阅读说明：本技术 一种耐磨釉料及其制备方法和大理石瓷砖 (Wear-resistant glaze, preparation method thereof and marble ceramic tile ) 是由 区邦熙 江泽峰 杨君之 黄山平 于 2020-11-24 设计创作，主要内容包括：本发明提供一种耐磨釉料及其制备方法和大理石瓷砖。耐磨釉料,其原料以质量百分比计算,包括：高岭土14％-17％、煅烧高岭土2％-4％、烧滑石28％-33％、方解石3％-5％、氧化锌5％-7％、石英3％-5％、堇青石2％-4％、镁铝尖晶石4％-6％、第一熔块16％-22％和第二熔块8％-12％。耐磨釉料的制备方法包括：将高岭土、煅烧高岭土、烧滑石、方解石、氧化锌、石英、堇青石、镁铝尖晶石均匀混合得到生釉料粉；将第一熔块、第二熔块、生釉料粉、水和印膏混合后球磨、陈腐,得到耐磨釉料。大理石瓷砖,使用包括耐磨釉料在内的原料制得。本申请提供的耐磨釉料制得的大理石瓷砖,耐磨度、硬度高和太阳光直接透射比高。(The invention provides a wear-resistant glaze, a preparation method thereof and a marble ceramic tile. The wear-resistant glaze comprises the following raw materials in percentage by mass: 14-17% of kaolin, 2-4% of calcined kaolin, 28-33% of calcined talc, 3-5% of calcite, 5-7% of zinc oxide, 3-5% of quartz, 2-4% of cordierite, 4-6% of magnesia-alumina spinel, 16-22% of first frit and 8-12% of second frit. The preparation method of the wear-resistant glaze comprises the following steps: uniformly mixing kaolin, calcined talc, calcite, zinc oxide, quartz, cordierite and magnesium aluminate spinel to obtain raw glaze powder; and mixing the first frit, the second frit, the raw glaze powder, water and the printing paste, and then performing ball milling and ageing to obtain the wear-resistant glaze. The marble tile is prepared from raw materials including wear-resistant glaze. The application provides a marble ceramic tile that wear-resisting glaze prepared, abrasion resistance, hardness are high and the direct transmittance ratio of sunlight is high.)

1. The wear-resistant glaze is characterized by comprising the following raw materials in percentage by mass:

14-17% of kaolin, 2-4% of calcined kaolin, 28-33% of calcined talc, 3-5% of calcite, 5-7% of zinc oxide, 3-5% of quartz, 2-4% of cordierite, 4-6% of magnesia-alumina spinel, 16-22% of first frit and 8-12% of second frit;

the sunlight direct transmittance of the first frit is 25% -30%, the Mohs hardness is 4 grade, and the wear-resisting coefficient is 4 grade 2100 revolutions;

the direct sunlight transmittance of the second frit is 15% -20%, the Mohs hardness is 6 grade, and the wear resistance coefficient is 4 grade 6000 turns.

2. The abrasion-resistant glaze according to claim 1 wherein the cordierite is a humanThe synthetic powder comprises the following chemical components in percentage by mass: SiO 2₂50-51％、Al₂O₃35-36％、Fe₂O₃0 to 0.8 percent and MgO12.9 to 13.5 percent.

3. The wear-resistant glaze material as claimed in claim 1, wherein the magnesia alumina spinel is an artificially synthesized powder by an electric melting method, and comprises the following chemical components in percentage by mass: 24% -29% of MgO and 71% -76% of Al₂O₃。

4. The wear-resistant glaze according to claim 1, wherein the chemical composition of the first frit comprises, in mass%:

49％-54％SiO₂、14％-16％Al₂O₃、0.05％-0.5％Fe₂O₃、5％-8％CaO、11％-13％MgO、0.5％-1％K₂O、0.1％-1％Na₂o, 3 to 6 percent of ZnO, 5.5 to 7.5 percent of SrO and 0.5 to 1.5 percent of B₂O₃(ii) a The ignition loss is 1% -2%;

the raw materials of the first frit include calcined alumina, magnesite, and cordierite.

5. The wear-resistant glaze according to claim 1, wherein the chemical composition of the second frit comprises, in mass%:

51％-56％SiO₂、17％-21％Al₂O₃、0.1％-0.8％Fe₂O₃、7％-9％CaO、5％-8％MgO、2％-4％K₂O、0.5％-1％Na₂O、0.005％-0.01％TiO₂4 to 7 percent of ZnO and 0.1 to 1 percent of B₂O₃(ii) a The ignition loss is 1% -2%;

the raw materials of the second frit comprise corundum, magnesite and magnesia-alumina spinel.

6. The abrasion-resistant glaze according to any one of claims 1 to 5, wherein the chemical composition of the abrasion-resistant glaze is calculated by mass percentage, and the coating isComprises the following steps: 47% -51% SiO₂、16％-18％Al₂O₃、0.05％-0.5％Fe₂O₃、5％-7％CaO、13％-16％MgO、0.5％-1.5％K₂O、0.05％-0.5％Na₂O、0.005％-0.06％TiO₂6 to 9 percent of ZnO, 1 to 2 percent of SrO and 0.1 to 0.5 percent of B₂O₃The loss on ignition is 4-6%.

7. A method of preparing the abrasion resistant glaze according to any one of claims 1 to 6, comprising:

uniformly mixing kaolin, calcined talc, calcite, zinc oxide, quartz, cordierite and magnesium aluminate spinel to obtain raw glaze powder;

and mixing the first frit, the second frit, the raw glaze powder, water and the paste ink, and then performing ball milling and ageing to obtain the wear-resistant glaze.

8. The method according to claim 7, wherein the mass ratio of the total mass of the first frit, the second frit and the raw glaze powder to the mass of the water and the paste is 1:0.35: 0.65.

9. The preparation method of claim 7, wherein the ball milling time is 8-10h, and the aging time is not less than 48 h;

the surplus of the glaze slurry obtained by ball milling after being sieved by a 325-mesh sieve is 0.6-1%.

10. A marble tile, characterized by being made using a raw material comprising the abrasion-resistant glaze of any one of claims 1 to 6;

the abrasion resistance of the marble tile is 4-grade 2100-6000 turns, the Mohs hardness is 5-6 grades, and the direct transmittance of sunlight is 22% -25%.

Technical Field

The invention relates to the field of ceramics, in particular to a wear-resistant glaze, a preparation method thereof and a marble ceramic tile.

Background

The glaze polishing is used as the last transparent glaze on the surface of the marble tile, and the physical and chemical properties of the glaze polishing directly influence the surface performance of the product, so the glaze polishing 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 prior art for producing the marble ceramic tile glaze in the market uses all raw glaze and common fritted glaze.

At present, the domestic glaze technology is not advanced, and meanwhile, based on cost consideration, all enterprises in the market basically use common frits for polishing marble tiles, so that the abrasion resistance of the marble tile glaze is poor and the hardness is small due to too many low-temperature glass phases, the surface hardness after polishing is below 4 Mohs hardness, the abrasion resistance level is generally 1-3 levels, and the abrasion resistance hardly meets the requirements of consumers. These products have a long service life, a very marked reduction in gloss, a dull surface, and a severe aesthetic impact, which makes it difficult to meet consumer requirements.

For example, patent 201911144473.8 proposes a method of adding 10% to 20% of corundum into frit to increase the content of alumina in the frit and improve the abrasion resistance of the frit, but the light transmittance of the glaze surface is significantly reduced when the corundum addition exceeds 10%, and the total porosity is increased when the corundum crystals are too much, which results in the reduction of the antifouling performance of the frit.

In addition, the abrasion resistance of the glaze can be improved by adding a large amount of materials such as burning talc and the like to improve the content of magnesium oxide in the glaze, but the magnesium oxide component can reduce the refractive index of a glass phase of the glaze, so that the transparency of the glaze is reduced.

Disclosure of Invention

The invention aims to provide a wear-resistant glaze, a preparation method thereof 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:

the wear-resistant glaze comprises the following raw materials in percentage by mass:

14-17% of kaolin, 2-4% of calcined kaolin, 28-33% of calcined talc, 3-5% of calcite, 5-7% of zinc oxide, 3-5% of quartz, 2-4% of cordierite, 4-6% of magnesia-alumina spinel, 16-22% of first frit and 8-12% of second frit;

the sunlight direct transmittance of the first frit is 25% -30%, the Mohs hardness is 4 grade, and the wear-resisting coefficient is 4 grade 2100 revolutions;

the direct sunlight transmittance of the second frit is 15% -20%, the Mohs hardness is 6 grade, and the wear resistance coefficient is 4 grade 6000 turns.

Preferably, the cordierite is an artificial synthetic powder, and the chemical components of the cordierite comprise, by mass: SiO 2₂50-51％、Al₂O₃35-36％、Fe₂O₃0 to 0.8 percent and MgO12.9 to 13.5 percent.

Preferably, the magnesia-alumina spinel is artificially synthesized powder by an electric melting method, and comprises the following chemical components in percentage by mass: 24% -29% of MgO and 71% -76% of Al₂O₃。

Preferably, the chemical composition of the first frit comprises, in mass percent:

49％-54％SiO₂、14％-16％Al₂O₃、0.05％-0.5％Fe₂O₃、5％-8％CaO、11％-13％MgO、0.5％-1％K₂O、0.1％-1％Na₂o, 3 to 6 percent of ZnO, 5.5 to 7.5 percent of SrO and 0.5 to 1.5 percent of B₂O₃(ii) a The ignition loss is 1% -2%;

preferably, the raw materials of the first frit include calcined alumina, magnesite, and cordierite.

Preferably, the chemical composition of the second frit comprises, in mass percent:

51％-56％SiO₂、17％-21％Al₂O₃、0.1％-0.8％Fe₂O₃、7％-9％CaO、5％-8％MgO、2％-4％K₂O、0.5％-1％Na₂O、0.005％-0.01％TiO₂4 to 7 percent of ZnO and 0.1 to 1 percent of B₂O₃(ii) a The ignition loss is 1% -2%;

preferably, the raw materials of the second frit comprise corundum, magnesite and magnesia alumina spinel.

Preferably, the chemical composition of the wear-resistant glaze comprises the following components in percentage by mass: 47% -51% SiO₂、16％-18％Al₂O₃、0.05％-0.5％Fe₂O₃、5％-7％CaO、13％-16％MgO、0.5％-1.5％K₂O、0.05％-0.5％Na₂O、0.005％-0.06％TiO₂6 to 9 percent of ZnO, 1 to 2 percent of SrO and 0.1 to 0.5 percent of B₂O₃The loss on ignition is 4-6%.

The preparation method of the wear-resistant glaze comprises the following steps:

uniformly mixing kaolin, calcined talc, calcite, zinc oxide, quartz, cordierite and magnesium aluminate spinel to obtain raw glaze powder;

and mixing the first frit, the second frit, the raw glaze powder, water and the paste ink, and then performing ball milling and ageing to obtain the wear-resistant glaze.

Preferably, the mass ratio of the total mass of the first frit, the second frit and the raw glaze powder to the mass of the water and the paste is 1:0.35: 0.65.

Preferably, the ball milling time is 8-10h, and the staling time is not less than 48 h;

preferably, the surplus of the glaze slurry obtained by ball milling after being sieved by a 325-mesh sieve is 0.6-1%.

The marble tile is prepared from raw materials including the wear-resistant glaze;

preferably, the abrasion resistance of the marble tile is 2100-6000 revolutions on a 4-grade scale, the Mohs hardness is 5-6 grades, and the direct transmittance of sunlight is 22% -25%.

Compared with the prior art, the invention has at least the following beneficial effects:

according to the wear-resistant glaze provided by the application, through the matching of kaolin, calcined talc, calcite, zinc oxide, quartz, cordierite, magnesia-alumina spinel, a first frit and a second frit, especially the matching of cordierite, magnesia-alumina spinel, the first frit and the second frit, the glaze has a cordierite main crystal phase and magnesia-alumina spinel, anorthite microcrystal and other auxiliary crystal phases, and the crystal phases have the characteristics of high transparency and high hardness, so that the glaze with good antifouling property, high transparency and high wear resistance can be produced; according to the glaze formula, the firing range of the glaze is adjusted by adding a first frit which has high transparency and low firing temperature and contains calcined alumina, magnesite and cordierite synthetic powder, so that the number and size of separated cordierite crystals are adjusted, and the wear resistance of the glaze can be increased by adding a second frit which contains corundum, magnesite and magnesia alumina spinel and has high wear resistance, so that the contradiction between the wear resistance and the transparency of a polished layer of a marble ceramic tile is solved;

the wear-resistant glaze material provided by the application has a high matching degree between the expansion coefficient and the blank, the surface hardness of a glazed tile prepared from the glaze material is improved, the Mohs hardness can reach 5-6 levels, the wear resistance is improved, the wear resistance can be stabilized at 4 levels (2100-6000 revolutions), and the tile is free of scratches after being used for a long time and is up to the new level after long time; and the first frit and the second frit can generate compact glass bodies during fusion and vitrification, pores of the glaze surface are few after cooling, pollutants are difficult to accumulate on the glaze surface, the antifouling performance is improved, and the antifouling grade of the marble ceramic tile prepared from the glaze can reach 4-5 grades.

The preparation method of the wear-resistant glaze material is simple in process, low in cost and stable in product performance;

the application provides a marble ceramic tile, wear resistance is good, and the transparency is high.

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 unspecified elements, steps or components. 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 subject matter of the claims rather than 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 stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

In these 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 we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is 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).

The wear-resistant glaze comprises the following raw materials in percentage by mass:

14-17% of kaolin, 2-4% of calcined kaolin, 28-33% of calcined talc, 3-5% of calcite, 5-7% of zinc oxide, 3-5% of quartz, 2-4% of cordierite, 4-6% of magnesia-alumina spinel, 16-22% of first frit and 8-12% of second frit;

the sunlight direct transmittance of the first frit is 25% -30%, the Mohs hardness is 4 grade, and the wear-resisting coefficient is 4 grade 2100 revolutions;

the direct sunlight transmittance of the second frit is 15% -20%, the Mohs hardness is 6 grade, and the wear resistance coefficient is 4 grade 6000 turns.

The kaolin, calcined kaolin and calcined talc in the glaze all serve as providers of the elements silicon, aluminum and magnesium in the cordierite crystal structure. In addition, kaolin is matched with calcite, the calcium ion lattice radius of the kaolin is larger than that of magnesium ions, cordierite lattice distortion is caused after the kaolin enters the crystal lattice, stress vacancies are formed, the reduction of the synthesis temperature is facilitated, the sintering temperature is widened, and the cordierite microcrystal and the anorthite microcrystal can be fully crystallized from the glaze under the firing process condition (1200 +/-6 ℃) of a production kiln, and have the characteristics of transparency, high hardness and the like and good mechanical properties. Therefore, the cordierite crystal can enhance the hardness of the glaze, avoid the glaze from being rubbed by hard objects, obviously increase the wear resistance of the glaze, and the glaze layer has high transparency and good color development.

Further, cordierite has a decomposition temperature of 1460 ℃ and does not completely melt under the firing condition of 1200 ℃, and the addition of cordierite to the glaze causes a significant decrease in the transparency of the glaze. 325-mesh fine cordierite powder is prepared by a specific process, and alpha-cordierite crystals can be fused out from the fine-particle cordierite synthetic powder under the firing environment of 1200 ℃ by adding active flux such as zinc oxide and the like. Cordierite powder with the mass fraction ratio of 2% -4% is directly added into the glaze, the amount of alpha-cordierite crystals in the glaze can be obviously increased, the amount of the alpha-cordierite crystals is lower than the addition amount of 2%, the amount of the cordierite crystals in the formula is not obviously increased, and the effect is not large; above 4%, the cordierite synthetic powder in the formula can not be completely dissolved, so that the transparency of the glaze is directly reduced.

The Mohs hardness of the magnesia-alumina spinel is 8.5, the melting point is 2135 ℃, the magnesia-alumina spinel synthesized by an artificial electric melting method has large volume density, good color and luster, good thermal shock stability and strong erosion resistance, the crystal system belongs to a cubic crystal system, larger oxygen ions form a cubic close packing lattice, the crystal system is isotropic, and the magnesium ions and the aluminum ions occupy 1/4 of gaps, wherein the larger magnesium ions occupy one eighth of the gaps of a tetrahedron and present four coordination; the smaller aluminum ions occupy half of the octahedral gap and exhibit octadentation, and thus it can be seen that the magnesium aluminate spinel structure is stable and there is no phase transition at high temperature. The crystal has a refractive index of 1.68-1.72, and can be made into transparent ceramic. Therefore, it has the characteristics of transparency and high hardness similar to cordierite. Because the glaze has high hardness and high melting point, 325-mesh fine powder is homogenized in a conventional mode and added into the glaze, the transparency of the glaze cannot be reduced due to complete melting, and the glaze is ground to 3000-mesh fine powder, so that the surface area of the glaze is increased, the melting efficiency can be effectively improved, a certain amount of magnesia-alumina spinel paracrystalline phase is contained in the glaze, the hardness and the wear resistance of the glaze can be enhanced, and the glaze layer has high transparency and good color development.

Alternatively, the content of kaolin in the raw material of the abrasion-resistant glaze can be any value between 14%, 15%, 16%, 17% and 14% -17%; the calcined kaolin can be present in an amount of any of 2%, 3%, 4%, and 2% -4%; the content of the calcined talc may be any value between 28%, 29%, 30%, 31%, 32%, 33% and 28% -33%; the content of calcite may be any value between 3%, 4%, 5% and 3% -5%; the content of zinc oxide can be any value between 5%, 6%, 7% and 5% -7%; the quartz content can be any value between 3%, 4%, 5% and 3% -5%; the cordierite content may be any value between 2%, 3%, 4% and 2% -4%; the content of the magnesium aluminate spinel can be any value between 4%, 5%, 6% and 4% -6%; the content of the first frit may be any value between 16%, 17%, 18%, 19%, 20%, 21%, 22% and 16% -22%; the content of the second frit may be any value between 8%, 9%, 10%, 11%, 12% and 8% -12%; the first frit may have a direct solar transmittance of any value between 25%, 26%, 27%, 28%, 29%, 30% and 25% -30%, and the second frit may have a direct solar transmittance of any value between 15%, 16%, 17%, 18%, 19%, 20% and 15% -20%.

Preferably, the cordierite is an artificial synthetic powder, and the chemical components of the cordierite comprise, by mass: SiO 2₂50-51％、Al₂O₃35-36％、Fe₂O₃0 to 0.8 percent and MgO12.9 to 13.5 percent.

Preferably, the magnesia-alumina spinel is artificially synthesized powder by an electric melting method, and comprises the following chemical components in percentage by mass: 24% -29% of MgO and 71% -76% of Al₂O₃。

Optionally, the chemical composition of the magnesium aluminate spinel may be any value between 24%, 25%, 26%, 27%, 28%, 29% and 24% -29% of MgO, and Al₂O₃The amount of (c) may be any value between 71%, 72%, 73%, 74%, 75%, 76% and 71% -76%.

Preferably, the chemical composition of the first frit comprises, in mass percent:

49％-54％SiO₂、14％-16％Al₂O₃、0.05％-0.5％Fe₂O₃、5％-8％CaO、11％-13％MgO、0.5％-1％K₂O、0.1％-1％Na₂o, 3 to 6 percent of ZnO, 5.5 to 7.5 percent of SrO and 0.5 to 1.5 percent of B₂O₃(ii) a The ignition loss is 1% -2%;

preferably, the raw materials of the first frit include calcined alumina, magnesite, and cordierite.

Optionally, the chemical composition of the first frit is SiO₂Can be any value between 49%, 50%, 51%, 52%, 53%, 54% and 49% -54%, Al₂O₃Can be any value between 14%, 15%, 16% and 14% -16%, Fe₂O₃Can be any value between 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5% and 0.05% -0.5%, CaO can be any value between 5%, 6%, 7%, 8% and 5% -8%, MgO can be any value between 11%, 12%, 13% and 11% -13%, K₂The content of O may be any value between 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% and 0.5% -1%, Na₂The 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%, the content of ZnO may be any value between 3%, 4%, 5%, 6% and 3% -6%, the content of SrO may be any value between 5.5%, 6%, 6.5%, 7%, 7.5% and 5.5% -7.5%, B₂O₃The amount of (c) may be any value between 0.5%, 1%, 1.5% and 0.5% to 1.5%, and the loss on ignition may be any value between 1%, 1.5%, 2% and 1% to 2%.

Preferably, the chemical composition of the second frit comprises, in mass percent:

51％-56％SiO₂、17％-21％Al₂O₃、0.1％-0.8％Fe₂O₃、7％-9％CaO、5％-8％MgO、2％-4％K₂O、0.5％-1％Na₂O、0.005％-0.01％TiO₂4 to 7 percent of ZnO and 0.1 to 1 percent of B₂O₃(ii) a The ignition loss is 1% -2%;

preferably, the raw materials of the second frit comprise corundum, magnesite and magnesia alumina spinel.

Optionally, the second frit comprises a chemical composition of SiO₂Can be any value between 51%, 52%, 53%, 54%, 55%, 56% and 51% -56%, Al₂O₃Can be any value between 17%, 18%, 19%, 20%, 21% and 17% -21%, Fe₂O₃Can be any value between 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% and 0.1% -0.8%, CaO can be any value between 7%, 8%, 9% and 7% -9%, MgO can be any value between 5%, 6%, 7%, 8% and 5% -8%, K₂The content of O can be any value between 2%, 3%, 4% and 2% -4%, Na₂The content of O may be any of 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and 0.5% -1%Value, TiO₂The content of (B) can be any value between 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.01% and 0.005% -0.01%, the content of ZnO can be any value between 4%, 5%, 6%, 7% and 4% -7%, B₂O₃The amount of (b) 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%, and the loss on ignition may be any value between 1%, 1.5%, 2% and 1% -2%.

Preferably, the chemical composition of the wear-resistant glaze comprises the following components in percentage by mass: 47% -51% SiO₂、16％-18％Al₂O₃、0.05％-0.5％Fe₂O₃、5％-7％CaO、13％-16％MgO、0.5％-1.5％K₂O、0.05％-0.5％Na₂O、0.005％-0.06％TiO₂6 to 9 percent of ZnO, 1 to 2 percent of SrO and 0.1 to 0.5 percent of B₂O₃The loss on ignition is 4-6%.

Optionally, SiO in the chemical composition of the wear-resistant glaze₂Can be 47%, 48%, 49%, 50%, 51% and any value between 47% and 51%, Al₂O₃Can be any value between 16%, 17%, 18% and 16% -18%, Fe₂O₃Can be any value between 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5% and 0.05% -0.5%, CaO can be any value between 5%, 6%, 7% and 5% -7%, MgO can be any value between 13%, 14%, 15%, 16% and 13% -16%, K can be any value between₂The content of O may be any value between 0.5%, 1%, 1.5% and 0.5% -1.5%, Na₂The content of O may be any value between 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 0.05% -0.5%, TiO₂The content of (A) may be any value between 0.005%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06% and 0.005% to 0.06%, the content of ZnO may be any value between 6%, 7%, 8%, 9% and 6% to 9%, and the content of SrO may be any value between 1%, 1.5%, 2% or moreAnd any value between 1% and 2%, B₂O₃The amount of (b) may be any value between 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 0.1% to 0.5%, and the loss on ignition may be any value between 4%, 5%, 6% and 4% to 6%.

The preparation method of the wear-resistant glaze comprises the following steps:

uniformly mixing kaolin, calcined talc, calcite, zinc oxide, quartz, cordierite and magnesium aluminate spinel to obtain raw glaze powder;

and mixing the first frit, the second frit, the raw glaze powder, water and the paste ink, and then performing ball milling and ageing to obtain the wear-resistant glaze.

Preferably, the mass ratio of the total mass of the first frit, the second frit and the raw glaze powder to the mass of the water and the paste is 1:0.35: 0.65.

Preferably, the ball milling time is 8-10h, and the staling time is not less than 48 h;

preferably, the surplus of the glaze slurry obtained by ball milling after being sieved by a 325-mesh sieve is 0.6-1%.

Optionally, the ball milling time can be any value between 8h, 9h, 10h and 8-10h, and the aging time can be not less than 48h, such as 48h, 50h, 54h, 60h, 66h, 72h and the like; the surplus of the glaze slurry obtained by ball milling after being sieved by a 325-mesh sieve can be any value between 0.6%, 0.7%, 0.8%, 0.9%, 1% and 0.6% -1%.

The marble tile is prepared from raw materials including the wear-resistant glaze;

preferably, the abrasion resistance of the marble tile is 2100-6000 revolutions on a 4-grade scale, the Mohs hardness is 5-6 grades, and the direct transmittance of sunlight is 22% -25%.

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 not indicated by the manufacturer, and are all conventional products available commercially.

Example 1

Preparing materials:

raw material preparation was performed according to 16kg of kaolin, 3kg of calcined kaolin, 31kg of calcined talc, 5kg of calcite, 6kg of zinc oxide, 4kg of quartz, 4kg of cordierite, 5kg of magnesia-alumina spinel, 16kg of first frit and 10kg of second frit.

Wherein, cordierite is synthetic powder, and the chemical components of the cordierite, calculated by mass percentage, include: SiO 2₂50％、Al₂O₃36％、Fe₂O₃0.5% and MgO13.5%. The magnesium aluminate spinel is artificially synthesized powder by an electric melting method, and comprises the following chemical components in percentage by mass: 24% MgO and 76% Al₂O₃. The chemical components of the first frit comprise, by mass: 50.85% SiO₂、16％Al₂O₃、0.05％Fe₂O₃、8％CaO、11％MgO、1％K₂O、0.1％Na₂O, 6% ZnO, 5.5% SrO and 1.5% B₂O₃(ii) a The ignition loss is 1%; the raw materials for the first frit include calcined alumina, magnesite, and cordierite. The chemical components of the second frit calculated by mass percent comprise: 55.39% SiO₂、21％Al₂O₃、0.1％Fe₂O₃、9％CaO、5％MgO、4％K₂O、0.5％Na₂O、0.01％TiO₂4% ZnO and 1% B₂O₃(ii) a The ignition loss is 1%; the raw materials of the second frit comprise corundum, magnesite and magnesia alumina spinel. The sunlight direct transmittance of the first frit is 25%, the Mohs hardness is 4 grade, and the wear-resisting coefficient is 4 grade 2100 revolutions; the direct sunlight transmittance of the second frit is 15%, the Mohs hardness is 6 grade, and the abrasion resistance coefficient is 4 grade 6000 turns.

Adding water and printing paste into the raw materials according to the following raw materials: water: mixing and ball-milling the paste with the paste printing ratio of 1:0.35:0.65 for 8 hours to obtain glaze slurry, controlling the fineness to be 325 meshes, and ageing for 49 hours to prepare the wear-resistant glaze for the marble ceramic tile, wherein the screen residue accounts for 1.0 percent of the mass fraction; the chemical components of the wear-resistant glaze material are calculated by mass percent and comprise: 48.54% SiO₂、16.44Al₂O₃、0.4％Fe₂O₃、5.5％CaO、14.77％MgO、0.73％K₂O、0.22％Na₂O、0.06％TiO₂7.29% ZnO, 1.03% SrO and 0.24% B₂O₃The balance being impurities, the loss on ignition is 5.5%.

The glaze polishing in the existing production process of the marble ceramic tile is replaced by the wear-resistant glaze, the wear-resistant 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 and is merged into a kiln to be sintered at 1206 +/-6 ℃, and then the wear-resistant marble ceramic tile is prepared by polishing and grinding.

Example 2

Preparing materials:

raw material preparation was carried out for 14kg of kaolin, 4kg of calcined kaolin, 29kg of calcined talc, 4kg of calcite, 5kg of zinc oxide, 5kg of quartz, 3kg of cordierite, 6kg of magnesia-alumina spinel, 18kg of first frit and 12kg of second frit.

Wherein, cordierite is synthetic powder, and the chemical components of the cordierite, calculated by mass percentage, include: SiO 2₂51％、Al₂O₃35％、Fe₂O₃0.8% and MgO13.2%. The magnesium aluminate spinel is artificially synthesized powder by an electric melting method, and comprises the following chemical components in percentage by mass: 29% MgO and 71% Al₂O₃. The chemical components of the first frit comprise, by mass: 54% SiO₂、15％Al₂O₃、0.5％Fe₂O₃、5％CaO、13％MgO、0.5％K₂O、1％Na₂O, 3% ZnO, 7.5% SrO and 0.5% B₂O₃(ii) a The ignition loss is 2%; the raw materials for the first frit include calcined alumina, magnesite, and cordierite. The chemical components of the second frit calculated by mass percent comprise: 56% SiO₂、17％Al₂O₃、0.8％Fe₂O₃、7％CaO、8％MgO、3.095％K₂O、1％Na₂O、0.005％TiO₂7% ZnO and 0.1% B₂O₃(ii) a The ignition loss is 2%; the raw materials of the second frit comprise corundum, magnesite and magnesia alumina spinel. The first frit has a direct solar transmittance of 30% and a Mohs hardness of 4%Wear resistance coefficient 4 grade 2100 revolutions; the second frit has a direct solar transmittance of 20%, a mohs hardness of 6, and an abrasion resistance of 4-6000 rpm.

Adding water and printing paste into the raw materials according to the following raw materials: water: mixing and ball-milling the paste printing paste 1:0.35:0.65 for 10 hours to obtain glaze slurry, controlling the fineness to be 325 meshes, and ageing for 49 hours, wherein the mass fraction of the screen residue is 0.6 percent; the chemical components of the wear-resistant glaze material are calculated by mass percent and comprise: 50.35% SiO₂、17.31Al₂O₃、0.4％Fe₂O₃、6.6％CaO、15.5％MgO、1.5％K₂O、0.5％Na₂O、0.01％TiO₂6.02% ZnO, 1.15% SrO and 0.48% B₂O₃The balance being impurities, the loss on ignition being 6%.

The glaze polishing in the existing production process of the marble ceramic tile is replaced by the wear-resistant glaze, the wear-resistant 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 and is merged into a kiln to be sintered at 1206 +/-6 ℃, and then the wear-resistant marble ceramic tile is prepared by polishing and grinding.

Example 3

Preparing materials:

raw material preparation was carried out according to 17kg of kaolin, 2kg of calcined kaolin, 31kg of calcined talc, 3kg of calcite, 7kg of zinc oxide, 3kg of quartz, 4kg of cordierite, 4kg of magnesia-alumina spinel, 20kg of first frit and 9kg of second frit.

Wherein, cordierite is synthetic powder, and the chemical components of the cordierite, calculated by mass percentage, include: SiO 2₂50.7％、Al₂O₃35.7％、Fe₂O₃0.7% and MgO12.9%. The magnesium aluminate spinel is artificially synthesized powder by an electric melting method, and comprises the following chemical components in percentage by mass: 26% MgO and 74% Al₂O₃. The chemical components of the first frit comprise, by mass: 52% SiO₂、14％Al₂O₃、0.4％Fe₂O₃、7％CaO、12％MgO、0.8％K₂O、0.8％Na₂O, 5% ZnO, 7% SrO and 1% B₂O₃(ii) a The ignition loss is 1.5%; the raw material of the first clinker comprises calcined alumina and magnesiteOre and cordierite. The chemical components of the second frit calculated by mass percent comprise: 55% SiO₂、20.1％Al₂O₃、0.592％Fe₂O₃、8％CaO、7％MgO、3％K₂O、0.8％Na₂O、0.008％TiO₂5% ZnO and 0.5% B₂O₃(ii) a The ignition loss is 1.4%; the raw materials of the second frit comprise corundum, magnesite and magnesia alumina spinel. The sunlight direct transmittance of the first frit is 28%, the Mohs hardness is 4 grade, and the wear-resisting coefficient is 4 grade 2100 revolutions; the direct solar transmittance of the second frit is 17%, the mohs hardness is 6 grade, and the abrasion resistance coefficient is 4 grade 6000 r.

Adding water and printing paste into the raw materials according to the following raw materials: water: mixing and ball-milling the paste with the paste printing ratio of 1:0.35:0.65 for 9 hours to obtain glaze slurry, controlling the fineness to be 325 meshes, and ageing for 49 hours to prepare the wear-resistant glaze for the marble ceramic tile, wherein the screen residue accounts for 0.8 percent of the mass fraction; the chemical components of the wear-resistant glaze material are calculated by mass percent and comprise: 47.85% SiO₂、16.5Al₂O₃、0.05Fe₂O₃、6％CaO、13.25％MgO、1.26％K₂O、0.08％Na₂O、0.01％TiO₂8.36% ZnO, 1.23% SrO and 0.36% B₂O₃The balance being impurities, the loss on ignition being 4.8%.

The glaze polishing in the existing production process of the marble ceramic tile is replaced by the wear-resistant glaze, the wear-resistant 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 and is merged into a kiln to be sintered at 1206 +/-6 ℃, and then the wear-resistant marble ceramic tile is prepared by polishing and grinding.

Example 4

Preparing materials:

raw material preparation was performed according to 15kg of kaolin, 3kg of calcined kaolin, 30kg of calcined talc, 4kg of calcite, 6kg of zinc oxide, 4kg of quartz, 3kg of cordierite, 5kg of magnesia-alumina spinel, 20kg of first frit and 10kg of second frit.

The raw materials of cordierite, alumina-magnesia spinel, first frit and second frit were the same as in example 1.

Adding water and printing paste into the raw materials according to the following raw materials: water: mixing the paste with the ratio of 1:0.35:0.65, ball-milling for 9h to obtain glaze slip, and controllingPreparing a fineness of 325 meshes, wherein the screen residue accounts for 0.6 percent by mass, and then ageing for 49 hours to prepare the wear-resistant glaze for the marble ceramic tile; the chemical components of the wear-resistant glaze material are calculated by mass percent and comprise: 49.06% SiO₂、17.52Al₂O₃、0.2％Fe₂O₃、5.8％CaO、15.11％MgO、1.3％K₂O、0.2％Na₂O、0.03％TiO₂8.58% ZnO, 1.68% SrO and 0.45% B₂O₃The balance being impurities, the loss on ignition is 5.1%.

The glaze polishing in the existing production process of the marble ceramic tile is replaced by the wear-resistant glaze, the wear-resistant 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 and is merged into a kiln to be sintered at 1206 +/-6 ℃, and then the wear-resistant marble ceramic tile is prepared by polishing and grinding.

Example 5

Preparing materials:

raw material preparation was performed using 16kg of kaolin, 4kg of calcined kaolin, 33kg of calcined talc, 3kg of calcite, 5kg of zinc oxide, 3kg of quartz, 4kg of cordierite, 4kg of magnesia-alumina spinel, 19kg of first frit and 9kg of second frit.

The raw materials of cordierite, alumina-magnesia spinel, first frit and second frit were the same as in example 2.

Adding water and printing paste into the raw materials according to the following raw materials: water: mixing and ball-milling the paste with the paste printing ratio of 1:0.35:0.65 for 8 hours to obtain glaze slurry, controlling the fineness to be 325 meshes, and ageing for 49 hours to prepare the wear-resistant glaze for the marble ceramic tile, wherein the screen residue accounts for 1.0 percent of the mass fraction; the chemical components of the wear-resistant glaze material are calculated by mass percent and comprise: 47.28% SiO₂、17.89Al₂O₃、0.25％Fe₂O₃、5.92％CaO、14.27％MgO、1.42％K₂O、0.45％Na₂O、0.04％TiO₂6.64% ZnO, 1.74% SrO and 0.41% B₂O₃The balance being impurities, the loss on ignition is 5.8%.

The glaze polishing in the existing production process of the marble ceramic tile is replaced by the wear-resistant glaze, the wear-resistant 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 and is merged into a kiln to be sintered at 1206 +/-6 ℃, and then the wear-resistant marble ceramic tile is prepared by polishing and grinding.

Example 6

Preparing materials:

raw material preparation was performed according to 15kg of kaolin, 3kg of calcined kaolin, 28kg of calcined talc, 5kg of calcite, 5kg of zinc oxide, 3kg of quartz, 3kg of cordierite, 5kg of magnesia-alumina spinel, 22kg of first frit and 11kg of second frit.

The raw materials of cordierite, alumina-magnesia spinel, first frit and second frit were the same as in example 3.

Adding water and printing paste into the raw materials according to the following raw materials: water: mixing and ball-milling the paste printing paste 1:0.35:0.65 for 10 hours to obtain glaze slurry, controlling the fineness to be 325 meshes, and ageing for 49 hours, wherein the mass fraction of the screen residue is 0.6 percent; the chemical components of the wear-resistant glaze material are calculated by mass percent and comprise: 47.59% SiO₂、17.63Al₂O₃、0.45％Fe₂O₃、6.55％CaO、13.49％MgO、0.62％K₂O、0.47％Na₂O、0.035％TiO₂8.22% ZnO, 1.19% SrO and 0.34% B₂O₃The balance being impurities, the loss on ignition being 4%.

The glaze polishing in the existing production process of the marble ceramic tile is replaced by the wear-resistant glaze, the wear-resistant 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 and is merged into a kiln to be sintered at 1206 +/-6 ℃, and then the wear-resistant marble ceramic tile is prepared by polishing and grinding.

Comparative example 1

Example 1 was selected for comparison, and the cordierite was changed to kaolin, the mass percentage of which was changed to 20%, and the other components were not changed, and the marble tile was prepared according to the method of example 1.

Comparative example 2

Example 1 was selected for comparison, and a marble tile was prepared by replacing magnesium aluminate spinel with kaolin, 21% by mass of which was unchanged in other components, according to the method of example 1.

Comparative example 3

Example 3 was chosen for comparison, and in this example, the compositions of the components, in mass percent, were as follows: 7% of kaolin, 2% of calcined kaolin, 31% of calcined talc, 3% of calcite, 7% of zinc oxide, 20% of 1# frit, 9% of 2# frit, 3% of quartz, 14% of cordierite and 4% of magnesia alumina spinel, and the marble tile was prepared according to the method of example 1.

Comparative example 4

Example 4 was chosen for comparison, and in this example, the compositions of the components, in mass percent, were as follows: 5% of kaolin, 3% of calcined kaolin, 30% of calcined talc, 4% of calcite, 6% of zinc oxide, 20% of first frit, 10% of second frit, 4% of quartz, 3% of cordierite and 15% of magnesium aluminate spinel, and the marble tile was 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:

and (3) performance testing:

1. mohs hardness determination: the marble tile sample is stably placed on a hard support with the facing upward. The surface of a sample is scribed by selecting standard ores with different Mohs values from small to large, the surface of the sample is scribed uniformly and vertically by applying force through a new ore cutting edge, the force application needs to be moderate, and the cutting edge of the standard ore cannot be broken by excessive force application to form double-line or multi-line scribing traces. The lowest hardness value which just can generate obvious scratches is taken as the test result, and the lowest value of all the test values of the test sample is taken as the test result.

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 pollution agent for testing the pollution resistance of the ceramic tile comprises a paste pollution agent, a pollution agent capable of generating an oxidation reaction, a pollution agent capable of generating a film, olive oil and the like, wherein the pollution resistance is classified into 1-5 grades according to the difficulty of cleaning, and the higher the grade is, the better the pollution resistance is.

4. And (3) measuring the direct sunlight transmittance: the direct sunlight transmittance of the building glass is measured by using a method for measuring the direct sunlight transmittance of GB/T2680-94.

5. Determination of the light transmittance of the glaze: and (2) distributing glaze powder on the blank powder, wherein the thickness of the glaze powder is 5mm, the thickness of the blank powder is 2mm, pressing the blank powder into blocks by a press, after sintering in a kiln, throwing off the blank body to process the blank body into a sheet with the thickness of 1mm, and then carrying out sunlight direct transmittance measurement to obtain the result of light transmittance.

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 above embodiments, it can be seen that, by using the abrasion-resistant glaze for marble tiles described in embodiments 1 to 6, the fired product has higher mohs hardness, abrasion resistance, anti-fouling grade and light transmittance, and as the composition ratio of the high-abrasion-resistance 2# frit and the aluminum-magnesium spinel increases, the anti-fouling grade of the finished product decreases and the abrasion resistance coefficient is relatively improved.

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 mohs hardness, wear resistance and light transmittance of the glaze. It is demonstrated that the addition of a suitable amount of cordierite to the formulation has an effect on the mohs hardness, abrasion resistance and light transmittance of the glaze.

From comparative example 2, it can be seen that the mohs hardness and abrasion resistance of the glaze are reduced when the aluminum magnesium spinel is replaced with kaolin, indicating that the addition of a suitable amount of aluminum magnesium spinel has an effect on the mohs hardness and abrasion resistance of the glaze.

As can be seen from comparative examples 3 and 4, when the addition amounts of cordierite and aluminum-magnesium spinel exceed the defined mass ratio, the antifouling property and light transmittance to the glaze are reduced, the abrasion resistance to the glaze is not greatly improved, and white dots exist in the glaze, indicating that the component ratio cannot be completely melted in an environment of 1200 ℃.

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 the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the 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.