CN115536275A - Microcrystalline stain-resistant matte glaze composition and ceramic product - Google Patents
Microcrystalline stain-resistant matte glaze composition and ceramic product Download PDFInfo
- Publication number
- CN115536275A CN115536275A CN202211281525.8A CN202211281525A CN115536275A CN 115536275 A CN115536275 A CN 115536275A CN 202211281525 A CN202211281525 A CN 202211281525A CN 115536275 A CN115536275 A CN 115536275A
- Authority
- CN
- China
- Prior art keywords
- glaze
- stain
- microcrystalline
- composition
- resistant matte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000000919 ceramic Substances 0.000 title claims abstract description 28
- 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 21
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000010304 firing Methods 0.000 claims abstract description 14
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 13
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 12
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000454 talc Substances 0.000 claims abstract description 12
- 229910052623 talc Inorganic materials 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000004927 clay Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000013081 microcrystal Substances 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 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
- 239000010433 feldspar Substances 0.000 claims description 7
- 239000010434 nepheline Substances 0.000 claims description 7
- 229910052664 nepheline Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 20
- 238000005245 sintering Methods 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 239000011777 magnesium Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 4
- 238000003746 solid phase reaction Methods 0.000 abstract description 4
- 239000004575 stone Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 235000012239 silicon dioxide Nutrition 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 235000012245 magnesium oxide Nutrition 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052810 boron oxide 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
- 238000009472 formulation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000001354 calcination Methods 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
- 238000001514 detection method Methods 0.000 description 1
- 238000004031 devitrification Methods 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
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 238000003904 radioactive pollution Methods 0.000 description 1
- 230000035484 reaction time 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
- 239000002002 slurry Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012991 xanthate 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
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a microcrystalline stain-resistant matte glaze composition and a ceramic product. In the composition, the mullite is used as a main nucleating material without light crystallization, and dense and fine crystals are separated out in the firing process to form a matte effect; calcium metasilicate and calcined talc can form a magnesium yellow stone and a magnesium rosepside crystal in the solid phase reaction process, and further form a crystal assembly with mullite, so that the strength of a glaze surface is improved, and the matte effect is improved; the added low-expansion frit has a good sintering range, so that the frit keeps a liquid phase in the sintering process, is conveniently dispersed to crystal gaps in time for filling, finally effectively reduces a pinhole structure in a glaze surface, and achieves the purposes of good wear resistance, high hardness, fouling prevention, easy cleaning and the like.
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 sanitary ceramics and daily porcelain at present is to produce fine-grained crystals in the firing process through the preparation of raw materials, so that the matte effect can be produced through scattering. In selecting the raw material of the matte glaze, there are several common methods, such as using barium/strontium containing materials, high zirconium silicate content, and high alumina low silica content, to produce the matte effect. However, heavy metal barium has the problem of high toxicity, is easy to separate out and has a glaze surface which is easy to absorb dirt; the high content of strontium and zirconium brings high cost, and the overhigh content of zirconium causes serious radioactive pollution and also has the problems that the glaze surface is easy to absorb dirt and the like; the matte glaze surface produced by high alumina and low silica has too many pinholes, has very poor antifouling performance, and is easy to remain on the glaze surface to cause various bacteria breeding. Therefore, it is necessary to provide a low-cost microcrystalline matte glaze with strong stain resistance.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. Therefore, the microcrystalline stain-resistant matte glaze composition and the ceramic product are provided, the microcrystalline matte glaze composition can form a microcrystalline layer after being used, the matte effect is achieved, and meanwhile, the microcrystalline stain-resistant matte glaze composition does not contain a pinhole structure and is high in stain resistance.
In a first aspect of the application, the microcrystalline stain-resistant matt glaze composition comprises, by mass, 2-7 wt% of quartz, 30-45 wt% of feldspar, 4-8 wt% of white clay, 10-20 wt% of mullite, 15-25 wt% of calcium metasilicate, 4-10 wt% of low-expansion frit, 4-10 wt% of calcined talc and 1-6 wt% of calcined zinc oxide.
The microcrystalline stain resistant matte glaze composition according to the embodiment of the application has at least the following beneficial effects:
in the composition, the mullite is used as a main core forming material without light crystallization, dense and fine crystals can be separated out in the firing process to form a matte effect, and the composition has the advantages of low-temperature quick firing and quenching; in addition, by blending calcium metasilicate and calcined talc in a specific ratio, it is possible to form a magnesium yellow stone (2 CaO. MgO. Multidot.2SiOx) in the course of a solid-phase reaction 2 ) And magadiite (3 CaO. MgO. 2 SiO) 2 ) The crystal of (2) further forms a crystal assembly with mullite, thereby improving the strength of a glaze surface and simultaneously improving a matte effect; in addition, the added low-expansion frit has a good sintering range, so that the frit keeps a liquid phase in the sintering process, the frit is conveniently dispersed in crystal gaps in time to be filled, the pinhole structure in the glaze is finally effectively reduced, and the aims of improving the wear resistance, the hardness and the antifouling cleanness are fulfilled.
In some embodiments of the present application, the composition of the low expansion frit comprises CaO in an amount of 13 to 17wt%, 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 in the sintering process, boron oxide can dissolve silicon dioxide in the frit and cannot participate in the dissolution of quartz except the frit, thereby reducing the dissolution of crystals in 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 glaze due to the reaction of the high boron oxide content and silicon oxide in the glaze; on the other hand, the calcium oxide with higher content can also participate in the reaction of calcium metasilicate and calcined talc, so that the amount of the crystals of the magnesium xanthate and the magnesium roseptite is increased, and the matte effect is further improved.
In some embodiments of the present application, the composition of the low expansion frit includes CaO in an amount of 13 to 16wt%, and SiO in an amount of 68 to 71wt% 2 B in an amount of 2 to 5% 2 O 3 。
In some embodiments of the present application, the low expansion frit comprises a composition comprising, based on the total mass of the low expansion frit: caO 13-16 wt%, znO 4 &6wt％、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 can ensure that the generated glaze layer has a good matte effect, the sintering range is wide, and the frit is more easily decomposed and filled in gaps among crystals, so that pinholes caused by large crystal quantity are further reduced, and the stain resistance of the glaze layer is enhanced.
In some embodiments of the present application, the mullite has a mesh size of 300 to 625 mesh. The size of the mullite affects the size of the crystals, so that smaller mullite particles can be considered to form finer and denser crystals, and the matt, hardness and stain resistance of the glaze are improved. Furthermore, the mesh number of the mullite is 350-500 meshes, and is further 400 meshes.
In some embodiments of the present application, the feldspar comprises potassium feldspar and nepheline, and the mass ratio of the potassium feldspar to the nepheline is (16-28): (8 to 16).
In some embodiments of the present application, the clay comprises Al 2 O 3 20 to 30 weight percent of SiO 2 The content is 60-70 wt%. Further, al in the clay 2 O 3 20 to 30 weight percent of SiO 2 Content of 60-70 wt%, K 2 The content of O is 1 to 5 weight percent; further, al in said clay 2 O 3 25 to 30 weight percent of SiO 2 Content of 62-68 wt%, K 2 The content of O is 2 to 3 weight percent. The ball clay with low aluminum and high silicon with the characteristics is selected, so that the glaze slip has better suspension property than kaolin, and crystallization in the sintering process is facilitated.
In some embodiments of the present application, the clay is a water-washed clay from which sand and other impurities are removed by water washing.
In some embodiments of the present application, the clay is 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 of a microcrystalline stain-resistant matte glaze, the method comprising:
and grinding the microcrystal pollution-resistant matt glaze composition until the particles with the particle size of less than 10 mu m account for more than 70wt% of the total mass of the microcrystal pollution-resistant matt glaze composition to obtain the glaze slip.
In the preparation process, the finer the glaze slip is, the more uniform the glaze material is dispersed, the shorter the glaze reaction time is, the longer the devitrification time of the glaze slip is, and the more delicate microcrystalline glaze surface is easily formed; meanwhile, the finer the glaze slip, the smaller the crystal gap formed, the denser the filling of the low expansion frit, and the better the mechanical properties such as stain resistance and hardness, so that the glaze slip particle size is controlled to be less than 10 μm and accounts for more than 70wt%.
In some embodiments herein, the particles milled to a particle size of 10 μm or less comprise 70 to 99wt% of the total mass of the microcrystalline stain resistant matte glaze composition. Furthermore, the particles with the particle size of less than 10 mu m account for 70-98 wt%, 70-97 wt%, 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 microcrystal pollution-resistant matte glaze composition.
In a third aspect of the present application, there is also provided a method of manufacturing a ceramic article, the method comprising:
providing a blank body;
applying a glaze slip to the blank, the glaze slip being made from a raw material comprising the microcrystalline stain-resistant matte glaze or made using the preparation method;
and (5) firing.
In some embodiments of the present application, the firing temperature is 1180 to 1190 ℃, the firing time is 12 to 14 hours, and the temperature is reduced to room temperature in a cooling manner of 5 to 30 ℃/min after the firing is finished.
In some embodiments of the present application, the cooling manner is alternate quenching, specifically, quenching to 800 ℃ at 15-30 ℃/min, then slowly cooling to 600 ℃ at 5-15 ℃/min, and finally quenching to room temperature at 15-25 ℃/min.
In some embodiments of the present application, the slip has a rejects rate of 325 mesh screen in the slip of less than 0.02%.
In a fourth aspect of the present application, there is provided a ceramic article made by the method of making as previously described.
Additional aspects and advantages of the present 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 present application.
Drawings
Fig. 1 is a photograph of a glaze surface of a ceramic article made of a microcrystalline stain resistant matte glaze prepared in one embodiment of the present application, wherein a is a photograph at 300 times magnification and B is a photograph at 1000 times magnification.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by a person skilled in the art without making any inventive effort based on the embodiments of the present application are within the protection scope of the present application.
The following detailed description of embodiments of the present application is provided for the purpose of illustration only and is not intended to be construed as a limitation of the application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present number, and the above, below, within, etc. are understood as including the present number. If approximations are described, the meaning is. + -. 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.2%, 0.1% of the number. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood 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, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example" or "some examples" or the like 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, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 the raw materials of the microcrystalline stain-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 grinding balls to water to be 1.8.
TABLE 1 formulation of microcrystalline stain resistant matte glaze composition for various examples
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Quartz | 2 | 2 | 6 | 6 | 4 |
| Potassium feldspar | 25 | 20 | 23 | 23 | 20 |
| Chardontia feldspars | 10 | 16 | 16 | 16 | 16 |
| Chaozhou water-washed carclazyte | 4 | 8 | 4 | 8 | 4 |
| Mullite | 20 | 15 | 15 | 20 | 20 |
| Calcium metasilicates | 20 | 23 | 18 | 15 | 23 |
| Low expansion frit | 8 | 8 | 6 | 4 | 6 |
| Calcined talc | 8 | 6 | 8 | 6 | 6 |
| Calcining zinc oxide | 3 | 2 | 4 | 2 | 2 |
| Total up to | 100 | 100 | 100 | 100 | 101 |
The raw materials include Chaozhou water-washed clay obtained from Feitian Yan porcelain clay mineral of Chaozhou city of Guangdong province, and Al 2 O 3 About 28wt% SiO 2 Content about 65wt%, K 2 The O content was about 2.5wt%. The low expansion frit had a CaO content of about 13wt%, a ZnO content of about 5wt%, and Al 2 O 3 The content is about 7wt%,SiO 2 The content is about 69wt%, K 2 O content 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 clinker is prepared by self or entrusted to manufacturers according to the composition. The mullite is made of 400-mesh mullite powder.
The sanitary ceramic blank is prepared by adding water into a blank raw material by adopting the conventional sanitary ceramic blank raw material formula for wet ball milling, and when the mass of the raw material with the granularity of less than 10 mu m in the slurry obtained by ball milling accounts for 53 percent of the total mass of the blank raw material, performing mould grouting forming.
And spraying glaze slip obtained by ball milling to the surface of the sanitary ceramic body in a glaze spraying mode, wherein the thickness of the glaze slip is 1mm. Then the ceramic is put into a kiln to be fired at 1180-1190 ℃ for 12h, and the ceramic is rapidly quenched without heat preservation after the firing is finished, thus obtaining the sanitary ceramic product.
The sanitary ceramic product prepared by the method is subjected to stain absorption point number measurement according to a stain absorption method for detecting the performance of the sanitary ceramic product, namely 041.SN _T3253.1-2012, the glossiness is measured by adopting a GB/T13891-2008 glossiness measuring method, the hardness is tested by adopting an HVS-1000T digital display micro Vickers hardness tester, and the detection result is shown in the following table 2:
TABLE 2 test results of the respective examples
| Degree of gloss | Number of dirt-absorbing points | 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 |
It can be seen from table 2 that in examples 1 to 5, the matte glaze is prepared according to the formula ratio in the technical scheme, so that the ceramic sanitary ware prepared from the matte glaze has good appearance flatness, high hardness, no dirt absorption, and the glossiness of the ceramic sanitary ware is in the range of 10 to 30GU, thereby achieving the purpose of microcrystalline antifouling matte effect. The photo of the glaze 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 glaze of the microcrystalline stain-resistant matte glaze prepared by using the above raw materials and the process has dense precipitated tiny crystals, no obvious pinhole structure, and good matte effect and stain resistance.
Comparative experiment
Comparative examples 1 to 7 were set up, and the formulations of the respective comparative examples were as follows:
TABLE 3 formulation of microcrystalline stain resistant matte glaze composition of comparative example
Wherein, the alumina is calcined alumina powder with 325 meshes; the composition of a 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 ware were measured in the same manner as in the examples, and the results are shown in table 4:
TABLE 4 test results of respective comparative examples
| Degree of gloss | Number of dirt suction points | 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 examples, mullite is replaced by alumina in the comparative example 1, the glaze surface of the matt glaze prepared by the formula is rough, and although the matt effect is improved, large gaps exist in the matt glaze, so that the glaze surface absorbs dirt, and the pollution resistance is obviously reduced; the comparative examples 2 and 5 adopt common frits to replace low-expansion frits, and although the prepared ceramic products have good appearance flatness, the microcrystalline gap filling effect does not exist, the glaze surface is easy to absorb dirt, and the reduction degree of the pollution resistance is extremely obvious; in the comparative example 3, the content of calcium metasilicate exceeds the range, the liquid phase amount of the glaze surface is increased rapidly, so that the bright 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 the ceramic product cannot be met; in the comparative example 4, the content of calcium metasilicate is lower, the content of calcined talc is higher, and the content of the mackerite crystal and periclase on the surface layer of the glaze is further increased, so that pits of the glaze are gradually increased, the glossiness of the glaze is reduced, and the glaze starts to absorb dirt; in the comparative example 6 and the comparative example 7, the quartz content exceeds the range, the liquid phase amount of the glaze surface is increased, the glossiness of the ceramic product is obviously higher, the hardness value is lower, and the standard required by production cannot be reached; moreover, comparative example 6 also has a lower content of low-expansion clinker, which results in unacceptable dirt pick-up of the ceramic product, and also fails to meet the standards required for the production of sanitary ceramics.
Example 6
This example provides a microcrystalline stain resistant matte glaze composition comprising 2 parts by mass of quartz, 29 parts by mass of potassium feldspar, 8 parts by mass of nepheline, 4 parts by mass of Chaozhou water-washed 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 talc, and 3 parts by mass of calcined zinc oxide.
Example 7
The present 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, 4 parts by mass of Chaozhou water-washed 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 talc, and 3 parts by mass of calcined zinc oxide.
Example 8
This example provides a microcrystalline stain resistant matte glaze composition comprising 7 parts by mass of quartz, 27 parts by mass of potassium feldspar, 17 parts by mass of nepheline, 4 parts by mass of Chaozhou water-washed 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 talc, and 1 part by mass of calcined zinc oxide.
The above examples can obtain matte, stain resistant and hardness similar to those of examples 1 to 5, and are not described in detail herein.
It can be seen from the above examples and comparative examples that the microcrystalline matte in the scheme of the application is mainly crystallized as mullite crystals, and a large amount of dense fine crystals can be separated out by grinding the mullite crystals to keep a certain particle size, so that a matte effect is formed, and the microcrystalline matte has the advantages of low-temperature rapid-firing and rapid-cooling, and the like. Meanwhile, the calcium metasilicate and the calcined talc start solid phase reaction at 1160 ℃ to 1190 ℃ to gradually form the mawstone and the mawstone, and the mawstone are reserved by quenching under the condition that the mawstone and the mawstone are not further subjected to solid phase reaction to form more stable forms such as anorthite and the like, and a crystal assembly of the mawstone and the mullite is formed, so that the strength of a glaze surface and the matte effect are further improved. The low-expansion frits used in the method have a wide sintering range, can keep a liquid phase state at the sintering temperature in the application, and can be more easily dispersed in the gaps among the three crystals for filling, so that the glaze surface does not contain a pinhole structure, and the pollution resistance is improved under the condition of no gap; and these specific low-expansion frits have a high silica content, while B 2 O 3 The content is less, so that the internal reaction balance is enough, sufficient silicon dioxide in the frit can be dissolved firstly, and the silicon dioxide hardly participates in dissolving quartz outside the frit, so that the dissolution of crystals in the glaze can be greatly reduced, and the amount of precipitated crystals is ensured; meanwhile, caO in the glaze can also participate in the reaction of high-ratio calcium metasilicate and calcined talc to form mauveite and mauveite, and the crystal amount of the mauveite and the mauveite is increased, so that the crystal amount can be increased from multiple aspects, the microcrystal effect can be increased, and the dense microcrystal can bring the improvement of the hardness, compared with the Vickers hardness of about 630-650 of common white glaze, the Vickers hardness can reach more than 820 in the application, the glaze surface is more wear-resistant, and the glaze surface is antifouling and easy to clean, has no gap to store scale, reduces bacterial infection, and enables the matte glaze to have 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 those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
Claims (10)
1. The microcrystal stain-resistant matte glaze composition is characterized by comprising, by mass, 2-7 wt% of quartz, 30-45 wt% of feldspar, 4-8 wt% of white clay, 10-20 wt% of mullite, 15-25 wt% of calcium metasilicate, 4-10 wt% of low-expansion frit, 4-10 wt% of calcined talc and 1-6 wt% of calcined zinc oxide.
2. The microcrystalline stain resistant matte glaze composition according to claim 1, wherein the composition of the low expansion frit comprises CaO in an amount of 13-17 wt%, siO in an amount of 68-75 wt%, based on the total mass of the low expansion frit 2 B in an amount of 2 to 5wt% 2 O 3 。
3. The crystallite stain resistant matte glaze composition of claim 2, wherein 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 2～5wt％。
4. The microcrystalline stain resistant matte glaze composition of claim 1, wherein the mullite has a mesh size of 300 to 625 mesh.
5. The microcrystalline stain resistant matte glaze composition according to claim 1, wherein the feldspar comprises potassium feldspar and nepheline feldspar, and the mass ratio of the potassium feldspar to the nepheline feldspar is (16-28): (8 to 16).
6. The method of claim 1The microcrystalline stain-resistant matte glaze composition is characterized in that Al in the clay 2 O 3 The content of SiO is 20 to 30 weight percent 2 The content is 60-70 wt%.
7. A preparation method of glaze slip of microcrystal stain-resistant matte glaze is characterized by comprising the following steps:
taking the microcrystal pollution-resistant matte glaze composition as defined in any one of claims 1 to 6, and grinding the microcrystal pollution-resistant matte glaze composition until the particles with the particle size of less than 10 microns account for more than 70wt% of the total mass of the microcrystal pollution-resistant matte glaze composition to obtain the glaze slip.
8. A method of making a ceramic article, comprising the steps of:
providing a blank body;
applying to the body a slip made from a raw material comprising the microcrystalline stain resistant matte glaze of any one of claims 1 to 6 or made using the method of preparation of claim 7;
and (5) firing.
9. The preparation method according to claim 8, wherein the firing temperature is 1180 to 1190 ℃, the firing time is 12 to 14 hours, and the temperature is reduced to room temperature in a cooling manner of 5 to 30 ℃/min after the firing is finished.
10. A ceramic article produced by the production method according to any one of claims 8 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211281525.8A CN115536275B (en) | 2022-10-19 | 2022-10-19 | Microcrystalline stain-resistant matte glaze composition and ceramic product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211281525.8A CN115536275B (en) | 2022-10-19 | 2022-10-19 | Microcrystalline stain-resistant matte glaze composition and ceramic product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115536275A true CN115536275A (en) | 2022-12-30 |
| CN115536275B CN115536275B (en) | 2024-02-23 |
Family
ID=84735933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211281525.8A Active CN115536275B (en) | 2022-10-19 | 2022-10-19 | Microcrystalline stain-resistant matte glaze composition and ceramic product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536275B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178514A (en) * | 2018-01-19 | 2018-06-19 | 佛山科学技术学院 | A kind of building ceramic tiles gentle eye protection matting glaze and its preparation process |
| CN109020206A (en) * | 2018-09-17 | 2018-12-18 | 杨鹏飞 | A kind of pottery fancy glaze and preparation method thereof |
| CN111439931A (en) * | 2020-06-17 | 2020-07-24 | 佛山市东鹏陶瓷有限公司 | Low-cost zirconium-free white glaze suitable for sanitary ceramics and domestic porcelain and preparation method thereof |
| CN111807704A (en) * | 2020-09-02 | 2020-10-23 | 佛山东鹏洁具股份有限公司 | Matte glaze applied to sanitary ceramics, sanitary ceramics applying matte glaze and preparation method of sanitary ceramics |
| CN112299833A (en) * | 2020-09-30 | 2021-02-02 | 蒙娜丽莎集团股份有限公司 | High-strength high-toughness mullite ceramic sheet and preparation method thereof |
| CN113511922A (en) * | 2021-08-04 | 2021-10-19 | 佛山东鹏洁具股份有限公司 | Matte glaze for sanitary ceramics and preparation method of sanitary ceramics |
-
2022
- 2022-10-19 CN CN202211281525.8A patent/CN115536275B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178514A (en) * | 2018-01-19 | 2018-06-19 | 佛山科学技术学院 | A kind of building ceramic tiles gentle eye protection matting glaze and its preparation process |
| CN109020206A (en) * | 2018-09-17 | 2018-12-18 | 杨鹏飞 | A kind of pottery fancy glaze and preparation method thereof |
| CN111439931A (en) * | 2020-06-17 | 2020-07-24 | 佛山市东鹏陶瓷有限公司 | Low-cost zirconium-free white glaze suitable for sanitary ceramics and domestic porcelain and preparation method thereof |
| CN111807704A (en) * | 2020-09-02 | 2020-10-23 | 佛山东鹏洁具股份有限公司 | Matte glaze applied to sanitary ceramics, sanitary ceramics applying matte glaze and preparation method of sanitary ceramics |
| CN112299833A (en) * | 2020-09-30 | 2021-02-02 | 蒙娜丽莎集团股份有限公司 | High-strength high-toughness mullite ceramic sheet and preparation method thereof |
| CN113511922A (en) * | 2021-08-04 | 2021-10-19 | 佛山东鹏洁具股份有限公司 | Matte glaze for sanitary ceramics and preparation method of sanitary ceramics |
Non-Patent Citations (1)
| Title |
|---|
| 徐建华等编著: "陶瓷花釉与装饰技术", 中国轻工业出版社, pages: 196 - 197 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115536275B (en) | 2024-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111517649B (en) | Antibacterial glaze powder, antibacterial rock plate and preparation method thereof | |
| CN113511922B (en) | Matte glaze for sanitary ceramic and preparation method of sanitary ceramic | |
| US7579084B2 (en) | Ceramic material, compositions and methods for manufacture thereof | |
| CN111807704B (en) | Matte glaze applied to sanitary ceramics, sanitary ceramics applying matte glaze and preparation method of sanitary ceramics | |
| CN110790506A (en) | Granular double-layer reaction glaze and preparation method thereof | |
| CN107417115A (en) | A kind of preparation method of high-hardness, wearable glaze | |
| US20090280975A1 (en) | Ceramic material, compositions and methods for manufacture thereof | |
| KR100262181B1 (en) | Process for producing body of whiteware with high strength and excellent thermal impact resistance | |
| JPH0656516A (en) | Vitreous body and its production, sanitary pottery formed by using this body and blaze for vitreous body | |
| CN110642521A (en) | High-wear-resistance antifouling microcrystal decorative ceramic thick plate and preparation method thereof | |
| EP2123612A1 (en) | Wear resistant coatings and tiles and methods of making same | |
| CN108328927B (en) | Ultra-smooth white glaze and preparation method thereof | |
| CN108129029B (en) | Snowflake glaze material and related preparation method and overglaze formula adjustment method | |
| WO2022252930A1 (en) | Combined process antibacterial ceramic tile and production method therefor | |
| CN113429130B (en) | Flash super-wear-resistant diamond glaze, ceramic tile and preparation method thereof | |
| CN101891501A (en) | Lead-free and cadmium-free bone china glaze and preparation process thereof | |
| CN112408786A (en) | Dull color glaze mixed with waste ceramic powder, ceramic product and preparation method | |
| CN115838245B (en) | Micro-gloss glaze material for separating microcrystals, micro-gloss ceramic rock plate with ultra-flat fine glaze surface and preparation method thereof | |
| CN111517651A (en) | Wear-resistant glaze, preparation method thereof and glazed tile using wear-resistant glaze | |
| CN113511815A (en) | Cream-yellow glossy glaze for sanitary ceramics and preparation method of product thereof | |
| CN108191235A (en) | A kind of Bone China Glaze, glaze slip and preparation method | |
| CN108623164B (en) | Wear-resistant ceramic glaze | |
| CN112646416B (en) | Ceramic digital glaze ink with sterilization and far infrared composite functions and preparation method thereof | |
| CN105439532B (en) | A kind of high-performance pottery and preparation method thereof | |
| CN115536275A (en) | Microcrystalline stain-resistant matte glaze composition and ceramic product |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240429 Address after: 253000 west of Beijing Fuzhou Expressway, north of north outer ring road and east of Jinghua Road, songguantun sub district office, Dezhou Economic and Technological Development Zone, Shandong Province Patentee after: DEZHOU LEHUA CERAMIC SANITARY WARE Co.,Ltd. Country or region after: China Patentee after: Arrow Home Group Co.,Ltd. Address before: 528100 block 1, No.1, Kangyu Third Road, Nanshan Town, Sanshui District, Foshan City, Guangdong Province Patentee before: Arrow Home Group Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |