Method for producing zirconia-iron red material for ceramic ink of electro-fused zirconia

Abstract

The application relates to the field of ceramic ink preparation, and discloses a method for preparing zirconium-iron red material for ceramic ink prepared from fused zirconia, which comprises the following steps: S1, mixing and treating zircon sand with a modifier; S2, performing smelting treatment on the mixture so that the mixture is completely melted, and after quenching and drying, hollow particles are obtained and reserved; S3, performing grinding treatment on the melt until the melt meets the requirements and is reserved; S4, performing modified desiliconization treatment on the ground melt powder; and S5, mixing and grinding the obtained powder with other raw materials of zirconium-iron red, heating and calcining, and keeping warm, so that the zirconium-iron red material is obtained. The zirconium-iron red material prepared by the method has a color difference value close to that of a chemical zirconium standard material. Due to the improvement of the color development effect, the prepared zirconium-iron red material can be used for the preparation of ceramic ink, so that the ceramic product presents a more bright and uniform red color after firing, and the attraction and market competitiveness of the product are improved.

Description

Technical Field

[0001] This invention relates to the field of ceramic ink preparation technology, specifically a method for producing zirconium iron red pigment for ceramic ink using fused zirconium oxide. Background Technology

[0002] Ceramic inks have wide applications in the ceramic industry, and zirconium iron red pigment is one of the commonly used pigments in ceramic inks. Currently, the main production process for zirconium iron red pigment is the use of chemical zirconium as a raw material, while zirconium iron red pigment produced by fused zirconium oxide is less commonly used. This is because zirconium iron red pigment prepared by fused zirconium oxide, after being ground to the particle size required for use in ceramic inks, has poor tinting strength and cannot meet the requirements of ceramic ink products.

[0003] Compared to chemically produced zirconium, fused zirconium oxide powder has a higher impurity content and lower reactivity. This results in the incomplete synthesis of coloring elements during the coloring process of zirconium iron red pigment prepared by fused zirconium oxide, thus affecting its synthesis effect. This difference is due to the different production processes of fused zirconium oxide and chemically produced zirconium.

[0004] To address the above problems, this invention provides an improved method for producing zirconium iron red pigment for ceramic inks using fused zirconia. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a method for producing zirconium iron red pigment for ceramic inks using fused zirconia. By improving the ratio of modifiers and the modification and desilication treatment process, the purity, particle uniformity, and reactivity of the zirconium iron red pigment can be improved, thereby enhancing its coloring effect.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a method for producing zirconium iron red pigment for ceramic ink using fused zirconia, comprising the following steps:

[0007] S1. Zircon sand is mixed with a modifier, wherein the modifier includes microsilica powder, sodium fluoride and sodium carbonate;

[0008] In this step, zircon sand is mixed with a modifier. The silica fume, sodium fluoride, and sodium carbonate in the modifier react with the zircon sand surface, altering its surface properties and chemical composition. The silica fume provides surface active sites, while the sodium fluoride and sodium carbonate lower the melting point and viscosity of the zircon sand, promoting the melting process.

[0009] S2. Melt the mixture until it is completely melted, quench it, and then dry the hollow particles for later use.

[0010] In this step, the mixture treated with the modifier is heated to a high temperature for melting. At this temperature, the zircon sand reacts with the modifier to form a melt. The melt can mix and react more thoroughly in its molten state, resulting in a more homogeneous composition. Through quenching, the melt can form a porous structure during solidification, which is beneficial for subsequent grinding and desilication modification processes.

[0011] S3. Grind the molten material until it meets the requirements and set it aside for later use;

[0012] In this step, the molten material, after being melted, is ground to achieve the required particle size. Grinding further refines the particle size of the molten material, improves its uniformity and flowability, and facilitates subsequent modification, desilication, and mixing grinding processes.

[0013] S4. Modify and desiliconize the ground molten powder by first soaking it in an alkaline solution, then neutralizing it with an acid solution, then washing the precipitate with water and drying it for later use.

[0014] In this step, the molten powder, after being ground, undergoes a modification and desilication treatment. First, it is soaked in an alkaline solution. The alkaline substances in the solution react with the silicates in the molten powder, converting them into soluble alkali metal silicates, thereby removing the silicon.

[0015] Then, an acid solution is used for neutralization. Neutralizing acidic substances can neutralize alkaline substances, causing them to precipitate as silicates. After several rinses with clean water, residual acidic and alkaline substances in the precipitate can be removed.

[0016] By modifying and desilication, silicates in the molten material can be effectively removed, thereby improving the purity and quality of zirconium iron red material.

[0017] S5. Mix and grind the obtained powder with other raw materials of zirconium iron red, heat and calcine, and keep warm to obtain zirconium iron red material;

[0018] In this step, the modified and desilicationized molten powder is mixed and ground with other raw materials for zirconium iron red. This mixing and grinding ensures thorough mixing of the various raw materials and guarantees uniform composition. The mixed material is then subjected to calcination.

[0019] During the heating and calcination process, auxiliary materials such as iron oxide red and quartz powder in the raw materials react at high temperatures to form the crystalline phase of zirconium iron red pigment. The heat preservation process is beneficial to the growth and stability of the crystalline phase. Finally, through natural cooling, the final product of zirconium iron red pigment is obtained.

[0020] Preferably, the modifier comprises 88-93% microsilica powder, 2-7% sodium fluoride and 5-10% sodium carbonate.

[0021] Preferably, the proportion of the modifier is 5-10% of the mass of the zircon sand.

[0022] Preferably, the melting temperature of the melting process is 2350-2450℃, the melting time is 4-5 hours, and the melt is quenched with water.

[0023] Preferably, the grinding ball ratio in step S3 is 1:3, the powder particle size D50 is controlled at 17-18μm, and the D90 is controlled at 38-42μm.

[0024] Preferably, the concentration of the alkaline solution for soaking is 10-20%, and the soaking time is 3-4 hours; the concentration of the acid solution for neutralization is 5-10%, and the precipitate after neutralization is washed with clean water 4-5 times.

[0025] Preferably, the alkaline solution is a flake caustic soda solution, and the acid solution is a sulfuric acid solution.

[0026] Preferably, the other raw materials for zirconium iron red include auxiliary materials such as iron oxide red, quartz powder, magnesium fluoride, potassium chloride, and sodium fluorosilicate. Among them, the auxiliary material quartz powder is the main material for synthesizing zirconium silicate, iron oxide red is the colorant, and the other materials act as mineralizers. The purpose is to synthesize zirconium iron red material at a lower temperature.

[0027] Preferably, the heating and calcination in step S5 lasts for 6-8 hours, and when the temperature reaches 1050-1100℃, it is held at that temperature for 2-3 hours, followed by natural cooling.

[0028] Preferably, the use of the zirconium iron red material includes the following steps:

[0029] 1) Grind the prepared zirconium iron red material into a powder of 0.5-1 μm;

[0030] 2) Add the powder to the ceramic ink glaze at a ratio of 35-45%.

[0031] This invention provides a method for producing zirconium iron red pigment for ceramic inks using fused zirconium oxide. It has the following beneficial effects:

[0032] 1. The zirconium iron red pigment prepared by the method of this invention exhibits a color difference value at 1230℃ that is close to that of the chemical zirconium standard pigment, significantly superior to that of ordinary fused zirconium oxide. This means that the method of this invention can significantly improve the color development effect of fused zirconium oxide, making it closer to the ideal color standard.

[0033] 2. Due to the improved color development effect, the prepared zirconium iron red pigment can be used in the preparation of ceramic ink, making the ceramic products exhibit a brighter and more uniform red color after firing, thus increasing the product's attractiveness and market competitiveness.

[0034] 3. The modifier and desilication process used in this invention can achieve lower costs in the preparation of zircon sand, and the process steps are relatively simple. Compared with using chemical zirconium standard pigments, the cost of preparing zirconium iron red pigment is lower, which can reduce product manufacturing costs and improve production efficiency. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the process flow of the present invention. Detailed Implementation

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example

[0037] Step S1: Mix zircon sand with a modifier, which includes 88% silica fume, 2% sodium fluoride and 10% sodium carbonate, and the modifier accounts for 5% of the mass of zircon sand.

[0038] Step S2: Melt the mixture at 2350°C for 4 hours, and then quench it with water.

[0039] Step S3: Grind the molten material with a material-to-ball ratio of 1:3, and control the powder particle size D50 at 17μm and D90 at 38μm.

[0040] Step S4: Modify and desiliconize the ground molten powder by first soaking it in a 10% caustic soda solution for 3 hours, then neutralizing it with a 5% sulfuric acid solution. After neutralization, wash the precipitate with water 4 times and dry it for later use.

[0041] Step S5: Mix and grind the obtained powder with other raw materials of zirconium iron red, heat and calcine for 6 hours, hold at 1050℃ for 2 hours, and cool naturally to obtain zirconium iron red material. Example

[0042] Step S1: Mix zircon sand with a modifier. The modifier consists of 90% silica fume, 5% sodium fluoride, and 5% sodium carbonate. The modifier accounts for 7% of the mass of the zircon sand.

[0043] Step S2: Melt the mixture at 2400℃ for 5 hours, and then quench it with water.

[0044] Step S3: Grind the molten material with a material-to-ball ratio of 1:3, and control the powder particle size D50 at 18μm and D90 at 42μm.

[0045] Step S4: Modify and desiliconize the ground molten powder by first soaking it in a 20% caustic soda solution for 4 hours, then neutralizing it with a 10% sulfuric acid solution. After neutralization, wash the precipitate with water 5 times and dry it for later use.

[0046] Step S5: Mix and grind the obtained powder with other raw materials of zirconium iron red, heat and calcine for 8 hours, hold at 1100℃ for 3 hours, and cool naturally to obtain zirconium iron red material. Example

[0047] Step S1: Mix zircon sand with a modifier, which includes 93% silica fume, 2% sodium fluoride and 5% sodium carbonate, and the proportion of the modifier is 8% of the mass of zircon sand.

[0048] Step S2: Melt the mixture at 2450°C for 4.5 hours, and then quench it with water.

[0049] Step S3: Grind the molten material with a ball-to-particle ratio of 1:3, and control the powder particle size D50 at 17.5μm and D90 at 40μm.

[0050] Step S4: Modify and desiliconize the ground molten powder by first soaking it in a 15% caustic soda solution for 3.5 hours, then neutralizing it with a 7.5% sulfuric acid solution. After neutralization, wash the precipitate with water 4.5 times and dry it for later use.

[0051] Step S5: Mix and grind the obtained powder with other raw materials of zirconium iron red, heat and calcine for 7 hours, hold at 1075℃ for 2.5 hours, and cool naturally to obtain zirconium iron red material. Example

[0052] Step S1: Mix zircon sand with a modifier, which includes 91% silica fume, 4% sodium fluoride and 5% sodium carbonate, and the proportion of the modifier is 6% of the mass of zircon sand.

[0053] Step S2: Melt the mixture at 2400°C for 4.25 hours, and then quench it with water.

[0054] Step S3: Grind the molten material with a ball-to-particle ratio of 1:3, and control the powder particle size D50 at 17.75μm and D90 at 40μm.

[0055] Step S4: Modify and desiliconize the ground molten powder by first soaking it in a 12% caustic soda solution for 3.75 hours, then neutralizing it with a 7% sulfuric acid solution. After neutralization, wash the precipitate with water 4.75 times and dry it for later use.

[0056] Step S5: Mix and grind the obtained powder with other raw materials of zirconium iron red, heat and calcine for 7.5 hours, hold at 1080℃ for 2.75 hours, and cool naturally to obtain zirconium iron red material. Example

[0057] Step S1: Mix zircon sand with a modifier, which includes 92% silica fume, 3% sodium fluoride and 5% sodium carbonate, and the modifier accounts for 9% of the mass of zircon sand.

[0058] Step S2: Melt the mixture at 2425°C for 4.75 hours, and then quench it with water.

[0059] Step S3: Grind the molten material with a material-to-ball ratio of 1:3, and control the powder particle size D50 at 18μm and D90 at 41μm.

[0060] Step S4: Modify and desiliconize the ground molten powder by first soaking it in an 18% caustic soda solution for 3.25 hours, then neutralizing it with an 8% sulfuric acid solution. After neutralization, wash the precipitate five times with water and dry it for later use.

[0061] Step S5: Mix and grind the obtained powder with other raw materials of zirconium iron red, heat and calcine for 7.25 hours, hold at 1075℃ for 2.5 hours, and cool naturally to obtain zirconium iron red material.

[0062] Comparative experiment:

[0063] The prepared zirconium iron red material is subjected to a color development test, which is a concrete manifestation of the effectiveness of the invention.

[0064] The zirconium iron red material prepared in Examples 1-5 was ground into a powder of about 0.5-1μm and added to the ceramic ink glaze at a ratio of 35%. The mixture was then fired at 1230℃ and the color development effect was tested with a colorimeter after cooling.

[0065] Furthermore, the color development effect was tested simultaneously using chemical zirconium standard colorant and ordinary fused zirconium oxide at the same firing temperature.

[0066] The experimental data are shown in the table below:

[0067]

[0068] As shown in the table above, the L, a, and b values ​​of ordinary fused zirconium oxide (sample 2#) are significantly different from those of chemical zirconium standard pigment (sample 1#), with a total color difference value ΔE reaching 11.29, indicating that its color development effect is significantly different from that of the standard pigment.

[0069] The zirconium iron red pigments in Examples 1-5 (samples 3#-7#) showed relatively small variations in L, a, and b values, with a total color difference ΔE less than 0.3, indicating a color development effect close to that of chemical zirconium standard pigments. This demonstrates that the methods in these examples can effectively improve the color development effect of fused zirconium oxide.

[0070] Of all the embodiments, Example 2 (sample 4#) had the smallest total color difference value ΔE, only 0.15, indicating that its color development effect was closest to that of the chemical zirconium standard pigment. This demonstrates that the method of Example 2 is optimal.

[0071] Although Example 2 yielded the best results, the other examples also showed effects very close to the standard pigment and far superior to ordinary fused zirconia. This indicates that the method of the present invention has a significant effect on improving the color development of fused zirconia.

[0072] This invention effectively improves the tinting strength of zirconium iron red pigment produced by ordinary fused zirconia in ceramic ink applications. This is mainly reflected in its high redness value (a), low brightness value (L), and low yellowness value (b). The overall effect is close to that of the standard sample of zirconium iron red pigment produced by chemical zirconium under the same conditions, and is significantly superior to untreated ordinary fused zirconia. This meets the requirements for use in ceramic inks, enriches the colors of ceramic products, and solves the problem of weak tinting strength of zirconium iron red pigment produced by ordinary fused zirconia in ceramic ink applications.

[0073] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for producing zirconium iron red pigment for ceramic inks using fused zirconium oxide, characterized in that, Includes the following steps: S1. Zircon sand is mixed with a modifier, wherein the modifier includes microsilica powder, sodium fluoride and sodium carbonate; S2. The mixture is smelted at a temperature of 2350-2450℃ for 4-5 hours to completely melt it. After quenching with water, it is dried for later use. S3. Grind the molten material until it meets the requirements and set it aside for later use; S4. Modify and desiliconize the ground molten powder by first soaking it in an alkaline solution, then neutralizing it with an acid solution, then washing the precipitate with water and drying it for later use. S5. Mix and grind the obtained powder with other raw materials of zirconium iron red, heat and calcine, and keep warm to obtain zirconium iron red material; The modifier comprises 88-93% microsilica powder, 2-7% sodium fluoride and 5-10% sodium carbonate; The concentration of the alkaline solution used for immersion treatment is 10-20%, and the immersion time is 3-4 hours; the concentration of the acid solution used for neutralization treatment is 5-10%.

2. The method for producing zirconium iron red pigment for ceramic ink using fused zirconium oxide according to claim 1, characterized in that, The proportion of the modifier is 5-10% of the mass of the zircon sand.

3. The method for producing zirconium iron red pigment for ceramic ink using fused zirconium oxide according to claim 1, characterized in that, The grinding process in step S3 has a ball-to-particle ratio of 1:3, and the powder particle size D50 is controlled at 17-18 μm, while D90 is controlled at 38-42 μm.

4. The method for producing zirconium iron red pigment for ceramic ink using fused zirconium oxide according to claim 1, characterized in that, The alkaline solution is a caustic soda solution, and the acid solution is a sulfuric acid solution.

5. The method for producing zirconium iron red pigment for ceramic ink using fused zirconium oxide according to claim 1, characterized in that, Other raw materials for the zirconium iron red include iron oxide red, quartz powder, and mineralizing agents.

6. The method for producing zirconium iron red pigment for ceramic ink using fused zirconium oxide according to claim 5, characterized in that, The heating and calcination in step S5 lasts for 6-8 hours, and when the temperature reaches 1050-1100℃, it is held for 2-3 hours, followed by natural cooling.

7. A method for producing zirconium iron red pigment for ceramic ink using fused zirconium oxide according to any one of claims 1-6, characterized in that, The use of the zirconium iron red material includes the following steps: 1) Grind the prepared zirconium iron red material into a powder of 0.5-1 μm; 2) Add the powder to the ceramic ink glaze at a ratio of 35-45%.

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