Document ykd6xG4OV3D939rGLRJY2K4Zd

I . i 1IN 111 M M H .I ' . Llf-21512 LEAD INDUSTRIES ASSOCIATION o 0 CAST 41ND STRCCT NCW YORK 17, K. Y. December 13, 1957 SU3JBCT1 SnPPLTy?.T TO "LEAD 1ft THE CERAXIC INDUS TRIES" To Kenbers of ths Lead Industries Association! Enclosed is ths first supplement to our technical data book, "Lead in the Ceramic Industries," issued in December, 1956* This is being mailed to ell of the 5,COO people connec 0 ted with the ceramic Industries who hare already received the book and will also be included with future copies of ths book sent out in answer to requests for it. It will be followed by other ruppleoents from time to time, some of which are already in preparation, y?r^ truly yours. } O WHOP *JP M** I n* IIIJmi L. LIA21513 ] SECTION & p a m rxiii f------- vvszg'- o o t-k-- mr ENAMELS rOR APPLICATION TO GLASS* < Comparatively little ha* K*en published ami the prop A* the CAKfficient of expansion of the enamel it in erties of fbu enamel* in *pite of their wide use on creased, the strength falls off rapidly. There is a notice* many product*, e.g^ multiple tnp beverage Kmlev able weakening of the glass even when the Coefficient* z cosmetc containers, miiing bowk, casserole*. turn* of glass and cnemel are similar. When the expansion o Sler*, lighting goods structural gU*s gift glassware, of the enamel is ten p*nni\ higher than the g!*v sport- H among c m her*. lancsMs cra/ing will ivcur and frequently breakage o In the development of gla* enamel*, there are four of the glass. The heavier the enamel n applied, the properties of primary ccnvccrn. These are liability of greater will he the xtrrm. composition, chemical durability, coefficient of et* panoon, and melting temperature. ^"hilc these prosper* Malting Temperotur~Since all enamels are ap < ties are Jiscuswl more fully later in terms of specific companions the important cvms*dcxatksns arc out* plied Ia> articles of pre-formed glass, it is es*<ntiaj that the enamel has a melting temperature far cn*sugh oz lined hrieffy bekm. Kdow the vdtening point A*f the glass that the enamel Can he fired to a gskkl jkvss w iiKh j ( causing tiefoenva* Stability of Compoaltloc-First the composition tHn of the glass. z of the flux must he such that it will not doitrify under It ^tHer omsuteraihsm such as staKItty of cx*m* normal firing ci*ndit*His and second. it must rvM he [VKitkn. chemicaJ durability, and cvicffiesetst <>f cx- sufficiently chemically reactive that compswjnj* wtli he pansMHt need rmt be cn*idorod. then the priipcr mefi- fsirmed which aJvcrcty affect the .o*or. ing temperature would m itself be a scry easy goal to 0 Cbamlcol Durability' There is an increasing de mand for enamels which have an extremely high re sistance to acids and or alkalicv I namch which come in contact with lod must resist various acids and sulfides and concurrently resist achiese. lli*wocf. *o pnxJuce an enamel of sufficiently k*w evpansisKi, with pxsJ chemical durability, and a mehmg temperature sufficiently kw that it can he fired tn articles of glass without any warpage or diUiniod prewmis difficult problem. : the alkali detergents as used in auuwnatie dishwasherv foe tumbler decoralHn there ts still v*me Oefland tie Typical Compodtiotu of Enamel* soft, rv'O-revistant cokrv hut as the Use of mechanical Table b-2 givArs the ci*mp**sitkns kA ten tv p*cat com- dishwasher* increases, ink type etiainel is going way fywitKins ranging fr*m the 'cry kmeM md'mg. rvw- to tK*se having greater detergent resistance. Multi- resasiant type to the higher melting varieties with tnp hocragc Kittle enameh are subjected to repeated excellent chemical durability. Ihcse c**mps*Nj|kos will washings in strong. Km detergent solutioGs. NLh c re serve to discuss m**c fully the conuderatkMYs inv*d*cd cently there has K*en also a demanJ f**r ACT t applied in their design. v4or label) c*hr\, which ml] withstand KM acids, particularly hydrivhkHic. since Ksttlers have found this acid to be very utaMc for rcms*sing inn wains resulting from the n.c(ai closures. High aod-resistant colofs serve best in the field of structural glass where act iwlig lkr 1*4*11 (*kri * *m * f^* 4>*-T !< ***( *** 4-|l *t.(>,i(i * mt>4* m~4/w colors arc subject to attack h) weather. Cot&d*Qt of Expansion-'Ute problem exmeern* attaining sufficiently km thermal expansion rnamcfc to prmlucc a xatisfactofy Hi.** A* a general practice it can he stated that an enamel, to have a goiwJ fit aw the glass on which it i* applied, should have linear coefficient of expand**) aKnit three point* lower than the expansion of the glass. For example, if a g'atv has a CAiefTicient v*f HI x 10 \ then the enamel should have a uvnflicicnl of 7H % | 1 r levs There * little chanor of having lex) km a coefficient of the enamel, which could cause checking or weakening of the glass struc ture. * Ray Afdirsx Mmu mt . Ulm ('tin I>h mw s I f IhilnilrU A Ciwnpan). Iixnpttirt, Xtdwfha. Fa aiu nih b a i.< quip* N 1657.01 ! ............ l SECTION i I fAOl K>Vt in win i.jm^jii LlA215l^ // Flux Ho. 1 C'onijVKiininx such as this. which arc C'aJmium oxide, which is a gtxsd fluxing agent and r extremely km melting due to their high lead content, functions in this respect similarly lo lead oxide, k ted to desimfy i*f crystallize if subjected to a high used in lead containing enamels foe the purpose of temperature lor a prolonged period. When a flu* stabilizing cadmium sulphv-seJentde red pigments. L Jewlrifict, it ksex its gl.*\sy surface and a Urge in* NMicn this pigment is int'iduccd in a lead flux not crease m expansum tveurs. One flu*, has mg a co containing cadmium oxide, (he mixture w ill Are bUct. efficient id cxpansitso of 75 a ID * increased to 1441 x In I **.'*, a demand arise in the glass industry foe |0 * alter desilnfkalKKi. In the exent dcsunficaikm fluxes which would base gsxd chemical durability for j. occurs in this type cx*nipoutk.m it can he corrected by either- reducing the lead or increasing the silica c*n use s>n bsMh tableware and hescrage cootaincrv As a result of this demand. w**rk was started lo dcsckxp tent. As null he rxded in TaMe b-2 (hit is the lowest fluxes of giwd chemical durability. melting comf>**itktn and attempts to attain lower mch* ing hase resulted in fluves which are so unstable they flux No. 5-This c\Kngswjikn ts an cxevUent ex ifesttrily during a rv*rmal hung cycle. I lux No. t will ample of the high fluxing fxmer wxJmm oxide. In iV I disuse compkfcly in aN*ut ten minutes in a wdutk*n of 5 percent acetic acid. Its a*kali resistance is e\ esHiipartng this with flux No. 4 the melting tempera* lure was increased imly twenty degrees in spite of the tremcl) poor. substantial reducik*n in boric oxide end increase in r silica contents. fluxes of ihis i\p< hjs< fairty giwJ Flux Ho. 2 The rcJtR*iitn in lead and increase to alkali resistance. When tested in accordance wuh t!se i silica C4*nlcnt increases the firing temperature and de- Bureau of Standards rxc*mmendcd test, this flux the coefficient of cspjnsmn. Himocr, there is showed * lead v4ubiltty of aN*o( 5(XI pans per rnilUwx. only a slight impnnimnl in chemical durability. ? I luxes of this type dill find wwne application where km firing temperature is essential and chemical dura* Flux No. f - As desekspment w*k continued tf was (tHind that the introJucikn nanu into lead fluxes hilit) is rud an important factor. greatly increased the acid resistance, f/mo V < umJ h are quite similjr except that 4 percent titanium Flux No. 3 - The lead is further reduced and the dioxide has been added and the alkaii has Kxn in silica and hortc oxide contents increased resulting m creased in order to acct*mm.Klate this addi(k<n f a increased melting temperature and lower expansion. more refractory maicrul with no increase in melting Hi'weser. this ci*mpssitHn still has sery psv chemical temperature. The lead saluhitrtx i*( the flux has been durability. reduced fren 5t*o pails per millkn to only Kt parts Flux No. 4 1 his coni{v*sitkin represents inc of the early attempts lo prmJuce a lead cimtaining flux which wiHikl hasc improsed chemical durability, A cvn* per milh*n A recommended pftvcJure mcorpv fating tbc Bureau of Standards test r> included elsewhere in this section. posit nm of this ty pe is siiM quite soluble tn dilute acids Flux No. T -- I his c*mps*sjti*n employed lithtj in arut is subject to attack by sarkwrx alkali detergents. combination with sodium oxide as sevtHsdarx flutes. Perhaps the outstanding characteristic of a composi* Because there are sery few glavo hasing sr h*gh a lin of this type is its km vt*cffiCH*nt of ctpartsion. coefficient of expansion, thrs type flux windd hase a - TABU 6-2 Tffdenf CaiwpariWani ml OWsa Bw im AihMlCMfwlM -- e PVO M>| VOt C*0 MfO T0 Ut VO% thiMH C**N(i*a mt (a 1*-^ UW ipmt% pm >! AMI tnliii.w tJ fi N 4M 1*4 ta * raj 444 444 u 144 44 144 114 - 14 IM * llO 1014 not lt *47 m u nn mMM f*r ItJ 111 414 m 404 444 14 14 Lt 14 14 it .H4 W4 BJ 11/ 0*4 B4 44 U 44 14 14 14 14 44 44 14 44 14 44 4.1 44 14 14 14 14 1J - *4 *4 . 14 UM 111* no* lM no# t13* *<a4 k*4 HI UJ w **4 r n W N n *1 KM 4* a 44 tot \m ***4 *~4 Iww u N*ti n liluki mm JJ' WW.' 11.^ ^ PBmWWWWUWW.jlUjW LI A21515 UUh iTOlaAi SECTION 6 fAC4 KVt <<* o w V H < Oz z O TV# \--4*4 fJait tfli rnt*4 1m* tiVil t**t--a*r !* tkttmml 0 ' it * >* > K limited field of application. Hoxxocr, ihn flux hax xerx km Ic^J xoluhihty and pos%o*>o excellent Kcathermp characteristics a\ needed m the tvid of unKiur.il p!a>x. Dux No. I lhi\ vom;*vution prox idex fo a dec h mw in melting temperature x4 aNnit 5<t I*, reuihrnp oocriuJIi Inert the ineteaxe in the (cad oxide and decrease in ultca e*ntentx (ax comparid ith the prokxn. fluxi. IScw \ almiKt no change in the ctvflKicnf <4 expanx**! hut there n a marked increase m lead .oluhdit). Thix type eorrpoutH*n offer* the |***.uhdrt) of doit* rfkatM*n in writer faxhiiwi than hcreii4re drxCuvxed. II merhred the lead oxide may cxmhtne nh titania to form \ctUm lead titania and adversely affcvl the .<*W. If heating ix e*nlmucd for a pn4xngcd penial, xorttoent de>inhcatkin ma) txvuf and touh in Lk * ot pl**xx ard greatly increased coef1k.icTrt *H exjunwm. I Ik - conJf<**n can he impnncxJ by reducing the alkak < Wad oxide and increasing the utica contetxiv Flux No. 9 With the dcxelopment 4 compout om similar to No 7 the problem of aetd rcuxtancc became loss mjv*rtjnt and aMentk*n >n turned limardx at taining greater alkali resistance. It *a* found that out* standing impriHcmentx m rcu\tanee to alkali delctpentx C\uki he achieved by adJutom <4 /irciimj. In rexpect to chemical durability I/win Vo. 9 m**J 10 meet the requirement. 4 the hottlc trade xerx ulnfactiKiix U.mcxrf. {He ox'fhonti <4 cxpanx*n <4 No. t ix high. flux No. 10 Thix comfxKition prox tiled fH a re duction in ^<xdkK*n( i4 thermal cxpanskei. Ihe alkali flosutdex are valuable ax fluxing agenfx and are alw very hcnchctal in the dcxelopment 4 bright fexK. Ihh prox idex li*r excellent *ctd resistance and tux proxen to gtxc ftxxi xerxtee m the fWd. Sumcvpy fftamdx for plaxx can he roophJ) divided into l0 prxHJpx. the Wm rexiUam of rv*xn*rexjWanl cnameh 1 Hmcx \r*. /-4jand the rexadant tjpeenameH(Flusrt Xo $-101 lead oxide tx the primary flux in pUxx ctxamek. Ksric oxide h only rrv*dcfatdy active ax a fluxinp agent; hrmexcr, it h extremefy valuable for the reduc ing of cxveffvient of expansion. It Imcn chemical durahililx xerx rapidly ax it tx mercaved. Cadmium oxide ix xaluaMc ax a fluxing agent and oxentUl ax a Uahilucr fsK the prxxduciksn t4 bright rctN and cadmium xdUmv Bsrh xisJium and lithium ox idex are xaJuaNc a* fluxing agent* prsnidmg fie the addition c4 larger anvHintx of xilica and fi*r the intnxluclion of mania and /ircxetia. Ihe alkali otidcv Soxocr. rabe the 4**.KAJ* ,* fam/r cW. fim Wa m kaa Ka i#a im a n Ua W fi+rm--H* '5B \ giiiipx'ii,wuir^'^g LIA 21516 SECTION 6 coefficient of expansion very rapid!) and reduce chem ical durability. The alkali fluoride* are good flute* and aid in the development of bright red*. However, the) increase expansion and reduce durability. Silica attributes materially to chemical durability, especially *c k 1 resistance. It lowers the coefficient of expansion and increases melting temperature. Titanu b valuable for tlte improvement of acid resistance. Zirconua b essential to the product too of cnamcH having g*xvd alkali resistance. Load Solubility To* Malar!ala Raqulrad 1. 50 giarm glass color ground in alc*thol and stater. 2. Glass lea cups or nappies of about 150 cc. capacity. 3. Standard lead acetate solution. 4. Hcm/'s distilled white vinegar. 5. Several 250 cc P\rev beakers. n. Hydrogen sulphide. Procodum Fifty grams of the color being tested r* milled in a hall mil) with about 20 cc. of a mature of 3 parts w.vter and I part alcohol for a period of fifteen to twenty mtnulev The 4\if is transferred to a spray K>tile and two or three drops of 40 percent w Ju ik w i of m.ipncvum sulphate is added. This wilt improve the spraying qualities of the color considerably. After they are sprayed, the pieces of glass are )laced m a kiln or furnace al aixwxt 7UMU8 F. and the tem perature earned up to I lUU i* II 50 F. depending im the exact type of color being fired. They are hdJ at this temperature for a fwrriod of ten to fifteen minutes and allowed to coot in the furnace. Fhe color is then ready for test tog. One hundred cc- of Heiru'i diuilled white vinegar b placed in a 250 oc. beaker and brought to a hod. Thb h povred into the cup w nappy being tested and allowed to cool for exactly one-half hour. The vinegar b then poured back into the original beaker without policing or tn any way disturbing the surface of tbe color. Hydrogen Sulphide b then bubbled through the tead-cenuming vinegar for a period ai three and one-half minutes. The color developed b then com* pared with (he color of fmhly prepared standard*. Standards A standard solution of lead acetate is prepared by dbvolsing lOK mgm. of lead acetate CP Cryuab (Pb `C.HjO.I,* 3 H,Ol iu Heinz* white distilled vinegar and then made up to exactly 300 cc. One cc. of this wvlntiun is diluted to 200 cc. with vinegar and placed in a 25-0 cc. beaker. Thb b equivalent to 2 parts s*C PbO per million parts of vinegar. Two cc. of lead acetate solution diluted to 1 Otl cc. with vinegar b equivalent to 4 parts PtO per million, and so no. Through this standard solution K bubbled hydro gen sulphide foe a period of three and one-fall min utes. The color of this standard uJuttoo b then cxwopared with the color of the vinegar from the test. U the lead vduNlity of the enamel being tested exceeds 20 parts per million, the color of the vinegar after bubbling the hydrogen sulphide through it will be so dark as to make comparison inacruratc or impCKsihle. tn thb cave, it rv necessary to take an aliquot and dilute it to a suitable concentration. We have hnind that for most cavcv a 25 cc. aliquot diluted to MX) cc. with sitcgar works quite well. In running lead wduhility UVv it b advisable to run all of them in duplicate. If the glass bring used has an expansion of more than <*0 x 10 !*C. it b advisable to warm the cups or nappies to w atcr before jounng the vinegar into them. This wiQ avoid break age. Color comparison should be made in diffused daylight do a white table lop or other white material. c MA'..1 iMnio.il