A cuprous iodide ceramic glaze and its preparation method

Abstract

This invention relates to the field of traditional ceramic preparation technology, specifically to a cuprous iodide ceramic glaze and its preparation method. The method involves mixing micro / nano cuprous iodide powder and transparent glaze in a specific ratio to form a glaze slurry. The glaze is then applied to the surface of a ceramic blank using an immersion method. After drying, the glazed blank is placed in a programmable high-temperature furnace and fired under both air and reducing atmospheres, resulting in ceramic glaze products with yellow-green and reddish-brown glaze color effects, respectively. This invention utilizes the synergistic reaction, diffusion effect, and coagulation phenomena between micro / nano cuprous iodide and other components in the glaze formulation, as well as oxygen in the air, during high-temperature firing. Under both air and oxidizing atmospheres, a programmable high-temperature furnace is used to prepare ceramic glazes with uniform yellow-green and reddish-brown glaze colors, good gloss, a lustrous texture, and a certain jade-like quality. Under reducing atmospheres, the glaze products exhibit a small number of pinholes and are free of orange-brown defects.

Description

Technical Field

[0001] This invention relates to the field of traditional ceramic preparation technology, specifically to a cuprous iodide ceramic glaze and its preparation method. Background Technology

[0002] Chinese ceramics have a long and rich history, dating back thousands of years. From the Tang Dynasty's Tang tri-color ware, Yue ware celadon, Xing ware white porcelain, and polychrome porcelain, to the ceramics produced by the four major kilns of the Song Dynasty—Ge, Ding, Ru, and Jun—all focused on glaze color, marking the golden age of ancient ceramics. Ceramics have held an irreplaceable position in the history of ceramics. Currently, the focus of traditional ceramics development is on ceramic culture, ancient ceramics research, and the development and research of antique-style ceramics. Ceramic glaze is a key component of ceramics; it mainly covers the ceramic surface and possesses characteristics such as density, gloss, and beauty. With the progress of the times, people have higher requirements for the coloring effect of ceramics. To date, no research has been conducted on introducing nano-CuI as a colorant into ceramic glazes. This patent innovatively adds CuI to Jun porcelain glaze and applies it using an immersion glazing method. Modern analytical methods are used to explore the macroscopic morphology, microstructure, and coloring of the Jun porcelain glaze layer, providing new ideas for the development of Jun porcelain. Summary of the Invention

[0003] To overcome the problems of the prior art, this invention provides a cuprous iodide ceramic glaze and its preparation method. This invention utilizes the synergistic reaction, diffusion effect, and coagulation phenomena between micro-nano cuprous iodide, other components in the glaze formula, and oxygen in the air during the high-temperature glaze firing process. Under air atmosphere and reducing atmosphere conditions, a programmable high-temperature furnace is used to prepare a ceramic glaze with a uniform yellow-green and reddish-brown color, good glaze gloss, lustrous glaze, and a certain jade-like texture. Under reducing atmosphere, the ceramic glaze product has a small number of pinholes and no orange glaze defects. This ceramic glaze can be applied in the field of decorative art porcelain.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A cuprous iodide ceramic glaze and its preparation method, comprising the following steps:

[0006] Step 1: Using magnetic stirring, add an equal volume of 0.2-0.4 mol copper acetate monohydrate solution dropwise to a beaker containing 0.4-0.8 mol potassium iodide solution, stir thoroughly, and react for 2-3 hours. Then, use a circulating water multi-purpose vacuum pump for filtration, wash with anhydrous ethanol and deionized water to remove impurities, and finally dry in a drying oven for 8-10 hours to obtain CuI crystals.

[0007] Step 2: Mix the cuprous iodide crystals obtained in Step 1 and the transparent glaze in a certain proportion to prepare a glaze slurry;

[0008] The ceramic blank is heated to 890°C in air at a heating rate of 3°C / min, held at that temperature for 20-30 minutes, and then cooled to obtain a bisque-fired ceramic blank.

[0009] Step 3: Apply the glaze slurry obtained in Step 2 evenly to the surface of the bisque-fired ceramic body and dry it thoroughly to obtain a glazed ceramic body.

[0010] Step 4: Firing the glazed ceramic blank obtained in Step 3 in an air atmosphere to obtain a ceramic glaze product with a uniform yellow-green glaze surface; Firing the glazed ceramic blank obtained in Step 3 in a reducing atmosphere to obtain a ceramic glaze product with a uniform reddish-brown glaze surface.

[0011] Preferably, the molar ratio of potassium iodide solution to copper acetate monohydrate solution used in step 1 is 2:1.

[0012] Preferably, the cuprous iodide crystals obtained in step 1 have a plate-like petal structure with a plate thickness in the nanometer range and an overall size of about 5 micrometers.

[0013] Preferably, the density of the transparent glaze in step 2 is 1.5–1.8 g / cm³. 3 .

[0014] Preferably, the ceramic green body in step 2 has the following composition: 58% kaolin, 28.5% quartz, and 13.5% feldspar.

[0015] Preferably, the glaze thickness of the glazed ceramic blank in step 3 is 1.0-1.5 mm.

[0016] Preferably, the temperature for thorough drying in step 3 is 90-120℃, and the drying time is 6-12h.

[0017] Preferably, the firing process of the glazed ceramic blank in step 4 is as follows: the temperature is raised to 1180-1280℃ at a heating rate of 3-5℃ / min, and held for 20-90min.

[0018] Preferably, a yellow-green and reddish-brown ceramic glaze is prepared by a cuprous iodide ceramic glaze and its preparation method.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] The cuprous iodide ceramic glaze prepared by this invention has the following characteristics: the glaze surface is smooth and the color is uniform, the glaze layer has good gloss, the glaze is lustrous and has a certain jade-like feel, there are a few pinholes and no orange glaze defects under a reducing atmosphere, in addition, the glaze layer is stable and the firing yield is high.

[0021] In recent years, nanoscale cuprous iodide has attracted widespread attention from scientists due to its outstanding catalytic, electrical, magnetic, and optical properties, which distinguish it from bulk materials. Given the numerous advantages of micro / nano cuprous iodide, this invention innovatively introduces micro / nano cuprous iodide into ceramic glazes. Utilizing the synergistic reaction, diffusion effect, and agglomeration phenomena between micro / nano cuprous iodide, other components in the glaze formulation, and oxygen in the air atmosphere during high-temperature glazing, a programmable high-temperature furnace was used to fire the glazes in a wide temperature range (1180-1280℃) under both air and reducing atmospheres, resulting in ceramic glazes with uniform yellow-green and reddish-brown surfaces, respectively. The ceramic glaze fired in an air atmosphere exhibits a completely different color from existing glazes fired in air using different forms of copper, providing a new innovative point for using copper as a colorant. Compared to existing yellow-green glazes fired in air using coarse duck eggshell powder, this yellow-green ceramic glaze has a more uniform color and a denser internal structure. The ceramic glaze fired in a reducing atmosphere has a similar color to existing glazes fired in a reducing atmosphere using different forms of copper. Compared to traditional ceramic glaze preparation, which requires a dozen or even dozens of steps, this patented preparation process is simple (only requiring ingredient preparation, ball milling, slurry preparation, glazing, and firing). In addition, the glaze formula is simple and the yield is high (over 98%). (Each example below provides further details.) The firing process is carried out in an air atmosphere and a reducing atmosphere, causing no environmental pollution. Attached Figure Description

[0022] Figure 1 To prepare the XRD pattern of cuprous iodide and CuI standard card 6-246;

[0023] Figure 2 The image shows the surface morphology of the prepared CuI as analyzed by scanning electron microscopy.

[0024] Figure 3 This is a rendering of Embodiment 1 of the present invention;

[0025] Figure 4 This is a rendering of Embodiment 2 of the present invention;

[0026] Figure 5 This is a rendering of Embodiment 3 of the present invention;

[0027] Figure 6 This is a rendering of the effect of Comparative Embodiment 1 of the present invention;

[0028] Figure 7 This is a rendering of Comparative Embodiment 2 of the present invention;

[0029] Figure 8 This is a rendering of the effect of Comparative Example 3 of the present invention;

[0030] Figure 9This is the EDS energy spectrum of the yellow-green ceramic glaze sample surface in Example 2 of the present invention;

[0031] Figure 10 This is the EDS energy spectrum of the cross-section of the reddish-brown ceramic glaze sample in Example 2 of the present invention; Detailed Implementation

[0032] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but the embodiments are not intended to limit the present invention.

[0033] Unless otherwise specified, the test methods in the following embodiments were carried out in accordance with conventional methods and conditions in the art, and the materials used were all commercially available unless otherwise specified.

[0034] Example 1

[0035] A cuprous iodide ceramic glaze and its preparation method include the following steps:

[0036] Step 1: Using magnetic stirring, add an equal volume of 0.2-0.4 mol copper acetate monohydrate solution dropwise to a beaker containing 0.4-0.8 mol potassium iodide solution, stir thoroughly, and react for 2-3 hours. Then, use a circulating water multi-purpose vacuum pump for filtration, wash with anhydrous ethanol and deionized water to remove impurities, and finally dry in a drying oven for 8-10 hours to obtain CuI crystals.

[0037] Step 2: Weigh 1.19% of the cuprous iodide crystals obtained in Step 1 according to the mass percentage of the glaze, and mix them evenly with the transparent glaze to obtain the glaze slurry;

[0038] A ceramic blank with raw material composition of 58% kaolin, 28.5% quartz and 13.5% feldspar was placed in a programmable high-temperature furnace. Under air atmosphere, the temperature was raised to 890℃ at a set heating rate of 3℃ / min and held for 20 minutes before being cooled with the furnace to obtain a bisque-fired ceramic blank.

[0039] Step 3: Apply the glaze slurry prepared in Step 2 evenly to the surface of the bisque-fired ceramic body in Step 2, and control the glaze layer thickness to 1.0 mm to obtain a glazed ceramic body. Place the glazed ceramic body into a forced-air drying oven and dry it at 100°C for 9 hours to obtain a dried glazed ceramic body.

[0040] Step 4: Place the dried glazed ceramic blank obtained in Step 3 into a programmable high-temperature furnace and fire it in an air atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the yellow-green ceramic glaze product. Alternatively, fire it in a reducing atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the reddish-brown ceramic glaze product.

[0041] Figure 1 The XRD pattern of cuprous iodide prepared using step 1 of Example 1 and the CuI standard card 6-246 are presented. It can be observed that all diffraction peaks on the standard card perfectly match their corresponding data, indicating that the prepared sample is CuI crystal. Furthermore, the absence of other impurity peaks indicates that the sample has high purity. Figure 2 The surface morphology of the prepared CuI was analyzed using scanning electron microscopy. It can be observed that the prepared CuI has a plate-like petal structure with a plate thickness in the nanometer range and an overall size of about 5 micrometers.

[0042] Figure 3 The image shows the effect of the cuprous iodide ceramic glaze prepared using the method of Example 1. Under air firing, the glaze layer exhibits a yellowish-green color. Figure 3 -(a) Macroscopic color rendering effect of the sample in this embodiment Figure 3 -(b) Enlarged view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=50.26, a*=2.6, b*=25.36; under reducing atmosphere firing, the glaze layer appears reddish-brown, wherein, Figure 3 -(A) Macroscopic color rendering effect of the sample in this embodiment Figure 3 -(B) Magnified view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L* = 34.1, a* = 4.27, b* = 0.6, where L* represents brightness, a* represents (+red, -green), and b* represents (+yellow, -blue). Furthermore, the glaze layer has good gloss, a lustrous texture, and a certain jade-like quality, without defects such as pinholes or orange glaze. The color coordinates further demonstrate that the ceramic glaze prepared using the method of Example 1 exhibits a yellowish-green and reddish-brown hue. The firing yield of the cuprous iodide ceramic glaze prepared in this embodiment is 99.3%.

[0043] Example 2

[0044] A cuprous iodide ceramic glaze and its preparation method include the following steps:

[0045] Step 1: Using magnetic stirring, add an equal volume of 0.2-0.4 mol copper acetate monohydrate solution dropwise to a beaker containing 0.4-0.8 mol potassium iodide solution, stir thoroughly, and react for 2-3 hours. Then, use a circulating water multi-purpose vacuum pump for filtration, wash with anhydrous ethanol and deionized water to remove impurities, and finally dry in a drying oven for 8-10 hours to obtain CuI crystals.

[0046] Step 2: Weigh 1.78% of the cuprous iodide crystals obtained in Step 1 according to the mass percentage of the glaze, and mix them evenly with the transparent glaze to obtain the glaze slurry;

[0047] A ceramic blank with raw material composition of 58% kaolin, 28.5% quartz and 13.5% feldspar was placed in a programmable high-temperature furnace. Under air atmosphere, the temperature was raised to 890℃ at a set heating rate of 3℃ / min and held for 20 minutes before being cooled with the furnace to obtain a bisque-fired ceramic blank.

[0048] Step 3: Apply the glaze slurry prepared in Step 2 evenly to the surface of the bisque-fired ceramic body in Step 2, and control the glaze layer thickness to 1.0 mm to obtain a glazed ceramic body. Place the glazed ceramic body into a forced-air drying oven and dry it at 100°C for 9 hours to obtain a dried glazed ceramic body.

[0049] Step 4: Place the dried glazed ceramic blank obtained in Step 3 into a programmable high-temperature furnace and fire it in an air atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the yellow-green ceramic glaze product. Alternatively, fire it in a reducing atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the reddish-brown ceramic glaze product.

[0050] Figure 4 The image shows the effect of the cuprous iodide ceramic glaze prepared using the method of Example 2. Under air firing, the glaze layer exhibits a yellowish-green color. Figure 4 -(c) Macroscopic color rendering effect of the sample in this embodiment Figure 4 -(d) Enlarged view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=46.2, a*=-0.6, b*=25.46; under reducing atmosphere firing, the glaze layer appears reddish-brown, wherein, Figure 4 -(C) Macroscopic color rendering effect of the sample in this embodiment Figure 4-(D) Magnified view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=34, a*=11.57, b*=1.3, where L* represents brightness, a* represents (+red, -green), and b* represents (+yellow, -blue). Furthermore, the glaze layer has good gloss, a lustrous texture, and a certain jade-like quality, without defects such as pinholes or orange glaze. The color coordinates further demonstrate that the ceramic glaze prepared using the method of Example 1 exhibits a yellowish-green and reddish-brown hue. The firing yield of the cuprous iodide ceramic glaze prepared in this embodiment is 99.5%.

[0051] Example 3

[0052] A cuprous iodide ceramic glaze and its preparation method include the following steps:

[0053] Step 1: Using magnetic stirring, add an equal volume of 0.2-0.4 mol copper acetate monohydrate solution dropwise to a beaker containing 0.4-0.8 mol potassium iodide solution, stir thoroughly, and react for 2-3 hours. Then, use a circulating water multi-purpose vacuum pump for filtration, wash with anhydrous ethanol and deionized water to remove impurities, and finally dry in a drying oven for 8-10 hours to obtain CuI crystals.

[0054] Step 2: Weigh 2.38% of the cuprous iodide crystals obtained in Step 1 according to the mass percentage of the glaze, and mix them evenly with the transparent glaze to obtain the glaze slurry;

[0055] A ceramic blank with raw material composition of 58% kaolin, 28.5% quartz and 13.5% feldspar was placed in a programmable high-temperature furnace. Under air atmosphere, the temperature was raised to 890℃ at a set heating rate of 3℃ / min and held for 20 minutes before being cooled with the furnace to obtain a bisque-fired ceramic blank.

[0056] Step 3: Apply the glaze slurry prepared in Step 2 evenly to the surface of the bisque-fired ceramic body in Step 2, and control the glaze layer thickness to 1.0 mm to obtain a glazed ceramic body. Place the glazed ceramic body into a forced-air drying oven and dry it at 100°C for 9 hours to obtain a dried glazed ceramic body.

[0057] Step 4: Place the dried glazed ceramic blank obtained in Step 3 into a programmable high-temperature furnace and fire it in an air atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the yellow-green ceramic glaze product. Alternatively, fire it in a reducing atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the reddish-brown ceramic glaze product.

[0058] Figure 5The image shows the effect of the cuprous iodide ceramic glaze prepared using the method of Example 3. Under air firing, the glaze layer exhibits a yellowish-green color. Figure 5 -(e) Macroscopic color rendering effect of the sample in this embodiment Figure 5 -(f) Enlarged view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=37.56, a*=-0.4, b*=18.16; under reducing atmosphere firing, the glaze layer appears reddish-brown, wherein, Figure 5 -(E) Macroscopic color rendering effect of the sample in this embodiment Figure 5 -(F) Magnified view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L* = 33.34, a* = 11.3, b* = 1.47, where L* represents brightness, a* represents (+red, -green), and b* represents (+yellow, -blue). Furthermore, the glaze layer has good gloss, a lustrous texture, and a certain jade-like quality, without defects such as pinholes or orange glaze. The color coordinates further demonstrate that the ceramic glaze prepared using the method of Example 1 exhibits a yellowish-green and reddish-brown hue. The firing yield of the cuprous iodide ceramic glaze prepared in this embodiment is 99.6%.

[0059] Comparison Example 1

[0060] Step 1: Weigh 0.5% copper oxide powder (the same copper content as in cuprous iodide added in Example 1) according to the mass percentage of the glaze, and mix it evenly with the transparent glaze to obtain a glaze slurry;

[0061] A ceramic blank with raw material composition of 58% kaolin, 28.5% quartz and 13.5% feldspar was placed in a programmable high-temperature furnace. Under air atmosphere, the temperature was raised to 890℃ at a set heating rate of 3℃ / min and held for 20 minutes before being cooled with the furnace to obtain a bisque-fired ceramic blank.

[0062] Step 2: Apply the glaze slurry prepared in Step 1 evenly to the surface of the bisque-fired ceramic body in Step 1, and control the glaze layer thickness to 1.0 mm to obtain a glazed ceramic body. Place the glazed ceramic body into a forced-air drying oven and dry it at 100°C for 9 hours to obtain a dried glazed ceramic body.

[0063] Step 3: Place the dried glazed ceramic blank obtained in Step 2 into a programmable high-temperature furnace and fire it in an air atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain a blue-green ceramic glaze product. Alternatively, fire the ceramic blank in a reducing atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the red ceramic glaze product.

[0064] Figure 6The image shows the effect of the copper oxide ceramic glaze prepared using the method of Comparative Example 1. Under air firing, the glaze layer exhibits a blue-green color. Figure 6 -(i) Macroscopic color rendering effect of the sample in this embodiment Figure 6 -(j) Enlarged view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=46.93, a*=-2.0, b*=-2.43; under reducing atmosphere firing, the glaze layer appears red, wherein, Figure 6 -(I) Macroscopic color rendering effect of the sample in this embodiment Figure 6 -(J) Enlarged view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=35.07, a*=10.8, b*=2.3, where L* represents brightness, a* represents (+red, -green), and b* represents (+yellow, -blue). Furthermore, the glaze layer has good gloss, a lustrous texture, and a certain jade-like quality, without defects such as pinholes or orange glaze. The color coordinates further demonstrate that the ceramic glaze prepared using the method of Example 1 exhibits blue-green and red hues. The firing yield of the copper oxide ceramic glaze prepared in this embodiment is 97.8%.

[0065] Comparison Example 2

[0066] Step 1: Weigh 0.75% copper oxide powder (the same copper content as in cuprous iodide added in Example 2) according to the mass percentage of the glaze, and mix it evenly with the transparent glaze to obtain a glaze slurry;

[0067] A ceramic blank with raw material composition of 58% kaolin, 28.5% quartz and 13.5% feldspar was placed in a programmable high-temperature furnace. Under air atmosphere, the temperature was raised to 890℃ at a set heating rate of 3℃ / min and held for 20 minutes before being cooled with the furnace to obtain a bisque-fired ceramic blank.

[0068] Step 2: Apply the glaze slurry prepared in Step 1 evenly to the surface of the bisque-fired ceramic body in Step 1, and control the glaze layer thickness to 1.0 mm to obtain a glazed ceramic body. Place the glazed ceramic body into a forced-air drying oven and dry it at 100°C for 9 hours to obtain a dried glazed ceramic body.

[0069] Step 3: Place the dried glazed ceramic blank obtained in Step 2 into a programmable high-temperature furnace and fire it in an air atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain a blue-green ceramic glaze product. Alternatively, fire the ceramic blank in a reducing atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the red ceramic glaze product.

[0070] Figure 7The image shows the effect of the copper oxide ceramic glaze prepared using the method of Comparative Example 2. Under air firing, the glaze layer exhibits a blue-green color. Figure 7 -(g) Macroscopic colorimetric effect of the specimen in this embodiment Figure 7 -(h) Enlarged view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=45.63, a*=-6.6, b*=1.4; under reducing atmosphere firing, the glaze layer appears red, wherein, Figure 7 -(G) Macroscopic color rendering effect of the sample in this embodiment Figure 7 -(H) Magnified view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L* = 36.59, a* = 9.4, b* = -11.54, where L* represents brightness, a* represents (+red, -green), and b* represents (+yellow, -blue). Furthermore, the glaze layer has good gloss, a lustrous texture, and a certain jade-like quality, without defects such as pinholes or orange glaze. The color coordinates further demonstrate that the ceramic glaze prepared using the method of Example 1 exhibits blue-green and red hues. The firing yield of the copper oxide ceramic glaze prepared in this embodiment is 98.3%.

[0071] Comparison Example 3

[0072] Step 1: Weigh 1.0% copper oxide powder (the same copper content as in cuprous iodide added in Example 2) according to the mass percentage of the glaze, and mix it evenly with the transparent glaze to obtain a glaze slurry;

[0073] A ceramic blank with raw material composition of 58% kaolin, 28.5% quartz and 13.5% feldspar was placed in a programmable high-temperature furnace. Under air atmosphere, the temperature was raised to 890℃ at a set heating rate of 3℃ / min and held for 20 minutes before being cooled with the furnace to obtain a bisque-fired ceramic blank.

[0074] Step 2: Apply the glaze slurry prepared in Step 1 evenly to the surface of the bisque-fired ceramic body in Step 1, and control the glaze layer thickness to 1.0 mm to obtain a glazed ceramic body. Place the glazed ceramic body into a forced-air drying oven and dry it at 100°C for 9 hours to obtain a dried glazed ceramic body.

[0075] Step 3: Place the dried glazed ceramic blank obtained in Step 2 into a programmable high-temperature furnace and fire it in an air atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain a blue-green ceramic glaze product. Alternatively, fire the ceramic blank in a reducing atmosphere. The firing process is as follows: heat the ceramic blank from room temperature to 1200°C at a rate of 3°C / min, hold it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain the red ceramic glaze product.

[0076] Figure 8The image shows the effect of the copper oxide ceramic glaze prepared using the method of Comparative Example 3. Under air firing, the glaze layer exhibits a blue-green color. Figure 8 -(k) Macroscopic colorimetric effect of the sample in this embodiment Figure 8 -(l) Enlarged view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=45.63, a*=-6.6, b*=1.4; under reducing atmosphere firing, the glaze layer appears red, wherein, Figure 8 -(K) Macroscopic color rendering effect of the sample in this embodiment Figure 8 -(L) Magnified view of the glaze layer in this embodiment; the color coordinates of the glaze layer are L*=41.42, a*=9.23, b*=-9.74, where L* represents brightness, a* represents (+red, -green), and b* represents (+yellow, -blue). Furthermore, the glaze layer has good gloss, a lustrous texture, and a certain jade-like quality, without defects such as pinholes or orange glaze. The color coordinates further demonstrate that the ceramic glaze prepared using the method of Example 1 exhibits blue-green and red hues. The firing yield of the copper oxide ceramic glaze prepared in this embodiment is 98.7%.

[0077] The comparison between the examples and the comparative examples reveals that, in an air atmosphere, both cuprous iodide ceramic glaze and copper oxide ceramic glaze exhibit a yellowish-green color, showing completely different appearances. Furthermore, the cuprous iodide ceramic glaze exhibits fewer pinholes on its surface. In a reducing atmosphere, the cuprous iodide ceramic glaze appears reddish-brown, deepening in color with increasing amounts of cuprous iodide colorant, while the copper oxide ceramic glaze appears red, showing different color variations. Both exhibit pinholes on their surfaces. Neither group of samples showed obvious orange glaze.

[0078] Among them, the addition of nano-cuprous iodide to the glaze reduces the high-temperature viscosity of the glaze, and the flowability of the glaze is also enhanced. Small bubbles in the glaze are also easier to expel, resulting in very few pinholes on the glaze surface when gas escapes. The orange glaze phenomenon, which produces pits that are difficult to level, also rarely occurs.

[0079] The firing atmosphere also has a significant impact on pinholes in the glaze. In an air atmosphere, the chemical reactions in the glaze and the combustion of organic matter and carbon are facilitated, and the gases are quickly expelled before the glaze melts, thus avoiding the formation of pinholes or bubbles in the glaze. In a reducing atmosphere, the oxidation reaction in the glaze and the combustion of organic matter and carbon are inhibited, causing the expulsion of gases to be delayed until after the glaze melts, resulting in pinholes or bubbles in the glaze.

[0080] in, Figure 9 EDS spectra of the yellow-green ceramic glaze sample fired in air atmosphere in Example 2 were selected. It was observed that iodine and copper elements were uniformly distributed and had similar contents on the glaze surface. This indicates that iodine also contributes to the color of the glaze.

[0081] in, Figure 10 EDS spectra of the cross-section of the reddish-brown ceramic glaze sample fired under a reducing atmosphere in Example 2 were selected. It was observed that iodine and copper elements were uniformly distributed and had similar contents on the glaze surface. This indicates that iodine also contributes to the color development of the glaze.

[0082] Table 1. L*, a*, and b* values ​​of samples fired in air atmosphere.

[0083]

[0084] Table 2. L*, a*, and b* values ​​of samples fired under reducing atmosphere.

[0085]

[0086] It should be noted that when numerical ranges are mentioned in this invention specification, it should be understood that the two endpoints of each numerical range, as well as any value between the two endpoints, can be selected, since the steps and methods used are the same as in Examples 1-3; furthermore, the color space of the glaze color is measured using a colorimetric coordinate analyzer. Since the glaze surface has uniform color, the given color coordinates are the average of three randomly tested areas of the glaze surface; the elemental distribution in the glaze layer is measured using EDS. Since the elemental distribution in the glaze layer is uniform, the given EDS analysis spectrum is from a randomly selected test area of ​​the glaze surface; to avoid redundancy, this invention describes preferred embodiments, but those skilled in the art, once they understand the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of this invention.

[0087] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A method for preparing a cuprous iodide ceramic glaze, characterized in that, Includes the following steps: Step 1: Using magnetic stirring, add an equal volume of 0.2-0.4 mol copper acetate monohydrate solution dropwise to a beaker containing 0.4-0.8 mol potassium iodide solution, stir thoroughly, and react for 2-3 hours. Then, use a circulating water multi-purpose vacuum pump for filtration, wash with anhydrous ethanol and deionized water to remove impurities, and finally dry in a drying oven for 8-10 hours to obtain CuI crystals. Step 2: Mix the cuprous iodide crystals obtained in Step 1 and the transparent glaze in a certain proportion to prepare a glaze slurry; The ceramic blank was heated to 890 ℃ in air at a heating rate of 3 ℃ / min, held at that temperature for 20-30 min and then cooled to obtain the bisque-fired ceramic blank. Step 3: Apply the glaze slurry obtained in Step 2 evenly to the surface of the bisque-fired ceramic body and dry it thoroughly to obtain a glazed ceramic body. Step 4: Firing the glazed ceramic blank obtained in Step 3 in an air atmosphere to obtain a ceramic glaze product with a uniform yellow-green glaze surface; Firing the glazed ceramic blank obtained in Step 3 in a reducing atmosphere to obtain a ceramic glaze product with a uniform reddish-brown glaze surface.

2. The method for preparing a cuprous iodide ceramic glaze according to claim 1, characterized in that, The molar ratio of potassium iodide solution and copper acetate monohydrate solution used in step 1 is 2:

1.

3. The method for preparing a cuprous iodide ceramic glaze according to claim 1, characterized in that, The cuprous iodide crystals obtained in step 1 have a plate-like petal structure with a plate thickness in the nanometer range and an overall size of 5 micrometers.

4. The method for preparing a cuprous iodide ceramic glaze according to claim 1, characterized in that, The density of the transparent glaze mentioned in step 2 is 1.5~1.8 g / cm³. 3 .

5. The method for preparing a cuprous iodide ceramic glaze according to claim 1, characterized in that, The ceramic blank in step 2 has the following formula: 58% kaolin, 28.5% quartz, and 13.5% feldspar.

6. The method for preparing a cuprous iodide ceramic glaze according to claim 1, characterized in that, In step 3, the glaze thickness of the glazed ceramic blank is 1.0-1.5 mm.

7. The method for preparing a cuprous iodide ceramic glaze according to claim 1, characterized in that, In step 3, the temperature for thorough drying is 90-120 ℃, and the drying time is 6-12 h.

8. The method for preparing a cuprous iodide ceramic glaze according to claim 1, characterized in that, The firing process of the glazed ceramic blank in step 4 is as follows: the temperature is raised to 1180-1280 ℃ at a heating rate of 3-5 ℃ / min, and held for 20-90 min.

9. The yellow-green and reddish-brown ceramic glazes prepared by the method for preparing cuprous iodide ceramic glaze according to any one of claims 1-8.

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