Glaze with shell luster effect, shell pearly-luster glazed tile and preparation method of shell pearly-luster glazed tile

Abstract

The invention discloses a glaze with a shell luster effect, a shell pearlescent glazed tile and a preparation method thereof, and the glaze comprises the following raw material components in parts by weight: 14-24 parts of modified shell frit, 10-15 parts of albite, 9-16 parts of dolomite, 6-10 parts of kaolin, 6-9 parts of zinc oxide, 11-16 parts of strontium carbonate, 6-9 parts of limestone, 2-6 parts of barium carbonate and 15-25 parts of lithium feldspar. The modified shell frit is introduced and matched with other specific raw materials to prepare the glaze capable of presenting shell luster, so that a glass phase and a crystal phase with different refractive indexes are separated out in the firing process of the glaze, a shell-shaped iridescent and soft light effect is simulated, and a glaze surface has wear resistance, skid resistance and antifouling properties and has good physical properties.

Description

Technical Field

[0001] The invention relates to the field of building ceramics, and in particular to a glaze with shell gloss effect, a shell pearlescent glazed tile and a preparation method thereof. Background Art

[0002] In the prior art, the gloss of conventional ceramic tiles can be roughly divided into three types: medium gloss, soft gloss, and low gloss. The glossiness is single and the decorative effect is limited. With the limited mining of stone materials, people have an urgent need for marble tiles with rich decorative effects. To this end, the industry has developed a decorative ceramic tile with a shell-like crystalline glaze. The surface of the ceramic tile has a unique texture that is as sparkling as pearl luster, and is deeply loved by people for its special decorative effect.

[0003] However, due to the special raw materials and processing technology of shell gloss effect glaze, the mechanical properties of the tile glaze produced are poor, and it is easy to hide dirt, is not wear-resistant, and has poor practicality.

[0004] Therefore, the glazed tiles with shell gloss effect in the prior art still need to be further improved and enhanced. Summary of the invention

[0005] The main purpose of the present invention is to propose a glaze with a shell gloss effect, which can overcome the shortcomings of the prior art. The prepared tile glaze is delicate and soft, presents different colorful lusters at multiple angles, and has good anti-slip, wear resistance and anti-fouling properties.

[0006] To achieve the above-mentioned purpose, the present invention proposes a glaze with a shell gloss effect, which comprises the following raw material components, measured by weight: 14 to 24 parts of modified shell frit, 10 to 15 parts of albite, 9 to 16 parts of dolomite, 6 to 10 parts of kaolin, 6 to 9 parts of zinc oxide, 11 to 16 parts of strontium carbonate, 6 to 9 parts of limestone, 2 to 6 parts of barium carbonate and 15 to 25 parts of lithium feldspar.

[0007] Preferably, the raw materials for preparing the modified shell frit include, by weight: 8 to 12 parts of nepheline, 6 to 9 parts of strontium carbonate, 13 to 19 parts of high-purity quartz, 4 to 10 parts of talc, 2 to 5 parts of wollastonite, 5 to 14 parts of aluminum oxide, 2 to 7 parts of corundum, 3 to 6 parts of borax, 11 to 14 parts of diopside, 6 to 9 parts of calcined kaolin, 12 to 17 parts of fluorite and 1 to 3 parts of titanium dioxide.

[0008] The present invention formulates a glaze capable of presenting a shell luster by introducing a modified shell frit and combining it with other specific raw materials. During the firing process of the glaze, glass phases and crystal phases with different refractive indices are precipitated. The glass phase generated by the melting of quartz, feldspar, etc. serves as a continuous matrix, the uncompletely melted titanium dioxide and corundum crystals serve as dispersed phases, and the microbubbles generated by the decomposition of strontium carbonate serve as scattering points. The three together form a multiphase interface, so that light generates multiple reflections, refractions, and the superposition of scattering at the interface, simulating the iridescence and soft light effects of a shell, thereby enabling the tile surface to present gloss changes at multiple angles. At the same time, through the compounding of raw materials such as corundum, quartz, titanium dioxide, and zinc oxide, a ternary balance of hardness - denseness - roughness is achieved, realizing the comprehensive improvement of wear resistance, stain resistance, and anti-slip performance, and ensuring the mechanical properties of the glaze surface.

[0009] Preferably, the preparation process of the modified shell frit includes: preparing dry granules according to the ratio of each raw material component, mixing and wrapping with corundum powder, calcining at 900 - 1100 °C, soaking in an aqueous solution of titanium dioxide for 1 - 2 hours, drying and sieving to obtain the modified shell frit.

[0010] The present invention also provides a shell pearlescent glazed tile, which sequentially includes from bottom to top: a body layer, a surface glaze layer, a pattern layer, and a shell pearlescent glaze layer; the shell pearlescent glaze layer is fired with the glaze having a shell luster effect as described above.

[0011] The prepared marble tile takes into account both the decorative property of the shell luster effect and the practicality of high-quality tiles, and can meet the needs of market customers.

[0012] The present invention also provides a preparation method for the above-mentioned shell pearlescent glazed tile, including the following steps:

[0013] S1. Prepare a brick blank to obtain the body layer;

[0014] S2. Prepare the raw materials according to the ratio of each raw material of the surface glaze layer and prepare the surface glaze;

[0015] S3. Apply the surface glaze on the brick blank to obtain the surface glaze layer;

[0016] S4. Print a pattern on the surface of the brick blank after applying the surface glaze to obtain the pattern layer;

[0017] S5. Prepare the raw materials according to the ratio of each raw material of the shell pearlescent glaze layer and prepare the shell pearlescent glaze;

[0018] S6. Apply the shell pearlescent glaze on the surface of the brick blank after printing the pattern to obtain the shell pearlescent glaze layer;

[0019] S7. Fire and shape to obtain the shell pearlescent glazed tile.

[0020] Preferably, in the above preparation method, the raw materials for preparing the glaze layer include, by weight: 2-5 parts of zinc oxide, 5-10 parts of aluminum oxide, 10-20 parts of zirconium silicate, 35-55 parts of potassium feldspar, 5-10 parts of quartz, 5-15 parts of wollastonite, 5-9 parts of kaolin, 0.15-0.2 parts of methyl cellulose and 0.2-0.6 parts of sodium tripolyphosphate.

[0021] Preferably, in the above preparation method, the specific gravity of the glaze is 1.85-1.95 g / mL, the flow rate is 120-150 s / mL, and the glaze amount is 80-90 g / m 2 .

[0022] Preferably, in the above preparation method, the specific gravity of the shell pearlescent glaze is 1.60-1.70 g / mL, the flow rate is 100-120 s / mL, and the glazing amount is 100-120 g / m 2 .

[0023] Preferably, in the above preparation method, in step S7, the firing temperature is 1200-1220° C., and the firing time is 70-75 min.

[0024] The preparation method provided by the present invention adjusts and controls specific parameters according to the physicochemical properties of shell pearlescent glaze, and can obtain marble tiles with good mechanical properties and shell gloss effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying any creative work.

[0026] Figure 1 This is a real picture of the glaze surface of the shell pearlescent glazed tile prepared in Example 5;

[0027] Figure 2 This is a real picture of the glaze of the shell pearlescent glazed tile prepared in Comparative Example 2.

[0028] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0029] 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 belong to the scope of protection of the present invention. It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments may be combined with each other. At the same time, for the raw materials not detailedly described below, they are all commercially available products; for the process steps or preparation methods not detailedly mentioned, they are all process steps or preparation methods known to those skilled in the art.

[0030] The present invention provides a shell pearlescent glazed tile, which sequentially includes from bottom to top: a body layer, a surface glaze layer, a pattern layer, and a shell pearlescent glaze layer.

[0031] Specifically, the shell pearlescent glaze layer is fired from a glaze material with a shell gloss effect. Its raw material components are in parts by weight and include: 14 - 24 parts of modified shell frit, 10 - 15 parts of albite, 9 - 16 parts of dolomite, 6 - 10 parts of kaolin, 6 - 9 parts of zinc oxide, 11 - 16 parts of strontium carbonate, 6 - 9 parts of limestone, 2 - 6 parts of barium carbonate, and 15 - 25 parts of spodumene.

[0032] Among them, the raw materials for preparing the modified shell frit are in parts by weight and include: 8 - 12 parts of nepheline, 6 - 9 parts of strontium carbonate, 13 - 19 parts of high-purity quartz, 4 - 10 parts of talc, 2 - 5 parts of wollastonite, 5 - 14 parts of alumina, 2 - 7 parts of corundum, 3 - 6 parts of borax, 11 - 14 parts of diopside, 6 - 9 parts of calcined kaolin, 12 - 17 parts of fluorite, and 1 - 3 parts of titanium dioxide.

[0033] The present invention fires a tile glaze surface capable of presenting an iridescent effect by introducing a modified shell frit and synergistically acting with other components in the base glaze. High-purity quartz, alumina, etc. in the modified shell frit form a glass phase through high-temperature melting, while crystal particles of high refractive index materials such as titanium dioxide and corundum that are not completely melted are retained in the glass matrix, forming a multiphase structure. The refractive index difference between different phases leads to multiple reflections and interference of light, thereby generating an iridescent effect. Strontium carbonate in the glaze decomposes to produce gas during high-temperature calcination, forming microbubbles. The scattering of the microbubbles superimposed on the crystal reflection further enhances the three-dimensional sense of the gloss. At the same time, through the compounding of albite, fluorite, and borax, the melting temperature of the glaze is reduced, the high-temperature viscosity is reduced, the flow of the molten phase is promoted, the formation of the glass network structure is accelerated, and it is ensured that the high refractive index crystals are uniformly dispersed in the glass matrix without complete melting. Quartz and wollastonite in the glaze form a dense glass network skeleton after high-temperature melting, enhancing the structural stability of the glaze surface. Cooperating with calcined kaolin to form a porous structure through dehydroxylation, adsorbing gas and reducing glaze layer defects, the three are compounded to form a dense and stable glaze layer matrix. The compounding of corundum, titanium dioxide, lithium feldspar, etc. in the glaze system can significantly improve the physical properties such as the wear resistance, stain resistance, and anti-slip properties of the glaze layer.

[0034] The preparation process of the modified shell frit includes: preparing dry granules according to the ratio of each raw material component, mixing with corundum powder for coating, calcining at 900 - 1100 °C, soaking in an aqueous solution of titanium dioxide for 1 - 2 hours, drying in an oven at 200 - 250 °C, and screening through a 400-mesh sieve to obtain the modified shell frit. Among them, the step of preparing dry granules can adopt a well-known dry granule preparation process. For example, after weighing each raw material component, it is fired into a liquid state at a temperature of 1300 - 1350 °C, then water-quenched in water at 30 - 50 °C, and broken and screened to obtain the prefabricated dry granules of the modified shell frit. After coating and calcining with corundum powder, a dense structure can be formed, improving the hardness and surface smoothness, thereby reducing light scattering loss; the titanium dioxide soaking process can form a nanoscale coating layer on the surface of the frit, enhancing the local refractive index gradient and directly increasing the directional reflection intensity of incident light. By adjusting the microstructure through the above modification process, the display of the imitation shell pearlescent effect is further improved.

[0035] Specifically, the raw materials for preparing the surface glaze layer, by weight, include: 2 - 5 parts of zinc oxide, 5 - 10 parts of alumina, 10 - 20 parts of zirconium silicate, 35 - 55 parts of potassium feldspar, 5 - 10 parts of quartz, 5 - 15 parts of wollastonite, 5 - 9 parts of kaolin, 0.15 - 0.2 parts of methyl cellulose, and 0.2 - 0.6 parts of sodium tripolyphosphate. Using the surface glaze formula of the present application has good concealer ability and helps the coloring of the pattern layer.

[0036] The present invention also provides a preparation method for the above shell pearlescent glazed tile, including the following steps:

[0037] S1. Press a conventional ceramic blank raw material into a brick blank, dry it and set it aside to obtain a blank layer. Preferably, wet the dried blank with water so that the surface of the blank contains 3-5% moisture;

[0038] S2. Prepare materials according to the ratio of each raw material of the surface glaze layer. For example, mix each raw material of the surface glaze layer and add 38% of the weight of the surface glaze material in water, and ball mill for 20 minutes per 100 g. Obtain the surface glaze mixture and pass it through a 200-mesh sieve to prepare the surface glaze;

[0039] S3. Apply the surface glaze on the brick blank. The specific gravity of the surface glaze is 1.85-1.95 g / mL, the flow rate is 120-150 s / mL, and the glazing amount is 80-90 g / m 2 ; Obtain the surface glaze layer;

[0040] S4. Print a pattern on the surface of the brick blank after applying the surface glaze to obtain a pattern layer;

[0041] S5. Prepare materials according to the ratio of each raw material of the shell pearlescent glaze layer. For example, mix each raw material of the shell pearlescent glaze layer and add 8% of the weight of the shell pearlescent glaze material in water, 70% of printing paste, and 22% of printing oil. Ball mill for 40 minutes per 200 g. Obtain the shell pearlescent glaze mixture and pass it through a 500-mesh sieve to prepare the shell pearlescent glaze;

[0042] S6. Apply the shell pearlescent glaze on the surface of the brick blank after printing the pattern. The specific gravity of the shell pearlescent glaze is 1.60-1.70 g / mL, the flow rate is 100-120 s / mL, and the glazing amount is 100-120 g / m 2 ; Obtain the shell pearlescent glaze layer;

[0043] S7. Fire and shape. The firing temperature is 1200-1220 °C, and the firing time is 70-75 minutes to obtain the shell pearlescent glaze floor tile.

[0044] Furthermore, in step S4, in order to reflect different texture effects according to the pattern color change, this solution adjusts the color grayscale to fit the corresponding texture. Specifically, the ink grayscale scheme of the pattern layer is: 5-10% of blue ink amount, 7-12% of golden brown ink amount, 8-13% of red ink amount, 1-5% of yellow ink amount, and 7-15% of black ink amount. Through the combination of different grayscale ratios, the gloss change of the pattern layer is effectively controlled. Preferably, the ink grayscale scheme of the pattern layer is: 5% of blue ink amount, 8% of golden brown ink amount, 10% of red ink amount, 2% of yellow ink amount, and 7% of black ink amount. Cooperating with the shell pearlescent glaze layer provided in this solution can more restore the illusory color pattern texture like real stone.

[0045] The following are further examples to illustrate the present invention in detail. Unless otherwise specified, the test methods used in the examples are conventional methods; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial sources.

[0046] For the present application, the green body layer can be prepared using conventional ceramic green body materials well-known in the art. Exemplarily, the raw materials for the green body layer used in the following examples and comparative examples of the present application are in parts by weight and include: 30 parts of sodium sand, 5 parts of Takada potassium sand, 10 parts of black mud, 5 parts of stone powder, 18 parts of red sandy soil, 5 parts of magnesian soil, 10 parts of quartz powder, 10 parts of low-temperature sand powder, 2 parts of high-aluminum clay, and 5 parts of industrial porcelain sand.

[0047] Example 1

[0048] The raw materials for preparing the nacreous pearlescent glaze layer of this example are in parts by weight and include: 14 parts of modified shell frit, 15 parts of albite, 9 parts of dolomite, 6 parts of kaolin, 9 parts of zinc oxide, 11 parts of strontium carbonate, 6 parts of limestone, 5 parts of barium carbonate, and 25 parts of lithium feldspar.

[0049] The raw materials for preparing the modified shell frit of this example are in parts by weight and include: 8 parts of nepheline, 8 parts of strontium carbonate, 13 parts of high-purity quartz, 10 parts of talc, 2 parts of wollastonite, 14 parts of alumina, 2 parts of corundum, 6 parts of borax, 11 parts of diopside, 6 parts of calcined kaolin, 17 parts of fluorite, and 3 parts of titanium dioxide.

[0050] The preparation method of the modified shell frit is as follows: After weighing each raw material component, it is fired into a liquid state at a temperature of 1300 °C, then water-quenched in water at 30 °C, and the prefabricated dry particles of the modified shell frit are obtained after crushing and sieving; the prefabricated dry particles are wrapped with corundum powder, calcined at 950 °C, soaked in an aqueous solution of titanium dioxide for 1 hour, dried in an oven at 200 °C, and sieved through a 400-mesh sieve to obtain the modified shell frit.

[0051] The raw materials for preparing the surface glaze layer of this example are in parts by weight and include: 2 parts of zinc oxide, 5 parts of alumina, 10 parts of zirconium silicate, 40 parts of potassium feldspar, 5 parts of quartz, 10 parts of wollastonite, 5 parts of kaolin, 0.15 part of methyl cellulose, and 0.25 part of sodium tripolyphosphate.

[0052] A preparation method of a nacreous pearlescent glazed tile in this example includes the following steps:

[0053] S1. Press the ceramic green body raw materials into a brick blank, dry it for later use, moisten the dried green body with water so that the surface of the green body contains 5% moisture to obtain the green body layer;

[0054] S2, preparing materials according to the ratio of each raw material of the surface glaze layer, mixing each raw material of the surface glaze layer, adding 38% water by weight of the surface glaze material, ball milling for 20 minutes per 100g, obtaining a surface glaze mixture, passing through a 200 mesh sieve, and preparing the surface glaze;

[0055] S3, apply glaze on the brick, the specific gravity of the glaze is 1.90g / mL, the flow rate is 120s / mL, and the glaze amount is 90g / m 2 ; Obtaining a glaze layer;

[0056] S4, printing a pattern on the surface of the brick blank after applying the glaze, the ink grayscale scheme of the pattern layer is: 5% blue ink, 8% golden brown ink, 10% red ink, 2% yellow ink, 7% black ink; obtaining the pattern layer;

[0057] S5, preparing materials according to the ratio of each raw material of the shell pearlescent glaze layer, mixing each raw material of the shell pearlescent glaze layer, adding 8% water, 70% printing paste, and 22% printing oil by weight of the shell pearlescent glaze, ball milling for 40 minutes per 200g, obtaining a shell pearlescent glaze mixture, passing through a 500-mesh sieve, and preparing a shell pearlescent glaze;

[0058] S6. Apply shell pearlescent glaze on the surface of the brick after the pattern is printed. The specific gravity of the shell pearlescent glaze is 1.60g / mL, the flow rate is 100s / mL, and the glaze amount is 100g / m 2 ; Obtain shell pearlescent glaze layer;

[0059] S7, firing and molding, the firing temperature is 1200° C., and the firing time is 70 min, thereby obtaining the shell pearlescent glazed tile.

[0060] Example 2

[0061] The raw materials for preparing the shell pearlescent glaze layer of this embodiment include, by weight: 14 parts of modified shell frit, 10 parts of albite, 10 parts of dolomite, 6 parts of kaolin, 8 parts of zinc oxide, 15 parts of strontium carbonate, 8 parts of limestone, 5 parts of barium carbonate and 24 parts of lithium feldspar.

[0062] The raw materials for preparing the modified shell frit of this embodiment are calculated in parts by weight and include: 10 parts of nepheline, 8 parts of strontium carbonate, 15 parts of high-purity quartz, 10 parts of talc, 2 parts of wollastonite, 12 parts of aluminum oxide, 2 parts of corundum, 6 parts of borax, 11 parts of diopside, 7 parts of calcined kaolin, 15 parts of fluorite and 2 parts of titanium dioxide.

[0063] The preparation method of the modified shell frit is as follows: after weighing each raw material component, sinter it into a liquid at a temperature of 1320°C, then quench it in water at 44°C, and then crush and sieve to obtain pre-product dry particles of the modified shell frit; the pre-product dry particles are mixed with corundum powder for wrapping, calcined at 980°C, soaked in a titanium dioxide aqueous solution for 2 hours, dried in an oven at 225°C, and passed through a 400-mesh sieve to obtain the modified shell frit.

[0064] The raw materials for preparing the glaze layer of this embodiment include, by weight: 2 parts of zinc oxide, 5 parts of aluminum oxide, 10 parts of zirconium silicate, 39 parts of potassium feldspar, 5 parts of quartz, 10 parts of wollastonite, 6 parts of kaolin, 0.16 parts of methyl cellulose and 0.26 parts of sodium tripolyphosphate.

[0065] A method for preparing a shell pearlescent glazed tile of this embodiment comprises the following steps:

[0066] S1, pressing the ceramic green body raw material into a green body, drying it for standby use, and wetting the dried green body with water so that the green body surface contains 5% moisture to obtain a green body layer;

[0067] S2, preparing materials according to the ratio of each raw material of the surface glaze layer, mixing each raw material of the surface glaze layer, adding 38% water by weight of the surface glaze material, ball milling for 20 minutes per 100g, obtaining a surface glaze mixture, passing through a 200 mesh sieve, and preparing the surface glaze;

[0068] S3, apply glaze on the brick, the specific gravity of the glaze is 1.93g / mL, the flow rate is 140s / mL, and the glaze amount is 86g / m 2 ; Obtaining a glaze layer;

[0069] S4, printing a pattern on the surface of the brick blank after applying the glaze, the ink grayscale scheme of the pattern layer is: 5% blue ink, 8% golden brown ink, 10% red ink, 2% yellow ink, 7% black ink; obtaining the pattern layer;

[0070] S5, preparing materials according to the ratio of each raw material of the shell pearlescent glaze layer, mixing each raw material of the shell pearlescent glaze layer, adding 8% water, 70% printing paste, and 22% printing oil by weight of the shell pearlescent glaze, ball milling for 40 minutes per 200g, obtaining a shell pearlescent glaze mixture, passing through a 500-mesh sieve, and preparing a shell pearlescent glaze;

[0071] S6. Apply shell pearlescent glaze on the surface of the brick after the pattern is printed. The specific gravity of the shell pearlescent glaze is 1.69g / mL, the flow rate is 111s / mL, and the glaze amount is 111g / m 2 ; Obtain shell pearlescent glaze layer;

[0072] S7, firing and molding, the firing temperature is 1211° C., and the firing time is 73 min, thereby obtaining the shell pearlescent glazed tile.

[0073] Example 3

[0074] The raw materials for preparing the shell pearlescent glaze layer of this embodiment include, by weight: 18 parts of modified shell frit, 10 parts of albite, 11 parts of dolomite, 9 parts of kaolin, 7 parts of zinc oxide, 14 parts of strontium carbonate, 8 parts of limestone, 5 parts of barium carbonate and 18 parts of lithium feldspar.

[0075] The raw materials for preparing the modified shell frit of this embodiment are calculated in parts by weight and include: 11 parts of nepheline, 7 parts of strontium carbonate, 17 parts of high-purity quartz, 10 parts of talc, 2 parts of wollastonite, 11 parts of aluminum oxide, 2 parts of corundum, 6 parts of borax, 12 parts of diopside, 7 parts of calcined kaolin, 13 parts of fluorite and 2 parts of titanium dioxide.

[0076] The preparation method of the modified shell frit is as follows: after weighing each raw material component, sinter it into a liquid at a temperature of 1312°C, then quench it in water at 40°C, and then crush and sieve it to obtain pre-product dry particles of the modified shell frit; the pre-product dry particles are mixed with corundum powder for wrapping, calcined at 999°C, soaked in a titanium dioxide aqueous solution for 2 hours, dried in an oven at 210°C, and passed through a 400-mesh sieve to obtain the modified shell frit.

[0077] The raw materials for preparing the glaze layer of this embodiment include, by weight: 3 parts of zinc oxide, 5 parts of aluminum oxide, 10 parts of zirconium silicate, 38 parts of potassium feldspar, 5 parts of quartz, 10 parts of wollastonite, 6 parts of kaolin, 0.17 parts of methyl cellulose and 0.27 parts of sodium tripolyphosphate.

[0078] A method for preparing a shell pearlescent glazed tile of this embodiment comprises the following steps:

[0079] S1, pressing the ceramic green body raw material into a green body, drying it for standby use, and wetting the dried green body with water so that the green body surface contains 4.5% of moisture to obtain a green body layer;

[0080] S2, preparing materials according to the ratio of each raw material of the surface glaze layer, mixing each raw material of the surface glaze layer, adding 38% water by weight of the surface glaze material, ball milling for 20 minutes per 100g, obtaining a surface glaze mixture, passing through a 200 mesh sieve, and preparing the surface glaze;

[0081] S3, apply glaze on the brick, the specific gravity of the glaze is 1.92g / mL, the flow rate is 135s / mL, and the glaze amount is 90g / m 2 ; Obtaining a glaze layer;

[0082] S4, printing a pattern on the surface of the brick blank after applying the glaze, the ink grayscale scheme of the pattern layer is: 5% blue ink, 8% golden brown ink, 10% red ink, 2% yellow ink, 7% black ink; obtaining the pattern layer;

[0083] S5, preparing materials according to the ratio of each raw material of the shell pearlescent glaze layer, mixing each raw material of the shell pearlescent glaze layer, adding 8% water, 70% printing paste, and 22% printing oil by weight of the shell pearlescent glaze, ball milling for 40 minutes per 200g, obtaining a shell pearlescent glaze mixture, passing through a 500-mesh sieve, and preparing a shell pearlescent glaze;

[0084] S6. Apply shell pearlescent glaze on the surface of the brick after the pattern is printed. The specific gravity of the shell pearlescent glaze is 1.68g / mL, the flow rate is 112s / mL, and the glaze amount is 113g / m 2 ; Obtain shell pearlescent glaze layer;

[0085] S7, firing and molding, the firing temperature is 1212° C., and the firing time is 74 min, thereby obtaining the shell pearlescent glazed tile.

[0086] Example 4

[0087] The raw materials for preparing the shell pearlescent glaze layer of this embodiment include, by weight: 15 parts of modified shell frit, 10 parts of albite, 12 parts of dolomite, 9 parts of kaolin, 7 parts of zinc oxide, 14 parts of strontium carbonate, 7 parts of limestone, 4 parts of barium carbonate and 22 parts of lithium feldspar.

[0088] The raw materials for preparing the modified shell frit of this embodiment are calculated in parts by weight and include: 11 parts of nepheline, 7 parts of strontium carbonate, 18 parts of high-purity quartz, 9 parts of talc, 2 parts of wollastonite, 11 parts of aluminum oxide, 2 parts of corundum, 4 parts of borax, 12 parts of diopside, 9 parts of calcined kaolin, 13 parts of fluorite and 2 parts of titanium dioxide.

[0089] The preparation method of the modified shell frit is as follows: after weighing each raw material component, sinter it into a liquid at a temperature of 1330°C, then quench it in water at 36°C, crush and sieve it to obtain pre-product dry particles of the modified shell frit; the pre-product dry particles are mixed with corundum powder for wrapping, calcined at 1100°C, soaked in a titanium dioxide aqueous solution for 1.5 hours, dried in an oven at 225°C, and passed through a 400-mesh sieve to obtain the modified shell frit.

[0090] The raw materials for preparing the glaze layer of this embodiment include, by weight: 3 parts of zinc oxide, 5 parts of aluminum oxide, 12 parts of zirconium silicate, 36 parts of potassium feldspar, 5 parts of quartz, 10 parts of wollastonite, 6 parts of kaolin, 0.18 parts of methyl cellulose and 0.28 parts of sodium tripolyphosphate.

[0091] A method for preparing a shell pearlescent glazed tile of this embodiment comprises the following steps:

[0092] S1, pressing the ceramic green body raw material into a green body, drying it for standby use, and wetting the dried green body with water so that the green body surface contains 4.2% of moisture to obtain a green body layer;

[0093] S2. Prepare materials according to the ratio of each raw material of the surface glaze layer. After mixing each raw material of the surface glaze layer, add water accounting for 38% of the weight of the surface glaze material, and ball mill for 20 minutes per 100 g. Obtain the surface glaze mixture passing through a 200-mesh sieve to prepare the surface glaze;

[0094] S3. Apply the surface glaze on the brick blank. The specific gravity of the surface glaze is 1.90 g / mL, the flow rate is 120 s / mL, and the glazing amount is 88 g / m 2 ; Obtain the surface glaze layer;

[0095] S4. Print a pattern on the surface of the brick blank after applying the surface glaze. The ink gray scale scheme of the pattern layer is: 5% blue ink amount, 8% golden brown ink amount, 10% red ink amount, 2% yellow ink amount, and 7% black ink amount; Obtain the pattern layer;

[0096] S5. Prepare materials according to the ratio of each raw material of the shell pearlescent glaze layer. After mixing each raw material of the shell pearlescent glaze layer, add water accounting for 8% of the weight of the shell pearlescent glaze material, printing paste 70%, and printing oil 22%. Ball mill for 40 minutes per 200 g. Obtain the shell pearlescent glaze mixture passing through a 500-mesh sieve to prepare the shell pearlescent glaze;

[0097] S6. Apply the shell pearlescent glaze on the surface of the brick blank after printing the pattern. The specific gravity of the shell pearlescent glaze is 1.68 g / mL, the flow rate is 109 s / mL, and the glazing amount is 109 g / m 2 ; Obtain the shell pearlescent glaze layer;

[0098] S7. Fire and form. The firing temperature is 1213 °C, and the firing time is 74 minutes to obtain the shell pearlescent glazed brick.

[0099] Example 5

[0100] The preparation raw materials of the shell pearlescent glaze layer in this example are counted by weight, including: 20 parts of modified shell frit, 10 parts of albite, 12 parts of dolomite, 9 parts of kaolin, 7 parts of zinc oxide, 12 parts of strontium carbonate, 9 parts of limestone, 4 parts of barium carbonate, and 17 parts of lithium feldspar.

[0101] The preparation raw materials of the modified shell frit in this example are counted by weight, including: 12 parts of nepheline, 7 parts of strontium carbonate, 19 parts of high-purity quartz, 7 parts of talc, 2 parts of wollastonite, 11 parts of alumina, 2 parts of corundum, 4 parts of borax, 13 parts of diopside, 9 parts of calcined kaolin, 12 parts of fluorite, and 2 parts of titanium dioxide.

[0102] The preparation method of modified shell frit is as follows: after weighing each raw material component, sinter it into liquid at a temperature of 1310°C, then quench it in water at 35°C, crush and sieve it to obtain pre-product dry particles of modified shell frit; the pre-product dry particles are mixed with corundum powder for wrapping, calcined at 1000°C, soaked in a titanium dioxide aqueous solution for 1 hour, dried in an oven at 220°C, and passed through a 400-mesh sieve to obtain the modified shell frit.

[0103] The raw materials for preparing the glaze layer of this embodiment include, by weight: 3 parts of zinc oxide, 5 parts of aluminum oxide, 12 parts of zirconium silicate, 38 parts of potassium feldspar, 5 parts of quartz, 8 parts of wollastonite, 6 parts of kaolin, 0.19 parts of methyl cellulose and 0.29 parts of sodium tripolyphosphate.

[0104] A method for preparing a shell pearlescent glazed tile of this embodiment comprises the following steps:

[0105] S1, pressing the ceramic green body raw material into a green body, drying it for standby use, and wetting the dried green body with water so that the green body surface contains 3.5% of moisture to obtain a green body layer;

[0106] S2, preparing materials according to the ratio of each raw material of the surface glaze layer, mixing each raw material of the surface glaze layer, adding 38% water by weight of the surface glaze material, ball milling for 20 minutes per 100g, obtaining a surface glaze mixture, passing through a 200 mesh sieve, and preparing the surface glaze;

[0107] S3, apply glaze on the brick, the specific gravity of the glaze is 1.85g / mL, the flow rate is 126 / mL, and the glaze amount is 89g / m 2 ; Obtaining a glaze layer;

[0108] S4, printing a pattern on the surface of the brick blank after applying the glaze, the ink grayscale scheme of the pattern layer is: 5% blue ink, 8% golden brown ink, 10% red ink, 2% yellow ink, 7% black ink; obtaining the pattern layer;

[0109] S5, preparing materials according to the ratio of each raw material of the shell pearlescent glaze layer, mixing each raw material of the shell pearlescent glaze layer, adding 8% water, 70% printing paste, and 22% printing oil by weight of the shell pearlescent glaze, ball milling for 40 minutes per 200g, obtaining a shell pearlescent glaze mixture, passing through a 500-mesh sieve, and preparing a shell pearlescent glaze;

[0110] S6. Apply shell pearlescent glaze on the surface of the brick after the pattern is printed. The specific gravity of the shell pearlescent glaze is 1.68g / mL, the flow rate is 115s / mL, and the glaze amount is 108g / m 2 ; Obtain shell pearlescent glaze layer;

[0111] S7, firing and molding, the firing temperature is 1215° C., and the firing time is 74 min, thereby obtaining the shell pearlescent glazed tile.

[0112] Comparative Example 1

[0113] The raw materials for preparing the shell pearlescent glaze layer of this embodiment include, by weight, 20 parts of shell frit, 10 parts of albite, 12 parts of dolomite, 9 parts of kaolin, 7 parts of zinc oxide, 12 parts of strontium carbonate, 9 parts of limestone, 4 parts of barium carbonate and 17 parts of lithium feldspar.

[0114] The raw materials for preparing the shell frit of this embodiment are measured in parts by weight and include: 12 parts of nepheline, 7 parts of strontium carbonate, 19 parts of high-purity quartz, 7 parts of talc, 2 parts of wollastonite, 11 parts of aluminum oxide, 2 parts of corundum, 4 parts of borax, 13 parts of diopside, 9 parts of calcined kaolin, 12 parts of fluorite and 2 parts of titanium dioxide.

[0115] The preparation method of shell frit is as follows: after weighing each raw material component, calcining it into liquid at a temperature of 1310°C, and then quenching it in water at 35°C, and then crushing and sieving to obtain shell frit.

[0116] The raw materials for preparing the glaze layer of this embodiment include, by weight: 3 parts of zinc oxide, 5 parts of aluminum oxide, 12 parts of zirconium silicate, 38 parts of potassium feldspar, 5 parts of quartz, 8 parts of wollastonite, 6 parts of kaolin, 0.19 parts of methyl cellulose and 0.29 parts of sodium tripolyphosphate.

[0117] A method for preparing a shell pearlescent glazed tile of this embodiment comprises the following steps:

[0118] S1, pressing the ceramic green body raw material into a green body, drying it for standby use, and wetting the dried green body with water so that the green body surface contains 3.5% of moisture to obtain a green body layer;

[0119] S2, preparing materials according to the ratio of each raw material of the surface glaze layer, mixing each raw material of the surface glaze layer, adding 38% water by weight of the surface glaze material, ball milling for 20 minutes per 100g, obtaining a surface glaze mixture, passing through a 200 mesh sieve, and preparing the surface glaze;

[0120] S3, apply glaze on the brick, the specific gravity of the glaze is 1.85g / mL, the flow rate is 126s / mL, and the glaze amount is 89g / m 2 ; Obtaining a glaze layer;

[0121] S4, printing a pattern on the surface of the brick blank after applying the glaze, the ink grayscale scheme of the pattern layer is: 5% blue ink, 8% golden brown ink, 10% red ink, 2% yellow ink, 7% black ink; obtaining the pattern layer;

[0122] S5. Prepare materials according to the ratio of each raw material of the shell pearlescent glaze layer. After mixing each raw material of the shell pearlescent glaze layer, add 8% of water, 70% of printing paste, and 22% of printing oil based on the weight of the shell pearlescent glaze material. Ball mill for 40 minutes per 200 g, and obtain the shell pearlescent glaze mixture passing through a 500-mesh sieve to prepare the shell pearlescent glaze;

[0123] S6. Apply the shell pearlescent glaze on the surface of the brick blank after printing the pattern. The specific gravity of the shell pearlescent glaze is 1.68 g / mL, the flow rate is 115 s / mL, and the glazing amount is 108 g / m 2 ; Obtain the shell pearlescent glaze layer;

[0124] S7. Fire and shape. The firing temperature is 1215 °C and the firing time is 74 minutes to obtain the shell pearlescent glazed brick.

[0125] Comparative Example 2

[0126] In the preparation raw materials of the shell pearlescent glaze layer of this comparative example, the modified shell frit is not included, and the other raw material components and preparation parameters are the same as those in Example 5.

[0127] Comparative Example 3

[0128] In the preparation raw materials of the shell pearlescent glaze layer of this comparative example, strontium carbonate is not included, and the other raw material components and preparation parameters are the same as those in Example 5.

[0129] Comparative Example 4

[0130] In the preparation raw materials of the modified shell frit of this comparative example, corundum and titanium dioxide are not included, and the other raw material components and preparation parameters are the same as those in Example 5.

[0131] Comparative Example 5

[0132] In this comparative example, spodumene in the preparation raw materials of the shell pearlescent glaze layer is replaced with lithium porcelain stone, and the other raw material components and preparation parameters are the same as those in Example 5.

[0133] Comparative Example 6

[0134] In this comparative example, high-purity quartz in the preparation raw materials of the modified shell frit is replaced with quartz, and the other raw material components and preparation parameters are the same as those in Example 5.

[0135] Specifically, in the above-mentioned examples and comparative examples, after high-temperature calcination, a brushing and polishing process is also required. The polishing is carried out using the well-known brushing and polishing process in the art to make the gloss of the glaze surface more uniform and the hand feeling more delicate.

[0136] Perform performance tests on the above-mentioned examples and comparative examples. The test standards and test methods are as follows:

[0137] 1. Abrasion resistance: The abrasion resistance is detected according to GB / T 3810.7-2016. Observe the wear condition of the brick surface after grinding at a specific number of grinding revolutions, which is divided into levels 0-5. Among them, visible wear after 100 revolutions is level 0, visible wear after 150 revolutions is level 1, visible wear after 600 revolutions is level 2, visible wear after 750 / 1500 revolutions is level 3, visible wear after 2100 / 6000 / 12000 revolutions is level 4, and greater than 12000 revolutions is level 5.

[0138] 2. Stain resistance: Refer to the national standard GB / T 3810.14-2016 to detect the stain resistance. Conduct a stain resistance test on the brick surface treated with a surface treatment agent. The test principle is to make a contaminant (such as chrome green, iodine tincture, and olive oil) contact the front of the brick and act for a certain time, and then clean the brick surface according to the specified cleaning method. Observe the changes on the brick surface to determine the stain resistance of the brick, and the grade is divided into levels 1-5, with level 5 having the best stain resistance performance.

[0139] 3. Anti-slip property: Detect the anti-slip property according to the national standard GB / T 37798-2019. Use the ramp method (wearing shoes and applying oil) to test the anti-slip property of the ceramic tile surface. The grade marks are "-、R9、R10、R11、R12、R13". Among them, the anti-slip performance of R12-R13 is high, the anti-slip performance of R10-R11 is medium, and R9 and below have low anti-slip performance.

[0140] 4. Glossiness: Use a gloss meter to measure the glossiness at different positions on the brick surface. Generally, it is considered that: when the glossiness range is 80-100, the surface effect is good; when the glossiness range is 30-80, the surface effect is average; when the glossiness range is 0-30, the surface effect is poor.

[0141] 5. Surface effect: Judge the iridescent effect presented by the glaze surface through visual senses.

[0142] The performance test results of Examples 1-5 and Comparative Examples 1-6 are shown in Table 1:

[0143] Table 1

[0144]

[0145]

[0146] As can be seen from Table 1, the glaze surface of the nacreous pearlescent glaze ceramic tiles prepared by Examples 1-5 through this scheme is delicate and soft, and reflects different colorful nacreous pearlescent effects from multiple angles, as Figure 1 (Example 5) shows. It forms a three-dimensional gloss level in combination with the pattern texture. At the same time, the abrasion resistance reaches level 4 at 6000 revolutions; the anti-stain grade reaches R13; the anti-slip grade reaches R13, and it has good physical properties.

[0147] In Comparative Example 1, the shell frit in the shell pearlescent glaze was not subjected to the modification process, resulting in a slight decrease in the wear resistance and stain resistance of the tile glaze surface, a poor anti-slip effect, a low glossiness, and basically no shell pearlescent effect.

[0148] In Comparative Example 2, the modified shell frit was not added to the shell pearlescent glaze, not only resulting in a decrease in the overall physical properties, but also as Figure 2 shown, the tile glaze surface did not have a shell pearlescent effect, the glaze surface had a low glossiness, a poor surface effect, and no shell pearlescent effect.

[0149] In Comparative Example 3, strontium carbonate was not added to the shell pearlescent glaze, resulting in a significant decrease in the wear resistance and anti-slip properties of the tile glaze surface, a low glossiness, a poor surface effect, and no shell pearlescent effect.

[0150] In Comparative Example 4, corundum and titanium dioxide were not added to the modified shell frit, resulting in poor stain resistance of the glaze surface, a significant decrease in wear resistance, a slightly lower glossiness than in Examples 1-5, a bright light effect on the glaze surface, but no shell pearlescent gloss, and a general surface effect.

[0151] In Comparative Example 5, the spodumene in the raw materials for preparing the shell pearlescent glaze layer was replaced with spodumene porcelain, resulting in poor wear resistance, a general surface effect, a bright light effect on the glaze surface, but a weak shell pearlescent effect.

[0152] In Comparative Example 6, the high-purity quartz in the modified shell frit was replaced with ordinary quartz, resulting in a decrease in the overall physical properties, especially poor wear resistance, a slight decrease in glossiness, a general surface effect, a bright light effect on the glaze surface, but a weak shell pearlescent effect.

[0153] In summary, the present invention synergistically enhances the effect by introducing a modified shell frit in combination with special raw material components, formulating a glaze with a shell gloss effect, enabling the fired shell pearlescent glazed tile to have a colorful gloss effect imitating a shell, more three-dimensional with the cooperation of pattern textures, and at the same time having good glaze surface properties, high wear resistance, high stain resistance, and anti-slip properties.

[0154] The above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structural transformation made using the content of the specification of the present invention under the inventive concept of the present invention, or direct / indirect application in other related technical fields, is included in the patent protection scope of the present invention.

Claims

1. A glaze with a shell gloss effect, characterized in that: The raw material components are as follows, in parts by weight: 14 to 24 parts of modified shell frit, 10 to 15 parts of albite, 9 to 16 parts of dolomite, 6 to 10 parts of kaolin, 6 to 9 parts of zinc oxide, 11 to 16 parts of strontium carbonate, 6 to 9 parts of limestone, 2 to 6 parts of barium carbonate and 15 to 25 parts of lithium feldspar.

2. A glaze with shell gloss effect as claimed in claim 1, characterized in that: The raw materials for preparing the modified shell frit include, by weight, 8 to 12 parts of nepheline, 6 to 9 parts of strontium carbonate, 13 to 19 parts of high-purity quartz, 4 to 10 parts of talc, 2 to 5 parts of wollastonite, 5 to 14 parts of aluminum oxide, 2 to 7 parts of corundum, 3 to 6 parts of borax, 11 to 14 parts of diopside, 6 to 9 parts of calcined kaolin, 12 to 17 parts of fluorite and 1 to 3 parts of titanium dioxide.

3. The glaze with shell gloss effect as claimed in claim 1, characterized in that: The preparation process of the modified shell frit comprises: preparing dry particles according to the ratio of each raw material component and then mixing with corundum powder for wrapping, calcining at 900-1100° C., soaking in a titanium dioxide aqueous solution for 1-2 hours, drying and sieving to obtain the modified shell frit.

4. A shell pearlescent glazed tile, characterized in that: The shell pearlescent glazed tile comprises, from bottom to top, a body layer, a surface glaze layer, a pattern layer and a shell pearlescent glaze layer; the shell pearlescent glaze layer is fired using the glaze with shell luster effect as described in any one of claims 1 to 3.

5. A method for preparing shell pearlescent glazed tiles as claimed in claim 4, characterized in that: The steps include: S1, preparing a brick to obtain the green body layer; S2, preparing materials according to the ratio of each raw material of the glaze layer to prepare the glaze; S3, applying the glaze on the brick to obtain a glaze layer; S4, printing a pattern on the surface of the brick after applying the glaze to obtain a pattern layer; S5, preparing materials according to the ratio of each raw material of the shell pearlescent glaze layer to prepare the shell pearlescent glaze; S6, applying shell pearlescent glaze on the surface of the brick blank after the pattern is printed to obtain a shell pearlescent glaze layer; S7, firing and molding, thus obtaining the shell pearlescent glazed tile.

6. The method for preparing a shell pearlescent glazed tile according to claim 5, characterized in that: The raw materials for preparing the surface glaze layer include, by weight, 2 to 5 parts of zinc oxide, 5 to 10 parts of aluminum oxide, 10 to 20 parts of zirconium silicate, 35 to 55 parts of potassium feldspar, 5 to 10 parts of quartz, 5 to 15 parts of wollastonite, 5 to 9 parts of kaolin, 0.15 to 0.2 parts of methyl cellulose and 0.2 to 0.6 parts of sodium tripolyphosphate.

7. The method for preparing a shell pearlescent glazed tile according to claim 5, characterized in that: The specific gravity of the glaze is 1.85-1.95 g / mL, the flow rate is 120-150 s / mL, and the glaze amount is 80-90 g / m 2 .

8. The method for preparing a shell pearlescent glazed tile according to claim 5, characterized in that: The specific gravity of the shell pearlescent glaze is 1.60-1.70 g / mL, the flow rate is 100-120 s / mL, and the glaze application amount is 100-120 g / m 2 .

9. The method for preparing a shell pearlescent glazed tile according to claim 5, characterized in that: In step S7, the firing temperature is 1200-1220° C., and the firing time is 70-75 minutes.

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