CN111423124B - Wear-resistant transparent glaze, wear-resistant polished glazed brick and preparation method thereof - Google Patents
Wear-resistant transparent glaze, wear-resistant polished glazed brick and preparation method thereof Download PDFInfo
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- CN111423124B CN111423124B CN202010208328.8A CN202010208328A CN111423124B CN 111423124 B CN111423124 B CN 111423124B CN 202010208328 A CN202010208328 A CN 202010208328A CN 111423124 B CN111423124 B CN 111423124B
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- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000011449 brick Substances 0.000 title claims description 14
- 229910052661 anorthite Inorganic materials 0.000 claims abstract description 86
- 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 claims abstract description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 55
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 37
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 37
- 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 37
- 239000005350 fused silica glass Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052656 albite Inorganic materials 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
- 229910021532 Calcite Inorganic materials 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 239000010453 quartz Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000010433 feldspar Substances 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 12
- 229910021538 borax Inorganic materials 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910000514 dolomite Inorganic materials 0.000 claims description 11
- 239000010459 dolomite Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000004328 sodium tetraborate Substances 0.000 claims description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005299 abrasion Methods 0.000 claims 1
- 238000007688 edging Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 26
- 239000011362 coarse particle Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000292 calcium oxide Substances 0.000 description 14
- 235000012255 calcium oxide Nutrition 0.000 description 14
- 239000001913 cellulose Substances 0.000 description 10
- 229920002678 cellulose Polymers 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 235000019832 sodium triphosphate Nutrition 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- 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
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- 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
-
- 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
- C04B41/5023—Glass-ceramics
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a wear-resistant transparent glaze, which comprises the following raw materials in percentage by weight: 3-7% of nano anorthite, 20-30% of albite, 18-28% of fused quartz, 6-10% of kaolin, 40-50% of transparent frit, 0.01-0.5% of dispersing agent and 0.01-0.1% of plasticizer. By introducing special raw material components such as nano anorthite, fused quartz and transparent frit, the glaze can play a role in synergy among the raw material components in the conventional fusion sintering process, can efficiently generate a large amount of anorthite crystal phases, and further effectively and synchronously improve the hardness, wear resistance and light transmittance of the glaze.
Description
Technical Field
The invention relates to the field of building ceramic materials, in particular to a wear-resistant transparent glaze, a wear-resistant glazed brick and a preparation method thereof
Background
The prior glazed brick is characterized in that a layer of glaze (hereinafter referred to as glazed) with a transparent effect after firing is applied on the upper layer of a pattern, so that various exquisite patterns can be printed on the surface of the brick according to the pattern design, and the fired product can present the characteristics of rich patterns and high glossiness after polishing treatment, so that the glazed brick is deeply loved by wide consumption and quickly occupies most markets of building ceramics. However, the polished glaze on the polished glazed tile is mainly a glass phase, and the glass phase is not wear-resistant, so the polished glazed tile is easy to scratch. The glaze-polished tile is not wear-resistant and is easy to scratch, so that the problem to be solved urgently for glazed tile production enterprises is solved.
In order to solve the problem, patent CN107399911A discloses an anti-skid and wear-resistant glaze and a preparation method thereof, which improves the wear resistance of a glaze layer by adding anti-skid and wear-resistant particles, so that the method has the problems of uneven permeability of the glaze layer and untight combination of the wear-resistant particles and glass; patent CN106946460A discloses a cordierite transparent wear-resistant glaze and a preparation method thereof, which improves the wear resistance after firing of polished glaze by a method of generating a cordierite crystal phase in a polished glaze layer, and the method has the problems that the refractive index of cordierite has a large difference with the refractive index of a glass phase, the transparency effect is poor, the hardness of cordierite is low, and the improvement of the polished glaze wear-resistant performance is very limited.
Disclosure of Invention
The invention aims to provide a wear-resistant transparent glaze and a preparation method thereof and simultaneously provide a glazed brick applying the wear-resistant transparent glaze aiming at the defects of the prior art.
The technical scheme adopted by the invention is as follows: a wear-resistant transparent glaze comprises the following raw materials in percentage by weight: 3-7% of nano anorthite, 20-30% of albite, 18-28% of fused quartz, 6-10% of kaolin, 40-50% of transparent frit, 0.01-0.5% of dispersing agent and 0.01-0.1% of plasticizer.
Specifically, the nanometer anorthite is directly adopted as a seed crystal to be introduced into the glaze, meanwhile, fused quartz is selected to replace conventional common quartz, and the fused quartz and the transparent frit form a special system, and the three have a synergistic effect, wherein the nanometer anorthite is mainly beneficial to the efficient precipitation of an anorthite crystalline phase in the melting process; the fused quartz has high purity, is in a glass phase and mainly improves the transparency of glaze; the transparent frit is mainly used for improving the content of anorthite in the fired glaze. In addition, the fused silica described in the present invention is a high-purity, low-expansion material which is commonly used in high-end refractory materials and electronic materials. Besides the characteristics of glass phase and high transparency, the fused quartz has the characteristics of easy reaction with alkaline earth metal and effective reduction of the generation temperature of anorthite, so that the growth speed of the anorthite can be effectively improved. Therefore, the glaze material has good hardness, wear resistance and glossiness on the premise of not adjusting the subsequent conventional ceramic tile firing process by specially selecting and compounding part of raw materials.
As a further improvement of the scheme, the particle size of the nano anorthite is 10-100 nm. Specifically, too large or too small a particle size is not favorable for promoting the rapid generation of an anorthite crystal phase.
As a further improvement of the scheme, the nano anorthite has the hardness of 6-6.5 and the density of 2.55-2.67 g/cm3The refractive index is 1.572-1.588. Specifically, the anorthite in nature can only be used as one of glaze raw materials after being processed conventionally, but cannot be used as a seed crystal material, because most of the anorthite in nature is associated with calcium growthThe properties of the sintered material of the stone cannot meet the strict requirements on the seed crystal material.
According to the further improvement of the scheme, the preparation method of the nano-scale anorthite comprises the steps of mixing and ball-milling 28-32% of calcite, 15-20% of quartz and 45-52% of kaolin according to the weight percentage, dehydrating, drying, calcining at 1400-1450 ℃ for 2-4 hours, crushing, grinding, dehydrating and drying to obtain the nano-scale anorthite. Specifically, the invention selects calcite with high calcium carbonate content as one of the raw materials, the purity of the calcium carbonate can reach more than 99 percent, the defect that the light transmittance and the purity of the synthetic anorthite are reduced due to the influence of impurities in the raw materials on the components and the structure of the synthetic anorthite can be effectively reduced, and the nano-scale anorthite is calcined by quartz and kaolin according to a specific formula and a preparation method, so that the self-synthesized nano-scale anorthite has proper hardness, density and refractive index. Furthermore, the kaolin with the alumina content of more than 44% is selected as one of the raw materials, and compared with the method of simply using alumina and silicon oxide, the kaolin is easier to react, and is more beneficial to improving the generation efficiency of the anorthite crystal phase and obtaining the nano-scale anorthite with proper characteristics.
As a further improvement of the scheme, the chemical component of the transparent frit is SiO in percentage by mass246～52％，Al2O3 23～27％Fe2O3 0.05～0.10％TiO2 0～0.05％，CaO 17～19％，MgO 1.8～2.2％，K2O 2.3～2.7％，Na20.5 to 0.9 percent of O. Specifically, the transparent frit disclosed by the invention is high in aluminum trioxide content and calcium oxide content, belongs to a high-aluminum high-calcium frit, and can provide an environment suitable for anorthite precipitation during the fusion firing process of a glaze material. Further, the transparent frit provided by the invention comprises the following raw material components in percentage by weight: 23-28% of calcite, 26-34% of kaolin, 35-45% of feldspar, 3-8% of dolomite, 1-3% of zinc oxide and 1-3% of borax. Specifically, the transparent frit of the present invention increases the content of alumina and calcia in the glaze on the one hand, and on the other hand, the frit itself is in a transparent state, which exhibits anorthite and anorthiteThe glass has a molten glass state, and thus the chemical composition and raw material composition of the transparent frit have a significant effect on the properties of the transparent frit of the present invention.
In addition, the dispersing agent and the plasticizer both belong to common auxiliary agents in the ceramic glaze, preferably, the dispersing agent adopts sodium tripolyphosphate, and the plasticizer adopts polymethyl cellulose, so that the dispersing agent and the plasticizer have good adaptability with other raw material components in the glaze.
The invention also provides a preparation method of the wear-resistant transparent glaze, which comprises the following operation processes: mixing and ball-milling the raw material components until the residue of 325 meshes is below 3 percent.
Specifically, the preparation method of the wear-resistant transparent glaze comprises the following process steps:
1) mixing and ball-milling 28-32% of calcite, 15-20% of quartz and 45-52% of kaolin according to the weight percentage of the raw materials until more than 98% of particles are less than 50 mu m, dehydrating and drying, calcining the dried powder at 1400-1450 ℃ for 2-4 h to synthesize coarse anorthite particles, crushing, grinding, dehydrating and drying the coarse anorthite particles to obtain nano-scale anorthite for later use;
2) mixing, melting and firing 23-28% of calcite, 26-34% of kaolin, 35-45% of feldspar, 3-8% of dolomite, 1-3% of zinc oxide and 1-3% of borax according to the weight percentage of the raw materials to obtain transparent frit, and controlling the chemical component of the frit to be SiO2 46～52％，Al2O3 23～27％Fe2O3 0.05～0.10％TiO2 0～0.05％，CaO 17～19％，MgO 1.8～2.2％，K2O 2.3～2.7％，Na20.5-0.9% of O for standby;
3) and (3) mixing and ball-milling the raw material components of the wear-resistant transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the finished product of the wear-resistant transparent glaze.
The invention also provides a wear-resistant glazed brick which comprises a glazed layer, wherein the glazed layer is a wear-resistant transparent glazed layer formed by firing the wear-resistant transparent glaze.
The invention also provides a preparation method of the wear-resistant glazed brick, which comprises the following operation processes: and (3) distributing the wear-resistant transparent glaze on the surface of the ceramic tile green body with the decorative pattern layer to form a wear-resistant transparent glazed layer, then carrying out one-time firing, edge grinding and polishing in a kiln to obtain a wear-resistant glazed tile finished product.
As a further improvement of the scheme, the firing temperature of one-time firing in the kiln is 1210-1230 ℃.
The invention has the beneficial effects that:
by introducing special raw material components such as nano anorthite, fused quartz and transparent frit, the glaze can play a role in synergy among the raw material components in the conventional melting and firing process, can efficiently generate a large amount of anorthite crystal phases, and further effectively and synchronously improves the hardness, wear resistance and light transmittance of the glaze.
The wear-resistant transparent glaze prepared by the invention can form a wear-resistant transparent glaze-polished layer with excellent performance after a conventional glaze-polished brick firing process, and the Mohs hardness of the wear-resistant transparent glaze layer can reach 5 grades, the wear resistance of the wear-resistant transparent glaze layer can reach 4 grades, and the glossiness of the wear-resistant transparent glaze layer can reach more than 83, so that the glaze-polished brick using the wear-resistant transparent glaze has excellent wear resistance and light transmittance, and the application range of the wear-resistant glaze-polished brick is further expanded.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercial products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to the person skilled in the art.
Example 1
A wear-resistant transparent glaze comprises the following raw materials in percentage by weight: 3 percent of nano anorthite with the grain diameter of 100nm, 20 percent of albite, 28 percent of fused quartz, 6 percent of kaolin, 42.89 percent of transparent frit, 0.01 percent of sodium tripolyphosphate and 0.1 percent of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing 28% of calcite, 20% of quartz and 45% of kaolin according to the weight percentage of the raw materials, ball-milling until more than 98% of particles are less than 50 mu m, dehydrating, drying, calcining the dried powder at 1450 ℃ for 2h to synthesize anorthite coarse particles, crushing, grinding, dehydrating and drying the anorthite coarse particles to obtain nano-scale anorthite, and detecting that the hardness of the calcined anorthite is 6.5 and the density of the calcined anorthite is 2.55g/cm3The refractive index is 1.588 for standby;
2) mixing, melting and firing 23% of calcite, 30% of kaolin, 35% of feldspar, 8% of dolomite, 1% of zinc oxide and 3% of borax according to the weight percentage of the raw materials to obtain transparent frit, and controlling the chemical component of the transparent frit to be SiO2 50.1％，Al2O3 27％Fe2O3 0.05％，TiO2 0.05％，CaO 17％，MgO 2.2％，K2O 2.7％，Na20.9 percent of O for standby;
3) and (3) mixing and ball-milling the raw material components of the wear-resistant transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the wear-resistant transparent glaze finished product of the embodiment 1.
Comparative example 1
A transparent glaze comprises the following raw materials in percentage by weight: 3% of anorthite with the grain diameter of 2 mu m, 20% of albite, 28% of fused quartz, 6% of kaolin, 42.89% of transparent frit, 0.01% of sodium tripolyphosphate and 0.1% of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing, melting and firing 23% of calcite, 30% of kaolin, 35% of feldspar, 8% of dolomite, 1% of zinc oxide and 3% of borax according to the weight percentage of the raw materials to obtain transparent frit, and controlling the chemical component of the transparent frit to be SiO2 50.1％，Al2O3 27％Fe2O3 0.05％，TiO2 0.05％，CaO 17％，MgO 2.2％，K2O 2.7％，Na20.9 percent of O for standby;
2) and (3) mixing and ball-milling the raw material components of the transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the finished product of the transparent glaze in the comparative example 1.
Wherein, the anorthite described in the comparative example 1 is common anorthite, and the selected raw ore anorthite is specifically selected, and the chemical components of the anorthite are as follows: SiO 22 65.12％、Al2O3 17.31％、Fe2O3 0.15％、TiO2 0.08％、CaO 15.2％、MgO 0.22％、K2O 1.08％、Na2O 0.76％。
Comparative example 2
A transparent glaze comprises the following raw materials in percentage by weight: 3 percent of nano anorthite with the grain diameter of 100nm, 20 percent of albite, 28 percent of fused quartz, 6 percent of kaolin, 42.89 percent of transparent frit, 0.01 percent of sodium tripolyphosphate and 0.1 percent of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing 28% of calcite, 20% of quartz and 45% of kaolin according to the weight percentage of the raw materials, ball-milling until more than 98% of particles are less than 50 mu m, dehydrating, drying, calcining the dried powder at 1450 ℃ for 2h to synthesize anorthite coarse particles, crushing, grinding, dehydrating and drying the anorthite coarse particles to obtain nano-scale anorthite, and detecting that the hardness of the calcined anorthite is 6.5 and the density of the calcined anorthite is 2.55g/cm3The refractive index is 1.588 for standby;
2) and (3) mixing and ball-milling the raw material components of the transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the finished product of the transparent glaze in the comparative example 2.
The transparent frit in comparative example 2 is a common transparent frit, and the chemical components of the transparent frit are as follows: SiO 22 58.95％、Al2O3 12.78％、Fe2O3 0.17％、TiO2 8.05％、CaO 13.31％、MgO 0.62％、K2O 1.72％、Na2O 0.4％、ZnO 0.32％、B2O3 0.82％。
Comparative example 3
A transparent glaze comprises the following raw materials in percentage by weight: 3 percent of nano anorthite with the grain diameter of 100nm, 20 percent of albite, 28 percent of quartz, 6 percent of kaolin, 42.89 percent of transparent frit, 0.01 percent of sodium tripolyphosphate and 0.1 percent of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing 28% of calcite, 20% of quartz and 45% of kaolin according to the weight percentage of the raw materials, ball-milling until more than 98% of particles are less than 50 mu m, dehydrating, drying, calcining the dried powder at 1450 ℃ for 2h to synthesize anorthite coarse particles, crushing, grinding, dehydrating and drying the anorthite coarse particles to obtain nano-scale anorthite, and detecting that the hardness of the calcined anorthite is 6.5 and the density of the calcined anorthite is 2.55g/cm3The refractive index is 1.588 for standby;
2) mixing, melting and firing 23% of calcite, 30% of kaolin, 35% of feldspar, 8% of dolomite, 1% of zinc oxide and 3% of borax according to the weight percentage of the raw materials to obtain transparent frit, and controlling the chemical component of the transparent frit to be SiO2 50.1％，Al2O3 27％Fe2O3 0.05％，TiO2 0.05％，CaO 17％，MgO 2.2％，K2O 2.7％，Na20.9 percent of O for standby;
3) and (3) mixing and ball-milling the raw material components of the transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the finished product of the transparent glaze in the comparative example 3.
Wherein the quartz described in comparative example 3 is a normal quartz whose chemical composition is SiO2 98.5％、Al2O3 0.6％、Fe2O3 0.05％、TiO2 0.05％、CaO 0.04％、MgO0.05％、K2O 0.21％、Na2O 0.15％。
Comparative example 4
A transparent glaze comprises the following raw materials in percentage by weight: 10% of nano anorthite with the grain diameter of 10-100 nm, 15% of albite, 30% of fused quartz, 5% of kaolin, 39.49% of transparent frit, 0.5% of sodium tripolyphosphate and 0.01% of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing 28% of calcite, 20% of quartz and 45% of kaolin according to the weight percentage of the raw materials, ball-milling until more than 98% of particles are less than 50 mu m, dehydrating, drying, calcining the dried powder at 1450 ℃ for 2h to synthesize anorthite coarse particles, crushing, grinding, dehydrating and drying the anorthite coarse particles to obtain nano-scale anorthite, and detecting that the hardness of the calcined anorthite is 6.5 and the density of the calcined anorthite is 2.55g/cm3The refractive index is 1.588 for standby;
2) mixing, melting and firing 23% of calcite, 30% of kaolin, 35% of feldspar, 8% of dolomite, 1% of zinc oxide and 3% of borax according to the weight percentage of the raw materials to obtain transparent frit, and controlling the chemical component of the transparent frit to be SiO2 50.1％，Al2O3 27％Fe2O3 0.05％，TiO2 0.05％，CaO 17％，MgO 2.2％，K2O 2.7％，Na20.9 percent of O for standby;
3) and (3) mixing and ball-milling the raw material components of the transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the finished product of the transparent glaze in the comparative example 4.
Example 2
A wear-resistant transparent glaze comprises the following raw materials in percentage by weight: 7 percent of nano anorthite with the grain diameter of 10nm, 24.49 percent of albite, 18 percent of fused quartz, 10 percent of kaolin, 40 percent of transparent frit, 0.5 percent of sodium tripolyphosphate and 0.01 percent of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing 32% of calcite, 16% of quartz and 52% of kaolin according to the weight percentage of the raw materials, ball-milling until more than 98% of particles are less than 50 mu m, dehydrating, drying, calcining the dried powder at 1400 ℃ for 4h to synthesize anorthite coarse particles, crushing, grinding, dehydrating and drying the anorthite coarse particles to obtain nano-scale anorthite, and detecting that the hardness after firing is 6 and the density is 2.67g/cm31.572 for standby;
2) 28 percent of calcite and 2 percent of the raw materials by weight percentageMixing 6% of kaolin, 36% of feldspar, 8% of dolomite, 1% of zinc oxide and 1% of borax, melting and sintering to obtain transparent frit, wherein the chemical component of the transparent frit is controlled to be SiO2 52％，Al2O324.3％，Fe2O3 0.10％，CaO19％，MgO 1.8％，K2O 2.3％，Na20.5 percent of O for standby;
3) and (3) mixing and ball-milling the raw material components of the wear-resistant transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the wear-resistant transparent glaze finished product of the embodiment 2.
Example 3
A wear-resistant transparent glaze comprises the following raw materials in percentage by weight: 5 percent of nano anorthite with the grain diameter of 50nm, 25 percent of albite, 20 percent of fused quartz, 8 percent of kaolin, 41.75 percent of transparent frit, 0.2 percent of sodium tripolyphosphate and 0.05 percent of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing 30% of calcite, 18% of quartz and 52% of kaolin according to the weight percentage of the raw materials, ball-milling until more than 98% of particles are less than 50 mu m, dehydrating, drying, calcining the dried powder at the temperature of 1425 ℃ for 3h to synthesize anorthite coarse particles, crushing, grinding, dehydrating and drying the anorthite coarse particles to obtain nano-scale anorthite, and detecting that the hardness of the calcined anorthite is 6.2 and the density of the calcined anorthite is 2.6g/cm3The refractive index is 1.58 for standby;
2) mixing, melting and sintering 25% of calcite, 30% of kaolin, 40% of feldspar, 3% of dolomite, 1% of zinc oxide and 1% of borax according to the weight percentage of the raw materials to prepare transparent frit, and controlling the chemical component of the transparent frit to be SiO2 51.75％，Al2O3 25％，Fe2O3 0.05％，TiO2 0.05％，CaO 18％，MgO 2％，K2O 2.5％，Na20.65% of O for standby;
3) and (3) mixing and ball-milling the raw material components of the wear-resistant transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the wear-resistant transparent glaze finished product of the embodiment 3.
Example 4
A wear-resistant transparent glaze comprises the following raw materials in percentage by weight: 4 percent of nano anorthite with the grain diameter of 50nm, 24 percent of albite, 23 percent of fused quartz, 8.7 percent of kaolin, 40 percent of transparent frit, 0.2 percent of sodium tripolyphosphate and 0.1 percent of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing 32% of calcite, 20% of quartz and 48% of kaolin according to the weight percentage of the raw materials, ball-milling until more than 98% of particles are less than 50 mu m, dehydrating, drying, calcining the dried powder at 1400 ℃ for 2h to synthesize anorthite coarse particles, crushing, grinding, dehydrating and drying the anorthite coarse particles to obtain nano-scale anorthite, and detecting that the hardness of the calcined anorthite is 6.2 and the density of the calcined anorthite is 2.65g/cm3The refractive index is 1.578 for standby;
2) mixing, melting and sintering 24% of calcite, 26% of kaolin, 42% of feldspar, 4% of dolomite, 3% of zinc oxide and 1% of borax according to the weight percentage of the raw materials to prepare transparent frit, and controlling the chemical component of the transparent frit to be SiO2 48.94％，Al2O3 27％Fe2O3 0.05％，TiO2 0.01％，CaO 19％，MgO 2％，K2O 2.5％，Na20.5 percent of O for standby;
3) and (3) mixing and ball-milling the raw material components of the wear-resistant transparent glaze until the residue after being sieved by 325 meshes is less than 3 percent, thus obtaining the wear-resistant transparent glaze finished product of the embodiment 4.
Example 5
A wear-resistant transparent glaze comprises the following raw materials in percentage by weight: 4 percent of nano anorthite with the grain diameter of 100nm, 24 percent of albite, 23 percent of fused quartz, 8.7 percent of kaolin, 40 percent of transparent frit, 0.2 percent of sodium tripolyphosphate and 0.1 percent of polymethyl cellulose.
The preparation method comprises the following steps:
1) mixing calcite 32%, quartz 20% and kaolin 48% according to the weight percentage, ball milling until more than 98% of particles are less than 50 μm, dehydrating, drying, calcining the dried powder at 1450 ℃ for 2.5h to synthesize anorthite coarse particles, and calcining the anorthite coarse particlesCrushing, grinding, dehydrating and drying the coarse feldspar particles to obtain the nano-scale anorthite, and detecting the nano-scale anorthite to obtain the anorthite with the hardness of 6.35 and the density of 2.63g/cm after being sintered3The refractive index is 1.585 for later use;
2) mixing, melting and sintering 24% of calcite, 26% of kaolin, 42% of feldspar, 4% of dolomite, 3% of zinc oxide and 1% of borax according to the weight percentage of the raw materials to prepare transparent frit, and controlling the chemical component of the transparent frit to be SiO2 48.94％，Al2O3 27％Fe2O3 0.05％，TiO2 0.01％，CaO 19％，MgO 2％，K2O 2.5％，Na20.5 percent of O for standby;
3) and (3) mixing and ball-milling the raw material components of the wear-resistant transparent glaze until the residue after passing through 325 meshes is less than 3%, thus obtaining the wear-resistant transparent glaze finished product of the embodiment 5.
Example 6: performance detection
Respectively applying the wear-resistant transparent glaze finished products obtained in the examples 1-5 and the wear-resistant transparent glaze finished products obtained in the comparative examples 1-4 on the surface of the same ceramic tile green body with the decorative pattern layer to form a transparent glaze polishing layer, then performing primary firing at the firing temperature of 1210-1230 ℃ through a kiln, and performing edge grinding and polishing to obtain the samples of the examples 1-5 and the samples of the comparative examples 1-4. The samples of examples 1 to 5 and the samples of comparative examples 1 to 4 were subjected to the correlation performance test, and the test results are shown in table 1 below.
TABLE 1 Performance testing of examples 1-5 and comparative examples 1-4
The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.
Claims (8)
1. The wear-resistant transparent glaze is characterized by comprising the following raw materials in percentage by weight: 3-7% of nano anorthite, 20-30% of albite, 18-28% of fused quartz, 6-10% of kaolin, 40-50% of transparent frit, 0.01-0.5% of dispersing agent and 0.01-0.1% of plasticizer;
the preparation method of the nano-scale anorthite comprises the steps of mixing 28-32 wt% of calcite, 15-20 wt% of quartz and 45-52 wt% of kaolin, ball milling, dehydrating, drying, calcining at 1400-1450 ℃ for 2-4 hours, crushing, grinding, dehydrating and drying to obtain the nano-scale anorthite;
the chemical component of the transparent frit in percentage by mass is SiO2 46～52％，Al2O3 23～27％，Fe2O30.05～0.10％，TiO2 0～0.05％，CaO 17～19％，MgO 1.8～2.2％，K2O 2.3～2.7％，Na2O 0.5～0.9％。
2. The wear-resistant transparent glaze according to claim 1, wherein the nano anorthite has a particle size of 10-100 nm.
3. The wear-resistant transparent glaze according to claim 1, wherein the nano anorthite has a hardness of 6-6.5 and a density of 2.55-2.67 g/cm3The refractive index is 1.572-1.588.
4. The wear-resistant transparent glaze according to claim 1, wherein the raw material components of the transparent frit comprise, in weight percent: 23-28% of calcite, 26-34% of kaolin, 35-45% of feldspar, 3-8% of dolomite, 1-3% of zinc oxide and 1-3% of borax.
5. The preparation method of the wear-resistant transparent glaze according to any one of claims 1 to 4, which is characterized by comprising the following operation processes: mixing and ball-milling the raw material components until the residue of 325 meshes is below 3 percent.
6. A wear-resistant glazed tile, which comprises a glazed layer, and is characterized in that the glazed layer is a wear-resistant transparent glazed layer formed by firing the wear-resistant transparent glaze of any one of claims 1 to 4.
7. A method for preparing the abrasion-resistant glazed brick as claimed in claim 6, which comprises the following operation processes: and (3) distributing the wear-resistant transparent glaze on the surface of the ceramic tile green body with the decorative pattern layer to form a wear-resistant transparent glaze polishing layer, and then, firing in a kiln once, edging and polishing to obtain a finished product.
8. The preparation method of the wear-resistant glazed brick according to claim 7, wherein the once-fired firing temperature of the kiln is 1210-1230 ℃.
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| CN112851120B (en) * | 2021-01-21 | 2022-08-23 | 景德镇陶瓷大学 | Microcrystalline wear-resistant transparent glaze and preparation method and application of glaze slip thereof |
| CN115521073B (en) * | 2022-09-09 | 2023-08-25 | 杭州诺贝尔陶瓷有限公司 | Nano-calcium feldspar powder, anorthite microcrystalline frit and transparent microcrystalline glaze ceramic tile |
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Denomination of invention: Wear resistant transparent glaze, wear-resistant glazed tiles and their preparation methods Effective date of registration: 20231208 Granted publication date: 20220520 Pledgee: China Construction Bank Corporation Wuzhou Branch Pledgor: GUANGXI OUSHENNUO CERAMIC Co.,Ltd. Registration number: Y2023980070422 |