Jade-like color-changing ceramic dry granular glaze, ceramic tile and preparation method thereof

Abstract

The present invention discloses a jade-like color-changing ceramic dry granule glaze, a ceramic tile, and a preparation method thereof. The raw material components of the ceramic dry granule glaze include jade dry granules and color-changing dry granules, wherein: the jade dry granules are barium feldspar-type jade dry granules, and the content of BaO in the chemical composition of the jade dry granules is 5-10wt%; the chemical composition of the color-changing dry granules contains B2O3 and silver halide. The micro-nano crystals dispersed in the jade dry granules form a jade-like semi-transparent effect, and the silver halide in the color-changing dry granules is decomposed by ultraviolet light to form dispersed Ag. + The colloids preferentially occupy the large distorted voids and form larger scattering micro-regions with the micro-nano crystals in the jade dry particles, increasing the opacity of the glaze layer and reducing its transparency, thereby changing the jade effect of the glaze layer. After low-temperature heat treatment, the dispersed Ag + The colloids break away from the large voids and recombine with the halide ions, reducing the size of the diffuse micro-regions in the glaze layer and restoring the translucent effect of the glaze layer.

Description

Technical Field

[0001] The invention belongs to the technical field of building ceramics, and in particular relates to a jade-like color-changing ceramic dry granular glaze, a ceramic tile and a preparation method thereof. Background Art

[0002] The various styles of expression in architectural ceramics are often closely related to the corresponding design patterns and glaze layers. The overall display effect of ceramic tiles is achieved by combining the design of the specific pattern with the glaze thickness, the transparency of the glaze, and the glossiness of the glaze surface. At present, the glaze layer of ceramic tiles is mainly formed through the following methods: ① After the minerals are directly configured, wet ball milling is performed to form a slurry, which is applied to the pattern layer; ② Some of the raw materials in the minerals are pre-made into a glassy state and then quenched and crushed to form corresponding frits or dry particles, which are then wet ball milled with other minerals to form a slurry and applied to the pattern layer; ③ The mineral components and functional components are made into a glassy state and then quenched and crushed to form corresponding frits or dry particles, and then the corresponding glazing method (glue dry particles, dry stacking, wet stacking, high-pressure glazing, digital glazing, etc.) is used to form a glaze layer on the pattern layer; finally, the green bodies prepared by these methods are fired to obtain semi-finished ceramic tiles.

[0003] Through the preparation of dry particles, it is possible to solidify or crystallize specific components that may react with certain mineral components in the glaze, achieving both aesthetic and functional glaze effects on ceramic tiles. Natural jades such as jadeite, Hetian jade, agate, Xiuyan jade, and Dushan jade have become references for the glaze effects on ceramic tiles. The transparency and semi-transparency of these materials are one way to control the jade-like effect of the glaze on ceramic tiles. However, the jade-like effect of the glaze on ceramic tiles is often determined during firing, meaning that the transparency and jade-like effect are fixed.

[0004] Therefore, there is an urgent need to develop a ceramic glaze that can change color and automatically change the jade texture of the glaze layer when the external environment such as light and heat changes, giving it a changing visual effect. Summary of the Invention

[0005] The present invention provides a jade-like color-changing ceramic dry granular glaze, a ceramic tile and a preparation method thereof, in order to solve one or more technical problems existing in the prior art and at least provide a beneficial choice or create conditions.

[0006] The inventive concept of the present invention is that by introducing color-changing dry particles that can change with light or heat into specific jade dry particles, the micro-nano crystals dispersed in the jade dry particles form a jade-like semi-transparent effect, and the silver halide in the color-changing dry particles is decomposed by ultraviolet light to form dispersed Ag +The colloid preferentially occupies the large voids formed by the distortion of the boron element in the discoloration blank, and forms a larger scattering micro-region with the micro-nano crystals in the jade dry particles, increasing the opacity of the glaze layer and reducing the transparency of the glaze layer, thereby changing the jade effect of the glaze layer; and after being heated at low temperature, the diffused Ag + The colloids escape from the large voids and recombine with the halide ions, reducing the size of the diffuse micro-domains in the glaze layer and restoring the glaze's translucency. This creates a jade-like effect in the glaze layer that changes color with the environment, enriching the decorative properties of the ceramic product.

