Ceramic rock plate with skin texture and preparation method and application thereof

Abstract

The application belongs to the technical field of building ceramics, and particularly discloses a ceramic rock plate with skin texture and a preparation method and application thereof. The ceramic rock plate comprises, from bottom to top, a body, a bottom glaze layer, an isolation glaze layer, a pattern layer and a protective glaze layer. The preparation raw materials of the bottom glaze layer comprise first base glaze and calcined tin oxide; the preparation raw materials of the isolation glaze layer comprise second base glaze and calcined indium oxide; and the preparation raw materials of the protective glaze layer comprise third base glaze and calcined bismuth oxide. The raw material components of the first base glaze, the second base glaze and the third base glaze are the same. The ceramic rock plate prepared by the application not only has a delicate, smooth and soft matte skin texture, but also has high hardness, high wear resistance and high stain resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of building ceramics, and particularly relates to a ceramic rock plate with skin texture and a preparation method and application thereof. BACKGROUND

[0002] The ceramic rock plate is a new type of building decoration material with advantages of high strength, high hardness, high wear resistance, high stain resistance, high acid and alkali resistance, and high impermeability, and is widely used in indoor and outdoor wall surfaces, floors, countertops and other places. The surface glaze of the ceramic rock plate is an important factor affecting its aesthetic performance and use effect. The common ceramic rock plate glazes on the market mainly include matte glaze, bright glaze, semi-bright glaze, soft glaze and the like, each of which has advantages and disadvantages, but none of them can meet the needs of consumers for natural, delicate and skin-like texture.

[0003] The skin glaze ceramic tile is a kind of sub-light ceramic tile with delicate, smooth and soft glaze, and has simple, natural and elegant artistic characteristics. However, the skin glaze ceramic tile is also prone to some defects in the production and use process, such as pores, bubbles, poor dirt resistance, easy to penetrate dirt, etc., which affect its aesthetic property and use performance. The main reasons for these defects are as follows:

[0004] Pores and bubbles: this is due to the glaze properties of the skin glaze. The skin glaze adopts satin glaze, which has delicate and smooth glaze, but after high-temperature calcination, the glaze surface is prone to shrinkage and easy to produce pores and bubbles; these pores and bubbles not only affect the aesthetics of the ceramic tile, but also reduce the strength and durability of the ceramic tile.

[0005] Poor dirt resistance and easy to penetrate dirt: this is due to the low smoothness of the skin glaze surface, which leads to a large friction coefficient on the surface, making it difficult to clean and easy to stain dust and dirt; especially in a humid environment, the surface of the skin glaze ceramic tile is prone to bacterial and mold growth, causing hygiene problems.

[0006] Poor wear resistance and easy to scratch: this is due to the low hardness of the skin glaze surface, which leads to poor wear resistance of the surface and is easy to be scratched or worn by hard objects. Especially on the floor with high frequency of use, the surface of the skin glaze ceramic tile is prone to wear and polishing phenomenon, affecting its gloss and texture.

[0007] Therefore, it is urgent to develop a ceramic rock plate that has a skin texture glaze effect while achieving high hardness, high wear resistance and high stain resistance. SUMMARY

[0008] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application proposes a ceramic rock plate with skin texture and a preparation method and application thereof, which not only has delicate, smooth and soft sub-light skin texture, but also has high hardness, high wear resistance and high stain resistance.

[0009] To solve the above technical problems, the first aspect of the present application provides a ceramic rock plate, which comprises, from bottom to top, a body, a bottom glaze layer, an isolation glaze layer, a pattern layer and a protective glaze layer;

[0010] The preparation raw materials of the bottom glaze layer include a first base glaze and calcined tin oxide;

[0011] The preparation raw materials of the isolation glaze layer include a second base glaze and calcined indium oxide;

[0012] The preparation raw materials of the protective glaze layer include a third base glaze and calcined bismuth oxide;

[0013] The raw material components of the first base glaze, the second base glaze and the third base glaze are the same.

[0014] Specifically, the present application sets three glaze layers of bottom glaze, isolation glaze and protective glaze to increase the thickness and density of the glaze layer, improve the permeability resistance and stain resistance of the glaze layer, avoid the penetration of pollutants into the inside of the glaze layer, and thus improve the stain resistance of the product. At the same time, tin oxide, indium oxide and bismuth oxide are added in the bottom glaze, the isolation glaze and the protective glaze respectively, and the three oxides are semiconductor oxides, which can change the electrical conductivity and optical properties of the glaze layer, make different glaze layers have different optical properties, and thus produce the skin texture effect by adjusting the transparency and reflectivity of the glaze layer.

[0015] The tin oxide is an n-type semiconductor, which can absorb ultraviolet light and blue light in visible light, so that the glaze layer presents a light yellow or light gray tone, increasing the warmth of the glaze layer; at the same time, the calcined tin oxide is a mineral containing stannate, which is beneficial to improve the whiteness and luster of the glaze layer, improve the fluidity of the glaze layer, and make the glaze layer more uniform and smooth.

[0016] The indium oxide is a p-type semiconductor, which can absorb red light and orange light in visible light, so that the glaze layer presents a light blue or light green tone, increasing the freshness of the glaze layer; at the same time, the calcined indium oxide is a mineral containing indate, which is beneficial to improve the transparency and luster of the glaze layer, to ensure the transparency and stability of the glaze layer.

[0017] The bismuth oxide is a p-type semiconductor, which can absorb green light and yellow light in visible light, so that the glaze layer presents a light purple or light pink tone, increasing the softness of the glaze layer; at the same time, the calcined bismuth oxide is a mineral containing bismuthate, which is beneficial to improve the hardness and wear resistance of the glaze layer, and thus improve the stain resistance and permeability resistance of the glaze layer,

[0018] As a further improvement of the above-mentioned scheme, the raw material components of the body include, in parts by weight, 20-30 parts of talc clay, 20-35 parts of wollastonite, 5-10 parts of anorthite, 10-20 parts of soda anorthite, 5-10 parts of perlite, 5-10 parts of calcined alumina, 5-10 parts of calcined zinc oxide, 5-10 parts of calcined magnesium oxide, and 5-10 parts of calcined barium oxide.

[0019] Specifically, the body layer of the present application uses talc, wollastonite, (soda) anorthite, perlite and calcined oxides as the main raw materials for preparation, and optimizes the body formula to reduce the organic matter and impurities in the body, improve the air permeability and exhaust property of the body, thereby avoiding excessive gas generation during the sintering of the body.

[0020] Among them: talc is a clay raw material containing a lot of water and organic matter, which can improve the plasticity and drying strength of the body, but also increase the drying shrinkage and deformation of the body, and the gas generation during sintering; therefore, the amount of talc clay should not be too much, which is mainly used to ensure the forming performance and sintering performance of the body.

[0021] Wollastonite is a silicate-containing raw material that can reduce the plasticity and drying shrinkage of the body, shorten the drying time, and prevent the body from deforming. Wollastonite can also act as a flux during sintering to promote the densification and light transmittance of the body, but it can also reduce the refractoriness and thermal shock resistance of the body; by controlling the amount of wollastonite, the drying performance and sintering performance of the body can be ensured.

[0022] Anorthite and soda anorthite act as fluxes, mainly to reduce the sintering temperature and sintering time of the body, improve the density and light transmittance of the body, but also reduce the refractoriness and thermal shock resistance of the body. Among them: anorthite contains a lot of calcium oxide, which can increase the thermal expansion coefficient of the body, which is beneficial to the adaptability of the body to glaze, but also increases the risk of thermal stress and thermal cracks of the body; soda anorthite contains a lot of sodium oxide, which can reduce the thermal expansion coefficient of the body, which is beneficial to the thermal shock resistance of the body, but also reduces the adaptability of the body to glaze; therefore, by adjusting the amount of anorthite and soda anorthite, the matching of the body and glaze and the sintering quality can be ensured.

[0023] Perlite is a volcanic eruption of acidic lava, which is a glassy rock formed by rapid cooling, and its main component is silicon dioxide, containing a small amount of aluminum, iron, calcium, potassium, sodium, magnesium and other elements; as a filler for the body, perlite increases the air permeability and exhaust property of the body, reduces the gas generated during sintering of the body, avoids the defects of air holes and bubbles in the body, and improves the quality of the body.

[0024] Calcined alumina, calcined zinc oxide, calcined magnesium oxide, calcined barium oxide, four calcined oxides, mainly used to improve the refractoriness and thermal shock resistance of the body, increase the mechanical strength and wear resistance of the body, but also increase the sintering temperature and sintering time of the body, reduce the density and light transmittance of the body. Among them: calcined alumina is conducive to increasing the acid resistance and alkali resistance of the body, but also increases the thermal expansion coefficient of the body, reduces the adaptability of the body and glaze; calcined zinc oxide is conducive to increasing the refractive index and light transmittance of the body, but also increases the thermal expansion coefficient of the body, reduces the thermal shock resistance of the body; calcined magnesium oxide is conducive to reducing the thermal expansion coefficient of the body, increasing the thermal shock resistance of the body, but also reduces the acid resistance and alkali resistance of the body; calcined barium oxide is conducive to reducing the thermal expansion coefficient of the body, increasing the thermal shock resistance of the body, but also increases the weight and cost of the body. Therefore, the present application controls the matching relationship of the four calcined oxides to make the raw materials interact with each other to improve the comprehensive performance of the body.

[0025] As a further improvement of the above scheme, the raw material components of the first base glaze, the second base glaze and the third base glaze each include, by weight: wood knot soil 5-10 parts, montmorillonite 5-10 parts, boron magnesium stone 5-10 parts, calcined alumina 5-10 parts, calcined calcium oxide 5-10 parts, calcined magnesium oxide 5-10 parts, calcined barium oxide 5-10 parts, calcined strontium oxide 5-10 parts, potassium feldspar 10-20 parts, sodium feldspar 10-20 parts.

[0026] Specifically, each glaze layer of the present application uses wood knot soil, montmorillonite, boron magnesium stone, calcined alumina, calcined calcium oxide, calcined magnesium oxide, calcined barium oxide, calcined strontium oxide, potassium feldspar and sodium feldspar as the base glaze, and adjusts the formula composition of the base glaze to reduce the high temperature viscosity of the glaze layer, increase the fluidity and exhaust property of the glaze layer, and avoid premature closure of the glaze layer; at the same time, the formula adjustment also increases the surface tension of the glaze layer, reduces the hydrophilicity of the glaze layer, improves the stain resistance and wear resistance of the glaze layer, and avoids the glaze layer from being eroded or scratched by contaminants. Among them: wood knot soil and montmorillonite are clay raw materials with high plasticity and dry strength, which can improve the formability and stability of the glaze layer; boron magnesium stone is a boron-containing mineral that can reduce the sintering temperature and shrinkage of the glaze layer, increase the transparency and gloss of the glaze layer, and also adjust the thermal expansion coefficient of the glaze layer to avoid thermal stress between the glaze layer and the body; calcined alumina, calcined calcium oxide, calcined magnesium oxide, calcined barium oxide and calcined strontium oxide are high melting point oxides that can improve the fire resistance and thermal shock resistance of the glaze layer, and also reduce the thermal expansion coefficient of the glaze layer to enhance the bonding force between the glaze layer and the body; potassium feldspar and sodium feldspar are an alkali-containing mineral that can promote the sintering of the glaze layer, increase the density and strength of the glaze layer, and also adjust the thermal expansion coefficient of the glaze layer to avoid thermal stress between the glaze layer and the body.

[0027] Preferably, the mass ratio of the first base glaze to the calcined tin oxide is (5-25):1.

[0028] Preferably, the mass ratio of the second base glaze to the calcined indium oxide is (5-25):1.

[0029] Preferably, the mass ratio of the third base glaze to the calcined bismuth oxide is (5-25):1.

[0030] As a further improvement of the above-mentioned scheme, the raw material components of the first base glaze and the second base glaze each further include an additive A, which includes, by weight parts: water 35-40 parts, suspending agent 0.15-0.20 parts, water reducing agent 0.25-0.35 parts.

[0031] Specifically, the suspending agent is mainly used to increase the stability and uniformity of the glaze, prevent the precipitation and stratification of the glaze, and make the glaze have good fluidity and coating performance; the water reducing agent is mainly used to reduce the viscosity and surface tension of the glaze, reduce the water consumption and coating thickness of the glaze, and make the glaze easier to dry and sinter.

[0032] Preferably, the suspending agent is selected from at least one of polyacrylamide, polycarboxylate, phosphate, silicate.

[0033] Preferably, the water reducing agent is selected from at least one of polycarboxylate, polyvinyl alcohol, polyethylene glycol, carbonate.

[0034] As a further improvement of the above-mentioned scheme, the raw material components of the third base glaze further include an additive B, which includes, by weight parts: ethyl acetate 48-52 parts, acrylic resin 42-46 parts, polyamide 2-4 parts, defoaming agent 1-3 parts, pH value adjusting agent 0.5-1.5 parts.

[0035] Specifically, the components of the protective glaze layer are similar to the base glaze and the barrier glaze, and the reason for selecting different additives from the base glaze and the barrier glaze is mainly to improve the coating performance and wear resistance of the protective glaze layer. Among them: ethyl acetate and acrylic resin are organic solvents and organic adhesives, which can increase the fluidity and adhesion of the protective glaze layer, so that the protective glaze layer can be uniformly coated on the pattern layer, and also can increase the elasticity and toughness of the protective glaze layer, so that the protective glaze layer can resist external friction and scratching. The defoaming agent is mainly used to eliminate or reduce the bubbles in the glaze, so as to improve the coating performance and sintering performance of the glaze, and avoid defects such as air holes or pinholes in the glaze layer. The pH adjusting agent is mainly used to adjust or stabilize the pH value of the glaze, so that the pH value of the glaze is close to neutral, thereby improving the stability and color of the glaze, and avoiding phenomena such as color difference or discoloration of the glaze layer.

[0036] Preferably, the defoaming agent is selected from at least one of polyacrylamide, polyvinyl alcohol, and polyethylene glycol.

[0037] Preferably, the pH regulator is selected from at least one of sodium hydroxide, triethylamine, phosphoric acid, and acetic acid.

[0038] The second aspect of the present application provides a method for preparing the ceramic rock plate, comprising the following steps:

[0039] The base glaze, the isolation glaze, the pattern layer, and the protective glaze layer are sequentially formed on the green body, and after drying, the green body is fired in a kiln to obtain the ceramic rock plate.

[0040] Preferably, the drying temperature is 100-120℃.

[0041] Preferably, the drying time is 2-4 hours.

[0042] Preferably, the base glaze is sprayed on the surface of the green body by a spray gun to form a base glaze layer with a thickness of 0.1-0.2mm.

[0043] Preferably, the isolation glaze is sprayed on the surface of the base glaze layer by a glaze spraying machine to form an isolation glaze layer with a thickness of 0.1-0.2mm.

[0044] Preferably, the inkjet printing pattern is printed on the surface of the isolation glaze layer by a digital printer with a resolution of 300dpi or higher to form a pattern layer.

[0045] Preferably, the protective glaze is printed on the surface of the pattern layer by a digital printer with a resolution of 300dpi or higher to form a protective glaze layer with a thickness of 0.05-0.1mm.

[0046] As a further improvement of the above scheme, the temperature schedule of the firing is as follows: first, the temperature is raised from room temperature to 1000-1050℃ at a heating rate of 80-100℃ / hour; then, the temperature is raised to 1100-1150℃ at a heating rate of 40-50℃ / hour, and the temperature is kept for 40-70min; then, the temperature is lowered to 800-900℃ at a cooling rate of 80-100℃ / hour; then, the temperature is lowered to 400-500℃ at a cooling rate of 40-50℃ / hour; finally, the temperature is naturally cooled to room temperature.

[0047] Specifically, the present application controls the firing curve, appropriately prolongs the firing time, reduces the firing temperature, and keeps the atmosphere in the kiln stable to avoid overburning or overcooling of the kiln, improves the gloss and flatness of the glaze layer while improving the overall performance of the product, thereby obtaining a glaze effect with excellent skin texture. Wherein: control the firing curve, that is, according to a certain heating rate, holding time and cooling rate, avoid the mutation or gentle situation of the firing curve, to ensure the uniformity and completeness of the physical and chemical changes in the firing process, avoid the phenomenon of insufficient or excessive sintering; appropriately prolong the firing time, that is, keep the highest firing temperature, so that the sintering reaction between the body and the glaze layer is fully carried out, increase the density and strength of the ceramic product, and improve the gloss and flatness of the glaze layer; reduce the firing temperature, that is, on the premise of ensuring the sintering effect, try to reduce the highest temperature of firing, to avoid the thermal stress between the body and the glaze layer caused by too high temperature, leading to the phenomenon of cracking or deformation of the ceramic product. At the same time, keep the atmosphere in the kiln stable during firing to avoid the change of the atmosphere in the kiln affecting the color and texture of the ceramic product.

[0048] As a further improvement of the above scheme, after firing, the ceramic tile is further polished and sandblasted.

[0049] Specifically, the protective glaze is polished, which is beneficial to improve the clarity of the pattern layer, and at the same time improve the gloss and hand feeling of the protective glaze surface, so that it has more skin texture. Sandblasting is beneficial to enhance the texture and three-dimensional effect of the glaze surface, and improve the stain resistance and permeability resistance of the glaze surface.

[0050] The third aspect of the present application provides the application of the above-mentioned ceramic rock plate in building decoration.

[0051] The above technical scheme of the present application has at least the following technical effects or advantages compared with the prior art:

[0052] (1) The ceramic rock plate of the present application increases the thickness and density of the glaze layer by setting three glaze layers of base glaze, isolation glaze and protective glaze, improves the permeability and stain resistance of the glaze layer, and avoids the penetration of pollutants into the interior of the glaze layer, thereby improving the stain resistance of the product. At the same time, tin oxide, indium oxide and bismuth oxide are added in the base glaze, isolation glaze and protective glaze respectively, and the three oxides have different optical properties, which can produce the skin texture effect by adjusting the transparency and reflectivity of the glaze layer.

[0053] (2) The present application adjusts the formula composition of the base glaze to reduce the high temperature viscosity of the glaze layer, increase the fluidity and exhaustibility of the glaze layer, and avoid the premature closure of the glaze layer; at the same time, the formula is adjusted to increase the surface tension of the glaze layer, reduce the hydrophilicity of the glaze layer, improve the stain resistance and wear resistance of the glaze layer, and avoid the erosion or scratching of the glaze layer by pollutants.

[0054] (3) The application reduces the organic matter and impurities in the blank body, improves the air permeability and air exhaust property of the blank body, and avoids the generation of excessive gas during the sintering of the blank body, thereby reducing the generation of pinholes or air bubbles in the glaze layer.

[0055] (4) In the preparation of the ceramic rock plate, the sintering curve is controlled, the sintering time is appropriately prolonged, the sintering temperature is reduced, the atmosphere in the kiln is kept stable, and overburning or overcooling of the kiln is avoided; while improving the comprehensive performance of the product, the gloss and flatness of the glaze layer are improved, thereby obtaining a glaze surface effect with excellent skin texture. DETAILED DESCRIPTION

[0056] The application will be described in detail below with reference to examples, so as to facilitate the understanding of the application by those skilled in the art. It is necessary to point out here that the examples are only used to further illustrate the application and cannot be understood as limiting the protection scope of the application. Non-essential improvements and adjustments to the application made by those skilled in the art according to the above application content shall still fall within the protection scope of the application. Meanwhile, the raw materials mentioned below which are not described in detail are all commercially available products; the process steps or preparation methods which are not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0057] Example 1

[0058] A ceramic rock plate comprises, from bottom to top, a blank body, a bottom glaze layer, an isolation glaze layer, a pattern layer and a protective glaze layer.

[0059] The raw material components of the blank body include, by weight: 25 parts of pyrophyllite clay, 30 parts of wollastonite, 8 parts of anorthite, 15 parts of sodium anorthite, 8 parts of perlite, 8 parts of calcined alumina, 8 parts of calcined zinc oxide, 8 parts of calcined magnesium oxide and 8 parts of calcined barium oxide.

[0060] The preparation raw materials of the bottom glaze layer include, by weight: 8 parts of wood knot soil, 8 parts of montmorillonite, 8 parts of boron-magnesium stone, 8 parts of calcined alumina, 8 parts of calcined calcium oxide, 8 parts of calcined magnesium oxide, 8 parts of calcined barium oxide, 8 parts of calcined strontium oxide, 15 parts of potassium feldspar, 15 parts of sodium feldspar and 8 parts of calcined tin oxide.

[0061] The preparation raw materials of the isolation glaze layer include, by weight: 8 parts of wood knot soil, 8 parts of montmorillonite, 8 parts of boron-magnesium stone, 8 parts of calcined alumina, 8 parts of calcined calcium oxide, 8 parts of calcined magnesium oxide, 8 parts of calcined barium oxide, 8 parts of calcined strontium oxide, 15 parts of potassium feldspar, 15 parts of sodium feldspar and 8 parts of calcined indium oxide.

[0062] The raw materials for preparing the protective glaze layer include, in parts by weight, 8 parts of wood knot soil, 8 parts of montmorillonite, 8 parts of boron-magnesium stone, 8 parts of calcined alumina, 8 parts of calcined calcium oxide, 8 parts of calcined magnesium oxide, 8 parts of calcined barium oxide, 8 parts of calcined strontium oxide, 15 parts of potassium feldspar, 15 parts of sodium feldspar, 8 parts of calcined bismuth oxide, 50 parts of ethyl acetate, 45 parts of acrylic resin, 3 parts of polyamide, 2 parts of polyacrylamide, and 1 part of sodium hydroxide.

[0063] A method for preparing a ceramic rock plate, characterized by comprising the following steps:

[0064] (1) The raw materials for preparing the body are weighed according to the mass ratio, and water is added for ball milling (the mass ratio of the raw materials to water is 100:40), and then the body powder is obtained by spray drying, and the body is obtained by pressing the body powder;

[0065] (2) The raw materials for preparing the bottom glaze layer are weighed according to the mass ratio, and water, polyacrylamide and polyvinyl alcohol are added for ball milling (the mass ratio of the raw materials to water, polyacrylamide and polyvinyl alcohol is 100:38:0.18:0.3), and then the bottom glaze slurry with a fineness of 300 mesh is obtained; then the bottom glaze slurry is sprayed on the surface of the body prepared in step (1) by a spray gun to form a bottom glaze layer with a thickness of 0.15 mm;

[0066] (3) The raw materials for preparing the isolation glaze layer are weighed according to the mass ratio, and water, polyacrylamide and polyvinyl alcohol are added for ball milling (the mass ratio of the raw materials to water, polyacrylamide and polyvinyl alcohol is 100:35:0.18:0.3), and then the isolation glaze slurry with a fineness of 300 mesh is obtained; then the isolation glaze slurry is sprayed on the surface of the bottom glaze layer prepared in step (2) by a glaze spraying machine to form an isolation glaze layer with a thickness of 0.15 mm; then a pattern layer is obtained by inkjet printing a pattern on the surface of the isolation glaze layer by a digital printer;

[0067] (4) The raw materials for preparing the protective glaze layer are weighed according to the mass ratio, and ball milling is performed to obtain a protective glaze slurry with a fineness of 300 mesh; then the protective glaze slurry is printed on the surface of the pattern layer prepared in step (3) by a digital printer at a resolution of 400 dpi to form a protective glaze layer with a thickness of 0.08 mm; after drying at 110℃ for 3 hours, the ceramic rock plate of the present embodiment is obtained by firing in a kiln.

[0068] Wherein, the temperature schedule for firing is: first, increase the temperature from room temperature to 1050℃ at a rate of 100℃ / hour; then increase the temperature to 1150℃ at a rate of 50℃ / hour, and keep the temperature for 60 minutes; then decrease the temperature to 800℃ at a rate of 100℃ / hour; then decrease the temperature to 400℃ at a rate of 50℃ / hour; finally, naturally cool to room temperature.

[0069] Example 2

[0070] A ceramic rock plate comprises, from bottom to top, a body, a bottom glaze layer, an isolation glaze layer, a pattern layer and a protective glaze layer.

[0071] The raw material components of the body include, by weight fraction, 23 parts of pyrophyllite clay, 22 parts of wollastonite, 6 parts of anorthite, 15 parts of soda anorthite, 7 parts of perlite, 6 parts of calcined alumina, 8 parts of calcined zinc oxide, 8 parts of calcined magnesium oxide and 5 parts of calcined barium oxide.

[0072] The preparation raw materials of the bottom glaze layer include, by weight fraction, 5 parts of wood knot soil, 10 parts of montmorillonite, 5 parts of boron-magnesium stone, 10 parts of calcined alumina, 10 parts of calcined calcium oxide, 5 parts of calcined magnesium oxide, 10 parts of calcined barium oxide, 5 parts of calcined strontium oxide, 20 parts of potassium feldspar, 10 parts of soda feldspar and 7 parts of calcined tin oxide.

[0073] The preparation raw materials of the isolation glaze layer include, by weight fraction, 5 parts of wood knot soil, 10 parts of montmorillonite, 5 parts of boron-magnesium stone, 10 parts of calcined alumina, 10 parts of calcined calcium oxide, 5 parts of calcined magnesium oxide, 10 parts of calcined barium oxide, 5 parts of calcined strontium oxide, 20 parts of potassium feldspar, 10 parts of soda feldspar and 7 parts of calcined indium oxide.

[0074] The preparation raw materials of the protective glaze layer include, by weight fraction, 5 parts of wood knot soil, 10 parts of montmorillonite, 5 parts of boron-magnesium stone, 10 parts of calcined alumina, 10 parts of calcined calcium oxide, 5 parts of calcined magnesium oxide, 10 parts of calcined barium oxide, 5 parts of calcined strontium oxide, 20 parts of potassium feldspar, 10 parts of soda feldspar, 7 parts of calcined bismuth oxide, 50 parts of ethyl acetate, 45 parts of acrylic resin, 3 parts of polyamide, 2 parts of polyacrylamide and 1 part of sodium hydroxide.

[0075] A preparation method of a ceramic rock plate, characterized in that it comprises the following steps:

[0076] (1) The raw materials for preparing the body are weighed according to the mass ratio, and water is added for ball milling (the mass ratio of the raw materials to water is 100:40), and then the body powder is obtained by spray drying, and the body powder is pressed into a body;

[0077] (2) The raw materials for preparing the bottom glaze layer are weighed according to the mass ratio, and water, polyacrylamide and polyvinyl alcohol are added for ball milling (the mass ratio of the raw materials to water, polyacrylamide and polyvinyl alcohol is 100:38:0.18:0.3), and then a bottom glaze slurry with a fineness of 300 mesh is obtained; then the bottom glaze slurry is sprayed on the surface of the body prepared in step (1) by a spray gun to form a bottom glaze layer with a thickness of 0.15 mm;

[0078] (3) The raw materials for preparing the separation glaze layer were weighed according to the mass ratio, and water, polyacrylamide and polyvinyl alcohol were added for ball milling (the mass ratio of the raw materials to water, polyacrylamide and polyvinyl alcohol was 100:35:0.18:0.3), to obtain a separation glaze slurry with a fineness of 300 meshes; then the separation glaze slurry was sprayed on the surface of the base glaze layer prepared in step (2) by a glaze spraying machine to form a separation glaze layer with a thickness of 0.15 mm; then a pattern was printed on the surface of the separation glaze layer by a digital printer to obtain a pattern layer;

[0079] (4) The raw materials for preparing the protective glaze layer were weighed according to the mass ratio, and ball milling was performed to obtain a protective glaze slurry with a fineness of 300 meshes; then the protective glaze slurry was printed on the surface of the pattern layer prepared in step (3) by a digital printer at a resolution of 400 dpi to form a protective glaze layer with a thickness of 0.08 mm; after drying at 110℃ for 3 hours, the ceramic rock plate of the example was obtained by firing in a kiln.

[0080] The temperature schedule for firing was as follows: first, the temperature was raised from room temperature to 1000℃ at a rate of 80℃ / hour; then the temperature was raised to 1100℃ at a rate of 40℃ / hour, and the temperature was maintained for 40 min; then the temperature was lowered to 800℃ at a rate of 80℃ / hour; then the temperature was lowered to 400℃ at a rate of 40℃ / hour; finally, the temperature was naturally cooled to room temperature.

[0081] Example 3

[0082] A ceramic rock plate sequentially comprises a body, a base glaze layer, a separation glaze layer, a pattern layer and a protective glaze layer from bottom to top.

[0083] The raw material components of the body include, by weight fraction: 25 parts of pyrophyllite clay, 22 parts of wollastonite, 6 parts of anorthite, 15 parts of soda anorthite, 5 parts of perlite, 6 parts of calcined alumina, 8 parts of calcined zinc oxide, 8 parts of calcined magnesium oxide and 5 parts of calcined barium oxide.

[0084] The preparation raw materials of the base glaze layer include, by weight fraction: 10 parts of wood knot soil, 5 parts of montmorillonite, 10 parts of boracite, 5 parts of calcined alumina, 5 parts of calcined calcium oxide, 10 parts of calcined magnesium oxide, 5 parts of calcined barium oxide, 10 parts of calcined strontium oxide, 10 parts of potassium feldspar, 20 parts of soda feldspar and 9 parts of calcined tin oxide.

[0085] The preparation raw materials of the separation glaze layer include, by weight fraction: 10 parts of wood knot soil, 5 parts of montmorillonite, 10 parts of boracite, 5 parts of calcined alumina, 5 parts of calcined calcium oxide, 10 parts of calcined magnesium oxide, 5 parts of calcined barium oxide, 10 parts of calcined strontium oxide, 10 parts of potassium feldspar, 20 parts of soda feldspar and 9 parts of calcined indium oxide.

[0086] The raw materials for preparing the protective glaze layer include, in parts by weight, 10 parts of wood knot soil, 5 parts of montmorillonite, 10 parts of boron-magnesium stone, 5 parts of calcined alumina, 5 parts of calcined calcium oxide, 10 parts of calcined magnesium oxide, 5 parts of calcined barium oxide, 10 parts of calcined strontium oxide, 10 parts of potassium feldspar, 20 parts of sodium feldspar, 9 parts of calcined bismuth oxide, 50 parts of ethyl acetate, 45 parts of acrylic resin, 3 parts of polyamide, 2 parts of polyacrylamide, and 1 part of sodium hydroxide.

[0087] A method for preparing a ceramic rock plate, characterized by comprising the following steps:

[0088] (1) The raw materials for preparing the body are weighed according to the mass ratio, and water is added for ball milling (the mass ratio of the raw materials to water is 100:40), and then the body powder is obtained by spray drying, and the body is obtained by pressing the body powder;

[0089] (2) The raw materials for preparing the bottom glaze layer are weighed according to the mass ratio, and water, polyacrylamide and polyvinyl alcohol are added for ball milling (the mass ratio of the raw materials to water, polyacrylamide and polyvinyl alcohol is 100:38:0.18:0.3), and then the bottom glaze slurry with a fineness of 300 mesh is obtained; then the bottom glaze slurry is sprayed on the surface of the body prepared in step (1) by a spray gun to form a bottom glaze layer with a thickness of 0.15 mm;

[0090] (3) The raw materials for preparing the isolation glaze layer are weighed according to the mass ratio, and water, polyacrylamide and polyvinyl alcohol are added for ball milling (the mass ratio of the raw materials to water, polyacrylamide and polyvinyl alcohol is 100:35:0.18:0.3), and then the isolation glaze slurry with a fineness of 300 mesh is obtained; then the isolation glaze slurry is sprayed on the surface of the bottom glaze layer prepared in step (2) by a glaze spraying machine to form an isolation glaze layer with a thickness of 0.15 mm; then a pattern layer is obtained by inkjet printing a pattern on the surface of the isolation glaze layer by a digital printer;

[0091] (4) The raw materials for preparing the protective glaze layer are weighed according to the mass ratio, and ball milling is performed to obtain a protective glaze slurry with a fineness of 300 mesh; then the protective glaze slurry is printed on the surface of the pattern layer prepared in step (3) by a digital printer at a resolution of 400 dpi to form a protective glaze layer with a thickness of 0.08 mm; after drying at 110℃ for 3 hours, the ceramic rock plate of the present embodiment is obtained by firing in a kiln.

[0092] The temperature schedule for firing is as follows: first, the temperature is raised from room temperature to 1080℃ at a rate of 90℃ / hour; then the temperature is raised to 1120℃ at a rate of 50℃ / hour, and the temperature is maintained for 50 minutes; then the temperature is lowered to 800℃ at a rate of 90℃ / hour; then the temperature is lowered to 450℃ at a rate of 50℃ / hour; finally, the temperature is naturally cooled to room temperature.

[0093] Comparative Example 1

[0094] The difference between Comparative Example 1 and Example 1 is only that the ceramic rock plate of Comparative Example 1 does not contain the barrier glaze layer.

[0095] Comparative Example 2

[0096] The difference between Comparative Example 2 and Example 1 is only that the preparation raw materials of the base glaze layer are different, and the base glaze layer of Comparative Example 2 only contains the first base glaze material and does not contain calcined tin oxide.

[0097] Comparative Example 3

[0098] The difference between Comparative Example 3 and Example 1 is only that the preparation raw materials of the barrier glaze layer are different, and the barrier glaze layer of Comparative Example 3 only contains the second base glaze material and does not contain calcined indium oxide.

[0099] Comparative Example 4

[0100] The difference between Comparative Example 4 and Example 1 is only that the preparation raw materials of the protective glaze layer are different, and the protective glaze layer of Comparative Example 4 only contains the third base glaze material and does not contain calcined bismuth oxide.

[0101] Comparative Example 5

[0102] The difference between Comparative Example 5 and Example 1 is only that the additive in the preparation of the protective glaze layer is different, that is, Comparative Example 5 replaces the additive B (50 parts of ethyl acetate, 45 parts of acrylic resin, 3 parts of polyamide, 2 parts of polyacrylamide, and 1 part of sodium hydroxide) with the additive A (water, polyacrylamide, and polyvinyl alcohol), and the mass ratio of the other preparation raw materials of the protective glaze layer to water, polyacrylamide, and polyvinyl alcohol is 100:38:0.18:0.3.

[0103] Comparative Example 6

[0104] The difference between Comparative Example 6 and Example 1 is only that the temperature system of the firing is different, and the temperature system of the firing of Comparative Example 6 is: increasing from room temperature to 1150℃ at a heating rate of 100℃ / hour, keeping for 40 minutes, and naturally cooling to room temperature.

[0105] Performance test

[0106] The ceramic rock plate samples prepared in Examples 1-3 and Comparative Examples 1-6 were tested for related performances and the glaze quality was observed, and the results are shown in Table 1.

[0107] Among them, the glossiness test was detected by a glossiness meter; the wear resistance was detected according to GB / T3810.7-2016 “Determination of the Surface Abrasion Resistance of Ceramic Glazed Tiles”; and the anti-fouling grade was tested according to “GB / T3810.14-2016 Ceramic Tiles-Determination of Resistance to Staining”, and the anti-fouling performance was divided into grades, with Grade 1 indicating the worst anti-fouling effect and Grade 5 indicating the best anti-fouling effect.

[0108] Table 1: Performance comparison table of samples prepared in Examples 1-3 and Comparative Examples 1-6

[0109]

[0110] As can be seen from Table 1, the ceramic rock plate samples prepared in Examples 1-3 have a low gloss of 15-17°, are sub-matte ceramic products, have a hardness of 6-7, a glaze grinding amount of only 0.02-0.03 g, a stain resistance level of 4-5, a glaze surface with good skin texture, and no obvious defects such as bubbles, pinholes, and spots.

[0111] Compared with Example 1, Comparative Example 1 and Comparative Example 5 both have obvious defects such as pinholes and bubbles on the glaze surface due to the absence of the isolation glaze layer and the use of conventional glaze additives, and the gloss, hardness, and stain resistance performance are also decreased, the glaze surface is dull, and has no skin texture.

[0112] Compared with Example 1, Comparative Examples 2-4 have a glaze surface that is bright and has no skin texture, and the hardness and stain resistance performance are also decreased due to the absence of calcined tin oxide, calcined indium oxide, and calcined bismuth oxide in the base glaze layer, the isolation glaze layer, and the protective glaze layer, respectively.

[0113] Compared with Example 1, Comparative Example 6 has a glaze surface that is bright and has no skin texture, and has obvious defects such as bubbles, pinholes, and spots, and the stain resistance performance is also significantly decreased due to the absence of the segmented firing temperature.

[0114] For those skilled in the art to which the present application belongs, without departing from the concept of the present application, a number of simple deductions or substitutions can be made without having to undergo creative labor. Therefore, the simple improvements made by those skilled in the art to the present application based on the disclosure of the present application should be within the protection scope of the present application. The above examples are preferred embodiments of the present application, and any similar processes and equivalent changes made should be within the protection scope of the present application.

Claims

1. A ceramic rock slab, characterized by, The body, the bottom glaze layer, the isolation glaze layer, the pattern layer and the protective glaze layer are sequentially arranged from bottom to top. The preparation raw materials of the bottom glaze layer include a first base glaze and calcined tin oxide in a mass ratio of (5-25):1; The preparation raw materials of the isolation glaze layer include a second base glaze and calcined indium oxide in a mass ratio of (5-25):1; The preparation raw materials of the protective glaze layer include a third base glaze and calcined bismuth oxide in a mass ratio of (5-25):1; The first base glaze, the second base glaze and the third base glaze have the same raw material components and each include, in parts by weight, 5-10 parts of wood knot clay, 5-10 parts of montmorillonite, 5-10 parts of boron-magnesium stone, 5-10 parts of calcined aluminum oxide, 5-10 parts of calcined calcium oxide, 5-10 parts of calcined magnesium oxide, 5-10 parts of calcined barium oxide, 5-10 parts of calcined strontium oxide, 10-20 parts of potassium feldspar and 10-20 parts of sodium feldspar. The temperature system for sintering the ceramic rock plate is as follows: first, the temperature is raised from room temperature to 1000-1050℃ at a temperature rising rate of 80-100℃ / hour; then, the temperature is raised to 1100-1150℃ at a temperature rising rate of 40-50℃ / hour, and the temperature is kept for 40-70min; then, the temperature is lowered to 800-900℃ at a temperature lowering rate of 80-100℃ / hour; then, the temperature is lowered to 400-500℃ at a temperature lowering rate of 40-50℃ / hour; finally, the temperature is naturally lowered to room temperature.

2. The ceramic stone slab of claim 1, wherein, The raw material components of the body include, in parts by weight, 20-30 parts of pyrophyllite clay, 20-35 parts of wollastonite, 5-10 parts of calcium feldspar, 10-20 parts of sodium calcium feldspar, 5-10 parts of perlite, 5-10 parts of calcined aluminum oxide, 5-10 parts of calcined zinc oxide, 5-10 parts of calcined magnesium oxide and 5-10 parts of calcined barium oxide.

3. The ceramic stone slab of claim 1, wherein, The raw material components of the first base glaze and the second base glaze each further include an additive A, which includes, in parts by weight, 35-40 parts of water, 0.15-0.20 parts of a suspending agent and 0.25-0.35 parts of a water reducing agent; the suspending agent is at least one selected from polyacrylamide and polycarboxylate; and the water reducing agent is at least one selected from polycarboxylate, polyvinyl alcohol and polyethylene glycol.

4. The ceramic stone slab of claim 1, wherein, The raw material components of the third base glaze further include an additive B, which includes, in parts by weight, 48-52 parts of ethyl acetate, 42-46 parts of acrylic resin, 2-4 parts of polyamide, 1-3 parts of a defoaming agent and 0.5-1.5 parts of a pH value adjusting agent; the defoaming agent is at least one selected from polyacrylamide, polyvinyl alcohol and polyethylene glycol; and the pH value adjusting agent is at least one selected from sodium hydroxide, triethylamine, phosphoric acid and acetic acid.

5. A method of manufacturing a ceramic rock plate according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: The bottom glaze, the isolation glaze, the pattern and the mixed protective glaze are sequentially applied on the body to form the bottom glaze layer, the isolation glaze layer, the pattern layer and the protective glaze layer, respectively; and the ceramic rock plate is obtained after drying and sintering in a kiln. The temperature schedule of the sintering is: first, increasing from room temperature to 1000-1050℃ at a heating rate of 80-100℃ / hour; then increasing to 1100-1150℃ at a heating rate of 40-50℃ / hour, and keeping the temperature for 40-70min; then decreasing to 800-900℃ at a heating rate of 80-100℃ / hour; then decreasing to 400-500℃ at a heating rate of 40-50℃ / hour; finally, naturally cooling to room temperature. 6.The method of manufacturing a ceramic stone slab according to claim 5, wherein, After sintering, the ceramic rock plate is further polished and sandblasted.

7. Use of the ceramic rock plate according to any one of claims 1 to 4 in architectural decoration.

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