BE741888A - Treating glass articles containing an alkaline metal - oxide - Google Patents

Abstract

One surface of an article made from inorganic glass containing an alkaline metal oxide is put in a liquid. This liquid contains a different alkaline metal in the form of an organic acid salt. The surface is put in the liquid at a high temp. and for a period long enough to exchange part of the alkaline metal in the surface layer with the alkaline metal in the salt. The glass article is removed from the salt and cooled. Use is with inorganic glass.

Description

  

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  "Process for the treatment of glass articles".



   The present invention relates to a method of treating glass articles, including the glass components of the articles, to improve the strength of glass articles; it also relates to the articles resulting from the treatment by the method.



  The present invention relates, in particular, to a process for treating silicate glass consisting of silica and one or more alkali metal oxides, with or without one or more other compatible constituents. such as alkali earth metal oxides, alumina, zirconia, titanium oxide, boron oxide, glass coloring oxides such as iron, cobalt, nickel, ranganese oxides of chromium and vanadium, as well as refining gents, in particular, it also concornees articles in silicate glass resulting from the treatment by the latter

 <Desc / Clms Page number 2>

 
 EMI2.1
 - "t <" f.% µY5Ôd '* ** glass "ntilîséoe 1 l fiz;, ± nze disrràrtiov,:;

  . denotes the w rres inorgoniqv? s f? ui. 3 s, "nf cï'it & HisMt, 1? Tà #. + D8.aUre cO.4'trSl:. :: '! .-' ;; '' Í. That JM sn pauter, al =; - . pyetMiï "- ';; used ::: rr.tller: ent,; WîJi' ure dobby <:: rj $ 1 ;;: 11" '"lino, 1.abid: e"' ""! l! ... ns a "" 1ttt:! c of \ <;: f'f''f! ' before a Carçositian <ï @ tCT "" $ '? ; a = - the ccmicsition initiais and 1 'there c: oositiot1 d. crystalline; (2) 4'.1i snat dur ynië. r4 contr81a1; 1 by a treat: have tl.e: rrit1 '..! i: ce: (3) gul have been <: res- * lized from a r2nier controllable by a thermal.



  The glass q7at l tl..11 can crystallize d * t !!; # r "z, contr-81able niere is ha, bltuellerc,: 4t called co = position of zristillizable glass thersi.qï2ement, A crystallized glass is usually arpelled ' cifranic glass ". CoL-ze described in great detail, many opes of xilicstee glasses, noting glasses containing alkali metal ions, have been treated to high temperature by coutact with an inorganic alkali retal salt to change alkali ions. in a surface portion of the glass with the alkali netal ions of the inbrtanic salt. The conventional method is to immerse the glass in a slotted bath of an inorganic alkali metal salt or of an inorganic alkali metal salt with other inorganic salts.

   The din-errlon time is sufficient to cause this fch4n.ge unJ. '! UoJ :: le: r..t in a layer
 EMI2.2
 surface of the glass article. Lithiun ions from a glass with
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 were 6cngb 1.1 ternat1voz: cnt / scid and petMsi'aa ions in molten inorganic salt baths, Green sodiuad ions onr-ft6 exchanged3 with lithium ions and pota5 $ iu molten salt baths containing inorganic lithium salts * t of pams-
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 s1 & ..
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 your alkali metals have different titr-1., very ionic. as can be seen on page 900 of the 3rd edition of the Van Kostrand Scientific Encyclopedia, published in 19SS by% * Van Nostrand Co., Inc. ", Princeton. NJ It is the 1 ion which has the smallest ionic dîtobtre.

   The ionic diameters of the ions of others

 <Desc / Clms Page number 3>

 
 EMI3.1
 , 6 alkaline levels3 7ont in the following being: seaiaa, pot "sium., 1 '\ IbLUuI! And cesivt ie chiu!' !! 2yant 1 ... -. * The large ionic diameter.



  When more metal 11Ç>! 1.Íf! r * nplaco a more pelit ion of r-4-; tal alkali in the 5riçial layer of the glass t ne te1! péra "'re i.1'! {frieur au pcist 3e .iéforr.3.tion pn: Flnente du glass, the surface layer undergoes ai = -rs efort de coxTesxioa.



  ?, Areent, the larger! Cries tend to occupy the smallest spaces previously occupied by the small ions of al- caltas netal ions, thus creating the stress on the body in the superficial layer. Since the temperature of the glass is inferior to the point of permanent deformation, the structure of the glass cannot be rectified in order to suppress the stress of oppression.



  When a smaller alkali metal ion replaces a larger alkali metal ion in the surface layer of the glass, the coefficient of expansion of the surface layer will be changed to a lower value than that of the internal penetration. ïTe of the glass article, ent1n: mt ai.-i: n effort I cor.pression in the surface layer. We can perform this ion exchange moon temperature below the c '! Forr..3tion 1H! T'Mnen'te or dnt tecpëTtH.nre greater than the point of permanent deforration, go below the softening point of the glass.

   When we carry out the precedent of the sample 3.ne I have a tenperamer inferior to the point of JeforEatios perranente to replace a larger ion the alkali metal in the glass by a smaller ion of alkaline retal, we then heat The article, after the examination, at a ter.pratu1'e greater than the permissible point of erosion to erase the small cracks reducing the resistance, which formed during the treaty of exchange of ions. due to the difference between the expansion coefficients of the inner layer and the surface layer, the compressive stress and the improved test * 'tance obtained in the final product will then be due to
 EMI3.2
 the difference in composition.

   When we obtain, by the exchange
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 of ions, a surface layer having a net expansion coefficient less than that of the internal glass, the exchange is carried out

 <Desc / Clms Page number 4>

 
 EMI4.1
 , 3 '± t. ".4:".; .- j.,: Sit.ir. ": .- t ;." ",.;:. -l: J,; li -1; c; 1 ;;. trl,> - e>:> * int le Jfc <ri. <3 Fee z. iext #,.%> <Jw 3v & *: - 3y la f'y rAtion Jat craq.> ol.àrea lr7Jrt? x, tos, 1 '; i:': - 0 rO'lTJ'4hfit pM Ztro f '! "* r -: <t-to; la -Isrnif ;;;, i> Jfiii-0; K é = fl ± rit; ar * suuricurs att joisit -le: iéforrsticn? r? * tï) atet ..in rroc ± 1; K ->;,; n>> it il: rit => ar #. 5. *: istl'sy Jas9 <J; o j! LHe.tt? t U, 1. "" u ': 1'11? t * .dt: lr = * to <in 3jfa "4th Saiety" 45, non -2- S:> - 5J ot JtM 'Ji1 î.-yvet aat.tri <.> r.

    ; 0 1'tlVt n; tµri # Ji les% * Il iaor = x..ii. <. Ies 1 * iétiix al3Ï.i "n sr4ci ± 1 = aes a?" pr> priÀs s> 1;.; naa .'t, "J!? .rfi ,, -1 = SjJ ,.? ôl:? j. # '. i ntilàso esa .fiof JJ" J' ioert "izà ± 'Î% C c * Jt Tn 3? À ":' 1> à a '1n S31I 2Xt 5" (à.nii: o: nn 1: <1; .ix -3HjLtan' :, "'j.?. t'-Ia a <.3ti- * µlw. i: .i: rV'1tt; 1: tt'jri: ttr y? ent iffïta zalo Jo = 8titix; lenli # is yor 'utHisaUcH sc.is iarro fcn : at and va -1 * 1 *.: - hmn-o d'i? m3 avoc les 1 ':'; 13 la t ',} UY .11c: .1Hn 1 n er.'a, l "iri, 1 1); S 33.3j,: .u: s-yUa "t" fJ: 1t aint ÀeJ 5; 1, as-îl, i 1;.>: Z.inin .; 3 '9S .lé i .! '- <-; !! mia! i <"<, e'et - iya, Ut": ..;', h .., 11: "C 1 ': 1' ::! '; sz , h, 1. z-iëirix, i; o; - 1 LIS CS 1% sal9t nJe ': 3ttt ¯14 t -' 't3ri t, 1 "rée3 -Ir luit * 40 e'ïrs rni; tz .la 1: jion él;> li * "n les painn do fmisa sa r ± 1.ir = eant cet ,,, 13 .1iv-e: eZI3 dT r'jtx # a.lcaUnjt J - ,: 4 - f'U; J; (- ; 1 "; 11b.) ... t ''! RTttêlx ..

   H ': 1 & ST6 ges t.:t.Jr:' til1Je, ar .'chta- * d'i? N '3? *! T%? Issrw tT1 41e- clothes?: Ee! T -6 It les 1 le 9a3ion lc? {s 1. ces él1) 5, ''.-3 sols J. -etVIX IICIIÎnl J'ci1t Ir-Zrll'li-JIC3 ro1Jvu; t tr4, eofï'stif <at t9 '* ?? Atjtf <.ï'cï ', a .Pi'! L'J. 3a le, oInt -the fusion can vary with a # 'm' *: '* sï ir "' 3yn: iant # ac = wosîtion j of metal alcilin to the itîa lu makes! C4n; .o 4 'iar <this Jernier case ,, l "rs ;; a' un, 1" JI: 1'3 ::. 1 ion of: cftl alkaline 3ans le baIn 3 '<* 7l <te <a gy1.iS small ion d. c "tal alc * lll Jans le y.rre, the melting point of the bath took to be greatly increased * the sorting * one can use the moon bath just greater than the melting point of the initial bath composition , un1.nt during a long ptzîode.

   It is sotlhaitible of e ± f.ctu.r 1 * fchines a-, with the bath J-4, this is what the alkali retal ion deprives of the glass.

 <Desc / Clms Page number 5>

 
 EMI5.1
 # .i 1 ..: .i t: - .; C1: -; #: = 1 1 h, .. 1- :: t3 c a l <. # L ". J s: imx>
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 HC ',) L, se .li.? A; pr.:. 1l11 '; ur 1.3 baix do ûo-: itudra mappTOrrié for a 6ehan # o of ions ul? ràe # r E ± ¯jmrl r.Jx teEpëratuTes flevéc5 necessary f; iire f}' 1, -1re Self , 5, norganiq \ 1eS do alkaline retaux '!, these last z-3 z5oi-, t not pro? 2 * ius to be used $ ass back t9ryu? T -.!?!: A au%: oirit de defor- ration ys? r'23ta I B'src; % orzes, 'It o jt <29 la Fr; 5Jente iction 03t Jo provide a process using a nUic <ù'tchiar- à'i * bs y> iix: ant;} 1;' r0 c "lo" "'Ó to a terperature f'2lati? C.? At" .1 $ 5, s. = # .: l = "a J5m = ±; .z = # m Gilu6f} vec: a diluent 1 ... : "" ';

   , - 1 ..... ",,,,," - '"'" '""' '' '' '' '' '' ........ :: "" '.' ' ''. '' '' '1> 1' iters ions, .. ''; t '' 'tl1'; 1'es liqHa & csa t ''? Ture ss It? '"!: s.TS J * iî: Stsilic resions.
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 t'a n¯i; ro c; 1; jzt.?, J / pr3J <% rite "'' r ast -lo '' * Ô '' 13 # ro-"; 6 utili'1nt: 1 rat14rc 1: T "> r '" o 4 # iors #vP: lo glass and = l15 lci *> 1 la t:> n, eJr ûa ions #: 3til alsaliA #lJ ri'lieu r: is -9; knew i;> <; 1.nv: itre, pt dr tr3 f. weak'Bs, 41 sc? Ta que 1 *? Ri ': <de 1.i rm -'- ezt ii; ± <Lri <: ar to s-ii . C ritiLat = tJ HtUis' * os j; to # - <gu'B Frsett.



   j, ¯ ,, * ō,. *. A4> f # * o-ç 1 ,, -. ±> ,, o * ,, is expected i ;; yro; 1.14 ca # îli; an-t .Jn rHiTi; l'ér = ?: z # z,>:} - 3, ': ;;: 15 t or ::., in; 5 corx * csif ç, ie 1 # 5; "xti ± r>;? J # iliiµts j 'ityi'à' '' * '.' 'ln 3" <tT? "i-; j. # t + <TJvif.: '* S: ..'-' H -IiM3 1 # q i-al lcJ 3: M à.l? lncti 1 ,: Vu ??:"; v ? *; L; rT il # .à-iit #? = # Ù.iJ '. ". K ri-lie eà C ...) t3Ct> :. oe te v'j'T-3' <n 1-; ce 1. 11 y: 'ti * .l? *; ". ± a, bàli "ù = 1% coatzct.



  D'tTc subjects ct #ivict; ù.; S é-n 1 yf-J3 * ita inv-e; ïtics re5srtir; 1t '.le li 33 - :? Hc ei-f?;!.



  '1: ........ ",.;': / -? ....." ,, ',,,,,, -.....; "" 1 "" "'; '' '' '' 'ea # => is-3 "1!'; t" "'-" ...,., .. .. ",," ---- 0I'- "'" ' 1! ' '-' ï s's? ': t $ Iny "' '! cs "'.a t? & 3.ts.: * and 4'n Ttii: Ï9 93 yeyy $ H'" tnt la v-crr- *: ;;. zJ # <> t imfac * Jn ('0-1 r ± tal) - "<: 111n; l'rn .lJ jOO '!: J."' ". 1" '' ''., - 't -, - "," ""' '"' '' : '' "'' '' '5 rne te = .j6rature slilia * e' '' - l" Ej: rs: i3 .-? 3 s? '' Xl'2s 'm ten6r.m: Te snfflï?' '3t and "' 1.:!r.-!i !." '' '' .sxe? Rice aMfissXts - "'71T l' '' 'l'i1''e siiìsarTent elc #> ± é = -ônl ; nt .a = e #E; îrie "" '' - .. t- 51> 1ìsJat # y7: ar risîl proJi5e ua eo afir. trc 13 1, ons es = .3tal lclin 1, 1 Je l 'ac13e or: U':. 1t1: .e t les la.-il le t :: 6t: 1f.1x tl: T.Is. 1.v = - #
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 glass,
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 The salts of z-! TAux .1c: sliM: s .. 't des sils dhu: 1des crg-ixi.g.:is such as ac4âe -, $ elrioxyljq7aas tt It3 3, cies' Sul! O :: 1i .1es.

   The

 <Desc / Clms Page number 6>

 
 EMI6.1
 carboxylic acids can, for example, be aliphatic acids of 1 to 22 carbon atoms, namely formic acid, a-
 EMI6.2
 acetic acid, propionic acid, caproic acid, neodecanolic acid and stearic acid, aromatic carboxylic acids such as benzoic acid and toluic acid, as well as acids
 EMI6.3
 nsphtëniques.

   Among the sulfonic acids there are, for example, ethase-sulfonic acid, benzene-sulfonic acid, toluene-sulfonic acid and the two classes of sulfonic acids obtained by treatment with sulfuric acid. hydrocarbon oils, for example in the preparation of mineral oils that are clear like water. Both classes are, in the form of their sodim salt, known as water soluble sulfonate soap and soap.
 EMI6.4
 of oil soluble sulfenate.

   When the organic acid has a large number of carbon atones, the stability t3.era.qua is lower than that of organic acids having a small number of carbon atoms, so that the use of 'acid. 1 higher muscle weight is found at lower eras or at a shorter period. It is preferable that the alkali metal salt is a salt of acetic acid. It is further preferable that the salt is used with a vial.
 EMI6.5
 organic hicple. The organic vehicle is preferably a non-polar, non-ionic compound or a mixture of these compounds.

   The
 EMI6.6
 organic vehicle is used with the ad of the alkali metal of the organic acid in dispersion or in solution in this vehicle, followed by
 EMI6.7
 before the selected organic compound and salt. The organic vehicle is liquid in the 1-Ler case: net temperature less than 200 * C and is liquid at the temperature of the ion exchange process at a pressure greater than the at5phEric pressure, preferably of nitrogen or another Inert gas. Vehicles
 EMI6.8
 At most, they should only be partially decomposed. during ion-exchanging treatment.

   Nonpolar organic compounds are preferred. Among the hicu16s & pprcppi3! E there are, for example, paraffinic hydrocarbon oils, paraffin wax or wax fractions having melting points.

 <Desc / Clms Page number 7>

 
 EMI7.1
 relatively high concentration S5, that is to say greater than 65.55 ° C, polynuclear aromatic hydrocarbons, y short diphenyl, and aromatic ethers, such as diphenyl oxide and, of course, compatible mixtures such as Relance eutectic of diphenyl and diphenyl oxide.



   The alkali metal salt of an organic acid is used alone
 EMI7.2
 or in the organic vehicle, 1 an elevated temperature, between about 200 and 550 ° C, preferably between about 300 and 430 ° C. When using -sodium acetate or potassium acetate-
 EMI7.3
 Sium with the organic vehicle at about 371-399 ° C, contact for about 3 hours will give a little alternating layer by the abrasion test.

   The duration of contact with the glass surface for ion exchange depends on: the temperature, (2) the type of ion exchange, i.e. depending on whether an ion of smaller or larger alkali metal must be displaced from the surface part of the
 EMI7.4
 glass, (3) the composition of the glass, (4) whether it is a ceramic glass and (S) the thickness of the surface layer in which the ion exchange must take place. Consequently the duration pct be as short as 5 Kinutes or It '/ t1 "aecent can require a large number of hours, for example ten hours. The duration is also 3ëtaxrit, in: not restoring by the possible degree of dilution of the salt. alkaline organic acid from the organic vehicle.

   Of an unexpected consequence, in the event that the alkali metal salt of the organic acid is not
 EMI7.5
 not very soluble or dispersible in the organic vehicle to the terperate used for the ion exchange, a good dilution exchange can be obtained by putting the organic vehicle containing this small salt source, in contact with the glass at temperature. ion exchange. For example, sodium and potassium acetates are almost insoluble or non-dispersible in hydrogen oil.
 EMI7.6
 partffinic carbon and paraffin wax.

   Each of these acetates, i 380 * C, in a vessel containing the oil or wax * will be present under fOr8 of a thicker lower liquid phase and $ 61'.1'60. The content of #talalkin acetate in the oil or

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 EMI8.1
 1 = the melted wax will be "less than 1.11 by weight loé5qV? There are ten. Parts 4'ac! Uto. 380" C in a container containing Sl¯J1t 90 parts of any ortanic vehicle . It is preferred. qtJ.I4 the total content in the container should be treated with at least the weight of ac: 6Ute a -U1 alkaline, the remainder being essential for the vehicle and is essential to the body. &.

   It is very advantageous to use the vehicle combination
 EMI8.2
 Miaic and alkaline sêtai salt of an organic acid which is, only very slightly soluble or dispersible in the organic vehicle, at the high temperature used for ion exchange, After the exchange, the organic vehicle then contains organic acids
 EMI8.3
 Safe from the salts of the two alkali metal ions, the new Ition ion displaces from the glass and creeps the part of the initial alkali metal leion found in the glass, 4 appears: r: ten on a 6quiJDOlar base.

   The vehicle is 1 present
 EMI8.4
 cKati! 01t intoxicated by the new ion as long as he gets up to the appropriate subsequent use. However, the vehicle cools down
 EMI8.5
 after separation of the liquid alkali metal salt, if it is present under Ir for another lower liquid phase, at a t-aptrature (which may be less than 100 ° C) at which the mixture of salts of - ' alkali content will separate from the vehicle by cristoelli * ation * After filtration, the filtrate, ie the organic vehicle, may 1 ... r & ltà3%.



   The following examples illustrate the preferred embodiment of the present invention using the three types of glass as described above. Drops of glass, obtained from a furnace melt, were remelted in a platinum crucible,
 EMI8.6
 We detached from this molten glass, a glass cane and we formed by cuts.,. from this cane, sample stems 11 cu. in. long. The sample rods were approximately 4.76 mm in diameter. Some of these sample rods were tested for flexural strength, with or without abrasion.

   Sample rods were subjected to ion exchange by the procedure of
 EMI8.7
 1 $ pTésonto invention, then they were gradually cooled to

 <Desc / Clms Page number 9>

 
 EMI9.1
 avoid the formation of a tllenic tension, which e3ie. ea: aernt the resistance of the glass, and we elil "i. ':; then, without abrasion, where the oil and salt are deposited.) su? iz verrit du = ilie ;. ,, Î; T-. - t% treats% -et. Daus the example i t3xt of # ± Que le verra is of the type, that we c? 'Rttâ5s: <I'u3%: "". " tîrt coBtr3I? hjL <er *? # it '. 'txmtst "4. quI:'; ..." x 3 t'r, Tas'sf3â '' some of its stems are c "1ti! 1ons in vcyY" for the treatment of ion exchanges.

   Abrasion of the stems consists of shaking them in tanbour for
 EMI9.2
 1S ninutes in a ball mill containing No. 30 silicon carbide shot.



   The flexural strengths or the rupture nodurle have been
 EMI9.3
 Jftercinës using a Tinius-Olsen tester. This apparatus applies a load measured by a single cutting edge to the center of a sample rod supported on two cutting edges 10.16 cm apart (three point load). The load is applied at a constant rate of .885 kg per minute, until a break occurs, a marker indicating the highest load applied up to the point of failure.

   A microneter with a dial graduated in nn and equipped with a contact for bores is used instead
 EMI9.4
 of a contact on points, to measure the saxicuc and nminometers in the center of the sample with a precision of 12.7 nierons.



  Since few perfectly round smt sample rods, apply the load perpendicular to the maximum diameter and use the standard formula for an elliptical cut by calculating the modulus of rupture as follows:
 EMI9.5
 Ilodule rupture:

   (10.185) x load Modulus of rupture: - # - # "" '"' -" "Dl x D
The modulus of rupture of this formula gives the flexural strength in kg / cm2 of the area of the cross section at break.

 <Desc / Clms Page number 10>

   EXAMPLE
 EMI10.1
 A glass of the following composition in weight percent was obtained by melting these feedstuffs in a large continuous furnace: Sio2 71.3 A12o3 17 YiC2 1.8 MgO Li2O 3.5 ZrO2 1.3 P2O5 1.5 P2 0.1
 EMI10.2
 , f3 0.2 RO2O3 0,

  03
 EMI10.3
 This glass is very close to the look of glass indicated on page 25 of the prior patent application mentioned below and the loading dobby used was the same and the amounts differed somewhat from those mentioned on page 24 of This application The glass had a coefficient of thermal expansion of about 40 x 10-7 / C The drops of glass to force the rods were obtained from the glass contained .- = in the tank at the time
 EMI10.4
 had the glass been cooled to about 1245 ° C, then they were melted in a platinum crucible to obtain molten glass from which the cane was detached.

   The heat treatment of some of these
 EMI10.5
 iges.samples pcur forcing a ceramic glass was similar to that shown in said patent application of Killian E. âith, q, a is mentioned in the present description by way of reference
Glass initiated? had an annealing point of about 655 c.
 EMI10.6
 Go <of ceramic glass obtained from the heat treatment were slowly cooled to room temperature over a period of four hours.

   This ceramic glass had a coefficient
 EMI10.7
 Average linear thermal expansion of about 6 x 10-7 / ace Various mixtures of Duoseal pump oil and sodium or paraffin and sodium acetate were heated in a container at about 383 * C.

   Obviously, at this temperature, the two mixtures were liquid, pump oil or paraffin constituting the upper layer and sodium acetate, the lower layer.

 <Desc / Clms Page number 11>

 
 EMI11.1
 re, put with a small quantity5 of sodium acetate being: 3ànj lilwile Je parme vu la raroffire, "': 1 ft:, zrtiel1e!:! nt shoed the container with the rcye-n of a lid, arrs aycir dipped the rods flicker from the glass and the ceramic glass 3in the layer of oil or paraffin, the cover has a small hole rerr ttanf at the "apcurs de 3écowosiioa de s' éct;." f'r late: r.ent. ! "ab he was providing positive pressure through these ea-ors.

   The samples were retained in the rfci "? Ient rendering if: different periods and the following results were obtained which idicify the flexural strength of the untreated rods:
Glass rods
 EMI11.2
 Diersion duration &
 EMI11.3
 
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<tb> hours <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 4 <SEP> 5
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<tb>. <SEP> in <SEP> weight <SEP> 2.5 <SEP> 5 <SEP> 10 <SEP> 20 <SEP> 10 <SEP> 10
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 iluite de ponpe ou, -aruffin, 1 en kingés - 97.5 95 90 80 90 90
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 her;

   iz 3t at .3 1.12 "s $ ', a 3.64 3.99 3.92 4.97 f1.! resistance with abrJ! Sion x .3 (kg¯Oà x 10-) 0.91 1, 26 1.9 they 1.47, 5.î J-, 36
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<tb> Core thickness <SEP>
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 conpTessioa, mî-
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<tb> notches <SEP> 105 <SEP> 98 <SEP> 28 <SEP> 110 <SEP> 124 <SEP> 132
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 Ceramic glass rods
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 Duration of immersion .. heU1:

  '$ 4 - 3 3 3 3 4 Sodium acetate * t in weight Z, S 5 10 20 10 10
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<tb> Oil <SEP> from <SEP> porpe <SEP> or
<tb> paraffin, 1 <SEP> in <SEP> weight <SEP> - <SEP> 97.5 <SEP> 95 <SEP> 90 <SEP> 80 <SEP> 90 <SEP> 90
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 Abrasion resistance K - (Kg / cm., X 10-3) 1.68 2.94 3.64, 6 $ 4.20 4990 5.32
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<tb> Resistance <SEP> with
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 (kg / cm x ït3 ', 1.40 1.26 l, 8Z 2.24 2.45 3.71 309
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<tb> Average <SEP> thickness
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 c: omprfts.sion. mi- .12 -21 cro- 11 16 22 21 30 22 .., r.! if:
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 Po & T get the resistances. multiply the indicated digits "!" t * .. 4. '#######

 <Desc / Clms Page number 12>

 
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 par * 0 jAr excr; 10 1012 yrsetc ms doj 1.120.



  The above Glotnx- * 3 counter that the thickness of the surface layer of the stress of corc5, lon can vary over a wide range, for example <10 to 2CO "tcyons and which one obtains products without abrasion more resi3tants. Peir d * 3 products relieved z abrasion. the roillo'ars presd'jitat must have a mire qu 't \ blt! l1o ", ino coiche sinca having an effort of c, rc5sion.



  The Y41.r nîni-, 4n depends on whether the glass has been crystallized prior to 1 & bler3t, er.r'3 10 # a # trin at; s given '3 * in table * For example, lor3-kills the ion of : -H'11 alkaline is ec.: 1n: ': S towards U: 1st stress layer of eo-rcs51o of 30 rlcron "the glass' c6r3ilie corservera 1 plus gyJe part io its resistance t" lio? O with abrasion , t4n11, that a 1-level Sur8rieuro splitter is necessary for the -lino earpojiition the glass under forne: rlstal11, blc. In the case of glass do t'exe'-le 111. l'Eraisse.> R is SO rlcro.



  What leaks comes in p3 '! T "! U? I. The pysc3 la: resc: 1te1:' 1 \" O '; 1tion can be r2lis ec9te * tx 1ant 3 uses it *, Ceat 11tres 30 nitr2to do seilui p8soit 111 # 57,> ,; and c,:, - 6.erîient 6.520 F, tai!: 'J! i <read the K-Sse \ .clu: c> 1 <.> 1é on 1-1, r: 1C's in rolls., 1 t .c! tt., dt sollur and il> arties et 7CIls dtil0; jr !! iie c3ter31t lion ¯¯¯ - --- xr "': ïî.



  ; n a, rj1r des tlees I glass to '! xrtir U * tL-it e9 "? ctioat de vcrro the silàco, the alu" i-tie and.! o Sou.l.> the 1 * iiréll * nt; Following f> i orJr-; àt <: 3 x3à.ls Sio ±?, Fi AI 12 0 2d # 2 T15, TiO f.r176 this 1 glass) Flrtlr = atiéres chirg * making this glass 1 to be fried. r-atl-ires e-ir; e E21sant to melt from the ;; classic naire well co = ue -our C4 ty * 'e your *, The glass had a co! ± riint of expansion t4% ernlitit of about SS x 10 * '/ c, ± 1a placed the tizes of glass la.-It a Teipieat, in

 <Desc / Clms Page number 13>

 
 EMI13.1
 do paraffin foaduc, We will give below the results of the tests
 EMI13.2
 carried out on rough rods after inversion in melted wax during
 EMI13.3
 for about 2 1/2 hours 3 310.C.

   Resistance without abrasion of glass after ion heating: 2.520 kg / cn2 Resistance without abrasion of glass without ion chain: 840 kg / cmZ Thickness of the cor'pression layer 22 nierons. rM "ei Lx III Oa repeated the procedure of Example II using glass having the following composition in fear-one hundred by weight: 5.43 Al103 26 N20 18 T10: The glass had a thermal expansion coefficient of 93 x iC, '4.

   It treated the sample rods for S hours at 33J * C, where they were tested and the results are repeated after: Msist & ee Ju verrc arrins 1 '<chinqc d'ions rais à: * ant 1' & l-rasioa: 4.333 kz / -: sitca du v> rro: 1) '1.n suffered 1': c '> icas after abrasion: 3.3O kz / cnZ Epjtisï'jf de la <; Jcl: e Je cc * - r; ssin: SC riercns. ic:. pc # s ": J-3.I," t'3t vcr ...: var "'1: l0" t'le; 1 SsieRtific iyy'! S: ol1e. : ii..jlwi.i at3.efu be uallip4 <, ji '! ns the jg * -i, as f vi.1e. t'.st una 4 il1! . ' i ay.i àil.ef R339k!> 1; .. r11 :: é: '11 '1r'! lch st.! ; '; sp csnct, frhtl1tSU sx.IwAbrxd'irr 7ànsi <n I wr ti S'5 * C: .J,;? ± ± 31 rn do n b.s ôùzàité aa.t. ' .-u '' '- q.â> ây: 9Y:, y..ris' 23 * C:; l ', lr "";,' 1t1 ::: al 7; zr> lf # <} $, = i ttic1t: a; t 4, 7 .lJ..1!; ' -Y-Y4 / <t. ïsr '' 7, ':

    S Vl1c? Litf "Siyòlt 2àcOlÎLà; lv: r311" 1 1 î S4 Inlice of YiJit $ {t, screw): 9! P41nt 3'éClair ce 215 * C? Oin ± 4'if! & 11it! : 24P * C P41t of ecoexent t -3 "C 1 '= iô:, uurs: t nàaùoe The do pjtmffiae wax used in 1., 8xë: ples 1 lll, <1 t

 <Desc / Clms Page number 14>

 
 EMI14.1
 she ** S (moco 5512 "having a melting point greater than 6StS6 * C.



  It is sold by "Sun Oil Company" It is a narrow boiling fraction obtained by fractional distillation of paraffin wax obtained by removing waxes from a fraction of motor oil obtained from crude oil *
The present invention is not limited to the specific glass compositions, including ceramic glasses, of the preceding examples.

   They illustrate the invention not only for the types of glasses which can be considered as examples and they also illustrate the possibility of applying the invention to many types of glasses which, until now, have been subjected. to ion exchange using salts of inorganic deciduous alkali metals, as well as other types of glass, especially silicate glasses, containing alkali metal ions which may
 EMI14.2
 Ion exchange Otto smmis, V.A, 'ieyl tt E * C. Marboe sound, their book Entitled "The CcM: tit.s.ï of Glass" volur'e 11, prerl-1-re part, published in 1964 by "-7aterscîtnce Publisher8", a division of "John Kitey z Son.

   JftC.P :: C Ycrk. .Y.J concerning many types of 1-iorgenic glasses CU'3ct '! Rb ti <:;: e. Some of these types of inorganic resins are not generally useful in the present invention, except that they do not contain alkali metal oxide and. therefore, are not useful in this te! 8weatlon which. Requires an alkali etal oxide. that is, an alkali metal Tell ', by oxygen, the basic structure òr-211L'8t the' 1'81'1'8. Examples of glasses useful in the present invent1 ... oa silicate glasses, alkali metals $ ¯taX ..leaU.As silicates containing ua or oxides $ of alkaline salt $ "" Uuax 4IQ.1 state- 2-your ïvm-rt is that Weyl and Parboo call! 11- #? 6 of metua alkaliu..uux alcaU.tto-tenwx, slssiaasâli <Mt-es de Jli1; aVX alkalis and borosilicates de tlcalirls.

   For example, the silicate glass useful in the present invention II) ''. lei "ftrns d..11ke / .: i1" tcu./oxyd of alkali metal the glasses of $ il it toxydo of tît4moi-wave of lai .1a.11n. from em that worms

 <Desc / Clms Page number 15>

 silicate res of this *! alkaline / plonb, which are listed on page 4
 EMI15.1
 from the book of 5.B. Shand titled "Glass Engineering nandbook", Zero Edition, published in 1958 by "Me GraM-Hill Boom Company, Inc." w.York, NY, Some phosphate glasses contain an alkali metal oxide, cosre can be seen in paje 581 of the book of 1: eyl and Harboe mentioned above and these glasses can be treated by the method of the present invention for wearing articles in accordance therewith.



   It follows from the above that there are many types
 EMI15.2
 of silicate glasses containing silica and an alkali netal oxide. Some contain one or more other oxides which are the likely or actual glass formers; and some of them
 EMI15.3
 contain other oxides as diricte'lr! of glass, these expressions being used by Eyl and "a -.- boe. These chirdquel elements are shown in table XXII, 7aj; S, l'olvre (published in 1962) of the aforementioned book. Certain glasses contain 1 la both other glass drills and other glass drillers.

   These silicate glasses containing alkali metal oxide oxides are made up of the following bodies, the quantity intervals of which are indexed in percent by weight.
 EMI15.4
 r.xr oii $ i0 '"S-3S 5-3S'" "20 1-4S
 EMI15.5
 
<tb>
<tb> A12O3 <SEP> 0-40
<tb> CaO <SEP> 0-15
<tb> MgO <SEP> 0-28
<tb> BaO <SEP> c-15
<tb> SrO <SEP> O-15
<tb>
 
 EMI15.6
 12 3. ;

   bone
 EMI15.7
 
<tb>
<tb> Zro- <SEP> 0-25
<tb> Tio2 <SEP> 0-12
<tb>
 
 EMI15.8
 w7aliapF "'0-2 ±' rpo3r 1'1". o'io
 EMI15.9
 
<tb>
<tb> As2O5 <SEP> 0-3
<tb> Sb2O5 <SEP> 0-3
<tb>
 
 EMI15.10
 U20 represents the total content of alkali metal oxides of 1 and # lot3that 1 # alkali netal oxide is 1it & i oxide, al.

 <Desc / Clms Page number 16>

 
 EMI16.1
 ? otxssi; =, 1'axy * ie 3e rubidiu = oa the oxy3e of ceslun, it ccastitutes a <5tiT'UB of enviroP 2Sl in; OÎ * s lc the glass cpositicn. Ljt content of alkali retal oxide which must therefore be laced in the key. superficial 3M- another ex4vdt of - tal alczI: n, is, preferably, at cins 2: and * for other glasses trat cer1niae $ glasses. it is r? rer.ent; iÀi, ra ± it is at least 5%.



  For glass cositi9ns which are thersi- quenent crystallisable to form the glasses cEri # 1-1 # es, 10cxyie 3'an; 1 = ci; e where arsenic oxide is part I the ratiére of Cr.3r1e to òr, -er the glass. 9a uses either 11 of each or 11 in all of the two. They are used coe agent dlifflr-açe or oxylatlon. Most of these oxides are lost through evaporation in the glass furnace, so that the final glass body will still be contaminated by no more than a few percent lixi-res. arsenic oxide as a refining agent, a small quantity of sodium nitrate is also employed in the charging dobby; however it is not enlivened.



  Cn e-plo1c .habitel1er.cnt fluorine, under strong salt in the r4tiére load, allitive horn, in an amount not exceeding x4-ntrale.-ent not 0931 by weight in the final contosition. Fluorine is believed to promote crlst311i $ 3tion, but its content in cos'- '-osltlon is 11 - it -' * '. a low value, given that it is the morning cry. sometimes with an undesirable exothermic effect. "Within the limits of this cost of glass, it will become apparent from the photo of this that there are narrower lines at the intervals I quantities d4xy - ,, C '$ individual according to the oxyles present for forr- Create a c02pfttiblo relaunch in the form of a melted Russian which, after cooling, will pour into a glass.

   These glasses themselves do not form part of the present invention. They are rather the types which are treated by the process of the present invention for the purposes of the articles, made of a-61ior6 glass. -

 <Desc / Clms Page number 17>

 
 EMI17.1
 after different classes of glasses falling into this dropped nr.e. in order to illustrate the smallpox cited I glasses useful in the present 'Ire satie: ......--- .r ;;;.; - ..; * '*.' - ¯ ¯ The v r: L: .Zc ..: 115 simple containing netal oxide the COrX6 indicates on page 17 of the Cotte in3iqu il book. dough 11 from under Yra 1.'1t: .¯ '- :.

   P .... c..l.l1ana - ,, blié 1964 under:;! ' fcrt-e d ': # e êJiiiÀé ---,>; Lraî; e? 9r "Steelworks Near: Inc.", Xeu York, fer.-e .. ::: ee; ..: "': .. : ¯ (.I1.ne -jar "Acaderic Press ne.,% Eu .01": -., .SY, one can prepare two-sided glasses for the cosbisiisoss of alkali metal oxides with silica, boric oxide or phosphorus pentoxide In the case of silica, the amount raxinuc in: a3es t of alkali metal oxide is limited as follows: 4M for lithium oxide, 47% for sodium oxide and 5f01 for potassium oxide. Has a higher oxide content -
 EMI17.2
 of alkali metal, crystallization or de-vitrification will occur during cooling of the molten scrap.

   The replacement of one part of an alkaline retal by another in these binary glasses, according to the process of the present invention, would require
 EMI17.3
 generally factors of duration and temperature which are not economically feasible at present. In addition, mixtures of alkaline octal oxides in binary silica / alkali metal oxide binary glasses have expansion coefficients up to.
 EMI17.4
 a r'axisue for a specific ratio and a partial exchange of one alkali metal for another could give rise to an unreinforced glass.
 EMI17.5
 this. It again appears that the Rolaire percentage of silica should not be too high, nor too low, when refilling.
 EMI17.6
 place the sodium with potassiun.

   These expansion coefficients are given in Table III, on page 496 of the book by uyl and Marboe mentioned above.



   In view of the foregoing with respect to a binary system, the preferred glasses used in the present invention are those containing other metal oxides and / or other glass structure formers in addition to the alkali metal oxides and glass. silica. Below are various examples of multi-component glass systems.

 <Desc / Clms Page number 18>

 
 EMI18.1
 



  One example is the class of silica, one or more alkali metal oxides, and one or more alkaline earth metal oxides. A classic example of glass in this class is silica / lime / alkali glass, such as that
 EMI18.2
 used for v'r1'e, window glass, shot glass and rtci- # glass. t .. 'I! "t. ..... .. '...... chili peppers. Dm3 <these glasses cO :: -. = special. netal oxide - alkalkno-., -'" '. trre: .tx. fl; g ':; lrAnt ": from' Lime 'or an oxide Kêlaaçe of c $' lci! tB and .de raar.i", 6énne 1. 'en.-found in lolonitic lime. The '"'."] I: -de t; i1-s- vcrres' cOPJ "'. Eciaux is. The Nivaate--.' .



  , an'poacc :: a-cids: "'-1. th militia, 1:! - 161.de concern # - is 1,'":.



  .......> ot ..o .. 1 .. "" <¯ ;, ¯., ....... 13t \ P ': 9i2; d: cfe r.sgnds.ât eri to 't,.' aoit a-i2.wdE'o, xrâc-: y. ¯, 'caitiùfi, ètlt "# 1 d &? ZtfiJaiet.' L .alu!: 1ine- 4S t pt '$ èn t at -nts <7Í'fJd t e'n-v !. ". ro l,;,.:. o, '. ez:.: itr ét; ; rerr "ic :::. while, for glass in receptacles, it is generally about 1, S-2, S \ ,. ais exceeds S in some cases. We can ignore this glass having a low content of urine, to ion exchange to improve its strength, but after abrasion most, if not all, of the strength increase is lost and
 EMI18.3
 the ion exchange treatment is therefore only appropriate when the product is not abrasion-resistant during its use.



  However, corrc described and claimed by '= il3.far E. Snith in a related patent application, which was filed in view of the fact that the present application it is possible to provide a silica / pxide glass.
 EMI18.4
 of alkaline earth metal / alkali retal oxide, containing that small amount of alumina or not containing alunine and pms-reduced due to ion exchange, increased resistance even after a high degree of abrasion . The glass compositions and ranges of glass compositions disclosed in said William E. Snith patent application are included in the present specification as a refractor.



   Another class of glasses falling within the wide range of alkali metal silicate glasses is alkali metal / lead silicate glass, in which the alkali metal oxide is the oxide. potassium hydroxide alone or with soda, that is to say sodium oxide,

 <Desc / Clms Page number 19>

 
 EMI19.1
 = 07-e ir..li'l6 ae t: 1ble: 1 1-1 .1 la brje 4; ! i'f're of 5b: l1 = whole? r.né above. Similarly, another class of VC1res is the tcrosilicate glass system, viii is shown as glasses 10, 11 and 12 in Table 1-1.
 EMI19.2
 



  Another class of glasses useful in the present invention
 EMI19.3
 ccr-takes alucincsilicate glass exposures due # vise; alkalis, which are! written in the patent application a! "ery8in" 'n lsl.8F7, filed on 23 yars IPCZ # on laiq * jelle are based, in part, on French patent n * 1.329.124 and the suî patent -africain. not* . ! / = 35Z. This claim the anërieain patent Jbnne the broad inter-
 EMI19.4
 Values would follow for this coosition, in weight percent:
 EMI19.5
 5-15% silica, at least 5 and preferably 10% alumina -.% * And iris. 510 -251 of a20; the content of alumina and; 320 constituting, preferably, at least 151 of the
 EMI19.6
 cor position of glass and these two oxides plus the silica constituting
 EMI19.7
 at roins 35Q of the glass composition.

   It is indicated that the bivalent oxides of netax, potassium oxide, boron oxide, titanium oxide, phosphorus pentoxide and fluorine are present in an individual Raxirun content which can reach 10 and, enser: bie, in a raxinun content of up to 15%. It is also understood that the oxide of iit3it: r may be present, but should not exceed 11. Since these limitations are crude to obtain a high strength, after abrasion, these linitations, although they are preferred, do not constitute a
 EMI19.8
 limitation to the present invention.
 EMI19.9
 



  Another class of glass from the broad range of alkaline siltce / oxide glasses * includes lithium silicate glass disclosed in US Patent Application No. lSt..8S6 filed on March 23, 1962, to which French patent no. 1,329,125 and South African patent no. 62/2352 are based. The 3reCan patent application mentions that this glass contains 46-88% by weight of silica and 4-291 of lithium oxide. For 1 # este possible, this glass can
 EMI19.10
 contain alumina, because of the ratio between silica and alunina

 <Desc / Clms Page number 20>

 
 EMI20.1
 Nice kidney 2: 1. It therefore appears next to the glass cladding to be the binary type referred to above $ rit $ # when there is Italurineu it is the retal alkali alunlnosilicate, reported above.

   Instead of leilurins or part of the cI side, one or more of the following constituents can * and present: zircono, titanium oxide and boron oxyJa. ra o: tr *, d'aittes & 11os = la r.6tx alcsl1ns pytvent Otre
 EMI20.2
 pre3ents * notlrnt the oxyjo of sJliu; and llox> le patsssiun can be preferred in r3n * te-t, 3 ties of plorbate oxide (PbO) ot fluorine, in a total entity that can reach 15 roles 1. rv14crAnt, crt3incs 10 these lirlttio5 s'311cAt 1 of the eo * -po- .1tlons which -hnnent the resistance: 1co r: c3nl1'1 maxlrur. abrasion *, -also they do not constitute a bond for the present purpose in the broadest sense.



  Uno aatTc classifies the glasses cctrnt Jes ion Jo retlix alza- 1 las "our l '-! C1.'In; el' l: 1s -> re; 1 la cor-> titiTa I will see Jécràto in the tlgra.-lin - the patent aeetic3i.-I n * 1? 2, .SK? '.! *: the 23 rirs 1' !, sir la.11. are 161- * tsxs the tr * vet rr1; & 1s n * 1.3Z9.1 : 6 and the patent J-Aftictin fi- 62 / 233t.:, An! Cotte J! Cr'Anïe the patent a-pl.rlc2ino on.-E.-4ti> nzo that this 43 vert * is ccsti- 1- 1 fr..f.! R..c.

   J f1.t> in3 *; rils, tlfcote # le tzite 'tta-it la silica, sa --- f si 1 ci = -zcsiticn C9yps Ilexyje le 1 (+ hi :; rule slîl est,;,: r5-ent, ne 3 <, àas * ra not 1. \. o]? $ iéàdfli oi, aaf, à., ell * * àp% enô .lvs - à ;;. qé-lhntS <6 # ntiÉlq], É * - éi $ ൠ/ Baet. . oz $ iè3:] a: = / za> Jx "bivâi * ntJ ':". i # lÀ' éé lô- 1. "h *. ¯ = -. ¯., ¯ -. #, J> g ., .. ',,;,, ç; ùJjµi.t. <, i - #; -., = ¯j = ¯i,% ¯> .'r. - ¯, jj: r .. =, ,,, <j;, g.% -, - - jj, jx: exrao: - .. yi $; '}!, -.



  : $ µ $ iéÙiwe] ltnµ #) qf51 flx # 1 $ @ flji #fOE> fi, - ± j * é> fi '0 # µ; ¯i $ WhQ ± f1 .i'; '-.



  "; tiil, lin" dLilÉ ffl4r, '' "Y.gÀqµ ,, ù = o <îltaī'ait 'izdrs" ÎSiI on pÉ iàÀ. "the glass tet: mijrc, the c-oe $ it1.,: t can be the following t by * xer1> the 60 to 7SI in silica polls. S at 20% by weight of zircon # and 2C% by weight I oxy., e I Sediur. To describe some I these l1rit & t1ons. not concerned with the iorr4tion <iu glasses are not lin-

 <Desc / Clms Page number 21>

 
 EMI21.1
 The American patent darando z 2bzz255, filed on October 4, 1962, on which French patent n. 1.375.995 mentions only glasses of alkaline earth metal silicates /
 EMI21.2
 alkalis, which may contain alumina, boron oxide and
 EMI21.3
 Various suitable inorganic oxides can be ion exchanged using alkali metal salts.

   These glasses contain more than 40t by weight, except 65-751 by weight, of silica, 0-15t by weight of boron oxide, -33'1 by weight of alumina, 0-2SI by weight of boron oxide. calcium, strontian, oxide I bar> min, plosb oxide and / or zinc oxide and corbinations of the latter, ë = 3 4 'titanium oxide 0-10 % potassium oxide: sodium oxide and / or sodium oxide and / or sodium oxide and / or sodium oxide 2. Typical compositions of glass are described and are sourced to tcl.angos of ions to strengthen the glass.



  The dC3r.le% the African patent no 249,790, filed January 7, 1963 # on 13o11e is kissed, in part *, the South African patent n * 63 / Sv19, ro: tio .n que des c:) ositio: 1 = glass analogues 1 those of the c31 do patent & r3ricsia 2ricltéo, on 1.olle is b- * s8 the French brief d- 1.31S.9SJ pcvnt Stro scrmises to an ion-ectin. These writings are 55-75t in 10 siiics, lC-2Tt e pi1s Jfox! E 40 5011-J <3''5% ï3s to oxide do pot'jJiuJ 3-1st in ytids I oxidize I csci: : ,, C-1 ± 1 in. ro13% do rag-iesiel, 0 * 51 in al. yfids; 7ixe and C-5 M. çcills d'oye da barj "Jn.



  Cn can r.l cor some pittle from the X7. do co.i,.: pan "of the oxyJe of potassi: at an? 2lEontal o ... ta'4 ,. prior patentÎ1j n- t!% 3t. <46: O: t.è ,,,, 'ï. ia jkÀwi * =. ¯ 1963. on 3x ..., -, a'ii ast tt * 6, n rti.' 1 * t * r and sa-Xï-ieis.s * "e3 / s11t described & '& utt. clisse de c * atpOE * iiJhns do veoe *, '6i "* on%'. keys silicates of early alkali cont:; t da la r1r.si. otlou da 111 * x, v-le de ic. with oa alu- 1-0. In the etal oxides <the & Hs3 -terM'ix may be absent '.' -C.m '"or * these ccntoienneat earths, more than 401 in; olJ $, by <tx <jcp < 5? S # do silica.

   C-4 ± 1 3'lu-, S d1cxr. of calci1. = a; # 1sie, to * stte: Hi.ts <of OX1b of b s :, of oxy3a da pli # b and / cu 3'cxy-

 <Desc / Clms Page number 22>

 
 EMI22.1
 of zinc. as well as cont'in: J.ison :::> Ù-0 es -.yaieys, C-1C axydo of titanium, 0-la% potassium oxide and 2-201 sodium oxide and / or of litiiiun oxide, Hereinafter, an exerts da this composition
 EMI22.2
 of glass :
 EMI22.3
 Percent ea weight
 EMI22.4
 sioe ss-70 Al 203 1-30 1 'sO and / or Zn0 3-10 Lî2o 2- 3 ,, le 0 â3a 0 X20 S-2
 EMI22.5
 L-, t dxrnn ± .3 of the a ;; 3x.icain;

    26.S> J? Ét ?, l "" - c <: "" 1 "12;" M'3 1963, on est bisee -sa 13 'b? Sv'3X':;: 1ê1Jr:? I>: :; 1.in "63 / selce se rL7;: 00? Te;". des c #;.: p ;; sitions b v'3'T:.: li11:; lCS t1ld: doi = wind nicc $ i :: J.irr: - :: n1t contenj, r of 1 '±;:; :: lc a lizl: ± .i = * t'l1 ex3. "'l- & âe cotte -le vayyî rst le sUii'a?% t Pc,: r> CenÉ orA.? 93s
 EMI22.6
 1 2 55 "75 L1.0 NaZO 1-22 (* 'it is p?" Ssnt3 X20 ù-5 Al, 0 lC-7.J f if it is pfsnt) 5 and / or: .., 0 ù- 5: rC .., 3-1, J (if ot r; 3ct) ..!. 1 "0 ,, and Zr0 1: '- Z3
 EMI22.7
 le r4r; t "rt riai.? fntr. LIZ0 zt rs <3 *? t3 en => ris ostra oot: i and Stl and flc? ±; int pï'-st ea t.1 :: t -3 *. t ffic, loers that there is> 1 # I? i -: <::: ': 1 more of: #; à> 1 <s rri-it4s, glasses id-often csntcnir c-here in>; they 3'my-1a Je tlta # *, .31 t3 weight of oxide e and / ci Ç; eoxyllc le ct f'-H Je 5; '.., 1) "".

   It 3 * I çontoxyoc> àe z:, op:, mr * and d * fiuoer,: "c: x: - 'oec: 3.1 (' 1> J! 1 can 6tro present; t en '. Mtit mon, ààfi ; 1 ;. L? Rsçae 'cxy.t E> litM.'a et la. Scu "' * st zr.lsnt ,, their total quality is ascertained 8 <! 'Be S and 2Sl in ro13s * All classes of glasses :: ci: t, ctitt le? rer3er of the three types of your $ etic5, .1. <; s the d5 ± 1; 11; n Pr-5cltE *.

 <Desc / Clms Page number 23>

 
 EMI23.1
 dull "glass". The conpositicns of verro Ù1IJ 5ec: l and Ju three 13 "ra type resumed in this definition, are (1cr, it here-arras, rais some I between them under forne 4th Koranic glasses, result in the corners of a therric scifiuc treaty can not be heard at any point, even though they do not see the ion cluster as a thermally crisstillable glass body.

   This linitaticn is not> aticrl14.re a, J prccô; 1µ Je la! '' The in; entiona C rather found that it was emitted tl'm "1iitation when er. the classical ecb3ne & S * i.ons prJc5; le which uses a alkali nitrate fon4ii.



  The cé> ar; iques used4 # - = Le 1; r6 ± ùrcnce .lanser.te hivention are o> = çiaes OH translucent SoOut!,: 1'l''ti \: ulitrc: ''! cnt> reAr6s cer-a-iigues r ': yes cônten1mt an "ultit'ie da cris" rate in a sorted sa -the glass, bns which the <Iian3tra rayen the crystals z-aci-ves in! i,' Uuels is in ± Frien.Y 5 about 33 ricrons laas the largest aircnsirn. The e'sSffieie: tt linear coyen of thesis illatition. The opaque, cfrxriq glasses are generally less than about 20 x 10.1oC (between 25 and 3CC.C).



  The patent a =.! Ric3in n * 2.9O.11 dance of the exrpics of corcositians of glass I silicates cristllisabls -ar route tr.ernic. On the basis of the actual contents of the glass jiff6? Ents - * - included in CC patent, the intervals the q4ntits of the cores. '$ Itlcn5
 EMI23.2
 are the following :
 EMI23.3
 For-This; t in? O13s
 EMI23.4
 siez 56.1-73.1 AI, O3 lZ.1-1S '5 Liµ0 3, CS, 2> z0 0 -1.7 K0 0 -0 2 Cao 0 -11.1 MgO 0 - $ os T! Oz $ 4 S-1398 Ir0z 0 -3 9
 EMI23.5
 In some of these cor.positions, fluorine is present as
 EMI23.6
 refining agent.

   These compositions, after thermal crystallization

 <Desc / Clms Page number 24>

 
 EMI24.1
 4 '. "Li'p sent es glasses q'3'":. :: '' and cerai5 y '., .'T' them, as long as the 'T $' 'S'. "': W1" t '"' .2." '", 3'8 is e"', .. 'âr "Er3,' ','! C ..: '' 1.! tre 50uises at an interval of 4 # ions of â '' C, 13 "#., ^. ', The" "TTe c4ra * = içue with an alkaline netal in a tain of cel ior; anlJe and .ro: xt therefore be sour.izes a éc2ur., - Ie dlîcns by the 7rreelé of the inye-ition income.



  The in6rîcala patent No. 3.lS7.SZ2 d4 = rît class of glasses and the cera = 4-Clles glasses from these glasses. the ca3.tin of this glass is there, before: sst4 ^ t en * Ioî1-s
 EMI24.2
 S102 55-75 A1203 12-35 Li0 2-15 T10 3-7 S102 and T10 Sg-S2
 EMI24.3
 The aforementioned ingredients constitute in role 151 of li co, o5itin and the weight ratio between LizJ and A123 is c = 2ris between 0.1: 1 and ce6: 1.



  Another class of crystallizable glass cor.positions tlierciqter'eat, which can be xounites at one ec. * - anqe the ions under forre of glass and: r.1i, by a treated ti.er-ie, Such a suitable can be subjected to an ec3anro -tions, case drilled by ceramic glass, is described in the e:, 1c This Japanese patent 37-1S320, 1 filed on 27 sopterbro lfi52. The% lnttrvalles the qü2ntits has this co-position are lot .1vants: rour-Cc; t on poiJ?
 EMI24.4
 Sie, s1 AI 1'iai Làzpm 4-in 2, "4w -P rei 't e 1-
 EMI24.5
 .¯ - ..

   N ... -, lF atc corrosion, la * adorns them. above, hor- 'l # ¯ nàJg¯¯ # irccgep ext jUp6rieJrO j 65 do 1 coosi..t1.,. ,, the patent E> ciqc n8 <, CP, s29 J writes another corpositio; of verTe c3st, it ± sic t: urJ: ". i'1ue: tt" nt .. ,, '. nt the following sa ^ asïti Percent by weight
 EMI24.6
 
 EMI24.7
 51 2 43-73

 <Desc / Clms Page number 25>

 
 EMI25.1
 
<tb>
<tb> A12O3 <SEP> 14-25
<tb>
 
 EMI25.2
 1.1 ", 0 4-10 1'102 C-183 4.r C) 2 2-6
 EMI25.3
 In this conrsiio, the total of the ingredients combined, including the titanium oxide and the% iron, constitutes at the kidneys 55 'of the glass. Nor-breuses specific coEpssitions, which are described, contain 31 by weight -le 3? - ..



  The beige patent: $ 633.39 describes thermally crystallizable glass cccpositions, so cry them out cxai3s 0-it derives from it, all games can be mice! ion exchange in
 EMI25.4
 view of replacing one ion of alkaline rital by another. These configurations contain silica, alunine, lithium oxide, boron oxy and 3-71 wt. F3a? Tz0 and / or n0, plus a small amount of an agent. nucleation. The typical cor-position will have ua:; = --ur -1 of SS-561 by weight of silica, a content of 13-22% by weight of alunine and a content of 2.5-5t by weight of oxide of litium.



   Another class of thermic crystallizable glass compositions capable of being ion exchanged is described.
 EMI25.5
 in the ar.6rican patent n. 3.17C.8CS. In these compositions, the main components are silica, lithium oxide and zinc oxide, in amounts of 34-81, 2-27 and 10-591 by weight, respectively. Cens? indicated, other constituents may be present, as well as P2O5 in an amount of 0.5-6% by weight, when metallic nucleating agents are employed.

    
Thermally crystallizable glass compositions and ceramic glasses derived therefrom are described in African Patent Application No. 464,147, filed June 15, 1965 by Clarence.
 EMI25.6
 L. Babcock, Robert A. Busdiocker and Erwin C. Hagedorn, titled "Product and Process! Or Forming Same".

   This class of glass conpositions contains the following ingredients

 <Desc / Clms Page number 26>

 
 EMI26.1
 ? our "Ct an paMs
 EMI26.2
 
<tb>
<tb> SiC2 <SEP> 50-75
<tb> A12O3 <SEP> 16-35
<tb> Li2O <SEP> 3-5.5
<tb>
 
 EMI26.3
 Aent of 'a'1', '. C'4 variable LAA1r and agent I ## keyation have rains Its
 EMI26.4
 La '& ars la e4e de patenta les r.itil # = sd ehay zee du? = O = él-é ie! Ik # icati * -a 1 vera and ut-' tpa.3.ter'e ": tt: - .err4-e.: e of the glass to retain the chalks st ssepTisss 31; 5 the present specification as this reference.



  The amount of niacleation, such as titanium 4c oxy and irconia, depends on the particular composition and the agent or the combination of? agents the nuci5atior. individuals, etc. The nitrates may be present as colorants, in an amount of 0.005-2% by weight.

   To impart characteristics of lower expansion to the Koranic glass which can be erected from the glass corposition, the following components are employed:
Percent by weight
 EMI26.5
 
<tb>
<tb> SiO2 <SEP> 56-68
<tb> A12O3 <SEP> 18-27
<tb> Li2O <SEP> 3.4-4.5
<tb> CaO <SEP> 0-3
<tb> ZnO <SEP> 0-2
<tb> B2O3 <SEP> 0-4
<tb> TiO2 <SEP> 0-6
<tb> ZrO2 <SEP>.

   <SEP> 0-3
<tb> MgO <SEP> 0-3
<tb> Ma2O <SEP> 0-1
<tb> P2O5 <SEP> 0-3
<tb> (SiO2 <SEP> and <SEP> A12O3) <SEP> at <SEP> corners <SEP> 82
<tb>
 
 EMI26.6
 (S102 'Al 20 30 B203 and P205) 86-91 (CaO, l'g0, = n0 and Ka-0) "2.5-6 (sio2, A12038 P20S and Li.0) no more than 93 TiO7 and Zro2 2-6 ##################
 EMI26.7
 ..the ratio between (CaO, 1, 'gO, ZnO, K2Z0 and BZ03) and Li, O being less than 2.4 and the ratio between SiO2 and AL2O3 not being greater than 3.3 and, preferably not greater than 3.8.



   Another class of glass compositions, under glass

 <Desc / Clms Page number 27>

 
 EMI27.1
 crystallizable the1 ":,: iu ... ent and! c will see cer8.:", iGues is the subject 1 the ler-anle of brel.-et etâ'Ââîà gaz 2ZZ, 953, 1fpcséc on 13 Kars 1954, by ;.: il1iar .: E. ".3 '. and 3.T2 tû3 Ceranies ani yetl: o" La' .i .So, 7, tii "s eus, esssntiellenent la p .." 6'i'ûL Fear -Cent in kings
 EMI27.2
 
<tb>
<tb> SiO2 <SEP> 66-73
<tb> A12O3 <SEP> 15-19
<tb> Li2O <SEP> 2.5, <SEP> -4
<tb> @ <SEP> 3-7.7
<tb> @ <SEP> 1-1.7
<tb>
 
 EMI27.3
 .ri-.

   (1 tsp. 1, - '2 ¯ 1- <I, 9
 EMI27.4
 
<tb>
<tb> SnO2 <SEP> 0-1.7
<tb> P2O5 <SEP> 0-3
<tb> Lao <SEP> 0-5
<tb> ZnO <SEP> 0-3
<tb>
 
 EMI27.5
 the total conjurai percentage - 'e: r2' TiC ,, jnû2 and ± -tant au kidneys Z S and the total weight percentage of Li, O and .g0. from 6.5 to lobs *
 EMI27.6
 The glass compositions of the decanics of Ericains presented in the above paragraphs, force des; er ;? c-r3riques containing f-C'.lcr '}'! 'tite and / or / S-spo3urne. Cn has risen in the oint of co ": positioRS the safe glass of the thermally crystallizable ceramic glasses in which the crystals. The cistalliters or other dobbies constituting the pL: 1se crist311ine, scat the ncphcline. These cOl ":? Ositio5! The glass ..! U roins in ta-ït jie crystallizable glass, can be smiled at a burst of ions.

   A class of these compositions is written and claimed in the 1st ..: m: the patent a! 'Rica.in n *:; il.r';! 1 ù4prséT the 13 rai ige4 by :: il1 il!, R . !:. Srith and tit'.11ée- "CléiSS, Ce1'aics; n3 1? Ethod".



  This coosition contains the following Percent by Weight
 EMI27.7
 
<tb>
<tb> SiO2 <SEP> 44-52
<tb> A12O3 <SEP> 22-29
<tb> Na2O <SEP> 15-22
<tb> TiO2 <SEP> 6-12
<tb> K2O <SEP> 0-3
<tb>
 
 EMI27.8
 SiO, and A123 .59-76
 EMI27.9
 
<tb>
<tb> Ma2O <SEP> and <SEP> K20 <SEP> 17-22
<tb>
 

 <Desc / Clms Page number 28>

 
 EMI28.1
 The r ::? Rt, 1'.t '"between Si'5 (:', 1: /" '.t; 3 Ftant cm = 1% ràs it3: "G' 2,1 and 3 ot 1 ràrjoit shine entered (: 0 and 'l #) and Al 2 0 3 being J'au noir4s 1, ci * t'btcrval1'O! Hm: f'. \ l p. "; Tller: Preferred Ot1t pO'Jr!: * 2c% is 11 ..: U. La Cescri.-tlon, .lias la èC1 "3nJe '.'! ') Patent, f, \, t1rcs i cyc and .1u t> roc4, tà -le Íù' ... ric3t1ûn: 1> glass, the trialy.i = liiY7 ies KPI glass r (i; U 'o1Jt,: ni: r .1,} 5 vorr3 and' t "" ique5, are included lirs 13 pyaKtc 'iic1t1o titya of rAf1rcnce.



  1: a-itre c1.u \ t 1 \ 1 Sn8 / .JRL: .ik7 B9's glass would make the nFjh4A c '): -: c: U5e: xistllia: J;. \: 1, a vcfye: 3 " contains 105 nx: 3, ta riaaxs l'c: 1r-C !! nt tm poiJ
 EMI28.2
 S10: 4s-s7 Al 2, -33 A1Z3 = -J3:. 'T0 13-2: Ti?, 1r 0m 1-4 * IrC 52 ". # .1 4 t: i4, and 20 tu -cit.3 es
 EMI28.3
 en wjcc rir-crt 1C '".'s la so * # 3 Si'%, .Slz, Jy and î'AO.



  Li, r2 'p: rS and: es oxy- * Cs I .-. Ct% ux,; iv3lcnts? Euve?; T Be represented $ in # to.i * q, aantit8 total in'ôrin.Jro 1 51 * ¯ tg trivet aJ; liij: * t5? .321 t¯¯1J cù-t; 3itlo # 3 d5 will see ".yt" 1t trCt sou-hu un é: .a ;; e l'ionT e; r <* "'l *? 3t an alkalizing metal Ion Gu. This $ yst: -l.' , 10 glass contie # t ii) i'cxvje da sol1u =, al, i-ins and ai li silica, with c; y-le do titans ca "r <) <s9at de n.Jclé > tien, an CO: -i: l1bn with ut c'jt ::! uS ';' c ".1rs a-% tr * 3 a;: 1t ,.



  The content is Je t "-34 rol <s%. The cxy-ies! Tl111.'i'Jes ut. * Li2t.3 in e3" tiMiea with lalxrle 10 tltl -. 1 sa = t resumed 4 = $ the mTçlals patent and it is ln! l.Jf '11s must c * r.3tituate in: oins 1.9 mle4 * in excess raI "r2rt l la qJàn: it8 total rolaire of silica, alu'-ine, d sodium oxida, 0% 7.10 and pitassluis and 4'oxy4 <, 1 * cticina in the ca2pcsttlcn -4o glass, to give a cry! << tallisable glass thermally from a coittel rafler. When it is crystallized. the glass cerqritria comieat a crystalline phase d.
 EMI28.4
 nepheline.

 <Desc / Clms Page number 29>

 
 EMI29.1
 



  The cxrrcr: lon "} Anointed from dfol" r) .t1on pel ':::: men1: cu is defined on page 659 of the book by Weyl and Marboc mentioned above and in the American patent n * 2,779,136 .
 EMI29.2
 invention
 EMI29.3
 Nodificatinas of this will appear clearly on the whole hormone. The foregoing description has therefore been given by way of illustration and does not nullify the invention, which is limited unîqucrant by the following claims.
 EMI29.4
 CLAIMS
 EMI29.5
 1.

   Similar to treating an article consisting of an inorgi-ilque glass containing an alkali metal oxy, 1e, characterized in that it consists of a surface of said glass in contact with a liquid medium, these fading a r.t31 different alkaline under òrn ± of a salt of an organi-ue acid,! a high temperature and during one, eric, there! u: 7fb: vi.tc ri-ir ± cl: in-er nasty of the alkaline r5tal in the alkali rtal diff (: nt è1S lc1it zeïs "2ror the article in ccJci: # superficial with MRS the 1ttie du'Ut / vorre and the ruffle to refresh the glass article.



  2, Procd-1,1-i according to the rcdic4tÍCà Ig characterized in that Io glass is a green * I silicate and in that said cx.ya of alkaline r.t31 coe; te # "i in said glass constitutes black 1 \ en Soils> 1.a vrrx, .3a; s said co ':.: Ch "s> 7a-rfieiellà at Misa.



  3. rrtc1-4, uiv: t 1. ycvnU & aticn 2, 1rctrl! in that If1 Ut nilicu 11'7.1110 c-.::-;rc:'ll 1;: reads only cccra ccstlhant 1 "lneur and U yl: ale fsi *, ç1r- ca'ttJat naJuF, 4. 1> rezilà s;: lv.ant la rc; c.xdicatisn 3, <alxctflrinà en es que lt11t: -Illlu ii1c in contact 3 le.lia Varre is vIs #: 1 contact with an 11, .Ulle iu-eeït sel le rtl a1c & 11a.



  S. l'roc ± là Sai; àit la ia.itniicatic; s = r # ctéris "3 en; o qu <lalit ve * -Ict * 10 is a vi; hic-Jle c?; aiue poltire non iniq '.. 1 ..



  6. Procdt according to the revc3; ï.c <ticn 5, in: yi * lellt vehult * 3t an oil of hvJTcesr? E, 7. Froci3; 6 according to the? Eveaietti.? A cmwactéri "du '= Ct 1; to said vehicle is a paraffin wax *.

 <Desc / Clms Page number 30>

 



   8. Method according to claim 2, characterized in that said organic acid is a carboxylic acid.



   9. The method of claim 8, characterized in that said carboxylic acid is acetic acid.



   10. The method of claim 9, characterized in that said salt is sodium acetate, said alkali metal contained in said salt is sodium acetate, said alkali metal contained in said glass is lithium and said high temperature is lower than the point of permanent deformation of said glass.



   He. A method according to claim 10, characterized in that said elevated temperature is between about 200 C and about 550 * C.



   12. The method of claim 11, characterized in that
 EMI30.1
 said elevated ter.perature is between about 3000C and 430 ° C and in that the duration is at least three hours.



   13. frocéié according to claim 12, characterized in that the lodit glass is a ceraric glass,
 EMI30.2
 14. Froctl, 5 according to the rcvendi.cati.c 13, characterized in that said glass crsicue! is opaque, contains an output of crystals whose smallest transverse dimension is each less than ± 30 microns, and has a royal linear coefficient of thermal expansion - approximately 20 x 10.7'ar C (between 25 and 300 * C ).



  1S, The method of claim 12, characterized in that said glass is a thermally crystallizable glass.



  16. The method of claim 9 characterized in that the lotit Yirre is a 3 elde / alutin / silice glass containing titan o- xide ** said sol is potassium acetate and said. te = pmttJr. high is inf'friaure to the point of penanon damage. da vwyre 1 "17. Procedure according to claim 16, characterized in that" s - la4ite your peramre tlevît is between approximately 371.11 "C and emlirn 399 * C and had that the duration is at least 3 hours, , 18.

   Processing process of an article consisting of a Yf: n8 containing the following ingredients in percent by weight:

 <Desc / Clms Page number 31>

 
 EMI31.1
 
<tb>
<tb> SiO2 <SEP> 35-88
<tb> M2O <SEP> 1-48
<tb> A12O3 <SEP> 0-40
<tb> Cao <SEP> 0-15
<tb> MbO <SEP> 0-28
<tb> BaO <SEP> 0-15
<tb> SrO <SEP> 0-15
<tb> B2O3 <SEP> 0-15
<tb> ZrO2 <SEP> 0-25
<tb> TiO2 <SEP> 0-12
<tb> Sno2 <SEP> 0-2
<tb> psO5 <SEP> 0-10
<tb> As2O5 <SEP> 0-3
<tb> Sb2O5 <SEP> 0-3
<tb>
 M2O representing the total content of alkaline feta oxide, characterized in that it consists in immersing the glass article, for a certain period,

   in a liquid body of a non-polar, non-ionizing organic vehicle containing a rinsing percentage of an alkali metal salt of an organic acid and in contact with a body
 EMI31.2
 liquid separated from said salt, while retaining said bodies at a high temperature, said alkali metal or salt being a different chemical client from said alkali metal present in said glass at one time.
 EMI31.3
 quantity of lines 11 by weight (expressed as oxide) and said temperature and said temperature being sufficient to give rise to an ion exchange by said different chemical elements between a surface layer only of said glass and said salt in the liquid body of an organic vehicle.

   removing said glass article and removing any salt and organic vehicle adhering thereto.
 EMI31.4
 



  19. Proceeds according to claim 18, characterized in that said orzanique vehicle is a salt shaker of hydroc: aroore. the srg = niqoe acid of the salt is a carboxylic acid. the terperature is between turîzvn 3Lto C and about 430 ° C and the duration 3'innr <rsion is at least 3 hours. ,
20. process according to claim 19, characterized in that
 EMI31.5
 t.Me 1 / tit po # reestage rinser is less than by weight, and in that said different chir-ic eMMmts in the glass and in the scat salt the l1thso and the sodium respectively and in that the a " ide is zcetic acid.

 <Desc / Clms Page number 32>

 
 EMI32.1
 21.? Rc; é3é eaîyant la. xoveniicitîmu 20, esrsiEi in that le4it -., wanders --3-. us vcrrx cris t: ,,;: r ::: i7ecnt.



  22. i, 'aw.6yi. following the. claim 18. Çrâ.4 .. '' s in this 9 said vè:; ic:.: l OT; 1, a: ti '! ue is ue calibrated salt is a salt - the oiur, the r: < t-t3. s3 different 3rt i glass is him and the '! # 3 "Z'W tst: in glass i * x3 *" 1 r ",::'" 3 ^ t.:. '' 'i''i. ": 3. '"A rultituie --'-- crystals ....:" the most 1-7ranie' â ': 5; rsT $ 31e = ot' '"3SSr, râ:" s9, .w infsriùrrù 1 3 and qui alir., rj: É cce-ee.4-Cicnt linear t "r'1 00t âia.âv.3n $ i s.i9 * ,, '': 4w înf # rie.ar 1 cxvîrrn 22 x 1-, . "- 7 by * C (between 25 and 7 ¯ ....) 23., 6, tw '- = .w's rYJ Y lks la ü i A siwwZYÜ., Ii' 9riciSn i'an iry .fW r in this zone the read r4,, r3niucule is 3 .:

   : r.irc'rr, le4-t: *: xr.a fi.neur is i33 ': xiaax 1 *. in ni:% $ lelit sel e5t 1 '; c <tite le, t' $ - '..Î: ^ t ieiit vsrre is' S3' '""' '7 ".5.iT. of" i1'. :. ',.'. Ll "" 1 '.' .. 'Î51C co- = ten2nt -the titr, the tcfr1tre is coaarisc between about 3M and enviro-i .136 * C and the.! 1.1r <: : <e Y, .vGs i a7ivF.f is -! at rcin3 3 hours.



  24. Article on x.; Xx: ayint unw cueh <: Mperficiclle 3 effort de cO! Jressio; 1. : '::' tn'le '1 "31' le! '1'ot.: le $ IJive la reven: ic: .ttit" n 1.



  25. Article -, the vorrc ay, 1; t uns couc.ie, u? T'rficiel1e. \ Effort -le o1 '$$ ion on 1r le, rr.cfJ 3uivnt reveniction read, 25 *, irti; le -the glass: t) '.: 1t' ïnc layer $ 1J, f) c1 '±: icicl1, :: J effort do cr% rcssio-1 otf': lU rir 1 mrccé3é according to the Teieticn IS.



  11. Articie <** ;; rye the * eit a sweet ecuc! Hereelc effort of coqreosàon at: c -le xa '. next xrr: 3aia 16.
 EMI32.2
 
 EMI32.3
 



  2 *. Proc ± 1. 8.oivà; t the revenellcit1cn li. characterized in this read the V ± 1, µc: the r '' '': 1r: dq: I is 1 wax I, r3.f'fi: 1t '. the # étal, alkaline is 1 '& céhte due 50, liu = and the r-: t'1l aictila àiff8rent' 3 &? n! the glass is the l i t: .iUl'1 ..