Photochromic cover glaze as well as preparation method and application thereof

Abstract

The invention discloses photosensitive color-changing cover glaze as well as a preparation method and application thereof, and relates to the technical field of ceramics. The photochromic cover glaze is prepared from the following components in percentage by mass: 47.0 to 49.0 percent of SiO2, 29.0 to 33.0 percent of Al2O3, 25.0 to 10.0 percent of ZrO, 4.0 to 5.0 percent of Na2O, 2.0 to 5.0 percent of rare earth oxide, 1.0 to 2.0 percent of K2O, 0.5 to 1.5 percent of CaO, 0.5 to 1.5 percent of MgO, 0.3 to 0.9 percent of ZnO, 0.2 to 0.5 percent of B2O3, 0.1 to 0.2 percent of Fe2O3, 0.1 to 0.2 percent of TiO2 and 2.0 to 5.0 percent of ignition loss, and the sum of the mass percent of the components is 100 percent. Meanwhile, the invention also provides a preparation method of the photosensitive overglaze and application of the photosensitive overglaze in preparation of photosensitive color-changing fully-glazed ceramic tiles. The fully-glazed ceramic tile prepared by combining the photosensitive color-changing cover glaze with a specific process shows different colors under the irradiation of different light sources, the product has higher artistry and ornamental value, is practical and wear-resistant, and enriches the variety of fully-glazed products.

Description

Technical Field

[0001] The 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 glaze refers to a special effect glaze that can show different colors under different light sources. Color-changing glaze usually uses white glaze as the base glaze, and uses metal oxides, non-metal oxides and mixed rare earth oxides such as neodymium, cerium, and praseodymium as coloring elements. It is processed into glaze slurry through a specific process and applied to the surface of the body. It is fired at an appropriate firing temperature to produce a series of physical and chemical changes and generate a new solid solution. This solid solution has different degrees of selective absorption and reflection characteristics for various wavelengths of light in the visible light range. Therefore, the glaze surface of the color-changing glaze can change color as the light source changes.

[0003] For example, Chinese patent ZL200910254659.9 discloses a metallic luster ceramic glaze with color-changing effect and its preparation method, which consists of two parts: a basic metal base glaze and a color-changing surface glaze. The basic metal base glaze and the color-changing surface glaze are respectively prepared according to the requirements, and then ball-milled and sieved. The obtained color-changing metallic glaze has diversified colors, excellent glaze quality, strong mechanical properties, high chemical stability, metallic texture, and can change color under different light sources.

[0004] Chinese patent ZL200910047570.5 discloses a rare earth ceramic glaze pigment that can change color under different light sources, which is composed of color-changing neodymium red pigment and feldspar glaze. The rare earth neodymium red color-changing glaze combines the color-changing pigment with the glaze porcelain to form a color-changing glaze product, which 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 a preparation method thereof. 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 unique.

[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 view of the above shortcomings, the present invention provides a photosensitive color-changing glaze and a preparation method and application thereof. The photosensitive color-changing glaze is combined with a specific process to prepare a full-polished glazed 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-polished glaze products.

[0008] The specific technical solutions are as follows:

[0009] A photosensitive color-changing glaze comprises 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 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 ignition loss 2.0-5.0%, and the sum of the mass percentages of the above components is 100%.

[0010] Furthermore, the rare earth oxide is 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 mixing the weighed raw material components uniformly to obtain a mixed raw material;

[0013] (2) putting 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 0.5-0.8wt% after passing through a 325-mesh sieve to obtain a ball mill material;

[0014] (3) The ball mill material is aged 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-polished glaze ceramic tiles.

[0016] Furthermore, the preparation method of the photosensitive color-changing fully polished glaze ceramic tile comprises the following steps:

[0017] S1: Pressing the green body powder by a press 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 0.2-0.4wt%;

[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 to obtain a photosensitive blank;

[0021] S5: Printing a pattern on the surface of the photosensitive body by using a digital inkjet printer to obtain a printed body; 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 fully glazed ceramic tile.

[0024] Further, in step S1, the composition of the green body powder includes the following components by mass percentage: 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 ignition loss 3.8-4.6%. And the particle gradation of the green body powder includes: by mass percentage, 20 mesh: ≤1%, above 30 mesh: 10-20%, 30-60 mesh: 65-75%, 60-80 mesh: ≤12%, below 80 mesh: ≤6%.

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

[0026] Furthermore, in steps S4 and S6, the glaze application 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] Further, 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 of 325 mesh 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 full-glazed 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 a fully-polished glazed tile with photosensitive color-changing properties. The fully-polished glazed tile can present different colors under different light sources. It is not only practical, but also artistic and ornamental, enriching the variety of fully-polished glazed products.

[0032] 2. The present invention uses metal oxides, non-metal oxides and mixed rare earth oxides such as neodymium, cerium, praseodymium, etc. as coloring elements, reasonably formulates and processes them into photosensitive color-changing glaze slurry through 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. The 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 polished glazed tile can achieve a photosensitive color-changing effect, which is purple under natural light or incandescent lamps and sky blue under fluorescent lamps. It is 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 polished glaze tile, the preparation process of which is: 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 ignition loss 4.0%. The above components are mixed evenly, and the particle size distribution of the mixed powder is (by mass percentage): 20 mesh: 0.5%, above 30 mesh: 15%, 30-60 mesh: 71%, 60-80 mesh: 8.5%, below 80 mesh: 5%, so as to obtain the green body powder for standby use.

[0039] (2) Preparation of photosensitive color-changing glaze

[0040] The mixed raw materials include the following components in percentage by mass: 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 ignition loss 2.39%; the 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, so as to obtain a ball mill material; the ball mill material is aged for 18 hours to obtain the photosensitive color-changing glaze for standby use.

[0041] (3) Glaze preparation

[0042] Measured in mass percentage, 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 sieve of 325 mesh 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, and the water spraying amount is 85 g / m 2 ;

[0046] 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 520 g / m 2 , specific gravity is 1.90g / ml, flow rate is 30s, and photosensitive body is obtained;

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

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

[0049] 8) After the glazed body is dried in a pre-kiln drying kiln, it is placed in a kiln for firing at a temperature of 1210° C. for 45 minutes to obtain the photochromic fully glazed ceramic tile;

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

[0051] Example 2

[0052] A photosensitive color-changing fully polished glaze tile, the preparation process of which is: 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%, CaO0.8%, Na2O3.0%, MgO 1.0%, K2O 4.0%, Fe2O3 0.8%, TiO2 0.2% and ignition loss 3.8%; the above components are mixed evenly, and the particle size distribution of the mixed powder is (by mass percentage): 20 mesh: 1%, above 30 mesh: 10%, 30-60 mesh: 75%, 60-80 mesh: 12%, below 80 mesh: 2%, so as to obtain the green body powder for standby use.

[0056] (2) Preparation of photosensitive color-changing 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 ignition loss 3.27%; the 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, to obtain a ball mill material; the ball mill material is aged for 20 hours to obtain the photosensitive color-changing glaze for standby use.

[0058] (3) Glaze preparation

[0059] Measured in mass percentage, 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 requirement of the glaze is that the residue on the sieve of 325 mesh is 0.4wt%.

[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 0.52 mm to spray water to wet the surface of the blank, and the water spraying amount is 100 g / 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 application amount being 480g / m 2 , specific gravity is 1.82g / ml, flow rate is 32s, and photosensitive body is obtained;

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

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

[0066] 8) After the glazed body is dried in a pre-kiln drying kiln, it is placed in a kiln for firing at a temperature of 1215° C. for 40 minutes to obtain the photochromic fully glazed ceramic tile;

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

[0068] Example 3

[0069] A photosensitive color-changing fully polished glaze tile, the preparation process of which is: 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%, CaO0.3%, Na2O2.0%, MgO 0.5%, K2O 3.0%, Fe2O3 0.5%, TiO2 0.1% and ignition loss 4.6%. The above components are mixed evenly, and the particle size distribution of the mixed powder is (by mass percentage): 20 mesh: 0.8%, above 30 mesh: 20%, 30-60 mesh: 65%, 60-80 mesh: 8.2%, below 80 mesh: 6%, so as to obtain the green body powder for standby use.

[0073] (2) Preparation of photosensitive color-changing glaze

[0074] The mixed raw materials include the following components in percentage by mass: 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%, Fe2O30.2%, TiO2 0.15% and ignition loss 2.25%; the 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 0.8wt% 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 for standby use.

[0075] (3) Glaze preparation

[0076] Measured in mass percentage, 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 0.62 mm to spray water to wet the surface of the blank, and the water spraying amount is 60 g / 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 580g / m 2 , specific gravity is 1.92g / ml, flow rate is 26s, and photosensitive body is obtained;

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

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

[0083] 8) After the glazed body is dried in a pre-kiln drying kiln, it is placed in a kiln for firing. The firing time is 40-50 minutes at a temperature of 1200° C., and the photosensitive color-changing fully glazed ceramic tile can be obtained;

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

[0085] Example 4

[0086] A photosensitive color-changing fully polished glaze tile, the preparation process of which is: 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%, CaO0.6%, Na2O2.3%, MgO 0.6%, K2O 3.4%, Fe2O3 0.7%, TiO2 0.14% and ignition loss 4.12%. The above components are mixed evenly, and the particle size distribution of the mixed powder is (by mass percentage): 20 mesh: 0.4%, above 30 mesh: 17%, 30-60 mesh: 68%, 60-80 mesh: 10%, below 80 mesh: 4.6%, so as to obtain the green body powder for standby use.

[0090] (2) Preparation of photosensitive color-changing glaze

[0091] The mixed raw materials include the following components by mass percentage: 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 ignition loss 2.25%; the 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 0.65wt% after passing through a 325-mesh sieve, so as to obtain a ball mill material; the ball mill material is aged for 21 hours to obtain the photosensitive color-changing glaze for standby use.

[0092] (3) Glaze preparation

[0093] Measured in mass percentage, 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 is ground in turn by 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, and the water spraying amount is 79 g / m 2 ;

[0097] 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 510 g / m 2 , specific gravity is 1.88g / ml, flow rate is 28s, and photosensitive body is obtained;

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

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

[0100] 8) After the glazed body is dried in a pre-kiln drying kiln, it is placed in a kiln for firing at a temperature of 1140° C. for 40-50 minutes to obtain the photochromic full-glazed tile;

[0101] 9) After the photosensitive color-changing fully polished glaze 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 basically the same as that of Example 1, except that the raw materials of the photosensitive color-changing 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 ignition loss 2.39%. That is, the mass ratio of SiO2 and Al2O3 is changed.

[0104] Comparative Example 2

[0105] The preparation process of the fully glazed ceramic tile of Comparative Example 2 is basically the same as that of Example 1, except that the raw materials of the photosensitive color-changing glaze are as follows: SiO2 48.73%, Al2O3 30.99%, ZrO2 3.77%, Na2O4.29%, Nd2O35.5%, K2O 1.36%, CaO 0.94%, MgO 0.89%, ZnO 0.56%, B2O3 0.28%, Fe2O30.16%, TiO20.14% and ignition loss 2.39%. That is, the mass ratio of Nd2O3 and ZrO2 has changed.

[0106] Comparative Example 3

[0107] The preparation process of the fully glazed ceramic tile of Comparative Example 3 is basically the same as that of Example 1, except that the raw materials of the photosensitive color-changing glaze are as follows: SiO2 48.73%, Al2O3 30.99%, ZrO2 5.5%, Na2O 4.29%, Nd2O33.77%, K2O 1.36%, CaO 0.94%, MgO 0.89%, ZnO 0.56%, B2O3 0.28%, Fe2O3 0.3% and ignition loss 2.39%. That is, the component of TiO2 is missing.

[0108] Comparative Example 4

[0109] The preparation process of the fully glazed ceramic tile of Comparative Example 4 is basically the same as that of Example 1, except that the raw materials of the photosensitive color-changing 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 ignition loss 2.39%. That is, the component 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, except that the photosensitive color-changing 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 polished 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] It can be seen from Table 1 that 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 the 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 The 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 polished glazed tile to change.

[0121] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. A photosensitive color-changing glaze, characterized in that: Calculated in mass percentage, it includes the following components: 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%, K2O1.0-2.0%, CaO0.5-1.5%, 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%.

2. The photosensitive color-changing glaze according to claim 1, characterized in that: The rare earth oxides are one or more of neodymium oxide, erbium oxide and praseodymium oxide.

3. The method for preparing a photosensitive color-changing glaze according to claim 1 or 2, characterized in that: The following steps are involved: (1) weighing each raw material component by mass percentage, and mixing the weighed raw material components uniformly to obtain a mixed raw material; (2) putting 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 0.5-0.8wt% 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.

4. Use of a photochromic glaze as claimed in claim 1 or 2 in the preparation of photochromic fully polished glazed ceramic tiles.

5. The use of a photochromic glaze according to claim 4 in preparing photochromic full-polished glaze ceramic tiles, characterized in that: The preparation method of the photosensitive color-changing fully polished glaze ceramic tile comprises the following steps: S1: Pressing the green body powder by a press 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 the photochromic glaze on the wetted surface of the blank by a bell-shaped glaze pouring method to form a photochromic layer to obtain 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.

6. The use of a photochromic glaze according to claim 5 in preparing photochromic full-polished glaze ceramic tiles, characterized in that: In step S3, the amount of water sprayed is 60-100 g / m 2 .

7. The use of a photochromic glaze according to claim 5 in preparing photochromic full-polished glaze ceramic tiles, characterized in that: In steps S4 and S6, the glaze amount of the bell jar is 480-580g / m 2 , specific gravity is 1.82-1.92g / ml, and flow rate is 26-32s.

8. The use of a photochromic glaze according to claim 5 in preparing photochromic full-polished glaze ceramic tiles, characterized in that: 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%.

9. The use of a photochromic glaze according to claim 5 in preparing photochromic full-polished glaze ceramic tiles, characterized in that: In step S7, the sintering time is 40-50 minutes and the temperature is 1100-1215°C.

10. The photochromic fully polished glazed ceramic tile prepared according to any one of claims 5 to 9.

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