Tianmu marble glaze, low-temperature fast-firing screen-printed Tianmu marble tiles, and preparation methods thereof

Abstract

The present invention relates to the field of ceramic tile technology, and in particular to a low-temperature fast-firing screen-printed Tianmu marble tile and a preparation method thereof. The present application provides a Tianmu marble glaze, which comprises the following raw materials, in parts by weight: 20-35 parts of albite, 5-10 parts of potassium feldspar, 15-20 parts of a modified lithium carbonate composition, 10-15 parts of Tianmu crystal frit, 1-5 parts of barium carbonate, 1-5 parts of corundum, 1-2 parts of fine pig iron powder, 2-6 parts of zinc acetate, 1-5 parts of wollastonite, 1-5 parts of quartz, 4-8 parts of kaolin, 1-4 parts of cobalt oxide, and 10-15 parts of water. The Tianmu marble tile prepared in the present application has a pure color, a crystal flower pattern and a screen-printed pattern that complement each other, a strong concave-convex contrast, rich layers, a moist texture, excellent physical and chemical properties, and a strong three-dimensional effect, bringing a new decorative effect to the surface decoration of the marble tile.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic tiles, in particular to a Tianmu marble glaze, a low-temperature fast-firing screen-printed Tianmu marble ceramic tile and a preparation method thereof. Background Art

[0002] The present invention hopes to develop a Tianmu marble glaze formula that conforms to modern architectural ceramic products based on the traditional Tianmu glaze formula, and then quickly fire it at low temperature to make Tianmu marble tiles. The new Tianmu glaze on the marble tiles is required to have a texture effect and a varied marble decorative effect. Summary of the Invention

[0003] In order to overcome the shortcomings of the existing technology, the present invention provides a Tianmu marble glaze, a low-temperature fast-firing screen-printed Tianmu marble tile and a preparation method thereof. The prepared Tianmu marble tile has a pure color, a crystal flower pattern and a screen-printed pattern that complement each other, a strong concave-convex contrast, rich layers, a moist texture, excellent physical and chemical properties, and a strong three-dimensional effect, bringing a new decorative effect to the surface decoration of the marble tile.

[0004] The technical solution adopted by the present invention to solve its technical problem is:

[0005] The first object of the present invention is to provide a Tianmu marble glaze, which comprises the following raw materials in parts by weight:

[0006] 20-35 parts of sodium feldspar, 5-10 parts of potassium feldspar, 15-20 parts of modified lithium carbonate composition, 10-15 parts of Tianmu crystal frit, 1-5 parts of barium carbonate, 1-5 parts of corundum, 1-2 parts of fine pig iron powder, 2-6 parts of zinc acetate, 1-5 parts of wollastonite, 1-5 parts of quartz, 4-8 parts of kaolin, 1-4 parts of cobalt oxide, and 10-15 parts of water.

[0007] In this application, the above-mentioned Tianmu marble glaze is applied to the preparation of ceramic tiles and marble tiles. The Tianmu marble glaze is screen-printed during the preparation. The decorative effect of the obtained Tianmu marble tiles is closer to the fine crystals and texture effect of natural marble. At the same time, it also has a higher hardness, with a hardness grade of 4 and an acid and alkali resistance grade of A. It has a wide range of application scenarios and can be used as floor tiles, toilets, washbasins or background walls.

[0008] The fine pig iron powder and zinc acetate in the raw materials easily react to form iron-zinc micro-ions, which are easily attached to Tianmu marble tiles. The iron-zinc micro-ions play an antibacterial role.

[0009] Furthermore, the modified lithium carbonate composition comprises the following raw materials in parts by weight:

[0010] 8-9 parts of lithium carbonate, 4-5 parts of sodium carbonate, 1-2 parts of aluminum phosphate, 1-2 parts of aluminum dihydrogen phosphate, 0.5-0.6 parts of strontium phosphate, 0.2-0.5 parts of borax, 0.1-0.3 parts of aluminum borate, 0.1-0.3 parts of sodium tripolyphosphate, and 0.1-0.3 parts of manganese dioxide.

[0011] In this application, lithium carbonate is an inorganic compound with the chemical formula Li2CO3, which is a colorless monoclinic crystal or white powder with a density of 2.11g / cm 3 , melting point 723℃; lithium carbonate salt is prepared by soaking lithium carbonate in dilute hydrochloric acid for 2-5 hours, taking it out and drying it at 100-200℃ for 5-7 hours. It can be used after lithium carbonate salt is formed on the surface. Lithium carbonate salt has stable chemical properties, good acid and alkali resistance, and obvious antibacterial effect.

[0012] Furthermore, the Tianmu crystal frit comprises the following raw materials in parts by weight:

[0013] 3-4 parts of limestone, 2-2.5 parts of ball clay, 1-2 parts of alumina, 1-2 parts of talc, 1-1.5 parts of zinc oxide, 1-1.5 parts of spodumene, and 1-1.5 parts of dolomite.

[0014] In the present application, the Tianmu crystal frit prepared by using the above raw materials has a good Tianmu crystal absorption effect.

[0015] Furthermore, the preparation method of the modified lithium carbonate composition comprises the following steps:

[0016] Prepare the raw materials of the modified lithium carbonate composition according to parts by weight;

[0017] Add lithium carbonate, sodium carbonate, aluminum phosphate, aluminum dihydrogen phosphate, strontium phosphate, borax and aluminum borate into a frit furnace for calcination;

[0018] After the calcination reaction is completed, the mixture is cooled to room temperature, filtered, and dried;

[0019] Manganese dioxide and sodium tripolyphosphate are added and mixed evenly to obtain a modified lithium carbonate composition.

[0020] Furthermore, the calcination reaction process is at a temperature of 900-1000° C. and a time of 3-4 hours.

[0021] In the present application, aluminum phosphate and aluminum dihydrogen phosphate are added to the firing reaction to generate lithium aluminate in the firing reaction, which can solve the low-temperature rapid crystallization absorber problem of Tianmu marble glaze (Tianmu layer) firing (the traditional crystal absorption time takes 5-6 hours) to improve the rapid crystal absorption process and increase the hardness performance. The addition of aluminum borate and borax can improve the firing temperature of Tianmu marble glaze (Tianmu layer), the addition of strontium phosphate can improve the viscosity of lithium carbonate salt, and can also increase the firing melting point of Tianmu marble glaze. During the firing process of sodium and lithium aluminate, more sodium aluminum lithium ions are generated, which provides a living space for the antibacterial ions in the Tianmu marble glaze (Tianmu layer), is beneficial to the preparation of glaze crystals of the low-temperature Tianmu layer and the protective effect of the antibacterial ions, and solves the problem of the lack of long-term antibacterial effect; after calcination in a frit furnace at 900-1000°C for 3-4 hours, the modified lithium carbonate composition obtained is applied to the Tianmu marble glaze to form a Tianmu layer, which has a bactericidal function and has a certain improvement in wear resistance.

[0022] Furthermore, the preparation method of the Tianmu marble glaze comprises the following steps:

[0023] Prepare materials according to the weight proportion of Tianmu marble glaze raw materials; fully mix the raw materials; add 3-4 times of water in an amount equal to the total weight of the Tianmu marble glaze raw materials after mixing, ball mill for 5-10 minutes, and pass 100g of the raw materials through a 150-mesh sieve to obtain Tianmu marble glaze.

[0024] The second object of the present invention is to provide a low-temperature fast-firing screen-printed Tianmu marble tile, which includes a body layer, a base glaze layer, a pattern layer, and a Tianmu layer arranged in sequence from bottom to top, and the Tianmu layer is formed by the Tianmu marble glaze described above.

[0025] The third object of the present invention is to provide a method for preparing low-temperature fast-firing screen-printed Tianmu marble tiles, the method comprising the following steps:

[0026] S1. Prepare the green body layer;

[0027] S2. Prepare the base glaze mixture;

[0028] S3. Preparation of Tianmu marble glaze;

[0029] S4. Preparing a base glaze layer and a pattern layer, applying the base glaze layer mixture to the surface of the body layer, and then screen printing a preset pattern;

[0030] S5. Prepare Tianmu marble tiles, continue to apply Tianmu marble glaze on the preset pattern, and obtain Tianmu marble tiles after calcination.

[0031] Furthermore, in step S5, the calcination temperature is 1130-1150° C., and the calcination time is 1-1.5 h.

[0032] The beneficial effects of the present invention are:

[0033] 1. The present invention adds a modified lithium carbonate composition, barium carbonate, corundum, pig iron fine powder, zinc acetate, and cobalt oxide to the Tianmo layer to obtain a stable Tianmo marble glaze, which has good antibacterial properties. During the firing process, the modified lithium carbonate composition, barium carbonate, corundum, and pig iron fine powder in the Tianmo layer are mixed and adsorbed on the surface of the tile, and the performance of the marble glaze slurry is more easily controlled, so that the fired marble glaze layer has high hardness and high wear resistance.

[0034] 2. The tiles made of this low-temperature fast-firing screen-printed Tianmu marble glaze have a glossiness of more than 80° when they leave the kiln. After one year of use, they still have an excellent anti-bacterial rate of more than 80%, and the anti-slip coefficient is R12. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The present invention will be further described below with reference to the accompanying drawings and examples.

[0036] Figure 1 This is the effect diagram of the Tianmu marble tile after molding described in this application;

[0037] Figure 2 This is a crystal absorption effect diagram of the Tianmu marble tile described in this application;

[0038] Figure 3 This is a rendering of the screen-printed Tianmo glaze texture obtained after step S4 of this application. DETAILED DESCRIPTION

[0039] In order to facilitate understanding by those skilled in the art, the present invention will be further described below with reference to the embodiments. The contents mentioned in the embodiments are not intended to limit the present invention.

[0040] Example 1

[0041] A method for preparing low-temperature fast-firing screen-printed Tianmu marble tiles comprises the following steps:

[0042] S1. Prepare the green body layer

[0043] The raw materials are mixed in proportion, and then powdered in a spray tower to make a green powder, which is then pressed into a green body layer by a press. The thickness of the green body layer is controlled to be 12-13 mm. The chemical composition of the green body layer is controlled to be: SiO2: 50-52%, Al2O3: 16-18%, TiO2: 0.1-0.3%, K2O: 6-8%, Na2O: 5-6%, CaO: 1-2%, MgO: 1.5-3%, Fe2O3: 0.01-0.03%;

[0044] S2. Prepare the base glaze mixture

[0045] The bottom glaze layer is prepared by mixing the following raw materials in parts by weight and then ball-milling: 32 parts of potassium feldspar powder, 1 part of wollastonite, 2 parts of calcined zinc acetate, 10 parts of quartz, 4 parts of kaolin, 1 part of limestone, 1 part of barium carbonate, 2 parts of corundum, 1 part of zirconium silicate, 0.1 part of methyl cellulose, and 0.2 part of sodium tripolyphosphate;

[0046] After mixing the raw materials for the bottom glaze layer, add water 3 times the total weight of the raw materials for the bottom glaze layer, ball mill for 10 minutes per 100g, and pass through a 320-mesh sieve to obtain a bottom glaze layer mixture;

[0047] S3. Preparation of Tianmu marble glaze

[0048] Tianmu marble glaze, in parts by weight, comprises the following raw materials:

[0049] 20 parts of sodium feldspar, 5 parts of potassium feldspar, 15 parts of modified lithium carbonate composition, 10 parts of Tianmu crystal frit, 1 part of barium carbonate, 1 part of corundum, 1 part of pig iron fine powder, 2 parts of zinc acetate, 1 part of wollastonite, 1 part of quartz, 4 parts of kaolin, 1 part of cobalt oxide, and 10 parts of water;

[0050] Wherein: Tianmu crystal frit is in parts by weight and includes the following raw materials:

[0051] 3 parts of limestone, 2 parts of ball clay, 1 part of aluminum oxide, 2 parts of talc, 1 part of zinc oxide, 1 part of spodumene, and 1 part of dolomite.

[0052] Soak lithium carbonate in 1% by weight dilute hydrochloric acid for 2 hours, take it out and dry it at 100°C for 5 hours until lithium carbonate salt forms on the surface before use;

[0053] The preparation method of the modified lithium carbonate composition comprises the following steps:

[0054] Prepare the raw materials of the modified lithium carbonate composition according to parts by weight; the modified lithium carbonate composition includes the following raw materials in parts by weight: 8 parts of lithium carbonate salt, 4 parts of sodium carbonate, 1 part of aluminum phosphate, 1 part of aluminum dihydrogen phosphate, 0.5 parts of strontium phosphate, 0.2 parts of borax, 0.1 parts of aluminum borate, 0.1 parts of sodium tripolyphosphate, and 0.1 parts of manganese dioxide;

[0055] Lithium carbonate, sodium carbonate, aluminum phosphate, aluminum dihydrogen phosphate, strontium phosphate, borax, and aluminum borate are added to a frit furnace and calcined; the reaction process is at a temperature of 900°C and a time of 3 hours;

[0056] After the calcination reaction is completed, the mixture is cooled to room temperature, filtered, and dried;

[0057] Manganese dioxide and sodium tripolyphosphate are added and mixed evenly to obtain a modified lithium carbonate composition.

[0058] Prepare materials according to the weight composition of Tianmu marble glaze raw materials; fully mix the raw materials; add water 3 times the total weight of the Tianmu marble glaze raw materials after mixing, ball mill for 5 minutes, and pass each 100g through a 150-mesh sieve to obtain Tianmu marble glaze.

[0059] S4. Preparation of base glaze layer and pattern layer

[0060] Use bell jar equipment to pour the bottom glaze mixture, with a specific gravity of 1.85-1.90, a flow rate of 33-40 seconds, and a thickness controlled at 0.1-0.4mm;

[0061] Screen printing a preset pattern on the base glaze layer; Screen printing process: screen printing file output → film production → screen production → top glaze adjustment and printing → top glaze solidification texture on the surface of the base glaze layer;

[0062] S5. Preparation of Tianmu marble tiles

[0063] On the preset pattern, continue to apply Tianmu marble glaze with a thickness of 0.5-1.0mm, and calcine at a firing temperature of 1130℃ and a firing time of 1h. After the calcination is completed, Tianmu marble tiles are obtained.

[0064] Example 2

[0065] A method for preparing low-temperature fast-firing screen-printed Tianmu marble tiles comprises the following steps:

[0066] S1. Prepare the green body layer

[0067] The raw materials are mixed in proportion, and then powdered in a spray tower to produce green powder, which is then pressed into a green body layer by a press. The green body layer thickness is controlled to be 12-13 mm. The chemical composition of the green body layer is controlled to be: SiO2: 53-55%, Al2O3: 16-18%, TiO2: 0.4-0.6%, K2O: 8-10%, Na2O: 7-8%, CaO: 1-2%, MgO: 1.5-3%, Fe2O3: 0.01-0.03%.

[0068] S2. Prepare the base glaze mixture

[0069] The bottom glaze layer is prepared by mixing the following raw materials in parts by weight and then ball-milling: 46 parts of potassium feldspar powder, 5 parts of wollastonite, 7 parts of calcined zinc acetate, 14 parts of quartz, 9 parts of kaolin, 3 parts of limestone, 5 parts of barium carbonate, 6 parts of corundum, 5 parts of zirconium silicate, 0.25 parts of methyl cellulose, and 0.45 parts of sodium tripolyphosphate;

[0070] After mixing the raw materials for the bottom glaze layer, add water 4 times the total weight of the raw materials for the bottom glaze layer, ball mill for 10-15 minutes, and pass 100g of the mixture through a 320-mesh sieve to obtain a bottom glaze layer mixture;

[0071] S3. Preparation of Tianmu marble glaze

[0072] Tianmu marble glaze, in parts by weight, comprises the following raw materials:

[0073] 35 parts of sodium feldspar, 10 parts of potassium feldspar, 20 parts of modified lithium carbonate composition, 15 parts of Tianmu crystal frit, 5 parts of barium carbonate, 5 parts of corundum, 2 parts of fine pig iron powder, 6 parts of zinc acetate, 5 parts of wollastonite, 5 parts of quartz, 8 parts of kaolin, 4 parts of cobalt oxide, and 15 parts of water;

[0074] Wherein: Tianmu crystal frit is in parts by weight and includes the following raw materials:

[0075] 4 parts of limestone, 2.5 parts of ball clay, 2 parts of aluminum oxide, 2 parts of talc, 1.5 parts of zinc oxide, 1.5 parts of spodumene, and 1.5 parts of dolomite.

[0076] Soak lithium carbonate in 1% by weight dilute hydrochloric acid for 5 hours, take it out and dry it at 200°C for 7 hours until lithium carbonate salt forms on the surface before use;

[0077] The preparation method of the modified lithium carbonate composition comprises the following steps:

[0078] Prepare the raw materials of the modified lithium carbonate composition according to parts by weight; the modified lithium carbonate composition includes the following raw materials in parts by weight: 9 parts of lithium carbonate salt, 5 parts of sodium carbonate, 2 parts of aluminum phosphate, 2 parts of aluminum dihydrogen phosphate, 0.6 parts of strontium phosphate, 0.5 parts of borax, 0.3 parts of aluminum borate, 0.3 parts of sodium tripolyphosphate, and 0.3 parts of manganese dioxide;

[0079] Lithium carbonate, sodium carbonate, aluminum phosphate, aluminum dihydrogen phosphate, strontium phosphate, borax, and aluminum borate are added to a frit furnace and calcined; the reaction process is a temperature of 1000°C and a time of 4 hours;

[0080] After the calcination reaction is completed, the mixture is cooled to room temperature, filtered, and dried;

[0081] Manganese dioxide and sodium tripolyphosphate are added and mixed evenly to obtain a modified lithium carbonate composition.

[0082] Prepare materials according to the weight proportion of Tianmu marble glaze raw materials; fully mix the raw materials; add water 4 times the total weight of the Tianmu marble glaze raw materials after mixing, ball mill for 5-10 minutes, and pass 100g of the raw materials through a 150-mesh sieve to obtain Tianmu marble glaze.

[0083] S4. Preparation of base glaze layer and pattern layer

[0084] Use bell jar equipment to pour the bottom glaze mixture, with a specific gravity of 1.85-1.90, a flow rate of 33-40 seconds, and a thickness controlled at 0.1-0.4mm;

[0085] Screen printing a preset pattern on the base glaze layer; Screen printing process: screen printing file output → film production → screen production → top glaze adjustment and printing → top glaze solidification texture on the surface of the base glaze layer;

[0086] S5. Preparation of Tianmu marble tiles

[0087] On the preset pattern, continue to apply Tianmu marble glaze with a thickness of 0.5-1.0mm, and calcine at a firing temperature of 1150℃ and a firing time of 1.5h. After the calcination is completed, Tianmu marble tiles are obtained.

[0088] Example 3

[0089] A method for preparing low-temperature fast-firing screen-printed Tianmu marble tiles comprises the following steps:

[0090] S1. Prepare the green body layer

[0091] The raw materials are mixed in proportion, and then powdered in a spray tower to prepare a green powder, which is then pressed into a green body layer by a press. The green body layer thickness is controlled to be 12-13 mm. The chemical composition of the green body layer is controlled to be: SiO2: 50-55%, Al2O3: 16-18%, TiO2: 0.1-0.6%, K2O: 6-10%, Na2O: 5-8%, CaO: 1-2%, MgO: 1.5-3%, Fe2O3: 0.01-0.03%.

[0092] S2. Prepare the base glaze mixture

[0093] The bottom glaze layer is prepared by mixing the following raw materials in parts by weight and then ball-milling: 40 parts of potassium feldspar powder, 4 parts of wollastonite, 5 parts of calcined zinc acetate, 13 parts of quartz, 5 parts of kaolin, 2 parts of limestone, 3 parts of barium carbonate, 4 parts of corundum, 3 parts of zirconium silicate, 0.2 parts of methyl cellulose, and 0.35 parts of sodium tripolyphosphate;

[0094] After mixing the raw materials for the bottom glaze layer, add water 3.5 times the total weight of the raw materials for the bottom glaze layer, ball mill for 12 minutes, and pass 100g of the mixture through a 320-mesh sieve to obtain a bottom glaze layer mixture;

[0095] S3. Preparation of Tianmu marble glaze

[0096] Tianmu marble glaze, in parts by weight, comprises the following raw materials:

[0097] 30 parts of sodium feldspar, 8 parts of potassium feldspar, 17.6 parts of modified lithium carbonate composition, 12 parts of Tianmu crystal frit, 4 parts of barium carbonate, 3 parts of corundum, 1.5 parts of fine pig iron powder, 4 parts of zinc acetate, 3 parts of wollastonite, 4 parts of quartz, 6 parts of kaolin, 3 parts of cobalt oxide, and 13 parts of water;

[0098] Wherein: Tianmu crystal frit is in parts by weight and includes the following raw materials:

[0099] 3.5 parts of limestone, 2 parts of ball clay, 1.5 parts of aluminum oxide, 1.5 parts of talc, 1 part of zinc oxide, 1 part of spodumene, and 1.5 parts of dolomite.

[0100] Soak lithium carbonate in 1% by weight dilute hydrochloric acid for 3 hours, then dry it at 150°C for 6 hours to form lithium carbonate salt on the surface before use;

[0101] The preparation method of the modified lithium carbonate composition comprises the following steps:

[0102] Prepare the raw materials of the modified lithium carbonate composition according to parts by weight; the modified lithium carbonate composition includes the following raw materials in parts by weight: 8.5 parts of lithium carbonate salt, 4.5 parts of sodium carbonate, 1.5 parts of aluminum phosphate, 1.5 parts of aluminum dihydrogen phosphate, 0.5 parts of strontium phosphate, 0.5 parts of borax, 0.2 parts of aluminum borate, 0.2 parts of sodium tripolyphosphate, and 0.2 parts of manganese dioxide;

[0103] Lithium carbonate, sodium carbonate, aluminum phosphate, aluminum dihydrogen phosphate, strontium phosphate, borax, and aluminum borate were added to a frit furnace and calcined; the reaction process was performed at a temperature of 950°C for 3.5 hours;

[0104] After the calcination reaction is completed, the mixture is cooled to room temperature, filtered, and dried;

[0105] Manganese dioxide and sodium tripolyphosphate are added and mixed evenly to obtain a modified lithium carbonate composition.

[0106] Prepare materials according to the weight proportion of Tianmu marble glaze raw materials; fully mix the raw materials; add 3.5 times the total weight of water of the Tianmu marble glaze raw materials after mixing, ball mill for 8 minutes, and pass 100g of the raw materials through a 150-mesh sieve to obtain Tianmu marble glaze.

[0107] S4. Preparation of base glaze layer and pattern layer

[0108] Use bell jar equipment to pour the bottom glaze mixture, with a specific gravity of 1.85-1.90, a flow rate of 33-40 seconds, and a thickness controlled at 0.1-0.4mm;

[0109] Screen printing a preset pattern on the base glaze layer; Screen printing process: screen printing file output → film production → screen production → top glaze adjustment and printing → top glaze solidification texture on the surface of the base glaze layer;

[0110] S5. Preparation of Tianmu marble tiles

[0111] On the preset pattern, continue to apply Tianmu marble glaze with a thickness of 0.5-1.0mm, and calcine at a firing temperature of 1140℃ and a firing time of 1.2h. After the calcination is completed, Tianmu marble tiles are obtained.

[0112] Example 4

[0113] A method for preparing low-temperature fast-firing screen-printed Tianmu marble tiles comprises the following steps:

[0114] S1. Prepare the green body layer

[0115] The raw materials are mixed in proportion, and then powdered in a spray tower to make a green powder, which is then pressed into a green body layer by a press. The green body layer thickness is controlled to be 12-13 mm. The chemical composition of the green body layer is controlled to be: SiO2: 52-54%, Al2O3: 17-18%, TiO2: 0.3-0.4%, K2O: 7-8%, Na2O: 6-7%, CaO: 1-2%, MgO: 2-2.5%, Fe2O3: 0.01-0.02%.

[0116] S2. Prepare the base glaze mixture

[0117] The bottom glaze layer is prepared by mixing the following raw materials in parts by weight and then ball-milling: 32 parts of potassium feldspar powder, 5 parts of wollastonite, 2 parts of calcined zinc acetate, 14 parts of quartz, 4 parts of kaolin, 3 parts of limestone, 1 part of barium carbonate, 6 parts of corundum, 1 part of zirconium silicate, 0.25 parts of methyl cellulose, and 0.45 parts of sodium tripolyphosphate;

[0118] After mixing the raw materials for the bottom glaze layer, add water 4 times the total weight of the raw materials for the bottom glaze layer, ball mill for 10 minutes, and pass 100g of the mixture through a 320-mesh sieve to obtain a bottom glaze layer mixture;

[0119] S3. Preparation of Tianmu marble glaze

[0120] Tianmu marble glaze, in parts by weight, comprises the following raw materials:

[0121] 35 parts of sodium feldspar, 5 parts of potassium feldspar, 20 parts of modified lithium carbonate composition, 10 parts of Tianmu crystal frit, 5 parts of barium carbonate, 1 part of corundum, 2 parts of fine pig iron powder, 2 parts of zinc acetate, 5 parts of wollastonite, 1 part of quartz, 8 parts of kaolin, 1 part of cobalt oxide, and 15 parts of water;

[0122] Wherein: Tianmu crystal frit is in parts by weight and includes the following raw materials:

[0123] 3 parts of limestone, 2 parts of ball clay, 1 part of aluminum oxide, 1 part of talc, 1 part of zinc oxide, 1 part of spodumene, and 1 part of dolomite.

[0124] Soak lithium carbonate in 1% by weight dilute hydrochloric acid for 5 hours, take it out and dry it at 100°C for 5 hours until lithium carbonate salt forms on the surface before use;

[0125] The preparation method of the modified lithium carbonate composition comprises the following steps:

[0126] Prepare the raw materials of the modified lithium carbonate composition according to parts by weight; the modified lithium carbonate composition includes the following raw materials in parts by weight: 9 parts of lithium carbonate salt, 5 parts of sodium carbonate, 2 parts of aluminum phosphate, 2 parts of aluminum dihydrogen phosphate, 0.6 parts of strontium phosphate, 0.5 parts of borax, 0.3 parts of aluminum borate, 0.3 parts of sodium tripolyphosphate, and 0.3 parts of manganese dioxide;

[0127] Lithium carbonate, sodium carbonate, aluminum phosphate, aluminum dihydrogen phosphate, strontium phosphate, borax, and aluminum borate are added to a frit furnace and calcined; the reaction process is at a temperature of 900°C and a time of 4 hours;

[0128] After the calcination reaction is completed, the mixture is cooled to room temperature, filtered, and dried;

[0129] Manganese dioxide and sodium tripolyphosphate are added and mixed evenly to obtain a modified lithium carbonate composition.

[0130] Prepare materials according to the weight composition of Tianmu marble glaze raw materials; fully mix the raw materials; add water 3 times the total weight of the Tianmu marble glaze raw materials after mixing, ball mill for 10 minutes, and pass each 100g through a 150-mesh sieve to obtain Tianmu marble glaze.

[0131] S4. Preparation of base glaze layer and pattern layer

[0132] Use bell jar equipment to pour the bottom glaze layer mixture, with a specific gravity of 1.85-1.90, a flow rate of 33-40 seconds, and a thickness controlled at 0.1-0.4mm. After the glazing is completed, the bottom glaze layer is obtained;

[0133] Screen printing a preset pattern on the base glaze layer; Screen printing process: screen printing file output → film production → screen production → top glaze adjustment and printing → top glaze solidification texture on the surface of the base glaze layer;

[0134] S5. Preparation of Tianmu marble tiles

[0135] On the preset pattern, continue to apply Tianmu marble glaze with a thickness of 0.5-1.0 mm, and calcine at a firing temperature of 1130°C and a firing time of 1.5 hours. After the calcination is completed, Tianmu marble tiles are obtained.

[0136] Example 5

[0137] A method for preparing low-temperature fast-firing screen-printed Tianmu marble tiles comprises the following steps:

[0138] S1. Prepare the green body layer

[0139] The raw materials are mixed in proportion, and then powdered in a spray tower to produce green powder, which is then pressed into a green body layer by a press. The thickness of the green body layer is controlled to be 12-13 mm. The chemical composition of the green body layer is controlled to be: SiO2: 50-51%, Al2O3: 16-17%, TiO2: 0.5-0.6%, K2O: 6-7%, Na2O: 5-6%, CaO: 1.5-2%, MgO: 2.5-3%, Fe2O3: 0.02-0.03%.

[0140] S2. Prepare the base glaze mixture

[0141] The bottom glaze layer is prepared by mixing the following raw materials in parts by weight and then ball-milling: 32 parts of potassium feldspar powder, 1 part of wollastonite, 7 parts of calcined zinc acetate, 14 parts of quartz, 4 parts of kaolin, 1 part of limestone, 5 parts of barium carbonate, 6 parts of corundum, 1 part of zirconium silicate, 0.1 part of methyl cellulose, and 0.45 part of sodium tripolyphosphate;

[0142] After mixing the raw materials for the bottom glaze layer, add water 4 times the total weight of the raw materials for the bottom glaze layer, ball mill for 10-15 minutes per 100g, and pass through a 320-mesh sieve to obtain a bottom glaze layer mixture;

[0143] S3. Preparation of Tianmu marble glaze

[0144] Tianmu marble glaze, in parts by weight, comprises the following raw materials:

[0145] 35 parts of sodium feldspar, 10 parts of potassium feldspar, 15 parts of modified lithium carbonate composition, 15 parts of Tianmu crystal frit, 1 part of barium carbonate, 1 part of corundum, 2 parts of fine pig iron powder, 6 parts of zinc acetate, 1 part of wollastonite, 1 part of quartz, 8 parts of kaolin, 4 parts of cobalt oxide, and 10 parts of water;

[0146] Wherein: Tianmu crystal frit is in parts by weight and includes the following raw materials:

[0147] 4 parts of limestone, 2.5 parts of ball clay, 2 parts of aluminum oxide, 2 parts of talc, 1.5 parts of zinc oxide, 1.5 parts of spodumene, and 1.5 parts of dolomite.

[0148] Soak lithium carbonate in 1% by weight dilute hydrochloric acid for 3 hours, take it out and dry it at 120°C for 5 hours until lithium carbonate salt forms on the surface before use;

[0149] The preparation method of the modified lithium carbonate composition comprises the following steps:

[0150] Prepare the raw materials of the modified lithium carbonate composition according to parts by weight; the modified lithium carbonate composition includes the following raw materials in parts by weight: 8 parts of lithium carbonate salt, 4 parts of sodium carbonate, 1 part of aluminum phosphate, 1 part of aluminum dihydrogen phosphate, 0.5 parts of strontium phosphate, 0.2 parts of borax, 0.1 parts of aluminum borate, 0.1 parts of sodium tripolyphosphate, and 0.1 parts of manganese dioxide;

[0151] Lithium carbonate, sodium carbonate, aluminum phosphate, aluminum dihydrogen phosphate, strontium phosphate, borax, and aluminum borate are added to a frit furnace and calcined; the reaction process is at a temperature of 1000°C and a time of 3 hours;

[0152] After the calcination reaction is completed, the mixture is cooled to room temperature, filtered, and dried;

[0153] Manganese dioxide and sodium tripolyphosphate are added and mixed evenly to obtain a modified lithium carbonate composition.

[0154] Prepare materials according to the weight proportion of Tianmu marble glaze raw materials; fully mix the raw materials; add water 4 times the total weight of the Tianmu marble glaze raw materials after mixing, ball mill for 5 minutes, and pass 100g of the raw materials through a 150-mesh sieve to obtain Tianmu marble glaze.

[0155] S4. Preparation of base glaze layer and pattern layer

[0156] Use bell jar equipment to pour the bottom glaze mixture, with a specific gravity of 1.85-1.90, a flow rate of 33-40 seconds, and a thickness controlled at 0.1-0.4mm;

[0157] Screen printing a preset pattern on the base glaze layer; Screen printing process: screen printing file output → film production → screen production → top glaze adjustment and printing → top glaze solidification texture on the surface of the base glaze layer;

[0158] S5. Preparation of Tianmu marble tiles

[0159] On the preset pattern, continue to apply Tianmu marble glaze with a thickness of 0.5-1.0mm, and calcine at a firing temperature of 1150℃ and a firing time of 1h. After the calcination is completed, Tianmu marble tiles are obtained.

[0160] Comparative Example 1

[0161] The preparation steps and parameters in this comparative example are the same as those in Example 1, except that no Tianmu crystal frit is added in this comparative example.

[0162] Comparative Example 2

[0163] The preparation steps and parameters in this comparative example are the same as those in Example 1, except that lithium carbonate is added in this comparative example (the modified lithium carbonate composition is converted into lithium carbonate).

[0164] The performance of the Tianmu marble glazed tiles prepared in Examples 1-5 and Comparative Examples 1-2 was tested, and the specific test results are shown in the following table:

[0165]

[0166] From the test results in the above table, it can be seen that the tiles prepared in Examples 1-5 have a wear resistance of 6000 revolutions, a hardness of 5, an acid and alkali resistance of A, an anti-slip grade of R12, a water absorption rate of 0.11-0.13%, a glossiness of 80-82° before use, and a glossiness of 74-78° after 5 years of use, showing high hardness, high wear resistance, good acid and alkali resistance, and a high anti-slip grade, and the glossiness can be well maintained. Figure 1-3 It can be seen that the marble tiles, crystal flower patterns and screen printing patterns complement each other, with strong concave and convex contrast, rich layers, moist texture, excellent physical and chemical properties, and a strong three-dimensional effect, which brings new decorative effects to the surface decoration of marble tiles.

[0167] In Comparative Example 1, the ceramic tile produced had a wear resistance rating of 4,000 revolutions, a hardness of level 3, acid and alkali resistance of level A, a slip resistance rating of R12, and a water absorption rate of 0.10%. The glossiness was 35° before use and 5° after five years of use, demonstrating high hardness, average wear resistance, excellent acid and alkali resistance, and a high slip resistance rating. However, the glossiness was low and could not be maintained over time. Therefore, in Comparative Example 1, the absence of the Tianmu crystal frit significantly resulted in the low glossiness of the ceramic tile, which also significantly decreased with prolonged use.

[0168] In Comparative Example 2, the ceramic tile produced had a wear resistance rating of 2100 revolutions, a hardness of level 3, acid and alkali resistance of level B, a slip resistance rating of R9, and a water absorption rate of 0.12%. The glossiness was 69° before use and 52° after five years of use, demonstrating average hardness, average wear resistance, good acid and alkali resistance, and average slip resistance. However, the glossiness was average and could not be maintained over time. Therefore, the use of lithium carbonate in Comparative Example 2 resulted in a significant decrease in the wear resistance, hardness, slip resistance, and glossiness of the ceramic tile, and the glossiness decreased significantly with prolonged use.

[0169] The antibacterial performance test was conducted on the Tianmu marble glaze tiles and ordinary tiles prepared in Examples 1-5 and Comparative Examples 1-2. The same size 20*20 cm tiles were taken respectively. The test method was adopted: JC / T897-2014 Antibacterial Performance Standard for Antibacterial Ceramic Products. The specific test results are shown in the following table:

[0170]

[0171] From the test results in the above table, it can be seen that the tiles prepared in Examples 1-5 have an antibacterial rate of greater than 99% after molding, an antibacterial rate of greater than 88% after 1 year, an antibacterial rate of greater than 60% after 3 years, and an antibacterial rate of greater than 50% after 5 years, showing long-lasting antibacterial properties.

[0172] In comparative example 1, the prepared ceramic tiles have an antibacterial rate of about 30-32% after molding, an antibacterial rate of about 20-22% after 1 year, an antibacterial rate of about 10-12% after 3 years, and an antibacterial rate of about 5-8% after 5 years; therefore, in comparative example 1, no Tianmu crystal frit was added, resulting in a significantly low antibacterial rate of the ceramic tiles after molding, and with long-term use, the antibacterial properties were basically lost.

[0173] Therefore, in Comparative Example 2, lithium carbonate was used, which caused a significant decrease in the wear resistance, hardness, anti-slip level and glossiness of the tiles to a certain extent, and the glossiness was significantly reduced with long-term use.

[0174] In comparative example 2, the prepared tiles had an antibacterial rate of about 50-60% after molding, an antibacterial rate of about 40-45% after 1 year, an antibacterial rate of about 18-20% after 3 years, and an antibacterial rate of 9-10% after 5 years; therefore, in comparative example 2, lithium carbonate was used, which resulted in the tiles having an obvious antibacterial rate of only a medium level, and with long-term use, the antibacterial properties were basically lost.

[0175] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the scope of protection of the present invention.

Claims

1. A glaze for Tianmu marble, characterized in that: In parts by weight, it includes the following raw materials: 20-35 parts of sodium feldspar, 5-10 parts of potassium feldspar, 15-20 parts of modified lithium carbonate composition, 10-15 parts of Tianmu crystal frit, 1-5 parts of barium carbonate, 1-5 parts of corundum, 1-2 parts of fine pig iron powder, 2-6 parts of zinc acetate, 1-5 parts of wollastonite, 1-5 parts of quartz, 4-8 parts of kaolin, 1-4 parts of cobalt oxide, and 10-15 parts of water; The modified lithium carbonate composition comprises the following raw materials in parts by weight: 8-9 parts of lithium carbonate, 4-5 parts of sodium carbonate, 1-2 parts of aluminum phosphate, 1-2 parts of aluminum dihydrogen phosphate, 0.5-0.6 parts of strontium phosphate, 0.2-0.5 parts of borax, 0.1-0.3 parts of aluminum borate, 0.1-0.3 parts of sodium tripolyphosphate, and 0.1-0.3 parts of manganese dioxide; The Tianmu crystal frit comprises the following raw materials in parts by weight: 3-4 parts of limestone, 2-2.5 parts of ball clay, 1-2 parts of alumina, 1-2 parts of talc, 1-1.5 parts of zinc oxide, 1-1.5 parts of spodumene, and 1-1.5 parts of dolomite.

2. The Tianmu marble glaze according to claim 1, characterized in that: The lithium carbonate salt is a solid obtained by soaking lithium carbonate in dilute hydrochloric acid for 2-5 hours, taking it out and drying it at 100-200° C. for 5-7 hours.

3. The Tianmu marble glaze according to claim 2, characterized in that: The preparation method of the modified lithium carbonate composition comprises the following steps: Prepare the raw materials of the modified lithium carbonate composition according to parts by weight; Add lithium carbonate, sodium carbonate, aluminum phosphate, aluminum dihydrogen phosphate, strontium phosphate, borax and aluminum borate into a frit furnace for calcination; After the calcination reaction is completed, the mixture is cooled to room temperature, filtered, and dried; Manganese dioxide and sodium tripolyphosphate are added and mixed evenly to obtain a modified lithium carbonate composition.

4. The Tianmu marble glaze according to claim 3, characterized in that: The calcination reaction process is a temperature of 900-1000° C. and a time of 3-4 hours.

5. The Tianmu marble glaze according to claim 1, characterized in that: The preparation method of the Tianmu marble glaze comprises the following steps: Prepare materials according to the weight proportion of Tianmu marble glaze raw materials; fully mix the raw materials; add 3-4 times of water in an amount equal to the total weight of the Tianmu marble glaze raw materials after mixing, ball mill for 5-10 minutes, and pass 100g of the raw materials through a 150-mesh sieve to obtain Tianmu marble glaze.

6. A low-temperature fast-firing screen-printed Tianmu marble tile, characterized in that: The invention comprises a body layer, a base glaze layer, a pattern layer and a Tianmo layer which are sequentially arranged from bottom to top, wherein the Tianmo layer is formed by the Tianmo marble glaze according to any one of claims 1 to 5.

7. The method for preparing low-temperature fast-firing screen-printed Tianmu marble tiles according to claim 6, characterized in that: The following steps are involved: S1. Prepare the green body layer; S2. Prepare the base glaze mixture; S3. Preparation of Tianmu marble glaze; S4. Preparing a base glaze layer and a pattern layer, applying the base glaze layer mixture to the surface of the body layer, and then screen printing a preset pattern; S5. Prepare Tianmu marble tiles, continue to apply Tianmu marble glaze on the preset pattern, and obtain Tianmu marble tiles after calcination.

8. The method for preparing low-temperature fast-firing screen-printed Tianmu marble tiles according to claim 7, characterized in that: In step S5, the calcination temperature is 1130-1150° C., and the calcination time is 1-1.5 h.

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