Corrosion-resistant ceramic glaze and method for preparing the same

Abstract

The application discloses a kind of corrosion-resistant ceramic glaze and preparation method thereof, it is related to the production technical field of ceramic glaze, it is prepared by the following raw material components: feldspar, kaolin, refractory clay, zirconium silicate, zirconia, zircon, graphene oxide, calcium oxide and deionized water;By feldspar, kaolin and zircon are crushed and ground, then it is together with remaining solid raw material is put into the ball mill tank of ball mill equipment and is ball milled 1-2h, and the ball mill tank is heated, so that glaze particle particle is more small and uniform;Then powder is soaked in deionized water, mixed liquid is stirred using high-speed stirrer 0.5-0.6h, forms glaze pulp;In the application, by adding zirconium silicate in ceramic glaze, the strength, wear resistance, hydrolysis resistance and corrosion resistance of ceramic glaze layer are improved, graphene oxide has excellent acid resistance, alkali resistance, which can effectively improve the corrosion resistance of ceramic glaze.

Description

Technical Field

[0001] This invention relates to the field of ceramic glaze production technology, specifically to a corrosion-resistant ceramic glaze and its preparation method. Background Technology

[0002] Ceramic glaze is a suspended powder used on the surface of ceramic products, composed of various chemical substances. Glaze can be applied to the surface of ceramic objects by spraying, brushing, or dipping. After firing, it forms a hard, smooth, waterproof, acid and alkali resistant, and corrosion resistant glaze layer, protecting the ceramic surface, beautifying the appearance of the ceramic, and also making the ceramic easier to clean.

[0003] Ceramic products are generally coated with a ceramic glaze. During use, ceramic products frequently come into contact with water, acids, or alkalis, leading to chemical reactions. Acidic substances typically cause corrosion of the oxide layer on the ceramic glaze, resulting in dissolution or peeling and reducing the glaze's gloss. Alkaline substances, on the other hand, react to form toxic alkali metal glasses, further damaging the ceramic's integrity and aesthetics. Existing ceramic glazes have less than ideal corrosion resistance, failing to meet the demands of practical use. Therefore, this invention provides a corrosion-resistant ceramic glaze and its preparation method. Summary of the Invention

[0004] The technical problem solved by this invention is that, in the prior art, the ceramic glaze layer on the surface of ceramic products is easily corroded by acids and alkalis, and the corrosion resistance of ceramic glaze is not ideal, which cannot meet the needs of actual use.

[0005] The present invention can be achieved through the following technical solution: a corrosion-resistant ceramic glaze, which is prepared from the following raw material components: 15-25 parts feldspar, 15-20 parts kaolin, 18-22 parts refractory clay, 5-10 parts zirconium silicate, 5-7 parts zirconium oxide, 5-10 parts zircon, 10-15 parts graphene oxide, 18-20 parts calcium oxide and 20-30 parts deionized water.

[0006] A method for preparing a corrosion-resistant ceramic glaze involves first weighing the raw materials according to the above-mentioned raw material formula for ceramic glaze, and then preparing it according to the following method:

[0007] Step 1: First, dry the feldspar, kaolin, and zircon, then crush and grind them into powder, and then sieve them to select powder with the required particle size.

[0008] Step 2: Put the powder obtained in Step 1 and the remaining solid raw materials into the ball mill jar of the ball milling equipment and ball mill for 1-2 hours. Heat the ball mill jar to make the glaze particles smaller and more uniform.

[0009] Step three: the powder obtained in step two is soaked in deionized water, and the mixture is stirred by a high-speed blender for 0.5-0.6h to form a glaze slurry;

[0010] Step four: the glaze particles obtained in step three are sprayed on the surface of a ceramic object, and then the ceramic object is placed in a furnace for high-temperature firing at a temperature of 800-1200℃ to obtain a corrosion-resistant ceramic glaze layer.

[0011] Further technical improvements of the present application are that in step one, the feldspar, kaolin and zirconite are vacuum dried, and are placed in a vacuum drying box, the vacuum degree of the vacuum drying box is set to -0.1MPa, and the temperature is raised to 500-600℃ at a rate of 5-8℃ / min in nitrogen and kept for 0.5-1h.

[0012] Further technical improvements of the present application are that in step one, the powder is sieved to 100-150 mesh.

[0013] Further technical improvements of the present application are that in step two, high-temperature nitrogen is introduced into the inside of the ball mill tank of the ball milling equipment, so that the temperature inside the ball mill tank reaches 1000-1200℃.

[0014] Further technical improvements of the present application are that in step three, the stirring rate is 200-300rpm / min.

[0015] Compared with the prior art, the present application has the following beneficial effects:

[0016] 1、In the present application, by adding zirconium silicate and graphene oxide to the ceramic glaze, the strength, wear resistance, hydrolysis resistance and corrosion resistance of the ceramic glaze layer are improved, and the self-cleaning ability is also enhanced. Graphene oxide has excellent acid and alkali resistance, which can effectively improve the corrosion resistance of the ceramic glaze.

[0017] 2、In the present application, the feldspar, kaolin and zirconite are first vacuum dried when preparing the ceramic glaze, which can reduce the moisture content of the feldspar, kaolin and zirconite, so that the powder is less likely to adhere to the inner wall of the crushing and grinding equipment, reducing the subsequent cleaning work of the workers.

[0018] 3、In the present application, when the raw materials are further ground, the raw materials are placed in the ball mill tank and high-temperature nitrogen is introduced, which reduces the adhesion of zirconium silicate and graphene oxide to the inner wall of the ball mill tank, so that the components in the raw materials are not reduced, and sufficient zirconium silicate and graphene oxide can be ensured to play a corrosion-resistant role in the ceramic glaze. DETAILED DESCRIPTION

[0019] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined object of the present application, the following describes the specific embodiments, structures, features and effects according to the present application in combination with preferred embodiments.

[0020] Embodiment one

[0021] Step one: weigh the raw materials as follows: 15 parts of feldspar, 15 parts of kaolin, 18 parts of refractory clay, 5 parts of zirconium silicate, 5 parts of zirconia, 5 parts of zircon, 10 parts of graphene oxide, 18 parts of calcium oxide and 20 parts of deionized water;

[0022] Step two: first vacuum dry the feldspar, kaolin and zircon, place them in a vacuum drying oven, set the vacuum degree of the vacuum drying oven to-0.1MPa, heat to 500℃ at a rate of 5℃ / min in nitrogen and keep for 0.5h; then crush and grind them into powder, and then sieve the powder to select the powder with the required particle size;

[0023] Step three: put the powder obtained in step two and the remaining solid raw materials into the ball mill tank of the ball mill equipment for ball milling for 1h, and introduce nitrogen with a temperature of 1000℃ into the ball mill tank to make the glaze particles more uniform and smaller;

[0024] Step four: soak the powder obtained in step three in deionized water, and use a high-speed stirrer to stir the mixture for 0.5h at a stirring rate of 200rpm / min to form a glaze slurry;

[0025] Step five: spray the glaze particles obtained in step four on the surface of the ceramic ware, and then place it in a furnace for high-temperature firing at a temperature of 800℃ to obtain a corrosion-resistant ceramic glaze layer.

[0026] Embodiment two

[0027] Step one: weigh the raw materials as follows: 15 parts of feldspar, 15 parts of kaolin, 18 parts of refractory clay, 5 parts of zirconium silicate, 5 parts of zirconia, 5 parts of zircon, 10 parts of graphene oxide, 18 parts of calcium oxide and 20 parts of deionized water;

[0028] Step two: first vacuum dry the feldspar, kaolin and zircon, place them in a vacuum drying oven, set the vacuum degree of the vacuum drying oven to-0.1MPa, heat to 500℃ at a rate of 5℃ / min in nitrogen and keep for 0.5h; then crush and grind them into powder, and then sieve the powder to select the powder with the required particle size;

[0029] Step three: the powder obtained in step two and the remaining solid raw materials are put into the ball mill tank of the ball milling equipment for ball milling for 2h, and nitrogen gas with a temperature of 1100°C is introduced into the ball mill tank to make the enamel particles smaller and more uniform;

[0030] Step four: the powder obtained in step three is soaked in deionized water, and the mixture is stirred by a high-speed stirrer for 0.6h at a stirring rate of 300rpm / min to form an enamel slurry;

[0031] Step five: the enamel particles obtained in step four are sprayed on the surface of the ceramic object, and then the ceramic object is placed in a furnace for high-temperature firing at a temperature of 1200°C to obtain a corrosion-resistant ceramic glaze layer;

[0032] Example three

[0033] Step one: the raw materials are weighed according to the following proportions: 15 parts of feldspar, 15 parts of kaolin, 18 parts of refractory clay, 5 parts of zirconium silicate, 5 parts of zirconium oxide, 5 parts of zircon, 10 parts of graphene oxide, 18 parts of calcium oxide, and 20 parts of deionized water;

[0034] Step two: the feldspar, kaolin and zircon are first vacuum dried by placing them in a vacuum drying oven with a vacuum degree of-0.1MPa, and then heated to 550°C at a rate of 6°C / min in nitrogen and kept for 1h; then they are crushed and ground into powder, and then sieved to obtain powder with a particle size meeting the requirements;

[0035] Step three: the powder obtained in step two and the remaining solid raw materials are put into the ball mill tank of the ball milling equipment for ball milling for 1.5h, and the ball mill tank is heated until the temperature inside the ball mill tank reaches 110°C, so that the enamel particles are smaller and more uniform;

[0036] Step four: the powder obtained in step three is soaked in deionized water, and the mixture is stirred by a high-speed stirrer for 0.55h at a stirring rate of 250rpm / min to form an enamel slurry;

[0037] Step five: the enamel particles obtained in step four are sprayed on the surface of the ceramic object, and then the ceramic object is placed in a furnace for high-temperature firing at a temperature of 1000°C to obtain a corrosion-resistant ceramic glaze layer;

[0038] Comparative example one

[0039] Step one: the raw materials are weighed according to the following proportions: 15 parts of feldspar, 15 parts of kaolin, 18 parts of refractory clay, 5 parts of zirconium oxide, 5 parts of zircon, 18 parts of calcium oxide, and 20 parts of deionized water;

[0040] Step two: firstly, the feldspar, kaolin and zircon are vacuum dried, and are put into a vacuum drying oven, the vacuum degree of the vacuum drying oven is set to-0.1 MPa, and the temperature is raised to 500℃ at a rate of 5℃ / min in nitrogen and is kept for 0.5h; then, the feldspar, kaolin and zircon are crushed and ground to be powdery, and then are sieved to obtain the powder with a particle size meeting the requirements;

[0041] Step three: the powder obtained in step two and the remaining solid raw materials are put into a ball mill tank of a ball mill device to be ball milled for 1h, and nitrogen with a temperature of 1200℃ is introduced into the ball mill tank until the temperature inside the ball mill tank reaches 100℃, so that the enamel particles are more uniform and smaller;

[0042] Step four: the powder obtained in step three is soaked in deionized water, and the mixture is stirred by a high-speed stirrer for 0.5h at a stirring rate of 200rpm / min to form an enamel slurry;

[0043] Step five: the enamel particles obtained in step four are sprayed on the surface of a ceramic object, and then the ceramic object is placed in a furnace for high-temperature firing at a temperature of 800℃ to obtain a corrosion-resistant ceramic enamel layer;

[0044] The difference between the comparative example one and the example one is that the comparative example one does not add zirconium silicate and graphene oxide, and the rest of the steps and parameters are the same;

[0045] Comparative example two

[0046] Step one: the raw materials are weighed according to the following proportions: feldspar 15 parts, kaolin 15 parts, refractory clay 18 parts, zirconium silicate 5 parts, zirconia 5 parts, zircon 5 parts, graphene oxide 10 parts, calcium oxide 18 parts and deionized water 20 parts;

[0047] Step two: firstly, the feldspar, kaolin and zircon are vacuum dried, and are put into a vacuum drying oven, the vacuum degree of the vacuum drying oven is set to-0.1 MPa, and the temperature is raised to 500℃ at a rate of 5℃ / min in nitrogen and is kept for 0.5h; then, the feldspar, kaolin and zircon are crushed and ground to be powdery, and then are sieved to obtain the powder with a particle size meeting the requirements;

[0048] Step three: the powder obtained in step two and the remaining solid raw materials are put into a ball mill tank of a ball mill device to be ball milled for 1h, and nitrogen with a temperature of 1200℃ is introduced into the ball mill tank until the temperature inside the ball mill tank reaches 100℃, so that the enamel particles are more uniform and smaller;

[0049] Step four: the powder obtained in step three is soaked in deionized water, and the mixture is stirred by a high-speed stirrer for 0.5h at a stirring rate of 200rpm / min to form an enamel slurry;

[0050] Step five: the enamel particles obtained from step four are sprayed on the surface of the ceramic ware, and then the ceramic ware is placed in a furnace for high-temperature firing at a temperature of 800 DEG C, to obtain a corrosion-resistant ceramic glaze layer;

[0051] feldspar 15-25 parts, kaolin 15-20 parts, refractory clay 18-22 parts, zirconium silicate 5-10 parts, zirconia 5-7 parts, zircon 5-10 parts, graphene oxide 10-15 parts, calcium oxide 18-20 parts and deionized water 20-30 parts;

[0052] The difference between the comparative example two and the example one is that the comparative example two does not pass high-temperature nitrogen into the ball mill tank, and the rest of the steps and parameters are the same.

[0053] The corrosion-resistant ceramic glaze layers obtained from examples 1-3 and comparative examples 1-2 are tested for performance:

[0054] (1) According to GB / T3810.13-2016, the chemical corrosion resistance test is carried out, and the ceramic products containing the above-mentioned ceramic glaze layer are respectively placed in 6wt% nitric acid solution and 22wt% potassium hydroxide solution, and after 12h, the change of the surface of the ceramic product is observed, and the results are shown in the following table 1;

[0055] (2) According to GB / T3810.7-2016, the wear resistance of glazed brick surface is determined, and the results are shown in the following table 1; wherein, the glaze surface wear resistance is divided into four levels, namely PEI1-4 level, and the use range is respectively: 1 level, only suitable for household floor; 2 level, used in places with less people flow; 3 level, suitable for public places with more people flow; 4 level, can be used in public places such as square with more people flow;

[0056] The test results are shown in table 1;

[0057] Table 1

[0058]

[0059] In the comparative example two, when the raw materials are further ground, the raw materials are placed in the ball mill tank, and because the viscosity of zirconium silicate and graphene oxide is larger, they are easily adhered to the inner wall of the ball mill tank, thereby reducing the content of zirconium silicate and graphene oxide in the raw materials, so that the ceramic glaze lacks enough zirconium silicate and graphene oxide, thus causing the ceramic product surface to appear spots, and the color of the ceramic surface also becomes dark;

[0060] The ceramic glaze layer on the surface of the ceramic product in Comparative Example 1-2 is corroded, while the ceramic product obtained in Example 1-3 of the present application has no change on the surface, which indicates that the present application has good acid and alkali corrosion resistance; the ceramic product obtained in Comparative Example 1-2 of the present application has the ceramic glaze layer on the surface, and its wear resistance reaches the standard 3 level requirement, while the ceramic product obtained in Example 1-3 of the present application has the ceramic glaze layer on the surface, and its wear resistance reaches the standard 4 level requirement, and has good wear resistance, and can be used on the ground where pedestrians walk frequently.

[0061] It should be noted that the relational terms herein such as first and second and the like are used solely to distinguish one entity or action from another, without necessarily requiring or implying any such actual relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0062] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, alternatives, and variations can be made in the embodiments without departing from the spirit and scope of the present application as defined by the appended claims and their equivalents.

Claims

1. A corrosion resistant ceramic enamel, characterized by: The following raw material components are prepared by weight parts: feldspar 15-25 parts, kaolin 15-20 parts, refractory clay 18-22 parts, zirconium silicate 5-10 parts, zirconium oxide 5-7 parts, zircon 5-10 parts, graphene oxide 10-15 parts, calcium oxide 18-20 parts and deionized water 20-30 parts; Step one: dry feldspar, kaolin and zircon first, then crush and grind them into powder, and then sieve the powder to obtain powder with a particle size meeting the requirements; Step two: put the powder obtained in step one and the remaining solid raw materials into the ball mill tank of the ball milling equipment for ball milling for 1-2 hours, and heat the ball mill tank to make the glaze particles smaller and more uniform; high-temperature nitrogen is introduced into the ball mill tank to make the temperature inside the ball mill tank reach 1000-1200℃; Step three: soak the powder obtained in step two in deionized water, and stir the mixture with a high-speed stirrer for 0.5-0.6 hours to form a glaze slurry; Step four: spray the glaze particles obtained in step three on the surface of the ceramic object, and then place it in a furnace for high-temperature firing at a temperature of 800-1200℃ to obtain a corrosion-resistant ceramic glaze layer.

2. A method of preparing the corrosion-resistant ceramic enamel according to claim 1, characterized in that, First, the raw materials are weighed according to the raw material formula of the ceramic glaze as claimed in claim 1, and then prepared according to the following preparation method: Step one: dry feldspar, kaolin and zircon first, then crush and grind them into powder, and then sieve the powder to obtain powder with a particle size meeting the requirements; Step two: put the powder obtained in step one and the remaining solid raw materials into the ball mill tank of the ball milling equipment for ball milling for 1-2 hours, and heat the ball mill tank to make the glaze particles smaller and more uniform; Step three: soak the powder obtained in step two in deionized water, and stir the mixture with a high-speed stirrer for 0.5-0.6 hours to form a glaze slurry; Step four: spray the glaze particles obtained in step three on the surface of the ceramic object, and then place it in a furnace for high-temperature firing at a temperature of 800-1200℃ to obtain a corrosion-resistant ceramic glaze layer.

3. A method of preparing a corrosion resistant ceramic enamel according to claim 2, characterized in that, In step one, the feldspar, kaolin and zircon are vacuum dried by placing them in a vacuum drying oven with a vacuum degree of -0.1 MPa, and then heated to 500-600℃ at a rate of 5-8℃ / min in nitrogen and held for 0.5-1h.

4. The method of claim 2, wherein the corrosion resistant ceramic enamel is prepared by the steps of: In step one, the powder is sieved to 100-150 mesh.

5. The method for preparing a corrosion-resistant ceramic glaze according to claim 2, characterized in that, In step two, high-temperature nitrogen is introduced into the ball mill tank to make the temperature inside the ball mill tank reach 1000-1200℃.

6. The method of claim 2, wherein the corrosion resistant ceramic enamel is prepared by the steps of: In step three, the stirring rate is 200-300 rpm / min.

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