig. $6.$.). ;ith each re9ol tion o: the test 5iece the am5lit de o: the stress 5asses :rom a in one direction to a in the o55osite direction so that the stress range is 0a whilst the mean stress is 7ero. ,esting is carried o t ntil the test 5iece :ails or withstands an Bin:initeB n m!er o: re9ersals o: stress= s ally 04 H $46 in 5ractice since an Bin:inite n m!erB wo ld ta8e too long a timeG ,he n m!er o: re9ersals end red is recorded. ,his 5roced re is re5eated :or a series o: a55lied loads a55lied to similar test 5ieces and the res ltant stresses, a 5lotted 9ers s the n m!er o: re9ersals, N, s stained

gi9ing what is s ally termed a S=N c r9e (#ig. $6.$1). #or many steels the c r9e le9els o t at a hori7ontal asym5tote (i) indicating that at any stress !elow D the material will not :ail !y :atig re no matter how many re9ersals o: stress are a55lied. ,he 9al e D is called the :atig e limit o: the material. Many non=:erro s metals and alloys, and also some steels o5erating nder corrosi9e conditions, gi9e S=N c r9es o: the ty5e shown in #ig. $6.$1(ii). Here there is no :atig e limit as s ch and any mem!er will :ail i: it is s !3ected to the a55ro5riate n m!er o: stress re9ersals e9en at e<tremely small stresses. (n the case o: these materials

which show no :atig e limit an end rance limit, SN, is ? oted instead. ,his is de:ined as the ma<im m stress which can !e s stained :or N cycles o: stress. Com5onents in materials o: this ty5e m st o: co rse !e designed with some s5eci:ic li:e in mind and B3 n8edB, as Americans so descri5ti9ely 5 t it, !e:ore the n m!er o: cycles N (:or stress SN ) has !een attained.

1( ' $ Many :atig e testing machines are o: the ;zhler ty5e since it o::ers a sim5le and ra5id means o: testing, Howe9er, other :orms o: testing machine are in se in which stress can !e a55lied in a more a55ro5riate :ashion, :or e<am5leD (i) in which a 5 sh=5 ll :orce is a55lied a<iallyM (ii) in which the test 5iece is stressed torsionally !y alternating tor? eM (iii) in which re9ersed !ending is a55lied to a test 5iece o: rectang lar cross=section !y an alternating !ending moment. (n some cases a s5ecialised test 5roced re has to !e de9elo5ed as in the :atig e testing o: com5lete aircra:t :rames. 1( ' % ,he ;zhler :orm o: test ses a system o: loading in which the stress am5lit de is a ! t the mean stress m is 7ero (#ig. $6.$6(i)).

Fig 1( 1(

(n 5ractical engineering this will rarely !e the case and whilst the am5lit de o: the a55lied stress may well !e a, the mean stress is not 7ero (#ig.$6.$6(ii)). E<5eriments show that as m increases the :atig re li:e o: a metal decreases and so it has !ecome necessary to de9ise modi:ications which ta8e into acco nt the e::ects o: tensile mean stress, m, in order to ada5t res lts o: the ;zhler test :or F=BC in engineering 5ractice A n m!er o: em5irical e? ations named a:ter their originators are a9aila!le in order to relate a and m, with t the tensile

strength, y the yield strength and D the :atig e limit (or N the end rance limit where a55lica!le). ,he most 5o5 lar o: these e? ations areD a P D b$=(m 2t ) c a P D b$=(m 2y ) c a P D b$=(m 2t )0 c Eoodman Soder!erg Eer!er

,he e? ations can !e re5resented in gra5hical :orm (#ig. $6.$>). Re:erring to the Eoodman e? ation (#ig. $6.$>(i)) any 5oint re5resenting the wor8ing conditions in terms o: a and m which :alls !elow the line connecting D and t (i.e. within the hatched area) indicates that :ail re will not occ r d e to :atig e. Similarly 5oints !elow e? i9alent lines re5resenting the Eer!er and Soder!erg e? ations (#ig. $6.$>(ii)) will also indicate sa:e wor8ing conditions with res5ect to those e? ationsM th s Eer!er gi9es the most o5timistic :orecast. (t is :o nd that the greater 5ro5ortion o: :atig e test res lts :all within the area !etween the two lines re5resenting the Eoodman and Eer!er e? ations (#ig. $6.$>(ii)). Ne9ertheless the Soder!erg e? ation is 9ery 5o5 lar !eca se it o::ers a greater margin o: sa:ety, wor8ing as it does on stresses !elow the yield

stress, y. ,his margin is o:ten increased still : rther !y a55lying a :actor o: sa:ety, #, to !oth the alternating stress a, and to the mean stress m, so that the Soder!erg e? ation !ecomesD

1( ' ' C"m"lative -amage ,he e::ects o: :atig e are c m lati9e and it is di::ic lt to 5redict the :atig e li:e o: com5onents which wor8 nder 9arying conditions o: stress. #or e<am5le, the :light o: an aircra:t thro gh stormy weather will res lt in a greater red ction in its :atig e li:e than a similar :light in calm conditions. ,he

assessment o: s ch damage !ecomes 5artic larly im5ortant when we are dealing with materials in which the :atig e 5ro5erties are meas red !y a :inite end rance limit rather than !y a :atig e limit. 'ario s attem5ts ha9e !een made to assess the :atig e li:e o: com5onents s !3ected to s ch 9aria!le stresses. Many s ch r les are com5le< and 5ossi!ly the sim5lest and most widely sed is 8nown as MinerBs -aw. Miner s ggested that in a com5onent which was !eing :atig ed, c m lati9e internal damage was ta8ing 5lace and that the e<tent o: this internal damage was directly 5ro5ortional to the n m!er o: cycles :or a s5eci:ic stress le9el. ,h s, s 55ose a com5onent ndergoes nl cycles in a cyclic loading sit ation which wo ld lead to :ail re a:ter N$ cycles, then n$2N$ is the 5ro5ortion o: damage which has occ rred. (: the stress am5lit de now changes :or a : rther n0 cycles and at that am5lit de :ail re wo ld ha9e occ rred a:ter N0 cycles then n02N0 is a meas re o: the 5ro5ortion o: damage ca sed d ring that 5eriod. MinerBs -aw states that the com5onent will :ail when the s m o: all these Bcyclic ratiosB e? als nity, i.e.D

(n 5ractice it is :o nd that = yields a 9al e somewhere !etween 4.1 and 0.4 and that this 9al e is go9erned !y the order in which the 9ariations in a are a55lied. ,h s large 9al es o: a :ollowed !y smaller 9al es will gi9e a shorter :atig e li:e than the re9erse sit ation, that is, small 9al es o: a :ollowed !y larger ones.
n

1( ' ( Some Ca"ses of Fatig"e Fail"re ,he :atig e characteristics o: most engineering materials are now well 8nown or can !e meas red with some acc racy. (t wo ld there:ore !e reasona!le to e<5ect that :atig e :ail re wo ld not arise d e to

inade? ate design on the 5art o: the engineerG Iet :atig e :ail re does occ r and s ch :ail re can s ally !e traced toD (i) the action o: n:oreseen :actors in the wor8ing en9ironmentM (ii) s r:ace or s !c taneo s :laws=the 5resence o: either microsco5ical :a lts in the original material or a ro gh s r:ace :inish d e to 5oor machining 5ractice.

As an e<am5le o: the :ormer ( was once called o t to a :actory site to in9estigate the :ail re !y :ract re o: a sto t co55er t !e which had carried, cantile9er :ashion, a small 5ress re ga ge o: ! t a :ew grams in mass. A:ter a :ew daysB ser9ice the t !e had !ro8en=witho t warning. ,he :ract re was o: the characteristic :atig e ty5e and when ( 9isited the scene o: :ail re the reason :or this was immediately a55arent. ,he ga ge had !een attached !y means o: the co55er t !e to an air com5ressor the 9i!rations :rom which co ld !e e<5erienced :rom a distance o: se9eral h ndred metres. Since co55er is re5resented !y an S=N c r9e o: the ty5e shown in #ig. $6.$.(ii) it is o!9io s that e9en 9ery small stresses will ca se in:l ence in the en9ironment 9i7. high=:re? ency 9i!rations carrying stress re9ersals, was at :a lt ! t it was some time !e:ore ( co ld con9ince the engineer=in=charge that the co55er :rom which the t !e had !een man :act red was o: 5er:ectly good ? ality and not contaminated !y some mysterio s ! t highly ndesira!le im5 rities. :ail re when the n m!er o: stress cycles reaches N. Here an Fn:oreseen ,he disasters to the early Comet airliners :ollowed a similar 5attern in that :l ct ations in ca!in 5ress res in this case ca sed :atig e :ail re. Many ca ses o: :atig e :ail re are d e to Fn:oreseen and sometimes ndetected 9i!rations gi9ing rise to re9ersals o: stress at 9al es a!o9e SD (or SN). S ch 9i!rations are o:ten sym5athetic. (: we !egin with the ass m5tion thatD the engineering design has !een im5ecca!le then we m st loo8 elsewhere :or the ca se o: :ail re. Small ca9ities at or near the s r:ace will o: co rse act as stress raisers and the same may !e tr e o: small incl sions o: im5 rities, 5artic larly when these are wea8 and !rittle and conse? ently ha9e a similar e::ect on 5ro5erties to a ca9ity. S ch :a lts may raise the local stress a!o9e D (or N ) and so initiate a crac8. Howe9er s r:ace ? ality is 5ro!a!ly o: greater im5ortance since 5oor s r:ace :inish, e.g. the 5resence o: machining tool mar8s will tend to n cleate :atig e crac8s.

(: ? ench crac8s occ r in com5onents s ch as heat=treated steel sha:ts they are certain to de9elo5 as :atig e crac8sM whilst corrosi9e conditions in the en9ironment 5artic larly when stress corrosion ($%.1) is in9ol9ed, can also generate stress raisers in the :orm o: etch 5its and grain !o ndary :iss res which can n cleate :atig e crac8s. 1( ' 4 The -evelopment and 6ro,th of Fatig"e Cracks A :atig e crac8 is li8ely to !e generated !y stress concentrations arising :rom any o: the s r:ace or s !c taneo s de:ects en merated a!o9e. Ne9ertheless in a material which is :ree o: !lemishes contin al cyclic stressing 5rod ces a state o: 5lastic :low e9en in regions where the stress range is still !elow the normal static yield stress. S ch sli5 !ands as do a55ear on the s r:ace are either intr si9e or e<tr si9e (#ig. $6.$& (i) and (ii)). Altho gh s ch an intr sion is 9ery small. !eing o: the order o: $ m long and 4.1 m thic8, it can act as a stress raiser and initiate a :atig e crac8. A :atig e :ract re is generally considered to de9elo5 in three stages= n cleation, crac8 growth and ltimate :ail re( #ig. $6.$%). #ollowing the initiation o: a crac8 !y one o: the 5roced res o tlined a!o9e, the second stage, that o: crac8 5ro5agation, !egins. As indicated in #ig. $6.$&(iii) the crac8 emanating :rom the initial intr sion (ii) :irst changes co rse and !ecomes normal to the direction in which mess is acting.

,he crac8 ti5 then comes nder the in:l ence o: a s ccession o: tensile and com5ressi9e stresses. As com5ression changes to tension the crac8 o5ens and a system o: shear stresses !egins to o5erate at the crac8 ti5. As the tensile stress increases 5lastic de:ormation and tearing ta8es 5lace leading to crac8 growth, :ollowed !y !l nting o: the crac8 ti5. ;hen the cycle enters on its com5ressi9e 5hase the shear stresses are re9ersed and as a state o: ma<im m com5ression almost closes the crac8 5lastic :low re9erses. ,his ca ses a new striation to :orm and also leads to the re=o5ening o: the crac8 ti5. A s ccession o: striations is generated in this way on the :ract red s r:aces. As the crac8 5ro5agates slowly :rom the so rce the :ract red s r:aces r ! together d e to the 5 lsating nat re o: the stress and so the s r:aces !ecome ! rnished. ):ten conchoidal mar8ings are 5resent showing the direction o: s5read o: the :atig e crac8. D ring this second stage o: crac8 5ro5agation the rate o: crac8 growth da2dN is go9erned !y the +aris=Erdogan -awD

where C and m are constants associated with the material (m s ally !eing in the region o: 0 to 1 :or most d ctile materials). * is the range o: stress intensity :actor (*) and there is a 9al e o: * !elow which the crac8 will not 5ro5agate. Stage three o: crac8 5ro5agation is s dden and catastro5hic and descri!es the ltimate :ract re o: the section when the n!ro8en 5ortion is no longer a!le to s stain the load. ,his 5ortion has the ty5ical BcrystallineB a55earance o: a !rittle :ract re.

$> Methods o: Koining Material

14 1 At a!o t the time that Diogenes, the original Cynic, was li9ing in his, t !, a :ellow Eree8, Archytas o: ,arent m, is !elie9ed to ha9e in9ented the screw. By the second cent ry B.C. this de9ice was !eing sed e<tensi9ely !y the Eree8s in their wine 5resses, whilst a less e<otic se was made o: the screw !y Archimedes in his machine :or raising irrigation water. Strangely, no one seems to 8now when the screw was :irst sed as a :astening de9ice. +rimiti9e man e<5erienced great di::ic lty in 3oining his materials. He sed sinews and thongs o: hide to tie together the :ramewor8 o: his h ts and also to tie on the heads o: his stone a<es. By /444 B.C., howe9er, the co55ersmiths o: Egy5t were 5rod cing nails whilst, a little later, the woodwor8ers o: that region were sing ? ite so5histicated si<=layer 5lywoods cemented !y animal gl es. Almost certainly !y /444 B.C. the smith had mastered the art o: 5ress re welding sing hammer and an9il ! t it was less than a cent ry ago that the de9elo5ment o: welding technology, as we now nderstand it, really !egan.

Adhesion and Adhesives

14 # ;hen the s r:aces o: two solids are !ro ght s ::iciently close together the interaction o: s r:ace :orces will gi9e rise to some degree o: adhesion where the two s r:aces are within ro ghly

atomic range. ,his adhesion o:ten mani:ests itsel: as :riction i: the two s r:aces are made to slide relati9e to each other and the heat energy 5rod ced is a meas re o: the wor8 done against these inter= s r:ace :orces o: attraction. R !!er tyres do not s8id i: they can ma8e contact with a dry road s r:ace.

14 # 1 ,wo :reshly drawn glass :i!res will adhere to each other i: they are !ro ght into contact. ,his can !e demonstrated i: the :i!res are held !etween the :inger and th m! o: each hand (#ig. $>.$) and the 55er :i!re (H) then gently drawn across the lower (I). ,he motion will !e :o nd to !e BsnatchyB, indicated !y the de:lection and 3er8ing o: the lower :i!re. (: the two :i!res are now drawn thro gh the :ingers and the e<5eriment re5eated the snatching motion is =red ced almost to 7ero. +res ma!ly grease :rom the :ingers 5rod ces a l !ricating :ilm s5acing the glass s r:aces a5art so that adhesion is no longer 5ossi!le. Similarly i: the :reshly drawn :i!res are allowed to remain in contact with the atmos5here :or some time they will no longer adhere, a55arently

d e to contamination o: the s r:aces with d st, moist re and : mes. 14 # # (n 5ractical terms an adhesi9e may !e regarded as any s !stance ca5a!le o: holding materials together !y s r:ace attachment. ,y5ical adhesi9es incl de gl e, m cilage, 5aste and a wide range o: 5olymeric cements. Eenerally the mechanism !y which s r:ace attachment occ rs isD (i) s5eci:ic adhesion which de5ends 5rinci5ally 5on the action o: 9an der ;aals :orces (0..) !etween molec les in the adhesi9e and the s r:ace layers o: the materials (adherands) !eing 3oinedM (ii) mechanical adhesion in which the adherands are to some e<tent 8eyed together !y molec lar :ilaments o: the adhesi9e which 5ene= trate into the s !strates o: the adherands. Since materials li8e glass and metal can !e s ccess: lly !onded !y adhesi9es it is reasona!le to s 55ose that s5eci:ic adhesion is the more im5ortant o: these two 5ossi!ilities. Eenerally. s5ea8ing the larger the molec les in9ol9ed the greater the adhesion since 9an der ;aals :orces will then !e greater. Conse? ently most adhesi9es are organic com5o nds o: 9ery large and com5le< molec les ha9ing a high density o: 5olar gro 5s.,he more common 5olar gro 5s met with in adhesi9es incl de hydro<yl,car!onyl, nitro, nitrile, amide, s l5honic and some others. (t is reasona!le to s ggest that the stic8iness o: s gar is d e to the 5resence o: hydro<yl gro 5s in s gar molec les. ,he strength o: the adhesi9e !ond is deri9ed :rom the s m o: all the 9ander ;aals attractions !etween the molec les o: the adhesi9es and neigh!o ring molec les in the s !strate o: the adherand. ,he molec les themsel9es will !e strong d e to the co9alent !onds o5erating within them. Howe9er, not all large 5olymer molec les 5ro9ide good adhesion. #or e<am5le the :l oro= car!on gro 5ing is associated with s ch 5oor adhesi9e 5ro5erties that +,#E (,a!le $0.0) is sed as a non=stic8 coating and also as a !earing material. Needless to say cohesion within the adhesi9e

itsel: is 3 st as im5ortant as adhesion !etween the adhesi9e and the adherand, otherwise :ail re in the adhesi9e layer will !e li8ely. #or this reason mo!ile li? ids s ch as alcohol and nitro!en7ene, whilst ha9ing s ita!le 5olar gro 5s, are seless as adhesi9es since there is little cohesion !etween their relati9ely small molec les. (n adhesi9es molec les are o:ten so large as to ha9e molec lar masses o: se9eral h ndred tho sands or e9en millions. ,he s m total o: 5olar !onds each molec le then 5ro9ides is 9ery great. Another im5ortant :eat re is that the adhesi9e m st mo ld itsel: 5er:ectly to the s r:aces !eing 3oined in order that its molec les will remain as close as 5ossi!le to the molec les in these s r:aces. #or this reason ordinary gl e m st !e a55lied hot whilst it is s ::iciently mo!ile. Many 5olymeric adhesi9es are o: the cold=setting ty5e in which two mo!ile li? ids are mi<ed together and then 5roceed to harden !y 5olymeri7ation in the manner o: cold=setting 5lastics materials ($0./.0) a:ter the 3oint has !een made. 14 # $ So :ar only the le9el o: adhesion !etween adhesi9e and adherand has !een considered. ,he mechanical 5ro5erties o: the hardened adhesi9e layer are o!9io sly im5ortant. As a modem 3oining method in engineering 5ractice an adhesi9e is seless i: it 5rod ces a !rittle 3oint so that high to ghness as well as shear strength is essential. Modem 5olymeric adhesi9es can !e designed to gi9e di::erent com!inations o: these 5ro5erties as indicated in #ig. $>.0. Here, c r9e B re5resents the com!ination o: 5ro5erties in a modem high=5er:ormance adhesi9e in which the elastic shear stress limit is a55ro<imately .4 M+a and the ma<im m shear stress 14 M+a. ,he more e<treme 9al es re5resented !y c r9es A and C can !e o!tained !y increasing the degree o: cross lin8ing d ring setting o: the 5olymerM c r9e A in which ma<im m sti::ness wo ld gi9e good high tem5erat re 5ro5ertiesM or !y decreasing the degree o: cross lin8ing, c r9e C, the latter !eing ty5ical o: the many acrylic=!ased adhesi9es. ,he length o: the near=hori7ontal 5arts o: A, B or C is a meas re o: the Bto ghnessB o: the adhesi9e. (n some a shear strain o: $44R can !e o!tained with an adhesi9e o: ty5e C.

14 # % Adhesi9es !ased on e5o<y=ty5e resins will !e :amiliar to most D(I readers. (n these the s5eed o: setting=an im5ortant :actor in ind strial 5rod ction=can !e raised !y :orm lation. as can the 9al e o: ,g in relation to the s5eci:ied wor8ing tem5erat re.

