CN116947536B - Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof - Google Patents
Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof Download PDFInfo
- Publication number
- CN116947536B CN116947536B CN202311198234.7A CN202311198234A CN116947536B CN 116947536 B CN116947536 B CN 116947536B CN 202311198234 A CN202311198234 A CN 202311198234A CN 116947536 B CN116947536 B CN 116947536B
- Authority
- CN
- China
- Prior art keywords
- glaze
- titanium
- raw material
- percent
- zirconium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010936 titanium Substances 0.000 title claims abstract description 149
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 147
- 239000002994 raw material Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 21
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 21
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010453 quartz Substances 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 17
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 13
- 238000000034 method 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
- 229910052656 albite Inorganic materials 0.000 claims abstract description 11
- 239000010456 wollastonite Substances 0.000 claims abstract description 11
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 11
- 239000005350 fused silica glass Substances 0.000 claims abstract description 9
- 239000010434 nepheline Substances 0.000 claims abstract description 7
- 229910052664 nepheline Inorganic materials 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 59
- 238000010304 firing Methods 0.000 claims description 38
- 229910052861 titanite Inorganic materials 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 20
- 239000004408 titanium dioxide Substances 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011449 brick Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 abstract description 23
- 239000012458 free base Substances 0.000 abstract description 14
- 239000001038 titanium pigment Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 37
- 235000010215 titanium dioxide Nutrition 0.000 description 20
- 230000007547 defect Effects 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 239000000292 calcium oxide Substances 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 206010027627 Miliaria Diseases 0.000 description 6
- 201000004169 miliaria rubra Diseases 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001448624 Miliaria Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
- Finishing Walls (AREA)
Abstract
The invention relates to the field of ceramic preparation, and in particular discloses a zirconium-free ground glaze and titanium raw material opacified glazed tile and a preparation method thereof. Wherein the zirconium-free ground coat comprises titanium raw material opacified glaze and titanium sphene seed crystal with the mass ratio of (0.005-0.02); the preparation raw materials of the titanium raw material opacifying glaze comprise the following components in percentage by weight: 10 to 30 percent of albite, 0 to 10 percent of potassium feldspar, 20 to 45 percent of quartz, 0 to 15 percent of fused quartz, 0 to 7 percent of calcined kaolin, 0 to 3 percent of calcined alumina, 15 to 30 percent of wollastonite, 0 to 10 percent of calcite, 0 to 10 percent of water-washed kaolin, 0 to 10 percent of nepheline and 5 to 10 percent of titanium pigment. The zirconium-free base glaze has high whiteness and high sintering temperature, and can be suitable for the current rapid sintering process.
Description
Technical Field
The invention relates to the field of ceramic preparation, in particular to a zirconium-free ground glaze and titanium raw material opacified glazed tile and a preparation method thereof.
Background
The whiteness of the ceramic body is usually not high, so that a layer of base glaze with higher whiteness needs to be applied on the surface of the ceramic body for covering, and then decoration work such as ink-jet printing and the like is carried out. In order to increase the whiteness of the base glaze, besides the raw materials with low content of coloring elements (such as iron and manganese), zirconium silicate with high refractive index is generally required to be added to enhance the scattering of visible light, so that the whiteness is increased. Zirconium silicate is an important common mineral raw material, and the price rises rapidly with the increasing use of the zirconium silicate in recent years, so that the cost of ceramic tiles is continuously increased.
In order to reduce the production cost, titanium-based opacifying glaze is gradually adopted as a ground glaze to replace zirconium silicate opacifying glaze nowadays, for example, patent applications with publication numbers of CN115304277A and CN111499202A disclose related technical schemes, but the technical schemes disclosed in the patent applications all have different problems in practical application.
For example, patent application publication No. CN115304277A discloses that titanium frit, potassium feldspar, sodium feldspar, wollastonite, quartz, kaolin and other raw materials are adopted to prepare the titanium white opacifying primer, but the sintering temperature of the titanium white opacifying primer is lower than 1100-1150 ℃, and the sintering temperature of the prior high-strength high-aluminum-content ceramic rock plate blank is usually higher than 1150 ℃, so that the adaptability is not wide enough.
While patent application publication No. CN111499202A discloses the preparation of high solar reflectance opacified titanium white glaze using titanium frit, titanium dioxide, calcite, potash feldspar, quartz, sintered clay, kaolin, and the like. The glaze material of the technical proposal has more components containing calcium oxide and aluminum oxide, which is easy to lead the titanium glaze with high content of aluminum oxide and calcium oxide to form anorthite, the titanium oxide component is separated out in rutile crystal phase, and in the high temperature firing process, the titanium element can be formed from Ti 4+ Ti changing valence into rutile 3+ Resulting in yellowing of the glaze.
In addition, the titanium frit used in the patent application has the defects of high energy consumption (the sintering temperature is up to 1400-1600 ℃), large dust during mixing, high construction and maintenance cost of a frit furnace, large raw material waste during transfer, incapability of being interrupted in the production process and the like. When the titanium frit consumption in the titanium opaque glaze is higher, the titanium glaze firing temperature is low, the application temperature range is narrow, and the expansion coefficient of the glaze is difficult to adjust due to the too high titanium frit consumption, so that the titanium opaque glaze is difficult to adapt to blanks of different types and has a faster firing period. If the expansion coefficients of the glaze and the green body are large, cracks are easy to appear on the glaze surface in the rapid firing process, and meanwhile, the brick type of the ceramic brick does not reach the standard.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a zirconium-free ground glaze, titanium raw material opacified glazed tile and a preparation method thereof, and aims to solve the technical problems that the sintering temperature range of titanium opacified glaze is low and whiteness does not reach the standard in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a zirconium-free ground coat, which comprises titanium raw material opacifying glaze and titanium sphene seed crystal with the mass ratio of 1 (0.005-0.02); the preparation raw materials of the titanium raw material opacifying glaze comprise the following components in percentage by weight: 10 to 30 percent of albite, 0 to 10 percent of potassium feldspar, 20 to 45 percent of quartz, 0 to 15 percent of fused quartz, 0 to 7 percent of calcined kaolin, 0 to 3 percent of calcined alumina, 15 to 30 percent of wollastonite, 0 to 10 percent of calcite, 0 to 10 percent of water-washed kaolin, 0 to 10 percent of nepheline and 5 to 10 percent of titanium pigment.
The zirconium-free base glaze, wherein the grain diameter D50 of the titanite seed crystal is 500 nm-2000 nm.
The zirconium-free base glaze is characterized in that the titanium dioxide is rutile titanium dioxide.
The zirconium-free ground glaze comprises TiO in the chemical components of the titanium raw material opacifying glaze 2 The mass content of (2) is 5-10%.
The zirconium-free ground glaze comprises the following chemical components of the titanium raw material opacifying glaze, wherein the chemical components comprise Al 2 O 3 The mass content of (2) is 5-12%.
The zirconium-free base glaze comprises a base glaze layer, wherein,the titanium raw material opacifying glaze comprises the following chemical components in percentage by weight: 60% -75% of SiO 2 5 to 12 percent of Al 2 O 3 5 to 10 percent of TiO 2 0 to 2 percent of K 2 O, 1-4% Na 2 O, 6-20% of CaO, 0-1% of MgO, 0-1% of BaO, 0-1% of SrO, 0-1% of ZnO and 0-1% of P 2 O 5 0 to 0.2 percent of Fe 2 O 3 ZrO 0-1% 2 0 to 6 percent of burn-out.
The invention provides a titanium raw material opacified glazed tile, which comprises a green brick layer, a titanium base ground coat layer, a pattern layer and a surface glaze layer which are sequentially arranged; the titanium base primer layer is prepared by firing the zirconium-free primer.
The third aspect of the invention provides a method for preparing a ceramic tile for preparing the opacified glazed tile of titanium raw material as described above, comprising the steps of:
spraying the zirconium-free primer on the green brick layer to form a titanium-based primer layer; printing a pattern on the titanium base primer layer by ink jet to form a pattern layer; spraying full polished glaze on the pattern layer to form a surface glaze layer; firing, wherein the firing temperature is 1150-1250 ℃ and the firing time is 30-80 min.
The preparation method of the ceramic tile, wherein the grain size D50 of the glaze slip of the zirconium-free ground coat is 5-8 micrometers, and the specific gravity is 1.7-1.9 g/cm 3 The flow rate is 30-50 s, the glazing quantity is 400-600 g/m 2 。
The preparation method of the ceramic tile comprises the following steps of: firstly ball milling to make the grain diameter D50 of the glaze slurry of the titanium raw material opacified glaze reach 5-8 microns, and then adding titanium sphene seed crystal for mixing.
Advantageous effects
The invention provides a zirconium-free ground glaze, which adopts titanium raw material opacifying glaze and titanium sphene crystal seeds to match, and the titanium raw material opacifying glaze is promoted to separate out more fine titanium sphene crystals through the titanium sphene crystal seeds in the sintering process. Besides high whiteness, the zirconium-free base glaze has the advantages of wider sintering temperature and higher sintering temperature, and the expansion coefficient can be flexibly adjusted to match different blanks, so that the glaze can meet the sintering state, and the defects of prickly heat, pinholes and the like are overcome.
The invention provides a titanium raw material opacified glazed tile, which adopts the zirconium-free primer, has strong adaptability, is suitable for products with different colors, and can flexibly adjust the gray level of an ink-jet printing pattern. The titanium raw material opacified glazed tile has clear patterns and strong contrast.
The third aspect of the invention provides a preparation method of ceramic tiles, which is used for preparing the titanium raw material opacified glazed tile, and the preparation method has high sintering temperature, can be suitable for a rapid sintering roller kiln in the prior art, does not need to increase production equipment of enterprises, and has wide applicability.
Drawings
FIG. 1 is an XRD analysis chart of the titanium-based primer layer in example 1.
FIG. 2 is a physical diagram of example 1.
FIG. 3 is a physical diagram of comparative example 2.
FIG. 4 is a physical diagram of comparative example 3.
FIG. 5 is a physical diagram of comparative example 6.
FIG. 6 is a physical diagram of comparative example 8.
Detailed Description
The invention provides a zirconium-free ground glaze, titanium raw material opacified glazed tile and a preparation method thereof, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The first aspect of the invention provides a zirconium-free primer, which comprises titanium raw material opacified glaze and titanium sphene seed crystal with the mass ratio of 1 (0.005-0.02); the preparation raw materials of the titanium raw material opacifying glaze comprise the following components in percentage by weight: 10 to 30 percent of albite, 0 to 10 percent of potassium feldspar, 20 to 45 percent of quartz, 0 to 15 percent of fused quartz, 0 to 7 percent of calcined kaolin, 0 to 3 percent of calcined alumina, 15 to 30 percent of wollastonite, 0 to 10 percent of calcite, 0 to 10 percent of water-washed kaolin, 0 to 10 percent of nepheline and 5 to 10 percent of titanium pigment.
The zirconium-free base glaze forms a high-silicon system by using high-temperature resistant quartz and fused quartz raw materials, and solves the problem of yellowing caused by high aluminum content in the prior art. The expansion coefficient of the zirconium-free base glaze can be flexibly adjusted according to the expansion coefficient of a blank body, and the zirconium-free base glaze can adapt to brick type changes caused by a sintering system of more rapid sintering.
The titanite seed crystal is used as a nucleating agent to promote the precipitation of titanite crystals in the titanium raw opaque glaze in the firing process, so that the whiteness of the glaze layer is improved. If the adding amount of the titanite seed crystal is less than 0.5% of the using amount of the titanite raw material opacified glaze, the titanite crystal is not easy to be generated by the glaze under the condition of quick firing, and the whiteness of the glaze is poor and the glaze is yellow; if the adding amount of the titanite seed crystal is more than 2% of the amount of the titanite raw opaque glaze, the firing temperature of the glaze can be reduced, and prickly heat can appear on the glaze surface.
Preferably, the particle diameter D50 of the titanite seed crystal is 500 nm-2000 nm. The particle size of the titanite seed crystal is not less than 500nm, and the titanite seed crystal is easy to decompose at high temperature to form a glass phase, can not promote the crystallization of titanite in the titanite raw glaze, has the particle size of more than 2 microns, and can not play a nucleation role in the glaze firing process.
Preferably, the titanium dioxide is rutile titanium dioxide, and compared with anatase titanium dioxide, the rutile titanium dioxide is easier to react with other components to generate titanium sphene crystal phase, and the whiteness of the glaze after being sintered is higher.
Preferably, in the chemical components of the titanium raw material opacifying glaze, tiO 2 The mass content of (2) is 5-10%. When TiO 2 When the mass content of the titanium sphene is lower than 5%, the formed titanium sphene has low content, and correspondingly, the whiteness of the glaze layer is low; when TiO 2 When the mass content of (C) is more than 10%, the firing temperature of the glaze becomes high, and TiO in the glaze becomes high 2 The components cannot fully participate in the reaction for generating the titanite in the sintering process, and finally precipitate in a rutile crystal phase in the glaze layer, so that the glaze surface is yellow, and the whiteness is low.
Preferably, in the chemical components of the titanium raw material opacifying glaze, al 2 O 3 The mass content of (2) is 5-12%. Al of titanium raw material opacified glaze 2 O 3 The content is low, and the yellowing of the glaze layer can be effectively reduced.
Preferably, the chemical components of the titanium raw material opacifying glaze comprise the following components in percentage by weight: 60% -75% of SiO 2 5 to 12 percent of Al 2 O 3 5 to 10 percent of TiO 2 0 to 2 percent of K 2 O, 1-4% Na 2 O, 6-20% of CaO, 0-1% of MgO, 0-1% of BaO, 0-1% of SrO, 0-1% of ZnO and 0-1% of P 2 O 5 0 to 0.2 percent of Fe 2 O 3 ZrO 0-1% 2 0 to 6 percent of burn-out.
Specifically, the preparation method of the titanite seed crystal comprises the following steps: firstly, according to the theoretical ratio of each chemical component in titanite crystal, caO to TiO 2 :SiO 2 The molar ratio of titanium dioxide, quartz and calcite is 1:1:1, the weight ratio of titanium dioxide, quartz and calcite raw materials is calculated, then the titanium dioxide, quartz and calcite raw materials are uniformly mixed, the temperature is kept at 1300 ℃ for 1h, the titanium sphene crystals are generated through solid phase reaction, and finally the titanium sphene crystals are ground into corresponding granularity to form titanium sphene seed crystals.
The invention provides a titanium raw material opacified glazed tile, which comprises a green brick layer, a titanium base ground coat layer, a pattern layer and a surface glaze layer which are sequentially arranged; the titanium base primer layer is prepared by firing the zirconium-free primer.
The third aspect of the invention provides a method for preparing a ceramic tile, which is used for the titanium raw material opacified glazed tile, and comprises the following steps:
spraying the zirconium-free primer on the green brick layer to form a titanium-based primer layer;
printing a pattern on the titanium base primer layer by ink jet to form a pattern layer;
spraying full polished glaze on the pattern layer to form a surface glaze layer;
firing, wherein the firing temperature is 1150-1250 ℃ and the firing time is 30-80 min.
Preferably, the grain diameter D50 of the glaze slip of the zirconium-free ground coat is 5-8 micrometers, and the specific gravity is 1.7-1.9 g/cm 3 The flow rate is 30-50 s, the glazing quantity is 400-600 g/m 2 。
Specifically, the preparation method of the zirconium-free base glaze comprises the following steps: firstly ball milling to make the grain diameter D50 of the glaze slurry of the titanium raw material opacified glaze reach 5-8 microns, and then adding titanium sphene seed crystal for mixing.
The invention is further illustrated by the following examples and comparative examples.
Example 1
The preparation method of the titanium raw material opacified glazed tile comprises the following steps:
s001, preparing titanium raw material opacifying glaze: proportioning according to a formula, and then ball-milling the prepared raw materials into glaze slurry; adding methyl cellulose, sodium tripolyphosphate, a dispersing agent and water for ball milling together during ball milling, wherein the addition amounts of the methyl cellulose, the sodium tripolyphosphate, the dispersing agent and the water are respectively equivalent to 0.1%, 0.3%, 0.2% and 38% of the weight of the titanium raw material opacified glaze, and the raw material particle size D50 of the glaze slurry is controlled to be 5-8 microns;
the formula of the titanium raw material opacifying glaze comprises the following components in percentage by weight: 18% of albite, 6% of potassium feldspar, 25% of quartz, 7% of fused quartz, 3% of calcined kaolin, 25% of wollastonite, 2% of calcite, 6% of water-washed kaolin and 8% of titanium dioxide (rutile crystal phase); the corresponding chemical composition is as follows: 66.35% SiO 2 7.57% Al 2 O 3 8.08% TiO 2 0.69% of K 2 O, 1.84% Na 2 O, 13.01% CaO, 0.16% MgO, 0.01% P 2 O 5 0.16% Fe 2 O 3 2.13% burn off;
s002, adding titanium trabecite seed crystals into the titanium raw material opacified glaze slip, and uniformly stirring to obtain zirconium-free ground glaze; the mass ratio of the titanium raw material opacifying glaze to the titanium sphene seed crystal is 1:0.01, and the particle size D50 of the titanium sphene seed crystal is 1260nm;
s003, spraying zirconium-free primer on the green body layer to form a titanium-series primer layer, wherein the glazing amount of the zirconium-free primer is 450g/m 2 ；
S004, carrying out ink-jet printing on the titanium base primer layer to form a pattern layer;
s005, spraying full polished glaze on the pattern layer to form an overglaze layer;
s006, sintering, wherein the sintering temperature is 1200-1215 ℃ and the sintering time is 38min.
Example 2
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that: in the zirconium-free ground coat, the mass ratio of the titanium raw material opacifying coat to the titanium sphene seed crystal is 1:0.018.
Example 3
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that: in the zirconium-free ground coat, the mass ratio of the titanium raw material opacifying coat to the titanium sphene seed crystal is 1:0.006.
Example 4
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that: in the zirconium-free ground coat, the grain diameter D50 of the titanite seed crystal is 1850nm.
Example 5
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that: in the zirconium-free ground coat, the grain diameter D50 of the titanite seed crystal is 540nm.
Example 6
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
in the zirconium-free ground glaze, the titanium raw material opacified glaze has different formulas and different sintering temperatures;
in the embodiment, the formula of the titanium raw material opacifying glaze comprises the following components in percentage by weight: 18% of albite, 6% of potassium feldspar, 30% of quartz, 12% of fused quartz, 20% of wollastonite, 6% of water-washed kaolin and 8% of titanium dioxide (rutile crystal phase); the corresponding chemical composition is as follows: 72.18% SiO 2 6.23% Al 2 O 3 8.05% TiO 2 0.69% of K 2 O, 1.84% Na 2 O, 9.53% CaO, 0.13% MgO, 0.01% P 2 O 5 0.14% Fe 2 O 3 1.20% burn off;
the firing temperature of the titanium raw material opacified glazed tile of the embodiment is 1230-1240 ℃ and the firing time is 38 minutes.
Example 7
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
in the zirconium-free ground glaze, the titanium raw material opacified glaze has different formulas and different sintering temperatures;
in the embodiment, the formula of the titanium raw material opacifying glaze comprises the following components in percentage by weight: 22% of albite, 9% of potassium feldspar, 22% of quartz, 3% of fused quartz, 22% of wollastonite, 8% of calcite, 6% of water-washed kaolin and 8% of titanium dioxide (rutile crystal phase); the corresponding chemical composition is as follows: 61.40% SiO 2 7.31% Al 2 O 3 TiO 8.06% 2 0.97% of K 2 O, 2.28% Na 2 O, 14.93% CaO, 0.16% MgO, 0.01% BaO, 0.01% P 2 O 5 0.15% Fe 2 O 3 Burn-out of 4.72%;
the firing temperature of the titanium raw material opacified glazed tile of the embodiment is 1160-1170 ℃ and the firing time is 38 minutes.
Example 8
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
the firing time of the green body layer component is different from that of the glazed tile, the firing time of the embodiment is 32min, the expansion coefficient of the green body layer of the embodiment is larger under shorter firing time, and the average expansion coefficient is 8.03X10 at 30-400 DEG C -6 Per DEG C (the expansion coefficient of the blank of example 1 is 7.75X10) -6 /℃)；
In the zirconium-free ground glaze, the titanium raw material opacifying glaze has different formulas;
according to the embodiment, nepheline is introduced, the quartz content is improved, and the expansion coefficient of the zirconium-free ground coat is increased;
the formula of the titanium raw material opacifying glaze comprises the following components in percentage by weight: 12% of albite, 4% of potassium feldspar, 8% of nepheline, 35% of quartz, 1% of calcined kaolin, 25% of wollastonite, 1% of calcite, 6% of water-washed kaolin and 8% of titanium dioxide (rutile crystal phase); the corresponding chemical composition is as follows: 65.66% SiO 2 7.99% Al 2 O 3 TiO 8.06% 2 0.9% of K 2 O, 2.24% Na 2 O, 12.82% CaO, 0.17% MgO, 0.01% P 2 O 5 0.16% Fe 2 O 3 1.99% burn-out.
Comparative example 1
The process for preparing the glazed tile is different from that of example 1 in that:
the primer adopts zirconium-containing primer to replace zirconium-free primer (titanium-containing primer), and the formula of the zirconium primer is as follows in percentage by weight: 32% of albite, 10% of potassium feldspar, 5% of nepheline, 12% of quartz, 8% of calcined kaolin, 15% of calcined white alumina, 2% of calcined talcum, 6% of water-washed kaolin and 10% of zirconium silicate; the corresponding chemical composition is as follows: 56.23% SiO 2 29.38% of Al 2 O 3 6.51% ZrO 2 0.14% TiO 2 1.31% of K 2 O, 3.79% Na 2 O, 0.50% CaO, 0.72% MgO, 0.01% BaO, 0.05% P 2 O 5 0.18% Fe 2 O 3 1.18% burn-out.
Comparative example 2
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
in the zirconium-free ground coat, the mass ratio of the titanium raw material opacifying coat to the titanium sphene seed crystal is 1:0.004.
Comparative example 3
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
in the zirconium-free ground coat, the mass ratio of the titanium raw material opacifying coat to the titanium sphene seed crystal is 1:0.025.
Comparative example 4
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
in the zirconium-free ground coat, the grain diameter D50 of the titanite seed crystal is 2530nm.
Comparative example 5
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
in the zirconium-free ground glaze, anatase type titanium dioxide is selected.
Comparative example 6
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
formula of titanium raw material opacifying glazeDifferent, the dosage of titanium pigment is increased in the comparative example, and the chemical composition corresponding to the titanium raw material opacifying glaze is as follows according to weight percentage: 64.42% SiO 2 7.35% Al 2 O 3 10.76% TiO 2 0.67% of K 2 O, 1.78% Na 2 O, 12.63% CaO, 0.16% MgO, 0.01% P 2 O 5 0.16% Fe 2 O 3 2.06% burn-out.
Comparative example 7
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
the titanium raw material opacifying glaze has different formulas, the consumption of titanium pigment is reduced in the comparative example, and the corresponding chemical composition of the titanium raw material opacifying glaze is as follows according to weight percentage: 69.12% SiO 2 7.89% Al 2 O 3 4.25% TiO 2 0.72% of K 2 O, 1.92% Na 2 O, 13.55% CaO, 0.17% MgO, 0.01% P 2 O 5 0.17% Fe 2 O 3 2.20% burn-out.
Comparative example 8
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
the titanium raw material opacifying glaze has different formulas, and the titanium raw material opacifying glaze is prepared from the following raw materials in percentage by weight: 18% of albite, 6% of potassium feldspar, 28% of quartz, 11% of fused quartz, 25% of wollastonite, 2% of calcite, 2% of water-washed kaolin and 8% of titanium dioxide (rutile crystal phase); the corresponding chemical composition is as follows: 69.88% SiO 2 4.69% Al 2 O 3 8.04% TiO 2 0.68% of K 2 O, 1.84% Na 2 O, 13.00% CaO, 0.16% MgO, 0.01% P 2 O 5 0.12% Fe 2 O 3 1.58% burn-out.
Comparative example 9
The preparation method of the titanium raw material opacified glazed tile is different from that of the example 1 in that:
the titanium raw material opacifying glaze has different formulas, and the titanium raw material opacifying glaze comprises the following components in percentage by weightThe preparation raw materials are as follows: 18% of albite, 6% of potassium feldspar, 25% of quartz, 7% of calcined kaolin, 3% of alumina, 25% of wollastonite, 2% of calcite, 6% of water-washed kaolin and 8% of titanium dioxide (rutile crystal phase); the corresponding chemical composition is as follows: 61.49% SiO 2 12.38% of Al 2 O 3 8.12% TiO 2 0.69% of K 2 O, 1.83% Na 2 O, 13.01% CaO, 0.16% MgO, 0.01% P 2 O 5 0.18% Fe 2 O 3 2.13% burn-out.
The properties of the glazed tiles of the above examples and comparative examples were examined.
Wherein, blue light whiteness instrument is adopted to detect whiteness;
detecting glossiness by a photometer;
detecting the L/a/b value by using a Lab color difference meter;
judging the sintering vitrification degree by checking the ink absorption degree of the glaze after the ink drops are cleaned;
the quality of the glazed surface of the product after the full polished glaze is sprayed is checked visually, and the defects of color change, pinhole prickly heat and the like of the glazed surface are checked.
According to the application condition of the opacifying primer on products with different colors, the whiteness of the opacifying primer is determined to be more than 70, the b value is less than 2, and the effect of the glossiness is best between 3.5 and 4.5.
The detection results of each example and comparative example are as follows:
| ground coat sample | Whiteness degree | L*/a*/b* | Gloss level | Quality of glaze |
| Example 1 | 73.6 | 90.84/-1.12/1.24 | 4 | Normal glaze |
| Example 2 | 72.3 | 90.23/-1.16/1.75 | 4.5 | Normal glaze |
| Example 3 | 71.8 | 89.82/-1.08/1.72 | 4 | Normal glaze |
| Example 4 | 72.2 | 90.12/-1.13/1.85 | 4 | Normal glaze |
| Example 5 | 71.5 | 89.56/-1.16/1.86 | 4.5 | Normal glaze |
| Example 6 | 71.2 | 89.53/-0.93/1.16 | 4.5 | Normal glaze |
| Example 7 | 72.4 | 90.41/-0.97/1.04 | 4 | Normal glaze |
| Example 8 | 73.1 | 90.53/-0.92/0.98 | 4 | Normal glaze |
| Comparative example 1 | 70.3 | 89.87/-0.61/0.65 | 4 | Normal glaze |
| Comparative example 2 | 65.9 | 86.71/-0.73/2.83 | 3 | The ground glaze is not sintered, and the glaze surface is yellow and dark and has the defect of crater pinholes |
| Comparative example 3 | 69.3 | 88.67/-0.23/2.77 | 5.5 | Yellowing of glaze, pinholes on glaze and prickly heat |
| Comparative example 4 | 68.2 | 88.12/-1.53/2.65 | 3 | The ground glaze is not sintered, and the glaze surface is yellow and has the defect of crater pinholes |
| Comparative example 5 | 60.3 | 84.52/-0.69/4.57 | 3.5 | The ground glaze absorbs ink, has insufficient sintering, yellow and dark glaze surface and has the defect of small amount of crater pinholes |
| Comparative example 6 | 71.7 | 90.24/-0.95/3.87 | 3 | The ground glaze turns yellow and is not sintered, and the glaze has the defects of crater pinholes |
| Comparative example 7 | 68.7 | 88.58/-0.95/1.28 | 4.5 | The whiteness of the glaze is low, and the ground color of the product is dark |
| Comparative example 8 | 73.1 | 90.26/-1.17/1.64 | 5.5 | The glaze has pinholes and prickly heat with many defects |
| Comparative example 9 | 70.2 | 89.52/-1.36/4.18 | 3.5 | The ground glaze is not sintered, the glaze surface is yellow, and the defect of a small number of crater pinholes exists |
From the above results, the whiteness of the glazed tiles of examples 1 to 8 are all greater than 70, the b values are all less than 2, and the glossiness is between 4 and 4.5. FIG. 1 is an XRD analysis chart of the titanium-based primer layer in example 1, and it can be seen from the chart that the titanium sphene crystal is mainly formed in the titanium-based primer layer. Examples 2-5 used different amounts of titanium sphene seed crystals and seed crystals of different particle sizes, examples 6 and 7 used different firing temperatures, respectively, and example 8 was a tuned large expansion coefficient base coat to accommodate the brick type requirements of ceramic bricks under firing regime with faster firing rate (example 8 had an average expansion coefficient of 8.37X10 at 30-400 ℃ C.) -6 Per DEG C, whereas example 1 is 7.55X10 -6 I c), examples 8 and 1 show that the coefficient of expansion of the zirconium-free base coat of the present invention can be flexibly adjusted as needed,
as can be seen from the results of FIG. 2 and the above, the quality of the glaze surface after firing in the above embodiment is normal, the glaze surface is defect-free, and the physical and chemical properties of the product reach the national standard, which indicates that the firing temperature range of the zirconium-free base glaze of the invention is wide, the firing is stable, and the controllability is high; after the expansion coefficient of the zirconium-free base glaze is adjusted, the zirconium-free base glaze can adapt to different blanks and different firing times, and has the advantages of no firing defect and good stability. Compared with the comparative example 1 using the zirconium-containing primer, the performance of the glazed tile using the zirconium-free primer of the present invention can also reach the same level, while compared with the preparation cost, the zirconium-free primer of the present invention is lower than the zirconium-containing primer.
In the titanium raw material opacified glazed tile of comparative example 2, the titanium sphene seed crystal was added in an amount smaller than the protection range of the present invention, and from the detection result, the whiteness of the glazed tile was only 65.9, the b-value reached 2.83, the glazed tile was yellow and darkened, and there were crater pinhole defects or shrinkage defects (as shown in fig. 3). This is because the amount of the titanite seed crystal added is insufficient, resulting in insufficient formation of titanite crystals.
In the titanium raw material opacified glazed tile of comparative example 3, the addition amount of the titanium sphene seed crystal was larger than the protection range of the present invention, and from the detection result, the whiteness of the glazed tile was not higher than 70, the glazed surface was also yellowish, and the glazed surface had defects of pinholes and prickly heat (as shown in fig. 4). This is caused by the fact that the addition amount of the titanite seed crystal is too large and the firing temperature of the glaze is lowered.
In the titanium raw material opacified glazed tile of comparative example 4, the grain diameter D50 of the titanium sphene seed crystal is larger than the protection range of the invention, and from the detection result, the whiteness of the glazed tile cannot reach more than 70, no zirconium ground glaze is not sintered, the glazed surface is yellow, and the glazed surface has the defect of a crater pinhole. This is because the titanite seed crystal particle size is too large to function well as a nucleating agent.
In the titanium raw material opacified glazed tile of comparative example 5, anatase type titanium dioxide is selected as titanium dioxide in zirconium-free base coat, the whiteness of the glaze is very low and only 60.3 from the detection result, and the defects of ink absorption of the base coat, huang Faan (b is 4.18) of the glaze and a small amount of craters on the glaze occur. The anatase type titanium dioxide cannot play a role in improving the whiteness of the zirconium-free ground coat.
Compared with example 1, the titanium raw material opacified glazed tile of comparative example 6 has the advantages that the titanium pigment consumption is increased, and the detection result shows that the whiteness can reach more than 70, but no defects of yellowing (b is 3.87) of zirconium-free ground enamel, unsintered and crater pinholes on the glaze surface exist. As shown in FIG. 5, the titanium raw material opacified glazed tile of comparative example 6 was polished, and the glazed surface had many pinholes, which was a defective product. The reason for this is TiO 2 Too high a content of (c) may cause the firing temperature of the glaze to become high, which is unfavorable for sintering the glaze.
Compared with the example 1, the titanium raw material opacified glazed tile of the comparative example 7 has the advantages that the titanium pigment consumption is reduced, the whiteness of the titanium raw material opacified glazed tile is less than 70 from the detection result, and the base color of the product is darker. The method shows that the whiteness of the titanium raw material opacified glazed tile can be improved by properly increasing the consumption of the titanium dioxide.
In the titanium raw material opacified glazed tile of comparative example 8, al was reduced as compared with example 1 2 O 3 From the detection result, the whiteness of the titanium raw material opacified glazed tile can reach more than 70, but the glaze has more pinholes and miliaria, and the quality of the glaze is not too good. As shown in FIG. 6, after the gray pattern is printed on the zirconium-free ground glaze in an inkjet manner, a lot of white spots are obviously present on the glaze after the full-polished ceramic tile which is fired by the glazed tile preparation process is polished.
In the titanium raw material opacified glazed tile of comparative example 9, al was increased as compared with example 1 2 O 3 From the detection result, although the whiteness of the titanium raw material opacified glazed tile can reach more than 70, the ground glaze is not sintered, and the glaze has the defects of yellowing (b is 4.18) and crater pinholes.
It will be understood that equivalents and modifications will occur to those skilled in the art in light of the present invention and their spirit, and all such modifications and substitutions are intended to be included within the scope of the present invention as defined in the following claims.
Claims (5)
1. The zirconium-free ground glaze is characterized by comprising titanium raw material opacifying glaze and titanium sphene seed crystal with the mass ratio of 1 (0.005-0.02); the titanium raw material opacifying glaze is prepared from the following raw materials in percentage by weight: 10-30% of albite, 0-10% of potassium feldspar, 20-45% of quartz, 0-15% of fused quartz, 0-7% of calcined kaolin, 0-3% of calcined alumina, 15-30% of wollastonite, 0-10% of calcite, 0-10% of water-washed kaolin, 0-10% of nepheline and 5-10% of titanium dioxide, wherein the sum of the components of the raw materials is 100%; the titanium dioxide is rutile titanium dioxide; the particle size D50 of the titanite seed crystal is 500 nm-2000 nm; the titanium raw material opacifying glaze comprises the following chemical components: 60% -75% of SiO 2 5 to 12 percent of Al 2 O 3 5 to 10 percent of TiO 2 0 to 2 percent of K 2 O, 1-4% Na 2 O, 6-20% of CaO, 0-1% of MgO, 0-1% of BaO, 0-1% of SrO, 0-1% of ZnO and 0-1% of P 2 O 5 、0～0.2% Fe 2 O 3 ZrO 0-1% 2 0-6% of burning loss, and the sum of the chemical components is 100%.
2. The titanium raw material opacified glazed tile is characterized by comprising a green brick layer, a titanium base ground coat layer, a pattern layer and a ground coat layer which are sequentially arranged; the titanium base primer layer is obtained by firing the zirconium-free primer according to claim 1.
3. A method for preparing a ceramic tile, characterized in that it is used for preparing the titanium raw material opacified glazed tile as defined in claim 2, comprising the steps of:
spraying the zirconium-free primer according to claim 1 on the green brick layer to form a titanium-based primer layer;
printing a pattern on the titanium base primer layer by ink jet to form a pattern layer;
spraying full polished glaze on the pattern layer to form a surface glaze layer;
firing, wherein the firing temperature is 1150-1250 ℃ and the firing time is 30-80 min.
4. The method for producing ceramic tiles according to claim 3, wherein the zirconium-free under glaze has a glaze slip particle diameter D50 of 5 to 8 μm and a specific gravity of 1.7 to 1.9g/cm 3 The flow rate is 30-50 s, the glazing quantity is 400-600 g/m 2 。
5. The method of producing ceramic tiles of claim 4, wherein the method of producing zirconium-free primer is as follows: firstly ball milling to make the grain diameter D50 of the glaze slurry of the titanium raw material opacified glaze reach 5-8 microns, and then adding titanium sphene seed crystal for mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311198234.7A CN116947536B (en) | 2023-09-18 | 2023-09-18 | Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311198234.7A CN116947536B (en) | 2023-09-18 | 2023-09-18 | Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116947536A CN116947536A (en) | 2023-10-27 |
| CN116947536B true CN116947536B (en) | 2024-02-23 |
Family
ID=88458654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311198234.7A Active CN116947536B (en) | 2023-09-18 | 2023-09-18 | Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116947536B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045963A (en) * | 1989-03-28 | 1990-10-10 | 湖南省陶瓷研究所 | Aspidelite type compound opacifier and manufacture method thereof |
| CN102775191A (en) * | 2012-07-06 | 2012-11-14 | 佛山市南海万兴材料科技有限公司 | Seed crystal introduced chromium tin pink ceramic pigment and preparation method thereof |
| CN102775192A (en) * | 2012-07-06 | 2012-11-14 | 佛山市南海万兴材料科技有限公司 | Seed crystal introduced agate red ceramic pigment and preparation method thereof |
| CN103145447A (en) * | 2013-03-29 | 2013-06-12 | 佛山市南海万兴材料科技有限公司 | Blue inkjet ceramic pigment and preparation method thereof |
| CN103145452A (en) * | 2013-03-29 | 2013-06-12 | 佛山市南海万兴材料科技有限公司 | Red colorant for ceramic ink and preparation method thereof |
| CN104909570A (en) * | 2015-07-15 | 2015-09-16 | 中国地质大学（北京） | Opacifier, preparation method thereof and ceramic glaze with the opacifier |
| CN111499202A (en) * | 2020-06-30 | 2020-08-07 | 蒙娜丽莎集团股份有限公司 | Opaque glaze with high solar light reflectivity and preparation method thereof |
| CN113716606A (en) * | 2021-08-25 | 2021-11-30 | 中国科学院上海硅酸盐研究所 | PLZT micron seed crystal, preparation method thereof and application thereof in inducing ceramic growth |
| CN114249534A (en) * | 2021-12-22 | 2022-03-29 | 佛山欧神诺陶瓷有限公司 | Ceramic glaze material with infrared reflection, light glazed external tile and preparation method thereof |
| CN115974411A (en) * | 2023-02-02 | 2023-04-18 | 重庆唯美陶瓷有限公司 | Ceramic tile base glaze, ceramic tile and preparation method thereof |
-
2023
- 2023-09-18 CN CN202311198234.7A patent/CN116947536B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045963A (en) * | 1989-03-28 | 1990-10-10 | 湖南省陶瓷研究所 | Aspidelite type compound opacifier and manufacture method thereof |
| CN102775191A (en) * | 2012-07-06 | 2012-11-14 | 佛山市南海万兴材料科技有限公司 | Seed crystal introduced chromium tin pink ceramic pigment and preparation method thereof |
| CN102775192A (en) * | 2012-07-06 | 2012-11-14 | 佛山市南海万兴材料科技有限公司 | Seed crystal introduced agate red ceramic pigment and preparation method thereof |
| CN103145447A (en) * | 2013-03-29 | 2013-06-12 | 佛山市南海万兴材料科技有限公司 | Blue inkjet ceramic pigment and preparation method thereof |
| CN103145452A (en) * | 2013-03-29 | 2013-06-12 | 佛山市南海万兴材料科技有限公司 | Red colorant for ceramic ink and preparation method thereof |
| CN104909570A (en) * | 2015-07-15 | 2015-09-16 | 中国地质大学（北京） | Opacifier, preparation method thereof and ceramic glaze with the opacifier |
| CN111499202A (en) * | 2020-06-30 | 2020-08-07 | 蒙娜丽莎集团股份有限公司 | Opaque glaze with high solar light reflectivity and preparation method thereof |
| CN113716606A (en) * | 2021-08-25 | 2021-11-30 | 中国科学院上海硅酸盐研究所 | PLZT micron seed crystal, preparation method thereof and application thereof in inducing ceramic growth |
| CN114249534A (en) * | 2021-12-22 | 2022-03-29 | 佛山欧神诺陶瓷有限公司 | Ceramic glaze material with infrared reflection, light glazed external tile and preparation method thereof |
| CN115974411A (en) * | 2023-02-02 | 2023-04-18 | 重庆唯美陶瓷有限公司 | Ceramic tile base glaze, ceramic tile and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 钛乳浊釉的研制;段国平;李建锡;潘丽萍;;陶瓷(05);第37-39, 47页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116947536A (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112279684B (en) | Magnesia-alumina spinel wear-resistant full-glazed ceramic tile and preparation method thereof | |
| CN112707644A (en) | Low-gloss transparent glaze, ceramic tile using same and preparation method thereof | |
| KR101036093B1 (en) | Glaze compositions | |
| CN110776256B (en) | White radial crystal flower dry grain glaze, light-transmitting ceramic tile and preparation method thereof | |
| CN105198217B (en) | It is a kind of to be used for throwing vitreous brick production entirely, beneficial to the ground-coat enamel of ceramic ink color development | |
| CN112279512B (en) | Wear-resistant full-polished magnesia-alumina spinel glaze as well as preparation method and application thereof | |
| CN114292131B (en) | Glazed tile with bright star effect on surface and preparation method thereof | |
| CN109279780A (en) | A kind of ceramic glaze and preparation method thereof of resistance to alkali corrosion | |
| CN111943724A (en) | Method for manufacturing matt transparent glazed ceramic chip | |
| CN115304276B (en) | Composite glaze layer, ceramic plate and preparation method thereof | |
| CN108395101A (en) | A kind of low light exquisiteness glaze, glaze slip preparation method, glazed tile and preparation method | |
| CN106977097B (en) | Raw glaze for transparent high-gloss medium-temperature hard porcelain and preparation method thereof | |
| CN109678345A (en) | A kind of high whiteness ground coat enamel and preparation method thereof | |
| CN106278387B (en) | There is the glazed tile and preparation method thereof of gold decorative effect on surface | |
| CN111499202B (en) | Opaque glaze with high solar light reflectivity and preparation method thereof | |
| CN112299718B (en) | Magnesium aluminate spinel wear-resistant printing glaze and preparation method and application thereof | |
| CN111253174B (en) | High-white overglaze for thin ceramic plate, thin ceramic plate and preparation method of thin ceramic plate | |
| CN112408786A (en) | Dull color glaze mixed with waste ceramic powder, ceramic product and preparation method | |
| CN109942288A (en) | High silicon porcelain Antique Imitation Tiles and its production method | |
| CN108423993A (en) | One kind building pottery aerolite glaze and its application process | |
| CN116693330B (en) | Digital microlite ceramic tile with skin texture and preparation method and application thereof | |
| CN115304277B (en) | Titanium white opacifying primer and ceramic plate | |
| CN114873917B (en) | Glaze, ceramic tile and ceramic tile preparation method | |
| CN111453994B (en) | White glaze, ceramic tile and preparation method of ceramic tile | |
| CN116947536B (en) | Zirconium-free ground glaze, titanium raw material opacified glazed tile 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |