Photosensitive color-changing glaze and its preparation method and application

Abstract

The present invention discloses a photochromic glaze, a preparation method, and an application thereof, and relates to the field of ceramic technology. The photochromic glaze comprises the following components, calculated by mass percentage: SiO2 47.0-49.0%, Al2O3 29.0-33.0%, ZrO2 5.0-10.0%, Na2O 4.0-5.0%, rare earth oxides 2.0-5.0%, K2O 1.0-2.0%, CaO 0.5-1.5%, MgO 0.5-1.5%, ZnO 0.3-0.9%, B2O3 0.2-0.5%, Fe2O3 0.1-0.2%, TiO2 0.1-0.2%, and a loss on ignition of 2.0-5.0%, with the sum of the mass percentages of the above components being 100%. The present invention also provides a method for preparing the photosensitive glaze and its application in preparing photosensitive color-changing full-glazed tiles. The photosensitive color-changing glaze of the present invention, combined with a specific process, produces fully-glazed tiles that exhibit different colors under different light sources, making the product more artistic and ornamental, practical and wear-resistant, and enriching the variety of fully-glazed products.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramics, and in particular to a photosensitive color-changing glaze and a preparation method and application thereof. Background Art

[0002] Color-changing glazes are special-effect glazes that appear different colors under different light sources. These glazes typically use a white base glaze, with coloring elements such as metal oxides, non-metal oxides, and mixed rare earth oxides like neodymium, cerium, and praseodymium. These glazes are processed through a specialized process to create a glaze slurry, which is then applied to the surface of the base. Firing at an appropriate temperature triggers a series of physical and chemical changes, creating a new solid solution with varying degrees of selective absorption and reflection across various wavelengths within the visible light range. Therefore, the color of these glazes changes with the light source.

[0003] For example, Chinese patent ZL200910254659.9 discloses a metallic luster ceramic glaze with a color-changing effect and its preparation method. The glaze consists of a base metallic base glaze and a color-changing top glaze. The base metallic base glaze and the color-changing top glaze are separately blended according to the desired ingredients, then ball-milled and sieved. The resulting color-changing metallic glaze features diverse colors, excellent glaze quality, strong mechanical properties, high chemical stability, a metallic texture, and changes color under different light sources.

[0004] Chinese Patent ZL200910047570.5 discloses a rare earth ceramic glaze pigment that changes color under different light sources. The pigment is composed of a color-changing neodymium red pigment and a feldspar glaze. This rare earth neodymium red color-changing glaze combines the color-changing pigment with the glaze's ceramic base to create a color-changing glaze product that displays different colors under different light sources. For example, it appears light blue under fluorescent light, lilac red under natural light, and light green under energy-saving light.

[0005] Chinese patent CN201110416722 discloses a neodymium-doped color-changing glaze and its preparation method. The neodymium-doped color-changing glaze displays different colors under different lighting conditions, such as orange under fluorescent light and pink under natural light. It has a unique color-changing advantage and is quite distinctive.

[0006] In recent years, white fully glazed tiles are a classic product that is very popular in the market. At present, there is no research on the application of color-changing glaze in fully glazed glaze and fully glazed tiles to make fully glazed tiles have photosensitive color-changing effects, resulting in insufficient richness of fully glazed tile product categories. Summary of the Invention

[0007] In response to the above shortcomings, the present invention provides a photosensitive color-changing glaze, a preparation method and application thereof. The photosensitive color-changing glaze is combined with a specific process to prepare a full-glazed ceramic tile that presents different colors under different light sources. The product is more artistic and ornamental, practical and wear-resistant, enriching the variety of full-glazed products.

[0008] The specific technical solutions are as follows:

[0009] A photosensitive color-changing glaze comprises the following components, measured in percentage by mass: SiO2 47.0-49.0%, Al2O3 29.0-33.0%, ZrO2 5.0-10.0%, Na2O 4.0-5.0%, rare earth oxide 2.0-5.0%, K2O 1.0-2.0%, CaO 0.5-1.5%, MgO 0.5-1.5%, ZnO 0.3-0.9%, B2O3 0.2-0.5%, Fe2O3 0.1-0.2%, TiO2 0.1-0.2% and loss on ignition 2.0-5.0%, and the sum of the percentages by mass of the above components is 100%.

[0010] Furthermore, the rare earth oxides are one or more of neodymium oxide, erbium oxide, and praseodymium oxide.

[0011] The present invention also provides a method for preparing the photosensitive color-changing glaze, comprising the following steps:

[0012] (1) Weighing each raw material component by mass percentage and uniformly mixing the weighed raw material components to obtain a mixed raw material;

[0013] (2) placing the above mixed raw materials, water, carboxymethyl cellulose and sodium tripolyphosphate into a ball mill for ball milling, and controlling the ball fineness to be 0.5-0.8 wt% after passing through a 325 mesh sieve to obtain a ball mill material;

[0014] (3) aging the ball mill material for 18-24 hours to obtain the photosensitive color-changing glaze.

[0015] The present invention also provides application of the photochromic glaze in preparing photochromic full-glazed ceramic tiles.

[0016] Furthermore, the preparation method of the photochromic fully polished glazed ceramic tile comprises the following steps:

[0017] S1: Pressing the green body powder to obtain a green body;

[0018] S2: grinding and drying the green body in sequence to obtain a green body, wherein the green body has a moisture content of 0.2-0.4 wt %;

[0019] S3: spraying water to moisten the surface of the blank;

[0020] S4: applying the photochromic glaze on the wetted surface of the blank by a bell-shaped glaze pouring method to form a photochromic layer, thereby obtaining a photosensitive blank;

[0021] S5: Printing a pattern on the surface of the photosensitive blank using a digital inkjet printer to obtain a printed blank; the pattern is a simple, elegant, and classic popular white ceramic tile pattern in recent years;

[0022] S6: applying a glaze on the surface of the printed body by a bell-shaped glaze pouring method to form a glaze layer, thereby obtaining a glaze body;

[0023] S7: drying, firing, polishing and edge grinding the glazed body in sequence to obtain the photochromic full-glazed ceramic tile.

[0024] Furthermore, in step S1, the composition of the green body powder includes, by mass percentage, the following components: SiO2 65.0-70.0%, Al2O3 18.0-22.0%, CaO 0.3-0.8%, Na2O 2.0-3.0%, MgO 0.5-1.0%, K2O 3.0-4.0%, Fe2O3 0.3-0.8%, TiO2 0.1-0.2%, and a loss on ignition of 3.8-4.6%. The green body powder also has a particle size distribution, by mass percentage, of 20 mesh: ≤1%, 30 mesh and above: 10-20%, 30-60 mesh: 65-75%, 60-80 mesh: ≤12%, and below 80 mesh: ≤6%.

[0025] Furthermore, in step S3, the amount of water sprayed is 60-100 g / m 2 The water is sprayed using two spray guns, and the nozzle size of the spray gun is 0.52-0.62 mm.

[0026] Furthermore, in steps S4 and S6, the glaze amount of the bell jar is 480-580 g / m 2 , specific gravity is 1.82-1.92g / ml, and flow rate is 26-32s.

[0027] Furthermore, in step S6, the glaze comprises the following components in mass percentage: SiO2 48.0-50.0%, Al2O3 14.0-16.0%, CaO 8.0-9.0%, Na2O 5.0-5.5%, MgO 4.0-5.0%, SrO 3.0-4.0%, ZnO 2.0-3.0%, SO3 2.0-2.5%, K2O 0.4-0.6%, BaO 0.1-0.2%, Fe2O3 0.1-0.2% and loss on ignition 8.0-10.0%, and the sum of the mass percentages of the above components is 100%, and the fineness requirement of the glaze is that the residue on the sieve passing through a 325-mesh sieve is 0.4-0.6wt%.

[0028] Furthermore, in step S7, the sintering time is 40-50 minutes and the temperature is 1100-1215°C.

[0029] The present invention also provides a photosensitive color-changing fully polished glaze ceramic tile prepared by the above method.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1. The present invention innovatively applies the principle of color-changing glaze to research and develop fully-glazed ceramic tiles with photosensitive color-changing properties. The fully-glazed ceramic tiles can present different colors under different light sources. They are not only practical, but also artistic and ornamental, enriching the variety of fully-glazed products.

[0032] 2. The present invention uses metal oxides, non-metal oxides and mixed rare earth oxides such as neodymium, cerium, and praseodymium as coloring elements, reasonably formulates and processes them into photosensitive color-changing glaze slurry through a specific process, and applies it to the surface of the blank, and then glazes it and burns it under appropriate conditions to produce a series of physical and chemical changes to generate a new solid solution. This solid solution has different degrees of selective absorption and reflection characteristics for various wavelengths of light within the visible light range. The glaze surface can change color with the change of light source, so that the surface of the glazed ceramic tile can achieve a photosensitive color-changing effect, appearing purple under natural light or incandescent lamps, and sky blue under fluorescent lamps. It is also practical and wear-resistant. DETAILED DESCRIPTION

[0033] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0034] Example 1

[0035] A photosensitive color-changing fully glazed ceramic tile, the production process of which is as follows: press molding → body drying → glaze application → inkjet printing pattern → glaze application → drying → firing → polishing → edge grinding → packaging. The specific method is as follows:

[0036] 1) Material preparation

[0037] (1) Preparation of green body powder

[0038] The green body powder comprises the following components by mass percentage: SiO2 68.15%, Al2O3 20%, CaO 0.5%, Na2O2.5%, MgO 0.7%, K2O 3.5%, Fe2O3 0.5%, TiO2 0.15% and loss on ignition 4.0%. The above components are mixed evenly, and the particle size distribution of the mixed powder is adjusted to (by mass percentage): 20 mesh: 0.5%, above 30 mesh: 15%, 30-60 mesh: 71%, 60-80 mesh: 8.5%, and below 80 mesh: 5%, thereby obtaining the green body powder for later use.

[0039] (2) Preparation of photochromic glaze

[0040] The mixed raw materials include the following components in mass percentage: SiO2 48.73%, Al2O3 30.99%, ZrO2 5.5%, Na2O 4.29%, Nd2O3 3.77%, K2O 1.36%, CaO 0.94%, MgO 0.89%, ZnO 0.56%, B2O3 0.28%, Fe2O3 0.16%, TiO2 0.14% and loss on ignition 2.39%; the above mixed raw materials, 38% of water, 0.13% of carboxymethyl cellulose and 0.3% of sodium tripolyphosphate are put into a ball mill for ball milling, and the ball fineness is controlled to be 0.5wt% after passing through a 325-mesh sieve, thereby obtaining a ball-milled material; the ball-milled material is aged for 18 hours to obtain the photosensitive color-changing glaze, which is ready for use.

[0041] (3) Glaze preparation

[0042] Calculated in percentage by mass, it includes the following components: SiO2 48.54%, Al2O3 15.31%, CaO 8.64%, Na2O5.24%, MgO 4.73%, SrO 3.35%, ZnO 2.48%, SO3 2.31%, K2O 0.51%, BaO 0.15%, Fe2O30.16% and loss on ignition 8.58%, and the fineness requirement of the glaze is that the residue on the 325-mesh sieve is 0.50wt%.

[0043] 2) Pressing the green body powder by a press to obtain a green body.

[0044] 3) The green body is ground in turn by a grinding machine, and then placed in a drying kiln for drying for 50 minutes to obtain a green body with a certain strength and a moisture content of 0.3 wt%.

[0045] 4) Use two spray guns with a nozzle size of 0.58 mm to spray water to wet the surface of the blank, with a water spray rate of 85 g / m 2 ;

[0046] 5) Apply the photochromic glaze on the wetted surface of the blank by using a bell jar glazing method to form a photochromic layer, with a glaze amount of 520g / m 2 , specific gravity is 1.90g / ml, flow rate is 30s, and photosensitive blank is obtained;

[0047] 6) Printing a white pattern on the surface of the photosensitive blank using a digital inkjet printer to obtain a printed blank;

[0048] 7) Apply glaze to the surface of the printed body by bell jar glazing to form a glaze layer, with a glaze amount of 520g / m 2 , specific gravity is 1.90g / ml, flow rate is 30s, and glaze body is obtained;

[0049] 8) The glazed green body is dried in a pre-kiln drying kiln and then fired in a kiln at a temperature of 1210° C. for 45 minutes to obtain the photochromic full-glazed ceramic tile;

[0050] 9) After the photosensitive color-changing fully glazed ceramic tiles are polished and edge-ground, they can be packed and put into storage.

[0051] Example 2

[0052] A photosensitive color-changing fully glazed ceramic tile, the production process of which is as follows: press molding → body drying → glaze application → inkjet printing pattern → glaze application → drying → firing → polishing → edge grinding → packaging. The specific method is as follows:

[0053] 1) Material preparation

[0054] (1) Preparation of green body powder

[0055] The green body powder comprises the following components by mass percentage: SiO2 65.0%, Al2O3 22.0%, CaO 0.8%, Na2O 3.0%, MgO 1.0%, K2O 4.0%, Fe2O3 0.8%, TiO2 0.2% and loss on ignition 3.8%. The above components are mixed evenly, and the particle size distribution of the mixed powder is adjusted to (by mass percentage): 20 mesh: 1%, above 30 mesh: 10%, 30-60 mesh: 75%, 60-80 mesh: 12%, and below 80 mesh: 2%, thereby obtaining the green body powder for later use.

[0056] (2) Preparation of photochromic glaze

[0057] The mixed raw materials include the following components in mass percentage: SiO2 47.0%, Al2O3 29.0%, ZrO2 10.0%, Na2O 5.0%, a mixture of Er2O3 and Nd2O3 2.0%, K2O 2.0%, CaO 0.5%, MgO 0.5%, ZnO 0.3%, B2O3 0.2%, Fe2O3 0.1%, TiO2 0.13% and loss on ignition 3.27%; the above mixed raw materials, 38% of water, 0.13% of carboxymethyl cellulose and 0.3% of sodium tripolyphosphate are put into a ball mill for ball milling, and the ball fineness is controlled to be 0.7wt% after passing through a 325-mesh sieve, thereby obtaining a ball-milled material; the ball-milled material is aged for 20 hours to obtain the photosensitive color-changing glaze, which is ready for use.

[0058] (3) Glaze preparation

[0059] Calculated in percentage by mass, it includes the following components: SiO2 48.0%, Al2O3 14.0%, CaO 9.0%, Na2O5.5%, MgO5.0%, SrO 4.0%, ZnO 3.0%, SO3 2.5%, K2O 0.6%, BaO 0.2%, Fe2O3 0.2% and loss on ignition 8.0%, and the fineness of the glaze is required to be 0.4wt% of the residue on the 325-mesh sieve.

[0060] 2) Pressing the green body powder by a press to obtain a green body.

[0061] 3) The green body is ground in turn by a grinding machine, and then placed in a drying kiln for drying for 40 minutes to obtain a green body with a certain strength and a moisture content of 0.2 wt%.

[0062] 4) Use two spray guns with a nozzle size of 0.52mm to spray water to wet the surface of the blank, with a water spray rate of 100g / m 2 ;

[0063] 5) Apply the photochromic glaze on the wetted surface of the blank by means of bell jar glazing to form a photochromic layer, with the glaze amount being 480g / m 2 , specific gravity is 1.82g / ml, flow rate is 32s, and photosensitive blank is obtained;

[0064] 6) Printing a white pattern on the surface of the photosensitive blank using a digital inkjet printer to obtain a printed blank;

[0065] 7) Apply glaze to the surface of the printed body by bell jar glazing to form a glaze layer, with a glaze amount of 480g / m 2 , specific gravity is 1.82g / ml, flow rate is 32s, and the glaze body is obtained;

[0066] 8) The glazed green body is dried in a pre-kiln drying kiln and then fired in a kiln at a temperature of 1215° C. for 40 minutes to obtain the photochromic full-glazed ceramic tile;

[0067] 9) After the photosensitive color-changing fully glazed ceramic tiles are polished and edge-ground, they can be packed and put into storage.

[0068] Example 3

[0069] A photosensitive color-changing fully glazed ceramic tile, the production process of which is as follows: press molding → body drying → glaze application → inkjet printing pattern → glaze application → drying → firing → polishing → edge grinding → packaging. The specific method is as follows:

[0070] 1) Material preparation

[0071] (1) Preparation of green body powder

[0072] The green body powder comprises the following components by mass percentage: SiO2 70.0%, Al2O3 19.0%, CaO 0.3%, Na2O 2.0%, MgO 0.5%, K2O 3.0%, Fe2O3 0.5%, TiO2 0.1% and loss on ignition 4.6%. The above components are mixed evenly, and the particle size distribution of the mixed powder is adjusted to (by mass percentage): 20 mesh: 0.8%, above 30 mesh: 20%, 30-60 mesh: 65%, 60-80 mesh: 8.2%, below 80 mesh: 6%, thereby obtaining the green body powder for later use.

[0073] (2) Preparation of photochromic glaze

[0074] The mixed raw materials include the following components in mass percentage: SiO2 49%, Al2O3 29%, ZrO2 5%, Na2O4.0%, Nd2O3 and Er2O3 5.0%, K2O 1.0%, CaO 1.5%, MgO 1.5%, ZnO 0.9%, B2O3 0.5%, Fe2O3 0.2%, TiO2 0.15% and ignition loss 2.25%; the above mixed raw materials, 38% water, 0.13% carboxymethyl cellulose and 0.3% sodium tripolyphosphate are put into a ball mill for ball milling, and the ball fineness is controlled to be 0.8wt% after passing through a 325 mesh sieve to obtain a ball mill material; the ball mill material is aged for 24 hours to obtain the photosensitive color-changing glaze, which is ready for use.

[0075] (3) Glaze preparation

[0076] Calculated in percentage by mass, it includes the following components: SiO2 50%, Al2O3 16%, CaO 8.0%, Na2O 5.0%, MgO4.0%, SrO 3.0%, ZnO 2.0%, SO3 2.0%, K2O 0.4%, BaO 0.1%, Fe2O3 0.1% and loss on ignition 9.4%, and the sum of the mass percentages of the above components is 100%, and the fineness requirement of the glaze is that the residue on the sieve of 325 mesh is 0.6wt%.

[0077] 2) Pressing the green body powder by a press to obtain a green body.

[0078] 3) The green body is ground in turn by a grinding machine, and then placed in a drying kiln for drying for 60 minutes to obtain a green body with a certain strength and a moisture content of 0.2 wt%.

[0079] 4) Use two spray guns with a nozzle size of 0.62mm to spray water to wet the surface of the blank, with a water spray rate of 60g / m 2 ;

[0080] 5) Apply the photochromic glaze on the wetted surface of the blank by means of bell jar glazing to form a photochromic layer, with the glaze amount being 580 g / m 2 , specific gravity is 1.92g / ml, flow rate is 26s, and photosensitive blank is obtained;

[0081] 6) Printing a white pattern on the surface of the photosensitive blank using a digital inkjet printer to obtain a printed blank;

[0082] 7) Apply glaze to the surface of the printed body by bell jar glazing to form a glaze layer, with a glaze amount of 580g / m 2 , specific gravity is 1.92g / ml, flow rate is 26s, and glaze body is obtained;

[0083] 8) The glazed green body is dried in a pre-kiln drying kiln and then fired in a kiln. The firing time is 40-50 minutes at a temperature of 1200° C. to obtain the photochromic full-glazed ceramic tile.

[0084] 9) After the photosensitive color-changing fully glazed ceramic tiles are polished and edge-ground, they can be packed and put into storage.

[0085] Example 4

[0086] A photosensitive color-changing fully glazed ceramic tile, the production process of which is as follows: press molding → body drying → glaze application → inkjet printing pattern → glaze application → drying → firing → polishing → edge grinding → packaging. The specific method is as follows:

[0087] 1) Material preparation

[0088] (1) Preparation of green body powder

[0089] The green body powder comprises the following components by mass percentage: SiO2 69.04%, Al2O3 19.1%, CaO 0.6%, Na2O 2.3%, MgO 0.6%, K2O 3.4%, Fe2O3 0.7%, TiO2 0.14% and loss on ignition 4.12%. The above components are mixed evenly, and the particle size distribution of the mixed powder is adjusted to (by mass percentage): 20 mesh: 0.4%, above 30 mesh: 17%, 30-60 mesh: 68%, 60-80 mesh: 10%, and below 80 mesh: 4.6%, thereby obtaining the green body powder for later use.

[0090] (2) Preparation of photochromic glaze

[0091] The mixed raw materials include the following components in percentage by mass: SiO2 48.9%, Al2O3 29.12%, ZrO2 5.7%, Na2O 4.42%, rare earth oxides 4.22% (rare earth oxides are Nd2O3, Er2O3 and Pr2O3), K2O 1.48%, CaO 1.27%, MgO 1.19%, ZnO 0.76%, B2O3 0.42%, Fe2O3 0.14%, TiO2 0.13% and loss on ignition 2.25%; the mixed raw materials, 38% water, 0.13% carboxymethyl cellulose and 0.3% sodium tripolyphosphate are put into a ball mill for ball milling, and the ball fineness is controlled to be 0.65wt% after passing through a 325 mesh sieve to obtain a ball mill material; the ball mill material is aged for 21 hours to obtain the photosensitive color-changing glaze, which is ready for use.

[0092] (3) Glaze preparation

[0093] Calculated in percentage by mass, it includes the following components: SiO2 49.15%, Al2O3 14.38%, CaO 8.85%, Na2O5.31%, MgO 4.32%, SrO 3.57%, ZnO 2.4%, SO3 2.1%, K2O 0.53%, BaO 0.17%, Fe2O3 0.17% and loss on ignition 9.22%, and the fineness requirement of the glaze is that the residue on the sieve of 325 mesh is 0.45wt%.

[0094] 2) Pressing the green body powder by a press to obtain a green body.

[0095] 3) The green body was ground in turn using a grinding machine, and then placed in a drying kiln for drying for 45 minutes to obtain a green body with a certain strength and a moisture content of 0.33 wt%.

[0096] 4) Use two spray guns with a nozzle size of 0.58 mm to spray water to wet the surface of the blank, with a water spray rate of 79 g / m 2 ;

[0097] 5) Apply the photochromic glaze on the wetted surface of the blank by using a bell jar glazing method to form a photochromic layer, with a glaze amount of 510g / m 2 , specific gravity is 1.88g / ml, flow rate is 28s, and photosensitive blank is obtained;

[0098] 6) Printing a white pattern on the surface of the photosensitive blank using a digital inkjet printer to obtain a printed blank;

[0099] 7) Apply glaze to the surface of the printed body by bell jar glazing to form a glaze layer, with a glaze amount of 510g / m 2 , specific gravity is 1.88g / ml, flow rate is 28s, and glaze body is obtained;

[0100] 8) The glazed green body is dried in a pre-kiln drying kiln and then fired in a kiln at a temperature of 1140° C. for 40-50 minutes to obtain the photochromic full-glazed ceramic tile;

[0101] 9) After the photosensitive color-changing fully glazed ceramic tiles are polished and edge-ground, they can be packed and put into storage.

[0102] Comparative Example 1

[0103] The preparation process of the fully glazed ceramic tile of Comparative Example 1 is substantially the same as that of Example 1, with the only difference being that the raw materials of the photochromic glaze are as follows: SiO2 52.0%, Al2O3 27.72%, ZrO2 5.5%, Na2O 4.29%, Nd2O3 3.77%, K2O 1.36%, CaO 0.94%, MgO 0.89%, ZnO 0.56%, B2O3 0.28%, Fe2O3 0.16%, TiO2 0.14%, and the loss on ignition is 2.39%. That is, the mass ratio of SiO2 to Al2O3 is changed.

[0104] Comparative Example 2

[0105] The preparation process of the fully glazed ceramic tile of Comparative Example 2 is substantially the same as that of Example 1, with the only difference being that the raw materials for the photochromic glaze are as follows: SiO2 48.73%, Al2O3 30.99%, ZrO2 3.77%, Na2O4.29%, Nd2O3 5.5%, K2O 1.36%, CaO 0.94%, MgO 0.89%, ZnO 0.56%, B2O3 0.28%, Fe2O3 0.16%, TiO2 0.14%, and a loss on ignition of 2.39%. That is, the mass ratios of Nd2O3 and ZrO2 are somewhat different.

[0106] Comparative Example 3

[0107] The preparation process of the fully glazed ceramic tile of Comparative Example 3 is essentially the same as that of Example 1, with the only difference being that the raw materials for the photochromic top glaze are as follows: SiO₂ 48.73%, Al₂O₃ 30.99%, ZrO₂ 5.5%, Na₂O 4.29%, Nd₂O₃ 3.77%, K₂O 1.36%, CaO 0.94%, MgO 0.89%, ZnO 0.56%, B₂O₃ 0.28%, Fe₂O₃ 0.3%, and a loss on ignition of 2.39%. In other words, the TiO₂ component is absent.

[0108] Comparative Example 4

[0109] The preparation process of the fully glazed ceramic tile of Comparative Example 4 is substantially the same as that of Example 1, with the only difference being that the raw materials of the photochromic glaze are as follows: SiO2 48.73%, Al2O3 30.99%, ZrO2 5.5%, Na2O 4.29%, Nd2O3 3.77%, K2O 1.36%, CaO 0.79%, MgO 0.89%, ZnO 0.56%, B2O3 0.28%, Fe2O3 0.16%, TiO2 0.14%, SrO 0.15%, and a loss on ignition of 2.39%. That is, SrO is added.

[0110] Comparative Example 5

[0111] The preparation process of the fully glazed ceramic tile of Comparative Example 5 is basically the same as that of Example 1, with the only difference being that the photochromic surface glaze is the neodymium-doped color-changing glaze disclosed in Chinese patent CN201110416722.

[0112] The whiteness, glossiness, antifouling performance, wear resistance and glaze crack resistance of the fully glazed tiles of Examples 1-4 and Comparative Examples 1-5 were measured, and the results are shown in Table 1 below.

[0113] Table 1 Performance test results of each group of fully glazed tiles

[0114] Group Whiteness Glossiness wear resistance Antifouling performance Example 1 68 70 Level 5 A-level Example 2 69 71 Level 5 A-level Example 3 68 71 Level 5 A-level Example 4 68 70 Level 5 A-level Comparative Example 1 68 73 Level 4 Class B Comparative Example 2 66 68 Level 4 Class B Comparative Example 3 67 69 Level 4 Class B Comparative Example 4 68 70 Level 4 Class B Comparative Example 5 68 67 Level 4 Class B

[0115] As can be seen from Table 1, the performance test results of the fully glazed tiles of Examples 1-4 are significantly better than those of Comparative Examples 1-5, indicating that the photosensitive color-changing glaze of the present invention combined with the remaining process steps of the fully glazed glaze of the present invention can achieve the best performance effect. If the quality or composition of its ingredients is changed, it will be combined with the remaining process steps to affect the final performance of the tiles.

[0116] At the same time, the glaze colors of the fully glazed tiles of Examples 1-4 and Comparative Examples 1-5 were observed under different light sources, and the results are shown in Table 2 below.

[0117] Table 2 Glaze color changes of each group of fully glazed tiles under different light sources

[0118]

[0119]

[0120] It can be seen from Table 2 that changes in the ratio or composition of the photochromic glaze will cause the final color of the fully glazed ceramic tile to change.

[0121] The foregoing descriptions of specific exemplary embodiments of the present invention are for purposes of illustration and description. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is apparent that many variations and modifications are possible in light of the foregoing teachings. The exemplary embodiments have been selected and described for the purpose of explaining the specific principles of the invention and their practical application, thereby enabling those skilled in the art to realize and utilize a variety of exemplary embodiments of the invention and various options and modifications. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A method for preparing photosensitive color-changing fully polished glazed tiles, characterized in that: The following steps are involved: S1: Pressing the green body powder to obtain a green body; S2: grinding and drying the green body in sequence to obtain a green body; S3: spraying water to moisten the surface of the blank; S4: applying a photochromic glaze on the wetted surface of the blank by a bell-shaped glaze pouring method to form a photochromic layer, thereby obtaining a photosensitive blank; S5: Printing a pattern on the surface of the photosensitive body to obtain a printed body; S6: applying a glaze on the surface of the printed body by a bell-shaped glaze pouring method to form a glaze layer, thereby obtaining a glaze body; S7: drying, firing, polishing, and edge grinding the glazed body in sequence to obtain the photochromic fully glazed ceramic tile; the firing time is 40-50 minutes and the temperature is 1100-1215°C; The photochromic glaze is composed of the following components, measured by mass percentage: SiO2 47.0-49.0%, Al2O3 29.0-33.0%, ZrO2 5.0-10.0%, Na2O 4.0-5.0%, rare earth oxides 2.0-5.0%, K2O 1.0-2.0%, CaO 0.5-1.5%, MgO 0.5-1.5%, ZnO 0.3-0.9%, B2O3 0.2-0.5%, Fe2O3 0.1-0.2%, TiO2 0.1-0.2% and loss on ignition 2.0-5.0%, and the sum of the mass percentages of the above components is 100%; the rare earth oxides are one or more of neodymium oxide, erbium oxide, and praseodymium oxide; The polishing glaze includes the following components in mass percentage: SiO2 48.0-50.0%, Al2O3 14.0-16.0%, CaO 8.0-9.0%, Na2O 5.0-5.5%, MgO 4.0-5.0%, SrO 3.0-4.0%, ZnO 2.0-3.0%, SO3 2.0-2.5%, K2O 0.4-0.6%, BaO 0.1-0.2%, Fe2O3 0.1-0.2% and loss on ignition 8.0-10.0%, and the sum of the mass percentages of the above components is 100%.

2. The method for preparing a photosensitive color-changing fully polished glazed ceramic tile according to claim 1, characterized in that: The preparation method of the photosensitive color-changing glaze comprises the following steps: (1) Weigh each raw material component by mass percentage, and mix the weighed raw material components uniformly to obtain a mixed raw material; (2) The mixed raw materials, water, carboxymethyl cellulose and sodium tripolyphosphate are placed in a ball mill for ball milling, and the ball fineness is controlled to be 0.5-0.8 wt% after passing through a 325 mesh sieve to obtain a ball mill material; (3) The ball mill material is aged for 18-24 hours to obtain the photosensitive color-changing glaze.

3. The method for preparing a photosensitive color-changing fully polished glazed ceramic tile according to claim 1, characterized in that: In step S3, the amount of water sprayed is 60-100 g / m 2 .

4. The method for preparing a photosensitive color-changing fully polished glazed ceramic tile according to claim 1, characterized in that: In steps S4 and S6, the glaze amount of the bell jar is 480-580 g / m 2 , specific gravity is 1.82-1.92 g / ml, and flow rate is 26-32 s.

5. The photochromic fully polished glazed ceramic tile prepared as claimed in any one of claims 1 to 4.

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