CN116425518A - Stable-coloring non-color-difference ceramic and preparation method thereof - Google Patents
Stable-coloring non-color-difference ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims description 21
- 238000004040 coloring Methods 0.000 title description 14
- 239000000049 pigment Substances 0.000 claims abstract description 121
- 229960000892 attapulgite Drugs 0.000 claims abstract description 78
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 78
- 238000002156 mixing Methods 0.000 claims abstract description 38
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 26
- 238000007873 sieving Methods 0.000 claims abstract description 25
- PSUYMGPLEJLSPA-UHFFFAOYSA-N vanadium zirconium Chemical compound [V].[V].[Zr] PSUYMGPLEJLSPA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000010304 firing Methods 0.000 claims description 46
- 239000002002 slurry Substances 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 18
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000011787 zinc oxide Substances 0.000 claims description 16
- 230000005484 gravity Effects 0.000 claims description 15
- 229910003321 CoFe Inorganic materials 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 14
- 239000003086 colorant Substances 0.000 claims description 11
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052656 albite Inorganic materials 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 9
- 229910000278 bentonite Inorganic materials 0.000 claims description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 9
- 239000010440 gypsum Substances 0.000 claims description 9
- 229910052602 gypsum Inorganic materials 0.000 claims description 9
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 239000004575 stone Substances 0.000 claims description 9
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 9
- 235000012222 talc Nutrition 0.000 claims description 9
- 229910052623 talc Inorganic materials 0.000 claims description 9
- 229910052845 zircon Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000004075 alteration Effects 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000001055 blue pigment Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 235000021388 linseed oil Nutrition 0.000 description 3
- 239000000944 linseed oil Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000000037 vitreous enamel Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/19—Alkali metal aluminosilicates, e.g. spodumene
-
- 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
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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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
- C09C1/0012—Pigments for ceramics containing zirconium and silicon
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention discloses a color-stable non-color-difference ceramic, which comprises a blank body, a ground coat layer and a transparent glaze layer, wherein the ground coat layer contains ceramic pigment; the ceramic pigment is prepared by sieving the prepared vanadium-zirconium blue/attapulgite ceramic pigment and cobalt black/attapulgite ceramic pigment, grinding the sieved materials until the sieved materials pass through a 400-mesh sieve, mixing the two ceramic pigment according to different proportions according to ceramic color requirements to obtain a mixed pigment, further sintering the mixed pigment, and grinding the mixed pigment until the particle size is less than 50 mu m. According to the invention, the attapulgite, the vanadium-zirconium blue ceramic pigment and the cobalt black ceramic pigment are combined to form the inorganic hybrid pigment, so that the dispersion performance of the ceramic pigment in a ceramic system is obviously improved, the ceramic pigment has excellent thermal stability, tinting strength and luster, the ceramic has no chromatic aberration, and the cost of the ceramic pigment is reduced to a certain extent. Meanwhile, the ceramic is provided with the transparent glaze layer to cover and protect the glaze layer from color development.
Description
Technical Field
The invention belongs to the technical field of ceramic products, and particularly relates to a color-stable non-color-difference ceramic and a preparation method thereof.
Background
Ceramic colorants (ceramic colors) refer to powdered metal oxides and other mixtures used in ceramic glazes for decorating ceramics, porcelain and terracotta, and also in porcelain enamel for decorating metallics. In the prior art, the quality and the quality of the ceramic pigment can directly influence the chromaticity after ceramic molding, the preparation of the ceramic pigment becomes one of important links of ceramic coloring, and whether the ceramic pigment can be prepared into ceramic with good chromaticity is the key of ceramic production.
The following conditions are required for the ceramic coloring material: (1) High temperature stability, no decomposition and volatilization in the firing temperature range of ceramic products; (2) The structure is stable, and the glass can bear the erosion of molten glass or solvent in the sintering process; (3) The chemical property is stable, and the reaction with glaze or solvent can not occur. The ceramic coloring materials can be classified into low temperature type (600 to 1000 ℃) and high temperature type (1000 to 1400 ℃) according to the use temperature. The high-temperature pigment is characterized in that the pigment becomes a crystal after high-temperature calcination, and the pigment with the crystal structure is added into the basic glaze, so that the crystal is not decomposed in the glaze firing process. However, the high-temperature coloring material in the present stage has very few types, high preparation cost and unstable coloring due to the solid phase method.
In recent years, the inorganic hybrid pigment gradually attracts wide attention, and natural clay minerals become popular materials in the inorganic hybrid pigment due to rich reserves, greenness, no toxicity, low price and the like, and researches show that the introduction of the clay minerals in the preparation process of the cobalt blue pigment can obviously reduce the raw material cost and the high-temperature crystallization temperature of the cobalt blue pigment, and simultaneously improve the chromaticity and the dispersion performance of the cobalt blue pigment. At present, no inorganic hybrid pigment is applied to the research of ceramic products, has a larger research value, and solves the problems of high cost, unstable coloring effect and the like of the existing high-temperature pigment.
Disclosure of Invention
The invention aims to provide a color-stable non-color-difference ceramic, which is used for achieving color stability and no color difference, and an inorganic hybrid pigment is formed by combining attapulgite, a vanadium-zirconium-blue ceramic pigment and a cobalt black ceramic pigment, so that the dispersion performance of the hybrid pigment is obviously improved, and the color-difference ceramic has excellent thermal stability, tinting strength and luster as a ceramic pigment and no color difference. Meanwhile, the ceramic is provided with the transparent glaze layer to coat and protect the colored glaze layer.
In the invention, the two pigments are used in combination according to different proportions to give different color effects to the ceramic.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the non-color-difference ceramic comprises a blank body, a ground coat layer and a transparent glaze layer, wherein the ground coat layer contains ceramic pigment;
the preparation method of the ceramic pigment comprises the following steps:
s1, preparing a vanadium zirconium blue/attapulgite ceramic pigment: tetraethoxysilane and ZrOCl 2 ·8H 2 Mixing O with water for 20-40 min, slowly dropping ammonia water to pH 9-10 while stirring, centrifugal washing until no chloride ion exists, and adding coloring agent V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; calcining the powder at 900-1000 deg.c for 2-3 hr and maintaining for 10 min;
s2, preparing cobalt black/attapulgite ceramic pigment: fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1, a step of; then adding attapulgite, adding alkali liquor to adjust the pH value to 9-10 under stirring, continuously reacting for 2-3 h, centrifugally washing to be neutral, drying, grinding and sieving to obtain powder; calcining the powder at 950-1050 ℃ for 2-3 h;
s3, mixing and sintering: sieving the prepared vanadium-zirconium blue/attapulgite ceramic pigment and cobalt black/attapulgite ceramic pigment, grinding to pass through a 400-mesh sieve, mixing the two according to different proportions according to the ceramic color requirement to obtain a mixed pigment, further sintering the mixed pigment, and grinding to a particle size below 50 um.
The attapulgite is a water-containing magnesium-rich aluminosilicate clay mineral with a chain layered structure, the structure belongs to a 2:1 type clay mineral, in each 2:1 unit structural layer, the angles and tops of tetrahedral wafers are reversed at a certain distance to form a chain shape, channels parallel to the chains are formed among tetrahedral strips, the cross section of each channel is about 3.7 x 6.3A degrees, zeolite water, crystal water and a large amount of surface silicon hydroxyl groups are filled in each channel, so that the attapulgite is combined with ceramic pigment, the reaction activity is high, the combination effect is good, the dispersibility of the ceramic pigment in a slurry system can be obviously improved, the coloring effect is stable, no chromatic aberration exists, the cost of the pigment is reduced to a certain extent, and the attapulgite can be subjected to acid treatment before use, sieving, refining, washing and drying to improve the surface activity of the attapulgite.
The invention prepares the inorganic hybrid pigment through a coprecipitation method, particularly researches and optimizes the preparation process of the inorganic hybrid pigment, adjusts parameters such as calcination temperature, pH value of a reaction system and the like, and improves the tinting strength and stability of ceramic pigment.
In the present invention, preferably, in S1, tetraethyl orthosilicate and ZrOCl are used 2 ·8H 2 Mixing O with water for 30 min, slowly dripping ammonia water to pH 9 under stirring, centrifuging, washing until no chloride ion exists, and adding colorant V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; the powder is calcined at 950 ℃ for 3 hours, and the temperature is kept for 10 minutes, so that the raw materials in the inorganic hybrid pigment, especially the mineralizer NaF, can be well developed, the reaction parameters are set at 950 ℃ for 3 hours, and the heat is kept for 10 minutes, so that the tinting strength and stability of the inorganic hybrid pigment are improved.
In the present invention, preferably, in S1, the vanadium zirconium blue prepared has a molecular formula of V x Zr 1-x SiO 4 Wherein x is 0.2 to 0.4; the addition amount of the mineralizer NaF is V x Zr 1-x SiO 4 7-9 wt% of the weight, wherein the dosage of the attapulgite is V x Zr 1-x SiO 4 55-70 wt% of mineralizer NaF, and use of attapulgiteThe amount is obtained by the inventor through a large amount of experimental adjustment, and the prepared hybrid pigment has the optimal effect.
In the present invention, preferably, in S2, fe (NO 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1, a step of; then adding attapulgite, adding sodium hydroxide solution under stirring to adjust the pH value to 10, continuously reacting for 2 hours, centrifugally washing to be neutral, drying, grinding and sieving to obtain powder; the powder is calcined at 1000 ℃ for 2 hours, and the pH value is set for the reaction parameters, the calcining temperature is 1000 ℃ and the calcining time is 2 hours, so that the tinting strength and the stability of the inorganic hybrid pigment are improved.
In the invention, the molecular formula of the prepared cobalt black is CoFe 2 O 4 Preferably, the attapulgite is used in an amount of CoFe 2 O 4 50-70 wt% of the weight, and the dosage of the attapulgite is adjusted by a large amount of experiments, so that the prepared hybrid pigment has optimal effect.
In the invention, the blank is preferably prepared from the following raw materials in parts by weight: 40-50 parts of potassium feldspar, 25-30 parts of quartz, 15-20 parts of albite, 8-12 parts of bentonite, 6-8 parts of talcum, 5-8 parts of alumina and 3-6 parts of strontium carbonate; the ground coat layer is prepared from the following raw materials in parts by weight: 20-25 parts of quartz, 10-15 parts of potassium feldspar, 10-15 parts of kaolin, 8-12 parts of kieselguhr, 6-8 parts of zirconium silicate, 5-7 parts of lithium porcelain stone, 5-7 parts of zinc oxide, 3-5 parts of zircon, 3-5 parts of gypsum and 3-5 parts of ceramic pigment, and further preferably, the green body comprises the following raw materials in parts by weight: 45 parts of potassium feldspar, 28 parts of quartz, 16 parts of albite, 10 parts of bentonite, 7 parts of talcum, 6 parts of aluminum oxide and 5 parts of strontium carbonate; the ground coat layer is prepared from the following raw materials in parts by weight: 25 parts of quartz, 13 parts of potassium feldspar, 12 parts of kaolin, 10 parts of diatomite, 7 parts of zirconium silicate, 6 parts of lithium porcelain stone, 6 parts of zinc oxide, 5 parts of zircon, 4 parts of gypsum and 4 parts of ceramic pigment. The raw material content of the green body and the ground coat is obtained through a great deal of experiments and theoretical knowledge adjustment analysis, and the dosage is the preferable scheme of the invention, and the firing effect is good, the color development effect is good and no color difference exists.
In the present invention, preferably, the transparent glaze layer is composed of transparent frit, and the chemical composition of the transparent frit comprises, in weight percent: siO (SiO) 2 45～50％、B 2 O 3 20～25％、Al 2 O 3 8～10％、Na 2 O 6～8％、MgO 5～8％、K 2 O 2～4％、ZnO 1～2％、TiO 2 1～2％、CaCO 3 1～2％、LiO 2 0.5 to 1 percent, and the transparent frit of the invention is added with more B 2 O 3 The sintering temperature can be reduced, the density of the transparent glaze layer can be improved, and the gloss, uniformity and fineness of the glaze surface can be improved.
The invention also provides and protects the preparation method of the color stable non-color difference ceramic, which comprises the following steps:
s1, preparing a blank: uniformly mixing the raw materials of the green body, performing wet ball milling, performing ball milling until the granularity is 300-400 meshes, and granulating in a spray tower to obtain green body granules; pressing and forming the green body granules to obtain a coarse green body, and naturally air-drying;
s2, applying ground coat: mixing the raw materials of the ground coat, performing wet ball milling to obtain a granularity of 400-500 meshes, sieving to remove iron, and adding water to obtain glaze slurry with the solid content of 50-55%; spraying glaze slurry on the blank body, and then drying for standby; when the glaze slurry is sprayed, the specific gravity of the glaze is 1.7-1.8 g/ml, and the glazing quantity is 700-750 g/m 2 ；
S3, firing: firing the green body after applying the primer at 900-1100 ℃ for 120-160 minutes;
s4, shi Touming glaze: continuously spraying transparent glaze on the ground coat layer, wherein the solid content of the transparent glaze slurry is 30-40%, the specific gravity is 1.40-1.50 g/ml, and the glazing quantity is 300-400 g/m 2 ；
S5, low-temperature firing: and (3) continuously firing the transparent glaze layer after drying, wherein the firing temperature is 700-800 ℃ and the firing time is 2-3 hours.
When the glaze slurry is sprayed, the concentration of the glaze slurry is too low, and an excessively thin glaze layer is easily formed on a green body, so that the surface of the fired glaze layer is not smooth. However, the glaze slurry has too high concentration, relatively weakened fluidity and difficult and uniform flowThe invention optimizes the specific gravity and glazing quantity of the glaze slip according to the respective effects of the ground glaze layer and the transparent glaze layer, preferably, the ground glaze and the transparent glaze are both in vacuum degree of 10 before the glaze slip is sprayed -3 ～1×10 -2 The bubbles are removed in vacuum under the conditions of 50-55 ℃ under the pressure of MPa, the bubbles are removed in vacuum from the glaze slip, and the defects of air holes and the like are not easy to generate in the firing process.
The present invention may also add other raw material components to the ceramic raw material according to conventional knowledge in the art, and is not particularly limited thereto, but falls within the scope of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the attapulgite is combined with the vanadium-zirconium blue ceramic pigment and the cobalt black ceramic pigment to form the inorganic hybrid pigment, so that the dispersion performance of the ceramic pigment in a ceramic system is obviously improved, the ceramic pigment has excellent thermal stability, tinting strength and luster, the ceramic has no chromatic aberration, the cost of the pigment is reduced to a certain extent, and meanwhile, the ceramic is provided with a transparent glaze layer to coat and protect the glaze layer;
2. the invention researches and optimizes the preparation process of the inorganic hybrid pigment, adjusts parameters such as calcination temperature, pH value of a reaction system and the like, prepares the inorganic hybrid pigment by a coprecipitation method, and improves the tinting strength and stability of the ceramic pigment;
3. the attapulgite/vanadium zirconium blue hybridized pigment and the attapulgite/cobalt black hybridized pigment prepared by the invention can be combined according to different proportions to give different color effects to ceramics, and can be adjusted according to the needs of the technicians in the field.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but the scope of the present invention is not limited to the examples.
The test methods or test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are obtained from conventional commercial sources or prepared in conventional manner.
Example 1:
the preparation method of the color-stable non-color-difference ceramic comprises the following steps:
s1, preparing a blank: uniformly mixing the raw materials of the green body, performing wet ball milling, and granulating in a spray tower after ball milling to reach 300 meshes of granularity to obtain green body granules; pressing and forming the green body granules to obtain a coarse green body, and naturally air-drying;
s2, applying ground coat: mixing the raw materials of the ground glaze layer, performing wet ball milling until the granularity is 400 meshes, sieving to remove iron, and adding water to obtain glaze slurry with the solid content of 50%; spraying glaze slurry on the blank body, and then drying for standby; when the glaze slurry is sprayed, the specific gravity of the glaze is 1.7g/ml, and the glazing quantity is 700g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the ground coat is 10 before the coating of the glaze slurry -3 Vacuum bubble removal under the condition of 50 ℃ at the temperature of MPa;
s3, firing: firing the green body subjected to the primer application at 900 ℃ for 160 minutes;
s4, shi Touming glaze: continuously spraying transparent glaze on the ground coat, wherein the solid content of the transparent glaze slurry is 30%, the specific gravity is 1.40g/ml, and the glazing quantity is 300g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the transparent glaze is 10 before the glaze slip is coated -3 Vacuum bubble removal under the condition of 50 ℃ at the temperature of MPa;
s5, low-temperature firing: and (3) continuously firing the transparent glaze layer after drying, wherein the firing temperature is 700 ℃ and the firing time is 3 hours.
The raw materials of the green body are as follows: 40Kg of potassium feldspar, 25Kg of quartz, 15Kg of albite, 8Kg of bentonite, 6Kg of talcum, 5Kg of alumina and 3Kg of strontium carbonate.
The raw materials of the ground coat layer are as follows: 20Kg of quartz, 10Kg of potassium feldspar, 10Kg of kaolin, 8Kg of diatomite, 6Kg of zirconium silicate, 5Kg of lithium porcelain stone, 5Kg of zinc oxide, 3Kg of zircon, 3Kg of gypsum and 3Kg of ceramic pigment.
The preparation method of the ceramic pigment comprises the following steps:
s1, preparing a vanadium zirconium blue/attapulgite ceramic pigment: tetraethoxysilane and ZrOCl 2 ·8H 2 Mixing O with water for 20min, slowly dripping ammonia water to pH 9 under stirring, centrifuging, and washing until no chloride ion existsAdding the colorant V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; calcining the powder at 900 ℃ for 3 hours, and preserving the heat for 10 minutes; the molecular formula of the prepared vanadium-zirconium blue is V 0.2 Zr 0.8 SiO 4 The addition amount of the mineralizer NaF is V 0.2 Zr 0.8 SiO 4 7wt% of the weight of the attapulgite, wherein the dosage of the attapulgite is V 0.2 Zr 0.8 SiO 4 60wt% of the weight.
S2, preparing cobalt black/attapulgite ceramic pigment: fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1, a step of; then adding attapulgite, adding alkali liquor to adjust the pH value to 10 under stirring, continuously reacting for 3 hours, centrifugally washing to be neutral, drying, grinding and sieving to obtain powder; calcining the powder at 950 ℃ for 2 hours; the molecular formula of the prepared cobalt black is CoFe 2 O 4 The dosage of the attapulgite is CoFe 2 O 4 60wt% of the weight.
S3, mixing and sintering: sieving the prepared vanadium-zirconium blue/attapulgite ceramic pigment and cobalt black/attapulgite ceramic pigment, grinding to pass through a 400-mesh sieve, mixing the two according to different proportions according to the ceramic color requirement to obtain a mixed pigment, further sintering the mixed pigment, and grinding to a particle size below 50 um.
The transparent glaze layer consists of transparent frit, wherein the chemical components of the transparent frit comprise the following components in percentage by weight: siO (SiO) 2 46％、B 2 O 3 23％、Al 2 O 3 9％、Na 2 O 7％、MgO 6％、K 2 O 3％、ZnO 1.2％、TiO 2 1.3％、CaCO 3 1.6％、LiO 2 0.6% and the balance of loss on ignition.
Example 2:
the preparation method of the color-stable non-color-difference ceramic comprises the following steps:
s1, preparing a blank: uniformly mixing the raw materials of the green body, performing wet ball milling, and granulating in a spray tower after ball milling to reach the granularity of 400 meshes to obtain green body granules; pressing and forming the green body granules to obtain a coarse green body, and naturally air-drying;
s2, applying ground coat: mixing the raw materials of the ground glaze layer, performing wet ball milling to obtain a particle size of 500 meshes, sieving to remove iron, and adding water to obtain glaze slurry with a solid content of 55%; spraying glaze slurry on the blank body, and then drying for standby; when the glaze slurry is coated, the specific gravity of the glaze is 1.8g/ml, and the glazing quantity is 750g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the ground coat is 1 multiplied by 10 before the coating of the glaze slurry -2 Vacuum bubble removal under the condition of the temperature of 55 ℃ under the pressure of MPa;
s3, firing: firing the base glazed green body at 1100 ℃ for 120 minutes;
s4, shi Touming glaze: continuously spraying transparent glaze on the ground coat, wherein the solid content of the transparent glaze slurry is 40%, the specific gravity is 1.50g/ml, and the glazing quantity is 400g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the transparent glaze is 1 multiplied by 10 before the glaze slurry is sprayed -2 Vacuum bubble removal under the condition of the temperature of 55 ℃ under the pressure of MPa;
s5, low-temperature firing: and (3) continuously firing the transparent glaze layer after drying, wherein the firing temperature is 800 ℃ and the firing time is 2 hours.
The raw materials of the green body are as follows: 50Kg of potassium feldspar, 30Kg of quartz, 20Kg of albite, 12Kg of bentonite, 8Kg of talcum, 8Kg of alumina and 6Kg of strontium carbonate.
The raw materials of the ground coat layer are as follows: 25Kg of quartz, 15Kg of potassium feldspar, 15Kg of kaolin, 12Kg of diatomite, 8Kg of zirconium silicate, 7Kg of lithium porcelain stone, 7Kg of zinc oxide, 5Kg of zircon, 5Kg of gypsum and 5Kg of ceramic pigment.
The preparation method of the ceramic pigment comprises the following steps:
s1, preparing a vanadium zirconium blue/attapulgite ceramic pigment: tetraethoxysilane and ZrOCl 2 ·8H 2 Mixing O with water for 40 min, slowly dripping ammonia water to pH of 10 under stirring, centrifuging, washing until no chloride ion exists, and adding colorant V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; calcining the powder at 1000 ℃ for 2 hours, and preserving the heat for 10 minutes; the molecular formula of the prepared vanadium-zirconium blue is V 0.4 Zr 0.6 SiO 4 The mineralizer NaFThe addition amount is V 0.4 Zr 0.6 SiO 4 9wt% of the weight of the attapulgite, wherein the dosage of the attapulgite is V 0.4 Zr 0.6 SiO 4 60wt% of the weight.
S2, preparing cobalt black/attapulgite ceramic pigment: fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1, a step of; then adding attapulgite, adding alkali liquor to adjust the pH value to 10 under stirring, continuously reacting for 3 hours, centrifugally washing to be neutral, drying, grinding and sieving to obtain powder; calcining the powder at 1000 ℃ for 3 hours; the molecular formula of the prepared cobalt black is CoFe 2 O 4 The dosage of the attapulgite is CoFe 2 O 4 60wt% of the weight.
S3, mixing and sintering: sieving the prepared vanadium-zirconium blue/attapulgite ceramic pigment and cobalt black/attapulgite ceramic pigment, grinding to pass through a 400-mesh sieve, mixing the two according to different proportions according to the ceramic color requirement to obtain a mixed pigment, further sintering the mixed pigment, and grinding to a particle size below 50 um.
The transparent glaze layer consists of transparent frit, wherein the chemical components of the transparent frit comprise the following components in percentage by weight: siO (SiO) 2 47％、B 2 O 3 22％、Al 2 O 3 8％、Na 2 O 6％、MgO 6％、K 2 O 3％、ZnO 1.5％、TiO 2 1.5％、CaCO 3 1.0％、LiO 2 0.5% and the balance of loss on ignition.
Example 3:
the preparation method of the color-stable non-color-difference ceramic comprises the following steps:
s1, preparing a blank: uniformly mixing the raw materials of the green body, performing wet ball milling, and granulating in a spray tower after ball milling to reach the granularity of 400 meshes to obtain green body granules; pressing and forming the green body granules to obtain a coarse green body, and naturally air-drying;
s2, applying ground coat: mixing the raw materials of the ground glaze layer, performing wet ball milling to obtain a particle size of 500 meshes, sieving to remove iron, and adding water to obtain glaze slurry with a solid content of 53%; spraying on the blankThe glaze slip is dried for standby; when the glaze slurry is sprayed, the specific gravity of the glaze is 1.72g/ml, and the glazing quantity is 720g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the ground coat is 5 multiplied by 10 before the coating of the glaze slurry -2 Vacuum bubble removal under the condition of the temperature of 55 ℃ under the pressure of MPa;
s3, firing: firing the base glazed blank at 1000 ℃ for 150 minutes;
s4, shi Touming glaze: continuously spraying transparent glaze on the ground coat, wherein the solid content of the transparent glaze slurry is 35%, the specific gravity is 1.43g/ml, and the glazing quantity is 350g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The transparent glaze is vacuum degree of 4 x 10 before the glaze slurry is sprayed -2 Vacuum bubble removal under the condition of the temperature of 55 ℃ under the pressure of MPa;
s5, low-temperature firing: and (3) continuously firing the transparent glaze layer after drying, wherein the firing temperature is 750 ℃ and the firing time is 3 hours.
The raw materials of the green body are as follows: 45Kg of potassium feldspar, 28Kg of quartz, 16Kg of albite, 10Kg of bentonite, 7Kg of talcum, 6Kg of alumina and 5Kg of strontium carbonate.
The raw materials of the ground coat layer are as follows: 25Kg of quartz, 13Kg of potassium feldspar, 12Kg of kaolin, 10Kg of diatomite, 7Kg of zirconium silicate, 6Kg of lithium porcelain stone, 6Kg of zinc oxide, 5Kg of zircon, 4Kg of gypsum and 4Kg of ceramic pigment.
The preparation method of the ceramic pigment comprises the following steps:
s1, preparing a vanadium zirconium blue/attapulgite ceramic pigment: tetraethoxysilane and ZrOCl 2 ·8H 2 Mixing O with water for 30 min, slowly dripping ammonia water to pH 9 under stirring, centrifuging, washing until no chloride ion exists, and adding colorant V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; calcining the powder at 950 ℃ for 2 hours, and preserving the heat for 10 minutes; the molecular formula of the prepared vanadium-zirconium blue is V 0.2 Zr 0.8 SiO 4 The addition amount of the mineralizer NaF is V 0.2 Zr 0.8 SiO 4 8wt% of the weight of the attapulgite, wherein the dosage of the attapulgite is V 0.2 Zr 0.8 SiO 4 60wt% of the weight.
S2, preparing cobalt black/attapulgite ceramic pigment: fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1, a step of; then adding attapulgite, adding alkali liquor to adjust the pH value to 10 under stirring, continuously reacting for 3 hours, centrifugally washing to be neutral, drying, grinding and sieving to obtain powder; calcining the powder at 1000 ℃ for 2 hours; the molecular formula of the prepared cobalt black is CoFe 2 O 4 The dosage of the attapulgite is CoFe 2 O 4 60wt% of the weight.
S3, mixing and sintering: sieving the prepared vanadium-zirconium blue/attapulgite ceramic pigment and cobalt black/attapulgite ceramic pigment, grinding to pass through a 400-mesh sieve, mixing the two according to different proportions according to the ceramic color requirement to obtain a mixed pigment, further sintering the mixed pigment, and grinding to a particle size below 50 um.
The transparent glaze layer consists of transparent frit, wherein the chemical components of the transparent frit comprise the following components in percentage by weight: siO (SiO) 2 48％、B 2 O 3 22％、Al 2 O 3 8％、Na 2 O 7％、MgO 5％、K 2 O 2％、ZnO 1.2％、TiO 2 1.2％、CaCO 3 1.0％、LiO 2 0.6% and the balance of loss on ignition.
Example 4:
the preparation method of the color-stable non-color-difference ceramic comprises the following steps:
s1, preparing a blank: uniformly mixing the raw materials of the green body, performing wet ball milling, and granulating in a spray tower after ball milling to reach 300 meshes of granularity to obtain green body granules; pressing and forming the green body granules to obtain a coarse green body, and naturally air-drying;
s2, applying ground coat: mixing the raw materials of the ground glaze layer, performing wet ball milling to obtain a particle size of 500 meshes, sieving to remove iron, and adding water to obtain glaze slurry with a solid content of 54%; spraying glaze slurry on the blank body, and then drying for standby; when the glaze slurry is sprayed, the specific gravity of the glaze is 1.76g/ml, and the glazing quantity is 730g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the ground coat is 3 multiplied by 10 before the coating of the glaze slurry -2 Vacuum bubble removal under the condition of 50 ℃ at the temperature of MPa;
s3, firing: firing the base glazed blank at 1050 ℃ for 140 minutes;
s4, shi Touming glaze: continuously spraying transparent glaze on the ground coat, wherein the solid content of the transparent glaze slurry is 33%, the specific gravity is 1.42g/ml, and the glazing quantity is 360g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the transparent glaze is 6 multiplied by 10 before the glaze slurry is sprayed -2 Vacuum bubble removal under the condition of the temperature of 55 ℃ under the pressure of MPa;
s5, low-temperature firing: and (3) continuously firing the transparent glaze layer after drying, wherein the firing temperature is 760 ℃ and the firing time is 2.5 hours.
The raw materials of the green body are as follows: 48Kg of potassium feldspar, 26Kg of quartz, 16Kg of albite, 9Kg of bentonite, 8Kg of talcum, 6Kg of alumina and 4Kg of strontium carbonate.
The raw materials of the ground coat layer are as follows: 25Kg of quartz, 12Kg of potassium feldspar, 13Kg of kaolin, 9Kg of diatomite, 6Kg of zirconium silicate, 5Kg of lithium porcelain stone, 6Kg of zinc oxide, 4Kg of zircon, 3Kg of gypsum and 5Kg of ceramic pigment.
The preparation method of the ceramic pigment comprises the following steps:
s1, preparing a vanadium zirconium blue/attapulgite ceramic pigment: tetraethoxysilane and ZrOCl 2 ·8H 2 Mixing O with water for 35 min, slowly dripping ammonia water to pH 9.5 under stirring, centrifuging, washing until no chloride ion exists, and adding colorant V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; calcining the powder at 960 ℃ for 2.5h, and preserving the heat for 10 min; the molecular formula of the prepared vanadium-zirconium blue is V 0.2 Zr 0.8 SiO 4 The addition amount of the mineralizer NaF is V 0.2 Zr 0.8 SiO 4 8wt% of the weight of the attapulgite, wherein the dosage of the attapulgite is V 0.2 Zr 0.8 SiO 4 70wt% of the weight.
S2, preparing cobalt black/attapulgite ceramic pigment: fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1, a step of; then adding attapulgite, adding alkali liquor under stirring to adjust the pH value to 9.5, continuously reacting for 3 hours, centrifuging, washing to be neutral, drying, grinding and sieving to obtain powder; calcining the powder at 1050 ℃ for 2.5 hours; prepared byCobalt black has a formula of CoFe 2 O 4 The dosage of the attapulgite is CoFe 2 O 4 65wt% of the weight.
S3, mixing and sintering: sieving the prepared vanadium-zirconium blue/attapulgite ceramic pigment and cobalt black/attapulgite ceramic pigment, grinding to pass through a 400-mesh sieve, mixing the two according to different proportions according to the ceramic color requirement to obtain a mixed pigment, further sintering the mixed pigment, and grinding to a particle size below 50 um.
The transparent glaze layer consists of transparent frit, wherein the chemical components of the transparent frit comprise the following components in percentage by weight: siO (SiO) 2 47％、B 2 O 3 23％、Al 2 O 3 8％、Na 2 O 7％、MgO 6％、K 2 O 3％、ZnO 1.0％、TiO 2 1.0％、CaCO 3 1.0％、LiO 2 0.5% and the balance of loss on ignition.
Example 5:
the preparation method of the color-stable non-color-difference ceramic comprises the following steps:
s1, preparing a blank: uniformly mixing the raw materials of the green body, performing wet ball milling, and granulating in a spray tower after ball milling to reach the granularity of 400 meshes to obtain green body granules; pressing and forming the green body granules to obtain a coarse green body, and naturally air-drying;
s2, applying ground coat: mixing the raw materials of the ground glaze layer, performing wet ball milling until the granularity is 400 meshes, sieving to remove iron, and adding water to obtain glaze slurry with the solid content of 54%; spraying glaze slurry on the blank body, and then drying for standby; when the glaze slurry is coated, the specific gravity of the glaze is 1.77g/ml, and the glazing amount is 750g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the ground coat is 4.5X10 before the coating of the glaze slip -2 Vacuum bubble removal under the condition of the temperature of 55 ℃ under the pressure of MPa;
s3, firing: firing the base glazed blank at 1000 ℃ for 150 minutes;
s4, shi Touming glaze: continuously spraying transparent glaze on the ground coat, wherein the solid content of the transparent glaze slurry is 38%, the specific gravity is 1.46g/ml, and the glazing quantity is 370g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The vacuum degree of the transparent glaze is 3.2 multiplied by 10 before the glaze slurry is sprayed -2 Vacuum bubble removal under the condition of the temperature of 53 ℃ under the pressure of MPa;
s5, low-temperature firing: and (3) continuously firing the transparent glaze layer after drying, wherein the firing temperature is 750 ℃ and the firing time is 2.5 hours.
The raw materials of the green body are as follows: 42Kg of potassium feldspar, 27Kg of quartz, 16Kg of albite, 11Kg of bentonite, 6Kg of talcum, 6Kg of alumina and 4Kg of strontium carbonate.
The raw materials of the ground coat layer are as follows: 24Kg of quartz, 13Kg of potassium feldspar, 13Kg of kaolin, 9Kg of diatomite, 6Kg of zirconium silicate, 5Kg of lithium porcelain stone, 5Kg of zinc oxide, 3Kg of zircon, 4Kg of gypsum and 3Kg of ceramic pigment.
The preparation method of the ceramic pigment comprises the following steps:
s1, preparing a vanadium zirconium blue/attapulgite ceramic pigment: tetraethoxysilane and ZrOCl 2 ·8H 2 Mixing O with water for 35 min, slowly dripping ammonia water to pH of 10 under stirring, centrifuging, washing until no chloride ion exists, and adding colorant V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; calcining the powder at 980 ℃ for 2.5h, and preserving the heat for 10 min; the molecular formula of the prepared vanadium-zirconium blue is V 0.3 Zr 0.7 SiO 4 The addition amount of the mineralizer NaF is V 0.3 Zr 0.7 SiO 4 7.5wt% of the weight, wherein the dosage of the attapulgite is V 0.3 Zr 0.7 SiO 4 65wt% of the weight.
S2, preparing cobalt black/attapulgite ceramic pigment: fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1, a step of; then adding attapulgite, adding alkali liquor to adjust the pH value to 10 under stirring, continuously reacting for 2.5 hours, centrifuging, washing to be neutral, drying, grinding and sieving to obtain powder; calcining the powder at 1050 ℃ for 2 hours; the molecular formula of the prepared cobalt black is CoFe 2 O 4 The dosage of the attapulgite is CoFe 2 O 4 65wt% of the weight.
S3, mixing and sintering: sieving the prepared vanadium-zirconium blue/attapulgite ceramic pigment and cobalt black/attapulgite ceramic pigment, grinding to pass through a 400-mesh sieve, mixing the two according to different proportions according to the ceramic color requirement to obtain a mixed pigment, further sintering the mixed pigment, and grinding to a particle size below 50 um.
The transparent glaze layer consists of transparent frit, wherein the chemical components of the transparent frit comprise the following components in percentage by weight: siO (SiO) 2 46％、B 2 O 3 23％、Al 2 O 3 9％、Na 2 O 7％、MgO 6％、K 2 O 3％、ZnO 1.5％、TiO 2 1.5％、CaCO 3 1.0％、LiO 2 0.7% and the balance of loss on ignition.
Performance testing
The mixed ceramic coloring materials prepared in examples 1 to 5 were subjected to performance tests of coloring power, oil absorption and hiding power, and the mass ratio of the vanadium-zirconium-blue/attapulgite ceramic coloring material to the cobalt-black/attapulgite ceramic coloring material in the mixed ceramic coloring material was 1:1.
The test method is as follows:
the tinting strength is obtained by adding the same amount of thinner (lithopone, HG 1-1059) and varnish (pure linseed oil, viscosity 2600-2800 mPa.s at 25 ℃), color not more than 8, ferrocobalt colorimeter, acid value not more than 8mg KOH/g) to a certain amount of pigment standard (commercial sample) and mixed ceramic pigment, and comparing the tinting strength shown by grinding.
Oil absorption the oil absorption refers to the ability of a pigment to blend with an oily substance (e.g., linseed oil), reflecting the ability of the pigment to absorb lipophilic media, the smaller the oil absorption, the less lipophilic media is consumed to make the ink; on the contrary, when the oil absorption is large, the concentration of the ink is not easily increased, and the product cost is affected to some extent. Typically, an oily substance (such as linseed oil) is added to a certain amount of pigment and ground, loose pigment particles are gradually bonded until the oil amount consumed by all the bonded clusters is the oil absorption, the measured oil absorption can be measured by using an ink regulating oil (ASTM D281-31), 2.00g (accurate to 0.01 g) of a sample is weighed and placed on a glass plate, the ink regulating oil is gradually added dropwise, and the sample is carefully ground by an ink regulating knife to enable all the sample to be fully contacted with the oil, and when the last drop of the ink regulating oil is added, the final drop of the ink regulating oil is just bonded with an oil point, and when the final drop of the ink regulating oil is scooped up by the ink regulating knife, the bonded clusters are not scattered, and are the end point. All operations are completed within 15-20 min.
Hiding power pigment hiding power refers to the minimum pigment usage that pigment and ink are ground into color paste and uniformly painted on a black-white grid substrate, so that the black-white grid is just hidden.
The test results are shown in Table 1.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes of the invention should fall within the scope of the claims of the invention, and furthermore, although specific terms are used in the description, these terms are for convenience of description and are not to be construed as limiting the invention.
Claims (10)
1. The non-color-difference ceramic is characterized by comprising a green body, a ground coat layer and a transparent glaze layer, wherein the ground coat layer contains ceramic pigment;
the preparation method of the ceramic pigment comprises the following steps:
s1, preparing a vanadium zirconium blue/attapulgite ceramic pigment: tetraethoxysilane and ZrOCl 2 ·8H 2 Mixing O with water for 20-40 min, slowly dropping ammonia water to pH 9-10 while stirring, centrifugal washing until no chloride ion exists, and adding coloring agent V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; calcining the powder at 900-1000 deg.c for 2-3 hr and maintaining for 10 min;
s2, preparing cobalt black/attapulgite ceramic pigment: fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1The method comprises the steps of carrying out a first treatment on the surface of the Then adding attapulgite, adding alkali liquor to adjust the pH value to 9-10 under stirring, continuously reacting for 2-3 h, centrifugally washing to be neutral, drying, grinding and sieving to obtain powder; calcining the powder at 950-1050 ℃ for 2-3 h;
s3, mixing and sintering: sieving the prepared vanadium-zirconium blue/attapulgite ceramic pigment and cobalt black/attapulgite ceramic pigment, grinding to pass through a 400-mesh sieve, mixing the two according to different proportions according to the ceramic color requirement to obtain a mixed pigment, further sintering the mixed pigment, and grinding to a particle size below 50 um.
2. The color stable non-color difference ceramic according to claim 1, wherein the green body is prepared from the following raw materials in parts by weight: 40-50 parts of potassium feldspar, 25-30 parts of quartz, 15-20 parts of albite, 8-12 parts of bentonite, 6-8 parts of talcum, 5-8 parts of alumina and 3-6 parts of strontium carbonate; the ground coat layer is prepared from the following raw materials in parts by weight: 20-25 parts of quartz, 10-15 parts of potassium feldspar, 10-15 parts of kaolin, 8-12 parts of diatomite, 6-8 parts of zirconium silicate, 5-7 parts of lithium porcelain stone, 5-7 parts of zinc oxide, 3-5 parts of zircon, 3-5 parts of gypsum and 3-5 parts of ceramic pigment.
3. A color stable, non-color difference ceramic according to claim 1, wherein in S1, tetraethyl orthosilicate and ZrOCl are used 2 ·8H 2 Mixing O with water for 30 min, slowly dripping ammonia water to pH 9 under stirring, centrifuging, washing until no chloride ion exists, and adding colorant V 2 O 5 Continuously stirring the mineralizer NaF, the attapulgite and the ethanol uniformly, and performing rotary evaporation after reacting for a period of time to obtain powder; calcining the powder at 950 ℃ for 3 hours, and preserving the heat for 10 minutes.
4. A color stable, non-color difference ceramic according to claim 1, wherein in S1, the vanadium zirconium blue is prepared having the formula V x Zr 1-x SiO 4 Wherein x is 0.2 to 0.4; the addition amount of the mineralizer NaF is V x Zr 1-x SiO 4 7-9 wt% of the weight, wherein the dosage of the attapulgite is V x Zr 1-x SiO 4 55 to 70 weight percent of the weight.
5. A color stable, non-color difference ceramic according to claim 1, wherein in S2 Fe (NO 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water, wherein Fe 3+ With Co 2+ The mass ratio of the substances is 2:1, a step of; then adding attapulgite, adding sodium hydroxide solution under stirring to adjust the pH value to 10, continuously reacting for 2 hours, centrifugally washing to be neutral, drying, grinding and sieving to obtain powder; calcining the powder at 1000 ℃ for 2 hours.
6. A color stable, non-color difference ceramic according to claim 1, wherein the cobalt black is of the formula CoFe 2 O 4 The dosage of the attapulgite is CoFe 2 O 4 50-70 wt% of the weight.
7. The color stable, non-color-difference ceramic according to claim 1, wherein the transparent glaze layer is composed of transparent frit, and the chemical composition of the transparent frit comprises, in weight percent: siO (SiO) 2 45～50％、B 2 O 3 20～25％、Al 2 O 3 8～10％、Na 2 O 6～8％、MgO 5～8％、K 2 O 2～4％、ZnO 1～2％、TiO 2 1～2％、CaCO 3 1～2％、LiO 2 0.5～1％。
8. The color stable non-color difference ceramic according to claim 2, wherein the green body is prepared from the following raw materials in parts by weight: 45 parts of potassium feldspar, 28 parts of quartz, 16 parts of albite, 10 parts of bentonite, 7 parts of talcum, 6 parts of aluminum oxide and 5 parts of strontium carbonate; the ground coat layer is prepared from the following raw materials in parts by weight: 25 parts of quartz, 13 parts of potassium feldspar, 12 parts of kaolin, 10 parts of diatomite, 7 parts of zirconium silicate, 6 parts of lithium porcelain stone, 6 parts of zinc oxide, 5 parts of zircon, 4 parts of gypsum and 4 parts of ceramic pigment.
9. The method for producing a color stable, non-color difference ceramic according to any one of claims 1 to 8, comprising the steps of:
s1, preparing a blank: uniformly mixing the raw materials of the green body, performing wet ball milling, performing ball milling until the granularity is 300-400 meshes, and granulating in a spray tower to obtain green body granules; pressing and forming the green body granules to obtain a coarse green body, and naturally air-drying;
s2, applying ground coat: mixing the raw materials of the ground coat, performing wet ball milling to obtain a granularity of 400-500 meshes, sieving to remove iron, and adding water to obtain glaze slurry with the solid content of 50-55%; spraying glaze slurry on the blank body, and then drying for standby; when the glaze slurry is sprayed, the specific gravity of the glaze is 1.7-1.8 g/ml, and the glazing quantity is 700-750 g/m 2 ；
S3, firing: firing the green body after applying the primer at 900-1100 ℃ for 120-160 minutes;
s4, shi Touming glaze: continuously spraying transparent glaze on the ground coat layer, wherein the solid content of the transparent glaze slurry is 30-40%, the specific gravity is 1.40-1.50 g/ml, and the glazing quantity is 300-400 g/m 2 ；
S5, low-temperature firing: and (3) continuously firing the transparent glaze layer after drying, wherein the firing temperature is 700-800 ℃ and the firing time is 2-3 hours.
10. The method for preparing color stable non-color difference ceramic according to claim 9, wherein the under-glaze and the transparent glaze are both in vacuum degree of 10 before the glaze slip -3 ～1×10 -2 Vacuum bubble removal is carried out under the conditions of 50-55 ℃ under the pressure of MPa.
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