CN112408793B - High-light-transmission wear-resistant frit, preparation method thereof, glaze and marble ceramic tile - Google Patents
High-light-transmission wear-resistant frit, preparation method thereof, glaze and marble ceramic tile Download PDFInfo
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- CN112408793B CN112408793B CN202011333383.6A CN202011333383A CN112408793B CN 112408793 B CN112408793 B CN 112408793B CN 202011333383 A CN202011333383 A CN 202011333383A CN 112408793 B CN112408793 B CN 112408793B
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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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
- E04F13/14—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass
- E04F13/147—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass with an outer layer imitating natural stone, brick work or the like
-
- 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
Abstract
The invention provides a high-light-transmission wear-resistant frit, a preparation method thereof, a glaze and a marble tile. The high light-transmitting abrasion-resistant frit comprises: 22-26% of kaolin, 2-4% of calcined alumina, 22-26% of calcined talc, 2-5% of magnesite, 15-18% of quartz, 9-11% of calcite, 3-5% of zinc oxide, 7-9% of strontium carbonate, 2-4% of borax and 3-5% of cordierite. The preparation method of the high-light-transmission wear-resistant frit comprises the following steps: uniformly mixing the raw materials according to the raw material proportion; placing the raw materials in a frit furnace, sintering and melting the raw materials at 1450 ℃ to obtain molten glass, and quenching the molten glass with water; and drying, crushing and screening the water-quenched frit to obtain the high-light-transmittance wear-resistant frit. Glaze comprising a high light transmission abrasion resistant frit. The raw material of the marble tile comprises the glaze. The application provides a wear-resisting frit of high printing opacity, firing temperature is low, luminousness and abrasion resistance are high.
Description
Technical Field
The invention relates to the field of ceramics, in particular to a high-light-transmission wear-resistant frit, a preparation method thereof, a glaze and a marble ceramic tile.
Background
The polished glaze is used as the last transparent glaze on the surface of the marble tile, and the physical and chemical properties of the polished glaze directly influence the surface performance of the product, so the polished glaze is a key factor for determining the surface hardness of the marble tile. Based on the comprehensive consideration of production cost and production process, the combination mode of the main formula for producing the marble ceramic tile glaze in the market at present is the combination of raw glaze powder and clinker powder.
The frit is used as an important raw material for glaze polishing, and the quality of the frit directly affects the glaze quality of a product, so that the quality of the product is directly affected. In order to improve the glossiness and the permeability of a glaze surface, transparent frits are usually added into the glaze, at present, a large amount of potassium, albite and other raw materials are introduced into a formula mainly for increasing the transparency of the frits, but the introduction of the raw materials can greatly reduce the wear resistance of the transparent frits, so that the wear resistance of the glaze is reduced. In addition, in order to improve the wear resistance of the frit, a large amount of materials containing high aluminum, such as corundum and alumina, are added into the frit formula to improve the aluminum content in the formula, so that the sintering temperature of the frit exceeds 1500 ℃, the sintering temperature is high, and the heat preservation time is long.
Disclosure of Invention
The invention aims to provide a high-light-transmission wear-resistant frit, a preparation method thereof, a glaze and a marble ceramic tile, so as to solve the problems.
In order to achieve the above purpose, the invention provides the following technical scheme:
a high-light-transmission wear-resistant frit comprises the following raw materials in percentage by mass:
22-26% of kaolin, 2-4% of calcined alumina, 22-26% of calcined talc, 2-5% of magnesite, 15-18% of quartz, 9-11% of calcite, 3-5% of zinc oxide, 7-9% of strontium carbonate, 2-4% of borax and 3-5% of cordierite.
Preferably, the cordierite is an artificial synthetic powder, and the chemical components of the cordierite comprise, by mass: SiO 2 2 47-51％、Al 2 O 3 32-35％、Fe 2 O 3 0-0.6 percent and MgO13-15 percent.
The cordierite addition amount is less than 2%, the abrasion resistance of the frit is not remarkably improved, the addition amount exceeds 5%, the light transmittance of the frit starts to be reduced, and the raw material cost is remarkably increased. Cordierite has good refractoriness (> 1400 ℃), and is difficult to completely melt in a 1450 ℃ firing environment, so cordierite powder is preferably processed to 325 meshes so that the cordierite powder can be completely melted in the 1450 ℃ firing environment through the cooperation of a high-strength flux.
Alternatively, the amount of kaolin used in the raw material of the high-light-transmittance abrasion-resistant frit may be any of 22%, 23%, 24%, 25%, 26% and 22-26% by mass; the amount of calcined alumina may be any value between 2%, 3%, 4% and 2-4%; the amount of calcined talc may be any value between 22%, 23%, 24%, 25%, 26% and 22-26%; the amount of magnesite can be any value between 2%, 3%, 4%, 5% and 2% -5%; the amount of quartz may be any value between 15%, 16%, 17%, 18% and 15-18%; the amount of calcite may be any of 9%, 10%, 11% and between 9 and 11%; the amount of zinc oxide can be any value between 3%, 4%, 5% and 3-5%; the amount of strontium carbonate can be any of 7%, 8%, 9%, and 7-9%; the amount of borax may be any of 2%, 3%, 4% and 2-4%; the amount of cordierite used may be any of 3%, 4%, 5%, and 3-5%.
Preferably, the cordierite has a cordierite phase content of 95-97% and a bulk density of not less than 1.6g/cm 3 。
The cordierite phase content may be any of 95%, 96%, 97% and 95-97%, and the bulk density may be 1.6g/cm 3 、1.65g/cm 3 、1.7g/cm 3 、1.75g/cm 3 、1.8g/cm 3 Equal to or more than 1.6g/cm 3 An optional value of.
Preferably, the high light-transmitting wear-resistant frit comprises the following chemical components in percentage by mass:
14-16％Al 2 O 3 、49-54％SiO 2 、5-8％CaO、0.05-0.5％Fe 2 O 3 、0.5-1％K 2 O、11-13％MgO、3-6％ZnO、0.1-1％Na 2 O、0.01-0.1％TiO 2 5.5-7.5% SrO and 0.5-2% B 2 O 3 The loss on ignition is 1-2%.
Optionally, the high light-transmission wear-resistant frit comprises the following chemical components in percentage by mass, Al 2 O 3 Can be any value between 14%, 15%, 16% and 14-16%; SiO 2 2 Can be 49%, 50%, 51%, 52%, 53%, 54% and any value between 49-54%; the content of CaO can be any value between 5%, 6%, 7%, 8% and 5-8%; fe 2 O 3 The content of (b) may be any value between 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, and 0.05-0.5%; k 2 The content of O may be 05%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and any value between 0.5-1%; the content of MgO can be any value between 11%, 12%, 13% and 11-13%; the content of ZnO can be any value between 3%, 4%, 5%, 6% and 3-6%; na (Na) 2 The content of O may be any value between 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and 0.1-1%; TiO 2 2 The content of (b) may be any value between 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, and 0.01-0.1%; the SrO content may be any value between 5.5%, 6%, 6.5%, 7%, 7.5% and 5.5-7.5%; b is 2 O 3 Can be any value between 0.5%, 1%, 1.5%, 2% and 0.5-2%; the loss on ignition can be any value between 1%, 1.5%, 2% and 1-2%.
A preparation method of a high-light-transmission wear-resistant frit comprises the following steps:
(1) uniformly mixing the raw materials according to the raw material proportion;
(2) placing the raw materials in a frit furnace, sintering and melting the raw materials at 1450 ℃ to obtain molten glass, and quenching the molten glass with water;
(3) and drying, crushing and screening the water-quenched frit to obtain the high-light-transmittance wear-resistant frit.
Preferably, the firing temperature profile is:
(1) heating to 300 deg.C from normal temperature, and taking 60 min;
(2) heating from 300 deg.C to 1100 deg.C, and taking 120 min;
(3) heating to 1100 deg.C to 1450 deg.C, and taking 45 min;
(4) keeping the temperature at 1450 ℃ for 60 min.
The frit has the advantages that the heating rate in the high-temperature firing process is low, the heating is slow, raw materials in the frit can be fully melted, and a system for synthesizing cordierite, namely kaolin-firing talc-calcined alumina, kaolin-magnesite-firing talc and kaolin-magnesite-quartz, can synthesize complete alpha-cordierite crystals in a temperature range of 1300-1500 ℃, so that the wear resistance of the low-temperature wear-resistant frit is improved, and the transparency of the low-temperature wear-resistant frit cannot be greatly influenced.
Preferably, each stage of heating independently adopts constant-speed temperature rise.
