DE1596913A1 - Process for the production of objects from glassy-ceramic material - Google Patents

Description

iuaterial.

The invention relates to a method of manufacture of objects made of vitreous ceramic material; in one or more kriotalline phases in finely-dispersed state of one are surrounded by glassy rabbits, and are produced in this way

For the manufacture of these types of objects, such as It has been known for a number of years that objects of a completely vitreous nature are assumed to be used in glass manufacture usual i.eiee are formed from a glass melt, which from a Number of known glass-forming components exists and continues to be one or contains several components that ale Krietalliöaticneickeicfeildner are effective. These objects of vitreous nature become permanent up to heated in a certain temperature range, whereby the Jtristalliea germs are eliminated and finally on a higher level

109809/0366 '^

■. 8AD ORIGINAL -

- 2 - ·. * Hli.'iQ! 8C

leiupera door area, with deu one or more specific crystalline Connections on the trees grow until the desired level of crystallization is reached. ·

there is a material known in which the Bacic ^ las * '·. . ■ ·. ■ ■

contains the oxides t3iO ₂ , Al ₂ O, and Li ₂ O and in which the combination ^ rG ₂ , P ₂ O ^ and optionally TiO _{2 is present} as crystallization nucleating agents, so that the total composition of the starting material in percent by weight is as follows: '

öiü ₂ 55 - 70 .36

Al ₂ O ₃ 20-35 P

Li ₂ O 3 -5>

UrO ₂ 1 - 4 *

• - ■; ■ ■ ·. · ^Ρ 2 ° 5 '· ^:. -s': ■■ - ■ · ν * ⁵ *

TiO ₂ . 1-3 Jt ·;

This product is subjected to a thermal treatment, said first step of heating to a temperature between 700 and 800 ⁰ C and for the "large step from a ür- hitζιμΐ £ to a temperature between 800 and 1200 ⁰ C is. Depending on the temperature in the second heating step, the properties of the end product can be influenced if; If this temperature is kept low, (810 C) the most important crystalline phase consists of ß-acid cryptite, but if it becomes very low (115O ⁰ U), this crystalline phase consists of ß-3 modules. In both cases the coefficient of thermal expansion is low, ie in the order of magnitude of about 1p 10 "" / ⁰ C, but positive in the second case and negative in the first case. The second valley results in a white product, οχιά urchcclieir.erdes product and iia first ialle a transparent a

BATH ORIGINAL

- 3 - i'ilK-.1O48 C

Although in this area of the United States there are pro

dulvte with beautiful exterior can be obtained is in general The glass base material is not particularly good in terms of technology (, ünstiü. ± * he most glasses in this area bind, according to a naming of the (ilastechnik, too "short", i.e. that in the i'eaperat-irbereich To process the molten glass, the viscosity as a function of the temperature is too steep, which causes pressing and in particular the blowing of the glass objects is made considerably more difficult ■ Λ-ircl.

Another disadvantage of the well-known k / usamnienaetzunijen is that the crystallization only starts when the temperature is relatively high or, in other words, when the viscosity of the glass is relatively low, so that deformation of the product during the crystallization process practically occurs is not defensible. UioG brings about a considerable limitation of the fcrmgebane, the products ait themselves. To avoid, among other things Verforoiung of the article, the crystallization has a viscosity of at least 10 oei ^f5 i> oise effected. No glass could be earthed within the well-known area of amalgamation, which fulfills this condition and is also favorable for the manufacture of objects from glassy-rerattic a -ifcterial. '"

Above the difficulties of λ s re sen have been i of Glaegegenstünden; i. Lulle of to "recently" G la a eruShnt. Liese difficulties occur in significantly higher Luisse cul _'f if is iressvorgang performed automatically. ,

The connection creates an area where unsatisfactory jobs are found in each. Ir. good condition has d & n material favorable

BATH

- 4 - ·. PHN.1048 C

and läsüt for the automatic rreεsvorgang to form articles · also complicated forms use because this glass "lSnger ¹¹ than the aforementioned known types of glass. Crystallization i'üngt also at higher Biokosität namely at a Viskosita't of more than 10 'poise. Deformation therefore does not occur during the crystallization treatment. In addition, the possibility of phase separation in the glass melt and uncontrolled crystallization of 2.rO ₂ when the temperature of the glass melt in the tank sinks is considerably lower than with the known types of glass. Me most important crystalline phase in opaqueness

v / eiυoen products ale at Kristalliaationotemperaturen more are formed as "1000 ° ü is beta-spodumene. Similar to the well-known Z us strains na et tongue η may be obtained by 'v * ahl a lower iiristallisationsteaiperatur a slightly opalea, Obtain a transparent product instead of a white, opaque product, the most important, crystalline phase ß-iüucryptit let.

The method according to the invention is characterized in that that the base glass is a glass of composition in weights per ^ ent of the following area is used »

; _ OiO ₂ · 53 - 51 Ji

Al ₂ O ₃ 23 - 28.5 * * ^Γ * ' ^M

Li ₂ O 2.5-5>

xagO 0-1.5 "£

ünO. 2-5 pounds

P ₂ ⁰ S 2 - 4.5 ^

4Γ0 «2.5 - 4 %

TiO ₂ * 0 - 2.5 * ■

The content of ^ a ₅ O is preferably less than

109809/0386 *

- 5 - 'PHK.1048 C

1 percent by weight. Uia objects made of juaterial with a white, opaque finish. Aeuseerem, wherein the second ochritt the heating at a temperature between about 1000 and 1200 ⁰ C performed, the üusaniKienaetzung de3 iiasisglases preferably is chosen between aen following limits in weight percent:

. 53 - - 61

₂₃ 23 · '-. 28.5 · "

Li ₂ O "2i5 - 4.5

üitgO. 0.5 -. 1.5 I.

ZnO. 2.5-4.5

^ ₂ O ₅ 2-4.5

2.5-4

TiO ₂ 1 - 2 *

If objects are to be made of material that is slightly opalescent, ' transparent »» exterior, whereby the second heating step at a temperature between about 100 and 10üü ° C is carried out, the iiusaauoensetzung of the iiasisglasea preferably chosen between the following limits in percent by weight: '.

; ■. 53 -61, ..,. ',,. ₃ 23 - 28.5 '

Li ₂ O 2.5-4.5

kgO * 0 - 1 '

2.5-4.5 2-4.5 2.5-4 '1.5-2.5

κη ll.ur.d of some examples the lirfindun ^ j naoh-3tohcndnüher explained _Q _ _(eAD ORIGINAL

- ό - · Hü ;. 1048 C

Ks were melting glass of the rolling oxycliüchen Zuin Weight percent added together and eο were from it pressed glass bowls with wide, horizontally protruding ears *

12 3 45 6 7'e 9

59.3 60.7 54.8 54.1 59.9 53.5 54.8 59.4. 59.3

Al ^ O ₅ 24, Γ 24.4 38.5. 28.2 24.3 27.9 28.5 24.2 24.1

Li ₂ O 3.9 4.0 4.3 4.3 4.0 "4.3 4.3 4.0 3.9

0.8 0.9 .0.8 0.8 0.8 - 0.8 0.8 0.8

3.6 3.7 3.6 3.5 3.6 4.7 2.4 3.6 3.6

ι ₅ 4.2 2.1 4.2 4.1 3.2 4.1 4.2 3.2 4.2

₂ - 2.7 2.8 3.6 3.6 2.8 3.6 3.6 2.8 2.7

₂ 1.2 1.2 - 1.2 1.2 1.7 1.2 1.8>, 8

0 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

In the case of the ochals of compositions 3 and 4, there was one irra-treated; from one and a half otuiiden at a temperature of 770 ⁰ U or 730 ⁰ C crystallization at a viscosity of 10 ¹⁰ » ⁶ or 10 ¹¹ » ⁵ poise. .

Comparing a not in the Zuaaaaencetzungsgebiet according to the invention lying Gla · the following initially £ in weight "." ·

iiiO ₂ 55.8

Al ₂ O ₃ 29.1-

4.4 2.6. 3.7 t, 2 0.2

109809/0368

- 7 - PHM.1048 C

• ·

wherein, after a one and a half hour "armebehändlung at a temperature of 815 ⁰ C KriBtailiaierung entered at a viscosity of

10 ', Poise, one recognizes that on the basis of this composition otark> deformed indproaucts will be obtained.

The old trays Beliandlung.dieser the compositions 1 to 9 of the table included a ..rhitüung to a temperature of 750 * door, 740, 770, 730, 740, 710, 740, 740 or 74o ⁰ C for 90 minutes. The dishes were then moved at a rate of 4 to 5 ° C / iain. heated to a temperature of 650, 050, 900, 850, 850, 900, \ 9üO, 850 or 650 ⁰ G; they were all kept at this temperature for three hours and then cooled to room temperature in air.

The final products had a transparent, slightly opalescent appearance, with the exception of the composition 3 »which was egg-colored opal, without any trace of deformation. The size of the wheel was about 40 to 50 #. The linear thermal expansion coefficient was between -10 and -2.x 10 ""'/ ⁰ C, measured between 20 and 300 ⁰ C- If the shells of the compositions were 1 bit 5 after the first heating at a rate of Heated 4 to 5 ° C / month to a temperature of 1100, 1120, 1100, 1120 or 1120 ° 0 and for 4, 3 »41 3 or 3 hours at this temperature and finally in the air at room temperature When cooled, the end products had a nice white-porsellan-arti ^ es, gliinzendea exterior without any trace of forcing. l> er hxistalli *. sutloji8grad in this case was about 60 bla 90 f> and the linear;, thermal stretch coefficient was between 10 and 15 x 10 "/ ⁰ C ₁ between 20 and 300 ° C. Bowls * of the ue & mmenaettings. U at 9 v are also brought to a temperature of 900 _{f. For 90 minutes}

109809/036 & _tr . bad original

- 8 - * PHK. 104C C

900, 850 and 85O ⁰ C, then at a rate of. 4 to 5 ^e C / min. heated to a .Temperature of 1120 C. i> he dishes were leading for hours kept at the latter temperature for three and schlieoslich at the ^ .tift abgektlhlj immertenperatur to L. ·

• Shells treated in this way had a nice, weiseporr.ellanarti ^ Gs, QlUnzondeB Aeucoeres, even without any trace

by Verforcwni ;. The degree of crystallization of the products was about BO to 907 ». The linear expansion coefficient is between 10 and 15 x 10 ""'/ ⁰ ^ t measured between 20 and 300 ⁰ C.

BATH ORIGINAL

109809/0369

Claims (1)

? -ü..104fc C * - ■ ' S-. - fc UJ ^ ν -. 4-1 m. 1,. ... - Process for the production of objects from material, in which one or more crystalline phases in finely dispersed fourth state of a glassy phase is (are) uneven, where 2uni "ch3t a-uf a customary in the manufacture of glass, the (objects are formed from a glass melt, which contains the oxides SiO ₂ , Al ₂ O ^ ₅ , Li ₂ O and also, as a crystallization formation, the Koabination ^ rO ₂ , P ₃ O ₅ and optionally TiO _2, wherein dan obtained glass-like product is subjected to a thermal treatment, the first of the steps AU3 the heating to a temperature LAT Doiien 700 and 860 ⁰ G and the second step of a .Jrhitsuns to a " Temperature between 800 and 1200 ⁰ C, characterized in that a glass of the composition in 3 weight ratio is used as the base material in the following area:. SiO ₂ "53-61 Al ₂ O ₅ 23 - 2fa, 5 Li ₂ O 2.5-5. & gO 0-1.5 ZnO 2 - 5th . · P ₀ Oc · '■' 2 - 4.5:. " .., ^ rO _2. 2.5-4 TiO _{2 0-2.5} 2,. Method according to claim 1 for the production of counter eats & iden made of material old and white opaque · «neuocorem ,. wöbet the zwtlte üchritt dtr irhiteun "to tint Teeptratur zwlecbtn .fltwa 100Ü and 1200 ⁰ C is carried out, characterized in that _t the Lueamaensetsung of Baeieglatee" Wiechen the naohfolßenden Jronaen _c ev * Ühlt which efeeben in uewiohteprosent UNR is eind; - ^ ■■ • v ·. ■■ ·· '.109801 / 03It ·., ... · ■ -. ■ f te ^ pJ ₀ ORIGINAL SiO ₂ 10 - · 53 1596913 thereby gelcennzeic ^v - 53 - ⁶¹ - - • - ^A1 2 ° 3 ' 23 Ph; .. 1048 C net that the composition of the base glass between the following 23 28.5 Li ₂ O 2.5 - 61 The following limits are selected in percent by weight: 2.5 - 4.5 .ago 0.5 28.5 UiO ₂ O 1 ZnO 2.5 4.5 ' ^A1 2 ° 3 2.5 " 4.5 P ₂ O ₅ 2 1.5 Li ₂ O 4.5 ZrO ₂ . 2.5 4.5 MgO 2.5 - "4 TiC ₂ Γ 4.5. ünO 1.5 2.5. * ' 3. Procedure according to Claim 1, for ♦ \ >'PoOc
• hours made of material not light opalescent -2. eercni, being the second step . Manufacture of counter TiO ₀ transparent exterior heating to a temperature between about Θ00 and 1000 ⁰ C is carried out, 4. Products made by tin method na oh tine m der • · Claims 1 to 3 are obtained . 109109/0311