[0007] To solve the above technical problems, the first aspect of the present invention provides a ceramic dry particle glaze, the raw material components of which include jade dry particles and color-changing dry particles, the jade dry particles are baryte-type jade dry particles (jade dry particles with baryte as the main crystallization phase), and the BaO content in the chemical composition of the jade dry particles is 5-10wt%;

[0008] The chemical composition of the color-changing dry particles comprises, by weight percentage, 55.00-58.00% SiO2, 14.00-17.00% Al2O3, 0.01-0.03% Fe2O3, 0.01-0.05% TiO2, 5.00-7.00% CaO, 1.00-2.00% MgO, 3.50-4.50% K2O, 1.50-3.00% Na2O, 4.00-7.00% B2O3, 0.05-0.20% ZrO2, 1.50-3.00% ZnO, 1.50-3.00% BaO, 1.00-2.00% SrO, 0.20-0.80% silver halide, and 0.05-0.20% loss on ignition.

[0009] Specifically, after firing, the size of the diffusion point of the visible light scattering of ordinary jade dry particles is fixed, and will not change with changes in the environment during subsequent use, so the jade effect will not change. The present invention increases the content of BaO in the components of the jade dry particles to form a jade effect containing micro-nano crystals such as sodium barium feldspar and potassium barium feldspar. The glaze layer made of the jade dry particles forms a translucent jade state after firing. At the same time, in the color-changing dry particles containing boron oxide, due to B 3+ (4 coordination: ) has a radius greater than Si under the same coordination 4+ (4 coordination: ) and Al 3+ (4 coordination: ) is small, it is easier to distort the gap formed by oxygen atoms with the same coordination number, and B 3+ As a network former, with Si 4+Compared with the electricity price, it is easier to cause the formation of disconnected structure and the appearance of large gaps; through the induction of silver halide by ultraviolet light, based on AgX→Ag + +X - Reaction (X represents halogen), Ag in silver halide + Ions are free and aggregated into Ag + Colloidal particles, agglomerated Ag + Colloidal particles occupy large gaps and become diffusion points within the visible light wavelength range. The interaction between the diffusion points and micro-nano crystals forms larger diffusion micro-regions, which increases the scattering effect of the glaze layer on light and enhances the opacity of the glassy glaze layer, thereby reducing the transparency of the jade-like glaze layer and changing the jade-like effect of the glaze layer. Under the influence of heat source, free Ag + Reconnect with X - Combined with the large gaps around the boron element, it reduces the scattering effect of the glaze layer on light, increases the transparency of the glaze layer, and ultimately achieves the transformation of the glaze layer into different jade effects under environmental changes.

[0010] Preferably, the chemical composition of the celsium feldspar-type jade dry particles comprises, by weight percentage, 56.00-61.00% SiO2, 16.00-18.00% Al2O3, 0.01-0.03% Fe2O3, 0.01-0.05% TiO2, 1.50-2.50% CaO, 1.00-2.00% MgO, 3.50-4.50% K2O, 3.50-4.50% Na2O, 0.05-0.20% ZrO2, 2.50-3.50% ZnO, 6.50-9.00% BaO, 1.00-2.00% SrO, and 0.05-0.20% loss on ignition.

[0011] Preferably, the mass ratio of the jade-like dry particles to the color-changing dry particles is (7-22):1.

[0012] Preferably, the silver halide is AgBr or AgI.

[0013] Preferably, the preparation steps of the jade-like dry particles include:

[0014] The raw materials for preparing the jade dry particles are mixed, melted at 1400-1450° C. for 8-10 hours, poured into water for quenching to obtain jade frit particles, and crushed to obtain the jade dry particles.

[0015] Preferably, the particle size of the jade dry particles is between 58-106 μm.

[0016] Preferably, the preparation steps of the color-changing dry particles include: mixing the raw materials for preparing the color-changing dry particles, melting them at 1300-1400° C. for 8-10 hours, pouring them into water for quenching to obtain color-changing frit particles, and crushing them to obtain the color-changing dry particles.

[0017] Preferably, the color-changing dry particles have a particle size between 45 and 75 μm. The particle size of the color-changing dry particles is smaller than that of the jade dry particles, which facilitates their uniform dispersion around the jade dry particles and allows them to be evenly dispersed among the micro-nano crystals of sodium barite, potassium barite, etc. in the jade dry particles after firing.

[0018] The second aspect of the present invention provides a ceramic tile, which includes, from bottom to top, a body layer, a surface glaze layer, a pattern layer, a dry granular glaze layer and a protective glaze layer. The dry granular glaze layer includes a color-changing area and a jade area. The color-changing area is formed by firing the above-mentioned ceramic dry granular glaze; the jade area is formed by firing the jade dry particles.

[0019] Preferably, the color-changing areas are distributed in the jade area in the form of dots, lines or blocks.

[0020] A third aspect of the present invention provides a method for preparing a ceramic tile, comprising the following steps:

[0021] Taking the raw material of the green body layer to prepare the green body layer;

[0022] Mixing jade dry particles, color-changing dry particles, glue and water to obtain color-changing dry particle glaze slurry;

[0023] Mixing jade dry particles, glue and water to obtain jade dry particle glaze slurry;

[0024] The raw materials of the surface glaze layer and the protective glaze layer are respectively taken to prepare the surface glaze slurry and the protective glaze slurry;

[0025] The surface glaze slurry is applied on the surface of the green body layer in sequence, a pattern is inkjet printed, the jade-like dry granular glaze slurry, the color-changing dry granular glaze slurry and the protective glaze slurry are applied, and after drying and firing, the ceramic tile is obtained.

[0026] Preferably, the glue is a mixture of polyvinyl acetate, polyethylene glycol, acrylate polymer, and propylene glycol block copolymer in a mass ratio of (3-5): (1-3): (10-13): (6-10); the flow rate measured using a Tu-4 cup is in the range of 55-85 seconds, and the viscosity of the glue measured by a rotational viscometer is in the range of 900-1100 mPa·s.

[0027] Preferably, in the color-changing dry particle glaze slurry, the mass ratio of jade dry particles, color-changing dry particles, glue and water is (7-22):1:(10-20):(3-10).

[0028] Preferably, the specific gravity of the color-changing dry granular glaze slurry is 1.45-1.55 g / cm 3 .

[0029] Preferably, in the jade dry particle glaze slurry, the mass ratio of jade dry particles, glue and water is 1: (0.7-1): (0.3-0.7).

[0030] Preferably, the specific gravity of the jade dry granular glaze slurry is 1.45-1.55 g / cm 3 .

[0031] Preferably, the chemical composition of the green body layer comprises, by mass percentage, 66.00-72.00% SiO2, 18.20-20.10% Al2O3, 0.20-0.40% Fe2O3, 0.10-0.30% TiO2, 0.30-1.00% CaO, 0.10-0.50% MgO, 2.40-2.80% K2O, 3.20-3.70% Na2O, and 4.00-4.80% loss on ignition.

[0032] Preferably, the chemical composition of the glaze layer includes, by mass percentage: 48.50-54.00% SiO2, 33.00-37.50% Al2O3, 0.05-0.15% Fe2O3, 0.30-0.50% TiO2, 0.80-1.20% CaO, 0.30-0.50% MgO, 0.70-1.20% K2O, 4.00-4.80% Na2O, 0.30-0.50% ZrO2, 1.50-2.50% ZnO, and 2.00-3.00% loss on ignition.

[0033] Preferably, the specific gravity of the glaze slurry is 1.85-1.95 g / cm 3 .

[0034] Preferably, the chemical composition of the protective glaze layer includes, by mass percentage: 48.0-53.0% SiO2, 19.0-22.0% Al2O3, 0.30-0.50% Fe2O3, 0.10-0.30% TiO2, 5.50-7.50% CaO, 1.00-1.70% MgO, 4.0-5.0% K2O, 1.0-3.0% Na2O, 0.30-0.50% ZrO2, 3.0-5.0% ZnO, and 9.0-13.0% loss on ignition.

[0035] Preferably, the specific gravity of the protective glaze slurry is 1.35-1.45 g / cm 3 .

[0036] Preferably, the maximum firing temperature is 1170-1210°C.

[0037] Preferably, the firing cycle is 55-65 minutes.

[0038] Preferably, the holding time of the firing at the highest firing temperature is 7-15 minutes.

[0039] Compared with the prior art, the above technical solution of the present invention has at least the following technical effects or advantages:

[0040] (1) The ceramic dry particle glaze of the present invention comprises jade dry particles and color-changing dry particles. By increasing the content of BaO in the components of the jade dry particles, translucent jade sodium barium feldspar, potassium barium feldspar and other micro-nano crystals are formed in the glaze layer; at the same time, boron oxide and silver halide are introduced into the color-changing dry particles. The silver halide is decomposed by ultraviolet light to form large voids, and the dispersed Ag + The colloids preferentially occupy the large voids formed by the distortion of boron elements, and form larger scattering micro-regions with the micro-nano crystals in the jade dry particles, increasing the opacity of the glaze layer and reducing its transparency, thus changing the jade effect of the glaze layer. + Reconnect with X - Combined with the large gaps around the boron element, it reduces the scattering effect of the glaze layer on light, increases the transparency of the glaze layer, and ultimately achieves the transformation of the glaze layer into different jade effects under environmental changes.

[0041] (2) The present invention introduces color-changing dry particles that can change with light or heat into specific jade dry particles. The color-changing dry particles can change the transparency of part of the glaze layer. Combined with the colored dry particles in the glaze layer, the jade effect of the glaze layer showing different colors and transparencies as the environment changes is finally achieved, enriching and enhancing the decorative effect of the jade ceramic tiles. DETAILED DESCRIPTION

[0042] The present invention is described in detail below with reference to the examples to facilitate understanding of the present invention by those skilled in the art. It is necessary to point out that the examples are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made to the present invention by those skilled in the art based on the above-mentioned invention should still fall within the scope of protection of the present invention. At the same time, the raw materials mentioned below that are not described in detail are all commercially available products; the process steps or preparation methods that are not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0043] The chemical composition of the blanks used in the embodiments of the present invention and the comparative examples includes, by mass percentage, 68.25% SiO2, 19.34% Al2O3, 0.31% Fe2O3, 0.26% TiO2, 0.76% CaO, 0.34% MgO, 2.73% K2O, 3.53% Na2O, and 4.48% loss on ignition.

[0044] The chemical composition of the glaze layer, by mass percentage, includes: 52.48% SiO2, 34.68% Al2O3, 0.12% Fe2O3, 0.39% TiO2, 1.08% CaO, 0.44% MgO, 1.12% K2O, 4.62% Na2O, 0.37% ZrO2, 2.08% ZnO, and 2.62% loss on ignition.

[0045] The chemical composition of the protective glaze layer includes, by mass percentage: 51.35% SiO2, 20.53% Al2O3, 0.39% Fe2O3, 0.18% TiO2, 6.23% CaO, 1.48% MgO, 4.37% K2O, 2.13% Na2O, 0.41% ZrO2, 3.65% ZnO, and 9.28% loss on ignition.

[0046] The glue is a mixture of polyvinyl acetate, polyethylene glycol, acrylate polymer, and propylene glycol block copolymer in a mass ratio of 2:1:6:4; the flow rate measured using a Tu-4 cup ranges from 55 to 85 seconds, and the viscosity of the glue measured using a rotational viscometer ranges from 900 to 1100 mPa·s.

[0047] Example 1

[0048] A ceramic dry particle glaze, the raw material components of which include jade dry particles and color-changing dry particles.

[0049] The chemical composition of the color-changing dry particles, by weight percentage, includes: 56.35% SiO2, 16.72% Al2O3, 0.02% Fe2O3, 0.04% TiO2, 6.58% CaO, 1.36% MgO, 3.74% K2O, 1.96% Na2O, 6.41% B2O3, 0.09% ZrO2, 2.05% ZnO, 2.77% BaO, 1.24% SrO, 0.51% AgBr, and 0.16% loss on ignition; the particle size D90 of the color-changing dry particles is 64 μm.

[0050] The chemical composition of the jade dry particles, by weight percentage, includes: 58.42% SiO2, 17.15% Al2O3, 0.02% Fe2O3, 0.03% TiO2, 1.83% CaO, 1.78% MgO, 4.07% K2O, 3.95% Na2O, 0.11% ZrO2, 3.22% ZnO, 7.58% BaO, 1.75% SrO, and 0.09% loss on ignition; the particle size D90 of the jade dry particles is 90 μm.

[0051] A method for preparing a ceramic tile comprises the following steps:

[0052] (1) According to the chemical composition, the raw materials of jade dry particles are weighed and mixed, melted at 1400° C. for 9 hours, and then poured into water for quenching to obtain frit particles; the frit particles are then ground to obtain jade dry particle powder;

[0053] (2) weighing the raw materials of the color-changing dry granules according to their chemical composition, mixing them, melting them at 1300° C. for 8 hours, then pouring them into water and quenching them to obtain frit particles; then grinding the frit particles to obtain color-changing dry granule powder;

[0054] (3) The jade dry powder obtained in step (1), the color-changing dry powder obtained in step (2), glue and water are mixed in a mass ratio of 15:1:16:8 to obtain a specific gravity of 1.52 g / cm 3 Color-changing dry granular glaze slurry;

[0055] (4) The jade dry powder obtained in step (1), glue and water were mixed in a mass ratio of 1:0.9:0.6 to obtain a specific gravity of 1.51 g / cm 3 Jade dry granular glaze slurry;

[0056] (5) According to the chemical composition, the raw materials of the glaze layer were weighed, and water was added (the mass ratio of the material to the water was 100:39) and ball milled. After screening and iron removal, the specific gravity was 1.91 g / cm 3 glaze slurry;

[0057] (6) According to the chemical composition, the raw materials of the protective glaze layer were weighed, and water was added (the mass ratio of the material to the water was 100:61) and ball milled. After screening and iron removal, the specific gravity was 1.41 g / cm 3 protective glaze slurry;

[0058] (7) Apply the glaze slurry prepared in the above steps on the surface of the green body layer (the glaze amount is 705g / m 2 ), inkjet print pattern; then according to the preset pattern, use digital glaze spraying to apply jade dry granular glaze slurry and color-changing dry granular glaze slurry; finally spray protective glaze slurry (spraying amount is 64g / m 2), dried, and fired at 1195° C. for 59 minutes (the holding time at the highest firing temperature is 9 minutes) to obtain the ceramic tile of this embodiment.

[0059] Example 2

[0060] A ceramic dry particle glaze, the raw material components of which include jade dry particles and color-changing dry particles.

[0061] The chemical composition of the color-changing dry particles, by weight percentage, includes: 56.26% SiO2, 16.43% Al2O3, 0.02% Fe2O3, 0.04% TiO2, 6.75% CaO, 1.42% MgO, 3.86% K2O, 2.05% Na2O, 6.21% B2O3, 0.11% ZrO2, 2.24% ZnO, 2.48% BaO, 1.32% SrO, 0.65% AgI, and 0.16% loss on ignition; the particle size D90 of the color-changing dry particles is 60 μm.

[0062] The chemical composition of the jade dry particles, by weight percentage, includes: 59.15% SiO2, 16.52% Al2O3, 0.02% Fe2O3, 0.03% TiO2, 1.92% CaO, 1.48% MgO, 4.08% K2O, 4.05% Na2O, 0.13% ZrO2, 2.77% ZnO, 8.07% BaO, 1.69% SrO, and 0.09% loss on ignition; the particle size D90 of the jade dry particles is 93 μm.

[0063] A method for preparing a ceramic tile comprises the following steps:

[0064] (1) According to the chemical composition, raw materials of jade dry particles are weighed and mixed, melted at 1420° C. for 9 hours, and then poured into water for quenching to obtain frit particles; the frit particles are then ground to obtain jade dry particle powder;

[0065] (2) weighing the raw materials of the color-changing dry granules according to their chemical composition, mixing them, melting them at 1350° C. for 9 hours, pouring them into water and quenching them to obtain frit particles; then grinding the frit particles to obtain the color-changing dry granule powder;

[0066] (3) The jade dry powder obtained in step (1), the color-changing dry powder obtained in step (2), glue and water are mixed in a mass ratio of 21:1:20:9.5 to obtain a specific gravity of 1.55 g / cm 3 Color-changing dry granular glaze slurry;

[0067] (4) The jade dry powder obtained in step (1), glue and water were mixed in a mass ratio of 1:0.88:0.6 to obtain a specific gravity of 1.54 g / cm 3 Jade dry granular glaze slurry;

[0068] (5) According to the chemical composition, the raw materials of the glaze layer were weighed, and water was added (the mass ratio of the material to the water was 100:39) and ball milled. After screening and iron removal, the specific gravity was 1.91 g / cm 3 glaze slurry;

[0069] (6) According to the chemical composition, the raw materials of the protective glaze layer were weighed, and water was added (the mass ratio of the material to the water was 100:61) and ball milled. After screening and iron removal, the specific gravity was 1.41 g / cm 3 protective glaze slurry;

[0070] (7) Apply the glaze slurry prepared in the above steps on the surface of the green body layer (the glaze amount is 705g / m 2 ), inkjet print pattern; then according to the preset pattern, use digital glaze spraying to apply jade dry granular glaze slurry and color-changing dry granular glaze slurry; finally spray protective glaze slurry (spraying amount is 66g / m 2 ), dried, and fired at 1200° C. for 56 minutes (the holding time at the highest firing temperature is 8 minutes) to obtain the ceramic tile of this embodiment.

[0071] Example 3

[0072] A ceramic dry particle glaze, the raw material components of which include jade dry particles and color-changing dry particles.

[0073] The chemical composition of the color-changing dry particles, by weight percentage, includes: 55.42% SiO2, 16.83% Al2O3, 0.02% Fe2O3, 0.04% TiO2, 6.84% CaO, 1.61% MgO, 3.95% K2O, 2.15% Na2O, 6.83% B2O3, 0.08% ZrO2, 1.83% ZnO, 2.68% BaO, 1.38% SrO, 0.25% AgBr, and 0.09% loss on ignition; the particle size D90 of the color-changing dry particles is 63 μm.

[0074] The chemical composition of the jade dry particles, by weight percentage, includes: 57.62% SiO2, 16.65% Al2O3, 0.03% Fe2O3, 0.04% TiO2, 2.13% CaO, 1.69% MgO, 4.21% K2O, 4.13% Na2O, 0.14% ZrO2, 3.33% ZnO, 8.27% BaO, 1.64% SrO, and 0.12% loss on ignition; the particle size D90 of the jade dry particles is 95 μm.

[0075] A method for preparing a ceramic tile comprises the following steps:

[0076] (1) According to the chemical composition, raw materials of jade dry particles are weighed and mixed, melted at 1450° C. for 8 hours, and then poured into water for quenching to obtain frit particles; the frit particles are then ground to obtain jade dry particle powder;

[0077] (2) weighing the raw materials of the color-changing dry granules according to their chemical composition, mixing them, melting them at 1400° C. for 8 hours, then pouring them into water and quenching them to obtain frit particles; then grinding the frit particles to obtain color-changing dry granule powder;

[0078] (3) The jade dry powder obtained in step (1), the color-changing dry powder obtained in step (2), glue and water are mixed in a mass ratio of 18:1:19:6 to obtain a specific gravity of 1.53 g / cm 3 Color-changing dry granular glaze slurry;

[0079] (4) The jade dry powder obtained in step (1), glue and water were mixed in a mass ratio of 1:1:0.52 to obtain a specific gravity of 1.50 g / cm 3 Jade dry granular glaze slurry;

[0080] (5) According to the chemical composition, the raw materials of the glaze layer were weighed, and water was added (the mass ratio of the material to the water was 100:39) and ball milled. After screening and iron removal, the specific gravity was 1.91 g / cm 3 glaze slurry;

[0081] (6) According to the chemical composition, the raw materials of the protective glaze layer were weighed, and water was added (the mass ratio of the material to the water was 100:62) and ball milled. After screening and iron removal, the specific gravity was 1.39 g / cm 3 protective glaze slurry;

[0082] (7) Apply the glaze slurry prepared in the above steps on the surface of the green body layer (the glaze amount is 708g / m 2 ), inkjet print pattern; then according to the preset pattern, use digital glaze spraying to apply jade dry granular glaze slurry and color-changing dry granular glaze slurry; finally spray protective glaze slurry (spraying amount is 68g / m 2 ), dried, and fired at 1185° C. for 64 minutes (the holding time at the highest firing temperature is 14 minutes) to obtain the ceramic tile of this embodiment.

[0083] Comparative Example 1

[0084] The only difference between Comparative Example 1 and Example 1 is that the ceramic dry particle glaze of Comparative Example 1 does not contain color-changing dry particles, but only jade-like dry particles.

[0085] Comparative Example 2

[0086] The difference between Comparative Example 2 and Example 1 is only that the chemical composition of the jade dry particles is different. The chemical composition of the jade dry particles in the ceramic dry particle glaze of Comparative Example 2 includes, by weight percentage, 57.78% SiO2, 17.31% Al2O3, 0.03% Fe2O3, 0.04% TiO2, 7.83% CaO, 2.12% MgO, 3.96% K2O, 3.82% Na2O, 0.14% ZrO2, 3.18% ZnO, 1.58% BaO, 2.08% SrO, and 0.13% loss on ignition.

[0087] Comparative Example 3

[0088] The difference between Comparative Example 3 and Example 1 is only the chemical composition of the color-changing dry particles. The chemical composition of the color-changing dry particles in the ceramic dry particle glaze of Comparative Example 3 includes, by weight percentage: 57.35% SiO2, 16.78% Al2O3, 0.02% Fe2O3, 0.05% TiO2, 6.78% CaO, 2.36% MgO, 4.34% K2O, 4.16% Na2O, 0.11% ZrO2, 3.32% ZnO, 2.77% BaO, 1.24% SrO, 0.56% AgBr, and 0.16% loss on ignition.

[0089] Comparative Example 4

[0090] The only difference between Comparative Example 4 and Example 1 is that the particle sizes of the color-changing dry particles and the jade-like dry particles are different. In Comparative Example 4, the particle size D90 of the color-changing dry particles is 96 μm; the particle size D90 of the jade-like dry particles is 90 μm.

[0091] Performance Testing

[0092] 1. Transmittance

[0093] According to the test requirements of the ultraviolet-visible spectrophotometer in the standard "GB / T 2680-2021 Architectural glass - Determination of visible light transmittance, direct sunlight transmittance, total solar energy transmittance, ultraviolet transmittance and related window glass parameters", the measurement wavelength range is 400-2000nm, and the transmittance performance test of the ceramic dry granular glaze samples prepared in the above Examples 1-3 and Comparative Examples 1-3 is carried out. The measuring equipment is a Japan Shimadzu UV-1800 ultraviolet-visible spectrophotometer, and the transmittance of the sample is a 2 mm thick double-sided mirror-polished sample at a wavelength of 750nm (red light). The results are shown in Table 1.

[0094] Table 1:

[0095] sample Transmittance (%) Transmittance after UV treatment (%) Example 1 51.96 34.30 Example 2 51.16 33.67 Example 3 53.75 36.24 Comparative Example 1 54.37 53.95 Comparative Example 2 76.35 68.55 Comparative Example 3 28.26 26.46

[0096] Table 1 shows that the transmittance of the samples prepared in Examples 1-3 all showed a significant decrease before and after UV irradiation, indicating that the effect of UV light on the silver halide significantly increased the scattering area in the glaze layer. Specifically, Example 2 shows a similar transmittance trend compared to Example 1, except that silver bromide was replaced with silver iodide. Example 3 shows a slight increase in transmittance compared to Example 1, except that the silver bromide content was reduced.

[0097] Since the ceramic dry particle glaze of Comparative Example 1 does not contain color-changing dry particles, the transparency of the glaze layer does not change significantly before and after ultraviolet light irradiation.

[0098] Since the BaO content in the jade dry particles of Comparative Example 2 is low, the transparency of the glaze layer is significantly improved, indicating that the crystals in the glaze layer are reduced.

[0099] Since the color-changing dry particles of Comparative Example 3 do not contain B2O3 and only use silver bromide as a colorant, the transparency of the glaze layer does not change significantly before and after ultraviolet light irradiation.

[0100] 2. Color change performance

[0101] Using an American X-Rite Ci64 colorimeter, the glaze surface of the ceramic tile samples prepared in Example 1 and Comparative Examples 1-4 was tested before and after ultraviolet light irradiation and 3 minutes before and after hot water splashing in accordance with the standard "GB / T 36142-2018 Measurement of color and color difference of architectural glass". The results are shown in Table 2.

[0102] Table 2:

[0103]

[0104] It can be seen from Table 2 that after the ceramic tile sample prepared in Example 1 was irradiated with ultraviolet light, the yellow color became significantly darker and the milky feeling was obvious; after being splashed with hot water, the sample returned to a light yellow, transparent and crystal effect.

[0105] Since the ceramic dry particle glaze of Comparative Example 1 does not contain color-changing dry particles, the glaze layer presents a milky white jade effect. After being irradiated with ultraviolet light, no color change effect occurs; after being splashed with hot water, no obvious change occurs.

[0106] The jade-like dry particles in Comparative Example 2 have a lower BaO content, and the transparency of the glaze layer increases, but do not have a jade-like effect. After ultraviolet irradiation, the glaze layer changes from light yellow to light gray. Due to the enhanced light transmission ability, the light gray can return to light yellow after a period of time. After being splashed with hot water, there is no obvious change compared with before splashing.

[0107] Since the color-changing dry particles in Comparative Example 3 do not contain B2O3 and only use silver bromide as a colorant, the color of the glaze layer does not change significantly before and after ultraviolet exposure and before and after hot water splashing.

[0108] In Comparative Example 4, since the particle size of the color-changing dry particles is close to that of the jade dry particles, the area of ​​the color-changing dry particles becomes larger, affecting the color distribution in the glaze layer and forming a variegated area in the milky white transparent glaze layer.

[0109] For those skilled in the art to which the present invention belongs, a number of simple deductions or substitutions can be made without departing from the concept of the present invention, without having to resort to creative work. Therefore, based on the disclosure of the present invention, simple improvements made by those skilled in the art to the present invention should be within the scope of protection of the present invention. The above embodiments are preferred embodiments of the present invention, and all processes similar to the present invention and equivalent changes made should fall within the scope of protection of the present invention.

Claims

1. A ceramic dry granular glaze, characterized in that: The raw material components include jade dry particles and color-changing dry particles. The jade dry particles are celsium feldspar-type jade dry particles, and the content of BaO in the chemical composition of the jade dry particles is 5-10wt%; The chemical composition of the color-changing dry particles comprises, by weight percentage, 55.00-58.00% SiO2, 14.00-17.00% Al2O3, 0.01-0.03% Fe2O3, 0.01-0.05% TiO2, 5.00-7.00% CaO, 1.00-2.00% MgO, 3.50-4.50% K2O, 1.50-3.00% Na2O, 4.00-7.00% B2O3, 0.05-0.20% ZrO2, 1.50-3.00% ZnO, 1.50-3.00% BaO, 1.00-2.00% SrO, 0.20-0.80% silver halide, and 0.05-0.20% loss on ignition. The particle size of the jade-like dry particles is between 90-106 μm; and / or the particle size of the color-changing dry particles is between 45-75 μm.

2. The ceramic dry granular glaze according to claim 1, characterized in that The chemical composition of the jade dry particles comprises, by weight percentage, 56.00-61.00% of SiO2, 16.00-18.00% of Al2O3, 0.01-0.03% of Fe2O3, 0.01-0.05% of TiO2, 1.50-2.50% of CaO, 1.00-2.00% of MgO, 3.50-4.50% of K2O, 3.50-4.50% of Na2O, 0.05-0.20% of ZrO2, 2.50-3.50% of ZnO, 6.50-9.00% of BaO, 1.00-2.00% of SrO, and 0.05-0.20% of loss on ignition.

3. The ceramic dry granular glaze according to claim 1, characterized in that The mass ratio of the jade-like dry particles to the color-changing dry particles is (7-22):

1.

4. The ceramic dry granular glaze according to claim 1, characterized in that The silver halide is AgBr or AgI.

5. The ceramic dry granular glaze according to claim 1, characterized in that The preparation steps of the jade-like dry particles include: The raw materials for preparing the jade dry particles are mixed, melted at 1400-1450° C. for 8-10 hours, poured into water for quenching to obtain jade frit particles, and crushed to obtain the jade dry particles; And / or, the preparation steps of the color-changing dry particles include: mixing the raw materials for preparing the color-changing dry particles, melting them at 1300-1400° C. for 8-10 hours, pouring them into water for quenching to obtain color-changing frit particles, and crushing them to obtain the color-changing dry particles.

6. A ceramic tile, characterized in that: From bottom to top, it includes a body layer, a surface glaze layer, a pattern layer, a dry granular glaze layer and a protective glaze layer. The dry granular glaze layer includes a color-changing area and a jade area. The color-changing area is formed by firing the ceramic dry granular glaze according to any one of claims 1 to 5; the jade area is formed by firing the jade dry granules.

7. The ceramic tile according to claim 6, characterized in that The color change areas are distributed in the jade area in the form of dots, lines or blocks.

8. A method for preparing a ceramic tile according to claim 6 or 7, characterized in that: The following steps are involved: Taking the raw material of the green body layer to prepare the green body layer; Mixing jade dry particles, color-changing dry particles, glue and water to obtain color-changing dry particle glaze slurry; Mixing jade dry particles, glue and water to obtain jade dry particle glaze slurry; The raw materials of the surface glaze layer and the protective glaze layer are respectively taken to prepare the surface glaze slurry and the protective glaze slurry; The surface glaze slurry is applied on the surface of the green body layer in sequence, a pattern is inkjet printed, the jade-like dry granular glaze slurry, the color-changing dry granular glaze slurry and the protective glaze slurry are applied, and after drying and firing, the ceramic tile is obtained.

9. The method for preparing ceramic tiles according to claim 8, characterized in that: The maximum firing temperature is 1170-1210° C.; and / or the firing period is 55-65 minutes.

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