Preferably, the crushing further comprises screening, and the particle size of the particles obtained by screening is less than or equal to 120 meshes.
A glaze material comprises the high-light-transmission wear-resistant frit.
The raw materials of the marble tile comprise the glaze.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the high-light-transmission wear-resistant frit, feldspar is not added, and materials such as calcite and magnesite are used for replacing the feldspar, so that the contents of magnesium and calcium in a formula are increased, and the firing temperature of the low-temperature wear-resistant frit is reduced; the magnesite is introduced, the carbonate of the magnesite has a fluxing function, a large amount of magnesium ions are provided, and the sintering temperature of the clinker can reach 1450 ℃ by matching with active fluxes such as zinc oxide, strontium carbonate, borax and the like, which is 50 ℃ lower than that of common wear-resistant frits; the crystal phase separated out by the high-light-transmission wear-resistant frit is mainly cordierite; kaolin, calcined alumina, calcined talc, magnesite and quartz are used as providers of silicon, aluminum and magnesium elements in a cordierite crystal structure, three systems of kaolin-calcined talc-calcined alumina, kaolin-magnesite-calcined talc and kaolin-magnesite-quartz exist simultaneously, so that cordierite microcrystalline crystal nuclei and cordierite microcrystalline crystals can be more easily separated out from the low-temperature wear-resistant frit, and the cordierite is introduced and fused into mature cordierite crystals at a high temperature state, so that the distribution rate of the cordierite crystals in the frit exceeds 60%; the frit has good transparency and wear resistance due to the large amount of cordierite crystals in the frit, and a wear-resistant frit sample with the thickness of 1mm has the light transmittance of 25-30% and the wear resistance of 4-grade 2100 turns.
The preparation method of the high-light-transmission wear-resistant frit is simple to operate;
the glaze provided by the application can increase transparency on the basis of keeping original wear resistance by adding the high-light-transmission wear-resistant frit;
the application provides a marble ceramic tile, the luminousness is high, and wear resistance and antifouling performance are excellent, and decorative effect is good.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any non-specified element, step, or component. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In the examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If the parts by mass of the component A are a parts and the parts by mass of the component B are B parts, the mass ratio of the component A to the component B is expressed as a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
Preparing raw materials:
23kg of kaolin, 4kg of calcined alumina, 25kg of calcined talc, 4kg of magnesite, 16kg of quartz, 9kg of calcite, 4kg of zinc oxide, 7kg of strontium carbonate, 3kg of borax and 5kg of cordierite.
The cordierite is artificially synthesized powder, and the chemical components of the cordierite, calculated by mass percent, comprise: SiO 2 2 47-51％、Al 2 O 3 32-35％、Fe 2 O 3 0-0.6 percent and MgO13-15 percent.
Detecting the chemical components of the finished frit, wherein the chemical components comprise the following components in percentage by mass: 15.99% Al 2 O 3 、51.90％SiO 2 、6.42％CaO、0.43％Fe 2 O 3 、0.63％K 2 O、12.46％MgO、4.56％ZnO、0.61％Na 2 O、0.05％TiO 2 5.61% SrO and 1.25% B 2 O 3 。
Mixing the raw materials of the wear-resistant frit according to the proportion, firing at high temperature (from normal temperature to 300 ℃ for 60 min; from 300 ℃ to 1100 ℃ for 120 min; from 1100 ℃ to 1450 ℃ for 45 min; and preserving heat at 1450 ℃ for 60min), and quenching in water to obtain the wear-resistant frit;
drying, crushing and sieving the high-light-transmission wear-resistant frit, and taking a 120-mesh screen underflow for later use;
preparing raw glaze powder, and mixing 22kg of kaolin, 21kg of calcined kaolin, 42kg of calcined talc, 6kg of calcite and 9kg of zinc oxide;
mixing the raw glaze powder and the frit (the mass ratio of the raw glaze powder to the frit is 7: 3), adding water and the printing paste according to the mass ratio of the glaze: water: ball milling the paste at a ratio of 1:0.35:0.65 for 9h to obtain glaze slurry, controlling the fineness to be 325 meshes and the screen residue to be 0.8%, and then aging for 49h to prepare glaze;
glaze polishing in the existing production process of the marble ceramic tile is replaced by the glaze, the glaze is printed on the surface of the ceramic tile through a silk screen with the aperture of 100 meshes back and forth for 2 times, the ceramic tile is dried, is mixed into a kiln, is sintered at 1206 +/-6 ℃, and is polished to obtain the marble ceramic tile.
Example 2
Preparing raw materials:
26kg of kaolin, 3kg of calcined alumina, 22kg of calcined talc, 5kg of magnesite, 17kg of quartz, 10kg of calcite, 3kg of zinc oxide, 8kg of strontium carbonate, 2kg of borax and 4kg of cordierite.
The preparation method is the same as that of example 1.
Detecting the chemical components of the finished frit, wherein the chemical components comprise the following components in percentage by mass: 15.89% Al 2 O 3 、52.69％SiO 2 、7.07％CaO、0.47％Fe 2 O 3 、0.72％K 2 O、11.81％MgO、3.46％ZnO、0.42％Na 2 O、0.05％TiO 2 6.49% SrO and 0.84% B 2 O 3 。
Example 3
Preparing raw materials:
22kg of kaolin, 4kg of calcined alumina, 26kg of calcined talc, 2kg of magnesite, 18kg of quartz, 9kg of calcite, 5kg of zinc oxide, 9kg of strontium carbonate, 2kg of borax and 3kg of cordierite.
The preparation method is the same as that of example 1.
Detecting the chemical components of the finished product frit, wherein the chemical components comprise the following components in percentage by mass: 14.63% Al 2 O 3 、52.51％SiO 2 、6.37％CaO、0.37％Fe 2 O 3 、0.60％K 2 O、11.38％MgO、5.63％ZnO、0.41％Na 2 O、0.05％TiO 2 7.13% SrO and 0.82% B 2 O 3 。
Example 4
Preparing raw materials:
24kg of kaolin, 3kg of calcined alumina, 24kg of calcined talc, 3kg of magnesite, 17kg of quartz, 10kg of calcite, 4kg of zinc oxide, 8kg of strontium carbonate, 3kg of borax and 4kg of cordierite.
The preparation method is the same as that of example 1.
Detecting the chemical components of the finished frit, wherein the chemical components comprise the following components in percentage by mass: 14.93% Al 2 O 3 、52.47％SiO 2 、7.06％CaO、0.42％Fe 2 O 3 、0.66％K 2 O、11.46％MgO、4.58％ZnO、0.60％Na 2 O、0.05％TiO 2 6.44% SrO and 1.25% B 2 O 3 。
Example 5
Preparing raw materials:
25kg of kaolin, 2kg of calcined alumina, 23kg of calcined talc, 5kg of magnesite, 15kg of quartz, 11kg of calcite, 5kg of zinc oxide, 7kg of strontium carbonate, 2kg of borax and 5kg of cordierite.
The preparation method is the same as that of example 1.
Detecting the chemical components of the finished product frit, wherein the chemical components comprise the following components in percentage by mass: 14.74% Al 2 O 3 、51.13％SiO 2 、7.74％CaO、0.47％Fe 2 O 3 、0.69％K 2 O、12.36％MgO、5.77％ZnO、0.42％Na 2 O、0.05％TiO 2 5.68% SrO and 0.84% B 2 O 3 。
Example 6
Preparing raw materials:
23kg of kaolin, 3kg of calcined alumina, 24kg of calcined talc, 4kg of magnesite, 17kg of quartz, 9kg of calcite, 5kg of zinc oxide, 7kg of strontium carbonate, 4kg of borax and 4kg of cordierite.
The preparation method is the same as that of example 1.
Detecting the chemical components of the finished product frit, wherein the chemical components comprise the following components in percentage by mass: 14.54% Al 2 O 3 、52.03％SiO 2 、6.43％CaO、0.42％Fe 2 O 3 、0.63％K 2 O、11.98％MgO、5.73％ZnO、0.79％Na 2 O、0.05％TiO 2 5.64% SrO and 1.68% B 2 O 3 。
Comparative example 1
Unlike example 1, the cordierite was changed to kaolin in an amount of 28kg without changing other components, and the marble tile was prepared according to the method of example 1.
Comparative example 2
Unlike example 1, marble tiles were prepared according to the method of example 1, except that the amount of cordierite was changed to 10kg, the amount of kaolin was changed to 18kg, and the other components were not changed.
Comparative example 3
Different from example 2, the magnesite was changed to burnt talc, the amount of the burnt talc was changed to 27kg, and other components were not changed, and the marble tile was prepared according to the method of example 1.
Comparative example 4
A conventional transparent frit comprises the following raw materials in percentage by mass: 18kg of potash feldspar, 27kg of albite, 32kg of kaolin, 20kg of calcined talc and 3kg of zinc oxide, mixing the raw materials of the transparent frit, carrying out high-temperature firing (wherein the temperature curve of the high-temperature firing is from normal temperature to 1100 ℃ for 100min, from 1100 ℃ to 1500 ℃ for 60min, carrying out heat preservation at 1500 ℃ for 25min, and independently raising the temperature at constant speed in each stage), and carrying out water quenching to obtain the transparent frit. Glazes and marble tiles were prepared according to the method of example 1.
The performance test methods used in the examples and comparative examples of the present application are briefly described:
1. measurement of light transmittance of frit: the light transmittance is measured according to GB/T2860-94 building glass, and the direct sunlight transmittance is measured according to window glass parameters.
Name of the test instrument: the visible light transmittance and shading coefficient calibrator for building glass has the product types as follows: SK-SL 500.
The test sample manufacturing method comprises the following steps: mixing and ball-milling 100g of frit, 0.2g of sodium tripolyphosphate, 0.2g of sodium carboxymethylcellulose and 40g of water into slurry, drying, and sieving by a 40-mesh sieve; then weighing 20g of fusion cake powder and 10g of blank powder, pressing into small square bricks by using a mould under the pressure of 30MPa, and drying; the small blocks are fired by a kiln and then processed into 1mm pure glaze sheets by a polishing and grinding machine.
2. And (3) determining the wear resistance: GB/T3810.7-2016, part 7 of the ceramic tile testing method: the method for testing the wear resistance of the glazed surface of the glazed tile tests the wear resistance of the glazed surface of the product, and the wear resistance of the ceramic tile is evaluated by placing a grinding medium on the glazed surface and rotating the glazed surface and observing and comparing a worn sample with an unworn sample.
3. And (3) antifouling rating measurement: the antifouling property of the glaze of the product is tested by using a test method of GB/T3810.14-2016 (determination of the antifouling property of the part 14 of the test method of ceramic tiles), wherein the antifouling agents comprise a plurality of pasty antifouling agents, a plurality of fouling agents capable of generating oxidation reaction, a plurality of fouling agents capable of generating films, olive oil and the like, the antifouling property is classified into 1-5 grades according to the difficulty of cleaning, and the higher the grade is, the better the antifouling property is.
The frits and tiles obtained in examples 1 to 6 and comparative examples 1 to 4 were subjected to the above-mentioned property test using the method, and the results are shown in the following table 1:
TABLE 1 test results
From the test results, in examples 1 to 6, cordierite powder is added into a frit, so that complete cordierite crystals are melted from the cordierite powder at 1450 ℃, and a large amount of cordierite crystals are contained in a crystal phase of the frit, wherein the mohs hardness of cordierite is 7, and the refractive index of sunlight is 1.542 to 1.551, so that the wear resistance of the frit is improved while the transparency of the frit is kept good, the light transmittance of a wear-resistant frit sample with the thickness of 1mm is 25 to 30%, and the wear resistance of the prepared polished glazed brick reaches 4 grades (2100 revolutions).
It can be seen from comparative example 1 that when cordierite is replaced with kaolin, the cordierite crystal phase of the glaze is significantly reduced, and more microcrystalline nuclei are generated from mullite produced after kaolin is melted, resulting in a reduction in both the abrasion resistance and the light transmittance of the glaze. The addition of cordierite can ensure that the abrasion resistance is improved while the frit glaze keeps good transparency.
As can be seen from comparative example 2, when the amount of cordierite added exceeds the defined mass ratio, the abrasion resistance, antifouling property and light transmittance of the frit glaze were all lowered, and the finished product was not smooth to the touch, indicating that the raw materials in the frit could not be completely fused into a glass phase during firing.
As can be seen from the comparative example 3, the magnesite plays a role of fluxing, the chemical component of the magnesite is magnesium oxide, the magnesium content of the magnesite is higher than that of calcined talc, and more magnesium elements can be provided for the formula to synthesize cordierite crystals with aluminum elements and silicon elements in the formula; and carbonate has the melting-assisting function, so that the synthesis temperature of cordierite crystals is reduced, and more cordierite crystals can be separated out at the firing temperature of 1450 ℃.
It can be seen from comparative example 4 that the transparent frit of comparative example 4 is prepared by using the conventional transparent frit formula, and the transparency of the frit is high, but the abrasion resistance of the prepared polished glazed tile is poor and can only reach grade 3 (1500 revolutions), so that the formula of the invention can play a role in improving the abrasion resistance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The high-light-transmission wear-resistant frit is characterized by comprising the following raw materials in percentage by mass:
22-26% of kaolin, 2-4% of calcined alumina, 22-26% of calcined talc, 2-5% of magnesite, 15-18% of quartz, 9-11% of calcite, 3-5% of zinc oxide, 7-9% of strontium carbonate, 2-4% of borax and 3-5% of cordierite;
the preparation method of the high-light-transmission wear-resistant frit comprises the following steps:
(1) uniformly mixing the raw materials according to the raw material proportion;
(2) placing the raw materials in a frit furnace, sintering and melting the raw materials at 1450 ℃ to obtain molten glass, and quenching the molten glass with water;
(3) drying, crushing and screening the water-quenched frit to obtain the high-light-transmission wear-resistant frit;
the firing temperature curve is as follows: (1) heating to 300 deg.C from normal temperature, and taking 60 min; (2) heating from 300 deg.C to 1100 deg.C, and taking 120 min; (3) heating to 1100 deg.C to 1450 deg.C, and taking 45 min; (4) keeping the temperature at 1450 ℃ for 60 min.
2. The high light transmission and abrasion resistant frit according to claim 1, wherein the cordierite is a synthetic powder, which is a synthetic powderThe chemical components comprise the following components in percentage by mass: SiO 2 2 47-51%、Al 2 O 3 32-35%、Fe 2 O 3 0-0.6 percent and MgO13-15 percent.
3. The high light transmission and abrasion resistant frit according to claim 2, wherein the cordierite has a cordierite phase content of 95-97% and a bulk density of not less than 1.6g/cm 3 。
4. The high light transmission and abrasion resistant frit according to any one of claims 1 to 3, wherein the chemical composition comprises, in mass percent:
14-16%Al 2 O 3 、49-54%SiO 2 、5-8%CaO、0.05-0.5%Fe 2 O 3 、0.5-1%K 2 O、11-13%MgO、3-6%ZnO、0.1-1%Na 2 O、0.01-0.1%TiO 2 5.5-7.5% SrO and 0.5-2% B 2 O 3 The ignition loss is 1-2%.
5. The method for preparing a high-light-transmission wear-resistant frit according to any one of claims 1 to 4, comprising:
(1) uniformly mixing the raw materials according to the raw material proportion;
(2) placing the raw materials in a frit furnace, sintering and melting the raw materials at 1450 ℃ to obtain molten glass, and quenching the molten glass with water;
(3) and drying, crushing and screening the water-quenched frit to obtain the high-light-transmittance wear-resistant frit.
6. The method of claim 5, wherein the firing temperature profile is:
(1) heating to 300 deg.C from normal temperature, and taking 60 min;
(2) heating from 300 deg.C to 1100 deg.C, and taking 120 min;
(3) heating to 1100 deg.C to 1450 deg.C, and taking 45 min;
(4) keeping the temperature at 1450 ℃ for 60 min.
7. The method according to claim 5, wherein each stage of the firing temperature profile independently employs a constant temperature rise.
8. The method according to any one of claims 5 to 7, wherein the particle size of the particulate matter obtained by sieving is 120 mesh or smaller.
9. Glaze, characterized in that it comprises a high-light-transmission, abrasion-resistant frit according to any one of claims 1 to 4.
10. A marble tile characterized in that its raw material comprises the glaze of claim 9.
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Effective date of registration: 20230522 Address after: 511500 Shengping Industrial Park, Feilaixia Town, Qingcheng District, Qingyuan City, Guangdong Province Patentee after: QINGYUAN JIANYI CERAMICS Co.,Ltd. Patentee after: Guangdong Jianyi (Group) Ceramics Co.,Ltd. Patentee after: Guangxi Jianyi Ceramics Co.,Ltd. Address before: 511500 Shengping Industrial Park, Feilaixia Town, Qingcheng District, Qingyuan City, Guangdong Province Patentee before: QINGYUAN JIANYI CERAMICS Co.,Ltd. |