DE702057C - Black enamels and glazes - Google Patents

Black enamels and glazes

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Publication number
DE702057C
DE702057C DE1938K0149813 DEK0149813D DE702057C DE 702057 C DE702057 C DE 702057C DE 1938K0149813 DE1938K0149813 DE 1938K0149813 DE K0149813 D DEK0149813 D DE K0149813D DE 702057 C DE702057 C DE 702057C
Authority
DE
Germany
Prior art keywords
glazes
black
enamels
enamel
titanium dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DE1938K0149813
Other languages
German (de)
Inventor
Richard Boncke
Dr-Ing Adolf Dietzel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KAISER WILHELM INST fur SILIK
Original Assignee
KAISER WILHELM INST fur SILIK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KAISER WILHELM INST fur SILIK filed Critical KAISER WILHELM INST fur SILIK
Priority to DE1938K0149813 priority Critical patent/DE702057C/en
Application granted granted Critical
Publication of DE702057C publication Critical patent/DE702057C/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00Compositions for glass with special properties

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Cookers (AREA)
  • Glass Compositions (AREA)

Description

Schwarze Emails und Glasuren Titandioxyd wurde bisher, wie aus zahlreichen Veröffentlichungen hervorgeht, in Emails und Glasuren vor allem zur Verbesserung der chemischen Widerstandsfähigkeit angewandt. In diesen Fällen stellt man zweckmäßig bereits den Grundversatz des Emails (Glasur) möglichst säurefest ein. Dies erreicht man, wie bekannt, z. B. durch eine Erhöhung des Tonerde- oder Kieselsäuregehalts. Das nun noch eingeführte Titandioxyd hat dann lediglich ein schon ziemlich säurefestes Email (Glasur) zu verbessern. Neben dieser Wirkung auf die chemische Widerstandsfähigkeit spielt Titandioxyd auch als Weißtrübungsmittel eine gewisse Rolle, wenngleich die Gefahr einer Gelbfärbung hier oft störend ist. Schließlich hat man beobachtet, daß schon kleine Mengen von Ti0#, zur Mühle zugegeben, eine gewisse Stellwirkung haben und hier den Ton als Stellmittel zu vertreten geeignet sind.Black enamels and glazes Titanium dioxide has so far been made from numerous Publications show in enamels and glazes especially for improvement chemical resistance applied. In these cases it is appropriate to provide the basic offset of the enamel (glaze) is as acid-proof as possible. Achieved this one, as known, z. B. by increasing the alumina or silica content. The titanium dioxide that has now been introduced only has a fairly acid-resistant one Enamel (glaze) to improve. In addition to this effect on chemical resistance Titanium dioxide also plays a certain role as a whitening agent, albeit that The risk of yellowing is often annoying here. After all, it has been observed that Even small amounts of Ti0 #, added to the mill, have a certain actuating effect and here the sound is suitable as a means to represent.

Diese Erfahrungstatsachen gelten für weiße oder farbige Emails oder Glasuren ohne weiteres. Schwierigkeiten entstehen jedoch, wenn man schwarze Emails oder Glasuren durch Zusatz von Titandioxyd, das meist in die Fritte .eingeschmolzen wird, chemisch widerstandsfähiger machen will. Fast regelmäßig beobachtet man bei solchen Emails (Glasuren), daß sie entweder schon nach dem Schmelzprozeß (Fritten) oder aber nach dem Aufbrennen häßlich grau bis braun, anstatt schwarz aussehen. Man mußte deshalb bisher auf eine Verbesserung der Säurebeständigkeit durch Ti02 entweder ganz verzichten oder konnte nur kleine und entsprechend weniger wirksame Titangehalte anwenden.These facts of experience apply to white or colored emails or Glazes without further ado. Difficulties arise, however, when looking at black enamels or glazes by adding titanium dioxide, which is usually melted into the frit wants to make it more chemically resistant. One observes at almost regularly such enamels (glazes) that they are either already after the melting process (frits) or look ugly gray to brown instead of black after burning. So up to now, one had to look for an improvement in the acid resistance through TiO2 either entirely or could only be small and accordingly less effective Apply titanium levels.

Gemäß der vorliegenden Erfindung ergeben überraschenderweise solche Emailsund Glasuren, die im fertigen, aufgebrannten Zustand weniger als 7,5 % Tonerde (in Form von Feldspat, Ton usw.) enthalten, auch bei hohen Titandioxydgehalten diese häßlichen grauen bis braunen Töne nicht, sondern sind tiefschwarz. Zweckmäßig ist es dabei, einen absichtlichen Zusatz von Eisenoxyd möglichst niedrig zu halten oder diesen Stoff ganz wegzulassen.According to the present invention surprisingly result in such Enamels and glazes that contain less than 7.5% clay in the finished, fired state (in the form of feldspar, clay, etc.), even with high titanium dioxide contents ugly gray to brown tones, but are deep black. Is expedient it is thereby to keep an intentional addition of iron oxide as low as possible or to omit this substance altogether.

- Die nachteilige Wirkung eines normalen oder zuY.Verbesserüng der Säurebeständigteit nach den bisherigen Regeln sogar noch erhöhten Tonerdegehalts auf die Schwarzfärbung bei gleichzeitiger Anwesenheit von Titandioxyd beruht darauf, daß das Titandioxyd sich in solchen Schmelzen nicht restlos löst, sondern zu einem gewissen Teil suspendiert bleibt, also etwas trübt und das beabsichtigte Schwarz aufhellt. Dies ist in um so stärkerem Maß der Fall, je höher der Tonerdegehalt ist.- The adverse effect of a normal or excessive improvement of the Acid resistance even increased according to the previous rules Alumina content on the blackening with the simultaneous presence of titanium dioxide is based on the fact that the titanium dioxide does not completely dissolve in such melts, but remains suspended to a certain extent, so something cloudy and the intended one Black brightens. This is the more the case, the higher the alumina content is.

Die Wirkung des verringerten Tonerde-(Feldspat-)Gehaltes möge an Hand der folgenden Emailversätze als Beispiele gezeigt werden. Email Nr. I Versatz Berechnete F rittenzusammensetzung Feldspat ................................ 25,87 Gewichtsteile Si02 33,9% Flußspat ...................................... 4,20 - B203 I7,2% Kryolith ...................................... 3,44 - A1203 6,7% Quarz ....................................... 8,59 - Ba0 2,6% Borax ........................................ 37,80 - Zn0 6,6% Soda ......................................... 2,57 - Na20 I3,6% Kalisalpeter ................................... 3,69 - K20 1,9% Bariumcarbonat ................................ 2,58, - CaF2 5,4% Kobaltoxyd ................................... o,52 - Na3AIFa 4,4% Manganoxyd ................................... 3,01 - C00 o,6% Kupferoxyd ................................... o,52 - Mn02 3,9% Zinkoxyd ..................................... 5,15 - Cu0 o,6% Eisenoxyd ..................................... 2,o6 - Fe203 2,6% 100,0 % Zur mühle: Ton 6,o entsprechend .................................. S102 3,2 % A1203 2,0 % Z05;2 °/o Tonerdegehalt im fertigen Email 8,7 Gewichtsteile in 10s,2 Gewichtemail oder 8,25 % A1203.The effect of the reduced alumina (feldspar) content should be shown using the following enamel offsets as examples. Email No. I. Offset calculated F rite composition Feldspar ................................ 25.87 parts by weight Si02 33.9% Fluorspar ...................................... 4.20 - B203 I7.2% Cryolite ...................................... 3.44 - A1203 6.7% Quartz ....................................... 8.59 - Ba0 2.6% Borax ........................................ 37.80 - Zn0 6.6% Soda ......................................... 2.57 - Na20 I3.6 % Potash nitrate ................................... 3.69 - K20 1.9% Barium carbonate ................................ 2.58, - CaF2 5.4% Cobalt oxide ................................... o. 52 - Na3AIFa 4.4% Manganese oxide ................................... 3.01 - C00 o.6% Copper oxide ................................... o.52 - Mn02 3.9% Zinc oxide ..................................... 5.15 - Cu0 o.6% Iron oxide ..................................... 2, o6 - Fe203 2.6% 100.0% To the mill: tone 6, o corresponding to .................................. S102 3.2% A1203 2.0% Z05; 2 ° / o Alumina content in the finished enamel 8.7 parts by weight in 10s, 2 weight enamel or 8.25% A1203.

Dieser Versatz ergibt mit 6% Ton und gegebenenfalls mit dem üblichen Schwarzkörper vermahlen und aufgebrannt ein tiefschwarzes, wenig säurebeständiges Email mit insgesamt 8,25% Tonerde. Email Nr.2 Versatz Berechnete Frittenzusammensetzung Feldspat ...................................... 25,87 Gewichtsteile Si02 30,6% Flußspat ..................................... 4,20 - B203 15,6% Kryolith ...................................... 3,44 - A1203 6,1% Quarz ........................................ 8,59 - Ba0 2,3% Borax ........................................ 37,80 - Zn0 6,0% Soda ......................................... 2,57 - Na20 12,4% Kalisalpeter ................................... 3,69 - K20 1,8% Bariumcarbonat............................... 2,58 - CaF2 4.9% Kobaltoxyd ................................... 0,52 - Na3AIF4 4,1o/0 Manganoxyd ................................... 3,01 - C00 0,5% Kupferoxyd ................................... 0,52 - Mn02 3,5% Zinkoxyd ..................................... 5,Z5 - CuO 0,5% Eisenoxyd ..................................... 2,o6 - Fe203 2,3% Tifandioxyd ................................... 8,0o - T102 9,4% 100,0% Zur Mühle: Ton 6,o entsprechend .................................. Si02 3,2% Al203 20% 105,2% Tonerdegehalt im fertigen Email .................................... 7,7% Al203 Dieser Versatz ergibt unter denselben Verarbeitungsbedingungen wie oben ein häßliches gelbbraunes Email mit 7,7% Tonerde. Email Nr.3 Versatz Berechnete Frittenzusammensetzung Feldspat- ....................................... I5,oo Gewichtsteile Si02 26,o°% Flußspat ...................................... 4,20 - B203 18,3% Kryolith "...................................... 3,44 - A123 4,1% Quarz ........................................ 8,59 ' - Ba0 2,8% Borax ........................................ 37,8o - Zn0 7,0% Soda ......................................... 2,57 - Na20 12,80/0 Kalisalpeter................................... 3,69 - K20 2,00/0 Bariumcarbonät . . .............................. 2,58 - CaF2 . 5,80/0 Kobaltoxyd ................................... 0,52 - Na3A1F6 4.,7% Manganoxyd .................................... 3,01 - C00 0,7% Kupferoxyd .................................. 0,52 - Mn02 4,10/0 Zinkoxyd ..................................... 5,15 - Cu0 0,7% Titandioxyd ................................:.. 8,00 - Ti02 II,o0/0 100,0% Si02 3,2% A1203 2,00/0 . 105,2% Tonerdegehalt im fertigen Email ..................................... 5,80/0 A1203 Dieser Versatz ergibt, wiederum unter denselben Verarbeitungsbedingungen wie oben, ein tiefschwarzes Email mit 5,8% A1203; sein besonderer Vorzug gegenüber dem Versatze Nr. t ist, daß dieses Email Nr. 3 eine erhöhte chemische Widerstandsfähigkeit und einen wesentlich besseren Glanz hat.This offset results in a deep black, little acid-resistant enamel with a total of 8.25% clay, ground with 6% clay and possibly ground with the usual black body and burned on. Email # 2 Offset calculated Fries composition Feldspar ...................................... 25.87 parts by weight Si02 30.6% Fluorspar ..................................... 4.20 - B203 15.6% Cryolite ...................................... 3.44 - A1203 6.1% Quartz ........................................ 8.59 - Ba0 2.3% Borax ........................................ 37.80 - Zn0 6.0% Soda ......................................... 2.57 - Na20 12.4 % Potash nitrate ................................... 3.69 - K20 1.8% Barium carbonate ............................... 2.58 - CaF2 4.9% Cobalt oxide ................................... 0.52 - Na3AIF4 4.1o / 0 Manganese oxide ................................... 3.01 - C00 0.5% Copper oxide ................................... 0.52 - Mn02 3.5% Zinc oxide ..................................... 5, Z5 - CuO 0.5% Iron oxide ..................................... 2, o6 - Fe203 2.3% Tifan dioxide ................................... 8.0o - T102 9.4% 100.0% To the mill: tone 6, o corresponding to .................................. Si02 3.2% Al203 20% 105.2% Alumina content in the finished enamel .................................... 7.7% Al203 Under the same processing conditions as above, this offset results in an ugly yellow-brown enamel with 7.7% clay. Email # 3 Offset calculated Fries composition Feldspar- ....................................... I5, oo parts by weight Si02 26, o ° % Fluorspar ...................................... 4.20 - B203 18.3% Cryolite "...................................... 3.44 - A123 4.1% Quartz ........................................ 8.59 '- Ba0 2.8 % Borax ........................................ 37.8o - Zn0 7.0% Soda ......................................... 2.57 - Na20 12.80 / 0 Potash nitrate ................................... 3.69 - K20 2.00 / 0 Barium carbonate. . .............................. 2.58 - CaF2. 5.80 / 0 Cobalt oxide ................................... 0.52 - Na3A1F6 4th, 7% Manganese oxide .................................... 3.01 - C00 0.7% Copper oxide .................................. 0.52 - Mn02 4.10 / 0 Zinc oxide ..................................... 5.15 - Cu0 0.7% Titanium dioxide ................................: .. 8.00 - Ti02 II, o0 / 0 100.0% Si02 3.2% A1203 2.00 / 0 . 105.2% Alumina content in the finished enamel ..................................... 5.80 / 0 A1203 This offset results, again under the same processing conditions as above, a deep black enamel with 5.8% A1203; Its particular advantage over offset no. t is that this enamel no. 3 has increased chemical resistance and a significantly better gloss.

ee

Claims (1)

PATENTANSPRUCH: Schwarze Emails und Glasuren, die zur Erhöhung der chemischen Widerstandsfähigkeit Titandioxyd enthalten, dadurch gekennzeichnet, daß zur Erzielung eines tiefen Schwarz mittels der üblichen Farboxyde der Aluminiumoxydgehalt in den fertigen, eingebrannten Emails und Glasuren höchstens 7,5% beträgt.PATENT CLAIM: Black enamels and glazes used to increase the chemical resistance contain titanium dioxide, characterized in that to achieve a deep black using the usual Farboxyde the aluminum oxide content in the finished, fired enamels and glazes does not exceed 7.5%.
DE1938K0149813 1938-03-05 1938-03-05 Black enamels and glazes Expired DE702057C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE1938K0149813 DE702057C (en) 1938-03-05 1938-03-05 Black enamels and glazes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1938K0149813 DE702057C (en) 1938-03-05 1938-03-05 Black enamels and glazes

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DE702057C true DE702057C (en) 1941-01-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2498912A (en) * 1944-05-11 1950-02-28 Rhone Poulenc Sa Process for glazing earthenware and glaze therefor
US2697159A (en) * 1951-08-14 1954-12-14 Foote Mineral Co Welding electrode and coating and method of making the same
DE973699C (en) * 1943-03-13 1960-05-05 Bayer Ag Melt offset for the production of white enamels clouded by titanium

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE973699C (en) * 1943-03-13 1960-05-05 Bayer Ag Melt offset for the production of white enamels clouded by titanium
US2498912A (en) * 1944-05-11 1950-02-28 Rhone Poulenc Sa Process for glazing earthenware and glaze therefor
US2697159A (en) * 1951-08-14 1954-12-14 Foote Mineral Co Welding electrode and coating and method of making the same

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