Crystallized greening colored glaze and preparation method thereof

Abstract

The invention discloses a crystallized greening colored glaze and a preparation method thereof, and belongs to the technical field of crystallized glazes, the crystallized greening colored glaze comprises a ground glaze and a cover glaze, the ground glaze comprises the following raw materials by mass: 45-55 parts of borax, 8-11 parts of lithium carbonate, 4-6 parts of titanium dioxide, 4-6 parts of silicon spar, 18-23 parts of quartz, 6-10 parts of talcum powder, 3-5 parts of magnesium-aluminum hydrotalcite, 3-6 parts of Guizhou soil, 8-10 parts of zinc oxide and 3-5 parts of malachite green; the cover glaze comprises the following raw materials in parts by mass: 22-28 parts of borax, 4-7 parts of lithium carbonate, 8-12 parts of zinc oxide, 23-28 parts of potassium feldspar, 8-12 parts of calcite, 10-12 parts of quartz and 4-6 parts of Guizhou soil. The magnesium-aluminum hydrotalcite in the ground glaze can obviously broaden the mature temperature interval of the crystal glaze, improve the color reproducibility and improve the crystallization process. And the lanthanum oxide intercalated and compounded magnesium-aluminum hydrotalcite can further improve the glossiness of the crystal glaze.

Description

Technical Field

[0001] The invention belongs to the technical field of crystallized glazes, and in particular relates to a crystallized greening colored glaze and a preparation method thereof. Background Art

[0002] Crystalline glaze is a high-grade ceramic art glaze, an artificial crystal flower glaze developed on the basis of ancient Chinese glaze. Its basic characteristics are: crystals of various shapes are separated in the glaze or on the surface of the glaze. These crystal flowers are formed by the natural growth of crystallization substances in the glaze melt under a supersaturated state through cooling and proper heat preservation, and can also produce colorful and unusually bright effects by adding colorants.

[0003] Among them, peacock green glaze is a crystal glaze with a bright green color like peacock feathers. However, due to its bright green color, poor color reproducibility, and great influence of conditions, it is difficult to ensure that the color effect can be consistent every time it is fired. In addition, in industrial production, the crystal growth of crystal glaze is also difficult to control. Therefore, it is of great significance to fire a crystal glaze with high color gloss, easy-to-control process conditions, and bright green color that is highly ornamental. Summary of the invention

[0004] The object of the present invention is to provide a crystalline greening colored glaze and a preparation method thereof, so as to solve the problems of poor color reproducibility of the crystalline glaze and difficult control of process conditions.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] In a first aspect, the present invention provides a crystalline greening colored glaze, including a base glaze and a surface glaze;

[0007] The base glaze includes the following raw materials in parts by weight: 45-55 parts of borax, 8-11 parts of lithium carbonate, 4-6 parts of titanium dioxide, 4-6 parts of silica spar, 18-23 parts of quartz, 6-10 parts of talc, 3-5 parts of magnesium aluminum hydrotalcite, 3-6 parts of Guizhou soil, 8-10 parts of zinc oxide and 3-5 parts of malachite green;

[0008] The glaze comprises the following raw materials in parts by weight: 22-28 parts of borax, 4-7 parts of lithium carbonate, 8-12 parts of zinc oxide, 23-28 parts of potassium feldspar, 8-12 parts of calcite, 10-12 parts of quartz and 4-6 parts of Guizhou soil.

[0009] Preferably, the particle size of the magnesium aluminum hydrotalcite is 1 to 5 μm.

[0010] By adopting the above technical scheme, the crystalline greening colored glaze of the present invention is composed of a base glaze and a surface glaze. By selecting and combining raw materials and proportions, the obtained crystalline greening colored glaze has good color reproducibility, a large processing width, and is easy to control.

[0011] Magnesium-aluminum hydrotalcite is also added to the base glaze. Magnesium-aluminum hydrotalcite is an ionic layered compound. Its layered structure characteristics can significantly improve the thermal stability of magnesium-aluminum hydrotalcite, which helps to prevent magnesium-aluminum hydrotalcite from deteriorating due to poor thermal stability during high-temperature sintering, thereby affecting other compound components. In addition, the grain size and distribution of magnesium-aluminum hydrotalcite can be controlled within a wide temperature range by changing the synthesis conditions, so it has a good processing window.

[0012] The present invention finds that by adding magnesium aluminum hydrotalcite, the melting process of the glaze can be promoted at a lower temperature, thereby helping to expand the mature temperature range of the glaze, making the process control conditions less harsh, and forming a good crystal structure within a certain temperature range, thereby improving the color reproducibility. In addition, magnesium aluminum hydrotalcite has good dispersibility and fine particle morphology, which can make the base glaze more evenly covered on the body, and can also regulate the thermal expansion coefficient of the glaze to better match it with the body, reduce the risk of cracking, and reduce the occurrence of defects or unevenness.

[0013] At the same time, magnesium-aluminum hydrotalcite can provide additional nucleation sites, which helps to form more crystal nuclei. It can serve as a template to guide the directional growth of crystals. Its unique layered structure can guide the crystals to arrange according to certain rules, which helps to form a larger and more regular crystal structure. The thermal stability of magnesium-aluminum hydrotalcite also makes it insoluble in reaction with other substances in the base glaze raw materials. During the sintering process of the base glaze, it can help to build a more stable microenvironment to prevent the intrusion of impurities. It helps to form a crystalline glaze product with uniform color and smooth glaze surface without impurities and defects.

[0014] Preferably, the magnesium aluminum hydrotalcite is also intercalated with composite lanthanum oxide.

[0015] Preferably, the raw materials of magnesium aluminum hydrotalcite intercalated composite lanthanum oxide include magnesium aluminum hydrotalcite and water-soluble lanthanum salt in a molar ratio of 1: (0.2-0.3).

[0016] Preferably, the water-soluble lanthanum salt includes a combination of one or more of lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate and lanthanum sulfate nonahydrate.

[0017] Preferably, the magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide is prepared according to the following method:

[0018] Add a ligand to water, stir and mix, adjust the pH value of the solution to 6.5-7, add a water-soluble lanthanum salt, maintain the pH value of the solution, stir and dissolve, and then introduce nitrogen to obtain a lanthanum coordination solution; add magnesium aluminum hydrotalcite to water, stir and disperse, add the lanthanum coordination solution in a nitrogen atmosphere, increase the temperature to 50-60°C, stir and react for 15-24 hours, centrifuge, wash and dry, and then calcine at 500-600°C for 5-6 hours to obtain the product.

[0019] Preferably, the complexing agent includes one of diethyltriaminepentaacetic acid, ethylenediaminetetraacetic acid and citric acid; the molar ratio of the complexing agent to the water-soluble lanthanum salt is (1-1.05):1.

[0020] By adopting the above technical solution, in order to increase the gloss of the glaze, a gloss agent is usually added to the crystalline glaze. Among them, lanthanum oxide, as a rare earth oxide, has a higher refractive index, which can increase the gloss of the glaze and improve the transparency of the glaze layer, making it easier for optical fibers to penetrate the glaze layer and reflect inside, thereby enhancing the visual gloss effect.

[0021] However, if lanthanum oxide is directly added to the raw materials of the base glaze or the top glaze, the thermal expansion coefficient of the glaze will change, which may easily lead to a large difference in the thermal expansion coefficient between the glaze and the body during high-temperature sintering, thereby generating internal stress during the cooling process, causing the glaze surface to crack or peel off. Moreover, if lanthanum oxide is directly added to the raw materials of the crystalline glaze, it will affect the crystal growth pattern in the glaze, and it itself will affect the color performance of other colorants including the malachite green used in the present invention, resulting in the crystalline glaze being unable to present the theoretical green and translucent effect.

[0022] To this end, the present invention performs a modification treatment on magnesium aluminum hydrotalcite, utilizes the unique layered structure of magnesium aluminum hydrotalcite, and intercalates lanthanum oxide between the layers. Specifically, a water-soluble lanthanum salt is first configured into a coordination solution, which is easy to be intercalated between the layers of the hydrotalcite, and then the magnesium aluminum hydrotalcite is dispersed in water, and the lanthanum coordination compound is introduced into the layers of the magnesium aluminum hydrotalcite through electrostatic attraction, and finally calcined at high temperature in an aerobic environment to form lanthanum oxide, thereby obtaining a composite material in which lanthanum oxide is intercalated between the magnesium aluminum hydrotalcite.

[0023] The intercalation compound obtained in this way not only helps to expand the mature temperature range of the crystallized glaze, making the process production easier to control and reducing the risk of product defects caused by temperature fluctuations, but also helps to better integrate lanthanum oxide into the base glaze raw material combination, while ensuring good coloring effect and glaze glossiness, avoiding the negative effects of directly adding lanthanum oxide. It helps to obtain a crystallized greening glaze with high gloss, bright color, few surface defects, high reproducibility and easy process control.

[0024] In a second aspect, the present invention provides a method for preparing a crystalline greening glaze, comprising the following process steps:

[0025] S1. Weigh the corresponding mass parts of the base glaze raw materials and the glaze raw materials, mix them evenly and set aside;

[0026] S2. The base glaze raw materials are wet ball-milled for 10 to 12 hours, sieved and then prepared into base glaze slurry, the green body is immersed in the base glaze slurry, and dried for later use;

[0027] S3. The glaze raw materials are wet-milled for 11 to 13 hours, sieved and mixed into glaze slurry, the glaze slurry is sprayed on the dried body obtained in step S2, and finally sintered at high temperature to obtain a crystalline green glaze.

[0028] Preferably, the high temperature sintering step is: preheating at 800-900°C for 30-60min, raising the temperature to 1150-1200°C, sintering for 0.5-1.5h, then cooling to 1000-1050°C, keeping warm for 3-5h, and finally cooling naturally to room temperature.

[0029] Preferably, the concentration of the base glaze slurry and the top glaze slurry is 50-70° Bé.

[0030] Preferably, the material-water ratio of wet ball milling is 1:(0.4-0.6).

[0031] By adopting the above technical scheme, the present invention adopts a staged heating method in the preparation process of the crystalline glaze, first preheating to remove the moisture and other volatile substances in the glaze, reducing the influence of impurities on crystallization, effectively avoiding the appearance of surface defects such as pinholes in the obtained crystalline greening glaze, and improving the ornamental value of the obtained crystalline glaze. Then the temperature is raised to the crystallization temperature, and high-temperature sintering is performed to ensure that the glaze is fully melted and the crystals can grow evenly, at which time most of the glaze layer is mature. Finally, the temperature is slowly lowered in a lower temperature range, which provides sufficient time for the crystal growth without excessive diffusion, and also allows the bottom glaze slurry and the surface glaze slurry to be better spread on the blank, and finally the crystals can grow fully, so that a crystalline greening glaze with uniform color and good crystallinity can be obtained.

[0032] Beneficial effects of the present invention:

[0033] 1. The crystalline greening glaze of the present invention is composed of a base glaze and a top glaze. The base glaze raw material includes magnesium aluminum hydrotalcite, which can help form a good crystal structure, help the base glaze to evenly cover the body, enhance the bonding between the base glaze and the body, and reduce cracking and crystal defects. In addition, magnesium aluminum hydrotalcite can also provide additional nucleation sites, and the layered structure can also better regulate the direction of crystal growth, which helps to form a larger and more regular crystal structure.

[0034] 2. The magnesium-aluminum hydrotalcite of the present invention is also intercalated with lanthanum oxide, and the addition of lanthanum oxide can enhance the glossiness of the glaze surface. After intercalation, the effect of directly adding lanthanum oxide on the color performance of the colorant and the crystal growth can be effectively avoided, and the mature temperature range of the crystalline glaze can be further expanded, the effect of temperature fluctuation on the color can be reduced, and the color reproducibility can be improved. Thus, a crystalline green glaze with high gloss, bright color and few surface defects can be obtained. DETAILED DESCRIPTION

[0035] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] Preparation Example

[0037] Preparation Example 1: A magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide is prepared according to the following method:

[0038] Add 0.025 mol of diethyltriamine pentaacetic acid to 100 mL of water, stir and mix, adjust the pH value of the solution to 6.5, add 0.025 mol of lanthanum nitrate hexahydrate, maintain the pH value of the solution, stir and dissolve, and introduce nitrogen to remove air in the solution to obtain a lanthanum coordination solution;

[0039] Add 0.1 mol of magnesium aluminum hydrotalcite (average particle size of 3 μm) into 250 mL of water, stir and disperse, then add the above lanthanum coordination solution in a nitrogen atmosphere, raise the temperature to 60°C, stir and react for 20 hours, centrifuge, wash and dry, and calcine at 550°C for 5 hours to obtain the product.

[0040] Preparation Example 2, a magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide, is different from Preparation Example 1 only in that the added amounts of lanthanum nitrate hexahydrate and diethyltriaminepentaacetic acid are 0.02 mol.

[0041] Preparation Example 3, a magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide, is different from Preparation Example 1 only in that the added amounts of lanthanum nitrate hexahydrate and diethyltriaminepentaacetic acid are 0.03 mol.

[0042] Preparation Example 4, a magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide, is different from Preparation Example 1 only in that the added amounts of lanthanum nitrate hexahydrate and diethyltriaminepentaacetic acid are 0.01 mol.

[0043] Preparation Example 5, a magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide, is different from Preparation Example 1 only in that the added amounts of lanthanum nitrate hexahydrate and diethyltriaminepentaacetic acid are 0.04 mol.

[0044] Example

[0045] Example 1, a crystalline greening glaze is prepared according to the following process steps:

[0046] S1. Weigh the corresponding mass parts of the base glaze raw materials and the surface glaze raw materials, wherein the base glaze raw materials include 50 parts of borax, 10 parts of lithium carbonate, 5 parts of titanium dioxide, 5 parts of silica spar, 20 parts of quartz, 8 parts of talc, 4 parts of magnesium aluminum hydrotalcite (average particle size of 3 μm), 5 parts of Guizhou soil, 8 parts of zinc oxide and 4 parts of malachite green;

[0047] The glaze ingredients include 25 parts of borax, 5 parts of lithium carbonate, 10 parts of zinc oxide, 25 parts of feldspar, 10 parts of calcite, 10 parts of quartz and 5 parts of Guizhou soil;

[0048] Mix the above raw materials evenly and set aside;

[0049] S2. The base glaze raw material is wet ball milled for 11 hours, wherein the material-water ratio is 1:0.5, and then the base glaze slurry is prepared after passing through a 160-mesh sieve. The concentration of the base glaze slurry is 60°Bé, and the body is immersed in the base glaze slurry and dried for use;

[0050] S3. The glaze raw material is wet-milled for 12 hours, wherein the material-water ratio is 1:0.5, and then prepared into a glaze slurry after passing through a 160-mesh sieve. The concentration of the glaze slurry is 550°Bé, and the glaze slurry is sprayed on the dried body obtained in step S2, and finally sintered at high temperature to obtain a crystalline green glaze.

[0051] The high-temperature sintering steps are as follows: preheat at 850°C for 40 minutes, increase the temperature to 1150°C, sinter for 1 hour, then cool to 1050°C, keep warm for 4 hours, and finally cool naturally to room temperature.

[0052] Example 2, a crystalline greening colored glaze, is different from Example 1 only in that the mass fractions of the base glaze raw materials and the surface glaze raw materials are adjusted, specifically:

[0053] The base glaze raw materials include 48 parts of borax, 8 parts of lithium carbonate, 4 parts of titanium dioxide, 6 parts of silica spar, 21 parts of quartz, 10 parts of talc, 3 parts of magnesium aluminum hydrotalcite (average particle size of 3 μm), 5 parts of Guizhou soil, 10 parts of zinc oxide and 4 parts of malachite green;

[0054] The glaze raw materials include 26 parts of borax, 6 parts of lithium carbonate, 8 parts of zinc oxide, 26 parts of potassium feldspar, 8 parts of calcite, 12 parts of quartz and 4 parts of Guizhou soil.

[0055] Example 3, a crystalline greening colored glaze, is different from Example 1 only in that the mass fractions of the base glaze raw materials and the surface glaze raw materials are adjusted, specifically:

[0056] The base glaze raw materials include 53 parts of borax, 10 parts of lithium carbonate, 6 parts of titanium dioxide, 4 parts of silica spar, 18 parts of quartz, 6 parts of talc, 5 parts of magnesium aluminum hydrotalcite (average particle size of 3 μm), 5 parts of Guizhou soil, 8 parts of zinc oxide and 4 parts of malachite green;

[0057] The glaze raw materials include 22 parts of borax, 4 parts of lithium carbonate, 12 parts of zinc oxide, 24 parts of potassium feldspar, 12 parts of calcite, 10 parts of quartz and 6 parts of Guizhou soil.

[0058] Example 4 is a crystalline greening glaze, which is different from Example 1 only in that the magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide prepared in Preparation Example 1 is used to replace the magnesium-aluminum hydrotalcite.

[0059] Example 5 is a crystalline greening glaze, which is different from Example 1 only in that the magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide prepared in Preparation Example 2 is used to replace the magnesium-aluminum hydrotalcite.

[0060] Example 6, a crystalline greening glaze, is different from Example 1 only in that the magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide prepared in Preparation Example 3 is used to replace the magnesium-aluminum hydrotalcite.

[0061] Example 7, a crystalline greening glaze, is different from Example 1 only in that the magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide prepared in Preparation Example 4 is used to replace the magnesium-aluminum hydrotalcite.

[0062] Example 8, a crystalline greening glaze, is different from Example 1 only in that an equal amount of the magnesium-aluminum hydrotalcite intercalated composite lanthanum oxide prepared in Preparation Example 5 is used to replace the magnesium-aluminum hydrotalcite.

[0063] Comparative Example

[0064] Comparative Example 1 is a crystalline greening glaze, which is different from Example 1 only in that the added amount of magnesium aluminum hydrotalcite is 1 part.

[0065] Comparative Example 2 is a crystalline greening glaze, which is different from Example 1 only in that the added amount of magnesium aluminum hydrotalcite is 7 parts.

[0066] Comparative Example 3 is a crystalline greening glaze, which is different from Example 1 only in that 4 parts of lanthanum oxide are also added to the base glaze raw material.

[0067] Comparative Example 4 is a crystalline greening glaze, which is different from Example 1 only in that magnesium aluminum hydrotalcite is not added to the base glaze raw materials.

[0068] Performance testing

[0069] The effects of the glaze surfaces of the crystallized greening colored glazes obtained in the examples and comparative examples were observed and statistically analyzed. The test results are shown in Table 1:

[0070] Table 1 Glaze effect display

[0071]

[0072] According to Table 1, in combination with Example 1, Example 2 and Example 3, it can be seen that the glaze effects of Example 2 and Example 3 are similar to that of Example 1. The reason is that the difference between Example 2 and Example 3 compared with Example 1 is only that the ratio of raw materials is changed within the required range, which means that under the selection of raw materials and the ratio of raw materials, the adjustment of process parameters has little effect on the performance of the finally obtained crystalline glaze, which means that the crystalline glaze of the present invention has good color reproducibility, the process is easy to control, and the fluctuation is small due to external influences.

[0073] Combining Example 1 and Example 4 to Example 8, it can be seen that Example 4 has better gloss than Example 1, and the obtained crystalline green glaze is more stable. The reason is that the magnesium aluminum hydrotalcite in Example 4 is modified by lanthanum oxide intercalation and composite modification, so that the obtained intercalation composite can further expand the mature temperature range of the crystalline glaze, making process control easier; at the same time, the addition of lanthanum oxide also greatly improves the gloss of the crystalline glaze, and because lanthanum oxide is intercalated with magnesium aluminum hydrotalcite, it can effectively avoid many effects on the color of the crystalline glaze and the performance of the crystalline glaze caused by the direct addition of lanthanum oxide. The crystalline green glaze obtained in Example 5 and Example 6 is not much different from Example 4. The reason is that the difference between Example 5 and Example 6 and Example 4 is that the raw material ratio in the preparation process of magnesium aluminum hydrotalcite intercalation composite lanthanum oxide is adjusted within the required range, indicating that the intercalation composite prepared within the required range has a certain effect of improving the gloss of the crystalline glaze. The glossiness of Examples 7 and 8 is lower than that of Example 4. The reason is that in Example 7, the amount of water-soluble lanthanum salt added is reduced, so the lanthanum oxide content between the magnesium-aluminum hydrotalcite layers is reduced, and further, the gloss improvement effect is reduced; in Example 8, the amount of water-soluble lanthanum salt added is increased, and the excessive lanthanum oxide content will change the properties of the magnesium-aluminum hydrotalcite itself, causing the fluidity of the base glaze slurry to deteriorate, the number of bubbles to increase, and defects in the crystalline glaze surface.

[0074] Combining Example 1, Comparative Example 1 and Comparative Example 2, it can be seen that the glazes of Comparative Example 1 and Comparative Example 2 are uneven, the glossiness is also reduced compared with Example 1, and surface defects appear. The reason is that the amount of magnesium aluminum hydrotalcite added in Comparative Example 1 is reduced, and the mature temperature range of the glaze is reduced accordingly, which is not conducive to forming a good crystal structure, but also affects the reproducibility of the color, and the bonding effect between the base glaze slurry and the body is reduced, increasing the probability of surface defects on the glaze. In Comparative Example 2, the amount of magnesium aluminum hydrotalcite added is increased. On the one hand, the addition of excessive hydrotalcite will lead to an imbalance in the raw material ratio. The oxides released during the decomposition process will affect the original component ratio, which is not conducive to the crystallization process, resulting in a small size and irregular shape of the formed crystals; on the other hand, excessive addition of hydrotalcite will generate a large number of bubbles during the crystallization process, resulting in pinhole defects on the glaze surface, thereby greatly affecting the quality of the obtained crystallized greening glaze and the glossiness of the glaze surface. Finally, excessive hydrotalcite will also affect the fluidity of the base glaze slurry, and the glaze layer will become thinner, making the crystalline green glaze surface uneven.

[0075] Combining Example 1 and Comparative Example 3, it can be seen that the glaze surface of the crystallized green glaze obtained in Comparative Example 3 is uneven, and the glaze surface effect that should have been green and translucent is lost, and there are defects on the glaze surface. The reason is that in Comparative Example 3, lanthanum oxide mixed with magnesium aluminum hydrotalcite is directly added to the base glaze raw material, and lanthanum oxide will affect the coloring effect and color performance of the colorant in the base glaze, namely malachite green, so that the glaze surface obtained by firing cannot present the original green and translucent performance effect. At the same time, the direct addition of lanthanum oxide is likely to affect the thermal expansion coefficient of the base glaze slurry and the growth process of the crystal. The change in the thermal expansion coefficient is likely to cause internal stress between the body and the glaze, and the growth of the crystal deviates from the original growth mode, which not only causes defects on the glaze surface but also causes a significant decrease in reproducibility, making it difficult to obtain a consistent crystallized green glaze.

[0076] Combining Example 1 and Comparative Example 4, it can be seen that the glaze surface of Comparative Example 4 is uneven compared with Example 1, the glossiness is significantly reduced, and it is also difficult to present the green and bright color effect of Example 1. The reason is that no hydrotalcite is added in Comparative Example 4. On the one hand, the mature temperature range of the crystalline glaze is significantly narrowed, the difficulty of process control is increased, the color reproducibility is greatly reduced, the fluidity of the base glaze slurry changes, the bonding effect with the body is reduced, and the glaze surface on the body surface is evenly distributed, resulting in uneven glaze surface of the obtained crystalline glaze; on the other hand, the lack of magnesium-aluminum hydrotalcite will affect the crystallization process of the material. The crystals originally regularly arranged by hydrotalcite will lose guidance, and the crystal growth will be affected, resulting in the obtained crystalline glaze color is not bright and the glaze surface is uneven.

[0077] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0078] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A crystalline greening glaze, characterized in that: Includes base glaze and top glaze; The base glaze comprises the following raw materials in parts by weight: 45-55 parts of borax, 8-11 parts of lithium carbonate, 4-6 parts of titanium dioxide, 4-6 parts of silica spar, 18-23 parts of quartz, 6-10 parts of talc, 3-5 parts of magnesium aluminum hydrotalcite, 3-6 parts of Guizhou clay, 8-10 parts of zinc oxide and 3-5 parts of malachite green; The glaze comprises the following raw materials in parts by weight: 22-28 parts of borax, 4-7 parts of lithium carbonate, 8-12 parts of zinc oxide, 23-28 parts of potassium feldspar, 8-12 parts of calcite, 10-12 parts of quartz and 4-6 parts of Guizhou soil.

2. The crystallized greening colored glaze according to claim 1, characterized in that: The particle size of the magnesium aluminum hydrotalcite is 1 to 5 μm.

3. The crystallized green glaze according to claim 1, characterized in that: The magnesium aluminum hydrotalcite is also intercalated with composite lanthanum oxide.

4. The crystallized greening colored glaze according to claim 3, characterized in that: The raw materials of the magnesium aluminum hydrotalcite intercalated composite lanthanum oxide include magnesium aluminum hydrotalcite and water-soluble lanthanum salt in a molar ratio of 1: (0.2-0.3).

5. The crystallized greening colored glaze according to claim 4, characterized in that: The water-soluble lanthanum salt includes a combination of one or more of lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate and lanthanum sulfate nonahydrate.

6. The crystallized green glaze according to claim 3, characterized in that: The magnesium aluminum hydrotalcite intercalated composite lanthanum oxide is prepared according to the following method: Add a ligand to water, stir and mix, adjust the pH value of the solution to 6.5-7, add a water-soluble lanthanum salt, maintain the pH value of the solution, stir and dissolve, and then introduce nitrogen to obtain a lanthanum coordination solution; add magnesium aluminum hydrotalcite to water, stir and disperse, add the lanthanum coordination solution in a nitrogen atmosphere, increase the temperature to 50-60°C, stir and react for 15-24 hours, centrifuge, wash and dry, and then calcine at 500-600°C for 5-6 hours to obtain the product.

7. The crystalline greening glaze according to claim 1, characterized in that: The complexing agent includes one of diethyltriaminepentaacetic acid, ethylenediaminetetraacetic acid and citric acid; the molar ratio of the complexing agent to the water-soluble lanthanum salt is (1.05-1):

1.

8. A method for preparing a crystalline green glaze according to any one of claims 1 to 7, characterized in that: The process steps include: S1. Weigh the corresponding mass parts of the base glaze raw materials and the glaze raw materials, mix them evenly and set aside; S2. The base glaze raw materials are wet ball-milled for 10 to 12 hours, sieved and then prepared into base glaze slurry, the green body is immersed in the base glaze slurry, and dried for later use; S3. The glaze raw materials are wet-milled for 11 to 13 hours, sieved and mixed into glaze slurry, the glaze slurry is sprayed on the dried body obtained in step S2, and finally sintered at high temperature to obtain a crystalline green glaze.

9. The method for preparing the crystallized green glaze according to claim 8, characterized in that: The high temperature sintering step is: preheating at 800-900°C for 30-60min, raising the temperature to 1150-1200°C, sintering for 0.5-1.5h, then cooling to 1000-1050°C, keeping the temperature for 3-5h, and finally cooling naturally to room temperature.

10. The method for preparing the crystalline green glaze according to claim 8, characterized in that: The concentration of the bottom glaze slurry and the top glaze slurry is 50-70° Bé.

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