CN113698189A - 一种细腻哑光大理石瓷砖及其制备方法 - Google Patents
一种细腻哑光大理石瓷砖及其制备方法 Download PDFInfo
- Publication number
- CN113698189A CN113698189A CN202110965587.XA CN202110965587A CN113698189A CN 113698189 A CN113698189 A CN 113698189A CN 202110965587 A CN202110965587 A CN 202110965587A CN 113698189 A CN113698189 A CN 113698189A
- Authority
- CN
- China
- Prior art keywords
- layer
- glaze
- parts
- matte
- marble
- 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.)
- Granted
Links
- 239000004579 marble Substances 0.000 title claims abstract description 41
- 239000000919 ceramic Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000010410 layer Substances 0.000 claims abstract description 86
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 29
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 29
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 25
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000011241 protective layer Substances 0.000 claims abstract description 19
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000395 magnesium oxide Substances 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000004576 sand Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- 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 claims description 5
- 239000010427 ball clay Substances 0.000 claims description 5
- 229910001570 bauxite Inorganic materials 0.000 claims description 5
- 239000010433 feldspar Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 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 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229910052845 zircon Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- 239000000976 ink Substances 0.000 description 29
- 229910052681 coesite Inorganic materials 0.000 description 15
- 229910052906 cristobalite Inorganic materials 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- 229910052682 stishovite Inorganic materials 0.000 description 15
- 229910052905 tridymite Inorganic materials 0.000 description 15
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052656 albite Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- -1 ester compound Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3215—Barium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/447—Phosphates or phosphites, e.g. orthophosphate or hypophosphite
