CN115304276A - Composite glaze layer, ceramic plate and preparation method thereof - Google Patents
Composite glaze layer, ceramic plate and preparation method thereof Download PDFInfo
- Publication number
- CN115304276A CN115304276A CN202210928827.3A CN202210928827A CN115304276A CN 115304276 A CN115304276 A CN 115304276A CN 202210928827 A CN202210928827 A CN 202210928827A CN 115304276 A CN115304276 A CN 115304276A
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- China
- Prior art keywords
- parts
- glaze layer
- glaze
- titanium white
- portions
- Prior art date
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- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 273
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 232
- 238000002955 isolation Methods 0.000 claims abstract description 154
- 239000002994 raw material Substances 0.000 claims abstract description 52
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 46
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 46
- 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 abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 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 abstract description 39
- 229910052656 albite Inorganic materials 0.000 claims abstract description 36
- 239000010453 quartz Substances 0.000 claims abstract description 36
- 239000010456 wollastonite Substances 0.000 claims abstract description 35
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 35
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 30
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 21
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000010436 fluorite Substances 0.000 claims abstract description 20
- 239000010434 nepheline Substances 0.000 claims abstract description 20
- 229910052664 nepheline Inorganic materials 0.000 claims abstract description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 58
- 238000010304 firing Methods 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 28
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 25
- 238000007590 electrostatic spraying Methods 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims 5
- 239000000976 ink Substances 0.000 abstract description 76
- 239000010936 titanium Substances 0.000 abstract description 48
- 238000011161 development Methods 0.000 abstract description 36
- 230000000694 effects Effects 0.000 abstract description 23
- 239000013078 crystal Substances 0.000 abstract description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 16
- 230000002829 reductive effect Effects 0.000 abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 abstract description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 12
- 239000011707 mineral Substances 0.000 abstract description 12
- 150000003624 transition metals Chemical class 0.000 abstract description 12
- 229910052596 spinel Inorganic materials 0.000 abstract description 11
- 239000011029 spinel Substances 0.000 abstract description 11
- 238000005034 decoration Methods 0.000 abstract description 10
- 229910052861 titanite Inorganic materials 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000001939 inductive effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 324
- 238000012360 testing method Methods 0.000 description 66
- 230000018109 developmental process Effects 0.000 description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 33
- 235000012239 silicon dioxide Nutrition 0.000 description 33
- 229910052719 titanium Inorganic materials 0.000 description 33
- 238000007641 inkjet printing Methods 0.000 description 28
- 229910017052 cobalt Inorganic materials 0.000 description 27
- 239000010941 cobalt Substances 0.000 description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 27
- 239000000292 calcium oxide Substances 0.000 description 26
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 26
- 239000012071 phase Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 24
- 238000005498 polishing Methods 0.000 description 24
- 239000004408 titanium dioxide Substances 0.000 description 23
- 238000005245 sintering Methods 0.000 description 19
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000001976 improved effect Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000002087 whitening effect Effects 0.000 description 7
- 229910021532 Calcite Inorganic materials 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010459 dolomite Substances 0.000 description 4
- 229910000514 dolomite Inorganic materials 0.000 description 4
- 239000003605 opacifier Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 239000005368 silicate glass Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052634 enstatite Inorganic materials 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 3
- 239000004579 marble Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035800 maturation Effects 0.000 description 3
- 238000001579 optical reflectometry Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011022 opal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000102542 Kara Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- -1 polymethylsiloxane Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/04—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
- B28B11/044—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers with glaze or engobe or enamel or varnish
-
- 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
-
- 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
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- 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
-
- 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
- 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
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Finishing Walls (AREA)
Abstract
The invention discloses a composite glaze layer, a ceramic plate and a preparation method thereof, wherein the composite glaze layer comprises a titanium white ground glaze layer and an isolation glaze layer formed on the surface of the titanium white ground glaze layer, and the isolation glaze layer comprises the following raw materials in parts by mass: 15 to 35 parts of zirconium silicate, 0 to 10 parts of aluminum silicate, 0 to 10 parts of zirconium oxide, 5 to 25 parts of quartz, 5 to 8 parts of kaolin, 3 to 8 parts of wollastonite, 0 to 8 parts of fluorite, 0 to 25 parts of potassium feldspar, 0 to 15 parts of albite and 0 to 35 parts of nepheline. The invention is arranged on the surface of the titanium white ground coatThe isolation glaze layer is formed to obtain the composite glaze layer, and when the ink-jet decoration is carried out on the isolation glaze layer in the composite glaze layer, the possibility that various ink-jet inks are in direct contact with the titanium white base glaze can be effectively reduced. Avoids the yellow green glaze surface caused by the preferential reaction of the crystal phase of the titanic titanite synthesized in the titanium white ground coat and spinel minerals in the ink-jet ink to generate rutile titanium dioxide, and avoids the Ti in the titanium white ground coat 4+ Inducing the color development effect of various color development elements of the valence-variable transition metal in the ink-jet ink to cause the tone variation of the ink-jet ink.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a composite glaze layer, a ceramic plate and a preparation method thereof.
Background
In the building ceramic industry, the opaque ground glaze (commonly called as makeup soil) has strong covering effect, most of the opaque ground glaze takes substances with higher refractive index as dispersed particles, and the opaque ground glaze with good covering rate often has strong reflection effect on sunlight. Common opacifying agents for opacifying ground glaze include titanium dioxide, cerium oxide, tin oxide, zinc oxide, zirconium silicate, and the like.
Cerium oxide and tin oxide are rarely used in architectural ceramic opaque ground glazes due to the problems of high price and the like. The superfine zirconium silicate is the most common opacifier for opacifiing the ground glaze at present, has the refractive index of 1.93-2.01, is a high-quality opacifier, is widely used in the production of various building ceramics, sanitary ceramics, daily ceramics, first-level artware ceramics and the like, and has wide application range and large application amount in the processing and production of ceramic glaze materials. The zirconium silicate can be widely applied to ceramic production, and has good chemical stability, is not influenced by the firing atmosphere of the ceramic, and can obviously improve the blank glaze bonding performance of the ceramic and improve the hardness of the ceramic glaze. Zirconium silicate has a whitening effect by forming baddeleyite or the like after firing of the ceramic, thereby causing Scattering of incident light waves, which is commonly referred to as macroparticle Scattering or Mie Scattering. For the production of the ceramic tile with white background color, the whiter the ground coat is, the higher the product grade is, for example, high-grade marble ceramic tiles such as kara white, snow white and the like need the whiteness of the background color to be more than 80 degrees. The addition of zirconium silicate in the prime coat of most marble ceramic tiles is 15-20%, the whiteness is generally about 65 degrees, the use amount of zirconium silicate is continuously increased, the whiteness is not obviously increased, the flatness of the ceramic tiles cannot reach the standard, and the cost is increased, so that the performance effect or the economic benefit of the marble ceramic tiles needs to be improved urgently.
In addition, in recent years, the price of bulk commodities in the world is rising continuously, the competition among all ceramic brands is very tragic under the requirement of double carbon and double control, the best way for reducing the cost is sought through various technical advances, and technologists are gradually promoted to be new, and various technical means are adopted to seek the substitute of zirconium silicate to reduce the comprehensive cost of the ground glaze. Titanium dioxide is also an oxide with a very high refractive index, the refractive index is as high as 2.55-2.76, and the titanium dioxide has a very strong reflection effect on light and is the whitest substance in the world. Titanium dioxide is often applied to building ceramic tiles as a main component of impervious ground coatIn (1). The titanium dioxide is usually introduced in the form of conventional titanium white frits, the firing temperature is generally lower than the ring temperature of 1080 ℃, and the titanium dioxide comprises the following chemical components in parts by mass: li 2 O/Na 2 O/K 2 O2.0-8.0 parts, caO 5-18 parts, mgO 2-5 parts, siO 2 50 to 75 portions of Al 2 O 3 3 to 6 portions of B 2 O 3 0 to 3 portions of ZrO 2 0 to 5 portions of P 2 O 5 0 to 5 portions of TiO 2 3 to 10 portions of BaO and 0 to 2.0 portions of BaO. However, titanium dioxide is a polycrystalline oxide, and titanium is typically Ti in silicate glass systems at temperatures in excess of 1000 deg.C 4+ The valence state exists. Ti (titanium) 4+ Meaning the nuclear outermost electron 3d of titanium 2 4s 2 All losses, all voids in the d orbital, no "d-d" transitions between electrons in the d orbital can occur, so Ti 4+ The valence state should appear colorless. However, due to Ti 4+ The ions strongly absorb ultraviolet rays, and the absorption band of the ions usually enters into the violet part of a visible light region, so that titanium dioxide (titanium is in a valence of + 4) existing in a rutile crystal form after being fired has a strong absorption effect on violet light, and a glaze surface is yellowed; after the impermeable ground glaze adopting the conventional titanium white frit is sintered for 60min in a kiln at the environment temperature of 1100-1150 ℃, the crystalline phase content of titanium sphene generated by the solid-phase reaction of titanium dioxide and wollastonite is reduced, the crystalline phase content of wollastonite is increased, the content of enstatite mineral phase is increased to be more than 2wt%, the glossiness of the sintered body is more than 40 ℃, the sintered body is gradually changed from milky white into translucent, and the whiteness of blue light is greatly reduced and is generally lower than 55 ℃; the b value representing yellow tone in the Lab value is generally more than 6, so the sintering temperature of the conventional titanium white impervious ground coat used for building ceramic wall and floor tiles needs to be lower than 1100 ℃.
