Yue kiln celadon glaze as well as preparation method and application thereof

Abstract

The invention relates to a Yue kiln celadon glaze as well as a preparation method and application thereof. The glaze comprises the following raw materials in parts by weight: 45-50 parts of feldspar, 25-30 parts of quartzite, 8-12 parts of calcite, 6-10 parts of chinastone, 3-5 parts of wollastonite, 2-3 parts of silicon carbide, 1-2 parts of silicon nitride, 1-2 parts of borax, 2-3 parts of zinc oxide, 1-2 parts of ferric oxide, 0.5-1 part of manganese oxide and 1-2 parts of a dispersing agent. Compared with the prior art, the preparation method has the advantages that the dispersing agent is obtained through polymerization among monomers, a more efficient dispersing effect is achieved in glaze, the stability of celadon is effectively improved, and the cracking risk is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic glazes, and in particular to a Yue kiln celadon glaze and a preparation method and application thereof. Background Art

[0002] Blue and white porcelain is a type of underglaze colored porcelain, created by coloring the base with cobalt, then applying a transparent glaze and firing it at high temperatures in a single pass. The cobalt underglaze, after firing at high temperatures, produces a blue hue, commonly known as "blue and white." Blue and white porcelain exemplifies the perfect fusion of art and practicality in China's rich traditional culture. While its earliest manifestations date back to the Tang Dynasty, its craftsmanship and forms were relatively primitive. During the Song Dynasty, blue and white porcelain was officially created, and the craftsmanship gradually developed. By the Yuan Dynasty, the production process had matured, driven by growing market demand and a period of prosperity. The Ming Dynasty marked the peak of blue and white porcelain's development, pushing its production to new heights.

[0003] There are several key reasons for the popularity of blue and white porcelain. First, its unique craftsmanship: After inking patterns with blue and white pigment on a porcelain base, it is then covered with a transparent glaze and fired at high temperatures. Because the blue and white pigment resides beneath the glaze, it becomes chemically stable after high-temperature treatment, resistant to atmospheric corrosion and acid and alkali corrosion, maintaining its color over time. Second, its artistic effect is exceptional: the white porcelain base and the blue and white pigment create a clear, elegant hue. The blue and white pigment's rich color gradations resemble the subtle variations in shades of ink. Third, blue and white porcelain has a long history. Through years of production and use, it has accumulated extensive production experience and a broad public base. Fourth, its raw materials are of superior quality. Early imported blue and white pigments, such as Sumaliqing, were primarily composed of cobalt oxide. High-temperature firing imparts a vibrant blue and white color, and firing them simultaneously with the white glaze further enhances the porcelain's vibrant color palette.

[0004] CN014926282A showcases an innovative blue-and-white glaze ceramic formula. The body comprises kaolin, natural clay, talc, feldspar, alumina powder, silicon nitride, barium carbonate, and wollastonite, while the glaze includes zinc oxide, cobalt oxide, quartz, limestone, lithium feldspar, ulexite, silicon carbide, silicon nitride, ferric oxide, tin dioxide, zinc borate, montmorillonite, sodium hydroxymethylcellulose, and sodium humate. By carefully adjusting the formulas of the body and glaze, the ceramic product's physical and chemical properties, including color, hardness, and overall stability, are effectively enhanced.

[0005] CN118598514A focuses on porcelain production technology, proposing a celadon glaze formula and production process with high light transmittance and crack resistance. The formula includes potassium feldspar (40%-45%), quartz (20%-25%), clay (10%-15%), aluminum oxide (5%-8%), calcite (5%-10%), calcite (4%-8%), wollastonite (3%-5%), barium carbonate (2%-4%), calcium phosphate (3%-5%), borax (1%-2%), and iron oxide (1.2%-3%). Through precise formulation optimization and rigorous control of the production process, this invention successfully imparts exceptional transparency to the celadon glaze while significantly reducing the risk of cracking during firing and significantly increasing the acceptable quality rate of the finished product. Firing under reducing atmosphere conditions also ensures the celadon glaze's color uniformity, further enhancing the product's visual appeal.

[0006] However, celadon glazes still suffer from post-firing cracking. This is primarily due to a mismatch in the coefficient of thermal expansion (CTE) between the glaze and the body. When the glaze's CTE is greater than that of the body, cooling can easily lead to tensile stress cracking. Furthermore, during the firing process, rapid heating / cooling rates, insufficient insulation, and large temperature differences within the kiln can lead to internal stress accumulation within the glaze. Furthermore, excessively thick glaze layers, poor dispersion or uneven glazing, low silica content or excessive alkaline oxides in the glaze formula, and improper body pretreatment (such as incomplete drying or the presence of hidden cracks) can also increase the risk of cracking. Furthermore, the traditional celadon thick glaze process and improper control of the reducing atmosphere can also exacerbate the glaze's tendency to crack. Summary of the Invention

[0007] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a Yue kiln celadon glaze and a preparation method and application thereof.

[0008] Dispersants evenly disperse the various particles in the glaze in the solvent, preventing them from agglomerating. This helps improve the stability and uniformity of the glaze slurry, ensuring a more even distribution of the glaze layer on the body. This improved glaze uniformity allows for more uniform heating and cooling of all parts of the glaze during firing, reducing the likelihood of cracking due to localized stress concentrations. Dispersants also reduce the viscosity of the glaze slurry and increase its fluidity, allowing it to better fill tiny pores and defects on the body's surface. This creates a tighter bond between the glaze layer and the body, improving adhesion and ultimately strengthening the glaze's resistance to cracking.

[0009] Commonly used dispersants in glazes include kaolin and sodium carboxymethyl cellulose (CMC). However, kaolin and sodium carboxymethyl cellulose have certain drawbacks as ceramic glaze dispersants. Kaolin has limited dispersing effectiveness, and its impurity content and particle size distribution affect the glaze's color and smoothness. CMC has limited thermal stability and is prone to decomposition at high temperatures. Improper use can increase the risk of cracking in the green body, and it also has water resistance issues. Therefore, the present invention provides a polyacrylic acid dispersant. Polyacrylic acid is obtained through polymerization between monomers. The carboxylic acid groups become negatively charged after dissociation. Upon adsorption on the surface of glaze particles, the repulsion of like charges prevents particle aggregation. The long-chain polymer structure forms an adsorption layer on the particle surface, physically hindering particle collisions. The carboxylic acid groups can also form coordination bonds with metal oxides in the glaze, thereby enhancing adsorption. The ammonium ions in 2-acrylic acid ammonium salt give the dispersant a positive charge. The introduced cations bind to the negatively charged pigment surface through Coulombic forces, further enhancing electrostatic attraction. The lone pairs of electrons in the amino groups can also coordinate with metal ions on the metal oxide surface, achieving efficient and stable dispersion.

[0010] To achieve the above object, the present invention provides a Yue kiln celadon glaze, comprising the following raw materials in parts by weight: 45-50 parts of feldspar, 25-30 parts of quartz, 8-12 parts of calcite, 6-10 parts of porcelain stone, 3-5 parts of wollastonite, 2-3 parts of silicon carbide, 1-2 parts of silicon nitride, 1-2 parts of borax, 2-3 parts of zinc oxide, 1-2 parts of iron oxide, 0.5-1 parts of manganese oxide, and 1-2 parts of a dispersant.

[0011] The preparation method of the dispersant comprises the following steps:

[0012] Add acrylic acid, 2-acrylic acid ammonium salt and modified monomer to 60wt% ethanol aqueous solution, stir evenly at 40-50°C, then add thioglycolic acid and 10wt% ammonium persulfate aqueous solution, heat and stir until the reaction is completed, and adjust the pH to 7-8 to obtain a dispersant.

[0013] Furthermore, the mass ratio of the acrylic acid to 2-acrylic acid ammonium salt, the modified monomer, thioglycolic acid, and ammonium persulfate is 1:1.1-1.3:0.2-0.3:0.1-0.2:0.05-0.15.

[0014] Furthermore, the modified monomer is one of ethyl methacrylate, propyl-2-methyl-2-acrylate or 2-methyl-2-acrylate-2,3-dihydroxypropyl ester.

