CN115304276B - Composite glaze layer, ceramic plate and preparation method thereof - Google Patents
Composite glaze layer, ceramic plate and preparation method thereof Download PDFInfo
- Publication number
- CN115304276B CN115304276B CN202210928827.3A CN202210928827A CN115304276B CN 115304276 B CN115304276 B CN 115304276B CN 202210928827 A CN202210928827 A CN 202210928827A CN 115304276 B CN115304276 B CN 115304276B
- Authority
- CN
- China
- Prior art keywords
- parts
- glaze layer
- glaze
- titanium white
- isolation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 262
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 217
- 238000002955 isolation Methods 0.000 claims abstract description 111
- 239000002994 raw material Substances 0.000 claims abstract description 48
- 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 45
- 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 38
- 239000010453 quartz Substances 0.000 claims abstract description 35
- 239000010456 wollastonite Substances 0.000 claims abstract description 34
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 34
- 229910052656 albite Inorganic materials 0.000 claims abstract description 33
- 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
- 239000010434 nepheline Substances 0.000 claims abstract description 20
- 229910052664 nepheline Inorganic materials 0.000 claims abstract description 20
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000010436 fluorite Substances 0.000 claims abstract description 19
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims description 324
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 31
- 238000010304 firing Methods 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 28
- 238000007590 electrostatic spraying Methods 0.000 claims description 25
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 210000003298 dental enamel Anatomy 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000976 ink Substances 0.000 abstract description 92
- 239000010936 titanium Substances 0.000 abstract description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 33
- 229910052719 titanium Inorganic materials 0.000 abstract description 32
- 239000013078 crystal Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 24
- 230000008859 change Effects 0.000 abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 11
- 239000011707 mineral Substances 0.000 abstract description 11
- 229910052596 spinel Inorganic materials 0.000 abstract description 11
- 239000011029 spinel Substances 0.000 abstract description 11
- 150000003624 transition metals Chemical class 0.000 abstract description 11
- 238000005034 decoration Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000001939 inductive effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 66
- 238000005245 sintering Methods 0.000 description 41
- 235000012239 silicon dioxide Nutrition 0.000 description 34
- 239000004408 titanium dioxide Substances 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
- 239000012071 phase Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- 238000007641 inkjet printing Methods 0.000 description 24
- 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 22
- 238000005498 polishing Methods 0.000 description 21
- 239000000292 calcium oxide Substances 0.000 description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 238000011161 development Methods 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 241001270131 Agaricus moelleri Species 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000002087 whitening effect Effects 0.000 description 7
- 229910021532 Calcite Inorganic materials 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910052861 titanite Inorganic materials 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 5
- 239000003605 opacifier Substances 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
- 239000003086 colorant Substances 0.000 description 4
- 239000010459 dolomite Substances 0.000 description 4
- 229910000514 dolomite Inorganic materials 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 239000003381 stabilizer Substances 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
- 230000000996 additive effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 229910052634 enstatite Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000006872 improvement 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
- 238000007639 printing Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 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
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000004579 marble Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 230000007704 transition Effects 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 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
- 206010027627 Miliaria Diseases 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
- 230000002411 adverse 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 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
- 239000011449 brick Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 201000004169 miliaria rubra Diseases 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- -1 polymethylsiloxane Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000005070 ripening 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 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: 15-35 parts of zirconium silicate, 0-10 parts of aluminum silicate, 0-10 parts of zirconium oxide, 5-25 parts of quartz, 5-8 parts of kaolin, 3-8 parts of wollastonite, 0-8 parts of fluorite, 0-25 parts of potassium feldspar, 0-15 parts of albite and 0-35 parts of nepheline. 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, and when the isolation glaze layer in the composite glaze layer is subjected to inkjet decoration, the possibility that various inkjet inks are in direct contact with the titanium white ground glaze can be effectively reduced. Avoiding the yellow green color of the glaze surface caused by the preferential reaction of the titanium sphene crystal phase synthesized in the titanium white ground glaze and the spinel mineral in the inkjet ink to generate rutile titanium dioxide, and avoiding Ti in the titanium white ground glaze 4+ And inducing various valence-changing transition metal color-forming elements in the inkjet ink to generate a color-forming effect so as to cause the tone change of the inkjet 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 opacifying ground glaze (commonly called cosmetic soil) has extremely strong covering effect, and most of the opacifying ground glaze takes substances with higher refractive indexes as dispersed particles, so that the opacifying ground glaze with good covering rate has extremely strong reflecting effect on sunlight. Common opacifiers for opacifying underglaze include titanium dioxide, cerium oxide, tin oxide, zinc oxide, zirconium silicate, and the like.
Cerium oxide and tin oxide are rarely used in the opacified primer of building ceramic due to the problems of high price and the like. Ultrafine zirconium silicate is the most commonly adopted opacifier for opacifying ground coat at present, has a refractive index of 1.93-2.01, is a high-quality opacifier, and is widely applied to the production of various architectural ceramics, sanitary ceramics, daily ceramics, first-grade artware ceramics and the like, and has wide application range and large application amount in the processing production of ceramic glaze. Zirconium silicate is widely applied to ceramic production, and has good chemical stability, is not influenced by ceramic firing atmosphere, and can obviously improve the blank glaze bonding performance of ceramic and the ceramic glaze hardness. Zirconium silicate has a whitening effect because it forms baddeleyite or the like after firing the ceramic, thereby forming Scattering of incident light waves, which is generally called large particle Scattering or Mie Scattering (Mie Scattering). For producing the ceramic tile with white background color, the whiter the base glaze is, the higher the product grade is, for example, the higher grade marble ceramic tile such as carrageenan white, snow white and the like needs the whiteness of the background color to be more than 80 degrees. The addition amount of zirconium silicate in most marble tile base glaze is 15-20%, the whiteness is generally about 65 ℃, the use amount of zirconium silicate is continuously increased, the whiteness increase is not obvious, the flatness of the tile cannot reach the standard, and meanwhile, the cost is increased, so that improvement of the performance effect or economic benefit is needed.
In addition, the global commodity price is continuously increased in recent years, under the requirement of double carbon and double control, the competition among ceramic brands is very tragic, the best mode for reducing the cost is sought through various technical progress, the process technicians are continuously promoted to be new, various technical means are adopted to find the substitute of zirconium silicate, and the comprehensive cost of the primer is reduced. Titanium dioxide is also an oxide with a very high refractive index, the refractive index is as high as 2.55-2.76, the titanium dioxide has extremely strong reflection effect on light, and the titanium dioxide is the whitest substance in the world. Titanium dioxide is often used as the major component of water-impermeable underglaze in architectural ceramic tiles. Titanium dioxide is generally introduced in the form of conventional titanium white frit, 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 (Li) 2 O/Na 2 O/K 2 2.0 to 8.0 parts of O, 5 to 18 parts of CaO, 2 to 5 parts of MgO and SiO 2 50 to 75 parts of Al 2 O 3 3 to 6 parts of B 2 O 3 0 to 3 parts of ZrO 2 0 to 5 parts of P 2 O 5 0 to 5 parts of TiO 2 3 to 10 portions of BaO and 0 to 2.0 portions of BaO. Titanium dioxide, however, is a polycrystalline oxide, titanium being generally present as Ti in silicate glass systems at temperatures in excess of 1000 DEG C 4+ The valence state exists. Ti (Ti) 4+ The valence state of (2) means the outermost electron 3d of the titanium core 2 4s 2 All are lost, all are empty in the d-track, no "d-d" transition between electrons in the d-track can occur, so Ti 4+ The valence state should be colorless. However, due to Ti 4+ The ions strongly absorb ultraviolet rays, and the absorption band thereof often enters the violet part of the visible light region, so that titanium dioxide (titanium is +4 valent) existing in a rutile crystal form after firing has a strong absorption effect on the violet light, and the yellowing of the glaze surface can be caused; after the waterproof ground glaze adopting the conventional titanium white frit is sintered for 60min in a kiln with the ring temperature of 1100-1150 ℃, titanium dioxideThe titanium sphene crystal phase content generated by the solid phase reaction with wollastonite is reduced, the wollastonite crystal phase content is increased, the enstatite crystal phase content is increased to be more than 2 weight percent, the glossiness is more than 40 ℃ after firing, the white light is gradually changed into semitransparent, the whiteness of blue light is greatly reduced, and the whiteness is generally lower than 55 ℃; the b value representing yellow tone in the Lab value is generally more than 6, so that the firing temperature of the conventional titanium white waterproof ground glaze used for building ceramic wall and floor tiles is required to be lower than 1100 ℃.
Chinese patent CN 111499202A discloses a high solar reflectance opacified titanium white glaze and a preparation method thereof, and the high solar reflectance opacified titanium white glaze in the invention can be applied to porcelain bricks fired at 1150 ℃, can weaken the defect that the ground glaze is yellow due to the ultraviolet absorption effect of rutile type titanium dioxide, but has a plurality of limitations and defects for really realizing stable industrialized application:
(1) In practice, the general glossiness of the base glaze for ceramic production should be controlled to be 5-10 ℃, otherwise, the lowest eutectic point is easy to occur to cause prickly heat or pinhole defect, the patent reports that the technical proposal of using titanite crystal grains as seed crystal to induce the reaction of titanium dioxide and calcite to generate titanite crystal phase with the grain diameter of 450-600 nm needs to add a large amount of calcite, so the base glaze must be melted to completely react without yellowing, which leads to extremely high glossiness of the base glaze after the actual kiln sintering, and a large amount of aluminum is additionally added to inhibit the glossiness (the aluminum oxide content reaches 19-21 percent in the patent), and in silicate systems with high titanium component content, more cationic Al with middle type characteristics exists 3+ In the case of (2), rutile titanium dioxide having a suitable particle size is easily precipitated, and the glaze is yellow;
(2) After the primer is applied, the subsequent process needs to carry out inkjet decoration, and most of inkjet ink components with different colors contain spinel minerals and various valence-changing transition metal coloring elements. Therefore, with the increase of the firing temperature, the titanite crystal phase in the base glaze silicate glass system reacts with spinel minerals in the inkjet ink to generate rutile titanium dioxide, so that the glaze turns yellow green. In silicate glasses, titanium is generally represented by Ti 4+ In the valence state, from the discussion aboveThe Ti can be known 4+ The valence state would make it yellow. Although Ti is 4+ Does not cause darker colors alone, but strongly influences the coloration of other transition metal elements of variable valence, even though the content of these transition metal elements is very small, especially for iron, the most obvious example being the coloration of many colorants often with TiO 2 The color mixture is realized by mixing with other color components: tiO (titanium dioxide) 2 With Fe 2 O 3 The mixture turns brown (this with Fe 2 O 3 And MnO 2 Similar in color for combinations of (a); tiO (titanium dioxide) 2 With MnO 2 The combination is light yellow to dark yellow; tiO (titanium dioxide) 2 Combined with NiO to appear grey to yellow brown; tiO (titanium dioxide) 2 Blue green when combined with CuO; tiO (titanium dioxide) 2 With CeO 2 The mixture is used for showing bright yellow; chrome titanium yellow is also a rutile-type structural pigment. Thus, with increasing firing temperature, ti in the under-glazed silicate glass system 4+ The valence state (such as residual titanium dioxide) can easily induce various valence transition metal color-developing elements in the ink-jet ink to generate color-developing effect so as to make the color of the ink-jet ink change. Further, when the CaO content in the primer formulation reaches more than 10%, the primer formulation is extremely unfavorable for the color development of the brown series of ink-jet printing. To sum up, the titanium white primer in the patent is relatively easy to cause the inkjet ink of each channel to be obviously yellowish green or changed (the b value representing the yellow tone in the Lab value is seriously larger), so that the color development gamut, the intensity 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 more than 4) occurs in production, so that the quality of the inkjet ink is not guaranteed.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
Based on the shortcomings of the prior art, the invention aims to provide a composite glaze layer, a ceramic plate and a preparation method thereof, which aim to solve the problems that the titanium sphene crystal phase in the existing titanium white ground glaze is easy to react with ink-jet ink to generate rutile type titanium dioxide to cause the glaze to turn yellow-green, and the Ti in the existing titanium white ground glaze 4+ The color change and tone change of the inkjet ink are caused by the color change effect of various valence-changing transition metal color-forming elements in the inkjet inkThe channel ink-jet ink has the problem of obviously yellowish green or tone change.
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:
15-35 parts of zirconium silicate, 0-10 parts of aluminum silicate, 0-10 parts of zirconium oxide, 5-25 parts of quartz, 5-8 parts of kaolin, 3-8 parts of wollastonite, 0-3 parts of fluorite, 0-25 parts of potassium feldspar, 0-15 parts of albite and 0-35 parts of nepheline.
Optionally, the chemical composition of the isolating glaze layer comprises the following components in parts by mass:
SiO 2 42.5 to 55.5 portions of Al 2 O 3 13.0 to 20.5 parts, 1.4 to 3.5 parts of CaO and TiO 2 0.03 to 1.3 parts of Fe 2 O 3 0 to 0.13 part, 0.1 to 0.35 part of MgO and K 2 O2.4-5 parts, na 2 O1.5-3.0 parts, zrO 2 10 to 25 parts and 0 to 5.1 parts of burning loss.
Alternatively, the process may be carried out in a single-stage,
the grain diameter of the zirconium silicate is D50 less than or equal to 1.4 mu m, and D90 less than or equal to 4.0 mu m;
the grain diameter of the aluminum silicate is D90 which is less than or equal to 2.0 mu m;
the grain diameter of the zirconia is D50 less than or equal to 1.4 mu m, and D90 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.
Optionally, the raw materials of the titanium white ground glaze layer comprise the following components in parts by mass:
35-45 parts of titanium white frit, 0-10 parts of calcined kaolin, 3-8 parts of wollastonite, 0-35 parts of potassium feldspar and albite, 15-45 parts of quartz and 5-15 parts of kaolin;
the chemical composition of the titanium white frit comprises the following components in parts by mass:
SiO 2 57-70 parts of Al 2 O 3 5 to 7 parts of CaO, 15 to 19 parts of TiO 2 12 to 15 parts of MgO, 0.1 to 0.6 part of K 2 O2.4-4.6 parts, na 2 O 0.1 to 1.2 portions and 0.2 to 0.5 portion of burning loss.
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 parts of CaO, 7 to 9 parts of TiO 2 4 to 5 parts of Fe 2 O 3 0.05 to 0.21 part, 0.1 to 0.3 part of MgO and K 2 O1.4-3.0 parts, na 2 0.1 to 0.8 part of O and 1.0 to 1.5 parts of burning loss.
According to a second aspect of the invention, a ceramic plate is provided, which comprises a ceramic body and an inkjet decorative layer, and further comprises the composite glaze layer provided between the ceramic body and the inkjet decorative layer, wherein the titanium white under glaze layer in the composite glaze layer is attached to the ceramic body, and the isolation glaze layer in the composite glaze layer is attached to 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 ground enamel layer on the surface of the ceramic body;
according to the raw material components and the mass portion ratio of the isolation glaze layer, the raw materials of the isolation glaze layer, water and additives are mixed 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 the particles in the isolating glaze slurry is D97 less than or equal to 45 mu M, the specific gravity of the isolating glaze slurry is 1.20-1.40, the flow rate of the isolating glaze slurry is 11-13 s, the pH of the isolating glaze slurry is 7-8, and the resistivity of the isolating glaze slurry is less than or equal to 1.2MΩ & cm.
Alternatively, the electrostatic spraying method is adopted on a disc type electrostatic spraying device at the speed of 300-100 g/m 2 And spraying the isolation glaze slurry on the titanium white ground glaze layer to form an isolation glaze layer.
Optionally, the firing temperature is 1100-1150 ℃.
The beneficial effects are 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 inkjet decoration is carried out on the isolation glaze layer in the composite glaze layer, various inkjet inks can be effectively prevented from being in direct contact with the titanium white ground glaze, the raw material components in the isolation glaze layer do not react with the inkjet inks and the titanium white ground glaze adversely, the preferential reaction of the titanium spherule crystal phase synthesized in the titanium white ground glaze and the spinel mineral in the inkjet inks is avoided, the yellowing green of the glaze surface caused by the generation of rutile titanium dioxide is avoided, and the Ti in the titanium white ground glaze is avoided 4+ The color change of the inkjet ink caused by the color change effect of various color-changing transition metal color-forming elements in the inkjet ink is induced, the whiteness of the titanium white ground glaze layer is ensured (the b value representing yellow tone in the Lab value can be controlled to be less than-0.6-0.3), the phenomenon that the inkjet ink of each channel is obviously greenish yellow or changed in color (the delta E value representing total color difference in the Lab value can be controlled to be less than 3) is avoided, the color gamut, the intensity and the color tone of the color development of the inkjet ink are not influenced, the production and manufacturing cost is greatly reduced, and the production stability and the competitiveness of products are improved.
