High-temperature pigment for ceramics and preparation method of high-temperature pigment

Abstract

The invention relates to the technical field of ceramic pigments, in particular to a high-temperature pigment for ceramics and a preparation method of the high-temperature pigment. The ink is prepared from the following raw materials in parts by weight: 36-85 parts of a coloring agent, 5-10 parts of kaolin, 2-6 parts of aluminum oxide, 3-8 parts of sodium carbonate, 8-16 parts of a dispersing agent, 3-12 parts of modified nano zinc oxide, 2-5 parts of a surfactant, 3-5 parts of diazonium salt and 5-18 parts of a solvent. The coloring agent is Y3Ga3MgSiO12: xCr < 3 + >, wherein x is equal to 0.1 to 0.2. The prepared ceramic pigment can maintain color and structural stability at extremely high temperature, has excellent chemical inertness, and is not easy to react with glaze or a ceramic matrix. In addition, the ceramic pigment can resist corrosion of acid, alkali and other corrosive substances, so that the stability and attractiveness of the ceramic product in a severe environment are ensured.

Description

Technical Field

[0001] This invention relates to the field of ceramic pigment technology, and more specifically, to a high-temperature pigment for ceramics and a method for preparing the same. Background Technology

[0002] Ceramic pigments are essential materials for ceramic coloring and surface decoration. During the glazing process, ceramic pigments must withstand high-temperature treatment; therefore, high-temperature stability and color saturation are two important indicators characterizing the performance of high-temperature ceramic pigments. Ceramic pigments are mainly used for overglaze, underglaze, and body coloring, possessing excellent heat resistance, chemical stability, and color retention. They maintain their color and properties during high-temperature firing, without fading or discoloration, providing a long-lasting and stable color effect. There are many types of ceramic pigments, including inorganic oxide pigments, organic pigment compounds, and metal compounds, among which inorganic oxide pigments are the most commonly used due to their high-temperature stability and wide color range.

[0003] Existing ceramic pigments suffer from the following shortcomings: They exhibit poor stability in glazes, easily influenced by glaze components (such as zinc, calcium, and aluminum), leading to color changes or instability. Ceramic pigments must be compatible with glazes, opacifiers, and additives for successful use. However, some pigments are relatively inert in conventional glazes, while others are highly reactive, easily reacting and causing color changes or glaze defects. Furthermore, ceramic pigments are prone to chemical reactions during firing, resulting in color changes or glaze defects. Summary of the Invention

[0004] This invention provides a high-temperature pigment for ceramics and its preparation method. The resulting ceramic pigment maintains color and structural stability at extremely high temperatures. It also exhibits excellent chemical inertness, making it resistant to reaction with glazes or ceramic matrices. Furthermore, the ceramic pigment resists erosion by acids, alkalis, and other corrosive substances, ensuring the stability and aesthetics of ceramic products even in harsh environments.

[0005] In a first aspect, the present invention provides a high-temperature pigment for ceramics, comprising the following raw materials in parts by weight: 36-85 parts colorant, 5-10 parts kaolin, 2-6 parts alumina, 3-8 parts sodium carbonate, 8-16 parts dispersant, 3-12 parts modified nano zinc oxide, 2-5 parts surfactant, 3-5 parts diazonium salt, and 5-18 parts solvent; wherein the colorant is Y3Ga3MgSiO 12 ∶xCr 3+ , where x = 0.1 to 0.2.

[0006] Preferably, the dispersant is prepared from hydroxyl-terminated polyethylene glycol methacrylate and styrene, wherein the mass ratio of polyethylene glycol methacrylate to styrene is 3-7:5-11.

[0007] Preferably, the modified nano zinc oxide uses zinc acetate dihydrate as a zinc precursor, and nano ZnO material matrix is ​​prepared by high-temperature decomposition, and then prepared by solvothermal method using melamine and terephthalaldehyde as ligands.

[0008] Preferably, the mass ratio of the nano-ZnO material, melamine, and terephthalaldehyde is 3-5:1-2:1.

[0009] Preferably, the surfactant is one or more of fatty acid guanidine salts, polyethylene glycol, sodium lignosulfonate, and polymethacrylate.

[0010] Preferably, the diazonium salt is one or more of p-nitrobenzene diazonium salt, 4-aminobenzoic acid diazonium salt, 4-aminobenzylthiophenol diazonium salt, and pyrazole diazonium inner salt.

[0011] Secondly, the present invention provides a method for preparing a high-temperature pigment for ceramics, comprising the following steps:

[0012] (1) Add colorant, kaolin, alumina, sodium carbonate, dispersant and modified nano zinc oxide into a sand mill in proportion, stir evenly, add diazonium salt and grind.

[0013] (2) Add surfactant to the ground powder while stirring with a high-speed mixer, stir, and sieve to obtain the matrix component;

[0014] (3) Add solvent to the matrix components and mix evenly to obtain a high-temperature pigment for ceramics.

[0015] Preferably, in step (2), the sieving condition is to pass through an 800-1200 mesh sieve for later use.

[0016] In summary, the present invention has the following beneficial effects:

[0017] 1. The colorant in this invention is Y3Ga3MgSiO 12 ∶xCr 3+ Where x = 0.1–0.2, the garnet structure possesses high chemical stability, mechanical hardness, and a wide bandgap, effectively suppressing Cr. 3+ Thermal ionization enhances coloring stability, resulting in excellent colorimetric values. It exhibits significant coloring ability and stability at high temperatures, making it suitable for medium-temperature ceramic applications.

[0018] 2. The dispersant added in this invention is prepared from hydroxyl-terminated polyethylene glycol methacrylate and styrene. It adsorbs onto the surface of ceramic pigment particles through styrene segments (hydrophobic anchoring groups), while hydrophilic polyethylene glycol segments extend in the medium to form a steric hindrance layer, preventing particle agglomeration. The content of anchoring groups directly affects the adsorption strength, and thus the dispersion stability. As a surfactant, its hydrophilic-hydrophobic structure reduces the surface tension of ceramic pigment particles, promotes rapid wetting of particles, and improves slurry flowability. In ceramic pigments, this adjusts the water retention of the pigment, enhances particle binding force, and improves glazing efficiency and glaze quality.

[0019] 3. This invention's modified nano-zinc oxide uses zinc acetate dihydrate as a zinc precursor, and prepares a nano-ZnO material matrix using a high-temperature decomposition method. Then, using melamine and terephthalaldehyde as ligands, it is prepared via a solvothermal method. The modified nano-zinc oxide has a small particle size (typically 10-50 nm) and high activity. Adding it to ceramic glazes promotes the melting process and reduces its coefficient of thermal expansion. This helps reduce thermal stress in the glaze layer during firing, preventing cracking or peeling and improving the yield of the finished product. By reducing the coefficient of thermal expansion, nano-zinc oxide significantly enhances the thermal stability of ceramic products, making them less prone to deformation or damage at high temperatures. The modified nano-zinc oxide optimizes the optical properties of the glaze surface. Its highly active surface reflects more light, enhancing the gloss of the glaze.

[0020] 4. The ceramic pigments prepared by this invention can maintain color and structural stability at extremely high temperatures. These pigments also possess excellent chemical inertness and are not prone to reacting with glazes or ceramic matrices. Furthermore, they resist the erosion of acids, alkalis, and other corrosive substances, ensuring the stability and aesthetics of ceramic products even in harsh environments.

[0021] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit the scope of protection of the present invention. Detailed Implementation

[0022] The present invention will be further described in detail below with reference to the embodiments. It should be noted that: unless otherwise specified, the conditions in the following embodiments are carried out according to conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following embodiments can be obtained from commercially available sources.

[0023] Example

[0024] Example 1

[0025] A high-temperature pigment for ceramics is composed of the following raw materials in parts by weight: 36 parts colorant, 5 parts kaolin, 2 parts alumina, 3 parts sodium carbonate, 8 parts dispersant, 3 parts modified nano zinc oxide, 2 parts surfactant, 3 parts diazonium salt, and 5 parts solvent.

[0026] The colorant is Y3Ga3MgSiO 12 0.05Cr 3+ The chromaticity values ​​are L* = 81.16, a* = -12.53, and b* = 12.71.

[0027] The dispersant is prepared from hydroxyl-terminated polyethylene glycol methacrylate and styrene, with a mass ratio of polyethylene glycol methacrylate to styrene of 3:5.

[0028] Modified nano-zinc oxide uses zinc acetate dihydrate as a zinc precursor and prepares the nano-ZnO material matrix by high-temperature decomposition. Then, it is prepared by solvothermal method using melamine and terephthalaldehyde as ligands. The mass ratio of nano-ZnO material, melamine and terephthalaldehyde is 3:1:1.

[0029] The surfactant is a guanidine salt of fatty acids; the diazonium salt is a p-nitrobenzene diazonium salt.

[0030] A method for preparing a high-temperature pigment for ceramics includes the following steps:

[0031] (1) Add colorant, kaolin, alumina, sodium carbonate, dispersant and modified nano zinc oxide into a sand mill in proportion, stir evenly, add diazonium salt and grind.

[0032] (2) Add surfactant to the ground powder while stirring with a high-speed mixer, stir, and sieve to obtain the matrix component; the sieve condition is to pass through an 800-mesh sieve for later use.

[0033] (3) Add solvent to the matrix components and mix evenly to obtain a high-temperature pigment for ceramics.

[0034] Example 2

[0035] A high-temperature pigment for ceramics is composed of the following raw materials in parts by weight: 56 parts colorant, 8 parts kaolin, 4 parts alumina, 6 parts sodium carbonate, 12 parts dispersant, 9 parts modified nano zinc oxide, 4 parts surfactant, 4 parts diazonium salt, and 15 parts solvent.

[0036] The colorant is Y3Ga3MgSiO 12 0.05Cr 3+ The chromaticity values ​​are L* = 81.16, a* = -12.53, and b* = 12.71.

[0037] The dispersant is prepared from hydroxyl-terminated polyethylene glycol methacrylate and styrene, with a mass ratio of polyethylene glycol methacrylate to styrene of 7:5.

[0038] Modified nano-zinc oxide uses zinc acetate dihydrate as a zinc precursor and prepares the nano-ZnO material matrix by high-temperature decomposition. Then, it is prepared by solvothermal method using melamine and terephthalaldehyde as ligands. The mass ratio of nano-ZnO material, melamine and terephthalaldehyde is 4:1:1.

[0039] The surfactant is a guanidine salt of fatty acids; the diazonium salt is a p-nitrobenzene diazonium salt.

[0040] A method for preparing a high-temperature pigment for ceramics includes the following steps:

[0041] (1) Add colorant, kaolin, alumina, sodium carbonate, dispersant and modified nano zinc oxide into a sand mill in proportion, stir evenly, add diazonium salt and grind.

[0042] (2) Add surfactant to the ground powder while stirring with a high-speed mixer, stir, and sieve to obtain the matrix component; the sieve condition is to pass through an 800-mesh sieve for later use.

[0043] (3) Add solvent to the matrix components and mix evenly to obtain a high-temperature pigment for ceramics.

[0044] Example 3

[0045] A high-temperature pigment for ceramics is composed of the following raw materials in parts by weight: 85 parts colorant, 10 parts kaolin, 6 parts alumina, 8 parts sodium carbonate, 16 parts dispersant, 12 parts modified nano zinc oxide, 5 parts surfactant, 5 parts diazonium salt, and 18 parts solvent.

[0046] The colorant is Y3Ga3MgSiO 12 0.05Cr 3+ The chromaticity values ​​are L* = 81.16, a* = -12.53, and b* = 12.71.

[0047] The dispersant is prepared from hydroxyl-terminated polyethylene glycol methacrylate and styrene, with a mass ratio of polyethylene glycol methacrylate to styrene of 7:11.

[0048] Modified nano-zinc oxide uses zinc acetate dihydrate as a zinc precursor and prepares the nano-ZnO material matrix by high-temperature decomposition. Then, it is prepared by solvothermal method using melamine and terephthalaldehyde as ligands. The mass ratio of nano-ZnO material, melamine and terephthalaldehyde is 5:2:1.

[0049] The surfactant is a guanidine salt of fatty acids; the diazonium salt is a p-nitrobenzene diazonium salt.

[0050] A method for preparing a high-temperature pigment for ceramics includes the following steps:

[0051] (1) Add colorant, kaolin, alumina, sodium carbonate, dispersant and modified nano zinc oxide into a sand mill in proportion, stir evenly, add diazonium salt and grind.

[0052] (2) Add surfactant to the ground powder while stirring with a high-speed mixer, stir, and sieve to obtain the matrix component; the sieve condition is to pass through an 800-mesh sieve for later use.

[0053] (3) Add solvent to the matrix components and mix evenly to obtain a high-temperature pigment for ceramics.

[0054] Comparative Example 1

[0055] The difference compared to Example 2 is that no dispersant was added.

[0056] Comparative Example 2

[0057] The difference compared to Example 2 is that no modified nano zinc oxide was added.

[0058] Comparative Example 3

[0059] The difference compared to Example 2 is that no diazonium salt was added.

[0060] Comparative Example 4

[0061] The difference compared to Example 2 is that no surfactant was added.

[0062] The pigments prepared in Examples 1-3 and Comparative Examples 1-4 were tested for heat resistance according to the national standard HG / T 3853-2006, "Determination of Heat Resistance of Dry Pigment Powder," with test temperatures set at 1000 and 1500℃. Specific procedures: The oven temperature was raised to the set temperature. After the oven temperature stabilized, a crucible containing 2.5g of the sample powder was placed in the oven. Timing began when the oven temperature returned to the set temperature. After 30 minutes, the sample was removed, and the color difference ΔE before and after baking was measured after cooling. The test results are shown in Table 1.

[0063] Table 1. Performance test results of the pigments in this invention.

[0064] Color difference ΔE at 1000℃ Color difference ΔE at 1500℃ Example 1 0.17 0.35 Example 2 0.15 0.32 Example 3 0.16 0.36 Comparative Example 1 0.56 0.89 Comparative Example 2 0.62 1.21 Comparative Example 3 0.52 0.96 Comparative Example 4 0.33 1.05

[0065] As shown in Table 1, the high-temperature pigment for ceramics prepared in Example 2 exhibits high chemical stability, indicating that the prepared ceramic pigment can maintain color and structural stability at extremely high temperatures. The ceramic pigment also possesses excellent chemical inertness and is not prone to reacting with glazes or ceramic matrices. Furthermore, the ceramic pigment resists the erosion of acids, alkalis, and other corrosive substances, ensuring the stability and aesthetics of ceramic products under harsh environments.

[0066] The above description is merely an exemplary embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A high-temperature pigment for ceramics, characterized in that, It is composed of the following raw materials in parts by weight: 36-85 parts colorant, 5-10 parts kaolin, 2-6 parts alumina, 3-8 parts sodium carbonate, 8-16 parts dispersant, 3-12 parts modified nano zinc oxide, 2-5 parts surfactant, 3-5 parts diazonium salt, and 5-18 parts solvent; wherein the colorant is Y3Ga3MgSiO 12 ∶xCr 3+ , where x = 0.1 to 0.

2.

2. The high-temperature pigment for ceramics according to claim 1, characterized in that, The dispersant is prepared from hydroxyl-terminated polyethylene glycol methacrylate and styrene as raw materials, and the mass ratio of polyethylene glycol methacrylate to styrene is 3-7:5-11.

3. The high-temperature pigment for ceramics according to claim 1, characterized in that, The modified nano-zinc oxide uses zinc acetate dihydrate as a zinc precursor and prepares the nano-ZnO material matrix by high-temperature decomposition. Then, it is prepared by solvothermal method using melamine and terephthalaldehyde as ligands.

4. The high-temperature pigment for ceramics according to claim 3, characterized in that, The mass ratio of the nano-ZnO material, melamine, and terephthalaldehyde is 3-5:1-2:

1.

5. The high-temperature pigment for ceramics according to claim 1, characterized in that, The surfactant is one or more of fatty acid guanidine salts, polyethylene glycol, sodium lignosulfonate, and polymethacrylate.

6. The high-temperature pigment for ceramics according to claim 1, characterized in that, The diazonium salt is one or more of p-nitrobenzene diazonium salt, 4-aminobenzoic acid diazonium salt, 4-aminobenzylthiophenol diazonium salt, and pyrazole diazonium inner salt.

7. The method for preparing high-temperature pigments for ceramics according to any one of claims 1-6, characterized in that, Includes the following steps: (1) Add colorant, kaolin, alumina, sodium carbonate, dispersant and modified nano zinc oxide into a sand mill in proportion, stir evenly, add diazonium salt and grind. (2) Add surfactant to the ground powder while stirring with a high-speed mixer, stir, and sieve to obtain the matrix component; (3) Add solvent to the matrix components and mix evenly to obtain a high-temperature pigment for ceramics.

8. The method for preparing high-temperature pigments for ceramics according to claim 7, characterized in that, In step (2), the sieving condition is to pass through an 800-1200 mesh sieve for later use.