Marble crystal glaze, marble tile using the same and preparation process

Abstract

The present invention relates to the technical field of ceramic tiles, and in particular to a marble crystal glaze, a marble tile using the same, and a preparation process. The marble crystal glaze comprises the following raw materials, which are mixed and then ball-milled: 25-30 parts of albite, 10-25 parts of lithium feldspar, 6-8 parts of wollastonite, 5-10 parts of kaolin, 6-11 parts of zinc oxide, 2-7 parts of barium carbonate, 5-15 parts of barium lithium aluminum crystal dry granule frit, 2-5 parts of fluorite, 5-10 parts of quartz, 1-5 parts of corundum, 1-2 parts of lithium carbonate, 40-60 parts of suspending agent, 5-10 parts of printing ink, and 10-20 parts of quartz. Barium-lithium-aluminum crystalline dry granular frit is made by mixing and ball-milling the following ingredients: 20-30 parts barium carbonate, 1-2 parts ball clay, 6-10 parts diopside, 1-5 parts limestone, 5-13 parts lithium carbonate, 10-15 parts aluminum oxide, 1-5 parts corundum, 1-5 parts boric acid, 3-5 parts sodium carbonate, 3-5 parts strontium carbonate, 7-15 parts albite, and 2-6 parts quartz. Marble tiles have excellent anti-slip properties, hardness, and stain resistance. Due to the ultra-thin marble crystal glaze layer, the glaze surface of marble tiles is smooth, with clear texture and bright colors.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic tiles, and in particular to a marble crystal glaze, marble ceramic tiles using the same, and a preparation process. Background Art

[0002] Marble tiles, a type of ceramic tile with the texture, color, and feel of natural marble, have gained widespread market adoption due to their ability to combine the decorative effects of natural marble with the superior performance of ceramic tiles. However, existing marble tiles typically have a thick glaze, and the clarity of the imitation marble texture on their surfaces is poor, resulting in a poor decorative effect. The glaze also suffers from relatively poor hardness and anti-slip properties. Summary of the Invention

[0003] The main purpose of the present invention is to provide a marble crystal glaze, marble tiles using the same and a preparation process, aiming to improve the technical problems of existing imitation marble tiles having a thick glaze surface and relatively poor hardness and anti-slip effect of the glaze surface.

[0004] To achieve the above object, the present invention provides a marble crystal glaze, which is prepared by mixing the following raw materials, in parts by weight, and then ball-milling: 25-30 parts of albite, 10-25 parts of lithium feldspar, 6-8 parts of wollastonite, 5-10 parts of kaolin, 6-11 parts of zinc oxide, 2-7 parts of barium carbonate, 5-15 parts of barium lithium aluminum crystal dry granule frit, 2-5 parts of fluorite, 5-10 parts of quartz, 1-5 parts of corundum, 1-2 parts of lithium carbonate, 40-60 parts of suspending agent, 5-10 parts of printing ink, and 1-8 parts of water;

[0005] The barium-lithium-aluminum crystalline dry particle frit is prepared by mixing and then ball-milling the following raw materials, in parts by weight: 20-30 parts of barium carbonate, 1-2 parts of ball clay, 6-10 parts of diopside, 1-5 parts of limestone, 5-13 parts of lithium carbonate, 10-15 parts of aluminum oxide, 1-5 parts of corundum, 1-5 parts of boric acid, 3-5 parts of sodium carbonate, 3-5 parts of strontium carbonate, 7-15 parts of albite and 2-6 parts of quartz.

[0006] Corundum and aluminum oxide are also added to the raw materials of marble crystal glaze, which can further improve the hardness of the glaze layer; the addition of strontium carbonate and sodium carbonate can further improve the anti-slip level of the glaze layer; the addition of barium lithium aluminum crystal dry granular frit, barium carbonate and lithium carbonate can reduce the firing time of marble crystal glaze (marble tile) and improve the transparency of the glaze layer; the addition of diopside and zinc oxide can make the marble crystal glaze more anti-fouling. In addition, compared with ordinary tiles, the marble crystal glaze in this scheme is added with barium lithium aluminum crystal dry granular frit (which contains strontium carbonate, boric acid, sodium carbonate, etc.), lithium carbonate and barium carbonate. During the firing process, the above raw materials can combine to form barium lithium aluminum crystal nuclei. The performance of the barium lithium aluminum crystal nuclei is stable, which can make the produced glaze denser, thinner, more transparent and harder. It can also be used as anti-slip crystal particles to play an anti-slip role and can be used as a reinforcement material for marble glaze.

[0007] The added printing ink mainly serves to suspend the marble crystal glaze, thereby improving the glaze slurry performance and preventing it from settling. This is beneficial for the special requirements of screen printing the ultra-thin marble crystal glaze in this solution, and also improves the lubricity of production. The suspending agent in this solution can be an aqueous solution of methylcellulose.

[0008] Preferably, the raw materials of the barium lithium aluminum crystalline dry particle frit are mixed evenly, melted at 1550-1560°C, quenched in water at a temperature of 0-20°C, ball-milled, calcined at 1100-1130°C for 1-3h, cooled, and sieved through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

[0009] The barium-lithium-aluminum crystalline dry granule frit in this solution is modified before use, specifically by high-temperature melting, water quenching, and secondary calcination. This modification method improves the performance of the barium-lithium-aluminum crystalline dry granule frit, resulting in a melting point of 1310-1350°C (partial melting during subsequent calcination), a Mohs hardness of 7, a tensile strength of >7.5 MPa, and a tensile modulus of elasticity of >50 MPa, demonstrating high mechanical strength, high elongation, and high heat resistance. The barium-lithium-aluminum crystalline dry granule frit can also be coarsely crushed before ball milling, with the particle size after coarse crushing ranging from 30-60 mesh to 2-20 mesh before coarse crushing, to ensure that the particle size during ball milling is not excessively large.

[0010] Preferably, during ball milling of the marble crystalline glaze raw materials, water is added, representing 25-35% of the total weight of the raw materials, and the milling time is 30-40 minutes. Adding water allows for mixing and dispersion of the glaze slurry, promoting leveling and bonding of the raw materials. Under these ball milling conditions, the barium-lithium-aluminum crystalline dry particle frit can be broken down to a suitable size, while also achieving a good degree of mixing of all raw materials.

[0011] Preferably, when adding water during ball milling, 0.5-2% of a defoamer and 0.5-2% of an ink-draining agent based on the total weight of the marble crystalline glaze raw materials are also added. In addition to adding water during ball milling, 0.5% of a defoamer is also added. The defoamer can be a copolymer of ethylene oxide or propylene oxide, which facilitates the elimination of bubbles generated during the ball milling process and prevents subsequent effects on the glaze surface quality. The 1% ink-draining agent added can be a water-soluble high molecular polymer, which can effectively improve the unstable combination of oil-based ink and water-based glaze in inkjet printing, and avoid problems such as glaze peeling, glaze concavity, glaze cracking, and pinholes caused by oil-water separation.

[0012] In addition, the present invention also proposes a preparation process for marble tiles, comprising the following steps:

[0013] S1. The ceramic raw material is pressed and dried to form a ceramic body;

[0014] S2. A glaze is evenly applied on the ceramic body to form a glaze layer;

[0015] S3 inkjet printing a preset marble pattern on the glaze layer to form a pattern layer;

[0016] S4. Evenly applying the marble crystal glaze on the pattern layer to form a marble crystal glaze layer, and then firing to obtain the marble tile.

[0017] The marble tiles produced by the above preparation process have the advantages of ultra-thin glaze layer, smooth glaze surface, clearer texture, more vivid color, high hardness and good anti-fouling effect.

[0018] Preferably, in step S4, the firing temperature is 1100-1185° C. and the firing time is 40-55 min. The marble tiles in this solution adopt the above firing parameters, and the obtained marble tiles are of better quality.

[0019] Preferably, the marble crystalline glaze layer has a thickness of 1-3 mm. Unlike conventional ceramic tiles, the marble crystalline glaze layer of the marble tiles of this solution can be ultra-thin, specifically 1-3 mm. In some tiles, the thickness of the marble crystalline glaze layer can even reach 1-1.5 mm. As a result, the marble pattern in the underlying pattern layer has a better display effect, with clear texture, bright colors, and a better decorative effect.

[0020] Preferably, in step S2, the top glaze comprises the following raw materials, in parts by weight, which are mixed and then ball-milled: 1-5 parts of wollastonite, 15-20 parts of quartz, 1-4 parts of limestone, 5-10 parts of kaolin, 30-43 parts of feldspar, 3-6 parts of calcined kaolin, 3-5 parts of barium carbonate, 3-5 parts of limestone, 1-4 parts of zinc oxide, 1-5 parts of aluminum oxide, 8-14 parts of zirconium silicate, 0.10-0.15 parts of methyl cellulose, and 0.25-0.50 parts of sodium tripolyphosphate. The main function of the top glaze layer is to cover the base color of the ceramic body and serve to bond the ceramic body and the ultra-thin marble crystal glaze layer. At the same time, it can also adjust the shape of the ceramic tile, which is beneficial to the color development of the marble pattern in the pattern layer, further improving the decorative effect.

[0021] Preferably, in step S2, after the raw materials of the glaze are evenly mixed, 32-35% of water by weight of the total weight of the raw materials of the glaze is added, and the mixture is ball-milled for 10-15 minutes and then passed through a 325-mesh sieve to obtain the glaze.

[0022] The present invention also provides a marble tile produced using any of the aforementioned processes for producing marble tiles. The marble tile comprises, from bottom to top, a body layer, a glaze layer, a pattern layer, and a marble crystal glaze layer. The marble tile exhibits the same beneficial effects as the aforementioned processes, and a detailed description thereof will not be given here.

[0023] Compared with the prior art, the marble crystalline glaze of the present invention, the marble tiles using the same, and the preparation process have the following beneficial effects: by adding barium lithium aluminum crystal dry granular frit, barium carbonate, barium carbonate, and lithium carbonate to the marble crystalline glaze, these materials can form barium lithium aluminum crystal nuclei during the firing process. The performance of the barium lithium aluminum crystal nuclei is stable, making the produced glaze denser, thinner, more transparent, and harder, and also having an anti-slip effect. After the marble crystalline glaze is applied to the tiles, the glossiness of the prepared marble tiles is 70-80 degrees. Due to the extremely thin nature of the marble crystalline glaze layer, the marble tiles have clear texture and transparent color. At the same time, the glaze surface is relatively flat, with high hardness and anti-slip properties. DETAILED DESCRIPTION

[0024] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0025] In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the fact that ordinary technicians in this field can implement them. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0026] A preparation process for marble tiles comprises the following steps:

[0027] S1. The ceramic raw material is pressed and dried to form a ceramic body;

[0028] S2. A glaze is evenly applied on the ceramic body to form a glaze layer;

[0029] S3. Apply a preset marble pattern on the glaze layer in accordance with the 8-channel inkjet requirements to form a pattern layer;

[0030] S4. The marble crystalline glaze is evenly applied to the pattern layer to form a marble crystalline glaze layer having a thickness of 1-3 mm. The marble tile is obtained after firing at a temperature of 1100-1185°C for 40-50 minutes. After high-temperature firing, a polishing process can be performed. The polishing process of ordinary marble requires 33 sets of polishing grinding heads, while the ultra-thin barium lithium aluminum crystalline glaze marble tile in this solution only requires approximately 20 sets of polishing grinding heads. Due to the thinner glaze layer, the number of polishing grinding heads is greatly reduced, resulting in a smoother glaze surface, a delicate feel, and a clearer visual effect of the pattern.

[0031] Marble tiles include a body layer, a glaze layer, a pattern layer and a marble crystal glaze layer, which are arranged in sequence from bottom to top.

[0032] The marble crystal glaze is prepared by uniformly mixing and ball-milling the following raw materials, in parts by weight: 25-30 parts of albite, 10-25 parts of lithium feldspar, 6-8 parts of wollastonite, 5-10 parts of kaolin, 6-11 parts of zinc oxide, 2-7 parts of barium carbonate, 5-15 parts of barium lithium aluminum crystalline dry granular frit, 2-5 parts of fluorite, 5-10 parts of quartz, 1-5 parts of corundum, 1-2 parts of lithium carbonate, 40-60 parts of suspending agent, 5-10 parts of printing ink and 1-8 parts of water. During the ball milling, 25-35% of water, 0.5-2% of defoaming agent and 0.5-2% of ink discharge agent are added and the ball milling is carried out for 30-40 minutes.

[0033] The barium lithium aluminum crystalline dry particle frit is prepared by mixing and then ball-milling the following raw materials, in parts by weight: 20-30 parts of barium carbonate, 1-2 parts of ball clay, 6-10 parts of diopside, 1-5 parts of limestone, 5-13 parts of lithium carbonate, 10-15 parts of aluminum oxide, 1-5 parts of corundum, 1-5 parts of boric acid, 3-5 parts of sodium carbonate, 3-5 parts of strontium carbonate, 7-15 parts of albite, and 2-6 parts of quartz;

[0034] The raw materials of the barium lithium aluminum crystalline dry particle frit are mixed evenly, melted at 1550-1560° C., quenched with water, roughly crushed, and then calcined at 1100-1130° C. for 1-3 hours. After cooling, the mixture is passed through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

[0035] In particular, the marble crystal glaze in this solution is applied differently from ordinary ceramic tiles. Conventional ceramic tiles are either glazed with a bell jar or sprayed in a glaze cabinet, with a glaze weight of approximately 720 grams per square meter. Marble crystal glaze is applied using screen printing. During the firing process, the barium carbonate and lithium carbonate in the raw materials are better adsorbed on the surface of the ceramic tile, significantly reducing firing time. The screen mesh size is 120, with a glaze weight of 320-400 grams per square meter.

[0036] The glaze is prepared by mixing and ball-milling the following raw materials, in parts by weight: 1-5 parts wollastonite, 15-20 parts quartz, 1-4 parts limestone, 5-10 parts kaolin, 30-43 parts feldspar, 3-6 parts calcined kaolin, 3-5 parts barium carbonate, 3-5 parts limestone, 1-4 parts zinc oxide, 1-5 parts aluminum oxide, 8-14 parts zirconium silicate, 0.10-0.15 parts methylcellulose, and 0.25-0.50 parts sodium tripolyphosphate. After the raw materials for the glaze are uniformly mixed, 32-35% of water by weight of the total weight of the raw materials for the glaze is added, and the mixture is ball-milled for 10-15 minutes and then passed through a 325-mesh sieve to prepare the glaze.

[0037] The technical solutions of the present invention are further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0038] The ceramic green body materials used in this solution are conventional. A set of ceramic green body materials is provided for use in the following examples: by weight, they include 21-31 parts potassium feldspar, 9-19 parts quartz, 16-20 parts white clay, 1-5 parts black clay, 5-10 parts high-temperature sand, 1-5 parts talc, and 5-10 parts aluminum oxide. In the following examples, the ceramic green body materials include 28 parts potassium feldspar, 13 parts quartz, 17 parts white clay, 3 parts black clay, 6 parts high-temperature sand, 2 parts talc, and 8 parts aluminum oxide. In other examples, the raw materials and amounts of the ceramic green body can be adjusted as needed. Before applying the top glaze, the dried ceramic green body can be moistened with water to a surface moisture content of 2-5%, which will improve the quality of the tile.

[0039] Example 1

[0040] A preparation process for marble tiles comprises the following steps:

[0041] S1. The ceramic raw material is pressed and dried to form a ceramic body;

[0042] S2. A glaze is evenly applied on the ceramic body to form a glaze layer;

[0043] S3. Apply a preset marble pattern on the glaze layer in accordance with the 8-channel inkjet requirements to form a pattern layer;

[0044] S4. Screen printing the marble crystalline glaze on the pattern layer to form a marble crystalline glaze layer, which is fired to obtain the marble tile. The firing temperature is 1180° C. and the firing time is 45 min.

[0045] The marble crystal glaze is prepared by mixing the following raw materials, in parts by weight, and then ball-milling: 30 parts of albite, 25 parts of lithium feldspar, 8 parts of wollastonite, 10 parts of kaolin, 11 parts of zinc oxide, 7 parts of barium carbonate, 12 parts of barium lithium aluminum crystalline dry granular frit, 5 parts of fluorite, 10 parts of quartz, 5 parts of corundum, 2 parts of lithium carbonate, 60 parts of suspending agent, 10 parts of printing ink and 6 parts of water; 25% of water, 1% of defoaming agent and 0.5% of ink discharge agent are added during ball-milling, and the mixture is ball-milled for 30 minutes.

[0046] The barium lithium aluminum crystalline dry particle frit is prepared by mixing the following raw materials, in parts by weight, and then ball milling: 30 parts of barium carbonate powder, 2 parts of ball clay, 10 parts of diopside, 5 parts of limestone, 13 parts of lithium carbonate, 10 parts of aluminum oxide, 5 parts of corundum, 5 parts of boric acid, 5 parts of sodium carbonate, 5 parts of strontium carbonate, 12 parts of albite, and 6 parts of quartz. The mixture is then passed through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

[0047] In parts by weight, the glaze is prepared by mixing and then ball-milling the following raw materials: 5 parts of wollastonite, 20 parts of quartz, 4 parts of limestone, 10 parts of kaolin, 30 parts of feldspar, 3 parts of calcined kaolin, 5 parts of barium carbonate, 5 parts of limestone, 4 parts of zinc oxide, 5 parts of aluminum oxide, 14 parts of zirconium silicate, 0.15 parts of methyl cellulose, and 0.5 parts of sodium tripolyphosphate. After the raw materials of the glaze are evenly mixed, 33% of the total weight of the glaze raw materials is added to the glaze, and the mixture is ball-milled for 10 minutes and then passed through a 325-mesh sieve to prepare the glaze.

[0048] Example 2

[0049] A preparation process for marble tiles comprises the following steps:

[0050] S1. The ceramic raw material is pressed and dried to form a ceramic body;

[0051] S2. A glaze is evenly applied on the ceramic body to form a glaze layer;

[0052] S3. Apply a preset marble pattern on the glaze layer in accordance with the 8-channel inkjet requirements to form a pattern layer;

[0053] S4. Screen printing the marble crystalline glaze on the pattern layer to form a marble crystalline glaze layer, which is fired to obtain the marble tile. The firing temperature is 1200° C. and the firing time is 58 min.

[0054] The marble crystal glaze is prepared by mixing the following raw materials, in parts by weight, and then ball milling: 28 parts of albite, 23 parts of lithium feldspar, 7 parts of wollastonite, 8 parts of kaolin, 8 parts of zinc oxide, 6 parts of barium carbonate, 12 parts of barium lithium aluminum crystal dry granular frit, 4 parts of fluorite, 8 parts of quartz, 4 parts of corundum, 1.5 parts of lithium carbonate, 55 parts of suspending agent, 8 parts of printing ink and 7 parts of water; 28% of water, 1.2% of defoaming agent and 1% of ink discharge agent are added during ball milling, and the mixture is ball milled for 33 minutes;

[0055] The barium lithium aluminum crystalline dry particle frit is prepared by mixing and then ball-milling the following raw materials, in parts by weight: 28 parts of barium carbonate powder, 1 part of ball clay, 9 parts of diopside, 4 parts of limestone, 12 parts of lithium carbonate, 11 parts of aluminum oxide, 4 parts of corundum, 4 parts of boric acid, 4 parts of sodium carbonate, 4 parts of strontium carbonate, 12 parts of albite, and 4 parts of quartz;

[0056] The raw materials of the barium lithium aluminum crystalline dry particle frit are mixed uniformly, melted at 1550° C., ball-milled with water quenching, calcined at 1120° C. for 2 h, cooled, and sieved through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

[0057] The top glaze is prepared by mixing and ball-milling the following raw materials, in parts by weight: 4 parts wollastonite, 18 parts quartz, 3 parts limestone, 9 parts kaolin, 38 parts feldspar, 5 parts calcined kaolin, 4 parts barium carbonate, 4 parts limestone, 3 parts zinc oxide, 4 parts aluminum oxide, 12 parts zirconium silicate, 0.12 parts methylcellulose, and 0.45 parts sodium tripolyphosphate. After the raw materials for the top glaze are uniformly mixed, 34% of the total weight of the raw materials for the top glaze is added, and the mixture is ball-milled for 15 minutes before being passed through a 325-mesh sieve to prepare the top glaze.

[0058] Example 3

[0059] A preparation process for marble tiles comprises the following steps:

[0060] S1. The ceramic raw material is pressed and dried to form a ceramic body;

[0061] S2. A glaze is evenly applied on the ceramic body to form a glaze layer;

[0062] S3. Apply a preset marble pattern on the glaze layer in accordance with the 8-channel inkjet requirements to form a pattern layer;

[0063] S4. Screen printing the marble crystalline glaze on the pattern layer to form a marble crystalline glaze layer, which is fired to obtain the marble tile. The firing temperature is 1150° C. and the firing time is 50 min.

[0064] The marble crystal glaze is prepared by mixing the following raw materials, in parts by weight, and then ball milling: 27 parts of albite, 23 parts of lithium feldspar, 7.5 parts of wollastonite, 8 parts of kaolin, 9 parts of zinc oxide, 4 parts of barium carbonate, 11 parts of barium lithium aluminum crystal dry granular frit, 3 parts of fluorite, 7 parts of quartz, 3 parts of corundum, 1 part of lithium carbonate, 50 parts of suspending agent, 7 parts of printing ink and 6 parts of water; 32% of water, 1.4% of defoaming agent and 1.3% of ink discharge agent are added during ball milling, and the mixture is ball milled for 33 minutes;

[0065] The barium lithium aluminum crystalline dry particle frit is prepared by mixing and then ball-milling the following raw materials, in parts by weight: 27 parts of barium carbonate powder, 2 parts of ball clay, 7 parts of diopside, 3 parts of limestone, 7 parts of lithium carbonate, 10 parts of aluminum oxide, 3 parts of corundum, 3 parts of boric acid, 4.5 parts of sodium carbonate, 4.5 parts of strontium carbonate, 9 parts of albite and 4 parts of quartz;

[0066] The raw materials of the barium lithium aluminum crystalline dry particle frit are mixed uniformly, melted at 1554° C., ball-milled with water quenching, calcined at 1130° C. for 1.8 h, cooled, and sieved through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

[0067] The glaze (a commercially available glaze was used in this example) was prepared by mixing and ball-milling the following raw materials, in parts by weight: 35 parts potassium feldspar, 6 parts limestone, 15 parts quartz, 7 parts wollastonite, 4 parts zinc oxide, 6 parts kaolin, 12 parts zirconium silicate, 0.12 parts methylcellulose, and 0.42 parts sodium tripolyphosphate. After the glaze raw materials were uniformly mixed, 33% of the total weight of water was added, and the mixture was ball-milled for 15 minutes before being passed through a 325-mesh sieve to produce the glaze.

[0068] Example 4

[0069] A preparation process for marble tiles comprises the following steps:

[0070] S1. The ceramic raw material is pressed and dried to form a ceramic body;

[0071] S2. A glaze is evenly applied on the ceramic body to form a glaze layer;

[0072] S3. Apply a preset marble pattern on the glaze layer in accordance with the 8-channel inkjet requirements to form a pattern layer;

[0073] S4. Screen printing the marble crystalline glaze on the pattern layer to form a marble crystalline glaze layer, which is fired to obtain the marble tile. The firing temperature is 1160° C. and the firing time is 50 min.

[0074] The marble crystal glaze is prepared by mixing the following raw materials, in parts by weight, and then ball milling: 25 parts of albite, 10 parts of lithium feldspar, 6 parts of wollastonite, 5 parts of kaolin, 6 parts of zinc oxide, 2 parts of barium carbonate, 5 parts of barium lithium aluminum crystal dry granular frit, 2 parts of fluorite, 5 parts of quartz, 2 parts of corundum, 2 parts of lithium carbonate, 45 parts of suspending agent, 5 parts of printing ink, and 3 parts of water; 31% of water, 1.7% of defoaming agent, and 1.7% of ink discharge agent are added during ball milling, and the mixture is ball milled for 36 minutes;

[0075] The barium lithium aluminum crystalline dry particle frit is prepared by mixing and then ball-milling the following raw materials, in parts by weight: 24 parts of barium carbonate powder, 1 part of ball clay, 8 parts of diopside, 2 parts of limestone, 7 parts of lithium carbonate, 11 parts of aluminum oxide, 2 parts of corundum, 3 parts of boric acid, 3 parts of sodium carbonate, 3 parts of strontium carbonate, 8 parts of albite, and 5 parts of quartz;

[0076] The raw materials of the barium lithium aluminum crystalline dry particle frit are mixed uniformly, melted at 1560° C., ball-milled with water quenching, calcined at 1126° C. for 2.3 h, cooled, and sieved through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

[0077] The top glaze is prepared by mixing and ball-milling the following raw materials, in parts by weight: 1 part wollastonite, 15 parts quartz, 1 part limestone, 5 parts kaolin, 30 parts feldspar, 3 parts calcined kaolin, 3 parts barium carbonate, 3 parts limestone, 1 part zinc oxide, 1 part aluminum oxide, 8 parts zirconium silicate, 0.1 part methylcellulose, and 0.25 part sodium tripolyphosphate. After the raw materials for the top glaze are evenly mixed, 32% of the total weight of the raw materials for the top glaze is added, and the mixture is ball-milled for 14 minutes before being passed through a 325-mesh sieve to prepare the top glaze.

[0078] Comparative Example 1

[0079] This comparative example is commercially available marble tiles produced by Xinjincheng Ceramics Factory.

[0080] Comparative Example 2

[0081] The conditions in this comparative example were the same as those in Example 4, except that in step S4, a conventional protective glaze was screen-printed on the pattern layer to form a protective glaze layer. The protective glaze was prepared by mixing and ball-milling the following raw materials, by weight: 28 parts albite, 6 parts limestone, 15 parts quartz, 3 parts wollastonite, 8 parts zinc oxide, 9 parts kaolin, 7 parts aluminum oxide, and 9 parts barium carbonate.

[0082] Comparative Example 3

[0083] The conditions in this comparative example are the same as those in Example 4, except that no barium-lithium-aluminum crystalline dry particle frit is added to the raw materials of the marble crystal glaze.

[0084] The marble tiles prepared in Examples 1-4 and Comparative Examples 1-3 were subjected to performance tests, and the specific test results are shown in the following table:

[0085]

[0086]

[0087] Note: 1. The anti-fouling grade test is conducted by smearing the tile surface with an oil-based marker, letting it stand for 10 minutes, and then rinsing it with clean water to evaluate the residual traces on the surface. The higher the anti-fouling grade, the less traces remain on the tile surface, and the better the surface anti-fouling effect.

[0088] 2. The decorative effect was observed directly by the naked eye by 30 inspectors, who mainly compared the color similarity and gloss of the marble tiles in this scheme with those of natural marble. If 27 or more people thought the surface effects of the two were similar, the result was marked as excellent; if 24-26 people thought the surface effects of the two were similar, the result was marked as good; if 20-23 people thought the surface effects of the two were similar, the result was marked as fair; and the rest was marked as poor.

[0089] The test results in the table above demonstrate that the marble tiles in this solution offer superior hardness, slip resistance, and wear resistance compared to conventional marble tiles on the market. Furthermore, due to the thinner marble crystalline glaze layer, the inkjet-printed marble pattern offers a superior decorative effect and clearer texture. Specifically, the marble tiles in this solution have a hardness of over 5, a wear resistance coefficient of over 4,000 revolutions, a slip resistance rating of approximately R11, and a stain resistance rating of approximately 5.

[0090] The test results of Example 4 and Comparative Example 2 show that replacing the surface marble crystal glaze with a conventional protective glaze results in a thicker glaze layer on the surface of the tile. Consequently, the decorative effect of the marble pattern is poor, and both the anti-slip and anti-fouling properties are reduced. The test results of Example 4 and Comparative Example 3 show that the performance of the marble tile deteriorates to varying degrees when barium lithium aluminum crystalline dry particle frit is not added.

[0091] Example 5

[0092] The conditions in this embodiment are the same as those in Example 1, except that the barium lithium aluminum crystalline dry particle frit is modified, specifically comprising: mixing the raw materials of the barium lithium aluminum crystalline dry particle frit evenly, melting at 1558° C., then water-quenching and ball milling, calcining at 1128° C. for 2.7 h, cooling, and passing through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

[0093] Example 6

[0094] The conditions in this embodiment are the same as those in embodiment 2, except that the firing temperature is 1185° C. and the firing time is 47 minutes.

[0095] Example 7

[0096] The conditions in this embodiment are the same as those in Example 3, except that the glaze is prepared by mixing and then ball-milling the following raw materials: 3 parts of wollastonite, 18 parts of quartz, 2 parts of limestone, 7 parts of kaolin, 41 parts of feldspar, 4 parts of calcined kaolin, 3 parts of barium carbonate, 3 parts of limestone, 3 parts of zinc oxide, 1 part of aluminum oxide, 11 parts of zirconium silicate, 0.11 parts of methyl cellulose, and 0.45 parts of sodium tripolyphosphate.

[0097] The marble tiles prepared in Examples 5-7 were subjected to performance testing, and the specific test results are shown in the following table.

[0098]

[0099] From the test data in the above table, it can be seen that, as shown in the test results of Example 1 and Example 5, after the barium lithium aluminum crystalline dry particle frit is modified, the hardness, wear resistance and anti-slip properties of the marble tiles are improved. It should be noted that the decorative effects of the marble tiles obtained in Example 1 and Example 5 are both good, but the decorative effect of the marble tiles obtained in Example 5 is better. In Example 1, 27 testers believed that the surface effects of the two (the marble tiles of this scheme and the natural marble) were similar, and in Example 5, 29 testers believed that the surface effects of the two were similar.

[0100] As shown in the test results of Examples 2 and 6, the performance of the marble tiles did not deteriorate after the firing temperature was lowered and the firing time was relatively shortened. In fact, the marble crystalline glaze layer became thinner. In other words, the tiles of this solution can adapt to different firing parameters and have relatively stable performance. As shown in the test results of Examples 3 and 7, after replacing the top glaze with the top glaze in this solution that is more compatible with the marble crystalline glaze, the hardness, wear resistance, and anti-slip properties of the marble tiles were improved. When the top glaze and the top glaze are used together, the thickness of the marble crystalline glaze layer is also thinner, and the marble pattern decorative effect of the tiles is also better.

[0101] The performance of marble tiles can be further improved by further defining the marble crystal glaze and barium lithium aluminum crystal dry particle frit. Specifically, the marble crystal glaze comprises the following raw materials, by weight, which are mixed and then ball-milled: 26-29 parts of albite, 22-24 parts of lithium feldspar, 6-8 parts of wollastonite, 8-10 parts of kaolin, 9-10 parts of zinc oxide, 5-7 parts of barium carbonate, 9-11 parts of barium lithium aluminum crystal dry particle frit, 4-5 parts of fluorite, 7-10 parts of quartz, 3-5 parts of corundum, 1-2 parts of lithium carbonate, 55-60 parts of suspending agent, 8-10 parts of printing ink, and 6-8 parts of water. The barium lithium aluminum crystalline dry particle frit is prepared by mixing and ball milling the following raw materials, in parts by weight: 28-30 parts of barium carbonate, 1-2 parts of ball clay, 8-10 parts of diopside, 4-5 parts of limestone, 10-12 parts of lithium carbonate, 10-13 parts of aluminum oxide, 3-5 parts of corundum, 4-5 parts of boric acid, 4-5 parts of sodium carbonate, 4-5 parts of strontium carbonate, 10-13 parts of albite and 4-6 parts of quartz, as shown in the following Example 8: Example 8

[0102] A preparation process for marble tiles comprises the following steps:

[0103] S1. The ceramic raw material is pressed and dried to form a ceramic body;

[0104] S2. A glaze is evenly applied on the ceramic body to form a glaze layer;

[0105] S3. Apply a preset marble pattern on the glaze layer in accordance with the 8-channel inkjet requirements to form a pattern layer;

[0106] S4. Screen printing the marble crystalline glaze on the pattern layer to form a marble crystalline glaze layer, which is fired to obtain the marble tile. The firing temperature is 1180° C. and the firing time is 48 min.

[0107] The marble crystal glaze is prepared by mixing the following raw materials, in parts by weight, and then ball-milling: 29 parts of albite, 23 parts of lithium feldspar, 7 parts of wollastonite, 8 parts of kaolin, 9 parts of zinc oxide, 6 parts of barium carbonate, 9 parts of barium lithium aluminum crystal dry granular frit, 5 parts of fluorite, 9 parts of quartz, 4 parts of corundum, 2 parts of lithium carbonate, 56 parts of suspending agent, 8 parts of printing ink and 7 parts of water; 35% of water, 1.1% of defoaming agent and 0.8% of ink discharge agent are added during ball milling, and the mixture is ball-milled for 32 minutes;

[0108] The barium-lithium-aluminum crystalline dry particle frit is prepared by mixing and then ball-milling the following raw materials, in parts by weight: 30 parts of barium carbonate, 2 parts of ball clay, 10 parts of diopside, 4 parts of limestone, 10 parts of lithium carbonate, 13 parts of aluminum oxide, 3 parts of corundum, 5 parts of boric acid, 4 parts of sodium carbonate, 5 parts of strontium carbonate, 13 parts of albite and 6 parts of quartz.

[0109] The raw materials of the barium lithium aluminum crystalline dry particle frit are mixed uniformly, melted at 1558° C., quenched with water, ball-milled, calcined at 1113° C. for 1.1 h, cooled, and sieved through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

[0110] The top glaze is prepared by mixing and ball-milling the following raw materials, in parts by weight: 5 parts wollastonite, 17 parts quartz, 3 parts limestone, 8 parts kaolin, 40 parts feldspar, 5 parts calcined kaolin, 3 parts barium carbonate, 3 parts limestone, 4 parts zinc oxide, 2 parts aluminum oxide, 10 parts zirconium silicate, 0.11 parts methylcellulose, and 0.45 parts sodium tripolyphosphate. After the top glaze raw materials are uniformly mixed, 35% of the total weight of the glaze raw materials is added to the mixture. The mixture is ball-milled for 14 minutes and then passed through a 325-mesh sieve to prepare the top glaze.

[0111] The marble tiles prepared in the above embodiment have a marble crystal glaze layer with a thickness of 1 mm, a hardness of level 7, a wear resistance coefficient of 6000 revolutions, an anti-slip grade of R12, an anti-fouling grade of level 5, clear texture and excellent decorative effect.

[0112] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention specification under the inventive concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A marble crystal glaze, characterized in that: The preparation method comprises the following raw materials, in parts by weight, being mixed and then ball-milled: 25-30 parts of albite, 10-25 parts of lithium feldspar, 6-8 parts of wollastonite, 5-10 parts of kaolin, 6-11 parts of zinc oxide, 2-7 parts of barium carbonate, 5-15 parts of barium lithium aluminum crystalline dry granule frit, 2-5 parts of fluorite, 5-10 parts of quartz, 1-5 parts of corundum, 1-2 parts of lithium carbonate, 40-60 parts of suspending agent, 5-10 parts of printing ink and 1-8 parts of water; The barium-lithium-aluminum crystalline dry particle frit is prepared by mixing and then ball-milling the following raw materials, in parts by weight: 20-30 parts of barium carbonate, 1-2 parts of ball clay, 6-10 parts of diopside, 1-5 parts of limestone, 5-13 parts of lithium carbonate, 10-15 parts of aluminum oxide, 1-5 parts of corundum, 1-5 parts of boric acid, 3-5 parts of sodium carbonate, 3-5 parts of strontium carbonate, 7-15 parts of albite and 2-6 parts of quartz.

2. The marble crystal glaze according to claim 1, characterized in that: The raw materials of the barium lithium aluminum crystalline dry particle frit are mixed evenly, melted at 1550-1560° C., water quenched and ball milled, calcined at 1100-1130° C. for 1-3 hours, cooled, and sieved through a 400-mesh sieve to obtain the barium lithium aluminum crystalline dry particle frit.

3. A marble crystal glaze according to claim 1 or 2, characterized in that: When the raw materials of the marble crystal glaze are ball-milled, 25-35% of water by weight of the total weight of the raw materials of the marble crystal glaze is added, and the ball-milling time is 30-40 minutes.

4. The marble crystal glaze according to claim 3, characterized in that: When adding water during ball milling, a defoamer in an amount of 0.5-2% by weight of the total weight of the marble crystal glaze raw materials and an ink discharger in an amount of 0.5-2% by weight of the total weight of the marble crystal glaze raw materials are also added.

5. A process for preparing marble tiles, characterized in that: The steps include: S1. The ceramic raw material is pressed and dried to form a ceramic body; S2. A glaze is evenly applied on the ceramic body to form a glaze layer; S3 inkjet printing a preset marble pattern on the glaze layer to form a pattern layer; S4. The marble crystalline glaze according to any one of claims 1 to 4 is evenly applied on the pattern layer to form a marble crystalline glaze layer, and the marble tile is obtained after firing.

6. The process for preparing marble tiles according to claim 5, characterized in that: In step S4, the sintering temperature is 1100-1185° C., and the sintering time is 40-55 minutes.

7. The process for preparing marble tiles according to claim 5, characterized in that: The thickness of the marble crystal glaze layer is 1-3 mm.

8. The process for preparing marble tiles according to claim 5, characterized in that: In step S2, the glaze includes the following raw materials, which are mixed and then ball-milled, in parts by weight: 1-5 parts of wollastonite, 15-20 parts of quartz, 1-4 parts of limestone, 5-10 parts of kaolin, 30-43 parts of feldspar, 3-6 parts of calcined kaolin, 3-5 parts of barium carbonate, 3-5 parts of limestone, 1-4 parts of zinc oxide, 1-5 parts of aluminum oxide, 8-14 parts of zirconium silicate, 0.10-0.15 parts of methyl cellulose and 0.25-0.50 parts of sodium tripolyphosphate.

9. The process for preparing marble tiles according to claim 8, characterized in that: In step S2, after the raw materials of the glaze are evenly mixed, 32-35% of water by weight of the total weight of the raw materials of the glaze is added, and the mixture is ball-milled for 10-15 minutes and then passed through a 325-mesh sieve to obtain the glaze.

10. A marble tile, characterized in that: The marble tile is prepared by the preparation process of any one of claims 5 to 9, and comprises a body layer, a surface glaze layer, a pattern layer and a marble crystal glaze layer arranged in sequence from bottom to top.

Images