Detailed Description
The invention provides a composite glaze layer, a ceramic plate and a preparation method thereof, which are used for making the purposes, the technical scheme and the effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of 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 is remained at the same time, the ground coat is applied, the subsequent process needs to be subjected to inkjet decoration, and most of inkjet ink components with different colors contain spinel minerals and various valence transition metalsBelongs to a chromophoric element. Along with the rise of temperature, spinel minerals in the inkjet ink can react with titanium sphene crystal phase synthesized in the base glaze preferentially to generate rutile type titanium dioxide, and rutile has strong absorption effect on purple light at high temperature, so that the glaze is yellow-green, and the inkjet ink of each channel is obviously yellowish-green or changed in tone, and the color development color gamut, intensity and tone of the inkjet ink are greatly influenced; ti in titanium white ground glaze 4+ The color development effect of various valence-variable transition metal color development elements in the ink-jet ink is easily induced, so that the color development and tone change of the ink-jet ink are realized. In addition, the higher the firing temperature is, the more remarkable the influence of the titanium white under glaze 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:
15-35 parts of zirconium silicate, 0-10 parts of aluminum silicate, 0-10 parts of zirconium oxide, 5-25 parts of quartz, 5-8 parts of kaolin, 3-8 parts of wollastonite, 0-3 parts of fluorite, 0-25 parts of potassium feldspar, 0-15 parts of albite and 0-35 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 the titanium white ground glaze layer is required to be subjected to inkjet decoration, the inkjet ink is decorated on the isolation glaze layer in the composite glaze layer (namely, the isolation glaze layer isolates the titanium white ground glaze layer from the inkjet decoration layer), even under the condition of high-temperature sintering, the preferential reaction of the titanium spherule crystal phase synthesized in the titanium white ground glaze and the spinel mineral in the inkjet ink can be effectively avoided, the yellow-green color of the glaze surface caused by the generation of rutile titanium dioxide is avoided, and the Ti in the titanium white ground glaze is avoided 4+ The color change of the inkjet ink caused by the color change effect of various color change transition metal color-forming elements in the inkjet ink is induced, the whiteness of a titanium white primer layer is ensured (the b value representing yellow tone in the Lab value can be controlled to be less than-0.6-0.3), the technical bottleneck of the yellowing of the primer is eliminated, the inhibition of the titanium white primer with high calcium content on the color development of brown series ink is better avoided, the phenomenon that the inkjet ink of each channel is obviously yellowish green or changed in tone is avoided (the delta E value representing total color difference in the Lab value can be controlled to be less than3) Therefore, the color gamut, intensity and tone of the color development of the inkjet ink are not affected, the production and manufacturing cost is greatly reduced, and the production stability and the competitiveness of the product are improved.
In the embodiment, zirconium silicate, zirconium oxide and titanium dioxide are all opacifiers and have whitening effect; wollastonite, calcite, fluorite and dolomite can be introduced with calcium to play a role in cooling; fluorite and wollastonite are strong fluxes, and the proper introduction of the fluorite and wollastonite can play a role in cooling and promote sintering; the nepheline, the potassium feldspar and the sodium feldspar are introduced into the glaze to promote sintering, and can also play a part of whitening effect. The kaolin and the aluminum silicate are introduced into the glaze, so that the maturity temperature of the glaze can be increased, and the effect of whitening and reducing the glossiness of the glaze can be achieved; in addition, the aluminum silicate can be doped to achieve good plasticizing and reinforcing effects, so that the cost can be reduced. Silica is introduced into the glaze by adding quartz, so that a glass network agent is partially formed, and sintering is promoted; part of the glass still exists in cristobalite, so that the sintering temperature is increased, and the glossiness is reduced.
In this example, the parts of potassium feldspar, albite, nepheline are not 0 at the same time.
In one embodiment, the chemical composition of the insulating glaze layer includes, in parts by mass:
SiO 2 42.5 to 55.5 portions of Al 2 O 3 13.0 to 20.5 parts, 1.4 to 3.5 parts of CaO and TiO 2 0.03 to 1.3 parts of Fe 2 O 3 0 to 0.13 part, 0.1 to 0.35 part of MgO and K 2 O2.4-5 parts, na 2 O1.5-3.0 parts, zrO 2 10 to 25 parts and 0 to 5.1 parts of burning loss.
In one embodiment, the zirconium silicate has a particle size D50. Ltoreq.1.4 μm and D90. Ltoreq.4.0 μm; the grain diameter of the aluminum silicate is D90 which is less than or equal to 2.0 mu m; the grain diameter of the zirconia is D50 less than or equal to 1.4 mu m, and D90 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.
In order to solve the problems that the glaze gloss is high, the ground glaze turns yellow-green or the tone change phenomenon is generated after the conventional titanium white ground glaze for replacing the zirconium white ground glaze is sintered, and the like, in a further embodiment of the invention, the titanium white ground glaze layer comprises the following raw materials in parts by mass:
35-45 parts of titanium white frit, 0-10 parts of calcined kaolin, 3-8 parts of wollastonite, 0-35 parts of potassium feldspar and albite, 15-45 parts of quartz and 5-15 parts of kaolin;
the chemical composition of the titanium white frit comprises the following components in parts by mass:
SiO 2 57-70 parts of Al 2 O 3 5 to 7 parts of CaO, 15 to 19 parts of TiO 2 12 to 15 parts of MgO, 0.1 to 0.6 part of K 2 O2.4-4.6 parts, na 2 0.1 to 1.2 parts of O and 0.2 to 0.5 part of burning loss.
In the present embodiment, caO/TiO is synthesized in compliance with titanite 2 ·SiO 2 In principle, the content of aluminum oxide 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. The titanium white opacified primer composed of the raw materials can enable titanium dioxide and wollastonite to perform solid-phase reaction to synthesize titanium sphene without enabling the titanium dioxide to exist in a rutile crystal form in the sintering process of the ring temperature of 1100-1150 ℃ and the sintering period of 60min, so that the tendency of yellowing of the rutile titanium dioxide is better inhibited, and the glaze is prevented from yellowing. The characteristic phase composition after firing in the kiln contains 13-21 wt% of titanite crystal phase, 6-12 wt% of wollastonite crystal phase and no enstatite phase. The titanium white opacified primer provided by the invention can adapt to the firing temperature of more than 1100 ℃, and 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 opacifying primer provided by the invention is more suitable for being used as primer decoration, greatly improves the stability and applicability of the titanium white opacifying primer in high-temperature sintering, and can completely replace the existing zirconium white primer. The titanium white ground glaze and the isolation glaze layer in the embodiment are mutually matched, the titanium white ground glaze has higher blue light hundred degrees, the isolation glaze layer ensures the whiteness of the titanium white ground glaze, simultaneously better avoids the inhibition of the titanium white ground glaze with high calcium content on the color development of brown series ink, avoids the preferential reaction of the titanium sphene crystal phase synthesized in the titanium white ground glaze and spinel mineral in the inkjet ink, and generates rutile type titanium dioxide to cause The glaze turns yellow green, and avoids Ti in the titanium white ground coat 4+ The color change of the inkjet ink caused by the color-developing effect of various valence-changing transition metal color-developing elements in the inkjet ink is induced, so that the color gamut, the intensity and the color tone of the color development of the inkjet 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 phases are synthesized in the firing process of the base glaze, so that the covering power of the base glaze is increased. The material of magnesium, aluminum oxide or corundum crystal phase can accelerate the reaction of generating rutile crystal phase, but the titanium white frit does not contain magnesium component, the content of the material of aluminum oxide or corundum crystal phase is also very small, and the titanium white opacifying primer is titanium sphene crystal phase and does not contain enstatite phase in the characteristic phase composition after firing.
Calcium is an alkaline earth metal element, calcium oxide is a fluxing agent in the glaze, the high calcium proportion can rapidly reduce the melting temperature of the glaze, the liquid phase of the glaze dissolution is increased, and more color particles can be eroded and dissolved by the increase of the liquid phase, so that the color development of the inkjet ink is affected. According to the embodiment of the invention, calcium is introduced in the form of wollastonite, the calcium content is low, the color development of the ink is not affected, and meanwhile, the wollastonite can be added to achieve the effect of cooling.
Introducing silicon dioxide into the titanium white opacifying ground glaze by adding quartz, wherein the silicon dioxide partially forms a glass network agent to promote sintering; part of the titanium white opaque primer exists as cristobalite, so that the firing temperature of the titanium white opaque primer is increased, and the glossiness of the glaze is reduced.
The potassium feldspar and the albite are used as fluxes, so that sintering is promoted, and the whiteness of the glaze can be further improved.
The addition of the kaolin introduces alumina or silicon dioxide, so that the maturation temperature of the titanium white opacifying ground glaze can be increased, and the effects of whitening and reducing glossiness are achieved.
The calcined kaolin is introduced into the titanium white opacifying primer, so that the ripening temperature of the titanium white opacifying primer can be increased, and the effects of whitening and reducing the glossiness of the glaze surface can be achieved in the titanium white opacifying primer. Therefore, the addition of the calcined kaolin further improves the whiteness of the glaze and reduces the glossiness of the glaze.
In this example, the specific ratio of the potassium feldspar and the albite is not limited, and the sum of the two is 0 to 35 parts, and in a further embodiment, the potassium feldspar and the albite are 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:
35-40 parts of titanium white frit, 0-10 parts of calcined kaolin, 3-8 parts of wollastonite, 5-35 parts of potassium feldspar and albite, 15-45 parts of quartz and 5-15 parts of kaolin.
In a further embodiment, the titanium white ground glaze layer comprises the following raw materials in parts by mass:
35-40 parts of titanium white frit, 0-10 parts of calcined kaolin, 3-5 parts of wollastonite, 5-15 parts of potassium feldspar and albite, 25-45 parts of quartz and 5-15 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 parts of CaO, 16 to 19 parts of TiO 2 13.8 to 15 parts of MgO, 0.2 to 0.6 part of K 2 2.4 to 3.6 portions of O, na 2 0.1 to 1.2 parts of O and 0.2 to 0.3 part of burning loss.
In one embodiment, the chemical composition of the titanium white opacifying primer comprises, by mass:
SiO 2 62 to 80 portions of Al 2 O 3 3 to 13 parts of CaO, 7 to 9 parts of TiO 2 4 to 5 parts of Fe 2 O 3 0.05 to 0.21 part, 0.1 to 0.3 part of MgO and K 2 O1.4-3.0 parts, na 2 0.1 to 0.8 part of O and 1.0 to 1.5 parts of burning loss.
The embodiment of the invention also provides a ceramic plate, which comprises a ceramic body and an ink-jet decorative layer, and further comprises the composite glaze layer arranged between the ceramic body and the ink-jet decorative layer, wherein the titanium white ground glaze layer in the composite glaze layer is attached to the ceramic body, and the isolation glaze layer in the composite glaze layer is attached to the ink-jet decorative layer. In the present embodiment, in The titanium white ground coat layer and the inkjet decorative layer are provided with the isolation glaze layer, so that the possibility of direct contact between various inkjet inks and the titanium white ground coat can be effectively reduced: avoiding the preferential reaction of the titanium sphene crystal phase synthesized in the titanium white ground glaze and spinel minerals in the inkjet ink, generating yellow green glaze caused by rutile titanium dioxide, avoiding Ti in the titanium white ground glaze 4+ The color change of the inkjet ink caused by the color change effect of various color change transition metal color-forming elements in the inkjet ink is induced, so that the problem that the inkjet ink of each channel is obviously yellowish green or changed in color is avoided.
In the embodiment, the isolating glaze layer is arranged on the titanium white primer, so that the direct contact between the titanium white primer and the inkjet ink is theoretically avoided, and the problem that spinel minerals in the inkjet ink react with titanite crystal phases synthesized in the titanium white primer preferentially to generate rutile type titanium dioxide and Ti can be well solved 4+ The problem of influencing the color development of the color-changing transition metal color-forming element is solved, but the current production equipment and process technical scheme still have no practical implementation feasibility, and particularly for large-specification ceramic plates (ceramic rock plates and ceramic thin plates), the industrial production cannot be realized, and a plurality of improvements are still needed in the existing production equipment and process technology. For example, the rock plate blank with the thickness of 3mm is thin, the production difficulty is high, and the conventional bell jar glazing, water jet glazing, ink jet printing digital glaze and the like have more or less problems only in the glazing process. When the glaze throwing cabinet is adopted for glazing, the atomization capability and the implementation area are limited, the general working specific gravity is lower than 1.40, the maximum glazing area of the green body is difficult to exceed 800mm, and the smoothness of the glaze is not ideal; the high-pressure automatic glazing system can be used for large-area glazing of ceramic large-plate products, but the working specific gravity is generally lower than 1.55, and once the glazing amount is smaller than 300g/m 2 The flatness of the glaze surface can not meet the requirement; the biggest advantage of bell jar glazing is that the specific gravity can exceed 1.70, the flatness is good, the kiln moisture is relatively low, but once glazing is less than 300g/m 2 Difficult problems to implement; the glaze is easy to break and branch when the glaze is sprayed. The biggest drawback of using the above several devices is also the ceramic plate specification problem, since once the specification exceeds 1.2m, the deviceThe precision is difficult to control and operate, the requirements on the glaze line yield and the glazing quantity are also greatly limited, the line speed is generally difficult to exceed 30 m/min, and various production defects such as sticking the net and the like are easy to occur; the amount of glaze per square is difficult to exceed 80g, the glaze has obvious ripple defect, and the process requires skilled technical work, increases the processing and using links of the glaze, and custom links such as a flat plate pattern net, a rubber roller and the like; the ink-jet printing digital glaze mainly comprises oily ink, the working specific gravity is less than 1.40, and the single-channel glazing amount is difficult to exceed 40g/m 2 The cost of the inkjet ink is high due to the special requirements on the oil solvent, the additive and the particle size of the ink, and the universal unit price is 3-12 ten thousand/ton.
Based on the above, the embodiment of the invention also provides a preparation method of the ceramic plate, which can effectively solve the glazing process difficulties of the ceramic rock plate and the thin plate, wherein the preparation method comprises the following steps:
S1, providing a ceramic blank;
s2, forming a titanium white ground enamel layer on the surface of the ceramic body;
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 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 the insulating glaze layer;
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 the large-area ceramic rock plate or the ceramic thin plate, not only solves the technical bottleneck that a layer of thin glaze cannot be stably and uniformly distributed on a large-specification product by the traditional technical means, but also ensures that the color gamut and the color development intensity adjustability of the ink-jet ink reach the technical effect which is indistinguishable from that of the ink-jet on the conventional zirconium white cosmetic ground glaze.
The embodiment of the invention does not limit the raw materials and the proportion of the ceramic blank in the step S1.
In step S3, in one embodiment, 100 parts by weight of the raw materials of the insulating glaze layer, 0-3 parts by weight of the additive, 40-95 parts by weight of water and the aqueous suspension stabilizer are added into a ball mill, mixed and then intermittently ball-milled for 6-15 hours until the obtained slurry can completely pass through a 325-mesh screen to obtain the insulating glaze slurry.
In one embodiment, the additive comprises the following components in parts by mass:
0.3 to 0.5 part of sodium tripolyphosphate, 0.1 to 0.25 part of sodium carboxymethyl cellulose, 0 to 2 parts of conductive agent and 0 to 1 part of surfactant.
In one embodiment, the conductive agent is selected from at least one of basf EFKA VOK-6782 conductive agent, pick BYK-ES80, internal 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, central European M400, but is not limited thereto.
In one embodiment, the mass ratio of the water to the aqueous suspension stabilizer in the water and aqueous suspension stabilizer is (30-60): 10-35.
In one embodiment, the aqueous suspension stabilizer is at least one selected from the group consisting of methyl glycol, bentonite, polymethylsiloxane, ammonium polyacylate formulation, STELLMITTEL (manufactured by german judicial chemical company), judicial pepadon 5, PEPTAPON 5 (manufactured by german judicial chemical company, expansion compound), but not limited thereto.
In one embodiment, the particle size of the particles in the isolating glaze slurry is D97 less than or equal to 45 mu M, the specific gravity of the isolating glaze slurry is 1.20-1.40, the flow rate of the isolating glaze slurry is 11-13 s, the pH of the isolating glaze slurry is 7-8, and the resistivity of the isolating glaze slurry is less than or equal to 1.2MΩ cm. In the embodiment, the particle size of the particles in the isolating glaze slurry is D97 less than or equal to 45 mu m, so that the defects of good suspension property of the isolating glaze slurry, lower melting temperature of glaze, tight combination of glaze blanks, small drying shrinkage rate of a glaze layer, difficult crack generation and the like can be ensured. In addition, the pH value of the isolating glaze slurry is between 7 and 8, the pH value is moderate, and the isolating glaze slurry is not easy to agglomerate.
In one embodiment, the barrier glaze slurry is sprayed on the titanium white base glaze layer by adopting an electrostatic spraying method to form a barrier glaze layer. According to the embodiment, the isolation glaze layer with the specific gravity of 1.20-1.40 can be uniformly sprayed on the titanium white ground glaze layer, the technical bottleneck that a thin layer of glaze cannot be stably and uniformly distributed on a large-specification product by the traditional technical means is solved, and the color gamut and the color development intensity adjustability of the ink-jet ink achieve the technical effect which is indistinguishable from that of the ink-jet on the conventional zirconium white cosmetic.
In specific implementation, on a disc type electrostatic spraying device (working voltage is set to be 50-75 KV), an electrostatic spraying method is adopted to obtain the product with the particle size of 30-100 g/m 2 And spraying the isolation glaze slurry on the titanium white ground glaze layer to form an isolation glaze layer. The disk type electrostatic spraying device is applied to the spraying of the isolation glaze layer, and the isolation glaze layer is successfully sprayed on the titanium white ground glaze layer with a large area.
A disk type (also called omega) electrostatic spraying device adopts a disk type atomizer as a spraying center, and a workpiece moves around a disk along an omega-shaped track. When the spray-coating device works, the disc rotates at a high speed and moves up and down in a reciprocating manner, and after a workpiece enters a spray-coating area, the workpiece can rotate 90-360 degrees or continuously rotate according to the requirement, so that the efficiency of the atomizer is fully exerted, the spray-coating geometric space is enlarged, and the spray-coating device is an ideal spray-coating method. The rotary disk atomizing disk is a main part of a disk type electrostatic automatic paint spraying machine, and is used for bearing the atomizing function of an isolating glaze layer, and the uniformity and the size of atomized particles of the isolating glaze layer are directly related to the isolating glaze layer. The electrostatic atomization disk is arranged at the connecting end of the pneumatic high-speed motor, and the insulating glaze layer is quantitatively conveyed to the inner wall of the disk by a pump and is thrown out to form mist tiny particles through high-speed centrifugal rotation to small holes at the bottom of the disk; the mist insulating glaze layer is provided with negative static electricity which is rapidly adsorbed to the positive workpiece (grounded positive electrode), and the electrostatic spraying insulating glaze layer operation is completed.
In step S4, in one embodiment, an inkjet decoration layer is formed on the surface of the insulating glaze layer, and then an overglaze 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 ground enamel layer on the surface of the ceramic body;
the titanium white ground 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 chemical composition of the titanium white frit comprises the following components in parts by mass: siO (SiO) 2 58.7 parts of Al 2 O 3 6.2 parts of CaO 16 parts of TiO 2 13.8 parts of MgO, 0.2 part of K 2 O3.6 parts, na 2 1.2 parts of O and 0.3 part of burn-out.
(1) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the titanium white ground glaze layer in a kiln, sintering at 1100 ℃ for 60min, testing glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to the gray scales of 20% and 60%, putting the titanium white ground glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at the temperature of 1100 ℃ for 60 min.
(2) And (3) testing the insulating 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:
wollastonite 3 parts, quartz 15 parts, ultrafine aluminum silicate 5 parts, ultrafine zirconium silicate 20 parts, ultrafine zirconium oxide 5 parts, nepheline 6 parts, potassium feldspar and albite 35 parts, fluorite 3 parts and kaolin 8 parts.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, sintered for 60 minutes at 1100 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1100 ℃ for 60 min.
Comparative example 1
Providing a ceramic body;
forming a titanium white ground enamel layer on the surface of the ceramic body;
the titanium white ground coat layer is made of high solar reflectance opacified titanium white glaze in China patent CN 111499202A, and 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, the chemical composition of the titanium frit comprises the following components in percentage by mass: siO (SiO) 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) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the titanium white ground glaze layer in a kiln, sintering at 1100 ℃ for 60min, testing glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to the gray scales of 20% and 60%, putting the titanium white ground glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at the temperature of 1100 ℃ for 60 min.
(2) And (3) testing the insulating 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:
wollastonite 3 parts, quartz 15 parts, ultrafine aluminum silicate 5 parts, ultrafine zirconium silicate 20 parts, ultrafine zirconium oxide 5 parts, nepheline 6 parts, potassium feldspar and albite 35 parts, fluorite 3 parts and kaolin 8 parts.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, sintered for 60 minutes at 1100 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1100 ℃ for 60 min.
Comparative example 2
Providing a ceramic body;
forming a titanium white ground enamel layer on the surface of the ceramic body;
the titanium white ground coat layer is prepared from 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 chemical composition of the titanium frit comprises the following components in parts by weight:
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, B 2 O 3 1.1 parts of ZrO 2 3 parts, P 2 O 5 3.3 parts of TiO 2 10 parts of BaO 2 parts.
(1) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the titanium white ground glaze layer in a kiln, sintering at 1100 ℃ for 60min, testing glossiness by using a photometer, and testing the whiteness of blue light by using a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to the gray scales of 20% and 60%, putting the titanium white ground glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at the temperature of 1100 ℃ for 60 min.
(2) And (3) testing the insulating 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:
wollastonite 3 parts, quartz 15 parts, ultrafine aluminum silicate 5 parts, ultrafine zirconium silicate 20 parts, ultrafine zirconium oxide 5 parts, nepheline 6 parts, potassium feldspar and albite 35 parts, fluorite 3 parts and kaolin 8 parts.
Then, the ceramic body containing the isolation glaze layer and the titanium white ground glaze layer is placed in a kiln, sintered for 60 minutes at 1100 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1100 ℃ for 60 min.
Comparative example 3
Providing a ceramic body;
forming a zirconium white background glaze layer on the surface of the ceramic blank;
the raw materials of the zirconium white background glaze layer are the conventional zirconium white background glaze, and the zirconium white background glaze layer comprises the following raw materials in parts by mass:
20 parts of zirconium white frit, 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 7-9% and loss on ignition of 0.1-0.5%.
(1) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the zirconium white background glaze layer in a kiln, sintering at 1100 ℃ for 60min, testing glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) printing cobalt blue, red brown, orange and black ink-jet ink color cards on the zirconium white background glaze layer according to 20% and 60% gray, putting the ink-jet ink color cards in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1100 ℃ for 60 min.
(2) And (3) testing the insulating glaze layer:
forming an isolation glaze layer on the zirconium white background 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:
wollastonite 3 parts, quartz 15 parts, ultrafine aluminum silicate 5 parts, ultrafine zirconium silicate 20 parts, ultrafine zirconium oxide 5 parts, nepheline 6 parts, potassium feldspar and albite 35 parts, fluorite 3 parts and kaolin 8 parts.
Then, the ceramic body containing the isolating glaze layer and the zirconium white background glaze layer is placed in a kiln, sintered for 60 minutes at 1100 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) printing cobalt blue, red brown, orange and black ink-jet ink color cards on the isolation glaze layer according to 20% and 60% gray, putting the isolation glaze layer into a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1100 ℃ for 60 min.
The results of the gloss and whiteness test of the insulating glaze layer of each of the above examples 1 and comparative examples 1 to 3 are shown in the following table 1, and when each of the above examples 1 and comparative examples 1 to 3 is coated with cobalt blue, red brown, orange, and black ink, each of the values of Δ E, L, a, b is shown in the following tables 2 to 4, and the total color difference deviation (Δe) of each of the above examples 1 and comparative examples 1 to 2 is calculated by using the zirconium white under glaze of comparative example 3 as a standard comparison. Δe= [ (Δl) 2 +(△a*) 2 +(△b*) 2 ] 1/2
Table 1 results of gloss and whiteness test
As can be seen from table 1, under the condition of no insulating glaze layer, the glossiness of the titanium white primer in example 1 is obviously lower than that of the existing titanium white primer, and the whiteness of the titanium white primer in example 1 is obviously higher than that of the existing titanium white primer; the titanium white ground glaze in example 1 has the same glossiness and whiteness as those of the zirconium white ground glaze in comparative example 3, and can replace the zirconium white ground glaze.
In addition, from the above results, it is clear that the presence of the barrier glaze layer can improve the whiteness of the ceramic plate glaze surface, and for the primer layer with high glossiness, the presence of the barrier glaze layer can also reduce the glossiness of the ceramic plate glaze surface.
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 to 5, the total color difference delta E can be greatly reduced after the isolation glaze is applied, 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 enamel layer on the surface of the ceramic body;
the titanium white ground 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 chemical composition of the titanium white frit comprises the following components in parts by mass: siO (SiO) 2 58.7 parts of Al 2 O 3 6.2 parts of CaO 16 parts of TiO 2 13.8 parts of MgO, 0.2 part of K 2 O3.6 parts, na 2 1.2 parts of O and 0.3 part of burn-out.
(1) And (3) testing the isolation-free glaze layer:
placing the ceramic body containing the titanium white ground glaze layer in a kiln, sintering at 1130 ℃ for 60min, testing glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to the gray scales of 20% and 60%, after full glazing, placing the titanium white ground glaze layer in a kiln, and after firing for 60min at the temperature of 1130 ℃, respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter.
(2) And (3) testing the insulating 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 ultrafine aluminum silicate, 15 parts of ultrafine zirconium silicate, 10 parts of ultrafine 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, sintered at the temperature of 1130 ℃ for 60min, and then the glossiness is tested by a photometer, and the whiteness of blue light is tested by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after firing at 1130 ℃ for 60 min.
Comparative example 4
Providing a ceramic body;
forming a titanium white ground enamel layer on the surface of the ceramic body;
the titanium white ground coat layer is made of high solar reflectance opacified titanium white glaze in China patent CN 111499202A, and 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, the chemical composition of the titanium frit comprises the following components in percentage by mass: siO (SiO) 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) And (3) testing the isolation-free glaze layer:
placing the ceramic body containing the titanium white ground glaze layer in a kiln, sintering at 1130 ℃ for 60min, testing glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to the gray scales of 20% and 60%, after full glazing, placing the titanium white ground glaze layer in a kiln, and after firing for 60min at the temperature of 1130 ℃, respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter.
(2) And (3) testing the insulating 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 ultrafine aluminum silicate, 15 parts of ultrafine zirconium silicate, 10 parts of ultrafine 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, sintered at the temperature of 1130 ℃ for 60min, and then the glossiness is tested by a photometer, and the whiteness of blue light is tested by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after firing at 1130 ℃ for 60 min.
Comparative example 5
Providing a ceramic body;
forming a titanium white ground enamel layer on the surface of the ceramic body;
the titanium white ground coat layer is prepared from 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 chemical composition of the titanium frit comprises the following components in parts by weight:
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, B 2 O 3 1.1 parts of ZrO 2 3 parts, P 2 O 5 3.3 parts of TiO 2 10 parts of BaO 2 parts.
(1) And (3) testing the isolation-free glaze layer:
placing the ceramic body containing the titanium white ground glaze layer in a kiln, sintering at 1130 ℃ for 60min, testing glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) printing cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to 20% and 60% gray, putting the titanium white ground glaze layer into a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after firing for 60min at the temperature of 1130 ℃.
(2) And (3) testing the insulating 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 ultrafine aluminum silicate, 15 parts of ultrafine zirconium silicate, 10 parts of ultrafine 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, sintered at the temperature of 1130 ℃ for 60min, and then the glossiness is tested by a photometer, and the whiteness of blue light is tested by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after firing at 1130 ℃ for 60 min.
Comparative example 6
Providing a ceramic body;
forming a zirconium white background glaze layer on the surface of the ceramic blank;
the raw materials of the zirconium white background glaze layer are the conventional zirconium white background glaze, and the zirconium white background glaze layer comprises the following raw materials in parts by mass:
15 parts of zirconium white frit, 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 7-9% and loss on ignition of 0.1-0.5%.
(1) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the zirconium white background glaze layer in a kiln, sintering at the temperature of 1130 ℃ for 60min, testing the glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the zirconium white background glaze layer according to the gray levels of 20% and 60%, after full glazing, placing in a kiln, sintering at the temperature of 1130 ℃ for 60min, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter.
(2) And (3) testing the insulating glaze layer:
forming an isolation glaze layer on the zirconium white background 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 ultrafine aluminum silicate, 15 parts of ultrafine zirconium silicate, 10 parts of ultrafine 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 isolating glaze layer and the zirconium white background glaze layer is placed in a kiln, sintered for 60 minutes at the temperature of 1130 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1100 ℃ for 60 min.
The results of the gloss and whiteness tests of the insulating glaze layer of the above example 2 and comparative examples 4 to 6 are shown in the following table 6, and the delta E, L, a, b values of the above example 2 and comparative examples 4 to 6, respectively, when cobalt blue, red brown, orange, and black inks were sprayed on the insulating glaze layer, respectively, are shown in the following tables 7 to 10. The total color difference deviation (. DELTA.E) in the above-mentioned example 2, comparative examples 4 to 6 was measured as a comparative exampleThe zirconium white ground glaze in 6 was used as a standard comparison for calculation. Δe= [ (Δl) 2 +(△a*) 2 +(△b*) 2 ] 1/2
Table 6 gloss and whiteness test results
As can be seen from table 6, under the condition of no insulating glaze layer, the glossiness of the titanium white primer in example 2 is obviously lower than that of the existing titanium white primer, and the whiteness of the titanium white primer in example 2 is obviously higher than that of the existing titanium white primer; the titanium white ground glaze in example 2 has the same glossiness and whiteness as those of the zirconium white ground glaze in comparative example 6, and can replace the zirconium white ground glaze.
In addition, from the above results, it is clear that the presence of the barrier glaze layer can improve the whiteness of the ceramic plate glaze surface, and for the primer layer with high glossiness, the presence of the barrier glaze layer can also reduce the glossiness of the ceramic plate glaze surface.
Table 7L, a, b, delta E test results
Table 8 results of L, a, b, ΔE test
Table 9L, a, b, delta E test results
/>
Table 10L, a, b, delta E test results
/>
As can be seen from the results of tables 7 to 10, the total color difference delta E can be greatly reduced after the isolation glaze is applied, and the phenomenon that the ink-jet ink of each channel is obviously yellowish green or changed in tone is avoided.
Example 3
Providing a ceramic body;
forming a titanium white ground enamel layer on the surface of the ceramic body;
the titanium white ground glaze layer comprises the following raw materials in parts by mass:
40 parts of titanium white frit, 10 parts of calcined kaolin, 5 parts of wollastonite, 5 parts of potassium feldspar and sodium feldspar, 25 parts of quartz and 15 parts of kaolin.
The chemical composition of the titanium white frit comprises the following components in parts by mass: siO (SiO) 2 58.7 parts of Al 2 O 3 6.2 parts of CaO 16 parts of TiO 2 13.8 parts of MgO, 0.2 part of K 2 O3.6 parts, na 2 1.2 parts of O and 0.3 part of burn-out.
(1) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the titanium white ground glaze layer in a kiln, sintering at 1150 ℃ for 60min, testing glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to the gray scales of 20% and 60%, putting the titanium white ground glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at the temperature of 1150 ℃ for 60 min.
(2) And (3) testing the insulating 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, sintered for 60 minutes at 1150 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1150 ℃ for 60 min.
Comparative example 7
Providing a ceramic body;
forming a titanium white ground enamel layer on the surface of the ceramic body;
the titanium white ground coat layer is made of high solar reflectance opacified titanium white glaze in China patent CN 111499202A, and 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, the chemical composition of the titanium frit comprises the following components in percentage by mass: siO (SiO) 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) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the titanium white ground glaze layer in a kiln, sintering at 1150 ℃ for 60min, testing glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to the gray scales of 20% and 60%, putting the titanium white ground glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at the temperature of 1150 ℃ for 60 min.
(2) And (3) testing the insulating 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, sintered for 60 minutes at 1150 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1150 ℃ for 60 min.
Comparative example 8
Providing a ceramic body;
forming a titanium white ground enamel layer on the surface of the ceramic body;
the titanium white ground coat layer is prepared from 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 chemical composition of the titanium frit comprises the following components in parts by weight:
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, B 2 O 3 1.1 parts of ZrO 2 3 parts, P 2 O 5 3.3 parts of TiO 2 10 parts of BaO 2 parts.
(1) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the titanium white ground glaze layer in a kiln, sintering at 1150 ℃ for 60min, testing glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink color cards on the titanium white ground glaze layer according to the gray scales of 20% and 60%, putting the titanium white ground glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at the temperature of 1150 ℃ for 60 min.
(2) And (3) testing the insulating 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, sintered for 60 minutes at 1150 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1150 ℃ for 60 min.
Comparative example 9
Providing a ceramic body;
forming a zirconium white background glaze layer on the surface of the ceramic blank;
the raw materials of the zirconium white background glaze layer are the conventional zirconium white background glaze, and the zirconium white background glaze layer comprises the following raw materials in parts by mass:
10 parts of zirconium white frit, 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 7-9% and loss on ignition of 0.1-0.5%.
(1) And (3) testing the isolation-free glaze layer:
and (3) placing the ceramic blank containing the zirconium white background glaze layer in a kiln, sintering at 1150 ℃ for 60min, testing glossiness by a photometer, and testing the whiteness of blue light by a whiteness instrument.
And (3) respectively carrying out ink-jet printing on cobalt blue, red brown, orange and black ink-jet ink cards on the zirconium white background glaze layer according to the gray levels of 20% and 60%, putting the cards in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at the temperature of 1150 ℃ for 60 min.
(2) And (3) testing the insulating glaze layer:
forming an isolation glaze layer on the zirconium white background 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, sintered for 60 minutes at 1150 ℃, and then tested for glossiness by a photometer and blue light whiteness by a whiteness instrument.
And (3) 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% gray and 60% gray, putting the isolation glaze layer in a kiln after full glaze polishing, and respectively reading the corresponding color gamut numerical range and L, a and b values by using a color difference meter after sintering at 1150 ℃ for 60 min.
The results of the gloss and whiteness tests of the insulating glaze layer of the above example 3 and comparative examples 7 to 9 are shown in the following table 11, and the values of delta E, L, a, b when cobalt blue, red brown, orange and black inks were sprayed on the insulating glaze layer of the above example 3 and comparative examples 7 to 9, respectively, are shown in the following tables 12 to 15, respectively. The total color difference deviation (ΔE) in the above-mentioned example 3 and comparative examples 7 to 9 was calculated with the zirconium white background glaze in comparative example 9 as a standard comparison.
△E＝[(△L*) 2 +(△a*) 2 +(△b*) 2 ] 1/2
Table 11 results of gloss and whiteness test
As can be seen from Table 11, under the condition of no insulating glaze layer, the glossiness of the titanium white primer in example 3 is obviously lower than that of the existing titanium white primer, and the whiteness of the titanium white primer in example 3 is obviously higher than that of the existing titanium white primer; the titanium white ground glaze in example 3 has the same glossiness and whiteness as those of the zirconium white ground glaze in comparative example 9, and can replace the zirconium white ground glaze.
In addition, from the above results, it is clear that the presence of the barrier glaze layer can improve the whiteness of the ceramic plate glaze surface, and for the primer layer with high glossiness, the presence of the barrier glaze layer can also reduce the glossiness of the ceramic plate glaze surface.
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
The result of 12-15 shows 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.
Examples 1, 2 and 3 show that when the insulating glaze layer is arranged at the ring temperature of 1100-1150 ℃, the total color difference delta E is smaller than 3, and the whiteness and the glossiness are close to those of the conventional zirconium white ground glaze, so that the invention has obvious effect by arranging the insulating glaze layer on the ground glaze layer; in the scheme without an isolation glaze layer, the total color difference delta E after ink spraying is mostly more than 3; the whiteness and glossiness data are very different from the technical scheme of the conventional zirconium white ground glaze, and the fact that the ring temperature is higher than 1100 ℃ is explained again, and the conventional various titanium white ground glazes are difficult to stably produce after being subjected to ink jet.
In summary, according to the invention, the isolation glaze layer is formed on the surface of the titanium white base glaze layer to obtain the composite glaze layer, when the inkjet decoration is carried out on the isolation glaze layer in the composite glaze layer, the preferential reaction of the titanium sphene crystal phase synthesized in the titanium white base glaze and the spinel mineral in the inkjet ink is avoided, the glaze surface is yellowish green caused by the generation of rutile titanium dioxide, and the occurrence of various valence transition metal coloring elements due to Ti is avoided 4+ The color change of the inkjet ink caused by the induced color effect ensures the whiteness of the titanium white ground glaze layer (the b value representing yellow tone in the 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 to the color development of brown series ink is better avoided, the phenomenon that the ink-jet ink of each channel is obviously greenish yellow or changed in tone (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 intensity 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 in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (9)
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:
15-35 parts of zirconium silicate, 0-10 parts of aluminum silicate, 0-10 parts of zirconium oxide, 5-25 parts of quartz, 5-8 parts of kaolin, 3-8 parts of wollastonite, 0-8 parts of fluorite, 0-25 parts of potassium feldspar, 0-15 parts of albite and 0-35 parts of nepheline;
The titanium white ground coat layer comprises the following raw materials in parts by mass:
35-45 parts of titanium white frit, 0-10 parts of calcined kaolin, 3-8 parts of wollastonite, 0-35 parts of potassium feldspar and albite, 15-45 parts of quartz and 5-15 parts of kaolin;
the chemical composition of the titanium white frit comprises the following components in parts by mass:
SiO 2 57-70 parts of Al 2 O 3 5 to 7 parts of CaO, 15 to 19 parts of TiO 2 12 to 15 parts of MgO, 0.1 to 0.6 part of K 2 O2.4-4.6 parts, na 2 0.1 to 1.2 parts of O and 0.2 to 0.5 part of burning loss;
and an ink-jet decorative layer is arranged on the isolation glaze layer.
2. The composite glaze layer according to 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 parts, 1.4 to 3.5 parts of CaO and TiO 2 0.03 to 1.3 parts of Fe 2 O 3 0 to 0.13 part, 0.1 to 0.35 part of MgO and K 2 O2.4-5 parts, na 2 O1.5-3.0 parts, zrO 2 10 to 25 parts and 0 to 5.1 parts of burning loss.
3. The composite glaze layer according to claim 1, wherein,
the grain diameter of the zirconium silicate is D50 less than or equal to 1.4 mu m, and D90 less than or equal to 4.0 mu m;
the grain diameter of the aluminum silicate is D90 which is less than or equal to 2.0 mu m;
the grain diameter of the zirconia is D50 less than or equal to 1.4 mu m, and D90 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 according to claim 1, wherein the chemical composition of the titanium white ground glaze layer comprises, in parts by mass:
SiO 2 62 to 80 portions of Al 2 O 3 3 to 13 parts of CaO, 7 to 9 parts of TiO 2 4 to 5 parts of Fe 2 O 3 0.05 to 0.21 part, 0.1 to 0.3 part of MgO and K 2 O1.4-3.0 parts, na 2 0.1 to 0.8 part of O and 1.0 to 1.5 parts of burning loss.
5. A ceramic plate comprising a ceramic body and an inkjet decorative layer, characterized by further comprising the composite glaze layer of any one of claims 1-4 arranged between the ceramic body and the inkjet decorative layer, wherein a titanium white under glaze layer in the composite glaze layer is attached to the ceramic body, and an isolation glaze layer in the composite glaze layer is attached to the inkjet decorative layer.
6. A method for preparing a ceramic plate, comprising the steps of:
providing a ceramic body;
forming a titanium white ground enamel layer on the surface of the ceramic body;
according to the raw material components and the mass portion ratio of the isolation glaze layer of any one of claims 1-3, the raw materials of the isolation glaze layer, water and additives are mixed 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.
7. The method of producing ceramic board according to claim 6, wherein the particle diameter of the particles in the insulating glaze slurry is d97.ltoreq.45 μm, the specific gravity of the insulating glaze slurry is 1.20 to 1.40, the flow rate of the insulating glaze slurry is 11 to 13s, the pH of the insulating glaze slurry is 7 to 8, and the specific resistance of the insulating glaze slurry is 1.2mΩ·cm or less.
8. A method for producing ceramic plates according to claim 6, wherein the electrostatic spraying method is performed at 30 to 100g/m on a disk type electrostatic spraying apparatus 2 And spraying the isolation glaze slurry on the titanium white ground glaze layer to form an isolation glaze layer.
9. A method of producing a ceramic board according to claim 6, wherein the firing temperature is 1100-1150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210928827.3A CN115304276B (en) | 2022-08-03 | 2022-08-03 | Composite glaze layer, ceramic plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210928827.3A CN115304276B (en) | 2022-08-03 | 2022-08-03 | Composite glaze layer, ceramic plate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115304276A CN115304276A (en) | 2022-11-08 |
| CN115304276B true CN115304276B (en) | 2023-12-26 |
Family
ID=83858250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210928827.3A Active CN115304276B (en) | 2022-08-03 | 2022-08-03 | Composite glaze layer, ceramic plate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115304276B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1372719A (en) * | 1972-09-11 | 1974-11-06 | ||
| CN104533039A (en) * | 2014-12-04 | 2015-04-22 | 信阳天意节能技术有限公司 | Reflective thermal insulation type waste rock, gravels and natural stone wall decoration plate |
| CN105313572A (en) * | 2015-12-14 | 2016-02-10 | 杨仲华 | Titanium blank colored enamel product and manufacturing method |
| CN107188528A (en) * | 2017-05-18 | 2017-09-22 | 德化县如瓷生活文化有限公司 | The ceramic and its preparation technology of imitative tree line effect |
| CN107673616A (en) * | 2017-10-16 | 2018-02-09 | 广东家美陶瓷有限公司 | The collocation method of the Ceramic Tiles of glaze containing isolation, manufacturing process and product gray scale |
| CN109439069A (en) * | 2018-09-17 | 2019-03-08 | 佛山市高明丰霖新型材料有限公司 | A kind of preparation method of ceramic ink jet ink brown colorant |
| CN110128173A (en) * | 2019-05-23 | 2019-08-16 | 佛山市东鹏陶瓷有限公司 | A kind of ecological negative ion ceramic enamel layer structure, ceramic tile and ceramic tile preparation method |
| CN110790507A (en) * | 2019-11-22 | 2020-02-14 | 重庆唯美陶瓷有限公司 | Ground glaze and preparation method thereof, black ink-jet ceramic tile and manufacturing method thereof |
| CN110885189A (en) * | 2019-11-13 | 2020-03-17 | 蒙娜丽莎集团股份有限公司 | Zirconium-free mutton tallow glaze and positioning crystal pattern ceramic tile prepared from same |
| CN111253174A (en) * | 2020-04-27 | 2020-06-09 | 蒙娜丽莎集团股份有限公司 | High-white overglaze for thin ceramic plate, thin ceramic plate and preparation method of thin ceramic plate |
| CN111470884A (en) * | 2020-06-24 | 2020-07-31 | 蒙娜丽莎集团股份有限公司 | High-hardness high-wear-resistance full-glazed ceramic tile and preparation method thereof |
| CN111499202A (en) * | 2020-06-30 | 2020-08-07 | 蒙娜丽莎集团股份有限公司 | Opaque glaze with high solar light reflectivity and preparation method thereof |
| CN111620563A (en) * | 2020-06-08 | 2020-09-04 | 东莞市唯美陶瓷工业园有限公司 | Preparation method of high-gray black ink-jet ceramic tile and preparation method of modified glaze slip |
| CN111875414A (en) * | 2020-06-30 | 2020-11-03 | 蒙娜丽莎集团股份有限公司 | High solar light reflectivity ceramic plate and preparation method thereof |
| CN113620605A (en) * | 2021-08-30 | 2021-11-09 | 江苏高淳陶瓷股份有限公司 | Method for producing star glaze |
| 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 |
-
2022
- 2022-08-03 CN CN202210928827.3A patent/CN115304276B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1372719A (en) * | 1972-09-11 | 1974-11-06 | ||
| CN104533039A (en) * | 2014-12-04 | 2015-04-22 | 信阳天意节能技术有限公司 | Reflective thermal insulation type waste rock, gravels and natural stone wall decoration plate |
| CN105313572A (en) * | 2015-12-14 | 2016-02-10 | 杨仲华 | Titanium blank colored enamel product and manufacturing method |
| CN107188528A (en) * | 2017-05-18 | 2017-09-22 | 德化县如瓷生活文化有限公司 | The ceramic and its preparation technology of imitative tree line effect |
| CN107673616A (en) * | 2017-10-16 | 2018-02-09 | 广东家美陶瓷有限公司 | The collocation method of the Ceramic Tiles of glaze containing isolation, manufacturing process and product gray scale |
| CN109439069A (en) * | 2018-09-17 | 2019-03-08 | 佛山市高明丰霖新型材料有限公司 | A kind of preparation method of ceramic ink jet ink brown colorant |
| CN110128173A (en) * | 2019-05-23 | 2019-08-16 | 佛山市东鹏陶瓷有限公司 | A kind of ecological negative ion ceramic enamel layer structure, ceramic tile and ceramic tile preparation method |
| CN110885189A (en) * | 2019-11-13 | 2020-03-17 | 蒙娜丽莎集团股份有限公司 | Zirconium-free mutton tallow glaze and positioning crystal pattern ceramic tile prepared from same |
| CN110790507A (en) * | 2019-11-22 | 2020-02-14 | 重庆唯美陶瓷有限公司 | Ground glaze and preparation method thereof, black ink-jet ceramic tile and manufacturing method thereof |
| CN111253174A (en) * | 2020-04-27 | 2020-06-09 | 蒙娜丽莎集团股份有限公司 | High-white overglaze for thin ceramic plate, thin ceramic plate and preparation method of thin ceramic plate |
| CN111620563A (en) * | 2020-06-08 | 2020-09-04 | 东莞市唯美陶瓷工业园有限公司 | Preparation method of high-gray black ink-jet ceramic tile and preparation method of modified glaze slip |
| CN111470884A (en) * | 2020-06-24 | 2020-07-31 | 蒙娜丽莎集团股份有限公司 | High-hardness high-wear-resistance full-glazed ceramic tile and preparation method thereof |
| CN111499202A (en) * | 2020-06-30 | 2020-08-07 | 蒙娜丽莎集团股份有限公司 | Opaque glaze with high solar light reflectivity and preparation method thereof |
| CN111875414A (en) * | 2020-06-30 | 2020-11-03 | 蒙娜丽莎集团股份有限公司 | High solar light reflectivity ceramic plate and preparation method thereof |
| CN113620605A (en) * | 2021-08-30 | 2021-11-09 | 江苏高淳陶瓷股份有限公司 | Method for producing star glaze |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| B1-2钛白面釉的性能改进;孟丹竹;《中国搪瓷》;全文 * |
| 硅灰石在陶瓷工业中的应用;蔡克勤, 张强;佛山陶瓷(09);全文 * |
| 黑色喷墨全抛釉产品的避釉缺陷处理;邓兴智等;《佛山陶瓷》;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115304276A (en) | 2022-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115304276B (en) | Composite glaze layer, ceramic plate and preparation method thereof | |
| EP3284732B1 (en) | Ceramic decoration high-temperature bright red inkjet ink | |
| CN110746117B (en) | Colored seeding glaze and positioning crystal ceramic tile prepared by using colored seeding glaze | |
| CN110776256B (en) | White radial crystal flower dry grain glaze, light-transmitting ceramic tile and preparation method thereof | |
| CN112707644A (en) | Low-gloss transparent glaze, ceramic tile using same and preparation method thereof | |
| CN110885189B (en) | Zirconium-free mutton tallow glaze and positioning crystal pattern ceramic tile prepared from same | |
| CN107129150A (en) | A kind of high abrasion glaze for glazed tile and preparation method thereof | |
| CN105198217B (en) | It is a kind of to be used for throwing vitreous brick production entirely, beneficial to the ground-coat enamel of ceramic ink color development | |
| CN109678345A (en) | A kind of high whiteness ground coat enamel and preparation method thereof | |
| CN103360121A (en) | High-strength electric-porcelain ash glaze formula and its preparation method | |
| CN110835234B (en) | Colored chrysanthemum-shaped crystal flower glaze, chrysanthemum-shaped crystal flower light-transmitting ceramic tile and preparation method thereof | |
| CN102010126A (en) | Lead-free frit for glass color ceramic glaze and preparation method thereof | |
| CN111253174B (en) | High-white overglaze for thin ceramic plate, thin ceramic plate and preparation method of thin ceramic plate | |
| CN108298818A (en) | Enamel ceramics mica titanium perlatolic glaze and its glaze slip preparation method and application | |
| CN103332968A (en) | Full-polishing glaze production process and prepared product | |
| EP4230600A1 (en) | Soft-light super-wear-resistant diamond glaze, ceramic tile and preparation method there of | |
| CN115304277B (en) | Titanium white opacifying primer and ceramic plate | |
| CN115974411A (en) | Ceramic tile base glaze, ceramic tile and preparation method thereof | |
| CN111777432A (en) | Porcelain high-whiteness glazed tile and preparation method thereof | |
| CN106147395A (en) | The big red ink of refractory ceramics and preparation method | |
| CN117142765A (en) | Low-zirconium ultra-white ceramic overglaze, glazed brick and preparation method thereof | |
| CN115536272B (en) | Wear-resistant glazed brick with good color development, strong penetration and high hardness and preparation process thereof | |
| CN115432926B (en) | Fine sliding surface wear-resistant ceramic tile produced by digital protection glaze ink and preparation method thereof | |
| CN105776864A (en) | High-transparency frit and preparation method thereof | |
| CN115893838A (en) | Low-cost porcelain tile super-white overglaze and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231116 Address after: 523281 Tangxia village, Gaopo Town, Dongguan City, Guangdong Province Applicant after: DONGGUAN CITY WONDERFUL CERAMICS INDUSTRIAL PARK Co.,Ltd. Address before: 331100 No. 31 Torch Avenue, Fengcheng High-tech Industrial Park, Yichun City, Jiangxi Province Applicant before: JIANGXI WONDERFUL CERAMICS Co.,Ltd. Applicant before: DONGGUAN CITY WONDERFUL CERAMICS INDUSTRIAL PARK Co.,Ltd. Applicant before: CHONGQING WONDERFUL CERAMICS Co.,Ltd. Applicant before: Guangdong Dongwei New Material Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |