CN111943724A - Method for manufacturing matt transparent glazed ceramic chip - Google Patents
Method for manufacturing matt transparent glazed ceramic chip Download PDFInfo
- Publication number
- CN111943724A CN111943724A CN202010799733.1A CN202010799733A CN111943724A CN 111943724 A CN111943724 A CN 111943724A CN 202010799733 A CN202010799733 A CN 202010799733A CN 111943724 A CN111943724 A CN 111943724A
- Authority
- CN
- China
- Prior art keywords
- glaze
- matt
- printing
- frit
- matt transparent
- 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
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
- 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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—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
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a method for manufacturing a matt transparent glaze ceramic chip, which comprises the following steps of preparing a biscuit by spraying ground glaze → printing → spraying matt transparent glaze → burning → edging → finished product, wherein the matt transparent glaze raw material comprises the following components in percentage by weight: 80-93% of frit, 3-11% of calcined zinc oxide, 4-8% of air knife soil, 0.1-0.4% of methyl cellulose and 0.2-0.6% of sodium tripolyphosphate; the frit comprises the following raw materials: calcite, barium carbonate, strontium carbonate, potash feldspar, kaolin, soda ash, quartz sand and dolomite. The matt transparent glazed ceramic chip obtained by the invention is not added with zirconium dioxide, the transparency is better, the calcined zinc oxide is used for adjusting the expansion of the glaze so as to achieve the purpose of adjusting the brick shape, and the air knife soil improves the suspension property and the viscosity of the glaze. The gloss of the fired matt transparent glaze is 5-20 degrees, the glaze surface is smooth, the printing layer can be arranged under the matt transparent glaze to protect the printing layer from scratching, and the matt transparent glaze layer can also be used for polishing.
Description
Technical Field
The invention belongs to the field of ceramic building decoration materials, and particularly relates to a manufacturing method of a matt transparent glazed ceramic chip.
Background
The ceramic chip is a kind of ceramic tile, and has many names such as inner wall tile and glazed tile. The ceramic chip belongs to ceramic bricks, the water absorption rate is between 10% and 20%, the water absorption rate in the market is about 16% generally, and the main application place is indoor. The traditional glazed tile is generally classified according to gloss by the limitation of the type of the formula of the overglaze, wherein the gloss of the bright glazed tile is between 90 and 98 degrees, and the gloss of the matt glazed tile is between 10 and 30 degrees.
The ceramic tile bright products are the mainstream in the market at present, but the matt glazed tile products are slowly popular with consumers because of smoothness and no brightness. CN102531696A discloses a titanium-strontium matte glaze, which is a glaze prepared from 97% of frit and 3% of kaolin, wherein the frit comprises the following raw materials in parts by weight: 3-15 parts of lithium china stone powder, 1-5 parts of potassium feldspar powder, 18-30 parts of talcum powder, 20-30 parts of quartz powder, 4-22 parts of calcium carbonate, 5-20 parts of zircon powder, 6-20 parts of zinc oxide, 10-20 parts of potassium nitrate, 20-30 parts of strontium carbonate, 15-36 parts of titanium dioxide and 12-24 parts of alumina powder. The titanium strontium matt glaze is prepared by mixing 97% of frit and 3% of kaolin into glaze, and the fired matt glaze has good glaze surface texture, whiteness exceeding 82, wide firing range and easy production control. However, the relatively matt transparent glaze is rarely seen in the market, and is mainly limited in that the matt and the transparent glaze are a pair of spearheads, the matt is slow in reflection, a certain opaque phase needs to exist, and the opaque phase adversely affects the transparency effect, the opaque phase such as zirconium dioxide is reduced when the transparency of the matt ceramic tile is adjusted, but the reduction of the zirconium dioxide causes the reduction of the glaze strength and the thermal stability, and the glaze is easy to be ink-permeable and brick-shaped to warp.
Disclosure of Invention
Aiming at the defects of the prior matt transparent glazed ceramic chip, the invention aims to provide a manufacturing method of the matt transparent glazed ceramic chip, which comprises the steps of base glaze spraying → printing → matt transparent glaze spraying → sintering → edge grinding → finished product treatment, wherein the obtained matt transparent glazed ceramic chip is not added with zirconium dioxide, has better transparency, good glaze strength and thermal stability, and can adjust the brick shape.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method for manufacturing a matt transparent glazed ceramic tile comprises the following steps:
s1, spraying base glaze on a biscuit;
s2, printing;
s3, applying a matt transparent glaze, uniformly applying the glaze to the ground glaze, wherein the specific gravity of the glaze is 1.7-2.0 g/m during glaze pouring3The glaze amount is 400-800 g/m2；
The matt transparent glaze comprises the following raw materials in percentage by weight: 80-93% of frit, 3-11% of calcined zinc oxide, 4-8% of air knife soil, 0.1-0.4% of methyl cellulose and 0.2-0.6% of sodium tripolyphosphate; the frit raw materials are as follows according to important percentage: 13-17% of calcite, 10-14% of barium carbonate, 1-3% of strontium carbonate, 20-26% of potassium feldspar, 23-27% of kaolin, 1.5-4% of soda ash, 15-19% of quartz sand and 2-5% of dolomite; preparing the frit: weighing raw materials, mixing the raw materials, adding the mixed raw materials into a frit furnace, calcining and melting at 1400-1600 ℃, and flowing out of the frit furnace for water quenching to prepare the material;
s4, firing, wherein the firing temperature is 1050-1200 ℃, the firing period is 40-60 minutes, and the glossiness is 5-20 degrees after firing;
and S5, edging to obtain a finished product.
The raw material of the matt transparent glaze comprises 80-93 wt% of frit, 3-11 wt% of calcined zinc oxide and 4-8 wt% of air knife soil, and the frit accounts for 80-93 wt% of the raw material of the matt transparent glaze, and the calcined zinc oxide and the air knife soil are added. Zirconium dioxide is not added in the matt transparent glaze in order to increase the transparency; the calcined zinc oxide is added for adjusting the expansion of the glaze so as to achieve the purpose of adjusting the brick shape, and the calcined zinc oxide can reduce the expansion coefficient of the glaze and has the functions of whitening and improving the thermal stability of the glaze; air knife soil is added for adjusting the suspension property and the viscosity of the glaze.
The firing temperature of the matt transparent glaze of the invention is researched by carrying out long-term experiments based on the selection of raw materials of the matt transparent glaze and the reaction of each component in the firing process, particularly, the matt transparent glaze does not contain zirconium dioxide, and the firing temperature and time are adjusted according to the characteristics of each component of the raw materials so as to obtain good glaze performance.
In the present invention, preferably, the sub-gloss transparent glaze has a chemical composition of: SiO 2248 to 53% of Al2O313.5 to 15%, 0.8 to 1.5% of MgO, 7.3 to 11.7% of CaO, Na21.0 to 2.4% of O and K22.9-3.5% of O and SrO20.8 to 2.4 percent of BaO, 7.7 to 11.6 percent of BaO, 3 to 11 percent of ZnO, 0.9 to 1.5 percent of ignition loss and Fe2O3+TiO2Less than 0.5%.
In the present invention, the sequence of S2 and S3 can be interchanged, i.e. the matt transparent glaze is applied and then printed. The invention can place the printing layer under the matt transparent glaze to protect the printing layer from scratching, and can also use the matt transparent glaze layer for polishing.
In the invention, the printing of S2 is preferably one or a mixture of two or more of inkjet printing, roller printing and screen printing. The particular printing operation may be carried out by means conventional in the art, preferably by ink-jet printing.
In the present invention, preferably, the frit has a chemical composition of: SiO 2251 to 58% of Al2O313 to 15.5% of MgO, 0.9 to 1.7% of CaO, 8.5 to 13% of Na2O is 1.1-2.8%, K2O is 3-4%, SrO21-2.6 percent of BaO, 9-13 percent of BaO, 0-0.3 percent of ignition loss and Fe2O3+TiO2Less than 0.5%.
In the present invention, preferably, the method for preparing the matt transparent glaze comprises: the method comprises the steps of uniformly mixing raw materials, adding water for ball milling for 8-12 hours to obtain glaze slurry, sieving and ball milling the glaze slurry to obtain glaze, sieving the glaze with a 80-120-mesh sieve, and ageing for 12-48 hours for later use. Specifically, the adding amount of the water is 38-40% of the weight of the raw material dry material, and the glaze slip screening and ball milling process comprises the following steps: and (3) sieving the glaze slip by using a sieve of 80-120 meshes, then sieving by using a sieve of 300-350 meshes, controlling the screen residue to be 0.1-0.6%, and further performing ball milling according to the final screen residue. The ball milling time is prolonged when the surplus is large, and the ball milling time is shortened when the surplus is small. In the process of preparing the matt transparent glaze, the fineness of the glaze needs to be ensured. The glaze material is crushed to be too fine, so that the glaze slip has too large viscosity and too much water content, and after the dried blank body is glazed, the glaze surface is easy to crack, and the glaze layer is tilted to separate from the blank body. This defect is more pronounced if the glazing is thicker. However, if the glaze is not sufficiently crushed, the adhesion of the glaze slip is too low, and the components in the glaze are liable to settle. And the adhesion of the glaze layer and the blank is not firm.
In the invention, preferably, the glaze specific gravity is 1.7-2.0 g/m during the glaze pouring of S23The flow rate is 35-40 seconds, and the glaze amount is 400-800 g/m2. The concentration of the glaze slip is properly selected during glazing. If the concentration of the glaze slip is too low, an excessively thin glaze layer is easily formed on the blank, so that the traces on the glaze of the fired product are rough, and the gloss of the fired glaze is poor. However, if the concentration of the glaze slip is too high, the glazing operation is not easy to be mastered, and the glaze cannot be coated on the edge part inside the blank. The glaze surface is easy to crack after glazing, and the phenomena of glaze accumulation and the like can be generated on the surface of the product after firing. The specification of the matt transparent glaze pouring glaze enables the glaze to be uniformly spread, the glaze is uniformly distributed with consistent thickness, and the glaze surface is flat and smooth after firing.
