CN116693195A - White glaze material, digital white glaze ink, ceramic rock plate and preparation method - Google Patents
White glaze material, digital white glaze ink, ceramic rock plate and preparation method Download PDFInfo
- Publication number
- CN116693195A CN116693195A CN202310744431.8A CN202310744431A CN116693195A CN 116693195 A CN116693195 A CN 116693195A CN 202310744431 A CN202310744431 A CN 202310744431A CN 116693195 A CN116693195 A CN 116693195A
- Authority
- CN
- China
- Prior art keywords
- parts
- glaze
- digital
- ink
- powder
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 97
- 239000011435 rock Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 65
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002131 composite material Substances 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 30
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 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 12
- 239000005350 fused silica glass Substances 0.000 claims abstract description 12
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 11
- 239000000976 ink Substances 0.000 claims description 178
- 238000000227 grinding Methods 0.000 claims description 57
- 239000012752 auxiliary agent Substances 0.000 claims description 33
- 239000007921 spray Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 230000001681 protective effect Effects 0.000 claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000009792 diffusion process Methods 0.000 claims description 12
- 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 12
- 239000011787 zinc oxide Substances 0.000 claims description 12
- 239000002518 antifoaming agent Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 239000010431 corundum Substances 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 238000005282 brightening Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 67
- 239000004575 stone Substances 0.000 description 43
- 239000002245 particle Substances 0.000 description 31
- 239000002002 slurry Substances 0.000 description 24
- 238000005507 spraying Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000004576 sand Substances 0.000 description 16
- 238000005034 decoration Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000007639 printing Methods 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- UNOGLHIYPXTOGD-UHFFFAOYSA-N isooctyl laurate Chemical compound CCCCCCCCCCCC(=O)OCCCCCC(C)C UNOGLHIYPXTOGD-UHFFFAOYSA-N 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 9
- -1 polyethylene Polymers 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011449 brick Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000009700 powder processing Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- AMEMLELAMQEAIA-UHFFFAOYSA-N 6-(tert-butyl)thieno[3,2-d]pyrimidin-4(3H)-one Chemical compound N1C=NC(=O)C2=C1C=C(C(C)(C)C)S2 AMEMLELAMQEAIA-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 2
- 229940033357 isopropyl laurate Drugs 0.000 description 2
- 229940105132 myristate Drugs 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- AMUTYVGRCVFCCD-UHFFFAOYSA-N 5,6-diaminopyridine-3-carboxylic acid Chemical compound NC1=CC(C(O)=O)=CN=C1N AMUTYVGRCVFCCD-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- COHCXWLRUISKOO-UHFFFAOYSA-N [AlH3].[Ba] Chemical compound [AlH3].[Ba] COHCXWLRUISKOO-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- CJFLBOQMPJCWLR-UHFFFAOYSA-N bis(6-methylheptyl) hexanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCC(=O)OCCCCCC(C)C CJFLBOQMPJCWLR-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 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
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a white glaze material, digital white glaze ink, a ceramic rock plate and a preparation method thereof, wherein the white glaze material comprises the following raw materials in parts by mass: 85-95 parts of composite zirconium powder, 1-3 parts of bauxite powder, 2-5 parts of potassium feldspar and 2-7 parts of fused quartz; the composite zirconium powder comprises zirconia powder and zirconium silicate powder, or the composite zirconium powder comprises zirconia powder, zirconium silicate powder and aluminum zirconium composite powder. The invention uses the characteristics of high expansion coefficient of zirconia and low expansion coefficient of zirconium silicate, ensures that the white glaze has more proper expansion coefficient (the linear expansion coefficient is 6.5 multiplied by 10 at 0-600 ℃ after reasonable blending) ‑6 ～6.9×10 ‑6 ) Slightly smaller than the linear expansion coefficient (7+/-0.5) multiplied by 10 at 0-600 ℃ of the ceramic rock plate blank ‑6 The flatness of the ceramic rock plate is guaranteed to be good, and the deformation is controllable.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a white glaze material, digital white glaze ink, a ceramic rock plate and a preparation method.
Background
The product performance is relatively highThe difference of the expansion coefficients of the blank glaze of the ceramic products is less than or equal to 1 multiplied by 10 -6 . The linear expansion coefficient of the ceramic rock plate/ceramic plate blank is generally (7+/-0.5) multiplied by 10 -6 . The existing white glaze adopts pure zirconia (such as Chinese patent No. CN 113978171A) as raw material, and has linear expansion coefficient of 10.5X10 -6 The expansion coefficient of the ceramic rock plate/ceramic plate blank is far greater than that of the ceramic rock plate/ceramic plate blank, so that the flatness of the product is easy to generate large concave deformation, and simultaneously, the carrying and cold working cutting are easy to generate cracking, explosion defects and the like. In addition, the pure zirconia type digital white glaze ink is decorated on the surface of the green body to be in an unsintered state after being burned, and the color of each ceramic color ink on the surface is poor, lighter and has an incorrect color tone.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a white glaze material, digital white glaze ink, a ceramic rock plate and a preparation method thereof, and aims to solve the problem that the expansion coefficient of the existing white glaze material is too large and is not matched with the ceramic rock plate body.
The technical scheme of the invention is as follows:
the invention provides a white glaze material, which comprises the following raw materials in parts by mass:
85-95 parts of composite zirconium powder, 1-3 parts of bauxite powder, 2-5 parts of potassium feldspar and 2-7 parts of fused quartz;
The composite zirconium powder comprises zirconia powder and zirconium silicate powder, or the composite zirconium powder comprises zirconia powder, zirconium silicate powder and aluminum zirconium composite powder.
Optionally, the composite zirconium powder comprises 60-70 parts by weight of zirconia powder, 20-25 parts by weight of zirconium silicate powder and 5-20 parts by weight of aluminum-zirconium composite powder.
In a second aspect of the invention, a digital white glaze ink is provided, wherein the digital white glaze ink comprises 57-62 parts of the white glaze material and 55-67 parts of a first organic solvent according to the invention in parts by mass.
Optionally, the digital white glaze ink further comprises 4.9-8.9 parts by weight of a first auxiliary agent and 0.3-1.0 part by weight of a second auxiliary agent;
the first auxiliary agent is a dispersing agent; the second auxiliary agent comprises at least one of an anti-settling agent, an anti-diffusion agent, a leveling agent and a defoaming agent.
In a third aspect of the present invention, a method for preparing digital white glaze ink is provided, wherein the method comprises the steps of:
mixing the raw materials according to the proportion of the raw materials in the white glaze material, and then sequentially performing ball milling, iron removal, spray granulation and calcination to obtain the calcined glaze material;
crushing and grinding the calcined glaze to obtain the white glaze;
And (3) mixing 57-62 parts of white glaze and 55-67 parts of first organic solvent by mass, and ball milling to obtain the digital white glaze ink.
Optionally, 57 to 62 parts of white glaze material, 55 to 67 parts of first organic solvent, 4.9 to 8.9 parts of first auxiliary agent and 0.3 to 1.0 part of second auxiliary agent are mixed and ball-milled according to the mass parts to obtain the digital white glaze ink.
According to a fourth aspect of the invention, there is provided a ceramic rock plate comprising a green body layer, a digital glaze layer, a ground glaze decoration layer, a pattern decoration layer and a transparent protective glaze layer which are sequentially laminated, wherein the digital glaze layer is prepared from the white glaze material comprising the invention or the digital white glaze ink prepared by the preparation method.
Optionally, the digital glaze layer has a preset pattern texture, and is prepared from the digital white glaze ink and digital transparent bright ink;
the digital transparent brightening ink comprises the following raw materials in parts by mass:
40 to 45 parts of bright glaze, 48 to 55.7 parts of second organic solvent, 4 to 7 parts of third auxiliary agent and 0.3 to 1.0 part of fourth auxiliary agent;
The raw materials of the bright glaze material comprise the following components in parts by mass:
60-65 parts of calcined wollastonite, 25-35 parts of calcined quartz, 0-5 parts of calcined kaolin and 3-5 parts of GN134 frit;
the GN134 frit comprises the following chemical components in parts by mass:
SiO 2 57.9 to 59 portions of Al 2 O 3 14.5 to 15.8 portions of Fe 2 O 3 0 to 0.1 part of TiO 2 0 to 0.1 part, 5.4 to 5.9 parts of CaO, 0.1 to 0.4 part of MgO and K 2 5.6 to 5.9 portions of O, na 2 13.4 to 14.5 parts of O, 0 to 0.1 part of ZnO, 0.15 to 0.2 part of BaO and 2.3 to 3.0 parts of discounting.
Optionally, the transparent protective glaze layer is prepared from transparent protective glaze, and the transparent protective glaze comprises the following raw materials in parts by mass:
1 to 3 parts of calcined zinc oxide, 25 to 37 parts of potassium feldspar, 15 to 25 parts of A215 frit, 25 to 35 parts of B39 frit, 8 to 10 parts of kaolin, 1 to 3 parts of corundum and 5 to 10 parts of calcined kaolin;
the A215 frit comprises the following chemical components in parts by mass:
SiO 2 48-49 parts of Al 2 O 3 21.5 to 22.1 parts of Fe 2 O 3 0 to 0.1 part, 9.8 to 10 parts of CaO, 3.1 to 3.4 parts of MgO and K 2 O1.2-1.4 parts, na 2 3.6 to 4 parts of O, 1.3 to 1.5 parts of ZnO, 8.5 to 9.0 parts of BaO and 5.5 to 6.0 parts of discounting;
the B39 frit comprises the following chemical components in parts by mass:
SiO 2 39-40 parts of Al 2 O 3 14.8 to 15.5 portions of Fe 2 O 3 0 to 0.1 part, 1.0 to 1.2 parts of CaO, 2.0 to 2.5 parts of MgO and K 2 0.2 to 0.4 part of O, na 2 2.9 to 3.2 portions of O, 39 to 40 portions of BaO and 4.3 to 5.0 portions of discounting.
In a fifth aspect of the present invention, there is provided a method for preparing the ceramic rock plate according to the present invention, comprising the steps of:
providing a blank;
applying the digital white glaze ink and the digital transparent clear ink to the blank according to a preset pattern texture on the blank; forming a digital glaze layer with a preset pattern texture;
applying a primer on the digital glaze layer to form a primer decorative layer with preset pattern textures;
according to the preset pattern textures, applying different color inks to the primer decorative layer or applying different color inks and digital transparent bright ink to the primer decorative layer to form a pattern decorative layer;
and applying transparent protective glaze on the pattern decorative layer to form a transparent protective glaze layer, so as to obtain the ceramic rock plate with the surface provided with the preset pattern textures.
Alternatively, according to 40 to 120g/m respectively 2 、25～75g/m 2 The digital white glaze ink and the digital transparent light ink are applied to the blank body to form a digital glaze layer with concave-convex textures in dot and line shapes.
The beneficial effects are that: the main raw material of the white glaze provided by the invention is composite zirconium powder, and the composite zirconium powder has a linear expansion coefficient of 10.5 multiplied by 10 when the temperature is between 0 and 600℃ with the existing common pure zirconium oxide -6 ) The expansion coefficients of the types of white glaze are greatly different. The invention utilizes the high expansion coefficient of zirconia and the low expansion coefficient of zirconium silicate (the linear expansion coefficient is 4.2 multiplied by 10 at 0-600℃) -6 ) Is characterized in that the white glaze material is ensured to have a proper expansion coefficient (the linear expansion coefficient is 6.5 multiplied by 10 at 0-600 ℃ C.) after reasonable blending -6 ～6.9×10 -6 ) Slightly smaller than the linear expansion coefficient (7+/-0.5) multiplied by 10 at 0-600 ℃ of the ceramic rock plate blank -6 The flatness of the ceramic rock plate is guaranteed to be good, and the deformation is controllable.
Drawings
Fig. 1 is a schematic diagram of a preparation flow of the digital white glaze ink in the embodiment 1 of the present invention.
FIG. 2 is a graph showing the particle size distribution of the digital white glaze ink in example 1 of the present invention.
Fig. 3 is a graph showing the effect of various colors of ceramic color inks on the green body decorated with the digital white glaze ink in example 1.
FIG. 4 is a graph of the shape of an aqueous ink of the same weight after it has been dried on the surface of a different body.
Fig. 5 is a schematic structural view of a glazed thin ceramic rock plate with three-dimensional fine concave-convex textures on the surface in embodiment 4 of the invention.
FIG. 6 is a graph of the texture of points, lines in a point, line-shaped glossy ink layer in example 4 of the present invention.
Fig. 7 is a physical diagram of a primer decorative layer with concave-convex texture in example 4 of the present invention.
Fig. 8 is a physical texture chart of the pattern decorative layer consistent with the concave-convex texture on the primer decorative layer in example 4 of the present invention.
Fig. 9 is a graph showing the effect of the concave-convex texture of the glaze thin ceramic rock plate with three-dimensional fine concave-convex texture on the surface, which is prepared in example 4 of the present invention.
Detailed Description
The invention provides a white glaze material, digital white glaze ink, a ceramic rock plate and a preparation method thereof, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention clearer and more definite. 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 embodiment of the invention provides a white glaze, which comprises the following raw materials in parts by mass:
85-95 parts of composite zirconium powder, 1-3 parts of bauxite powder, 2-5 parts of potassium feldspar and 2-7 parts of fused quartz;
the composite zirconium powder comprises zirconia powder and zirconium silicate powder, or the composite zirconium powder comprises zirconia powder, zirconium silicate powder and aluminum zirconium composite powder.
The main raw material of the white glaze provided by the invention is composite zirconium powder, and the composite zirconium powder has a linear expansion coefficient of 10.5 multiplied by 10 when the temperature is between 0 and 600℃ with the existing common pure zirconium oxide -6 ) The expansion coefficient of the type of white glaze is largerAnd the same is true. The invention utilizes the high expansion coefficient of zirconia and the low expansion coefficient of zirconium silicate (the linear expansion coefficient is 4.2 multiplied by 10 at 0-600℃) -6 ) Is characterized in that the white glaze material is ensured to have a proper expansion coefficient (the linear expansion coefficient is 6.5 multiplied by 10 at 0-600 ℃ C.) after reasonable blending -6 ～6.9×10 -6 ) Slightly smaller than the linear expansion coefficient (7+/-0.5) multiplied by 10 at 0-600 ℃ of the ceramic rock plate blank -6 The flatness of the ceramic rock plate is guaranteed to be good, and the deformation is controllable.
The existing white glaze decoration of the conventional pure zirconia type is in an unsintered state after being sintered on a ceramic rock plate blank, and various ceramic color inks are poor in color development, lighter and uneven in color tone on the surface of the ceramic rock plate blank. The white glaze provided by the embodiment of the invention is added with bauxite powder, potassium feldspar and fused quartz besides main composite zirconium powder raw materials, and the three raw materials can form SiO 2 -Al 2 O 3 -K 2 And an O system ensures that the white glaze is in a better sintering state after being sintered, is favorable for the color development of various ceramic color inks on the surface of the white glaze, and solves the problems that the ceramic color inks are poor in color development, lighter and uneven in color tone and insufficient due to the fact that the conventional pure zirconia type white glaze is in an unsintered state after being sintered. Meanwhile, the white glaze is small in change of breaking modulus after being decorated on the green body (the difference between the breaking modulus of the white glaze decorated on the green body and the breaking modulus of the original green body is small), has strong water blocking permeability, namely good water blocking effect, is beneficial to transportation of ceramic products after being decorated on a glaze line, is not easy to generate water cracking phenomenon, and lays a good foundation for implementation of a water-based transparent glaze decoration procedure after pattern inkjet decoration in ceramic product production.
In some embodiments, the composite zirconium powder comprises 60 to 70 parts by mass of zirconium oxide powder, 20 to 25 parts by mass of zirconium silicate powder, and 5 to 20 parts by mass of aluminum zirconium composite powder. The proportion can ensure that the white glaze has a proper expansion coefficient.
In some embodiments, the aluminum zirconium composite powder comprises the following chemical components in parts by mass: siO (SiO) 2 21.16 to 23.23 portions of Al 2 O 3 43.04 to 45.35 parts of Fe 2 O 3 0.37 to 0.46 part, 0.35 to 0.38 part of CaO, 0.1 to 0.4 part of MgO, and K 2 0.2 to 0.3 part of O, na 2 1.5 to 2.0 portions of O and TiO 2 0.15 to 0.3 part of ZrO 2 28 to 29 portions, and 1.5 to 1.8 portions of the total weight.
In some embodiments, the composite zirconium powder has a particle size D50 less than or equal to 5 μm, D97 less than or equal to 10 μm; the grain diameter of the fused quartz is D50 less than or equal to 2 mu m and D97 less than or equal to 3 mu m.
In some embodiments, the bauxite powder is diasporic bauxite powder that produces anhydrous alpha-Al after heating the diasporic bauxite powder to remove water 2 O 3 Corundum.
The embodiment of the invention also provides digital white glaze ink, which comprises 57-62 parts of the white glaze material and 55-67 parts of the first organic solvent according to the embodiment of the invention.
The digital white glaze ink provided by the embodiment of the invention has a proper linear expansion coefficient (6.5 multiplied by 10 at 0-600℃) -6 ～6.9×10 -6 And between) is slightly smaller than the linear expansion coefficient (7+/-0.5) x 10 of the ceramic rock plate blank -6 The flatness of the ceramic rock plate can be guaranteed to be good at the temperature of 0-600 ℃, and the deformation is controllable; the ceramic color ink is in a better sintering state after sintering, and the color of various ceramic color inks on the surface of the ceramic color ink is favorable when the ceramic color ink is decorated on the surface of a green body, so that the problems that the ceramic color ink is poor in color, lighter and uneven in color tone and insufficient due to the fact that the digital white glaze ink of the conventional pure zirconia type in the market is decorated in an unsintered state after the surface of the green body is sintered are solved. Meanwhile, the digital white glaze ink has stronger water blocking permeability, namely good water blocking effect after the green body is decorated, has smaller change of fracture modulus, is beneficial to transportation of ceramic products after decoration on a glaze line, is not easy to generate the phenomenon of cracking when meeting water, and lays a good foundation for implementation of an aqueous transparent glaze decoration procedure after pattern inkjet decoration in ceramic product production.
In some embodiments, the digital white glaze ink comprises 57-62 parts of white glaze, 55-67 parts of first organic solvent, 4.9-8.9 parts of first auxiliary agent and 0.3-1.0 part of second auxiliary agent by mass, wherein the first auxiliary agent is a dispersing agent; the second auxiliary agent comprises at least one of an anti-settling agent, an anti-diffusion agent, a leveling agent and a defoaming agent. In this embodiment, whether to add the dispersing agent, the anti-settling agent, the anti-diffusion agent, the leveling agent, and the defoaming agent can be selected according to actual needs.
In some embodiments, the first organic solvent includes an ester solvent including at least one of diisooctyl adipate, isooctyl palmitate, isopropyl laurate, isooctyl laurate, myristate, diisooctyl triethylene glycol, and D120 solvent oil, but is not limited thereto.
In some embodiments, the dispersant includes at least one of, but not limited to, huihong HP166, huihong HP1068, lubo Solsperse13940, pick BYKJET-9142, polyvinyl acetate, polyvinyl versatate, isopropanol. The dispersing agent is hyper-dispersing agent, and has good dispersing effect.
In some embodiments, the anti-settling agent includes at least one of polyamide wax, oxidized polyethylene, and in particular, at least one of disperson NS-5501, disperson 6650, but not limited thereto.
In some embodiments, the diffusion inhibitor includes at least one of polypropylene glycol 2000, isomeric deca-alcohol polyoxyethylene ether E-05, glycerol polyoxypropylene ether HSH-330, but is not limited thereto.
In some embodiments, the leveling agent includes polyether modified siloxane, and may include at least one of BYK306, BYK333, and levalslip 8629, but is not limited thereto.
In some embodiments, the defoaming agent is a polymer type defoaming agent containing no silicone, and may specifically include at least one of BYK051, BYK052, BYK065, and BYK066N, BYK088, but is not limited thereto.
The embodiment of the invention also provides a preparation method of the digital white glaze ink, which comprises the following steps:
s11, mixing the raw materials according to the proportion of the raw materials in the white glaze material, and then sequentially performing ball milling, iron removal, spray granulation and calcination to obtain a calcined glaze material;
s12, crushing and grinding the calcined glaze to obtain the white glaze;
and S13, mixing and ball milling 57-62 parts of white glaze and 55-67 parts of first organic solvent according to the parts by mass to obtain the digital white glaze ink.
In step S11, in some embodiments, the calcination is carried out at a temperature of 800-1000℃and for a time of 2-3 hours. The adoption of calcination treatment can ensure that the white glaze does not contain moisture and ensures that the glaze components react sufficiently, so that the phenomenon of flash nozzle caused by the moisture of raw materials can not occur in the process of decorating by adopting digital white glaze ink, and simultaneously, the hydroxyl contained in the raw material components can be reacted, so that the white glaze can be quickly and uniformly mixed when being ground and mixed with a solvent, and the layering phenomenon is avoided.
In step S12, in some embodiments, the calcined glaze is crushed by mechanical and air flow double grinding, and calcium stearate with the mass of 0.1-2% of the calcined glaze can be added in the process for modification so as to prevent agglomeration phenomenon in powder processing, and then the powder is passed through a 300-mesh vibrating screen to obtain the white glaze.
In step S13, in some embodiments, 57-62 parts by mass of white glaze material, 55-67 parts by mass of first organic solvent, 4.9-8.9 parts by mass of first auxiliary agent and 0.3-1.0 part by mass of second auxiliary agent are mixed and ball-milled to obtain the digital white glaze ink.
In some embodiments, the steps of mixing and ball milling 57 to 62 parts by mass of the white glaze material, 55 to 67 parts by mass of the first organic solvent, 4.9 to 8.9 parts by mass of the first auxiliary agent and 0.3 to 1.0 part by mass of the second auxiliary agent to obtain the digital white glaze ink specifically comprise:
mixing 57-62 parts of white glaze, 35-42 parts of first organic solvent and 3-5 parts of first auxiliary agent (dispersing agent), and ball milling to obtain slurry with fineness less than 10 mu m;
circularly grinding the slurry through a multistage serial continuous sand mill to obtain stable white suspension liquid with high concentration and coarser particle size, wherein the particle size D50 is less than or equal to 0.7 mu m and the particle size D97 is less than or equal to 2.0 mu m;
According to a certain ball ratio (the ratio of stable white suspension liquid with high concentration and coarser grain diameter to grinding ball stone is 1:2-2.5; ball stone is Y-TZP high-purity zirconia ball stone, and its ball stone size is two kinds, and its ball stone size is small ball Big ball is +.>The ratio of the small ball to the big ball is 60:40 Mixing and grinding the stable white suspension liquid with high concentration and coarser grain diameter with 20-25 parts of grinding ball stone, 1.9-3.9 parts of first auxiliary agent (dispersing agent) and 0.3-1.0 part of second auxiliary agent; the obtained digital white glaze ink has the particle size D50 of less than or equal to 0.4 mu m and the particle size D97 of less than or equal to 1.0 mu m and meets the requirements of a digital ink-jet production machine.
In the embodiment, according to the proportion of each raw material in the digital white glaze ink, firstly, mixing and ball milling the white glaze, a part of the first organic solvent and a part of the first auxiliary agent, and then adding the second auxiliary agent, the rest of the first organic solvent and the first auxiliary agent.
Wherein the selection of the first and second adjuvants is as described above.
The embodiment of the invention also provides a ceramic rock plate, which comprises a green body layer, a digital glaze layer, a ground glaze decorative layer, a pattern decorative layer and a transparent protective glaze layer which are sequentially stacked, wherein the digital glaze layer is prepared from the white glaze material comprising the embodiment of the invention or the digital white glaze ink prepared by the preparation method of the embodiment of the invention.
In some embodiments, the digital glaze layer has a preset pattern texture, and is prepared from the digital white glaze ink and digital transparent clear ink;
the digital transparent brightening ink comprises the following raw materials in parts by mass:
40 to 45 parts of bright glaze, 48 to 55.7 parts of second organic solvent, 4 to 7 parts of third auxiliary agent and 0.3 to 1.0 part of fourth auxiliary agent;
the raw materials of the bright glaze material comprise the following components in parts by mass:
60-65 parts of calcined wollastonite, 25-35 parts of calcined quartz, 0-5 parts of calcined kaolin and 3-5 parts of GN134 frit;
the GN134 frit is a high-sodium high-expansion-coefficient frit with a linear expansion coefficient of (8.7+/-0.1) multiplied by 10 -6 (0-600 ℃) and the chemical components of the GN134 frit comprise the following components in parts by weight:
SiO 2 57.9 to 59 portions of Al 2 O 3 14.5 to 15.8 portions of Fe 2 O 3 0 to 0.1 part of TiO 2 0 to 0.1 part, 5.4 to 5.9 parts of CaO, 0.1 to 0.4 part of MgO and K 2 5.6 to 5.9 portions of O, na 2 13.4 to 14.5 parts of O, 0 to 0.1 part of ZnO, 0.15 to 0.2 part of BaO and 2.3 to 3.0 parts of discounting.
The glaze layer prepared from the digital white glaze ink and the digital transparent light ink can realize the preset pattern texture, so that the surface of the ceramic rock plate has the preset pattern texture.
In some embodiments, the ceramic rock plate surface has a pre-set pattern of relief texture. In some specific embodiments, the ceramic rock plate surface has a concave-convex texture in the shape of dots and lines.
In some embodiments, the second organic solvent includes at least one of isopropyl laurate, isooctyl laurate, myristate, cyclohexane, hexane, and heptane, but is not limited thereto.
In some embodiments, the third auxiliary agent is a dispersant, and the dispersant includes at least one of Huihong HP166, huihong HP1068, lubo Solsperse13940, pick BYKJET-9142, polyvinyl acetate, polyvinyl versatate, and isopropanol, but is not limited thereto.
In some embodiments, the fourth aid comprises at least one of an anti-settling agent, an anti-diffusion agent, a leveling agent, and an antifoaming agent. In particular, the anti-settling agent, the anti-diffusion agent, the leveling agent and the defoaming agent are selected as described above.
In some embodiments, the transparent protective glaze layer is prepared from transparent protective glaze, and the transparent protective glaze comprises the following raw materials in parts by mass:
1 to 3 parts of calcined zinc oxide, 25 to 37 parts of potassium feldspar, 15 to 25 parts of A215 frit, 25 to 35 parts of B39 frit, 8 to 10 parts of kaolin, 1 to 3 parts of corundum and 5 to 10 parts of calcined kaolin;
The A215 frit is high-calcium barium aluminum high Wen Yaguang frit, and the chemical components of the A215 frit comprise, by mass:
SiO 2 48-49 parts of Al 2 O 3 21.5 to 22.1 parts of Fe 2 O 3 0 to 0.1 part, 9.8 to 10 parts of CaO, 3.1 to 3.4 parts of MgO and K 2 O1.2-1.4 parts, na 2 3.6 to 4 parts of O, 1.3 to 1.5 parts of ZnO, 8.5 to 9.0 parts of BaO and 5.5 to 6.0 parts of discounting;
the B39 frit comprises the following chemical components in parts by mass:
SiO 2 39-40 parts of Al 2 O 3 14.8 to 15.5 portions of Fe 2 O 3 0 to 0.1 part, 1.0 to 1.2 parts of CaO, 2.0 to 2.5 parts of MgO and K 2 0.2 to 0.4 part of O, na 2 2.9 to 3.2 portions of O, 39 to 40 portions of BaO and 4.3 to 5.0 portions of discounting.
In some embodiments, the corundum is ultra-fine corundum having a particle size D90. Ltoreq.0.52. Mu.m.
In the prior art, a thin ceramic plate with a three-dimensional concave-convex die effect is formed on a blank body mainly by adopting a digital glaze decoration process. Printing digital white ink and common color ink on the surface of the green body in an inkjet mode, printing deep ink after drying, and then applying high wear-resistant protective glaze to form concave-convex textures; the technology is more suitable for preparing thin ceramic plates/rock plates with shallow surface concave-convex mould textures (less than 0.1 mm), concave-convex textures with depth of more than 0.2mm can not be achieved, and meanwhile, the adopted digital white glaze ink also has the problems recorded in the background technology.
Based on the above, the embodiment of the invention also provides a preparation method of the ceramic rock plate, which comprises the following steps:
s21, providing a blank;
s22, applying the digital white glaze ink and the digital transparent clear ink to the blank according to the preset pattern texture on the blank; forming a digital glaze layer with a preset pattern texture;
s23, applying a primer on the digital glaze layer to form a primer decorative layer with preset pattern textures;
s24, applying different color inks to the primer decorative layer or applying different color inks and digital transparent bright ink to the primer decorative layer according to preset pattern textures to form a pattern decorative layer;
and S25, applying transparent protective glaze on the pattern decorative layer to form a transparent protective glaze layer, so as to obtain the ceramic rock plate with the surface provided with the preset pattern textures.
The digital white glaze ink of the invention has a proper linear expansion coefficient (6.5 multiplied by 10 at 0-600℃) -6 ～6.9×10 -6 And between) is slightly smaller than the linear expansion coefficient (7+/-0.5) x 10 of the ceramic rock plate blank -6 The flatness of the ceramic rock plate is guaranteed to be good at the temperature of 0-600 ℃, and the deformation is controllable; the ceramic color ink is in a better sintering state after sintering, and the color of various ceramic color inks on the surface of the ceramic color ink is favorable when the ceramic color ink is decorated on the surface of a green body, so that the problems that the ceramic color ink is poor in color, lighter and uneven in color tone and insufficient due to the fact that the digital white glaze ink of the conventional pure zirconia type in the market is decorated in an unsintered state after the surface of the green body is sintered are solved. The surface of the ceramic rock plate prepared by the preparation method provided by the embodiment of the invention has three-dimensional fine concave-convex texture, the depth and width of the concave-convex texture can be regulated and controlled, the concave-convex feeling presents multi-gradient gradation depth, the depth of the groove can reach 1mm, the width can reach 11mm, the thickness of the ceramic rock plate is less than or equal to 6mm, and the area is more than or equal to 1.62m 2 . The invention is not limited to the formulation of the ceramic rock plate blank and the formulation of the primer, and any blank and primer formulation suitable for use with ceramic rock plates is suitable for use with the invention.
In step S21, in some embodiments, the step of providing a blank specifically includes:
spraying water to the surface of the blank body to obtain the blank body with uniformly wetted surface. The water spray plays roles of cooling the blank and wetting capillary holes on the blank surface.
In some specific embodiments, high pressure spray guns are used at 10-20 g/m 2 The spray pressure of the high-pressure spray gun is 7-9 bar, and the spray nozzle model of the spray gun is 0.36mm.
In step S22, in some embodiments, the ratio is 40-120 g/m, respectively 2 、25～75g/m 2 The digital white glaze ink and the digital transparent clear ink are applied to the blank (such as a blank with uniformly wetted surface) to form a digital glaze layer with concave-convex textures in the shape of dots and lines. Thus obtaining the ceramic rock plate with concave-convex textures on the surface. Specifically, the digital white glaze ink and the digital transparent bright ink can be applied to the blank through a digital ink-jet printer, the digital ink-jet printer is provided with 4 to 6 channels, each channel is provided with 15 to 25 large-aperture large-ink-jet-volume spray heads, and the type of the large-aperture large-ink-jet-volume spray heads is Seer GS40 or starlight 1024HFL.
In step S23, the thickness of the primer decorative layer is mainly determined according to the amounts of the digital white glaze ink and the digital transparent clear ink in step S22. In some embodiments, the primer decorative layer has a thickness of 0.2 to 0.8mm.
In step S24, the color ink has the color effect of decorating the ceramic rock plate patterns, and comprises purple blue, cyan blue, red brown, dark brown, packed scarlet, orange, lemon yellow, packed yellow, green, cobalt blue black, iron red black and the like; the digital transparent light ink has the effects of increasing the matt change effect of the glaze of the ceramic rock plate and enhancing the concave-convex texture of the glaze.
Specifically, different color inks and digital transparent glossy inks are applied to the base glaze decorative layer by a color digital ink-jet machine. The type of the color digital ink jet machine installed printing spray heads is respectively as follows: the spray heads used for printing the color ink are of the types of Sier GS6, sier GS12, starlight 1024S, starlight 1024M and the like; the model of a spray head used for printing the digital transparent glossy ink is Sier GS40 or star 1024HFL.
Illustratively, the pattern texture of the digital transparent clear ink printed by the ink jet printing method is consistent with the dark texture of the color pattern, and the digital transparent clear ink can be a line pattern, and the line width of the digital transparent clear ink is 0.2-0.8 mm.
In step S25, in some embodiments, the transparent protective glaze layer has a thickness of 0.05 to 0.25mm.
In some embodiments, the step of forming a transparent protective glaze layer on the patterned decorative layer specifically includes:
applying transparent protective glaze on the pattern decorative layer by adopting a high-pressure glaze spraying or knife-type linear glaze spraying device, and drying to form a transparent protective layer;
and then sintering for 50-80 min at 1185-1195 ℃ to obtain the ceramic rock plate with the surface provided with the preset pattern textures.
Wherein, 5-8 high-pressure spray guns are arranged in the high-pressure glaze spraying device, the size of the nozzle of the high-pressure spray gun is 0.36mm or 0.43mm, and the working pressure is 10-15 bar;
the specific gravity of the transparent protective glaze applied by the knife-type linear glaze spraying device is 1.45-1.75.
The invention is further illustrated by the following specific examples.
Example 1
The embodiment provides digital white glaze ink which comprises the following raw materials in parts by mass:
60 parts of white glaze, 66 parts of isooctyl laurate, 6.9 parts of dispersing agent (Huihong HP 166), 0.25 part of flatting agent (BYK 306), 0.15 part of anti-settling agent (Disparlon NS-5501), 0.3 part of anti-diffusion agent (polypropylene glycol 2000) and 0.1 part of defoaming agent (BYK 051);
Wherein, the raw materials of the white glaze material comprise the following components in parts by mass:
90 parts of composite zirconium powder, 2 parts of diasporic bauxite powder, 3 parts of high-purity potassium feldspar and 5 parts of fused quartz;
the composite zirconium powder comprises 65 parts of zirconium oxide, 22 parts of zirconium silicate and 13 parts of aluminum-zirconium composite powder by mass;
calculated according to parts by massThe aluminum-zirconium composite powder comprises the following chemical components: siO (SiO) 2 22.20 parts of Al 2 O 3 44.20 parts of Fe 2 O 3 0.41 part, 0.37 part of CaO, 0.25 part of MgO and K 2 O0.25 part, na 2 O1.75 parts, tiO 2 0.18 part of ZrO 2 28.5 parts, 1.64 parts as appropriate;
the grain diameter of the composite zirconium powder is D50 less than or equal to 5 mu m and D97 less than or equal to 10 mu m; the grain diameter of the fused quartz is D50 less than or equal to 2 mu m and D97 less than or equal to 3 mu m.
As shown in fig. 1, the preparation method of the digital white glaze ink comprises the following steps:
batching and calcining: proportioning and ball milling the raw materials of the white glaze according to the proportion to prepare slurry (the fineness of the slurry is 325 meshes, the slurry is completely filtered), sequentially filtering by a 120-mesh sieve, removing iron, spraying and granulating, calcining for 3 hours at 900 ℃, and cooling to obtain the calcined glaze;
crushing: crushing the calcined glaze in a mechanical and air flow double-grinding mode (the grinding fineness is less than 50 mu m, and adding calcium stearate with the mass of 0.15% of the calcined glaze for modification in the grinding process to prevent agglomeration phenomenon in powder processing); then sieving with a 300-mesh vibrating screen to obtain superfine white glaze powder, namely the white glaze;
Pre-dispersion rapid grinding: adding 60 parts of white glaze, 41 parts of isooctyl laurate and 166 parts of Huihong HP into a 150L pre-dispersion barrel together according to the proportion, and grinding to obtain slurry with fineness less than 10 mu m; wherein the grinding medium used for the pre-dispersion grinding is Y-TZP high-purity zirconia beads (the density thereof is more than 6 g/cm) 3 Mohs hardness of 9), ball stone size of
Multistage serial continuous cyclic rapid grinding: delivering the slurry to a multistage serial continuous sand mill for cyclic grinding through a diaphragm feed pump, wherein the multistage serial continuous sand mill is a 25L rod pin type sand mill, and a 1500-2000L high-flow and high-energy density cyclic grinding mode is adopted; the rotating speed of the rod pin type sand mill is more than 11m/s, and the ball stone filling rate in the mill is 85 percentThe ball stone is Y-TZP high-purity zirconia beads; the circulating grinding primary of the multistage serial continuous sand mill adopts the ball stone with the size ofThe size of the middle grinding ball stone is +.>The size of the final ground ball stone is +.>
And (3) three-stage filtration: three-stage filtering with absolute polypropylene filter with 5-3-2 micron filter core to obtain stable white suspension with particle size D50 less than or equal to 0.7 micron and D97 less than or equal to 2.0 micron;
Slow trimming of particle morphology: according to a certain ball ratio (the ratio of stable white suspension liquid with high concentration and coarser grain diameter to grinding ball stone is 1:2; ball stone is Y-TZP high-purity zirconia ball stone, and the ball stone size is two kinds of ball stone sizeBig ball is +.>The ratio of the small ball to the big ball is 60:40 The slurry was prepared by adding a high-concentration, coarser particle size stable white suspension and grinding ball stones to a 1500L batch ball mill, and then adding 25 parts of isooctyl laurate, 2.9 parts of Huihong HP166, 0.25 part of BYK306, 0.15 part of Disparlon NS-5501, 0.3 part of polypropylene glycol and 0.1 part of BYK051 to the batch ball mill, followed by finishing grinding in the form of particles.
After finishing and grinding for 10 hours, filtering by a polypropylene absolute filter device with a 1 mu m filter element to obtain the digital white glaze ink with the particle size D50 of less than or equal to 0.4 mu m and the particle size D97 of less than or equal to 1.0 mu m which accords with the use of a digital ink-jet production machine.
Example 2
The embodiment provides digital white glaze ink which comprises the following raw materials in parts by mass:
57 parts of white glaze, 67 parts of isooctyl laurate, 5.5 parts of dispersing agent (Huihong HP 166), 0.25 part of flatting agent (BYK 306), 0.15 part of anti-settling agent (Disparlon NS-5501), 0.3 part of anti-diffusion agent (polypropylene glycol 2000) and 0.1 part of defoaming agent (BYK 051);
Wherein, the raw materials of the white glaze material comprise the following components in parts by mass:
85 parts of composite zirconium powder, 1 part of diasporic bauxite powder, 4 parts of high-purity potassium feldspar and 3 parts of fused quartz;
the composite zirconium powder comprises 60 parts of zirconium oxide, 23 parts of zirconium silicate and 17 parts of aluminum-zirconium composite powder by mass;
the aluminum-zirconium composite powder comprises the following chemical components in parts by mass: siO (SiO) 2 22.20 parts of Al 2 O 3 44.20 parts of Fe 2 O 3 0.41 part, 0.37 part of CaO, 0.25 part of MgO and K 2 O0.25 part, na 2 O1.75 parts, tiO 2 0.18 part of ZrO 2 28.5 parts, 1.64 parts as appropriate;
the grain diameter of the composite zirconium powder is D50 less than or equal to 5 mu m and D97 less than or equal to 10 mu m; the grain diameter of the fused quartz is D50 less than or equal to 2 mu m and D97 less than or equal to 3 mu m.
The preparation method of the digital white glaze ink comprises the following steps:
batching and calcining: proportioning and ball milling the raw materials of the white glaze according to the proportion to prepare slurry (the fineness of the slurry is 325 meshes, the slurry is completely filtered), sequentially filtering by a 120-mesh sieve, removing iron, spraying and granulating, calcining for 2 hours at 900 ℃, and cooling to obtain the calcined glaze;
crushing: crushing the calcined glaze in a mechanical and air flow double-grinding mode (the grinding fineness is less than 50 mu m, and adding calcium stearate with the mass of 0.15% of the calcined glaze for modification in the grinding process to prevent agglomeration phenomenon in powder processing); then sieving with a 300-mesh vibrating screen to obtain superfine white glaze powder, namely the white glaze;
Pre-dispersion rapid grinding: according to the proportion, the white glaze 57, 42 parts of isooctyl laurate and the bright are mixed3.6 parts of iridescent HP166 are added into a 150L pre-dispersing barrel together for grinding, and slurry with fineness less than 10 mu m is obtained; wherein the grinding medium used for the pre-dispersion grinding is Y-TZP high-purity zirconia beads (the density thereof is more than 6 g/cm) 3 Mohs hardness of 9), ball stone size of
Multistage serial continuous cyclic rapid grinding: delivering the slurry to a multistage serial continuous sand mill for cyclic grinding through a diaphragm feed pump, wherein the multistage serial continuous sand mill is a 25L rod pin type sand mill, and a 1500-2000L high-flow and high-energy density cyclic grinding mode is adopted; the rotating speed of the rod pin type sand mill is more than 11m/s, the filling rate of the ball stones in the mill is 85%, and the ball stones are Y-TZP high-purity zirconia beads; the circulating grinding primary of the multistage serial continuous sand mill adopts the ball stone with the size ofThe size of the middle grinding ball stone is +.>The size of the final ground ball stone is +.>
And (3) three-stage filtration: three-stage filtering with absolute polypropylene filter with 5-3-2 micron filter core to obtain stable white suspension with particle size D50 less than or equal to 0.7 micron and D97 less than or equal to 2.0 micron; slow trimming of particle morphology: according to a certain ball ratio (the ratio of stable white suspension liquid with high concentration and coarser grain diameter to grinding ball stone is 1:2; ball stone is Y-TZP high-purity zirconia ball stone, and the ball stone size is two kinds of ball stone size Big ball is +.>The ratio of the small ball to the big ball is 60:40 The slurry was prepared by adding a high-concentration, coarser particle size stable white suspension and grinding ball stones to a 1500L batch ball mill, and then adding 25 parts of isooctyl laurate, 1.9 parts of Huihong HP166, 0.25 part of BYK306, 0.15 part of Disparlon NS-5501, 0.3 part of polypropylene glycol and 0.1 part of BYK051 to the batch ball mill, followed by finishing grinding in the form of particles. After finishing and grinding for 10 hours;
filtering with a polypropylene absolute filter with a 1 μm filter core to obtain the digital white glaze ink with the particle size D50 of less than or equal to 0.4 μm and the particle size D97 of less than or equal to 1.0 μm which accords with the use of a digital ink-jet production machine.
Example 3
The embodiment provides digital white glaze ink which comprises the following raw materials in parts by mass:
62 parts of white glaze, 55 parts of isooctyl laurate, 5 parts of dispersing agent (Huihong HP 166), 0.25 part of flatting agent (BYK 306), 0.15 part of anti-settling agent (Disparlon NS-5501), 0.3 part of anti-diffusion agent (polypropylene glycol 2000) and 0.1 part of defoaming agent (BYK 051);
wherein, the raw materials of the white glaze material comprise the following components in parts by mass:
95 parts of composite zirconium powder, 1 part of diasporic bauxite powder, 3 parts of high-purity potassium feldspar and 2 parts of fused quartz;
The composite zirconium powder comprises 70 parts of zirconium oxide, 20 parts of zirconium silicate and 10 parts of aluminum-zirconium composite powder by mass;
the aluminum-zirconium composite powder comprises the following chemical components in parts by mass: siO (SiO) 2 22.20 parts of Al 2 O 3 44.20 parts of Fe 2 O 3 0.41 part, 0.37 part of CaO, 0.25 part of MgO and K 2 O0.25 part, na 2 O1.75 parts, tiO 2 0.18 part, 28.5 parts of ZrO2 and 1.64 parts of appropriate reduction;
the grain diameter of the composite zirconium powder is D50 less than or equal to 5 mu m and D97 less than or equal to 10 mu m; the grain diameter of the fused quartz is D50 less than or equal to 2 mu m and D97 less than or equal to 3 mu m.
The preparation method of the digital white glaze ink comprises the following steps:
batching and calcining: proportioning and ball milling the raw materials of the white glaze according to the proportion to prepare slurry (the fineness of the slurry is 325 meshes, the slurry is completely filtered), sequentially filtering by a 120-mesh sieve, removing iron, spraying and granulating, calcining for 3 hours at 900 ℃, and cooling to obtain the calcined glaze;
crushing: crushing the calcined glaze in a mechanical and air flow double-grinding mode (the grinding fineness is less than 50 mu m, and adding calcium stearate with the mass of 0.15% of the calcined glaze for modification in the grinding process to prevent agglomeration phenomenon in powder processing); then sieving with a 300-mesh vibrating screen to obtain superfine white glaze powder, namely the white glaze;
pre-dispersion rapid grinding: adding 62 parts of white glaze, 35 parts of isooctyl laurate and 3.1 parts of Huihong HP166 into a 150L pre-dispersion barrel together according to the proportion, and grinding to obtain slurry with fineness less than 10 mu m; wherein the grinding medium used for the pre-dispersion grinding is Y-TZP high-purity zirconia beads (the density thereof is more than 6 g/cm) 3 Mohs hardness of 9), ball stone size of
Multistage serial continuous cyclic rapid grinding: delivering the slurry to a multistage serial continuous sand mill for cyclic grinding through a diaphragm feed pump, wherein the multistage serial continuous sand mill is a 25L rod pin type sand mill, and a 1500-2000L high-flow and high-energy density cyclic grinding mode is adopted; the rotating speed of the rod pin type sand mill is more than 11m/s, the filling rate of the ball stones in the mill is 85%, and the ball stones are Y-TZP high-purity zirconia beads; the circulating grinding primary of the multistage serial continuous sand mill adopts the ball stone with the size ofThe size of the middle grinding ball stone is +.>The size of the final ground ball stone is +.>
And (3) three-stage filtration: three-stage filtering with absolute polypropylene filter with 5-3-2 micron filter core to obtain stable white suspension with particle size D50 less than or equal to 0.7 micron and D97 less than or equal to 2.0 micron;
slow trimming of particle morphology: according to a certain ball ratio (the ratio of stable white suspension liquid with high concentration and coarse particle size to grinding ball stone is 2.5; ball stone is Y-TZP high-purity zirconia ball stone, its ball stone size is two kinds of ball stone sizeBig ball is +.>The ratio of the small ball to the big ball is 60:40 The slurry was prepared by adding a high-concentration, coarser particle size stable white suspension and grinding ball stones to a 1500L batch ball mill, and then adding 20 parts of isooctyl laurate, 1.9 parts of Huihong HP166, 0.25 part of BYK306, 0.15 part of Disparlon NS-5501, 0.3 part of polypropylene glycol and 0.1 part of BYK051 to the batch ball mill, followed by finishing grinding in the form of particles.
After finishing and grinding for 10 hours, filtering by a polypropylene absolute filter device with a 1 mu m filter element to obtain the digital white glaze ink with the particle size D50 of less than or equal to 0.4 mu m and the particle size D97 of less than or equal to 1.0 mu m which accords with the use of a digital ink-jet production machine.
Testing
(1) The digital white glaze ink of example 1 was subjected to particle size testing using a Mastersizer 3000 laser particle size analyzer from malvern, uk, with specific particle size distributions as shown in fig. 2 and table 1 below.
TABLE 1 grinding particle size of digital white ink
| Ink | D10(nm) | D50(nm) | D90(nm) | Specific surface area m 2 /kg |
| Digital white glaze ink in example 1 | 195 | 349 | 611 | 18930 |
(2) The color effect of the various color ceramic color inks on the green body with and without the digital white glaze ink decoration of example 1 is shown in fig. 3. Therefore, the color development effect of the various ceramic color inks on the surface of the ink is good.
(3) The digital white glaze ink in the embodiment 1 is decorated on an ultrathin green body by adopting a spray head with large aperture and large ink jet quantity (a Sier GS40 spray head), and then the water blocking effect of the white glaze ink with countless codes and the influence of the water blocking effect on the breaking modulus of the green body are tested by adopting water-based ink or transparent glaze slurry.
Concretely, (1) dripping aqueous ink on the surface of the dried green body; (2) After the digital white glaze ink is decorated on the surface of the dried green body, water-based ink with the same quality is dripped; (3) After the existing cosmetic ground glaze slurry is decorated on the surface of a dried green body, water-based ink with the same quality is dripped, and the ink bleeding time is tested.
(1) Carrying out fracture modulus test on the dried green body; (2) Spraying digital white glaze ink on the dried green body, spraying transparent glaze, and drying to test the breaking modulus; (3) Spraying the existing cosmetic soil base glaze slurry on the dried green body, spraying transparent glaze, and drying and then carrying out fracture modulus test. The results are shown in FIG. 4, table 2 and Table 3 below.
Table 2 Water blocking effect and modulus of rupture test conditions for different technological schemes
TABLE 3 modulus of rupture test cases for different process schemes
From the analysis of the results in tables 2 and 3, it can be seen that:
from the analysis of the penetration time, the penetration time of the scheme of drying green bodies and spraying digital glaze white ink is about 7 times of that of pure drying green bodies, which proves that the white glaze provided by the invention has strong water-blocking permeability;
according to the analysis of the breaking modulus of the dried green bricks obtained from different decoration processes, the breaking modulus of the dried green bricks is reduced by 56.85% compared with the dried green bricks after being dried by the conventional method of spraying the earth-base glaze slurry and spraying the transparent glaze, the breaking modulus of the dried green bricks after being dried by the method of spraying the digital white glaze ink and spraying the transparent glaze is reduced by 18.15% compared with the dried green bricks after being dried, and the method of spraying the transparent glaze after spraying the digital white ink on the dried green bricks is proved to be small in breaking modulus change, so that the ceramic products are convenient to transport after being decorated on a glaze line and difficult to generate the phenomenon of cracking when meeting water;
From the analysis of the results in fig. 4, it can be seen that:
analyzing the pattern of the aqueous ink after the blank surface of different schemes is dried, namely the pattern of the ink of the scheme of green body and digital white glaze ink is the most round, and the scheme of green body and ground glaze is the next to the scheme of green body and ground glaze, because the surface of the green body after the powder materials with different sizes are pressed and formed is provided with a plurality of capillary holes, water in the aqueous ink can permeate and diffuse downwards and around along the capillary holes or gaps among the particles, and the density of the powder materials of the green body is different, so that the pattern shape with larger difference from the round shape appears; when the surface of the green body is decorated by adopting the cosmetic ground glaze or the digital white glaze ink, the capillary holes are filled, so that the infiltration of water-based ink can be reduced, the diffusion speed to the periphery is more uniform, and the patterns are more similar to circles; in addition, because the organic solvent in the digital white glaze ink and the water in the aqueous ink can mutually repel each other, the diffusion of the aqueous ink can be greatly reduced, and the aqueous ink forms the most round pattern on the decorative surface.
The digital white glaze ink in examples 2 and 3 was similar to the digital white glaze ink in example 1 in terms of its color development, water blocking properties, and impact on the breaking modulus of the green body after being decorated on the surface of the green body.
Example 4
As shown in fig. 5, the glaze thin ceramic rock plate with the three-dimensional fine concave-convex textures on the surface comprises an ultrathin blank layer, a digital glaze layer, a ground glaze decorative layer, a pattern decorative layer and a transparent protective glaze layer which are sequentially laminated. The digital transparent clear ink used in the following preparation method comprises the following raw materials in parts by mass: 42 parts of bright glaze, 52 parts of hexane, 166 parts of Huihong HP, 306.25 parts of BYK, 0.15 part of Disparlon NS-5501, 0.1 part of polypropylene glycol 2000 and 0.1 part of BYK 051;
the bright glaze comprises the following raw materials in percentage by weight: 63 parts of superfine calcined wollastonite, 30 parts of superfine calcined quartz, 3 parts of calcined kaolin and 4 parts of GN134 frit powder;
the GN134 frit powder in the raw material of the glaze material of the bright glaze is high-sodium high-expansion-coefficient frit powder, and the linear expansion coefficient of the frit powder is (8.7+/-0.1) multiplied by 10 -6 (0-600 ℃) and comprises the chemical components of SiO by weight percent 2 58.0 parts of Al 2 O 3 14.5 parts of Fe 2 O 3 0.03 part of TiO 2 0.02 part, 5.4 parts of CaO, 0.25 part of MgO and K 2 O5.8 parts, na 2 13.5 parts of O, 0.05 part of ZnO, 0.15 part of BaO and 2.3 parts of appropriate reduction.
The transparent protective glaze used in the following preparation method comprises the following raw materials in parts by mass: 2 parts of calcined zinc oxide, 30 parts of potassium feldspar, 22 parts of A215 frit powder, 28 parts of B39 frit powder, 9 parts of Zhangzhou kaolin, 2 parts of superfine corundum powder (D90 is less than or equal to 0.52 mu m) and 8 parts of calcined kaolin;
Wherein, the A215 frit powder is high calcium barium aluminum high Wen Yaguang frit powder, and comprises the following chemical components in parts by weight: siO (SiO) 2 48 parts of Al 2 O 3 21.5 parts of Fe 2 O 3 0.05 part, 10 parts of CaO, 3.2 parts of MgO and K 2 O1.2 parts, na 2 3.8 parts of O, 1.4 parts of ZnO, 8.5 parts of BaO and 5.5 parts of the rest.
The B39 high-barium matte frit powder comprises the following chemical components in parts by mass 2 39 parts of Al 2 O 3 15 parts of Fe 2 O 3 0.05 part, 1.0 part of CaO, 2.2 parts of MgO and K 2 O0.3 part, na 2 3.0 parts of O, 39 parts of BaO and 4.5 parts of appropriate reduction.
Wherein, the chemical components of the GN134 frit powder in the formula of the transparent protective glaze are the same as the GN134 frit powder in the raw materials of the glaze material.
The preparation method of the thin ceramic rock plate with the three-dimensional fine concave-convex textures on the surface comprises the following steps:
(1) Uniformly spraying water on the surface of the dried green body by adopting a high-pressure spray gun, wherein the spray pressure of the high-pressure spray gun is 9bar, the spray nozzle model of the spray gun is 0.36mm, and the spray water quantity is 15g/m 2 ；
(2) On the surface of a uniformly wetted green body, according to the pre-designed pattern texture of the thin ceramic rock plate, adopting a digital ink-jet printer with a large-aperture large-ink-jet nozzle to decorate the digital white glaze ink and the digital transparent bright ink in the embodiment 1 on the green body, and forming a digital glaze layer on the surface of the green body;
The upper digital ink-jet printer is provided with 5 channels, each channel is provided with 20 large-aperture large-ink-jet-volume spray heads, and the spray heads are of the type of Sier GS40;
wherein the digital white glaze ink in example 1 was mounted in 3 channels in the front part of a digital ink-jet printer, and the ink amount of the ink-jet printed decoration was 60g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Digital transparent clear ink is arranged on 2 channels of the rear part of the digital ink-jet printer, and the ink quantity of ink-jet printing is 40g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, as shown in FIG. 6, the digital glaze layer comprises a large-area full-coverage on the surface of the green bodyA digital white glaze layer on the surface, and a dot and linear bright ink layer inlaid in the digital white glaze layer; the line-shaped textures of the points and the lines in the light ink layer are consistent with the directions of the textures of the ultra-thin ceramic rock plate patterns, wherein the width of the line shape is less than 1.1cm, and the design gray level of the point line is more than or equal to 70%;
(3) Performing primer decoration on the digital glaze layer by adopting a spraying device to form a primer decoration layer with concave-convex textures (shown in figure 7); wherein the thickness of the ground coat decorative layer is 0.3mm;
(4) Conveying the green body containing the digital glaze layer and the ground coat decorative layer in the step (3) to a thermal intelligent control dryer for moisture drying, wherein the moisture of the dried green body is less than or equal to 0.4%;
The heat sensing intelligent control dryer can intelligently sense moisture and temperature of a green body and then automatically adjust a hot air volume and drying temperature curve, and main parameters of the heat sensing intelligent control dryer are as follows: the length is 30m, the highest drying temperature is 180 ℃, and the drying time is 5min; the main energy power is the power generated by natural gas or photovoltaic power generation;
(5) Printing ceramic ink on the ground glaze decorative layer obtained after the drying in the step (4) by adopting a color digital ink-jet machine according to the pre-designed pattern texture of the thin ceramic rock plate to form a pattern decorative layer; wherein the pattern textures of different colors of the formed pattern decorative layer are consistent with the concave-convex textures on the ground coat decorative layer (as shown in figure 8);
the color digital ink jet machine has 12 printing functions, and the maximum effective width of each printing is 2m;
wherein, the ceramic ink installed on the color digital ink jet machine comprises two kinds of ceramic color ink and digital transparent light ink, and the printing sequence of the ceramic ink on the color digital ink jet machine is as follows: purple blue, bluish blue, reddish brown, dark brown, wrapping scarlet, orange, lemon yellow, green, cobalt blue black, iron red black, digital transparent clear ink and digital transparent clear ink; the pattern texture of the digital transparent light ink printed by the digital ink jet is consistent with the dark texture of the color pattern, the pattern is a line pattern, and the line width is 0.2-0.8 mm;
Wherein, the type of the color digital ink jet machine installed printing nozzle is respectively as follows: the model of a spray nozzle used for printing the ceramic color ink is Sier GS6; the model of a spray head used for printing the digital transparent clear ink is Sier GS40;
(6) Applying transparent protective glaze by adopting a high-pressure glaze spraying device, and drying to form a transparent protective glaze layer with the thickness of 0.2 mm;
wherein, 6 high-pressure spray guns are arranged in the high-pressure glaze spraying device, the size of the nozzle of the high-pressure spray gun is 0.36mm, and the working pressure is 15bar;
(7) And (3) delivering the semi-finished product decorated in the step (6) into a kiln for firing, wherein the fired fuel adopts natural gas, the highest firing temperature is 1190 ℃, and the firing time is 60 minutes. The length of the kiln is 300m, and the width of the interior of the kiln is 2.2m;
(8) After the kiln is fired, the glazed thin ceramic rock plate with the three-dimensional fine concave-convex texture on the surface is obtained after the automatic brick storage line is kept stand for 24 hours until natural cooling, the surface is provided with the three-dimensional fine concave-convex texture, the concave-convex texture corresponds to the color pattern texture (as shown in fig. 9), the pickling natural surface effect similar to that of natural stone is formed, and the thickness of the ceramic rock plate is 3mm.
In summary, the invention provides a white glaze material, digital white glaze ink, ceramic rock plate and preparation method, the white glaze material and digital white glaze ink in the invention have more proper linear expansion coefficient (6.5 multiplied by 10 at 0-600℃) -6 ～6.9×10 -6 And between) is slightly smaller than the linear expansion coefficient (7+/-0.5) x 10 of the ceramic rock plate blank -6 The flatness of the ceramic rock plate is guaranteed to be good at the temperature of 0-600 ℃, and the deformation is controllable; the ceramic color ink is in a better sintering state after sintering, and the decoration is favorable for the color development of various ceramic color inks on the surface of the ceramic color ink when the ceramic color ink is decorated on the surface of a green body, so that the problems that the color development of the ceramic color ink is poor, lighter and the color tone is not correct and insufficient due to the fact that the digital white glaze of the conventional pure zirconia type in the market and the corresponding ink are in an unsintered state after sintering are solved. The ceramic rock plate with three-dimensional fine concave-convex texture prepared by the preparation method provided by the invention has adjustable depth and width of the three-dimensional fine concave-convex texture on the surface, and the concave-convex feeling presents multiple gradient gradation depthsThe depth of the groove can reach 1mm, the width can reach 11mm, the thickness of the ceramic rock plate is less than or equal to 6mm, and the area is more than or equal to 1.62m 2 。
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 (11)
1. The white glaze is characterized by comprising the following raw materials in parts by mass:
85-95 parts of composite zirconium powder, 1-3 parts of bauxite powder, 2-5 parts of potassium feldspar and 2-7 parts of fused quartz;
the composite zirconium powder comprises zirconia powder and zirconium silicate powder, or the composite zirconium powder comprises zirconia powder, zirconium silicate powder and aluminum zirconium composite powder.
2. The white glaze according to claim 1, wherein the composite zirconium powder comprises 60 to 70 parts by mass of zirconia powder, 20 to 25 parts by mass of zirconium silicate powder, and 5 to 20 parts by mass of aluminum zirconium composite powder.
3. A digital white glaze ink, which is characterized by comprising 57-62 parts of the white glaze material according to any one of claims 1-2 and 55-67 parts of a first organic solvent in parts by mass.
4. The digital white glaze ink according to claim 3, further comprising, by mass, 4.9 to 8.9 parts of a first auxiliary agent and 0.3 to 1.0 part of a second auxiliary agent;
the first auxiliary agent is a dispersing agent; the second auxiliary agent comprises at least one of an anti-settling agent, an anti-diffusion agent, a leveling agent and a defoaming agent.
5. The preparation method of the digital white glaze ink is characterized by comprising the following steps:
mixing the raw materials according to the proportion of the raw materials in the white glaze material according to any one of claims 1-2, and then sequentially performing ball milling, iron removal, spray granulation and calcination to obtain a calcined glaze material;
Crushing and grinding the calcined glaze to obtain the white glaze;
and (3) mixing 57-62 parts of white glaze and 55-67 parts of first organic solvent by mass, and ball milling to obtain the digital white glaze ink.
6. The preparation method according to claim 5, wherein 57-62 parts of white glaze material, 55-67 parts of first organic solvent, 4.9-8.9 parts of first auxiliary agent and 0.3-1.0 part of second auxiliary agent are mixed and ball-milled according to parts by mass to obtain the digital white glaze ink.
7. A ceramic rock plate, which is characterized by comprising a green body layer, a digital glaze layer, a ground glaze decorative layer, a pattern decorative layer and a transparent protective glaze layer which are sequentially laminated, wherein the digital glaze layer is prepared from the white glaze material according to any one of claims 1-2, or is prepared from the digital white glaze ink according to any one of claims 3-4, or is prepared from the digital white glaze ink prepared by the preparation method according to any one of claims 5-6.
8. The ceramic rock plate of claim 7, wherein the digital glaze layer has a preset pattern texture, and is prepared from the digital white glaze ink and a digital transparent clear ink;
The digital transparent brightening ink comprises the following raw materials in parts by mass:
40 to 45 parts of bright glaze, 48 to 55.7 parts of second organic solvent, 4 to 7 parts of third auxiliary agent and 0.3 to 1.0 part of fourth auxiliary agent;
the raw materials of the bright glaze material comprise the following components in parts by mass:
60-65 parts of calcined wollastonite, 25-35 parts of calcined quartz, 0-5 parts of calcined kaolin and 3-5 parts of GN134 frit;
the GN134 frit comprises the following chemical components in parts by mass:
SiO 2 57.9 to 59 portions of Al 2 O 3 14.5 to 15.8 portions of Fe 2 O 3 0 to 0.1 part of TiO 2 0 to 0.1 part, 5.4 to 5.9 parts of CaO, 0.1 to 0.4 part of MgO and K 2 5.6 to 5.9 portions of O, na 2 13.4 to 14.5 parts of O, 0 to 0.1 part of ZnO, 0.15 to 0.2 part of BaO and 2.3 to 3.0 parts of discounting.
9. The ceramic rock plate of claim 7, wherein the transparent protective glaze layer is prepared from transparent protective glaze, and the transparent protective glaze comprises the following raw materials in parts by mass:
1 to 3 parts of calcined zinc oxide, 25 to 37 parts of potassium feldspar, 15 to 25 parts of A215 frit, 25 to 35 parts of B39 frit, 8 to 10 parts of kaolin, 1 to 3 parts of corundum and 5 to 10 parts of calcined kaolin;
the A215 frit comprises the following chemical components in parts by mass:
SiO 2 48-49 parts of Al 2 O 3 21.5 to 22.1 parts of Fe 2 O 3 0 to 0.1 part, 9.8 to 10 parts of CaO, 3.1 to 3.4 parts of MgO and K 2 O1.2-1.4 parts, na 2 3.6 to 4 parts of O, 1.3 to 1.5 parts of ZnO, 8.5 to 9.0 parts of BaO and 5.5 to 6.0 parts of discounting;
the B39 frit comprises the following chemical components in parts by mass:
SiO 2 39-40 parts of Al 2 O 3 14.8 to 15.5 portions of Fe 2 O 3 0 to 0.1 part, 1.0 to 1.2 parts of CaO, 2.0 to 2.5 parts of MgO and K 2 0.2 to 0.4 part of O, na 2 2.9 to 3.2 portions of O, 39 to 40 portions of BaO and 4.3 to 5.0 portions of discounting.
10. A method of making a ceramic rock laminate according to any one of claims 8 to 9, comprising the steps of:
providing a blank;
applying the digital white glaze ink and the digital transparent clear ink to the blank according to a preset pattern texture on the blank; forming a digital glaze layer with a preset pattern texture;
applying a primer on the digital glaze layer to form a primer decorative layer with preset pattern textures;
according to the preset pattern textures, applying different color inks to the primer decorative layer or applying different color inks and digital transparent bright ink to the primer decorative layer to form a pattern decorative layer;
and applying transparent protective glaze on the pattern decorative layer to form a transparent protective glaze layer, so as to obtain the ceramic rock plate with the surface provided with the preset pattern textures.
11. The method according to claim 10, wherein,
according to 40-120 g/m respectively 2 、25～75g/m 2 The digital white glaze ink and the digital transparent light ink are applied to the blank body to form a digital glaze layer with concave-convex textures in dot and line shapes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310744431.8A CN116693195A (en) | 2023-06-21 | 2023-06-21 | White glaze material, digital white glaze ink, ceramic rock plate and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310744431.8A CN116693195A (en) | 2023-06-21 | 2023-06-21 | White glaze material, digital white glaze ink, ceramic rock plate and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116693195A true CN116693195A (en) | 2023-09-05 |
Family
ID=87823688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310744431.8A Pending CN116693195A (en) | 2023-06-21 | 2023-06-21 | White glaze material, digital white glaze ink, ceramic rock plate and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116693195A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642317A (en) * | 2013-12-20 | 2014-03-19 | 佛山市三水区康立泰无机合成材料有限公司 | Low temperature ceramic inkjet ink |
| CN110746203A (en) * | 2019-10-24 | 2020-02-04 | 广东萨米特陶瓷有限公司 | Ceramic product with mold effect texture manufactured by digital process and manufacturing method thereof |
| CN111454615A (en) * | 2020-06-09 | 2020-07-28 | 佛山市扬子颜料有限公司 | Glaze ink for ink-jet printing and preparation method thereof |
| CN113860853A (en) * | 2021-09-26 | 2021-12-31 | 江西唯美陶瓷有限公司 | 3mm glazed full-polished ceramic rock plate with light transmission effect and manufacturing method thereof |
| CN113978171A (en) * | 2021-09-26 | 2022-01-28 | 蒙娜丽莎集团股份有限公司 | High-wear-resistance thin ceramic plate with three-dimensional die effect and preparation method thereof |
| CN114292023A (en) * | 2022-01-21 | 2022-04-08 | 山东国瓷康立泰新材料科技有限公司 | Digital glaze ink for all-digital glaze spraying and preparation method and application thereof |
| CN115872782A (en) * | 2022-12-23 | 2023-03-31 | 广东金牌陶瓷有限公司 | Terrazzo surface texture imitated ceramic rock plate and preparation method thereof |
-
2023
- 2023-06-21 CN CN202310744431.8A patent/CN116693195A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642317A (en) * | 2013-12-20 | 2014-03-19 | 佛山市三水区康立泰无机合成材料有限公司 | Low temperature ceramic inkjet ink |
| CN110746203A (en) * | 2019-10-24 | 2020-02-04 | 广东萨米特陶瓷有限公司 | Ceramic product with mold effect texture manufactured by digital process and manufacturing method thereof |
| CN111454615A (en) * | 2020-06-09 | 2020-07-28 | 佛山市扬子颜料有限公司 | Glaze ink for ink-jet printing and preparation method thereof |
| CN113860853A (en) * | 2021-09-26 | 2021-12-31 | 江西唯美陶瓷有限公司 | 3mm glazed full-polished ceramic rock plate with light transmission effect and manufacturing method thereof |
| CN113978171A (en) * | 2021-09-26 | 2022-01-28 | 蒙娜丽莎集团股份有限公司 | High-wear-resistance thin ceramic plate with three-dimensional die effect and preparation method thereof |
| CN114292023A (en) * | 2022-01-21 | 2022-04-08 | 山东国瓷康立泰新材料科技有限公司 | Digital glaze ink for all-digital glaze spraying and preparation method and application thereof |
| CN115872782A (en) * | 2022-12-23 | 2023-03-31 | 广东金牌陶瓷有限公司 | Terrazzo surface texture imitated ceramic rock plate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110759751B (en) | Preparation method of carved grain brick and prepared carved grain brick | |
| CN107685383B (en) | Production process of antique brick ceramic | |
| CN109455933B (en) | Crystalline glaze and ceramic tile prepared from same | |
| CN108715516B (en) | White glaze, whole body borderless ceramic tile containing white glaze and preparation method thereof | |
| CN109049300B (en) | Negative ion carved brick and preparation method thereof | |
| CN110436963B (en) | Dry grain glaze, dry grain ceramic tile with white suspended floccules and preparation method thereof | |
| CN113788620B (en) | Ceramic dry grain glaze and crystal diamond flashing ceramic tile and preparation method thereof | |
| CN101425352B (en) | Technical process for enhancing stability of NTC heat variable resistor | |
| CN114276121B (en) | Ceramic tile with starlight stereoscopic effect and preparation method thereof | |
| CN105198490B (en) | A kind of preparation method of ink-jet infiltration micro powder polished brick | |
| CN106554156B (en) | The primary preparation method for firing porcelain heap ornamental slab for paving the floor | |
| CN109455934B (en) | Ceramic tile with stream color decoration effect and preparation method thereof | |
| CN105753511B (en) | Longquan celadon glaze ink-jet ink and preparation method thereof | |
| CN110978221B (en) | Preparation process for solving polishing yellow edge problem of gray glazed brick | |
| CN101717274B (en) | Brown pigment for ceramic ink jet printing and preparation method thereof | |
| CN114292023B (en) | Digital glaze ink for full-digital glaze spraying and preparation method and application thereof | |
| CN111646786B (en) | Ceramic brick prepared by micro powder composite ink-jet positioning dry particle process and preparation method thereof | |
| CN110453112B (en) | High-performance composite material grinding head and preparation method thereof | |
| CN105907177A (en) | Tempered glass ink for ink-jet printing and preparation method thereof | |
| CN110104952A (en) | A kind of super abrasive Dali stone ceramic tile formula and processing technology | |
| CN113698174B (en) | Ceramic rock plate with uniform upper and lower grains on green body glaze surface and preparation method thereof | |
| CN110668846A (en) | Preparation process of matte wear-resistant dry particle brick | |
| CN102417373A (en) | Manufacture method of non-aqueous printing ink wet underglaze colour self-sharpening polishing ceramic glazed tile | |
| CN111704480A (en) | Method for manufacturing marbled ceramic tile | |
| CN110903080B (en) | Special blank large particle combined digital cloth ink-jet infiltration polished brick 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 |