阅读说明：本技术 一种具有热舒适性的陶瓷材料及其制备方法、陶瓷砖和用途 (Ceramic material with thermal comfort, preparation method thereof, ceramic tile and application ) 是由 林要军 马云龙 马会川 张俊 于 2021-08-10 设计创作，主要内容包括：本发明提供一种具有热舒适性的陶瓷材料,所述陶瓷材料的组分包括：氧化钙、氧化钠、氧化钾、氧化硅、碳化硅、氧化锰、硅灰石、三氧化二硼和三氧化二铝；其中,三氧化二铝的含量≤20wt％,碳化硅的含量为0.3～5wt％,碳化硅的粒径为1～5μm。本发明通过降低陶瓷材料中三氧化二铝的含量并严格控制碳化硅的含量,能够在制得气孔均匀性良好的陶瓷同时显著提高陶瓷的机械性能,应用前景广阔。(The invention provides a ceramic material with thermal comfort, which comprises the following components: calcium oxide, sodium oxide, potassium oxide, silicon carbide, manganese oxide, wollastonite, boron trioxide and aluminum oxide; wherein the content of aluminum oxide is less than or equal to 20 wt%, the content of silicon carbide is 0.3-5 wt%, and the particle size of the silicon carbide is 1-5 μm. According to the invention, by reducing the content of aluminum oxide in the ceramic material and strictly controlling the content of silicon carbide, the ceramic with good pore uniformity can be prepared, and the mechanical property of the ceramic is obviously improved, so that the ceramic has a wide application prospect.)

1. A thermally comfortable ceramic material, characterized in that the composition of the ceramic material comprises: calcium oxide, sodium oxide, potassium oxide, silicon carbide, manganese oxide, wollastonite, boron trioxide and aluminum oxide;

wherein the content of aluminum oxide is less than or equal to 20 wt%, the content of silicon carbide is 0.3-5 wt%, and the particle size of the silicon carbide is 1-5 μm.

2. The ceramic material of claim 1, wherein the content of alumina in the ceramic material is less than or equal to 15 wt%;

preferably, the mass ratio of the aluminum oxide to the boron trioxide is 0.2-0.8: 1, and preferably 0.76: 1.

3. The ceramic material according to claim 1 or 2, wherein the mass fraction of manganese oxide in the ceramic material is 0.01-0.2%;

preferably, the mass ratio of the manganese oxide to the silicon carbide is 0.01-0.1: 1.

4. The ceramic material according to any one of claims 1 to 3, wherein the ceramic material further comprises magnesium oxide;

preferably, the content of the magnesium oxide is 3.5-6 wt%;

preferably, the particle size of the magnesium oxide is 250-450 μm.

5. The ceramic material according to any one of claims 1 to 4, wherein the mass fraction of calcium oxide in the ceramic material is 6 to 12%;

preferably, the mass fraction of sodium oxide in the ceramic material is 2.5-4.5%;

preferably, the mass fraction of potassium oxide in the ceramic material is 1.2-2.5%;

preferably, the mass fraction of the silicon oxide in the ceramic material is 30-41%;

preferably, the mass fraction of the wollastonite in the ceramic material is 5-15%.

6. The ceramic material according to any one of claims 1 to 5, wherein the ceramic material further comprises cerium oxide;

preferably, the content of the cerium oxide is 2.6-5.3 wt%.

7. A method for preparing a thermally comfortable ceramic material according to any one of claims 1 to 6, comprising: mixing the components of the ceramic material to obtain a mixture; and firing the mixture to obtain the ceramic material.

8. The production method according to any one of claims 1 to 7, wherein the firing temperature is 1200 to 1350 ℃.

9. A ceramic tile with thermal comfort, characterized in that the surface of the ceramic tile is provided with a glaze layer, and the glaze layer is the ceramic material as claimed in any one of claims 1-6.

10. Use of a ceramic material according to any one of claims 1 to 6 in tile surface materials or glazes.

Technical Field

The invention relates to the technical field of building materials, in particular to a ceramic material with thermal comfort, a preparation method thereof, a ceramic tile and application.

Background

With the continuous development of the demand of people for building ceramics, the purposes of environmental protection, comfort and health become consumption targets, then the existing bottom plate always gives people a cold feeling, and how to improve the thermal comfort performance of the surface of the ceramic material is the future research and development direction.

CN102718549A discloses a ceramic light-weight heat-insulating decorative external wall tile, which forms uniform and fine closed air holes and has the function of heat insulation.

CN101003433A discloses a ceramic tile with heat insulation and preservation functions and a preparation method thereof, wherein the ceramic tile comprises a tile body formed by the existing ceramic tile base material, and closed air holes formed by added foaming materials are arranged in the ceramic tile body; the ceramic tile with the heat insulation function has good heat insulation and heat preservation effects and is simple to install.

CN201011074A discloses a ceramic brick with heat insulation and preservation functions, which has closed pores formed by adding foaming materials in the ceramic brick body. The closed air holes are formed by connecting a plurality of air bubbles into a honeycomb shape or arranging a plurality of air bubbles at intervals, and the closed air holes are arranged at the bottom layer of the brick body.

However, the above-mentioned bricks are all the pore structures of the brick body itself, which do not improve the thermal comfort of the ceramic surface.

Therefore, there is a need to develop a ceramic material with thermal comfort properties that can be applied to the surface of ceramic tiles.

Disclosure of Invention

In view of the problems in the prior art, the invention provides a ceramic material with thermal comfort, which can obtain a ceramic material with uniform pores and excellent mechanical properties by regulating and controlling components, is suitable for being arranged on the surface of a brick body, improves the touch feeling of floors or walls and the like, can effectively avoid the conditions of damage and the like due to excellent mechanical properties, and prolongs the service life of the floors and the walls.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a thermally comfortable ceramic material, the composition of which comprises: calcium oxide, sodium oxide, potassium oxide, silicon carbide, manganese oxide, wollastonite, boron trioxide and aluminum oxide;

wherein the content of aluminum oxide is less than or equal to 20 wt%, the content of silicon carbide is 0.3-5 wt%, and the particle size of the silicon carbide is 1-5 μm.

According to the ceramic material with thermal comfort, the oxidation of silicon carbide is promoted by adding manganese oxide, so that the foaming effect can be improved, and a uniform and fine pore structure is obtained; the particle size requirement on the silicon carbide is very strict, and the silicon carbide with the particle size of 1-5 microns can improve a proper reaction surface, so that a proper amount of gas can be generated in the initial stage, uniform pores with proper pore diameters can be formed in the whole ceramic material, and finally, the low heat conductivity coefficient and the excellent mechanical property are ensured at the same time; meanwhile, when the content of the silicon carbide is higher, excessive particles participating in the reaction are easily caused, the pore volume is large, the pore diameter of pores is large, and the mechanical property is rapidly reduced; when the content of the silicon carbide is low, the generated pores are insufficient, so that the gas diffusion is not uniform, the pores are not uniform, and finally the overall mechanical property of the ceramic material is still poor and the thermal comfort is poor. Further, the present inventors have unexpectedly found that controlling the content of alumina to 20% or less can suitably reduce the viscosity of the high-temperature liquid phase, promote the growth of pores, and increase the porosity.

The content of alumina in the present invention is not more than 20% by weight, and may be, for example, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 15%, 16%, 18% or 20% by weight, but is not limited to the values listed, and other values not listed in the range are also applicable.

The content of silicon carbide is 0.3 to 5 wt%, and for example, it may be 0.3 wt%, 0.9 wt%, 1.4 wt%, 1.9 wt%, 2.4 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, but is not limited to the above-mentioned values, and other values not mentioned in this range are also applicable.

The particle size of the silicon carbide is 1 to 5 μm, and may be, for example, 1 μm, 1.5 μm, 1.9 μm, 2.4 μm, 2.8 μm, 3.3 μm, 3.7 μm, 4.2 μm, 4.6 μm or 5 μm, but is not limited to the above-mentioned values, and other values not mentioned in the above range are also applicable.

Preferably, the content of the aluminum oxide in the ceramic material is less than or equal to 15 wt%.

Preferably, the mass ratio of the alumina to the diboron trioxide is 0.2-0.8: 1, for example, 0.2:1, 0.27:1, 0.34:1, 0.4:1, 0.47:1, 0.54:1, 0.6:1, 0.67:1, 0.74:1 or 0.8:1, but not limited to the values listed, and other values not listed in this range are equally applicable, preferably 0.76: 1.

According to the invention, the aluminum oxide and the boron trioxide act synergistically to adjust the viscosity of a high-temperature liquid phase, overcome the problem of increased brittleness of a ceramic material caused by adding wollastonite, promote the growth and diffusion of pores, improve the porosity of a final product, synergistically improve the toughness of the ceramic material and improve the fracture modulus of the ceramic material.

Preferably, the mass fraction of manganese oxide in the ceramic material is 0.01 to 0.2%, for example, 0.01%, 0.04%, 0.06%, 0.08%, 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, or 0.2%, but not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the mass ratio of the manganese oxide to the silicon carbide is 0.01 to 0.1:1, and may be, for example, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, or 0.1:1, but not limited to the above-mentioned values, and other values not listed in this range are also applicable.

According to the invention, the manganese oxide can promote the oxidation of silicon carbide and improve the foaming effect, so that uniform and fine pores can be obtained, the mechanical property of the product can be ensured, and the heat conductivity coefficient of the final ceramic can be reduced.

Preferably, the composition of the ceramic material further comprises magnesium oxide.

The ceramic material preferably also contains magnesium oxide, has the function of a foam stabilizer, can effectively avoid the conditions of bubble breakage and the like, and is more favorable for ensuring the uniformity of pores in the finally formed ceramic material.

Preferably, the magnesium oxide is contained in an amount of 3.5 to 6 wt%, and for example, may be 3.5 wt%, 3.8 wt%, 4.1 wt%, 4.4 wt%, 4.7 wt%, 4.9 wt%, 5.2 wt%, 5.5 wt%, 5.8 wt%, or 6 wt%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the particle size of the magnesium oxide is 250 to 450 μm, and may be, for example, 250 μm, 273 μm, 295 μm, 317 μm, 339 μm, 362 μm, 384 μm, 406 μm, 428 μm or 450 μm, but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the mass fraction of calcium oxide in the ceramic material is 6 to 12%, for example, 6%, 6.7%, 7.4%, 8%, 8.7%, 9.4%, 10%, 10.7%, 11.4%, or 12%, etc., but not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the mass fraction of sodium oxide in the ceramic material is 2.5 to 4.5%, for example, 2.5%, 2.8%, 3%, 3.2%, 3.4%, 3.7%, 3.9%, 4.1%, 4.3%, or 4.5%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the mass fraction of potassium oxide in the ceramic material is 1.2 to 2.5%, and may be, for example, 1.2%, 1.4%, 1.5%, 1.7%, 1.8%, 2%, 2.1%, 2.3%, 2.4%, or 2.5%, but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the mass fraction of the silicon oxide in the ceramic material is 30 to 41%, and may be, for example, 30%, 32%, 33%, 34%, 35%, 37%, 38%, 39%, 40%, or 41%, but is not limited to the values listed, and other values not listed in the range are also applicable.

Preferably, the mass fraction of the wollastonite in the ceramic material is 5 to 15%, and may be, for example, 5%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.

Preferably, the component of the ceramic material further comprises cerium oxide.

The ceramic material of the invention preferably further comprises cerium oxide, which can be further matched with silicon carbide to form a foaming material, so that the formed pores are more uniform, and the existence of the cerium oxide can promote the catalytic action of manganese oxide on the silicon carbide and promote the formation and diffusion of the pores, thereby forming uniform pores with proper pore size.

Preferably, the cerium oxide is contained in an amount of 2.6 to 5.3 wt%, for example, 2.6 wt%, 2.9 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4.1 wt%, 4.4 wt%, 4.7 wt%, 5 wt%, or 5.3 wt%, etc., but not limited to the recited values, and other values not recited in this range are also applicable.

In a second aspect, the present invention provides a method for preparing a ceramic material having thermal comfort according to the first aspect, the method comprising: mixing the components of the ceramic material to obtain a mixture; and firing the mixture to obtain the ceramic material.

Preferably, the firing temperature is 1200 to 1350 ℃, for example, 1200 ℃, 1217 ℃, 1234 ℃, 1250 ℃, 1267 ℃, 1284 ℃, 1300 ℃, 1317 ℃, 1334 ℃ or 1350 ℃, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.

In a third aspect, the invention provides a ceramic tile with thermal comfort, the surface of the ceramic tile is provided with a glaze layer, and the glaze layer is the ceramic material of the first aspect.

The glaze layer of the ceramic tile disclosed by the invention adopts the ceramic material disclosed by the first aspect, so that the ceramic tile has excellent mechanical properties, can resist various abrasion and mechanical collision, has uniform and fine air holes, remarkably improves the touch feeling of the product and improves the use experience of a user.

In a fourth aspect, the present invention provides the use of a ceramic material according to the first aspect in tile surface materials or glazes.

The ceramic material with thermal comfort provided by the invention has the advantages of uniform pores, low thermal conductivity coefficient, excellent touch, excellent compressive strength and modulus of rupture, suitability for various mechanical impacts such as friction on the surface of a ceramic tile and long service life.

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

(1) the ceramic material with thermal comfort provided by the invention has uniform air holes and excellent mechanical property, and can be well suitable for the surface of a ceramic tile;

(2) the thermal comfort ceramic material provided by the invention has the advantages that the porosity is 20-30%, the pore diameter of pores is controlled to be 0.01-0.55 mm, the pores are uniform, the heat conductivity coefficient is more than 0.2W/m.K, the compressive strength is more than 15MPa, and the modulus of rupture is more than 50 MPa;

(3) the invention provides a ceramic material with thermal comfort.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

The embodiment provides a ceramic material with thermal comfort, and the components of the ceramic material comprise: 10.23 percent of calcium oxide, 3.56 percent of sodium oxide, 2.25 percent of potassium oxide, 34.96 percent of silicon oxide, 3.57 percent of silicon carbide, 0.09 percent of manganese oxide, 11.65 percent of wollastonite, 13.78 percent of boron trioxide, 10.55 percent of aluminum oxide, 5.28 percent of magnesium oxide and 4.08 percent of cerium oxide; the particle size of the magnesium oxide is 300-380 μm, and the particle size of the silicon carbide is 1.5-4.5 μm.

The preparation method of the ceramic material with thermal comfort comprises the following steps: mixing the components of the ceramic material to obtain a mixture; and firing the mixture at 1280 ℃ to obtain the ceramic material.

The ceramic material with thermal comfort prepared by the embodiment is formed to have a uniform pore channel structure, the pore diameter of pores is 0.01-0.05 mm, the apparent porosity is tested by adopting a method in the national standard GB/T3810.1-16-2006, and the porosity is found to be 28%; the thermal conductivity of the material is tested by a thermal conductivity meter, and the thermal conductivity is found to be 0.31W/m.K. Meanwhile, a TYE-300 type pressure tester is adopted to test the compressive strength of the sample according to GB/T5486-2008, the result shows that the compressive strength of the sample can reach 16.2MPa, the fracture modulus is measured according to the standard GB/T3810.4 ceramic tile fracture modulus and fracture strength measurement, and the result is 62 MPa.

Example 2

The embodiment provides a ceramic material with thermal comfort, and the components of the ceramic material comprise: 6.12 percent of calcium oxide, 4.5 percent of sodium oxide, 1.2 percent of potassium oxide, 31.2 percent of silicon oxide, 0.34 percent of silicon carbide, 0.01 percent of manganese oxide, 5.15 percent of wollastonite, 25.32 percent of boron trioxide, 20 percent of aluminum oxide, 3.55 percent of magnesium oxide and 2.61 percent of cerium oxide; the particle size of the magnesium oxide is 250 to 400 μm, and the particle size of the silicon carbide is 1 to 4.5 μm.

The preparation method of the ceramic material with thermal comfort comprises the following steps: mixing the components of the ceramic material to obtain a mixture; and firing the mixture at 1200 ℃ to obtain the ceramic material.

Example 3

The embodiment provides a ceramic material with thermal comfort, and the components of the ceramic material comprise: 12 percent of calcium oxide, 2.53 percent of sodium oxide, 2.5 percent of potassium oxide, 40.56 percent of silicon oxide, 4.79 percent of silicon carbide, 0.2 percent of manganese oxide, 14.98 percent of wollastonite, 6.62 percent of boron trioxide, 4.52 percent of aluminum oxide, 6 percent of magnesium oxide and 5.3 percent of cerium oxide; the particle size of the magnesium oxide is 320-450 μm, and the particle size of the silicon carbide is 1.8-5 μm.

The preparation method of the ceramic material with thermal comfort comprises the following steps: mixing the components of the ceramic material to obtain a mixture; and sintering the mixture at 1350 ℃ to obtain the ceramic material.

Example 4

The present example provides a thermal comfort ceramic material, which has the same composition as in example 1 except that the mass fraction of diboron trioxide is 20.52%, and the mass fraction of aluminum oxide is 3.81%.

Example 5

The present embodiment provides a thermal comfort ceramic material, which has the same components as those in embodiment 1 except that the mass fraction of diboron trioxide is 12.35%, and the mass fraction of aluminum oxide is 11.98%.

Example 6

This example provides a thermally comfortable ceramic material having the same composition as in example 1, except that the mass fraction of silicon carbide is 3.26% and the mass fraction of manganese oxide is 0.4%.

Example 7

This example provides a thermally comfortable ceramic material having the same composition as in example 1, except that the mass fraction of silicon carbide is 3.63% and the mass fraction of manganese oxide is 0.03%.

Comparative example 1

This comparative example provides a thermally comfortable ceramic material having the same composition as in example 1, except that the alumina content was 25% and the mass fraction of silica was reduced to 20.51%.

Comparative example 2

This comparative example provides a thermally comfortable ceramic material having the same composition as in example 1 except that the silicon carbide content was 7 wt% and the silicon oxide content was reduced to 31.53%.

Comparative example 3

This comparative example provides a thermally comfortable ceramic material having the same composition as in example 1 except that the content of silicon carbide was 0.1 wt% and the content of silicon oxide was increased to 38.43%.

Comparative example 4

The comparative example provides a thermal comfort ceramic material, which is the same as that of example 1 except that the silicon carbide has a particle size of 10 to 25 μm.

The test method comprises the following steps: the pore diameter, porosity, thermal conductivity, compressive strength and modulus of rupture of the pores in the above examples and comparative examples were measured by the same method as in example 1.

The test results of the above examples and comparative examples are shown in table 1.

TABLE 1

In conclusion, the ceramic material with thermal comfort provided by the invention can simultaneously take account of the mechanical property and the heat conductivity coefficient of the ceramic material, wherein the porosity is 20-30%, the pore diameter of the pores is controlled to be 0.01-0.55 mm, under the better condition, the pore diameter of the pores can be controlled to be 0.01-0.1 mm, the pores are uniform, the heat conductivity coefficient is more than 0.2W/m.K, the compressive strength is more than 15MPa, and the modulus of rupture is more than 50MPa, so that the service life of the ceramic surface material is obviously prolonged, and the touch feeling of a user is improved.

The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.