DE2338154C3 - Ceramic stains containing praseodymium and process for their manufacture - Google Patents
Ceramic stains containing praseodymium and process for their manufactureInfo
- Publication number
- DE2338154C3 DE2338154C3 DE19732338154 DE2338154A DE2338154C3 DE 2338154 C3 DE2338154 C3 DE 2338154C3 DE 19732338154 DE19732338154 DE 19732338154 DE 2338154 A DE2338154 A DE 2338154A DE 2338154 C3 DE2338154 C3 DE 2338154C3
- Authority
- DE
- Germany
- Prior art keywords
- oxide
- praseodymium
- color
- metals
- niobium
- 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
Links
- 229910052777 Praseodymium Inorganic materials 0.000 title claims description 12
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 title claims description 12
- 239000000919 ceramic Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- SFPKXFFNQYDGAH-UHFFFAOYSA-N oxomolybdenum;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.[Mo]=O SFPKXFFNQYDGAH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- CZGLYMZAAVMELC-UHFFFAOYSA-N [O-2].[Pr+3].[Si](=O)=O.[O-2].[O-2].[Zr+4] Chemical compound [O-2].[Pr+3].[Si](=O)=O.[O-2].[O-2].[Zr+4] CZGLYMZAAVMELC-UHFFFAOYSA-N 0.000 claims 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N Antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- HPZIIFVSYNLWNX-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3] HPZIIFVSYNLWNX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DLVOPAQBSQIZPI-UHFFFAOYSA-N [O-2].[Pr+3].[Si](=O)=O.[O-2].[Zr+4] Chemical compound [O-2].[Pr+3].[Si](=O)=O.[O-2].[Zr+4] DLVOPAQBSQIZPI-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- YIXQSYHBXUBLPM-UHFFFAOYSA-N dioxido(oxo)silane;zirconium(4+) Chemical compound [Zr+4].[O-][Si]([O-])=O.[O-][Si]([O-])=O YIXQSYHBXUBLPM-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Description
3030th
Die vorliegende Erfindung betrifft praseodymhaltige keramische Farbkörper, die zusätzlich 0,01 bis 10% eines Oxids der Metalle Antimon, Wismut, Niob und/oder Tantal enthalten, und ein besonders vorteilhaftes Verfahren zur Herstellung dieser Farbkcirper unter Verwendung eines Molybdänoxid/Natriumchloridgemisches als Mineralisator.The present invention relates to praseodymium-containing ceramic stains which additionally contain 0.01 to 10% an oxide of the metals antimony, bismuth, niobium and / or tantalum, and a particularly advantageous one Process for the production of these colored bodies using a molybdenum oxide / sodium chloride mixture as a mineralizer.
Gelbe keramische Farbkörper des Systems Zirkoniumoxid-Siliziumdioxid-Praseodymoxid werden wegen ihrer Farbreinheit und Brennbeständigkeit in beträchtli- 4" chen Mengen zur Anfärbung von Glasuren verwendet. Diese einfachen praseodymhaltigen Zirkoniumsilikatfarbkörper haben jedoch den Nachteil, daß ihre gelbe Farbe wenig farbintensiv ist.Zirconia-silica-praseodymium oxide system yellow ceramic stains are due to their color purity and fire resistance in considerable 4 " Chen quantities used to color glazes. These simple praseodymium-containing zirconium silicate stains however, have the disadvantage that their yellow color is not very intense.
Es hat daher nicht an Versuchen gefehlt, die Intensität dieser Gelbfarbkörper zu steigern, indem mian weitere oxidische Zusätze einbaute, wie z. B. Oxide der Seltenen Erden, Wolframoxid, Erdalkalioxide, Bleioxid oder Kupferoxid (JA-PS 5239, US-PS 29 92 123 und 12 998, DT-AS 12 22 840 und 12 22841, DT-OS 71 484). Bei diesen Farbkörpern konnte die Farbintensität zwar gesteigert werden, für viele Anwendungszwecke sind jedoch noch intensivere Farbkörper erwünscht, die insbesondere auch zusätzliche Farbschattierungen aufweisen sollten.There has therefore been no lack of attempts to increase the intensity of these yellow color bodies by adding more built-in oxidic additives, such as B. Rare earth oxides, tungsten oxide, alkaline earth oxides, lead oxide or Copper oxide (JA-PS 5239, US-PS 29 92 123 and 12 998, DT-AS 12 22 840 and 12 22841, DT-OS 71 484). In the case of these color bodies, the color intensity could be increased, but for many purposes the color bodies are even more intense desirable, which in particular should also have additional shades of color.
Es war daher Aufgabe der vorliegenden Erfindung, praseodymhaltige keramische Farbkörper zu finden, die einen intensiveren Farbton und zusätzliche Farbschattierungen besitzen.It was therefore an object of the present invention to find praseodymium-containing ceramic stains which have a more intense shade and additional shades of color.
Diese Aufgabt: wurde erfindungsgemüß durch einen keramischen Farbkörper des Systems Zirkoniumoxid-Siliziumdioxid-Praseodymoxid gelöst, der zusätzlich 0,01 bis 10% eines Oxids der Metalle Antimon, Wismut, Niob und/oder Tantal enthält. Vorzugsweise enthält dieser Farbkörper 0,1 bis 1% der genannten Metalloxide. Besonders bewährt hat sich der Zusatz von Antimonoxid.This task: was according to the invention by a ceramic color body of the system zirconium oxide-silicon dioxide-praseodymium oxide dissolved in addition 0.01 to 10% of an oxide of the metals antimony, bismuth, niobium and / or tantalum. Preferably contains this color body 0.1 to 1% of the metal oxides mentioned. The addition of Antimony oxide.
Die erfindungsgemäßen Farbkörper haben einen grünstichig gelben Farbton und besitzen eine höhere Farbkraft als die bisher bekannten Praseodymgelbfarbkörper, bei guter chemischer und thermischer Stabilität.The color bodies according to the invention have a greenish yellow hue and have a higher hue Color strength than the previously known praseodymium yellow color bodies, with good chemical and thermal stability.
Die Herstellung der erfindungsgemäßen Farbkörper erfolgt durch Mischen der feingepulverten Ausgangsverbindungen, die in Form der Oxide oder von bei höheren Temperaturen oxidbildenden Verbindungen vorliegen können, und anschließendem Glühen bei 8500C bis 1250°C. Der bevorzugte Glühbereich liegt bei 1000 bis HOO0C. Vorteilhafterweise setzt man noch einen Mineralisator in Form von Natriumfluorid oder Natriumchlorid zu. Als Ausgangsverbindungen haben sich vor allem die reinen Oxide des Zirkoniums, des Siliziums, des Praseodyms und der Metalle Antimon, Wismut, Niob und/oder Tantal bewährt.The preparation of the pigments according to the invention is made by mixing the finely powdered starting compounds which may be present in the form of oxides or oxide-forming compounds at high temperatures, and followed by annealing at 850 0 C to 1250 ° C. The preferred glow range is 1000 to HOO 0 C. A mineralizer in the form of sodium fluoride or sodium chloride is also advantageously added. The pure oxides of zirconium, silicon, praseodymium and the metals antimony, bismuth, niobium and / or tantalum have proven particularly useful as starting compounds.
Die Oxide ZrO2 und SiO2 werden im molaren Verhältnis 1 :1 eingesetzt, dazu kommen 0,5 bis 10% Praseodymoxid und 0,01 bis 10% eines Oxids der Metalle Antimon, Wismut, Niob und/oder Tantal.The oxides ZrO 2 and SiO 2 are used in a molar ratio of 1: 1, plus 0.5 to 10% praseodymium oxide and 0.01 to 10% of an oxide of the metals antimony, bismuth, niobium and / or tantalum.
Besonders farbintensive Praseodymgelbfarbkörper enthält man, wenn das Kalzinieren der oxidischen Bestandteile in Gegenwart eines Mineralisatorsystems durchgeführt wird, das 1 bis 10% eines Oxids oder einer oxidbildenden Verbindung der Metalle Molybdän und/oder Wolfram enthält. Bewährt hat sich vor allem ein Mineralisatorsystem, das 1 bis 10% Molybäntrioxid und 10 bis 14% Natriumchlorid enthält, bezogen auf die Gesamtmenge der Ausgangsprodukte. Man erhält auf diese Weise einen besonders farbintensiven grünstichigen Praseodymgelbfarbkörper.Particularly intense praseodymium yellow pigments are contained when calcining the oxidic Ingredients is carried out in the presence of a mineralizer system containing 1 to 10% of an oxide or one oxide-forming compound of the metals molybdenum and / or tungsten. Above all, it has proven itself a mineralizer system containing 1 to 10% molybdenum trioxide and 10 to 14% sodium chloride, based on the Total amount of raw materials. In this way, a greenish tint with a particularly intense color is obtained Praseodymium yellow color bodies.
Das folgende Beispiel soll die Erfindung näher erläutert:The following example is intended to explain the invention in more detail:
36 g Zirkoniumdioxid werden mit 29 g Siliziumdioxid, 3 g Praseodymoxid und 1 g Antimontrioxid gemischt und fein gemahlen. Nach Zusatz einer Mischung von 26 g Natriumchlorid und 5 g Molybdäntrioxid wird 3 Stunden bei 1050°C geglüht. Das Glühprodukt wird gemahlen, salzfrei gewaschen und dann getrocknet. Man erhält hierbei einen sehr farbintensiven grünstichigen Gelbfarbkörper.36 g of zirconium dioxide are mixed with 29 g of silicon dioxide, 3 g praseodymium oxide and 1 g antimony trioxide mixed and finely ground. After adding a mixture of 26 g of sodium chloride and 5 g of molybdenum trioxide are calcined at 1050 ° C. for 3 hours. The glow product will ground, washed salt-free and then dried. A very color-intensive greenish tint is obtained here Yellow color bodies.
Ähnliche Farbkörper erhält man, wenn man statt Antimontrioxid die entsprechenden Oxide von Wismut, Niob und/oder Tantal verwendet. Durch Variation des zugesetzten Molybdänanteils läßt sich der Farbton des erfindungsgemäßen Farbkörpers bei gleichbleibender Farbintensilät in gewissen Grenzen verändern.Similar color bodies are obtained if, instead of antimony trioxide, the corresponding oxides of bismuth, Niobium and / or tantalum are used. By varying the amount of molybdenum added, the color of the Change color body according to the invention with constant color intensity within certain limits.
Claims (3)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732338154 DE2338154C3 (en) | 1973-07-27 | Ceramic stains containing praseodymium and process for their manufacture | |
| NL7409381A NL7409381A (en) | 1973-07-27 | 1974-07-11 | PRESEODYMIUM-CONTAINING CERAMIC COLOR BODIES. |
| ES428199A ES428199A1 (en) | 1973-07-27 | 1974-07-12 | Praseodymium containing ceramic pigments |
| US489435A US3899347A (en) | 1973-07-27 | 1974-07-17 | Praseodymium containing ceramic pigments |
| GB3179974A GB1435234A (en) | 1973-07-27 | 1974-07-18 | Praseodymium-containing ceramic pigments |
| IT69366/74A IT1016694B (en) | 1973-07-27 | 1974-07-25 | CERAMIC PIGMENTS CONTAINING PRASEO DIMIO AND PROCEDURE FOR THEIR PREPARATION |
| BR6193/74A BR7406193D0 (en) | 1973-07-27 | 1974-07-26 | CERAMIC PIGMENTS CONTAINING PRASEODYME AND PROCESS FOR ITS PREPARATION |
| JP8592474A JPS5710901B2 (en) | 1973-07-27 | 1974-07-26 | |
| BE6044703A BE818184A (en) | 1973-07-27 | 1974-07-26 | COLORING CERAMIC ELEMENTS CONTAINING PRASEODYM AND PROCESS FOR THEIR PREPARATION |
| FR7426308A FR2238689B1 (en) | 1973-07-27 | 1974-07-29 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732338154 DE2338154C3 (en) | 1973-07-27 | Ceramic stains containing praseodymium and process for their manufacture |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2338154A1 DE2338154A1 (en) | 1975-04-03 |
| DE2338154B2 DE2338154B2 (en) | 1977-02-03 |
| DE2338154C3 true DE2338154C3 (en) | 1977-09-22 |
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