Soldering and BraCing

14 $ ,hese 5rocesses di::er :rom : sion welding in that the solder which is sed melts at a lower tem5erat re than the metal 5arts !eing 3oined so that no direct : sion o: the latter occ rs. (t is essential, howe9er, that a solder shall BwetB the metallic s r:aces it is meant to 3oin, that is :orm a li? id sol tion with them. )n solidi:ication this li? id sol tion sho ld !e re5laced !y a solid sol tion i: ma<im m to ghness o: the 3oint is to !e attained, together with crystalline contin ity across the inter:ace.. ,he

:ormation o: an intermetallic com5o nd on the other hand will lead to !rittleness. #or e<am5le, the se o: a tin=!ase solder to 3oin co55er may 5rod ce a !rittle 3oint since at some 5oint !etween the 5 re co55er 5arts and the centre o: the solder 3oining them, the metals co55er and tin will !e 5resent in the correct 5ro5ortions to :orm 9ery !rittle com5o nds s ch as CF$1 Sn5 and C (Sn'. (: s ch a 3oint is tom a5art it will show a !l ish :ract re d e to the 5resence o: CF$1 Sn5 in the s r:ace thro gh which :ail re has occ rred. #or this reason co55er is soldered with a lead=sil9er solder in high=class wor8. Co55er does not :orm intermetallic com5o nds with either lead or sil9er. D ring soldering and !ra7ing 5rocesses o<ide :ilms tend to act as a !arrier to s ccess: l BwettingB o: the wor8 5ieces !y the solder. ,hese o<ide :ilms are s ally dissol9ed !y some s ita!le :l < in order to e<5ose a clean metallic s r:ace to the alloying action o: the solder. Ne9ertheless some metals, s ch as al mini m, which ha9e tenacio s o<ide :ilms are 5artic larly di::ic lt to solder. 14 $ 1 (n ordinary Bso:tB soldering tin=lead !ase alloys are sed. (deally tin=manBs solder sho ld !e o: e tectic com5osition (60R Sn=/&R +!) so that it solidi:ies shar5ly at $&/ZC th s red cing to a minim m the time re? ired to 5rod ce a 3oint and also the tem5erat re to which the wor8 5iece is e<5osed. Since tin is e<tremely e<5ensi9e relati9e to lead, commercial solders o:ten contain 14R or more lead. Fntil the earlier 5art o: the twentieth cent ry domestic 5l m!ing sed lead 5i5es. ,hese were 3oined or re5aired sing a tin=lead solder which was Bwi5edB aro nd the 3oint whilst in a 5art=li? id, 5art=solid state. (n order to achie9e this the solder re? ired as wide a li? id s=solid s range as 5ossi!le. #or this reason 5l m!erBs solder contained a!o t 6>R +!=//R Sn and solidi:ied !etween a!o t 061Z and $&/ZC. As the 5oisono s nat re o: lead !ecame more a55arent lead 5i5es sed in 5l m!ing were re5laced !y co55er and these co55er 5i5es were 3oined sing a lead=:ree solder (e.g. %&R Sn=0R Ag, molten !etween 00$Z and

00/ZC). Ne9ertheless the man who installs o r co55er=5i5e system is still re:erred to as a B5l m!erB (-atinD l m! m= lead (+!). So:t soldering may !e accom5lished with the aid o: some :orm o: soldering BironB. (n large=scale 5rod ction howe9er, a mi<t re o: solder and :l < may !e 5re5laced in the 3oints and the assem!lages heated enmasse !y high=:re? ency electrical c rrents. (n the electronics ind stry many ingenio s methods are sed :or soldering com5onents to circ it !oards. ,h s in Bwa9eB soldering the com5onents are 5re=5laced in 5osition on the !oard which is then s s5ended a!o9e a tro gh o: molten solder. A wa9e is then generated along the s r:ace o: the solder so that it to ches and BwetsB the contact 5oints to :orm a 3oint. 14 $ # (n !ra7ing the soldering iron is re5laced !y a gas torch. Alternati9ely !ra7ing solder2:l < mi<t re can !e 5re=5laced and the wor8 5ieces heated !y high=:re? ency ind ctionM salt !athsM : rnace or di5 methods. Bra7ing solders contain !etween 14 and 66% C (!alance=On). ,his 5rod ces a low=melting 5oint alloy ! t one which wo ld !e e<tremely !rittle were it not :or the :act that. d ring !ra7ing. some 7inc is lost so that the res ltant 3oint consists o: a to gh. D ctile !rass instead o: a hard, !rittle str ct re (#ig. $$.$). Sil9er solders contain 9arying ? antities o: sil9er in order to red ce the melting range and so 5rod ce a !ra7ing alloy with a melting 5oint as low as 6%4oC.

Aelding
14 % ,he 3oining o: 5ieces o: metal !y :irst heating them to a tem5erat re a!o9e that o: recrystallisation and then :orging them together is a 5ress re=welding 5rocess which the !lac8smith has o5erated :or many cent ries. A n m!er o: mechanical 5ress re= welding 5rocesses are now sed, ! t in the meantime : sion welding has gained the ascendancy in the e9er=widening range o: 5rocesses which contin e to !e introd ced and de9elo5ed.

F"sion1,elding Processes
14 % 1 6as Aelding sing the o<y=acetylene torch is now sed mainly :or 3o!!ing and re5air wor8. By sing s ita!leD mi<t res o: o<ygen and acetylene tem5erat res in the region o: /444ZC can !e attained so that ordinary metals and alloys are ? ic8ly melted. ,his is necessary in order to o9ercome the tendency o: metallic sheets and 5lates to cond ct heat away :rom the weld 7one so ? ic8ly that : sion is im5ossi!le. Metal :or the weld 3oint is, o: co rse, s 55lied :rom a welding rod which is normally o: a com5osition similar to that o:= the wor8 5ieces. (n addition to metals, some thermo5lastics s ch as rigid +'C are gas=welded. 14 % 1 1 BronCe Aelding resem!les !ra7ing in that little or no : sion o: the wor8 5ieces occ rs since the !ron7e :iller metal (generally ..1R SnM 4.1R +M !alance=C ) melts at a m ch lower tem5erat re than the wor8 5ieces which are s ally mild steel, cast iron or nic8el alloys. At the same time !ron7e welding di::ers :rom !ra7ing in the a55lication o: the :iller metal which is in rod :orm whereas in !ra7ing 5owdered solder is generally 5re5laced.

14 % # Electric Arc Aelding Processes ,hese now constit te !y :ar the most im5ortant : sion welding 5rocesses. ,he earliest electric=welding 5rocess em5loyed a car!on electrode :rom which an arc was str c8 to the wor8 itsel:. ;eld metal was s 55lied :rom a :iller rod, the end o: which was held in the arc. ,his method is now 9irt ally o!solete. 14 % # 1 )etallic Arc Process ,his is the most widely sed o: the arc=welding o5erations. (t ma8es se o: a cons ma!le electrode, that is, the electrode is a rod o: s ita!le com5osition so that when an arc is str c8 !etween it and the wor8 5iece, the rod melts and 5ro9ides the necessary weld metal (#ig. $>..(i)). ,he electrode is coated with a :l < which not

#ig. $>.. Electric=arc welding 5rocesses. (i) ,he metallic arc=here molten :l < 5ro9ides 5rotection :or the weld, hel5ed to some e<tent !y a gas shield 5ro9ided !y ! rning car!onaceo s matter in the :l < coating. (ii) ,he M(E (metallic inert gas) 5rocess in which a !lan8et o: argon gas 5rotects the weld. (iii) ,he ,(E (t ngsten inert gas) 5rocess in which a se5arate :iller rod is sed, the t ngsten electrode 5ro9iding the arc ! t !eing itsel: non=cons ma!le.

only 5ro9ides a 5rotecti9e slag co9er :or the weld ! t also assists in sta!ilising the arc. Altho gh it is sed 5rinci5ally :or steel, metallic=arc welding is also a55lica!le to many non=:erro s metals and alloys.

14 % # # S"*merged1arc Aelding essentially an a tomatic 5rocess sed :or straight=line 3oining o: metals. (t is a 9ariation o: the metallic=arc 5rocess in which 5owdered :l < is :ed into the 5re5ared 3oint 3 st in ad9ance o: the electrode. As the :l < melts it en9elo5s the melting end o: the electrode and so co9ers the arc. ,he weld area is th s 5rotected !y a coating o: slag so that a smooth clean weld is 5rod ced. 14 % # $ 6as1shielded Arc Processes sed :or welding those metals and alloys in which o<idation is tro !lesome. (n these 5rocesses the electrode 5rotr des :rom the end o: a t !e :rom which an inert gas also iss es. (n the F* the no!le gas argon is generally sed whilst in the FSA heli m, a !y=5rod ct o: the oil wells, is also a9aila!le. ,he metallic=inert=gas (or M(E) 5rocess em5loys a cons ma!le electrode (#ig. $> ..(ii)) as in ordinary metallic=arc welding. ;hilst in the t ngsten=inert=gas (or ,(E) 5rocess a 5ermanent t ngsten electrode is sed to stri8e the arc and an e<ternal :iller rod sed to s 55ly the weld metal (#ig.$>.. (iii)). ,hese 5rocesses were de9elo5ed d ring the Second ;orld ;ar in order to weld alloys containing magnesi m. a metal which reacts with most gases. (ncl ding nitrogen. #or this reason relati9ely e<5ensi9e inert gases m st !e sed to 5ro9ide the 5rotecti9e atmos5here. ,hese 5rocesses are now sed more widely :or the welding o: other metals and alloys. ,he C)# 5rocess was de9elo5ed more recently and has !ecome 9ery 5o5 lar :or welding steel. (t ses atmos5here o: car!on dio<ide ! t since this can o<idise steel at high tem5erat res. #iller rods containing deo<idants s ch as manganese and silicon are em5loyed. Altho gh nitrogen tends to !e regarded as an nreacti9e gas it dissol9es in steel and gi9es rise to !rittleness. (t also reacts with

se9eral non=:erro s metals, 5artic larly magnesi m. And is there:ore o: no interest in gas shielded welding 5rocesses. 14 % # % Electro1slag Aelding> ,his was introd ced in R ssia in $%1/ :or the 3oining o: hea9y steel 5lates in a 9ertical 5osition. ,he molten metal is deli9ered 5rogressi9ely to the 9ertical ga5 !etween the 5lates rather as in an ingot=casting 5rocess. ,he 5lates themsel9es :orm two sides o: the Bmo ldB whilst two tra9elling water=cooled co55er shoes dam the weld 5ool ntil solidi:ication is com5lete. 14 % # ' Plasma1arc Aelding a relati9ely new 5rocess in which a s ita!le gas s ch as argon is 5assed thro gh a constricted electric arc so that it dissociates into 5ositi9e and negati9e ions. ,his ion mi<t re !eing termed 5lasma. ) tside the arc the ions re=com!ine and the heat=energy released 5rod ces an e<tremely hot Aelectric :lame@. ,em5erat res 5 to $1444;C can !e 5rod ced in this manner. +lasma is sed as a high=tem5erat re heat so rce in c tting. Drilling and s5raying 9ery re:ractory materials li8e t ngsten, moly!den m and rani m as well as in welding. 14 % $ Thermit Aelding sed mainly to re5air large iron and steel castings. A sim5le mo ld is constr cted ro nd the 5arts to !e 3oined, and a!o9e this is a cr ci!le containing the ,hermit mi<t re. ,his thermit mi<t re consists o: 5owdered :erro s=:erric o<ide, #e$4%, and al mini m d st in molec lar 5ro5ortions. ,he chemical a::inity o: al mini m :or o<ygen is greater than the a::inity o: iron :or o<ygen hence, on ignition, al mini m red ces the iron o<ideD

,he heat o: reaction is so intense that molten iron is 5rod ced and this is ta55ed :rom the cr ci!le into the 5re5ared 3oint.

14 % % Electron1*eam Aelding ;hen a stream o: :ast=mo9ing electrons stri8es a s ita!le target H=rays are generated (04.&.0). At the same time a considera!le amo nt o: heat is 5rod ced as a res lt o: the con9ersion o: the 8inetic energy o: the :ast=mo9ing electrons. (: the electron !eam is :oc sed to im5inge at a 5oint 9ery high tem5erat res can !e 5rod ced. ,o !e really e::ecti9e the o5eration m st !e carried o t in 9ac o otherwise many o: the electrons will lose their 8inetic energy as a res lt o: collisions with relati9ely massi9e molec les o: o<ygen and nitrogen 5resent in the air s5ace !etween electron Bg nB and target. Electron=!eam welding is sed 5rinci5ally :or the re:ractory metals t ngsten, moly!den m and tantal m and also :or reacti9e metals s ch as !erylli m, rani m and 7irconi m which cannot o<idise i: welded in +acuo. 14 % ' Laser Aelding ,his has !een sed so :ar :or micro s5ot= welding and, to some e<tent, :or drilling and c tting. A laser (-ight Am5li:ication !y Stim lated Emission o: Radiation) de9ice consists essentially o: a generator o: light 5 lses along with a s ita!le acti9e s !stance so that a !eam o: light o: 9ery high intensity is emitted.

Press"re1,elding Processes
14 ' ,he smith has !een 5ractising his art :or at least 6444 years. (n order to weld together two 5ieces o: iron he :irst heats them to a high tem5erat re and then !rings them into contact nder 5ress re !y hammering them together on an an9il. De:ormation a!o9e the recrystallisation tem5erat re (1.&./) ind ces recrystallisation which occ rs across metal2metal inter:aces so that a strong contin o s 3oint is 5rod ced. Most modern 5ress re=welding 5rocesses are similar in 5rinci5le to smith welding e<ce5t that the welding tem5erat re is generally localised to the region where 3oining is to !e accom5lished.

14 ' 1 Electric Resistance1,elding Processes ,hese 5rocesses are sed to 5rod ce either Bs5otB, BseamB or B! ttB welds. 14 ' 1 1 Spot Aelding (n this 5rocess the wor8 5ieces are o9erla55ed and gri55ed !etween hea9y metal electrodes (#ig. $> . 1(i)). A c rrent s ::icient in magnit de to 5rod ce local heating o: the wor8 5ieces to a 5lastic state is

then 5assed thro gh the electrodes. Since the metal !etween the electrodes is nder considera!le 5ress re a s5ot weld is 5rod ced. ,his method is 5artic larly s ita!le :or Btac8ingB together 5lates and sheets, o:ten 5re5aratory to 5rod cing a more 5ermanent weld. 14 ' 1 # ProNection Aelding a modi:ied :orm o: s5ot welding in which the c rrent :low and hence, the res ltant heating e::ect, are localised !y em!ossing one o: the 5arts to !e 3oined. ,his method (#ig. $> .1(ii)) is 9ery s ita!le :or 3oining hea9y sections where s5ot welding wo ld !e di::ic lt !eca se o: the !ig heat losses !y cond ction and conse? ently hea9y c rrents re? ired.

14 ' 1 $ Seam Aelding (#ig. $>.6(i)) resem!les s5ot welding in 5rinci5(e ! t 5rod ces a contin o s weld !y sing wheel electrodes. +lastics can !e 3oined !y !oth s5ot and seam welding. the electrodes !eing heated !y high=:re? ency ind ction since these 5olymer materials are o: co rse non=cond ctors o: electricity. 14 ' 1 % B"tt Aelding (#ig. $> .6(ii)) sed :or 3oining lengths o: wire, rod or t !es. ,he ends are 5ressed together and heated at the 3oint !y a c rrent, which is 5assed thro gh the wor8. Since there will ine9ita!ly !e a higher electrical resistance at the 5oint o: contact o: the two wor8 5ieces, more heat will !e generated there. 14 ' 1 ' Flash Aelding somewhat similar to ! tt welding e<ce5t that the ends are !ro ght together momentarily in order to stri8e an arc !etween them. ,his melts away any irreg larities so that when the ends are then 5ressed together a so nd weld is :ormed. 14 ' 1 ( +nd"ction Aelding (n this 5rocess the wor8 5ieces are !ro ght into contact nder 5ress re and a high=:re? ency ind ction coil 5laced aro nd the 5ros5ecti9e 3oint. H# c rrents ind ced in the wor8 heats it to welding tem5erat re and the a55lied 5ress re ca ses welding to ta8e 5lace.

14 ' # Bther Press"re1,elding Processes Se9eral other 5ress re =welding 5rocesses ha9e !een introd ced d ring the last two decades or so. 14 ' # 1 Friction Aelding (#ig. $>. >(i)) can !e sed to 3oin some mate rials in rod :ormD ,he rods are gri55ed in ch c8s, one rotating and the other stationary. As the ends are !ro ght together heat is generated !y :riction !etween the sli55ing s r:aces, ltimately s ::icient to ca se welding. Rotation is sto55ed a tomatically as welding commences. A modi:ica$tion o: this 5rocess, sed to 3oin 5lastics, is re:erred to as s5in welding.

14 ' # # Cold Aelding in the :orm o: la5, seam or ! tt welding in9ol9es ma8ing the two s r:aces slide relati9e to each other nder great 5ress re. )<ide :ilms are disr 5ted and a cold weld :orms !etween the s r:aces. S5ot welds are made !y 5 nching the two wor8 5ieces together (#ig. $>.>(ii)). 14 ' # $ E/plosive Aelding can !e sed to BcladB one sheet o: metal with another. ,he B:lyerB 5late, to55ed with a sheet o: high e<5losi9e, is s s5ended at a slight angle to the target 5late. )n detonation o: the e<5losi9e the :lyer 5late stri8es the target at s5eeds o: 5 to /44 m2s and with inter=:ace 5ress res o: 5 to >444 M+a.. As a res lt the material in the region o: the im5act !eha9es :or a short time as a :l id o: ? ite low 9iscosity. ,he :lyer 5late 9irt ally B3etsB along the s r:ace o: the target so that cold welding ta8es 5lace (#ig. $> .&(i)).

14 ' # % Hltrasonic Aelding em5loys ltrasonic 9i!rations o: the order o: 04444 H7 to 5rod ce sli5 !etween two s r:aces, which are !eing 5ressed together. ,he 9i!rations lead to disr 5tion o: the s r:ace :ilms o: o<ide so that the s r:aces can cold=weld nder the 5ress re sed. ,he so not rode ti5 (#ig. $>.&(ii)) clam5s the wor8 5ieces to an an9il and 9i!rates laterally. 14 ' # ' -iff"sion Bonding sed to 3oin sheet metal. ,he sheets are held :ace to :ace nder light 5ress re in a 9ac m cham!er. ,he tem5erat re is

then raised to the range 4.1 to 4.& , m so that !onding occ rs in not more than two ho rs d ring which time di:: sion occ rs across the inter:ace so that the s r:aces !ecome 8nitted !y a region o: solid sol tion. Steel can !e BcladB with !rass in this way.

The Str"ct"re and Properties of Aelded Ooints

14 ( ,he common welding 5rocesses in9ol9e the se o: high tem5erat res so that the region containing the weld will !e relati9ely coarse=grained in contrast to the remainder o: the wor8 5iece which will generally !e o: a wro ght, and conse? ently.

#ine=grained str ct re. (: a : sion method o: welding has !een sed the weld metal itsel: will show a coarse as=cast ty5e o: str ct re. Here the crystals will !e large and other :eat res s ch as coring and segregation o: im5 rities at crystal !o ndaries may also !e 5resent. ,hese :eat res gi9e rise to !rittleness, which res lts :rom wea8ness at the crystal !o ndaries. ,he e::ect o: s ch :a lts can !e minimised i: it is 5ractica!le to hammer the weld whilst it is still hot. Not only will this ind ce :ine grain on recrystallisation ! t it will redistri! te more e9enly those im5 rities segregated as a res lt o: coring. 14 ( 1 +oor welding techni? e may res lt in gas 5orosity and2or the 5resence o: o<ide 5articles tra55ed in the weld metal. Eas 5orosity may arise either :rom gas dissol9ed !y the molten weld metal or :rom chemical reactions !etween s ch gases and constit ents already 5resent. )<ide 5articles are generally d e to reactions !etween atmos5heric o<ygen and constit ents o: the weld metal or those dissol9ed :rom the s r:aces o: the wor8 5ieces. S5eci:ic di::ic lties are associated with the welding o: some metals and alloys. ,h s, as the car!on content o: 5lain car!on steels increases so do the di::ic lties in welding them. Car!on tends to o<idise d ring the welding 5rocess and 5orosity is li8ely to arise d e to the gases released. ,hin sections in car!on steel may cool so ra5idly as to ca se !rittleness whilst m ch thic8er sections in oil= or air=hardening steels may !ecome !rittle near to the weld as a res lt o: martensite :ormation. ,he $/R Cr

air=hardening c tlery steel is 5artic larly di::ic lt to weld satis:actorily since !rittleness arises not only :rom e<cessi9e grain growth aro nd the weld ! t also the :ormation o: martensite in that region (#ig. $> .%(i)). 14 ( # ,he Bweld decayB o: some $&=& a stenitic steels has !een mentioned elsewhere ($4.1.$). (: they ha9e not !een B5roo:edB against s ch an e9ent ality these steels are normally ? enched :rom $414ZC in order to retain any car!on in solid sol tion in the a stenite. Heating in the range 144=%44ZC will ca se the 5reci5itation o: car!ide 5articles and this will lead to corrosion ($%.>.$). D ring a welding 5rocess some region either side o: the 3oint will !e maintained in this tem5erat re range :or long eno gh :or some s ch 5reci5itation to occ r and corrosion will s !se? ently ta8e 5lace in that region. Many items o: 5lant sed in the chemical ind stries are :a!ricated !y the welding o: stainless= steel sheets !eca se highly corrosi9e conditions are in9ol9ed. (t is then e9en more im5ortant to red ce the tendency towards weld decay. Ass ming that the welded str ct re cannot !e sol tion= treated :rom a!o9e $414ZC=and o!9io sly this will rarely !e 5ossi!le=one o: the :ollowing means o: limiting the 5reci5itation o: chromi m car!ide m st !e sedD

(i) the se o: stainless steel with a car!on content !elow 4.4/RM (ii) the sta!ilisation o: car!ides nder all conditions !y adding nio!i m or titani m. No dissol9ed car!on is then a9aila!le to 5reci5itate as chromi m car!ide since any car!on 5resent has already !een Btied 5B !y the strong car!ide=:orming nio!i m (or titani m). 14 ( $ Cast irons may !e s ccess: lly welded i: :iller rods rich in deo<idants s ch as manganese and silicon are sed. E9en so the weld metal may a!sor! considera!le amo nts o: car!on :rom the wor8 5ieces and since cooling will ine9ita!ly !e ra5id a 9ery !rittle white iron str ct re may !e :ormed ($4.6.0). #or this reason cast iron is o:ten 3oined !y !ron7e welding, tho gh s !se? ent electrolytic corrosion !etween the !ron7e weld and the s rro nding cast iron m st !e e<5ected i: moist re is 5resent in the en9ironment. Cast iron, !eing anodic to the !ron7e weld, wo ld ? ic8ly r st. 14 ( % Al mini m alloys o<idise readily so that d ring ordinary metallic arc welding they m st !e 5rotected ade? ately !y a :l <. #or this reason the ! l8 o: al mini m welding is now carried o t with the gas=shielded arc,a 5rocess de9elo5ed to deal with the e9en more di::ic lt magnesi m alloys.

