A kind of penetrating marble glaze, marble tiles using the same and a preparation method thereof

Abstract

The present invention relates to the technical field of ceramic tiles, and particularly to a penetrating marble glaze, a marble tile using the same, and a preparation method thereof. Calculated by weight parts, it includes the following raw materials which are ball-milled after being mixed evenly: 25-35 parts of nepheline, 12-16 parts of wollastonite, 6-10 parts of modified barium titanate frit, 6-13 parts of ball clay, 8-12 parts of zinc oxide, 3-6 parts of barium sulfate, 15-20 parts of quartz, 8-13 parts of dolomite, 1-2 parts of talc, 2-8 parts of barium carbonate, 10-20 parts of penetrant, 5-10 parts of binder, and 10-15 parts of deionized water. By sequentially applying a porous rough glaze and a penetrating marble glaze on the base glaze layer, wherein barium sulfate and modified barium carbonate frit are added to the penetrating marble glaze layer, which helps wollastonite and zinc oxide to combine into barium zinc titanate crystals, making the glaze layer have the characteristics of being porous, rough and easy to penetrate. At the same time, the performance of the penetrating marble glaze slurry is easier to control. The marble tile prepared after firing has good anti-slip property, erosion resistance and texture sense.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramics, and particularly relates to a penetrating marble glaze, a marble tile using the same, and a preparation method thereof. Background Art

[0002] The penetrating marble glaze is a glaze fired at high temperature, which is a glaze layer formed on the surface of a green body after being prepared through multiple processes according to the proportion of chemical raw materials. However, the current penetrating marble glazes generally have the disadvantages of low hardness and poor wear resistance, which cannot meet the market requirements, are not conducive to the safe use of users, and cannot meet people's requirements for high-quality tile products.

[0003] Moreover, the current manufacturing processes of penetrating marble glaze ceramic tiles mainly include the following: one is to apply the penetrating marble glaze on the surface of the ceramic tile by screen printing. Its advantage is that the particle size of the pores of the penetrating marble glaze can be controlled; the disadvantage is that when using conventional screen printing, the penetrating marble glaze is prone to uneven distribution and sometimes agglomeration phenomena will occur. The other is to spray the glaze on the surface of the ceramic tile by a wet method through a glaze spraying cabinet. Its advantage is good bonding with the green body; the disadvantage is that the fluidity of the penetrating marble glaze is poor, it is easy to block the spray gun nozzle, and it is difficult to control during production. Summary of the Invention

[0004] The main purpose of the present invention is to provide a penetrating marble glaze, a marble tile using the same, and a preparation method thereof, aiming to improve the technical problems that the existing penetrating marble glaze is prone to agglomeration or blockage of the spray gun nozzle during production, and the marble ceramic tile prepared using it has low hardness and poor wear resistance.

[0005] To achieve the above purpose, the present invention provides a penetrating marble glaze, which is prepared by ball milling the following raw materials in parts by weight after mixing evenly: 25-35 parts of nepheline, 12-16 parts of wollastonite, 6-10 parts of modified barium titanate frit, 6-13 parts of ball clay, 8-12 parts of zinc oxide, 3-6 parts of barium sulfate, 15-20 parts of quartz, 8-13 parts of dolomite, 1-2 parts of talc, 2-8 parts of barium carbonate, 10-20 parts of penetrant, 5-10 parts of binder, and 10-15 parts of deionized water. In addition to the above raw materials, some raw materials such as methyl cellulose and / or sodium tripolyphosphate can be added to improve the performance of the glaze.

[0006] Raw materials such as nepheline, wollastonite, dolomite, and talc in the penetrating marble glaze layer mainly play a melting role, which is beneficial to the addition of the modified barium titanate frit to the above raw materials during high-temperature melting; barium sulfate and modified barium carbonate frit are introduced into the penetrating marble glaze layer, which helps wollastonite and zinc oxide to combine with it to form barium zinc titanate crystals. The generated barium zinc titanate crystals have stable performance, excellent mechanical properties, and strong applicability. They can be used as a reinforcing material in ceramic glazes, making the penetrating marble glaze have the characteristics of porous roughness, good anti-slip property, easy penetration, and corrosion resistance.

[0007] The characteristic of being porous and rough means that there are multiple pores with extremely small particle sizes on the surface of the ceramic tile (or glaze), generally with a size of about 0.01 - 0.09 mm, which has a good anti-slip effect; at the same time, due to the extremely small particle size of the pores and the complete sintering of the tile (glaze), it is easy to clean, so the anti-fouling performance of the tile is not affected, and a good anti-fouling effect can be achieved.

[0008] The easy penetration of the glaze means that the penetrating marble glaze can make the inkjet-printed color penetrate downward more easily, combine better with the underglaze layer, and have a better texture; at the same time, the penetrating marble glaze has strong fusibility and compactness, and also has a good combination with the green body.

[0009] Preferably, by weight percentage, the modified barium titanate frit is prepared by melting, water quenching and drying the following raw materials: 50 - 60% barium titanate, 15 - 20% boric acid, 10 - 20% spodumene and 5 - 10% lithium carbonate. The raw materials of the modified barium titanate frit specifically include barium titanate, boric acid, spodumene and lithium carbonate. By mixing the above various raw materials, the prepared frit has the characteristics of higher melting point and stronger wear resistance, and applying it to the ceramic tile can make the finished ceramic tile have better quality.

[0010] Preferably, the temperature during melting is 1300 - 1310 °C, and it is kept at this melting temperature for 1 - 2 h. The melting temperature of the modified barium titanate frit is 1300 - 1310 °C. At this temperature, the above four raw materials can be better combined, so that the obtained modified barium titanate frit has better quality.

[0011] Preferably, the penetrant is an aqueous solution of triethanolamine; by weight percentage, the aqueous solution of triethanolamine includes 70 - 80% triethanolamine and 20 - 30% deionized water. Adding the aqueous solution of triethanolamine as a penetrant can make the penetrating marble glaze play a better penetrating role. Since triethanolamine has weak alkalinity, it can react with the modified barium titanate frit in the above glaze formula to generate barium ion salts, etc. Its fineness is better, it belongs to a water-based ion, and it is more likely to penetrate, thus being more conducive to the surface porous and rough penetration of the glaze.

[0012] Preferably, the binder is an aqueous solution of cyanoacrylate; by weight percentage, the aqueous solution of cyanoacrylate includes 60 - 70% aqueous solution of cyanoacrylate and 30 - 40% deionized water. Adding the aqueous solution of cyanoacrylate as a binder is mainly to improve the bonding effect of the penetrating marble glaze, make the various raw materials bond tightly, which is beneficial to improving the performance of the glaze slurry after the glaze is made into a slurry. The viscosity of the glaze slurry is reduced, the suspension is better, and it is easier to disperse, with strong fluidity, thus facilitating the subsequent glazing.

[0013] In addition, the present invention also provides a preparation process for marble tiles, which includes the following steps:

[0014] S1. After the green body raw materials are pressed into shape, a green body layer is obtained.

[0015] S2. A base glaze is applied on the green body layer to obtain a base glaze layer, and inkjet printing is performed on the base glaze layer to obtain a preset pattern.

[0016] S3. A porous rough glaze is applied on the base glaze layer after inkjet printing to obtain a porous rough glaze layer.

[0017] S4. The permeable marble glaze as described in any one of the above is continuously applied on the porous rough glaze layer to obtain a permeable marble glaze layer.

[0018] S5. After firing, polishing is carried out to obtain the marble tiles.

[0019] By sequentially performing the above multiple steps, a base glaze, a porous rough glaze, and a permeable marble glaze are sequentially applied on the green body. The fired tiles have the characteristics of being porous and rough, and at the same time have better anti-slip properties, texture, and erosion resistance.

[0020] Preferably, by weight percentage, the porous rough glaze is prepared by ball milling the following raw materials after mixing: albite 40 - 45%, modified barium titanate frit 3 - 6%, kaolin 4 - 8%, zinc oxide 6 - 10%, wollastonite 11 - 20%, calcite 12 - 15%, diopside 6 - 12%, corundum 2 - 6%, and deionized water 1 - 5%.

[0021] The above-mentioned modified barium titanate frit is also added to the porous rough glaze. Therefore, the porous and rough characteristics of the tiles can be further improved. The double-layer rough effect can play a more efficient protective layer role, making the ceramic tiles have better anti-slip properties, wear resistance, and more excellent texture, and the decorative effect is better. In addition, when preparing the porous rough glaze, printing paste and printing oil can be additionally added to facilitate the subsequent application of the glaze. Among them, the addition amount of the printing paste can be 40 - 50% of the total amount of the porous rough glaze raw materials, and the addition amount of the printing oil can be 5 - 10% of the total amount of the porous rough glaze raw materials.

[0022] Preferably, by weight percentage, the base glaze is prepared by ball milling the following raw materials after mixing: potassium feldspar 35 - 45%, lithium feldspar 11 - 20%, quartz 10 - 20%, limestone 8 - 15%, talc 3 - 10%, alumina 5 - 10%, zirconium silicate 8 - 15%, methyl cellulose 0.10 - 0.33%, sodium tripolyphosphate 0.20 - 0.60%. The selection of the base glaze raw materials is also relatively important. By using the above raw materials, better bonding between the base glaze and the underlying green body can be ensured, so that the marble tiles have better quality.

[0023] During the ball milling process of the base glaze, an appropriate amount of methyl cellulose and sodium tripolyphosphate can also be added, and the addition amounts of the two are 0.10 - 0.33% and 0.2 - 0.6% of the total amount of the base glaze raw materials respectively. Among them, sodium tripolyphosphate and methyl cellulose are added additionally during ball milling. Sodium tripolyphosphate can improve the fluidity of the penetrated marble glaze (slurry), reduce the water content under the condition of meeting the production process requirements, and the glaze is not easy to flocculate and precipitate.

[0024] Preferably, the firing temperature in step S5 is 1190 - 1200 °C, and the firing time is 60 - 70 min. The firing parameters are relatively important parameters in marble tiles. After controlling the firing temperature and firing time as above, the raw materials are melted more completely, and the obtained marble tiles have better product quality.

[0025] The present invention also provides a marble tile prepared by the preparation process of the marble tile described in any one of the above. The marble tile includes a body layer, a base glaze layer, an inkjet pattern layer, a porous rough glaze layer, and a penetrated marble glaze layer from bottom to top. Since this tile adopts all the above technical solutions, it has at least all the effects brought by the above technical solutions, which will not be elaborated one by one here.

[0026] Compared with the prior art, the technical solution of the present invention has the following beneficial effects: providing a penetrated marble glaze, a marble tile using the same, and a preparation method thereof. By sequentially applying a porous rough glaze and a penetrated marble glaze on the base glaze layer, wherein barium sulfate and modified barium carbonate frit are added to the penetrated marble glaze layer, which helps wollastonite and zinc oxide combine into barium zinc titanate crystals, making the glaze layer have the characteristics of being porous, rough, and easy to penetrate. At the same time, it is easier to control the performance of the penetrated marble glaze slurry. The marble tile prepared after firing has good anti-slip property, corrosion resistance, and texture. And because the pattern in the inkjet printing contains a variety of pigments, there are multiple colors on the pattern, and these colorful patterns will show different depths of changes in the porous rough glaze. Combining with the good penetration effect of the penetrated marble glaze, the three-dimensional effect of the pattern on the tile is better. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other relevant drawings can also be obtained based on these drawings.

[0028] Figure 1 It is a microscope structure diagram (magnification factor is 1000 times) of the surface of the marble tile prepared in Example 5;

[0029] Figure 2 The physical diagram of the marble tile obtained in Example 5;

[0030] Figure 3 The schematic diagram of the layered structure of the marble tile obtained by this solution.

[0031] The realization of the purpose of this application, functional features and advantages will be further described in conjunction with the embodiments with reference to the accompanying drawings. Specific Embodiments

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0033] In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the fact that those of ordinary skill in the art can implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the protection scope required by the present invention.

[0034] A preparation process of a marble tile, comprising the following steps:

[0035] S1. After the green body raw materials are pressed into shape, a green body layer is obtained;

[0036] S2. Apply a base glaze on the green body layer to obtain a base glaze layer, and perform inkjet printing on the base glaze layer to obtain a preset pattern;

[0037] S3. Apply a porous rough glaze on the inkjet-printed base glaze layer to obtain a porous rough glaze layer;

[0038] S4. Continuously apply a penetrating marble glaze on the porous rough glaze layer to obtain a penetrating marble glaze layer;

[0039] S5. After firing and polishing, the marble tile is obtained. Among them, the firing temperature is 1190 - 1200 °C, and the firing time is 60 - 70 min.

[0040] Calculated by weight percentage, the base glaze is prepared by ball milling the following raw materials after mixing: potassium feldspar 35 - 45%, lithium feldspar 11 - 20%, quartz 10 - 20%, limestone 8 - 15%, talc 3 - 10%, alumina 5 - 10%, zirconium silicate 8 - 15%. When ball milling, methyl cellulose 0.10 - 0.33% and sodium tripolyphosphate 0.20 - 0.60% are additionally added.

[0041] The porous rough glaze is prepared by ball milling the following raw materials after mixing: albite 40-45% by weight, modified barium titanate frit 3-6% by weight, kaolin 4-8% by weight, zinc oxide 6-10% by weight, wollastonite 11-20% by weight, calcite 12-15% by weight, diopside 6-12% by weight, corundum 2-6% by weight, and deionized water 1-5% by weight. 。

[0042] The penetrating marble glaze is prepared by ball milling the following raw materials after mixing: nepheline 25-35 parts by weight, wollastonite 12-16 parts by weight, modified barium titanate frit 6-10 parts by weight, ball clay 6-13 parts by weight, zinc oxide 8-12 parts by weight, barium sulfate 3-6 parts by weight, quartz 15-20 parts by weight, dolomite 8-13 parts by weight, talc 1-2 parts by weight, barium carbonate 2-8 parts by weight, penetrant 10-20 parts by weight, binder 5-10 parts by weight, and deionized water 10-15 parts by weight. Among them, the modified barium titanate frit is prepared by melting, water quenching, and drying the following raw materials: barium titanate 50-60%, boric acid 15-20%, lithium porcelain stone 10-20%, and lithium carbonate 5-10%. The melting temperature is 1300-1310 °C, and the holding time is 1-2 h. The penetrant is an aqueous solution of triethanolamine. By weight percentage, the aqueous solution of triethanolamine includes 70-80% triethanolamine and 20-30% deionized water; the binder is an aqueous solution of cyanoacrylate. By weight percentage, the aqueous solution of cyanoacrylate includes 60-70% aqueous solution of cyanoacrylate and 30-40% deionized water.

[0043] As Figure 3 shown, the obtained marble tile includes a body layer, a base glaze layer, an inkjet pattern layer, a porous rough glaze layer, and a penetrating marble glaze layer from bottom to top.

[0044] The technical solution of the present invention will be 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.

[0045] In this solution, the body raw materials can be any conventional body raw materials. By weight, 1 group of body raw materials is provided for the preparation of the following embodiments: clay 30 parts, white clay 10 parts, black clay 5 parts, quartz sand 20 parts, feldspar powder 15 parts, low-temperature sand 5 parts, and aluminum sand 15 parts. In other embodiments, the body raw materials and their dosages can be adjusted adaptively.

[0046] Comparative Example 1

[0047] A preparation process of a conventional marble tile includes the following steps:

[0048] S1. After the body raw materials are pressed into shape, a body layer is obtained;

[0049] S2. Apply a base glaze on the green body layer to obtain a base glaze layer, and perform inkjet printing on the base glaze layer to obtain a preset pattern. By weight percentage, the base glaze is prepared by ball milling the following raw materials after mixing: potassium feldspar 38.5%, lithium feldspar 13%, quartz 11.5%, limestone 12%, talc 6%, alumina 7%, zirconium silicate 12%. (When ball milling, 0.3% of methyl cellulose and 0.25% of sodium tripolyphosphate are additionally added based on the total amount of the above raw materials);

[0050] S3. Apply a top glaze on the base glaze layer after inkjet printing to obtain a top glaze layer. By weight percentage, the top glaze is prepared by ball milling the following raw materials after mixing: albite 41%, modified barium titanate frit 5%, kaolin 4%, zinc oxide 8%, wollastonite 13%, calcite 13%, diopside 10%, corundum 4% and deionized water 2%;

[0051] S4. Continuously apply a protective glaze on the top glaze to obtain a protective glaze layer. By weight parts, the protective glaze is prepared by ball milling the following raw materials after mixing: kaolin 12 parts, albite 27 parts, lithium feldspar 18 parts, zirconium silicate 8 parts, corundum 6 parts, calcined talc 5 parts, quartz 8 parts, frit powder 16 parts;

[0052] S5. Fire at 1200 °C for 60 min and then polish to obtain a conventional marble tile.

[0053] Example 1

[0054] All parameters and preparation steps of this example are the same as those of Comparative Example 1, except that: the conventional protective glaze is replaced with the permeable marble glaze of this scheme, that is, the permeable marble glaze is applied on the top glaze to obtain a permeable marble glaze layer.

[0055] By weight percentage, the permeable marble glaze is prepared by ball milling the following raw materials after mixing: nepheline 31 parts, wollastonite 16 parts, modified barium titanate frit 10 parts, ball clay 6 parts, zinc oxide 8 parts, barium sulfate 3 parts, quartz 15 parts, dolomite 8 parts, talc 1 part, barium carbonate 2 parts, penetrant 10 parts, binder 5 parts and deionized water 10 parts; the penetrant is an aqueous solution of triethanolamine, including 75% triethanolamine and 25% deionized water; the binder is an aqueous solution of cyanoacrylate, including 63% aqueous cyanoacrylate solution and 37% deionized water.

[0056] By weight percentage, the modified barium titanate frit is prepared by melting barium titanate 56%, boric acid 18%, lithium porcelain stone 17% and lithium carbonate 9% at 1305 °C and holding for 1.5 h, and then quenching with water and drying.

[0057] Comparative Example 2

[0058] All parameters and preparation steps of this comparative example are the same as those of Example 1, except that: the modified barium titanate frit for permeable marble glaze is replaced with conventional barium titanate.

[0059] Comparative Example 3

[0060] All parameters and preparation steps of this comparative example are the same as those of Example 1, except that: barium sulfate is not added to the permeable marble glaze of this comparative example, and the dosage of barium carbonate is increased to 3 parts, and the dosage of talc is increased to 3 parts.

[0061] The marble tiles prepared in Example 1 and Comparative Examples 1-3 were subjected to performance tests, and the specific test results are shown in the following table:

[0062]

[0063]

[0064] Note: The acid and alkali resistance grade is detected according to the national standard GB / T 1766. The stain resistance grade is detected according to the national standard GB / T 1766-1995.

[0065] It can be seen from the test results in the above table that the marble tiles prepared by this solution have excellent anti-slip and anti-stain effects at the same time, the wear resistance can be maintained above 1500 revolutions, the penetration depth of the permeable marble glaze can reach about 0.5 mm, the three-dimensional effect is good, and it also has good acid and alkali corrosion resistance characteristics, so that the marble tiles prepared by this solution have a long service life whether they are applied indoors or outdoors. Using the same preparation steps and raw materials as in Example 1, only changing the raw materials of the permeable marble glaze, multiple groups of examples were made. The pore size of the marble tile products measured was 0.05-0.09 MM, the wear resistance grade was 1500 revolutions and above, the flexural strength of the tile was at least above 40 MPa, the acid and alkali resistance grade could reach Grade A, the anti-slip grade was above R11, the erosion resistance was good, and the penetration depth was at least 0.5 mm.

[0066] From the test results of Comparative Example 1 and Example 1, it can be seen that conventional marble tiles generally use a protective glaze. When the protective glaze is replaced with the penetrating marble glaze of this solution, the abrasion resistance, flexural strength, acid and alkali resistance, and three-dimensional effect of the tiles are all improved to varying degrees. From the test results of Example 1 and Comparative Example 2, it can be seen that when the modified barium titanate frit of this solution is replaced with conventional barium titanate, the abrasion resistance, flexural strength, acid and alkali resistance, and three-dimensional effect of the obtained marble tiles are significantly reduced. From the test results of Example 1 and Comparative Example 3, it can be seen that when barium sulfate is not added to the raw materials of the penetrating marble glaze, barium zinc titanate crystals cannot be formed, and at the same time, the melting point of the raw materials is relatively high, and the melting state is not good, which is not conducive to the penetration of the glaze layer. Therefore, the abrasion resistance, flexural strength, acid and alkali erosion resistance, and three-dimensional effect of the marble tiles will also decrease.

[0067] Example 2

[0068] All the parameters and preparation steps of this example are the same as those of Example 1, except that: the conventional surface glaze is replaced with the porous rough glaze of this solution. That is, S3 is adjusted to apply the porous rough glaze on the underglaze layer after inkjet printing to obtain a porous rough glaze layer; S4 is adjusted to continue to apply the penetrating marble glaze on the porous rough glaze layer to obtain a penetrating marble glaze layer.

[0069] By weight percentage, the porous rough glaze is prepared by ball milling the following raw materials after mixing: 41% albite, 4% modified barium titanate frit, 7% kaolin, 8% zinc oxide, 11% wollastonite, 12% calcite, 8% diopside, 4% corundum, and 5% deionized water. In addition, printing paste accounting for 49% of the total amount of the above raw materials and printing oil accounting for 11% are also added.

[0070] Example 3

[0071] A preparation process of marble tiles includes the following steps:

[0072] S1. After the blank body raw materials are pressed into shape, a blank body layer is obtained;

[0073] S2. Apply an underglaze on the blank body layer to obtain an underglaze layer, and perform inkjet printing on the underglaze layer to obtain a preset pattern; by weight percentage, the underglaze is prepared by ball milling the following raw materials after mixing: 43% potassium feldspar, 18% lithium feldspar, 10% quartz, 9% limestone, 7% talc, 5% alumina, 8% zirconium silicate. When ball milling, 0.31% methyl cellulose and 0.58% sodium tripolyphosphate are additionally added to the total amount of the above raw materials;

[0074] S3. Apply a porous rough glaze on the underglaze layer after inkjet printing to obtain a porous rough glaze layer. By weight percentage, the porous rough glaze is prepared by ball milling the following raw materials after mixing: 40% albite, 4% modified barium titanate frit, 7% kaolin, 9% zinc oxide, 11% wollastonite, 13% calcite, 8% diopside, 3.5% corundum, and 4.5% deionized water. Additionally, printing paste accounting for 48% of the total amount of the above raw materials and printing oil accounting for 12% are also added.

[0075] By weight percentage, the modified barium titanate frit is prepared by melting 50% barium titanate, 20% boric acid, 20% spodumene, and 10% lithium carbonate at 1308 °C and holding for 1 h, followed by water quenching and drying.

[0076] S4. Continuously apply a penetrated marble glaze on the porous rough glaze layer to obtain a penetrated marble glaze layer. By weight percentage, the penetrated marble glaze is prepared by ball milling the following raw materials after mixing: 27 parts nepheline syenite, 14 parts wollastonite, 10 parts modified barium titanate frit (the production process is the same as that of the modified barium titanate frit in step S3), 6 parts ball clay, 12 parts zinc oxide, 3 parts barium sulfate, 16 parts quartz, 8 parts dolomite, 2 parts talc, 2 parts barium carbonate, 10 parts penetrant, 5 parts binder, and 10 parts deionized water; the penetrant is an aqueous solution of triethanolamine, including 70% triethanolamine and 30% deionized water; the binder is an aqueous solution of cyanoacrylate, including 66% aqueous cyanoacrylate solution and 34% deionized water.

[0077] S5. Fire at 1190 °C for 65 min and then polish to obtain the marble tile.

[0078] Example 4

[0079] A preparation process of a marble tile, comprising the following steps:

[0080] S1. After the green body raw materials are pressed into shape, a green body layer is obtained.

[0081] S2. Apply an underglaze on the green body layer to obtain an underglaze layer, and perform inkjet printing on the underglaze layer to obtain a preset pattern. By weight percentage, the underglaze is prepared by ball milling the following raw materials after mixing: 38% potassium feldspar, 19% lithium feldspar, 16% quartz, 9% limestone, 5% talc, 5% alumina, 8% zirconium silicate. When ball milling, 0.30% methyl cellulose and 0.56% sodium tripolyphosphate are additionally added to the total amount of the above raw materials.

[0082] S3. Apply a porous rough glaze on the underglaze layer after inkjet printing to obtain a porous rough glaze layer. By weight percentage, the porous rough glaze is prepared by ball milling the following raw materials after mixing: 40% albite, 3% modified barium titanate frit, 7% kaolin, 10% zinc oxide, 13% wollastonite, 12% calcite, 8% diopside, 3% corundum, 4% deionized water; in addition, printing paste accounting for 45% of the total amount of the above raw materials and printing oil accounting for 15% are also added.

[0083] By weight percentage, the modified barium titanate frit is prepared by melting 60% barium titanate, 15% boric acid, 20% lithium porcelain stone, and 5% lithium carbonate at 1300 °C, holding for 2 h, then quenching with water and drying.

[0084] S4. Continuously apply a penetrating marble glaze on the porous rough glaze layer to obtain a penetrating marble glaze layer. By weight percentage, the penetrating marble glaze is prepared by ball milling the following raw materials after mixing: 25 parts nepheline syenite, 14 parts wollastonite, 10 parts modified barium titanate frit (the production process is the same as that of the modified barium titanate frit in step S3), 6 parts ball clay, 10 parts zinc oxide, 5 parts barium sulfate, 16 parts quartz, 10 parts dolomite, 2 parts talc, 2 parts barium carbonate, 10 parts penetrant, 5 parts binder, 10 parts deionized water. The penetrant is an aqueous solution of triethanolamine, including 80% triethanolamine and 20% deionized water; the binder is an aqueous solution of cyanoacrylate, including 7-% aqueous solution of cyanoacrylate and 30% deionized water.

[0085] S5. Fire at 1193 °C for 68 min and then polish to obtain the marble tile.

[0086] Comparative Example 4

[0087] All parameters and preparation steps of this comparative example are the same as those of Example 4, except that: the penetrant - triethanolamine is not added to the raw materials of the penetrating marble glaze, and the other raw materials and dosages remain unchanged.

[0088] Perform performance tests on the marble tiles prepared in Examples 2 - 4 and Comparative Example 4. The specific test results are shown in the following table:

[0089]

[0090]

[0091] From the test results of Example 1 and Examples 2 - 4, it can be seen that when the porous rough glaze and the penetrating marble glaze in this solution are successively applied on the underglaze, the double - layer effect can play a more efficient protective layer role, making the ceramic tile have better anti - slip characteristics, wear resistance and more excellent texture sense, and the three - dimensional decorative effect is better.

[0092] From the test results of Example 2 and Comparative Example 4, it can be seen that when the penetrant - triethanolamine is not added to the raw materials of the penetrating marble glaze, it cannot react with the modified barium titanate frit in the above glaze formula to generate barium ion salt, and the wear - resistance and anti - slip performance of the ceramic tile are reduced.

[0093] Example 5

[0094] All the parameters and preparation steps of this example are the same as those of Example 4, except that: the raw material dosages of the modified barium titanate frit are different, as shown in the following table:

[0095]

[0096] Comparative Example 5

[0097] All the parameters and preparation steps of this comparative example are the same as those of Example 4, except that: the raw materials of the modified barium titanate frit do not contain boric acid, and the dosage of barium titanate is increased to 78%.

[0098] Comparative Example 6

[0099] All the parameters and preparation steps of this comparative example are the same as those of Example 4, except that: the raw materials of the modified barium titanate frit do not contain lithium carbonate, and the dosage of barium titanate is increased to 66%.

[0100] The performance of the marble ceramic tile prepared in Example 5 was tested, and the specific test results are shown in the following table:

[0101]

[0102]

[0103] From the test results in the above table, it can be seen that the raw materials and their dosages of the modified barium titanate frit have a great influence on the performance of the marble ceramic tile. Only when barium titanate, boric acid, spodumene and lithium carbonate co - exist can the modified barium titanate frit required by this scheme be formed. The preferred dosages of each raw material are 52 - 60% barium titanate, 17 - 18% boric acid, 15 - 16% spodumene and 6 - 8% lithium carbonate. The most preferred are 60% barium titanate, 18% boric acid, 16% spodumene and 6% lithium carbonate. At this time, the anti - pollution, anti - slip, wear - resistance and three - dimensional effects of the marble ceramic tile are better.

[0104] Example 6

[0105] All the parameters and preparation steps of this example are the same as those of Example 4, except that: the raw material dosages of the modified barium titanate frit are different, as shown in the following table:

[0106] Melting temperature Holding time Example 4 1300℃ 2h Example 6-1 1303℃ 2h Example 6-2 1305℃ 1.5h Example 6-3 1308℃ 1.3h Example 6-4 1310℃ 1h Example 6-5 1280℃ 2h Example 6-6 1316℃ 1.5h

[0107] The marble tiles prepared in Example 6 were subjected to performance testing, and the specific test results are shown in the following table:

[0108]

[0109]

[0110] As can be seen from the test results in the above table, the melting parameters of the modified barium titanate frit are also relatively important, which determine the corresponding properties of the modified barium titanate frit. The preferred melting parameter range of this solution is a melting temperature of 1300 - 1305 °C and a holding time of 1 - 2 h. Within this preferred range, the modified barium titanate frit has stable performance, superior mechanical properties, and strong applicability, and the anti-fouling, anti-slip, and erosion resistance of the marble tiles are improved.

[0111] Example 7

[0112] A preparation process of marble tiles includes the following steps:

[0113] S1. After the green body raw materials are pressed into shape, a green body layer is obtained;

[0114] S2. A base glaze is applied on the green body layer to obtain a base glaze layer, and inkjet printing is performed on the base glaze layer to obtain a preset pattern; by weight percentage, the base glaze is prepared by ball milling the following raw materials after mixing: potassium feldspar 45%, lithium feldspar 12%, quartz 10%, limestone 8%, talc 5%, alumina 5%, zirconium silicate 15%;

[0115] S3. A porous rough glaze is applied on the inkjet-printed base glaze layer to obtain a porous rough glaze layer; by weight percentage, the porous rough glaze is prepared by ball milling the following raw materials after mixing: sodium feldspar 42%, modified barium titanate frit 6%, kaolin 4%, zinc oxide 6%, wollastonite 12%, calcite 12%, diopside 12%, corundum 2% and deionized water 4%;

[0116] By weight percentage, the modified barium titanate frit is prepared by melting 60% of barium titanate, 18% of boric acid, 16% of lithium porcelain stone, and 6% of lithium carbonate at 1305 °C and holding for 1.6 h, and then quenching with water and drying.

[0117] S4. Continuously apply permeable marble glaze on the porous rough glaze layer to obtain a permeable marble glaze layer. It is prepared by ball milling the following raw materials after mixing them by weight percentage: 25 parts of nepheline, 12 parts of wollastonite, 10 parts of modified barium titanate frit, 6 parts of ball clay, 8 parts of zinc oxide, 3 parts of barium sulfate, 15 parts of quartz, 8 parts of dolomite, 1 part of talc, 2 parts of barium carbonate, 10 parts of penetrant, 5 parts of binder, and 10 parts of deionized water. The penetrant is an aqueous solution of triethanolamine, including 79% triethanolamine and 21% deionized water. The binder is an aqueous solution of cyanoacrylate, including 68% aqueous cyanoacrylate solution and 32% deionized water.

[0118] S5. Fire at 1190 - 1200 °C for 60 - 70 min and then polish to obtain the marble tile.

[0119] Perform performance tests on the marble tile prepared in Example 7. The specific test results are shown in the following table:

[0120]

[0121] It can be seen from the test results in the above table that in this solution, by using special porous rough glaze and permeable marble glaze, and determining the preferred raw materials and addition amounts of the above glazes, especially using modified barium titanate frit, through optimizing the raw materials and melting parameters of the modified barium titanate frit, the anti-slip grade of the marble tile can reach above R11, the pore size is about 0.05 MM, the erosion resistance is relatively good, the flexural strength is 42 MPa, the water absorption rate is 0.3%, the abrasion resistance test can withstand 2100 revolutions, the hardness grade reaches 6, and the acid and alkali resistance grade reaches AA, and it also has a better three-dimensional effect.

[0122] The above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. All equivalent structural transformations made under the inventive concept of the present invention by using the content of the specification of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A penetrating marble glaze, characterized in that, It is prepared by ball milling after uniformly mixing the following raw materials by weight parts: 25-35 parts of nepheline, 12-16 parts of wollastonite, 6-10 parts of modified barium titanate frit, 6-13 parts of ball clay, 8-12 parts of zinc oxide, 3-6 parts of barium sulfate, 15-20 parts of quartz, 8-13 parts of dolomite, 1-2 parts of talc, 2-8 parts of barium carbonate, 10-20 parts of penetrant, 5-10 parts of binder and 10-15 parts of deionized water; By weight percentage, the modified barium titanate frit is prepared by melting, water quenching and drying the following raw materials: 50-60% of barium titanate, 15-20% of boric acid, 10-20% of lithium porcelain stone and 5-10% of lithium carbonate.

2. The penetrating marble glaze according to claim 1, wherein The temperature during melting is 1300-1310 °C, and it is kept at this melting temperature for 1-2 h.

3. The penetrating marble glaze according to claim 1, wherein The penetrant is an aqueous solution of triethanolamine; By weight percentage, the aqueous solution of triethanolamine comprises 70-80% of triethanolamine and 20-30% of deionized water.

4. The penetrating marble glaze according to claim 1, characterized in that, The binder is an aqueous solution of cyanoacrylate; By weight percentage, the aqueous solution of cyanoacrylate comprises 60-70% of aqueous cyanoacrylate solution and 30-40% of deionized water.

5. A preparation process of marble tiles, characterized in that, It includes the following steps: S1. After the green body raw materials are pressed into shape, a green body layer is obtained; S2. Apply a base glaze on the green body layer to obtain a base glaze layer, and perform inkjet printing on the base glaze layer to obtain a preset pattern; S3. Apply a porous rough glaze on the inkjet-printed base glaze layer to obtain a porous rough glaze layer; S4. Continuously apply the penetrated marble glaze as described in any one of claims 1-4 on the porous rough glaze layer to obtain a penetrated marble glaze layer; S5. After firing, polish to obtain the marble tile.

6. The preparation process of the marble tile according to claim 5, characterized in that, By weight percentage, the porous rough glaze is prepared by ball milling after uniformly mixing the following raw materials: 40-45% of albite, 3-6% of modified barium titanate frit, 4-8% of kaolin, 6-10% of zinc oxide, 11-20% of wollastonite, 12-15% of calcite, 6-12% of diopside, 2-6% of corundum and 1-5% of deionized water.

7. The preparation process of the marble tile according to claim 5, characterized in that, By weight percentage, the base glaze is prepared by ball milling after uniformly mixing the following raw materials: 35-45% of potassium feldspar, 11-20% of lithium feldspar, 10-20% of quartz, 8-15% of limestone, 3-10% of talc, 5-10% of alumina, 8-15% of zirconium silicate.

8. The preparation process of the marble tile according to claim 5, characterized in that, The firing temperature in step S5 is 1190-1200 °C, and the firing time is 60-70 min.

9. A marble tile, characterized in that, Prepared by the preparation process of the marble tile as described in any one of claims 5-8, and the marble tile includes a green body layer, a base glaze layer, an inkjet pattern layer, a porous rough glaze layer and a penetrated marble glaze layer from bottom to top.

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