[0015] Furthermore, the volume of the ethanol aqueous solution is 5 to 10 times the total volume of acrylic acid, 2-acrylic acid ammonium salt and the modified monomer.

[0016] Furthermore, the temperature range of the heating and stirring is 70-80°C.

[0017] Preferably, the preparation method of the dispersant comprises the following steps:

[0018] Acrylic acid, 2-acrylic acid ammonium salt and modified monomer are added to a 60wt% ethanol aqueous solution with a volume of 5 to 10 times the total volume, and after stirring evenly at 40 to 50°C, thioglycolic acid and a 10wt% ammonium persulfate aqueous solution are added. The mass ratio of acrylic acid to 2-acrylic acid ammonium salt, modified monomer, thioglycolic acid and ammonium persulfate is 1:1.1 to 1.3:0.2 to 0.3:0.1 to 0.2:0.05 to 0.15. The temperature is raised to 70 to 80°C and stirred until the reaction is completed. The pH is adjusted to 7 to 8 to obtain a dispersant.

[0019] A method for preparing Yue kiln celadon glaze comprises the following steps:

[0020] The components are mixed according to the proportions, ball-milled, filtered and dried to obtain the Yue kiln celadon glaze.

[0021] Furthermore, the ball milling time is 3 to 5 hours.

[0022] Furthermore, the filter particle size is 30-50 mesh.

[0023] Furthermore, the drying conditions are 100-120° C. and drying for 4-8 hours.

[0024] The present invention also provides an application of Yue kiln celadon glaze, which is applied to the surface of porcelain through a glazing method combining points, lines and surfaces.

[0025] Beneficial effects of the present invention:

[0026] 1. Compared with the prior art, the glaze prepared by the present invention has better stability and is not easy to crack, which not only improves the performance of the product but also reduces the risk of damage.

[0027] 2. The present invention produces a dispersant through polymerization between monomers. The carboxylic acid groups become negatively charged after dissociation. After adsorption on the surface of glaze particles, the repulsion of like charges prevents particle aggregation. The long-chain polymer structure forms an adsorption layer on the particle surface, reducing particle collisions through physical hindrance. The carboxylic acid groups can also form coordination bonds with metal oxides in the glaze, thereby enhancing adsorption. The ammonium ions in the 2-acrylate ammonium salt give the dispersant a positive charge. The introduced cations bind to the negatively charged pigment surface through Coulombic forces, further enhancing electrostatic attraction. The lone pair electrons in the amino group can also coordinate with metal ions on the metal oxide surface, achieving a highly efficient and stable dispersion effect. DETAILED DESCRIPTION

[0028] Polyacrylic acid, model: HR9011, was sourced from Shandong Henry International Trade Co., Ltd.

[0029] Example 1

[0030] A method for preparing Yue kiln celadon glaze comprises the following steps, calculated in parts by weight:

[0031] 48 parts of feldspar, 27 parts of quartz, 10 parts of calcite, 8 parts of porcelain stone, 4 parts of wollastonite, 2 parts of silicon carbide, 1 part of silicon nitride, 2 parts of borax, 2 parts of zinc oxide, 2 parts of iron oxide, 1 part of manganese oxide and 2 parts of dispersant were mixed and ball-milled for 4 hours, filtered through 50 mesh and dried at 110°C for 6 hours to obtain Yue kiln celadon glaze.

[0032] The preparation method of the dispersant comprises the following steps:

[0033] Acrylic acid, 2-acrylic acid ammonium salt and ethyl methacrylate are added to a 60wt% ethanol aqueous solution with a volume 8 times the total volume, and after stirring evenly at 45°C, thioglycolic acid and a 10wt% ammonium persulfate aqueous solution are added. The mass ratio of acrylic acid to 2-acrylic acid ammonium salt, ethyl methacrylate, thioglycolic acid and ammonium persulfate is 1:1.2:0.25:0.12:0.08. The temperature is raised to 80°C and stirred until the reaction is completed. A 3mol / L sodium hydroxide aqueous solution is added to adjust the pH to 8 to obtain a dispersant.

[0034] Example 2

[0035] A method for preparing Yue kiln celadon glaze comprises the following steps, calculated in parts by weight:

[0036] 48 parts of feldspar, 27 parts of quartz, 10 parts of calcite, 8 parts of porcelain stone, 4 parts of wollastonite, 2 parts of silicon carbide, 1 part of silicon nitride, 2 parts of borax, 2 parts of zinc oxide, 2 parts of iron oxide, 1 part of manganese oxide and 2 parts of dispersant were mixed and ball-milled for 4 hours, filtered through 50 mesh and dried at 110°C for 6 hours to obtain Yue kiln celadon glaze.

[0037] The preparation method of the dispersant comprises the following steps:

[0038] Acrylic acid, 2-acrylic acid ammonium salt and propyl-2-methyl-2-acrylate are added to a 60wt% ethanol aqueous solution with a volume 8 times the total volume, and after stirring evenly at 45°C, thioglycolic acid and a 10wt% ammonium persulfate aqueous solution are added. The mass ratio of acrylic acid to 2-acrylic acid ammonium salt, propyl-2-methyl-2-acrylate, thioglycolic acid and ammonium persulfate is 1:1.2:0.25:0.12:0.08. The temperature is raised to 80°C and stirred until the reaction is completed. A 3mol / L sodium hydroxide aqueous solution is added to adjust the pH to 8 to obtain a dispersant.

[0039] Example 3

[0040] A method for preparing Yue kiln celadon glaze comprises the following steps, calculated in parts by weight:

[0041] 48 parts of feldspar, 27 parts of quartz, 10 parts of calcite, 8 parts of porcelain stone, 4 parts of wollastonite, 2 parts of silicon carbide, 1 part of silicon nitride, 2 parts of borax, 2 parts of zinc oxide, 2 parts of iron oxide, 1 part of manganese oxide and 2 parts of dispersant were mixed and ball-milled for 4 hours, filtered through 50 mesh and dried at 110°C for 6 hours to obtain Yue kiln celadon glaze.

[0042] The preparation method of the dispersant comprises the following steps:

[0043] Acrylic acid, 2-acrylic acid ammonium salt and 2-methyl-2-acrylic acid-2,3-dihydroxypropyl ester are added to a 60wt% ethanol aqueous solution with a volume 8 times the total volume, and after stirring evenly at 45°C, thioglycolic acid and a 10wt% ammonium persulfate aqueous solution are added. The mass ratio of acrylic acid to 2-acrylic acid ammonium salt, 2-methyl-2-acrylic acid-2,3-dihydroxypropyl ester, thioglycolic acid and ammonium persulfate is 1:1.2:0.25:0.12:0.08. The temperature is raised to 80°C and stirred until the reaction is completed. A 3mol / L sodium hydroxide aqueous solution is added to adjust the pH to 8 to obtain a dispersant.

[0044] Comparative Example 1

[0045] A method for preparing Yue kiln celadon glaze comprises the following steps, calculated in parts by weight:

[0046] 48 parts of feldspar, 27 parts of quartz, 10 parts of calcite, 8 parts of porcelain stone, 4 parts of wollastonite, 2 parts of silicon carbide, 1 part of silicon nitride, 2 parts of borax, 2 parts of zinc oxide, 2 parts of iron oxide, 1 part of manganese oxide and 2 parts of sodium carboxymethyl cellulose were mixed and ball-milled for 4 hours, filtered through 50 mesh and dried at 110°C for 6 hours to obtain Yue kiln celadon glaze.

[0047] Comparative Example 2

[0048] A method for preparing Yue kiln celadon glaze comprises the following steps, calculated in parts by weight:

[0049] 48 parts of feldspar, 27 parts of quartz, 10 parts of calcite, 8 parts of porcelain stone, 4 parts of wollastonite, 2 parts of silicon carbide, 1 part of silicon nitride, 2 parts of borax, 2 parts of zinc oxide, 2 parts of iron oxide, 1 part of manganese oxide and 2 parts of polyacrylic acid were mixed and ball-milled for 4 hours, filtered through 50 mesh and dried at 110°C for 6 hours to obtain Yue kiln celadon glaze.

[0050] Comparative Example 3

[0051] A method for preparing Yue kiln celadon glaze comprises the following steps, calculated in parts by weight:

[0052] 48 parts of feldspar, 27 parts of quartz, 10 parts of calcite, 8 parts of porcelain stone, 4 parts of wollastonite, 2 parts of silicon carbide, 1 part of silicon nitride, 2 parts of borax, 2 parts of zinc oxide, 2 parts of iron oxide, 1 part of manganese oxide and 2 parts of dispersant were mixed and ball-milled for 4 hours, filtered through 50 mesh and dried at 110°C for 6 hours to obtain Yue kiln celadon glaze.

[0053] The preparation method of the dispersant comprises the following steps:

[0054] Acrylic acid, methacrylic acid and ethyl methacrylate are added to a 60 wt % ethanol aqueous solution with a volume 8 times the total volume, and after stirring evenly at 45° C., thioglycolic acid and a 10 wt % ammonium persulfate aqueous solution are added. The mass ratio of acrylic acid to methacrylic acid, ethyl methacrylate, thioglycolic acid and ammonium persulfate is 1:1.2:0.25:0.12:0.08. The temperature is raised to 80° C. and stirred until the reaction is completed. A 3 mol / L sodium hydroxide aqueous solution is added to adjust the pH to 8 to obtain a dispersant.

[0055] Test Example 1

[0056] The glazes obtained in the examples and the comparative examples were evenly applied on the celadon body, fired in a reducing atmosphere, fired at 1300° C. for 3 h, and then naturally cooled. The thermal expansion coefficient and thermal shock resistance of the obtained glaze surface were tested.

[0057] Thermal expansion coefficient The thermal expansion curve of the sintered sample was analyzed using a thermal dilatometer to obtain the thermal expansion coefficient;

[0058] Thermal shock resistance refers to GB / T 3298-2022 "Determination of thermal shock resistance of daily-use ceramics". The sintered sample is heated to 180°C and then immersed in 20°C water. This is repeated three times to observe whether cracks appear on the glaze surface.

[0059] Table 1

[0060] Experimental plan <![CDATA[Coefficient of thermal expansion / K -1 > Whether there are cracks Example 1 <![CDATA[5.1×10 -6 ]]> none Example 2 <![CDATA[5.3×10 -6 ]]> none Example 3 <![CDATA[4.2×10 -6 ]]> none Comparative Example 1 <![CDATA[7.1×10 -6 ]]> There are obvious cracks Comparative Example 2 <![CDATA[6.0×10 -6 ]]> There are obvious cracks Comparative Example 3 <![CDATA[5.8×10 -6 ]]> Slight cracks

[0061] The coefficient of thermal expansion is defined as the relative rate of change in length (linear expansion coefficient) or volume (volumetric expansion coefficient) per unit temperature of a material when the temperature changes. For isotropic materials such as glazes, the linear expansion coefficient is typically used. During the firing and cooling process of celadon, if the thermal expansion coefficients of the glaze layer and the body of the porcelain are significantly different, thermal stresses can be generated due to the different shrinkage rates, leading to cracking (such as crazing and crazing) or flaking of the glaze surface. Therefore, the thermal expansion coefficient of the glaze surface is a key parameter for evaluating its crack resistance, directly reflecting the thermal stress matching between the glaze layer and the body of the porcelain.

[0062] Thermal shock resistance can directly evaluate whether the glaze surface is prone to cracking, bursting, etc. when it withstands large temperature changes in a short period of time, thereby characterizing its structural and performance stability.

[0063] As can be seen from Table 1, the celadon glaze prepared in the embodiment has better stability, is less prone to cracks, and has a smaller thermal expansion coefficient. This may be because when the various components in the glaze are evenly dispersed, the glaze structure formed after the glaze is fired is more dense and uniform. The particles of different components can fully contact and be evenly distributed, so that the thermal expansion and contraction behavior of each part of the glaze during heating and cooling is more coordinated, thereby reducing the overall thermal expansion coefficient difference. Good dispersibility can enable the components in the glaze to play their role evenly during the firing process. Some components with high melting points or special properties can be evenly distributed in the glaze to form a uniform microstructure, such as fine crystals and evenly distributed glass phases. This uniform structure helps to improve the fracture strength and fracture toughness of the glaze, and can effectively resist the generation of thermal stress and the expansion of cracks when the temperature changes suddenly. At the same time, the uniform structure is also conducive to reducing the elastic modulus of the glaze, improving its ability to buffer stress, thereby enhancing thermal shock resistance.

[0064] In the examples, polyacrylic acid is obtained through polymerization between monomers. The carboxylic acid groups become negatively charged after dissociation. After adsorption on the surface of glaze particles, the repulsion of like charges prevents particle agglomeration. The long-chain polymer structure forms an adsorption layer on the particle surface, reducing particle collisions through physical hindrance. The carboxylic acid groups can also form coordination bonds with metal oxides in the glaze, thereby enhancing adsorption. The ammonium ions in the 2-acrylic acid ammonium salt give the dispersant a positive charge. The introduced cations bind to the negatively charged pigment surface through Coulombic forces, further enhancing electrostatic attraction. The lone pairs of electrons in the amino group can also coordinate with metal ions on the metal oxide surface, achieving a highly efficient and stable dispersion effect.

[0065] The thermal expansion coefficient of Example 3 is lower than that of Examples 1~2. This may be because the modified monomer in Example 3 has multiple hydroxyl groups, which can further form hydrogen bonds with the hydrogen bonds on the surface of the metal oxide, thereby increasing the repulsive force between the glazes and enhancing the dispersion effect, so that the glaze structure obtained in Example 3 is denser and more uniform, and thus the anti-cracking performance is the best.

[0066] The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions that can be derived by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.

Claims

1. A Yue kiln celadon glaze, characterized in that: The invention comprises the following raw materials in parts by weight: 45-50 parts of feldspar, 25-30 parts of quartz, 8-12 parts of calcite, 6-10 parts of porcelain stone, 3-5 parts of wollastonite, 2-3 parts of silicon carbide, 1-2 parts of silicon nitride, 1-2 parts of borax, 2-3 parts of zinc oxide, 1-2 parts of iron oxide, 0.5-1 parts of manganese oxide and 1-2 parts of dispersant; The preparation method of the dispersant comprises the following steps: Add acrylic acid, 2-acrylic acid ammonium salt and modified monomer to 60wt% ethanol aqueous solution, stir evenly at 40-50°C, then add thioglycolic acid and 10wt% ammonium persulfate aqueous solution, heat and stir until the reaction is completed, and adjust the pH to 7-8 to obtain a dispersant.

2. The Yue Kiln celadon glaze according to claim 1, characterized in that: The mass ratio of acrylic acid to 2-acrylic acid ammonium salt, modified monomer, thioglycolic acid and ammonium persulfate is 1:1.1-1.3:0.2-0.3:0.1-0.2:0.05-0.

15.

3. The Yue Kiln celadon glaze according to claim 1, characterized in that: The modified monomer is one of ethyl methacrylate, propyl-2-methyl-2-acrylate or 2-methyl-2-acrylate-2,3-dihydroxypropyl ester.

4. The Yue kiln celadon glaze according to claim 1, characterized in that: The volume of the ethanol aqueous solution is 5 to 10 times the total volume of acrylic acid, 2-acrylic acid ammonium salt and the modified monomer.

5. The Yue Kiln celadon glaze according to claim 1, characterized in that: The temperature range of the heating and stirring is 70-80°C.

6. The method for preparing the Yue kiln celadon glaze according to any one of claims 1 to 5, characterized in that: The steps include: The components are mixed according to the proportions, ball-milled, filtered and dried to obtain the Yue kiln celadon glaze.

7. The method for preparing Yue kiln celadon glaze according to claim 6, characterized in that: The ball milling time is 3 to 5 hours.

8. The method for preparing Yue kiln celadon glaze according to claim 6, characterized in that: The filter particle size is 30-50 mesh.

9. The method for preparing Yue kiln celadon glaze according to claim 6, characterized in that: The drying conditions are 100-120° C. and drying for 4-8 hours.

10. The use of the Yue kiln celadon glaze according to any one of claims 1 to 5, characterized in that: The Yue kiln celadon glaze is applied to the porcelain surface through a glazing method that combines points, lines and surfaces.