A functionalized magnetically positionable ceramic glaze and its preparation method and magnetization process for decorative ceramics

Abstract

This invention belongs to the field of architectural ceramics, and relates to a functionalized magnetically positionable ceramic glaze, its preparation method, and magnetization process for decorative ceramics. The functionalized magnetically positionable ceramic glaze comprises a base glaze and a magnetic core-shell coating uniformly dispersed in the base glaze after surface treatment and activation. The core of the magnetic core-shell coating is a functional material and the shell is a magnetic material, or vice versa. This invention prepares the functional material and magnetic material into a magnetic core-shell coating and performs surface activation treatment on its surface. This not only allows for precise and effective control of the movement trajectory (including direction and position) of the magnetic core-shell coating, achieving synchronous directional movement of the functional and magnetic materials, but also reduces the frictional resistance of the magnetic core-shell coating during glaze movement, providing a new solution for obtaining rich, three-dimensional decorative effects similar to natural stone.

Description

Technical Field

[0001] This invention belongs to the field of architectural ceramics, and specifically relates to a functionalized magnetically positionable ceramic glaze, its preparation method, and magnetization process for decorative ceramics. Background Technology

[0002] With the improvement of living standards, people have placed higher demands on building ceramics. Texture, color, and surface feel are key consumer concerns. Natural stone, with its vibrant colors, strong transparency and three-dimensionality, and smooth texture, has always been a sought-after decorative effect in the ceramics industry. To achieve a decorative effect similar to natural stone, the building ceramics industry mainly combines improved glazes with screen printing, inkjet printing, and dry granule adhesive processes. Among these processes, positioning technology is crucial for achieving three-dimensional decorative effects. Currently, positioning decorative effects are primarily achieved using positioning adhesives and dry granule processes. Adhesive is printed onto the surface glaze, and then functional dry granules are adhered to the printed adhesive positions. This process offers good stability but lacks functionality, failing to achieve multi-layered three-dimensional decorative effects or the directional positioning of functional materials.

[0003] Magnetofluids are homogeneous colloidal systems formed by coating surfactants onto the surface of nanoscale magnetic particles and then dispersing them in a carrier liquid. Due to the high specific surface area of ​​magnetic particles and their high sensitivity to applied magnetic fields, the dynamic behavior of magnetic particles can be precisely confined, positioned, and controlled using an applied magnetic field.

[0004] Existing technologies incorporate functional and ceramic materials directly into the base glaze. This method mixes functional and magnetic materials with the base glaze, but the magnetic and functional materials exist completely independently. Synchronous movement between the functional and magnetic materials is impossible, as is precise positioning of the functional materials. Furthermore, this direct mixing method significantly weakens the characteristic properties of both the functional and magnetic materials. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a functionalized magnetically positionable ceramic glaze, its preparation method, and a magnetization process for decorative ceramics. This invention prepares a magnetic core-shell coating from functional and magnetic materials, and then performs surface activation treatment on its surface. This not only allows for precise and effective control of the movement trajectory (including direction and position) of the magnetic core-shell coating, achieving synchronous directional movement of the functional and magnetic materials, but also reduces the frictional resistance of the magnetic core-shell coating during glaze movement, providing a new solution for obtaining rich, three-dimensional decorative effects similar to natural stone. This invention is achieved through the following technical means:

[0006] In a first aspect, the present invention provides a functionalized magnetically positionable ceramic glaze. The functionalized magnetically positionable ceramic glaze comprises a base glaze and a magnetic core-shell coating uniformly dispersed in the base glaze and activated by a surface treatment agent; wherein the core of the magnetic core-shell coating is a functional material and the shell is a magnetic material, or the core is a magnetic material and the shell is a functional material; the mass content of the magnetic core-shell coating activated by the surface treatment agent in the functionalized magnetically positionable ceramic glaze is 0.5% to 3%.

[0007] Preferably, the functional material is at least one of the following: glitter material, pigment, dry granules, photochromic material, thermochromic material, antibacterial material, wear-resistant material, and anti-slip material; the magnetic material is at least one of the following: elemental iron, elemental cobalt, elemental nickel, iron oxide, cobalt oxide, nickel oxide, iron-cobalt oxide, nickel-cobalt oxide, iron-nickel oxide, iron-cobalt-nickel oxide, neodymium iron boron composite material, and iron-cobalt-nickel composite material.

[0008] Preferably, the surface treatment agent is at least one selected from polyvinyl butyral, paraffin, stearic acid, palmitic acid, and pentaerythritol stearic acid.

[0009] Preferably, the mass ratio of the surface treatment agent to the magnetic core-shell coating is 2~5:5~10; and the mass ratio of the magnet to the shell of the magnetic core-shell coating is 1~3:1~3.

[0010] Secondly, the present invention provides a method for preparing a functionalized magnetically positionable ceramic glaze. The method includes: coating a core material with a shell material using a coating technique to obtain a magnetic core-shell coating; activating the magnetic core-shell coating with a surface treatment agent to obtain a surface-activated magnetic core-shell coating; and dispersing the surface-activated magnetic core-shell coating in a base glaze to obtain a functionalized magnetically positionable ceramic glaze.

[0011] Preferably, the coating technique is as follows: the core material is added to the coating slurry, mixed evenly, and then filtered to obtain the filter cake to obtain the primary coating body; then the primary coating body is added to the curing liquid by sieving for curing, filtered again, and the filter cake is obtained to obtain the secondary coating body; finally, the secondary coating body is dried to obtain the magnetic core-shell coating body.

[0012] Preferably, the coating slurry is a mixture of sodium alginate aqueous solution and shell material; the mass ratio of shell material to sodium alginate aqueous solution is 1:10 to 5:10; the mass ratio of core material to coating slurry is 1:10 to 5:10; and the curing liquid is a calcium chloride aqueous solution or calcium carbonate aqueous solution with a mass concentration of 2% to 6%.

[0013] Preferably, the activation treatment method is as follows: the magnetic core-shell coating is added to a solvent, a surface treatment agent is added under stirring conditions, the mixture is stirred until homogeneous, the filter cake is collected, the filter cake is placed in water and stirred again, and finally the surface-activated magnetic core-shell coating is obtained by filtration.

[0014] Preferably, the solvent is at least one selected from anhydrous ethanol, toluene, xylene, cyclohexane, No. 60 solvent oil, No. 90 solvent oil, and No. 120 solvent oil; and the surface treatment agent is at least one selected from polyvinyl butyral, paraffin wax, stearic acid, palmitic acid, and pentaerythritol stearic acid.

[0015] Thirdly, the present invention provides a magnetized decorative ceramic. The magnetized decorative ceramic includes a glaze layer having the aforementioned functionalized magnetically positionable ceramic glaze; wherein the movement trajectory of the magnetic core-shell coating is controlled by controlling the position and intensity of an applied magnetic field.

[0016] Preferably, the specific gravity of the base glaze of the functionalized magnetically positionable ceramic glaze is 1.65~1.70 g / cm³. 3 The amount of the functionalized magnetically positionable ceramic glaze applied is 500~750 g / m³. 2 .

[0017] Preferably, the functionalized magnetically locatable ceramic glaze is applied by glazing.

[0018] The present invention has the following beneficial effects:

[0019] (1) This invention combines functional materials and magnetic materials to prepare a magnetic core-shell coating that responds to a magnetic field, and disperses it in a ceramic glaze so that the magnetic core-shell coating can move in a direction under the action of a magnetic field.

[0020] (2) By applying an external magnetic field, the present invention can effectively control the movement direction and dwell position of the magnetic core-shell coating, thereby realizing the control and positioning of the functional material.

[0021] (3) This invention achieves the positioning and orientation of different layers of functional materials by changing the size of the magnetic core-shell coating, the strength of the magnetic material and the magnetic field strength. Attached Figure Description

[0022] Figure 1 This shows a scanning electron microscope image of the magnetic core-shell coating obtained in Example 1 of the present invention;

[0023] Figure 2 This shows a scanning electron microscope image of the surface-activated magnetic core-shell coating obtained in Example 1 of the present invention;

[0024] Figure 3This image shows the surface effect of the magnetized decorative ceramic plate obtained in Embodiment 1 of the present invention.

[0025] Figure 4 The surface effect diagram of the magnetized decorative ceramic plate obtained in Embodiment 2 of the present invention is shown.

[0026] Figure 5 The surface effect diagram of the magnetized decorative ceramic plate obtained in Embodiment 3 of the present invention is shown.

[0027] Figure 6 A surface effect diagram of a common decorative ceramic plate prepared according to Comparative Example 1 of the present invention is shown.

[0028] Figure 7 This shows a transmission electron microscope image of the magnetic core-shell coating obtained in Example 1 of the present invention;

[0029] Figure 8 A surface effect diagram of the magnetized decorative ceramic plate prepared in Comparative Example 2 of the present invention is shown.

[0030] Figure 9 The image shows the surface effect of the magnetized decorative ceramic plate prepared in Comparative Example 3 of the present invention. Detailed Implementation

[0031] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0032] The functionalized magnetically positionable ceramic glaze comprises a base glaze and a magnetic core-shell coating uniformly dispersed in the base glaze and activated by a surface treatment agent. The core of the magnetic core-shell coating is a functional material and the shell is a magnetic material, or vice versa.