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/606—Drying
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
- Finishing Walls (AREA)
Abstract
本发明公开了一种细腻哑光大理石瓷砖及其制备方法，涉及瓷砖技术领域。本发明所述细腻哑光大理石瓷砖由下至上依次为坯体层、釉料层、图案色彩层、功能墨水层、釉料保护层；以质量百分比计，制备所述釉料保护层的化学成分为：SiO249～50％、Al2O319～20％、Fe2O30.2～0.4％、TiO20.1～0.2％、CaO 14～16％、MgO 3.1～3.3％、K2O 0.8～1％、Na2O 2～2.5％、ZrO20.1～0.2％、BaO 0～0.05％、ZnO5～5.5％和P2O50.1～0.3％，灼减2.6～2.9％。本发明所述瓷砖手感细腻，表面光泽度为5～15度，不透水，且具有良好的耐污性、耐蚀性和耐磨性。
Description
技术领域
本发明涉及建筑陶瓷装饰材料技术领域，尤其涉及一种细腻哑光大理石瓷砖及其制备方法。
背景技术
大理石瓷砖特指具有天然大理石逼真纹理、色彩和质感的一类瓷砖产品，其具有天然大理石逼真的装饰效果和瓷砖的优越性能，摒弃天然大理石的各种天然缺陷，它是建陶行业划时代的革新者，也是现代顶级瓷砖制造工艺的代表作。目前大理石瓷砖表现手法多样灵活，有亮光面的，光泽度大都在50度以上，另外还有柔光面的，在20度以上，此种20度以上的柔光砖耐污性一直是行业未能完全彻底解决的硬伤，极大影响产品的使用效果；对于20度以下的哑光瓷砖来说，其耐污性更难解决。
除此之外，哑光瓷砖的制备方法往往较为复杂，例如中国专利CN 107555790 B公开了一种16度哑光大理石瓷砖的生产工艺，通过对釉线工艺进行改进，使瓷砖在去除了抛光工艺后，砖体表面依然能够保留柔和的光泽，整体光泽度达到16度。但是该瓷砖的制备工序复杂，劳动强度大，技术控制要求苛刻，需要调整光泽时难度大；中国专利申请CN111943729 A公开了一种哑光大理石瓷砖的制造方法，包括如下步骤：S1.素坯制备；S2.施大理石面釉；S3.印花，然后淋哑光抛釉；S4.烧成，烧成温度1050～1200℃、烧成周期40～60分钟，烧成后光泽度为5～10°；S5.哑抛，采用泡沫弹性抛光模块，抛光目数为240目～300目，制成成品；同样地，工艺流程繁琐，劳动强度大，生产成本高。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种细腻哑光大理石瓷砖及其制备方法，所述瓷砖具有良好的耐污性、耐蚀性和耐磨性，并且不透水，而且所述制备方法较为简单，更为节能环保。
为实现上述目的，本发明所采取的技术方案为：一种细腻哑光大理石瓷砖，由下至上依次为坯体层、釉料层、图案色彩层、功能墨水层、釉料保护层；以质量百分比计，制备所述釉料保护层的化学成分为：SiO2 49～50％、Al2O3 19～20％、Fe2O3 0.2～0.4％、TiO2 0.1～0.2％、CaO 14～16％、MgO 3.1～3.3％、K2O 0.8～1％、Na2O 2～2.5％、ZrO2 0.1～0.2％、BaO 0～0.05％、ZnO 5～5.5％和P2O5 0.1～0.3％，灼减2.6～2.9％。
SiO2是瓷砖的主要成分，对瓷砖的强度及热稳定性等有较大的影响，SiO2含量过少，瓷砖的强度不够，含量过高，热稳定性变差；Al2O3可以与SiO2反应生成网状莫来石晶体，作为骨架，提高瓷砖的机械性能、化学稳定性和热稳定性，但含量过高会提高烧成温度；CaO具有良好的助熔作用，可以与SiO2、Al2O3反应生成低共熔硅酸盐和铝硅酸盐的混合物。ZnO在釉中具有良好的助溶作用，可以降低釉的热膨胀系数，提高热稳定性。ZrO2的添加可以改善瓷砖的强度和硬度，提高瓷砖的耐蚀性。通过控制釉料保护层中各氧化物的含量在上述范围内可以形成细腻的釉面效果，并且提高釉面的耐污性。
优选地，以质量百分比计，制备所述釉料层的化学成分为：SiO2 57～59％、Al2O324～26％、Fe2O3 0.11～0.3％、TiO2 0.1～0.3％、CaO 0.3～0.5％、MgO 0.5～0.7％、K2O0.8～1.1％、Na2O 3.6～4％、ZrO2 8.5～9％、BaO 0.4～0.6％、HfO2 0.1～0.3％、ZnO 0.1～0.3％和P2O5 0.1～0.3％，灼减2～2.5％。
氧化锆具有良好的耐磨性、耐蚀性和耐高温性，并且可以增加瓷砖的强度和硬度等机械性能，对釉料层的成分作上述限定可以使釉料层与釉料保护层在烧制后不会出现变形等缺陷。
优选地，制备所述釉料层的原料包含如下重量份的成分：哑光釉粉90～100份、ZrSiO4 15～20份、煅烧滑石1～3份、煅烧高岭土1～3份、三聚磷酸钠0.3～0.5份、羧甲基纤维素钠0.15～0.35份和分散剂0.2～0.4份。
三聚磷酸钠可以改善釉浆料的流动性，使浆料水份少，流动性能好，不絮凝沉淀，便于操作。羧甲基纤维素钠(CMC)是一种陶瓷釉浆悬浮剂，在釉浆中加入少量的CMC可以防止密度大的组分过快地沉淀下来，在釉浆中具有增稠的作用，同时还具有一定的分散效果，可以提高釉料层的加工速度，降低生产能耗，防止滚釉、缺釉等缺陷，对于提高釉层的机械性能也具有一定的作用，可以使坯料中水分均匀蒸发，防止干燥开裂。分散剂的作用是让釉浆达到均匀分散，使浆料更加细腻均匀，增加浆料各组分的相容性，有效的提高浆料的颗粒润湿性、悬浮稳定性及浆体流变性，并使浆料具有适宜的黏度，达到节能降耗的目的。
优选地，以质量百分比计，所述哑光釉粉的化学成分为：SiO2 47～50％、Al2O3 21～23％、Fe2O3 0.1～0.2％、TiO2 0.05～0.1％、CaO 9～10％、MgO 3.5～4％、K2O 0.1～0.3％、Na2O 5.3～5.8％、ZrO2 0～0.01％、BaO 0.05～0.1％、P2O5 0.3～0.5％和ZnO 0.05～0.1％，灼减9～12％。
优选地，以质量百分比计，制备所述坯体层的化学成分为：SiO2 68～69％、Al2O318.5～19.5％、Fe2O3 1.10～1.35％、TiO2 0.15～0.25％、CaO 0.75～1.85％、MgO 1.35～1.45％、K2O 2.6～2.7％和Na2O 1.9～2.1％，灼减4.85～4.95％。
坯体中SiO2的含量相对更高一点，因为SiO2除了可以与Al2O3反应生成网状莫来石(3 Al2O3·2 SiO2)晶体成为粉体骨架外，余下的游离态的SiO2同样具有骨架的作用，可以进一步提高坯体的强度。
优选地，制备所述坯体层的原料包含如下重量份的成分：球土12～16份、瓷坭8～12份、铝矾土4～8份、水磨料28～33份、长石粉19～23份、钠砂10～14份、高强砂5～7份、中温砂3～5份，多功能聚合液0.2～0.3份和解胶剂0.3～0.4份。
以质量百分比计，所述球土的化学成分为：SiO2 48.5～50％、Al2O3 34～35％、K2O1.5～1.7％、Na2O 0.03～0.08％、CaO 0.08～0.12％、MgO 0.18～0.25％、Fe2O3 1.35～1.5％、TiO2 0.15～0.25％、灼减11～13％。
以质量百分比计，所述瓷坭的化学成分为：SiO2 62～63％、Al2O3 23～24％、K2O0.8～1.2％、Na2O 0.05～0.1％、CaO 0.1～0.15％、MgO 0.2～0.35％、Fe2O3 1.9～2.2％、TiO2 0.45～0.55％、灼减9～10％。
以质量百分比计，所述铝矾土的化学成分为：SiO2 30～31.5％、Al2O3 49～50％、K2O 0.9～1.2％、Na2O 0.1～0.2％、CaO 0.35～0.45％、MgO 0.5～1％、Fe2O3 1.5～2.2％、TiO2 2～2.5％、灼减12～13％。
以质量百分比计，所述水磨料的化学成分为：SiO2 64～66％、Al2O3 19～20.5％、K2O 2～3％、Na2O 2～3％、CaO 2～3％、MgO 1～2％、Fe2O3 1.2～2％、TiO2 0.2～0.3％、灼减3.5～4.5％。
以质量百分比计，所述长石粉的化学成分为：SiO2 69～71％、Al2O3 11～11.5％、K2O 0.3～1％、Na2O 4.5～5.5％、CaO 4～4.5％、MgO 2.5～3％、Fe2O3 0.2～0.7％、TiO20.02～0.1％、灼减5～6.5％。
以质量百分比计，所述钠砂的化学成分为：SiO2 72～73.5％、Al2O3 16～17％、K2O0.8～1.2％、Na2O 6.8～7.5％、CaO 0.3～0.7％、MgO 0.1～0.5％、Fe2O3 0.1～0.35％、TiO2 0.1～0.2％、灼减0.5～1.5％。
以质量百分比计，所述高强砂的化学成分为：SiO2 75～77％、Al2O3 14～15％、K2O0.5～1.5％、Na2O 0.3～0.9％、CaO 0.4～1％、MgO 0.5～1.2％、Fe2O3 0.5～0.7％、TiO20.1～0.3％、灼减4～5.2％。
以质量百分比计，所述中温砂的化学成分为：SiO2 70.8～72.5％、Al2O3 17～18％、K2O 2.8～3.7％、Na2O 0.5～1.5％、CaO 0.2～0.4％、MgO 0.4～0.75％、Fe2O3 0.5～1.1％、TiO2 0.05～0.25％、灼减3～4.5％。
多功能聚合液是一种陶瓷坯体增强剂，包含环氧树脂聚合液、丙烯酸树脂聚合液、聚氨酯树脂聚合液中的至少一种，可以增强坯体的强度，提高泥浆的流动性；解胶剂能够有效提高浆料颗粒的润湿性，悬浮稳定性及其流变性，降低水分，节约球磨和干燥的能耗。
优选地，所述图案色彩层的制备原料包含蓝色墨水、棕色墨水、包裹黄墨水、黑色墨水、桔色墨水、包裹红墨水等陶瓷墨水中的至少一种；所述功能墨水层的制备原料包含精雕墨水。所述精雕墨水，其组分包含高硼熔块、钒酸铋、钠长石、碳酸钡、矿化剂，分散剂、酯类化合物和溶剂。其制备方法包括如下步骤：
(1)将高硼熔块、钒酸铋、钠长石、碳酸钡、矿化剂气流粉碎至2000目以下；
(2)将气流粉碎后的原料与分散剂、酯类化合物、溶剂分别加入到砂磨机中研磨；
(3)过滤，滤液即为功能墨水。
同时，本发明还公开了一种所述细腻哑光大理石瓷砖的制备方法，包括如下步骤：
(1)将制备坯体层的原料混合，球磨，得到泥浆；
(2)对泥浆进行喷雾造粒，得到粉料；
(3)将粉料压制成型，得到生坯；
(4)对生坯进行干燥，得到坯体层；
(5)将釉料层淋到坯体层表面，得到釉料层；
(6)喷墨打印图案色彩层和功能墨水层；
(7)采用高压喷釉技术将釉料保护层喷覆在图案色彩层和功能墨水层上；
(8)在1200～1230℃下烧制50～70min，得到所述细腻哑光大理石瓷砖。
烧制温度对瓷砖的性能具有至关重要的作用，烧制温度低，瓷砖的硬度不足，使用过程中容易出现划痕，易被磨损；烧制温度过高容易使坯体的气孔率增大，膨胀。对于本发明所述瓷砖，在1200～1230℃烧结时可保证其兼具良好的机械性能和耐污性。
优选地，所述步骤(1)中，泥浆的比重为1.6～1.7g/mL，流速为30～80s，水分为34～36％，250目标准筛余为0.9～1.1g/100mL；所述步骤(2)中，在喷雾干燥塔中造粒，所得粉料的颗粒级配为20目≤1％，40目28～36％，60目42～52％，80目8～13％，120目≤6％，水分为6.4～7％。
对粉料的颗粒级配进行调控的目的在于提高粉料的堆积密度，进而降低气孔率，抑制烧结后冷却过程中的收缩变形。
优选地，所述坯体层的热膨胀系数为210～230E-5/℃，所述釉料层的热膨胀系数为210～220E-5/℃；所述釉料层的施工参数为：釉量430～500g/m2，比重1.75～1.85g/mL，流速35～45s；所述釉料保护层使用的釉浆的325目标准筛余为0.8～1g/100mL，比重为1.35～1.45g/mL，流速为20～40s，釉料保护层的釉量为280～340g/m2。
坯体层和釉料层的热膨胀系数比较接近，并且坯体层的热膨胀系数略高于釉料层，在冷却时，坯釉的收缩可以相互适应，保持一致，因此制备的瓷砖的平整度非常好。
相比于现有技术，本发明的有益效果为：
本发明通过对瓷砖的成分进行选择，使得制备的瓷砖具有光泽度为5～15度的哑光色泽，不透水，并且具有良好的机械性能、耐污性和耐蚀性；此外，通过图案色彩层和功能墨水层增加了瓷砖的美感，使其呈现出超精细的接近天然大理石的纹理和立体触感。另外，本发明还提供了一种工艺简单的制备方法，该方法更加节能环保，适于工业化应用。
附图说明
图1为实施例1细腻哑光大理石瓷砖的结构图；
其中，1为坯体层，2为釉料层，3为图案色彩层，4为功能墨水层，5为釉料保护层；
图2为实施例1细腻哑光大理石瓷砖的制备流程图。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将结合附图和具体实施例对本发明作进一步说明。
实施例1
本发明所述细腻哑光大理石瓷砖的一种实施例，本实施例所述细腻哑光大理石瓷砖的结构如图1所示，由下至上包含坯体层1、釉料层2、图案色彩层3、功能墨水层4和釉料保护层5，制备所述釉料保护层的化学成分如下(以质量百分比计)：
SiO2 50％、Al2O3 20％、Fe2O3 0.3％、TiO2 0.15％、CaO 15％、MgO 3.2％、K2O0.9％、Na2O 2.37％、ZrO2 0.2％、BaO 0.03％、ZnO 5％、P2O5 0.25％，灼减2.6％。
制备所述细腻哑光大理石瓷砖的釉料层的化学成分如下(以质量百分比计)：
SiO2 58％、Al2O3 24％、Fe2O3 0.2％、TiO2 0.2％、CaO 0.4％、MgO 0.6％、K2O1％、Na2O 3.8％、ZrO2 8.7％、BaO 0.5％、HfO2 0.2％、ZnO 0.2％、P2O5 0.2％，灼减2％。
釉料层使用的原料按重量份计包含哑光釉粉95份、ZrSiO4 16份、煅烧滑石2份、煅烧高岭土2份、三聚磷酸钠0.35份、羧甲基纤维素钠0.3份、分散剂0.3份。所述分散剂购自东莞澳达环保新材料有限公司，型号为AD8089。
所述哑光釉粉的化学成分如下(以质量百分比计)：
SiO2 48％、Al2O3 22％、Fe2O3 0.1％、TiO2 0.05％、CaO 9％、MgO 3.5％、K2O0.2％、Na2O 5.5％、BaO 0.05％、P2O5 0.4％、ZnO 0.05％，烧失量为11.15％。
制备所述坯体层的化学成分如下(以质量百分比计)：
SiO2 68％、Al2O3 18.5％、Fe2O3 1.15％、TiO2 0.2％、CaO 1.2％、MgO 1.4％、K2O2.65％、Na2O 2％，灼减4.9％。
制备所述坯体层使用的原料按重量份计包含球土14份、瓷坭10份、铝矾土46份、水磨料30份、长石粉21份、钠砂13份、高强砂6份、中温砂4份、多功能聚合液0.25份和解胶剂0.35份。所述多功能聚合液购自四会市奥耳新材料有限公司，型号为D3；所述解胶剂为工业三聚磷酸钠，购自贵州开阳川东化工有限公司，白度≥90％、五氧化二磷≥57％、三聚磷酸钠≥96％、水不溶物≤0.1％、铁≤0.007％，pH值(1％溶液)为9.2-10。
所述各原料的化学分析成分如表1所示：
表1(质量分数％)
| 名称 | SiO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> | K<sub>2</sub>O | Na<sub>2</sub>O | CaO | MgO | Fe<sub>2</sub>O<sub>3</sub> | TiO<sub>2</sub> | 灼减 | 合计 |
| 球土 | 49.34 | 34.89 | 1.58 | 0.05 | 0.1 | 0.22 | 1.42 | 0.19 | 12.21 | 100 |
| 瓷坭 | 62.82 | 23.6 | 1 | 0.07 | 0.12 | 0.29 | 2.18 | 0.52 | 9.4 | 100 |
| 铝矾土 | 31.27 | 49.38 | 1.16 | 0.18 | 0.42 | 0.72 | 2.01 | 2.27 | 12.59 | 100 |
| 水磨料 | 65.63 | 19.61 | 2.45 | 2.61 | 2.54 | 1.41 | 1.4 | 0.25 | 4.1 | 100 |
| 长石粉 | 70.31 | 11.18 | 0.5 | 4.7 | 4.23 | 2.79 | 0.48 | 0.07 | 5.74 | 100 |
| 钠砂 | 72.61 | 16.67 | 1.07 | 7.21 | 0.53 | 0.35 | 0.23 | 0.15 | 1.18 | 100 |
| 高强砂 | 76.51 | 14.78 | 1.13 | 0.64 | 0.56 | 0.86 | 0.66 | 0.2 | 4.66 | 100 |
| 中温砂 | 72.07 | 17.56 | 3.37 | 1 | 0.35 | 0.53 | 1.04 | 0.2 | 3.88 | 100 |
所述图案色彩层使用了黑色墨水(CXN40118，购自陶丽西公司)；所述功能墨水层使用了精雕墨水(CZN00078，购自陶丽西公司)。
所述细腻哑光大理石瓷砖的制备方法如图2所示，包括如下步骤：
(1)将制备坯体层的成分放入100T球磨机中，加水，球磨14h，得到泥浆；泥浆的比重为1.65g/mL，流速为50s，水分为35.5％，250目标准筛余为1g/100mL；
(2)将泥浆置于喷雾干燥塔中造粒，筛分，得到的粉料的颗粒级配为20目≤1％，40目35％，60目48％，80目13％，120目≤6％，水分为6.5％；
(3)将粉料在SACMI PHC3500压机上压制成型得到生坯；
(4)将生坯放入干燥窑中干燥，干燥温度为200℃，干燥时间为65min，得到干燥坯，干燥坯水分为0.5％；
(5)将釉料层的原料加水制成浆料，采用钟罩将其淋到干燥坯表面；所述浆料的比重为1.8g/mL，流速为39s，含水率为34.2％，釉料层的釉量为480g/m2；
(6)采用喷墨打印机将黑色墨水和精雕墨水打印到釉料层上，制成图案色彩层和功能墨水层；其中，黑色墨水的墨量为5.174g/m2，以星光1024MC*14组喷头进行喷墨；精雕墨水的墨量为15.36g/m2，以星光1024LC*14组喷头进行喷墨；
(7)采用意大利Airpower的喷釉设备(AIRLE5S 50000 HP ECO)，喷芯孔径为0.52mm，共4个，以5bar高压喷釉，高压喷枪将釉料保护层的浆料均匀喷在功能墨水层和图案色彩层上面；其中，浆料的325目标准筛余为0.9g/100mL，比重为1.4g/mL，流速为21s，含水率为51.6％，釉量为300g/m2；
(8)对步骤(7)得到的半成品进行烧制，烧成温度为1200～1230℃，烧成时间为65min.；
(9)经过磨边得到所述细腻哑光大理石瓷砖。
对坯体层和釉料层的体积热膨胀系数进行测量，分别测量三次，坯体层的体积热膨胀系数COE为210～230E-5/℃，釉料层的体积热膨胀系数COE为210～220E-5/℃。
实施例2
本发明所述细腻哑光大理石瓷砖的一种实施例，本实施例所述细腻哑光大理石瓷砖与实施例1的区别仅在于，制备所述釉料保护层的成分不同，具体如下(以质量百分比计)：
SiO2 49.9％、Al2O3 19.8％、Fe2O3 0.4％、TiO2 0.2％、CaO 14.05％、MgO 3.3％、K2O 1％、Na2O 2.5％、ZrO2 0.2％、BaO 0.05％、ZnO 5.5％、P2O5 0.3％，灼减2.8％。
实施例3
本发明所述细腻哑光大理石瓷砖的一种实施例，本实施例所述细腻哑光大理石瓷砖与实施例1的区别仅在于，制备所述釉料保护层的成分不同，具体如下(以质量百分比计)：
SiO2 49.7％、Al2O3 19％、Fe2O3 0.2％、TiO2 0.15％、CaO 16％、MgO 3.1％、K2O0.9％、Na2O 2.3％、ZrO2 0.16％、BaO 0.01％、ZnO 5.4％、P2O5 0.2％，灼减2.88％。
对比例1
一种哑光大理石瓷砖，所述细腻哑光大理石瓷砖与实施例1的区别仅在于，制备釉料保护层的成分不同，具体如下(以质量百分比计)：
SiO2 52％、Al2O3 19.17％、Fe2O3 0.3％、TiO2 0.15％、CaO 12％、MgO 4.15％、K2O0.9％、Na2O 3.2％、ZrO2 0.2％、BaO 0.03％、ZnO 5.2％、P2O5 0.2％，灼减2.5％。
对比例2
一种哑光大理石瓷砖，所述细腻哑光大理石瓷砖与实施例1的区别仅在于，制备釉料保护层的成分不同，具体如下(以质量百分比计)：
SiO251％、Al2O3 18.75％、Fe2O3 0.3％、TiO2 0.18％、CaO 17％、MgO 2％、K2O0.9％、Na2O 2.2％、ZrO2 0.2％、BaO 0.03％、ZnO 3.7％、P2O5 0.2％，灼减3.54％。
对实施例1～3和对比例1～2制备的哑光大理石瓷砖进行性能测试，测试标准及测试结果见表2。
表2
从表2中可知，实施例1～3中各种氧化物的组分配比合理，制备的细腻哑光大理石瓷砖物理性能明显更好；对比例1中，氧化钠、氧化镁的含量增加，降低了釉面的熔融温度，导致釉面光泽度变亮，同时熔融温度过低带来过早封闭釉面而堵住坯体层、面釉层排气产生针孔，产品有轻微吸污，主要排气物质有结晶水气、碳酸盐分解出的CO2、硫酸盐分解出的SO2；MgO在釉中起助熔作用，还可以提高釉面的力学强度和热稳定性，ZnO在釉中有较强的助熔作用，能提高产品的热稳定性，同时能增加釉面的光泽度，Al2O3具有提高釉面熔融温度、提高耐磨性等的作用，对比例2中，MgO、ZnO、Al2O3都减少导致釉面表面变粗糙变哑，产生吸污问题，不耐磨，热稳定性也变差。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，但并不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种细腻哑光大理石瓷砖，其特征在于，由下至上依次为坯体层、釉料层、图案色彩层、功能墨水层、釉料保护层；以质量百分比计，制备所述釉料保护层的化学成分为：SiO249～50％、Al2O3 19～20％、Fe2O3 0.2～0.4％、TiO20.1～0.2％、CaO 14～16％、MgO 3.1～3.3％、K2O 0.8～1％、Na2O 2～2.5％、ZrO20.1～0.2％、BaO 0～0.05％、ZnO 5～5.5％和P2O5 0.1～0.3％，灼减2.6～2.9％。
2.如权利要求1所述的细腻哑光大理石瓷砖，其特征在于，以质量百分比计，制备所述釉料层的化学成分为：SiO2 57～59％、Al2O3 24～26％、Fe2O30.11～0.3％、TiO2 0.1～0.3％、CaO 0.3～0.5％、MgO 0.5～0.7％、K2O 0.8～1.1％、Na2O 3.6～4％、ZrO2 8.5～9％、BaO 0.4～0.6％、HfO2 0.1～0.3％、ZnO 0.1～0.3％和P2O50.1～0.3％，灼减2～2.5％。
3.如权利要求2所述的细腻哑光大理石瓷砖，其特征在于，制备所述釉料层的原料，包含如下重量份的成分：哑光釉粉90～100份、ZrSiO4 15～20份、煅烧滑石1～3份、煅烧高岭土1～3份、三聚磷酸钠0.3～0.5份、羧甲基纤维素钠0.15～0.35份和分散剂0.2～0.4份。
4.如权利要求3所述的细腻哑光大理石瓷砖，其特征在于，以质量百分比计，所述哑光釉粉的化学成分为：SiO2 47～50％、Al2O3 21～23％、Fe2O3 0.1～0.2％、TiO2 0.05～0.1％、CaO 9～10％、MgO 3.5～4％、K2O 0.1～0.3％、Na2O 5.3～5.8％、ZrO2 0～0.01％、BaO 0.05～0.1％、P2O5 0.3～0.5％和ZnO 0.05～0.1％，灼减9～12％。
5.如权利要求1所述的细腻哑光大理石瓷砖，其特征在于，以质量百分比计，制备所述坯体层的化学成分为：SiO2 68～69％、Al2O3 18.5～19.5％、Fe2O31.10～1.35％、TiO2 0.15～0.25％、CaO 0.75～1.85％、MgO 1.35～1.45％、K2O 2.6～2.7％和Na2O 1.9～2.1％，灼减4.85～4.95％。
6.如权利要求5所述的细腻哑光大理石瓷砖，其特征在于，制备所述坯体层的原料，包含如下重量份的成分：球土12～16份、瓷坭8～12份、铝矾土4～8份、水磨料28～33份、长石粉19～23份、钠砂10～14份、高强砂5～7份、中温砂3～5份、多功能聚合液0.2～0.3份和解胶剂0.3～0.4份。
7.如权利要求1所述的细腻哑光大理石瓷砖，其特征在于，所述图案色彩层的制备原料包含陶瓷墨水，所述功能墨水层的制备原料包含精雕墨水。
8.一种如权利要求1～7任一项所述的细腻哑光大理石瓷砖的制备方法，其特征在于，包括如下步骤：
(1)将制备坯体层的原料混合，球磨，得到泥浆；
(2)对泥浆进行喷雾造粒，得到粉料；
(3)将粉料压制成型，得到生坯；
(4)对生坯进行干燥，得到坯体层；
(5)将釉料层淋到坯体层表面，得到釉料层；
(6)喷墨打印图案色彩层和功能墨水层；
(7)采用高压喷釉技术将釉料保护层喷覆在图案色彩层和功能墨水层上；
(8)在1200～1230℃下烧制50～70min，得到所述细腻哑光大理石瓷砖。
9.如权利要求8所述的细腻哑光大理石瓷砖的制备方法，其特征在于，所述步骤(1)中，泥浆的比重为1.6～1.7g/mL，流速为30～80s，水分为34～36％，250目标准筛余为0.9～1.1g/100mL；所述步骤(2)中，在喷雾干燥塔中造粒，所得粉料的颗粒级配为20目≤1％，40目28～36％，60目42～52％，80目8～13％，120目≤6％，水分为6.4～7％。
10.如权利要求8所述的细腻哑光大理石瓷砖的制备方法，其特征在于，所述坯体层的热膨胀系数为210～230E-5/℃，所述釉料层的热膨胀系数为210～220E-5/℃；所述釉料层的施工参数为：釉量430～500g/m2，比重1.75～1.85g/mL，流速35～45s；所述釉料保护层使用的釉浆的325目标准筛余为0.8～1g/100mL，比重为1.35～1.45g/mL，流速为20～40s，釉料保护层的釉量为280～340g/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110965587.XA CN113698189B (zh) | 2021-08-20 | 2021-08-20 | 一种细腻哑光大理石瓷砖及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110965587.XA CN113698189B (zh) | 2021-08-20 | 2021-08-20 | 一种细腻哑光大理石瓷砖及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113698189A true CN113698189A (zh) | 2021-11-26 |
| CN113698189B CN113698189B (zh) | 2023-05-05 |
Family
ID=78653865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110965587.XA Active CN113698189B (zh) | 2021-08-20 | 2021-08-20 | 一种细腻哑光大理石瓷砖及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113698189B (zh) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845307A (zh) * | 2021-11-30 | 2021-12-28 | 佛山科海意诺陶瓷科技有限公司 | 一种高仿真数码模具陶瓷砖及其制备方法 |
| CN114873916A (zh) * | 2022-04-12 | 2022-08-09 | 东莞市唯美陶瓷工业园有限公司 | 一种稳色保护釉、陶瓷砖及其制备方法 |
| CN115180982A (zh) * | 2022-06-24 | 2022-10-14 | 新明珠集团股份有限公司 | 一种仿真微水泥陶瓷砖及其制备方法 |
| CN115557701A (zh) * | 2022-09-19 | 2023-01-03 | 江西新明珠建材有限公司 | 一种釉料组合物、肌肤釉瓷砖及其制备方法 |
| CN116023171A (zh) * | 2022-12-07 | 2023-04-28 | 新明珠(广东)新材料有限公司 | 具有亲肤质感的陶瓷板材及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483103A (zh) * | 2019-08-26 | 2019-11-22 | 广东萨米特陶瓷有限公司 | 一种立体精细编织纹理效果的陶瓷板材及其制备方法 |
| CN110498608A (zh) * | 2019-08-26 | 2019-11-26 | 广东萨米特陶瓷有限公司 | 一种高硬度耐磨的低光岩板及其制备方法 |
| CN110734303A (zh) * | 2019-11-14 | 2020-01-31 | 广东清远蒙娜丽莎建陶有限公司 | 无光细腻柔和釉面的瓷质仿古砖及其制备方法 |
| CN111943729A (zh) * | 2020-08-26 | 2020-11-17 | 江西新明珠建材有限公司 | 一种哑光大理石瓷砖的制造方法 |
-
2021
- 2021-08-20 CN CN202110965587.XA patent/CN113698189B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483103A (zh) * | 2019-08-26 | 2019-11-22 | 广东萨米特陶瓷有限公司 | 一种立体精细编织纹理效果的陶瓷板材及其制备方法 |
| CN110498608A (zh) * | 2019-08-26 | 2019-11-26 | 广东萨米特陶瓷有限公司 | 一种高硬度耐磨的低光岩板及其制备方法 |
| CN110734303A (zh) * | 2019-11-14 | 2020-01-31 | 广东清远蒙娜丽莎建陶有限公司 | 无光细腻柔和釉面的瓷质仿古砖及其制备方法 |
| CN111943729A (zh) * | 2020-08-26 | 2020-11-17 | 江西新明珠建材有限公司 | 一种哑光大理石瓷砖的制造方法 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845307A (zh) * | 2021-11-30 | 2021-12-28 | 佛山科海意诺陶瓷科技有限公司 | 一种高仿真数码模具陶瓷砖及其制备方法 |
| CN113845307B (zh) * | 2021-11-30 | 2022-03-15 | 佛山科海意诺陶瓷科技有限公司 | 一种高仿真数码模具陶瓷砖及其制备方法 |
| CN114873916A (zh) * | 2022-04-12 | 2022-08-09 | 东莞市唯美陶瓷工业园有限公司 | 一种稳色保护釉、陶瓷砖及其制备方法 |
| CN115180982A (zh) * | 2022-06-24 | 2022-10-14 | 新明珠集团股份有限公司 | 一种仿真微水泥陶瓷砖及其制备方法 |
| CN115557701A (zh) * | 2022-09-19 | 2023-01-03 | 江西新明珠建材有限公司 | 一种釉料组合物、肌肤釉瓷砖及其制备方法 |
| CN115557701B (zh) * | 2022-09-19 | 2024-03-29 | 江西新明珠建材有限公司 | 一种釉料组合物、肌肤釉瓷砖及其制备方法 |
| CN116023171A (zh) * | 2022-12-07 | 2023-04-28 | 新明珠(广东)新材料有限公司 | 具有亲肤质感的陶瓷板材及其制备方法和应用 |
| CN116023171B (zh) * | 2022-12-07 | 2024-01-23 | 新明珠(广东)新材料有限公司 | 具有亲肤质感的陶瓷板材及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113698189B (zh) | 2023-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113698189B (zh) | 一种细腻哑光大理石瓷砖及其制备方法 | |
| CN115010465B (zh) | 一种低温快烧陶瓷岩板及其制备方法 | |
| CN109761583A (zh) | 黑色喷墨全抛釉陶瓷砖及其制备方法 | |
| CN114292023B (zh) | 一种全数码喷釉用数码釉墨水及其制备方法和应用 | |
| CN113860887B (zh) | 一种陶瓷板及其制备方法 | |
| CN109849163B (zh) | 一种利用刮边废料制得的立体釉饰砖及其制造方法 | |
| CN108484114B (zh) | 一种高掺量抛光废料的釉面瓷质砖及其制备方法 | |
| CN111689769A (zh) | 一种由丝绸面的瓷质仿古砖及其制备方法 | |
| CN108706961B (zh) | 一种实验台环保型陶瓷面板及其制备方法 | |
| CN116395968B (zh) | 一种功能性墨水陶瓷产品的釉料、陶瓷产品及其制备方法和应用 | |
| CN115180982B (zh) | 一种仿真微水泥陶瓷砖及其制备方法 | |
| CN108484123A (zh) | 一种高掺量冶金钢渣废料的陶瓷砖及其制备方法 | |
| CN113800879A (zh) | 一种透光石陶瓷板及其制备方法 | |
| CN110963791B (zh) | 自释釉诱发剂、自释釉陶瓷砖及其制备方法 | |
| CN113121199B (zh) | 一种超厚岩板及其制备方法和应用 | |
| CN113800770A (zh) | 一种中温双层窑变花釉和制作方法 | |
| CN116606071B (zh) | 一种绘画颜色釉棒的制备方法及绘画颜色釉棒 | |
| CN108046603A (zh) | 一种一式多类的陶瓷砖的制作方法 | |
| CN111453994A (zh) | 一种白釉与陶瓷砖及陶瓷砖制备方法 | |
| CN113998993B (zh) | 一种精雕仿石瓷抛砖及制备方法 | |
| CN111704446B (zh) | 一种钠基膨润土型发泡陶瓷坯体、钠基膨润土型发泡陶瓷砖及其制备方法 | |
| CN113666639B (zh) | 一种黑色岩板及其制备方法 | |
| CN107540342A (zh) | 一种深红棕色且具金属光泽的复古外墙砖及其制备方法 | |
| CN112592208A (zh) | 一种丝绸釉瓷砖及其制备方法 | |
| CN113683308A (zh) | 一种超白陶瓷砖及其生产工艺 |
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 | ||
| CB02 | Change of applicant information |
Address after: 528000 first floor, No. 18, taobo Avenue, Huaxia Ceramic Expo City, Nanzhuang Town, Chancheng District, Foshan City, Guangdong Province Applicant after: New Pearl Group Co.,Ltd. Applicant after: FOSHAN SANSHUI NEW PEARL CONSTRUCTION CERAMICS INDUSTRIAL Co.,Ltd. Applicant after: New Pearl (Guangdong) New Materials Co.,Ltd. Applicant after: Jiangxi Xinmingzhu Building Materials Co.,Ltd. Applicant after: Hubei new Ming Zhu Green Building Materials Technology Co.,Ltd. Address before: 528061 1st floor, No.18 taobo Avenue, Huaxia Ceramics Expo City, Nanzhuang Town, Chancheng District, Foshan City, Guangdong Province Applicant before: GUANGDONG NEWPEARL CERAMIC GROUP Co.,Ltd. Applicant before: FOSHAN SANSHUI NEW PEARL CONSTRUCTION CERAMICS INDUSTRIAL Co.,Ltd. Applicant before: GUANGDONG SUMMIT CERAMICS Co.,Ltd. Applicant before: Jiangxi Xinmingzhu Building Materials Co.,Ltd. Applicant before: Hubei new Ming Zhu Green Building Materials Technology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |