Marble-imitated recarved glaze, preparation method thereof and application of marble-imitated recarved glaze in preparation of marble-imitated ceramic tiles

Abstract

The invention relates to marble-imitated reengraved glaze, a preparation method thereof and application of the marble-imitated reengraved glaze in preparation of marble-imitated ceramic tiles. The reengraved glaze comprises dry particles, glaze slip and a suspending agent in a mass ratio of (0.2-0.6): (0.5-0.8): 1, the glaze slip comprises a dry powder glaze material and water in a mass ratio of 100: (40-50), and the dry powder glaze material comprises 15-20 parts of albite, 15-20 parts of potassium feldspar, 20-25 parts of a modified kaolin-aluminum borate whisker compound, 5-8 parts of dolomite, 5-10 parts of calcium borate, 5-10 parts of strontium carbonate and 5-10 parts of barium carbonate. According to the marble-imitated recarving glaze disclosed by the invention, through the synergistic effect of multiple components, the wear resistance of a glaze surface is remarkably improved, and a high-performance ceramic tile with a marble-imitated effect is finally obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic tile glazes, in particular to a marble-imitating transfer glaze and a preparation method thereof and application thereof in preparing marble-imitating ceramic tiles. BACKGROUND

[0002] Marble-imitating ceramic tiles can perfectly reproduce the unique charm of natural marble due to their highly realistic texture, rich and varied colors, delicate and natural texture, warm and comfortable touch, and excellent visual effects, and are far superior to natural stone in terms of decorative effect. In particular, with the advent and widespread use of full-polished glazes and inkjet technology, these advanced technologies have endowed marble-imitating ceramic tiles with more realistic expression, enabling them to rapidly stand out in the market and win the favor and recognition of consumers.

[0003] However, the glaze surface of existing marble ceramic tiles has a fatal flaw that cannot be ignored, that is, poor wear resistance. During daily use, due to frequent friction, collision and other wear factors, the originally bright and new ceramic tile surface is easily scratched. These scratches not only damage the overall aesthetics of the ceramic tile, but also seriously affect its gloss and surface effect, greatly shortening the service life of the ceramic tile. Therefore, how to effectively improve the wear resistance of marble-imitating ceramic tiles has become a major problem that needs to be solved in the ceramic industry. SUMMARY

[0004] The present application aims to overcome the shortcomings of the prior art and provide a marble-imitating transfer glaze, a preparation method thereof and application thereof in preparing marble-imitating ceramic tiles.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows:

[0006] In a first aspect, the present application provides a marble-imitating transfer glaze, which comprises dry particles, glaze slurry and suspending agent in a mass ratio of (0.2-0.6):(0.5-0.8):1; the glaze slurry comprises dry powder glaze and water in a mass ratio of 100:40-50, and the dry powder glaze comprises the following raw materials in parts by weight: 15-20 parts of sodium feldspar, 15-20 parts of potassium feldspar, 20-25 parts of modified kaolin-aluminum borate whisker compound, 5-8 parts of dolomite, 5-10 parts of calcium borate, and 5-10 parts of strontium carbonate.

[0007] The preparation method of the modified kaolin-aluminum borate whisker compound comprises the following steps:

[0008] (1) zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water are mixed to carry out hydrolytic polymerization reaction to obtain a suspension; wherein the mass ratio of the zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water is 1:(1-4):(1-4):(1-2):(200-300);

[0009] (2) the suspension obtained in step (1) is stirred and mixed with kaolin, and then is left to stand, filtered, and the obtained solid is heat treated to obtain modified kaolin; wherein the solid-liquid ratio of the kaolin and the suspension is (0.1-0.15) g:1 mL;

[0010] (3) the modified kaolin obtained in step (2) is cooled to room temperature, and then is stirred and mixed with aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate, and then is washed with water, suction filtered and dried to obtain the modified kaolin-aluminum borate whisker compound; wherein the mass ratio of the modified kaolin, aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate is (1-6):(1-5):(6-10):(2-3), and the mass concentration of the chitosan solution is 5-10%.

[0011] In the preparation method of the modified kaolin-aluminum borate whisker compound of the application, in step (1), zinc acetate, manganese nitrate, magnesium nitrate and triethanolamine are mixed in water to perform hydrolysis polymerization reaction. The hydroxyl groups of triethanolamine and zinc ions, manganese ions and magnesium ions form a stable suspension containing polymeric zinc hydroxide, polymeric manganese hydroxide and polymeric magnesium hydroxide through coordination. In step (2), the suspension is mixed with kaolin to stir, so that the polymeric zinc hydroxide, polymeric manganese hydroxide and polymeric magnesium hydroxide are loaded on the kaolin to obtain modified kaolin. The specific mechanism is as follows: the surface of kaolin is negatively charged, which attracts the positively charged polymeric zinc hydroxide ions, polymeric manganese hydroxide ions and polymeric magnesium hydroxide ions. At the same time, the hydroxyl groups (—OH) of the polymeric zinc hydroxide, polymeric manganese hydroxide and polymeric magnesium hydroxide form a hydrogen bond network with the silicon hydroxyl groups (Si—OH) or aluminum hydroxyl groups (Al—OH) on the surface of kaolin to achieve stable loading. When the glaze is sintered later, the polymeric zinc hydroxide, polymeric manganese hydroxide and polymeric magnesium hydroxide on the surface of kaolin will decompose into zinc oxide, manganese oxide and magnesium oxide, respectively. Among them, zinc oxide is a strong flux, which can reduce the melting point of the glaze, promote the formation of silicate glass phase, and the uniform distribution of the glass phase can promote the densification of the glaze surface. Moreover, zinc oxide reacts with aluminum to form zinc aluminum spinel, which has high hardness and can effectively improve the wear resistance and hardness of the glaze surface; manganese oxide can react with aluminum, silicon and other elements in the glaze to form manganese spinel and other high-hardness crystal structures, which are uniformly distributed in the glaze layer, significantly improving the density and hardness of the glaze surface; magnesium oxide can also enhance the structural strength of the glass phase, reduce the internal stress of the glaze during the cooling process, and reduce the risk of cracking. Moreover, MgO can promote the formation of fine olivine (Mg2SiO4) crystals in the glaze layer. When these crystals are uniformly dispersed, they can simulate the "crystalline spots" in natural marble, enhance the natural texture, and at the same time, the high melting point property of olivine can improve the heat resistance of the glaze. The process of the modified kaolin of the application can avoid the composition segregation caused by directly doping kaolin, zinc oxide, manganese oxide and magnesium oxide in the traditional way, and ensure the uniform distribution of the reinforcing phase in the glaze.

[0012] In step (3), the modified kaolin is heat-treated at 150-160℃, which can remove the surface adsorbed water (or weakly bound water) to expose more Si—OH and Al—OH groups that were originally covered, thereby increasing the active sites. Chitosan is rich in amino groups (-NH2) and hydroxyl groups (-OH), which can form a hydrogen bond network with the surface hydroxyl groups of kaolin and wrap the aluminum borate whiskers, achieving interfacial toughening. Sodium dodecyl benzene sulfonate reduces the interfacial energy and generates electrostatic repulsion, preventing the agglomeration of modified kaolin and aluminum borate whisker particles and ensuring uniform dispersion. The hydrogen bonds between the hydroxyl groups on the surface of chitosan solution (containing amino and hydroxyl groups) and the hydroxyl groups on the surface of kaolin and aluminum borate whiskers, combined with the surface activity of sodium dodecyl benzene sulfonate, reduce the interfacial tension between modified kaolin and aluminum borate whiskers, allowing them to disperse uniformly in the glaze and tightly bond with the glass phase, avoiding particle detachment due to interfacial separation during rubbing. During sintering, aluminum borate whiskers fill micropores, reducing pinholes and glaze bubbles, and improving wear resistance. Their high thermal conductivity promotes uniform temperature distribution during firing, avoiding local overfiring. Aluminum borate whiskers align in the glaze layer, simulating the mineral fiber structure of natural marble and enhancing the texture and levelness.

[0013] After sintering, the marble-like replica glaze of the present application forms a low-viscosity glass phase with fluxes such as sodium feldspar and potassium feldspar in the glaze, and calcium borate and strontium carbonate as fluxing agents, which reduce the glass phase melting point and refine the grain size, reducing the scattering effect of glaze crystallization on gloss, further enhancing the mirror effect. Dolomite introduces CaO and MgO, improving glaze layer hardness and crack resistance, adjusting the thermal expansion coefficient, and reducing body-glaze stress. The polymeric zinc hydroxyl, polymeric manganese hydroxyl, and polymeric magnesium hydroxyl in the modified kaolin-aluminum borate whisker compound decompose ZnO and MnO at high temperatures, and ZnO and MnO act as hard points to improve the scratch resistance of the glaze surface. The "hard point-lamella" composite reinforcement is formed by the lamellar structure of kaolin and ZnO and MnO, and the lamellar kaolin buffers the friction stress through the sliding effect, both of which synergistically reduce the wear rate. Moreover, aluminum borate whiskers partially liquefy at high temperatures, filling the grain boundary voids and forming a structure of needle-like whiskers covering the grains, further improving wear resistance.

[0014] Preferably, in step (1) of preparing the modified kaolin-aluminum borate whisker compound, the temperature of the hydrolysis polymerization reaction is 30-50℃, the rotation speed is 500-600 rpm, and the time is 2-4 h.

[0015] Preferably, the mass ratio of zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine, and deionized water is 1:(3-4):(2-3):(1-2):(200-300).

[0016] Preferably, in the preparation step (2) of the modified kaolin-aluminum borate whisker compound, the stirring speed of the mixed materials is 500-600 rpm, and the stirring time is 6-8 h; the temperature of the standing is 20-50℃, and the standing time is 5-7 h; the temperature of the heat treatment is 150-160℃, and the heat treatment time is 10-20 min.

[0017] Preferably, the mass ratio of the modified kaolin, aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate is (2-4) : (1-3) : (6-10) : (2-3).

[0018] Preferably, in the preparation step (3) of the modified kaolin-aluminum borate whisker compound, the stirring speed of the mixed materials is 500-600 rpm, and the stirring time is 1-2 h.

[0019] Preferably, the dry particles comprise the following raw materials in parts by weight: 25-35 parts of sodium feldspar, 5-10 parts of potassium feldspar, 10-15 parts of nepheline powder, 6-10 parts of calcined aluminum oxide, 5-8 parts of calcined zinc oxide and 18-25 parts of barium carbonate.

[0020] Preferably, the suspending agent is sodium carboxymethyl cellulose.

[0021] In a second aspect, the application provides an application of the marble-imitating overglaze in the first aspect in the preparation of marble-imitating ceramic tiles.

[0022] In a third aspect, the application provides a marble-imitating ceramic tile, which comprises, from bottom to top, a body, a surface glaze layer, an inkjet printing layer and an overglaze layer; wherein the overglaze layer is obtained by sintering the marble-imitating overglaze according to any one of claims 1-5.

[0023] In a fourth aspect, the application provides a preparation method of the marble-imitating ceramic tile in the third aspect, comprising the following steps:

[0024] S1, uniformly mixing raw materials of dry particles, melting at 1350-1450℃, water quenching, ball milling, drying, and sieving to obtain the dry particles;

[0025] S2, uniformly ball milling the mixed sodium feldspar, potassium feldspar, modified kaolin-aluminum borate whisker compound, dolomite, calcium borate, strontium carbonate and barium carbonate according to the formula amount to obtain dry powder glaze, and uniformly mixing the dry powder glaze with water according to the formula amount to obtain the glaze slurry;

[0026] S3, mixing the dry particles, the glaze slurry and the suspending agent according to the formula amount to obtain the marble-imitating overglaze;

[0027] S4, applying a surface glaze on the green body to obtain a surface glaze layer, performing inkjet printing on the surface glaze layer to obtain an inkjet printing layer, and applying a marble-imitating transfer glaze on the inkjet printing layer and performing sintering treatment to obtain the marble-imitating ceramic tile; wherein the sintering treatment is performed at a temperature of 1200-1400 DEG C for 2-4 hours.

[0028] Preferably, in steps S1 and S2, the rotation speed of the ball mill is 1400-1600 r / min, and the time is 40-60 min.

[0029] Preferably, in step S4, the application amount of the marble-imitating transfer glaze is 400-600 g / m 2 .

[0030] Compared with the prior art, the present application has the following advantages:

[0031] The modified kaolin-aluminum borate whisker compound of the present application first hydrolyzes zinc acetate, manganese nitrate and magnesium nitrate into polymeric zinc hydroxide, polymeric manganese hydroxide and polymeric magnesium hydroxide through hydrolysis polymerization, and then loads the polymeric zinc hydroxide, polymeric manganese hydroxide and polymeric magnesium hydroxide into kaolin through electrostatic adsorption and hydrogen bonding to obtain modified kaolin; then the modified kaolin is blended with aluminum borate whiskers, chitosan solution and sodium dodecylbenzenesulfonate, so that the aluminum borate whiskers are inserted into the interlayer of the kaolin as a rigid skeleton, which not only ensures the skeleton strengthening effect of the whiskers, but also fills the interstices between the whiskers through the lamellar structure of the kaolin to form a continuous strengthening network, thereby improving the wear resistance of the glaze surface. After subsequent calcination of the glaze at high temperature, the polymeric zinc hydroxide, polymeric manganese hydroxide and polymeric magnesium hydroxide on the surface of the kaolin are decomposed into zinc oxide, manganese oxide and magnesium oxide, respectively, avoiding the composition segregation caused by the traditional direct doping of kaolin, zinc oxide, manganese oxide and magnesium oxide, and ensuring the uniform distribution of the reinforcing phase in the glaze, thereby improving the gloss and wear resistance of the glaze. The marble-imitating transfer glaze of the present application realizes a significant improvement in the wear resistance of the glaze surface through the synergistic effect of multiple components, and finally obtains a high-performance glaze surface that imitates marble. DETAILED DESCRIPTION

[0032] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in conjunction with specific examples.

[0033] Unless otherwise specified, other materials, reagents, etc. used in the examples and comparative examples can be obtained from commercial channels.

[0034] Example 1

[0035] A marble-imitating replica glaze, the replica glaze comprising dry particles, glaze slurry and suspending agent in a mass ratio of 0.5:0.6:1; the glaze slurry comprising dry powder glaze and water in a mass ratio of 100:45, the dry powder glaze comprising raw materials in parts by weight: 17 parts of sodium feldspar, 18 parts of potassium feldspar, 22 parts of modified kaolin-aluminum borate whisker compound, 7 parts of dolomite, 8 parts of calcium borate, 7 parts of strontium carbonate; the dry particles comprising raw materials in parts by weight: 30 parts of sodium feldspar, 8 parts of potassium feldspar, 12 parts of nepheline powder, 9 parts of calcined aluminum oxide, 6 parts of calcined zinc oxide and 21 parts of barium carbonate, and the suspending agent being sodium carboxymethyl cellulose;

[0036] A preparation method of the modified kaolin-aluminum borate whisker compound, comprising the following steps:

[0037] (1) mixing zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water and then performing hydrolysis polymerization reaction to obtain a suspension; wherein the mass ratio of the zinc acetate, the manganese nitrate, the magnesium nitrate, the triethanolamine and the deionized water is 1:4:2:1:258; wherein the hydrolysis polymerization reaction is performed at a temperature of 40℃, a rotation speed of 550rpm and for a time of 3h;

[0038] (2) stirring and mixing the suspension obtained in step (1) with kaolin, standing, filtering, and heat treating the obtained solid to obtain modified kaolin; wherein the solid-liquid ratio of the kaolin and the suspension is 0.12g:1mL, the stirring is performed at a rotation speed of 550rpm for a time of 7h, the standing is performed at a temperature of 30℃ for a time of 6h, and the heat treatment is performed at a temperature of 155℃ for a time of 15min;

[0039] (3) after the modified kaolin obtained in step (2) is cooled to room temperature, stirring and mixing the modified kaolin with aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate, washing with water, suction filtering and drying to obtain the modified kaolin-aluminum borate whisker compound; wherein the mass ratio of the modified kaolin, the aluminum borate whisker, the chitosan solution and the sodium dodecyl benzene sulfonate is 3:2:8:2.5, the mass concentration of the chitosan solution is 8%, and the stirring and mixing is performed at a rotation speed of 550rpm for a time of 1.5h.

[0040] Example 2

[0041] A marble-imitating replica glaze, the replica glaze comprising dry particles, glaze slurry and suspending agent in a mass ratio of 0.2:0.5:1; the glaze slurry comprising dry powder glaze and water in a mass ratio of 100:40, the dry powder glaze comprising raw materials in parts by weight: sodium feldspar 15 parts, potassium feldspar 15 parts, modified kaolin-aluminum borate whisker compound 20 parts, dolomite 5 parts, calcium borate 5 parts, strontium carbonate 5 parts; the dry particles comprising raw materials in parts by weight: sodium feldspar 25 parts, potassium feldspar 5 parts, nepheline powder 10 parts, calcined aluminum oxide 6 parts, calcined zinc oxide 5 parts and barium carbonate 18 parts, the suspending agent being sodium carboxymethyl cellulose;

[0042] A preparation method of the modified kaolin-aluminum borate whisker compound, comprising the following steps:

[0043] (1) mixing zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water and then performing hydrolysis polymerization reaction to obtain a suspension; wherein the mass ratio of the zinc acetate, the manganese nitrate, the magnesium nitrate, the triethanolamine and the deionized water is 1:3:3:1:200; wherein the temperature of the hydrolysis polymerization reaction is 30℃, the rotation speed is 500rpm, and the time is 4h;

[0044] (2) stirring and mixing the suspension obtained in step (1) with kaolin, standing, filtering, and heat treating the solid obtained by filtering to obtain modified kaolin; wherein the solid-liquid ratio of the kaolin and the suspension is 0.1g:1mL, the stirring rotation speed is 500rpm, the stirring time is 8h, the standing temperature is 20℃, the standing time is 7h, the heat treatment temperature is 150℃, and the heat treatment time is 20min;

[0045] (3) after the modified kaolin obtained in step (2) is cooled to room temperature, stirring and mixing the modified kaolin with aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate, washing with water, suction filtering and drying to obtain the modified kaolin-aluminum borate whisker compound; wherein the mass ratio of the modified kaolin, the aluminum borate whisker, the chitosan solution and the sodium dodecyl benzene sulfonate is 2:1:6:2, the mass concentration of the chitosan solution is 5%, and the stirring and mixing rotation speed is 500rpm and the stirring and mixing time is 2h.

[0046] Example 3

[0047] A marble-imitating replica glaze, the replica glaze comprising dry particles, glaze slurry and suspending agent in a mass ratio of 0.6:0.8:1; the glaze slurry comprising dry powder glaze material and water in a mass ratio of 100:50, the dry powder glaze material comprising raw materials in parts by weight of 20 parts of sodium feldspar, 20 parts of potassium feldspar, 25 parts of modified kaolin-aluminum borate whisker compound, 8 parts of dolomite, 10 parts of calcium borate, 10 parts of strontium carbonate; the dry particles comprising raw materials in parts by weight of 35 parts of sodium feldspar, 10 parts of potassium feldspar, 15 parts of nepheline powder, 10 parts of calcined alumina, 8 parts of calcined zinc oxide and 25 parts of barium carbonate, and the suspending agent being sodium carboxymethyl cellulose;

[0048] A preparation method of the modified kaolin-aluminum borate whisker compound, comprising the following steps:

[0049] (1) mixing zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water and then performing hydrolysis polymerization reaction to obtain a suspension; wherein the mass ratio of the zinc acetate, the manganese nitrate, the magnesium nitrate, the triethanolamine and the deionized water is 1:4:3:2:300; wherein the temperature of the hydrolysis polymerization reaction is 50℃, the rotation speed is 600rpm and the time is 2h;

[0050] (2) stirring and mixing the suspension obtained in step (1) with kaolin, standing, filtering, and performing heat treatment on the solid obtained by filtering to obtain modified kaolin; wherein the solid-liquid ratio of the kaolin and the suspension is 0.15g:1mL, the stirring rotation speed is 600rpm and the time is 6h; the standing temperature is 50℃ and the time is 5h, and the heat treatment temperature is 160℃ and the time is 15min;

[0051] (3) after the modified kaolin obtained in step (2) is cooled to room temperature, stirring and mixing the modified kaolin with aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate, washing with water, suction filtering and drying to obtain the modified kaolin-aluminum borate whisker compound; wherein the mass ratio of the modified kaolin, the aluminum borate whisker, the chitosan solution and the sodium dodecyl benzene sulfonate is 4:3:10:3, the mass concentration of the chitosan solution is 10%, the stirring and mixing rotation speed is 600rpm and the time is 1h.

[0052] Example 4

[0053] Example 4 differs from Example 1 only in that in the preparation step (3) of the modified kaolin-aluminum borate whisker compound, the total mass of the modified kaolin, the aluminum borate whisker, the chitosan solution and the sodium dodecyl benzene sulfonate remains unchanged, and the mass ratio of the modified kaolin, the aluminum borate whisker, the chitosan solution and the sodium dodecyl benzene sulfonate is 1:5:8:2.5.

[0054] Example 5

[0055] Example 5 differs from Example 1 only in that the total mass of the modified kaolin, aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate is unchanged, and the mass ratio of the modified kaolin, aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate is 6:1:8:2.5.

[0056] Example 6

[0057] Example 6 differs from Example 1 only in that the total mass of the zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water is unchanged, and the mass ratio of the zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water is 1:4:1:2:258.

[0058] Example 7

[0059] Example 7 differs from Example 1 only in that the total mass of the zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water is unchanged, and the mass ratio of the zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water is 1:1:4:2:258.

[0060] Comparative Example 1

[0061] Comparative Example 1 differs from Example 1 only in that the modified kaolin-aluminum borate whisker compound is not added in the dry powder glaze.

[0062] Comparative Example 2

[0063] Comparative Example 2 differs from Example 1 only in that the modified kaolin-aluminum borate whisker compound is replaced with an equal amount of modified kaolin; wherein the preparation method of the modified kaolin comprises the following steps:

[0064] (1) mixing zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water and then performing hydrolysis polymerization reaction to obtain a suspension; wherein the mass ratio of zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water is 1:4:2:1:258; wherein the temperature of the hydrolysis polymerization reaction is 40°C, the rotation speed is 550 rpm, and the time is 3h;

[0065] (2) stirring and mixing the suspension obtained in step (1) with kaolin, standing, filtering, and heat treating the solid obtained by filtering to obtain modified kaolin; wherein the solid-liquid ratio of the kaolin and the suspension is 0.12g:1mL, the stirring rotation speed is 550 rpm, and the time is 7h; the standing temperature is 30°C, and the time is 6h; the heat treatment temperature is 155°C, and the time is 15min.

[0066] Comparative Example 3

[0067] Comparative Example 3 differs from Example 1 only in that the modified kaolin-aluminum borate whisker compound is replaced with an equal amount of kaolin compound aluminum borate whisker, wherein the preparation method of the kaolin compound aluminum borate whisker comprises the following steps:

[0068] (1) heat treating kaolin at 155°C for 15 min to obtain heat-treated kaolin;

[0069] (2) cooling the kaolin obtained in step (1) to room temperature, stirring and mixing the kaolin with aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate, washing with water, suction filtering and drying to obtain the kaolin-aluminum borate whisker compound; wherein the mass ratio of the kaolin, aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate is 3:2:8:2.5, the mass concentration of the chitosan solution is 8%, and the stirring and mixing speed is 550 rpm for 1.5 h.

[0070] Comparative Example 4

[0071] Comparative Example 4 differs from Example 1 only in that the preparation method of the modified kaolin-aluminum borate whisker compound comprises the following steps:

[0072] (1) heat treating kaolin at 155°C for 15 min, cooling to room temperature, then stirring and mixing the kaolin with aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate, washing with water, suction filtering and drying to obtain the kaolin-aluminum borate whisker compound; wherein the mass ratio of the kaolin, aluminum borate whisker, chitosan solution and sodium dodecyl benzene sulfonate is 3:2:8:2.5, the mass concentration of the chitosan solution is 8%, and the stirring and mixing speed is 550 rpm for 1.5 h;

[0073] (2) mixing zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water and then performing hydrolysis polymerization to obtain a suspension; wherein the mass ratio of zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water is 1:4:2:1:258; wherein the hydrolysis polymerization temperature is 40°C, the stirring speed is 550 rpm, and the time is 3 h;

[0074] (3) stirring and mixing the suspension with the kaolin-aluminum borate whisker compound, standing, filtering, and heat treating the obtained solid to obtain the modified kaolin-aluminum borate whisker compound; wherein the solid-liquid ratio of the kaolin compound aluminum borate whisker and the suspension is 0.12 g:1 mL, the stirring speed is 550 rpm, the time is 7 h; the standing temperature is 30°C, the time is 6 h; and the heat treatment temperature is 155°C, the time is 15 min.

[0075] Comparative Example 5

[0076] The difference between Comparative Example 5 and Example 1 is only that in the preparation step (1) of the modified kaolin-aluminum borate whisker compound, no manganese nitrate is added, and an equivalent amount of magnesium nitrate is used to make up the missing amount.

[0077] Comparative Example 6

[0078] The difference between Comparative Example 6 and Example 1 is only that in the preparation step (1) of the modified kaolin-aluminum borate whisker compound, no magnesium nitrate is added, and an equivalent amount of manganese nitrate is used to make up the missing amount.

[0079] Application Examples 1-7 and Comparative Application Examples 1-6

[0080] The marble-imitating ceramic tiles of Application Examples 1-7 and Comparative Application Examples 1-6 include a body and a glaze layer covering the surface of the body, and the glaze layer is sintered from the marble-imitating overglaze of Examples 1-7 and Comparative Examples 1-6.

[0081] The preparation method of the marble-imitating ceramic tiles of Application Examples 1-7 and Comparative Application Examples 1-6 includes the following steps:

[0082] S1, uniformly mix the dry particles of the raw materials, melt at 1400°C, quench in water, ball mill, dry, and pass through a 20-mesh sieve to obtain the dry particles; wherein the ball milling speed is 1500 r / min, the time is 60 min, the drying temperature is 75°C, and the time is 20 min;

[0083] S2, mix sodium feldspar, potassium feldspar, modified kaolin-aluminum borate whisker compound (modified kaolin or kaolin-aluminum borate whisker compound), dolomite, calcium borate, strontium carbonate, and barium carbonate according to the formula amount, ball mill uniformly to obtain a dry powder glaze, mix the dry powder glaze with water according to the formula amount to obtain the glaze slurry; wherein the ball milling speed is 1500 r / min, and the time is 60 min;

[0084] S3, mix the dry particles, the glaze slurry, and the suspending agent according to the formula amount to obtain the marble-imitating overglaze;

[0085] S4, apply the face glaze on the body to obtain a face glaze layer, perform inkjet printing on the face glaze layer to obtain an inkjet printing layer, apply the marble-imitating overglaze on the inkjet printing layer, and perform sintering treatment to obtain the marble-imitating ceramic tile; wherein the sintering treatment temperature is 1350°C, and the time is 3h; the glaze amount of the marble-imitating overglaze is 500g / m 2 .

[0086] The body includes the following raw materials in parts by weight: clay 22 parts, high alumina sand 9.5 parts, potassium feldspar 22 parts, sodium feldspar 22 parts, quartz sand 22 parts, raw talc 1.0 parts, and methyl cellulose 0.5 parts;

[0087] The preparation method of the body comprises the following steps: uniformly mixing body raw materials of the ceramic tile according to a formula amount, pouring into a mold for dry pressing forming to obtain a body; wherein the pressure of the dry pressing forming is 3800T;

[0088] The face glaze comprises the following raw materials in parts by weight: 30 parts of potassium feldspar, 20 parts of sodium feldspar, 9 parts of kaolin, 13 parts of quartz, 7 parts of wollastonite, 7 parts of calcined alumina and 5 parts of zirconium silicate;

[0089] Performance test

[0090] The marble-imitating ceramic tiles of application examples 1-7 and comparative application examples 1-6 are detected for the hardness of the glaze surface by using a Mohs hardness tester according to JCT 908-2013 "Artificial Stone", and the wear resistance of each group of marble-imitating ceramic tiles is detected according to the detection standard of GBT3810.7-20166 "Ceramic Tiles Test Methods Part 7: Determination of the Surface Wear Resistance of Glazed Tiles", and the grading standard is shown in Table 1, and the test results of each group are shown in Table 2.

[0091] Table 1 Wear resistance grading standard of glazed ceramic tiles

[0092] abrasive revolutions of visible wear fractionation 100 0 150 1 600 2 750、1500 3 2100、6000、12000 4 ＞12000 5

[0093] Table 2 Hardness and wear resistance data of each group of marble-imitating ceramic tiles

[0094]

[0095] As shown in Table 1, in combination with the data of Example 1, Example 4 and Example 5, it can be seen that the hardness and wear resistance performance of Example 4 and Example 5 are lower than that of Example 1, which may be because the amount of modified kaolin in Example 4 is insufficient, resulting in less ZnO and MnO hard points after sintering, so that the content of zinc aluminate spinel and manganese spinel is low, the basic hardness of the glaze layer is reduced, and the excess whiskers may cause defects in the glaze layer, reducing the wear resistance. In Example 5, the amount of modified kaolin is excessive and the amount of aluminum borate whisker is insufficient, the modified kaolin provides more ZnO and MnO hard points, the content of zinc aluminate spinel and manganese spinel is higher, and the basic hardness is still better, but due to the insufficient aluminum borate whisker, the skeleton support and crack resistance may be weakened, the friction stress cannot be effectively dispersed, and the wear rate is slightly higher than that of Example 1. Therefore, when the mass ratio of the modified kaolin, aluminum borate whisker, chitosan solution and sodium dodecylbenzenesulfonate is (2-4):(1-3):(6-10):(2-3), the hardness and wear resistance of the glaze are better.

[0096] Compared with the data of Example 1 and Example 6-7, the hardness and wear resistance of Example 6-7 are slightly lower than that of Example 1. This may be because: in Example 6, the lack of magnesium nitrate leads to a decrease in forsterite crystals, a decrease in the density of the glaze layer, an increase in micropores, and an increase in local stress concentration during wear; in Example 7, the lack of manganese nitrate leads to a sharp decrease in the amount of spinel generated, a significant decrease in the basic hardness of the glaze layer, and a significant weakening of the scratch resistance, which is the main reason for the decrease in wear resistance. Moreover, the excessive magnesium nitrate generates more forsterite, but the excessive forsterite is prone to agglomeration to form coarse crystals, which in turn forms stress concentration points in the glaze layer and becomes a source of cracks during wear, accelerating the peeling of the glaze. Therefore, when the mass ratio of zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine, and deionized water is 1:(3-4):(2-3):(1-2):(200-300), the hardness and wear resistance of the glaze are at a relatively optimal level.

[0097] Compared with the data of Example 1 and Comparative Example 1, the hardness and wear resistance of Comparative Example 1 are significantly lower than those of Example 1, and are the worst among all groups. This may be because Comparative Example 1 lacks the modified kaolin-aluminum borate whisker complex, leading to the absence of spinel and forsterite modified by zinc, manganese, and magnesium ions in the glaze layer, and the glaze layer is mainly composed of glass phase formed by feldspar, which has low hardness and weak scratch resistance. At the same time, it also lacks the skeleton support of aluminum borate whiskers, which cannot hinder crack propagation, and the friction stress is concentrated locally, easily forming scratches and rapidly expanding. Without forsterite to fill micropores, the number of defects such as pinholes and bubbles in the glaze layer increases, and defects become stress concentration points during wear, accelerating the peeling of the glaze. Therefore, it is shown that the modified kaolin-aluminum borate whisker complex is an important parameter affecting the performance of the glaze.

[0098] Compared with the data of Example 1 and Comparative Examples 2-3, the hardness and wear resistance of Comparative Examples 2-3 are significantly lower than those of Example 1. This may be because: in Comparative Example 2, the modified kaolin is not compounded with aluminum borate whiskers, and the skeleton support of aluminum borate whiskers interpenetrating between the layers of kaolin is lacking. In Comparative Example 3, the kaolin is not modified by zinc, manganese, and magnesium, and cannot effectively load polymeric zinc hydroxide, polymeric manganese hydroxide, and polymeric magnesium hydroxide, and lacks the hard points of spinel and forsterite modified by zinc, manganese, and magnesium ions, which reduces the hardness and wear resistance of the glaze layer. This proves the necessity of the two steps of zinc-manganese modification and whisker compounding.

[0099] Compared with the data of Example 1 and Comparative Example 4, the performance of Comparative Example 4 is significantly lower than that of Example 1. This may be because: the aluminum borate whiskers hinder the combination of zinc and manganese ions with the surface hydroxyl groups of kaolin, leading to uneven distribution of ZnO and MnO after sintering (local aggregation), and weakening the effect of hard points; chitosan and sodium dodecylbenzenesulfonate cannot effectively coordinate the interface after reversing the order, and the enhanced phase is prone to fall off. This shows the irreplaceability of the order of zinc-manganese-magnesium modification and whisker compounding.

[0100] According to the data of example 1 and comparative examples 5-6, the hardness and wear resistance of comparative examples 5-6 are significantly reduced, which may be because: in comparative example 5, manganese nitrate is missing, only magnesium nitrate is supplemented, and there is no Mn 2+ Manganese spinel is generated, the total amount of hard points is greatly reduced, and the basic hardness is reduced; excessive magnesium nitrate leads to Mg 2+ Agglomeration, forsterite crystals are coarse, and stress concentration points are formed, which are easy to crack during wear. In comparative example 6, magnesium nitrate is missing, and only manganese nitrate is supplemented, and there is no Mg 2+ Magnesium olivine is generated, the density of the glaze layer is reduced due to the lack of magnesium olivine to fill the micropores of the glaze layer, and local peeling is easy to occur during wear; excessive manganese nitrate leads to Mn 2+ Agglomeration (triethanolamine cannot completely coordinate), manganese spinel is unevenly distributed, the effect of hard points is weakened, and Mg is also lacking 2+ Adjust the viscosity of the glass phase, the flowability of the glaze is unbalanced, which may lead to uneven local glaze layer thickness and aggravate wear.

[0101] In summary, the marble-imitating re-creation glaze of the application realizes the significant improvement of the wear resistance of the glaze surface through the synergistic effect of multiple components, and finally obtains a high-performance marble-imitating glaze surface.

[0102] Finally, it should be explained that the above examples are only used to illustrate the technical solutions of the application and not to limit the protection scope of the application. Although the application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the application.

Claims

1. A marble-imitating overglaze, characterized by comprising, The replica glaze comprises dry particles, glaze slurry and suspending agent in a mass ratio of (0.2-0.6):(0.5-0.8):1; the glaze slurry comprises dry powder glaze and water in a mass ratio of 100:40-50, and the dry powder glaze comprises the following raw materials in parts by weight: sodium feldspar 15-20 parts, potassium feldspar 15-20 parts, modified kaolin-aluminum borate whisker compound 20-25 parts, dolomite 5-8 parts, calcium borate 5-10 parts, strontium carbonate 5-10 parts; The preparation method of the modified kaolin-aluminum borate whisker compound comprises the following steps: (1) mixing zinc acetate, manganese nitrate, magnesium nitrate, triethanolamine and deionized water and then performing hydrolysis polymerization reaction to obtain a suspension; wherein the mass ratio of the zinc acetate, the manganese nitrate, the magnesium nitrate, the triethanolamine and the deionized water is 1:(1-4):(1-4):(1-2):(200-300); (2) stirring and mixing the suspension obtained in step (1) with kaolin, standing, filtering, and heat treating the obtained solid to obtain modified kaolin; wherein the solid-liquid ratio of the kaolin and the suspension is (0.1-0.15) g:1 mL; (3) stirring and mixing the modified kaolin obtained in step (2) with aluminum borate whisker, chitosan solution and sodium dodecylbenzenesulfonate after cooling to room temperature, washing with water, suction filtering and drying to obtain the modified kaolin-aluminum borate whisker compound; wherein the mass ratio of the modified kaolin, the aluminum borate whisker, the chitosan solution and the sodium dodecylbenzenesulfonate is (1-6):(1-5):(6-10):(2-3), and the mass concentration of the chitosan solution is 5-10%.

2. The marble-imitating transfer enamel according to claim 1, wherein In the preparation step (1) of the modified kaolin-aluminum borate whisker compound, the temperature of the hydrolysis polymerization reaction is 30-50℃, the rotation speed is 500-600 rpm, and the time is 2-4 h; the mass ratio of the zinc acetate, the manganese nitrate, the magnesium nitrate, the triethanolamine and the deionized water is 1:(3-4):(2-3):(1-2):(200-300).

3. The marble-imitation engraved glaze according to claim 1, wherein In the preparation step (2) of the modified kaolin-aluminum borate whisker compound, the rotation speed of the stirring and mixing is 500-600 rpm, and the time is 6-8 h; the standing temperature is 20-50℃, and the time is 5-7 h; the heat treatment temperature is 150-160℃, and the time is 10-20 min.

4. The marble-imitation transfer enamel according to claim 1, wherein In the preparation step (3) of the modified kaolin-aluminum borate whisker compound, the mass ratio of the modified kaolin, the aluminum borate whisker, the chitosan solution and the sodium dodecylbenzenesulfonate is (2-4):(1-3):(6-10):(2-3); and the rotation speed of the stirring and mixing is 500-600 rpm, and the time is 1-2 h.

5. The marble-imitation engraved glaze according to claim 1, wherein The dry particles comprise the following raw materials in parts by weight: sodium feldspar 25-35 parts, potassium feldspar 5-10 parts, nepheline powder 10-15 parts, calcined aluminum oxide 6-10 parts, calcined zinc oxide 5-8 parts and barium carbonate 18-25 parts; and / or the suspending agent is sodium carboxymethyl cellulose.

6. Use of the marble-imitating replica glaze in any one of claims 1-5 in the preparation of marble-imitating ceramic tiles.

7. A marble-imitating ceramic tile, characterized by, From bottom to top, the body, the surface glaze layer, the inkjet printing layer and the marble-imitating overglaze layer are sequentially included; wherein the marble-imitating overglaze layer is obtained by sintering the marble-imitating overglaze according to any one of claims 1-5.

8. The method for preparing marble-look ceramic tiles as described in claim 7, characterized in that, The method comprises the following steps: S1, uniformly mixing the dry granular raw materials, melting at 1350-1450℃, water quenching, ball milling, drying, and sieving to obtain the dry granules; S2, mixing sodium feldspar, potassium feldspar, modified kaolin-aluminum borate whisker compound, dolomite, calcium borate, strontium carbonate and barium carbonate according to the formula amount, ball milling to obtain dry powder glaze, mixing the dry powder glaze with water according to the formula amount to obtain the glaze slurry; S3, mixing the dry granules, the glaze slurry and the suspending agent according to the formula amount to obtain the marble-imitating overglaze; S4, applying the surface glaze on the body to obtain the surface glaze layer, performing inkjet printing on the surface glaze layer to obtain the inkjet printing layer, applying the marble-imitating overglaze on the inkjet printing layer, and performing sintering treatment to obtain the marble-imitating ceramic tile; wherein the sintering treatment temperature is 1200-1400℃, and the time is 2-4h.

9. The method for preparing marble-look ceramic tiles as described in claim 8, characterized in that, In steps S1 and S2, the ball milling speed is 1400-1600r / min, and the time is 40-60min.

10. The method for preparing marble-look ceramic tiles as described in claim 8, characterized in that, In step S4, the application amount of the marble-imitating transfer glaze is 400-600 g / m 2 .

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