Ooining Plastics )aterials

14 4 Since thermo5lastic 5olymers can !e so:tened !y heat and will harden again on cooling they can !e : sion welded !y a n m!er o: +rocesses. ,hermosetting 5olymers, howe9er, cannot !e welded ! t are Fs ally 3oined sing s ita!le adhesi9es s ch as are sed :or many com5osite materials ($>.%). 14 4 1 Aelding Processes for Thermoplastic Pol&mers ,hese can !e di9ided into two gro 5sD 5rocesses where heat is

deri9ed :rom mechanical mo9ement and 5rocesses in9ol9ing e<ternal heating. 14 4 1 1 Processes +nvolving )echanical )ovement ,hese incl de ltrasonic welding ($>.1.0..) which is s ita!le :or mass 5rod ction ind stries since weld times o: 4.1=$.1 s can !e achie9ed. (n the case o: 5lastics materials the 5arts are held together nder 5ress re and then s !3ected to ltrasonic 9i!rations o: the order o: 04=.4 8H7 at right angles to the contact area. A55lications range :rom 9al es and :ilters sed in medical e? i5ment to cassette !odies and 9ac m cleaner 5arts. #riction welding has !een sed :or many years and is similar in 5rinci5le to that sed :or 3oining metals ($>.1.0.$). ;elded acetal :loats :or domestic cisterns, aerosol !ottles and 5i5e :ittings are ty5ical hollow 5rod cts in addition to solid circ lar sections. (n 9i!ration (linear :riction) welding the two s r:aces are 5ressed together sing similar 5ress res to those em5loyed in ltrasonic and :riction welding ($=. M+a). A linear 9i!ration o: $44=044 H7 is then sed to ca se : sion and welding in $=1 s. -arge com5le< linear 3oints can !e made and the 5rocess is widely sed in the a tomo!ile ind stries :or com5onents s ch as ! m5ers. 14 4 1 # Processes +nvolving E/ternal .ealing ,here are a n m!er o: techni? es which ma8e se o: a heating tool. ,he sim5lest o: these ses a hot :lat 5late which is clam5ed !etween the two s r:aces to !e 3oined ntil they so:ten. ,he 5late is then withdrawn and the s r:aces are !ro ght together nder controlled 5ress re :or a s5eci:ied 5eriod. A:ter the : sed s r:aces ha9e cooled the res ltant 3oint has strength o: at least %4R o: the 5arent material. Bra8e :l id reser9oirs (where strong, li? id=tight 3oints are re? ired) and lam5 assem!lies :or motor 9ehicles, 5lastics 5i5es :or water and sewage are 3oined in this way. Hoc=gas we2ding is similar in 5rinci5le to o<yacetylene welding o: metals ($>...$). the o5en :lame !eing re5laced !y a stream o: hot gas. ,he :iller rod is o: similar com5osition to the edges !eing 3oined and

tem5erat res o: 044=/44ZC are sed. Eases are com5ressed air, C)# and nitrogen=the latter :or materials s ch as, 5olythene, which are sensiti9e to o<idation. ,his 5rocess is sed mainly :or re5air wor8 o: +'C, 5olythene, 5ers5e<, nylons and 5olycar!onates. $m.lant welding in9ol9es tra55ing a metal insert !etween the two hal9es to !e 3oined and then heating the insert !y high=:re? ency ind ction so that the 5lastics material ad3acent to the insert : ses to :orm a 3oint. ,he 5rocess is sed :or com5le< 3oints in large com5onents s ch as 9ehicle ! m5ers and sailing dinghy h lls. (n a similar 5rocess, electro: sion welding (#ig. $>.$4),

sed !y British Eas :or 3oining the yellow 5olythene 5i5es 5 to $&4 mm diameter, the 5i5e ends are inserted into a connecting collar which has a heater element mo lded in. Resistance heating in this case com5letes the 3oint in, ty5ically, /4 min tes.

Ooining Ceramic )aterials

14 5 A5art :rom 5 rely mechanical methods s ch as screwing, shrin8 :itting and ta5er :itting ceramics can !e !onded to other materials in a n m!er o: ways with 9arying s ccess. 14 5 1 Adhesives Con9entional 5henolic and e5o<ide adhesi9es are a9aila!le ! t their se is restricted !y an 55er tem5erat re

limit o: (14ZC and a low mechanical stress limit. A ty5ical a55lication is the mo nting o: ceramic magnets in electric motors. High=tem5erat re adhesi9es !ased on organic !inding com5o nds, al8ali=metal silicates and 5hos5hates containing a 5owdered B:illerB material (car!on, al mina, silica, magnesia or 7irconia as a55ro5riate) o::er ser9ice tem5erat res 5 to 0044ZC. By ad3 sting the com5osition o: the B:illerB material the coe::icient o: e<5ansion o: the adhesi9e can !e reg lated to match that o: the wor8 5ieces and so minimise stresses generated d ring tem5erat re changes. Fn:ort nately 3oints made this way do not generally reach standards o: relia!ility re? ired in engineering.

14 5 # BraCing an esta!lished method :or 3oining ceramics to ceramics and also ceramics to metals. ,he main 5ro!lem is in :inding a !ra7ing solder which will BwetB the ceramic s r:ace (#ig. $>.$$). Eenerally it is necessary to metallise the ceramic s r:ace either !y 9a5o r e5osition, Bs5 tterB ion 5lating or !y coating with a mi<t re o: Mo, Mn and glass 5owders and then heating in a hydrogen atmos5here at $144ZC. ,he ceramic can then !e !ra7ed !y con9entional methods, generally sing a !ra7ing alloy o: >0 Ag= 0& C (e tectic) com5osition !eca se o: its moderate melting 5oint ( >>%;C) and good d ctility to co nteract thermal contraction mismatches.

14 5 $ Active )etal BraCing se: l in 3oining o<ide or nitride ceramics to steel. A metal which will react with the ceramic s r:ace is added to the !ra7ing solder and so 5romote BwettingB o: the s r:ace. ,he !est 8nown modi:ied solder is the >0 Ag=0& C e tectic to which 1=$4R ,i is added mechanically. 14 5 % Friction Aelding ($>.1.0.$) A n m!er o: ceramics ha9e !een s ccess: lly welded to metals, e.g. Al#)$=AlD SiC=Al and AlN=Al, the latter where al mini m heat sin8s need to !e attached to A$N com5onents in the electronics ind stry. Fs ally the ceramic is held stationary whilst the metal is rotated ra5idly in contact with it.

Ooining Composite )aterials

14 7 Many com5osites 5artic $arly those with a 5olymer matri<, are sensiti9e to high tem5erat res. ,hey are there:ore most con9eniently 3oined, either to each other or to metals with some :orm o: adhesi9e. ): the many adhesi9es a9aila!le the three gro 5s most s ita!le areD (i) e5o<yM(ii) acrylicM (iii) 5oly rethane. Each o: these gro 5s is a9aila!le in Bone= or two=5artB systems. ,he Aone= 5artB adhesion are those which will 5olymerise and harden a:ter a55lication at am!ient tem5erat res. ,he 5olymerisation 5rocess can !e accelerated in most cases !y raising the tem5erat re. ,he Btwo=5art@ systems, as the term s ggests. consists o: two se5arate li? ids which, when mi<ed. !egin to co=5olymerise ntil a strong, to gh, hea9ily cross=lin8ed solid is the res lt. Again with some mi<t res co=5olymerisation is s5eeded 5, and 5roceeds to gi9e a higher degree o: cross lin8ing, !y heating.

14 7 1 )ne or other o: these adhesi9es will !ond well with most materials ! t :re? ently some s r:ace treatment is re? ired to e::ect good adhesion. Alternati9ely additions are necessary to the adhesi9e to im5ro9e its !ond with the adherand. Similarly Br !!ery@ additions are sometimes made to im5ro9e the to ghness o: an otherwise !rittle adhesi9e. Some characteristics o: the main gro 5s o: adhesi9es are gi9en in ,a!le $>.0. 14 7 # Metal matri< com5osites (MMCs) can !e 3oined s ccess: lly !y #rictions welding 5rocesses ! t : sion welding methods are limited in their a55lication. ,h s in the welding o: Al= SiC MMCs the se o: the ,(E 5rocess ($>...0./) a55ears to !e satis:actory. B t when electron= or laser !eam welding is attem5ted the higher tem5erat re attained in the weld 5ool gi9es rise to ad9erse chemical reactions. (n 5artic lar the SiC :i!res are attac8ed !y the molten al mini m o: the weld 5oolD ,he al mini m car!ide, Al%C$, so :ormed solidities as an inter5enetrating networ8 o: thin needle=li8e 5lates. Since Al %C$ is 9ery !rittle s ch a str ct re is indeed a materials scientist@s nightmare. A weld containing a str ct re o: this ty5e wo ld !e !rittle in the e<treme. Nor does the horror story end there since the weld wo ld corrode and disintegrate in a matter o: days in the 5resence o: moist reD Metallic car!ides, which e9ol9e methane in this way, are 8nown as Methanides .

15 Electrical and )agnetic Properties of )aterials

15 1 (ne9ita!ly a !oo8 o: this ty5e is concerned mainly with s ch mechanical 5ro5erties o: materials as concern the engineer ! t it is also a55ro5riate to ma8e !rie: mention o: some o: the more im5ortant electrical and magnetic 5ro5erties since these are in9ol9ed in so many im5ortant de9ices in modern engineering 5ractice.

Electrical Cond"ctivit&
15 # (t was s ggested early in this !oo8 that what we re:er to as a Bc rrent o: electricityB in a metal is in :act a mo9ement o: electrons. ,h s metals, in which the 9alency electrons may !ecome de=locali7ed and relati9ely :ree to mo9e among the metallic ions which constit te the crystal str ct re o: the metal, are conse? ently good cond ctors o: electricity. Since electrons will re5el each other they tend to mo9e :rom regions o: high concentration to regions o: low concentration. ,h s )hmBs -aw go9erning the electric c rrent :ollows the same 5rinci5le as #ic8Bs -aw o: Di:: sion (>...0) go9erning the mo9ement o: sol te ions. (onic crystals, howe9er, are non=cond ctors since 9alency electrons are held rigidly !y ions constit ting the crystal. Similarly materials s ch as 5olymers, in which all chemical !onding is o: the co9alent ty5e, are also non=cond ctors since shared 9alency

electrons are or!itals.

na!le to mo9e o t o: their 5artic lar molec lar

15 # 1 ;hilst an electric c rrent in metals is d e to a mo9ement o: electrons, in other materials 5ositi9e or negati9e ions may !e in9ol9ed. ,h s ions are res5onsi!le :or cond ction thro gh electrolytes.

The !at"re of an Electric C"rrent

15 $ ,he Belectron clo dB theory is a con9enient way o: e<5laining some o: the 5ro5erties o: metals ! t in some res5ects we m st regard it as an o9ersim5li:ication o: the tr e state o: a::airs. S ch shortcomings can !e 5artially e<5lained when ? ant m restrictions and +a liBs e<cl sion 5rinci5le ($././) are a55lied to the !eha9io r o: electrons. 15 $ 1 (n a single atom the electrons occ 5y a n m!er o: discrete energy le9els and these energy le9els !ecome closer together the : rther they are :rom the n cle s. (n so :ar as 5ro5erties li8e electrical cond cti9ity are concerned it is the o ter=shell or 9alency electrons which interest s. ,h s the sodi m atom has $$ electrons arranged in .K shells (i.e. the second shell is di9ided into two s !=shells, 0s= and 0.5). Shells $s, 0s= and 05 are :illed

! t the 9alency s !=shell /s co ld hold another electron according to +a liBs e<cl sion 5rinci5le. ,he electrons in each s !=shell occ 5y s5eci:ic le9els (#ig. $&.$(i)). (: sodi m atoms are now !ro ght into close association, that is a Crystal o: sodi m is considered, they !egin to in:l ence one another and the electrons are com5elled to see8 slightly di::erent energy le9els since again according to +a liBs e<cl sion 5rinci5le = not more than two electrons can occ 5y the same ? ant m state. ;ithin e9en a small crystal, containing ne9ertheless many millions or atoms, the energy le9els will !e re5laced !y densely :illed !ands (#ig. $&.$(ii)). ,he sodi m=atom has only one 9alency electron so that only hal: o: the energy states in the /s (or 9alency) !and are :illed. #or this reason the energy re? ired to raise a 9alency electron to an em5ty state is negligi!le. ,his ena!les it to mo9e :reely within the crystal and so to cond ct electricity. (n=the case o:, say, magnesi m the /s !and is :illed ! t since it act ally energies increased within the /5 !and so that magnesi m cond cts

electricity 9ery easily. Howe9er, in some materials the ad3acent energy !ands do not o9erla5 in this way and energy is then re? ired to mo9e electrons across this Benergy ga5B. ,h s in the diamond allotro5e o: car!on the 9alency !and is :illed !y the :o r o ter=shell electrons and a large energy ga5 e<ists !etween this !and and the ne<t 5ossi!le energy !and. 15 $ # (n the case o: diamond the magnit de o: the energy ga5 is a meas re o: the amo nt o: energy needed !y an electron to !rea8 away :rom the co9alent !ond and !ecome a :ree electron. (n diamond this energy ga5 is great (a!o t &.1 < $4=$% K at 04ZC) so that it has a 9ery high electrical resisti9ity. ,he other elements o: Ero 5 (' ha9e similar 9alency electron str ct res and crystallise in 5atterns li8e that o: diamond, that is with :o r co9alent !onds 5er atom. (n silicon and germani m, howe9er, the energy ga5 !etween the B9alency !andB and the Bcond ction !andB is m ch less than in the case o: diamond. #or silicon it is $.& H $4=$% K and :or germani m only $.$ < $4 =$%K (at 04ZC). ,in, also an element o: Ero 5 (', occ rs as an allotro5e, Bgrey tinB, sta!le !elow $&ZC. ,his allotro5e which is non=metallic in character has a similar str ct re to that o: diamond, silicon and germani m and an energy ga5 o: only 4.$/ < $4=$% K. ,h s, in each o: the elements silicon, germani m and grey tin, the

energy ga5 is so small that they can easily recei9e eno gh thermal energy to ca se the release o: 9alency electrons into the cond ction !and. ,hese elements are 8nown as semicond ctors.

The Electrical Cond"ctivit& of )etals

15 % ,he high electrical cond cti9ity o: metals is d e to the high mo!ility o: the o ter=shell or 9alency electrons which, in t rn, is de5endent on the ease with which these electrons can 5ass :rom the B9alencyB !and to the Bcond ctionB !and. Since an electric c rrent is a :low o: electrons amongst the 5ositi9e ions in a metallic crystal any :actor which im5edes this mo9ement will red ce cond cti9ity. ,h s an increase in tem5erat re introd ces greater thermal agitation as ions 9i!rate a!o t their mean 5ositions. ,his o!9io sly red ces the mean :ree 5ath which electrons can :ollow and conse? ently their mo!ility, res lting in a decrease in cond cti9ity (#ig. $&./).

Similarly the 5resence o: sol te atoms, whether s !stit tional or interstitial, will increase the 5ossi!ility o: collisions !etween mo9ing electrons and the ions constit ting the crystal str ct re. ,h s alloys are always less cond cti9e

than the 5 re metals :rom which they are made (#ig. $&..). ,he cond cti9ity o: co55er may !e red ced !y as m ch as .4R !y the 5resence o: only 4.41R 5hos5hor s (#ig. $&.1).

15 % 1 ,he 5resence o: lattice :a lts s ch as dislocations will also red ce cond cti9ity !y increasing the ris8 o: collisions o: the mo!ile electrons with atom cores in the lattice. #or e<am5le hea9ily cold=wor8ed co55er is some $4R less cond cti9e than annealed co55er. 15 % # S"percond"ctivit& ,he electrical resisti9ity o: a metal decreases as its tem5erat re :alls :or reasons s ggested a!o9e. Howe9er, it was disco9ered as long ago as $%$$ !y *ammerlingh )nnes that the electrical resisti9ity o: some metals :alls s ddenly to 7ero when they are cooled !elow a certain 9ery low tem5erat re, termed the transition tem5erat re, ,c (#ig. $&.6). A n m!er o: remar8a!le e<5eriments ha9e !een carried o t with these s 5ercond ctors. )ne well=8nown e<5eriment is to cool a metal ring !elow , c in a magnetic= :ield at right angles to its 5lane. (: the magnetic :ield is then altered a c rrent is ind ced in the ring (this is 9irt ally the 5rinci5le o: the dynamo). ,his ind ced c rrent

will :low almost inde:initely as long as the tem5erat re o: the ring remains !elow , c. S ch an ind ced c rrent has !een 8nown to :low :or se9eral years witho t a55recia!le decay. Most 5 re=metal s 5ercond ctors are in the Btransition gro 5sB o: the +eriodic Classi:ication ! t some metals, which, !y themsel9es, are not s 5ercond ctors :orm intermetallic com5o nds which are. ,h s gold and !ism th as se5arate 5 re metals are not s 5ercond cti9e whilst A 0Bi is. ,his enco raged : rther research and !y the $%14s a , c 9al e o: $&.$ * had !een achie9ed with the com5o nd N!/Sn :ollowed some years later !y N!/EeB with a ,c o: 00.1 *.

A considera!le !rea8thro gh came in $%&6 when the :irst o: the ceramic s 5ercond ctorsB was de9elo5ed. (t has a :orm la -a$.&Sr4.0C ). and a ,c o: .4 *. (t was 9irt ally the com5o nd -a0C ). in which -a ions had !een re5laced in some o: their lattice sites !y Sr ions. (n the :ollowing year came the most :amo s o: these s 5ercond ctors to date = I.Ba0C /)> (,c=%/ *). ;hilst this tem5erat re, %/ * or =$&4C, is not one which wo ld !e associated with the Costa del Sol =or e9en the de5ths o: a Si!erian winter

= I.Ba0C /)> was the :irst s 5ercond ctor to !rea8 the Bli? id nitrogen !arrierB (>> *). ,he signi:icance o: this is that 5rior to its disco9ery s 5ercond ctors wo ld only o5erate as s ch when cooled in e<5ensi9e li? id heli m whereas I.Ba0C /)> can !e cooled in relati9ely ine<5ensi9e li? id nitrogen. As might !e e<5ected the race is now on to 5rod ce a s 5ercond ctor with room=tem5erat re s 5ercond cti9ity, and as ( write the lead has 5assed to the ceramic ,(0Ba0Ca0C /)$4 with a ,c o: $$0 *= tho gh ( s s5ect this will ha9e !een o9erta8en !e:ore these lines lea9e the 5rinterG ,heories which attem5t to e<5lain s 5ercond cti9ity are generally com5le< and !eyond the sco5e o: this !oo8, ! t 9ery !rie:ly, some modem theories s ggest that with s 5ercond cti9e metals and alloys the Bcond ction electronsB !ecome B5airedB then the tem5erat re :alls !elow , c. ,his means that an electron with Bs5inB in one direction !ecomes 5aired with an electron with Bs5inB in the o55osite direction. As a res lt o: this 5airing the electrons 5rod ce no res ltant :ield and. since they s ::er no resistance, can mo9e :reely thro gh the lattice.

Fn:ort nately the 9al e o: ,c is not the sole criterion !y which the merit o: a s 5ercond ctor can !e 3 dged. Fnder the in:l ence o: a s ita!ly strong magnetic :ield the s 5ercond cti9ity o: a material !elow ,c is destroyed and the material re9erts to !eing a normal cond ctor. Since magnetism is de5endent 5rinci5ally 5on the s5in o: electrons ($&.6.$) it is reasona!le to s 55ose that s 5ercond cti9ity is also connected with the mo9ement and s5in o: electrons, 5ossi!ly as o tlined a!o9e. S 5ercond cti9ity !elow ,c is also destroyed when a high c rrent density is em5loyed. Conse? ently s 5ercond cti9ity disa55earsD (i) i: the tem5erat re o: the material is raised a!o9e ,cM (ii) i: a s ::iciently strong magnetic :ield is a55liedM (iii) when a high c rrent density 5re9ails in the cond ctor. Critical :ield strength, Hc, transition tem5erat re ,c, and c rrent density, Kc, are interde5endent. ,he general relationshi5 !etween :ield strength, Hc, and tem5erat re, ,c, as this a::ects s 5ercond ctors is indicated in #ig. $&.>. Regretta!ly the 9al e o: Kc tends to !e 9ery low with most new

s 5ercond ctors and this, co 5led with their e<treme !rittleness, means that m ch de9elo5ment wor8 is necessary to 5rod ce a s 5ercond ctor o: 5ractical se. Ei9en a material with high 9al es o: ,c, Kc and Hc and which can also !e wo nd to :orm a solenoid, then s 5ercond ctors ha9e a great : t re in !oth electrical and electronic engineering. ,a!le $&.0 lists 5ro5erties o: some metals, alloys, intermetallic com5o nds and ceramics which ha9e :eat red as s 5ercond ctors since $%$$.

