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    Kingery Introduction To Ceramics 2ordf Ediccedilatildeo Copiar

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    Prof. Jaqueline Ferro

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    © All Rights Reserved
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    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

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