Ceramic tile with glazed amber decoration effect and preparation method thereof

Abstract

The invention discloses a ceramic tile with a glazed amber decoration effect and a preparation method of the ceramic tile, and belongs to the technical field of building ceramic materials. The components and the proportion of the frit particles are optimized, the frit particles are subjected to polishing and grinding treatment and interact with the zirconite particles, multi-angle repeated reflection and refraction are achieved, and the glaze decoration effect or the glaze amber decoration effect of diamond-in-jade is excellent. The components and proportion of the transparent glaze are also optimized, so that the expansion coefficient of the transparent glaze is close to that of zirconite particles, the glaze shrinkage generated by high-temperature firing of the transparent glaze is effectively reduced, and glaze microcracks are avoided; in addition, by means of dip angle spraying of transparent glaze, glazing dead corners at the bottoms of the crystal nucleus particles are effectively eliminated, then the transparent glaze is applied, the crystal nucleus particles are wrapped in the transparent glaze, the artistic effect of'diamond in jade 'or glazed amber is more remarkable, and the overall wear resistance, pollution resistance and corrosion resistance of the ceramic tile can meet the use requirements.

Description

Technical Field

[0001] The present invention relates to the technical field of building ceramic materials, and more specifically, to a ceramic tile with a glaze amber decorative effect and a preparation method thereof. Background Art

[0002] Glaze decoration has always been the focus of technology and product innovation in the ceramic tile industry. With the improvement of living quality, people's pursuit of home decoration styles tends to return to nature. Therefore, in recent years, the proportion of ceramic tiles imitating the effects of natural stones has been increasing. There are many process methods to reflect the surface effects of natural stones, mainly including two process directions: the first is to imitate the pattern textures of stones through printing technologies (including overglaze printing, underglaze printing, etc.); the second is to reflect the three-dimensional textures of stones through concave-convex surfaces (including concave-convex mold forming, concave-convex glaze printing, semi-polishing process, etc.). However, these two process directions are limited by the relatively thin glaze layer of ceramic tiles, resulting in poor three-dimensional effects.

[0003] In the prior art, a certain decorative effect is achieved by applying ceramic glaze. However, traditional ceramic glazes (transparent glazes) are generally composed of a single glass melt, which can only produce reflection or refraction on the surface of the glaze layer and at the interface between the glaze and the body, and cannot perform repeated reflection and refraction from multiple interfaces and angles. Naturally, it is impossible to produce a glowing sphere, and it is impossible to create a "diamond in jade" glaze decorative effect or a glaze amber decorative effect. For example, the patent with the Chinese patent application number CN201911300688.4 discloses an imitation transparent amber ceramic tile and a preparation method thereof, whose structure includes a body layer, a surface glaze layer, a first pattern layer, a microcrystalline layer, a second pattern layer, a transparent glaze layer, and a liquid glass layer from bottom to top; the microcrystalline layer is fired from colored transparent microcrystalline glass powder, and the colored transparent microcrystalline glass powder. In addition, the surface glaze in the prior art will undergo volume (linear) shrinkage after being fired and solidified at high temperature. If the shrinkage of the glaze layer is greater than that of the particles, tensile stress will be generated in the surface glaze layer. When the tensile stress exceeds the yield value of the surface glaze layer, cracks will appear in the surface glaze layer, thereby affecting the quality of the product. Therefore, there are still technical problems to be solved urgently in the prior art. Summary of the Invention

[0004] Based on this, in order to solve one of the above problems, the present invention provides a ceramic tile with a glaze amber decorative effect and a preparation method thereof, and the specific technical solutions are as follows: A ceramic tile with a glaze amber decorative effect, the structure of the ceramic tile includes a body layer, a bottom glaze layer, a surface glaze layer, a pattern layer, a crystal nucleus particle layer, and a transparent glaze layer from bottom to top; Among them, the crystal nucleus particles used in the crystal nucleus particle layer include the following preparation raw materials in parts by weight: 80 parts to 95 parts of zircon sand particles and 5 parts to 20 parts of frit particles, and the frit particles need to be polished before use; The frit particles comprise the following components by mass percentage: 10.0% - 20.0% SiO2, 5.0% - 10.0% Al2O3, 15.0% - 17.0% B2O3, 15.0% - 17.0% Y2O3, 1.0% - 3.0% ZrO2, 5.0% - 6.0% Nb2O5, 1.0% - 2.0% CeO2, 8.0% - 12.0% K2O, 5.0% - 9.0% Na2O, 5.0% - 7.0% CaO, 3.0% - 5.0% MgO, 0.1% - 0.5% BaO, 0.1% - 0.5% ZnO, 1.0% - 5.0% loss on ignition; The transparent glaze material used in the transparent glaze layer comprises the following preparation raw materials by weight ratio: 85 - 90 parts of transparent frit, 8 - 12 parts of kaolin, 0.1 - 0.25 part of additive; The transparent frit comprises the following components by mass percentage: 50.0% - 55.0% SiO2, 5.0% - 6.0% Al2O3, 5.0% - 6.0% B2O3, 5.0% - 8.0% ZnO, 5.0% - 6.0% K2O, 1.0% - 2.0% Na2O, 3.0% - 5.0% LiO2, 10.0% - 15.0% CaO, 1.0% - 2.0% MgO, 1.0% - 2.0% BaO, 1.0% - 5.0% loss on ignition.

[0005] Further, the refractive index of the zircon particles is 1.9 - 2.0, and the refractive index of the frit particles is 1.6 - 1.7; The melting temperature of the zircon particles is 2340°C - 2550°C, and the melting temperature of the frit particles is 1280°C - 1300°C.

[0006] Further, the process of the polishing treatment is as follows: the frit particle raw materials are screened by a rectangular grid sieve for shape, then placed in a V-type mixer, zirconia beads are added according to a material-to-ball ratio of 1:22, and the cylinder is rotated at a speed of 10 r / min - 20 r / min for treatment, and then sieved to obtain frit particles with an average particle size of 0.10 mm - 0.20 mm.

[0007] Further, the additive is at least one of a dispersant, an antifoaming agent, a flux, a suspending agent, a thickening agent, an anti-cracking agent, an antibacterial agent, and an antistatic agent.

[0008] Further, the refractive index of the transparent glaze material is 1.4 - 1.5.

[0009] In addition, the present invention also provides a method for preparing a glazed amber decorative effect tile, and the preparation method comprises the following steps: Apply a base glaze on the green body layer, and after drying, form a base glaze layer; Apply the surface glaze on the bottom glaze layer, and after drying, form a surface glaze layer; Spray glue on the surface glaze layer to print a pattern, forming a pattern layer; Apply crystal nucleus particles on the pattern layer, suck out the excess crystal nucleus particles, spray glue again for fixation, and after drying treatment, form a crystal nucleus particle layer; Use a spray gun to spray transparent glaze obliquely on the crystal nucleus particle layer, then apply transparent glaze again, and after drying treatment, fire it to obtain a ceramic tile with a glazed amber decorative effect.

[0010] Further, the expansion coefficient of the transparent glaze at 25°C to 500°C is (4.5 to 4.9)×10 -6 / °C.

[0011] Further, when spraying transparent glaze obliquely, adjust the density of the transparent glaze to (1.46 to 1.48) g / cm 3 , the water content of the transparent glaze is 48% to 50%, and the glaze application amount is (20 to 25) g / m 2 .

[0012] Further, when applying transparent glaze, adjust the density of the transparent glaze to (1.80 to 1.82) g / cm 3 , the water content of the transparent glaze is 30% to 32%, and the glaze application amount is (500 to 510) g / m 2 .

[0013] Further, the firing temperature is 1200°C to 1220°C.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. By optimizing the composition and ratio of the frit particles and subjecting them to polishing treatment, the present invention makes them have a more significant optical reflection effect. Interacting with zircon particles, it can also perform repeated reflection and refraction from multiple angles and emit light in a highly transparent transparent glaze layer, achieving a "diamond in jade" glazed decorative effect or a glazed amber decorative effect, which is artistic and has a strong three-dimensional sense.

[0015] 2. By optimizing the composition and ratio of the transparent glaze, while ensuring that the expansion coefficient of the transparent glaze is (4.5 to 4.9)×10 -6 / °C, so that its expansion coefficient is the same as that of zircon particles (4.5×10 -6When [the temperature / ℃] is close [to a certain value], it can effectively reduce the glaze surface shrinkage generated during the high-temperature firing of the transparent glaze, and avoid the generation of microcracks on the glaze surface. Additionally, by combining with the inclined-angle spraying of the transparent glaze in the process, it can eliminate the glazing dead angle at the bottom of the crystal nucleus particles, promote exhaust gas, and apply the transparent glaze again, so that the crystal nucleus particles are completely wrapped in the transparent glaze. After firing, it further ensures the glaze surface decoration effect of "diamond in jade" or the glaze surface amber decoration effect.

[0016] 3. The overall compatibility of the ceramic tiles of the present invention is excellent. While ensuring its artistic effect, the wear resistance, stain resistance, and corrosion resistance can all meet the usage requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic diagram of the glaze surface of the ceramic tile sample with the glaze surface amber decoration effect prepared in Example 1; Figure 2 It is a schematic diagram of the glaze surface of the ceramic tile sample with the glaze surface amber decoration effect prepared in Example 2; Figure 3 It is a schematic diagram of the glaze surface of the ceramic tile sample with the glaze surface amber decoration effect prepared in Example 3; Figure 4 In [the figure], a is the frit particles without polishing treatment, Figure 4 In [the figure], b is the frit particles after polishing treatment; Figure 5 It is a schematic diagram of the process of inclined-angle spraying of the transparent glaze in Example 1; Figure 6 It is a schematic diagram of the structure of the ceramic tile with the glaze surface amber decoration effect prepared in Example 1; Figure 7 It is a schematic diagram of the effect when the inclined-angle spraying of the transparent glaze is not adopted when preparing the ceramic tile with the glaze surface amber decoration effect in Comparative Example 8.

[0018] Description of the reference numerals in the drawings: 1. Spray gun; 2. Crystal nucleus particles; 3. Body layer; 4. Base glaze layer; 5. Top glaze layer; 6. Pattern layer; 7. Crystal nucleus particle layer; 8. Transparent glaze layer; 9. Bubbles; 10. Glazing dead angle. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0019] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with its embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and do not limit the protection scope of the present invention.

[0020] A ceramic tile with a glaze surface amber decoration effect, the structure of the ceramic tile from bottom to top includes a body layer, a base glaze layer, a top glaze layer, a pattern layer, a crystal nucleus particle layer, and a transparent glaze layer; Among them, the crystal nucleus particles used in the crystal nucleus particle layer include the following raw materials for preparation in parts by weight: 80 parts to 95 parts of zircon particles and 5 parts to 20 parts of frit particles, and the frit particles need to be polished before use; The frit particles include the following components in mass percentage: 10.0% to 20.0% SiO2, 5.0% to 10.0% Al2O3, 15.0% to 17.0% B2O3, 15.0% to 17.0% Y2O3, 1.0% to 3.0% ZrO2, 5.0% to 6.0% Nb2O5, 1.0% to 2.0% CeO2, 8.0% to 12.0% K2O, 5.0% to 9.0% Na2O, 5.0% to 7.0% CaO, 3.0% to 5.0% MgO, 0.1% to 0.5% BaO, 0.1% to 0.5% ZnO, 1.0% to 5.0% loss on ignition; The transparent glaze used in the transparent glaze layer includes the following raw materials for preparation in parts by weight: 85 parts to 90 parts of transparent frit, 8 parts to 12 parts of kaolin, 0.1 part to 0.25 part of additive; The transparent frit includes the following components in mass percentage: 50.0% to 55.0% SiO2, 5.0% to 6.0% Al2O3, 5.0% to 6.0% B2O3, 5.0% to 8.0% ZnO, 5.0% to 6.0% K2O, 1.0% to 2.0% Na2O, 3.0% to 5.0% LiO2, 10.0% to 15.0% CaO, 1.0% to 2.0% MgO, 1.0% to 2.0% BaO, 1.0% to 5.0% loss on ignition.

[0021] In some embodiments, the refractive index of the zircon particles is 1.9 to 2.0, and the refractive index of the frit particles is 1.6 to 1.7.

[0022] In some embodiments, the melting temperature of the zircon particles is 2340 °C to 2550 °C, and the melting temperature of the frit particles is 1280 °C to 1300 °C.

[0023] In some embodiments, the zircon particles have a tetragonal crystal system island structure.

[0024] In some embodiments, the average particle size of the zircon particles is 0.08 mm to 0.30 mm.

[0025] In some embodiments, the coefficient of thermal expansion of the zircon particles is 4.5×10 -6 / °C.

[0026] In some embodiments, the addition amount of the crystal nucleus particles is (100 to 150) g / m 2 .

[0027] In some embodiments, the process of the polishing treatment is as follows: The frit particle raw materials are screened by a rectangular grid sieve, and then placed in a V-type mixer. Zirconia beads are added at a material-to-ball ratio of 1:22, and the cylinder is rotated at a speed of 10 r / min to 20 r / min for treatment. After sieving, frit particles with an average particle size of 0.10 mm to 0.20 mm are obtained. After the frit particles are mechanically crushed in a conventional manner, most of them present irregular shapes, and even present a shape with three sharp points and eight corners, resulting in poor optical reflection effect, and also leading to poor application effect, making the glaze decoration effect or glaze amber decoration effect of the "diamond in jade" not good.

[0028] In some embodiments, the additive is at least one of a dispersant, an antifoaming agent, a flux, a suspending agent, a thickening agent, an anti-cracking agent, an antibacterial agent, and an antistatic agent.

[0029] In some embodiments, the antifoaming agent is at least one of polydimethylsiloxane, calcium carbonate, and barium carbonate.

[0030] In some embodiments, the refractive index of the transparent glaze is 1.4 to 1.5.

[0031] In addition, the present invention also provides a method for preparing a tile with a glaze amber decoration effect, and the preparation method includes the following steps: Apply a base glaze on the body layer, and after drying, form a base glaze layer; Apply a top glaze on the base glaze layer, and after drying, form a top glaze layer; Spray glue on the top glaze layer to print a pattern, and form a pattern layer; Apply crystal nucleus particles on the pattern layer, suck out the excess crystal nucleus particles, spray glue again for fixation, and after drying treatment, form a crystal nucleus particle layer; Use a spray gun to spray the transparent glaze obliquely on the crystal nucleus particle layer, then apply the transparent glaze again, and after drying treatment, fire it to obtain a tile with a glaze amber decoration effect.

[0032] In some embodiments, a body with a coefficient of thermal expansion of 5.1×10 -6 / °C is selected for the body layer.

[0033] In some embodiments, the coefficient of thermal expansion of the transparent glaze at 25°C to 500°C is (4.5 to 4.9)×10 -6 / °C. The coefficient of thermal expansion is close to that of the crystal nucleus particles, which can reduce the tensile stress and avoid the appearance of microcracks on the glaze surface.

[0034] In some embodiments, the preparation method of the transparent glaze is as follows: Crush the transparent frit and sieve it through a 80-100 mesh sieve, then add kaolin, additives, and an appropriate amount of water, and perform wet ball milling for 2 h to 4 h, and let it stand and age for 12 h to 24 h to obtain the transparent glaze.

[0035] In some embodiments, when the transparent glaze is sprayed at an inclined angle, the density of the transparent glaze is adjusted to (1.46 - 1.48) g / cm 3 , the water content of the transparent glaze is 48% - 50%, and the glaze application amount is (20 - 25) g / m 2 .

[0036] In some embodiments, when the transparent glaze is sprayed at an inclined angle, the fluidity of the transparent glaze is 10S - 11S.

[0037] In some embodiments, when the transparent glaze is applied by pouring, the density of the transparent glaze is adjusted to (1.80 - 1.82) g / cm 3 , the water content of the transparent glaze is 30% - 32%, and the glaze application amount is (500 - 510) g / m 2 .

[0038] In some embodiments, when the transparent glaze is applied by pouring, the fluidity of the transparent glaze is 35S - 40S.

[0039] In some embodiments, the melting temperature of the transparent glaze is 1190°C - 1205°C.

[0040] In some embodiments, the firing temperature is 1200°C - 1220°C.

[0041] In some embodiments, the firing cycle is 60 min - 110 min.

[0042] In some embodiments, the green body layer, the base glaze layer, and the top glaze layer are obtained by conventional existing technologies, which will not be elaborated here.

[0043] The overall compatibility of the ceramic tiles prepared by the above solutions is excellent. While having the glaze surface decoration effect of "diamond in jade" or the glaze surface amber decoration effect, the wear resistance, stain resistance, and corrosion resistance can all meet the usage requirements.

[0044] The following is further described in conjunction with specific embodiments. Example 1:

[0045] A method for preparing a ceramic tile with a glaze surface amber decoration effect, comprising the following steps: S1: Select a green body with a coefficient of thermal expansion of 5.1×10 -6 / °C, then apply a base glaze on the green body layer, and after drying, form a base glaze layer; S2: Apply a top glaze on the base glaze layer, and after drying, form a top glaze layer; S3: Spray glue and print a pattern on the top glaze layer to form a pattern layer; S4: Apply crystal nucleus particles on the pattern layer with an addition amount of 120 g / m 2 , suck out the excess crystal nucleus particles, spray glue again for fixation, and after drying treatment, form a crystal nucleus particle layer; the crystal nucleus particles include the following preparation raw materials in parts by weight: 85 parts of zircon sand particles and 15 parts of frit particles, and the frit particles need to be polished before use; The frit particles include the following components in mass percentage: 15.0% SiO2, 7.0% Al2O3, 16.5% B2O3, 16.5% Y2O3, 2.5% ZrO2, 6.0% Nb2O5, 1.0% CeO2, 10.0% K2O, 8.5% Na2O, 6.5% CaO, 4.5% MgO, 0.5% BaO, 0.5% ZnO, 5.0% loss on ignition; The process of the polishing treatment is as follows: Use a rectangular grid sieve to screen the shape of the frit particle raw materials, then place them in a V-type mixer, add zirconia beads according to a material-ball ratio of 1:22, and process at a cylinder rotation speed of 15 r / min, and sieve to obtain frit particles with an average particle size of 0.20 mm; S5: Spray transparent glaze obliquely on the crystal nucleus particle layer with a spray gun, then apply transparent glaze again, and perform drying treatment; By weight ratio, crush 90.0 parts of transparent frit through a 100-mesh sieve, then add 10 parts of kaolin, 0.25 part of polydimethylsiloxane and an appropriate amount of water, perform wet ball milling treatment for 3 h, and let it stand for aging for 20 h to obtain transparent glaze; when spraying transparent glaze obliquely, adjust the density of the transparent glaze to 1.47 g / cm 3 , the fluidity is 11 S, and the glaze application amount is 25 g / m 2 ; when applying transparent glaze, adjust the density of the transparent glaze to 1.82 g / cm 3 , the fluidity is 38 S, and the glaze application amount is 500 g / m 2 ; The transparent frit includes the following components in mass percentage: 55.0% SiO2, 6.0% Al2O3, 5.5% B2O3, 7.0% ZnO, 6.0% K2O, 1.5% Na2O, 3.0% LiO2, 12.0% CaO, 1.0% MgO, 2.0% BaO, 1% loss on ignition; The expansion coefficient of the transparent glaze reaches 4.8×10 -6 / °C at 25°C to 500°C; S6: Fire at a firing temperature of 1220°C and a firing cycle of 80 min to obtain a tile with a glazed amber decorative effect. Example 2:

[0046] A method for preparing a tile with a glazed amber decorative effect, comprising the following steps: S1: Select a green body with a coefficient of thermal expansion of 5.1×10 -6 / ℃, then apply a base glaze on the green body layer, and after drying, form a base glaze layer; S2: Apply a top glaze on the base glaze layer, and after drying, form a top glaze layer; S3: Spray glue on the top glaze layer to print a pattern, forming a pattern layer; S4: Apply crystal nucleus particles on the pattern layer with an addition amount of 120 g / m 2 , suck out the excess crystal nucleus particles, spray glue again for fixation, and after drying treatment, form a crystal nucleus particle layer; The crystal nucleus particles include the following raw materials for preparation in parts by weight: 90 parts of zircon sand particles and 10 parts of frit particles, and the frit particles need to be polished before use; The frit particles include the following components in mass percentage: 16.0% SiO2, 6.0% Al2O3, 16.5% B2O3, 16.5% Y2O3, 2.5% ZrO2, 5.5% Nb2O5, 2.0% CeO2, 10.5% K2O, 8.5% Na2O, 5% CaO, 5% MgO, 0.5% BaO, 0.5% ZnO, 5% loss on ignition; The process of the polishing treatment is as follows: Use a rectangular grid sieve to screen the shape of the frit particle raw materials, then place them in a V-type mixer, add zirconia beads according to a material-ball ratio of 1:22, and process at a cylinder rotation speed of 15 r / min, and sieve to obtain frit particles with an average particle size of 0.20 mm; S5: Spray transparent glaze at an inclination angle on the crystal nucleus particle layer with a spray gun, then apply transparent glaze again, and perform drying treatment; By weight, crush 88 parts of transparent frit through a 100-mesh sieve, then add 12 parts of kaolin, 0.25 parts of polydimethylsiloxane and an appropriate amount of water, carry out wet ball milling for 3 h, and let it stand for 24 h to obtain transparent glaze; When spraying transparent glaze at an inclination angle, adjust the density of the transparent glaze to 1.48 g / cm 3 , the fluidity is 10 S, and the glaze application amount is 24 g / m 2 ; When applying transparent glaze, adjust the density of the transparent glaze to 1.81 g / cm 3 , the fluidity is 37 S, and the glaze application amount is 500 g / m 2 ; The transparent frit includes the following components in mass percentage: 54.5% SiO2, 5.5% Al2O3, 6.0% B2O3, 7.5% ZnO, 5.5% K2O, 1.5% Na2O, 3.5% LiO2, 12.0% CaO, 1.5% MgO, 1.5% BaO, 1% loss on ignition; The expansion coefficient of the transparent glaze is 4.6×10 -6 / °C; S6: Firing at a firing temperature of 1220°C for a firing cycle of 80 min to obtain a tile with an amber decorative effect on the glaze surface. Example 3:

[0047] A method for preparing a tile with an amber decorative effect on the glaze surface, comprising the following steps: S1: Select a green body with an expansion coefficient of 5.1×10 -6 / °C, then apply a base glaze on the green body layer, and after drying, form a base glaze layer; S2: Apply a top glaze on the base glaze layer, and after drying, form a top glaze layer; S3: Spray glue on the top glaze layer to print a pattern, forming a pattern layer; S4: Apply crystal nucleus particles on the pattern layer with an addition amount of 120 g / m 2 , suck out the excess crystal nucleus particles, spray glue again for fixation, and after drying treatment, form a crystal nucleus particle layer; The crystal nucleus particles include the following preparation raw materials by mass percentage: 88 parts of zircon sand particles and 12 parts of frit particles, and the frit particles need to be polished before use; The frit particles include the following components by mass percentage: 15.0% SiO2, 6.5% Al2O3, 16.5% B2O3, 15.5% Y2O3, 2.5% ZrO2, 6.0% Nb2O5, 1.5% CeO2, 11.0% K2O, 9% Na2O, 6.5% CaO, 4.0% MgO, 0.5% BaO, 0.5% ZnO, 5% loss on ignition; The process of the polishing treatment is as follows: Use a rectangular grid sieve to screen the shape of the frit particle raw materials, then place them in a V-type mixer, add zirconia beads according to a material-ball ratio of 1:22, and process at a cylinder rotation speed of 15 r / min, and sieve to obtain frit particles with an average particle size of 0.20 mm; S5: Spray the transparent glaze obliquely on the crystal nucleus particle layer with a spray gun, then apply the transparent glaze again, and perform drying treatment; By weight ratio, 89 parts of transparent frit are crushed and sieved through a 100-mesh sieve, then 11 parts of kaolin, 0.25 part of polydimethylsiloxane and an appropriate amount of water are added, and wet ball milling is carried out for 4 h, and static aging is carried out for 24 h to obtain the transparent glaze; When spraying the transparent glaze obliquely, adjust the density of the transparent glaze to 1.46 g / cm 3 , the fluidity is 11 S, and the glaze application amount is 25 g / m 2 ; When applying the transparent glaze, adjust the density of the transparent glaze to 1.80 g / cm 3 , the fluidity is 40 S, and the glaze application amount is 500 g / m2 ; The transparent frit comprises the following components by mass percentage: 54.0% SiO2, 5.5% Al2O3, 6.0% B2O3, 7.5% ZnO, 6.0% K2O, 1.0% Na2O, 3.5% LiO2, 13.0% CaO, 1.0% MgO, 1.5% BaO, 1% loss on ignition; The expansion coefficient of the transparent glaze reaches 4.7×10 -6 / °C at 25°C to 500°C; S6: Firing is carried out at a firing temperature of 1210°C and a firing cycle of 80 min to obtain a tile with an amber decorative effect on the glaze surface.

[0048] Comparative Example 1: Compared with Example 1, the crystal nucleus particle layer in Comparative Example 1 uses a single zirconia particle, and the others are the same as in Example 1.

[0049] Comparative Example 2: Compared with Example 1, the crystal nucleus particle layer in Comparative Example 2 uses a single frit particle, and the others are the same as in Example 1.

[0050] Comparative Example 3: Compared with Example 1, in Comparative Example 3, the frit particles that have not been polished are used, and the others are the same as in Example 1.

[0051] Comparative Example 4: Compared with Example 1, in Comparative Example 4, ordinary glass microspheres are used to replace the frit particles, and the others are the same as in Example 1.

[0052] Comparative Example 5: Compared with Example 1, the chemical composition and the component ratio of the transparent frit of the transparent surface glaze in Comparative Example 5 are different, and the expansion coefficient of the transparent glaze prepared in Comparative Example 5 reaches 5.6×10 -6 / °C at 25°C to 500°C, and the others are the same as in Example 1.

[0053] The chemical composition of the transparent frit in Comparative Example 5 is as follows: The transparent frit comprises the following components by mass percentage: 59.0% SiO2, 6.0% Al2O3, 1.5% B2O3, 7.0% ZnO, 6.0% K2O, 1.5% Na2O, 3.0% LiO2, 12.0% CaO, 1.0% MgO, 2.0% BaO, 1% loss on ignition.

[0054] Comparative Example 6: Compared with Example 1, the chemical composition and ingredient ratio of the transparent frit in the transparent surface glaze in Comparative Example 6 are different, and the expansion coefficient of the transparent glaze prepared in Comparative Example 6 reaches 5.4×10 -6 / °C, and the others are the same as those in Example 1.

[0055] The chemical composition of the transparent frit in Comparative Example 6 is as follows: The transparent frit comprises the following ingredients by mass percentage: 57.0% SiO2, 6.0% Al2O3, 5.5% B2O3, 7.0% ZnO, 6.0% K2O, 1.5% Na2O, 1.0% LiO2, 12.0% CaO, 1.0% MgO, 2.0% BaO, 1% loss on ignition.

[0056] Comparative Example 7: Compared with Example 1, the chemical composition and ingredient ratio of the transparent frit in the transparent surface glaze in Comparative Example 7 are different, and the expansion coefficient of the transparent glaze prepared in Comparative Example 7 reaches 5.8×10 -6 / °C, and the others are the same as those in Example 1.

[0057] The chemical composition of the transparent frit in Comparative Example 7 is as follows: The transparent frit comprises the following ingredients by mass percentage: 59.0% SiO2, 8.0% Al2O3, 5.5% B2O3, 7.0% ZnO, 6.0% K2O, 1.5% Na2O, 3.0% LiO2, 6.0% CaO, 1.0% MgO, 2.0% BaO, 1% loss on ignition.

[0058] Comparative Example 8: Compared with Example 1, the step of spraying the transparent glaze at an inclination angle is not carried out in Comparative Example 8, and the others are the same as those in Example 1.

[0059] Performance tests were carried out on the glazed amber decorative effect ceramic tile samples prepared in Examples 1 to 3 and the glazed amber decorative effect ceramic tile comparative samples prepared in Comparative Examples 1 to 8 and recorded. The results are shown in Table 1 below. Among them, the glazed surface appearance and quality were observed by the naked eye of those skilled in the art, and a microscope or magnifying glass was used for assistance when necessary; the abrasion resistance, Mohs hardness, stain resistance, and chemical corrosion resistance refer to GB / T 39156-2020.

[0060] Table 1: Performance test results Group Items Appearance Quality Wear Resistance / r Hardness Stain Resistance / Level Chemical Resistance / Level Example 1 The glaze surface is smooth, without bubbles and cracks, has multi-angle twinkling, obvious light emission, and excellent amber decoration effect. 2100 7 5 GA Example 2 The glaze surface is smooth, without bubbles and cracks, has multi-angle twinkling, obvious light emission, and excellent amber decoration effect. 2100 7 5 GA Example 3 The glaze surface is smooth, without bubbles and cracks, has multi-angle twinkling, obvious light emission, and excellent amber decoration effect. 2100 7 5 GA Comparative Example 1 The glaze surface is smooth, without bubbles and cracks, the twinkling and light emission effects are average, and the amber decoration effect is worse than that of Example 1. 2100 7 5 GA Comparative Example 2 The glaze surface is smooth, without bubbles and cracks, the twinkling and light emission effects are average, and the amber decoration effect is worse than that of Example 1. 2100 7 5 GA Comparative Example 3 The glaze surface has bubbles and cracks, the twinkling and light emission effects are average, and the amber decoration effect is worse than that of Example 1. 2000 6 3 GB Comparative Example 4 The glaze surface has no bubbles and cracks, the twinkling and light emission effects are average, and the amber decoration effect is worse than that of Example 1. 2100 7 5 GA Comparative Example 5 The glaze surface has no bubbles but has cracks, the twinkling and light emission effects are average, and the amber decoration effect is worse than that of Example 1. 2000 6 3 GB Comparative Example 6 The glaze surface has no bubbles but has cracks, the twinkling and light emission effects are average, and the amber decoration effect is worse than that of Example 1. 2000 6 3 GB Comparative Example 7 The glaze surface has no bubbles but has cracks, the twinkling and light emission effects are average, and the amber decoration effect is worse than that of Example 1. 2000 6 3 GB Comparative Example 8 The glaze surface has bubbles and cracks, the twinkling and light emission effects are average, and the amber decoration effect is worse than that of Example 1. 2000 6 3 GB From the data analysis in Table 1, it can be seen that in the present invention, by compounding zircon particles and frit particles as the raw materials of the crystal nucleus particle layer, while ensuring the apparent quality of the glaze surface, optical refraction can occur from multiple angles, showing more excellent scintillation, "diamond in jade" or glaze amber decorative effects. In addition, after optimizing the composition and proportion of the transparent surface glaze, the expansion coefficient of the transparent glaze is close to that of the zircon particles, which can effectively avoid the problems of bubbles and cracks during high-temperature firing. While ensuring the glaze surface quality, it also endows the ceramic tiles with excellent wear resistance, hardness, stain resistance, and chemical corrosion resistance.

[0061] In addition, combined with Figures 1 - 7 The technical solution of this application is further described as follows: Figure 1 It is a schematic diagram of the glaze surface of the ceramic tile sample with glaze amber decorative effect prepared in Example 1; Figure 2 It is a schematic diagram of the glaze surface of the ceramic tile sample with glaze amber decorative effect prepared in Example 2; Figure 3 It is a schematic diagram of the glaze surface of the ceramic tile sample with glaze amber decorative effect prepared in Example 3. From Figures 1 - 3 Analysis shows that the zircon particles and frit particles used in the ceramic tiles prepared in the present invention have excellent refractive indices and can form an optical refraction effect from multiple angles, with high artistry.

[0062] Figure 4 In [diagram] a is the frit particles without polishing treatment, Figure 4 In [diagram] b is the frit particles after polishing treatment. From Figure 4 It can be seen that the polishing treatment can grind away the three-pointed and eight-angled parts on the surface of the glass particles, thereby obtaining short-columnar and nearly spherical frit particles, making them have more optical refraction surfaces and reducing the glazing dead angles between them and the transparent glaze, which helps to improve the glaze quality. Therefore, through the polishing treatment process in the present invention, it can help to improve the scintillation and light-emitting effects of the ceramic tiles, making the "diamond in jade" or glaze amber decorative effects more excellent.

[0063] Figure 5 It is a schematic diagram of the process of spraying transparent glaze at an inclined angle in Example 1. From Figure 5 It can be clearly seen that spraying transparent glaze at an inclined angle can reduce the glazing dead angles at the bottom of the crystal nucleus particles, which helps to reduce the problems of glaze surface bubbles and cracks, and thus ensures the glaze surface quality.

[0064] Figure 6 It is a schematic diagram of the structure of the ceramic tile with glaze amber decorative effect prepared in Example 1. From Figure 6 It can be seen that the structure of the ceramic tile with glaze amber decorative effect prepared in Example 1 includes a body layer, a bottom glaze layer, a surface glaze layer, a pattern layer, a crystal nucleus particle layer, and a transparent glaze layer from bottom to top, and the crystal nucleus particles can be wrapped by the transparent glaze.

[0065] Figure 7 When preparing the tile with the glazed amber decorative effect for Comparative Example 8, the schematic diagram of the effect without using the inclined-angle spraying of the transparent glaze is shown. As can be seen from Figure 7 this, the non-use of the inclined-angle spraying process results in the obstruction of the exhaust of the green body layer, affecting the discharge of bubbles 9. At the same time, glazing dead angles 10 also appear, ultimately leading to bubbles and cracks in the glaze quality. Moreover, in the areas where the transparent surface glaze is not applied, it will also affect the final flashing, light-emitting effect and the amber decorative effect.

[0066] In summary, the present invention optimizes the composition and the component ratio of the crystal nucleus particle layer, optimizes the composition and the component ratio of the transparent glaze, and also optimizes the application method of the transparent glaze, making the overall compatibility and adaptability of the tile more excellent. Furthermore, a tile with excellent quality and a glazed amber decorative effect is obtained, which has high ornamental and practical value.

[0067] It should be noted here that the description of the above embodiments is used to help understand the present invention, but does not constitute a limitation to the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

Claims

1. A tile with a glazed amber decorative effect, characterized in that, The structure of the tile from bottom to top includes a body layer, a bottom glaze layer, a surface glaze layer, a pattern layer, a crystal nucleus particle layer, and a transparent glaze layer; Among them, the crystal nucleus particles used in the crystal nucleus particle layer include the following raw materials for preparation in parts by weight: 80 parts to 95 parts of zircon particles and 5 parts to 20 parts of frit particles, and the frit particles need to be polished before use; The frit particles include the following components in mass percentage: 10.0% to 20.0% SiO2, 5.0% to 10.0% Al2O3, 15.0% to 17.0% B2O3, 15.0% to 17.0% Y2O3, 1.0% to 3.0% ZrO2, 5.0% to 6.0% Nb2O5, 1.0% to 2.0% CeO2, 8.0% to 12.0% K2O, 5.0% to 9.0% Na2O, 5.0% to 7.0% CaO, 3.0% to 5.0% MgO, 0.1% to 0.5% BaO, 0.1% to 0.5% ZnO, 1.0% to 5.0% loss on ignition; The transparent glaze used in the transparent glaze layer includes the following raw materials for preparation in parts by weight: 85 parts to 90 parts of transparent frit, 8 parts to 12 parts of kaolin, and 0.1 part to 0.25 part of additive; The transparent frit includes the following components in mass percentage: 50.0% to 55.0% SiO2, 5.0% to 6.0% Al2O3, 5.0% to 6.0% B2O3, 5.0% to 8.0% ZnO, 5.0% to 6.0% K2O, 1.0% to 2.0% Na2O, 3.0% to 5.0% LiO2, 10.0% to 15.0% CaO, 1.0% to 2.0% MgO, 1.0% to 2.0% BaO, 1.0% to 5.0% loss on ignition.

2. The tile according to claim 1, characterized in that, The refractive index of the zircon particles is 1.9 to 2.0, and the refractive index of the frit particles is 1.6 to 1.7; The melting temperature of the zircon particles is 2340 °C to 2550 °C, and the melting temperature of the frit particles is 1280 °C to 1300 °C.

3. The tile according to claim 1, characterized in that, The process of the polishing treatment is as follows: The frit particle raw materials are screened for shape by a rectangular grid sieve, then placed in a V-type mixer, zirconia beads are added according to a material-ball ratio of 1:22, and the treatment is carried out at a cylinder rotation speed of 10 r / min to 20 r / min, and then sieved to obtain frit particles with an average particle size of 0.10 mm to 0.20 mm.

4. The tile according to claim 1, characterized in that, The additive is at least one of a dispersant, an antifoaming agent, a flux, a suspending agent, a thickening agent, an anti-cracking agent, an antibacterial agent, and an antistatic agent.

5. The tile according to claim 1, characterized in that, The refractive index of the transparent glaze is 1.4 to 1.

5.

6. A preparation method of a tile with a glazed amber decorative effect, characterized in that, The preparation method is used to prepare the tile with the glazed amber decorative effect as described in any one of claims 1 to 5, and the preparation method includes the following steps: Apply the bottom glaze on the body layer, and after drying, form the bottom glaze layer; Apply the surface glaze on the bottom glaze layer, and after drying, form the surface glaze layer; Spray glue on the surface glaze layer to print the pattern, and form the pattern layer; Apply the crystal nucleus particles on the pattern layer, suck out the excess crystal nucleus particles, spray glue again to fix, and after drying treatment, form the crystal nucleus particle layer; The transparent glaze is sprayed obliquely on the nucleating particle layer by a spray gun, and then the transparent glaze is applied. After drying, it is fired to obtain a tile with a glazed amber decorative effect.

7. The preparation method according to claim 6, characterized in that, The expansion coefficient of the transparent glaze at 25°C to 500°C is (4.5 to 4.9)×10 -6 / °C.

8. The preparation method according to claim 6, characterized in that, When spraying the transparent glaze at an inclined angle, adjust the density of the transparent glaze to (1.46 - 1.48) g / cm 3 , the water content of the transparent glaze is 48% - 50%, and the glaze application amount is (20 - 25) g / m 2 .

9. The preparation method according to claim 6, characterized in that, When applying the transparent glaze, adjust the density of the transparent glaze to (1.80~1.82) g / cm 3 , the water content of the transparent glaze is 30%~32%, and the glaze application amount is (500~510) g / m 2 .

10. The preparation method according to claim 6, characterized in that, The firing temperature is 1200°C to 1220°C.

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