+ns"lators
15 ' Non=cond cting materials=or ins lators=are those in which !onding is either co9alent or ionic. (n s ch materials the 9alency electrons are :irmly retained in :i<ed or!itals and are na!le to mo9e :reely as they are in metals. 'alency !ands in ins lators are com5letely :illed and there is a wide energy ga5 !etween the 9alency !and and the ne<t 5ossi!le energy !and. Fnder s ch circ mstances a large in5 t o: energy wo ld !e

re? ired in order that an electron co ld cross the ga5. A 9ery small n m!er o: electrons may ac? ire s ch energy i: the material is s !3ected to a high 5otential di::erence and these ins lators 5ossess 9ery low ! t ne9ertheless meas ra!le cond cti9ities. At high tem5erat res indi9id al electrons will 5ossess greater energies and so the chances o: them Besca5ingB is increased. Cond cti9ity will there:ore increase. (ns lating materials may !rea8 down nder the 5ress re o: an electrical, 5otential di::erence which is high eno gh to raise the energies o: large n m!ers o: electrons to the 5oint where they can cross the energy ga5 and !ecome B:reeB. S ch a 5otential di::erence is generally termed the [!rea8down 9oltageB. 15 ' 1 (ntermediate !etween cond ctors and ins lators are the semicond ctors, !ased mainly on the Ero 5 $'. elements silicon and germani m, which d ring the latter hal: o: the twentieth cent ry ha9e re9ol tioni7ed the electronics ind stry and rendered o!solete the thermionic 9al9e in domestic radio and ,' recei9ers. Howe9er, their st dy is really the :ield o: the electronics engineer and s5ace here m st !e sacri:iced to other im5ortant engineering materials to5ics.

)agnetism
15 ( (ron is the metal generally associated with magnetism ! t three other BtransitionB metals ^ co!alt, nic8el and gadolini m = are also strongly magnetic, or :erromagnetic, as it is s ally termed, ,his distinction is necessary !eca se many other elements and materials 5ossess wea8 magnetic 5ro5erties. Most metals are 5aramagnetic that is they are wea8ly attracted !y a strong magnetic :ield, whilst some metals and all o: the non=metals are diamagnetic, that is they are re5elled !y a strong magnetic :ield.

)nly the :erromagnetic metals ha9e characteristics which ma8e them technologically se: l as magnets, either alloyed with each other or with other s ita!le materials. 15 ( 1 Ferromagnetism ;hat we re:er to as a Bmagnetic :ieldB associated, with a :erromagnetic material is 5rod ced !y the Bs5inB o: electrons. (n :act we can 5rod ce an electromagnetic :ield !y 5assing a stream o: electrons thro gh an electrical cond ctor. (n a sta!le atom the electrons may !e regarded as mo9ing 5articles rotating in or!itals aro nd the n cle s. At the same time each electron !eha9es as tho gh it were s5inning on its own a<is and it is this s5in which generates the magnetic :ield, that is, it is in e::ect a min te magnet. ;e ha9e seen that in a sta!le atom, whether it e<ists as a single nit or is 5art o:$ a crystal, not more than two electrons are 5ermitted to occ 5y the same energy le9el. ,hese two electronsB ha9e s5ins which are in o55osite directions. Conse? ently in the ma3ority o: elements as many electrons will ha9e s5ins in one direction as in the other and indi9id al :ields 5rod ced !y electrons will cancel o t. Hence there will !e little, i: any, res ltant magnetic :ield associated with the atom. S ch elements tend to !e either 5aramagnetic or diamagnetic (#ig. =$&.&(i)). Some o: the transition element,

howe9er, ha9e n:illed s !9alency shells so that n5aired electrons will !e 5resent. As a res lt, in any atom, more

electrons will s5in in one direction than in the other (#ig. $&.&(ii)) and s ch an atom will ha9e a res ltant magnetic moment. (n the elements a=iron, co!alt, nic8el and gadolini m the magnetic moments o: the atoms are great eno gh and the ions s ::iciently close together that when the atoms !ecome magnetically aligned=d ring Bmagneti7ationsB= a 5ower: l magnetic :ield is 5rod ced. 15 ( # Magnetic 5ro5erties are a::ected critically !y atomic s5acing. (: atoms are too :ar a5art then :orces !etween them are too wea8 to resist the e::ects o: thermal agitation which throws s5ins o t o: alignment so that indi9id al :ields cancel. (: atoms are too close together then inter=atomic :orces are too great to allow alignment o: s5ins. Conditions a55ear to !e :a9o ra!le when the atomic radi s is !etween $.1 and 0.4 times the radi s o: the shell containing the n=5aired electrons. ,he elements a= iron, co!alt, nic8el and gadolini m : l:ill these re? irements ! t other transition elements s ch as titani m, chromi m and manganese are only 3 st o tside the range. ,h s i: manganese contains interstitial nitrogen atoms it !ecomes :erromagnetic d e to a modi:ication in the atomic s5acing. Similarly interatomic s5acing in s ch ceramics as Ba=#e$04$% ma8es them a9aila!le as magnetic materials. Alloys containing 9ario s 5ro5ortions o: the metals iron, chromi m, t ngsten, co!alt, nic8el, al mini m and titani m (,a!le $&./) are 5artic larly s ita!le as 5ermanent magnets. Contained within the crystals which com5rise a :erromagnetic material are small regions 8nown as magnetic domains. ,hese are regions, 5ossi!ly not more than 4.41 mm in diameter, in which atoms are aligned so that their orientations are in the same direction. (n the nmagnetised state these domains are randomly orientated so that there is no res ltant :ield, ! t material !ecomes magneti7ed (#ig. $&.%). ,his alignment may !e retained when the magneti7ing :ield is remo9ed and in this case the material is said to !e

magnetically hard. (n many cases the magnetism is not retained when the magneti7ing :ields is

remo9ed and the material is said to !e magnetically so:t. (n :act magnetic hardness s ally coincides with 5hysical hardness, that is, hardened steel is o:ten s ita!le as a 5ermanent magnet, whilst so:t steel is also magnetically so:t and there:ore ns ita!le as a 5ermanent magnet. +ossi!ly the resid al strains 5resent in the hardened material o55ose randomi7ation o: the domains once the material has !een magneti7ed. (: a magneti7ed material is heated it loses its magnetism !eca se the thermal energy s 55lied 5ro9ides the necessary acti9ity which 5ermits randomi7ation o: domain alignment. 15 ( $ A 5ermanent magnet is designed to 5ro9ide a magnetic :ield o: :orce which does not in9ol9e the se o: energy :rom an e<ternal so rce. (t m st also !e a!le to retain its magnetism :or an nlimited 5eriod e9en nder the action o: limited demagneti7ing in:l ences. ,he act al magnetic strength, or :l <, in a 5ermanent magnet is de5endent 5on its design and the material :rom which it is made. ,he essential characteristics o: a 5ermanent=magnetic material a:ter it has !een magneti7ed areD (i) coerci9e :orceM (ii) resid al magnetism or remanenceM (iii) energy 5rod ct 9al e.

i: these domains are aligned !y a55lying an e<ternal magnetic :ield the ,he coerci9e :orce is a meas re o: the materialBs resistance to demagneti7ation !y electrical means, whilst remanence relates to the intensity o: magnetism remaining in the magnet a:ter the magnetising :ield has !een switched o::. ,he energy 5rod ct 9al e is 9irt ally the ? antity o: magnetic energy stored in the magnet :ollowing magnetisation. (t is deri9ed :rom the demagnetisation c r9e RF (#ig. $&.$4). 15 ( % #ig re $&.$4 shows what is 8nown as a hysteresis loo5 :or a magnetically hard material. Here the ind ced magnetic :l < density (meas red in teslas and denoted !y B) is 5lotted against the magneti7ing :ield (e<5ressed in am5ere=t rns 5er metre, H). S ch in:ormation is o!tained when a :erromagnetic material is 5laced in a solenoid thro gh which a c rrent can !e 5assed. (ncreased 9al es o: c rrent will 5rod ce an increased magnetic :ield strength H which, in t rn, will ind ce an increasing :l < density B in the magnet.

Beginning with a small 9al e o: H and increasing it grad ally, corres5onding 9al es o: Band H are 5lotted to gi9e the

c r9e )+. ,his is the magnetisation c r9e which ltimately Ale9els o tB at + where the material reaches magnetic sat ration. (: the magnetising :ield is now red ced to 7ero the corres5onding :all in the ind ced magnetic :l < density is indicated !y +R. ,h s )R re5resents the 9al e o: the magnetic :l < density remaining in the material when all e<ternal magnetising in:l ence is remo9ed. ,his is the remanent magnetism or remanence, Brem. ,o demagnetise the material and at the same time meas re the :orce re? ired to do this, a c rrent is 5assed thro gh the solenoid in the re9erse direction and grad ally increased. ,his 5rod ces the c r9e RF which is the demagnetisation c r9e. (nterce5t )F re5resents the :orce re? ired to demagnetise the material com5letely and is called the coerci9e :orce. ,o com5lete the hysteresis loo5 the o5erations o tlined are carried on to Bnegati9eB sat ration and then re5eated in the re9erse sense. ,he hysteresis loo5 re5resents the lagging o: the magnetic :l < ind ced !ehind the magnetising :orce 5rod cing it. ,he area within the loo5 is 5ro5ortional to the ? antity o: energy lost when the material is magnetised or demagnetised and, :or 5ermanent magnet materials the area o: the loo5 m st !e as large as 5ossi!le. 15 ( ' ,he ltimate criterion o: a 5ermanent magnet is the ma<im m 5rod ct o: Band H o!tained :rom a 5oint O on the demagnetisation c r9e. i.e. the 5osition o: O is s ch that the 5rod ct o: HO and IO is a ma<im m. ,his 9al e, BH ma<, corres5onds to the ma<im m energy the magnet can 5ro9ide in a circ it e<ternal to itsel:. A sim5le method o: assessing the e::iciency o: a magnet in terms o: its remanence is to determine its Bs? areness ratioB (B rem 2 Bsat) where Bsat is the sat ration 9al e o: the a55lied :ield and B rem the remanence. A s? areness ratio near to one. i.e. B rem2Bsat k $, means that any stored 5attern o: domains is retained in 7ero :ield. A high 9al e o: Hc ens res that the 9al e Brem will !e sta!le with time and against any stray magnetic :ields.

15 ( ( Hardened car!on steels were :irst sed as 5ermanent magnets, later !eing re5laced !y alloy steels containing chromi m and t ngsten. ,hese were :ollowed !y /1R co!alt steel in the early days o: the BwirelessB, ntil in the $%/4s the #e=Al=Ni=Co range o: 5ermanent magnets was de9elo5ed. ):ten the choice o: a 5ermanent magnet material relates to whether high remanence or a high coerci9e :orce is re? ired. ,h s BCol ma<B has a high remanence whilst BHycoma< /B has a high coerci9e :orce. More recently, alloys containing Brare=earthB elements s ch as neodymi m and samari m ha9e 5ro9ided high 9al es o: !oth remanence and coerci9e :orce in a single alloy. (n :act the 9ery high :l < densities a9aila!le with the Nd=#e=B alloys ha9e 5ermitted smaller magnets to !e sed so that d.c. motors with the magnets in the rotor and windings in the stator are 5ossi!le = a re9ersal o: 5re9io s 5ractice. Some magnetic materials are anisotro5ic, that is they ha9e s 5erior 5ro5erties along a 5re:erred a<is. ,his e::ect is o!tained !y heating the alloy to a. high tem5erat re and allowing it to cool in a magnetic :ield. As thermal agitation is red ced gro 5s o: atoms !ecome orientated along the :ield and this orientation is 9irt ally B:ro7en inB. 15 ( 4 ;hilst magnetically hard materials are re? ired :or 5ermanent= magnet a55lications s ch as lo ds5ea8ers, magnetic ch c8s, generators, small electric motors, magnetic recording ta5es and the li8e, s ch com5onents as trans:ormer core and dynamo 5ole=5ieces need to !e magnetically so:t ! t o: high magnetic 5ermea!ility. +ermea!ility (u) is gi9en !y the ratio B2 H and its 9al e alters with the magnetising :ield, reaching a ma<im m and then :alling. Since a trans:ormer core is nder the in:l ence o: alternating c rrent, the core is :irst magnetised, then demagnetised and then demagnetised with re9erse 5olarity. S ch a cycle 5rod ces the closed hysteresis loo5 +RF_S, (#ig. $&.$4) and the area o: this=loo5 re5resents the amo nt o: energy wasted in o9ercoming remanent magnetic :orces each time the c rrent is re9ersed (:or e<am5le 14 times 5er second). ,his energy is lost as

heat and it is there:ore necessary to se materials which gi9e 9ery narrow hysteresis loo5s and conse? ently small Bhysteresis lossB (#ig. $&.$$(ii)). So:t 5 re iron and #e=.Si ha9e a 9ery low hysteresis and ha9e !een sed in the :orm o: stam5ings :or trans:ormer cores and the li8e. Some #e=Ni alloys are also im5ortant as low=hysteresis, high= 5ermea!ility alloys. ,h s >.Ni=1C =lMn=!al, #e has !een sed in comm nications engineering, 5artic larly as a shielding material. As with 5ermanent magnet materials the c rrent tendency is towards the se o: magnetically so:t ceramic materials 8nown as B:erritesB the com5osition o: which is !ased on :erroso=:erric o<ide, #e/)., or more 5ro5erly, #e).#e0)/. (n, this :orm la some o: the #e0W ions in #e) are s !stit ted !y either Ni 0W and On0W or Mn0W and On0W gi9ing s !stances which can !e ro ghly e<5ressed !y the :orm lae, #e0(Ni<Ony)). or #e0(Mn<Ony)). where < W y P $. (t sho ld !e noted that the com5osition o: either is not strictly stoichiometric (that is, o!eying the r les o: chemical com!inations !y :i<ed 5ro5ortions). ,hese materials are man :act red as 5owders and then sintered to gi9e a solid ceramic. At 5resent :errites dominate the :ield o: electronics. Since their 5ro5erties can !e 9aried !y ad3 sting com5osition and also !y 9arying 5article si7e and treatment, they can !e tailored to meet s5eci:ic re? irements. 15 ( 5 A : rther gro 5 o: magnetically so:t materials is metallic glasses ($/.6.&) the !asic com5osition o: which incl de transition metals s ch as #e, Co, Ni and Cr and non=metals or metalloids li8e B, Si, + and C. ,he molten sol tion is cooled

9ery ra5idly (some $464C2s) !y s? irting on to a cooled rotating wheel ($/.6.&) to 5rod ce a ta5e some 14 microns thic8. Ra5id cooling 5rod ces an amor5ho s (glassy) str ct re (/.>.1) since the tem5erat re dro5 is too ra5id to 5ermit the onset o: crystallisation. ,he most im5ortant ind strial 5rod ct o: this ty5e to date is BMetglasB 06412S0 made in the FSA. ,his is an #e&4=B04 metallic glass man :act red as ri!!on (#ig. $/.0/) :or the 5rod ction o: laminated trans:ormer cores. (ts lac8 o: crystal !o ndaries, along with the relati9e a!sence o: de:ects, aids the mo9ement o: domain walls d ring the magnetisation cycle, res lting in a 9ery low hysteresis loss and a high 5ermea!ility. ,he hysteresis loss in 5ower=s 55ly trans:ormers sing #e&4=B04 BMetglasB is only a!o t 01R o: that in those sing the con9entional #e=/Si alloy. (t has !een estimated that the re5lacement in the F* o: trans:ormers !ased on the con9entional alloy !y new ones em5loying #e&4=B04 cores wo ld lead to a : el sa9ing e? i9alent to some $./ Mt o: oil 5er ann m res lting in a red ction o: Bgreenho se gasB emissions o: ..1 Mt o: C)0 and $04 8t o: S)0 each year ($.6). +erha5s it is time to introd ce the threatened BCar!on ,a<BG

17 The Environmental Sta*ilit& of )aterials

17 1 ,he realisation that metallic corrosion is a 9ery costly 5rocess is !ro ght home to most o: s !y the :act that the wor8ing li:e o: an e<5ensi9e Atin li77ieB is limited !y the r sting o: its !odywor8 rather than the wearing o: its mechanical 5arts. ;hilst the latter are generally re5lacea!le nothing can !e done when the welded shell !egins to disintegrate d e to cree5ing r st. A recent EEC s r9ey estimated that a staggering ..0R o: the EN+ was the cost to most ind strial co ntries o: the e::ects o: corrosion on ! ilding str ct res, shi5s, a tomo!iles, agric lt ral e? i5ment and o::shore installations. As :ar as the EEC is concerned this cost is meas red in h ndreds o: millions o: ECF@s 5er ann m. Materials other than metals also 5ossess 9arying degrees o: insta!ility. R !!er B5erishesB 5artic larly when e<5osed to air and s nlight and some 5lastics materials !ecome 5rogressi9ely more !rittle nder the in:l ence o: ltra=9iolet light. Concrete and other ceramic materials are grad ally eroded !y :rost and the chemical e::ects o: o r 5oll ted atmos5here. A large gro 5 o: materials, !oth metallic and non=metallic, may !e damaged to some degree !y 9ario s :orms o: radiation. Most materials will deteriorate more ? ic8ly at high tem5erat res d e to attac8 !y atmos5heric o<idants s ch as C)0 and some s l5h r com5o nds as well as o<ygen. Brittle materials o: high e<5ansion coe::icient s ch as : rnace re:ractories are lia!le to s5all=or :la8e away=i: the rate o: heating or cooling is e<cessi9e.

-r& Corrosion or the B/idation of )etals

17 # ;hilst many metals tend to o<idise to some e<tent at all tem5erat res, most engineering metals do not scale a55recia!ly e<ce5t at high tem5erat res. ;hen iron is heated strongly in an atmos5here containing o<ygen it !ecomes coated with a :ilm o: !lac8 scale. A chemical reaction has ta8en 5lace !etween atoms o: iron and molec les o: atmos5heric o<ygenD 0#e W )0 X 0#e) Altho gh the reaction can !e e<5ressed !y the a!o9e sim5le e? ation in :act atoms o: iron ha9e !een o<idised whilst atoms o: o<ygen ha9e !een red ced. ,hese 5rocesses are associated with a trans:er o: electrons :rom one atom to the other. )<idation #e X #eWW W 0electrons(e=) Red ction ) W 0 electrons (e=) X ){ (t sho ld !e noted that, in the chemical sense, the terms o<idation and red ction ha9e a wider meaning than the com!ination or se5aration o: a s !stance with o<ygen. ,h s a s !stance is o<idised i: its atoms lose electrons whilst it is red ced i: its atoms (or gro 5s o: atoms) gain electrons. #or this reason we say that iron is o<idised i: it com!ines with s l5h r, chlorine or any other s !stance which will acce5t electrons :rom the atoms o: iron. 17 # 1 (n some cases the :ormation o: the o<ide :ilm 5rotects the metal :rom : rther o<idation yet in many instances o<idation and scaling contin e. #or this to occ r either molec les o: o<ygen m st 5ass thro gh a 9ery 5oro s :ilm o: o<ide, or ions o: either o<ygen or the metal m st migrate within a contin o s :ilm. ,he chemical com5osition o: a sta!le :ilm o: :erro s o<ide wo ld !e #e), ! t the sit ation indicated in #ig. $%.$, where a 5iece o: iron is !eing strongly heated, res lts in that 5art o: the o<ide :ilm nearest to the

iron s r:ace containing an e<cess o: #eWW ions whilst that ad3acent to the air contains an e<cess o: )== ions. ,hese )== ions are :ormed when electrons, released :rom iron atoms (which then !ecome #e WW ions) 5ass thro gh the o<ide :ilm to o<ygen atoms at the s r:aceD ) W 0e= X )==. ;hilst the :ilm remains thin the :orce o: attraction !etween )== ions at the o<ide s r:ace and #e WW ions at the metal s r:ace will !e great so that )== ions will di:: se ra5idly to :ill 9acant Bo<ygen sitesB at the metal s r:ace. As the o<ide :ilm e<5ands away :rom the metal s r:ace, se5aration o: the #eWW ions and the )== ions increases. Conse? ently attraction !etween them decreases and the rate o: di:: sion and hence growth o: the o<ide :ilm also decreases.Q
Q ;ith 5rolonged o<idation o: iron at high tem5erat res s ch as occ rs when large steel ingots are heated :or se9eral ho rs 5rior to rolling, the o<ide layer !ecomes so thic8 and the di:: sion o: 4== ions conse? ently so slow that a layer o: #e/4. (#e). #e04,) :orms on to5 o: the layer o: #e), and this in t rn !ecomes co9ered with a layer o: #e04/ at the o<ide2air inter:ace.

-et the thic8ness o: the o<ide :ilm !e < at a time t, then ass ming the concentrations o: the ions at the s r:aces o: the o<ide layer remain constant, there will !e a di::erence &c in concentration across the o<ide :ilm. (n accordance with #ic8Bs -aw the rate o: di:: sion o: ions across nit area is D. dc2dr, which is 5ro5ortional to a rate o: dr2dr. ,here:oreD
d< l <=$
dt

or

<0 P8t

where 8 is related to D, the di:: sion constant. ,his indicates that the :ilm growth :ollows a 5ara!olic law. ;hen the tendency o: this growth is to increase the density o: the o<ide :ilm witho t red cing its mechanical sta!ility then it will o!9io sly im5ro9e the 5rotection against : rther o<idation. (:, howe9er, the stresses generated in the :ilm as a res lt o: increased density, lead to :ract re and !rea8. 5 o: the :ilm, the metal s r:ace will !e e<5osed and : rther o<idation will !e the res ltD )<idation rates also de5end 5on the 5orosity o: the o<ide :ilm. Some metals :orm ions which are m ch smaller than the original atoms. Conse? ently as ions are :ormed there is a 9ol me red ction o: the scale which, as a res lt, !ecomes 5oro s and 5ermits easier access o: o<ygen to the metal s r:ace. Contraction o: the o<ide :ilm may also ca se it to :la8e o:: th s e<5osing a :resh metal s r:ace. (n some cases e<5ansion o: the :ilm may occ r ca sing it to ! c8le and !ecome detached.

17 # # An o<ide :ilm which adheres tightly to the s r:ace o: the metal generally o::ers good 5rotection. Eood adhesion is the res lt o: coherence !etween the :ilm and the metal !eneath. (n #ig. $%.0(i) there is good BmatchingB !etween the ions in the metal s r:ace and the metallic ions in the o<ide :ilm s ch that the

str ct re is 9irt ally contin o s, whilst in #ig. $%.0(ii) matching is a!sent so that the two s r:aces will !e non=coherent and there will !e little adhesion. ,he high degree o: coherence !etween al mini m and its o<ide leads to the e::ecti9e 5rotection o: this metal es5ecially when the :ilm is arti:icially thic8ened !y anodising. 17 # $ (t :ollows :rom the a!o9e that the !est way to 5rotect a metal li8e iron :rom high=tem5erat re o<idation is to add an element which will coat the s r:ace with a dense and closely adherent o<ide layer in which the mo!ility o: !oth ions and electrons is low. Al mini m :orms a dense o<ide :ilm with a 9ery high electrical resistance ma8ing it ideal in this res5ect, ! t it has ad9erse e::ects on the mechanical 5ro5erties o: the steel i: added in the amo nts necessary to 5ro9ide o<idation 5rotection. ,he same is tr e o: silicon. ,his lea9es chromi m as the ne<t !est and most se: l metal in this res5ect. ,he o<ide Cr0)/ coats the s r:ace o: iron with a dense s8in !eneath the o ter :ilm o: #e 0)/. Chromi m is th s an essential constit ent o: heat=resisting steels ($4.1.0). Some alloys are 5rone to attac8 !y atmos5heres containing s l5h ro s gases. Since nic8el readily :orms a s l5hide at high tem5erat res it is 5artic larly lia!le to !e o<idised !y gases containing s l5h r. Heat= resisting steels sed in s ch conditions m st !e o: the high=chromi m ty5e, 5re:era!ly containing little or no nic8el.

Aet Corrosion or Electrochemical B/idation

17 $ (ron does not r st in a com5letely dry atmos5here nor will it r st in com5letely 5 re, o<ygen=:ree water, ! t in a moist atmos5here the well=8nown reddish=!rown de5osit o: :erric hydro<ide soon !egins to de9elo5. ,he o9erall chemical reaction re5resenting r sting can !e e<5ressed !y a sim5le chemical e? ationD .#e W 6H0) W /)0 .#e()H)/

,his general res lt, howe9er, is achie9ed in a n m!er o: stages and the : ndamental 5rinci5le in9ol9ed is that atoms o: iron in contact with o<ygen and water are o<idised, that is they lose electrons and enter sol tion as :erro s ions (#eWW)D #e X #eWW W 0 electrons (0e=) ,hese :erro s ions are ltimately o<idised : rther to :erric ions (#eWWW) !y the remo9al o: another electronD #eWW X #eWWW W e = As iron goes into sol tion in the :orm o: ions the corres5onding electrons are released. ,hese electrons immediately com!ine with other ions so that o9erall e? ili!ri m is maintained. ,he ease with which a metal can !e o<idised in this way de5ends 5on the ease with which 9alency electrons can !e remo9ed :rom its atoms. ,h s metals li8e calci m, al mini m and 7inc hold their 9alency electrons com5arati9ely loosely and can there:ore !e o<idised more easily than ironM ! t the no!le metals gold, sil9er and 5latin m retain their 9alency electrons more strongly and are there:ore m ch more di::ic lt to o<idise than iron. Co55er holds on to its 9alency electrons more strongly than does iron and, nder s ita!le conditions, co55er ions will BstealB 9alency electrons :rom atoms o: iron. ,h s when a 5en8ni:e !lade is immersed in co55er s l5hate sol tion the !lade !ecomes coated with metallic co55er. Co55er ions at the s r:ace o: the !lade ha9e remo9ed electrons :rom the atoms o: iron there so that the res ltant :erro s ions ha9e gone into sol tion th s re5lacing the co55er ions which ha9e !een de5osited as co55er atoms #e X #eWWW0e= C WW W 0e= X C Co55er s l5hate sol tion is `sometimes sed to coat the s r:ace o: steel with a thin layer o: co55er as an aid to Bmar8ing o tB, in the tool room.

17 $ 1 ,h s di::erent metals ha9e di::erent o<idation 5otentials since the amo nt o: energy re? ired to remo9e their 9alency electrons 9aries :rom metal to metal. ,he ionisation 5rocess ! ilds 5 an electrical 5otential called an electrode 5otential and this de5ends 5on the nat re o: the sol tion as well as 5on the nat re o: the metal. Electrode 5otentials are meas red with re:erence to hydrogen (#ig. $%./) and are se: l in assessing the tendencies o: the metal to corrode. ,o do this standard hydrogen electrode is sed as indicated and some :orm o: 5otentiometer em5loyed to meas re the 5otential di::erence (in 9olts) 5rod ced !etween the hydrogen electrode and the metal electrode, since hydrogen is a gas the electrode sed consists o: a 5latin m t !e (which is relati9ely inert) into which hydrogen is 5assed. Hydrogen dissol9es interstitially in 5latin m and in this way :orms an electrode. By sing similar methods an

electrochemical series can !e 5re5ared :or the metals as indicated in ,a!le $%.$.

17 $ # 6alvanic Action +nvolving -issimilar )etals (n #ig. $%./ the electrode which will s 55ly electrons to the e<ternal circ it (when the latter is [closedB) in each case is called the anode and the electrode which will recei9e electrons 9ia the e<ternal circ it is called the cathode. ,h s in #ig.$%./(i) the hydrogen electrode is the anode whilst in #ig. $%./(ii) the iron 5late is the anode. At this 3 nct re it is necessary to mention an im5ortant 5oint connected with electrochemical nomenclat re and one which may otherwise 5 77le the reader. ,he Eree8 deri9ation o: the term Aanode@ im5lies Bsomething which is !eing ! ilt 5B and in :act the anode was so named in the early days o: the st dy o: electricityB !eca se it was ass med that 5ositi9ely charged B5articles o: electricity were :lowing thro gh the e<ternal circ it :rom the cathode to the anode. (t is now realised that what we call an electric c rrent is in :act a :low o: negati9ely charged 5articles{or electrons in the o55osite direction, i.e. :rom the anode to the cathode 9ia the e<ternal circ it.

,h s, instead o: recei9ing 5ositi9ely charged 5articles :rom the e<ternal circ it the anode s 55lies negati9ely charged electrons to the e<ternal circ it and is conse? ently le:t with 5ositi9ely charged 5articles (ions) which it immediately releases into sol tion. ;e there:ore 9is alise the anode as !eing negati9ely charged !eca se it is the so rce o:

Electrons to the e<ternal circ it. (n the ill strations which :ollow, electrons will !e seen to !e :lowing in the o55osite direction to that which is ascri!ed to Bc rrentB !y long=esta!lished con9ention
#e #eWW W 0e=
.(:

an e<ternal electrical contact is made !etween the electrodes o: the system shown in #ig. $%./(ii) as indicated in #ig. $%.., the lower electrode +otential o: the iron will ca se it to lose electrons, which will :low away #rom the anode thro gh the e<ternal circ it

to the cathode the res ltant #eWW ions entering sol tion. ,he electrons, which arri9e at the cathode Com!ine with HW ions in the s rro nding electrolyte and :orm molec lar Hydrogen, which s !se? ently esca5es as small ! !!lesD
HW W e= H H W H H0

,his reaction ca ses : rther electrons to :low :rom the iron anode so that More atoms ionise li!erating electrons and entering the electrolyte as #eWW ions. ,he Bdri9ing :orceB !ehind this reaction is the di::erence in electrode5otential !etween iron and hydrogen. ,hese reactions contin e s5ontaneo sly, iron dissol9ing :rom the anode and hydrogen 5reci5itation at the cathode. ,he hydrogen ions (HW) 5resent in the electrolyte are :ormed !y the ionisation o: water molec lesD H0) f HW W )H= As HW ions are Bne trali7edB on recei9ing electrons to :orm hydrogen atoms (and s !se? ently molec les) more water ionises s5ontaneo sly. ,he Concentration o: hydrogen ions in 5 re water is e<tremely low=o: the order o: $4=> gram=atoms2litre=and so the :ormation o: hydrogen atoms and the sim ltaneo s sol tion o: iron wo ld !e 9ery slow. (n 5ractice some sol !le im5 rities in water lead to a m ch higher degree o: ionisation o: the water and so gal9anic corrosion ta8es 5lace at a greater rate. A sol tion in which :ree ions are 5resent, and which will there:ore allow an electric C rrent to !e transmitted in an e<ternal circ it is termed an electrolyte. Most organic li? ids s ch as alcohol, t r5entine, oils, etc. are non=electrolytes since the 5resence o: co9alent !onds thro gho t their. molec les ma8es ionisation im5ossi!le. Eal9anic corrosion is not 5ossi!le in the a!sence o: an electrolyte. As mentioned a!o9e 5 re water is, a 9ery wea8 electrolyte since an e<tremely small 5ro5ortion o: its molec les are ionised, ! t when it contains dissol9ed im5 rities s ch as car!on dio<ide or s l5h r

dio<ide (5re9alent in ind strial atmos5heres) its degree o: ionisation is considera!le. 17 $ $ ;e are now in a 5osition to consider the reactions, which will occ r when, say, a co55er 5late and an iron 5late are connected e<ternally and are in m t al contact with an electrolyte (#ig. $%.1). (ron is anodic towards

#ig. $%.1 ,he reactions in an iron=co55er gal9anic cell.

hydrogen whilst co55er is cathodic towards hydrogen. (t :ollows then that iron will !e strongly anodic towards co55er and so electrons will immediately !egin to :low :rom the iron anode to the co55er cathode thro gh the e<ternal circ it. Ha9ing lost electrons some iron atoms will 5ass into the electrolyte as #e WW ions. (n the meantime the co55er cathode !ecomes negati9ely charged as it recei9es electrons :rom the iron anode, 9ia the e<ternal circ it. +ositi9ely charged hydrogen ions, HW, 5resent in the electrolyte will !e attracted to the cathode where they will com!ine with electrons to :orm hydrogen atoms and, s !se? ently, molec lesD

0HW W0e= X 0H X H0 th s restoring the !alance. As more and more HW ions are ne tralised !y electrons :rom the anode in this way to :orm hydrogen atoms, so more and more water molec les will ionise to restore the !alance !etween molec les and ions.. ,he concentration o: hydro<yl ions ()H=), also :ormed !y the ionisation o: water molec les, will ! ild 5 in the region o: the cathode (#ig. $%.6).

Altho gh #eWW ions are released into the electrolyte at the anode they do not remain there. ,here is a m t al attraction !etween them and the )H= ions. Howe9er, since #eWW ions are m ch smaller than )H= ions they are a!le to migrate ra5idly towards the cathode where the concentration o: )H= ions is high. ,here the two ty5es o: ion reactD #eWW W 0()H=) X #e()H)0 (n addition to the #eWW ions ha9ing a greater mo!ility than )H = ions, only one #eWW ion is re? ired to ne tralise two )H= ions.

,he :erro s hydro<ide, #e()H)0, which is :ormed ra5idly o<idises to insol !le :erric hydro<ide, #e()H)/, which collects as the reddish=!rown de5osit we call Br stB. M ch o: this :alls :rom the cathode to the !ottom o: the cell. .#e()H)0 W0H0) W )0 X .#e()H)/ | Br stB Dissol9ed o<ygen also 5lays its 5art in increasing the rate o: corrosion o: the anode !y reacting with water molec les at the cathode (where electrons are a9aila!le)D )0 W 0H0) W . e= X .)H= ,he rate o: :ormation o: hydro<yl ions is th s increased. 17 $ % S"mmar& of Reactions 6H0) | 6HW W 6)H= W /40 W $0 e= ============== e $0()H=) dissol9ed } o<ygen } | :rom cathode

At anode a 6#e X 6#eWW W $0 e=

At cathode a 6#eWW W $0()H=) X :erro s hydro<ide

6#e()H)0

,he :erro s hydro<ide is then grad ally o<idised d e to the 5resence o: dissol9ed o<ygenD 6#e()H)0 W /H0) W $ $20)0 X 6#e()H)/ :erric hydro<ide (Br stB) ,hese reactions can !e Bcom!inedB to gi9e the :ollowingD 6#e W %H0) W . $20)0 X 6#e()H)/ ,his single e? ation re5resents chemically the o9erall reaction ! t it does not e<5lain the ste5s !y which the res lt is achie9ed. (n many o: the e<am5les which :ollow the electro=chemistry has !een sim5li:ied !y ass ming that FeHHH ions are formed at the anode to gi9e a res ltant de5osit o: #e()H)/ near to the cathode. 17 $ ' Common E/amples of 6alvanic Corrosion +nvolving -issimilar )aterials Readers who are also 5ractising engineers will !y now ha9e realised why it is generally considered !ad 5ractice to se dissimilar metals in contact with each other and in m t al contact with an electrolyte al!eit the latter is only condensed atmos5heric moist re. Ne9ertheless, in domestic 5l m!ing one o:ten does not need to loo8 :ar to disco9er e<am5les o: electrochemical mal5ractice. #or e<am5le, most cold=water cisterns sed to !e o: gal9anised iron and whilst s ch material was ? ite ade? ate when 5ro5erly sed, the li:e o: the 7inc coating co ld only !e shortened i: a co55er inlet 5i5e was allowed to enter the water ad3acent to the side o: the tan8. Oinc is strongly anodic to co55er and since the water was e::iciently aerated at the inlet the 7inc co ld only !e e<5ected to corrode e<5osing the iron !eneath. (ron too is anodic to co55er and so a lea8ing tan8 was ine9ita!le. S ch lea8s s ally de9elo5ed when one was away on holiday, o::ering a melancholy 5ros5ect on oneBs ret rn. #ort nately +'C cold=water cisterns are now sed and are o: co rse imm ne :rom any sort o: gal9anic attac8, ! t i: yo r ho se was ! ilt !e:ore a!o t

$%>4 an ins5ection o: the cistern may !e ad9isa!le. (: it t rns o t to !e o: gal9anised iron ta8e a closer loo8 at its conditionG Mi<ing o: lengths o: iron and co55er :or carrying water leads to the

Fig 17 4 An e<am5le o: !ad 5l m!ing. accelerated corrosion o: the iron 5i5e near to its 3oint with the co55er (#ig. $%.>). E<am5les o: this ty5e o: !ad 5ractice are o:ten 5ro9ided !y those who sho ld 8now !etter. ,he motor=car ind stry has a ha!it o: stic8ing !its o: stainless=steel BtrimB on to the mild= steel !ody=wor8. ,his is ? ite sa:e so long as the mild steel is com5letely coated with 5aint ! t in9aria!ly the 5aintwor8 aro nd the :i<ing hole is damaged d ring the :i<ing 5rocess and the design is s ch that water collects in the region o: the 3oint th s constit ting a gal9anic cell. Since the mild=steel !ody is anodic to the stainless=steel BtrimB the !ody=wor8 ltimately r sts away, no do !t to the ltimate satis:action o: the man :act rer who :inds s ch ca5rices good :or trade. (ron and steel m st generally !e 5rotected :rom !oth atmos5heric and a? eo s corrosion !y coating with some 5rotecti9e :ilm. +ainting, electro5lating, tinning and gal9anising are 5rocesses which can !e sed to this end. Howe9er, when metallic coatings are sed the e::ect o: 5ossi!le :ilm damage m st !e considered, 5artic larly as to whether the :ilm will !e anodic or cathodic to the s r:ace o: the iron !eneath. .

,h s a damaged or discontin o s tin coating can act ally accelerate the r sting o: the mild steel it is meant to 5rotect. ,in is cathodic to iron and so the gal9anic corrosion o: iron will ta8e 5lace as indicated in #ig. $%.&. ,he tin and iron are already in electrical contact with the Be<ternal circ itB and when the scratch is !ridged !y moist re (containing dissol9ed o<ygen) corrosion will !egin. As electrons :low :rom the iron to the tin, #eWWW ions will enter sol tion and migrate to the tin cathode where hydro<yl ions will !e :orming d e to the reactionD 0H0) W )0 W .e= X .)H=

Fig 17 5 ,he disastro s e::ect o: a de:ecti9e tin coating on mild steel. ,he :ormation o: r st on the cathode then :ollows the 5roced re already descri!ed, 9i7. #eWWW W /)H= X #e()H)/ | ,in is th s e::ecti9e as a 5rotecti9e coating only i: the coating is 5er:ect. Since it is an e<5ensi9e metal tin is now only sed as a coating in the canning ind stry and :or coating :ood=5rocessing e? i5ment where its high corrosion=resistance to animal and

9egeta!le s !stances is tilised, and the :act that any com5o nds which may !e :ormed are non=to<ic. 17 $ ( #or engineering 5 r5oses either 7inc or al mini m are more e::ecti9e since !oth are anodic to iron. Oinc is the more widely sed o: the two since it is easier to a55ly to mild steel either !y gal9anising (hotdi55ing o: the steel into molten 7inc)M s5raying (as in the Schoo5 5rocess sed to coat the #orth Road Bridge)M sherardising (a 9a5o r condensationG cementation 5rocess)M or electro5lating. Consider a damaged 7inc coating as indicated in #ig. $%.%. Since 7inc is

Fig 17 7 ,he Bsacri:icialB 5rotection o::ered !y a de:ecti9e 7inc coating. (ron is rendered cathodic so that the 7inc goes into sol tion 5re:erentially. anodic towards iron it will send electrons thro gh the Be<ternal circ itB to the s r:ace o: the iron and as a res lt OnWW ions enter sol tion. Hydro<yl ions ()H=) will :orm at the s r:ace o: the iron as a res lt o: the standard reaction in9ol9ing o<ygen, water and electrons.On WW ions and )H= ions will then reactD OnWW W0)H= XOn()H)0 | ,h s, On()H)0 5reci5itates as a white corrosion 5rod ct on the s r:ace o: the iron cathode.

(n this case it is the coating metal which corrodes in 5re:erence to the mild steel. ,his :orm o: corrosion is o:ten termed Bsacri:icialB, since iron will not r st signi:icantly as long as 7inc remains in the 9icinity o: the initial scratch. (t wo ld !e wrong to ass me, howe9er, that there is any lasting merit in 5rod cing a 5oor=? ality 5oro s coating. As with all methods o: s r:ace 5rotection the aim sho ld !e to 5rod ce a 5er:ect coating which will gi9e no o55ort nity :or gal9anic action. ;ith a 7inc coating, howe9er, the 5osition is less serio s i: the coating is in :act de:ecti9e since some meas re o: tem5orary sacri:icial 5rotection is a::orded the mild steel.

#ig.$%.$4 ,he cathodic e::ect o: o<ide scale in accelerating the r sting o: mild steel sheet.

17 $ 4 )n the ? estion o: the gal9anic e::ect o: s r:ace coatings on iron the in:l ence o: o<ide scale cannot !e neglected. )rdinary B!lac8B sheet will r st more ? ic8ly than will clean sheet !eca se o<ide scale is cathodic to the metal !eneath. Corrosion o: the metal will then :ollow the s al 5attern (#ig. $%.$4). 17 $ 5 Cases in9ol9ing gal9anic corrosion on a microsco5ic scale are 9ery common. ,h s 5articles o: im5 rity may !e either anodic _r cathodic to the s rro nding metal (#ig. $%.$$). (n either case 5itting o: the metal will

#ig. $%.$$ ,he e::ect o: grain=!o ndary im5 rities on gal9anic corrosion. (n (i) the im5 rity is cathodic to the metal, whilst in (ii) the im5 rity is anodic to the metal.

res lt and since im5 rities are commonly segregated at the crystal !o ndaries in cast metals then intercrystalline corrosion will ta8e 5lace. Alloys o: d 5le< str ct re can !e e<5ected to corrode more ? ic8ly than single=5hase materials o: similar com5osition. Car!on steel in the 5earlitic condition r sts :ar more ? ic8ly than it does in the : lly hardened state. A steel in the 5earlitic condition contains a str ct re in which the :errite lamellae are anodic to the cementite lamellae. Conse? ently the :errite tends to :orm #e W W W ions and corrosion 5roceeds in the s al manner (#ig. $%.$0). A steel o: similar com5osition in the ? enched state will !e wholly martensitic and so gal9anic corrosion will !e at a minim m !eca se o: the ni:orm nat re o: the str ct re. ,em5ering will increase the tendency towards corrosion as cementite is 5rogressi9ely 5reci5itated. As a general 5rinci5le, there:ore. 9ery 5 re metals or ni:orm soli

Fig 17 1#

The galvanic corrosion of pearlite

sol tions constit te the most corrosion=resistant materials as tar as gal9anic corrosion is concerned. (n cast solid sol tions, howe9er, e<cessi9e coring may lead to gal9anic action !etween di::erent regions o: a crystal d e to di::erences in chemical com5osition.

17 % 1 #ig re $%.$/ ill strates the e::ects o: E h and 5H on the e<tent to

fig 17 1$

The Eh = p. diagram for ,ater

which water will li!erate either hydrogen or o<ygen !y what we s ally term BelectrolysisB. Hydrogen e9ol tion is only 5ossi!le nder conditions o: Eh and 5H which are re5resented !y a 5oint !elow a! and o<ygen can !e e9ol9ed only i: Eh and 5H are re5resented !y a 5oint a!o9e cd. ,here:ore there is a domain !etween a! and cd on the. Eh25H diagram where the electrolysis o: water is thermodynamically im5ossi!le. ,h s the electrolysis o: water will not ta8e 5lace, regardless o: the 5H o: the electrolyte, nless the electrodes sed ha9e a minim m 5otential di::erence o: more than $.0 9olts, that is the distance a5art in terms o: Eh o: a! and cd. 17 % # (n #ig. $%.$/ the e? ili!ria o: hydrogen and o<ygen red ction reactions are re5resented on the Eh25H diagram. Howe9er, e? ili!ria :or a metal in con3 nction with water can also !e re5resented. Since the corrosion o: iron is most im5ortant :rom a technical stand5oint this is re5resented in terms o: Eh and 5H in #ig. $%.$.. ,he com5lete +o r!ai<

diagram :or iron is com5le< since a n m!er o: e? ili!ria are in9ol9ed. #ort nately a sim5li:ied diagram can !e drawn :rom a st dy o: the :ollowing e? ili!ria, a n m!er o: which we ha9e already enco ntered in this cha5terD (i) #e f #eWW W 0e= #eWW ions. (ii) #eWW f #eWWW W e= #eWWW ions. (iii) #eWW W /)H= f #e()H)/ W e= 5reci5itates. (i9) #eWWW W /H0) f #e()H)/ W /HW 5reci5itates. (ron atoms :orm sol !le #eWWions are o<idised to (nsol !le :erric hydro<ide (nsol !le :erric hydro<ide

(9) #e W /H0) f #e()H)/ W /H= W /e= 5reci5itates.

(nsol !le :erric hydro<ide #errite ions go into

(9i) #e W 0 H0) f #e)0H= W/HW W 0e= sol tion. (9ii) #e)0H= W H0)f#e()H)/ W e= as :erric hydro<ide.

Sol !le :errites 5reci5itate

(: the electrode 5otential Eh o: mild steel is meas red in 5 re water (5H P >) it will !e re5resented on the diagram (#ig. $%.$.) !y 5oint ). ,his indicates that corrosion will ta8e 5lace nder s ch conditions o: Eh and 5H. ,he diagram also s ggests three ways in which the e<tent o: corrosion can !e red ced. #irst, the 5otential can !e changed in the negati9e direction so that it enters the domain o: imm nity (H). ,his is the normal cathodic 5rotection s ch as is o::ered !y 7inc, either as a coating or as a se5arate anode ($%.>..). Secondly, the 5otential can !e changed in a 5ositi9e direction into the domain o: 5assi9ity (I) !y a55lying a s ita!le e<ternal e.m.:. ,hirdly, the electrolyte can !e made more al8aline (7) so that the metal !ecomes 5ossi!le, (nhi!itors ha9e this e::ect=amongst others=! t need to !e care: lly controlled since with some metals the 5assi9ity domain e<tends o9er a 9ery limited 5H range and contin o s s r9eillance o: the electrolyte com5osition wo ld !e necessary. Electrochemical Corrosion d"e to +nternal )echanical Stresses 17 ' Cold=wor8ed materials o: ni:orm com5osition thro gho t may ne9ertheless s ::er se9ere electrochemical corrosion d e to di::erent energy le9els 5re9ailing in di::erent 5arts o: the material. (: 5art o: a com5onent is hea9ily cold=wor8ed it will contain

Aloc8ed= 5@ stresses which are internally !alanced and which wi$$ 5rod ce some elastic strain. ,he internal energy associated with this state o: a::airs ca ses the hea9ily wor8ed material to corrode more ? ic8ly than the less hea9ily wor8ed material, that is, the hea9ily wor8ed material is anodic to the remainder o: the com5onent. ,his is commonly 8nown as stress corrosion. Consider the cold=:ormed rim o: a motor=car Awing@ (#ig. $%.$1(i)). ,he :orming o5eration ;ill ha9e cold=wor8ed the rim more hea9ily than the remainder o: the wing. (: the 5aintwor8 is de:ecti9e in this relati9ely inaccessi!le 5osition corrosion can !e e<5ected to occ r :airly ra5idly in the hea9ily wor8ed and. hence. anodic region. Similarly the cold=:orged head o: an ordinary nail will !e anodic to the remainder o: the nail and will r st more ? ic8ly as a res lt (#ig. $%.$1(ii) ). (t is o!9io s that heat treatment can !e se: l in limiting gal9anic corrosion o: this ty5e. Sim5le stress=relie: annealing 5rocesses will !e s ::icient to remo9e energy arising :rom loc8ed= 5 stress and will th s red ce local corrosion. S ch heat treatment is not always 5ossi!le since cold=wor8ing is o:ten a means o: sti::ening and strengthening a com5onent as in the case o: !oth o: those mentioned a!o9e.

#ig. $%.$1 E<am5les o: electro=chemical corrosion d e to local cold=wor8, (i) ,he rim o: a motor car BwingB, (ii) ,he cold=:orged head o: an iron nail.

17 ' 1 (ntercrystalline corrosion associated with the 5resence o: im5 rities at grain !o ndaries has already !een mentioned ($%./.&). Howe9er,grain !o ndaries are also regions o: higher energy le9el, e9en in 9ery 5 re metals, 5ossi!ly d e to the irreg lar arrangement o: ions there (#ig. /.01). Conse? ently corrosion tends to occ r more ? ic8ly at grain !o ndaries. Hard=drawn a=!rasses are 5rone o: a 5henomenon 8nown as Bseasoncrac8ingB in which corrosion :ollows the crystal !o ndaries ntil the com5onent, na!le any longer to s stain internal stresses, crac8s e<tensi9ely along these !o ndaries. ,he tendency towards this !eha9io r can !e eliminated !y a low=tem5erat re anneal which, altho gh it does not ca se recrystallisation, res lts in the remo9al o: loc8ed= 5 stresses as atoms mo9e small distances into 5ositions nearer to e? ili!ri m.

Electrochemical Action +nvolving Variations in the Composition of the Electrol&te

$%.6 #ig re $%.$6 ill strates a concentration cell in which !oth o: the electrodes are o: e<actly the same material ! t in which the concentration o: the electrolyte in contact with each electrode is di::erent. ,he general reaction in the cell is re5resented !yD

#e f #eWW W0e= and the direction in which this reaction 5roceeds is go9erned, as in many chemical reactions, !y the concentration o: the reactants. ,h s on the le:t=hand side o: the cell a low concentration o: #e WW ions will ca se the reaction to 5roceed to the rightD #e X#eWW W 0e= so that iron atoms will tend to go into sol tion as #eWW ions and release

-il"te Ferro"s Chloride Sol"tion Fig 17 1( A 0concentration cell0

Conc Ferro"s Chloride Sol"tion

electrons into the e<ternal circ it. )n the right=hand side o: the cell the already high concentration o: #eWW ions tend to ma8e the reaction mo9e in the other directionD #e ~ #eWW W0e= ,h s the le:t=hand electrode !ecomes the anode and the right=hand

electrode the cathode o: the. gal9anic system as indicated !y the direction o: electron mo9ement in the e<ternal circ it. 17 ( 1 'ariations in the amo nt o: o<ygen dissol9ed in water will lead to corrosion o: this ty5e ta8ing 5lace in many di::erent sit ations. (n the case ill strated in #ig. $%.$> the two steel sheets are o: the same com5osition

Fig 17 14 The Porevice corrosionM of steel plate and in the same condition ! t the com5osition o: the electrolyte 9aries since dissol9ed o<ygen is nli8ely to 5enetrate into the : rther recesses o: the cre9ice !etween the 5lates altho gh water will ha9e !een drawn there !y ca5illary action. Conse? ently the more e<5osed 5arts o: the sheet !ecome cathodic since electrons will tra9el to these areas and react with o<ygen and water 5resent to :orm hydro<yl ionsD )0 W 0H0) W .e= X )H= ,h s, the region o: metal e<5osed to electrolyte containing less dissol9ed o<ygen will !ecome anodic and go into sol tion. ,his sit ation is hel5ed !y the :act that #eWWW ions ha9e greater mo!ility than )H= ions and so r st :orms :reely o tside the cre9ice. ,his 5henomenon is o:ten termed Bcre9ice corrosionB and is ty5i:ied !y

the :act that corrosion will !e more se9ere in the regions which one might ha9e e<5ected to !e the !etter 5rotected. ,he general a<iom is that the o<idation2concentration cell accelerates corrosion ! t it accelerates it where the concentration o: o<ygen is lower. 17 ( # ,his state o: a::airs e<5lains why corrosion ta8es 5lace with increasingly ra5idity when once the 5aintwor8 o: a motor=car has !een scratched == or was initially 5oro s as is so o:ten the case (#ig. $%.$&).

Fig 17 15 ,he s !=5art r sting o: a motor=car !ody=a : rther maintainence o: cer9ice corrosion

;ater !egins to 5enetrate !eneath the 5aint layer ! t o<ygen does not and so the metal !eneath the 5aint layer !ecomes anodic and goes into sol tion th s 5rogressi9ely detaching the 5aint layer. Acc m lations o: otherwise chemically inert dirt on the s r:ace will 5rod ce a similar e::ect in allowing moist re to 5enetrate to the s r:ace o: the metal ! t at the same time !eing de:icient in o<ygen. Hence the reader is ad9ised to wash the nder side o: his car e9en more care: lly than the 55er 5aintwor8, 5artic larly a:ter a :rosty s5ell d ring which large ? antities o: salt (a most e::icient electrolyte and the car man :act rerBs :riend) ha9e !een thrown on to the roads !y the -ocal A thority. ,he :act that the salt does not 5enetrate cre9ices accelerates rather than diminishes the rate o: corrosion since Cl= ions will congregate along with )H = ions o tside the cre9ice (or dirt 5atch) and greatly increase the concentration gradient within the electrolyte. Cynics may claim that we get the rotten cars we deser9e ! t the sit ation is certainly not hel5ed !y road salt.

#inally, we will consider the corrosi9e e::ect o: a sim5le rain dro5 on the s r:ace o: mild steel (#ig. $%.$%). Here the concentration o: dissol9ed

Fig 17 17 ,he r sting o: iron !eneath a rain dro5, d e mainly to 9ariations concentration o: dissol9ed o<ygen !etween centre and rim o: the dro5.

o<ygen in water will o!9io sly !e higher at I than at H where the de5th o: water is greater. A Bconcentration cellB will there:ore !e set 5 so that at H iron atoms will go into sol tion as #e WWW ions, releasing electrons which 5ass thro gh the e<ternal circ it to react with o<ygen and water at I, 5rod cing )H= ionsD )0 W 0H0) W .e= X .)H= ,he #eWWW ions released will migrate towards the )H = ions :orming a de5osit o: #e()H)/==Br stB==mainly at the 5eri5hery o: the rain dro5. B t :or the 9ariation in concentration o: o<ygen in the rain dro5 .the r sting o: mild steel !y its 5resence wo ld !e a m ch slower 5rocess since then electrolytic corrosion wo ld de5end entirely on the small 9ariation in com5osition within the mild steel.

The Limitation of 6alvanic Corrosion

17 4 Corrosion is a 5henomenon which is 9ery e<5ensi9e to eliminate com5letely. At !est we can limit its action !y one o: the :ollowing methodsD 17 4 1 Choosing a )aterial in Ahich 6alvanic Attack is Hnlikel& + re metals and com5letely ni:orm solid sol tions o::er the greatest :reedom :rom gal9anic corrosion ass ming that ste5s

are ta8en to 5re9ent Bcre9ice corrosionB !y ens ring that all s ch :iss res are ade? ately sealed. Either :erritic or a stenitic stainless steels ($4.1) o::er good resistance to corrosion largely !eca se o: the 5rotecti9e :ilm o: chromi m o<ide which adheres to the s r:ace. At the same time, ni:ormity o: the solid sol tion str ct re almost eliminates the chance o: gal9anic corrosion e9en in the 5resence o: 9ery strong electrolytes. ,o attain this ni:orm solid sol tion str ct re it is generally necessary to ? ench stainless steel. :rom $414ZC. ,his has no e::ect on the hardness o: these 9ery low=car!on steels ! t as the e::ect o: retaining in sol tion car!on which wo ld otherwise 5reci5itate as car!ides. Slow cooling will allow chromi m car!ide to 5reci5itate at grain !o ndaries (#ig. $%.04) th s de5leting the region immediately ad3acent to the grain !o ndaries with res5ect to chromi m. ,hese low chromi m regions !ecome anodic to the chromi m=rich matri< so that, in the 5resence o: a s ita!le electrolyte, inter=gran lar corrosion wo ld occ r.

17 4 # The Hse of Protective Coatings ,he 5rotection o: a s r:ace :rom gal9anic corrosion !y sealing o:: that s r:ace :rom contact with a 5otential electrolyte has already !een mentioned. +ainting, enamelling, 9ario s methods o: tinning and gal9anising= or e9en coating with a non=reacti9e grease=all ha9e this : ndamental aim in the 5rotection o: steel ! t are seldom com5letely e::ecti9e nder commercial conditions. ,he anodising o: al mini m in which the nat ral o<ide :ilm is arti:icially thic8ened is also a 5rocess o: this ty5e.

17 4 $ The Avoidance of Potential 0Crevices0 #iss res are !est sealed or :illed in some way to 5re9ent the entrance o: thin :ilms o: electrolyte which, in the 5resence o: e<ternal o<ygen, may lead to this :orm o: attac8. 17 4 % The Hse of 6alvanic Protection (n some cases the close 5ro<imity o: two dissimilar metals in m t al contact with an electrolyte is na9oida!le. #or e<am5le, shi5sB 5ro5ellors are commonly o: Bmanganese !ron7eB (a high=tensile !rass=,a!le=((. $) which is strongly cathodic towards the steel h ll. (n the 5resence o: sea water which is a strong electrolyte, the h ll co ld !e e<5ected to r st ? ic8ly d e to the close 5ro<imity o: the manganese=!ron7e 5ro5ellor. ,his tendency is largely eliminated !y :i<ing some 7inc sla!s to the h ll near to the 5ro5ellor (#ig. $%.0$). Since 7inc is

anodic !oth to (ron and manganese !ron7e it will corrode sacri:icially and can !e re5laced as re? ired. B ried iron 5i5es can !e 5rotected in a similar way !y ! rying sla!s o: 7inc or magnesi m ad3acent to the 5i5e at s ita!le inter9als. An alternati9e method (#ig. $%.00) is to em5loy a small e<ternal e.m.:. as shown sing the 5olarity to ma8e the 5i5e cathodic=to its s rro ndings. Either a !attery or a low=9oltage d.c. generator (o5erated !y a small windmill) can !e sed s ccess: lly.

Radiation -amage in )aterials

17 5 ;hilst the e::ects o: radiation :rom n clear so rces ha9e come nder consideration in recent years we m st remem!er that the e::ects o: other :orms o: radiation are also signi:icant. Radiation can !e classi:ied into two main gro 5sD = (i) electromagnetic radiations which incl de radio Bwa9esBM lightM H=rays and [(=rays. ,hese are now commonly considered in terms o: small Benergy 5ac8etsB or 5hotonsM (ii) BradiationsB which in :act consist o: mo9ing 5articles. ,hey incl de :ast=mo9ing electrons (originally called (/=rays or cathode rays)M 5rotons (once 8nown as B5ositi9e raysB)M heli m n clei (the original a=rays)M and ne trons. ): these :orms o: radiation the e::ects o: [(=rays and :ast=mo9ing ne trons are o: 5ossi!ly the greatest signi:icance, 5artic larly to the n clear=5ower engineer, ! t in e9eryday li:e the e::ect o: ltra= 9iolet light on modem 5lastics materials cannot !e com5letely neglected. 17 5 1 Radiation -amage in )etals o: interest 5rinci5ally to the n clear engineer. High=s5eed ne trons :rom n clear :ission 5rocesses may collide with the n clei o: atoms and i: the *E trans:erred is s ::icient the ion may !e dis5laced into an interstitial

5osition lea9ing !ehind a 9acancy. ,his will ca se limited wor8 hardening since sli5 will !e im5eded !y the dis5laced ion. ): more im5ortance howe9er, is the :inal resting 5lace o: the ne tron. (: it enters a near!y n cle s the latter may !ecome a radioacti9e isoto5e emitting dangero s t=rays. 17 5 # Radiation -amage in Pol&mers (rradiation o: 5olymer materials with either ne trons or [(=rays maG[ lead to cross=lin8ing, degradation, chain !ranching or 5olymerisation. ;hich o: these 5rocesses occ rs de5ends 5on the nat re o: the irradiated 5olymer. the amo nt o: radiation, the tem5erat re and the 5resence or a!sence o: other s !stances. Controlled

irradiation o: 5olythene can !e sed to e::ect se: l side !ranching and other desira!le 5ro5erties ! t ncontrolled irradiation may lead to degradation=or scission==e9en o: 5olythene and is e9en more li8ely to occ r with many other linear 5olymers. As a res lt strength generally :alls !eca se o: a red ction in 9an der ;aals :orces as molec lar chains decrease in length. Radiation in the ordinary 9isi!le s5ectr m (light) is s ::icient to ca se deterioration in some 5lastics materials. M se m s5ecimens o: +ar8esene ($0.$) and other early 5lastics materials c rrently on dis5lay in ill minated ca!inets are !eginning to cr m!le to 5owder.

The Ageing of Thermoplastics and R"**ers

17 7 ,his o:ten occ rs as a res lt o: cross=lin8ing !etween molec les which contain nsat rated !onds. #or e<am5le 5olythene will !ecome 5rogressi9ely more !rittle d e to the :ormation o: co9alent !onds !y o<ygen atoms which lin8 together ad3acent molec les in this way

(#ig. $%.0.). Since the co9alent cross=lin8 5re9ents sli5 !etween the chain molec les 5olythene !ecomes 5rogressi9ely harder and more !rittle.,his ty5e o: cross=lin8ing with o<ygen is li8ely to occ r more readily in the 5resence o: ltra=9iolet light (strong s nlight) which catalyses the reaction. (t can there:ore !e limited !y ma8ing the material o5a? e !y adding some car!on !lac8 ! t a more a55ro5riate method is to incl de an anti=o<idant, s ally 4.$ to 4.0R o: 5henol or an amine. 17 7 1 +oor ? ality r !!er B5erishesB in a similar way d e to the :ormation o: o<ygen cross=lin8s, 5artic larly at those nsat rated !onds not already sed d ring the 9 lcanisation 5rocess. Fltimately it !ecomes

!rittle as degradation generally :ollows the :all in elasticity 5rod ced !y cross=lin8ing. Again intensity o: light and also the 5resence o: o7one will accelerate 5erishing. ,he reader may ha9e noticed that continental car owners o:ten co9er their tyres to 5rotect them :rom strong s nlight. Again o<idation can !e s 55ressed !y adding car!on !lac8 as well as small amo nts o: aromatic amines or 5henol deri9ati9es as antio<idants. 17 7 # ,here are o: co rse instances when the controlled disintegration o: 5olymers s ch as 5olythene wo ld !e desira!le. Some years ago we towed o r cara9an many miles north o: the Arctic Circle in Norway :ollowing the Arctic Highway, then nder constr ction, ntil it ran o t on s in a wild and lonely 5lace where great glaciers came down to the sea. Sadly 5oll tion is ne9er :ar away and we were con:ronted !y a shore line littered with tho sands o: 5lastics containers 5res ma!ly carried across :rom the New ;orld !y the E l: Stream. +rocesses were de9elo5ed some years ago !y the Fni9ersity o: Aston in Birmingham (England) to ma8e s ch containers Bsel: destr ctB a:ter a reasona!le 5eriod o: time. Fn:ort nately these 5rocesses ha9e not !een ado5ted=5ossi!le man :act rers :ear that containers may Bdestr ctB whilst still on the shel9es o: the s 5ermar8et in times when sales are slow. Recycling o: 5lastic !ottles wo ld s rely !e a !etter sol tion than throwing them into the sea.

-eterioration of Ceramic )aterials

17 1; Most ceramic materials are chemically sta!le when in contact with ordinary atmos5heres, tho gh some nat ral stones sed :or ! ilding s ::er attac8 !y ind strial atmos5heres containing s l5h r dio<ide. ,he latter com!ines with atmos5heric moist re to :orm s l5 ro s acid. 17 1; 1 Concrete !ased on +ortland cement and sed in ! ilding :o ndations is li8ely to !e attac8ed !y s l5hate ions (S) .==) 5resent in the soil, in gro nd water or in sea water. ,hese ions react :irst with tri=calci m al minate in the concrete, :ollowed !y a reaction with lime, Ca()H)0, so e<5osed, to :orm a ! l8y reaction 5rod ct== crystalline CaS). which crac8s the concrete locally th s e<5osing new s r:aces to contin ed attac8. S l5hate=resistant concrete made :rom cement in which the 5ro5ortion o: tri=calci m al minate has !een red ced to less than 1R and the 5ro5ortion o: tetra=calci m al mino=:errite (,a!le $...) increased, is there:ore sed. 17 1; # Car*onation Shrinkage -ime. Ca()H)0, :ormed d ring hydration o: +ortland cement ($..1.0) reacts 9.ith any atmos5heric C)0 5resentD Ca()H)0 W C)0X CaC)/ W H0) ($)

,his reaction tends to 5rod ce a 9ol me increase in the cement 5aste ! t at the same time C)0 also attac8s and !rea8s down the hydration 5rod cts o: !oth calci m silicates and calci m al minates leading to a 9ol me decrease which o tstri5s the e<5ansion ca sed in e? ation ($). Conse? ently there is an o9erall Bcar!onation shrin8ageB. ,he e<tent o: this is go9erned !yD (i) the C)0 concentrationM (ii) the 5orosity o: the cement 5asteM (iii) the moist re content.

,he :ormation o: CaC)/ (e? ation ($)) increases strength sim5ly !eca se CaC)/ is stronger than Ca()H)0 )ther reactions tend to decrease the 5ermea!ility o: the 5aste. Drying shrin8age which reaches a ma<im m at 14R relati9e h midity is 5artic larly a::ected. Some :irms 5rod cing==concrete !loc8s :or the ! ilding ind stry treat them in an atmos5here o: waste :l e gases (rich in C)0), ,his accelerates the car!onation shrin8age 5rocess so that it is 5ractically com5lete !e:ore the !loc8s are ! ilt into walls. ,his lea9es only the drying=o t shrin8age to !e com5leted. ,he weathering action o:. :rost is also destr cti9e o: many ! ilding ceramics. S r:ace 5ores which a!sor! moist re will !ecome disr 5ted when the moist re :ree7es and, as a res lt, e<5ands. 17 1; $ Re:ractory ceramics sed in : rnace lining s ::er !oth 5hysical and chemical damage. Since re:ractory ceramics ha9e a relati9ely low thermal cond cti9ity they may s ::er thermal shoc8. An a55recia!le tem5erat re gradient may ! ild 5 when the s r:ace tem5erat re is s ddenly increased and as the hot s r:ace layers e<5and relati9e to the cold layers !eneath, s5alling, or :la8ing o: the s r:ace is li8ely to occ r. Slags may react destr cti9ely with some re:ractories at high tem5era= t res. Sometimes a slag will ha9e a sim5le sol9ent action on the re:ractory ! t s ally s ch reactions are o: an acid2!asic nat re. ,h s silica re:ractories which are acid=will !e attac8ed !y !asic slags containing lime and other metallic o<ides. Since the 5rod ct o: the reaction o:ten has a low melting 5oint :l <ing o: the : rnace lining ta8es 5lace. ,he general 5rinci5le in choosing a re:ractory material which is to wor8 in contact with a slag is that it sho ld ha9e a similar chemical nat re to that o: the slag. ,h s a !asic slag will demand a !asic lining o: dolomite, magnesite or 7ircona, whilst an acid slag will re? ire a : rnace lining o: silica !ric8 or some silica deri9ati9e.

17 1; % Beca se o: the 5ower: l co9alent !onds o5erating so e::ecti9ely !etween the atoms in diamonds (/.&.$), they, a!o9e all other materials, are commonly regarded as !eing indestr cti!le. Ne9ertheless, A9erani and ,argioni ! rnt one sing a sim5le B! rning glassB as long ago as $6%.. So 5erha5s the a5horism BDiamonds are :or e9erB is not strictly tr e=sorry girlsG

#; !on1destr"ctive Testing
#; 1 No material 5rod ced nder ind strial conditions is e9er 5er:ect. ,he incidence o: im5er:ections in any !atch o: material will de5end not only 5on the degree o: care and attention 5aid to 5rod ction !y the o5erator and the e<tent to which 5lant has recei9ed maintenance, ! t also 5on the ty5e o: 5rocess. ,h s a casting may s ::er :rom one or more o: a large n m!er o: de:ects s ch as incorrect com5ositionM the 5resence o: !low holes, shrin8age ca9ities, non=metallic incl sions, segregation, s r:ace :laws and crac8sM and so on. Many o: these de:ects will not s !mit to sim5le 9is al e<amination and an a55arently acce5ta!le casting may contain a n m!er o: internal de:ects. Rolled, :orged or e<tr ded metal, howe9er, is less li8ely to !e de:ecti9e, ass ming that no s r:ace de:ects are a55arent. Had the internal str ct re !een nsatis:actory or its com5osition incorrect it is li8ely that the ingot wo ld ha9e crac8ed d ring the initial stages o: the wor8ing 5rocess, or that gas=:illed ca9ities wo ld ha9e gi9en rise to !listers near the s r:ace.
Considera!le lengths o: a wro ght section may !e 5rod ced :rom a single cast ingot. Ass ming that the 5i5ed 5ortion o: the ingot has !een ade? ately cro55ed the remainder can !e e<5ected to ha9e 5rod ced material o: reasona!ly ni:orm 5ro5erties and ? ality. Hence e<amination !y analysis and !y mechanical or 5hysical tests o: sam5les ta8en :rom the !atch will generally !e ade? ate to control ? ality. ,he same 5rinci5les, howe9er, do not a55ly to com5onents made indi+idually !y casting, welding and other :orms o: :a!rication in9ol9ing mainly man al s8ill. A large n m!er o: 9aria!le in:l ences o:ten 5re9ails d ring the man :act re o: s ch a com5onent. Moreo9er , since it is in :inished :orm ordinary mechanical tests o: a destr cti9e nat re cannot !e sed, other than the ma8ing o: test 5ieces :rom the r nner or risers o: a casting. Hence some :orm o: a55ro5riate non=destr cti9e test m st !e ado5ted so that the ? ality o: the :inished com5onent can !e assessed. ,he 5ro5ortion o: com5onents th s tested can 9ary. ;hilst :or chea5 cons mer articles the re5resentati9e 5ro5ortion, which is tested, may !e 9ery

small, in the aircra:t ind stries it will o:ten !e $44R. ,his non=destr cti9e e<5loration o: materials has traditionally !een 8nown as non-destructi+e testing (ND,) ! t, whilst its 5rimary o!3ecti9e is to re9eal de:ects, it can !e sed in a more so5histicated manner to gi9e an a55raisal o: the o9erall ? ality o: the material. (t is there:ore sometimes re:erred to as non-destructi+e e+aluation (ND E).

The B*Nects of !on1destr"ctive Testing

#; # ,he general aims o: ND, may !e classi:ied as :ollowsD #; # 1 +mproved Prod"ctivit& De:ecti9e material may !e isolated at an early stage in 5rod ction so that : rther man5ower is not :r strated in : tile 5rocessing. Sho5 ca5acity is also sa9ed in this way and there is less seless wear and tear on 5lant. ,hese are o!9io s ad9antages o: testing at an early stage !asic wor8 5ieces s ch as castings and welds. E? ally im5ortant the 8nowledge that ND, is !eing a55lied o:ten leads to the 5rod ction o: less scra5 d e to indi::erent wor8manshi5. (n the case o: welding, instances ha9e !een re5orted where a .4R scra5 rate :ell to less than 1R when it was anno nced that radiogra5hic e<amination was to !e installed. #; # # +ncreased Servicea*ilit& Here ND, is sed to detect :a lts, which are li8ely to red ce the ser9ice li:e o: the :inished com5onent. #or e<am5le, some de:ects whether occ rring at the s r:ace or !elow the s r:ace, can initiate :atig e :ail re ($6.1.6). _ ench crac8s in heat=treated steel com5onents are in this category. ,he 5ro!lem o: sa:ety m st also !e considered in this connection. #ail re can in some cases lead to disaster 5artic larly in aircra:t str ct res.

T&pes of -efect
#; $ De:ects in metall rgical materials may !e inherent in the original casting or they may arise d e to :a lty techni? e d ring

s !se? ent 5rocessing. (t is con9enient to classi:y de:ects into two gro 5sD (i) ,hose occ rring at the s r:ace. ,hese incl de crac s res lting :rom nsatis:actory conditions d ring cooling o: the castingM crac8s 5rod ced d ring heat=treatment 5rocessesM s r:ace scale and de:ects d e to the rolling in o: la.s or sca,s and seams; (ii) ,hose occ rring !elow the s r:ace. ,he more common de:ects here incl de .orosity; laminations; inclusions o: 9ario s ty5esM segregation; ,lowholes; internal crac s and other less o!9io s :a lts s ch as coarse grain! ;elds may s ::er :rom lac8 o: 5enetration and nsatis:actory !onding as well as many o: the de:ects already mentioned s ch as 5orosity, incl sions and crac8ing.

Vis"al +nspection
#; % ,his is ndo !tedly the most widely sed, yet least costly and 9ery e::ecti9e method o: ND,. ;hate9er other method o: ins5ection is a55lied it will in9aria!ly !e s 55lemented !y 9is al e<amination. #or e<am5le thoro gh 9is al ins5ection o: a weld !y an e<5erienced o5erator can re9eal the :ollowing :a ltsD (i) -ac8 o: 5enetration !y the weld metal (#ig. 04.$(ii))M (ii) Badly o<idi7ed or ro gh s r:acesM iii) ,he 5resence o: large crac8s and their 5osition relati9e to the weldM (i9) s r:ace 5orosityM (9) (nade? ate : sion o: the weld metal as shown !y B nderc ttingB and conca9ity o: the weld (#ig. 04.$ (iii) )D (9i) ,he se o: ins ::icient weld metal (#ig. 04.$(i9)).

,he 5rinci5al re? irement==other than em5loying an intelligent o5erator who 8nows what he is loo8ing :or=is to ill minate the com5onent ade? ately so that it can !e e<amined !y the eye or in a :ew cases !y some light=sensiti9e de9ice s ch as a 5hotoelectric cell. 'is al e<amination can !e assisted !y sing a small hand= magni:ier gi9ing a magni:ication o: a!o t0.1H #; % 1 Now that many a tomated 5rocesses are in se 9is al e<amination !y so5histicated techni? es is necessary. ,h s on=line s r:ace ins5ection o: contin o sly cast sla!s can !e assisted either !y high=5owered lam5s or !y laser in con3 nction with 9ideo camera. CCD camera or 5hoto m lti5lier, all o: which de9ices intensi:y the recorded image.

LiE"id Penetrants
#; ' (ns5ection !ased on the se o: li? id 5enetrants can !e em5loyed to detect crac8s and other :iss re :laws occ rring at the s r:ace o: a material. ,ho gh most :a lts o: this ty5e co ld !e detected !y care: l 9is al ins5ection the se o: the 5enetrant method 5ro9ides a more 5ositi9e aid to detection and ma8es it less de5endent on the h man element as well as less time cons ming +enetrant methods can !e sed to locate crac8s in castings, weld crac8s, grinding crac8s, 5inhole 5orosity at the surface o: welds and castings, :atig e crac8s, seams and la5s in rolled stoc8, :orging la5s and many other ca9ity de:ects 5ro9iding they !rea8 o t at the s r:ace. #; ' 1 ,he earliest 5enetrant tests em5loyed oil and whiting. ,he s r:ace to !e e<amined was coated with a 5enetrating oil (o:ten 5ara::in), which was s ally heated so that its 9iscosity was red ced. Moreo9er the hot oil ca sed any s r:ace crac8s to e<5and so that oil wo ld !e drawn into them. A:ter allowing s ::icient time :or the oil to 5enetrate any s r:ace de:ects the e<cess was wi5ed o:: and the s r:ace thoro ghly dried. A thin coating o: whiting, either as a dry 5owder or as a s s5ension in alcohol

(ind strial Bmethylated s5iritB) was then a55lied to the s r:ace and allowed to dry. As the s r:ace cooled any crac8s contracted again so that the oil was :orced o t to stain the coating o: whiting. #; ' # More so5histicated modi:ications o: this sim5le test were de9elo5ed s !se? ently. (n most o: these tests a !rightly co$o red dye is carried in some s ita!le 5enetrant, the colo r !eing chosen to 5rod ce a high degree o: contrast with the coating o: Bde9elo5erB. (n most cases this de9elo5er is !ased on whiting, talc or some s ch 5owder s s5ended in water. -ight=alloy castings are e<amined :or s r:ace crac8s !y :irst immersing them in a !oiling sol tion containing a !rilliant red dye. As the crac8s e<5and the 5enetrant dye is drawn into them. ,he castings are then remo9ed :rom the 5enetrant tan8, rinsed to remo9e e<cess 5enetrant :rom the s r:ace and then di55ed into a hot s s5ension o: whiting in water. )n withdrawal o: the casting its s r:ace soon dries and as any crac8s contract dye is s? ee7ed o t into the layer o: whiting Bde9elo5erB (#ig. 04.0).

#; ' $ #l orescent 5enetrants are also sed. Most o: these s !stances are oil sol !le so that a 5enetrating oil is sed as the 9ehicle. Di5, !r sh or s5ray methods are em5loyed to coat the 5enetrant on to the test s r:ace. A:ter e<cess 5enetrant has !een cleaned :rom the s r:ace the latter is 9iewed nder ltra=9iolet light (a55ro<imately /.61 H $4=> m wa9elength). ,his (S o tside the 9isi!le s5ectr m and so, ass ming that the test s r:ace is ins5ected in a dar8ened c !icle, it remains com5letely dar8. ,he action o: ltra=9iolet light on the :l orescent s !stance in

the 5enetrant, howe9er, ca ses it to :l oresce so that any crac8s containing the 5enetrant a55ear as !right yellow=green lines on a dar8 !ac8gro nd.

)agnetic )ethods
#;>( Discontin ities s ch as crac8sM incl sions and ca9ities in a magnetic material 5rod ce distortion in a magnetic :ield, which may !e ind ced in that material. ,he direction o: the magnetic lines o: :orce is altered !eca se the discontin ities ha9e m ch lower magnetic 5ermea!ilities than the main !ody o: the com5onent. Conse? ently i: a magnetic com5onent is carrying a high magnetic :l < density any discontin ity will tend to ca se Blines o: :orceB to !rea8 o t at the s r:ace o: the com5onent (#ig. 04./).

(: some :ine magnetic 5owder is !ro ght into contact with the s r:ace it will collect where the lines o: :orce !rea8 o t th s indicating the 5resence o: some :a lt at or near to the s r:ace. #; ( 1 A n m!er o: di::erent methods are a9aila!le :or 5rod cing the necessary high :l < density in the com5onent. ,he method chosen will de5end to some e<tent on the direction in which the lines o: :orce are re? ired to 5ass. ,o o!tain ma<im m sensiti9ity the lines o: :orce sho ld !e 5er5endic lar to the line o: the :law as already indicated in #ig. 04./. ,wo ways in which a desired :ield direction can !e 5rod ced are indicated in #ig. 04...

,he magnetic 5articles can !e a55lied to the s r:ace either !y wet or dry techni? es. (n the BdryB method :inely di9ided :erromagnetic 5articles ha9ing a high 5ermea!ility are sed and these can !e sim5ly sha8en on to the s r:ace :rom a 5e55er 5ot. ,hey will align themsel9es along any lines o: :orce emerging :rom the s r:ace o: the s5ecimen in the region o: the :law. ,he s r5l s can !e gently !lown away. (n the BwetB 5rocess a s s5ension o: :inely di9ided magnetic iron o<ide in a light 5etrole m B:ractionB is generally sed. ,his can !e a55lied !y s5raying or !y immersion. Magnetic 5articles with a :l orescent coating can !e sed in which case the s r:ace will !e o!ser9ed nder s ita!le ltra=9iolet light (04.1./). ,his method is se: l when dealing with ro gh s r:aces.

,hese methods o: :a lt detection are o: co rse a55lica!le only to :erromagnetic materials ! t they a::ord 9ery 5ositi9e means o: locating crac8s and crac8=li8e :a lts so long as they are not more than a!o t $4 mm !eneath the s r:ace.

Thermal and Electrical Tests

#; 4 A n m!er o: non=destr cti9e tests !ased on thermal 5ro5erties ha9e !een de9ised :rom time to time. Many o: these rely on the high thermal cond cti9ity o: metal and 5on the :act that any discontin ity ,eneath the s r:ace will act as a !arrier to heat trans:er. ,h s i: the s r:ace o: the com5onent is coated with some heat=sensiti9e indicator and the com5onent then heated at a s ita!le ni:orm rate, any ! ild= 5 o: heat will !e re9ealed

!y an a55ro5riate change in the indicator. Areas on the s r:ace where heat has !een 5re9ented :rom esca5ing inwards. !y the 5resence of some s !c taneo s de:ect, will !e indicated !y melting (or colo r change) of the indicator sed. (n some of these tests the s r:ace is :irst B:rostedB !y s5raying it with a coating of some s ita!le indicator s ch as acena5hthene ( Acena5hthene= C $0H$). m.5t. %1oC. is deri9ed :rom the anthracene :raction o: coal tar) ,he com5onent is then 5assed at a ni:orm s5eed thro gh an ind ction coil. Eddy c rrents ind ced in the outer s in of the com5onent generate heat, which is 5re9ented :rom di:: sing into the core i: any discontin ities of low thermal cond cti9ity e<ist !etween the s8in and the core. ,his ty5e of test has !een sed to e<amine the degree of contin ity !etween rani m n clear : el rods and their 5rotecti9e cladding cans

#; 4 1 'ario s electrical methods ha9e !een de9elo5ed to test :or contin ity o: str ct re in cond cting materials. Most o: these de5end 5on the meas rement o: electrical resistance or alternati9ely, 5otential di::erence across a standard section o: material. #or e<am5le railway rails can !e tested !y attaching electrodes at each end of a meas red length of rail. ,he 5otential dro5 is then meas red. ,he 5resence of discontin ities s ch as :iss res will ca se an increase in electrical resistance, or a decrease in 5otential dro5 across the section. #; 4 # P"lse1video Thermograph& 2PVT3 de9elo5ed in recent years to co5e with the ND, of some of the new materials, e.g. lamellar or :i!re=rein:orced com5osites. ,he s r:ace of the test material is heated ? ic8ly, generally sing a 5 lsed laser so rce and then scanned !y an in:ra=red camera the sensiti9ity of which is s ::icient to detect any hot s5ots on the s r:ace. ,hese will ha9e !een ca sed !y any s !c taneo s :laws which were s ::iciently large to interr 5t the dissi5ation of heat inwards :rom the heated s r:ace. #; 4 $ Edd&1c"rrent Testing (n this method a 5rimary magnetic :ield is generated !y an alternating c rrent 5assing thro gh a solenoid. ,his :ield ind ces eddy c rrents in the s r:ace of the metal nder test. ,hese :low in concentric 5aths normal to the direction of the 5rimary :ield (#ig. 6<!E)! ,he magnit de of the eddy c rrents de5ends on the :re? ency of the :ield, the 5hysical 5ro5erties of the metal nder test and the distance !etween solenoid and test s r:ace. ,he eddy c rrents in t rn generate their own magnetic :ield which is in o55osition to the 5rimary :ield which is conse? ently modi:ied so that an im5edence change occ rs in the solenoid circ it. Crac8s or other :a lts in or near the test s r:ace will de:lect the eddy c rrents which m st 5ass nder or ro nd s ch discontin ities. ,his ca se a 9ariation in the im5edence of the

solenoid circ it which can !e meas red and con9erted into a 9is al signal. An ad9antage of this method of testing is that it is a Bli:t off2 method, i.e. the solenoid 5ro!e does not to ch the test s r:ace so that it can !e sed :or testing mo9ing hot metals s ch as ingot s r:aces in a contin o s casting 5rocess (6.0.$.0). (t is ns ita!le :or steel in the region o: the C rie 5oint (>6%ZC) since s dden loss (or gain) o: :erromagnetic 5ro5erties wo ld ca se :l ct ation o: readings #; 4 % The A C Potential -rop 2ACP-3 )ethod se: l in determining the de.th o:.. s r:ace :laws in a metal. (t is !ased on the 5rinci5le that, high=:re? ency electrical c rrent tends to :low close to the s r:ace o: cond ctor. ,his is 8nown as the Bs8in e::ectB. ,here:ore any 5otential dro5 meas red along the c rrent 5ath is a : nction o: the 5ath length. Since anD increase in 5ath length d e to the 5resence o: :laws near to the s r:ace will increase the 5otential dro5 this gi9es a meas re o: the :law de5th. H=ray Methods o: Radiogra5hy #; 5 Metals and many other solids are o5a? e to B9isi!leB light, that is electromagnetic radiation o: s ch wa9elength as can !e Brecei9edB !y o r organs o: sight ! t are trans5arent to t=rays and also to those H=rays o: short wa9elength. Hence radiogra5hy is one o: the oldest non=destr cti9e testing methods ha9ing !een introd ced in the $%04s.

#; 5 1 -i8e light, H=rays tra9el in straight lines and can there:ore !e se to 5rod ce a reasona!ly shar5 image on a 5hotogra5hic :ilm, the em lsior o: which is a::ected in m ch the same way !y H=rays as it is !y 9isi!le light H=rays are a!sor!ed logarithmicallyD 85 $<e-Md where $< and $ are the intensities o: the incident and emergent rays res5ecti9ely, d the thic8ness and M the linear coe::icient o: a!sor5tion o: radiation :or the medi m thro gh which the rays are 5assing. M is de5endent 5on the wa9elength o: the radiation and is lower :or that o: shorter wa9elength. Since H=rays are th s a!sor!ed di::erentially the density o: the 5hotogra5hic image will 9ary with the thic8ness o: the material thro gh which the rays ha9e 5assed (#ig. 04.>). ,hose rays which 5ass thro gh a region containing a ca9ity will !e less e::ecti9ely a!sor!ed than those which tra9el. thro gh the entire thic8ness o: material. Conse? ently

the ca9ity will show as a dar8 5atch on the res ltant 5hotogra5hic negati9e in a similar way to which greater density o: 9isi!le light 5rod ces a dar8er area on the negati9e in ordinary monochrome 5hotogra5hy. Altho gh a 5hotogra5hic em lsion is the most sensiti9e means o: detecting !oth H=rays and t=rays other means s ch as Eeiger co nters and s !stances which :l oresce nder the action o: these radiations can also !e sed. #l orosco5y is o!9io sly chea5er and ? ic8er than 5hotogra5hy ! t is less sensiti9e and its se is limited to the less dense metals and alloys. #; 5 # Q=rays are 5rod ced when high=iB9elocity electrons stri8e a metal target. Hence the !asic re? irements :or 5rod cing a !eam o: H=rays areD (i) A s ita!le so rce o: electronsD (ii) Some means o: accelerating these electrons to a high 9elocityM (iii) A s ita!le metal target (n an H=ray t !e the electrons are generated :rom a heated metal :ilament !y 5assing a c rrent o: electricity, thro gh it electrons :rom the c rrent !ecome so thermally acti9ated that they Besca5eB :rom the :ilament. ,he :ilament also acts as the cathode o: the high=tension circ it (#ig. 04.>) sed to accelerate the electrons. ,he target==or anti=cathode=is o: t ngsten which will resist melting at the high tem5erat res in9ol9ed and is sealed into the other end o: the t !e, ,he t !e is e9ac ated since the 5resence o: relati9ely massi9e gas molec les wo ld o!str ct the 5assage o: electrons. A high 5otential di::erence !etween cathode and target will ca se the negati9ely charged electrons to !e accelerated away :rom the cathode and towards the 5ositi9ely charged target. By the time the electrons reach the target they will ha9e ac? ired considera!le 9elocity and, hence, 8inetic energy and this is a!sor!ed in collision, H=rays !eing generated. (n addition to H=rays, m ch heat is also li!erated and this :act is tili7ed in electron=!eam welding

($>....). Here, howe9er, heat is an ndesira!le !y=5rod ct and m st !e cond cted away :rom the target e9en tho gh the latter is o: high melting 5oint t ngsten. (nternal water=cooling o: the target or air cooling !y a system o: radiator :ins e<ternal to the t !e can !e sed #; 5 $ H=rays sed in metall rgical radiogra5hy are BharderB than those sed in medicine. ,hat is, they are o: shorter wa9elengths, which are a!le !etter to 5enetrate metals. At the same time these 5ro5erties ma8e them more dangero s to h man !ody tiss es and the 5lant 5rod cing radiations o: this ty5e m st !e 9ery care: lly shielded so that stray radiations do not reach the o5erators ,he wa9elength, A, o: H=rays 5rod ced is go9erned !y the accelerating 9oltage, /, a55lied !etween cathode and targetD

so that as the 5otential di::erence across the t !e is increased the wa9elength o: the H=rays 5rod ced !ecomes shorter. ,he a!sor5tion o: H=rays is a : nction o: the density o: the material !eing 5enetrated and :or this reason incl sions as well as ca9ities can !e detected. At the same time the increased a!sor5tion o: H= rays !y the denser metals means that only thin sections o: s ch metals can !e e::ecti9ely e<amined. Conse? ently H=rays are sed mainly in the radiogra5hy o: light=alloy castings and sections. ,he ma<im m sensiti9ity o: this method o: e<amination is o: the order o: 0R, that is a de:ect a!o t 4.0 mm in diameter may !e detected in a sectional thic8ness o: $4 mm.

R1ra& )ethods of Radiograph&

#; 7 t=rays are electromagnetic radiations o: 9ery short wa9elength (#ig. 04.6) and are a!le to 5enetrate considera!le thic8nesses o:

many metals. (n 5ractice t =ray methods are sed to e<amine steel :rom 01 to 014 mm or more in thic8ness. A : rther ad9antage o: the se o: t =rays is the 9ery small si7e o: so rce as com5ared with that o: an H=ray nit. Moreo9er the cost o: the t =ray so rce is com5arati9ely low. #; 7 1 Nat ral t =ray so rces, chie:ly radi m and radon, ha9e !een sed :or ind strial radiogra5hy since the late $%04s ! t their se ne9er !ecame common d e to the scarcity and high cost o: radi m and, in the case o: radon, a decay 5rod ct o: radi m, its 9ery short hal:=li:e. ,he de9elo5ment o: the n clear reactor, howe9er, has 5ro9ided new and more e::ecti9e t ray so rces. ,hese are generally 5rod ced !y irradiation o: some s ita!le element in a n clear reactor. #or e<am5le when co!alt 1%0> is !om!arded with slow= mo9ing ne trons in a n clear reactor the radioacti9e isoto5e 640> Co is :ormedD

#; 7 # Radioacti9e isoto5es are also :ormed as a res lt o: :ission ! t in most cases a mi<t re o: di::erent isoto5es is= 5rod ced and this is generally ns ita!le :or se as a t=ray so rce !eca se, :or e<am5le, o: the ra5id decay o: some o: the com5onents relati9e to others. (n choosing a s ita!le radioacti9e isoto5e :or this ty5e o: wor8 the :ollowing criteria are im5ortant (i) (ts hal:=li:eM (ii) ,he t =ray energy o t5 tM (iii) the characteristics o: the material to !e radiogra5hed

,he hal:=li:e o: some radioisoto5es is ! t a :ew days, ho rs=or e9en seconds. ,hese will generally !e less s ita!le :or this ty5e o: wor8 since corrections wo ld need to !e a55lied contin ally to com5ensate :or their decrease in intensity o: radiation. Conse? ently isoto5es with a hal:=li:e meas red in years or months will !e more s ita!le ass ming that its t =ray emission energy is ade? ate. (n addition to co!alt 640> Co already mentioned, other arti:icially 5rod ced radioisoto5es which are se: l in this wor8 incl de $%0>> (r, $/>11 Cs and $>4%6 ,m (,a!le 04.0) ,he a!sor5tion o: t =rays !y matter :ollows the same general 5attern as :or H=rays

,he Bhal:=9al e thic8nessB o: a material is sometimes ? oted. ,his is the thic8ness o: the a!sor!er which will red ce the intensity o: the !eam to one=hal: o: its incident 9al e (,a!le 04.$).

#; 7 $ ,he e<treme danger o: e<5os re o: the h man !ody to t =rays and to BhardB H=rays is well 8nown ! t whereas the latter are not emitted once the t !e has !een switched o::, a t =ray so rce contin es to emit as long as the so rce remains acti9e (640>Co has a hal:=li:e o: 1./ years). ,here:ore t =ray so rces m st !e 9ery care: lly stored and shro ded at all times so that o5erators are 5rotected. A ty5ical storage container is shown in #ig 04.&(i)

,he general 5roced re in t =radiogra5hy is similar to that Fsing <= rays in that the com5onent to !e radiogra5hed is inter5osed !etween t =ray so rce and 5hotogra5hic :ilm (#ig. 04.&(ii)). ,he whole 5rocess will !e cond cted in a radiation=5roo:ed c !icle the so rce !eing nca55ed !y remote control in order that the o5erator shall !e : lly 5rotected. A disad9antage in the se o: t =rays is that the wa9elength o: the radiation (which determines the 5enetrating 5ower) cannot !e 9aried whereas with H=rays wa9elength can !e altered to s it the material and also its thic8ness so that a radiogra5h o: s ita!le 5hotogra5hic contrast can !e o!tained. #; 7 % ,a!le 04.0 shows the main characteristics o: the more im5ortant t=rays so rces and indicate thic8nesses which can !e radiogra5hed.,hese ranges o: thic8ness are only a55ro<imate and greater thic8nesses can !e delt with 5ro9ided that e<5os re times are s ita!le increased ,he lower le9el o: thic8ness in each case is that associated with ade? ate 5hotogra5hic ? ality. -esser

thic8nesses wo ld 5rod ce negati9es o: lower contrast which may not re9eal the de:ects so ght ,he relati9ely small si7e o: the t =ray so rces and their associated handling e? i5ment ma8e t =rays se: l :or radiogra5hy on sites inaccessi!le to ! l8y H=ray e? i5ment. ,he initial cost o: these t ray so rces is also m ch lower than that o: H=ray e? i5ment ! t the res lts o!tained may !e in:erior to those o: H=rays !eca se o: the lac8 o: :le<i!ility o: wa9elength, which is o!tained with H= rays.

Hltrasonic Testing
#; 1; Sonic methods :or meas ring the de5th o: the sea and so 5rotecting shi5s :rom r nning agro nd ha9e !een 5racticed :or many years. Here a so nd is emitted :rom the !ottom o: the shi5 and the echo recei9ed and s ita!ly am5li:ied. ,he inter9al which ela5ses !etween transmitting the sonic im5 lse and recei9ing its echo is a meas re o: the distance the im5 lse had to tra9el, that is to the :loor o: the ocean and !ac8. Sonic methods ha9e also !een sed to test metals :or the 5resence o: :laws. ,he railway wheel= ta55er was :or some strange reason always Bgood :or a la ghB in the old=time m sic hall ! t he was none the less doing a 9ery se: l 3o! o: ND,. Howe9er, ordinary so nd wa9es a di!le to the h man

ear, are o: relati9ely long wa9elength and co9er a :re? ency o: a!o t /4=$6444 H7 (according to the more o5timistic hi=:i e<5erts who 5ro!a!ly waste a lot o: money 5rod cing so nds they cannot hear). S ch long wa9elengths tend to !y=5ass small de:ects in a metallic com5onent and will there:ore not re9eal them. Conse? ently ltrasonic :re? encies o: more than 04444 H7 are sed in this :orm o: testing=generally) 4.1 to $1 MH7 :or metals ins5ection #; 1; 1 ,ho gh here we are concerned 5rinci5ally with the detection o: :a lts these methods are also s ita!le :or meas ring wall thic8nesses o: 9essels where other methods are im5ossi!le. ,hic8ness o: sheet and 5late and the thic8ness o: cladding can also !e meas red in this way. ;hen an ltrasonic 9i!ration is transmitted :rom one medi m to another some re:lection occ rs at the inter:ace. Any de:ect s ch as an incl sion or an internal ca9ity will there:ore 5ro9ide a re:lecting s r:ace :or ltrasonic im5 lses (#ig. 04.%). ,he ltrasonic 9i!rations are 5rod ced in a 5ie7o= electric crystal !y stim lating it with an electrical im5 lse. Since ltrasonic 9i!rations are dissi5ated 9ery ? ic8ly in air there m st !e close contact

!etween the :ace o: the crystal 5ro!e and the s r:ace nder test and this is most easily achie9ed !y s5reading a :ilm o: oil !etween the two. ,he crystal sed is generally either o: ? art7 or !ari m titanate. (n some systems (#ig. 04.$4) se5arate crystals are sed as transmitter and recei9er and the time inter9al !etween transmission o: 5 lse and rece5tion o: echo is recorded on a cathode=ray t !e (CR,) #; 1; # (n many modern testing de9ices a single crystal 5ro!e is sed so that it acts !oth as transmitter and recei9er. Since the crystal is 9ery highly Bdam5edB a 5 lse o: e<tremely short d ration is emitted. Hence the crystal is dormant and a!le to recei9e the ltrasonic echo and so con9ert it into an electrical signal which is s !se? ently am5li:ied and dis5layed on the CR, Altho gh ltrasonic testing is closely associated with the e<5loration o: large :lat areas o: 5late materials it is 9ery 9ersatile

in other directions. (t can !e sed :or testing most materials and in great de5ths, :or e<am5le, $4 m or more thic8ness o: steel

)iscellaneo"s !-T )ethods

#; 11 (t was once the rather gr esome 5ractice in the East to sacri:ice a 9illage 9irgin into the molten !ron7e destined :or casting large tem5le !ells. (: the !ell t rned o t to !e a d d it was ass med that the B9irginB had not !een all that she sho ld ha9e !een and her :ather was se9erely ostracised= or worse=:or not e<ercising ade? ate s r9eillance o9er her ,he test :or ? ality o: s ch a !ell was, and is, sim5le re? iring no so5histicated e? i5ment. ;hen str c8 it sho ld ring, that is 9i!rate on the re? ired :re? encies which will !e a com!ination o: its : ndamental :re? ency and certain harmonics and s !=harmonics. Any :a lt 5resent will ca se a dam5ing o: 9i!rations whilst a crac8ed !ell may also 9i!rate on a di::erent :re? ency to that intended !eca se its dimensions ha9e in e::ect !een changed. ,he railway wheel ta55er=:or some o!sc re reason always good :or a la gh in Bolde tymeB m sic halls=was sing his s8ill in a similar manner. #; 11 1 ND, methods o:ten ha9e to !e de9ised :or s5ecial cases and many s ch methods are 9ery ingenio s. #or e<am5le, in detecting lea8s in 9ery long water or oil 5i5e lines a radioacti9e method is o:ten sed. A ? antity o: radioacti9e isoto5e (in sol tion as one o: its com5o nds) is in3ected into the li? id :low at the in5 t end. A:ter s ::icient time has 5assed :or the isoto5e to ha9e tra9elled a!o t 0.1 8m a !attery=o5erated radiation detector2recorder is 5assed into the line so that it :loats along in the li? id stream. +oints along the line where the radioacti9e isoto5e has lea8ed o t, and is there:ore still 5resent in the s rro nding sand, are located and recorded !y the detector. Small t =ray so rces are sited along the o tside o: the 5i5eline at :i<ed inter9als to act as

distance cali!ration mar8ers. ,he detector2recorder is reco9ered :rom the o tlet end o: the line so that the record can !e e<amined Ne9ertheless the [!ig :i9eB among ND, methods are, traditionally, those which in9ol9e ltrasonic, H= (and =y=) radiogra5hy, magnetic :l < lea8age, dye=5enetration or eddy c rrents.

Some Applications of ! -T
#; 1# ND, =or more 5ro5erly, non=destr cti9e e+aluation-is now sed to e<amine a 9ast range o: materials and com5onents ! t is more commonly associated with the :ollowingD #; 1# 1 Castings Des5ite im5ro9ed instr ment control d ring recent decades the incidence o: de:ects in castings is 5ro!a!ly greater than in most other man :act red com5onents. ,his is not s r5rising when one considers the n m!er o: 9aria!le :actors which 5re9ail d ring the casting 5rocesses. ,hese incl de melting conditions in so :ar as they a::ect gas sol tion or s r:ace o<idationM casting tem5erat reM rate o: 5o ringM mo ld tem5erat re and conditionsM the design o: the mo ld itsel: and many other :actors ,he 5rinci5al internal de:ects li8ely= to arise incl deD (i) gas 5orosity arising :rom gas dissol9ed d ring melting and 5reci5itated d ring solidi:ication. B !!les o: entra55ed air may also !e 5resent i: the mo ld was inade? ately 9ented to allow air to esca5e as the mo ld Bwas !eing :illedD (ii) shrin8age ca9ities :ormed when molten metal is na!le to :eed into regions where solidi:ication. and conse? ently shrin8age, is ta8ing 5laceM (iii) (nternal incl sions d e to entra55ed slag and dross.

,hese internal de:ects are re9ealed most e::ecti9ely !y H= radiogra5hy 5artic larly in the case o: light alloys. #or steel castings =y=radiogra5hy may !e sed.

Some of the s"rface defects in castings incl"de>

(i) Crac8s :ormed !y ne9en cooling o: the casting d ring or a:ter solidi:ication. Sometimes crac8s are initiated !y sand cores which are too strong and do not colla5se nder the 5ress re o: the solidi:ying metalM (ii) Cold Bsh tsB, generally :ormed when two streams o: molten metal :ail to nite at an interlace !eca se o: the 5resence o: s r:ace o<ideM (iii) S r:ace incl sions o: mo lding sand, dross or slag E<tensi9e hot crac8s which consist o: se9eral 5arallel :iss res !ranching to :ollow grain !o ndaries may also occ r internally d ring cooling. ,hese, and s r:ace :iss res, may show on H=ray :ilm as irreg lar dar8 lines. S r:ace crac8s, howe9er, are. more easily and chea5ly re9ealed !y one o: the hot li? id 5enetrant methods. ,he ! l8 o: sheet metal 5rod ced now originates :rom contin o s= cast sla! (6.0.$.0) and the detection and= control o: s r:ace im5er:ections (#ig. 04.$$) is most im5ortant since, i: e::ecti9e, it ma8es 5ossi!le the

direct rolling o: sla!s. Most s r:ace crac8s originate in the mo ld d e to incorrect cooling rates, stresses d e to casting and straightening o5erations or 5oor mo ld design. (ncl sions are the res lt o: lac8 o: BcleanlinessB o: the molten steel or o: inade? ate control o: the metal le9el in the 5o ring tro gh so that slag enters the mo ld. +inholes are d e to e<cessi9e dissol9ed gas in the li? id steel. De:ects o: this ty5e at or near the s r:ace o: contin o s=cast sla!s can !e detected !y on=line non=contact methods s ch as o5tical ins5ection (04...$) or !y eddy=c rrent ins5ection methods (04.>./) #; 1# # Aelds ,he in9estigation o: welded 3oints 5as !een well de9elo5ed and most o: the orthodo< ND, methods are se: l. Radiogra5hy, sing !oth H=rays and BI=rays, will detect ca9ities, incl sions and those s r:ace irreg larities which res lt in a change in thic8ness o: the metal. ,hese de:ects will also !e recorded !y ltrasonic testing methods as also will incom5lete 5enetration, lac8 o: : sion and 5i5ing. Crac8s and other s r:ace and s !s r:ace im5er:ections in magnetic materials are 9ery relia!ly detected !y sing a magnetic method o: e<amination. (n non=magnetic materials s r:ace im5er:ections can !e re9ealed sing a :l orescent 5enetrant method or one o: the other 5enetrant methods, ass ming that the de:ects act ally !rea8 o t to the s r:ace #; 1# $ Plate and Similar )aterials S ch materials may s ::er :rom the 5resence o: incl sions, laminations and other discontin ities elongated in the direction o: rolling. ,hese de:ects are most con9eniently detected in cold materials sing ltrasonic methods, which are 9ery sensiti9e e9en when a55lied to a considera!le thic8ness o: material. ,he on=line ins5ection o: hot 5late can !e carried o t !y some enhanced o5tical method or other non=contact system s ch as eddy=c rrent testing.

#; 1# % Concrete str ct res in situ may !e tested !y some :orm o: 5 lse method. ,he 5 lse may !e 5ro9ided !y a sim5le hammer !low or !y some :orm o: electro=aco stic transd cer. As with ltrasonic testing methods already descri!ed, the time ta8en :or the 5 lse to tra9el :rom one !o ndary s r:ace to the other==or to !e re:lected !ac8 to the so rce=is meas red. )!str ctions or im5er:ections inter:ere with the 5assage o: the wa9e as in the case o: ltrasonic testing. #; 1# ' CeramicsF Plastics )aterials and Bther !on1metallic )aterials S r:ace crac8s are li8ely to occ r in materials s ch as these and are s ally detected !y some :orm o: 5enetrant method. /ery small s r:ace crac8s in ceramics are di::ic lt to detect, 9et they are m ch more serio s in these relati9ely !rittle materials. #laws !elow the s r:ace o: ceramics are also di::ic lt to detect #; 1# ( Com5osite materials o: the :i!re=rein:orced and laminated ty5es are now widely tested sing ltrasonics. + lse=9ideo thermogra5hy is also se: l in detecting im5act damage which has occ rred ,elow the s r:ace and is there:ore in9isi!le to sim5le 9is al ins5ection. Since com5osites are relati9ely trans5arent to H= rays. radiogra5hic methods em5loying low= 9oltage H=ray so rces are sed. (: the 5resence o: :a lts which !rea8 the s r:ace is s s5ected, then the com5osite is :irst treated with a 5enetrant containing a s !stance which is o5a? e to H=rays. #a lts will then show more 5ositi9ely when the material is H=rayed.