Chinese patent CN 111499202A discloses a high solar reflectance opacified titanium white glaze and a preparation method thereof, the opacified titanium white glaze with high solar reflectance in the invention can be applied to porcelain tiles fired at 1150 ℃, can weaken the defect that the glaze surface of a ground glaze is yellowish due to the ultraviolet absorption effect of rutile titanium dioxide, but has a plurality of limitations and defects in truly realizing stable industrial application:
(1) For producing ceramics in practiceThe patent reports that titanium sphene crystal grains are used as crystal seeds to induce titanium dioxide and calcite to react to generate titanium sphene crystal phases with the grain diameters of 450-600 nm, a large amount of calcite needs to be added, so that the ground glaze can completely react without yellowing, the glossiness of the ground glaze is very high after the ground glaze is fired at the actual kiln temperature, and a large amount of aluminum needs to be added to inhibit the luster (the content of aluminum oxide in the patent reaches 19-21 percent), and in a silicate system with high titanium content, more cations Al with the characteristics of an intermediate type exist 3+ In the case of (2), rutile titanium dioxide of an appropriate particle size is easily precipitated, resulting in yellowing of the glaze;
(2) After the ground coat is applied, ink-jet decoration is required in the subsequent process, and most of the ink-jet ink components with different colors contain spinel minerals and various variable-valence transition metal chromophoric elements. Therefore, with the rise of the firing temperature, the titanium sphene crystal phase in the ground glaze silicate glass system reacts with the spinel mineral in the ink-jet ink to generate rutile type titanium dioxide, and the glaze surface turns yellow and green. In addition, in silicate glasses, titanium is generally Ti 4+ The valence exists, and from the above discussion, ti is known 4+ The valence state causes it to appear yellow. Albeit Ti 4+ The pigment does not cause darker color independently, but can strongly influence the color generation of other variable valence transition metal elements, and the color generation can still be realized even if the content of the variable valence transition metal elements is small, particularly the iron is obvious, and the most obvious example is the color generation of a plurality of pigments which are usually TiO 2 And is mixed with other toner components to realize: tiO 2 2 With Fe 2 O 3 The mixture turns brown (this is mixed with Fe) 2 O 3 And MnO 2 Similar in color); tiO 2 2 And MnO with MnO 2 The combination is light yellow to dark yellow; tiO 2 2 Combined with NiO to be gray to yellow brown; tiO 2 2 Combined with CuO, the green color is blue; tiO 2 2 With CeO 2 The mixture is used to present bright yellow; chrome titanium yellow is also a rutile type structure pigment. Thus, as the firing temperature increases, the ground-glaze silicate glass systemMiddle Ti 4+ The valence state (such as residual titanium dioxide) is easy to induce the color development effect of various valence-variable transition metal color development elements in the ink-jet ink so as to change the color development of the ink-jet ink. Further, when the content of CaO in the ground glaze formula is more than 10%, the color development of the brown series of the ink-jet printing is extremely unfavorable. In conclusion, the titanium white base coat in the patent relatively easily causes the inkjet ink of each channel to be obviously yellowish green or change tone (the b value representing yellow tone in the Lab value is seriously larger), the color gamut, the strength and the tone of the inkjet ink are greatly influenced, and even serious color difference (the delta E value representing the total color difference in the Lab value is far larger than 4) occurs in production, so that the plate-to-plate is not produced.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a composite glaze layer, a ceramic plate and a preparation method thereof, aiming at solving the problems that the crystal phase of titanium sphene in the existing titanium white ground coat is easy to react with inkjet ink to generate rutile type titanium dioxide, so that the glaze surface turns yellow green, and the Ti in the existing titanium white ground coat 4+ The color development effect of various valence-variable transition metal color development elements in the ink-jet ink is easily induced to cause color development and tone change of the ink-jet ink, and further the problem that the ink-jet ink of each channel is obviously yellowish green or tone-changed is caused.
The technical scheme of the invention is as follows:
the invention provides a composite glaze layer, which comprises a titanium white ground glaze layer and an isolation glaze layer formed on the surface of the titanium white ground glaze layer, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
15 to 35 parts of zirconium silicate, 0 to 10 parts of aluminum silicate, 0 to 10 parts of zirconium oxide, 5 to 25 parts of quartz, 5 to 8 parts of kaolin, 3 to 8 parts of wollastonite, 0 to 3 parts of fluorite, 0 to 25 parts of potassium feldspar, 0 to 15 parts of albite and 0 to 35 parts of nepheline.
Optionally, the chemical composition of the insulating glaze layer comprises, in parts by mass:
SiO 2 42.5 to 55.5 portions of Al 2 O 3 13.0 to 20.5 portions of CaO, 1.4 to 3.5 portions of TiO 2 0.03-1.3 parts of Fe 2 O 3 0 to 0.13 portion, 0.1 to 0.35 portion of MgO and K 2 2.4 to 5 portions of O and Na 2 O1.5-3.0 parts, zrO 2 10 to 25 portions and 0 to 5.1 portions of loss on ignition.
Or,
the particle size of the zirconium silicate is that D50 is less than or equal to 1.4 mu m, and D90 is less than or equal to 4.0 mu m;
the grain diameter of the aluminum silicate is that D90 is less than or equal to 2.0 mu m;
the grain diameter of the zirconia is that D50 is less than or equal to 1.4 mu m, and D90 is less than or equal to 4.0 mu m;
the particle size of the quartz is D50 which is less than or equal to 5 mu m.
Optionally, the raw materials of the titanium white ground glaze layer comprise the following components in parts by mass:
35 to 45 portions of titanium white clinker, 0 to 10 portions of calcined kaolin, 3 to 8 portions of wollastonite, 0 to 35 portions of potassium feldspar and albite, 15 to 45 portions of quartz and 5 to 15 portions of kaolin;
the titanium white frit comprises the following chemical components in parts by mass:
SiO 2 57-70 parts of Al 2 O 3 5 to 7 portions of CaO, 15 to 19 portions of CaO and TiO 2 12 to 15 portions of MgO0.1 to 0.6 portion and K 2 O2.4-4.6 parts, na 2 0.1 to 1.2 portions of O and 0.2 to 0.5 portion of loss on ignition.
Optionally, the chemical composition of the titanium white ground glaze layer comprises the following components in parts by mass:
SiO 2 62 to 80 portions of Al 2 O 3 3 to 13 portions of CaO, 7 to 9 portions of CaO and TiO 2 4 to 5 portions of Fe 2 O 3 0.05 to 0.21 portion, 0.1 to 0.3 portion of MgO and K 2 1.4 to 3.0 portions of O and Na 2 0.1 to 0.8 portion of O and 1.0 to 1.5 portions of loss on ignition.
In a second aspect of the present invention, there is provided a ceramic plate comprising a ceramic body and an inkjet decorative layer, wherein the ceramic plate further comprises the composite glaze layer of the present invention as described above disposed between the ceramic body and the inkjet decorative layer, the titanium white glaze layer in the composite glaze layer is disposed in conformity with the ceramic body, and the barrier glaze layer in the composite glaze layer is disposed in conformity with the inkjet decorative layer.
In a third aspect of the present invention, there is provided a method for manufacturing a ceramic plate, comprising the steps of:
providing a ceramic body;
forming a titanium white base glaze layer on the surface of the ceramic blank;
according to the raw material components and the mass part ratio of the isolation glaze layer, the raw material of the isolation glaze layer is mixed with water and additives to form isolation glaze slurry, and the isolation glaze slurry is sprayed on the titanium white ground glaze layer by adopting an electrostatic spraying method to form the isolation glaze layer;
and forming an ink-jet decorative layer on the surface of the isolation glaze layer, and firing to obtain the ceramic plate.
Optionally, the particle size of particles in the isolation glaze slurry is D97 ≤ 45 μ M, the specific gravity of the isolation glaze slurry is 1.20-1.40, the flow rate of the isolation glaze slurry is 11-13 s, the pH of the isolation glaze slurry is 7-8, and the resistivity of the isolation glaze slurry is ≤ 1.2M Ω · cm.
Optionally, on a disc type electrostatic spraying device, the electrostatic spraying method is adopted to spray the coating at 300-100 g/m 2 The insulating glaze slurry is sprayed on the titanium white ground glaze layer to form an insulating glaze layer.
Optionally, the firing temperature is 1100-1150 ℃.
Has the beneficial effects that: according to the invention, the isolation glaze layer is formed on the surface of the titanium white ground glaze layer to obtain the composite glaze layer, when the ink-jet decoration is carried out on the isolation glaze layer in the composite glaze layer, various ink-jet inks can be effectively prevented from being in direct contact with the titanium white ground glaze, raw material components in the isolation glaze layer do not have adverse reactions with the ink-jet inks and the titanium white ground glaze, the problem that the crystal phase of titanic sphene synthesized in the titanium white ground glaze is preferentially reacted with spinel minerals in the ink-jet inks to generate rutile titanium dioxide, so that the glaze surface is yellowish green is avoided, and the problem that the Ti in the titanium white ground glaze is yellow green is avoided 4+ Inducing color development effect of various valence-variable transition metal color development elements in the ink-jet ink to cause the color-changing of the ink-jet ink, ensuring the whiteness of the titanium white ground coat (the b value representing yellow in Lab value can be controlled to be less than-0.6-0.3), and avoiding the phenomenon that the ink-jet ink of each channel is obviously yellowish green or changed in color(the Delta E value representing the total color difference in the Lab value can be controlled to be less than 3), so that the color gamut, the strength and the color tone of the color development of the ink-jet ink are not influenced, the production and manufacturing cost is greatly reduced, and the production stability and the product competitiveness are improved.
Detailed Description
The present invention provides a composite glaze layer, a ceramic plate and a method for manufacturing the same, and the present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The conventional titanium white ground coat forms titanium sphene crystal phase in the firing process, titanium dioxide remains, the ground coat is applied, the subsequent process needs ink-jet decoration, and most of the ink-jet ink components with different colors contain spinel minerals and various valence-variable transition metal coloring elements. With the rise of temperature, spinel minerals in the ink-jet ink preferentially react with a crystal phase of titanium sphene synthesized in ground glaze to generate rutile titanium dioxide, and rutile has a strong absorption effect on purple light at high temperature, so that the glaze surface is yellow and green, the ink-jet ink of each channel is obviously yellow and green or changed in tone, and the color development color gamut, the strength and the color tone of the ink-jet ink are greatly influenced; ti in titanium white ground coat 4+ And the coloring effect of various color development elements of the valence-variable transition metal in the ink-jet ink is easily induced to cause the color development of the ink-jet ink to be modified. In addition, the higher the firing temperature is, the more significant the above-mentioned effect of the titanium white base coat on the inkjet ink is. Based on the above, the embodiment of the invention provides a composite glaze layer, which comprises a titanium white ground glaze layer and an isolation glaze layer formed on the surface of the titanium white ground glaze layer, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
15 to 35 parts of zirconium silicate, 0 to 10 parts of aluminum silicate, 0 to 10 parts of zirconium oxide, 5 to 25 parts of quartz, 5 to 8 parts of kaolin, 3 to 8 parts of wollastonite, 0 to 3 parts of fluorite, 0 to 25 parts of potassium feldspar, 0 to 15 parts of albite and 0 to 35 parts of nepheline.
According to the embodiment of the invention, the isolation glaze layer is formed on the surface of the titanium white ground glaze layer to obtain the composite glaze layer, when ink jet decoration is required to be carried out on the titanium white ground glaze layer, the ink jet ink is decorated on the isolation glaze layer in the composite glaze layer (namely, the titanium white ground glaze layer and the ink jet decoration layer are isolated by the isolation glaze layer), even under the high-temperature sintering condition, the condition that the titanic sphene crystal phase synthesized in the titanium white ground glaze is preferentially reacted with spinel minerals in the ink jet ink to generate rutile titanium dioxide to cause the yellowish green glaze surface is effectively avoided, and the Ti in the titanium white ground glaze is avoided 4+ The method induces the color development effect of various valence-variable transition metal color development elements in the ink-jet ink to cause the color development of the ink-jet ink, ensures the whiteness of a titanium white ground coat layer (the b value representing the yellow color development in a Lab value can be controlled to be less than-0.6-0.3), eliminates the technical bottleneck of the yellowing of the ground coat, better avoids the inhibition of the titanium white ground coat with high calcium content on the color development of brown series ink, and avoids the phenomenon that the ink-jet ink of each channel is obviously yellowish green or changed in color (the delta E value representing the total color difference in the Lab value can be controlled to be less than 3), thereby not influencing the color gamut, the strength and the color tone of the ink-jet color development ink, greatly reducing the production and manufacturing cost, and improving the production stability and the competitiveness of products.
In the embodiment, zirconium silicate, zirconium oxide and titanium dioxide are all opacifiers and have whitening effect; calcium can be introduced into wollastonite, calcite, fluorite and dolomite to play a role in cooling; fluorite and wollastonite are strong fluxes, and the fluorite and the wollastonite can play a role in cooling and promote sintering by properly introducing the fluorite and the wollastonite; the nepheline, the potassium feldspar and the albite introduce potassium-sodium flux into the glaze to promote sintering and also have partial whitening effect. The kaolin and the aluminum silicate are introduced into the glaze, so that the maturation temperature of the glaze can be increased, and the effects of whitening and reducing the glossiness of the glaze can be achieved; in addition, the aluminum silicate can also play a good plasticizing and reinforcing effect, and the cost can be reduced. Silica is introduced into the glaze by adding quartz, and a glass network agent is partially formed to promote sintering; part of the quartz still exists, the firing temperature is improved, and the glossiness is reduced.
In this example, the number of parts of potassium feldspar, albite, and nepheline is not 0 at the same time.
In one embodiment, the chemical composition of the barrier glaze layer comprises, in parts by mass:
SiO 2 42.5 to 55.5 portions of Al 2 O 3 13.0 to 20.5 portions of CaO, 1.4 to 3.5 portions of TiO 2 0.03-1.3 parts of Fe 2 O 3 0 to 0.13 portion, 0.1 to 0.35 portion of MgO and K 2 O2.4-5 parts, na 2 O1.5-3.0 parts, zrO 2 10 to 25 portions and 0 to 5.1 portions of loss on ignition.
In one embodiment, the zirconium silicate has a particle size of D50. Ltoreq.1.4. Mu.m, D90. Ltoreq.4.0. Mu.m; the grain diameter of the aluminum silicate is that D90 is less than or equal to 2.0 mu m; the grain diameter of the zirconia is that D50 is less than or equal to 1.4 mu m, and D90 is less than or equal to 4.0 mu m; the particle size of the quartz is D50 which is less than or equal to 5 mu m.
In order to solve the problems that the glaze surface gloss is high, the ground glaze is yellowish green or the phenomenon of tone change and the like of the conventional titanium white ground glaze which replaces the zirconium white ground glaze is still to be improved after the conventional titanium white ground glaze is fired, in a further embodiment of the invention, the titanium white ground glaze layer comprises the following raw materials in parts by mass:
35 to 45 portions of titanium white clinker, 0 to 10 portions of calcined kaolin, 3 to 8 portions of wollastonite, 0 to 35 portions of potassium feldspar and albite, 15 to 45 portions of quartz and 5 to 15 portions of kaolin;
the titanium white frit comprises the following chemical components in parts by mass:
SiO 2 57 to 70 portions of Al 2 O 3 5 to 7 portions of CaO, 15 to 19 portions of CaO and TiO 2 12 to 15 portions of MgO0.1 to 0.6 portion and K 2 O2.4-4.6 parts, na 2 0.1 to 1.2 portions of O and 0.2 to 0.5 portion of loss on ignition.
In this embodiment, the titanite is used to synthesize CaO. TiO 2 ·SiO 2 The principle is that the content of alumina and calcium is reduced, the content of quartz is greatly improved, magnesium is removed, titanium is extracted, and the content of calcium is introduced in a wollastonite mode. Titanium white emulsion composed of the raw materialsThe turbid ground glaze can enable titanium dioxide and wollastonite to carry out solid phase reaction to synthesize titanium titanite without enabling the titanium dioxide to exist in a rutile crystal form in the sintering process with the environment temperature of 1100-1150 ℃ and the sintering period of 60min, so that the yellowing tendency of rutile titanium dioxide is better inhibited, and the glaze surface is not yellowed. The content of the titanium titanite crystal phase in the composition of the characteristic phase after sintering in the kiln is 13-21 wt%, the content of the wollastonite crystal phase is 6-12 wt%, and the characteristic phase does not contain enstatite ore phase. The titanium white opaque ground glaze provided by the invention can adapt to the firing temperature of more than 1100 ℃, the glaze surface after firing has low glossiness (the glossiness can be controlled between 3 and 8 ℃), the glaze surface does not yellow, and the whiteness of blue light is more than 65 ℃. The titanium white opacified ground glaze provided by the invention is more suitable for decoration application as the ground glaze, greatly improves the stability and applicability of the titanium white opacified ground glaze in high-temperature sintering, and can completely replace the existing zirconium white ground glaze. The titanium white base coat and the isolation glaze layer are matched with each other, the titanium white base coat has high blue light Baidu, the isolation glaze layer ensures the whiteness of the titanium white base coat and simultaneously better avoids the inhibition of the titanium white base coat with high calcium content on the color development of brown series ink, avoids the preferential reaction of the crystal phase of titanium sphene synthesized in the titanium white base coat and spinel minerals in ink-jet ink to generate rutile titanium dioxide, so that the glaze surface turns yellow and green, and avoids the Ti in the titanium white base coat 4+ The color development effect of various color development elements of the variable-valence transition metal in the ink-jet ink is induced to cause the tone of the ink-jet ink to be changed, so that the color gamut, the strength and the color tone of the color development of the ink-jet ink are not influenced.
The titanium white frit is used as an opacifier to play a role in whitening, and a large amount of titanium sphene crystal phase is synthesized in the process of firing the ground glaze, so that the hiding power of the ground glaze is increased. The material of magnesium, alumina or corundum crystal phase can accelerate the reaction of generating rutile crystal phase, and in the embodiment of the invention, the titanium white frit does not contain magnesium component, the material content of alumina or corundum crystal phase is very little, and the titanium white opacified ground glaze is in titanium sphene crystal phase and does not contain enstatite ore phase in the composition of the characteristic phase after being fired.
Calcium is an alkaline earth metal element, calcium oxide is a fluxing agent in the glaze, the melting temperature of the glaze can be rapidly reduced due to the high calcium proportion, the liquid phase for dissolving the glaze is increased, and more color particles are corroded and dissolved due to the increase of the liquid phase, so that the color development of the ink-jet ink is influenced. In the embodiment of the invention, calcium is introduced in the form of wollastonite, the content of calcium is less, the color development of ink is not influenced, and meanwhile, the addition of the wollastonite can also play a role in cooling.
Silica is introduced into the titanium white opacified ground coat by adding quartz, and a part of the silica forms a glass network agent to promote sintering; part of the titanium dioxide opal ground coat still exists in cristobalite, the firing temperature of the titanium dioxide opal ground coat is improved, and the glossiness of the glaze surface is reduced.
The potassium feldspar and the albite are used as a flux, so that the sintering is promoted, and the whiteness of the glaze surface can be further improved.
The aluminum oxide or silicon dioxide is introduced into the kaolin, so that the maturation temperature of the titanium white opaque ground coat can be increased, and the effects of whitening and reducing the glossiness are achieved.
The calcined kaolin introduces alumina and silica into the titanium white opaque ground coat, which can increase the maturation temperature of the titanium white opaque ground coat and play a role in whitening and reducing the glossiness of the glaze surface in the titanium white opaque ground coat. Therefore, the addition of the calcined kaolin further improves the whiteness of the glaze and reduces the glossiness of the glaze.
In the present example, the specific ratio of potassium feldspar and albite is not limited, and the sum of the potassium feldspar and albite is 0 to 35 parts, and in a further embodiment, the sum of the potassium feldspar and albite is 0 to 35 parts, but not equal to 0.
In a further embodiment, the titanium white ground glaze layer comprises the following raw materials in parts by mass:
35 to 40 parts of titanium white clinker, 0 to 10 parts of calcined kaolin, 3 to 8 parts of wollastonite, 5 to 35 parts of potassium feldspar and albite, 15 to 45 parts of quartz and 5 to 15 parts of kaolin.
In a further embodiment, the titanium white ground glaze layer comprises the following raw materials in parts by mass:
35 to 40 parts of titanium white clinker, 0 to 10 parts of calcined kaolin, 3 to 5 parts of wollastonite, 5 to 15 parts of potassium feldspar and albite, 25 to 45 parts of quartz and 5 to 15 parts of kaolin.
In one embodiment, the chemical composition of the titanium white frit comprises, in parts by mass:
SiO 2 58.7 to 70 portions of Al 2 O 3 6.2 to 7 portions of CaO, 16 to 19 portions of CaO and TiO 2 13.8 to 15 portions of MgO 0.2 to 0.6 portion of K 2 O2.4-3.6 parts, na 2 0.1 to 1.2 portions of O and 0.2 to 0.3 portion of loss on ignition.
In one embodiment, the chemical composition of the titanium white opacified ground glaze comprises the following components in parts by mass:
SiO 2 62 to 80 portions of Al 2 O 3 3 to 13 portions of CaO, 7 to 9 portions of CaO and TiO 2 4 to 5 portions of Fe 2 O 3 0.05 to 0.21 portion, 0.1 to 0.3 portion of MgO and K 2 1.4 to 3.0 portions of O and Na 2 0.1 to 0.8 portion of O and 1.0 to 1.5 portions of loss on ignition.
The embodiment of the invention also provides a ceramic plate, which comprises a ceramic blank and an ink-jet decorative layer, and further comprises the composite glaze layer arranged between the ceramic blank and the ink-jet decorative layer, wherein the titanium white ground glaze layer in the composite glaze layer is arranged to be attached to the ceramic blank, and the isolation glaze layer in the composite glaze layer is arranged to be attached to the ink-jet decorative layer. In the embodiment, the isolation glaze layer is arranged on the titanium white ground glaze layer and the ink-jet decorative layer, so that the possibility that various ink-jet inks are in direct contact with the titanium white ground glaze can be effectively reduced: avoid the preferential reaction of the crystal phase of the titanite synthesized in the titanium white ground glaze and spinel minerals in the ink-jet ink to generate rutile titanium dioxide, so as to avoid the yellow and green glaze surface and avoid Ti in the titanium white ground glaze 4+ The color development effect of various valence-variable transition metal color development elements in the ink-jet ink is induced to cause the tone of the ink-jet ink to be changed, so that the problem that the ink-jet ink of each channel is obviously yellowish green or changed in tone is avoided.
In the above embodiment, the isolation glaze layer is provided on the titanium white ground glaze, so as to theoretically avoid direct contact between the titanium white ground glaze and the inkjet ink, and to better solve the problem that the spinel minerals in the inkjet ink preferentially react with the crystalline phase of titanium titanite synthesized in the titanium white ground glaze to generate rutile titanium dioxide and Ti 4+ Influence variable valence transition metal hairThe problem of color generation of color elements is solved, but the current production equipment and process technical scheme still do not have practical implementation feasibility, and particularly for large-size ceramic plates (ceramic rock plates and ceramic thin plates), industrial production cannot be realized, and the existing production equipment and process technology still have a lot of spaces for improvement. For example, a rock plate blank with the thickness of 3mm is thin, the production difficulty is high, and only in terms of the glazing process, the existing common bell jar glaze spraying, water jet glaze spraying, ink jet printing digital glaze and the like have more or less problems. When the glaze throwing cabinet is adopted for glazing, the atomization capability and the implementation area are very limited, the general work ratio weight average is lower than 1.40, the maximum green body glazing area is difficult to exceed the specification of 800mm, and the glaze surface flatness is not ideal; the high-pressure automatic glaze spraying system can be used for large-area glazing of large-sized ceramic plate products, but the working specific gravity of the system is generally lower than 1.55, and once the glazing amount is less than 300g/m 2 The flatness of the glaze surface cannot meet the requirement; the best advantage of adopting bell jar to spray glaze is that the specific gravity can exceed 1.70, the flatness is good, the moisture in the kiln is relatively low, but once the glazing amount is less than 300g/m 2 Difficult problems to implement; the glaze pouring is easy to break and branch. The biggest defect of adopting the devices is the ceramic plate specification problem, because once the specification exceeds 1.2m, the device precision is difficult to control, the operation is difficult to implement, the requirements on the glaze line yield and the glazing amount are also greatly limited, generally the linear speed is difficult to exceed 30 m/min, and a plurality of production defects such as net sticking and the like are easy to occur; the amount of each square glaze is hardly more than 80g, obvious ripple defects exist, the process requires skilled technical workers, and the steps of processing and using the glaze, and customizing links such as a flat screen, a rubber roller and the like are added; the ink-jet printing digital glaze is mainly prepared from oil ink, the working specific gravity is less than 1.40, and the single-channel glazing amount is difficult to exceed 40g/m 2 The ink-jet ink has high cost due to special requirements on oily solvents, additives and ink particle sizes, and the unit price is between 3 and 12 ten thousand per ton.
Based on the above, the embodiment of the invention further provides a preparation method of the ceramic plate, which can effectively solve the difficult point of the glazing process of the ceramic rock plate and the ceramic thin plate, wherein the preparation method comprises the following steps:
s1, providing a ceramic blank;
s2, forming a titanium white base glaze layer on the surface of the ceramic blank;
s3, mixing the raw materials of the insulating glaze layer, water and additives according to the raw material components and the mass part ratio of the insulating glaze layer, so as to form an insulating glaze slurry, and spraying the insulating glaze slurry on the titanium white ground glaze layer by adopting an electrostatic spraying method, so as to form an insulating glaze layer;
and S4, forming an ink-jet decorative layer on the surface of the isolation glaze layer, and firing to obtain the ceramic plate.
The preparation method provided by the embodiment can successfully realize the application of the isolation glaze on a large-area ceramic rock plate or ceramic thin plate, not only solves the technical bottleneck that a layer of thin glaze cannot be stably and uniformly distributed on a large-size product by the traditional technical means, but also enables the color gamut and the color development intensity tone of the ink-jet ink to achieve the technical effect which is not different from the ink-jet on the conventional zirconium white cosmetic ground glaze.
The embodiment of the invention does not limit the raw materials and the mixture ratio of the ceramic body in the step S1.
In step S3, in one embodiment, 100 parts by weight of the raw materials of the insulating glaze layer described above in the embodiments of the present invention, 0 to 3 parts by weight of the additive, 40 to 95 parts by weight of water and the aqueous suspension stabilizer are added to a ball mill, mixed and then intermittently ball-milled for 6 to 15 hours until the obtained slurry can completely pass through a 325-mesh screen, thereby obtaining the insulating glaze slurry.
In one embodiment, the additive comprises the following components in parts by mass:
0.3 to 0.5 portion of sodium tripolyphosphate, 0.1 to 0.25 portion of sodium carboxymethyl cellulose, 0 to 2 portions of conductive agent and 0 to 1 portion of surfactant.
