oS Introduction to Ceramics Second Eaton BC ~ URS initabe Hoalie rata age Sort © 0b Wy a oak maybe paddy ay mom idiot he write ermine ag EE yo Cnr at a “ei et oe ic od ay ot Ince ogra tsa i, Preface to the Second Edition using the Siteen years which have pissed since the Ast edition was publishes the approsen described as been widely gocepted sn pac. ‘Eat However the ndvances made in understanding and controling nd “lveoping new ceramic processes ind product ave required substan] snientions nthe text and the fetodtion ofa conigerable mount of ‘ew mata portly new and deeper waderstnding of the stare of sonerstaline sli andthe characteristics of stretusal imperection, ow insight ato the nature of surfaces and interfaces, rovgmton of ‘ino decomposition ar viable alternative fo clscal naceation, ‘Scognton of the widespread ooctience of pha separation, devon. ne of pisces clearer understanding of ome of the masness of crng phenomens, development of soanning elton meroncope and vrasmisston electron microscope techniques for the observation of Dcrostuctre, a better derstanding of factor and heealsresse, Sint 4 myriad of developments reve to clecrcal, delete, and ‘hngnsie ceramics have been inclided, The breath and importance af ‘ese advances hax made single ator text Beyond any fasials “The ascesaty expansion of mater relued 19 physical ceramics, rt ‘he recent avalaity of excelent text aimed processing and mantoc Turing methods [F. N-Nowton, Fite Cerames, McGraw Hil, New York LUvibj Fake Norton, Refroctovien MeGraw-Hil, New Vork (961: FL NNorton, Blenens of Ceramics, second ed, Addzon Wesley Publ. Co. Listas F. Vs Tookey, ed Handbook of Glass Manufacture, 2 Vols, feos Can (NA. Dolson, ed, Handbook of PrecisionBngncering, Vol 3, Fabrication of Non-Meal, McGraw-Hill Pub. Co (QUT; Fabrication Selene, Proc. Br. Ceram. Soe. No. 3 (196) Fabrication Slence, 2, Pre. Brit Cera, Soe. No, 12 (1969): Insite of Ceramics Textbook Sones: WE. Woral I: Raw Materials: F. Moore, 2: Rheology of Ceramic Systeme; R. W. Ford, 3: Drying; W.F. For, The Efecto leat on Ceramies, Maclaren & Sons, Loon (964-196), Modern Glass Practice, SR Scholes, re. C.H. Green, Cahners (1978) has fed‘ to eliminate most ofthe fiat edion's treatment of these subject, We regret hat theres stil ot aval a single compeehensive {ext on ceramic farieation methods ‘While we belive tha structure onthe atomic level and onthe level of simple assemblanes of phases has developed to a point where lack of Clarty most be ssrised to the author, there remain areas of ret Interest and concer tat have not seen the development of appropiate And useful paradigms. Ote of these, perhaps the most lnporat, i Felted to the interaction af lice imperfections and Impuries with Aisiocations, surfaces and grain boundaries n oxide stems. Another Felted to ordering clasering, andthe tay of ceami sold solitons nd lasses. A third methods of chersteriing and dealing wth the ‘ote complex structures fund for multiphase ml component ssh: tot effectively evaluated in terms of simple mols Many tbe te ‘rich the frontier open ave noted in the tet ee out hope that hit ook wil be of some help. not only in applying present krowedee, sito in encouraging the further extension of or preset Understand Finally the seoior author Dr. Kingery, woul keto ackrowadge the longterm support of Ceramic Science research a MLLT. bythe Divison fof Phyieal Research ofthe U.S. Atomic Energy Commission, now the ‘Energy Research and Development Agency. Wihoat that sppor ths took, and its infuence on ceramic scence, would not have developed "We aso gratluly seknowedge the help of out many colleagues especially, eL- Cob, B Ctr, 8.1, Wuensch, A. M. Alpe, and RM (Ceomon. W.D, Kivoray HK. Homes D-R Unzstan ambi, Mancha 1 INTRODUCTION 1 Ceramic Processes and Products Lt The Ceramie Industry 3 12 Ceramie Processes ¢ 13. Ceram Products) 16 Contents M1 CHARACTERISTICS OF CERAMIC SOLIDS 21 2 Structure of Crystals 2 Atomic Stuctue 25 2 Intestomic Bonds 36 23. Atomic Bondig in Solids 41 24 Cry Suuctures 46 25. Grouping of Tons and Paulng’s Rules 26 Onide Stuctures 61 27 Shhoute Sroctares 70 28 The Clay Miners 77 29.Oter Strctres 80 2110 Polymorphism 81 3 Structure of Glas, 34 Glass Formation 92 32. Modes of Glae Stcucure 95 % *Contents | conmeers « 33. The Structure of Ose Glasses 109 MI DEVELOPMENT OF MICROSTRUCTURE 34 Submerostruct 45 Misciiity Gaps in One Spat ep Features of Ginses 110 IN CERAMICS - 36. General Bacosson sg 7. Ceramic Phase-Equiibriam Diagrams 4 Siyctirat impr 88 | 72 Grecampanent Pine Duss 21 {1 otto ted fx Atomic Deets a5 13 ‘eciiut forDeemiing Paseo Disrans 42 Fomultion of Reston Sq 26, 14 TweConmnent Sytem aT 43. Sold Solations 13) 44 Frenkel Dsger 139 43. Schottky Disorder 3 15 Two-Component Phase Diagrams 2M 74 PreoCnpone Pas Dane 295 417. Phase Compostion versus Temperature 46 Order-Disorite Transformations 45 18 The System ALOrSiO, 308 47° Association of Defects was 19. ‘The System MgO-ALO,-Si0, 307 : 48 Electronic Siete 132 7.10 Noneqiam Phases 3 49, Nosstoishionetrie Sods 57 410 Disocstions gp 8 Phase Transformation, Glas Formation, and ( (las Ceramies a dete ee AON tt ia Ding ret gcse eaten Kt at 54. Suface Tension and Surface Enesty 379 82 Spinal Decomgositon 523 52 Curved Surtce sas 3 Nockaton 38 13 Gran Bosmdaries ‘ig 84 Coystl Growth 396 14, Grin Boundary Potential and Assisted Space Change 5 Gite Formation “M7 a “5 Boanaay Stee "ion 2 56 Compeatio 2 Varisl, se Flow, snd Prevpistion Sctte Seeston and Phase Separations and Near from Ginses 351 7 Gin onda S99 | 87 Catal Caos, Photosensive Gis, 4 Struct of Surfaces and Interaces 204 Photonic Gisnes 38 8 Weting ad Phase Datibuon i 88 Glueceromic Mails 368 19. Phase Separation laser 275 & stom stbiny ar ai ad tween Slits 1 Difsion nd Fee's Laws 219 ‘ ae 2 isi a a Thrall Activated Process 227 1s 94 Kinetics of Heterogeneous Reactions : 3 Nomenclature aad Concepts of tominic Pees 3 92 Rent Tar och Plan Bot Laver 38 £ onperatte an try Dependence of Dee, 2 33 Rent amr toh «Fl Pea 5 iferion in Crsaine Onset Se 34 Regctan Transport n Parole Systens § Discaton, Boundary, and Stee owen 250 95 Precptaon i eystalioe Ceramics 20 7 Dison in Glsres "Isp 9% Nonisthermal Processes 44D10 Grain Growth, Sintering, and Viteifiation 101 Reciystalization and Grain Growth 499 102 Soltstate Sinerms 4 103 Vitsfestion 0 10 Siting with » Restive Liquid 498 105 Pressure Sintering and Hot Peessing Ot 106 Secondary Phenomen 303 107 Firing Siakage 57 a8 11 MMerosteuctare of Ceramies 1 Chances of Mirosuwetre 42-Gue Sa 3 13 Trawial Woiteware Compostions 114 Refractories 8400 113 Sct Cay Prodiets — 1 Glaer and Emme sep 113 Ghance™ Sr Ma Glaenamics 85 119 Blecicl mt Magnetic Ceramics 540 Ut abs se 1M Conon and Concrete 569 111 Some Spec Composkions 573 IV PROPERTIES OF CERAMICS 581 12 Thermal Properties 121 Itradetion 588 122 Heat Capacity 86 123 Density and Thermal Expansion of Crystals 589 124 Density and Thermal Expansion of Glasses 538 125 Thermal Expansion of Composite Bodies 63 126 Thermal Conduction Process 612 127. Phonon Conductivity of Single Phase Crystline Cevamice 61s 128 Phonon Conductivity of Sine Phase Glisses 324 129 Photon Condictnty et 12.10 Conductivity of Mokiphase Ceramics 634 na 3 BS Be 12 is ts ss 182 183 ss 189 iss 164 162 166 m convents " 13 Optical Properties Introduction 66 Refractive Index aed Disparsen 658 Boundary Reflectance and Surfece Gloss Opacity and Trnsacency 6 ‘Xbsorprion and Color 677 ‘Areiations 68 os MM Plastic Deformation, Vises Flom, and Creep 706 Inwrodveton 704 Pstic Deformation of Rock Salt Stature Crystals 710 Plastic Deformation of Faoite Stuctre Costs. 727 Plastic Deformation of ALO, Crystals 728 Creep of Singe-Crystal and Poyerytaline Ceramics 734 Cheep of Retactoes 747 ‘iseour Flow in Ligue and Glases 155 1S Bastiity, Ametasiity, and Strength Inrodction 7658 Este Modul 773 Anelasticty 778 Bittle Fracture and Crack Propagation 782 Suenath and Fracture Surface Work Expeience 791 Creep Fracture 807 flocs of Microstucare 86 16 ‘Thermal and Compositional Stresses a Thermal Expansion and Thermal Sresies 816 Temperature Graiems and Theemal Stresses 817 Retutance to Thermal Snack sod Thermal Spaling £22 Thermally Tempered Glist 810 Anoeaing 85, {Chemical Strengthening 844 17 Blecriat Conductivity on lets: Condstion Phenomena R47 Tonie Conduction in Cota AS?ma 16 ts as ia ra G aa ke 93 38 Eetonic Condstion in Crystals Tonic Condoctign a Gases Electronic Conction in Glaser Nonsoichiomete and Solit-Contoled Bletonic Conduction 88 ‘Valeny-Contaled Semiconductors Mixed Conduction in Poor Condsctors A Polyerysaline Ceramice Soe 38 Dietre Propertien lectial Phepomens ca see ~ Disectc Conrtans of Crystals and Gaster Dielectric Loss Factor for Ceysals and Glsses Disecrs Conuctvay os Foberytline nd Polyphase Ceramics 947 Dicecte Streagth . Fenlecine Ceramics ot 19 Magutic Properties Magnetic Phenomena as a ox ‘The Origin of Ileractions Ia Ferrinagcte Materia Spinel Fewntes 91, Rare Earth Gurnets, Orhofertes, and tmenites “The Hexagonal Feries| Pobyerytaine Fertes ee 001 os ma os ee Introduction to Ceramics! | part | INTRODUCTION “This book is primi concerned with understanding the evelopment, tse, and como he proper of ceramics fom the pnt view of ‘what nas become koown a phe ceramic. Wat decade or a0 go, ceranics was i age part anemic a. Users of Eeramis procired their material from One supple and ene Deel plant of spl in order to Maina Uniform Some sil 4). Ceramic producers were Titan to change ny. dtl of tele ‘ocesting nd ranalatoring (some stl ce), The fens ws that the Ecoplex ssl Slag ured were nat shifclently wel know tof the ‘flags of changes to Be predited or uneerstood, and ton omaierBle “extent this remains thu. However, She Hrctins pat of undieted Empirism in ceramic techoaony has gelysimilhes ‘raljsis of ceramics how's them to bea mature of eystaline phases ‘and ghsses each of many iferetcomposion, usally combined with porosity ina wide vanity af proportions and arangements. Experience {ee shown that focusing our ftention onthe stuctre of hs snes inthe broadest sense, from the viewpoint of Both the oiin of the Sructure and its inlence on properties i x powerful and efective ‘preach Tis concretion onthe wriginof stretre and 5 nen con properties isthe ental concep of phys cers, "Jo be fly fai, suture must be understood in #5 most com prehensive sense O ne ha, We te concerned wily tae strytare {he enn vets i lame and aye tha ae so porto understanding {he formation of compounds the coors in Baaes, the opis popetes of Insers, seta! condutivity mane effects, aad host of other sharacterses of useful ceramics, Equally portant he way in whch Some or Sons are atanged is ryan solide ann roterystaline| tases rom he pit of view of not ol nies an del stucures BUSse 1) CERAMICS tht the randomness o ordering of theses nd at sl sltions,Prperiensaches fea iftsoe, mechani! Gtormaion leg fnfuence on mary. pshaps most proper of ca see oro lt th, wraeenet of pes Lysine, hes, Bsc tenth percent pron changes conn rans eet etic. A cane in'pore morpnsaey changes ge eg ermal dere in pin ns ay change a Comte tle to song and top. Ore ence Socom et i ce Ween grains forme realy. Chantae ae stange an nstatr nto Sol vice ves The ope crn . conductor ind vice versa. The soperston cn These observations are of peal ne [rovide a key tthe stccessu repiraton and wie of eeleoroe Se omONCA ove ws wth the ans for understeer amposion, nd anngsment of the phases tat sae i ye inadin, provides the bats or undestandn te net Ceramic Processes and Products We defie ceramics a5 the art and science of making and sing slid stiles which have as thei erential component and are compoxed in [ge prt of inorganic nonmetal material. This definition includes not ony terials such as pottery. porcelain, refacores,stuctral clay Prowets,shrasves, porelsin enamels. cements and gst bul iso ‘mae magnetic mleril, ferrecteiris,manuactred single cys {ls us-ceramies, apd avarety of other products which were not txistence unt a few years ag0 and many which €o rot exit toda ‘Our definition ebroner thi the ar and seience of aking ad ung told artes formed by the action of beat on exthy rv materia sh tension of fic Greek word heramot, and fr much broader tan 3 Mod fommonditoniy dein such as "potery" of “earthenware. ter developments in metho of ftuetion, he ure of materia t close Spesieatons, and thie new and unigue properties make traditional ‘ntions too restritive for our purposes, The oigntion of novel Ceramic materials and wow methods of manufacture requires 0 tke 3 fundamental approseh ‘othe rt and seience an aeoad view of the el LA The Ceramic Industry ‘The ceramic industry i one ofthe late industries ofthe United Sates, vith on annual production of nearly $20 blion in 1973 ‘One important characteristic ofthe ceramie nd that it bale 10 the sucetsatul operation of any her indies: For example, eae: tore are abate component ofthe metalogia indy. Arasives are ‘Sse! fo the machine tol and automobile indies, Class products Ste essential to the automobile indsty as well a t the echtstira, ‘Sectronc, snd electrical indstes, Urantim oxide fel age esental ts ‘he nuslear power indurry. Cements are exsenta tohetchitectra ti‘ _NrROBUCHTON TO CERAMICS Setar andi “ental couoston of he esentafconsinen ad Sottero och ter nd tector ter cone pes tebe de ation among ert oc ever withia they ues inepeane sd tho de baste esomee roc fhe cra nt td lemine os eaierite ce 5 form, Low-grade clays are avalible amor everywhere: 8 re, e manufacture of bung trick and te not requiring exer pina opr ees ny whch xen oe atthe ie anaicure © hh sachs magnetic crais cera ign "cine cums, al econ elt cheel ication and even chemical preparation of rv! sais may be fecessry and approprites ee particle hydrous aluminum silicates which de sly when mined parse carci ba comane chance ek erystaline shy rome sa orgie nd sows he arly gore ny none ante gee = ical Popes try sony el nda ceva Cee important fonctions ie eevamic bodies, Fest, their charve rae ey tl oman te om ceca ete sre atemperatire age cepntng on cope. a ch wa} 2333 Steed on ne ie nee Aloo ier oepestons Often center ow eae OT amen “ceRAMtc PROCESSES AND PRODUCTS me Ne Tae, ao ee Mail rhaeie (shee) oss» eres es NS om ‘rete mail sn, ros mages te wih Ws ne eT the clay mers a Bang he eal format meets Se tae aminportant rm mat the mete MasSiO. oT Taree components ad for making tle AeReos of len a hyarcusmagnesum tats wich ase 8 NO er ipl variety Tv enysotbe, MESKOAON rte The ousted cussed anyarous Gk ae Das raw mater for euch of the Sram: and i jor mre inne azes enamel ISL ‘ety SOs rena compotion. 1 widely wed PSIG atest chal sable ane eave ea on npn dcx Tite ns vty fier fovea WD SA aby or Brn ont moran a 84 mara GST HSS ea at ee um sand, and ey ound ft Toe = earl sandstone which onde f TN) ae rn A denne quris goiter seo 0 Ser i eine orf ee nesry prec cial ik Qua cay upland by sya cyt, manufac thr hydroternat roses. 1 hndrothere ras nich aces as a sfractny oskbone on rats cv ros sii, ain tral pres ae an Chin) nto flspa an oy ous alumi 2a lx wih isn the formation of & (eicontainng XN Sree aj mates of commer nlees 26 Fos) ass Pe cline or othoclse, KCASH}Os, wb espa (0 {sae oe ime tetdopa Cana, CASIO. Other coe NAAISiOn a one are nepicine sys a guattos mater som ele, NedALSHYO aie and mlrochne 9 "cok coma ene group of sate minerals the Simei eta pe composon AS sed fr the mance of fefractoies!NIKODUCTION 10 CERAMICS Most ofthe natura occuring nonslicte material ar used primarily as feactories. Aluminum oxide ix monly prepered from tke need bauste by the Bayer process, which involves the selective ache tn, iinine by caustic sods, followed by the precipitation of anes: hydroxide, Some baunite is used direc in the ects tase nto ‘on of shimina, but most is fist purled. Magncsum oxide & pean bath trom natural rngsesie, MEO, ad from mishests Bheieeae B(OH), obtained frm seawater or rite. Delon od soliton {alc and magnesium carbonates withthe formula CaNletCO tere to make basic rik for use In the sel industry, notes ieee widely used for metalic! purposes is hiome ore which conse Primarily of complex sli sotition of spina (MELFENALCsO. oc ‘aks up mos of the materi the rettnderGonsns Of Vrlow mea Or mineral tased materials which are widely used chide soda ash, NsCOs. mostly manufactured fom sodium chloe: bore sateeens Inctdng kei, NasB.Or.0, and bors, NusBOr HD, weed fuxing apes; Buorspar, CAF urd sea powerul fx for son des, ad lasses; and phosphate maerss mosty derived from teats CacOH.F1P 0.) Although mox tudinal ceramic formulations are bated on the we of tral ier materials which are expensive ad rent wales incresing fraction of specialized ceramic ware dependhon te pane ‘iy of chemically processed matras which may or may not ste ey ‘om mined prodits and i which the parciesic chance ‘hemical purty are closely onto: Siicon cable for nes nate are used as a mates A wide range of monet ee manufactured {com chemically precptted ion ode, Noce ta ‘lemens ate manufactured from chemically prepared UO Sogo oe {als of sapphife and ruby and alo portiee polycysuline ak age, lexi ate prepared from slumiaum oxide made by mechan tluly calcining alum in order to maint good “osteo teas chemist ad particle ie, Special techniques of mateial oe ch reze dying ropes of station to form Romoscneoes eric fsa ize and hiah purty are receiving increasing ction, fo tne ‘vapor deposition of thin materiale in cartuly contotes chest ‘nd physical form, to general, amar preparation seaty tee (CERAMIC PROCESSES AND PRODUCTS . toward he increasing ue of mechanic, physisl a chemical pis ted pang on oar th seal contol of re see npr btn tnd ey to he sole elanee {n materi in he form fond in are, ~~" Poriog and Firing. The mot eres fctors affecting forming and slependon very small partes owing over ogo emai Dronortonl tote densi and pre ie. Por pase forming the HMixigin a coarse teal alos te esto ithe nersties tween tert te fren consent For vain the weed mi ‘arn her norm somposion Ging ene. The eg sare {Etro Tmo os sew ado ren fn soscaew INTRODUCTION To CERAMICS Since the ring process also depends om the capillary forces resulting fuom srtace ene‘By to consolidate and desi the materi and since these forces ae Inversely propotonal to parle sie, substantial percentage of pe parte maar ig ncestary for scene ring, The ‘ny minerals ve unique in that thei tne pale sie provides oth the “pabiity for pas oring and sto suffently lngeeapany Caces {orsuccestul fring, Other aw mater have toe prepared by chen recitation at by ring int the mieron particle ange for equvaent sts to be obtained, Perhaps the simplest method of compacting ceramic shape consists of forming 2 dy or slishly damp powder sual with an orzanie binder, metal diet sufleenty hgh pressures to form a dense, strong Piece. “This method is used extansivey for refrctaris, les, spac elecrca ed ease ceramics, sparkplug. fsulators and other. techie Crass: mclea See elt, and vate of prodts for which large rumbers of simple shapes are requires is relatively inexpensive hd xn form shapes to close tolerances ressues inthe rnge of 300010 50,000 Psi are commonly used) the Higher pressures for the harder imateras such ay pure ides tid carbides. Automatic dry pests igh rates of speed hasbeen developed to a high state of efectveness. (One litaion that fora shape with a igh lengthto-Sameter aio the fretional fees ofthe powder, particularly spans the de wal ado pressure gradients and resting variation of density within the Piece uring ring these density varatone are climiated by mater Bow ‘using sintering: ie necessary follows tht there fs 4 vatiaton in Shrinkage nt los ofthe orga tolerance. One modification ofthe “rypeesing metbod which eas oa more uniform density Iso encose ‘the Semple ins ruber mold inserted fn hyenas chambe 0 Rake peces by hydrostatic madi, which the pressure e more wnfornly $pplies Variations in sample Senaty apd shrinkage ae lees abjcton able, Tas method ip widely used forthe manufactore of sptkpug ineuatre and fr spec electrical components in which a NBN epee of uniformity and high level gf product quality are required 'A ite diferent method of forming eto ext ti pati mix tough a de orice a method commonly used fo Bick: see pie, hollow te, techies! ceames elec ellos, and other material ‘raving ale norma! oa fixed eos section, The met wey peated ‘method fet sen vacinne suse o eliminate ar bubbles, thorouehy mix {he boay with 12 4p 0-2 water, and fore rough a hardened tel or abide ie Hysraie piston extruders are alo widely se “The earls method of forming clay ware, one sil Widely used, to add enough waterso that the Ware can teal formed at ow pressures shin may be done under hand prestre sch bung wate with cls Tere runners wee The es ree erming ta rsaing between pres ste aa ng, which conan of ping on. of soft a by toma Meee ota asters rol an tan st ‘Sets we ing pel! mo Be fe Ie ely a form tbe up sae _ : “When ager amount of water is added. the clay remains sticky PlaSOs enemas ben med, Uae scone eh a alsa ere aeztes fos HONETE, iti ot sen aed tote se, i sa any abso ier nai) suing ee, separate chee ng seat or deflccalate, Wi BTOEE 2 a an ted wih ms ie 82% and cont ld ped coment aul oes the ity. When 8 ‘ama hans cat nora pros paste ars mot he sepemin ek om the cone red an a ht ye ul Othe sol ss a econo ul heir te suc, Tis porn yal cn be ive athe ees ie sh cae wl tcess stupa eas. Pein each of the processes whit, require the addition of some water ena ee uhh tend x ennved ast be eT cote ey cnt mre sorte bs ia Ke Saree ot ie ying, the sl yin tes pendent of he al one an end here conn i of wae! 9 Seles eaten orice me od mes a ae ed ikage coe they at contact 945 ht ont a fm, Daring he sinha pv ses rut py rake may deep Rese tel ain Ter a ea drine ts pid rates must be cctlly cone Me rs armenia ign be cots more ph One he iy Foe the ryeennk or Rydon mM sae ie ener sone wi sige aoe a van or hse mets fore sic wane i normaly Hed to temperatures a8 se. deentng onthe composon and popes csc or ecrsed ay be ted in re WY a weet enn poate ore he wae witout» hf 08 Sa a fest aut the body: hen ae aoe sam ampere Ante mato tir the war ae teeha Manet thers) te asad matte Soret rata Meher tmermre Atl methodB INTRODUCTION 10 CERAMICS ppt the laze to the uted ware and heat them together in «one ‘During the fing process, either a viscous fig or scent atomic motility in the solidi developed to permit chemical Teactions, grin ‘sromth, and sintering: he lst consists of allowing the forces of surface Tension fo consolidate the ware and rede the porosity. The volume Shrike which oars jst equal to the porosity decrease and Varies {rom few to 30 or a0 vol, depending onthe forming process and the llmate deni’ of the fred ware. For some special applications, com plete densy and freedom from all porosity are required, but for ater $pplistions some resus porosity is deta If shiakage proceeds at fn uneven rate ding ring ori prt of the wares rertrined from ‘hrinking by ction with he materi on which it se, sterses, arin. 8nd racking cia develop. Consequently care required i stig the ware tavoid fiction, The at of temperature ise ad the t-mperature Unlormity mast b controlled to avoid vartions in post and she age The nature oF the proceses taking place fs dscussed in deta a (Chapters Ian (2 ‘Several diferent ype of ins are used for ing wate. The simples 1 skove kiln ia which benchvork of ask fs set up insides surface eating with combustion chambers wer the. material to be fied {Chamber kins of eter the updraft or downdraft type are widely used for batch fring a which temperature contol and voiormity need not be too precise. In oder to achleve uniform temperate and simu use lott chamber ins im whin he ir for eombusion fs peeeated bythe ‘Soong ware nan aacent chamber the mathod used in ancient Chine tnpioyed. The genealwallabiy of mare provisefemperstre controls {or gs, ol, and electric heating and the demands for ware wniforsty have led tothe increased use of tune! kins in which a temperatute profle [simaintainedconsant and the ware speed through the int provide 5 precne ring schedule under condone such that effective contol ean be abies Melting and Soiiaton. For most ceramic materials the hgh vl ume change securing ding solidifeticn he low thermal conductivity, $d the bile nature of the Sli phase hive mie mein a sex ton processes comparable with metal casting. and foundry practice Inappropriate. Recely, tschniques have Been developed for uniiee- tial sliifenion in ven any of thee eiication can be subst voided. This process has mainly been applied to forming controled evtures of metal aloys which are parculaly stacive fr aplcs "Sons see a turbine blades for hi emprature pn torbnes So far as swore aware, there io lage sale manufacture of ceramics nhs Wa. ‘CERAMIC PROCESSES AND PRODUCTS a but we anipate tht the development of techniques for the unis tional soldiiation of teramies wil e a aes of etive reserch ring the next decade, ‘Another ease in which these lmiudons do not apply is that of wassormiag materials in whieh the viscosity tacreacr over « broad temperature rage so that there sno sharp volume discootnaty dung Solitsation andthe forming presser canbe ausied tthe aid of the gss. Glass products are formed ina higsiemperstre vncous state by fve general methods: (1) blowing, pressing, ©) drawing. (rolling, nd (casting, The ably to use these procesres depends to large proach, depends on the observation hat the state of matter seq, thether aseoes, ligud. oF ettalig, is determined by the ther rmodynamic variables which desrbe the system (emperatre, volume Pressure, composition. The inlereaionship of these variable tthe te of the sytem hat been formally developed in the paneples of thermodynamic, which ae based on thee undamental ia. The Sst Taw requtes that the itera nergy E ofa system be conserved. The ‘cond law introduces another Tention, the envopy S.a measure af Fandorness which determine the destin of al spontaneous process the entopy ofthe word tends lower a mama. Thus the change inthe ntopy of the #stet andthe surroundings during any proces fay toward pester randomness Arman dScaontin 0 o ‘Ax equim, the entropy chang is 2ro, and theretre this eqsation Serves a «defriton of thermodsramie equa The hid Taw sets the zero in envopy of matter athe absolute ero of temperate the enopy ofa perfect ery at °K 2er0, rom these thee fundamen aw and trom the defn of interna energy and entropy other asefl state funeons sre defined: the ental, fbr eat content H, the Gibbs fee eneay G. and the Helabltz te fnerty F. The Gibbs free energy (G-= E-+PV TS = HTS) is the Stine function most commonly sed to deserbe the equim state of the system, For example, at equim (0 and Um pressure) ee and Stuer can coexist, andthe tee eneray of water etal to tha of fe From experience, we Know that hee isan enhaly change the heat of fusion, and alo’ an enlropy change assocsted with this equim AG-0=aH- nas: 2 al Seana = Ae ° When we deal with phases of varie-composiion (gaseous, Hau or tol soutions) the Gibbs fee onery it only afoetion of tempers- {Gre and pressure but als of composition I isthe moe action ofthe ih component. AG = Sars var +S max, « where we defn the chemical potent athe change in he tee entry Ul the systenn ith respost tos change Inthe concentation ofthe Hh omponet st constint temperature and pressure = (een 2 1 the sjstem is a equim, each ofthe terms in Eq, 4 mus be independent of ine tnd of poston in the system tho rier ‘Enpraar hemaleqirum), norm prevsre mechanical ei ‘Soon, and uniform chen potential cach component (chenica alien). iv sulpase nytem, ths ens that the cherie ental fs parclr component mst be the same Eh se, “ne proceed twill erome erensingy cls that he ney rcaonsip both on am stomstc sae and ona sale of aeroncoic Soemblages are reso nog diecly perience. May ‘iene are aie: pretty recommended C. Riel Ie “con to\Sokd Ste Posen and R.A. Saath, Themodyranis of ‘SoutStructure of Crystals IW this chapter we examine the strc of crystalline Soli, slide characterized bya ordeny period ara of atone. The thee sates of atten gaseous, iid, slldcan be represen a Fig... n the ‘snus tte atoms or molecoles are widely FAH and are fn rapid otto. The ire average separation between alone and nearly elastic iseaetons allow the aplication ofthe wellknown ides! gs as a8 3 tend approximation low and oderate pressures, n conta th gd Sold states are characterized hy the close asocialon of toms, which toa fst appronimation can be FEEded s spherical balls in contact with "rings between then presenting interatomic fores, (ngs there stint thermal energy to keep he atoms in random motion, ad there ie to long-range order. In crystals the atacive forces of interatomic ending vercame the wagaegating thermal effects, and an ordered serangement of atoms occur. (in gasses, covsiered im Chapter 3, a SSbordered arrangement persists even a Jw tempetatares) This chapter |Sconeerned with the structure of the ordesy periodic atomic arvana iets jn exjaals. What we consider here ate ea erystalsroeares [ater Chapters 4 and 8, we conser sme ofthe important departures from ideal Terder to understand the nate and formation of crystal strctes, it ‘eset t have some understanding of stone srt We present ome rests of quantum theory elatng to atomic structure ithe fret Section, Some additral aspects of Guantom thor are rough ler at ceded (partic p connection With slacscal and magnetic proper: tie) However, stongly ure siden who have ot dane 810 learn temach as possible stout modern stoic physics ats base for «beter Understanding of ceri. 21 Atombe Stractore ‘The basis for our prevent undestandingaf he structure ofthe atom es ln the development of guantum theory and wave mechanics. BY about—— 1900, extensive specuoscopic data fr the sees of spel ines emited by various atoms, the freavency dependence of thea radiation, ah the Sharsctersticn f photoelectis emision could not be atfactonly txpllned on the bass of clssealcontinaum physic, Planck (900) Scessflly explained thermal radiation by srsoming thst emited ‘scontinuousy in energy quanta ox photons having an energy he bese Wis the frequency and h'= 625% 10°"lage fe a unersa cont Einstein (1505) used this same ides to explain photoemission. About 10 yeas ater Bohr (913) suggested an strc model in which eeetrons can ‘move only im certain stale sett without raatton) and posted that leanaions between thee stable energy sats produce spectral Hines by {mission or aborgion of ih gunnt Thi concept lade toa ste tory explanation af observa setes of spectral ies. "The br Atom Inthe obr tom, Fl 22, quan theory reais that he angular momentum ofan electron bea integral mip of B/2s, Te lteral number by which h/2r 6 multi ie elle the princpal quantim number m AS ioresses th ena ofthe electron increases nd it efter (om the postive charged muceus. In adaion othe Drincipat quantum number, electrons are characterized by secondary Intra quantum number: fcorerponding io measure of eccentric ofthe of varies fom 010 Rtv ealled 8 C=O)ep (=I) (=D). {1 =3 orbitals; m comesponding to. measur felipe venation aks Inceprl vales from —1 to 41; 5 cortesponding to the dreton of electron spin is ether postive or nepative. As the vee of mand | Irorease, the energy of thet elesion ort also increases in peers. "A further tentrietion om atm sructre che Paul exluson principle ‘hat no two electrons can have all gaan mimbers he same oa ne stom As the aumber of electrons map atom inreaes, ed electront SAT ees Of Wislr enerey sates characterized by larger principal ‘quantum aambers The mmber of exetrons that canbe usgormdated it Shecessve orb in accordance withthe Pavltexchaion penile ‘etermines the periodic taeifaton of the elements ectron coaligurations are characterized y the principal quantom number (1.2.3.--andohe ori quantom amber Pf) topeter tnt the number of electron that canbe accommodated st tach energy level im accordance with he Paul excision principle (up to> ection foes ort, 6 fr p arta 10 ford ora ana 14 fo feria. The ‘esting electron configurations sa periodic table ofthe element sre piven in Tabi 2the case for hydionen (ae Table 2.2 forthe ionization enetres ofthe clement) Since there are no vacant sites in the n= shel, Ging 3m ‘lectron woul put itm the 2s opt far roms nvial core nat sable Configuration. Consequently, heim e One of the mot Inert cements Simla considerations app) tothe ther rare ses “The group | elements ate character by an oster «orbital such ax shat usrted in Fig 26 Ie him (152, the ones elecron ft an verge radios of about 3 A and can be ealy removed fot the inet fore of the nucleus and 1s" cletrons (lonzatlon potential = S39eV) 10 form the Lion, The eae of onzaion male ihm igly reactive end tlectropostice in chemical factions. Removal of @ secon letron fequites a much higher eneray +0 that thium i alvays monovalent te other group I elements In group I slement thereian outer + shell from which two electrons sxe Tost with am approximately equal expenditure of energy. These ‘ements ae eletropostve tnd divalent. Silty inthe group Uk and IV elements there ae thes and our outer clectrons; these clement ate les electroporitne ith typical valences f 3 and +4. The group V tlements ate characterized by an ter configuration of ¢” plas three STRUCTURE OF CRYSTALS s ‘ter outer electrons (9? od) and typically exhibit iter +3 or +3 ‘atence: In some case trogen ad phosphorae psn adiuonal elestons Toll completa te p ori to farm negative ios. ‘he formatien of negative fons is charctrinic of the group VIL kets, wh contin ve electrons inthe outer p orbital The addition tone eletton frm stable Fon for example Te binding energy foe this eon electon in forine fs 42eV.caled the electron afin “Ths binding energy arises because in the 2p orbital the addons cetom isnot sompleteysoreened fom the cles by other electrons,hetron Orbit. Although the Boe mod of the stom was succesful Fn uantatively expining many spew daa, the stilton of cern ‘lecton ors snd the fine strture of spect lines remained unex hind. De Broglie (1928) porated tat the dsm of observe ‘henomena, which can be discussed either as wave pheromens o fom {he standpoint of the energy and mornentm of photons, ute genera, According to the Planck and de Broglie equations, Momentum 7 on there smas.» elcty and wavelength, th tina ny pine Ie crrelated toa mivephcaomens of fed frewency and wavelonns “Teas reltionshpn have been epeinentl snfred by Says de ton nd neon afeston orate cleton rt ees ‘odes nfrnce.A standing wave rhs when the et Sicurerence coeiponds to an nogal number of wavelengths (Fig, 2.3). wes = inition xed om the wave ton by the de Broglie auton, te aril tne, and energy ate corporate inthe Schdnger ate aation. whic foe Sr sects is aa (as) where P is hepatic pote epegy and = V=T. Slaton of his ation sv he pate afte nan fonction nspce The sane af hae 22 ei Fe 23, Satay tei led do an ite abla value |p represents the probably of Fnng the eectron in the enclosed volume clement de. For umber of relly simple aves the distbotion of electrons i space has been demonstatd. nis representation sanding Wave imustbe viewed as smeared ou over & probability patter “The snst atm ie hyogen, which has a nucleus composed af one proton thd, inthe ground sate, one Te electron. Ths elscton has {pherical symmetry with a amen probably dstabuion atx rail Giance of shout OSA (Fg. 24), which cortesponds closely withthe Tals ofthe st Bob orbit For higher atomic numbers, the 1s electron tistribain i sna except tht the higher nuciar charge Ze Makes "hem more ey bound and closer to the mucous. The 25 ele din, it there is 2 appreciable vapor pressure the unstebie modes: toe ean vaporize and condense the more table Iwet-vapor presse {cen Sigil, many taoeSemations ate speeded up by the presence of aliguidia which the greater solubility ofthe unstable form allows to 20 tho Solution and then precipitate as the mare table form. (Ths method is ‘sedi the manoactte of refractory sea brick in which the aditon of 2 Small percentage of time sets a4 4 Mux at the fring temperature, ‘issving the quarts and precipitating sca a tidymite, Tete ie ‘sible because the high fo inversion invelvesa mich smaller valtioe ‘ange than the highlow guartz transformation) Reconstructive tra formations can also e speeded by the ation of mechanical energy. A iselear fiom the stricture changes, reconstructive Uansformations require a high activation eneray nd frequently donot take pace at allnropuCTION TO CERAMICS Suggested Reading ite, Iroucin to Sold Sate Pay Joba Wey & Sie Sproul, Modem Phuc: A Tetok for agus, Joba Wily & Sos Paling, Nato he Chemical Bond 3. Cenl Univery ress Fen Ns 5, ‘AF Welk Stal Inorganic Chena, 34 el, Cretan Pre MJ. Doerr. "Cystaognpie Aspects of Phe Trnsormations” Pha Trasormaioas a Solas, R-Smouchowsk 3, Maer ond W. A, We Bs, John Wey & Son Ine, New Yok 3S. p18 6. We Randy, Xiay lenient and Crs Stace of hea Mineral, Mitra! Soy, London, 138, University Pres, London, 1966 . LW. G. Wyctlt, Crystal Struct, Volk. I, etecense Paitin, 1 Brg 6. F Ching nd W-H, Talo, Cet Siac of Miner Crna iver Prev es, NY, DRE 1W-B. Person Handbook of Late Spine ed Stractrs of Metaead ‘loys Perunon Prev, Oxford 188, Vor ‘ination a tsa strctrs determined i even pear retest) ample hah Vol 39,6, asin te rain "198A a foe 140 Se ‘asriomoiene pw R'Con or poses ject mpc Een come ahs er os a a ‘rit neon hse ave ind sacs, gabe tect eel STRUCTURE OF CRYSTALS. ° net 2 Tr of Stet Asa llr a a 35ers 22, Sih pa aie oie, yd monn, tg (0) Far, 0309) 940" = 140A wht ttn amar wie rch m veel) EaateSuly) sve 9 re ‘Sieur centro S hve an for Go a Moncaans bo kirse APs ‘Emcee dmg om ping oe ftsrnapucTioN ro CEnasttes eeoeerne serene myer taanarerosos marten as et Neo cresre ae esr ree et eh at ‘pie se oa. ene earas Wecrmetans Sek eer nome cee Structure of Glasses ven though majority of natural and manufactured solids oe “xsi n ate, ax Sneseed in Chaper 2, material which ave vot {ystaline are of eat importance for both tational and newly de ‘laped crams, One important classi he Said sso, the proper tes of whi are am erent part of the ceramist' howled tthe Formulation of passes, gazes, and emacs Solid ghsses, of whieh the siteates ate the tchnologialy most important group, usually have | ‘nore complex stuctre than he igus from which he ae derived rd ‘ecen stulesiceate a complexity which i stil ot wll undetond, lth the broad srwtual characteristics ser resonably cleat toce newly developed clans of materials is thin fmw deposed as Sincyntaline slits tom the vapor phase, about which even less Is own sto stracora dea, te each of these clases of ceramic tras the shrtrange orders preserves athe medi vicinity of thy sleted atom, tha the fst coordination fing the fonterrange rier characteris ofthe ies! crystals dssipated in away hasacter leet by diversity among diferent soles and by icity In precise “scriton. Wefocts our attention on lasts Which re by fr the most important ‘eg of inorganic noncystaline sles. The sretire of passes may be usiered em tee sole! (I) te tale of 210 10 A, or that af Leal Sonic eeangeentss) the ssl of 300 few thousind sngstoms, ot farofsubmerostactre na) the sale of microns to milmeters ‘sie the tame strate aed the submieronstre of glses; the ‘omieraton of microstructural fentres fe deferred to Crater 12 rertonUCTON 10 cERAMeS | Glses are esl formed by soliton from the melt. The sunt of gases canbe erty dstingisbed ro tat of see fio stot neectcy independent of empertre Tn ean best be eenoye lt tte pei vole of the cyt id and ws 8 tint tener (Fb 31) On cole fhe ais ee isons gin Vue athe meng pot he Hl sal iter However ecstzaton occurs tne volume of te a Mccreapeat south same tear aborhemeking pot ntl here sa ‘crea in te cnpnson covet at aang temperature called te fins uensfonaton Tange, Below the temperature rage the 25 strc doesnot relax at the cooling rate uted, THe expansion Sio, op Sio Bin Inthisraconthe SOs resting fromthe ondeston of the sce i once Asn es one formed Oy the ec af Soktm eats ack These econ ae pray eet athe Scot hyimgntondedsicrer aguas mea Por example he ALO, + 64,20, #2 2AKH, PO.) 38.0 on {forms nonerystaline ge in whic hydrogen bonding predominates, Lie stien ge it makes 2 good insane cement. ‘Om the seule of atomic structure, the distinguishing structural charac terse of glasses, lke the lauds for which many’ are derived isthe Absence of atomic periodiety ov longange order Such a tck of ‘evoasty does no, however imply the absence of shore-range orton Ptr gas o lqul may be described i ers of an atom-ceatered coordinate system and is frequently fepresented in terms of radi Aistrbition funstione “The rad tribution fonction p(R) i defined asthe stom density in spherical shel of radios R from he center ofa selected tom in he ai (rats. The radial distribution function for a Se sla, determined fr ray diracton studies, is shown in Fig. 2. As shown there, mole ‘ions in the radia density of tom are observed for ileratom spars ‘ont af the order of afew angstroms; for arg datances the observed stom densiyapprotches the average valve p Theappreach of the atl ‘adl-denstyfuneton to the average ator deny a large distances Feflects the absence of strcture ov such a acae. Hence, a preie Aeseriptin can be piven tothe sale on which short-range order ‘observed, that i the sels on which sgiteant modulations are sen in the radialdensty farton the scale of 8 few angstoms STRUCTURE OF GLASSES ” dumber of modes have been sage t descr se stirs of Huss. Ciysaite Model Xray iection ptterm from sass generally exhibit bond peaks ceteedin the angen which song peaks re sso Seen inthe dation patterns ofthe corresponding sys: This ‘own in Fig. 33 for the cage of SiO, Such observation le to the Susgetion that glasses are composed of assemblages of very sail ‘ays, termed crystal, with the observed essth of tHe lass “fraction atery resulting from partlerve brosdening. It is wel ‘xablisied that measurable broadening of Xray difraeton pesksocears for parte sizes or grain sizes smaler than about. micron. The ‘woadening increases nearly with decreasing particle size, Tis model vs applied to both single component and muleomponent gases nthe Inter ‘ase, the structure was viewed ar compose of erytalites of compositions corresponding to compounds inthe particular ystm)but ‘hema! no oy sippored In ial form for fens Yeandom Network Model.” According to this model, asses ae viewsd as three-dmensonal networks or arrays, acing symmetry and poodle lyin which no uit ofthe structure fs repeated regular interval the ‘seo olde pistes, these networrs are compored af oxygen poled.ao ot a send a eee Adootng the hypothesis that a glass should fave an energy cont simi to that ofthe corespoouing crystal, W. H. Zacharissen™ cons ‘ered the condition or constructing a random network sch a shown Fg 24 and seegested fou es forthe Fotation of an oxide Bas 1. Each oxygen ion shouldbe inked to not more tha two cation 2. The cordinaton numberof oxygen ions about the Cental ation inst be smal 4 or less STRUCTURE OF GLASSES ” 3. Oxygen polyhedra share corners, not eae or Sass 4 Atleast three corners of each palpeion should be shared In practice, the glassforming oxygen polyhedra are, triangles and secaheea, and eatons forming such soordination poly heisa have been teed network former. Alka sileates form asses eat, and the alka ion re supposed to occupy random posons ditiuted through the suture located to provide teal charge aetality, ax petured in Fie 54. Since the major functions viewed as providing addtional oxy3e fons ‘which moily the network suture, they ate cae. network ‘modifere Caton of higher valence and lowar coordination mune than ie alkalis and alkaline eth may contribute In pat to the network Ssrycure and are refered tas Items. Ina generat way the rle of fatons depends om valence and coordination number Sn the ceated ‘ahve oF shgle-bond suena, as iltated i Table 3.1.” erRoDUETION Ta CERAMICS ‘able, Corton Number and Mod Strength of Over a es om OM a ok Sy Pace Colne yn atheuh sts = ot oF SP Sree ere eas |, oe 1: ed caehees ag edge ee eras Theme a ee ee mae grad Soo 8 Crh ——™”—" oe 1: eer perro pierre - mas Boob 8 i Mode Seve ate odes ate en mee _ to represent the structures of gasses. Oneof these, termed the pentagonal FP dodecahedron model, views silicate glasses a composed of pentagons0 srRoRECTION 10 CERAMICS ring Si, tetrbodra. From a gven tetrahedron the ngs extend ins lzectons to includ the st ges and form twelve sided dodecahedal fails. Becabse nf thes fivefold symmetry. these dodeahedral cages "nnot he extended in thee dimensions without an accompanying stain ‘which ulimatly prevent maitenance of the sileonenygen, bond. ‘ough peatagonl ring of SO. tceshedea ay indeed exist inthe srdtute of gasses such a fed sla, there site reas to belive thatthe stoctaret composed entirely of sich elements. ‘According to another med!, gasses are composed of mies o paraerystals characterized by a depee of order intermedise between hat ft perfec cystal and hat of random sr. These parscystaline tains may themselves be atranged strays with dieing depres of fret. The degree of order date grin shouldbe large enough to discer ‘heir tal misortation nan lett microscope and small nought ‘void burp Brag election in Xray sation patterns. ALOU sch ‘models em pause, he evidence for the existence a sch sete, blest i oxie glasses, fs marginal. 33. The Structure of Oxide Glaser In discussing the structures of one lst, it shouldbe emus ‘hat these strastres ae at iowa to anything like the confidence wth ‘whic he ryt structures escussed in Chapter have been deters. Recent advances in experimental techniques and means of atalyzing a have opened new ra of alas uctre sts, andthe nent decade sould be marked by signcant advances ia our knowledge of eh fret. Even the hest experiment echniqes ae inadequate, ov ‘rer, for extabishig any particular model ay the stuctce of «iv las, Rather, the eclleofstretural estgntins of glares shoul be ‘Peasded as providing information sith which any proporedstactre ‘Sica. Early controversies between proponents ofthe erste and random network models of glist stuctce were genrally decile f= favor of the random-netork model, based largely on the argumen's advaced by BE. Waren” From th width ofthe main broad diaction peakin the pase dracon patter the crystal size nthe cate of SIO, tras estimated atabout? 108 A Sie the sit of unit el oferta Salsoabout 8A, an exstalites would be ona singe willis extent fod such structures seem at variance with the notion of cystalee ‘ray This emuins a powerflargumens even ifthe estimate of erste SL Waren Ap Ps 8 1 57 STRUCTURE OF GLASSES ws size were only accurate to within a factor of 2. Further, in cats to Sis sel, theres no marked smalbangle scatering fom 2 sample of feed sca (oe Fig 43), This indicate tat he truce of the par It ‘omnuois andi pot composed of discrete partes lke the pl. Hence, iets of reasonable sie represent, there must be continuous ‘patil network cospeting them which as density sir to that of he wth advanced experimental techniques and means of soy zing dat.” fn ths study, the dstrution of slleon oxygensicon bord wales (Fa 3a) wns determined. As sown in ig 3.60 these angles are aisibuted Feb, (a Seon eee of an So teat soning S-0-ond ‘ie Gt ci once” 0) Darenon 0B AL Moen 8. Wann J App Cnt 2.16 98 Shoe RN ay‘over abroad range, from about 120 to about 185, centered about 145 “This range is much broader inthe glass than in the coeesponding Aisrbation for erystalline cristo. contrast the slcon-oxyBen od tryper-onyben dstnces are nenly aa uniform Io the tase ab inthe Comerponding crystal. “The essential randomness ofthe SiO, lass structure results, then from a variation inthe sionlcon distances the slicon-onyzen-ison bond ngs. Beyond this direct Joining of the tetrahedra over fange of 'SO-8 angles, the structte of fored sien setms 10 be completly dom. Xray dfsction work by GG. Wicks" provides tong evidence for 8 random distution of rotation angles of one teahedron with {spec tanother Tht tote appers tobe no prosunced preterence In fosed sles forodgetorface sharing of tetrad, whichis te oued fn crystal seats. “The structure of fosed silica seems, He, to be well described by « random network of SiO, ttabedra, wih sgniicant variability occu In ilconoxygenssicon bond opis. Sch a random network Is ow ver, not necessarily snifom, and Toca varaon in density and Sts ture are tobe expected BOs. Xray didtction and auclear magnet resonance studies of assy BO, indicate clerly thatthe sucure i composed of BO, Trangles. Lees clearly defined isthe way dm which these tangles are Tinker gettin the suuctre. A random network of tingle provides poor representation of the faction data? A Beller detenpion i Droviden by 2 model in which the tangles are Hnked fa 4 boroyl oniiuraion (Fig). A sil beter eepresenaton of the tai obtained 7 ” AAT, STRICTURE OF GLASSES 7 trom model bases on diorted verton of the erste struct in ‘ch the tangs are inked tbo Te Snorons se wh as estoy the essen yume ofthe cesta ante ation srs rts embedded tas mats i ot spray, Bite Glass The ndon of sk or san sarth oldest SiO, increases the tat Of oxygen to son 4 sae arene thay tod bres up the tee-incsina network wid fhe foreton os bonded anys which don partspte nthe network ig.) te Sette units found in cystine aces ase shows fe titres Oxymoron asi Table 3.2. ov eso of ochre antag, the mediving cats are lactedin the lyf the sy bonded oxygens, Wih talent ane wo singly bonded onyeens me reed 98 tom OBE +p “he 20 mmm tofor Tipe “ ob 19 ommicmion of 35 Peter,Be a ee For sicte glasses, when the oxyfen polyhedra are SiO, tetrahedra, Zand Ba 33 becomes Xa2k-4 and Y-8-2R ‘nthe case of shlete glasses containing more alkali and saline eae ‘ides an AKOy the AP" is beleved 10 occupy the centers of lO, teinhodra Hers the addon of ALOsin wc eases introduces oly 3 fxjgens per etworkorming cain, and nonbrgeing oxygens of the Sastre reused up and contd to bdping oxygen: Thins shown Table 33, which the vluct of XY, and Rare even fora umber of “Tunle3_ Vals othe Network Parameters Yond torRapratae Chane for each cation; for unvalest alla ions, only one such oxyzen i “Kn Kay dracon sty of & uber of K,0-SiOs sts by G6 ‘wink incatssytemade changes i the stustre asthe alka oxides, ae edt soy The ata soem to indiate a random-nctwork uct ih ich th alal ons sstbted i pairs room throu the Srocture So focatod adaceot sig bonded oxen Inthe eas of 50° Sios dss ensign THO, Bian! Miers? suse Closter of the mag eatons, wih an average clster Geter son 208 Tristometines convenient o desc the network character of slicale sfases in ems ofthe average number R of sxygen fos praetor forming ian, ual the onygen-icen ratio. For ample R=? ec Sion fora pass conaning 12 paton% N&O, H0gatom% CaO, and Featonrs S10, 410s 136 ieee Fellowing Steves for ghstes containing only one type of network: fovning xin sutounded by Z oxygens (Z = Sr, with X nonbedeng {Gen sily bonded and ¥ bide oxygens per plyeton. ok X4YeZ and X405! ® 63) Pan Goon 2, 57,25 1990, Bn0280, Poe Rnowaloasio, 235 as 3s Ruan Pg nose, er ‘Te parameter ¥ gives the average number of bridges between the oxyen tetrahedra and their neighbors. For ate lasses with Y values iecthan 2 no threecimensionl networks posible ince the erated have fewer thar two oaygen font in common with other tetrahedra, Chine of tetraeda of various lengths ae then expected athe charac ‘ee srbeturl feature Tr cystine slices, the SiO tetrahedra are found ina vaviety of ‘eatin’: depending on the oxyeentosiicon ratio, a sho}n I ‘Table 22, Such configurations may ako occur in glass of the cores. nding comreions nd mixtures of thee configurations may ocean Dnsesof intermedi compositions; oeurrene inthe crystalline phase nats tht these stuctra units present low-eneray conguratons However, size pases ae derived rom supercooled lig, in which the [etter entropy of more random arays mee controling, the anon) fetweescrystline and lasy Structural uns abou be pursed With For variety of glazes and enamels itis typically found tat the cygue-toetwork former rao inthe range f 2.25 0275, 98 shownhag 6) 9 ore tase et T ow. onbwto wt onset ao wo oon z we oe ooo wr ‘ousteo or rs or oe st so sso SEO. v0 oa see mi tee eos oe foamy oe set sto sar we onze oes 0 0 moet we on " eu ot ‘ we or vo ost SR me ws oe ow ow olf] of conan (Goi = OFF onan 9) woso08 {eTRODYETION 10 CERAMICS in Table 3.4, Usualy sda lim sca lasses have an oxygen-to-nelwork: former vito of shout 24 The compositions of there aa ster comme lal lasses are shown in Table 3. ‘Borate Glasses Tt has bee established” tht the axon ofall or alkaline crth oxides to B:Os reuse the formation of BO, tetrahes ‘The variation of he faction of four coordinated Dorn withthe concen. tration of sal ide it hown in Fig 29. The sooth curve shown inthe oan gts ee gure represents the assumption tht each of he oxyeens aed with the {Akal fons converts two triangles to terabeden Up to alli oxide ‘oneentatins of shout 30 mole neatly ll the moder oxides have the ‘et ofconvetng BO, tangles to BO, tetrahedr. Beyond this compo. Sion ong, the experienaly Jtormined factions of fue cooeinated botons depart sgnfeatly from the inated curve, aod ths sugsest {hat singly bonded oxygens are zrouuced in appreciable numbers. The ‘ingly bonded gapgune are presubly associated with BO, tages rather than with BO tetrahedra, ibe the requirements for local chart Compensation ty the modiyins ations Ie simpler tthe eave of Be TWbieAs,_Approviate Compson ot) Type Some Commer has | a g KO 80, MeO boo g her (ndbook of Gass Manufacture, Opie Pobshing Coy New York NY. Shure FV Tote, TimeGermania and Phosphate Glses. Glussy GeO: i composed of GeO, teerhedra, wit a mean germanivmoxygen germanium bond angle of shout 13H, The strotural model of a random network of oxygen tetrahedra seems rearonale fr this materia In contrat to fused se, however, the station ofinlertetrahesral angles (Ge-O-Ge fo thie se) Tor viveous germans is quite shar. The exten randomness of {88sy GeO, apparently resus from ara distribution ofthe otaton Sngles of one tahadeon with respect to anoher, and this represents + Second mode of generating random ttrahedal networks i addon the mode based on the Broad dtrbution of latettriadra! ange). Measurements of physical properties sich as density suggest thatthe addition of alka ode to GeOs may result in the formation of GeOs ‘Setahedra up to about 1S to 30 gato’ all oxi, For larger adaione ofall oxide, rapid return to tetrahedral configurations ees in fated, presumably aezompanied by the feration of singly Donde ‘oxygens in large Mmbers. These stcturl changes remain, BOWEN, be coatirmed by iaction stdles. "nformation onthe structure of phosphate glasses hs been determine lasgly from chromatographic statis. Like scat and Most germane slates, phosphate lasses are composed of oxygen tetrahedra; but uke {he alate and germanate analogs» PO, tetrahedron canbe bonded tat ‘most the ater sma tetrahedra The mont falar seta wis ‘hosphate glasses ze rng ox chains of PO, etrabodra. The results of the hromatographie studies have elicdated the change In aerape length of ‘hain athe POs concentration of phosphate eases Is varied With ‘ster aditons, suchas alumina, ti osteo simulate the charters tis of networkcasedsilate or germane passe, ‘34 SubmlcrostructuralFeators of Glises For several decades after the plonering work of Warren laste were regarded ss homogencaus mitts, abd the conceplualpctre of the ‘Fandom network war widely accepted a6 the best structural model for lses, Despite tis wide aeeptance, however, kms kon ha seve ‘dass sistem, such as she alkaline earth ites, exhibited misc bipsie thie phate diagrams, and twas also know that heterogeneities ‘rove he struct base forthe commercial Vscor proses. In he process, a ghss containing abou 75 Se SiO, 20'S BiDy and So NO is melted formed into desved shapes, and then heated inthe fang of 50 to €OC, Such heat estnet results inthe glass separating ina two alstnet phases one almost pure Si, and theater ich a N&O and B:0>- On expose toa stable solvent t modest temperate the Tater phase maybe leached out, leaving» SiQrch framework cones network of pores ona scale of ta 180A, Subsequent compaction st Slevated temperatures (in the ange of 90 to 1000) results Ia franspareat glass sontining 96 wit SiOx "The intodustion of econ microrcopy 48 10 for investing ‘materials revolutionized the eld of gles strocture when subaicroseopie features om a seale ofa few hundred A were observed in any gies, ‘sing both replication and diec-ransmisson ceston misroscpy. It ha ow been wel enabled tht submiroatacures. ona seal of 30t0 2 Few bundeed Aare characteristic of many gists systems, Such submit stctral features have been observed in licte, borate, calconenie. And fosed-sl lasses. Thee submicrotctures have been shown to est from a process of phate separation, in which ld which is bomogensous at high temperatures separtes ino two of more gud phases on cooling To understand this phenomenon, consider the miscibility gap inthe 'MgO-SiOs phase diagram shown i Fig. 3.102 At shown inthe corer ponding fee energy versus composion plot in Fig 3 10D at 2 hgh Temperature such as 2300°C. 4 homogenecss soliton represents he minlaum feeeenergy configuration for al conpostions and. the ‘hermosyamcaly sable phate At ric fexpersture, the fre ene ‘erss composition curve exhibits pose eurvatre everyone. As the sour proportional tthe entropy, sine aa. ms 64 Fer simple solutions, the solution entropy should be grestest in some ental region of composition and amalewt for pure components ana ‘compounds. For thi reason it miy be expected that with decreasing temperate the tee-eneray eure Aattns AU some lower temperate, soah as 2000, the fre energy versus composition cirve develops feyion of negative curvature and the ium free-energy confit ‘becomes a mixture of wo phaes rather than single phase. These phases are given by the comma angen tthe ffe-enerayeurve shonin Fe. Yih For composition Cx at temperate Ty, the lowest tee-nerty con raion cont of inte of two phases of compositions ©" and Cinrae 0 é we Mo npntntnn 9 Nascar rete heme proportions Xap given BY the familiar lever re (62 Chapter 7: % BGC 69 Ingest sion orth ptm abort i eer nmin heer asemblage of compontion sahara ot compotion Candid of composition C™ It ELSE NC cpa doe nt orm, bowever, the fee ctr of Ha et idk eocponton Coat temperate T cane ove aoaceereatng ns vo lof composiionC™ and © Abxret re eetigd pss in amount ven Oy te ever ale epesens te ‘ga Sonim of lower foe ene) aT a a commons eI, ee ti iit en NB 0, Pm ith tis backround, let us consider the eubmisrostrutaral features sl aaises inthe stem Ra-SIOy, The minty gap determined forthe ‘Sptem is metastable and is shown in Fig. .120 The diretransini ‘ton crographe shown Fig 3.12 td iatrate features observed {or uO concentrations off 10, and 24 gatomfe, For the 4g atomfe BaD ‘onposion which ison the sles ich side ofthe sty pap, the Sikmierosttuture consists of discete spherical particles of @ BaO.rich fhe eed ina continuous matrix of SiGereh phase, Sim larsompositions nea he barisch sie of the wisely ba, sich fe Mipatont Bad compostion, tue wbicrostuctere consists ‘Seri SiO,rich parses embeded ing cntious BaO-rch matins IsTmODUCTION ro CERAMICS For compositions ear the center of the misiblty gap, such asthe Westone Bo0 composition shows in Fig. 3.12, the sublrostevet ie frequently Observed to const of two. phase, each of whch tiyesdimensonally Interconnected. In ull the elton meroarns oven oth phases are amorphous, as determined from eectaon iin Th many respects, the most intresting characteristics on this sale stegtue telat to interconnected submierosttores such that shows in Fig 3120 Sine submirosractares have been reported fr sa Eases and seem general tobe characteristic of contions in whit ‘ere i large volume fraction of Sath phases preent, On sneqit He, Patel RO wa mm sia Bh deep nan Fm 8 Saw sD RUN Nat ye St CO, ening, such interconnected submicrostncturs in some eases coursen ‘hie maintaining a high degree of connectivity and in other cases tsuen, neck of, and spheroiie. An example of system I which Aerts pate siucares are observed ear the center of = misty bpp shown in Fig. 713 forthe system POO-B.Os 35 Mitty Gaps in Onde Systems The addition of mir oxides to the 140 most important ass {uring oxides, SiOs and 8.0, often leads to gui guid iiss. Examples ofthe ype of misciity gaps which result have already been shown forthe systems MgO -Si0 Fig. 102) ad B40-Si0s (Fig. 3.120). [av sppeciaton of the widespread tendency toward imisebiity ‘Mite and borat systems may beabained from Fig. 3.14 to 3.16 a0 ‘ale 3. AS shown in Fis. 114 misility gaps ae ound whe MEO. Feb, Zn0, C20, S10, 0 BuO ate addes to SiO and only in he case of 440 additions isthe misebilty gap metastabie- Among the all ihe files, metastable miscblity gaps, are found le the LLO-SiO. and [NicO-SiO. systems (Fig. 3.19. The exstenee ofa mettle msebity [Poin K.0-Si0, system bas been sygeste, but below temperatures of| [Rute occurrence, inthe reson of the sass ransion and below fr compositions, efestvely prelude the observation of pase separe- fan. Sabe misc gaps at 1000 in al alkaline earth borate syste, nt metatale gaps ate found ital the aba bortes (Table 3.6, ‘are misebity gap, sable over a wide range of composition, is foendin te system T1Or SiO; (i. 16) The extension of this range of ‘ube 34 Charnes of Metaale Misty Cape a As Boats Ccompostion — immisemity Cconstite (ole a (me alia system Temp. CC) ene). we) ono, ww ” Ze Na0-80; 30 ra oh Koei, 30 © be ROB 0 0 ie Gone, 5 0 0 ‘Stace RR. Show and DR Uniaaan, Am. Com Soe, 51 377 os,us inTHoDUCTION To CERAMICS a "sos tmie ‘ate in hich ie ems, ch eS cae ade ms Immisbity int ternary systems i important for the effective use cf ‘TiO, as 4 auleaiog agen in any giz, enamels, aad guse-cramie {ystems The avoidance ofthe an importa forthe formation o the ‘ery low expansion TiOeconaiiag sed sien A large reion st Inststble mmc also found in the ALO SiOs system, extend ing from ler than 10 to greter than SO stom’ ALO» “rhe ain of TOs and alla oxides tends to enhance icicle comple syetens the addition of ALO; tends to suppress fe A sting ample of th latter behavior is shown in Fig. 317 fr the system 1B10-S10~-Al0.. "The ranges of immisebilty i to commercially important syste, 1n0-B:0rSiO, aed Na{O-Ca0-SiOy, have heen extensively vest filed, In the NuO-B:0.-Si0, system, thre regions of immiseiby, ‘lesgnated TH, an Il in Fig 318, ave Been suggested. Classes of he rex type ad the Vycor type occur in diferent parts of iis eso ‘iran ope KS eo Pe Me 2 Nai od Blaine Cr sn, 8 HOOD, cic oce \ Le a™ IRerRODUCTION TO CERAMICS 0 ] pay resion I in his system. Pyrex lasses exhibit phase separation ana Be Seale, (pity less than 0A; the tty to conto the sce and onnecivy of immicbe regions forms the very basis of the Vyeer prncess, Inthe ease of NasO-C20-SIO, glasses, he coneentstion rit [ot the zee major constituents in standard commercial compositions Somewhat within the fmmisebilty boundary shown in Fg. 318. The ‘AUG concentration, spay im the range of 2 wt, vey likely at marked effect in deereasing the exten of sais sil perge {o that sown in Fig 3.1 for ALO, 288s to Ba0-SiO, composition The seating commerce prodts are thon homogeneous passes As discussed relative t Figs. 3.10 and 3.1, the oeurrence of fms bilty depends on the eltive re ener ofthe phases hich may frm ing system. BE. Warren and A. G. Pincus oignally sugested fot Tui guid pase spartion arises from competion between the & ‘ons to surround themscives with © minimumenergy oxygen a0 ‘onfguation,oubeet othe lations ef sh network forage) ofthe ies Moder and intermediate cain wth ned eapabity ‘Sst for sie inthe network and with astoag oxyuen bond sen Shanahan vere ire oy Telia tener isa a consi na ‘Bt nd W_ CoP Chm Ca 3) ‘annot be accommodated in large concentrations ina minimueneay ‘Sonfguration, which woud require excessive breakup ofthe etwork “Thelowest-energy configuration would then come about when the syn ‘arates lta tw lig phases, one favoring the network tnd the other favoring the lowest nergy modifier configuration “Tis view is bot conidred as 8 fest spproximation Which does mx dequately deseribe the range of inlscblty behavior ebserved in ‘ariovs systems. Ido, however, fous attention on some of the salen features ofthe problem, which wil undoubtedly be sniset ina) ‘eile treatment of immissiity. The ieation of icity saps cn, ofcourse, be inferred fom thermodynamic stv data whe these ‘vallble, but the relation between the actives sod varour srt] {ates the solos remain tobe eicatsorthe oxide systems Some 15 years ag, when the fist ein of his text wa prepare vas oly possible wo warn that the dale structure of ss was come nd that there was “some evidence” for eteropenetes in structure; uil,ium ims in the alkaline enth onesies systems wns, ff couse, well known. Primarily ox esl of rect sbseration sith ‘etalale ims and phase separation ss syste ae Que ommon has cared and also sigiteantlycompicte the problem of ‘horeceizng the stocture of gtsses In aditon fo the question of the {nfuenceof cooling rate onthe las tation leriperstate and the few ‘erent range of variation nthe specie vlume of single-phase, there mast be added the question of posible phase separation ‘Wit egard tothe pessibty of phase separation, it not scent to consider only the phse-qulibium gig, since metastable phase “Separation an rorpression of phate separation hy rapid cook often ‘cccur. In many cues, ast flan phan separation fess ops Srhich ean easly be associated, incorrect, with erst. tn other 0s, the sale ofthe submisrostructae tes of A) is 0 smal oe {deste Ay opie mensrements wth the much larger 7000-4) Srvelength of ght and only found with rather careful electron: rleroveope or small-angle Xray searing studies Carl. the properties of «glass and any desrption of its structure rust take int aceount whether is single phase or muliphsse system [ea result dtcussion of structure and correlations of properties with Sucre, particle he ode erature wich oot nelade deals thermal histories and phase-compostion information must be evaluates ‘ih cation, Seagested Reading 2 R.W. Dow and B Els, Es, Amorphous Meter ohn Wily & Sas, 5. G. Bk, Bareney, The Sincare and dachnical Propetis forgone ‘Science, Peaun Press, New York, 1972. Teer 1 LE Sunsorth, Pica Prpee of Glas, Oxtrd Universty Pres,Problems 1/ Leo ron form ao ny 76 Whats he on dey ld sie dt nga tse a) We nab ts on sc of io sb0k ie ie mei ln et (c) Tommi chains act be nin ines al 29, Ean ow on expensing ei, SO, a etna en ana tro ee ie 6 (isu ie ata od ear onan Se es ‘ats (MgO + CuO = 8) Thee amos 19 wh fos om ttn aba se ‘ert tnoal ner ropey sone iSPC cog eto ‘Sogersin nme a 10 sr tt eter eee ae ‘Ecphin heer sling tae For area nS He Au CR. a 1 Na. “ "Germaine saa ti BPC ii mt pe 1) Why dows inte el at stengertre ow the meting pla fra? 29.) ol en hh es Pa a sa io Ra Structural Imperfections In the previous two chapters Wwe have considered structures f ie ‘pias and alo sriture of some noacrystallne glasses. Thee ae fay properties tat ae markedly dependent on stall deviations from Seal srctres, and we can best approach thee stucturesensiive ‘Moyen om the Has of departures from Phe ies structures, Thome consider a perfect crysta as one with a completely ordered sactre having its toms a est except for zero-point oeiation at the alse zero temperature) nd wih the electrons dstibuted Io the Iovesteneay stats, there af several types of deviations or imperfec- tis which may occur. The st sinereased amplitude of wbrtion ofthe sions about thei equim rest positions asthe temperature is i= “Guued, (These ease vations are neal barmoni, nce the forces Terveen toms nearly abey Hooke's Taw waveike solutions fo the Imatns ofthe toms can be qvantzed and wmount of enerey hy, called onan, assisted with unit quanto excltion of the esti vation ‘Theeltomip between phonons and the vfratinal frequency fhe sae stat between ight photons and the vibrational fequeney of light ‘res Imperfestng lio joccurintelacroni energy level: lectont ‘my be excited into higher energy levels, leaving vacant positions he ‘mally ied elecuonic energy level bands called lecton hte. he ‘cid election femalas closely associated with the electron oie, the ‘ecton-leton-le pair is elle an ection, which also maybe looked ‘nas an eacitod state of an stom of um, Fialy there are a number of omic dct ieling substitution of» wrong ator fa fotlgn stom) fees normal on, infra some, nant atom ite, ioe imperer ‘ies ealed dlocaions Fially we might also eonsier the el tases or boundaries between crystals as impereciony, but thane ae Scuted separately inthe next shape ‘M the oust we must admit that there are a lage minber of consinations, permutations, and interactions among soles, atomic Aefess, electronic defects, dislocations, and surfaces. In the presentoy INTRODUCTION To CERAMICS chapter we describe some of thet stratus! imperfections inavidoly| nd bri ingieste how and shen they are key 0 occur. Eater, a \tsames imprtnt for the discussion of particular ceramle proceso Properties, we consider tha sharateeuce more filly. Thee fae ‘ceramic material fr which oor knowledge Complete, More eattee Slscursions of sctiral imperfections are avalable in the relerence 41 Notation used fr Atomic Detets Several types of stsctural imperfections are believed to oosue cezramic materials One departie from ideality inves the mation of ‘tom froma nora se to a interstitial postion, ay ilutated i Pe ‘a Tai type of asoeder, which ress in equal concentrations Fis.) Pent dade on ‘cont lattice sites and intetstitlatoms, i called Frenkel duo? “Another kindof disorder, which ivaves the simultaneoa production ‘oth cation and anion vacances as lusited in Fig 4. eter 8 Schowy disorder? Ceramic sysens are rarely Hever witout Tmpunes, ood slit afwes may either substi for Most atoms ot orm tice sites, in rUbsttonal soi vation, o incorporate ce ‘orm uovecupid intel sites inthe host lice 98 nei fel solution. These to arrangements ate istated in Tig. .1e and Inadition to atom iosstions one mast ls describ thet valence sate, to be more preci, he electons energy eves nthe cFYstal Which ae @°@- °@°0°0-0 @-+@e@e -@°-@r0-@ @°-@°@-e@e °@0@-@1®@ tend to dei from complete onder a sy temperature above absolute tera Such deviations are aso affected BY the presence of atomic impesections and solute atoms teeing track ofthe varios defees which may exist simultancousy in sale ceramic nasal, an esental requirement = an adsqute ‘see of nolation fr deseribing point defects a cersmies. The Kroger Vink notation (Refs. 1 and 2) eos widely used. Te hs notation. when elald or subtract elements fromthe crystal, we do 30 by ding or Ssoacting electrically nevtral atoms and thos avoid making jdsments nu decisions about bond type or aplication te lone systems thisrequites that we separately ad or subrat electrons. Let us consider ‘atious concesable detec and notations forthe imtginry binsy 1. Vacant Lattice Sites (Vacancies). When empl lice sites oc they are inaieate by the symbts Vig and Vs forthe Af and X sie respectively the stomic notation the subscript M indicates a mise IM atom. In ni tie such sodium chlor this would mean he femoval of a Ne ion together with an electron smarty. Vo weal {ndiate the removal of CI jon with the adtion of am eiecton 2 Inert Atoms In addon othe noemally cupid tice se of eystal structure, thet are also ntti sites, When stom Seco) ‘ese interstial psions, they are denoted by Cand “Misplaced Atoms. Its also possible i some compounds for 3 atoms tobe on X sites (Ma): the subset alvays indicates the poston ‘teach parca stom in the lt “4 "Asalted Centers con to single defects tix lo poste for one or more atc defects to associate wilh one another, ha ‘ster together. These ate indented by bracketing the components o Sch cluster: for example (Van oF (Xs) Sots. ‘These present are coded av to Ite position in te same way a native defects Land Sy indicate sue fom Lo on a ‘He and Son aX ste. dndeate tag the solute Ls ona ites 1 Free Electrons, Bletton Hols. Iq strony onic materials rons ae normally oelzed at's partir stm site na may which ca be deseibed in terms of the ton vale, However, ae diacussed {Chips 2, this snot alvays the case, and some fraeton of the elesrom, denoted may not be localized at partic a: snaly there my Deming electrons, dened eecton hols which ae not localize 2 pamtcular stom se JT Charged Deleds. In insulators and semiconductors we us think of the respective species as fons for example, sodium chloe ‘made up of Nav and CI ions f we conceive uf removing «pos ‘harged Na sodium fon rom the NaClatuctce, we remove te spin Sos witout one of ts electrons; av est the vacancy has aoc ‘vith san extra electon witha negative charge which we writes sihere the superscript refers Yo 4 anit negative charg. IE Ths enc ‘eston i localized the vacant ste, as woul normaly be the css act, we wnte Vy Silay if we conceive of renoving a neva Charged Cr chlorine ln, we remove the chlorine tom plus an associate ‘ecton, lesvings postive electron tole, which we write where he Superscit refers toa unk postive charge. I this excess positive cha isto at the vacant site as woud normaly be the case for NaCl, we ‘ite Va, te some materia stony toni than NaCl tess ence oF Ising electrons, «oe may not remain local the vacant ie, ie septation beng eepreicnted by the reactions oe Vint? a Van= Vath a2) _by separating the notation for atoms from the notation for electric charge, 1 avoid the prospect of unintentionally making pio assumptions owt the nature of the fects ‘ith ech of the other defect symbols—Vig Vas Ma Mi (VV) a0 fective charge relative tothe hot lative fs als possible. Ths Za ‘rouil indicate a. Zn ion at an Intersil site which ormally ‘occupied and without an effesive change. Substituting» divalent Ca™ fe for monovalent Na" ona sodium site pvesaloclelesroicsrtire ‘Momented by one extra positive charge an is represented an Cae Note iat the superscripts + and ~ are ured to dndate real charged fons sere the superserpts and Iniate effective postive and negative somes wih respect to the host lace. Other posites aree from teatichiometry. In FeO for exaple ie powble to have Fe ons in Matin tote oral Fe” fons In this case the Fe" fone ae Indiated Fe 42 Formation of Reaction Equation, As each type of defect and is concentration in a material can be sesibed in terms of associated enraiay of formation and other ther ‘edynanie properties, tis possibleto Went al impertections as chem {nis a reat them ia manner referred os defect chemistry. Detect ‘tenctions may be conceptualized in teri of massacton eau, ths enablag the eepresesation of such interactions by means of detect noes, The following rule ust be cbservee Tee Relaon. The umber of M sites fn compound M.Xy must alvaysbeincorect proportion tothe number ct X seein gO, 1-2 ‘U0, ec). In msintining his proportion, howeverthe total mmber of toh typeof site ay change 2 Ste Creation. "Some defect changes such ss introducing or lnsating vant M ste Vr correspond to an crete o decree tte numberof ate sts 1 isimpotant that this be done in way thst ‘Ses not change the ite relation derribed nul 1 Detects inaeatingsite creation are Vix Vas Mx Man Xx Nat so om. Noite rating fntiles are ey Ly ad so 00. "y Mae Beene. Asin any chemical equation, amas balance mist be maintained. Hee is elpul to remember thatthe subscript nthe dsfect symbol indicates the site under consideration and i of Slenileance forthe mass balance “ hetiat Newraty. The eystal must remain electrically neta COniy neutral atoms or molecules are exchanged wih ther phases oaise the crystal under conidration: within the yaa neal parties can ‘eld to of more oppositely cargo defers. The conto of elects etait reuies that hot sides ofa defer-renction equation have he 5, Surlce Shs. No special indication of surface sts i used. Whea an stom Mis dspace from the bulk of the crystal tots surface, te 'A his point we antpate the next section, in which we discuss te solution of CaCl in KCI to se bow these rules apply Ta KCI there are egal nmsbers of cation and anon sites; to trodoce the two chlorine atoms in CaCl, om anion sts, we must use potssum sles a8 wel as two chlorine sites since we ve en une Ca, we may tentatively assume tht the second K she required 10" the proper ae Felton may be vacant, Considering only tons ubstiuions, a pose solution proces is Ccach(sy “2+ Cae Vib 2 ws For strongly ionic material sul 28 CAC we may forther assume tht the subwtttions are fully owed, which giver ur am stems ané moe reat slution proces eats) 2+ Cah EHC ae which also conserves letra neutrality, mas balance, an site elation ‘So also» thd possibilty, the formation of charged Cx” ines, chlorine fons on chlorine ses, and potssium ion vacancies, for which we acide) + ai 42Vi4 20a as which also conserves electrical neutrality, mass balance, and site elation Deciding mong these and other posites ss 4 matter for dete chemistry and Is the main subject of the following sections. STRUCTURAL IMPERFECTIONS am 443 Sota Settions Of the many types of departure from an ideal crystal, the one esis to visalie ithe lls of forse stoms inthe hort ryt a stated in Fig: Le and a. If a marl erystalizes inthe presence of frei toms, they may be almost completly rejected by the eget if they Sroresiably incense she energy of the crystalline form, On the efter ‘ani builling he ito the host structure nan ordered ay leds to late lowering the wsten’s energy, anew cystine form develope In Intermediate cases foreign stom into the stir int randorn way a ‘he erytl fs bul up. When this occurs, there uel change athe fit sve with compostion im sccordance with Vepord’s law tht the ltuicecell dimensions vary Tnely with the concentration of soe sed ‘Sold oltions are stable when the mined crystal has lower free egy than the terative—buildigup two exysas of diferent compo ‘ono bling ups new sractae in which the forelg toms ae put on ered sites. As previously dacusted, the free eneey ie given Oy the o=e+pv—Ts « where is largely determined by the several energy and the entropy i 2 measure ofthe randomness (probably of the stuctre Ian som ‘Med at random greatly increases the structure ener, te soli solution ieurstable and tv crystal tuctres rel Or the other hand, the dition o foreign atom greatly lowers the statue ener. teste {ends to form an dered ne phase If he energy 0) much change, the entropy is inerensed by random sions that te sol slain hs ‘he lowest energy and isthe stable confguration Dileent res for the Tkeihood of solid solutions being stable in parcuar systems. are onlctons of these general principles to specif case, "Two examples of stable slid soliton are shown in Figs 42 and 43, or the MO-NIO system, both end members have the sodiom chide ysl strctre, and « complete series of solid solutions occurs. The ‘Schematic fee energy-compostion dlagram for ISIC i shown in Fig 428 The lowest free-eneray phate for ll compositions at 1500°C ste Sole salaion rather than any ordered trcture or the laud. For the ‘MgO-ALO, system shown im Fig. 43, the ond members have diferest ysl suuctres, anda third possibly ithe formation ofan er Imeintecompoung. Experimentally i found that fora 50°50 mature of ‘yO und ALO the spinel phase has the lowest fee energy snd at 750°C intheintervalso-b and e~d two Sli solutions of xed composition butmm INTRODUCTION T0 CERAMICS OF so = ean = Ao Fn sg of NW Shea real ese ‘atiale amounts are in librium with each oer the compositions 30) (22) at {san equa slope 2 common tangent, for the free-nergy-compitin ‘irves In each af the regions MgO-a, bc, and d~-AlO, dilerest {ae cnostion sod soiion the lovee eqn ‘Sone ules and generalizations useful for predicting sldsoation lehavior are isonsed in ssequent sections. Substiutlnal Solid Seton SUGsutOn of one fon for spoter i ‘common it the formation of eeranic crystals. The soli soation phases qulirim hve the sme values of chemical potent. = [STRUCTURAL IMPERFECTIONS ns ae tocten As ome cin As e439) Pe dng fhe Mg yen Sede repens ot (ena conpston doi Ma-Aidy or FT: shown in Figs, 42. and 43 repesent this kind of substitution, For trample crystals of magnesium oxide frequently cowtain appreciable aonts of NO or FeO witha eandom sitbuton of Ni" oF Fe ons telecine” the crystal ao thatthe Bal composition a he crystal {an be read Mg--Ni.O, & shown inthe phase diagram in lg. 42. A Siar series of slid soitons ext inthe system ALO»-C1O- (rubles fe 05 to 26 CxO, in ALO}, THO,-UO albite-anorthite, and many of The spinels In some systems there ia complete seis of Soi soltionsformed betueen end members(Fig. 4.2 However, inmost systems only 2 Tinted number of Torips aloms can be added to the substttional sols elution (Fig 43): an excess above the solubility Timit at given temperate reste n the formation of 3 second phase “There are several factors determining the extent of substitution that can take plein solid solution, nd @ number of rules expressing these {clon have been devised. These ules react variations inthe fet nergy, which Is made up of several terms, Since the free enery is function ofterperatre, a series of free-energy vs. composition cures for eich empersare canbe drwy sma tothe one shown in Figs 2 fn. Lowering there ener) resting fom an increase entopy “eques that there bear east sal Solubiyof foreign atoms in ax} Structure. Factors Which allow extensive substitution areas follows 1 Size Facton.” Ifthe is of wo ons fr bless tan about 15% conditions are favorable forthe Tormation of substutiona! sais Sons. Ifthe Telatve ion sizes ifr by more than 15%, sbetttion enealy ted and is sual less than a egtion of I This factor ieby {ar the most inpotant for ionic compounds 2 Waurncy FacToR. Ifthe added fon has ylence diferent fam that of the host fo, substation is mted. It em soca, inde below, bt other structural changes ae also reguzed to inn ove 3: Cuenca Armin. “The greater the chemical react of te two erytline mater, the more resirictd it solid solu, Sie a” few phate is usally move sue. For oxides this restriction wsuly limi in factors of fon valency and sie ‘SeStuucrune Tyre. For complete solid solubility & members mst have he sme ype o ert structure, For exaiple, TO; Could obviously not form s complete seis of sold solutions with SiO, (Gee Chapter 2 for desriptons of these strtures). This Joes not however retriet lmited old soon ‘On the Basi of thexe factors, an estimate ofthe extent of substnond soli Solution 1g be expected can usually be abled. For oxides, he iar factors are the relative fn sizes and valencies. Althoush see fon sizer deftly prochae extensive soit slution formation, vale Siterences ean feequenlly be made up in olhr ways, For exale fextenive sli solution among Mfg". AI", and Fe” ions is common ‘lay minerals having the montmorillonite structure, Te charge deficeny ‘de to replacing trivalent AD” ith divalent Ma" or Fe” i mide wp ‘exchangeable fons adsorbed on the surface ofthe small cay parks Simi, subeiaion ofthe Si ioos by AI" fons taeda cord tion in Eantnite lends to'a charge dilerence which te made up by STRUCTURAL IMPERFECTIONS Bs feachangeable ont adsorbed on the ptcle surfaces. These ‘ubstitational-solid solutionertcts are lrgely responsible forthe 8 served base-xchange properties andthe ably to form stable susp sions with the clay minerals. In much the some ay, many ate Alominosieae stractres are desvaive structures i which an Al" Tepaces an Si inthe crystal and an allo tealn cart io ts no ‘panded intersttalposton. Solid solutions trequety peau in which a tuber of diferent fon substations have take pla, “Tere is yet another vay in which the eobal-vleny requirement can te sreumventedy and this is by leaving am occasional sto te vacant, ‘The magnesiom aluminate spinel structure, MgALOy has been Sener in Chapter 2. Extensive substation solid slain occurs between th ‘material and ALO» This coreespondst he aubsituion Of AT ons for {eof the Mons In oder to atin electra neta each tw AAP" ions added st replace tree Melons, leaving one vacant ate ste, The end member ofthis complete eres is y ALO which has & facecenered cube packing of oxygen font asin spin! in stele ‘ortespondingto lO. with onennth ofthe ttl eaton sites vecat “Tis kindof sold solton in whieh diferent fon and vacant wom ses Me added in the right proportions to piv electieal estat 5 nat ‘ncommon For example, aditons of CaO to 20, Yorn 2 so volt withthe cable Rooritestractre In which Ca" are sutiated for Ze Eich time this is one, an oxygen fom sit eft vacant fo manta the -ctonanion site relationship of 1:2 C20(2) 22+ C55 4094+ V5 oy Simiariy,adtons of La,0, to CeOs or ZO; and C40 with BiOs sive "se sobstanda numbers of scant tsi the anon ray. sont, tons of MuCls to LIC ALO. to MBALO and POs to FeO lead to ‘acan ts Inthe eaton aeay-Althoueh in te system ost ntoned these ffs ate pe, similar effects occur in samples for which slid ‘elton is extemey tinted for example, CaCl essed in KCL inthis ‘system the sold solbiy is oss than 1 Inrceatory ones wit close-packed crystal tustres, the tempers me dependence ofthe soubly item ge see Fig. 3), About te setbity of ALO: in MgO is several percent at 200C. it dasreases to nly 0015 ata temperature of 00° At high temperatres the TS ‘oluct dominates the fee enery fr Slaton, but a the temperature it lowered, the are eathaipy term (E » PV) forthe formation af vacant lice ses dominates (Eq. 4.8, “The mos direct evince forthe formation of vacanies i obtained byetesmining the Istice constant for stuctve jn ofer to compare ‘theoretical wth megsred erytal dena. Several examples fallow ‘hers with the composition ZionCax Osu which erytaliaes ne Poort stature hs an Xray pater ndcating al anit cel bik fnelge of SI31A there are four estion sites and eight ion sites t (he eaion sites ae all ied, and oxygen ion vacancies gecur to eve ‘he proper ste Telainship, there are 0-18 x4b081603 x10" 8Ca, 1988 91221603 x 10g Zr and BLAS! 1601603 510" Oke 135114 fora toll of 8 lem [The weight of each on per ult elt ven by (ounber of sien) (fraction occupied) (atomic mesh Aves So's umber} Ths sin excellenaerenment wit he dec mena “alue of 547 glen! igre 4a shows the change in density calelated from the Xn latice parameter ab compared with the dell measured density: De Upper curve i caeulte for anther peaibe model in which the ext faton occupies an interstti position, The anion vacancy structure (Ea ‘Sry found tobe in aesoedance with these ealnlatons However, or Sonpes quenched from 18H, the data nF. 44h show tha the her Tenperatre egulibeur comesponds to ferent sort Of defect ste ‘ave (This peshaps our rat ler arting of the possible divergence between observations at room temperate andthe equim situation tig temperatures) When CaCl added to KCL, the density changes found wo be ia accordance with cation vacancy formation, onda Fg 4 and Fi, 450. When ALO, ie added to MgO, the density cages iso found tobe inaccordance with clion-vacane formation. Tse dla due shown in Tig 3h 'A sharpe bala can algo be achleved hy changes i the electronic structure, as discussed i Sections 48 and 49 Total Sold Slutins, fe some are stall bey can go ot intrstia stes nthe erytl to form sod sotons Thi te of sliioe| 'S particuley common with meta bonding, in which ade HC, B, fan N ft easy Ino imtersa sts. "The ability to form Sterstia! solid solutions depends on the same actor, except for seuctre tye, that apply for aubstitopal sod Selutions—size, valency and chemical afi, The sie elect Sependson the original host erystal suture In face-centered cube stctes, 3) SE MeO, the only svalaieInersial sie, ate tetrahedral ste si undedby four oxygen ion. In comeast, in THO, there ate normaly ‘Vacant getaedal trices ia the Porte srl tore ate are interstices with eightfold cooiaton; in some ofthe network sical "Heaceates sucha the 2clfes the interstilel positions ae Vey Lge. Therefore, we expect the order of ease Tor forming inerstial sld oe eo col tee aa g 2am oases thc nA er chee aon scene Seaman Fem Do sd Roy, Sd Sta Commarea 38305 neas srRopUCTION TO cuRAMtcs =a ' oot nee “Ce ——T— to ie aay (Bi i he ssn tc Pa solutions oe zeolite > THO:>O,> Ma, and this i found 0 Be "The addon of ions on inferstal sites reaures some asain charge balance to rafatan elects neutrality. Ths canbe accom {vacancy formation, substuonal sid slo. o change e ‘econ rare ocar For example shen Fy of THs {CaF a sold sluton's ord in whieh TH” or" subsite fo Sedat he same tine Fons are place onthe itera tes sot ‘locus! nentaiy mainaineé (ee Fig. 46). Titewie, the aaton of 240, © YO creates onyaen tern STRUCTURAL IMPERFECTIONS i maintain the proper site relation an electrical neutrality. The measured ‘esty data are piven in Fig. 4b and favor Ea. 48 (onygen ites) fae than Eq. 49 (yes vacances) Density increase: 225642) Ms 17654300407 48) Demity decrease: 3210s) 326460907 49) In many slcaestvsttes the additional charge due to an intestia| Be", Lior Naf balanced bythe replacement of sme ofthe SF” by AN in slid saaton 44 Frenkel Disorder Several diferent types of disorder an occur in crystals without the addon of any foreign atoms. The particular type af disorder in which fil numbers of vant tice «es nnd intersitalatoms occ sell Frenkel disorder" ands ilusate ip ig ta, Asthe extent of this kind ‘fonder increased th stu] energy inereased, but the ame fine the entropy (Fandomness of the srt) inereses. At Bierry IerRovUCTION To CERAMICS temperatures the higher entropy form, the caordered frm is favored to sive the minimom fee energy required for thermosiynaric stab "The fee energy ofthe crystal canbe writen asthe ee enetay of te perfect crystal plus theres eergy change ng necessary to rete inertia and vacances les the entropy ingress AS tha secre fom the diferent posible ways in which the detest canbe ranges 0 ~AGet nae Tas ain) ‘The configurational entropy AS. I proportional othe number of ways ln which the defects can be arange,W, and is sven By a8 =kinw an ea peret cyst he lon wh rndsingiae canoe Ded incn union et sce serch sea Sites etiy asthe Mlagmico am oveve herr ua ses et neu amber of ners {iets sane cb ang Wt ng Sait atx en be arnt Sov say Re ‘Sotto! ener) Tor ese ftom (lta aed ens Since Stin's approximation for targe numbers yiels in N!= Nin’ and singe re = he entropy is (N= nInGN— my miny 646 andthe total Sve nee change is AS, =2kIN 20-10 nau-24r[ in (h) ain (=4)] an ‘Auli the re energy ta inimur wth respect to the numer 280) ot detects; tus (282) | 0 y cterentitng Ea, 4.15 and sting squat to zero and thanking N= N, we have Bg = 247 InN, o¢ so(-BB)-eo(Gor(-8h) we In the appiation of a, 4.16 sometimes assumed thatthe entropy [STRUCTURAL IMPERFECTIONS a change ia aon tothe continuation enropyisneglisble, such that Sooo(-2H) seen Serie baa parece og Fae eietpeotinh ‘Agse®S Ag+ Win By dining (Vs) the fraction of charged vacant silver sites (Vs) SIN and the faction of sliver interstits a [AB] = Ny in, (a (vataet=ese ($4) a) see [Vis fr olomeie Abe tants (-38) a) Another general way in which we ean ook a he ormation of smal ‘ration of defaced aptetion othe a of mass ation, Creston of| vacancy and an intrstalfon n a fone crystal cam be ween 08 & ‘emical eguation: (oes o) +t site Ate HVE AE Vig 20 For this eqution the mase-stion constant i ABV) re = Tiana) ee for suit concentrations of defects, [V-1= (Apa 1 ths tagalVid=Ke or tAgh= VE «a ‘Pe concentration of Freel defects is determined by the energy of1 [INTRODUCTION TO CERAMICS forming» vacancy snd interstisl on and by the trpertire as ven in Eg. 6 For energies of formation inthe range of | to 6eV and temperatures between I0b and INO, concentration of defects may range between afew percent 1 part in 10, as shown in Table 1. The qulfbriom concentations a oom tenpeaiue ate alvays sl. The} Eanbecome appreciable higher temperatures ifthe energy of formation Tabet. Dutt Conentratin a ieren Tempeatrs Tw iore any? axw™ a" 9R2 paws Sivasore Geib! dua" bape 3810" bane civ aoe fio? dale? bans aww Palo Si avwomre fio? faaae belo tio" Dae Sivaiswre eq? fags bee Sato" S10 Uwaiware Gio? fame Dee bat Bao Uvaiome Gio! beige Deo Seto 210 Si atzmre eto" Guo? eo Daw Te Fiev=Dasteana Although the confgraional entropy change for forming Frenkel defects canbe clelaed trom tate mechanics, te energy change Pusting an atom Into an interstitial position depends toa great extent ot {he stictore and ion characteristics, ar diseseed in the Ist section. {Calculation ofthis enery sdf beease thee sa lrg correction teem required forthe ion poarzahiiies, making callin for alk Naldes ciel and for oxdes nearly imposible. Am example of such ‘aleslton is dscussed in the next section, For ala tide crystals with a rodlm chloride stricture the enegy equ to frm an nterstal ion ps a vacancy i of the order of 7 ‘eV, so that they donot occur in measurable numbers. For crystals wih ‘the fact stractore there is age inersial positon in he struct, the amount of eneray necessary for forming inertial lower, A= 2186 for Cas a p82) soa 1 hs Feel eects com, Tye nly poet i ey oto on ta bees tiphpoarizabiity and consequent are beter able to be secommodated ino interstitial sites. This t tre Tor ABB, for example, ia which ‘bsnl nurmers of itestin!Ag" fons occur along with associated ‘aeanein. The Frenkel formation eeray Ah = Ll eV the preexponentil ‘erm exp (212K) in he range of 30 to 150 ‘an onde sytem which Frenkel detects are formed is YO for whieh we can wie OVO HVE Keefornval an \Whan this relationship is combined with the solid-solution behavior sown for solid solutions of zirconia im ytrin (Eqn. 48), tht the Teematon of oxygen intersitls i a concentration determined by the solute concentration, we sexta the concentration of vacant oxyaen sts Inst be soltaneosly diminished, That the Frenkel equi, the ‘rouct of inerstil nd wacaney concentrations rminsin foes 45 Sehatky Dirder gioool- ah) oom en (-Bh-an(-A§) ean tacice tiene ga cee arcmin smeetin seen Show 2120V ah, 2or-219evSchotthy arder commonly ours inthe kl ast leva tcnpertre For ois the cleo wich ove Cul intraton, Bre tcplions and polrztion eet arc sbjct to subtataluncr ten, However, the egy for oematon of acaes noise thee tines ws lrgeas forthe sal ads, wich nana ht equines ‘Schott ner dos no fecome importa monde ys rt se gh tempers are rach: Thun the inte mtr of ect fused y thermal ects aimee nay sal the hse fro Solus, dssused in the ston oy Soh utr snd soe Stoney. abe 4.2 onfans me esprit data eto for Schottky and Frenket defect formation eerie, Compound Resction ee pare) abe Abe > AB ur so-1500 cr hever oe o ‘fia but significant principle must be remembered when consderig {orequivium conditions sufcent ne must be allowed for esullriin tobe reached. Since this usually involves eiusonal processes ove hy ‘tome dimensions equim alow temperatures may in practice nove be reached. Thus the hightemperature Jfest concentrations may te ‘an iportant distinction between Schothy defect an Fonte dees Is that Schothy defects requie a region of ase yertarbaton such 3 [STRUCTURAL IMPERFECTIONS us rin boundary, section, free surface for thet formation to occu. For example n MgO, magnesium ions must eave thet fatice positions tnd gate to Surface or grin boundary: Ue, Mac + Oo = Hig V8 # MB Ot 426, Since magseriam fons and oxygen Jonson the sutac form a layer over er ons previously kata atthe surface, this eavation equivalent to Testa fxm of the Schottky equation ull Viet Va! sd acts only the kines, not the equim sate "Asis tue for Frenkel defects, tithe grodect of the vacancy ‘oncenzations thats xed by the Schottky equlbrium. From Eq 27, K =(vaatve «29, Whee ALO. fade to MgO aa slut, cation vacancies ar created as shown in Fig 43h. This eect combined with the Senate equane {eq 424 requires thatthe concentration of anion vacancle be simle ‘areas iminshe. «an 46 OnkerDisrder Transtormations nan deat crystal thet is « regular arangement of stom sites with a esac arrangement of atoms on all these positions. In rea cys, weve, re have sen that foreign lore, vacant sts, nd the presence ‘otra atom ature ths complete order. Another type ot epee ture from order the exchange of alone between ferent Kinde of bso inthe strctre, leading certain ration ofthe toms being fnwrong"stes. This order silt to the other Kinds of structural Smperfections we have discussed, i that it alse the structure energ) tut ‘Sw increases the randomness ‘or entropy so tat dvorder comes increasinay important at high temperatures. This leads to. 9 onder ‘order risiton between the loiempeature form which is molly ‘rere andthe blghtempecatre form whichis inordered. Ths Sd of trrston i common observed is metal alloys 1 also occurs for foie ssems, but these are more likely to Se either Completely oedered oF oapltlydisorderes, anétanstions ae onl Itrequatiy observed, ‘There are some nmiares and also dilerences between orderdsorder {esions and high-low polymogphic transitions (Section 210). “The degree of order can be described on a longtange basis asthe fection of toms on feng” ses, oF on shori-ange tals a8 the fracon of “wrong” atoms ina flor second coordination ring. For otws srRODUCTION TO CERAMICS purposes a description of longsange order i sulcient Lat vs consider {wo Kinds of som, A and Bn lee having to Kinds of ites, ad {. wit the total numberof toms elt the numberof sites NE Res {he faction of a sites occupied by the “ight” A atoms and Ry she {action o sites occupied bythe B atoms ina perectly ordered cyst allthe toms are onthe "ight stesand B= Ry = Hf heres an x ‘number of and B toms and w and B sites, the fora complety Fandom arrangement only half the A atoms are a sites, Ro IP ‘only haf the B atoms are‘onB sites, Ry = I/We can dfine an sel parameter S, which sa measure of bow completly the sites are ld ‘with A atoms in sich a Way that for compete order, S eqs One, nd Tor complete disorder, § equsls Yer, st rr where Wis the fraction of « sites conning the wrong Batons. Tony small degre of seorderossurs, we sen deve the dependene of ofder on temperature and. the enersy Eo regu fr the exchange {of a pair of atoms ia exacty the same way ae was done for Pent Aisoeder i Bap. 11 to 4.16, wlth te vent We We cap (Be oR (-aF) oo For inereasng amounts of disorder, however, more of the neighbors of “wrong atom wl also be wiong*so that there san ineressng eae sf Aisordring (a tower value for ) sth amount of diorder increases. It the simplest and nem satisfactory theory of disorder iti ansbmed ht the enerayeequte for disorder of «plo ons dey proportion tothe amount of order, that Bens aan) ‘This isan oversinpliiestion because the valve of Ep depends onthe shortrange order even when the longage order is conrant, Moe Sstsactory relationships may be derived by considering the efecto Stortrange ordering onthe energy of disorder? tn eiher ease, a5 he Aisoader increases with temperature, owing to the cooperative nature st the pheoomenon, the rte of disorder also increases unt compe tsnder i eachod at some ransion temperature (Fig. 47. Generaty The mmber ofA and Bf atoms ae not cau so that reatioshis derived Inst inchde this variable as well An excellent review of the enti Subject i ten by FC. Ni and W, Shockley." Disorder transformations are common n metals in which the nearest seighbors In an AB alloy canbe ordered or Usordered without sarge Change in ener. In foniematevls exchanging a cation with one of fcordaton polyhedra of anion sso unfavorable energetically that it isthe cation substructure or anon posiions in the aon substrate. Ip ths ease the eneey change is one ofthe second coordination the Bist ‘ordination remains unchanged. Ifthe atoms are about the same ire ant ‘charg, the ener fromthe second coordination rng of ike charged ions [Satmost ently coulombic. Ital the eation ses ia the structure are equivalent, the energy change of disorder i smal and the disordered form ir the-only one that occurs: this Is trae, for exaripe in sok selutions of NIO-NgO and ALO,-C.Os (But at sueiety low tempera tues at which the TS product of Eq. 48 ls sucinty smal, phase Separation ito be expected in amos stems, as discussed n Chater {)tn addition, there are many materials which are alms complete}y ordered, even thous the valencies are diferent along only one indo onsite involved. For example, both LifesOvtnd L130, have the todim corde struct with tndom dition ofthe alors thection ses. These two compounds aso form a cotinuous sees of ‘ol eluions not ony with each ober but lso with MgO. In asmilar ‘ay, inthe compound (NH MoO.Fs itis impossible to tingsh there dsorder on the anon ste No ordered frm of here compounds The most important examples of onderdisoree transformation ia cers systems occur in matvls having to dlferent kinds af ction Sites, for example, the spinel stucture in which Some cations are on ‘cuheda sites and some ae on tetrahedral sites (se Fig. 225): various eyrees of order inthe cation postions oceur, depending on the beet treiment. IU has Been found in slmost all ferrites having te spiel structure that he cations ae disordered at elevated temperatres and te Stele equiv lor temperature forms ondered. The change of ocd ‘wt temperate follows a elation such 2 that liststed tn Fi. 42 ‘Another Kind of disorder may result when there are unoccupied ites sable fn the ordered structure This the case for ApHgle In theordered low-temperature form thee quarters ofthe avalable ste ae filed nao ordered way. A typical order-isrder transformation oceurt temperature of about SOO. Above this temperate thre is complete Ssorder, with one Hg and two Ae tons randomly arranged oa the out tation rer sealable 447° Asmaiton of Defects When Sehotthy or Frenkel defects are present in anni erst there is a Coulomb force of attraction betwoun the individual defects ef opposite elective charg. The electronic Interaction between defects {of opposite charge can be described hy the Debye-Huckel theory eh ettolyes (Refs 2 and 7). However, within the precision of aalile theory to take lato account repulsive fore, rearrangement of nearby soms apd polarzatio elects and eonsiering the pay of exprien tah data) iis preferable To focus on the major contribution of the ‘iectrosai interaction tsa distances ad consider the association st resulting inthe formation of complex detec, fr examples a vacaney Pal consitiag of an anion vacancy and a ction vacaney on Hears. ego sites ia a material eonsning Scotty defects, We can write or the formation of sucha vacaney pac Vint Va (Vavad an STRUCTURAL IMPERFECTIONS w ‘he tactional molar concentration of vacancy pair is gven by = 2exn (882) exp (=A) aa Wine 2 i he dint une of rensas of the pie which Cia oh anal say (ar VV pee, See ‘pnd af au ont cite en acc Bred by te Stuy colin, tvanvar~ en (2) 29 mi Uvavane Zeap(&) exo (%)exo(- 28H) cay the conceateation of vacancy pars sa thermodymamie characterise of ‘Be crystal (fonction of temperate) and independent f saute conces “The coulombic energy of traction between oppositely charged defects = hy a hy, = 39 where ga re the elective charges (lectronic charge valence) «is the Sale electric constant, and Rs the separation beeen defects. This Feladonshipis leary very approximate, butt gives about theriht values ta leads to useful insight. For sodium chloride the caton-anion Separation is 282, the dlectric constant is 5.62 such thatthe energy reqed to Separate a vacaney pari “(410 es 6.24% 10" eV Leon a SeECREDS TOE 092 (437) {ees a somewhat lower value tha thi, 6 For the combination of {vo vacant sites to form a vacaney pir ts reasonable assumption, Supported by some experimental dats, thatthe preexpenentil er, exp) Is nea vty. For oxie materi, in which vacances have linger effective charges, ibe enerey gnined by the formation of vacancy pais iv Irger as iMostated tn Table 2 Hence vacancy pts in ceramic oxides shoud be fore important than for the better-stdid alka halide, In Fig, 48 we tive calelated on a speculative basis the expected concentrations of19 vtRopucTiON To CERAMICS ‘Tale43, Approval Cull Deet Aecaton Bees ‘aiid from Ba. 436 Cisne vrei he ct by RD ah = aaleR OW) eae 63000" eV. Sehouhy defects and vctney ais in sodium chlor and in agnesin “The electrostatic stration of oppositely charged detec sso leads to ssoiton between sivies and intice defect, For the incorporation at ‘Sich into sodham chloride we have the fenton ACs), Cait Vi#2Cls “an “The ice energy of he sstem is eorensot by the association reaction aint Vin = (Catan) ean for which we can write a massacion ceasant (cassvig | tetieand7 0 (er STRUCTURAL IPERFECTIONS 18 arr AR Cold fr NA xia ‘See fo sag son pn soe, ete Zi the disivet number of solte-vacaney gar olentations (212 in the NaCI ltice for neighboring cation sts), and ie reasonable to sssume sat the preexpane tl erm involving vibrational uopy is ner unity. An etintion athe eneray of ssacaion Based on the coulomb ttraion 436) ies raul ors mabe 0 5)stems, trullstrated in Table 43 In conteat fo the ntnic naire weeny i, the concentration of solute-wacancysocates depends strony on IAS the temperstre of solute contain crystal is fre lowered, x scomeratute i reached which corespons to the slubity lit where ‘respltion of the volute ocous. At temperatures below his level, the Solute concentration semsising in sold souton inthe crv deter ined by the foe energy of the precision resem. Foe sodium Etre containing CaCl, we cam Wet (Cain Vig 2CIa = CaCh(on) (an, action TSR oF) eo) ao or warse(oS83) 7Siar, from Fig. 4.3 we see thatthe solubility of aluminum oxide i "MgO decrees fom almost 105 a 200°C to ets than 0.1% at ISOC ‘orresponing 1 Rest of soliton of about 3 eV. For the precptation Mow hla Vint 0.x MEALOMR) {ven ex (+8) as since il =21V5 as wane (t)" exp (+ Ste) wan ‘such thatthe defest concentration nthe erystal is approximately dete ‘mined by the heat f precipitation as defined by these reactions. lace he {otal sollity sls chads defect ssocates, Ay given Ia Eas. 43 and {£47 isnot equal tothe negative ofthe heal of Solution, 444, Blectonie Sretare In our ideal exystal, in ation to atoms being onthe ght sits wih tu sites led he electrons sou he nthe lowest energy conigurtin Because of the Pau exclsion pring the elcon energy levels at linted toa winter of eneray bands upto oan ssn cio ener. (7H tet i known athe Ferm energy £0). At higher temperate ‘era exctation gives an eglrum dstttion a some higher ener) States so tat there sa dst about the Ferm level 7) which {he enerey for which the probity of fi an electron leq ‘one half; Only smal fracuon ofthe total electron energy sates Sifected by this thermal energy, depending onthe electron emery band heme "The ferent tenigeratre effects observed fr mets, semicondvctor, and insulators are relted othe electronic energy band evels (Fig. 49). In Ita these bands overip so tha there i no bari fo excite electont Torhigher energy stats. In semiconductors and insulator & complete ed energy tani separated from a completely empty conduction hast ot higher electonenery states by a Bandgap of forbidden ner evel In inns semiconductors the energy ference between the led 308 {pty bands eat large compared withthe thermal eneray so that a fe "lesons are thermally excited ot the conduction band leaving empty "ection positions (leon bole) i the normally fled band. In pete lesulatre the gap between bands fs 30 lage that thermal excaion Inuit to change the electron energy sates, and at al temperate sravcronaL moxarscrins 1" wy Se e wy CLL 4 A a Epo ar ; e.49. son xy und Keele fr mene with pty ld eotion Sad eo elena sau udu wiih na Ee the conduction tnd is completly devoid of electons and the net ower ‘end of energy 8 completely ful with no vacant sates Inanintriste setondtor e2ch electzon whose energy x ncreased so that it ges ite the enndtion band leaves beiod am econ oly so Tat the numberof holes equals the umber of lector. p =m The nomenclature usually employed isto indcat the postive electron-hole centration by, thats, =[H], and the negative excess election ‘oocentation by m tat iy =e) Im this eave the Fe level Tatiay between the upper limit oF tne led and andthe lowe evel of he conduction band “The concentrations of the nase eectrone defects can be calculated inane lo th esi for Fre and Shot det isrelated to the probability ofa valence leiron in the fll bad baving ‘enough eneray to jung across the eneray gap Ey into the conduction Bande Because of the Paull exclusion principe; Ferm statisiy are ‘ee to calculate the dstebution The concentration of free eects No” Tepe ENT where m i the umber of eictrons por cubic cemineter, Ny is the easy ot aval wate nthe conducton bands pew (9) n= Y= rim arose ay isthe enray level atthe bottom ofthe conduction bund, and thease TNTRODUCTION TO CERAMICS Fermi eneray sillusated in Fig. 49. The Fermi energy represents the ‘hemi potential of he electon snd a UK ts the center ofthe Band ' similar eationship nos fr electron holes inthe valence band ant wen the concenestion af elstons ad electon hoes fs sl hese ante Rae [Eee] a pothi=f-ep[-E 5] asy hese N, isthe density of electron ole states inthe valence Band, ee eae" ‘he prod ofthe elation concentration pr evbic commer times th tole concentvation per cubic centimeter is given by stot one-one sy where, =~ Bis Planes constant, and et are the fectve ‘asses offre electrons ad elec hoes the crystal nice, analy Somewbat lager than the Mary of free elec¥on (in ides m8 {poroximatly2to 10m and ip aki halides m* approxima eqs IiBm- ima pute crystal the coneentaion of electrons equals the concentration of electron fies When soles oF abntoohiomety sects the electron energy level, the roof eletons to holes change but sie the cate for Ftenke and Sehothy equa, thei produc "The magnitude ofthe energy bandgap covers a wie rane, vaio from at smalls valve 32 0352V for POS toa tlue of shout #e¥ oe Sable oxides such a6 MgO and a0, i Tablet some characteris ‘ans ofthe Gand gap and the celing concentrations of elections ad hots in pure materi ae Husted, “Latice defects, atom Vacancies, itrstit! toms and slutestoms ae sites of perturbations t0 the energy sates tespresented ip the band Scheme in Fig. 49nd resulinovalaed enery states the band gp. Wan ailded electron o ole is loosely associated with a putty ste, we can spprosimatelycalulate the energy toa or fem am let by astuing that te electrons Bows the defect in ay ir tothe STRUCTURAL IMPERFECTIONS us Par Staaomene Ste eeewosion Metin Comal (eV) Room Temp Pont Temp CX) xa 7 = = ws xo ee ie 52 ee 5130 : fer by an ' it a oo 2000 o eta hdagen atom, except that thas an elective electron mass m? and is immersed medium with delectic constants, The energy issued 10 be propatana tothe fst exited level inthe hydrogen atom Be v99(\(e)ev as theres ithe fnization state of the defect. Far the alkali tides mis {Shout [tm andthe decile constant it out 5, 50th the ene “euitedolonize a sodium or elerine atom vacancy im NaCl oro exc (ae ir we assume thatthe exces elev located st the estes neighbor distance, we ean calculate that the enerty of HOnzation as falelated fr fon associates (ES, 4365 enna e1 INTROBUCHON To CERAMICS which gives the energy required to ionize a sodas or chlorine in ‘vacancy in WaClas about 09 eV. Final inthe casein whic the electron [ebound within natrow orbit, oteractons between th valence election find the impurity enter are decave andthe tonizaton eneay of the enters detemned by specie qs auch the onaion eae ‘or electron sini, polrteron terms, the local electrostatic potent {tnd so forth general i is'2 por unknown which of these caseh pps. Tn showing he electron energy levels at defects within the band esp we sways follow the convention of nding the ature of the level by Inblingit asf eccupied. Newt levee ear he conduction band ny Be ionized to ee oy electron an ate elle electron donor level Neue) levels near the valence band ay he eased by accepting electrons fin ace called aceptrs Ina sample of potassium chloride (8 410, ‘acon horine ster may be ionized with the expenditre of about Le {alc atoms subttated on potasiom sites may be longed wih the Expenditure of about eV. When s neural site sich pole om ‘peaney i ionized, approximately eV i roqired:Polassiim chloride 2 idetband-gap material with E~ TeV. The allerence in ces between the lowest donor level andthe highest acoptr lev! i £2 this isthe enesy tained fom the Jovzaian of «neta chlorine aoe Sacansyaod fhe anater oft cleston tthe potsesiam vacancy, which then has an elective negative charge Thus we can write fe KCI tat he Schottky equim fr omic anonized defect given by caiatnina 40) cnscson moste se) u Li Z Paciie, Foe | rong he VaR Fa FO ser Ba Boa Bs soit Ls rt) TT. os stn 0 oe (= E~Bs) ass (vatvalsexo[-89] 0 [80 ne] wt (vaavereve [894] neon 228] ‘Thais forthe pute material the ratio a anioized to onized vacancies is mat es ‘Ass consequence in wide-band gap mera the concentation of cal defects is many orders of mage smae than the cobcents- Sv of ionized defects» fet which we Rave sas ued in Seco 210 {For mates whch ave a asrrower band ap, particu the Ungion elements with fled d orbitals andthe higher stom Weight tlemens he defect enetgy levels approach the cater of the Bah gp, rear the Fer level Unonized or patil ionized defects cu, an theelactroneneraylvese both ore comploated and frequen more eotveria. Wal Ve. Wwatval 69 Nonstokhlmtre Sots 4 elementary chemistry aad in any analytical chemical tecigues| we lyon the idea that chemical compounds are formed with constant {tet proportions of constituents From a consideration of stretare ‘ances and intertil fons we ave sea sees that this nl) ‘pecal cae and that compounds witout simple ratios of salon to ‘Gon, that iy nonsoichiometie compounds, ave pot uncommon. Ap ‘ample for which the stoichiometric rato does ae even exit x wast Saving an approximate compoition of FeayO. Thin material has the sodium chide stuetoe; simples of dflerent compositions were Sted by BR Jete and F. Foote,” with the resus shown Table 4.3 For samples of diferent compoaition, the unitell ize andthe eystal femsity were determined. The departore feom soihiometry might be Second for either By o¥¥een fons in intel postions (to give FeOseyfor example) or by vacam ction sts Sine the density incrdses|Composon Atoms Fe Elbe of Unit el (A) eat) Fem 4785 = FeO 68 G10 “Sour Ree and P. Foote, Chem: Phy, 139 9, ss the oxygenso-fon ratio dereates, the charging structure must be due fo cation vacancies At more fon vacancies ae created, the donsty Aecreases a docs the sve ofthe unit ce "To compensate foe the sale aber of eatons and consequent ss of postive charge, two Fe" ons ust be uansformed into Fe sons ich vacancy formed. From a chemical point of view, we may cowie, ‘his simply a slid soltion of PesOs in FeO in which, in order te ‘matin eletrieal neural tree Fe ins are replaced byt Fe ani vacant Ince ste, ali Fe." VasO, replaces FsOy ia Which Vp Tepresets a vacant ction ste. To rat pproximaton¢he Fe ions a) be considered a dnirbuted a random. Suma stucures ae observed for FeS and FeSe, in which anges of stoichiometry occur orrespoodieg { vacancies inthe cation lee. Other exazpes ate CoO. Ci, NinsO, y-AKO,, and 7:Fe0s. Similarly. there are compounds wit ‘asanciy ia the anon latce seh ae ZrO, and TiO Alo one, ‘cca in which there ae intestialeatons such 8 2invO, Cems Ox an Chnc0. Compounds with interstii anion are less common, but UO Al these structures canbe considered from s chemical point of view sold solution of higher and lower oxidation states, thats, PesOs in Fed, U0. i8 UO, and Zein 20. Hosiever, he electrons associated with he Wslney ditécences ae fequently ot fixed at one specie ion ste bs realy migrate rom one postion to another. The idea tat this eectrons Independent of ny fed om position can he indicated by eapesenting separately inthe tesco of formation of the nonstlchometc com ound, For the reaction of TIO form TOs iss $08) tie .=2Ti+ Vs +} OMe) as i pia STRUCTURAL IMPERFECTIONS 1 ose ve fouyiae ws) hese eam added electron nthe strctre Sioa. the absence of an ‘ston normaly presen inthe stschiomelie stuctre corresponds 0 Fen sJOug)~2Fe:+ O04 Vi a Jole)=0n2 Vise28 ey rides in general show a variston of composition with oxygen resrore, wing Yo the existence of range of stoichiometry. Stable “nies having seation wih preference fora single valence tte ahi Ionization potenti) such 5 ALO and MgO have very tmited ranges of renstichiomety, and in these materials observed sonstlchiomete fects ate very often related to impulty coment. Oxides of ations ining tow fnlzation potential can show extensive repos of non Soiciometr. Por reations sich as thove illustrated in Egy #5710 8.4 Wwe eh write maseaction expressions and equilibrium constants and ene the atmosphere: presare to the ninount of nostichomet Dbserved. For example, coballous Oxide is found (0 form cain vaca Jour ove veeah un For this equation the equiteiam constant is ven by x =f9alve et ae oye aay Since the concentration of oxy2e8 fons inthe crystal eno sigleany ‘hanged! (Ox) = 1) andthe concentration of eleciron holes equals twice the concenttion of vacancies, 21Ve = Wwea~ Po ao) Situ, when 220 is heated in 2ne vapor, we obi a nonstoshomet ‘secompositioncoatlaig exces 2ie, ZnO, for which we can write Zolg)= Zi +e as (zace') (ani~ Pst 406) K a6)(Or simiarly forte oxygen pressure dependence Zag) +1120; s¢ Za) (ei) Poo ao [An ssc consideration in each cate isthe nature of the defi (substrional intestal, vacancy) and the degice of ionization. Fe ‘example, the Zine ltersitls in 70 might be Soul fone als) = Zn" 2 aa hich would gives dierent concenaton-parta pressure relationship: (071 =e} Paste) = Poy ae ‘The cocest model chucereqies experimental data, Since the elec

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