[0033] In the functionalized magnetically positionable ceramic glaze, the mass content of the magnetic core-shell coating, activated by a surface treatment agent, is 0.5% to 3%. If the content of the magnetic core-shell coating activated by the surface treatment agent is too low, it cannot form effective functional enrichment on the glaze surface; if the content is too high, it will affect the movement speed and positioning accuracy of the magnetic core-shell coating, and will also lead to reduced glaze transparency, a darker glaze color, and glaze defects. In some embodiments, the mass ratio of core to shell is 1~3:1~3.

[0034] The surface-activated core-shell magnetic coating has a smoother and hydrophobic surface, which greatly reduces its movement resistance in the glaze. Under the influence of a magnetic field, it can move to a specific position in a shorter time. If the magnetic core-shell coating is not surface-activated, it will affect the precise positioning trajectory of the magnetic core-shell coating. The surface treatment agent includes, but is not limited to, at least one of polyvinyl butyral, paraffin wax, stearic acid, palmitic acid, and pentaerythritol stearic acid. These surface treatment agents are all organic materials, soluble in organic solvents but insoluble in water, have excellent film-forming properties, and can be burned off during ceramic firing without affecting the glaze quality.

[0035] The mass ratio of the surface treatment agent to the magnetic core-shell coating can be 2~5:5~10. If the mass ratio is too low, the magnetic core-shell coating will not be completely covered, thus affecting the positioning accuracy and effect of the functional material. If the mass ratio is too high, the surface treatment agent will be excessive, which will also affect the glaze effect.

[0036] The functional material is a commonly used material with special functions in the ceramics field, including but not limited to at least one of the following: glitter materials, colorants, dry granules, photochromic materials, thermochromic materials, antibacterial materials, wear-resistant materials, and anti-slip materials. The particle size of the functional material can be 50 nm to 100 μm.

[0037] The magnetic material includes, but is not limited to, at least one of elemental iron, elemental cobalt, elemental nickel, iron oxides (e.g., ferric oxide, magnetite), cobalt oxide, nickel oxide, iron-cobalt oxide, nickel-cobalt oxide, iron-nickel oxide, iron-cobalt-nickel oxide, neodymium-iron-boron composites, and iron-cobalt-nickel composites. The particle size of the magnetic material can be 50 nm to 100 μm. Coating the surface of the magnetic material with a functional material does not affect the magnetic trajectory of the coated body. This is because coating the surface of the magnetic material with a small amount of functional material has a negligible effect on the magnetic properties of the material. The movement speed of the magnetic core-shell coated body can be adjusted by controlling the particle size of the magnetic material, the coating thickness of the functional material, and the magnetic field strength.

[0038] Preferably, the particle size ratio of the shell material to the core material of the magnetic core-shell coating is 1:50 to 50:1. A particle size ratio that is too low will result in low coating efficiency; a particle size ratio that is too high will result in incomplete coating.

[0039] The particle size of the magnetic core-shell coating can be 30~150 μm. Preferably, the particle size of the magnetic core-shell coating is 50~80 μm.

[0040] The preparation method of the functionalized magnetically positionable ceramic glaze includes: coating a core material with a shell material using a coating technique to obtain a magnetic core-shell coating; activating the magnetic core-shell coating with a surface treatment agent to obtain a surface-activated magnetic core-shell coating; and dispersing the surface-activated magnetic core-shell coating in a base glaze to obtain the functionalized magnetically positionable ceramic glaze. The details are explained below.

[0041] A coating technique is used to coat a core material with a shell material. In this technique, the core is the material being coated, and the shell is the coating material. For example, coating a functional material with a magnetic material or vice versa yields a magnetic core-shell coated body.

[0042] The coating technology can be as follows: the core material is added to the coating slurry, mixed evenly, filtered and the filter cake is obtained to obtain the primary coating body, the primary coating body is then added to the curing liquid for curing by sieving, filtered again, and the filter cake is obtained to obtain the secondary coating body; finally, the secondary coating body is dried to obtain the magnetic core-shell coating body.

[0043] The mass ratio of the core material to the coating slurry can be 1:10 to 5:10. If the mass ratio of the core material to the coating slurry is too small, it will easily lead to waste of the coating slurry; if the mass ratio of the core material to the coating slurry is too large, it will result in incomplete coating of the core material surface or insufficient amount of shell material.

[0044] The coating slurry is a mixture of sodium alginate aqueous solution and shell material. Sodium alginate has advantages such as good thickening properties, good film-forming properties, high gel strength, and good filamentation properties. The mass concentration of the sodium alginate aqueous solution can be 0.5% to 2%. If the concentration of the sodium alginate aqueous solution is too low, the shell material will not adhere sufficiently, preventing the formation of a complete coating layer; if the concentration of the sodium alginate aqueous solution is too high, it may lead to poor dispersibility of the shell material, resulting in uneven distribution of the shell material.

[0045] The mass ratio of shell material to sodium alginate aqueous solution is 1:10 to 5:10. A ratio that is too small results in wasted sodium alginate. A ratio that is too large leads to insufficient adhesion of the shell slurry.

[0046] The screening method involves using a 120-mesh sieve and vibrating it to allow the primary coating material passing through the sieve to fall directly into the curing liquid.

[0047] The curing solution can be a 2%–6% (w / w) aqueous solution of calcium chloride or calcium carbonate. Sodium alginate aqueous solution can undergo a cross-linking reaction with calcium ions through ion exchange. Curing is necessary to ensure the core-shell coating forms an independent whole, preventing the core material from separating from the coating material during glaze mixing, which would lead to a loss of magnetic field control over the functional material. Without curing, an effective magnetic core-shell coating cannot be formed; for example, the material may dissolve again in the aqueous slurry, forming independently dispersed particles.

[0048] The curing time can be greater than 30 minutes. The drying process involves drying in an oven at 100~150℃ for 8~12 hours.

[0049] After surface treatment of the magnetic core-shell coating, a surface-activated magnetic core-shell coating is obtained, which is then dispersed in a base glaze to obtain a magnetically positionable ceramic glaze.

[0050] The surface treatment method is as follows: add the magnetic core-shell coating to the solvent, gradually add the surface treatment agent under stirring conditions, continue stirring for 10-30 minutes, filter to obtain the filter cake, then immediately put the filter cake into water and continue stirring, and finally filter to obtain the surface-activated magnetic core-shell coating.

[0051] The solvent may be at least one of anhydrous ethanol, toluene, xylene, cyclohexane, No. 60 solvent oil, No. 90 solvent oil, and No. 120 solvent oil.

[0052] The surface treatment agent includes, but is not limited to, at least one of polyvinyl butyral, paraffin, stearic acid, palmitic acid, and pentaerythritol stearic acid.

[0053] The mass ratio of surface treatment agent, solution, and core-shell magnetic coating is 2~5:100:5~10. The main purpose of controlling the ratio range is to ensure that a complete, smooth, and uniformly thick film layer is formed on the surface of the core-shell magnetic coating. This film layer is smooth and hydrophobic, which can reduce the internal frictional resistance of the core-shell magnetic coating moving in the glaze slurry.

[0054] The composition of the base glaze is not limited. Any conventional ceramic glaze (including but not limited to transparent glazes) applicable in the ceramic field is suitable for this invention. For example, the chemical composition of the base glaze in the examples and comparative examples includes, by mass percentage: IL: 9.1%, SiO2: 49%, Al2O3: 13%, CaO: 7.4%, MgO: 5.2%, K2O: 2.6%, Na2O: 3.5%, BaO: 7.1%, ZnO: 3.1%.

[0055] The magnetic core-shell coatings, after being activated by a surface treatment agent, are dispersed in the base glaze by conventional stirring. The stirring time can be 30~60 min.

[0056] This invention also relates to the application of functionalized magnetically positionable ceramic glazes in ceramics. Magnetized decorative ceramics include a glaze layer having the aforementioned functionalized magnetically positionable ceramic glaze. Applying an external magnetic field can control the direction and position of movement of both the magnetic and functional materials. For example, the trajectory of a magnetic core-shell coating can be controlled by controlling the position and intensity of the external magnetic field. This invention magnetizes the functional material and bonds it to the glaze, then positions it using an external magnetic field, thereby achieving control over the position and orientation of the functional material.

[0057] The applied magnetic field is a permanent magnet magnetic field or an electromagnet magnetic field. The magnetic field strength can be 10,000 to 15,000 Gauss. The shape of the magnet can be set as needed, such as cube, arc, cylinder, etc.

[0058] The spray glazing method involves generating a mist-like droplets through a nozzle under certain pressure, which eventually accumulate and spread into a flat surface on the body. This spray glazing method is not suitable for the use of the functionalized magnetically positionable ceramic glaze of this invention. Firstly, the mist-like droplets are relatively independent microspheres, which can cause the core-shell magnetic coating to penetrate the droplets and adhere to the magnetic poles during the spraying process. Secondly, when the mist-like droplets contact the body surface, they are instantly dried, preventing the core-shell magnetic coating from moving.

[0059] The application method of functionalized magnetically positionable ceramic glaze is glazing by dripping. This glazing can be done using a bell-shaped glazing system. During the glazing process, the external magnetic field is applied by installing magnets of different shapes or magnetic field strengths around the glaze curtain, at the edge of the ceramic body, or on the bottom surface of the ceramic body. When the glaze slurry naturally flows from the flat opening of the bell-shaped glaze curtain to form a glaze curtain, the magnetic core-shell bodies within the glaze curtain are acted upon by the magnetic field, causing them to move and aggregate, adhering a layer of glaze to the surface of the ceramic body and forming a predetermined pattern. Furthermore, when the ceramic body passes under the glaze curtain, the magnetic core-shell bodies are acted upon by the magnetic field around or at the bottom of the ceramic body, causing them to move and aggregate, and then being fixed in a predetermined position as the glaze slurry moisture is absorbed by the ceramic body. For example, by applying external magnetic fields to the glaze curtain and different positions on the ceramic body, the movement direction and stopping position of the magnetic core-shell bodies can be effectively controlled, thereby achieving control and positioning of the functional material.

[0060] The specific gravity of the base glaze in the functionalized magnetically positionable ceramic glaze can be 1.65~1.70 g / cm³. 3 If the specific gravity is too low, it will cause ripples on the glaze surface; if the specific gravity is too high, it will cause excessive resistance to the movement of the core-shell coating. Water can be added after sieving the glaze to adjust it to the desired specific gravity.

[0061] This includes, but is not limited to, applying a functional magnetically positionable ceramic glaze to the surface of a brick blank, followed by firing to obtain a magnetized decorative ceramic slab. Firing takes place in a kiln. The firing temperature can be 1100~1200℃, and the firing time can be 40~70 minutes. It can also be combined with other processes on the ceramic production line.

[0062] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0063] Example 1

[0064] The preparation method of magnetized decorative ceramic panels includes the following steps:

[0065] (1) Weigh 1000g of zircon sand flash dry particles with a particle size of 5μm, add it to 9000g of sodium alginate aqueous solution with a mass concentration of 0.5%, stir evenly to obtain a coating slurry. Take 7000g of coating slurry, then add 3000g of iron oxide powder with a particle size of 100μm, stir for 30min, filter and take the filter cake to obtain the primary coating.

[0066] (2) The primary coating was placed in a 120-mesh vibrating sieve, and a 6% calcium chloride aqueous solution was placed below the sieve. The sieve was turned on, and the primary coating fell through the sieve into the calcium chloride aqueous solution, where a cross-linking reaction occurred on its surface. After 60 minutes, the filter cake was collected to obtain the secondary coating. The secondary coating was dried in a 100℃ forced-air drying oven for 12 hours to obtain a magnetic core-shell coating.

[0067] (3) Take 50g of magnetic core-shell coating and add it to 1000g of anhydrous ethanol. Under stirring conditions, gradually add 20g of stearic acid and continue stirring for 30min. Then filter and take the filter cake. Place the filter cake in water and stir for 10min. Then filter and take the filter cake to obtain the surface-activated magnetic core-shell coating.

[0068] (4) After passing the conventional (basic) glaze slurry through a 120-mesh sieve, add the surface-activated magnetic core-shell coating, controlling the content of the surface-activated magnetic core-shell coating to be 0.5 wt%. Stir and disperse for 30 min to obtain the functionalized magnetically positionable ceramic glaze. The specific gravity of the basic glaze of the functionalized magnetically positionable ceramic glaze is 1.65 g / cm³. 3 The application rate of the functionalized magnetically positioned ceramic glaze is 600 g / m³. 2 .

[0069] (5) Apply the aforementioned functionalized magnetically positioned ceramic glaze to the surface of the brick blank. During the glazing process in the bell jar, square permanent magnets with a magnetic field strength of 15000 Gauss are added to the left and right sides of the glaze curtain and around the brick blank to control the movement direction and position of the magnetized functional material. Then, it enters the roller kiln for firing, and the magnetized decorative ceramic plate is obtained after exiting the kiln. The firing temperature is 1150℃, and the firing cycle is 45min.

[0070] Example 2

[0071] The preparation method of magnetized decorative ceramic panels includes the following steps:

[0072] (1) Weigh 3000g of zircon sand flash dry particles with a particle size of 5μm, add them to 7000g of sodium alginate aqueous solution with a mass concentration of 2%, stir evenly to obtain a coating slurry. Take 9000g of coating slurry, then add 1000g of neodymium iron boron magnetic powder with a particle size of 50nm, stir for 60min, filter and take the filter cake to obtain the primary coating.

[0073] (2) The primary coating was placed in a 120-mesh vibrating sieve, and a 2% calcium chloride aqueous solution was placed below the sieve. The sieve was turned on, and the primary coating fell through the sieve into the calcium chloride aqueous solution, where a cross-linking reaction occurred on its surface. After 30 minutes, the filter cake was collected to obtain the secondary coating. The secondary coating was dried in a 150℃ forced-air drying oven for 8 hours to obtain a magnetic core-shell coating.

[0074] (3) Take 100g of magnetic core-shell coating and add it to 1000g of cyclohexane. Under stirring conditions, gradually add 50g of palmitic acid and continue stirring for 60min. Then filter and take the filter cake. Place the filter cake in water and stir for 10min. Then filter and take the filter cake to obtain the surface-activated magnetic core-shell coating.

[0075] (4) After passing the conventional (basic) glaze slurry through a 120-mesh sieve, add the surface-activated magnetic core-shell coating, controlling the content of the surface-activated magnetic core-shell coating to be 3wt%, and stir and disperse for 30 min to obtain the functionalized magnetically positionable ceramic glaze. The specific gravity of the basic glaze of the functionalized magnetically positionable ceramic glaze is 1.70 g / cm³. 3 The application rate of the functionalized magnetically positioned ceramic glaze is 600 g / m². 2 .

[0076] (5) Apply the aforementioned functionalized magnetically positioned ceramic glaze to the surface of the brick blank. During the glazing process in the bell jar, an arc-shaped permanent magnet with a magnetic field strength of 10,000 Gauss is added around the perimeter of the blank; a square magnet with a magnetic field strength of 10,000 Gauss is added to the center of the bottom surface to control the direction and position of the magnetized functional material. Then, it is fired in a roller kiln, and the magnetized decorative ceramic plate is obtained after firing. The firing temperature is 1150℃, and the firing cycle is 60 minutes.

[0077] Example 3

[0078] The preparation method of magnetized decorative ceramic panels includes the following steps:

[0079] (1) Weigh 3000g of iron-cobalt-nickel composite material powder with a particle size of 50μm, add it to 7000g of sodium alginate aqueous solution with a mass concentration of 2%, stir evenly to obtain a coating slurry. Take 7000g of coating slurry, then add 3000g of a mixture of green pigment and glitter dry particles with a particle size of 100μm (the mass ratio of green pigment to glitter dry particles is 1:1), stir for 30min, filter and take the filter cake to obtain the primary coating.

[0080] (2) The primary coating was placed in a 120-mesh vibrating sieve, and a 6% calcium chloride aqueous solution was placed below the sieve. The sieve was turned on, and the primary coating fell through the sieve into the calcium chloride aqueous solution, where a cross-linking reaction occurred on its surface. After 60 minutes, the filter cake was collected to obtain the secondary coating. The secondary coating was dried in a 100℃ forced-air drying oven for 12 hours to obtain a magnetic core-shell coating.

[0081] (3) Take 50g of magnetic core-shell coating and add it to 1000g of anhydrous ethanol. Under stirring conditions, gradually add 20g of stearic acid and continue stirring for 30min. Then filter and take the filter cake. Place the filter cake in water and stir for 10min. Then filter and take the filter cake to obtain the surface-activated magnetic core-shell coating.

[0082] (4) After passing the conventional (basic) glaze slurry through a 120-mesh sieve, add the surface-activated magnetic core-shell coating, controlling the content of the surface-activated magnetic core-shell coating to be 0.5 wt%. Stir and disperse for 30 min to obtain the functionalized magnetically positionable ceramic glaze. The specific gravity of the basic glaze of the functionalized magnetically positionable ceramic glaze is 1.65 g / cm³. 3 The application rate of the functionalized magnetically positioned ceramic glaze is 600 g / m³. 2 .

[0083] (5) Apply the aforementioned functionalized magnetically positioned ceramic glaze to the surface of the brick blank. During the glazing process in the bell jar, square permanent magnets with a magnetic field strength of 15000 Gauss are added to the left and right sides of the glaze curtain and around the brick blank to control the movement direction and position of the magnetized functional material. Then, it enters the roller kiln for firing, and the resulting ceramic slab with magnetized decorative effect is obtained. The firing temperature is 1150℃, and the firing cycle is 45 minutes.

[0084] Comparative Example 1: (Non-magnetic material)

[0085] (1) Weigh 1000g of zircon sand flash dry particles with a particle size of 5μm, add it to 9000g of sodium alginate aqueous solution with a mass concentration of 0.5%, stir evenly to obtain a coating slurry. Take 7000g of coating slurry, then add 3000g of zircon sand flash dry particles with a particle size of 100μm, stir for 30min, filter and take the filter cake to obtain the primary coating.

[0086] (2) The primary coating was placed in a 120-mesh vibrating sieve, and a 6% calcium chloride aqueous solution was placed below the sieve. The sieve was turned on, and the primary coating fell through the sieve into the calcium chloride aqueous solution, where a cross-linking reaction occurred on its surface. After 60 minutes, the filter cake was collected to obtain the secondary coating. The secondary coating was then dried in a 100°C forced-air drying oven for 12 hours to obtain the core-shell coating.

[0087] (3) Take 50g of core-shell coating and add it to 1000g of anhydrous ethanol. Under stirring conditions, gradually add 20g of stearic acid and continue stirring for 30min. Then filter and take the filter cake. Place the filter cake in water and stir for 10min. Then filter and take the filter cake to obtain the surface-activated core-shell coating.

[0088] (4) After passing the conventional (basic) glaze slurry through a 120-mesh sieve, add the surface-activated core-shell coating, controlling the mass content of the surface-activated core-shell coating to be 0.5%, and stir and disperse for 30 minutes to obtain the functionalized ceramic glaze. The specific gravity of the basic glaze of the functionalized ceramic glaze is 1.65 g / cm³. 3 The application rate of the functionalized ceramic glaze is 600 g / m³. 2 .

[0089] (5) Apply the functionalized ceramic glaze to the surface of the brick blank. During the glazing process in the bell jar, square permanent magnets with a magnetic field strength of 15,000 Gauss are added to the left and right sides of the glaze curtain and around the blank. Then, it is fired in a roller kiln, and ordinary ceramic slabs are obtained after exiting the kiln. The firing temperature is 1150℃ and the firing cycle is 45 minutes.

[0090] Results Explanation:

[0091] The scanning electron microscope (SEM) and transmission electron microscope (TEM) images of the magnetic core-shell coatings prepared in Example 1 of this invention are shown below. Figure 1 and Figure 7 The apparent morphology is a rough-surfaced sphere, a typical core-shell structure. After surface treatment, a surface-activated magnetic core-shell coated body is obtained. Figure 2 Its smooth surface greatly reduces the resistance to movement in the glaze slurry.

[0092] The magnetized decorative ceramic slabs prepared in Examples 1-3 of this invention all have good three-dimensional decorative effects. The functional materials in the glaze layer are multi-layered and have a magnetic field orientation tendency for irregular functional materials, which is very similar to the distribution of sparkling particles in natural stone. Figures 3-5 The surface effect diagrams of the magnetized decorative ceramic plates prepared in Examples 1-3 of the present invention are shown respectively. The functional materials used in Examples 1 and 3 are different. Example 1 uses zircon sand dry particles, while Example 3 uses green pigment and glitter dry particles, so the appearance effect has color difference.

[0093] The surface effect of the ordinary ceramic plate prepared in Comparative Example 1 is as follows: Figure 6 As shown, the glitter particles are evenly distributed but lack three-dimensionality and transparency. This is because Comparative Example 1 did not include magnetic materials. The functional materials are evenly dispersed in the glaze and cannot move directionally under the influence of a magnetic field, thus failing to form a concentrated, layered positioning effect, which greatly weakens the performance of the functional materials.

[0094] Comparative Example 2

[0095] Referring to Example 2, except for the different mass content of the magnetic core-shell coating treated with surface treatment agent in step (4), the preparation method and process are the same. Step (4) is as follows: After passing the conventional (basic) glaze slurry through a 120-mesh sieve, the surface-activated magnetic core-shell coating is added, and the content of the surface-activated magnetic core-shell coating is controlled at 4wt%. The mixture is stirred and dispersed for 30 minutes to obtain the functionalized magnetically positionable ceramic glaze. The specific gravity of the basic glaze of the functionalized magnetically positionable ceramic glaze is 1.65 g / cm³. 3 The application rate of the functionalized magnetically positioned ceramic glaze is 600 g / m³. 2 .

[0096] Comparative Example 3

[0097] Referring to Example 3, except that stearic acid is not added in step (3), the rest of the preparation methods and processes are the same. Step (3) is as follows: Take 50g of magnetic core-shell coating and add it to 1000g of anhydrous ethanol, stir for 30min, then filter and take the filter cake, place the filter cake in water and stir for 10min, then filter and take the filter cake.

[0098] Comparative Example 4

[0099] Referring to Example 2, except for the glazing parameters in step (4), the preparation methods and processes are the same. Step (4) is as follows: After passing a conventional (basic) ordinary glaze slurry through a 120-mesh sieve, surface-activated magnetic core-shell coatings are added, and the content of surface-activated magnetic core-shell coatings is controlled at 3wt%. The mixture is stirred and dispersed for 30 minutes to obtain a functionalized magnetically positionable ceramic glaze. The specific gravity of the base glaze of the functionalized magnetically positionable ceramic glaze is 1.80 g / cm³. 3The application rate of the functionalized magnetically positioned ceramic glaze is 600 g / m³. 2 .

[0100] Results Analysis: In Comparative Example 2, the mass content of the magnetic core-shell coating treated with surface treatment agent was increased to 4%. Due to the increased relative content of magnetic materials, the color of the glaze was greatly affected. Figure 8 Compared to Example 2, the glaze color of Comparative Example 3 shows a significant change. The surface effect of the magnetic core-shell coated ceramic slab with magnetized decorative effect prepared without surface activation treatment is as follows: Figure 9 As shown, due to the increased resistance to movement of the core-shell coating in the glaze, it cannot move to the set position within the set time, resulting in some functional materials failing to reach the expected position and thus failing to achieve precise positioning. In Comparative Example 4, increasing the specific gravity of the glaze and the viscosity of the glaze slurry will significantly increase the resistance to movement of the core-shell coating in the glaze, causing the functional materials to fail to move to the set position within the set time and thus failing to achieve precise positioning.

Claims

1. A functionalized magnetically positionable ceramic glaze, characterized in that, The functionalized magnetically positionable ceramic glaze comprises a base glaze and a magnetic core-shell coating uniformly dispersed in the base glaze and activated by a surface treatment agent; wherein the core of the magnetic core-shell coating is a functional material and the shell is a magnetic material, or the core is a magnetic material and the shell is a functional material; the mass content of the magnetic core-shell coating activated by the surface treatment agent in the functionalized magnetically positionable ceramic glaze is 0.5%~3%; the surface treatment agent is at least one of polyvinyl butyral, paraffin wax, stearic acid, palmitic acid and pentaerythritol stearic acid; the mass ratio of the surface treatment agent to the magnetic core-shell coating is 2~5:5~10.

2. The functionalized magnetically positionable ceramic glaze according to claim 1, characterized in that, The functional material is at least one of the following: glitter material, pigment, dry granules, photochromic material, thermochromic material, antibacterial material, wear-resistant material, and anti-slip material; the magnetic material is at least one of the following: elemental iron, elemental cobalt, elemental nickel, iron oxide, cobalt oxide, nickel oxide, iron-cobalt oxide, nickel-cobalt oxide, iron-nickel oxide, iron-cobalt-nickel oxide, neodymium iron boron composite material, and iron-cobalt-nickel composite material.

3. The functionalized magnetically positionable ceramic glaze according to claim 1, characterized in that, The mass ratio of the core to the shell of the magnetic core-shell coating is 1~3:1~3.

4. A method for preparing a functionalized magnetically positionable ceramic glaze according to any one of claims 1 to 3, characterized in that, The preparation method includes: coating a shell material onto the surface of a core material using a coating technique to obtain a magnetic core-shell coating; activating the magnetic core-shell coating with a surface treatment agent to obtain a surface-activated magnetic core-shell coating; dispersing the surface-activated magnetic core-shell coating in a base glaze to obtain a functionalized magnetically positionable ceramic glaze; the coating technique involves: adding the core material to a coating slurry, mixing it evenly, filtering it to obtain a filter cake to obtain a primary coating; then adding the primary coating to a curing liquid through a sieve for curing, filtering it again, and obtaining a filter cake to obtain a secondary coating; finally, drying the secondary coating. A magnetic core-shell coated body is obtained; the coating slurry is a mixture of sodium alginate aqueous solution and shell material; the mass ratio of shell material to sodium alginate aqueous solution is 1:10~5:10; the mass ratio of core material to coating slurry is 1:10~5:10; the curing solution is a calcium chloride aqueous solution or calcium carbonate aqueous solution with a mass concentration of 2%~6%; the activation treatment method is as follows: the magnetic core-shell coated body is added to the solvent, a surface treatment agent is added under stirring conditions, and after stirring evenly, the filter cake is collected by filtration, and then the filter cake is placed in water and stirred again. Finally, the surface-activated magnetic core-shell coated body is obtained by filtration.

5. The preparation method according to claim 4, characterized in that, The solvent is at least one of anhydrous ethanol, toluene, xylene, cyclohexane, No. 60 solvent oil, No. 90 solvent oil, and No. 120 solvent oil; the surface treatment agent is at least one of polyvinyl butyral, paraffin wax, stearic acid, palmitic acid, and pentaerythritol stearic acid.

6. A type of magnetized decorative ceramic, characterized in that, The magnetized decorative ceramic comprises a glaze layer having a functionalized magnetically positionable ceramic glaze according to any one of claims 1 to 3; wherein the movement trajectory of the magnetic core-shell coating activated by the surface treatment agent is controlled by controlling the position and intensity of the applied magnetic field; the functionalized magnetically positionable ceramic glaze is applied by glazing; the specific gravity of the base glaze of the functionalized magnetically positionable ceramic glaze is 1.65~1.70 g / cm³. 3 The amount of the functionalized magnetically positionable ceramic glaze applied is 500~750 g / m³. 2 .

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