In one embodiment, the conductive agent is selected from at least one of basf EFKA VOK-6782 conductive agent, BYK-ES80, add-in FD1092, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (EA 562), but is not limited thereto.
In one embodiment, the surfactant is selected from at least one of AEO-9, mesohm 400, but is not limited thereto.
In one embodiment, the water and aqueous suspension stabilizer has a mass ratio of (30-60) to (10-35) in the water and aqueous suspension stabilizer.
In one embodiment, the aqueous suspension stabilizer is selected from at least one of methyl glycol, bentonite, polymethylsiloxane, ammonium polyamic acid formulation, STELLMITTEL506 (manufactured by suma chemical company, germany), sumapeptopon 5, peptappon 5 (manufactured by suma chemical company, germany, swelling compound), but is not limited thereto.
In one embodiment, the particle size of the particles in the isolation glaze slurry is D97-45 μ M, the specific gravity of the isolation glaze slurry is 1.20-1.40, the flow rate of the isolation glaze slurry is 11-13 s, the pH of the isolation glaze slurry is 7-8, and the resistivity of the isolation glaze slurry is 1.2M omega-cm or less. In the embodiment, the particle size of the particles in the isolation glaze slurry is D97 not more than 45 μm, so that the defects of good suspension property of the isolation glaze slurry, low melting temperature of glaze, tight combination of glaze blanks, small drying shrinkage rate of a glaze layer, difficult generation of cracks and the like can be ensured. In addition, the pH value of the isolation glaze slurry is 7-8, and the isolation glaze slurry is not easy to agglomerate.
In one embodiment, the barrier glaze slurry is sprayed on the titanium white base glaze layer by an electrostatic spraying method to form a barrier glaze layer. The embodiment can uniformly spray a layer of isolation glaze layer with the specific gravity between 1.20 and 1.40 on the titanium white ground glaze layer, solves the technical bottleneck that a layer of thin glaze cannot be stably and uniformly distributed on a large-size product by the traditional technical means, and enables the color gamut and the color development intensity of the ink-jet ink to achieve the technical effect of no difference from the ink-jet on the conventional zirconium white cosmetic clay.
In specific implementation, an electrostatic spraying method is adopted on a disc type electrostatic spraying device (the working voltage is set to be 50-75 KV) and the voltage is 30-100 g/m 2 The insulating glaze slurry is sprayed on the titanium white ground glaze layer to form an insulating glaze layer. The invention applies the disc type electrostatic spraying device to the spraying of the isolation glaze layer, and successfully sprays the isolation glaze layer on the large-area titanium white base glaze layer.
A disc type (also called omega) electrostatic spraying device adopts a disc type atomizer as a spraying center, and a workpiece moves around the disc along an omega-shaped track. When the spraying device works, the disc rotates at a high speed and moves up and down in a reciprocating manner, and after entering a spraying area, a workpiece can rotate 90-360 degrees or rotate continuously as required, so that the efficiency of the atomizer is fully exerted, the spraying geometric space is enlarged, and the spraying device is an ideal spraying method. The rotary disc atomizing disc is a main part of a disc type electrostatic automatic paint spraying machine and plays a role in atomizing an isolation glaze layer, and the uniformity and the size of atomized particles of the isolation glaze layer are directly related to the isolation glaze layer. The electrostatic atomizing disc is arranged at the connecting end of the pneumatic high-speed motor, the isolation glaze layer is quantitatively conveyed to the inner wall of the disc by a pump and is thrown out to the bottom small hole of the disc through high-speed centrifugal rotation to form mist-shaped tiny particles; the fog-like isolation glaze layer with negative electrode static is quickly adsorbed to the positive electrode workpiece (grounding positive electrode) to complete the operation of electrostatic spraying isolation glaze layer.
In step S4, in one embodiment, an inkjet decoration layer is formed on the surface of the isolation glaze layer, and then a cover glaze is sprayed on the inkjet decoration layer, and the ceramic plate is obtained after firing.
In the present embodiment, the specific raw materials and composition of the overglaze are not limited.
In one embodiment, the firing temperature is 1100 to 1150 ℃.
The invention is further illustrated by the following specific examples.
Example 1
Providing a ceramic body;
forming a titanium white base glaze layer on the surface of the ceramic body;
the titanium white base glaze layer comprises the following raw materials in parts by mass:
40 parts of titanium white clinker, 5 parts of wollastonite, 15 parts of potassium feldspar and albite, 25 parts of quartz and 15 parts of kaolin.
Wherein, the titanium white frit comprises the following chemical components in parts by mass: siO 2 2 58.7 parts of Al 2 O 3 6.2 parts of CaO, 16 parts of TiO 2 13.8 parts, mgO 0.2 parts, K 2 O3.6 parts, na 2 1.2 parts of O, loss of ignition0.3 part.
(1) The test was carried out without an insulating glaze layer:
and (3) placing the ceramic body containing the titanium white ground glaze layer in a kiln, firing at the temperature of 1100 ℃ for 60min, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1100 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 5 parts of superfine aluminum silicate, 20 parts of superfine zirconium silicate, 5 parts of superfine zirconium oxide, 6 parts of nepheline, 35 parts of potassium feldspar and albite, 3 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1100 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on the cobalt blue, the red brown, the orange and the black ink-jet color cards on the isolation glaze layer according to the gray levels of 20% and 60%, placing the isolation glaze layer in a kiln after full glaze polishing, sintering the isolation glaze layer at the temperature of 1100 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the values L, a and b by using a color difference meter.
Comparative example 1
Providing a ceramic body;
forming a titanium white ground glaze layer on the surface of the ceramic blank;
the raw material of the titanium white ground glaze layer is the opacified titanium white glaze with high solar light reflectivity in Chinese patent CN 111499202A, and the opacified titanium white glaze comprises the following raw materials in parts by mass:
12 parts of titanium frit, 10 parts of titanium dioxide, 24 parts of calcite, 16 parts of quartz, 6 parts of calcined kaolin, 20 parts of potassium feldspar and 12 parts of kaolin.
Wherein, by mass percent, the chemical composition of titanium frit includes: siO 2 2 55％、Al 2 O 3 11％、CaO 16％、TiO 2 11％、Fe 2 O 3 0.09％、MgO 2.69％、K 2 O 3.2％、Na 2 O 0.8％、P 2 O 5 0.22％。
(1) Testing without an isolation glaze layer:
and (3) placing the ceramic body containing the titanium white ground glaze layer in a kiln, sintering for 60min at the temperature of 1100 ℃, testing the glossiness by using a photometer, and testing the blue light whiteness by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1100 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 5 parts of superfine aluminum silicate, 20 parts of superfine zirconium silicate, 5 parts of superfine zirconium oxide, 6 parts of nepheline, 35 parts of potassium feldspar and albite, 3 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1100 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the isolation glaze layer according to 20% and 60% gray levels, placing the isolation glaze layer in a kiln after full glaze polishing, firing the isolation glaze layer at 1100 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
Comparative example 2
Providing a ceramic body;
forming a titanium white ground glaze layer on the surface of the ceramic blank;
the raw materials of the titanium white ground glaze layer are the conventional opaque titanium white glaze, and the titanium white ground glaze layer comprises the following raw materials in parts by mass:
60 parts of titanium frit, 20 parts of potassium feldspar and albite, 12 parts of stone powder and 8 parts of kaolin.
Wherein, the titanium frit comprises the following chemical components in parts by mass:
Li 2 O/Na 2 O/K 2 o3, caO 13, mgO 3.2 and SiO 2 57.8 parts of Al 2 O 3 3.6 parts of B 2 O 3 1.1 parts of ZrO 2 3 parts of P 2 O 5 3.3 parts of TiO 2 10 parts of BaO 2.
(1) Testing without an isolation glaze layer:
and (3) placing the ceramic body containing the titanium white ground glaze layer in a kiln, firing at the temperature of 1100 ℃ for 60min, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1100 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 5 parts of superfine aluminum silicate, 20 parts of superfine zirconium silicate, 5 parts of superfine zirconium oxide, 6 parts of nepheline, 35 parts of potassium feldspar and albite, 3 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1100 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the isolation glaze layer according to 20% and 60% gray levels, placing the isolation glaze layer in a kiln after full glaze polishing, firing the isolation glaze layer at 1100 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
Comparative example 3
Providing a ceramic body;
forming a zirconium white ground glaze layer on the surface of the ceramic body;
the raw materials of the zirconium white base coat layer are the conventional zirconium white base coat, and the zirconium white base coat layer comprises the following raw materials in parts by mass:
20 parts of zirconium white clinker, 10 parts of zirconium silicate, 50 parts of potassium feldspar and albite, 5 parts of stone powder, 10 parts of kaolin and 5 parts of dolomite.
Wherein, the chemical composition of the zirconium white frit comprises the following components in percentage by mass:
SiO 2 45.66～51.43％、Al 2 O 3 7.5～13.09％、Fe 2 O 3 0.01～0.05％、TiO 2 0.01～0.05％、CaO 5.5～8.5％、MgO 2.5～4％、K 2 O 2～4％、Na 2 O 0.5～1.5％、ZnO 3～6％、P 2 O 5 1～2％、ZrO 2 7 to 9 percent and 0.1 to 0.5 percent of loss on ignition.
