| ate (OF CERAMICS TEXTBOOK SERIES WHIT EWARES - ee eS Ze Unie of Manche MIST PRODUCTION, TESTIN G [Sastre fee ede ie iauer tal AND QUALITY CONTROL ocd Cant Ceamie Drying ; fa sciepibtna arias Including Materials, Body Formulations INSTITUTE OF CERAMICS fh od Sale Ceramic, 2nd Eton ee areca MASKALL e WHITE Visor Enamaling gp of Cami Raw Mat 2 ad on BY (rami Gise Tecnology 7 and (Ceramic Raw Mitel, n8 Eon.” C. RADFORD ® Published on behalf of ‘THE INSTITUTE OF CERAMICS © . PERGAMON PRESS s cagonn NEWYORK BENG -mANKEURT TT ome «6Swe Introduetion ‘pd the “why” ofthe tests, ie the author have tried to describe how the $s are carted out and alo the significance ofthe tests in term ores {bd fundamental principles. Where postbl, typical examples nd values _bve been given. Some testshave been discussed which may not be of direct tert t0 the established manufacrurer who receives his aww materials fom 2 supplier, whose products ate sold to a definite specification ‘Towever the technologist setting up a faccory in a Thied World country, {Sing indigenows materials of unknown properties, notin this privileged sion, and wallneed Fundamental information, such as chemicl analy, hincralogy, and many other physical properties on representative samples ‘his materials 4 Chapter 5 deals with how the vasious tests are applied to contrlling eral, proceses and finished products to give an overall “Loss and ality Scheme''for the three branches of whitewares, namely, tableware, itaryware and wal Ge industries, "The earlier chapters on materials, body formulations and manufacturing rocewses are dealt with i les detail. There no shortage of information in cre aes in existing ceramic publication In the prevent text they serve nly to deseribe the materiale upon which tests ate carried ov, and the ea which can afer the results ofthe ests. They bave been included this limited form a an adjunct to the main theme ofthis book, namely testing and quality consrol” Finally on the vexed subject of unite; afer careful consideration the uchors decided to quote in the text the units which arein use snd accepted Joh by manufacturers and by material suppliers. These are in general not unis, bat they are units which are meaningful co the technologists and \dosrilists who the suthors think will comprise the vast majority of the ridership of this book. No doubs SI uni will one day find general plance within the industry, and to cater for that eventuality the reader ll find a table of conversion factors at the end of the text (see ‘ppendix IV). [The authors are grateful to Dr.G.}. Gitensand Mr. R. Grit for their Joggertions and wsefil comment ne Chapter 1 Materials INTRODUCTION [Raw material wsed in whiteware body compositions may be broadly clasified into clays and non-plastic materials. Each ofthese clasifiations ‘may then be subdivided. Detailed discussion of the formation, occurrence tnd structure of the various material ae not included here, but may be found in a number of existing eextboaks."™* ‘Mose whieeware body compositions consist of three types of constituent: Ccayr—to give plac to enable he body 0B shaped, and iti equate unfied woengh 10 that ay be banded suey tone he nping anf proces, Foxes slat cath containing riers wich elton ring and react with other body contents t0 form + lass whith teponible forthe sucagh of the Gred product. Thus foxes tec the equed fing emperaeof e body, Fiery scam whitewate tony man fenton bring 0 ontrol the thermal expnsion ofthe Bred body. Plaster of Pais, glazes and colours are also included inthis caper. 1. CLAYS In general clay minerals ace bebved to have ben formed fom the Tron of igneous rocks suchas granite, Granite is composed of decomposition of igneous rock s composed 0 ron of poate coe : “ALO, .6SiO,). The least stable of BEG) ah I OOS cee See i, Oe ere pe oe wh cerleed in the formation ofehe kaolinite ays + supecrg Hiue vfe to Refenc athe nd of ch capeK,0..A1,0).6510, 41,0, 10, feldspar Kaolinite sa crystalline mateah abe ccc ES Gh Bi sudeticas smal Cette aay eaten factions ofa micron in length (F msicron or mictomete ie ee andiistheirexremestmallnes combined wthihen ike one Residual and Sedimentary Clays ‘The lay once formed from the parent rock may have been deposited at its place of origin, ort may have been transported by waterandiuepeged tome ditan: away Inthe fis cathe clay ihn ast RESIDUAL o a clay, and inthe second ss 3 SEDIMENTARY or Fan RY or SECOND- “The particles or crystals of sedimentary clays had to stayin suspension y Me bey ih during transposition by water, and s0 only the very fine exyas uamely Sette Spe found thie way tothe place of eventoal deposition, Thusscdimentryclayy "Ton, cewng ate generally finer than residual lays and this face expaim many of te emia Prokey didtrenccs between the we types In cde aan a postedslong WG dy, For cmp Baginupoinotcanien cares sini eS Te stempe b made fo purty ceonaary Taye abo they may Be selected and blended co give afr as postble te properties refuted by whiteware manuficearers Impurities f xed with residual clays are the clay exystals, and can be separated on 3 sie basis, leaving a fine fraction t of comparatively pare By. Se Coone pexdPhina Clays ( Resdvel | Falmans cl English china clay, found in Coemwall nd Devon, ofthe primary type ny cbained fmt opens: pa by washing witbhigh power thc jos ot monitor The ater cs the cy and mel mater ee ess and quar) tothe bottom ofthe Cay pit From here te a ed to ge seing aks here econ pares of Per out eaving an ens cy sopesion containing cy 20d ince paviles of inpcey materi ene e parson x Ta0 microns caried out wing hydroeylones, 7 coarser than # Foufete Ses inehich hes ofthe hydrocyconeand dence downward toan undeow Te ne Sveti a Cente Of the rotating suspension i pased upward to the eeslow and emerge farther ected chy cont For craic fuuhet hydcocyloning operations cated out at 9 meron leaving te Talking Raith clay conten of typically 95% or more For wie in paper aking hydecyloning sagan wl bathe eat even hoes pals 21 3bout 15 mito giving ery pre and whe ca produce They seduced in ater cotent by eng. es peso, se aly epi Pte Li Seg Tak nd Hpdrscydaner—Chia Cy. By eure of Engh Cine Sie Because oftheir low impurity content, china clays have the desirable property of Bing to 2 very white colour, whereas mort secondary clays tetas of cheir higher impurity fie to colour which i at bese of-white ys nay be ivory, straw eoloored, brown or even red. bplageinthe china spin some ch "Untorsunately,becawse the clay. pati Ligier plstity and unfced sength are inferior secondary clay, “Tien bodies auch bone cits where ii esendal hate Dod Bet a a he manaacue cn only nerporte econ clays fot ee cat ay add none at all. He must then suffer the foa very limited extent, or beadow plesisty and unied strength impored on his body by the we of on the white baring china cay. Table [1 shows eyed eater eet pale size analy, and undred rengity of eaomeenee Sa ‘hina chy and some secondary tall cys: Note thatthe coe Gal analyst of pure” Kaolinite coneponding, eke he 18,0, 28:0,.21,0'h: AO, 395605 SO, 46.54% HC fos) 139% {eis primarily the Fe,O, and TiO, content of clays which ie responsible for “Tams 14. Treat Cntsucat Anateats ato Pyscat Phonarts cr Cua Ctay ano ‘Soue Dau Chars (CHEMICAL ANALYSES AA eeeSsSSeeeSSSSS (Chemical aaa 8) uy S10, TiO, 4,0, F530, MgO C20 KO NO tow ‘Chins Gay “00 <7 06 G3 Oi ta or wae (Corowa) ‘ack Ball Cy #08 3 10 03 02 18 03 150 (Deven) ‘Blue Ball Chay 5208 31 15 05 03 34 a4 95 ‘@ose Sliceou Bul Chey 401545, 08 03 01 16 03 50 PARTICLE SIZB AND UNFIRED STRENGTH Parise se analy Untied soph (oes than sie im microns) jn ee?) uy wo 5 2 1 05 ‘China Cy ao > wm (eH (Coral) Black Bal Chy --2 no m w& (@eroe) Blue Ball hy - % — 7» @ now Bones) ‘Siezous Ball Clay — 8-8 2 wey slung aude cont olen eae Sezer natconicion afb ana some ie of oan whch te ae we tes cee Er ne fee ‘nls in. warping or cracking af he onmed sade Y Opens og sir Secondary Clays Secondary clays wed in whiteware bodies inclode ball lays and to 3 muh leer extent Breclays Ball Clays (Seiorctary Clay poe prac) ‘The name drives fom the “eubes” or “balls in which the clay was cat fom the quaey In this county they at found inthe coundes of Devon and Dorit. Bal clays vary greatly in thr impurty content Atough the lay mincrl in the clays is aon, ie enemy sma in stactre to tha found inthe chin clays the eras ce much ne, and is chi fat ‘whichis manly responsible forthe high party and wed seength for ‘which ball clays re pried. Like other secondary ay they contin sage uantcy and vanety of impority which is very Ene and therfore extemly dificult to remove, Generally, cay from diferent sources nay be Blended together to prodsce propetics required by the whitewste ‘manufacturer. Iti common practice to se bwo or even three claysin body composition to lesen the effect on body properties of variation fn clay ropes. This variation in properties i more pronounced in ball days than in eins clays = Bill lays are often described on the bs of thei fied color. Thus they may be termed “black", "bie", or “ivory” clays. Thit colour however ia poor guid to eventual fred colour or example, lack clays derive most of thet colour feom organic material which on ving is burnt of leaving + near white fied sample. As already stated, ball clas vary widely inthe amounes and types of impurity present. "Siiceous clay contain much fe sic, increasing the {oul SiO, content ofthe clay t Over 60% (and possibly as high as 80%) dearly dese clays ate low in clay mineral content and show" "we plicit, untied scengch and drying shrinkage than cays of finer content. Ball clays containing organic material. Chemical analyses by high los-onignivon values) are urephstcty, unfited strength and drying ehsinkage. ‘Their defloccuation Darcie areal ten oc not contning pane suse Linc i altalie conditions they form complex onpaee stone wink {doeclaion ofthe cay ae : "Mos bll lays ae won by open-cat working but some ar obtsned underground mining. Inthe former csc the everburden shone the chy epost is ist removed, followed by mechan digging ofthe toy ‘One ofthe problems encountered bythe manufectrerin the we ball Foe cys, lays hat dae othe fine natu ofthe material itintealydgperedin oon, wate, since water does not readily penetrate between the devsely packed | ‘Erg po ig wih bes mers ede ball clays are now svt rom ely supplies The lamps of cay are fed through sshreding machine which ou teonine aon terwecafinand 2inin see Thistot nly slowsmasened ieee dhe cay in water, but ao produces eifcent mixing of ee che eaten body component, ‘More recently “pellecsed” ball days have become availabe eve the chy & exuded int rods which te cut into ther eke see “pelle day are nor only ery o disperse in water, but arcmuch ens to handle chan he lamp material Refined ball ays of Wigs ae el ervey hroughout the UK snitryware suauy Shee wed “peletied” cays have the following advavag ‘quicker and more efficient blunging is possible, Aegligibe wren ridoe, ‘mokture content i low and controle, {Go eating a higher Suiits posse, improvement in green strength, high tall ay slip desis of upto 1.65 gltl are posible, Ball clays may abo be availible from supplies in “slop” oF sspesion fon. Whi his asco the cost of transportation, it redoces the problems of dspension ofthe cay by the manuleeturer. Irreversible thermal expansion ‘The measurement of thermal expansion on raw materials ofers information on their composition and behaviour during firing. An example is provided by classifying English ball clays according to their irreversible thermal expansions. The tet iscatried out onthe “green” clay, and once it hat been completed ic obviously cannot be repeated since the test specimen i now “irreversibly” converted by the heat treatment into meee extn particles in the lamps of clay. This has resuled in the pas forthe aged for [Coe hoa Pee” prolonged blanging of ball clays wich water to entre their completed spss. yb fhe te. From th test data om balay ee main groups emerae (ef e 7 ‘Thete exits a close relationship beeween thermal expansion at 600°C snd the quatts content ofthe clay. Ths is due mainly to the a-P quarts inversion at 540°C. The clay subseance or day minerals have 2 marked tffect on the expansion of the chy. At approximately 700°C. lattice alterations oceue and this eauis shrinkage wo tke place ‘Therefore, in general the higher the ay content the Lower isthe expansion 20700" : poedieesee erate ig 1. terse hema expo tal ays Group A—High Silica Clays ‘Theirceverible thermal expansion is pproximately 1.0% 600°C. The S10, content i generally in excess of 66, The clays ate high in TiO, and FeO, (greater than 2%) and tend to fet buff colour. They ae cosrely igruned, because ofthe high perentage of fie quare, and therefore have fast casting rate. They are used mainly fr kiln famiture, efractory good! and abo for increasing the cating rat inthe production of santaryware Group B—Dark and Light Blue Clays ‘They have intermediate properties of Group A and C clays, Th ‘neeversible thetmal expansion is approximately 0.4% at 6OO°C. Group C—White Firing Clays “The ireverible thermal expansion approximates t0 0.2% at 600° “These clays ave strong and highly plane: They may have high carbleent—black ball clays af included in this group—but are white Jning. These clays are used in the manuticene of high, grade tena, tes, sanitaryware and porecain prods The use of ereveraibte thermal expansion aforsa means of clasifying {clays into distinctive groups. In 3 body composition, x chy en ee up cam generally be succesfully replaced by 2 cay’ fom that same Sup, sinceitis more likely to behave ina similat manner. Since thee pe ‘eral daysin any one group with relatively wide variations cme recld thhosen with similar chemical and physeat properties Fireclays [ike te china cay and all dye the fredsye were foe Finiaton of apr Thar aye ean ee md by fa aon. They ae secondary cay, often tamcried ees sd ths they raemble the bllday im tac ese epee ee Soa and they conan condense rene of oe eae pat found in ciation with col mesures wider eee lands and North of England and in Scotland le may have been the of vegetable lie which inter format Ge SE ea ee Stoorine loys Zaman now! Stoneware Gays 7 nee feo Bee thaved archighly plastic bu or brown fring clays which conti atural Si. 2 impurity. Because of the natural fx content they ate sed in Jpeware manufacture without che addition of 3 farther Hx component. ulated stoneware bodies ate alto produced by the addition offre, such spar, to ball clays. Sigh 0 eureig i Bentonites “ie. i "Thisisa general erm for clays, containing smectite (or montmorillonite)" Sut ie fico cy mit Theme ie dhes dnpnot esi | tute whichis able to adorb water between the yer ofthe suture jel at on the exernl suefice. Ths interlayer sdsorpuon reals in Jeling ofthe cay and hence ths typeof eay is sometimes termed an Fpaning leice” miner. ‘Ahough they are exemely plaid show very high dry seen, i Seas eat get) ley, i hs ges, bentonite ate never wed in high proportion in whiteware bodies since {Gey induce ver high dying henge sd vee afer defceclation Eines Soe bacatie dante ndash ed es stale the manuticrrer due to their smectite content. flleroporions up n about 14) of bentonite rchowever eequnt {aded wo tosesoflow piney at eh cvuecin, Seb» ‘iyo the materi that ever the salads resin inetesed { workablty and stengsh inthe body. Greater additions are avoided, since ‘hese would undoubtedly rel in drying fut, 2. FLUXES [A floc isa material which lowers the fasion temperature ofthe material ‘or mixcute to which it issdded. es not sey poate to divide materials into axes and refractory materials, ince whether ot not a material act3b 2 flux depends not only on the material el, but aio onthe material to which itis added. Nevertheless, there are certain materials which are generally regarded as fluxes and ssed a such in whiteware body formations. These materials ae high in alka or alkali cathe, Table 1.2 shows typical chemieal analysis ranges of rome commercial faxes “The higher the alkali content ofthe ting mineral, the more elective it ‘wil be in its fusing acton. Thus weight for weight the four material ‘eported in Table 1.2 will be in decresing order of efectvencis—"North Cape” nephelinesyente, "Lakefield" nephelinesyenie, eldipar, Cornish stone, However, alkali conten ofthe faxisnot the only consideration, The "Tae 12. Conaaare Anata oF Son Conc Pts a cma a ac a a a B se Be 5 & S ER EE & Ss ff ee f » ame sho below in Fe, content ot wil impr color to the ed Disraeli npr The Bete ‘is she morerzactiveand eecivethe fix wl be Ferre ground ied fincoesr—onaly about 59 ofthe macs than 10 mron Hine Another important spect that increasing fines of ponding {is ina grestr uric are inthe mace and this increwes slug ose stall component. This slaion of aba wil crete aise frciions which wl server paral defoccult he bod, tus posibly ising is ply "When body is fed, the fx ites and wes the particles father more irony materials AS the fring proceds thie srace meng by Ce i ps deveos sete re whch end ea the more fretry paris togethee. The pore space decrees and the body rinks. The las will be of diferent composition than the orignal a cout of action with other content ofthe body ears ed lint. As the temperature nthe kn seduce, the einy nts of ates and aluminaes slides and bonds together the endaselved sco and crystals, The porosity of the fired body will Jepend the joan and mature of flux n the body snd onthe iting condone IF too rch glsis formed on ring, of moken glass of high uit then the cic being reds iely co safer distortion. ealy tbody sold have vide fring range, ie. variations in Bring should mot cause too dea + igs in amount of glass formed or ints uit, Thus the manotecurer beable to produce acceptable wace eventhough oe vation i eat iment inevitably occur Feldspars Several types of feldspar occor, e.g. potash feldspar or onthocase 0 ALO. 6Si0,), soda feldspar of sbite (NO -ALO, 6810), lime iipar or tnorhite (C20. ALO,.25i0,), barium feldspar or celian 20 - ALO, .2Si0,). None ofthese is Found in a pure form, for example ah feldspar invatably contains rome rods feltpse. In addon they ay contain upto 15% quar and an sllowance must be made fr this in 1 body recipe { Generally, high soda feldspars give lower vitrification temperatares in be ‘than high potash feldspars, and they are more prone to xesule in tortion of dhe ware of firing, since the pas formed tends tobe of lower fone than tha formed wrth potsh fespar, | FRidoprs are wed as fluxes not only in cersmic body compotion, but [foi glazes, glasesand porcelain enenelt The chief sources are Newsy, [ede Fland, Retin, USA and Canada Cornish Stone eis clea fom the chemical analyses give in Table 1.2, de Commish stone isnot such» powerful fea ether feldspar or nepeline syeitey ‘Scoala ets comiery es rashes very Wey toed a a fx im ths coumry being the only native depose of Hoxing ‘patefl commercially able Ince yes the eof one hes eine’, feldspar and nephelne syenices bing tnprsed to pace ‘Comishstoneisin tac flspur ch steen prey Kolinised bet may be regarded as being efectively a mixeore of kali ad feldspar. eis traded on colour bass the vareiesbeing known asad purple, "mild Bure" and "dey white. Al eontinelaspc, quot, clay mineral, mia, [Bsorspor and other minor impure, the porple varices being riches fekspur and the white varity poor, hence Hard purple isthe strongest flex nd dry white the weaker Te calouris due tolmpurity found inthe fvorpar (clu fooride, Ca) content of teste. Th tthe apa content and fixing aiity ofthe tone ineresies, 20 docs the AUOE>aT Content. The use of the materal in body composions can result in tisions of fuorne compounds dering fing tes bring ijurous 1 [eth and detriment 9 the environment. For some time defrinted (oeDF sone was avaible, de tone being wexted to remove te harmful fisospar. However, the proces proved to be uneconomic and. was dhconsnaed. Nepheline Syenite “This rock contains nephlin, feldspar, mica and other minor consti= ‘wens, The material eontsnra high proportion of lk (ee Table 12) and isa very poweefl fax suse in body compositions, ghaes and porcelain ‘enamels has increased considerably over the lat 20 yous Tes claimed that ‘placement of felspars by nepheline yenite can rele not only inredaced firing emperatares (with the result aving in fue), butalso in inereated fring range of bodies, “The eo main sores are in Canada (the “Lakefield variety) and in Norway ("North Cape” vaiety). can be seen from Table 1.2 that the “North Cape" material hat 3 total alkali content eather greater than the "Lakefield" and ake hs 3 higher K,O(N,0 rit, Bone Ash “This material i uted in only one body, Le. bone china. Is prepared for we by de-glaiiing cattle boner with stam to remove mon of the A eeeproduce of ths pres) ca eet luc was aby tani on puny toe le finccey ca teed ee not the me pa ae cay ow. ete nary wala gia woh cen one cay ns elt Line ay jimporeant Sieteniate {ied idulepaiemuez tow contoarseareen crane oa rat esr te ehigi the amount of residual organic material left in the bone after | ‘aleinaton cna rl une de ae ster enaton a ara abe dmind oho cn gn St by the bone supplier. eae ay eee i esg ale ea ve Se SUN tm he: Dung ig of sd tahunces the trarstuceney ofthe product. =O" AHO» 250s Tale ‘Tale is a magnesium silicate and a member of che smectite ot ‘montmorillonite group. Ichas aa ideal formula 3MgO. 4810, 10 snd in Countries where itis found, iis a cheap source of magnesia which acts 28+ flux Iesinclusion in bodies iced at high temperatwres results inthe formation ‘of cordierite 2MgO . 2A1,0, 5SiO,, This imparts low thermal expansion ‘characteristics and hence excellent thermal shock rsitance to such bodies, ‘making them suitable or example for production of oven-to-tableware. ‘Theis dsedvantage isthat they havea nafrow Bing ringe and easily distort, ‘on Ging, Due to their low expansion they may also be dificule to "macch”” ‘with 2 glaze of suitable expansion, and t0 decorate to an acceptable standard, Tn low temperature bodies (Gced below 1200°C) tale increases thermal cgespden tic sthc temper gh expanion mineraensatie ‘MgO. SiO, and quartz are produce tion, moisture expansion of the body i seduced, both factors serving to reduc the amount of delayed crazing found in the product made from such bodies. Iti believed that lime bearing tale in particular give bodies of low shrinkage, high stengeh and ood etazing resistance, They are successfully used in both tableware and Wall tle bodies in countries having suitable tale deposi. oy Limestone Limestone din alee oy compotion ten a8) “ef da Sto Sy Lithium-containing Minerals ESO. eel a oly era econ orate of shel Seruing in sere ae rp cae oy Pulte When sued pal reps one efi mre conronnal Aare iy rp iw tt stn wae Woe seis ere anete pana aceeee cre ‘of these materials, i ee Micas and Illites Although these materials are not added st uxesto ceramic bodies, they ‘frequently occur in clays and ther presmce mos be taken into account by reducing the amount offax which would otherwisebe added. Potash mica ‘ormuscoviteK,O.3AL0, 6SiO,.2H,0 ocrursia many day depastsand the potash content reduce! thes feffacorines. "The ites (or hydrous mise) contain les potash and more water chan ‘muscovite, The potash minerals ofsimilae particle se tothe cay ivelfand ‘te thas not posible to achieve a commercial septation. Such claysare of lout reftactoriness and bodies in which they ae wsed must be formulated swith this in mind and ix additions reduced accordingly. The sructure of the hydrous micas i not certain, One posibiiy is that the hyroxoniam fon H,O™ replaces some Kin the miscovitestroture. Alternatively it may be that they ae intimate atoeiatins of true micas and clay mineral. 3, FILLERS sieht ole materi sed in ann ti cat foes npc leo htvare Pecan ern minor nd bough 2 toy tir sloof the fied body. eae he earsent a ltgepropertion ofthe total body composi- son, Hence the Patil sae dba i import a deconey rile packing the ody, which in eam affects deying aed Bee Stsnlage In addon he fnenesof the ile afc the otal ope of the fred body. In this sense, these material are note os ee “sll” might imply Silica Whitars ods conn icin the combined form sslicaey ein tpolnt, feldspar, and nephetinesyen, bur mow ine eee added i he form offs sand. An earthenware bedy Or or tak probably conn between 72% and 76% toul ica Roose a a the form of fink or sand, shout 3896's prceer ioe ‘gmbine form assent inthe clays and fates theremeinde tae io" conned inthe othe raw matras The teseal erat hence craze resanee ofthe hoy. dopends mainly mde EGS ohn fontent f te body since this as a mach gener desma cqeoee oes combine! alia ‘The Body mus haves greater thermal expansion than he glaze ocaure Sod ease esas (ee page 17) ese to produce comme zs with expansions of les than sboot 0.25% at 300°C. Withoct sion of “ee sla” an earthenware type body meu at {pean fsbo 0.25%, whe wt th lesan te expansion fincapeeerotpsy 295% mde dy cn “el wh hue of expansion of 029% pving adequate cane essence Hence les Ee Sey nd altos aa ae aban en a expansion ‘Alton of ics to a laze decrease rather than nee its expansion, [nin Sed ele he aii preentaslow expansion si gl wheres In bodies much ofthe lca remain, even inthe fied bay. in crane ‘ona in which it shows high thal cxpasin, Ste may be node nto bodies and ns her a fit oa sc S304. Like other non-plasics, its ation toa ecramic Body contsneg 2 decreases dey strength and plac, facies drying ood ers dying srg Traditionally, in the UK, flint has been the popular form ofthe sca EegRanent of whiteware bodies, akhough Continental counties bat ted quarts sand for any years nce tings onto sod aly czonemicretons, many British manufacusters have ken to Content Practice and replaced fine in thet formulation eek set Flint Flint contains small quantities of water, inate airspace and interstita smorphous slic. Thisisdue tits manne of formation fom tee selene of spongeclike organisms which dimolved in ca water sod mcs Tn ‘eperited in chalky deposits. Thisfine microstucrarcoffint maker mene [Spee flan quae and in porcalaritconvers daring Eeing more red {p.Sistobalie (sther cxysallne form of sles). THe i inponeee {he extent of eistobalite formation ins bady prooundly ateo ae er nay ‘expansion In preparation for tse, Bint pebbles fram the seashore or ffom chalk ‘spostsare calcined toa temperature ofabout 100°C. Thisheattcesrome ‘mainly to make the fle fable, which iciiates the grinding pees ca the Eeqired finenes (45-50% les than 10 microns). Busing Shernetor: the ins aly shatter duc to expansion of ir and water pocleownttan ar 230. The decreas in spectc gravity from 2.630250 covenally deena the exfoliation of the fint on hesting, and to 2 later creat eke Production of xstobalte (pectic gravity 2.3) Probably about 16% of he hats is converted to eritobalie during ealiation of Git The pete The calcined ints wet groundto the equired siz and wsedin op form in the body mix. Grinding to the correct fineness important hace ie {fluences the extent of conversion of quarto ecb ring ng oF the body The Inversions and Conversions of Silica ‘Thecear three main crysaline forms of sie, mmely quart, tidymite and ertobalie, Thee thee forms all hive the sume chem fae, SiO, but dite in the ways in which the slcon and onyges age ae arranged inthe structure In crtobalte and tridymite the nome oe ne closely packed than quarts, and hence they show lowerspeciicmeaceion,Whitewores Specific gravity Quartz 265 Ceistobaice 232 Teidymite 228 yi and rsobate are the high temperature forms of sie, wl Eres the table frm up ro 870°C, The tempera salty ines of Hynes beoween 67°C and 1470°G, and tha af tibale Secs FO"Cand the meling poin a 171°C, above which tempersnee seg fisor fined quar, noncyaalie form of sie oe Fe changes trom on rytine orm to smother se voy cgi and fever changes on cooling, ie om entobate and tidy trek a6 10 How 10 be inapprecble, The change fees caste lymite sho extremly sow, and may not ake pice walleseer he sence of sme impurity. In practic, lial etal hore ing quate 1470°C or more, and then on cooing to beewers 10°C 0 tidymieis formed. es pouibleto speed ape ares st scbalte and tdymite bythe adion of snl aman of tapnty of the three major forms can undergo minor structural changes wn as INVERSIONS. The inversions involve only a rotation of 1y bonds between the silicon and oxygen atoms, only small energy gesare involved, and the essential structures are unaltered. In each ese, 1 lower temperature form is known ax the alpha form, and the higher perature athe beta form. The main inversions which occur are at | @ Quarta g Quarts “5. p, Tridymite “"S p Criscobalite desist len B,Tridymite a Critobaite i- a Tedymite Meters ” Althoogh the changes in structure invalved in inversions are slight, ehe diferent forms show diferent physial properties, the most important Of {hese in ceramicsboeing the dffeencein thermal expansion. When a-qate changes to P-quaets there isa volume expansion of 10% "The enstobalite change produces an expansion of about 3% and the a-p, tridymite inversion involves a 0.3% volume expansion. Unlike ‘conversions, inversions occur almos instantaneously, 2 a the inversion temperatures size changes occur very quickly. These espid changes in size can lead cracking of ware during fring if the temperature reso falls too quickly, through the iaverion temperatures The a-B cristobalite inversion can be wied to advantage to prevent crating (ie. the cracking of plaze due to filure in tension). During the bisque fire, B-quartzisparially converced to B-erstobalite. On cooling the B form will invert to aecristobalte at 220°C, accompanied by. 2 contraction. On cooling down from the glo fie, the inversion and contraction will gain occu, At che eemperatue ofthe invetsion the glaze will have solidified, nd the contraction of the body om cooling: will therefore put che glaze into compresion (ie Fig. 12) ‘This process of poring the glaze into compresion is often termed the “eristobalte squeeze”. The glaze is capable of withsanding compressive forces very much greater chan those required o crac it in tension, thus the ele isles likely to fail fi isle in compresion. Tensile forces om the laze can result in practice when the ware becomes hot, or through adsorption of moisture into che bisque (f porous) through unglazed parts, for dhrough micro glaze imperfections. Adsorption of water result in ‘expansion ofthe body (known as moisture expansion) and the glaze layer it put into tension when ic is likely to fal and produce craving. The effectiveness of the “crstobalite squeeze” depends on production of csinobalite during the bisque fring operation and che use of finely ground (a. Cr (EE (LN LLIN **- ZEEE. eeperumnae Sg atctene "games Fg 12 Ge put inca comprenion by “rable suse”+ ff guar in the body. (Farther deal on Body/Glaze fit and it fees are Biyen in Chapter 4, Section 19) "at mmportant non-erystaline form of sca is fased silica, formed by +P pelting sty form of lca to above its melking point and then cooling the F etren mas, Pused ica has very low and almost linea expansion, which se particulaly useful where resistance to rapid changes in ak tui eqied (Le it bas good thermal shock fesistance). Dus 0 J, tempetence of faxes, sia in glazes melts a a much lower temperature the Brg normal melting point, and formea glass with the other constituent 4} Bal lof the glaze. The higher the silica content ofthe glaze, che more |) iStistared glaze resembles fied silica, and the lower is thermal | rion eth ie cote of he gfe ncn the econ SpPycrenes, so that for a glaze to “ft” a low expansion (thermal shock | ijeing) body ike porcelain, che slic content and the fring temperature Uke glaze mus be high. Silics in the body composition increases the thermal expansion of the body since it doesnot all enter into the glassy phase on fring. In vitreous | Soaiea high proportion of glass is formed, and these bodies show | Mosely low thermal expansion, particularly if the Bux conten islow and {bey te fied at high eemperatare (dhe body composition then becomes {inularco that ofthe gaze). Vitzeous bodies with high Hux content, ied a¢ lower temperatures, or porous bodies where the proportion of glass formed in the bisque small, show high expansions. Inthe latter case much [the alien remains in the crystallin form and in this sate has 2 igh Silica Sand Sand lends isl othe benfcinon process more seadly than dst. ioc fin occurs hg pebble, only race impurities ik imestone ate | -gualy removed. commercially farther punieaton isimpraciabe Send “ThencGcated bys wamber of methods including roth ton and acd Weathing. Sand of pry gente han 99% SiO, and low in the colouring ride 20, nd TO, can seadly be prepared from stable depois ‘ele ted, any UK manscaters have replaced the fint wed cadionall inher bodies by round nd. Sandhaseconomicadvan2g ver Bn pecially sce Soe nor equa clinaion operation in #8 proprndon for we Thece ae, however, fundamental ferences in Fiiad carstesi between flint and sand which real jn the lowing Grinding becomes more expensive, since calined flint is much more | fable than sand. ze Moterii 19 (Cranng resistance inthe body decreases due tothe fact that quartz sand ‘converts to eristobale rather le readily than the microcrystalline silica found in fin. "This problem may be overcome by either replacing the fine with 2 Highly greater amount of sand, or grinding ‘he snd fine than the fnenes to which fiat is taditionally ground. Alumina Ina very fevrbodies, alumina isnted aa filler instead of lia, thas some technical advantages in this respect, mainly in that i has a lower chermal ‘expansion than eyslline forms of slic, and producesa body with high, fired rrength na Bred body where Bint or sand has been ied 2 the Bille the particles sand ceysals ae held together by 2 complex sicat-aluminate glass, This [laty pee hat thermal expansion considerably le than the undissolved ‘lis particles: The misnamatch of expansion between the glass and silica putes remus the development sees during ring. I thet steses be too grest then mechanical ulure may occur, ie. the ware may crack oF "dane’"inthekiln. Even fdunting does novoccur,anerwork of fine cracks is Hkely to occur in the plas phase resing n body of low mechanical strength, Other problems ssciated withthe use of ica 2s fillerinlude its association with the "spit ot” ful in decorated ware and is health hazard ‘The use of alumina asa filler reduces chese problems, and produces bodies of higher mechanical strength. However, the use of alumina caries swith i other probleme. The main ore from which alumina is derived i, tauxite—a hydrated aluminiam oxide. This material is invariably contaminated with gon bearing impurities, and if used in ceramic bodies it produces unaceepable colour. High grade, purified and white burning ‘Slominas are avaiable, bu they are very expensive, Thos the we of alumina in whiteware bodies i langely retired by its price. Another drawback to the use of sling js that ic hs a high specie gravity (9 compared with 2.65 for quart). Thus ware made from bodies bhavng a high contene of alumina tends to be rather heavy. We Ary Prins ae SPH Key EXC weMPT long 4, PLASTER OF PARIS Phster_of Pais is, ia effect, calcium sulphate hemihydrate, €250,.181,0. 250). 2H,0= C450, 41,04 1,0 sypum plier wateres propued commercially by heating powdered gypam 0 pproxia- {ly IOC in neal pane Wae ek Ros hs bum a soe Ses Sage a IEC ft bo sa 163°C cal boll fe pees Sie then “dend-bared™ pln prodoced his seal i rons ccm sphere Gases resting; tvo forms othe plate maybe produced. he and b pc ite ure bel lager sree ea tee Ein to cee, then the Bvatiey of pines armed The & ee proucd by hsg gypsy dpa [Mould ae generally made Grom the B frm of pte bt cis may contin om ofthe form depending on he conden often ‘Toe arm gency make a mac stonger lr bet toch ‘regthin the mould may lend cter unl proper schsspeoe wear sorption FO adding wer to pit of Pit renly techy to form an | iterlocking. mass of gypmum crysls, When the plaster bas set te ,cmcombloc wer evapora lente ta oper poe thcore Therion ‘Eeore water added intitng the pcs tos he mite posses 4 | Sic pada td the more ceive sin stnring wt Sadog the i Casting moulds (1'plater0 water Flatware moulds 10) plater/70 water Older factors beside the platerwater ratio inflence mould proper- sies—the acral mixing ofthe pater and water i of vial important In tractce mouls of widely varying properties may stlbe produced du to {beinheen vanabity ta commercial supplies of pote’ plaster. “Theetec othe tree conditions on pstereitherin opened or snopened bags aes the proper. ‘Cun nd Walker sow chat er opening bus of plaster after Day-t the fy overrwing =108" (using » Tecnico Torsion Visometer O92 ven platerwster min), Aer 3 dayshad elapsed the fidty oversing "ale wat found to be 252 (e page 213). anges pster on storage in sealed bag show quite clery that the atefater mix becomes more Sud th longer the plasters wored.Day~ “ Lgave a valve of 108" forthe fidity et and afer 29 days the se beater mix gave 3 reading of 200" overswing on the torsion ‘ucometer Phster should theefore be used after asabilsation period that, I ay be up to four weeks in duration, Blonding and Setting of Plaster . ‘The miccostucture and properties ofthe pastet mould depend on the Brcvious uestmentof the plaster watersary, i, he blending rate andthe Jengeh ofthe blending ime are roca fire During the tee the lester it setting, ceysals are growing and a the moukdmaker comtanues (ost the iin dup ofthe cl growth ors. This mean tht moulds ae ‘composed of crystals which may vary in see and shape depending on he treatment which they have recived dung ibe lensing proses 5. GLAZES, Introduction A glareisa gas. Iisa vitreous teil which in effect asuper-cooted liga which has cooled below de point at which it might have yale lesa liquid with a very high viscosty and this may be demonststed by considering dhe fee thats (0 a gh od katy deforms nd eds when pended beeen oppor (snowing, Sisters an Bacon a empert age, bt does not exhibit a definite melting point, at Ontiary sis ate eqyrtaline and hae » deni arangement of atoms sd molecules, Ths can be shown by Keay dtsetonpatcan, aes, Sowever, have no define tucson se oeted nt oan, teork's this my be appeecned by company te une or rymiine seas meet eh gee "The oni of rere sco exabéron, hsp is dcated by the tee of the atoms, on 2 compunsve tale onjgen 1 38 aed Seon 039, ‘hn cxample ofthe rus ofa crs ia and sca gan sien in Fig 13 which clay shows fe tren: in the sewers ‘tas a gle ocr a andom dee drensonl meter but aan reps > Facade tra: On eng ta ‘soften. over given temperature rig sic, to the varying amount of fExeny seed to desch ferent pars ofthe network Which noe Suctralyequvlen The trees win the network may be Bed ‘th stort foes lament which motte psa properties sacha Colom rinsecaine ete 1.3 Sou pilin sir nde gla (oe the agp erent Fe ‘hom gh cement eee | i} i {| Classification of Glazes |] Since lise bave no dnincesrocure thie syemati dsieation {| proses dtc and many methods may be adopeed lo whch ae of Erp notre for extople planes ry be LEAD and LEADLESS FRITTED and RAW ‘Ged places ave 2 briliantsppearance and ean be wed upto glo fing ‘eoperstirs af 150°C. Above thi temperate lead tends t voatie | Ladle glzer bave been developed and improved and now have F) resonable bilancy and Seing range, however, gazes thit matere 2 temperatures below 1000°C generally have poor craze resistance. This is | deto the fact that high proportions ofzods and potash required to give the tlhe alow melng point alo confer eatively high expansion. (8 glaze Imostalwayshaves lower thermal expansion than the Body, se Chapter 4, Sesion 19) Alrite glee as one or more materia asd init formulation which have been subjected co the friting operation, Le. the heating together of components co form gla whichis vbrequently ground #9 a given partite sie ‘The main reasons for fiting ae: Soluble compounds when fitted with other selected material inthe ‘rect proporti, become insoluble. Glaze components should be inoue othe wis they tendo igs into he pores of te Bae ee and the line when ed my theives taved appearance Even if witeous wate ed wis gle with sigh) solu corzonct, segregation il ctu ee ying proms proceed Atthough lead compounds seashe tthe cele indy 3 eerily noble in water, they may have considerable slab Slate ad Ifhecompounar st lle ste by ocaone 24 then they ae toxins te gut ace weigh edie 17% hydrochose si) Lead compound ae reed to produce laze Gimponens which sre ison eos Stes ‘hae wih high proportion day bane muy cre. on drying emily combed water bs sl wo be ried dong oe elt fceand ths nay lend 9 forgot ni. proporon sche ny component shoulder ean pan gpronsstly 0%) ‘ed rr to gas espesin, Some compounds, rch a cen carbonate berate ga om heat ‘Any compound that behaves ins way when el SEES low maturing empertre. ited tat he ce stot eit sufer om pacing and bing Icscommon practice wo we is ea led itand a boro it ingore fermulasonsftelead nd By0,compcudsaefeued open ete led does not gearlyrenchticay ln of wolsbiny Hower, recent remeh hs shown shat lead broseate c be produce ‘toy when the POOTB,O, caw cel sled, ‘Gaze compounded fom fs wit low slay tate capable of asin the UK regulations fr lead sls are own 2 LOW SOL fac The tet on isan laser anole the eof iprohle a os fcagih of 025% at AOC. (This compan ws We asength of igachorcacdin the gsc ces fhe aman enya 017% baat tempestce of 37°C) The dy gle tsk in the te hyarochorc 2 for 24 hours in equpinent specially dciged for ths porpose To Cemmpy withthe eglaons he gase tax have les than Soe mlbiey ‘eased a PLO onthe original dy weight of te ze ‘Aw glace contains no fed meas gener wed 3 high temperance whee the we of nomad mately wold be mere acceptable, or example snitaryware lsat onc-ficd wth he bey ‘oappresinataiy 10°C “Another method of late casiaon red om sfeence othe pe offaeon which lee appli or ramps an EARTRENWAR, SANITARYWARE or PORCELAIN glaze. There is obviously a wide ‘ange of gles avlable within eich eegry and ths caniferon og ‘ee broadened inde the ing of matrng temperature ‘Nothin fllowingecample gle molar frmulachavebeeninewaces ¥en whee the oxides have bern cxegoried ba, phot le, ad the sum ofthe bul osides eu t ty. Tis convenient adopted that al laze compoiion maybe compucd seed i The emportoes eter foe manatng jolie 90 050°C 07 760) 20 10, deo} aio, 35% Ete 10009 110" | isdn | 04780 } ar a3cr0, fF oasano, {2550s } 0.3 (Na, K),0. (05 BO, {} teats ene { 055 c20 39 io, { as ren nyo} 410, 252, Senterpware 1200 to 1250°C 06:0 02 (Na,K),0} 035.40, {3.0Si0, 02220 [Note that tit glaze does not contain B,O,; it would probably be opacifed with approximately 10% addition of icon, Hard poste prelin 140°C + 0.468 C30 020 MgO} 1.040, {10.0 SiO, 012 K,0 Glaze Raw Materials Iki posible vo produce a glaze ofthe same ultimate composition and 4, formula in several rays. The physeal properties may depend onthe way the glaze is compounded and the nature of the caw materials wed inthe formulation, ‘The ratio of Grit to saw materials could vary Le. one glaze could have 20% ft whit a ac one of exc te same formulation could be Produced enty from aw mater. Ths covld, for example, alter dhe tute setae since the fated lee might ack the Body enore ‘gerotly thn he nen ted pve vesting 4 soba erent "ner lay. (The be layer hes componon and ropes intermediate beoneen tat of the body and Bae aad occu at the Sodbeie neise) : ompounds of vavow composons may be wid ro intodce the oxides shown in the various goat frmulaons Foe example, LOS ‘oul beintrodsced as BAUXITE, $0, FLINT oc both Azo, and SiO, SSCHINA CLAY (ently AIO, 280,210) Depenlng on the vei sed gts may be provctd ni iecen peal aeibues. ‘The "dipping" aod copending charscentce may shet and bier sree formed in the fring proces produce a range of nbd glces Sith wide vanstont of proper Basic Oxides Buti oder ten fits nd pins confer ese of Fsiblty bu exeesive ‘quantier ate undesirable since they are asocinted with ghacr of high ‘expansion and poor durability. Some typical oxides ae Srcatsed below Spi the reson nated forthe choice of particular compounds K,0.-Compounds commercially avsable are—pestl sh (K,CO), potassium mitate (KINO) and potash ldipr (KO "ALO, 6510. KO ould be introduced by any ofthe above compaunds. However, potish fElispar isa ikely choice, iis inpolube and inet andi would at the same ‘ime introduce AO, and SiO, iat the fit or gle [NejO. Sods ish (83,CO,), borax (N2,B,0,.10H,0) soda feldspar (820. ALO, 6Si0)) 18,0, isrequced nthe formulation then borne = cheap and realy avaiable compound, could be considered 362 suitable ‘aw materia. CaO is usally introduced as whiting (C2CO,) since this compornd is, txtremely abundant and cheap. Other soutes of lime include Ruorspar (Caf) of together with B,O, from colemanite @C:O.3B,0,.5H,0). [BaO May be added in the tineral form withere (BaCO,) or baryes 350). PEO. Generally introduced a8 lead isicate fit; the Weal formula is PLO 2510, Nore that white lead QPLCO,.PbOH),) and red ead (5,0) are aolonger wedi the raw sae beease of thee toxic properties, Meee sed lead and quarts and ar fase eogether under eaceflly Controlled conditions to prodiceisoluble lead bslcae fritWhitewares Amphoteric Oxide £ Ale nals 22ide gener introduced as china ea PhO, 25:0: 24.0), Painted inte he a, seams fiend | Biles may" g24 a8 Setindcr added to the ml batch Other mine, we ney te Considered ate baurite (ANOy-21K0), edie a | pephelinesyenite (810.210), feds i Acidic Oxides iol george mings one ind nga | supscheanrend ees ai {| htitimtatedae gates 0, tune i Samant Gio. "Hees att nd ma say feud a ona es NO 2, i) |= | Beck The gnding medatay be scum, echo Shea | SRM 09) fin pee or porta ball The high lan see | ing media ismoreciceneda tin oeioereeee Aa ne Ind gindng he gee coon | __ln ate round ogee than 1% ede on 200 meh eve For seer purposes te fens ofthe ge has 0 Peover les oy oh Puan ws blanc sad cue ttinanee,cefabne wie ot Specie Hat tec mie hus which are genelyopgue and emai up to 06cm Td con component that tends to produce fine har“Sedincnd seat ‘on firing. The particle size is of paramount ‘importance in controlling his fk hetfvesnisryware gees proundio cians pense exp, 75% le han 10 ner dames Ovepaie e ‘tacts the probe wit undegadiog maf ahr be neesne "og whch i rn mayen blr ed npg — ‘fer te erinding operation he laeisieved and paid over magnets {getmove any adventitious ron-bearing materiale The glaze iv now "3 2p" i terms ofslop density and vscory. The actual valves will depend on Whether the ware involved ist ‘The viscosity is alo controled by the addition of such alts as calcium chloride. Any sediment in the glze ub after Goceclation with eck nt clectolyc ha high “sedimentation volume” whieh, when mechanically ‘agitated, may readily be dsperied into the hae slp. ft lane spendin i too viscous then deflocclans, such sodium silicate, alpen bocioot hheametaphosphate), may be asd tine ane” the ep were Other additives, suchas gum arabic, gum tragaeanth SEM: (sign cxtboxy methyl cellulose), may be incorporated in the glass apecion te help preven the died glaze from bring dodged from the wer pronto the firing operation. Less than 0.1%, on 2 dey weight basin of shee “hadener" ie normaly requted. has to distinguish, by the suction ofthe plat, which wares "easy fred” and consequently has a higher porosity ‘The slop glaze may alo be sprayed on to the wate: this method of ‘pplication is universally adopted in the glaing proces for ranitaryware Lead Glazes Lead compounds are wed in gate formulation snc lead imparts brilliance, smoothness, improves flow properties and generally givet a beter glae finish. Lea les ate very tlernt offing condition and hhave a wide matuting range. Led isinroduced into glaze compositions ‘sentially aslead bislcate fri. The modern low solubility gaze (low sat sully compounded from two fis, ie. 2 lead fet and a borax fe although che use of a borax fit isnot esensal. Typically a lead glare ‘maturing a 1080°C without ny borax addon would have the following. rolecular formula:H IE | itd solsbilty. These fits are wied inthe walle indaty ocho, 015.K,0 02030, 085 PO, “The lead biscte fre wou formula approximating to 015 AL0, (25i0, td contain 3 few percent of ALO, and have a 1.0 PDO 0.08 A1,0, 1.86 SiO, For the vas majority of ad gles a bora it add, Ie ia relatively cheep material and enhances the properties endowed. by. aie 1a compounds and at the same time decrestes the fring tempore oat ‘planes he maton OKO oxo} osaio, f2350: 0.3 PbO. 6 BOs Although itis commen practice to wie lead and boric oxide in two pj posableco produce alead boronic twithaconael, “scatve glaze” effec. The lead boroilicate behaves i s'powteal fen ‘hich reac with sreen printed designs to produce 1 dfs boundery together with a heavy relief pauem, This type of “reactive” decom, {ives an atc cece which & quite dixinclve Leadless Glazes Lead planes always have the diadvantage that they have wo comply with regulations to sfeguard the health ofthe operative and ultimately the Percuer ofthe Enihedglost atte. Inthe put ladles gazes were not too bilan and had a poor witifieation range. There ae nowadays many ‘cepuble commercially avaiable ladles glazes. The nnn faxing agents kl oxdes (K.0 2nd NO), alkaline earths (CaO 2nd MgO) snd Bene onde (B,O,. I is common practice to use thes glazes in the {pbleware industry and to havea “lead-free” factory thus voiding all he ‘tilaionaocated wih fad containing ana etd rmulatinga ladles glaze the (Na,O. must be kept below ia prs since gh allh ce covet eo fone = with hig Lins (C0) tecfore becomes an important yy tp TolNeve, there are imitations to the use of CaO, since igh lime 7 £5 fend to devin (crysallae out). To prevent te formation of ~ 3 ii ‘cate crystals, ALO, must be increased to help. prevent ‘isifston. The introduction of 8,0, ais in fuxing the {Eger conulsent, and at the sume ime eedaes the tendency {Teettiation and reste glassy phae with a elativly low expaas Thetefore by appreciating the role of the consiuent onides the Bla ‘echnologi free to formulate enielytatsctory ladles glen Opaque Glazes 8f opacity i dicted If igh falls on 3 black objec then by the very matre of it appearing black light isabored the objec refeasal ‘The base methods of producing opacity ae ‘Adda substance which remains undisoled and suspended inthe fed Incorporate a substance which causes evolution of fine bubbles diting the glos fire and which Become fosen in the gny mattis oe cooling. ‘Select immivibe constituents for the glae formulation, ég. certain ‘concentrations of C2O and B.O, give an opaque efece Opaque else wedi the cram nds are nelly peodced by the nechanim outlined above, Le some inoliilty of he ensceey ombined with is soition nthe molten gles ubiequent Syl: Tue dope ‘of light by fier is related to the ‘The degree of sxtering of Hight by any opacier is slated co the Aierence i caine ina beeen Pa ae ees ae ‘efactve index of typieal cl gle Sand common grace Reactive ‘nde Tania 250 Zirconia 240 Tin oxide 204 Zircon 196this bass icon appears tohave the leat acceptable refactiveindex and ia the best Rute (IYO, mincrad is wed a8 an opacifier but only ia ous enamels that are Ged to ls than 850°C. fed in plaves Unt are ‘to 1200°C then solution occurs, the glaze developing + "yellowish and since no re-erystalitation occurs there fe no apacty. “Tin oxide used to be the main opaifying agent bu itr oe his now been mtinved snc iti fr too expensive to we ara glatecomponent. Glare ove been developed co accommodate nzcon at the opacfier. They are quite acceptable and extensively wied in the whitewate indy, "Te vircon mineral wed as glaze opacfir has the following typical gnicl and physical properties I % 2:0, es SiO, 369, f ALO, 03. Z Fe,0, 0.05, TO, 02 Tie alia black beach ands of South Australia ate rich in sitcom and oot bal he wort’ soppy anne’ ftom there depos, The Sadie waited and benefited soar Inthe UK the verb ground toa tery Be specfeaton ting» speily designed vibro-nergy mil Pot ‘eomple ssarple o be sed ar an opar in the ceric ay sy fovea ace ares oF 40000 el (Avacompaszo, tnd topo thee io paspecive fin or quar: md grosnd fore ta body foralaions tos parle ste approniating 105% les thon 10 meron dame ‘whch corespends fo a sorace are of about 6000 cm'lp) sco may beaded srs mil batch component ora addin othe fi. cons ded to the mal bach hen opacity of the resling lat aspen manly onthe insabity ofthe fincly ground virco pares Some patces ay dsolve an recep on cooling. However, te Gari sae of the recrystallised material i important—09 icon lamer gives the optimum opstcton nthe feiting proce the zon is dsalved, bu he gle consining the fit e-rysalse ding tke flo fre, as prevouly deserted, producing cys of suitable ne thereby opacitying the glaze, ‘Asp melt cones fora nary argh xing the , 030 04 Za0 81 Meo 0210 0325 ALO, (3.0 Sio, led Approximately 10% addition of suitably ground zircon would be includ ‘withthe other component inthe mill batch. The glaze would then be {ground to = definite spcitiation for example 80% less than 10 micron diameter. 6. coLourS. CColoue manufactarers produce a wide range of colouting agents oF stains which ae used extensively chroughout he ceramic industey. Within this context “colours” refer to thee commercally prepared colouring agents and sais ‘Whitewares may be decorated wsing colours in various ways, for example: Coloured bodies CColouted sips (engobes) Undersglze Coloured totes and stipshave a faw percent ofthe desired colour added to ‘he bulk mix during preparation inthe sliphouse. The major diadvantage (fusing coloured bodies i that shading ofthe ware may occur. This arises partcularly in colours that are sensitive to hea treatment in the kiln—the femperature over a croseection of any kilns never entcely constant "Froma manufactur viewpoint coloured bodieshave the disadvantage that there is always the esk that other non-coloured ware will be ‘contaminated. Generally, aw materials wed in colours ae in themaclves ‘quite 2 diferent colour in the raw state compaced with the fired commercial stain. For instance, cobalt oxide isa black compound but when talcined in a stain—a few percent is saficient—an intense blue colour: reaules, ‘A ceramic colour seldom consiss of simply a colouring oxide or compound. This fact is best understood by considering the following “Cobalt Blue” coloce known as ROYAL BLUE or MAZ BLUE Reve % Cobsleoxide 45 Whiting 10 Fline 18 ‘luring 5 Feléspae 2 ‘The colour may be analysed in eerms ofthe fnction ofits components:| writewares hate — this is the basic COLOURING COMPOUND giving an intense blue coloue. sing — sctsas a MODIFYING AGENT, that isit modifies the blue colour giving it a special blue tint nd seabilty. and alumina — finetion a3 DILUENT, ie. they cea a file P ging hy weaker ts more sable le i — Eafiandaidsinering of the colour component during the calcination process. : ‘Nu that underglse colous may equre only sal ect of x inthe over of 3, bu oe gti Colours may haves very high petsntage ‘high as 70%. i _ ami clos ae prepared to fined and carefily controled specie fn Evensoit is dficl to produce decorated ware of coniensality seommercalsale Ie be remembered thatthe fil color wil sho oon comportion ofthe glare Ein semonpere fring terperture | parameters are especially important jn the sanitaryware industry the finshed produc is sold t0 an exact colour standard. Vitreous iaryware is generally coloured with opaque paste glazes which have 10 ch other coloured fittings, in the cloakroom and bathroom, manufac ued from quite diferent materials, The metamerism phenomena (see age 282) must be taken into account and it i for this reason that tryware coloured glazes are formulated from colour and compatible se plze to an exact specification, F Production of Colours Weighing ond mixing. The ingredients are weighed out in a batch ‘weighing operation and wee ground ina ball mill. If successive batches are tobe the same itis very important that reliable and uniform rave materials xe avilable. The slop material ftom the ball mills pased through a ‘chive coats seve—80 mesh—and dried out ready for che next stage, 11 thas the calcination proces. * Note: Dry mixing in the ball mill may be acceptable for ceztain colours |.) Cainaion. Diferent calcination temperatutes have to be employed depending on the particular colour involved. For example, CHROME TIN PINKS requir temperature of 1250-1300"C with a strong oxidising leew muna EBRARY] m8 atmosphere, whist CORAL RED (e page) must not be calened to 2 temper in exces of 100°C. tis temperante exceeded then the sed colour turns to a muy green. Ar a general gue te cakinaton| sempertse should at eat bel oo ger than the temperate = which the decorated ware is fired. s ‘The calcination proces then 2 mox importan fctor in prodecing high quality colours is incre are out she the colour elt say ot develop and och fal Shing of the devorced wate mY ecu, Ths is endent ithe eee ot the acnaton prose considered Athigh temperatures solidateracionsacur which ate reaponsible for the actal production of the colour. An example of this Phenomenon sexplined in the production of bac and yellow colout {sing irconivm and vanadium the main components ee page 40). Decomposition of aw mates may ocer on henng various es tiny be evelved, eg. O, and CO, fom onde and carbonates, ‘The calcination process must be totally and completly efferve otherwite gsevolution may occur when the colour hae been applied to the wae. If fhisis the eave then “spitting” ofthe color to undecorated areas may cccar Teaving the actual decoration in a spoted and unacceptable condition, ‘Colour manufactarers generally carry obt the eanation of colour in enclosed refractory containers (sggen) and at all times carefully control fnd monitor the Bing proces Grinding and Washing. The next sage isto wee grind the clcined colourin bal ell uni al he milled material capable of pasing through a 300- sesh seve “The ground colour may require washing to remove soluble compounds that may have been formed dung the aleination proces. For example, a chrome colour may require washing to remove Soloble chromates that ‘ould otherwise tend eo give a yellow halo tothe green stain. "The wet ground materials filter pressed and dried out to give the final colouring agent oF stain [Note that some fiker prewes wed by colour manufictarers have been ‘alaptedso that the stain can actully be washed i iu atthe pres-eake tage luring the fiker pesing operation, Ceramic Colours colic range of colo s commercially svaable—no atempt ha setnFaade a cone hs spectzu here=bet ew wellknown sane ae SERRE Lad te mechan of cloar formason bey explainedCobar Blues Cola oxide ican extemely son feet adele iui ogveaninen ees acs scour canbe modified secodng tiene ee compounds A pel icp ROYAL BLUE i: known a MAZARINE or az be ea ba ey Been etree ex pge Sh No AZ sen cobs ints MATTE ble igh sky blu esos and to known a Tard "8 colouring compound. A few be, Typical rege 9g Akemina 5 Cobalt oxide 25 Zine oxide 2 1 gfe cba suminate—any sen the exp ted den the gh bls color since cobale sce a ney waa ft dh “The rong and dominant cobalt bas avo % Cobate oxide 40 Feldspar 6 Fline 15 CANTON BLUE is another blue colour modified by the introduction f{abariom compound. The recipe iin fice the Willow Blue formekngy plus 10% barium carbonate. PEACOCK BLUE recipe is based on: % Cobate oxide 3B *Seandard Black 7 Feldspar 45 Fle 15 "Standard Black stain is formulated from: Cobale oxide 20 Iron oxide 56 ‘Manganese dioxide a Chromium seiquioxide 68 kel oxide 8 bia es ee ae MULBERRY is nae cobalt stain that i modified to a purple clot incoduction of ma i mganese dione. A typical recipe % Cobate oxide 16 Manganese dioxide 48 Felipae 3% Cabsitn Body Stains © Fact that alight offewhite hve ma} cobale (blue) compound. Typically, fo eof tain added a 6000 parts by wel “whitened by the addition of carthenwate type of product |p The sli fori normally eb chloride CoC, 64,0) The advan of using the saluble form ave Freedom fiom specking No preparation of the cobalt compound i eguied Ik readily disperses in the body mine ‘The staining is very even throughous the mie ‘Notes The clay component hat + lige surface area and is capable sbrorbing about 85% ofthe soluble sain, The remaining 15% shoe me ress waters The insoluble ssn is made by mixing, calinng and grinding the fo components Cobalt oxide. 50 Fine 3 China clay 3 to pass 2 300-mesh seve Chrome Colours Chromium stquioxie, CxO, is sociated with many eslours. Cr in a sable oxide and is dark green in colour. Another soasce et Gas ppotasium dichromate, K,CrO,, 2 bright onnge colomed cece compound.The advantages of using the soluble sat ae: KO supplies certain amount of x ‘The CxO, that is produced is more reactive, Better mixing of the constituents occurs ‘The main diadvantage is that colours produced withthe soluble sale ifuoe ropely cain and washed tend co give a'yellow halo tothe sens flour. chrome Greens Recipe % C0, % Felispar 15 Flint o ‘This purelar formulation gives a sage green colou. If lime (CaO) ie | added a + modifier it brightens the gre shade and produces giecwe colour tat is commercially very attractive, and is known as VICEOR GS F GREEN. A typical recipe st E s eee a waingtsr 8 : Bee 3 Be 7 | [psn pra ty eine emp j brown patches that are likely to appear. A recommended flux is based on: f Redlead 70 i Flint 20 | Boricacid 10 | Obome rin Pink : k Recipe % f Tin oxide 2 Whiting % Fine 9 Potassium dichromate 3 ‘hs colour must be calcined to approximately 1250°C under oxidising ‘nditons. Lime helps to stabilise the colo why Since chrome colous ase grec is might well be asked WHY | formulation gives 3 pink colour Te is poxslated that chromium is absot! 444 very thin layer in colloidal form on the tin oxide thereby producin Pink colour. This very thin layer of chromium reflects light at the red ¢ Of the visible spectrune ‘The colour i prepared in che usu way by grinding the compone foscther in a wet state—calining—washing—regrinding and washing. Cova Rea Recipe % Lead dichromate (PCO) 74 Red lead 7 No. 8 Flux 19 ifisa ed coloured compound and when calcined wi {he other constants produces a bili td sain, Nov 8 Fly sb compounded ftom red ea, borax an fin in ate oes Since thse colour contain high proportions ofled ts quite pore set high “lead release” value ffom oylne deecoian? Finally, it should be noted the wave decorated with Coral Red shou not be fied in exces of 1000°C—too much het tre the ed eto es smudiy green Cadmium and Selenium Colours hse sains ae sociated with a brillant ange of yellow, orange anv ted colours. Typical recipes 2 Cam . (Clcincion Colous eben Sulphur spe Selena raat yellow mo 82 oe os oo m gS rey So = mss ah 3 3a ‘The ox wd with hes colour most be "sft"—eati witha low meting point and lees, Sulphur fiom the colour would rect with sp that was present to give Black lead sulphide.“Typical fox recipe: Boras 2 Fluorpar 1 Ceyolite 6 Soda ash 5 Potasium nite 2 (Quart nd 4 his rage of colours i expecially suitable forename kiln cempestees, Stoney oxidking condiont ae undesirable Note tat the colecegg fect 8 de othe exitence of oi cation of emia spas od ‘admium selenide Gold Colours ho apes fom rd pink and vi colours co metic gl, Purple of Cassius was originally developed by Dutchnas x 1685 Ie ‘depends on the reduction of gold chloside (AuCl) with aumron ce ade {SnCl) to give colloidal metalic gold eis the colloidal tate of he hele dispensed gold that produces the purple colour, by the sane meckenn detailed fr Chrome Tin Pinks ‘A Red Gald colour can be produced by adding gold chloride tothe sop lze. A small quantity of sodium carbonate is added to give sight alkaline conditions, followed by glucose which acts ss 2 mild radacing agent. On firing this glaze a red colour is produced. Metalic Gold ‘Two main types of gold are used in the decoration of tableware. 1. Liquid or Bright God. Essentially tis gold sulpho-resinate,contaiing 17-11% of metallic gold. The metalic gad i amalgamated with mercury and a trace of bismuth. The amalgam is dissolved in sulphur balsam, ie ‘urps plus sulphur. Rhodium metal i zometimes added. 2. Bumished or Best Gold, Gold is precipitated. from aqua regia ‘olution—separated, washed—and mixed with a spedal fx consisting of Bismach iteate Nos 8 Fox page Wn Ml onthe qty ofthe gd dconion Silver chloride, upto 3 maximum of 254, to brighten the gold Ace the enamel kil Ge (750°C) the gold i poihed or burnished wsing a acd brush or agate stone—a process not requited for bright gold. Zitconium Staine {Anew and excing range of ceramic colours became available in 1 withthe introdaconofstconumvanadiom componnds® With reference to colovformlatons and, muchaniam of col ‘ormation the following nomencauce must be clearly understood Zisconium (Zr) and refers to the element only Zirconia "= (2:0) sitconiam oxide Zircon = (2rSi0) sieconirn slate ‘Ammonium vanadste=NH.VO, ‘Typical coloue recipes: Int ne Blue colours, are calcined to 750-500°C, yellow and orange 1200-1400°C, The colours are all washed and ground very finely average particle siz is2.5 micron diameter 0% les than 23 micron. fe fssenial to mix, calcine and grind comecly otherwise faults may occ ©: pin-holing ofthe decoration and variation in the shade of colour spiced kereetentasenrens oniiies Se ceate Repsie Whitewares composition, Ia there type of cal ‘anadiom, enters the sirean eeysel that reflects light inthe blue regio Te must be noted tht ritcon es | | | hese percentage compositions ate“ ‘inthe proces of being formed 2 ‘ince yellow and range inde 20, esis ard fet cation The sen mys sordant for the inorganic chromoptore in thane ee 2 ‘cadium whch sabsoriedonvo tense of hearers ie: hd sve commenty day be subjected tos de, bur on ‘Biiniom aleswsed sso moreane “Seed. Thealaminn tis dep oro SiOsis present so that the ‘sed in the textile industry. A brie arhing the dyetus removed. fan bYior tthe dyeing operation the dyes sted inthe fibres ofthe cloth and tis causes the dyestff to be permanently sbrorked Ihorgei hromaphore refers tothe Colouring fon, they can be mixed together co form a stable sees. For exam, | EI atria fag esc nage of clon tan Heese % ( Zion me ' fie Ba | ‘Ammoniom vindae “48 [| Miesentty mitre ofthe bead yeow sain \ [Modification of rconium-Vanadium Bive Colours ; MSthoms modifies the blue co give a trie colout, Zixconiam Bosphate (2, 38.0) is sed fo intra the phosphor Avery ‘oint of phosphono i reured-—sbout O5te—the clout esken iis amount eneceded A greet 15% Mno,, ro15% lou & produced if manganese is added, for example, sa ype aditon, Ifthe manganere dioxide isincresed 2 Brey serren clover Replacing Vanadium with other Elements nthe Basie Zrcorium- Varad eee ium Blue Sees Zitconis- Manganese dioxide —Grey Zitconis-Chromiam flooride —Grege Zitconia-Texbims uorde | —Yellow Zitconi-PrateodymintnoxideYellow ‘with the exception of the pracedy brilisnt yellow. Thiscolosparteany welinowns aeerecir ed cally wellknown—therecipeis based % Zirconia sus Fine 301 Prateodyiam oxide 0.) 49 Soditim fueride 3.3, ‘The compounds are weighed out, mixed snd eaeinated to 1250°C for ‘hour, ground and washed ‘Modiication of Chome Tin Pink Stain ‘Chrome Tin Pink has become a rather expensive stain bette of the istve prec of in oxide Teas found that aatfacory pink tan cold ‘be produced by paral substituting nitcon for tn oxides mariznane of 70% of the total weight of sini permisible—giving a medifed recipe: % Ziscoa, 568 Tin oxide 72 Whiting 22 Porasiom dichromate 28 ‘The potasium dichromate is introduced 8 25% (by weight K,Cr,0) solution, Conetusion should be moted that theztconium range of ais ae extremely sable.ive to pastel shades that ae very much in demand sively ¥ andar colours choughout theses ern REFERENCES, orl, W.E.Cley and Crome Raw Mawr ri Appl Scene Publ, 197 {Worl WE Corn ew hol, tna at Goons Tee Be Se | Beirne RES CER Te ete te tema TR eid ia Sr ee i Further Reading 1 baal WF. Clye—Thit Nate, Orgs nd Gener Peper: Mae nS a i Madre sn Sent 4 Joab Rand Ball A.C. Geos Clin Tey Pergamon Pre 1986, ~ el i Chapter 2 Body Formulations and Properties INTRODUCTION ‘The formulations and propesie of whitewate bodies tableware, sanitaryware and ter--cover 2 very wide tange snd there realy no ‘efiniibe specification and property tat can be atibsed to any one body, ‘The values that have been glen eefer to pial values for basic body formulations nd inno way repreenta mathemati ean ofthe available information. Normally one figure only fas been given to strate the typiea value that might be expected for 3 given propery, but a range of valves Hat been quoted, eg. unfred module of rupture 450-600 Ijin? (62-42 kgleme) where ies thought to be more appropriate. In addition tothe basic standard recipes, che authors have, in selected ces, given actual fctory body formulations to iuseate the range of Formolations tht are available “Tableware producte may be ether porous or vitreous (generally assumed tobe les than 1% water sbsorption, The vitreous products may then be subdivided into opaque and tence ware. i "The following body formulations and thei propenves ae discussed in this chapter: EARTHENWARE EARTHENWARE TALC BODIES VITREOUS HOTELWARE HIGH ALUMINA BODIES STONEWARE ‘CONTINENTAL PORCELAIN ENGLISH TRANSLUCENT CHINA BONE CHINA SANITARYWARE, FIRECLAY SANITARYWARE WALL TILES