High-temperature under-glaze painted porcelain and painting and preparation process thereof

Abstract

The invention relates to the field of ceramic manufacturing, in particular to high-temperature under-glaze colored porcelain and an inkjet and preparation process thereof, a colored drawing layer and a transparent glaze layer are sequentially arranged on a green body from bottom to top, in inkjet slurry, chemical bonding formed by a melting agent and the surface of a biscuit enhances color adhesive force, and the high-temperature under-glaze colored porcelain is not prone to falling off or fading; the adhesive enhances the adhesion and shedding resistance of the pigment, the solvent is used for adjusting the viscosity and spraying performance of the slurry, and the raw materials of the colored drawing layer are suitable for making high-temperature underglaze colored porcelain products from biscuits of various shapes and sizes, and have wide market prospects and application space; and the developing layer and the transition layer are added between the colored drawing layer and the glaze layer to form a special glaze effect.

Description

Technical Field

[0001] The present invention relates to the field of ceramic manufacturing, and specifically to high-temperature underglaze color porcelain and its spraying and preparation processes. Background Art

[0002] High-temperature underglaze color porcelain is a ceramic product formed by applying a painted pattern on the surface of a porcelain and then covering it with a layer of transparent glaze and firing at a high temperature. Since the colors are wrapped by the glaze layer during the high-temperature firing process, it has characteristics such as bright colors and strong abrasion resistance, and is deeply loved by consumers. However, the traditional production process of underglaze color porcelain is complex, with high costs, the underglaze color patterns are prone to fading at high temperatures, and the colors are monotonous with a single form of expression. Therefore, developing a high-temperature underglaze color porcelain formula that can maintain a stable color effect at high temperatures and has rich color variations, as well as its spraying and preparation processes, is of great significance for enhancing the artistic value and market competitiveness of ceramic products. Summary of the Invention

[0003] One object of the present invention is to solve at least the above problems through high-temperature underglaze color porcelain and its spraying and preparation processes.

[0004] To solve the above technical problems, the technical solution adopted by the present invention is as follows: High-temperature underglaze color porcelain, including a blank body, on which a painted layer and a transparent glaze layer are sequentially provided from bottom to top. The raw materials of the spraying slurry of the painted layer, by weight, include the following components: 20 - 30 parts of inorganic pigment, 10 - 15 parts of flux, 5 - 8 parts of binder, and 15 - 18 parts of solvent.

[0005] Preferably, the inorganic pigment is one or more of iron oxide red and cobalt oxide blue, the flux is low-melting glass powder, the binder is selected from high molecular polymers, and the solvent is an organic solvent.

[0006] Preferably, the raw materials of the blank body, by weight, include the following components: 50 - 60 parts of kaolin, 20 - 25 parts of quartz, 15 - 20 parts of potassium feldspar, 4 - 8 parts of grossularite coarse powder, and 3 - 4 parts of astrophyllite fine powder.

[0007] Preferably, the raw materials of the transparent glaze layer, by weight, include the following components: 50 - 60 parts of feldspar, 25 - 30 parts of quartz, 15 - 20 parts of borax, and 50 - 55 parts of water.

[0008] Preferably, a color-developing layer and a transition layer are further provided from bottom to top between the painted layer and the glaze layer.

[0009] Preferably, the raw materials of the color display layer, by weight, include the following components: 35-38 parts of albite, 10-13 parts of quartz, 15-20 parts of grossularite colorant, 10-13 parts of epidote crystal nucleating agent, 5-8 parts of calcined zinc oxide, 6-8 parts of clay, and 45-55 parts of water.

[0010] Preferably, the raw materials of the transition layer, by weight, include the following components: 40-45 parts of albite, 10-13 parts of quartz, 5-8 parts of grossularite colorant, 3-5 parts of epidote crystal nucleating agent, 8-10 parts of calcined zinc oxide, 5-7 parts of clay, and 50-60 parts of water. The raw materials of the grossularite colorant, by weight, include the following components: 50 parts of grossularite powder, 15-20 parts of ilmenite. The raw material of the epidote crystal nucleating agent is epidote powder.

[0011] The spraying and preparation process of high-temperature underglaze color porcelain includes the following steps:

[0012] Step a: Form a green body and dry and biscuit fire it.

[0013] Step b: Spray underglaze color on the surface of the green body.

[0014] Step c: Glaze the surface of the green body.

[0015] Step d: Fire in a kiln for glaze firing.

[0016] Preferably, in step b, the spraying process includes the following steps: (1) Design the pattern: Design the pattern according to requirements and draw the required color image by computer; (2) Make the spraying template: Convert the designed pattern into a spraying template for subsequent spraying operations; (3) Prepare the spraying slurry: Mix the components in the above formula evenly to make the spraying slurry for underglaze color; (4) Spray: Spray the special spraying slurry according to the pattern requirements so that the required color and texture are formed on the surface of the porcelain; (5) Drying treatment: Dry the sprayed porcelain to remove excess moisture.

[0017] Preferably, in step c, spray the color display layer, transition layer and transparent glaze layer in sequence. First, use a spray gun with an air pressure of 0.3 MPa, spray the color display layer evenly at a distance of 20 cm from the green body, control the thickness at 0.8-1.0 mm, and dry for 1 h; then adjust the air pressure of the spray gun to 0.2 MPa, spray the transition layer obliquely at an angle of 45°, with a thickness of 0.5-0.7 mm, and dry for 2 h. Finally, apply the transparent glaze by dipping or pouring, with a glaze layer thickness of 0.3-0.5 mm, and dry for 2 h;

[0018] In step d, the firing curve is as follows:

[0019] Raise the temperature from room temperature to 600 °C at a speed of 3 °C / min and maintain an oxidizing atmosphere;

[0020] Heat from 600°C to 1000°C at a rate of 5°C / min with an oxygen content of ≥5%.

[0021] Heat from 1000°C to 1280°C at a rate of 4°C / min, introduce CO with a concentration of 3%-5%, and maintain a reducing atmosphere.

[0022] Hold at 1280°C for 40 min.

[0023] Cool in the furnace at a rate of 10°C / min to 800°C, then quickly cool to room temperature when opening the kiln.

[0024] As can be seen from the above description, the high-temperature underglaze color porcelain provided by the present invention and its spraying and preparation process have the following beneficial effects: In the spraying slurry, the chemical bonding formed between the melting agent and the surface of the green body enhances the adhesion of the color, making it not easy to fall off or fade. The binder enhances the adhesion and anti-shedding property of the pigment. The solvent is used to adjust the viscosity and spraying performance of the slurry. The raw materials of the painted layer are suitable for making high-temperature underglaze color porcelain products on green bodies of various shapes and sizes, having broad market prospects and application space; A color display layer and a transition layer are added between the painted layer and the glaze layer. The color display layer and the transition layer include different concentrations of topazolite and astrophyllite. After being superimposed with the transparent glaze layer, a special glaze effect with gradual change of glaze color, star crystallization, and hazy underglaze color pattern is formed. Specific Embodiments

[0025] The following further describes the present invention through specific embodiments.

[0026] To make the technical means, creative features, achieved purposes and effects of the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments.

[0027] The high-temperature underglaze color porcelain of the present invention includes a green body, and a painted layer and a transparent glaze layer are successively provided on the green body from bottom to top. The raw materials of the spraying slurry of the painted layer are in parts by weight and include the following components: 20-30 parts of inorganic pigment, 10-15 parts of melting agent, 5-8 parts of binder, and 15-18 parts of solvent. In the spraying slurry, the chemical bonding formed between the melting agent and the surface of the green body enhances the adhesion of the color, making it not easy to fall off or fade. The binder enhances the adhesion and anti-shedding property of the pigment. The solvent is used to adjust the viscosity and spraying performance of the slurry. The raw materials of the painted layer are suitable for making high-temperature underglaze color porcelain products on green bodies of various shapes and sizes, having broad market prospects and application space.

[0028] The inorganic pigment is one or more of iron oxide red and cobalt blue oxide, the flux is low-melting glass powder, the binder is selected from high molecular polymers, and the solvent is an organic solvent. The flux can be bismuth-based glass powder to reduce the melting point, improve the color development effect and fusibility of the pigment. The binder can be carboxymethyl cellulose or polyvinyl alcohol to enhance the adhesion and anti-shedding properties of the pigment. The organic solvent is selected from ethanol or isopropanol to adjust the viscosity and spraying performance of the slurry.

[0029] The raw materials of the green body, by weight, include the following components: 50-60 parts of kaolin, 20-25 parts of quartz, 15-20 parts of potassium feldspar, 4-8 parts of grossularite coarse powder, and 3-4 parts of astrophyllite fine powder. The grossularite is crushed to a particle size of 80-120 μm, retaining the integrity of the mineral structure; the astrophyllite is ball-milled to a particle size of ≤10 μm. Among the components, kaolin provides plasticity and firing whiteness of the green body, quartz enhances the strength and chemical stability of the green body, potassium feldspar reduces the firing temperature and promotes the combination of the body and glaze. Adding grossularite coarse powder to the green body introduces a Ca-Al-Si framework to improve the thermal stability. Adding astrophyllite fine powder to the green body provides a layered structure to improve the forming uniformity of the green body.