Specifically, the method for manufacturing the matt transparent glazed ceramic tile comprises the following steps:
a. the frit comprises the following raw materials in percentage by weight: 13-17% of calcite, 10-14% of barium carbonate, 1-3% of strontium carbonate, 20-26% of potassium feldspar, 23-27% of kaolin, 1.5-4% of soda ash, 15-19% of quartz sand and 2-5% of dolomite; . The raw materials are mixed, added into a frit furnace, calcined and melted at 1400-1600 ℃, and then flow out of the frit furnace to be water-quenched into frit particles for later use.
b. Weighing 80-93% of frit, 3-11% of calcined zinc oxide, 4-8% of air knife soil, 0.1-0.4% of methyl cellulose, 0.2-0.6% of sodium tripolyphosphate and 39% of water by weight of dry materials according to the weight percentage, and carrying out ball milling for 8-12 hours to obtain glaze slip, wherein the glaze slip is firstly sieved by a sieve of 80-120 meshes, the sieved residue is controlled to be 0.1-0.6% by a sieve of 325 meshes, and the ball milling time is properly adjusted according to the residual condition of the sieve of 325 meshes, the ball milling time is prolonged when the sieved residue is large, and the ball milling time is reduced when the sieved residue is small. And after the surplus is qualified, sieving the glaze discharged balls with a sieve of 80-120 meshes, and ageing for 12-48 hours for later use.
c. And (5) printing the biscuit after applying the ground coat.
d. After the biscuit is printed, spraying or sprinkling a matt transparent overglaze, wherein the specific gravity of the glaze during spraying is 1.7-2.0 g/m3The flow rate is 35-40 seconds, and the glaze amount is 400-800 g/m2(ii) a And sintering at 1050-1200 ℃ for 40-60 minutes to obtain the matt transparent glazed ceramic tile.
e. And c, the printing and the matt transparent glaze spraying in the step d can be exchanged, the ordinary matt product is obtained by spraying the matt transparent glaze firstly and then printing, and the under-matt product is obtained by spraying the matt transparent glaze firstly and then printing.
The invention also aims to provide the ceramic tile manufactured by the manufacturing method of the matt transparent glazed ceramic tile.
The invention has the beneficial effects that:
the matt transparent glaze does not add zirconium dioxide for improving the transparency, saves the cost of the glaze and reduces the possibility of radiation caused by the zirconium dioxide; the added calcined zinc oxide can be used for adjusting the expansion of the glaze so as to achieve the purpose of adjusting the brick shape, and the calcined zinc oxide can reduce the expansion coefficient of the glaze and has the functions of whitening and improving the thermal stability of the glaze. The introduction of partial strontium oxide in the frit formula can reduce the firing temperature, widen the firing range and enhance the wear resistance of the glaze; the glaze also contains air knife soil which is processed kaolin and mainly plays a role in improving the suspension property and the viscosity of the glaze. The gloss of the fired matt transparent glaze is 5-20 degrees, the glaze surface is smooth and moderate in brightness, the printing layer can be placed under the matt transparent glaze to protect the printing layer from scratching, and the matt transparent glaze layer can also be used for polishing.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, but the scope of the present invention is not limited to the embodiments.
The starting materials used in the following examples are all commercially available unless otherwise specified.
Example 1:
preparing a matt transparent glazed tile:
a. according to the important percentage of frit raw materials: 17.2% of quartz sand, 25.3% of kaolin, 3.5% of dolomite, 15.2% of calcite, 2.5% of soda ash, 23.2% of potassium feldspar, 11.9% of barium carbonate and 1.2% of strontium carbonate. Weighing raw materials, mixing, adding into a frit furnace, calcining at 1400 ℃, melting, flowing out of the frit furnace, and quenching into frit particles for later use. The frit comprises the following chemical components: SiO 2255.7% of Al2O314.5%, 1.4% MgO, 11% CaO, Na2O is 1.8%, K2O is 3.5%, SrO21% of BaO, 10.7% of BaO, 0.3% of ignition, Fe2O3+TiO2Is 0.1%.
b. Weighing 80.2% of frit, 11.2% of calcined zinc oxide, 8.2% of air-knife soil, 0.1% of methyl cellulose and 0.3% of sodium tripolyphosphate according to the raw material of the matt transparent glaze, adding water according to 39% of the weight of dry materials, and carrying out ball milling for 8-12 hours to obtain glaze slurry, wherein the glaze slurry is firstly sieved by a 80-120-mesh sieve, then sieved residues are measured by a 325-mesh sieve and controlled to be 0.1-0.6%, and according to the final condition of the 325-mesh sieve residues, the ball milling time is properly adjusted, the ball milling time is prolonged when the sieved residues are large, and the ball milling time is. And after the surplus is qualified, sieving the glaze discharged balls with a sieve of 80-120 meshes, and ageing for 12-48 hours for later use. The chemical composition of the matt transparent glaze is as follows: SiO 2249.1% of Al2O314.6% of MgO, 1.1% of MgO, 8.9% of CaO and Na2O is 1.5%, K2O is 3.0%, SrO20.8% of BaO, 8.7% of ZnO, 1.2% of ignition, and Fe2O3+TiO2Is 0.2 percent。
c. After the biscuit is subjected to ground coat application, printing is carried out in a printing mode, such as ink-jet printing, roller printing, screen printing or cross printing between the biscuit and the roller printing.
d. After printing, spraying or spraying matt transparent overglaze, uniformly applying the glaze on the printing layer, wherein the specific gravity of the glaze is 1.7g/m during glaze spraying3Flow rate of 40 seconds and glaze amount of 400g/m2。
e. And (4) after the sintering, the sintering temperature is 1050 ℃, the sintering period is 60 minutes, and the edge grinding or polishing working procedure is added to obtain the finished product.
The prepared matt transparent glaze ceramic chip has the glossiness of 5 degrees, the printing texture of the glaze surface is naturally and slightly whitish, the texture is clear after polishing, and the hand feeling is smooth and fine.
Example 2:
preparing a matt transparent glazed tile:
a. according to the important percentage of frit raw materials: 15% of quartz sand, 23% of kaolin, 3.5% of dolomite, 17% of calcite, 2.5% of soda ash, 23.2% of potassium feldspar, 12.8% of barium carbonate and 3% of strontium carbonate. Weighing raw materials, mixing, adding into a frit furnace, calcining at 1600 ℃, melting, flowing out of the frit furnace, and quenching into frit particles for later use. The frit comprises the following chemical components: SiO 2253% of Al2O313.5%, 1.4% MgO, 12.3% CaO, Na2O is 1.8%, K2O is 3.5%, SrO22.6% of BaO, 11.5% of BaO, 0.2% of ignition, Fe2O3+TiO2Is 0.2%.
b. Weighing 92.8% of frit, 3% of calcined zinc oxide, 3.9% of air-knife soil, 0.1% of methyl cellulose, 0.2% of sodium tripolyphosphate and 39% of water by weight of dry materials according to the raw materials of the matt transparent glaze, carrying out ball milling for 8-12 hours to obtain glaze slurry, firstly sieving the glaze slurry by a sieve of 80-120 meshes, then sieving the glaze slurry by a sieve of 325 meshes to control the screen residue to be 0.1-0.6%, and according to the final condition of the sieve residue of 325 meshes, properly adjusting the ball milling time, increasing the ball milling time when the sieve residue is large, and reducing the ball milling time when the sieve residue is. And after the surplus is qualified, sieving the glaze discharged balls with a sieve of 80-120 meshes, and ageing for 12-48 hours for later use. The chemical composition of the matt transparent glaze is as follows: SiO 2250.9% of Al2O3Is 14%, MgO 1.3%, CaO 11.5%, Na2O is 1.7%, K2O is 3.4%, SrO22.4%, BaO 10.8%, ZnO 3%, ignition loss 0.9%, Fe2O3+TiO2Is 0.1%.
c. After applying the ground coat to the biscuit, spraying or spraying a matte transparent overglaze, and uniformly applying the glaze to the ground coat layer, wherein the specific gravity of the glaze during glaze spraying is 1.84g/m3Flow rate of 40 seconds and glaze amount of 600g/m2。
d. Printing, the printing mode can be ink-jet printing or roller printing, silk screen printing, or cross printing between them.
e. Sintering at 1200 deg.c for 40 min, and grinding to obtain the product.
The prepared matt transparent glazed ceramic chip has the glossiness of 15 degrees, the printing texture of the glaze surface is naturally and slightly grey, the texture is clear after polishing, and the hand feeling is smooth and fine.
Example 3:
preparing a matt transparent glazed tile:
a. according to the important percentage of frit raw materials: 19% of quartz sand, 25.3% of kaolin, 5% of dolomite, 15.2% of calcite, 2.5% of soda ash, 20% of potassium feldspar, 12% of barium carbonate and 1% of strontium carbonate. Weighing raw materials, mixing, adding into a frit furnace, calcining at 1500 ℃, melting, flowing out of the frit furnace, and quenching with water to obtain frit particles for later use. The frit comprises the following chemical components: SiO 2255% of Al2O313.2% of MgO, 1.7% of CaO, 12.7% of Na2O is 1.7%, K2O is 3.2%, SrO20.9% of BaO, 11.1% of BaO, 0.1% of ignition, Fe2O3+TiO2Is 0.4%.
b. Weighing 84.7% of frit, 7% of calcined zinc oxide, 7.8% of air-knife soil, 0.15% of methyl cellulose, 0.35% of sodium tripolyphosphate and 38% of water by weight of dry materials according to the raw materials of the matt transparent glaze, carrying out ball milling for 8-12 hours to obtain glaze slurry, firstly sieving the glaze slurry by a sieve of 80-120 meshes, then sieving the glaze slurry by a sieve of 325 meshes to control the screen residue to be 0.1-0.6%, and according to the final condition of the sieve residue of 325 meshes, properly adjusting the ball milling time, increasing the ball milling time when the sieve residue is large, and reducing the sieve residue when the sieveThe ball milling time is shortened. And after the surplus is qualified, sieving the glaze discharged balls with a sieve of 80-120 meshes, and ageing for 12-48 hours for later use. The chemical composition of the matt transparent glaze is as follows: SiO 2250.5% of Al2O314% of MgO, 1.5% of MgO, 10.7% of CaO and Na2O is 1.5%, K2O is 2.9%, SrO20.8%, 9.3% BaO, 6.9% ZnO, 1.4% ignition, Fe2O3+TiO2Is 0.5%.
c. After the biscuit is subjected to ground coat application, printing is carried out in a printing mode, such as ink-jet printing, roller printing, screen printing or cross printing between the biscuit and the roller printing.
d. After printing, spraying or spraying matt transparent overglaze, and uniformly applying the glaze on the printing layer, wherein the specific gravity of the glaze is 1.82g/m during glaze spraying3Flow rate of 35 seconds and glaze amount of 600g/m2。
e. And (4) after the sintering, the sintering temperature is 1125 ℃, the sintering period is 50 minutes, and the edge grinding or polishing working procedures are added to obtain the finished product.
The prepared matt transparent glazed ceramic chip has the glossiness of 10 degrees, the printing texture of the glaze surface is naturally and slightly grey, the texture is clear after polishing, and the hand feeling is smooth and fine.
Example 4:
preparing a matt transparent glazed tile:
a. according to the important percentage of frit raw materials: 15% of quartz sand, 23% of kaolin, 4% of dolomite, 17% of calcite, 1.5% of soda ash, 22.5% of potassium feldspar, 14% of barium carbonate and 3% of strontium carbonate. Weighing raw materials, mixing, adding into a frit furnace, calcining at 1550 ℃ for melting, flowing out of the frit furnace, and quenching into frit particles for later use. The frit comprises the following chemical components: SiO 2251.2% of Al2O313% of MgO, 1.6% of MgO, 13.3% of CaO and Na2O is 1.1%, K2O is 3.4%, SrO22.7% of BaO, 13.2% of BaO, 0.2% of ignition, Fe2O3+TiO2Is 0.3%.
b. According to the weight percentage of the raw material of the matt transparent glaze, 87.73 percent of fusion cake, 5.8 percent of calcined zinc oxide, 6 percent of air-knife soil, 0.12 percent of methyl cellulose, 0.35 percent of sodium tripolyphosphate and 40 percent of water by weight of dry materials are weighedAnd ball-milling for 8-12 hours to obtain glaze slurry, sieving the glaze slurry by a sieve of 80-120 meshes, then sieving by a sieve of 325 meshes, controlling the sieved residue to be 0.1-0.6%, properly adjusting the ball-milling time according to the final condition of the sieved residue of 325 meshes, increasing the ball-milling time when the sieved residue is large, and reducing the ball-milling time when the sieved residue is small. And after the surplus is qualified, sieving the glaze discharged balls with a sieve of 80-120 meshes, and ageing for 12-48 hours for later use. The chemical composition of the matt transparent glaze is as follows: SiO 2248% of Al2O313.6% of MgO, 1.4% of CaO, 11.7% of Na2O is 1.0%, K2O is 3.1%, SrO22.4% of BaO, 11.6% of ZnO, 5.9% of ZnO, 1.0% of ignition, Fe2O3+TiO2Is 0.3%.
c. After the biscuit is subjected to ground coat application, printing is carried out in a printing mode, such as ink-jet printing, roller printing, screen printing or cross printing between the biscuit and the roller printing.
d. After printing, spraying or spraying matt transparent overglaze, and uniformly applying the glaze on the printing layer, wherein the specific gravity of the glaze is 2.0g/m during glaze spraying3Flow rate of 40 seconds and glaze amount of 800g/m2。
e. And (5) sintering at 1100 ℃ for 55 minutes in a sintering period, and edging or polishing to obtain a finished product.
The prepared matt transparent glazed ceramic chip has the glossiness of 20 degrees, the printing texture of the glaze surface is naturally and slightly grayish white, the printing texture is slightly fuzzy, the texture is clear after polishing, and the hand feeling is smooth and fine.
Example 5:
preparing a matt transparent glazed tile:
a. according to the important percentage of frit raw materials: 16.8% of quartz sand, 27% of kaolin, 2% of dolomite, 13% of calcite, 4% of soda ash, 26% of potassium feldspar, 10% of barium carbonate and 1.2% of strontium carbonate. Weighing raw materials, mixing, adding into a frit furnace, calcining at 1450 ℃, melting, flowing out of the frit furnace, and quenching with water to obtain frit particles for later use. The frit comprises the following chemical components: SiO 2258% of Al2O315.5% of MgO, 0.9% of CaO, 8.5% of Na2O is 2.8%, K2O is 3.9%, SrO21% of BaO, 9% of BaO, 0.2% of ignition, Fe2O3+TiO2Is 0.2%.
b. Weighing 85.7% of frit, 6.7% of calcined zinc oxide, 7% of air-knife soil, 0.2% of methyl cellulose and 0.4% of sodium tripolyphosphate according to the raw material of the matt transparent glaze, adding water according to 39% of the weight of dry materials, and carrying out ball milling for 8-12 hours to obtain glaze slurry, wherein the glaze slurry is firstly sieved by a 80-120-mesh sieve, then sieved residues are controlled to be 0.1-0.6% by a 325-mesh sieve, and the ball milling time is properly adjusted according to the final condition of the sieved residues of the 325-mesh sieve, the ball milling time is increased when the sieved residues are large, and the ball milling time. And after the surplus is qualified, sieving the glaze discharged balls with a sieve of 80-120 meshes, and ageing for 12-48 hours for later use. The chemical composition of the matt transparent glaze is as follows: SiO 2253.4% of Al2O315.8% of MgO, 7.3% of CaO and Na2O is 2.4%, K2O is 3.5%, SrO20.9%, 7.7% BaO, 6.9% ZnO, 1.1% ignition, Fe2O3+TiO2Is 0.2%.
c. After the biscuit is subjected to ground coat application, printing is carried out in a printing mode, such as ink-jet printing, roller printing, screen printing or cross printing between the biscuit and the roller printing.
d. After printing, spraying or spraying matt transparent overglaze, uniformly applying the glaze on the printing layer, wherein the specific gravity of the glaze is 1.9g/m during glaze spraying3Flow rate of 35 seconds and glaze amount of 700g/m2。
e. And (4) after the sintering, the sintering temperature is 1150 ℃, the sintering period is 53 minutes, and the edge grinding or polishing process is added to obtain the finished product.
The prepared matt transparent glaze ceramic chip has the glossiness of 15 degrees, the printing texture of the glaze surface is naturally and slightly grey, and the printing texture is slightly fuzzy. The texture is clear after polishing, and the hand feeling is smooth and fine.
Aiming at the specific embodiment, the matt transparent glaze does not add zirconium dioxide for increasing the transparency, so that the cost of the glaze is saved, the raw material selection and content optimization of the glaze are further required to be adjusted due to no addition of zirconium dioxide, the adaptive matching preparation process is researched according to the characteristics of each component of the raw material, and the manufacturing method of the matt transparent glaze ceramic chip is obtained through continuous optimization experiments. The gloss of the glazed transparent glazed ceramic chip is 5-20 degrees after firing, the glaze surface is smooth, and the transparency is good.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The method for manufacturing the matt transparent glazed ceramic tile is characterized by comprising the following steps:
s1, spraying base glaze on a biscuit;
s2, printing;
s3, applying a matt transparent glaze, uniformly applying the glaze to the ground glaze, wherein the specific gravity of the glaze is 1.7-2.0 g/m during glaze pouring3The glaze amount is 400-800 g/m2；
The matt transparent glaze comprises the following raw materials in percentage by weight: 80-93% of frit, 3-11% of calcined zinc oxide, 4-8% of air knife soil, 0.1-0.4% of methyl cellulose and 0.2-0.6% of sodium tripolyphosphate; the frit raw materials are as follows according to important percentage: 13-17% of calcite, 10-14% of barium carbonate, 1-3% of strontium carbonate, 20-26% of potassium feldspar, 23-27% of kaolin, 1.5-4% of soda ash, 15-19% of quartz sand and 2-5% of dolomite; preparing the frit: weighing raw materials, mixing the raw materials, adding the mixed raw materials into a frit furnace, calcining and melting at 1400-1600 ℃, and flowing out of the frit furnace for water quenching to prepare the material;
s4, firing, wherein the firing temperature is 1050-1200 ℃, the firing period is 40-60 minutes, and the glossiness is 5-20 degrees after firing;
and S5, edging to obtain a finished product.
2. The method of making a matt glazed ceramic tile according to claim 1, wherein the matt glaze has a chemical composition of: SiO 2248 to 53% of Al2O313.5 to 15%, 0.8 to 1.5% of MgO, and CaO is 7.3 to 11.7 percent and Na21.0 to 2.4% of O and K22.9-3.5% of O and SrO20.8 to 2.4 percent of BaO, 7.7 to 11.6 percent of BaO, 3 to 11 percent of ZnO, 0.9 to 1.5 percent of ignition loss and Fe2O3+TiO2Less than 0.5%.
3. The method for making matt glazed ceramic tiles according to claim 1, wherein the sequence of S2 and S3 is reversed by applying the matt glaze and then printing.
4. The method of making a matt glazed ceramic tile according to claim 1, wherein the frit has a chemical composition of: SiO 2251 to 58% of Al2O313 to 15.5% of MgO, 0.9 to 1.7% of CaO, 8.5 to 13% of Na2O is 1.1-2.8%, K2O is 3-4%, SrO21-2.6 percent of BaO, 9-13 percent of BaO, 0-0.3 percent of ignition loss and Fe2O3+TiO2Less than 0.5%.
5. The method for manufacturing a matt transparent glazed ceramic tile according to claim 1, wherein the printing of S2 is one or more of inkjet printing, roller printing and screen printing.
6. The method for manufacturing a matt glazed ceramic tile according to claim 1, wherein the matt transparent glaze is prepared by: the raw materials are uniformly mixed, water is added for ball milling for 8-12 hours to obtain glaze slurry, the glaze slurry is sieved and ball milled to obtain glaze, the glaze is sieved by a sieve of 80-120 meshes, and then the glaze is aged for 12-48 hours for later use.
7. The method for manufacturing a matt glazed ceramic tile according to claim 6, wherein the amount of water added is 38 to 40% by weight of the dry raw materials.
8. The method for manufacturing a matt transparent glazed ceramic tile according to claim 6, wherein the step of sieving and ball milling the glaze slip comprises the following steps: and (3) sieving the glaze slip by using a sieve of 80-120 meshes, then sieving by using a sieve of 300-350 meshes, controlling the screen residue to be 0.1-0.6%, and further performing ball milling according to the final screen residue.
9. The method for manufacturing a matt glazed ceramic tile according to claim 1, wherein the glaze density is 1.7-2.0 g/m at S23The flow rate is 35-40 seconds, and the glaze amount is 400-800 g/m2。
10. A tile made by the method of making a matt glazed ceramic tile according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010799733.1A CN111943724B (en) | 2020-08-11 | 2020-08-11 | Method for manufacturing matt transparent glazed ceramic chip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010799733.1A CN111943724B (en) | 2020-08-11 | 2020-08-11 | Method for manufacturing matt transparent glazed ceramic chip |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111943724A true CN111943724A (en) | 2020-11-17 |
| CN111943724B CN111943724B (en) | 2023-01-13 |
Family
ID=73332122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010799733.1A Active CN111943724B (en) | 2020-08-11 | 2020-08-11 | Method for manufacturing matt transparent glazed ceramic chip |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111943724B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876077A (en) * | 2021-03-05 | 2021-06-01 | 广东新润成陶瓷有限公司 | Protective glaze for matte antique brick, antique brick and preparation method of protective glaze |
| CN112897882A (en) * | 2021-04-02 | 2021-06-04 | 佛山市赣联建材有限公司 | Environment-friendly acid-pollution-free etching glaze and preparation method and application thereof |
| CN113213759A (en) * | 2021-05-20 | 2021-08-06 | 福建省德化友盛陶瓷有限公司 | Matte gold grain glaze and method for preparing matte gold grain glaze ceramic product by using same |
| CN113860742A (en) * | 2021-10-14 | 2021-12-31 | 新明珠集团股份有限公司 | Simulated marble glaze, simulated marble large plate and preparation method |
| CN114180841A (en) * | 2022-02-16 | 2022-03-15 | 广东大角鹿新材料有限公司 | Soft super-wear-resistant diamond glaze, ceramic tile and preparation method thereof |
| CN114195480A (en) * | 2021-12-23 | 2022-03-18 | 新明珠集团股份有限公司 | Fine stain-resistant antibacterial brick and preparation method thereof |
| CN114644530A (en) * | 2022-03-10 | 2022-06-21 | 江西唯美陶瓷有限公司 | One-glaze two-sided ceramic rock plate, one-glaze two-sided transparent glaze and preparation method thereof |
| CN114956573A (en) * | 2022-08-01 | 2022-08-30 | 新明珠集团股份有限公司 | Waxy glaze, waxy 3D ceramic tile and preparation method thereof |
| CN115180833A (en) * | 2022-07-11 | 2022-10-14 | 佛山市华力达材料科技有限公司 | Pearl dry particles, pearl glaze, preparation methods of pearl dry particles and pearl glaze and ceramic tile |
| CN115180980A (en) * | 2022-07-11 | 2022-10-14 | 佛山市华力达材料科技有限公司 | Preparation method of ceramic with pearlescent effect and ceramic tile |
| CN115196877A (en) * | 2022-08-23 | 2022-10-18 | 广西南山瓷器有限公司 | Shadow-penetrating wax glaze and preparation and use method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03205386A (en) * | 1989-12-29 | 1991-09-06 | Kunio Inagaki | Preparation of glaze for fine ceramics |
| CN102951932A (en) * | 2012-12-06 | 2013-03-06 | 广东金牌陶瓷有限公司 | Ceramic chip and manufacturing method thereof |
| CN107344814A (en) * | 2017-07-11 | 2017-11-14 | 佛山市华力达材料科技有限公司 | A kind of sheen brick cover-coat enamel and sheen brick |
| CN107365077A (en) * | 2017-09-05 | 2017-11-21 | 赵永强 | A kind of pottery glaze |
| CN110550958A (en) * | 2019-09-17 | 2019-12-10 | 广东新润成陶瓷有限公司 | Fine, soft and matte black brick and preparation method thereof |
| CN111233329A (en) * | 2020-02-21 | 2020-06-05 | 湖南省醴陵市湘强陶瓷制造有限公司 | Matte transmutation glaze and preparation method thereof |
-
2020
- 2020-08-11 CN CN202010799733.1A patent/CN111943724B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03205386A (en) * | 1989-12-29 | 1991-09-06 | Kunio Inagaki | Preparation of glaze for fine ceramics |
| CN102951932A (en) * | 2012-12-06 | 2013-03-06 | 广东金牌陶瓷有限公司 | Ceramic chip and manufacturing method thereof |
| CN107344814A (en) * | 2017-07-11 | 2017-11-14 | 佛山市华力达材料科技有限公司 | A kind of sheen brick cover-coat enamel and sheen brick |
| CN107365077A (en) * | 2017-09-05 | 2017-11-21 | 赵永强 | A kind of pottery glaze |
| CN110550958A (en) * | 2019-09-17 | 2019-12-10 | 广东新润成陶瓷有限公司 | Fine, soft and matte black brick and preparation method thereof |
| CN111233329A (en) * | 2020-02-21 | 2020-06-05 | 湖南省醴陵市湘强陶瓷制造有限公司 | Matte transmutation glaze and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| 周晓燕: "《陶瓷坯釉料制备技术》", 31 August 2017 * |
| 曾昭远: "《装修完全手册 家居篇》", 29 February 2012 * |
| 李小龙: "高温钡无光釉的研究", 《中国硅酸盐学会陶瓷分会2016学术年会会刊》 * |
| 杜海清: "《陶瓷釉彩》", 31 January 1979 * |
| 杨永善: "《中国传统工艺全集 陶瓷 续》", 31 May 2015 * |
| 池至铣: "《陶瓷釉色料及装饰》", 30 November 2015 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876077A (en) * | 2021-03-05 | 2021-06-01 | 广东新润成陶瓷有限公司 | Protective glaze for matte antique brick, antique brick and preparation method of protective glaze |
| CN112897882A (en) * | 2021-04-02 | 2021-06-04 | 佛山市赣联建材有限公司 | Environment-friendly acid-pollution-free etching glaze and preparation method and application thereof |
| CN113213759A (en) * | 2021-05-20 | 2021-08-06 | 福建省德化友盛陶瓷有限公司 | Matte gold grain glaze and method for preparing matte gold grain glaze ceramic product by using same |
| CN113860742A (en) * | 2021-10-14 | 2021-12-31 | 新明珠集团股份有限公司 | Simulated marble glaze, simulated marble large plate and preparation method |
| CN113860742B (en) * | 2021-10-14 | 2023-08-11 | 新明珠集团股份有限公司 | Simulated marble glaze, simulated marble slab and preparation method |
| CN114195480A (en) * | 2021-12-23 | 2022-03-18 | 新明珠集团股份有限公司 | Fine stain-resistant antibacterial brick and preparation method thereof |
| CN114180841A (en) * | 2022-02-16 | 2022-03-15 | 广东大角鹿新材料有限公司 | Soft super-wear-resistant diamond glaze, ceramic tile and preparation method thereof |
| US11807577B2 (en) | 2022-02-16 | 2023-11-07 | Guangdong Deer New Materials Co., Ltd. | Super-wear-resistant diamond glaze, ceramic tile and preparation method thereof |
| CN114644530B (en) * | 2022-03-10 | 2022-12-27 | 江西唯美陶瓷有限公司 | One-glaze two-side ceramic rock plate, one-glaze two-side transparent glaze and preparation method thereof |
| CN114644530A (en) * | 2022-03-10 | 2022-06-21 | 江西唯美陶瓷有限公司 | One-glaze two-sided ceramic rock plate, one-glaze two-sided transparent glaze and preparation method thereof |
| CN115180980A (en) * | 2022-07-11 | 2022-10-14 | 佛山市华力达材料科技有限公司 | Preparation method of ceramic with pearlescent effect and ceramic tile |
| CN115180833A (en) * | 2022-07-11 | 2022-10-14 | 佛山市华力达材料科技有限公司 | Pearl dry particles, pearl glaze, preparation methods of pearl dry particles and pearl glaze and ceramic tile |
| CN114956573B (en) * | 2022-08-01 | 2022-11-11 | 新明珠集团股份有限公司 | Waxy glaze, waxy 3D ceramic tile and preparation method thereof |
| CN114956573A (en) * | 2022-08-01 | 2022-08-30 | 新明珠集团股份有限公司 | Waxy glaze, waxy 3D ceramic tile and preparation method thereof |
| CN115196877A (en) * | 2022-08-23 | 2022-10-18 | 广西南山瓷器有限公司 | Shadow-penetrating wax glaze and preparation and use method thereof |
| CN115196877B (en) * | 2022-08-23 | 2023-08-08 | 广西南山瓷器有限公司 | Transparent wax glaze and preparation and use methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111943724B (en) | 2023-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111943724B (en) | Method for manufacturing matt transparent glazed ceramic chip | |
| CN107417115B (en) | Method for manufacturing high-hardness high-wear-resistance glaze | |
| CN111875415B (en) | Method for manufacturing soft glazed ceramic chip | |
| CN112592063B (en) | High-wear-resistance marble-imitated ceramic tile and preparation method thereof | |
| CN110776256B (en) | White radial crystal flower dry grain glaze, light-transmitting ceramic tile and preparation method thereof | |
| CN104529553B (en) | The surface of manufacturing with ceramic refuse is as glazed tile and the preparation of broken brill sand flicker starlight | |
| CN110759641B (en) | Crystal flower dry grain glaze and positioning crystal flower ceramic tile prepared from crystal flower dry grain glaze | |
| CN111548016B (en) | Matt protection glaze with glossiness of below 3 degrees for thin ceramic tile, thin ceramic tile and preparation method thereof | |
| WO2021232784A1 (en) | High-wear-resistance far-infrared ceramic polished glazed tile and preparation method therefor | |
| CN105198217B (en) | It is a kind of to be used for throwing vitreous brick production entirely, beneficial to the ground-coat enamel of ceramic ink color development | |
| CN111943727B (en) | Method for manufacturing micro-marble polished ceramic chip | |
| CN112142328B (en) | Manufacturing method of ceramic chip with fine die texture | |
| CN106977097B (en) | Raw glaze for transparent high-gloss medium-temperature hard porcelain and preparation method thereof | |
| CN110903033B (en) | Crystal nucleating agent and positioning crystal pattern ceramic tile prepared by using same | |
| CN109824270A (en) | A kind of decorative brick of diamond flash effect, colored dry granular and preparation method thereof | |
| CN113800879B (en) | Transparent stone ceramic plate and preparation method thereof | |
| CN113860736B (en) | Full-polished glaze and ceramic tile with iridescent glittering effect, and preparation method and application thereof | |
| CN108423993A (en) | One kind building pottery aerolite glaze and its application process | |
| CN113999054A (en) | Crystal-drilled marble porcelain tile and preparation method thereof | |
| CN113860740A (en) | Jade-like dry particles with opacifying effect, preparation method thereof and ceramic tile | |
| CN110862230B (en) | Dry ice crack nucleating agent particles, ice crack crystal flower light-transmitting ceramic tile and preparation method thereof | |
| CN114426397B (en) | Preparation method of snow-powder fritted glaze and ceramic tile with snow-powder effect | |
| CN114249586B (en) | Black ceramic tile with three-dimensional flashing effect and preparation method thereof | |
| CN115466056A (en) | Colored frit dry particles and ceramic tile decorated by same | |
| CN112592208B (en) | Silk glaze ceramic tile and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 528131 Central Industrial Development Zone, Baini Town, Sanshui District, Foshan City, Guangdong Province Applicant after: FOSHAN SANSHUI NEW PEARL CONSTRUCTION CERAMICS INDUSTRIAL Co.,Ltd. Applicant after: New Pearl Group Co.,Ltd. Address before: 528131 Central Industrial Development Zone, Baini Town, Sanshui District, Foshan City, Guangdong Province Applicant before: FOSHAN SANSHUI NEW PEARL CONSTRUCTION CERAMICS INDUSTRIAL Co.,Ltd. Applicant before: GUANGDONG NEWPEARL CERAMIC GROUP Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |