Grain Growth S.J. Bennison", Ceramics Division, Netional Institute of Standards & Technology GRAIN GROWTH occurs during the high- temperature fabrication of ceramics in response to the excess energy associated with inter- faces or boundaries between neighboring grains (Ref 1-4). The control of grain growth {s-@ major goal of the ceramics processor for two reasons. Firstly, the size and morphology ‘of grains generally play important roles in the resulting material properties, ss, for exam ple, in strength (Ref 5) or electrical behavior (Ret 4, 6). Secondly, the attainment of high density requires that coarsening processes be suppressed during firing (Ref 7-9). Associ- ated with both these motivations is the pre- vention of abnormal grain growth in which @ few grains grow rapidly to sizes many times the matrix grain size (Ref 1, 10), In this article, the fundamental grain growth mechanisms of relevance (0 ceramics are reviewed. Particular attention is devoted to the interactions between densification and coarsening together with the problem of abnormal grain growth, Recommendations for processing strategies aimed at fabricaung high- density ceramics with controlled microstruc- tures are offered Mechanisms and Kinetics of Grain Growth Driving Force. The change in volume of an individual grain is detenmined by migra tion of its componem boundaries under the influence of chemical potential gradients aris- ing from grain boundary curvature. Curva wre develops in order to balance surface tension forces acting between intersecting bbourraries under the constraint of filling space analogous to curved interfaces in soap films (Ref 11). Phe resulting pradient induces a flux (of ions from the concave side (© the convex side of the boundary, causing it to migrate against the flow of matter. The driving force for boundary motion, F%, expressed as the chemical potential gradient, du/ds, per ion across the interface, is related to the bound= ary curvature, x, by! Fi =e D/y aufa ay Where £1 is the volume of matter transported along with the rate limiting ion; By 15 the interface thickness; and yy is the interfacial ‘energy (Ref 12) ‘The specific grain shape determines the direction of boundary migration relative to its center, and therefore, whether shrinkage or growth occurs. Figure | is a micrograph of a ‘normal grain structure in an MO-loped Al,O; ceramic along with a two-dimensional model representation. Inspection of the hypothe microstructure reveals that grains with more than six sides grow and grains with less than six Sides shrink. The sign and magnitude of local boundary curvature is telated approxi rmacely 10 the size of the grain containing the boundary, €", and the size of the stable six- sided grain, @*, by Hillert’s expression (Ref 13) = e-ayer- 642) with £a constant (3/2 = £ = 1) (Ref 3), Sub- stituting for « in Eq 1 yields: Fo = Dey jee — 1/e/%, (F939 F,, is positive (with respect to motion of the boundary) for €° = €* Ghat is, growth) and is negative for (” = €* (shrinkage). During normal grain growth the microstructure scales in.a continuous self-similar manner with tke following characteristios: © buy = 206 © Average grain size € = yl, where 4 is 4 geometrical constant ( ~ 8/9 Far three dimensions) (Ref 13) ‘The average driving force for boundary motion, F,, derived from Eq 3 is (Ref 13): 2eyM/Oe ‘The driving force scales linearly with inverse ‘grain size, More detailed analyses of the geo- metrical changes accompanying grain growth have yielded altemative values for the con- stant in Eq 4 with no change in its form. General Kinetic Formulation. The aver- age rate of grain growth, dé fd, is related directly to the average velocity, », of the migrating boundaries through the differential equation: bjt = Boy where B is a constant (=2). The velocity can jm turn be represented as a product of the qt) (95) “Guest Sciems on feave fom the Depaaonnr of Matis Science and Eapneering. Leigh University average grain boundary mobility, My average driving force. Fs. namely: Bm Me By = C1 /B Et 4 A. specific mechanism governing bo migration is treated via the mobility te kinetic laws describing the grain gro derived by integrating the complete fy Eq.6 with respect to time (Ref 2,3). Intrinsic Mechanism. The inns pl ‘of a grain boundary in a pure system sd mined by the diffusional transley of j from the contracting grain 10 the exp grain, The mobility of an ion cross boundary. Mo, is given by’ the relation Mes r F where DS is the diffusion coefficient a rate limiting ion crossing the boundary easiest route, and T are the Bolezramee stant and the absolute temperature, tively (Ref 14). Combining Ba 41079 Alfa = BEDE AY ATID Therefore, @- B= (2pEFOy ATRL: where (isthe initial grain size a. that the main assumption made in di the parabolic law is thet all propetis considered to be isotropic and indepen the detailed atomie structure of the bm structure, Cbservations of the parabolic ra lng rare m single-phase ceramic systems. B tions from the parabolic rate law in-via sensitivity to grain size is decreased ‘example, linear kinetics) are usualy ated with the presence of soluble pinning cipitates or the initiation of abnomad growth, An increased sensitivity to gai (for example, cubic or higher ordet ki generally results from the impeding of attached species such as soles an fond phases, Solste Segregation, Impurities pus in solid solution tend to segregate too from the grain boundaries in respose clastic driving force resultieg from the Hi parameter mismatch and/or lect riving foree(s) resulting from valengy ferences and space charge effecs (Rel During migration, the impucitics mastJoys Suonipuoe fesnonsaxsnu soph s3nd50 UL “weno uve? feuuouge o1 pear pur Sue nuniog umes8 ayy wo3y Ame sem suorsN|>UT seud-puon9s ar04js POUAS_O SI JOINEHIq JO sojd puooas P “sDAIMOY SODHEISU esy wO}Os t a8utls Jo uasieo> sofonsed aseyd-puo Dasa 3 pavaud ypnosB utes four ION “(GE Joy) (€/¥=) URrst0D & st X a10u 1a) ryX=ry ‘Ka waned st 718 re18 Zuntuny yp a ‘uonsedy SwNjOs a4p pue J ‘smpes Jo sojajuvd Jo uonnqunstp w0}1un 404 “pourego st“) ‘az1s una xineur Sunt wif & [nun s82sre09 sumonnsex>tur 24) Ayjen (uf “uonesBtu 10} aos05 ZuAup ain sfonbs o10 3uiB8eup ay) jy sjuode Sonnnd Arepunog ANdaIJO Se Ie sey puoras apgouuiy OKA} Aujiqow © Zuypuooae sdnos® 8) OM POIFISSE]D 23P youd wea” souanyUL mu Sasend puodes Hoty nos S9pOw ALL (ZE Jou) 4 smupes Jo joqzed yesuayds © 40} riba) "haa ‘s ‘Aq uaa’ si “yp soy st ‘Baye rBuoNDas-sso49 a}Hed 249 OL pba axe Amptniog Jo [PAWS ath Yat pain oss Kou9 Saypundg-ove® jo uotronpay aif Jou} Sst S010} WOByoeUR ay, “sauzEpAnOR wert 0} payoene aq ot AOuSpUa) 1K) JO sn20q i018 Ulesd Sutanp sjos Rujouue> ced figermaut soseqd yong -wone>ugtsu2p yajduoout woay dunynsar Sisosod 20 (If “OE >) sotuadoid snipe 0} spunodusoo poppe eur roo 30 Uso 3k ye Hue sauM Sansoiais aes09 ut yoasaxd k|teI0008 380 seed puosag 's@s04d pus>0s parojos] ‘ote st Ut mot "P35 yeuwoUgy., Yona ay) UL jeep ut lapis 81 yiMor8 Ure aidonostuy “wisi cious quar wimad in Jo Hutpuerssopun po pownox! sey sauruons lest oidanostut Nr Jo woudo|snap <4 YBAaMoM “ease ew uy (OZ JOM) waTE PrmbxE aMN Won FOE /Ymasp UID uosngp_Xq Joncos prwor popu seq Sut “aoyurs aseyd-pnby 49j HEP qUNOse UIE 40 wonvrasdseny] “yinore) wei sido.nosty sonaury spa orfogemd zegRwey 1 £7e3t £1 bg Jo uonertaiyy sueisvoo stl au54% (cid) Grp = (6z~L2 PW) saunonsg diysuone|ay Msoqa4 au, | UESIOD uonsear qwepuadap-aineradws) A\jenuou ‘odxo ue q paytosiv0> ame sansury ap “v0n exBrus pojjosuod a0eyranut yo 2se9 pu0d9s ayy Jog “suosonay uowesdioaudoy /uonmossicy 8] AOI aigno w ut ‘auoyarayp “synsay zy be Aunes8o.U Sais uresd mim sway $37e08 1(9)'@ ‘S800 x91 wuts 24n pen Jo UoNDRIg auNyOR paxiy eo “WuRIstOD feorAauLOsH wv st g pure “pin by} tp ut Auugayos wres8 am st 19 ‘sonquenb uy pinbyt ssi0usp J adussqns ay? szo4) iba [ove see'ora8 = « Ke Jeu) Ka wont8 31s ayy om 4Jo Satooqan aij “a0ep.a10 ain Jo aMBAAT at 2% potjonwoo st somes jo Sagn(os a4p YK ur pimbry eur $y “so.aueIp aesAA" Jo $0131, -ed jrouauds yo Suruodir PreNSO 01 uoIyseS pqs UE payean u3aq Sey Ase 185 ORL ug pmbrT yénoays danoy fo worms, suonse 4 (soepo1u1) uonendioardas/uonnyossia @ ‘ary pinbyt tn wBnenp FoneW Jo VOISNEN ssassanoad ow Jo 240 q posjontvos to4p st aoepsmar ues /pinby /ares8 aqp 40 Uosr es8iyy “i9edur09 sopmod ¥ Jo uoResIsuap spre 3uuy Sutmnp pinby Zomz9m Jo souasaid BIN Yona. UE (OZ “SZ JOY voNBOHEATA 30 Buysaims aceyd-prnby eta pasmzeynueus oe sonuies2> yeiossuuos CURLY “suspLa PINBA susp pasy uA 01 FUIPED| pL (OL “t Jow) diwos8 ures euuoUge AuIssaiddns “C1Z 32a) apmuwBeus Jo 49p10 we o1 dn Kq sores uonesiu Arepunog 2onpas suomppr aprxo umisaudew soen ‘axed st ul (rz ‘8h JW) (xoTe>0) SO TW tUaaNjsuEN Jo uonEOLAeS aN Ur 10a};9 easB oO} posn s«usiueysaU woRIMOS pljos © YBvosy vorssazdans tpsos® ureag, suraisKs aseyd-2qaurs wr tonesB iu Arepunog ronuoo seme sattandus punosByoeq wr4p yons amdan s “401 oun 0) paras St “uoqenuaaUo9 tng 24) wun SurzF0D85 6 pautERD 3a Soap Gutmdun yo a> oth 20} S19) uonearos oy Sots uonepueir wears A tuonenuaouos “andwi at) Jo ana poner AOU Ky09}9% 2 (OL JM a -u99u09 faunal yng o4p 81 pu ing pe Arepuinog ay usa; A 34920} 1WaI9Y}909 -ptmog om 2s 19% santana 43940 9407 Jo URPIA ata g "SOI JO voHeAUEINOS aUIH|o aN stg) 3 wba) Mo '20e@r + D/H passasdva 9q nus Crepunog amp 30 A ‘ip woneBaides Buons pue 2010) ZumsUp a sopun yisou8 ures8 (eauioU jo ase 3p 30g ‘woran81guo fe aiqesoaey Sqjeona8rous a4) UyyUIEU of 4 0g ya ao ys s018 po no ope a Mint ii vote oe Pooper #5) sae a0 pope Sy WR ‘Spans ssa nguyen Apt utunse eons ua ouron fo vretamae “525 (9) 302i sop-O8H fad nis 8 yd Jo ooo)306/Firing/ Sintering: Densification the driving force is always greater than the pinning force, Breakaway phenomena are treated in the section “Abnonnal Grain Growth” in this article ‘Mobile Second Phases. Under conditions where the second phase is mobile, three dif- ferent classes of behavior may restilt dapend- ing on the relative mobilities of the boundary and second phase and the relative driving forces for migration, For particles that are altached 10 grain boundaries moving at a velocity, #, the following selatiog has been derived: = Ab, + M3 a1) where Ms isthe particle mobility and ‘Vis the density of parties at the grain boundary (Ref %. The fist class of behavior is observed for lasger, less mobile particles acted on by low ddsving force. In terms of Eg 17, the bound ‘sy velocity » = FuM,/N and migration is therefore controled by the motion of attached panicle, The second class of behavior arises for smaller, more mobile pasticles and higher driving foree for migration. The bourstary velocity, %y = Fybly, and therefore the boundary mobility Gnttinsic or with attached solute) controls migration. The third case concerns breakaway of the particle from the boundary Derivation of growth kinetics requites Knowledge of the dependence of particle probity on scale and the limiting migration bebavior. A general relation between particle riobiley, My, and particle cadins, x, i My = ADO /taAT>9) eats where A is a constant, and n and D are the growth exponent and the diffusion coefii- ent, respectively, pertaining 0 a specific ‘wansport mechinisin. Exprestions and values for these ae fisted in Table Consider, for example, the case of patti- lecontolled boundary migration wiiere an attached pore is moving by surface diffusion, ‘Assuming the areal pore density can be expressed in tens of @ grain size depen- dence, N ~ 1/€, and that the pore radius scales with rat size, r ~ ¢, then ded ™ Bry BERG INY (Bq 198) deft > BYR (RODD. okTOE YEP IC) (E4395) ‘Therefore, Cobar (F420) Note Eg 20 is derived assuming the system remains at constant density’ sad changes in pore size due (o coalescence are aocompanied by opposite changes in area density A summary of the possible kinetic growth laws discussed is presented in Table 2. 1¢ sould be aoted that observation of a partic~ ular growth exponent is not proot alone of a boundary control by any one mechanism (Ref 2, 19-21). Supporting microstructural and Parameters in the mobility expression of particles: M,, atkTe". Trensport through the vapor phase applies to pores only Table 1 ‘Coline meee o ‘Evaporation endenanon wa Vapor alfoson Ds Latice ditfsion Dio Surface merase Siosion por yaar oe 2 a 4 a8 (0) Ge wshing cotia Vago inn eon 6) Li fn ol (Su en tn kas oie te Table 2. Summary of grain growth kinetic laws for verious controlling mechanisms ran pews onan Tere Boundary controt Pre system 2 Spore sytem injury cay dow elects 3 exp dr (igh veliciy 3 Solty 3 si Seog phase ' CCoatescence of solid second hase ‘amice dius 3 CConescence of eat second phase boundary diferon) 4 ‘Contntous eid phase inteace conta 2 ‘Continuous guid phase (ation soon Ts) 3 Pore conteot ‘apne teenapart natrtice sont!) ‘Vapor anspor (fasion cont) Latice dies Surface difsin chemical evidence is generally needed to ‘unequivocally identify a specific mechanism, Abnormal Grain Growth During abnormal grain growth, a fraction of the grain population grows at rapid rte, generally leading (0 a broad o: even bimodal fain size distnbusion (Fig 2). Abnormal grain growth during fabrication should be avoided for two seasons, Firsly, @ degradation in raerial property may result from the ensuing microstructural heterogeneities; for example, large grains are effective nucteation sites foe large creep cavities that limit high-tempera- ture component lie (Ref 38). Secondly, abnormal grain gros is often associated with the separation of sevond phases from grain boundaties: if the secon! phase it porosity densification, processes are effectively te inated (Ref 3), Initiation of abnormal grain growth is often Tinked to the occurrence of local uctuations in boundary or particle yeloeities. Cammon mechanisms are characterized in terms of either an intrinsic oF exttinsic origin and whecher the velocity fluctuation arises from variations in mobility or the driving force Intrinsie Condition. Experimental and theoretical evidence is available t0 show IS Sp eae fw co vee Be anisotropy in both intrinsic yrain-boundery energies (Ref 39) and mobilities (Ref 40, 41), Computer simulations of grain growth, in which an orientation dependence of either the snving force (energy) (Ref 4) of the mobility (ReFA2, 43), shows abmormat structeres quickly develop when such anisauopies exist, Boundary anisotropies may te enhanced oF diminished by the presence of impurities ether relieving or exacerbating abnormal grain rowtt When impurities exist in sufficient quan tities (0 form a [iquid phase curing fioag 4 characteristic platelike grain morphology ma) develop, Figure 2(b) is an example of such grain morphology in an AO, material con taining trace (=0.2 w1%) impurities of Na,0, SiQ,, and CaO. High resalation transmission electron microscopy reveals tha the liquid wes the Jong basal {0001} type facets Gu Hot the facets making up the grain ends. ‘This anise tropic wetting is believed to lead 10 strong vaciabiticy ig graia interface mobilities. The shapes that evolve in the ALO, material shown therefore result from a combined anisotropy in surface energies and film/boundary mobil ities (Ref 44) Extrinsic Condition. Extsinsic influences embody a variety of mierastructursl phenom- cena and are the most common cause of aba smal grain growth A wide distribution in particle size of de staning powder tends (© promote abnormal grain growth, Grains Jagger than twice the critical size may develop abnormally due 10 the large driving force trom highly cuned boundaries hetween the {ange grain and the matrix (see the section “Driving Force” in ths article) (Ref 13). The driving force for matrix grtia growth i considerably lower (5 10 I limes) being dictated by the lesser curvatures in the matrix, This disparity in driving tore Jeads to linear growth kinetics of the absot imal grain, [9 many cases, after a pronounced ‘groab stage, abnormal grains that initiate vi this mechanism impinge on each other ant their migration cate diminishes as they now effectively become matrix grains. The Small rains continue growing and reach the size at the larger matrix grains Jeading to a normal but coarser microstructure. Bimodal mcr structures may in some instances be Wanslet ‘im nature if initialed by a wide distribution in size of the starting power. Distributions ia other microstructural chat acteristics may slso trigger abnormaf gratworeups9o9 9 Buusoyes) ones 218 mess Oy fxs atod ayn jo wonauiny w se aBeyuus 210d oj wouaq> a). Kas005 apeqsns 242 St "& pe (ezbay CAZI, 909 2 = > roa

34h, (ay02409 “5 sw 291039 aod aap 0 i90US0u uy 2nmsod 239 pyno4s os0d aap go 2:minain9 JO sapes 9 “ansoo 03 sup dod “(Gr °¢ JPA) Atmpunog pur aiod ayi yO UONDesION |YD 7e PpuLOy YSU xt 01 Supping wes ayy tuors poodsuea, ba pUoys sam “DoNayISIAP ax0W “oud oF 19pi0 oy ‘2an3Ns (233p) atod pur Ke -punog ured aya vaoming Shoipes pRUaEd olur3yp ye2ey AG UAALP st waNROM!S¥9q, Suopsmsapysu0> ayumuApounoys -Sayorus 286 uy tHE HoNdoUUOD UF SOMO} 28% wowssnosip af us pasapisuod auw si2aM12 382M, SesUNIP UOISRATP Buaseatour pue sadeys 208 Runsyppons K9 weoxU9 asayp Og BADE {pmor8 utes Cimestiuey ye SuN0u, 2} & Sqpoxd) auny dyapuostou v wpis ayQeurrae Si AusH9p ny Te ssuINbsd pur sandy bo pasng st PuoOd! HN :9{QExOAY} 81 WON! fay fo 2qas aod pus ayy mp sasinbas puw armen u4 seneeXpousoy 51 ISH! 24, “3nteA qesKsD 2jfars ayy ¥aU AusURD ¥ 0 JEpMON {us OF ops oF Tour 9 ISLE CLEMSON, woyn31{suoq PED ysmoID WIDE susp yaty 0) Guan Jo sojdieunss 2yp amnsu0U9p 01 day7] pasn 1 AaSUAP pus zx5 WEA yo GOD “puny 8 xP poeqnayna 9 KomeyTDUg HOY Gt Geus sup yo uoneuasaad parnpom Y “(sean “pe 40 95n 4p wnat ayduers 209) sexe ‘Angiqow SurBucyo yo sioayjo oun Aioatenen Rerquasap ut agaon st deci ¢ Gang “¢ Beg 1 suompued feimarussosoit Jo woNUNY & Se padde a30 conwsedos asod sos russi9 aq, «cba one Bad = he = 2 HERI TOL 8p JY) seteapents Sutwol0y 2 01 uoUNjOs RQ UoxIZ st LON Soredos “ont Armpuriog a\suIUY pu Sp s10d patjomuca wossmysip D9e5s 104 "uoHOU ‘ost Hujonuss suMIPaW 3u4 pu voRe-IE faepanog umjonuos tastueyoat ayls0ds & 403 2218 2108 pur a218 ures JO Konstiny & se pareynores aq ue SuOMIPUDS KEMETEAG SL (cba) CHEW + WIKI a a land st up “{1 pue pt ba tog “asod 20 ojan red 94) pouoxD 9540p Tes CoMUNEHeU 3H won sotea08 1 Spf “GHmOIE UTess 36} 2340p uraqp umuutxe aap yor 3apun suanIpUDS 408/ youn uyDsD smionnsororu 1 powet9pe9 St BOLI wo “eados ag. ORDAyISHap oF satsey 24 cr sypser ie souypunog tba? tox) Saiod fo voweredas 2p ses00H09 W942 fea Suva aso S286 pioaes sasfoa Tasos utes reusoUge 01 spe eH uoUELON “oxy Kesey jo way NOUR BOUT ior Jom¥0>. fus0,9% mop 941 pHEINOY BOLE Gromer ysad ot spt “Gon ren “habe ainios lle sosea¥29p 9920) B4iNIp 240 Spo2ooid timo ure st asmeaaq woroaun 39 01 pondifg st SemENaIg anor “Ps9H9e Gy “lap s3Qp SRO; DyazUY DH “sip gu ster? unsouge pue suonegim “Jad Aysojan 2qgnssun #9 B3/pED} Jn200 o8}P out Aroptinog Huoqe Suonemanig “Hs tes qoweouge ayrnmar a9 rep sew Ss0}9n ut nssa Kea AampumOg oF APNEA tang weotto> anos pee 290%, Seraup wF Sa “AD ISON s1SHU- HU YEN use oF Borwoyte Crue gt OE BIAS Da tim anjos paandos yo sos 9238) pqur ain $0156 voNIOAD Wo} SUN oF pore “s09 s8ofs 8 Uossn sep Sind 983M sven Wer ypuiion yin WondsuuED Uh 2fonte sy Uy .wSIUROHY aSULNEL, vORSAS Bay ut posstosip say 30}98 0p pala os aut (61 J) W9EH}9 Zep Due 2210) tu “sap 349 40 Sonya Saneyay aip vo Suypuadap SOASUEDAEIMYD.AUDO|SH DUASP OH ANH eu Siepunog & se) saVoypH alse eap Sonjos ain 30 SISKyOUY "wUDUONDYE hem “eypaig ai 40 Z9uanIR990 ay 8} svOHEMAY ‘Axjoojen Aaepunog, 633 fo ase sauuRY Y “suyea8 9F v.10 MOIS pide Kyeanda ‘31 1 Zampe9} anaso sanrpojae Aaepunog Sp ‘ur suopenes yond yp st sustey>oIN Sa srsanng 5a) UOUNIOD au] “(Op J) SO -y201t Sip aseyd-pUO22S 20 aIN}Os HANOAR pomp ypsos9 urs aouamgus Sous yuedop 0 2 §pA)pL) ypmeuk ured pu nome iap {eo0] baIye osye Aver yuPurueALED 1 TURP F Jo wancginsip soo “cb fay) Baty Bunay ‘aéeyuigs pur Sun(ard WOPUNAOU LI syNSAE ayo sapaiod Suiers aut jo wonesawoie “aomppe aj Bummuoy auyssant Suu Uy -seduio sapreod asiopnod iol “sea ao} “uousotiges uaa RNP poonpeAt 3 eu sivayper yong "wonott axputog slo too Sezp du0d Uayss saves qyNcas 21GEUER GH proj “ajdiuexa 204 “SiuIpead Kyso1od "qUNOAd, 4 soins “innit as poco fons peppe OB 24H 52'0 hm psseeK unce SDs (p) tot cu Ho yey yo oyonig (2) pm sas ey 8 SB) Jo money) "Ba SOE 7 gay sipausajr Bunny suo, spray ontog (0) “Olly U heucajop ynows vio jousouge yo eranbes © OL308 /Firing/Sintering: Densification Pose site (27 sin 100 yea 0! 100 Grain size (Gen 1 oot eT, Separation vegion Gh Pore contol region Grain Pore sae 2, wm Fig 3 ep dezitina pores boundary intercon for siece-dtinton corr! pore mirton, Tho ricrositsl contons for separation an be adjusted tough redcion ithe boundary ably. Source Rel 37 number) and the dibedal angle in 00 dimen. sions (Ref 5) is shown in Fig 4. For a given edral angle (~120° for alumina), the pore size should be kept below the grain size in order to satisfy the thermodynamic criterion for densification, For conditions where the pore curvature is convex (that is, when the Poros sink | oS Pore damatenGrain diameter ratio Theenadyromie criterion fo pore snkone Fig 4 [Centon of ho cesrol cng end te roto of pore tae fo gran ne (ceordnation mbar) {Gah 50 foe ordmetonelmcrorrorue, The hypo teal pres ae hd) ek on ‘pps sorear Sw paver io} and (i) wil Se Se ecare gro Gown end recoorinaton In ort soho for pore is several umes larger than the surround ing grains), shrinkage is predicted to cease ‘and further densification can only occur if grain ‘growth causes a reduction in coordination umber with an attendant change (0 a con- ‘cave curvature. From a thermodynamic view- point, it appears that coarsening is necessary Under certain microstructural conditions. to remove large pores (Ref 51, 52) Kinetic Considerations ‘The kinetic criterion for densification within reasonable times depends on the specific dif- fusion mechanism(s) controlling densitica- tion and the scale over which matter is t be transported, Analysis of the diffusion pro- ‘cesses for Final stage sintering in which there is no thermodynamic bamier to densification Table 3. Expressions and values for the parameters in th expression for densification during sinteri (BDy,0/KTC")-¢ ‘ame aituson BST Grin boundary Aiféwion Da) A ae (mia tae ae ites/eumay ton oct ‘yields the following general equation relating ensity to time: 2 po = (BDyA/ATE™) +1 eH where B is a constant, D is the pertinent dif. fusion coefficient, and mis an exponent (Ref 12): expressions and values for these paran- eters are given in Table 3, Note thatthe tine required to densify is strongly dependent oa microstructural scale and that grain row will lead ta a rapidly diminishing densifice tion rate. ‘The effect of grain growth on den: sification can be calculated by either solviag 4 differential equation incorporating. nth Uensification and coarsening dependemies op scale (Ref ) or by taking the separate expres sions for a specific densification process and a coarsening process and empioying a num ical method to simulate microstructure evo lution (Rer 7). Consider, for example, the scenario of & microstructure densifying via lattice diffusion and coarsening via a surface diffusion ean trolled por drag mechanism. ‘The respective equations describing densification at constat agaia size and coarsening at constant density ring final stage sintering are (E9250 = B= (4408.Dygsty/ATO — pyP-e 25 Microstructure evolution is then calculated using @ time/step iteration and the resulting grain size-density trajectory presented as amp Such as the one shown in Fig 5. The trajee tory is a measure of the competition betweet coarsening and densification and is an extremely useful guide 2s to how changes the relative diffusivities controling each ro- cess affect miierostructare evolution P~ po (BTN ATED] ¢ 2%9@———->—) Paegrin i me | | 20 £ a DUD, 7 : Alls Density. 5 fig 5 Mosrecurn lopment moe Fr AO, Fig’ 5 The grain vze-densty tcjectory wos cole lote for densification gs detrmined by lai dice ental ond gro grovih deternned by surfer da Soncontoled pore motion. The poregrain hurry Separation region isfy tne tap eight af ty dagon: Source: Bot 8sonoma Lad Jo mun mp psroanup pi (hseo%0)" pat je Res tld Sep pen ri ome voy oauppe ats hy sees ook seis onay bin Gin Seep eae 8 Bag Sagi Geo nautegnap ancontoony £ 5} 2 4 soIn0s “¢ Oy 19 HoH pues auos Japun eure 40h paseo “vouorese slod yo. poo passa eo ain Buse, pomp side uonooyuop OF null iy Y woNSas Yoyo. “24 oponos-and pub opin Aysuapars vos8 of co Bgems009 prousen 42 284s PH O> 2) Bumoyt dows woudopnap Sinpsansooyy 9 BAL 6 8090 or ee se re ‘4 Masus ° a ce ° = ° woo} —— q ye 70 i is evo 5 2 wo + g 2 J : f f Ea Sg vo ou s |4 VY 2 2 fi Tye Fegpt Vi NE eT acon 1 |S ‘ 3 Be To § zo} —4}—__| Is 3 two | |g oz pedop yy iv ee asopig tse Ve wise | re 1 oe 1 ‘Auepunog a ine Gee ao HS TuIal A098 ne 8 wower aoneindas oy jo Worrsad 4p per Aqqoisardée pauayey St onsale UL 2 3S uy panuasoid dew yuowudnjanap aunionutsoiouu 24 wo paces sf 19R5 pam aff (1z ‘Oz 32) Sound 2op mod wo Furpurdap Ais 61 AU 10 401984 Y 5g Auyiaos Ksepunod-ures3 ay seanpny @ (¢9 49x) sto} Jo 2012 & Aq worSAysIP 2OeHINS SasEa!ONT @ (z9 Jy) suoresu2>u09 2o9j9p Wad jo uaneoyIpOUT YBoostn SNR Jo 101985 & Aq uOIsKANP 29H] s9sEI!IU] (08 OB “Gk, 0162) 3, 0091 1 1H porwaxss aney sae -ainseat yuopuadapuy “RuyaiUts Buifjonu0y sronouresed 42 uo sey OB stoAsIS 2hdnyus 21H yim sayy WoneUIgulos Sanppe WSO Mp 30 Kood at (yz “BL JW) sHauxlsouste ay 1 uafompAy & pur suonIppE aos Oy JO PAB om atta (KOREN) LOY aur EIsAsDKFod Iaonisueay Jo wonrsugey axp 81 92159 3AM ippe ue Jo 2ydurexo poveago}2o sou! 242 ‘Suut) Sounp sqsaudsoune Patjonuos pur ‘saseyd pisses pros “saanyos se yons soanuppe jo asm ain sKoxdeee one nisuap Stnrodiar «1 uoeosdde pap ayy word fuo qt coaiyo st ascersiese amssaxt “(svotax(lde ese onus ‘3[duvexe 40)) pasinbos am stusuodios JGmygesysa yy axoy “TaADMOR -SomNRI0D ae J0 woneDtaRy 2th 40f dondo aaisuade ue sj amstaud Jo uomoydde ay, eHow diqeauiosap snoy\aduut ue qBIAs (pauUED) {2889 40 aks 2104 pasoT> axp ont parowtsoad sous am sung {19 Jy) sodrys xaidwoa 30 oNROUAE, BW) or Porias 9H st Y>ns sv pur aseyd se3 e Suusn 29 Sepa ueiS ayy YBnowp >ypr3 HorsMs HP uORES pe 2109 Krepunog ap v) 2sv2 98903419 SI Uuodsuen wore “saiod payseue tog “worn, "1p Buyznp ones ourawouyayors ay ur pad sung 29 a teu owe TON “YOneg ‘1 soung ay9u04 0} Bape] 287m AeA ‘ond suu099q sa9ueisip WoIsnst * ponmpy jo suas “Ow 5 Bunanng au) ut OB 40 3102 241 36 Aa01 “Suky V “TRULEY “IN PUP LOSTIUDG °S 8 =£88 “0661 “CF “ON) EL 0A ‘908 Hie) uy peureunyy Jo FUUDIUS 2h uy erssuteyy 10 oqoy am pu amtuddes uy uote 292g UO aInTos BISOUBEYY JO ays] SUL A) TN Pur UOSTIND fs PEOE-LIDE 4 “0861 “ZI “OND S110, “PS dane 7c NOFTY WE RUISSIIg “oy Jo SaReUIY| 3B UO SUOAIPPY OTW 30 on UL, ‘YoU "FY PE BUNK “s ote 56 9 ‘9161 “sau suwapeoy “pa “Seo, “Aa ASojouyany. Pleo I0UH9S 5/OUIIOH asnmeiy "6 JOA “savsareeg UONDIIADY owuia'y “BuIssasg-30H “Plog “HN Loge “86LP d “OLE “EION) LF IA SH dy 7 "soatoy Sayaug se sinayct ans -Sokd pe ABs0ug 298} yptm BUISSOLG WOH 20} SIAPOW vorsHyREG “3140 “TPA 8LI-[91 4 “1461 “OND 61 LOA “90H MMAD ‘neg dold “AS \On22IR “OFW-O 30 uon2uposd “Sally “£71 PUE SBUOE "MT 6rl-se1 41861 Hig ON) 08 IDA “208 "toiag “Mas SUDA QUEeE Da WOTYDIOS-UON JO 3 cap iteg "0058 °f°x PUR NORAPNON "HL epicert d TR6L "GS “ON) 08 104 “90S HAE TE f Souy 'Sygouog (esCIONINSOIOTA “Ful “Hg ea YOOIS fy puE AOE " So~z d “6461 “(1 “ON) BL TOA. “08 um95 aug suit “O'W-B padoq puv aing JO Suse paling “oorg (7% puw ssuagoy “Ay “IOUUNEHL “aT 961 “va “w42t som “AyssoNtUy, yRWT *uOHEUDSSIG, Tua. rvaadeyanag ameNsO.II A 0 woningunsc] 0g 50 SOON, “ORNZ “f 0119 4 “S464 ssalg wonUagg “pg 9)SSA4L TA ue pei O°y “siexopy ounosA Jo nove eq “OW $0 da9x TUOISAINTC) 40 ain *2lgeD "Py PUE TOULe “WY seule} ‘DMA pue vouwe) WY 68-8 d “Pa61 “(@ “ON) £9 1A “298 "eID "WY “fSI9pHOd PIP souiogsaly 0 Aimeqesowmts “aur “ara 86% tur 4 +1961 “yoeag uoptog “pa “tog gi 4° pu “HaRVOH VN "TIBURLON, JD ‘Puomouayg parnjey pun Surors ‘Salog pue soumpunog umpc) usMW9g swonsesana]—I Spyos 2unIs4u Jo 34) otis ‘sooueg “sf pue SieZury “CM 68¢-S1z 4 “rest {CE -0N) 72 (OA “one DY “sureEIC Sues vo nodee iss V 'Squsy “A The /ysmosg unig $9 9 z 19 09 os 86 us 9s ss os 6 soe-061 4 “6461 “OS4O4 eyendyny uayeng asinlaqey “pg “ous “pur eAnttag °g "s>muM19-) apr WON Pub oping Jo Biasenas po woroys “og wy sio1994 fo smscodu’g youowew cron 24i fo SBuipazo04ag ‘Saumpunog uqeip ve saiog pue suedog Aq payion -wo} woYnjoas aamonuisoIOHPY “Uamog, SUH pur “fsupmouy ‘Awe “y'HN “XL Seq ‘ay “vou Wy MSIeUIOA " 608-667 4 “9861 Sp -ON) 69 JOA “908 “wumse;D WY “F Ssonsuayae seu [PIMYONNSOIOIPY “FE AT ap coiesayy Kepunog usp ‘uouUED WA PUL UOMO WH HSI WY Lis-ZIS 4 661 (ON) 8 Joa “Img 209 -we4ay "wry “Seman suowez {E5qUIDUD ply [BoISAUg Jo SI92KTg ‘euRIL|, MEE ut quswdofosoq 25m ~DensoIogy “pary “Sf puE atOQED TL Lez d*906) Oy “OND Ig fq “Jog -windaD “wy “F suoneougey o1 2np voneueA jemmonns -O1sHN *21Q0D "TA pur ONS aA prci-ieet d 6B6I {LOND EE IA, "90S "MOLD “WY {F2seud pnbry © Jo sunow'y [jews Sut -uvejuod OAV Jo Buuayg ou! uF CSW 40 210¥ 21f 30) wstueyroyy WV SOULE “CW DUE “uostMtag “g's “HewIaIeg “VD Zos-£61 4 "y861 MG “ON) ZE TOA “ORGY DIY “So]WEUK [eo plu AFojoday, “uonnqunsich Dag IPI) “T]—UIMOID WIEID Jo wares Hays somdlwo “waIsy “$°D pu “LUIS Sd ‘vosmpny “gy “wNAIg “Ta Noe-e8e 4 “pg6t (ON) ZE [OA “OPH! MOY ‘sonoury ToD UID Jo uonE|A ig seindwo> “ayes gg pee Ysa SD “AWOPOIS “CA “wOSFOpUY “A “2 zo-ese 4 “6961. ON) £1 10A “qerane ony “ary woNEIagA, Arepanog ‘wei $0 Aeoyy, “JOE "HL LeL~611 4 6861 "STE WA “ZHIV sory “sSoyyy ULL-bsT ani, PAE peor] Auun audigy ut wonessipy KIepunog Nei) “ON "AVE pUD_BAY LK 769"889 @ °8961 (ZI ON) IS 100 os amie.) say PPK wR Uh panog YLE {9D} 2} Jo soxFicug sane soy ‘09g “CAL PUP puOFOHIPRUS “AE ietmeei d “EREK “CE ON) 69 TOA “295 mB wy TF -uouawouayt wapeodac Sv}stoa0x ¥ Auqaouey Tema "sueAT “OV 19-95 0 “6961 “(1 ON) 26 104 “90g “nay wy “fSudR>® -aaquy Arepunog, UIEID arog "yOOIgy “fy Olst-B0s7 # “0661 “(8 ON) €L 6A 208 "wr49 “wy aaRh onnsoiony Eunenawadiauy aseud-iena, rumsisay-SumasiPoD “TAIN “W'D pur ‘woqy WH SOUR “EW “YUN “GE oie 4 “161 “CL OND £9 194 “9e8 “tD12D uy “pCO Jo BUDS 28eY-PUOIE PHHES wee, POMIONUOLS *SAPOURE HA ar lp ‘oF se fe i oe se SeI-¢e1 4 “8961 “Cl °N) oT 10, “ypieHy bioy “soreKions EPR, Saag jo sS1AUIS HINO TIONS A 1 JOR 999 Sr “S §§°9 01 woryworenutuoa sent 5052 3 p96r ‘pURlsUy ‘wRUTALIO, “proquey pueasony Ue, soqry pun HPlopy ut Suowowaapinocy aNd “SEE doy “Bexuaiceg “> Due OA "VTE sid Us “1661205 ‘uma “ong “fem paotosulay- aunty wnecRY 1, mel “wostUog “Tg ple using, Ep I-11 41661 “Ul “OND PL I0A “208 “mse uy 7 “SE xoqdng. Jo JolaeyeR 269545 ‘atENg ‘AW pue ‘uossne[ (NAT “WE ose d “9961 “(L 'ON) IS (A “908 “widay ay “pf “ase Pb] B JO soURsaky am ae SoFYFON MH BmoID HED “KET A L6S-186 4 “1961 “(8-L OND SD JA ‘amuinyoostiong "2 woumosspeH iq Sat aredoaag Jo Koa, sauBey BFT~EFT J “9G5I “Uh ON) FIA “yporapy DY “su0H0}05 ut Samoa potiadste 10 ous ‘pOomUDaHD ‘AV 6OZ-EL1 4 “6961 ‘PO (OA “209 ueuay ig “suD4g "S883 (pI -PIOS) so0lg-omc, Uf YoNO30 UII Jo SUNY SUL SAMUAN “L PUE “PION ‘yA “WOE wots WT “Wosyeer@ “NE SO 805-106 4 “os61 EON) £104 “hye Ty “P6034 1 seg pinbey w jo. auatang ap wy TuLaMIS Sune vonwayisiac “S98uy “aM Se 796! J “CITE woyed “gs: uous JO. pOmeAt pue wtauinty iuaredoueay. “199 TA 10g -2406 0661 “(LL “ON) EL 104 “29g "NAD ‘uy “DULY Ut WIMOID. UID Adonosnuy “20820 WV Boe POR EPE-GEE 4 “LBL “CS “ON) 04 [A “IME uD) uly “Fenty Ut Oa HE 4 #opoudanyy 94) UO. ASH PROF Wad “HEPUTT Hy PUe ‘axpompuny VD oss WY OK VN, O-1 4 $586) “Ce “ON 99 1OA “0 “Dah uy of “oseug. pine] © Jo. SUY 2) Ut euWUMY 4p S904 NOD ameag “sou “wy pul UDsiNNDE “TS 1 269-062 *ER6¢ ‘4S ON) 99 OH 209 D1.) UY "F SOFY UL HOH ‘uess $6 sa9U"¥f 94) UO 2INI0§ OH JO woO]JA “LOWSPE “eA PUP YOSTIUDG "T'S PIE G0E d *ELET “(9 “OND 9S fA “38 "HDI02) ay "CONAN PAS fo NOLS “avai, way Sauincy s98u04> eimsaas OW “AIREY “Gx PUE UMNSDON Yh 66L-€6 41961 "SOND ZE 0A "HE ay “f “sigedwo> smoiog W S>PO orsngyigy Jo 3694, ewaweds ssp “10s ueIs43D Jo Haus “Qed "TH HL BLEMSLE D 'gOB) “ML ONDE A “yjuroptidians “Sonauy Witoss HD pe ayy Seacruniy 2.0008 TH312/Firing/ Sintering: Densification 66 Criteria for the Selection of Additives to Enable the Sintesing of Alumina (0 Pro ceed to Theoretical Density, Trans, Brit. Ceram, Soc., Vol 6 (No. 6), 1967, » 253- 264 S$, Wu, E, Gilbart, and R.J. Brook, Solid- State Sintering: The Attainment of High 67 Density, Structure and Properties of MgO ‘and ALO, Ceramics, Vol 10, Advances in Ceramics, W.D. Kingery, Ba., The American Ceramic Soviety, 1984, p 574— 582 8. Prochazka and R.M. Scanlan, Effect ‘of Boron and Cayboo op Sintering of SiC, 68 ©. J. Am. Ceram. Soc., Noh $8 (No. 1 1975, p72, R.L. Coble, Sintering of Alumina. pf Atmospheres, J, Am. Ceram. $ee, 45 (No. 2), 1962, p 123-127 MF, Yan and D-W, Johnson, J, Matt Set, Res., Vol tt, 1978, p 393