Frits for crystallizable glazes.
Abstract
1. Frits for crystal separation glazes consisting of 0 to 20% by weight each of calcium oxide, magnesium oxide, strontium oxide and/or barium oxide, 3 to 15% by weight alkali oxides, 5 to 20% by weight zinc oxide, 0 to 40% by weight lead oxide, 0.1 to 8% by weight aluminum oxide, 15 to 60% by weight silicon dioxide, 5 to 25% by weight boron oxide and molybdenum oxide, characterized in that they contain 2 to 30% by weight molybdenum oxide and, in addition, 0 to 40% by weight bismuth oxide, the total content of bismuth oxide, lead oxide and alkaline earth oxides having to be from 5 to 40% by weight.

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Projected expiry passed 13 December 2005, 20.8 years ago.
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3 claims: 1 independent, 2 dependent
- 1Fritten für Kristallausscheidungsglasuren, bestehend aus jeweils 0 bis 20 Gew.% Kalziumoxid, Magnesiumoxid, Strontiumoxid und/oder Bariumoxid, 3 bis 15 Gew.% Alkalioxide, 5 bis 20 Gew.% Zinkoxid, 0 bis 40 Gew.% Bleioxid, 0,1 bis 8 Gew.% Aluminiumoxid, 15 bis 60 Gew.% Siliziumdioxid, 5 bis 25 Gew.% Boroxid und Molybdänoxid, dadurch gekennzeichnet, daß sie 2 bis 30 Gew.% Molybdänoxid und zusätzlich 0 bis 40 Gew.% Wismutoxid enthalten, wobei der Gesamtgehalt an Wismutoxid, Bleioxid und/oder Erdalkalioxiden 5 bis 40 Gew.% betragen muß.
- 2Fritten nach Anspruch 1, dadurch gekennzeichnet, daß sie 0 bis 16 Gew.% Kalziumoxid, 0 bis 11 Gew.% Magnesiumoxid, 0 bis 10 Gew.% Strontiumoxid, 0 bis 10 Gew.% Bariumoxid, 3 bis 11 Gew.% Alkalioxide, 5 bis 16 Gew.% Zinkoxid, 0 bis 30 Gew.% Bleioxid, 0,3 bis 5 Gew.% Aluminiumoxid, 18 bis 50 Gew.% Siliziumdioxid, 7 bis 20 Gew.% Boroxid, 14 bis 20 Gew.% Molybdänoxid und 0 bis 25 Gew.% Wismutoxid enthalten, wobei der Gesamtgehalt an Wismutoxid, Bleioxid und/ oder Erdalkalioxiden 10 bis 36 Gew.% betragen muß.
- 3Fritten nach Anspruch 1 und 2, dadurch gekennzeichnet, daß sie 5 bis 30 Gew.% Wismutoxid enthalten.
Independent claims3
12 paragraphs, as filed
The invention relates to frits for crystal precipitation glazes, each consisting of 0 to 20% by weight calcium oxide, magnesium oxide, strontium oxide and / or barium oxide, 3 to 15% by weight alkali oxide, 5 to 20% by weight zinc oxide, 0 to 40% by weight lead oxide, 0.1 to 8% by weight of aluminum oxide, 15 to 60% by weight of silicon dioxide, 5 to 25% by weight of boron oxide and molybdenum oxide.
Glazes are glasses adapted to the ceramic body. A distinction is made between raw glazes, in which the predominantly natural raw materials are ground to a glaze slip without prior melting, and fritted glazes, in which a premelt is produced from the raw materials and granules are produced from them by quenching.
Ceramic surfaces have been decorated with glazes and protected for thousands of years. Fashion and technical progress result in a constant adaptation of the glazes to consumer habits. In many cases, crystal precipitation glazes are also used, in which crystals separate out in the glass phase due to controlled devitrification, which can grow up to a macroscopic size. Such glazes are described for example in DE-OS 32 29 838.
Glaze frits are known from EP-OS 25 187, which contain alkali oxides, alkaline earth oxides, zinc oxide, aluminum oxide, silicon dioxide, boron oxide and up to 1% molybdenum oxide in addition to other constituents. However, these glazes show no crystal precipitation effects.
In practice, known frits are added to produce large amounts of molybdenum salts, preferably molybdenum trioxide, for the preparation of crystal precipitation glazes containing molybdenum oxide. However, this method has the disadvantage that large amounts of the added molybdenum oxide sublimate during firing, depending on the firing temperature, and the formation of the glaze strongly depends on the firing conditions. Attempts to add the molybdenum salts to the raw materials prior to melting during frit production failed due to the fact that such melts explode explosively when quenched in water.
It was therefore an object of the present invention to develop frits for crystal precipitation glazes, each consisting of 0 to 20% by weight calcium oxide, magnesium oxide, strontium oxide and / or barium oxide, 3 to 15% by weight alkali oxide, 5 to 20% by weight zinc oxide, 0 up to 40% by weight of lead oxide, 0.1 to 8% by weight of aluminum oxide, 20 to 60% by weight of silicon dioxide, 5 to 25% by weight of boron oxide and molybdenum oxide, which form well-formed crystals in the glaze regardless of the firing conditions and do not tend to explode when the melt is quenched in water.
This object was achieved according to the invention in that the frits contain 2 to 30% by weight of molybdenum oxide and additionally 0 to 40% by weight of bismuth oxide, the total content of bismuth oxide, lead oxide and / or alkaline earth oxides having to be 5 to 40% by weight.
The frits preferably contain 0 to 16% by weight of calcium oxide, 0 to 11% by weight of magnesium oxide, 0 to 10 <sub>G</sub>% strontium oxide, 0 to 10% by weight barium oxide, 3 to 11% by weight alkali oxides, 5 to 16% by weight zinc oxide, 0 to 30% by weight lead oxide, 0.3 to 5% by weight aluminum oxide, 18 to 50 % By weight of silicon dioxide, 7 to 20% by weight of boron oxide, 14 to 20% by weight of molybdenum oxide and 0 to 25% by weight of bismuth oxide, the total content of bismuth oxide, lead oxide and / or alkaline earth oxides having to be 10 to 36% by weight. Frits containing 5 to 30% by weight bismuth oxide have proven to be the best. Corresponding melts show normal quenching behavior in water and can easily be crushed.
The frits according to the invention can be used in particular in the temperature range from 960 to 1200 ° C., where beautiful, star-shaped to fern-like crystals are obtained. These frits and the glazes made from them are also very acid-resistant.
Figures I and II show such crystals in magnification 10: 1 and 25: 1, respectively.
The frits are produced by melting together the raw materials, such as silicon dioxide, kaolin, calcite, potassium feldspar, soda, zinc oxide and boric acid. The molybdenum oxide is advantageously added in the form of molybdenum trioxide.
Below are some frit compositions that show particularly beautiful crystal deposits:<tables id="tabl0001" num="0001"><img file="EP0192844A2_D0001.tif" /></tables>
2 sheets
Sheet 1 Sheet 2
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| WO2013126369A1 | Cited by | World Intellectual Property Organization (WIPO) | Applicant |
| US11225433B2 | Cited by | United States of America | Applicant |
| EP3786121A4 | Cited by | European Patent Office (EPO) | Search report |
| EP0598199A1 | Cited by | European Patent Office (EPO) | Search report |
| US9315413B2 | Cited by | United States of America | Applicant |
| EP2817268A4 | Cited by | European Patent Office (EPO) | Search report |
| US5093285A | Cited by | United States of America | Search report |
| EP0598199A1 | Cited by | European Patent Office (EPO) | Search report |
| EP0402007A1 | Cited by | European Patent Office (EPO) | Search report |
| EP0402007A1 | Cited by | European Patent Office (EPO) | Search report |
| AU629940B2 | Cited by | Australia | Search report |
| US5091345A | Cited by | United States of America | Search report |
| US5203902A | Cited by | United States of America | Search report |
| US5304516A | Cited by | United States of America | Search report |
| FR2052326A5 | Cites | France | Search report |
| US3684536A | Cites | United States of America | Search report |
| BE628121A | Cites | Belgium | Search report |
6 members in 3 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 3507218 | Germany | A | |
| 3507218 | Germany | – | |
| 3507218 | – | – | – |
| DE19853507218 | – | – | – |
Members6
| Document | Office | Kind | |
|---|---|---|---|
| EP0192844A2This record | European Patent Office (EPO) | A2 | |
| DE3507218C1 | Germany | C1 | |
| EP0192844A3 | European Patent Office (EPO) | A3 | |
| EP0192844B1 | European Patent Office (EPO) | B1 | |
| AT54299T | Austria | T | |
| DE3578574D1 | Germany | D1 |
34 legal events, as 2 offices reported them to INPADOC
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| Fr: translation filedET | ET | EP | |
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Numbers
- Publication
- 0192844
- Publication, DOCDB
- 0192844
- Publication, EPODOC
- EP0192844
- Application
- 85115950
- Application, DOCDB
- 85115950
- Application, EPODOC
- EP19850115950
Titles6
- German
- Fritten für Kristallausscheidungsglasuren
- English
- Frits for crystallizable glazes
- French
- Frittes pour glaçures cristallisables
- German
- Fritten für Kristallausscheidungsglasuren.
- English
- Frits for crystallizable glazes.
- French
- Frittes pour glaçures cristallisables.
Classification
- CPC, 2
- C03C8/10
- C03C8/04
- IPC, 2
- C03C8 04
- C03C8 10
Designated states1
- Contracting states, 1
- Netherlands (Kingdom of the)