CN101400743A - Fused product intended for the manufacture of coloured ceramic pigments - Google Patents
Fused product intended for the manufacture of coloured ceramic pigments Download PDFInfo
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- CN101400743A CN101400743A CNA2007800087107A CN200780008710A CN101400743A CN 101400743 A CN101400743 A CN 101400743A CN A2007800087107 A CNA2007800087107 A CN A2007800087107A CN 200780008710 A CN200780008710 A CN 200780008710A CN 101400743 A CN101400743 A CN 101400743A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0009—Pigments for ceramics
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0009—Pigments for ceramics
- C09C1/0012—Pigments for ceramics containing zirconium and silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/62—L* (lightness axis)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
Abstract
Fused product intended for the manufacture of coloured ceramic pigments, comprising a silica matrix included within which there are granules of primarily monoclinic zirconium and chromophoric ions and/or ions of a chromophore precursor.
Description
Technical field
The present invention relates to be used to make the fused product of chromatic ceramics pigment, this product comprises silica matrices, comprises the crystal grain that is mainly monoclinic zirconia in described silica matrices.The invention still further relates to these chromatic ceramics pigment, relate to the method for making this fused product and these pigment.
Background technology
As described in US 2441447, the manufacturing of chromatic ceramics pigment is the following order step routinely:
A) preparation silicon oxide, Zirconium oxide powder, chromophoric group or chromophoric precursor and randomly for obtaining the mixture of the required color additive of desired color;
B) in foundation chromophoric group and desired color and definite this mixture for some time of temperature lower calcination.
In steps A), for making US 2441447 described blue pigmentss, silicon oxide and zirconic ratio are corresponding to zirconium silicate or " zircon " (ZrO
2SiO
2) ratio.
At step B), US2441447 recommends, and is in 550-1200 ℃ of calcining at least one hour down in the situation of vanadium at chromophoric group.During calcining, zirconium white combines with silicon oxide and forms zircon.Chromophoric group itself physically or is chemically combined closely into zircon, forms coloured pigment in zircon intragranular or its near zone.
Except using the mixture of silicon oxide and Zirconium oxide powder, also known implementation dissociative zircon powder.For example GB1447276 has described dissociative zircon powder.Dissociative zircon powder and praseodymium oxide powder mixes are then 800-1000 ℃ of calcining down.For improving the intensity of the color that obtains, US5324355 has also recommended use dissociative zircon powder, and the mean sizes of its zirconium white crystal grain is between 0.5 to 3 μ m.
Chromophoric group also is used to the stable zirconium white that is obtained by the disassociation zircon, as described in EP 1076036.Need not calcining step, obtain the pigment that directly to use thus, although color can be by adjusting 1400 ℃ of thermal treatments in 3 hours.This processing can not make the zirconium white unstability.
Need the lower strong color pigment of manufacturing cost always.The objective of the invention is to satisfy these needs.
Summary of the invention
According to the present invention, this purpose is by being used to make the fused product realization of chromatic ceramics pigment, and this product comprises silica matrices, comprises the crystal grain and chromophoric group ion and/or the chromophoric group precursor ion that are mainly monoclinic zirconia in described silica matrices.
By hereinafter being described in more detail as seen, the pigment that is obtained according to fused product of the present invention by calcining pigment compared to existing technology has stronger color.Be not subjected to this theory, the contriver has explained the improvement of color, because chromophoric group is incorporated the zircon intragranular to the effect of color into by it and improved, passes through to obtain bigger zircon crystal grain on the other hand on the one hand.Yet, according to the present invention, embed chromophoric group or chromophoric group precursor in the silica matrices with ionic species, when zircon forms physically near zirconium white crystal grain.Chromophoric this availability preferably can increase chromophoric group and incorporate amount in the zircon into, also can help the growth of zircon crystal grain.The color of pigment thereby can strengthen.
In addition, when occurring with form of powder according to fused product of the present invention, chromophoric group or chromophoric group precursor including in this particles of powder have promoted the manufacturing of pigment.In fact allow to obtain immediately to treat with the simple mixtures of mineralizer in the incinerating mixture.Compared to existing technology, the manufacturing of this pigment thereby more economical and more practical.
Preferably, also comprise one or more following characteristics according to product of the present invention:
-zirconic at least 95% according to fused product of the present invention, preferred basic 100% is monocline.Thereby advantageously promoted the formation of zircon during the calcining.
-fused product shows as diameter less than 1mm, preferably less than 500 μ m, is more preferably less than 200 μ m, and is preferably greater than the bead form of 5 μ m.Such bead can need not grinding steps and make, thereby has reduced cost.In addition, calcining makes these beads be fragility thereby be easy to grind.
The mol ratio of-silica content and zirconia content between 0.8:1.2 and 1.2:0.8, preferred 1:1.
-chromophoric group is selected from the ion of praseodymium, vanadium and iron.
The microstructure of-zirconium white crystal grain and silica matrices is the microstructure of dissociative zircon.
-zirconium white crystal grain has the size greater than 0.1 μ m.Preferably, the size of zirconium white crystal grain is no more than 20 μ m, preferred 5 μ m.Advantageously, thereby promoted the synthetic of zircon during the calcining.
-product also comprises one or more color additives that for example is selected from the oxide compound of cerium, titanium and yttrium.
-preferably, therefore also comprise one or more promotes zircon synthetic additive to product during calcining, and for example is selected from the oxide compound of sodium, potassium and magnesium.Advantageously, when the mixture of the powder that contains foundation fused product of the present invention was allowing to calcine under the synthetic condition with the manufacturing beramic color of zircon, such additive made the amount of mineralizer reduce, even makes it useless.
The mol ratio of-chromophoric group and zirconium is less than 0.2, and is preferably greater than 0.01.
The integral body of-zirconium white, silicon oxide, chromophoric group or their precursor and possible additive account for according to product of the present invention greater than 99 quality %, be preferably greater than 99.5 quality %.Surplus is made of the impurity that is difficult to avoid.It is believed that being less than or equal to 1% foreign matter content can significantly not change the product that is obtained by feature of the present invention.
The invention still further relates to the method for making the fused product be used to make chromatic ceramics pigment, comprise following sequential steps:
A) preparation comprises the raw material of mixture M, and described mixture M is silicon oxide powder and is mainly Zirconium oxide powder, chromophoric group and/or the chromophoric group precursor of monocline and is preferably the mixture that obtains desired color required (one or more) color additive;
B) molten mixture M makes to form the melting material material;
C) cooling melt substance.
Therefore obtained wherein can make beramic color with strong color by calcining this fused product according to fused product of the present invention.Preferably, the parameter of adjusting present method makes this product comprise one or more above-mentioned preferred features.
Preferably, also have optional feature below one or more according to method of the present invention:
-silicon oxide powder and Zirconium oxide powder are to small part but preferably replaced by the zircon powder fully.Determining step b like this) and fusion c) and cooling conditions causing the zircon disassociation of in step a), introducing, and do not make the Zirconia-stabilized of generation.Preferably, implementing cooling in step c) makes be less than and solidifies melting material in 1 minute fully.The disassociation of the zircon that may exist has advantageously been facilitated in such cooling.If silicon oxide and Zirconium oxide powder are replaced by the zircon powder fully, can thereby be considered to mix chromophoric disassociation zircon according to product of the present invention.
-in step a), chromophoric amount is lower than its solubility limit in the zircon that can recombinate by calcining.
-when chromophoric group was zirconium white potential stablizer, praseodymium for example determined that chromophoric amount makes and is lower than its solubility limit in the zircon that can recombinate that during calcining step this makes paints essential.
-chromophoric group and zirconic mol ratio be less than 0.1, and be preferably greater than 0.05.
-in step c), the melting material line is dispersed into bead, and the diameter of described bead preferably less than 500 μ m, is more preferably less than 200 μ m less than 1mm.Described bead preferably has the diameter greater than 5 μ m.
The invention still further relates to the method for making beramic color by calcining mixt, described mixture comprises:
Zero powder according to fused product of the present invention,
Zero mineralizer and/or promote at least a additive of zircon synthetic during calcining is preferably selected from the oxide compound of sodium, potassium and magnesium, and,
Zero when needing, one or more color additives,
Facilitate under the zircon synthetic condition well known to a person skilled in the art.
Preferably, present method comprises one or more following optional features:
The powder of-foundation product of the present invention shows as the form of one group of bead, and described bead diameter preferably less than 500 μ m, is more preferably less than 200 μ m less than 1mm, and/or is preferably more than 5 μ m.
-the fused product that obtained by implementation basis manufacture method of the present invention does not carry out grinding steps between the cooling melting material of the step c) of present method and calcining step.
-at 750-1600 ℃ of temperature lower calcination, preferably continue 0.5-6 hour.
Separate reunion after the-calcining, even grind, be preferably formed beramic color, described beramic color size is more than or equal to 10 μ m, and be preferably greater than or equal 20 μ m, and preferably less than 50 μ m, preferably less than 30 μ m.Therefore, have the advantage of the direct manufacturing dimension of permission greater than the pigment of 10 μ m according to method of the present invention, thereby durable especially (it is new), and separate the reunion condition by adjusting, even grinding condition, can make and have, for example the pigment of 3-15 μ m size less than 15 μ m.
The invention still further relates to the pigment of the method manufacturing that makes paints by the present invention.Preferably, the size of this beramic color is preferably greater than 20 μ m more than or equal to 10 μ m, and preferably less than 50 μ m, preferably less than 30 μ m.
At last, the present invention relates to the purposes according to pigment of the present invention, be used in particular in body or with enamel, making ceramic component painted, for example be used for ceramic tile, bathroom, dish, or even be used to make coloring plastic.
Embodiment
" be mainly the zirconium white of monocline " and be meant that wherein 90 quality % are zirconium whites of monocline.
" chromophoric group " generally is meant color molecule.In foundation fused product of the present invention, chromophoric group exists with ionic species.In according to the raw material for preparing in the step a) of method of the present invention, they can be any form, particularly oxide form.
" chromophoric group precursor " is meant can provide chromophoric component in according to the calcining of fused product of the present invention and/or manufacturing processed.Chromophoric group precursor thereby can be according to being included in the raw material in the step a) of method of the present invention, and/or be present in according in the fused product of the present invention.
" size " is meant the out to out of particle or crystal grain.
" fused product " is meant the product that solidifies acquisition by fusion then.
" calcining " is meant and can forms zircon from silicon oxide and the zirconium white that exists, promptly facilitate by the heat treatment step of making the pigment of strong color according to fused product of the present invention.Calcining comprises the enforcement of one or more mineralizers usually.
Comprise and silicon oxide (SiO according to fused product of the present invention
2) the continuous zirconium white (ZrO of matrix
2) crystal or " crystal grain ".
Preferably, zirconium white crystal grain has the size of 0.1-5 μ m.In fact this small size has promoted the reaction with silicon oxide during calcining.
Preferably, zirconic at least 95% according to product of the present invention, preferred basic 100% is monocline.In fact zirconic this form is necessary for facilitate the synthetic of zircon by calcining.
Preferably, the ratio of silicon oxide and zirconium white ratio is corresponding to the corresponding ratio of disassociation zircon, i.e. silicon oxide and zirconic mol ratio thereby be approximately 1:1, or mass ratio is approximately 1:2.Silicon oxide of Xian Dinging and zirconic ratio like this are in fact corresponding to zircon (SiO
4Zr) stoichiometric ratio of building-up reactions, described building-up reactions will be during calcining step the deuterogenesis.
Yet excessive silicon oxide or zirconium white also are acceptables, as long as silicon oxide and zirconic mol ratio remain between 0.8:1.2 and the 1.2:0.8.
For the mol ratio that guarantees silica content and zirconia content is 1:1, also be economic cause, preferably silicon oxide and zirconium white come from zirconic disassociation.Therefore, the microstructure that is included in the zirconium white crystal grain in the silica matrices is the microstructure of dissociative zircon, and zirconium white crystal grain is dispersed in the silica matrices in very uniform mode.
The method of disassociation zircon as well known to those skilled in the art.Especially, as making according in the preferred method of product of the present invention, disassociation can be produced by the violent cooling that the zircon base is bathed.Be different from known dissociative zircon product, include chromophoric group ion or chromophoric group precursor ion in according to product of the present invention.These can be dissolved in the glassy phase, or are dissolved in the zirconium white crystal grain, or even exist with the particle form that is dispersed in the zirconium white matrix.In this last situation, described particle has the mean sizes of 1-100nm.This dispersion is uniformly substantially, thereby has promoted the color development ion to incorporate into during calcining in the zircon of formation.
Chromophoric group or chromophoric group precursor can add by oxide form, and be compatible with manufacture method.They can be selected according to the pigment color of expectation.
Preferably, from the group that forms by praseodymium, select chromophoric group, from the group that forms by vanadium, select chromophoric group for obtaining blueness for obtaining yellow.
As the example of chromophoric group precursor, can mention praseodymium oxide (Pr for example especially
6O
11), praseodymium oxalate, praseodymium carbonate, barium oxide (V for example
2O
5), ammonium meta-vanadate and composition thereof.
Preferably, also comprise one or more required color additives of acquisition desired color according to product of the present invention.These well known to a person skilled in the art that additive can for example be selected from cerium, yttrium and titanyl compound.These additives can change the color of pigment, particularly its tone.Preferably, include in according in the product of the present invention obtaining all required additives of desired color.Advantageously, including the method that makes paints that these additives help describing subsequently in according in the product of the present invention.In fact, had only at this moment before calcining to adding mineralizer according in the product of the present invention.
According to product of the present invention can be any form and yardstick.
Yet in order to optimize the synthetic of zircon during the calcining, preferably the size of zirconium white crystal grain is no more than 20 μ m.But when the zirconium white according to product of the present invention was produced by the zircon disassociation, the size of zirconium white crystal grain depended on rate of cooling closely.Therefore, the quenching mode that depends on employing according to the preferred yardstick of product of the present invention.
Preferably, fused product shows as bead form, and described bead diameter preferably less than 500 μ m, be more preferably less than 200 μ m, and diameter is preferably greater than 5 μ m less than 1mm.
For making, implement above-mentioned steps) a) to c according to fused product of the present invention.
In step a), thorough mixing zircon powder or silicon oxide and Zirconium oxide powder, (one or more) chromophoric group or its precursor and preferred color additive.
Preferably use natural zircon sand (ZrSiO
4) replacing silicon oxide and Zirconium oxide powder, described natural zircon sand contains the monocline ZrO of the 66 quality % that have an appointment
2With 33% quality SiO
2(+impurity), determining step b) and c) with the disassociation zircon.Compare and use and mix pure zirconium white and silicon oxide powder, the disassociation zircon is more economical.Dissociative zircon powder is for example to be sold with title COLORTONE by Z-TECH company.
The powder that is used for raw material can have the mean diameter D50 of 5 μ m to 1mm, and this feature is not to be restrictive.Typically, zircon uses with the form of sand and has the mean diameter of 100-500 μ m.
Chromophoric amount is unrestricted and can set according to the desired color of pigment and tone.Yet, when being Zirconia-stabilized dose (for example praseodymium) and zirconium white, chromophoric group do not dissociate when producing by zirconium, determine chromophoric amount so that be lower than its solubility limit in zircon, may in calcining step, recombinate.Under this amount, chromophoric group can not make Zirconia-stabilizedization that produces during the zircon disassociation.Preferably, chromophoric group and zirconic mol ratio are lower than 0.2, and are preferably greater than 0.01.
Can use all known color additive, particularly cerium, yttrium and titanyl compound.
Implementation step b routinely) fusion avoids making Zirconia-stabilizedization of existence.Can be higher than 1700 ℃ and be lower than under 2500 ℃ of temperature, preferably in barometric point and air, in electric furnace or any melting plant that other is fit to, implement this fusion.
The rate of cooling of step c) is not restrictive.Yet, the zircon that dissociates if desired, cooling must be violent (quenching).Can consider all known fast cold modes, as long as melt substance solidified in preferred 30 seconds fully in 1 minute.
Preferably, by winding-up cooling fluid (for example air or water vapour), or the method for any other atomize molten material well known by persons skilled in the art is dispersed in the melting material thread in the particle.Because surface tension, the particle of melting material presents sphere.Preferably, determine the flow rate of winding-up cooling liqs during jetting, make the bead that obtains have diameter less than 1mm.
The sphere of bead has advantageously been given big outside exchange surface, thereby has improved rate of cooling, and the diameter of bead is littler.Therefore, allow to form little zirconium white crystal grain, be typically 0.1-3 μ m.Advantageously, such crystal grain has promoted the formation of zircon crystal grain big during the calcining.
The size of bead can be used by adjusting scattering parameter according to the expectation of pigment and regulate.Can produce the bead that has less than the 10mm diameter like this.
For by making chromatic ceramics pigment, can calcine the mixture of this product and mineralizer according to product of the present invention.
In product according to the present invention, include in and obtain coloured pigment required all components, particularly silicon oxide, zirconium white and chromophoric group/chromophoric group precursor, by with the simple mixtures of mineralizer, can obtain to treat to feed in incinerating.
During calcining, silicon oxide and monoclinic zirconia reaction form and merge color development ionic zircon.
Therefore this calcining is efficient, preferably shows as powder type according to product of the present invention, and its particle has the size less than 1mm.Yet these particulate sizes are determining the out to out of zircon crystal in the pigment.Preferably, this size is greater than 5 μ m.At this moment, zircon crystal can for example surpass 20 μ m, and advantageously very stable.According in pigment of the present invention and the situation that the material that is tending towards dissolving them (as enamel) contacts, enhanced stability is particularly useful.In addition, big zircon crystal allows in the color development ionic active set, thereby provides intensive intensity for the color of pigment.
Mineralizer is used to reduce the synthesis temperature of zircon.It also influences the color of pigment.As the example of mineralizer, can mention the fluorochemical and the muriate of basic metal and alkaline-earth metal.
Preferably, the foundation product of the present invention that obtains after the step c) is calcined, do not ground or intermediary operation independently and have.This calcining is called " directly ".Directly calcining makes the incinerating product have big scale, and therefore for example forms the zircon crystal of size greater than 10 μ m.
The pigment that calcining back obtains can directly use, if or use requiredly, can be ground or be crushed to than grain fineness number.In fact its color and tint that provides is provided the granularity of pigment.Grind if desired, directly calcining also is favourable.In fact, it makes that according to product of the present invention be fragility.Therefore, the preceding grinding of calcining is compared in the grinding after the calcining needs remarkable energy still less.Advantageously, so cost is significantly lower, allows to improve the colour stability of the pigment of making simultaneously.
Preferably, implement to grind in direct calcining back, to obtain to have the pigment of expectation yardstick, mean sizes is preferably greater than or equals 10 μ m, and be preferably greater than or equal 20 μ m, and preferably less than 50 μ m, preferably less than 30 μ m.As a comparison, beramic color has the mean sizes of 4-8 μ m routinely.
Can consider to make conventional all method for calcinating that use of coloured pigment by chromophoric group, silicon oxide and zirconium white.Preferably, under 750-1600 ℃ of temperature, in air, more preferably under barometric point, implement calcining.Select incinerating temperature and time length according to pigment desired color and the mineralizer that may exist.
During calcining, itself be transformed into the stronger pigment of color pigment compared to existing technology according to product of the present invention, this may be owing to zircon (SiO
4Zr) chromophoric better availability during the formation.Adopt praseodymium as chromophoric group, the component L that determines according to CIE-Lab-Colour color system (ASTME308-01 standard " by adopting the standard operation of CIE system-computed object color ") is weak (stronger pigment) especially significantly, and it is high-level that component b keeps.
Provide following embodiment and test as an illustration, do not limit the present invention.
Embodiment 1
The charging of preparation 30kg is by the zircon ZrSiO of 28.5kg
4With 1.5kg praseodymium oxide Pr
6O
11Constitute.Fusion should charging in electric smelter.Then, molten mixture cools off tempestuously by air quenched quilt.Obtained to have spheroidal particle less than the 1mm size.
The particulate material that obtains is composed as follows: ZrO
2: SiO 66%,
2: 27.7% and Pr
6O
11: 5.34%.Surplus is an impurity.
Then, account for standard mineralizer (NaF, the NH that forms 5 quality % in existence
4Cl) under the situation, under 1000 ℃ of temperature, these particles of calcining are 3 hours in the sealing mullite sagger.
By the processing in the waterborne suspension in being equipped with the wide-necked bottle of Ceramic Balls,, dry then to producing by reaction and separating reunion by the product that zircon constitutes.Therefore obtained to have the mean sizes of 23.8 μ m according to yellow of the present invention-Pr pigment.
By glazing in the marzacotto (frit) under 1180 ℃ of temperature, according to circulation in complete 1 hour, measure colorimetric parameter L, a, b according to ASTM E308-01 standard " by adopting the standard operation of CIE system-computed object color " then, estimate the chromaticity properties of pigment.Obtained following result: L=79.2; A=0.6; B=39.7.
Embodiment 2
The charging of current preparation 30kg is by the zircon ZrSiO of 14.5kg
4, 7kg zirconium white ZrO
2, 7kg silicon oxide sio
2, and 1.5kg praseodymium oxide Pr
6O
11Constitute.In the mode identical with embodiment 1, fusion should charging in electric smelter.Then, molten mixture cools off tempestuously by air quenched quilt, under the same terms that adopts with embodiment 1.Obtained to have spheroidal particle less than the 1mm size.
Gained particulate material is composed as follows: ZrO
2: SiO 65.5%,
2: 28.2% and Pr
6O
11: 5.45%.Surplus is an impurity.
Then, account for standard mineralizer (NaF, the NH that forms 5 quality % in existence
4Cl) under the situation, under 1000 ℃ of temperature, these particles of calcining are 3 hours in the sealing mullite sagger.
By the processing in the waterborne suspension in being equipped with the wide-necked bottle of Ceramic Balls,, dry then to producing by reaction and separating reunion by the product that zircon constitutes.Therefore obtained to have the mean sizes of 21.9 μ m according to yellow of the present invention-Pr pigment.
By glazing in marzacotto under 1180 ℃ of temperature, according to circulation in complete 1 hour, measure colorimetric parameter L, a, b according to ASTM E308-01 standard " by adopting the standard operation of CIE system-computed object color " then, estimate the chromaticity properties of pigment.Obtained following result: L=79.2; A=0.3; B=40.1.
Embodiment 3
In the present embodiment, prepare charging in the mode identical with embodiment 1.Melting condition is also identical.Then, molten mixture cools off tempestuously by air quenched quilt, under the condition more violent than embodiment 1.Obtained to have spheroidal particle less than the 0.2mm size.
Gained particulate material is composed as follows: ZrO
2: SiO 65%,
2: 29.1% and Pr
6O
11: 5.73%.Surplus is an impurity.
Then, account for standard mineralizer (NaF, the NH that forms 5 quality % in existence
4Cl) under the situation, under 1000 ℃ of temperature, these particles of calcining are 3 hours in the sealing mullite sagger.
By the processing in the waterborne suspension in being equipped with the wide-necked bottle of Ceramic Balls,, dry then to producing by reaction and separating reunion by the product that zircon constitutes.Therefore obtained to have the mean sizes of 18.5 μ m according to yellow of the present invention-Pr pigment.
By glazing in marzacotto under 1180 ℃ of temperature, according to circulation in complete 1 hour, measure colorimetric parameter L, a, b according to ASTM E308-01 standard " by adopting the standard operation of CIE system-computed object color " then, estimated the chromaticity properties of pigment.Obtained following result: L=79.5; A=-0.7; B=39.4.
Comparative example
As a comparison, by traditional method synthesizing yellow-Pr pigment, this pigment is made by the mixture of zirconium white, silicon oxide, praseodymium oxide reactant and mineralizer, according to following composition: ZrO
2: SiO 59.7%,
2: 29.9% and Pr
6O
11: 5.4% (or Pr/Zr ratio is very near ratio of front embodiment).Surplus is a mineralizer.
The mineralizer that adopts, and the identical of aggregation procedure and embodiment 1 conciliate in the calcining of pigment.The pigment that obtains has the mean sizes of 6 μ m.This size is significantly less than the size of the pigment that is obtained by previous embodiment.
By glazing in marzacotto under 1180 ℃ of temperature, according to circulation in complete 1 hour, measure colorimetric parameter L, a, b then, estimate the chromaticity properties of pigment.Obtained following result: L=80.9; A=-1.1; B=41.
Notice that the pigment that obtains according to traditional method has intensity and the red tone that significantly is lower than the pigment that is obtained by front embodiment.
Clear now, the invention provides a kind of fused product, it makes it possible to have by the simplified method manufacturing pigment of strong color, and this method is more more economical than currently known methods.These pigment comprise big zircon crystal and very stable, particularly with situation that enamel contacts in.
Certainly, the invention is not restricted to described embodiment, provide these embodiments only as an example.
For example, can before calcining, grind product of the present invention.
The calcining before and/or afterwards, also may be according to color of object and application implementation separating step.
It will also be appreciated that other method of disassociation zircon, as long as they do not cause stable zirconium white.
Claims (19)
1. be used to make the fused product of chromatic ceramics pigment, comprise silica matrices, comprise in the described silica matrices:
-zirconium white crystal grain, wherein greater than 90 quality % be monocline and
-chromophoric group and/or chromophoric group precursor exist with ionic species.
2. according to the fused product of claim 1, wherein at least 95% zirconium white is a monocline.
3. according to the fused product of claim 1 or 2, its form is the bead that diameter is lower than 1mm.
4. according to each fused product of aforementioned claim, wherein the mol ratio of silica content and zirconia content at 0.8:1.2 between the 1.2:0.8.
5. according to each fused product of aforementioned claim, wherein chromophoric group is selected from the ion of praseodymium and vanadium.
6. according to each fused product of aforementioned claim, wherein the mol ratio of chromophoric group and zirconium is less than 0.2 and greater than 0.01.
7. according to each fused product of aforementioned claim, this fused product comprises one or more color additives and/or one or more promote zircon synthetic additive during calcining.
8. according to each fused product of aforementioned claim, wherein zirconium white, silicon oxide, chromophoric group or its precursor and optional additive account for product greater than 99 quality %.
9. be used to make the manufacture method of the fused product of chromatic ceramics pigment, comprise the following order step:
A) preparation comprises the raw material of mixture M and/or zircon powder, and described mixture M is silicon oxide powder and is the mixture of the Zirconium oxide powder of monocline greater than 90 quality %;
B) molten mixture M is to form the melting material material;
C) cooling melt substance,
Determine raw material so that finishing the back in step c) obtains according to each fused product of aforementioned claim, bed blending/or step b) during add chromophoric group and/or chromophoric group precursor.
10. according to the manufacture method of last claim, determining step b wherein) and c) so that dissociate described zircon.
11. according to the manufacture method of claim 9 or 10, wherein in step a), chromophoric amount is less than its solubility limit in the zircon that can recombinate by calcining.
12. according to each manufacture method of claim 9-11, wherein, in step c), the melting material thread is dispersed into bead, the diameter of described bead less than 1mm and/or diameter greater than 5 μ m.
13., wherein, in step c), cool off in less than 1 minute, to solidify melting material fully according to each method of claim 9-12.
14. by the method for calcining mixt manufacturing beramic color, described mixture comprises:
-according to the powder of each fused product among the claim 1-8 and
-mineralizer and/or at least aly during calcining, promote zircon synthetic additive facilitating under the zircon synthetic condition.
15. the method for the manufacturing beramic color of the last claim of foundation, according to this method, the fused product by each method among the implementation basis claim 9-12 obtains does not carry out grinding steps between the step c) of this method is cooled off melting material and calcined.
16. the method for the manufacturing beramic color of the last claim of foundation according to this method, is ground after the calcining.
17. according to the method for each manufacturing beramic color among the claim 14-16, wherein, under 750-1600 ℃ of temperature, calcine, continue 0.5-6 hour.
18., wherein, during calcining, promote zircon synthetic additive to be selected from the oxide compound of sodium, potassium and magnesium and their mixture according to the method for each manufacturing beramic color among the claim 14-17.
19. according among the claim 14-18 each the method manufacturing or by each the pigment fused product manufacturing or that make by the fused product made according to each method among the claim 9-13 among the foundation claim 1-8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0600983 | 2006-02-03 | ||
| FR0600983A FR2897056B1 (en) | 2006-02-03 | 2006-02-03 | MELT PRODUCT FOR THE MANUFACTURE OF COLORED CERAMIC PIGMENTS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101400743A true CN101400743A (en) | 2009-04-01 |
Family
ID=37101393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800087107A Pending CN101400743A (en) | 2006-02-03 | 2007-01-30 | Fused product intended for the manufacture of coloured ceramic pigments |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1987105A2 (en) |
| CN (1) | CN101400743A (en) |
| BR (1) | BRPI0707416A2 (en) |
| EA (1) | EA012229B1 (en) |
| FR (1) | FR2897056B1 (en) |
| TW (1) | TW200734414A (en) |
| WO (1) | WO2007088304A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791124A (en) * | 2019-11-07 | 2020-02-14 | 湖南易兴建筑有限公司 | Nano inorganic pigment and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2441447A (en) * | 1946-02-15 | 1948-05-11 | Harshaw Chem Corp | Ceramic pigments |
| GB1447276A (en) * | 1973-09-17 | 1976-08-25 | Keeling Walker Ltd | Production of calcined ceramic pigments |
| DE4106536A1 (en) * | 1991-03-01 | 1992-09-03 | Degussa | THERMALLY-PAINTED ZIRCONYLICATE, METHOD FOR THE PRODUCTION AND USE THEREOF |
| FR2797440B1 (en) * | 1999-08-13 | 2003-08-29 | Cerdec Ag | PROCESS FOR PRODUCING STABILIZED CUBIC ZIRCONIUM OXIDE PRODUCTS, PRODUCTS OBTAINED BY THIS PROCESS AND THEIR USE |
-
2006
- 2006-02-03 FR FR0600983A patent/FR2897056B1/en not_active Expired - Fee Related
-
2007
- 2007-01-30 EP EP07731535A patent/EP1987105A2/en not_active Withdrawn
- 2007-01-30 BR BRPI0707416-6A patent/BRPI0707416A2/en not_active Application Discontinuation
- 2007-01-30 EA EA200801636A patent/EA012229B1/en not_active IP Right Cessation
- 2007-01-30 WO PCT/FR2007/050707 patent/WO2007088304A2/en active Application Filing
- 2007-01-30 CN CNA2007800087107A patent/CN101400743A/en active Pending
- 2007-02-02 TW TW096103910A patent/TW200734414A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791124A (en) * | 2019-11-07 | 2020-02-14 | 湖南易兴建筑有限公司 | Nano inorganic pigment and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007088304A3 (en) | 2007-09-20 |
| FR2897056A1 (en) | 2007-08-10 |
| FR2897056B1 (en) | 2008-07-04 |
| WO2007088304A2 (en) | 2007-08-09 |
| EP1987105A2 (en) | 2008-11-05 |
| EA200801636A1 (en) | 2008-12-30 |
| BRPI0707416A2 (en) | 2011-05-03 |
| TW200734414A (en) | 2007-09-16 |
| EA012229B1 (en) | 2009-08-28 |
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Open date: 20090401 |