CN115536275B - Microcrystalline stain-resistant matte glaze composition and ceramic product - Google Patents
Microcrystalline stain-resistant matte glaze composition and ceramic product Download PDFInfo
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- CN115536275B CN115536275B CN202211281525.8A CN202211281525A CN115536275B CN 115536275 B CN115536275 B CN 115536275B CN 202211281525 A CN202211281525 A CN 202211281525A CN 115536275 B CN115536275 B CN 115536275B
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000000919 ceramic Substances 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 22
- 239000004927 clay Substances 0.000 claims abstract description 19
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 15
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 15
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000454 talc Substances 0.000 claims abstract description 14
- 235000012222 talc Nutrition 0.000 claims abstract description 14
- 229910052623 talc Inorganic materials 0.000 claims abstract description 14
- 239000010433 feldspar Substances 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 239000010453 quartz Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 10
- 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 description 8
- 239000010434 nepheline Substances 0.000 claims description 8
- 229910052664 nepheline Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 abstract description 15
- 239000011777 magnesium Substances 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 4
- 238000003746 solid phase reaction Methods 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 2
- 229910052570 clay Inorganic materials 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 230000001965 increasing effect Effects 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 230000003373 anti-fouling effect Effects 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 235000012245 magnesium oxide Nutrition 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 239000010427 ball clay Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000007423 decrease Effects 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
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
Abstract
The invention discloses a microcrystalline stain-resistant matte glaze composition and a ceramic product, and in a first aspect of the application, the microcrystalline stain-resistant matte glaze composition comprises quartz, feldspar, clay, mullite, calcium metasilicate, low-expansion frit, calcined talcum and calcined zinc oxide. In the composition, mullite is used as a main nucleating material without crystallization, and dense and fine crystals are separated out in the sintering process to form a matte effect; the calcium metasilicate and the calcined talcum can form magnesium Huang Danhe magnesium rosepside crystals in the solid phase reaction process, further form a crystal combination with mullite, improve the glaze strength and improve the matte effect; the added low-expansion frit has a good sintering range, so that the frit can be kept in a liquid phase in the sintering process, so that the frit can be conveniently and timely dispersed into crystal gaps for filling, and finally, the pinhole structure in the glaze is effectively reduced, and the purposes of good wear resistance, high hardness, pollution prevention, easiness in cleaning and the like are realized.
Description
Technical Field
The application relates to the technical field of ceramics, in particular to a microcrystalline stain-resistant matte glaze composition and a ceramic product.
Background
The main method of the matte glaze realized on the sanitary ceramics and the daily porcelain at present is that the raw materials are blended to generate fine-grained crystals in the sintering process, so that the matte effect can be generated through scattering. There are several common ways to select raw materials for matte glaze, such as using barium/strontium containing materials, high zirconium silicate content, and high alumina low silica content, to create a matte effect. However, heavy metal barium has the extremely toxic problem, is easy to separate out and is easy to absorb dirt on the glaze; the high content of strontium and zirconium brings high cost, and the too high content of zirconium simultaneously causes serious radioactive pollution, and the problems of easy dirt absorption of the glaze and the like are also existed; the matte glaze produced by high alumina and low silica has too many pinholes, very poor antifouling performance and is easy to remain on the glaze surface, thus causing various bacteria to breed. Therefore, it is necessary to provide a low-cost microcrystalline matte glaze with high stain resistance.
Disclosure of Invention
The present application aims to solve at least one of the technical problems existing in the prior art. Therefore, the application provides a microcrystalline stain-resistant matte glaze composition and a ceramic product, and the microcrystalline stain-resistant matte glaze composition can form a microcrystalline layer after being used, achieves a matte effect, does not contain a pinhole structure, and is high in stain resistance.
In a first aspect of the application, a microcrystalline stain-resistant matte glaze composition is provided, and comprises, by mass, 2-7wt% of quartz, 30-45wt% of feldspar, 4-8wt% of clay, 10-20wt% of mullite, 15-25wt% of calcium metasilicate, 4-10wt% of low-expansion frit, 4-10wt% of calcined talcum and 1-6wt% of calcined zinc oxide.
The microcrystalline stain-resistant matte glaze composition provided by the embodiment of the application has at least the following beneficial effects:
in the composition, mullite is used as a main nucleating material without crystallization, dense and fine crystals can be separated out in the sintering process, a matte effect is formed, and the composition has the advantages of low-temperature rapid sintering and quenching; in addition, by mixing calcium metasilicate and calcined talc in a specific ratio, it is possible to form magnesium-yellow stone (2CaO.MgO.2SiO during the solid phase reaction 2 ) And magnofusite (3CaO.MgO.2SiO) 2 ) The crystal of (2) is further combined with mullite to form a crystal assembly, so that the matte effect is improved while the glaze strength is improved; in addition, the added low-expansion frit has a good sintering range, so that the frit can keep a liquid phase in the sintering process, so that the frit can be conveniently and timely dispersed into crystal gaps for filling, and finally, the pinhole structure in the glaze is effectively reduced, and the realization ofImproving the abrasion resistance, hardness and antifouling and cleaning properties.
In some embodiments of the present application, the composition of the low expansion frit comprises CaO in an amount of 13 to 17wt% and SiO in an amount of 68 to 75wt%, based on the total mass of the low expansion frit 2 B in an amount of 2 to 5wt% 2 O 3 . The low-expansion frit has high silicon dioxide content and low boron oxide content, so that boron oxide can dissolve silicon dioxide in the frit and can not participate in the dissolution of quartz except the frit in the sintering process, thereby reducing the dissolution of crystals in the glaze, increasing the crystal quantity of a glaze layer, improving the matte and hardness of the glaze layer, and avoiding the problems of forming liquid phase quantity and reducing the crystallization degree in the glaze due to the reaction of the boron oxide content with silicon oxide in the glaze; on the other hand, higher content of calcium oxide can also participate in the reaction of calcium metasilicate and calcined talc, increasing the amount of magnesium Huang Danhe magnesium rosaniline pyroxene crystals, further improving the matte effect.
In some embodiments of the present application, the low expansion frit composition includes CaO in an amount of 13 to 16wt% and SiO in an amount of 68 to 71wt% 2 B with the content of 2-5% 2 O 3 。
In some embodiments of the present application, the composition of the low expansion frit comprises, based on the total mass of the low expansion frit: 13 to 16 weight percent of CaO, 4 to 6 weight percent of ZnO and Al 2 O 3 6～9wt％、SiO 2 68～71wt％、K 2 O 3.5～4.7wt％，Li 2 O 0.5～1.5wt％、B 2 O 3 2 to 5 weight percent. The low-expansion frit with the composition not only can ensure that the generated glaze layer has better matte effect, but also has wide firing range, and the frit is easier to decompose and fill in gaps among crystals, thereby further reducing pinholes caused by larger crystal quantity and enhancing the stain resistance of the glaze layer.
In some embodiments of the present application, the mullite has a mesh number of 300 to 625 mesh. The size of mullite affects the size of the crystals, so it is contemplated that smaller mullite grains may be used to form finer and finer crystals, improving the matte, hardness, and stain resistance of the glaze. Further, the mesh number of the mullite is 350-500 mesh, and more preferably 400 mesh.
In some embodiments of the present application, the feldspar comprises potassium feldspar and nepheline feldspar, the mass ratio of the potassium feldspar to the nepheline feldspar is (16-28): (8-16).
In some embodiments of the present application, al in the clay 2 O 3 The content is 20-30wt%, siO 2 The content is 60-70 wt%. Further, al in the clay 2 O 3 The content is 20-30wt%, siO 2 The content is 60-70 wt%, K 2 The content of O is 1-5wt%; further, al in the clay 2 O 3 The content is 25-30wt%, siO 2 The content is 62 to 68 weight percent, K 2 The content of O is 2-3 wt%. The low-aluminum high-silicon type ball clay with the characteristics is selected, so that the glaze slip can obtain better suspension property than the kaolin, and crystallization in the sintering process is facilitated.
In some embodiments of the present application, the clay is a water-washed clay, and the sand and other impurities in the clay are removed by water washing.
In some embodiments of the present application, the clay is a Chaozhou clay.
In some embodiments of the present application, the clay is a Chaozhou water-washed clay.
In a second aspect of the present application, there is also provided a method for preparing a glaze slip for a microcrystalline stain-resistant matte glaze, the method comprising:
and grinding the microcrystalline stain-resistant matte glaze composition until the particles with the particle size of less than 10 mu m account for more than 70 weight percent of the total mass of the microcrystalline stain-resistant matte glaze composition, thereby obtaining the glaze slip.
In the preparation process, the finer the glaze slurry is, the more uniform the glaze is dispersed, the shorter the glaze reaction time is, the longer the crystallization time of the glaze slurry is, and the finer and finer microcrystalline glaze is easier to form; meanwhile, the finer the glaze slip, the smaller the formed crystal gap, the denser the filling of the low-expansion frit, and the better the mechanical properties such as stain resistance, hardness and the like, so that the grain size of the glaze slip is controlled to be more than 70wt% when the glaze slip is ground.
In some embodiments of the present application, the microparticles ground to a particle size of 10 μm or less account for 70 to 99wt% of the total mass of the microcrystalline stain resistant matte glaze composition. Further, particles with the particle size of less than 10 mu m account for 70-98wt%, 70-97wt%, 70-96 wt%, 70-95 wt%, 70-90 wt%, 70-85 wt%, 70-80 wt% and 70-75 wt% of the total mass of the microcrystalline stain-resistant matte glaze composition.
In a third aspect of the present application, there is also provided a method of preparing a ceramic article, the method comprising:
providing a blank;
applying a glaze slurry to the blank, wherein the glaze slurry is prepared from raw materials containing the microcrystalline stain-resistant matte glaze or prepared by adopting the preparation method;
and (5) sintering.
In some embodiments of the present application, the firing temperature is 1180-1190 ℃, the firing time is 12-14 hours, and the temperature is reduced to room temperature in a cooling manner of 5-30 ℃/min after the firing is finished.
In some embodiments of the present application, the cooling mode is an alternate quenching, specifically, quenching to 800 ℃ at 15-30 ℃/min, slow cooling to 600 ℃ at 5-15 ℃/min, and quenching to normal temperature at 15-25 ℃/min.
In some embodiments of the present application, the slip has a 325 mesh screen with a residue ratio of less than 0.02%.
In a fourth aspect of the present application, there is provided a ceramic article made by the aforementioned method of manufacture.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
FIG. 1 is a photograph of the glaze of a ceramic article made of a microcrystalline stain resistant matte glaze prepared according to one embodiment of the present application, wherein A is a photograph at 300 x magnification and B is a photograph at 1000 x magnification.
Detailed Description
The conception and technical effects produced by the present application will be clearly and completely described below in connection with the embodiments to fully understand the objects, features and effects of the present application. It is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort based on the embodiments of the present application are within the scope of the present application.
The following detailed description of embodiments of the present application is exemplary and is provided merely for purposes of explanation and not to be construed as limiting the application.
In the description of the present application, the meaning of a number is one or more, the meaning of a number is two or more, and greater than, less than, exceeding, etc. are understood to exclude the present number, and the meaning of a number above, below, within, etc. are understood to include the present number. If a divisor is described, it means the divisor + -10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.2%, 0.1%. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present application, a description with reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Examples 1 to 5
Taking all raw materials of the microcrystalline pollution-resistant matte glaze composition according to the formula in the table 1, adding the raw materials into a ball mill according to the proportion, performing wet ball milling (controlling the mass ratio of the composition to the grinding balls to the water to be 1:1.8:0.6), and ending ball milling until the raw materials of the composition with the particle size of less than 10 mu m account for 70-75wt% of the total mass of the composition to obtain glaze slurry.
TABLE 1 formulation of microcrystalline stain resistant matte glaze compositions of different examples
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Quartz | 2 | 2 | 6 | 6 | 4 |
| Potassium feldspar | 25 | 20 | 23 | 23 | 20 |
| Nepheline feldspar | 10 | 16 | 16 | 16 | 16 |
| Chaozhou water washing clay | 4 | 8 | 4 | 8 | 4 |
| Mullite | 20 | 15 | 15 | 20 | 20 |
| Calcium metasilicate | 20 | 23 | 18 | 15 | 23 |
| Low expansion frit | 8 | 8 | 6 | 4 | 6 |
| Calcined talc | 8 | 6 | 8 | 6 | 6 |
| Calcined zinc oxide | 3 | 2 | 4 | 2 | 2 |
| Totalizing | 100 | 100 | 100 | 100 | 101 |
Among the above raw materials, the Chaozhou water washing clay is purchased from Feitian Yan China clay mineral in Chaozhou of Guangdong, and its composition contains Al 2 O 3 About 28wt% of SiO 2 The content is about 65wt%, K 2 The O content was about 2.5wt%. The CaO content in the low-expansion frit is about 13wt%, the ZnO content is about 5wt%, and the Al content is about 2 O 3 About 7wt% of SiO 2 The content is about 69wt%, K 2 O content of about 3.5wt%, li 2 O content of about 0.5wt%, B 2 O 3 The content is about 2 percent, and the low-expansion frit is manufactured by self-made or commissioned manufacturers according to the composition. Mullite is 400-mesh mullite powder.
The method comprises the steps of adding water into a raw material of a green body of the conventional sanitary ceramic body to carry out wet ball milling, and when the mass of the raw material with the granularity smaller than 10 mu m in slurry obtained by ball milling accounts for 53% of the total mass of the raw material of the green body, carrying out slip casting by a mould to obtain the sanitary ceramic body.
And spraying glaze slurry obtained by ball milling on the surface of the sanitary ceramic body in a glaze spraying mode, wherein the thickness of the glaze slurry is 1mm. Then sintering in kiln at 1180-1190 deg.c for 12 hr, and fast quenching without heat preservation to obtain one kind of sanitary ceramic product.
The sanitary ceramic product prepared by the method is measured for stain absorption number according to a 041.SN_T 3253.1-2012 sanitary ceramic performance detection stain absorption method, the glossiness is measured by adopting a GB/T13891-2008 glossiness measuring method, the hardness is measured by adopting an HVS-1000T digital display micro Vickers hardness tester, and the detection results are shown in the following table 2:
TABLE 2 detection results of various examples
| Gloss level | Number of blots | Hardness of | |
| Example 1 | 10 | 0 | 842 |
| Example 2 | 12 | 0 | 829 |
| Example 3 | 24 | 0 | 811 |
| Example 4 | 18 | 0 | 822 |
| Example 5 | 16 | 0 | 832 |
As can be seen from Table 2, the formulation ratio in the technical scheme is used for preparing the matte glaze in each of examples 1 to 5, so that the ceramic sanitary appliance product prepared by adopting the matte glaze has good appearance evenness, high hardness, no dirt absorption, and glossiness ranging from 10 GU to 30GU, and achieves the aim of microcrystalline antifouling matte effect. The photo of the glaze surface prepared in the above example 1 is shown in fig. 1, wherein a is a photo under 300 times magnification, and B is a photo under 1000 times magnification, and it can be seen from the figure that the fine crystals densely precipitated on the glaze surface of the microcrystalline anti-fouling matte glaze obtained by adopting the above raw materials assisted by the process are visible, and no obvious pinhole structure exists, so that a better matte effect and anti-fouling performance can be achieved.
Comparative experiments
Comparative examples 1 to 7 were set up, and the formulation of each comparative example was as follows:
TABLE 3 formulation of microcrystalline stain resistant matte glaze composition of comparative example
Wherein the alumina is 325 mesh calcined alumina powder; the composition of the common frit is as follows: 13 to 15 weight percent of CaO, 3 to 5 weight percent of MgO, 2 to 4 weight percent of ZnO and Al 2 O 3 12～14wt％、SiO 2 60～65wt％、K 2 O 2.5～3.5wt％，Na 2 O 2.5～3.5％、B 2 O 3 0～1％。
The gloss, stain resistance and hardness of the ceramic articles were measured by the same method as in the examples, and the results are shown in Table 4:
TABLE 4 detection results for each comparative example
| Gloss level | Number of blots | Hardness of | |
| Comparative example 1 | 6 | 5 | 831 |
| Comparative example 2 | 8 | 55 | 818 |
| Comparative example 3 | 34 | 0 | 785 |
| Comparative example 4 | 4 | 15 | 829 |
| Comparative example 5 | 18 | 43 | 822 |
| Comparative example 6 | 38 | 10 | 767 |
| Comparative example 7 | 56 | 0 | 742 |
In the comparative example, the mullite is replaced by alumina in the comparative example 1, the matte glaze prepared by the formula has rough glaze surface, and larger gaps exist in the matte glaze, so that the stain absorption of the glaze surface and the obvious drop of stain resistance are caused; the common frit is used for replacing the low-expansion frit in comparative example 2 and comparative example 5, and although the prepared ceramic product has good appearance flatness, no microcrystalline gap filling effect exists in the ceramic product, the glaze is easy to absorb dirt, and the degree of decline of the dirt resistance is extremely obvious; in the comparative example 3, the content of the calcium metasilicate exceeds the range, the liquid phase amount of the glaze surface is rapidly increased, so that the gloss effect is caused, the glossiness is too high, the matte effect cannot be realized, and meanwhile, the hardness is too low, so that the related requirements of ceramic products cannot be met; in comparative example 4, the content of calcium metasilicate is lower, the content of calcined talc is higher, and the magnesium yellow stone crystal and periclase on the surface layer of the glaze are further increased, so that the pits on the glaze are gradually increased, the glossiness of the glaze is reduced, and the surface of the glaze starts to absorb dirt; the quartz content in the comparative examples 6 and 7 exceeds the range, the liquid phase amount of the glaze is increased, the glossiness of the ceramic product is obviously higher, the hardness value is lower, and the production requirement standard cannot be met; moreover, the low-expansion frit content of comparative example 6 is also low, resulting in poor dirt pick-up of the ceramic product and likewise failing to meet the standards required for the production of sanitary ceramics.
Example 6
The embodiment provides a microcrystalline stain-resistant matte glaze composition, which comprises 2 parts by mass of quartz, 29 parts by mass of potassium feldspar, 8 parts by mass of nepheline feldspar, 4 parts by mass of Chaozhou water washing clay, 20 parts by mass of mullite, 25 parts by mass of calcium metasilicate, 4 parts by mass of low-expansion frit, 5 parts by mass of calcined talcum and 3 parts by mass of calcined zinc oxide.
Example 7
The embodiment provides a microcrystalline stain-resistant matte glaze composition, which comprises 7 parts by mass of quartz, 16 parts by mass of potassium feldspar, 15 parts by mass of nepheline feldspar, 4 parts by mass of Chaozhou water washing clay, 10 parts by mass of mullite, 25 parts by mass of calcium metasilicate, 10 parts by mass of low-expansion frit, 10 parts by mass of calcined talcum and 3 parts by mass of calcined zinc oxide.
Example 8
The embodiment provides a microcrystalline stain-resistant matte glaze composition, which comprises 7 parts by mass of quartz, 27 parts by mass of potassium feldspar, 17 parts by mass of nepheline feldspar, 4 parts by mass of Chaozhou water washing clay, 20 parts by mass of mullite, 15 parts by mass of calcium metasilicate, 5 parts by mass of low-expansion frit, 4 parts by mass of calcined talcum and 1 part by mass of calcined zinc oxide.
The above examples can achieve matt, stain resistance and hardness similar to those of examples 1 to 5, and are not described here again.
By combining the above examples and comparative examples, the microcrystalline matte in the scheme of the application is mainly crystallized into mullite crystals, and a large number of dense and fine crystals can be separated out by grinding the mullite crystals under a certain granularity, so that a matte effect is formed, and the microcrystalline matte has the advantages of low-temperature quick-firing quenching and the like. At the same time, magnesium Huang Danji magnesium rosapside is gradually formed by starting solid phase reaction of calcium metasilicate and calcined talcum at about 1160 ℃ to about 1190 ℃, and magnesium Huang Danji magnesium rosapside is retained by quenching under the condition that the calcium metasilicate and calcined talcum do not further participate in solid phase reaction to form more stable forms such as anorthite, and a crystal combination of the magnesium Huang Danji magnesium rosapside and mullite is formedFurther increasing the intensity and the matte effect of the glaze. For the low-expansion frit used in the method, the firing range is wide, the liquid phase state can be kept at the firing temperature in the application, so that the frit can be more easily dispersed in gaps of the three crystals to be filled, the glaze does not contain a pinhole structure, and the pollution resistance is improved under the condition of no gaps; and, the silica content in these particular low expansion frits is high, while B 2 O 3 The content is low, so that the internal reaction balance is enough, sufficient silicon dioxide in the frit can be dissolved firstly, and quartz outside the frit is hardly dissolved, so that the dissolution of crystals in the glaze can be greatly reduced, and the quantity of the precipitated crystals is ensured; meanwhile, caO in the ceramic material also participates in the reaction of forming magnesium Huang Danhe magnesium rosaniline by high-ratio calcium metasilicate and calcined talcum, so that the crystal quantity of the magnesium Huang Danhe magnesium rosaniline is increased, the crystallization quantity can be increased from multiple aspects, the microcrystalline effect can be increased, and dense microcrystals can bring the improvement of hardness, compared with the Vickers hardness of about 630-650 of common white glaze, the ceramic material can reach more than 820, the glaze is more wear-resistant, the ceramic material is more antifouling and easy to clean, no void is hidden, bacterial infection is reduced, and the matte glaze has better sanitary experience.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments described above, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present application. Furthermore, embodiments of the present application and features of the embodiments may be combined with each other without conflict.
Claims (8)
1. The microcrystalline stain-resistant matte glaze composition is characterized by comprising, by mass, 2-7wt% of quartz, 30-45wt% of feldspar, 4-8wt% of clay, 10-20wt% of mullite, 15-25wt% of calcium metasilicate, 4-10wt% of low-expansion frit, 4-10wt% of calcined talcum and 1-6wt% of calcined zinc oxide; based on the total mass of the low expansion frit, the composition of the low expansion frit comprises: 13 to 16 weight percent of CaO and 4 to 6 weight percent of ZnO、Al 2 O 3 6～9wt％、SiO 2 68～71wt％、K 2 O 3.5～4.7wt％、Li 2 O 0.5～1.5wt％、B 2 O 3 2～5wt％。
2. The microcrystalline stain resistant matte glaze composition according to claim 1, wherein the mesh number of the mullite is 300-625 mesh.
3. The microcrystalline stain resistant matte glaze composition according to claim 1, wherein the feldspar comprises potassium feldspar and nepheline feldspar, the mass ratio of the potassium feldspar to the nepheline feldspar being (16-28): (8-16).
4. The microcrystalline stain resistant matte glaze composition according to claim 1, wherein Al in the clay 2 O 3 The content is 20-30wt%, siO 2 The content is 60-70 wt%.
5. The preparation method of the glaze slip of the microcrystalline stain-resistant matte glaze is characterized by comprising the following steps of:
taking the microcrystalline stain-resistant matte glaze composition as defined in any one of claims 1 to 4, and grinding until the particles with the particle size of below 10 μm account for more than 70wt% of the total mass of the microcrystalline stain-resistant matte glaze composition, thereby obtaining the glaze slip.
6. A method of making a ceramic article comprising the steps of:
providing a blank;
applying to the blank a glaze slip made from a raw material comprising the microcrystalline stain resistant matte glaze of any of claims 1 to 4 or prepared using the preparation method of claim 5;
and (5) sintering.
7. The method according to claim 6, wherein the firing temperature is 1180 to 1190 ℃, the firing time is 12 to 14 hours, and the temperature is reduced to room temperature by a temperature reduction method of 5 to 30 ℃/min after the firing is completed.
8. A ceramic article produced by the production method according to any one of claims 6 to 7.
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