(1) Testing without an isolation glaze layer:
and (3) placing the ceramic body containing the zirconium white ground glaze layer in a kiln, sintering for 60min at the temperature of 1100 ℃, testing the glossiness by using a photometer, and testing the blue light whiteness by using a whiteness instrument.
And (3) performing ink-jet printing on the cobalt blue, red brown, orange and black ink-jet color cards on the zirconium white base glaze layer according to 20% and 60% gray levels, after full glaze polishing, placing the zirconium white base glaze layer in a kiln, sintering the zirconium white base glaze layer at the temperature of 1100 ℃ for 60min, and then respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the zirconium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
the raw materials of the isolation glaze layer comprise:
3 parts of wollastonite, 15 parts of quartz, 5 parts of superfine aluminum silicate, 20 parts of superfine zirconium silicate, 5 parts of superfine zirconium oxide, 6 parts of nepheline, 35 parts of potassium feldspar and albite, 3 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the zirconium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1100 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) ink-jet printing cobalt blue, red brown, orange and black ink-jet ink color cards on the isolation glaze layer according to 20% and 60% gray levels, placing the isolation glaze layer in a kiln after full glaze polishing, firing the isolation glaze layer at 1100 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
The results of the gloss and whiteness tests with or without the insulating glaze layer in the above example 1 and comparative examples 1 to 3 are shown in table 1 below, the values of Δ E, L, a and b when the insulating glaze layer is provided in the above example 1 and comparative examples 1 to 3 and cobalt blue, red brown, orange and black inks are sprayed, respectively, are shown in tables 2 to 4 below, and the total color difference deviation (Δ E) in the above example 1 and comparative examples 1 to 2 is calculated by using the zirconium white base glaze in comparative example 3 as a standard comparison. Δ E = [ (. DELTA.L) 2 +(△a*) 2 +(△b*) 2 ] 1/2
Table 1 gloss and whiteness test results
As can be seen from Table 1, under the condition of no isolation glaze layer, the glossiness of the titanium white base glaze in the embodiment 1 is obviously lower than that of the existing titanium white base glaze, and the whiteness of the titanium white base glaze in the embodiment 1 is obviously higher than that of the existing titanium white base glaze; the glossiness and the whiteness of the titanium white base coat in the example 1 are equivalent to those of the zirconium white base coat in the comparative example 3, and the titanium white base coat can replace the zirconium white base coat.
Further, from the above results, it is understood that the presence of the insulating glaze layer can improve the whiteness of the ceramic plate glaze, and for the primer glaze layer having high glossiness, the presence of the insulating glaze layer can also reduce the glossiness of the ceramic plate glaze.
TABLE 2L, a, b, delta E test results
TABLE 3L, a, b,. DELTA.E test results
TABLE 4L, a, b,. DELTA.E test results
TABLE 5L, a, b,. DELTA.E test results
As can be seen from the results in tables 2-5, after the isolation glaze is applied, the total color difference Delta E value can be greatly reduced, and the phenomenon that the ink-jet ink of each channel is obviously yellowish green or changed in tone is avoided.
Example 2
Providing a ceramic body;
forming a titanium white ground glaze layer on the surface of the ceramic blank;
the titanium white base glaze layer comprises the following raw materials in parts by mass:
40 parts of titanium white frit, 5 parts of wollastonite, 15 parts of potassium feldspar and albite, 25 parts of quartz and 15 parts of kaolin.
The titanium white frit comprises the following chemical components in parts by mass: siO 2 2 58.7 parts of Al 2 O 3 6.2 parts of CaO, 16 parts of CaO and TiO 2 13.8 parts, mgO 0.2 parts, K 2 O3.6 parts, na 2 1.2 portions of O and 0.3 portion of loss on ignition.
(1) Testing without an isolation glaze layer:
and (3) placing the ceramic body containing the titanium white base glaze layer in a kiln, firing at the temperature of 1130 ℃ for 60min, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1130 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 5 parts of superfine aluminum silicate, 15 parts of superfine zirconium silicate, 10 parts of superfine zirconium oxide, 6 parts of nepheline, 35 parts of potassium feldspar and albite, 3 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1130 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the isolation glaze layer according to 20% and 60% gray levels, placing the isolation glaze layer in a kiln after full glaze polishing, firing the isolation glaze layer at the temperature of 1130 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
Comparative example 4
Providing a ceramic body;
forming a titanium white base glaze layer on the surface of the ceramic body;
the raw material of the titanium white ground glaze layer is the opacified titanium white glaze with high solar light reflectivity in Chinese patent CN 111499202A, and the opacified titanium white glaze comprises the following raw materials in parts by mass: 12 parts of titanium frit, 10 parts of titanium dioxide, 18 parts of calcite, 15 parts of quartz, 8 parts of calcined kaolin, 25 parts of potassium feldspar and 12 parts of kaolin.
Wherein, by mass percent, the chemical composition of the titanium frit comprises: siO 2 2 55％、Al 2 O 3 11％、CaO 16％、TiO 2 11％、Fe 2 O 3 0.09％、MgO 2.69％、K 2 O 3.2％、Na 2 O 0.8％、P 2 O 5 0.22％。
(1) Testing without an isolation glaze layer:
and (3) placing the ceramic body containing the titanium white base glaze layer in a kiln, firing at the temperature of 1130 ℃ for 60min, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1130 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 5 parts of superfine aluminum silicate, 15 parts of superfine zirconium silicate, 10 parts of superfine zirconium oxide, 6 parts of nepheline, 35 parts of potassium feldspar and albite, 3 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1130 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the isolation glaze layer according to 20% and 60% gray levels, placing the isolation glaze layer in a kiln after full glaze polishing, firing the isolation glaze layer at the temperature of 1130 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
Comparative example 5
Providing a ceramic body;
forming a titanium white ground glaze layer on the surface of the ceramic blank;
the raw materials of the titanium white ground glaze layer are the conventional opacified titanium white glaze, and the titanium white ground glaze layer comprises the following raw materials in parts by mass:
50 parts of titanium frit, 20 parts of potassium feldspar and albite, 22 parts of stone powder and 8 parts of kaolin.
Wherein, the titanium frit comprises the following chemical components in parts by mass:
Li 2 O/Na 2 O/K 2 o3, caO 13, mgO 3.2, siO 2 57.8 parts of Al 2 O 3 3.6 parts of B 2 O 3 1.1 parts of ZrO 2 3 parts of, P 2 O 5 3.3 parts of TiO 2 10 parts of BaO 2.
(1) Testing without an isolation glaze layer:
and (3) placing the ceramic body containing the titanium white base glaze layer in a kiln, firing at the temperature of 1130 ℃ for 60min, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And (3) performing ink-jet printing on the cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1130 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 5 parts of superfine aluminum silicate, 15 parts of superfine zirconium silicate, 10 parts of superfine zirconium oxide, 6 parts of nepheline, 35 parts of potassium feldspar and albite, 3 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1130 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on the cobalt blue, the red brown, the orange and the black ink-jet color cards on the isolation glaze layer according to the gray levels of 20% and 60%, placing the isolation glaze layer in a kiln after full glaze polishing, sintering the isolation glaze layer at the temperature of 1130 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the values L, a and b by using a color difference meter.
Comparative example 6
Providing a ceramic body;
forming a zirconium white base glaze layer on the surface of the ceramic body;
the raw materials of the zirconium white base coat layer are the conventional zirconium white base coat, and the zirconium white base coat layer comprises the following raw materials in parts by mass:
15 parts of zirconium white clinker, 10 parts of quartz, 10 parts of superfine zirconium silicate, 20 parts of nepheline, 30 parts of potassium feldspar and albite, 10 parts of kaolin and 5 parts of dolomite.
Wherein, the chemical composition of the zirconium white frit comprises the following components in percentage by mass:
SiO 2 45.66～51.43％、Al 2 O 3 7.5～13.09％、Fe 2 O 3 0.01～0.05％、TiO 2 0.01～0.05％、CaO 5.5～8.5％、MgO 2.5～4％、K 2 O 2～4％、Na 2 O 0.5～1.5％、ZnO 3～6％、P 2 O 5 1～2％、ZrO 2 7 to 9 percent and 0.1 to 0.5 percent of loss on ignition.
(1) The test was carried out without an insulating glaze layer:
and (3) placing the ceramic body containing the zirconium white base glaze layer in a kiln, firing at the temperature of 1130 ℃ for 60min, testing the glossiness by using a photometer, and testing the blue light whiteness by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the zirconium white base glaze layer according to 20% and 60% gray levels, placing the zirconium white base glaze layer in a kiln after full glaze polishing, firing the zirconium white base glaze layer at the temperature of 1130 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the zirconium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 5 parts of superfine aluminum silicate, 15 parts of superfine zirconium silicate, 10 parts of superfine zirconium oxide, 6 parts of nepheline, 35 parts of potassium feldspar and albite, 3 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the zirconium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1130 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the isolation glaze layer according to 20% and 60% gray levels, placing the isolation glaze layer in a kiln after full glaze polishing, firing the isolation glaze layer at 1100 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
The results of the gloss and whiteness tests of the above-mentioned example 2 and comparative examples 4 to 6 with or without a barrier glaze layer are shown in the following Table 6, and the values of Delta E, L, a and b when the above-mentioned example 2 and comparative examples 4 to 6 with or without a barrier glaze layer and cobalt blue, red brown, orange and black inks are sprayed, respectively, are shown in the following tables 7 to 10. The total color difference deviation (Δ E) in the above example 2 and comparative examples 4 to 6 was calculated using the zirconium white base coat in comparative example 6 as a standard comparison. Δ E = [ (. DELTA.L) 2 +(△a*) 2 +(△b*) 2 ] 1/2
Table 6 gloss and whiteness test results
From table 6, under the condition of no isolation glaze layer, the glossiness of the titanium white base glaze in the example 2 is obviously lower than that of the existing titanium white base glaze, and the whiteness of the titanium white base glaze in the example 2 is obviously higher than that of the existing titanium white base glaze; the glossiness and whiteness of the titanium white base coat in the example 2 are equivalent to those of the zirconium white base coat in the comparative example 6, and the titanium white base coat can replace the zirconium white base coat.
Further, from the above results, it is understood that the existence of the barrier glaze layer can improve the whiteness of the ceramic plate glaze, and the existence of the barrier glaze layer can also reduce the glossiness of the ceramic plate glaze for the primer glaze layer having high glossiness.
TABLE 7L, a, b,. DELTA.E test results
TABLE 8L, a, b,. DELTA.E test results
TABLE 9L, a, b,. DELTA.E test results
TABLE 10L, a, b,. DELTA.E test results
From the results in tables 7-10, it can be seen that the total color difference Δ E can be greatly reduced after the isolation glaze is applied, and the phenomenon that the inkjet ink of each channel is obviously yellowish green or changed in tone can be avoided.
Example 3
Providing a ceramic body;
forming a titanium white base glaze layer on the surface of the ceramic body;
the titanium white base glaze layer comprises the following raw materials in parts by mass:
40 parts of titanium white clinker, 10 parts of calcined kaolin, 5 parts of wollastonite, 5 parts of potassium feldspar and albite, 25 parts of quartz and 15 parts of kaolin.
Wherein, the titanium white frit comprises the following chemical components in parts by mass: siO 2 2 58.7 parts of Al 2 O 3 6.2 parts of CaO, 16 parts of CaO and TiO 2 13.8 parts of MgO, 0.2 part of K 2 O3.6 parts, na 2 1.2 portions of O and 0.3 portion of loss on ignition.
(1) The test was carried out without an insulating glaze layer:
and (3) placing the ceramic blank containing the titanium white ground glaze layer in a kiln, sintering for 60min at the temperature of 1150 ℃, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1150 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 0 part of superfine aluminum silicate, 25 parts of superfine zirconium silicate, 0 part of superfine zirconium oxide, 26 parts of nepheline, 15 parts of potassium feldspar and albite, 8 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1150 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the isolation glaze layer according to 20% and 60% gray levels, placing the isolation glaze layer in a kiln after full glaze polishing, firing the isolation glaze layer at 1150 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
Comparative example 7
Providing a ceramic body;
forming a titanium white ground glaze layer on the surface of the ceramic blank;
the raw material of the titanium white ground glaze layer is the opacified titanium white glaze with high solar light reflectivity in Chinese patent CN 111499202A, and the opacified titanium white glaze comprises the following raw materials in parts by mass: 8 parts of titanium frit, 10 parts of titanium dioxide, 18 parts of calcite, 15 parts of quartz, 9 parts of calcined kaolin, 28 parts of potassium feldspar and 12 parts of kaolin.
Wherein, by mass percent, the chemical composition of the titanium frit comprises: siO 2 2 55％、Al 2 O 3 11％、CaO 16％、TiO 2 11％、Fe 2 O 3 0.09％、MgO 2.69％、K 2 O 3.2％、Na 2 O 0.8％、P 2 O 5 0.22％。
(1) The test was carried out without an insulating glaze layer:
and (3) placing the ceramic body containing the titanium white ground glaze layer in a kiln, firing at the temperature of 1150 ℃ for 60min, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1150 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 0 part of superfine aluminum silicate, 25 parts of superfine zirconium silicate, 0 part of superfine zirconium oxide, 26 parts of nepheline, 15 parts of potassium feldspar and albite, 8 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1150 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on the cobalt blue, the red brown, the orange and the black ink-jet color cards on the isolation glaze layer according to the gray levels of 20% and 60%, placing the isolation glaze layer in a kiln after full glaze polishing, sintering the isolation glaze layer for 60min at the temperature of 1150 ℃, and respectively reading the corresponding color gamut numerical range and the values L, a and b by using a color difference meter.
Comparative example 8
Providing a ceramic body;
forming a titanium white base glaze layer on the surface of the ceramic body;
the raw materials of the titanium white ground glaze layer are the conventional opacified titanium white glaze, and the titanium white ground glaze layer comprises the following raw materials in parts by mass:
40 parts of titanium frit, 20 parts of potassium feldspar and albite, 32 parts of stone powder and 8 parts of kaolin.
Wherein, the titanium frit comprises the following chemical components in parts by mass:
Li 2 O/Na 2 O/K 2 o3, caO 13, mgO 3.2, siO 2 57.8 parts of Al 2 O 3 3.6 parts of B 2 O 3 1.1 parts of ZrO 2 3 parts of, P 2 O 5 3.3 parts of TiO 2 10 parts of BaO 2.
(1) The test was carried out without an insulating glaze layer:
and (3) placing the ceramic body containing the titanium white ground glaze layer in a kiln, firing at the temperature of 1150 ℃ for 60min, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the titanium white ground glaze layer according to 20% and 60% gray levels, placing the titanium white ground glaze layer in a kiln after full glaze polishing, firing the titanium white ground glaze layer at the temperature of 1150 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the titanium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 0 part of superfine aluminum silicate, 25 parts of superfine zirconium silicate, 0 part of superfine zirconium oxide, 26 parts of nepheline, 15 parts of potassium feldspar and albite, 8 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1150 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on the cobalt blue, the red brown, the orange and the black ink-jet color cards on the isolation glaze layer according to the gray levels of 20% and 60%, placing the isolation glaze layer in a kiln after full glaze polishing, sintering the isolation glaze layer for 60min at the temperature of 1150 ℃, and respectively reading the corresponding color gamut numerical range and the values L, a and b by using a color difference meter.
Comparative example 9
Providing a ceramic body;
forming a zirconium white base glaze layer on the surface of the ceramic body;
the raw materials of the zirconium white ground glaze layer are the conventional zirconium white ground glaze and comprise the following raw materials in parts by mass:
10 parts of zirconium white clinker, 18 parts of quartz, 10 parts of superfine zirconium silicate, 35 parts of nepheline, 7 parts of potassium feldspar and albite, 8 parts of stone powder, 10 parts of kaolin and 2 parts of dolomite.
Wherein, the chemical composition of the zirconium white frit comprises the following components in percentage by mass:
SiO 2 45.66～51.43％、Al 2 O 3 7.5～13.09％、Fe 2 O 3 0.01～0.05％、TiO 2 0.01～0.05％、CaO 5.5～8.5％、MgO 2.5～4％、K 2 O 2～4％、Na 2 O 0.5～1.5％、ZnO 3～6％、P 2 O 5 1～2％、ZrO 2 7 to 9 percent and 0.1 to 0.5 percent of loss on ignition.
(1) The test was carried out without an insulating glaze layer:
and (3) placing the ceramic body containing the zirconium white base glaze layer in a kiln, firing at the temperature of 1150 ℃ for 60min, testing the glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet color cards on the zirconium white base glaze layer according to 20% and 60% gray levels, placing the zirconium white base glaze layer in a kiln after full glaze polishing, firing the zirconium white base glaze layer at the temperature of 1150 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
(2) The test is carried out with an isolation glaze layer:
forming an isolation glaze layer on the zirconium white ground glaze layer by adopting an electrostatic spraying method, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
3 parts of wollastonite, 15 parts of quartz, 0 part of superfine aluminum silicate, 25 parts of superfine zirconium silicate, 0 part of superfine zirconium oxide, 26 parts of nepheline, 15 parts of potassium feldspar and albite, 8 parts of fluorite and 8 parts of kaolin.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, is sintered for 60min at the temperature of 1150 ℃, and then is tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the isolation glaze layer according to 20% and 60% gray levels, placing the isolation glaze layer in a kiln after full glaze polishing, firing the isolation glaze layer at 1150 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and the L, a and b values by using a color difference meter.
The results of the gloss and whiteness tests with and without the insulating glaze layer in the above example 3 and comparative examples 7 to 9 are shown in the following table 11, and the values of Δ E, L, a, and b when the insulating glaze layer is applied and cobalt blue, red brown, orange, and black inks are sprayed, respectively, in the above example 3 and comparative examples 7 to 9 are shown in the following tables 12 to 15, respectively. The total color difference deviation (Δ E) in the above example 3 and comparative examples 7 to 9 was calculated using the zirconium white base coat in comparative example 9 as a standard comparison.
△E＝[(△L*) 2 +(△a*) 2 +(△b*) 2 ] 1/2
Table 11 gloss and whiteness test results
From table 11, under the condition of no insulating glaze layer, the glossiness of the titanium white base glaze in the example 3 is obviously lower than that of the existing titanium white base glaze, and the whiteness of the titanium white base glaze in the example 3 is obviously higher than that of the existing titanium white base glaze; the glossiness and whiteness of the titanium white base coat in the embodiment 3 are equivalent to those of the zirconium white base coat in the comparative example 9, and the titanium white base coat can replace the zirconium white base coat.
Further, from the above results, it is understood that the existence of the barrier glaze layer can improve the whiteness of the ceramic plate glaze, and the existence of the barrier glaze layer can also reduce the glossiness of the ceramic plate glaze for the primer glaze layer having high glossiness.
TABLE 12L, a, b,. DELTA.E test results
TABLE 13L, a, b,. DELTA.E test results
TABLE 14L, a, b,. DELTA.E test results
TABLE 15L, a, b,. DELTA.E test results
From the results of 12-15, it can be known that after the isolation glaze is applied, the total color difference delta E value can be greatly reduced, and the phenomenon that the ink-jet ink of each channel is obviously yellowish green or changed in tone is avoided.
In the examples 1, 2 and 3, when the insulating glaze layer is arranged at the environment temperature of 1100-1150 ℃, the total color difference delta E is less than 3, and the whiteness and the glossiness are close to those of the conventional zirconium white ground glaze, which shows that the insulating glaze layer arranged on the ground glaze layer achieves obvious effect; in the scheme without the isolation glaze layer, the total color difference delta E after ink jetting is mostly larger than 3; the data of whiteness and glossiness are greatly different from the technical scheme of the conventional zirconium white base coat, the environment temperature is higher than 1100 ℃, and the existing various titanium white base coats are difficult to produce stably after ink jet.
In conclusion, the isolation glaze layer is formed on the surface of the titanium white ground glaze layer to obtain the composite glaze layer, when ink-jet decoration is carried out on the isolation glaze layer in the composite glaze layer, the phenomenon that the titanic sphene crystal phase synthesized in the titanium white ground glaze preferentially reacts with spinel minerals in ink-jet ink to generate rutile type titanium dioxide to cause the glaze to turn yellow and green is avoided, and various valence-variable transition metal chromophoric elements caused by Ti color development elements are avoided 4+ The color development effect is induced to cause the tone change of the ink-jet ink, the whiteness of the titanium white ground glaze layer is ensured (the b value representing the yellow tone in a Lab value can be controlled to be less than-0.6-0.3), the inhibition of the titanium white ground glaze with high calcium content on the color development of brown series ink is better avoided, the phenomenon that the ink-jet ink of each channel is obviously yellowish green or tone-changed (the delta E value representing the total color difference in the Lab value can be controlled to be less than 3) is avoided, the color gamut, the strength and the tone of the color development of the ink-jet ink are not influenced, the production and manufacturing cost is greatly reduced, and the production stability and the competitiveness of products are improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. The composite glaze layer is characterized by comprising a titanium white ground glaze layer and an isolation glaze layer formed on the surface of the titanium white ground glaze layer, wherein the isolation glaze layer comprises the following raw materials in parts by mass:
15 to 35 parts of zirconium silicate, 0 to 10 parts of aluminum silicate, 0 to 10 parts of zirconia, 5 to 25 parts of quartz, 5 to 8 parts of kaolin, 3 to 8 parts of wollastonite, 0 to 8 parts of fluorite, 0 to 25 parts of potassium feldspar, 0 to 15 parts of albite and 0 to 35 parts of nepheline.
2. A composite glaze layer as claimed in claim 1, wherein the chemical composition of the insulating glaze layer comprises, in parts by mass:
SiO 2 42.5 to 55.5 portions of Al 2 O 3 13.0 to 20.5 portions of CaO, 1.4 to 3.5 portions of TiO 2 0.03-1.3 parts of Fe 2 O 3 0 to 0.13 portion of MgO0.1 to 0.35 portion of K 2 2.4 to 5 portions of O and Na 2 1.5 to 3.0 portions of O and ZrO 2 10 to 25 portions and 0 to 5.1 portions of loss on ignition.
3. The composite glaze layer of claim 1 wherein,
the particle size of the zirconium silicate is that D50 is less than or equal to 1.4 mu m, and D90 is less than or equal to 4.0 mu m;
the grain diameter of the aluminum silicate is that D90 is less than or equal to 2.0 mu m;
the grain diameter of the zirconia is that D50 is less than or equal to 1.4 mu m, and D90 is less than or equal to 4.0 mu m;
the particle size of the quartz is D50 less than or equal to 5 mu m.
4. The composite glaze layer of claim 1 wherein the titanium white ground glaze layer comprises the following raw materials in parts by mass:
35 to 45 portions of titanium white clinker, 0 to 10 portions of calcined kaolin, 3 to 8 portions of wollastonite, 0 to 35 portions of potassium feldspar and albite, 15 to 45 portions of quartz and 5 to 15 portions of kaolin;
the titanium white frit comprises the following chemical components in parts by mass:
SiO 2 57 to 70 portions of Al 2 O 3 5 to 7 portions of CaO, 15 to 19 portions of CaO and TiO 2 12 to 15 portions of MgO0.1 to 0.6 portion and K 2 2.4 to 4.6 portions of O and Na 2 0.1 to 1.2 portions of O and 0.2 to 0.5 portion of ignition loss。
5. The composite glaze layer of claim 4 wherein the titanium white ground glaze layer has a chemical composition comprising, in parts by mass:
SiO 2 62 to 80 portions of Al 2 O 3 3 to 13 portions of CaO, 7 to 9 portions of CaO and TiO 2 4 to 5 portions of Fe 2 O 3 0.05 to 0.21 portion, 0.1 to 0.3 portion of MgO and K 2 1.4 to 3.0 portions of O and Na 2 0.1 to 0.8 portion of O and 1.0 to 1.5 portions of loss on ignition.
6. A ceramic plate comprises a ceramic blank and an ink-jet decorative layer, and is characterized by further comprising the composite glaze layer which is arranged between the ceramic blank and the ink-jet decorative layer and is used as claimed in any one of claims 1 to 5, wherein a titanium white base glaze layer in the composite glaze layer is arranged to be attached to the ceramic blank, and an isolation glaze layer in the composite glaze layer is arranged to be attached to the ink-jet decorative layer.
7. A method for preparing a ceramic plate, comprising the steps of:
providing a ceramic body;
forming a titanium white base glaze layer on the surface of the ceramic blank;
the insulating glaze layer of any one of claims 1 to 3, which is prepared by mixing the raw materials of the insulating glaze layer with water and additives in the mass ratio to form an insulating glaze slurry, and spraying the insulating glaze slurry onto the titanium white ground glaze layer by an electrostatic spraying method to form an insulating glaze layer;
and forming an ink-jet decorative layer on the surface of the isolation glaze layer, and firing to obtain the ceramic plate.
8. A method for manufacturing a ceramic board as claimed in claim 7, wherein the particle diameter of the particles in the glaze spacer slurry is D97. Ltoreq. 45 μ M, the specific gravity of the glaze spacer slurry is 1.20 to 1.40, the flow rate of the glaze spacer slurry is 11 to 13s, the pH of the glaze spacer slurry is 7 to 8, and the resistivity of the glaze spacer slurry is 1.2M Ω -cm or less.
9. A method for manufacturing a ceramic board as claimed in claim 6, wherein the electrostatic spraying method is used at 30 to 100g/m on a disc type electrostatic spraying device 2 The insulating glaze slurry is sprayed on the titanium white ground glaze layer to form an insulating glaze layer.
10. A method for manufacturing a ceramic board as claimed in claim 6, wherein the firing temperature is 1100 to 1150 ℃.
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| CN115849953B (en) * | 2022-12-13 | 2023-11-07 | 福建省德化县美景礼品有限公司 | Photochromic ceramic glaze and preparation method thereof |
| CN115872782A (en) * | 2022-12-23 | 2023-03-31 | 广东金牌陶瓷有限公司 | Terrazzo surface texture imitated ceramic rock plate and preparation method thereof |
| CN115872782B (en) * | 2022-12-23 | 2024-01-05 | 广东金牌陶瓷有限公司 | Ceramic rock plate imitating terrazzo surface texture and preparation method thereof |
| CN115650587A (en) * | 2022-12-26 | 2023-01-31 | 新明珠集团股份有限公司 | Reflective heat-insulation glaze, reflective heat-insulation ceramic tile and preparation method and application thereof |
| CN115650587B (en) * | 2022-12-26 | 2023-03-21 | 新明珠集团股份有限公司 | Reflective heat-insulation glaze, reflective heat-insulation ceramic tile and preparation method and application thereof |
| CN115974411A (en) * | 2023-02-02 | 2023-04-18 | 重庆唯美陶瓷有限公司 | Ceramic tile base glaze, ceramic tile and preparation method thereof |
| CN116040945A (en) * | 2023-02-02 | 2023-05-02 | 重庆唯美陶瓷有限公司 | Ceramic tile base glaze, ceramic tile and preparation method thereof |
| CN115974411B (en) * | 2023-02-02 | 2024-03-08 | 重庆唯美陶瓷有限公司 | Ceramic tile base glaze, ceramic tile and preparation method thereof |
| CN116040945B (en) * | 2023-02-02 | 2024-03-08 | 重庆唯美陶瓷有限公司 | Ceramic tile base glaze, ceramic tile and preparation method thereof |
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