Disclosure of Invention
The invention provides a ceramic tile with a fine wave surface and a preparation method thereof.
The invention adopts the following technical scheme for solving the technical problems:
a ceramic tile with a fine wavy surface comprises a green body layer and the fine wavy surface from bottom to top, wherein the fine wavy surface is formed by applying glaze on the green body layer and sintering;
the glaze is prepared from the following raw materials in parts by weight: 10-20 parts of cordierite, 8-15 parts of bauxite, 6-12 parts of silicon dioxide, 3-8 parts of modified boron nitride, 2-6 parts of sintering aid, 2-4 parts of magnesium oxide, 1-3 parts of calcium oxide, 1-2.5 parts of nucleating agent, 1-2 parts of borax, 0.3-0.8 part of barium sulfate and 40-48 parts of stamp-pad ink.
As a preferable scheme, the glaze is prepared from the following raw materials in parts by weight: 12-20 parts of cordierite, 8-12 parts of bauxite, 6-10 parts of silicon dioxide, 5-8 parts of modified boron nitride, 2-5 parts of sintering aid, 2-3 parts of magnesium oxide, 1.5-3 parts of calcium oxide, 1-1.8 parts of nucleating agent, 1-1.5 parts of borax, 0.3-0.6 part of barium sulfate and 40-46 parts of stamp-pad ink.
As a preferable scheme, the glaze is prepared from the following raw materials in parts by weight: 16 parts of cordierite, 10.9 parts of bauxite, 9 parts of silicon dioxide, 7 parts of modified boron nitride, 4 parts of sintering aid, 2.8 parts of magnesium oxide, 2 parts of calcium oxide, 1.6 parts of nucleating agent, 1.2 parts of borax, 0.5 part of barium sulfate and 45 parts of stamp-pad ink.
As a preferable scheme, the sintering aid is prepared from magnesium fluoride, yttrium nitrate and boric acid according to a weight ratio of 1: 0.4-1.5: 0.5 to 1.5.
According to the formula system, the sintering compactness of the ceramic tile can be effectively improved by adopting the sintering aid, so that crystal grains are refined, sintering at 1150-1180 ℃ is promoted, the rheological property of the glaze is improved, the formation of fine wave textures in the sintering process is promoted, the oxygen content of the system is reduced, and the thermal conductivity is improved.
The inventor finds that the above effect cannot be achieved by adopting other common sintering aids, such as alumina or titanium dioxide, namely, the glaze surface does not present fine wave texture and the heat conductivity coefficient is reduced by adopting other sintering aids.
As a preferable scheme, the sintering aid is prepared from magnesium fluoride, yttrium nitrate and boric acid according to a weight ratio of 1: 0.6: 1.2.
As a preferred embodiment, the stamp-pad ink comprises, by weight: 0.1-0.4 part of citric acid, 0.2-0.6 part of carboxymethyl cellulose, 0.4-0.8 part of sodium fluosilicate, 1.5-2.5 parts of triethylenetetramine, 1-3 parts of tetramethylammonium hydroxide, 10-15 parts of butyl carbitol, 18-28 parts of ethylene glycol and 45-65 parts of deionized water.
By adopting the stamp-pad ink, the rheological property can be effectively improved, the viscosity of a system can be reduced, the fluidity of the glaze can be controlled, and the glaze can form fine wave textures on the glaze by controlling the position of an air duct opening and the wind direction and the wind speed of an air outlet.
As a preferred embodiment, the stamp-pad ink comprises, by weight: 0.2 part of citric acid, 0.5 part of carboxymethyl cellulose, 0.6 part of sodium fluosilicate, 1.8 parts of triethylene tetramine, 2.5 parts of tetramethyl ammonium hydroxide, 12 parts of butyl carbitol, 25 parts of ethylene glycol and 57.4 parts of deionized water.
As a preferable scheme, the preparation method of the modified boron nitride comprises the following steps:
(1) adding 0.2-0.6 part by weight of silane coupling agent, 1-3 parts by weight of tartaric acid and 0.5-1.2 parts by weight of tween 60 into 20-40 parts by weight of absolute ethyl alcohol, uniformly mixing to obtain a mixed solution, adding 10 parts by weight of cubic boron nitride into 20-40 parts by weight of mixed solution, stirring at 200-500 rpm for 50-200 min, filtering and drying to obtain pretreated boron nitride;
(2) adding 2-5 parts by weight of cerium nitrate, 2-5 parts by weight of lanthanum nitrate, 0.2-1 part by weight of sodium dimercaptopropane sulfonate and 0.5-1 part by weight of ammonium phosphate into 15-30 parts by weight of absolute ethyl alcohol, and uniformly mixing to prepare a rare earth modified solution;
(3) adding 10 parts by weight of pretreated boron nitride into 20-30 parts by weight of rare earth modified liquid, stirring for 2-5 hours in a water bath at 45-60 ℃ at a rotating speed of 200-600 rpm, filtering, and drying to obtain a mixture;
(4) calcining the mixture at 300-600 ℃ for 0.8-2 h, and cooling to obtain the modified boron nitride.
According to the invention, the mixed solution is adopted to pretreat the boron nitride, then the rare earth modified solution is adopted to treat the boron nitride, and finally the boron nitride is calcined, so that the modified boron nitride capable of obviously improving the heat conductivity coefficient is obtained.
Preferably, the silane coupling agent is vinyltrimethoxysilane.
As a preferred embodiment, the nucleating agent is calcium phosphate.
The invention also provides a preparation method of the ceramic tile with the fine wavy surface, which is used for preparing the ceramic tile with the fine wavy surface and comprises the following steps:
(1) adding cordierite, bauxite, silicon dioxide, modified boron nitride, a sintering aid, magnesium oxide, calcium oxide, a nucleating agent, borax, barium sulfate and stamp-pad ink into a ball mill, and uniformly mixing to obtain a glaze;
(2) applying glaze cloth on the green body layer, sending the green body layer into a kiln, and sintering the green body layer at 1150-1180 ℃ for 40-70 min to form a fine wavy surface, wherein air duct openings are formed in the two sides and the top of the kiln, the included angle between the air outlet direction of the air duct openings in the two sides of the kiln and the horizontal plane is 42-46 ℃, the included angle between the air duct openings in the top of the kiln and the horizontal plane is 88-92 ℃, and the wind power of the air duct openings in the two sides of the kiln is 2.8-3.5 m/s; and the wind power of the air duct opening positioned at the top of the kiln is 2-2.5 m/s.
Under the formula system of the invention, the ceramic tile with the glaze surface having fine wave texture can be obtained by controlling the position of the air duct opening and the wind direction and the wind speed of the air outlet in the sintering process.
The invention has the beneficial effects that: the glaze surface of the ceramic tile has fine wave textures and good heat conductivity coefficient; the boron nitride is pretreated by adopting the mixed solution, treated by the rare earth modified solution and finally calcined, so that the modified boron nitride capable of remarkably improving the heat conductivity coefficient is obtained; under the formula system of the invention, the ceramic tile with the glaze surface having fine wave texture can be obtained by controlling the position of the air duct opening and the wind direction and the wind speed of the air outlet in the sintering process.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
In the present invention, the parts are all parts by weight unless otherwise specified.
Example 1
A ceramic tile with a fine wavy surface comprises a green body layer and the fine wavy surface from bottom to top, wherein the fine wavy surface is formed by applying glaze on the green body layer and sintering;
the glaze comprises 16 parts of cordierite, 10.9 parts of bauxite, 9 parts of silicon dioxide, 7 parts of modified boron nitride, 4 parts of sintering aid, 2.8 parts of magnesium oxide, 2 parts of calcium oxide, 1.6 parts of calcium phosphate, 1.2 parts of borax, 0.5 part of barium sulfate and 45 parts of stamp-pad ink.
The sintering aid is prepared from magnesium fluoride, yttrium nitrate and boric acid according to a weight ratio of 1: 0.6: 1.2.
The stamp-pad ink comprises the following components in percentage by weight: 0.2 part of citric acid, 0.5 part of carboxymethyl cellulose, 0.6 part of sodium fluosilicate, 1.8 parts of triethylene tetramine, 2.5 parts of tetramethyl ammonium hydroxide, 12 parts of butyl carbitol, 25 parts of ethylene glycol and 57.4 parts of deionized water.
The preparation method of the modified boron nitride comprises the following steps:
(1) adding 0.5 part by weight of vinyl trimethoxy silane, 2 parts by weight of tartaric acid and 1 part by weight of tween 60 into 36.5 parts by weight of absolute ethanol, uniformly mixing to obtain a mixed solution, adding 10 parts by weight of cubic boron nitride into 30 parts by weight of the mixed solution, stirring at the rotating speed of 300rpm for 100min, filtering and drying to obtain pretreated boron nitride;
(2) adding 3 parts by weight of cerium nitrate, 3 parts by weight of lanthanum nitrate, 0.8 part by weight of sodium dimercaptopropane sulfonate and 0.6 part by weight of ammonium phosphate into 22.6 parts by weight of absolute ethyl alcohol, and uniformly mixing to prepare a rare earth modified solution;
(3) adding 10 parts by weight of pretreated boron nitride into 25 parts by weight of rare earth modified liquid, stirring for 3 hours in a water bath at 55 ℃ at a rotating speed of 500rpm, filtering, and drying to obtain a mixture;
(4) and calcining the mixture at 500 ℃ for 1h, and cooling to obtain the modified boron nitride.
The preparation method of the ceramic tile with the fine wavy surface comprises the following steps:
(1) adding cordierite, bauxite, silicon dioxide, modified boron nitride, a sintering aid, magnesium oxide, calcium oxide, a nucleating agent, borax, barium sulfate and stamp-pad ink into a ball mill, and uniformly mixing to obtain a glaze;
(2) uniformly mixing 26.3 parts of potassium feldspar, 24 parts of wollastonite, 12 parts of quartz, 10 parts of alumina, 9 parts of kaolin, 7 parts of hydroxyapatite, 5 parts of bentonite, 4 parts of talcum powder, 1.2 parts of sodium carboxymethylcellulose, 1 part of zinc silicate and 0.5 part of sodium tripolyphosphate, sintering to obtain a blank layer, and applying a glaze material on the blank layer, wherein the glazing amount is 380g/m2The material is sent into a kiln and sintered for 50min at 1170 ℃ to form a fine wave surface, air duct openings are arranged on the two sides and the top of the kiln, the included angle between the air outlet direction of the air duct openings on the two sides of the kiln and the horizontal plane is 45 ℃, the included angle between the air duct opening on the top of the kiln and the horizontal plane is 90 ℃, and the wind power of the air duct openings on the two sides of the kiln is 3.2 m/s; the wind power of the air duct opening positioned at the top of the kiln is 2.4 m/s.
Example 2
A ceramic tile with a fine wavy surface comprises a green body layer and the fine wavy surface from bottom to top, wherein the fine wavy surface is formed by applying glaze on the green body layer and sintering;
the glaze is prepared from the following raw materials in parts by weight: 17.2 parts of cordierite, 15 parts of bauxite, 12 parts of silicon dioxide, 3 parts of modified boron nitride, 2 parts of sintering aid, 4 parts of magnesium oxide, 1 part of calcium oxide, 2.5 parts of calcium phosphate, 1 part of borax, 0.3 part of barium sulfate and 42 parts of stamp-pad ink.
The sintering aid is prepared from magnesium fluoride, yttrium nitrate and boric acid according to a weight ratio of 1: 0.8: 1.2.
The stamp-pad ink comprises the following components in percentage by weight: 0.1 part of citric acid, 0.6 part of carboxymethyl cellulose, 0.4 part of sodium fluosilicate, 2.5 parts of triethylene tetramine, 1 part of tetramethyl ammonium hydroxide, 15 parts of butyl carbitol, 21 parts of ethylene glycol and 59.4 parts of deionized water.
The preparation method of the modified boron nitride comprises the following steps:
(1) adding 0.4 part by weight of vinyl trimethoxy silane, 1.8 parts by weight of tartaric acid and 0.6 part by weight of tween 60 into 37.2 parts by weight of absolute ethyl alcohol, uniformly mixing to obtain a mixed solution, adding 10 parts by weight of cubic boron nitride into 30 parts by weight of the mixed solution, stirring at the rotating speed of 400rpm for 80min, filtering and drying to obtain pretreated boron nitride;
(2) adding 3.5 parts by weight of cerium nitrate, 2.5 parts by weight of lanthanum nitrate, 0.4 part by weight of sodium dimercaptopropane sulfonate and 0.8 part by weight of ammonium phosphate into 22.8 parts by weight of absolute ethyl alcohol, and uniformly mixing to prepare a rare earth modified solution;
(3) adding 10 parts by weight of pretreated boron nitride into 30 parts by weight of rare earth modified liquid, stirring for 4 hours in a water bath at 50 ℃ at a rotating speed of 400rpm, filtering, and drying to obtain a mixture;
(4) and calcining the mixture at 480 ℃ for 1.5h, and cooling to obtain the modified boron nitride.
The preparation method of the ceramic tile with the fine wavy surface comprises the following steps:
(1) adding cordierite, bauxite, silicon dioxide, modified boron nitride, a sintering aid, magnesium oxide, calcium oxide, a nucleating agent, borax, barium sulfate and stamp-pad ink into a ball mill, and uniformly mixing to obtain a glaze;
(2) uniformly mixing 26.3 parts of potassium feldspar, 24 parts of wollastonite, 12 parts of quartz, 10 parts of alumina, 9 parts of kaolin, 7 parts of hydroxyapatite, 5 parts of bentonite, 4 parts of talcum powder, 1.2 parts of sodium carboxymethylcellulose, 1 part of zinc silicate and 0.5 part of sodium tripolyphosphate, sintering to obtain a blank layer, and applying a glaze material on the blank layer, wherein the glazing amount is 380g/m2The material is sent into a kiln and sintered for 50min at 1170 ℃ to form a fine wave surface, air duct openings are arranged on the two sides and the top of the kiln, the included angle between the air outlet direction of the air duct openings on the two sides of the kiln and the horizontal plane is 45 ℃, the included angle between the air duct opening on the top of the kiln and the horizontal plane is 90 ℃, and the wind power of the air duct openings on the two sides of the kiln is 3.2 m/s; the wind power of the air duct opening positioned at the top of the kiln is 2.4 m/s.
Example 3
A ceramic tile with a fine wavy surface comprises a green body layer and the fine wavy surface from bottom to top, wherein the fine wavy surface is formed by applying glaze on the green body layer and sintering;
the glaze is prepared from the following raw materials in parts by weight: 11.2 parts of cordierite, 14 parts of bauxite, 6 parts of silicon dioxide, 6 parts of modified boron nitride, 6 parts of sintering aid, 2 parts of magnesium oxide, 3 parts of calcium oxide, 1 part of calcium phosphate, 2 parts of borax, 0.8 part of barium sulfate and 48 parts of stamp-pad ink.
The sintering aid is prepared from magnesium fluoride, yttrium nitrate and boric acid according to a weight ratio of 1: 0.4: 1.
The stamp-pad ink comprises the following components in percentage by weight: 0.4 part of citric acid, 0.2 part of carboxymethyl cellulose, 0.8 part of sodium fluosilicate, 1.5 parts of triethylene tetramine, 3 parts of tetramethyl ammonium hydroxide, 10 parts of butyl carbitol, 28 parts of ethylene glycol and 56.1 parts of deionized water.
The preparation method of the modified boron nitride comprises the following steps:
(1) adding 0.5 part by weight of vinyl trimethoxy silane, 2.5 parts by weight of tartaric acid and 1 part by weight of tween 60 into 26 parts by weight of absolute ethanol, uniformly mixing to obtain a mixed solution, adding 10 parts by weight of cubic boron nitride into 30 parts by weight of the mixed solution, stirring at the rotating speed of 300rpm for 120min, filtering and drying to obtain pretreated boron nitride;
(2) adding 4 parts by weight of cerium nitrate, 3 parts by weight of lanthanum nitrate, 0.5 part by weight of sodium dimercaptopropane sulfonate and 0.6 part by weight of ammonium phosphate into 21.9 parts by weight of absolute ethyl alcohol, and uniformly mixing to prepare a rare earth modified solution;
(3) adding 10 parts by weight of pretreated boron nitride into 20 parts by weight of rare earth modified liquid, stirring for 3 hours in a water bath at 60 ℃ at a rotating speed of 400rpm, filtering, and drying to obtain a mixture;
(4) and calcining the mixture at 550 ℃ for 0.8h, and cooling to obtain the modified boron nitride.
The preparation method of the ceramic tile with the fine wavy surface comprises the following steps:
(1) adding cordierite, bauxite, silicon dioxide, modified boron nitride, a sintering aid, magnesium oxide, calcium oxide, a nucleating agent, borax, barium sulfate and stamp-pad ink into a ball mill, and uniformly mixing to obtain a glaze;
(2) uniformly mixing 26.3 parts of potassium feldspar, 24 parts of wollastonite, 12 parts of quartz, 10 parts of alumina, 9 parts of kaolin, 7 parts of hydroxyapatite, 5 parts of bentonite, 4 parts of talcum powder, 1.2 parts of sodium carboxymethylcellulose, 1 part of zinc silicate and 0.5 part of sodium tripolyphosphate, sintering to obtain a blank layer, and applying a glaze material on the blank layer, wherein the glazing amount is 380g/m2The material is sent into a kiln and sintered for 50min at 1170 ℃ to form a fine wave surface, air duct openings are arranged on the two sides and the top of the kiln, the included angle between the air outlet direction of the air duct openings on the two sides of the kiln and the horizontal plane is 45 ℃, the included angle between the air duct opening on the top of the kiln and the horizontal plane is 90 ℃, and the wind power of the air duct openings on the two sides of the kiln is 3.2 m/s; the wind power of the air duct opening positioned at the top of the kiln is 2.4 m/s.
Example 4
Example 4 differs from example 1 in that the sintering aid described in example 4 differs from example 1, and is otherwise the same.
The sintering aid is prepared from titanium dioxide and aluminum oxide according to the weight ratio of 1: 1.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 does not contain the modified boron nitride, and the other is the same.
Comparative example 2
Comparative example 2 differs from example 1 in that comparative example 2 uses hexagonal boron nitride in place of the modified boron nitride, all other things being equal.
Comparative example 3
Comparative example 3 is different from example 1 in that comparative example 3 is different from example 1 in the preparation method of the modified boron nitride, and the other steps are the same.
In this comparative example, boron nitride was not treated with the rare earth modification liquid.
The preparation method of the modified boron nitride comprises the following steps:
(1) adding 0.5 part by weight of vinyl trimethoxy silane, 2 parts by weight of tartaric acid and 1 part by weight of tween 60 into 36.5 parts by weight of absolute ethanol, uniformly mixing to obtain a mixed solution, adding 10 parts by weight of cubic boron nitride into 30 parts by weight of the mixed solution, stirring at the rotating speed of 300rpm for 100min, filtering and drying to obtain pretreated boron nitride;
(2) calcining the pretreated boron nitride at 500 ℃ for 1h, and cooling to obtain the modified boron nitride.
Comparative example 4
Comparative example 4 is different from example 1 in that comparative example 4 describes a method for preparing modified boron nitride different from example 1, and the other steps are the same.
In this comparative example, boron nitride was modified by replacing rare earth with a metal salt.
The preparation method of the modified boron nitride comprises the following steps:
(1) adding 0.5 part by weight of vinyl trimethoxy silane, 2 parts by weight of tartaric acid and 1 part by weight of tween 60 into 36.5 parts by weight of absolute ethanol, uniformly mixing to obtain a mixed solution, adding 10 parts by weight of cubic boron nitride into 30 parts by weight of the mixed solution, stirring at the rotating speed of 300rpm for 100min, filtering and drying to obtain pretreated boron nitride;
(2) adding 3 parts by weight of calcium nitrate, 3 parts by weight of aluminum nitrate, 0.8 part by weight of sodium dimercaptopropane sulfonate and 0.6 part by weight of ammonium phosphate into 22.6 parts by weight of absolute ethyl alcohol, and uniformly mixing to prepare a metal modification liquid;
(3) adding 10 parts by weight of pretreated boron nitride into 25 parts by weight of metal modified liquid, stirring for 3 hours in a water bath at 55 ℃ at a rotating speed of 500rpm, filtering, and drying to obtain a mixture;
(4) and calcining the mixture at 500 ℃ for 1h, and cooling to obtain the modified boron nitride.
Comparative example 5
Comparative example 5 is different from example 1 in that the tile of comparative example 5 was prepared by a method different from that of example 1, and the rest was the same.
The preparation method of the ceramic tile with the fine wavy surface comprises the following steps:
(1) adding cordierite, bauxite, silicon dioxide, modified boron nitride, a sintering aid, magnesium oxide, calcium oxide, a nucleating agent, borax, barium sulfate and stamp-pad ink into a ball mill, and uniformly mixing to obtain a glaze;
(2) uniformly mixing 26.3 parts of potassium feldspar, 24 parts of wollastonite, 12 parts of quartz, 10 parts of alumina, 9 parts of kaolin, 7 parts of hydroxyapatite, 5 parts of bentonite, 4 parts of talcum powder, 1.2 parts of sodium carboxymethylcellulose, 1 part of zinc silicate and 0.5 part of sodium tripolyphosphate, sintering to obtain a blank, and spreading a glaze material on the blank, wherein the glazing amount is 380g/m2And sintering in a kiln at 1170 deg.C for 50 min.
To further demonstrate the effect of the present invention, the following test methods were provided:
1. the ceramic tiles of examples 1-4 and comparative examples 1-5 were subjected to a thermal conductivity test using a thermal conductivity tester, and the glaze was evaluated, with the test results shown in table 1.
TABLE 1 test results
As can be seen from Table 1, the glazed surface of the ceramic tile has fine wave texture and good thermal conductivity.
According to the invention, the ceramic tile with the glaze surface having fine wave textures is obtained by optimizing the formula of the ceramic tile and the preparation parameters of the modified boron nitride, and the ceramic tile has a good heat conductivity coefficient.
Comparing example 1 with example 4, it can be seen that when the sintering aid of the present invention is replaced by another sintering aid, the thermal conductivity will be reduced, and the glaze surface will not exhibit fine wave texture.
Compared with the comparative examples 1 to 4, the modified boron nitride provided by the invention can obviously improve the heat conductivity coefficient, and different preparation methods of the modified boron nitride can obviously influence the heat conductivity coefficient of the ceramic tile, namely, the modified boron nitride prepared by the preparation method of the modified boron nitride provided by the invention can obviously improve the heat conductivity coefficient compared with the modified boron nitride prepared by other methods.
Comparing example 1 with comparative example 5, it can be seen that the glaze has a fine wave texture only by adopting the sintering method of the present invention.
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.