[0030] The raw materials of the transparent glaze layer, by weight, include the following components: 50-60 parts of feldspar, 25-30 parts of quartz, 15-20 parts of borax, and 50-55 parts of water. Among the components, feldspar forms a high-transparency glass phase matrix, quartz enhances the hardness and chemical stability of the glaze surface, borax reduces the melting temperature and increases the light transmittance. Adding water adjusts the specific gravity to 1.3-1.4 g / cm 3 。

[0031] A color-developing layer and a transition layer are further provided between the painted layer and the glaze layer from bottom to top. Further, a color-developing layer and a transition layer are added between the painted layer and the glaze layer. The color-developing layer and the transition layer include different concentrations of grossularite and astrophyllite. After being superimposed with the transparent glaze layer, a special glaze surface effect with gradual change of glaze color, starburst crystallization and hazy underglaze color pattern is formed.

[0032] The raw materials of the color-developing layer, by weight, include the following components: 35-38 parts of albite, 10-13 parts of quartz, 15-20 parts of grossularite colorant, 10-13 parts of astrophyllite crystal nucleating agent, 5-8 parts of calcined zinc oxide, 6-8 parts of clay, and 45-55 parts of water. Among the components, albite is a low-melting flux to promote the melting of mineral components. The raw material of the grossularite colorant is grossularite powder containing Fe 3+ / Ti 4+ ions, providing a basic orange-yellow tone. The raw material of the astrophyllite crystal nucleating agent is astrophyllite powder, which is used to induce the precipitation of needle-shaped crystals on the glaze surface. Calcined zinc oxide is used to adjust the hardness and gloss of the glaze surface. Clay improves the suspension of the glaze and prevents the glaze from stratifying. Water is used to adjust the specific gravity of the glaze to 1.6-1.7 g / cm 3 。

[0033] The raw materials of the transition layer, by weight, include the following components: 40-45 parts of albite, 10-13 parts of quartz, 5-8 parts of grossular coloring agent, 3-5 parts of epidote crystal nucleating agent, 8-10 parts of calcined zinc oxide, 5-7 parts of clay, 50-60 parts of water. The raw materials of the grossular coloring agent, by weight, include the following components: 50 parts of grossular powder, 15-20 parts of ilmenite. The raw material of the epidote crystal nucleating agent is epidote powder. Among the components, albite is a low-melting flux, promoting the melting of mineral components. The grossular coloring agent contains Fe 3+ / Ti 4+ ions, providing a basic orange-yellow tone. The raw material of the epidote crystal nucleating agent is epidote powder, which is used to induce the precipitation of needle-like crystals on the glaze surface. Calcined zinc oxide is used to adjust the hardness and gloss of the glaze surface. Clay improves the suspension of the glaze and prevents the glaze from stratifying. Water is used to adjust the specific gravity of the glaze to 1.6-1.7 g / cm 3 . In the present invention, the high-concentration grossular is used in the lower color-developing layer, making the color development present a rich golden orange color. The low-concentration grossular is used in the upper transition layer, making the transition layer present a light yellow transition color. The glazes of the two layers diffuse with each other during firing, forming a natural halo effect of "flowing glow" and having a three-dimensional effect with gradient colors. The high-concentration epidote crystal nucleating agent is used in the lower color-developing layer, making the color-developing layer at the bottom densely crystallize, forming a group of needle-like crystals with a diameter of 2-5 μm. While the low-concentration epidote crystal nucleating agent is used in the upper transition layer, and the crystals are sparsely distributed, producing a three-dimensional visual effect of "near real and far virtual". The thickness of the top transparent glaze is 0.3-0.5 mm. After covering, the light transmittance of the glaze surface is increased to more than 75%. The painted pattern at the bottom layer is faintly visible through the golden orange color of the color-developing layer and the light yellow color of the transition layer, and is superimposed on the crystallization texture of the color-developing layer and the transition layer, forming a hierarchical effect of "scene within a scene". When observed from the side light, the star-shaped crystals under the transparent glaze reflect light, producing a twinkling "star sand" texture. Since the crystallization layer of the bottom glaze has micro-convex particles and the upper glaze is relatively smooth, the overall touch is delicate but retains a slight sandiness after being covered with the transparent glaze, which is different from the complete smoothness of the traditional flat glaze. The calcium-aluminum silicate structure of grossular wraps the coloring ions and is resistant to light aging after being fired at 1280°C, so the color stability is good. The composite structure composed of the color-developing layer, the transition layer and the transparent glaze layer has a relatively high Mohs hardness and mechanical wear resistance.

[0034] Specific Embodiment 1:

[0035] The raw materials of the spray-painting slurry of the painted layer, by weight, include the following components: 20 parts of inorganic pigment, 10 parts of melting agent, 5 parts of binder and 15 parts of solvent;

[0036] The raw materials of the green body, by weight, include the following components: 50 parts of kaolin, 20 parts of quartz, 15 parts of potassium feldspar, 4 parts of grossular coarse powder, 3 parts of epidote fine powder;

[0037] The raw materials of the transparent glaze layer, by weight, include the following components: 50 parts of feldspar, 25 parts of quartz, 15 parts of borax, and 50 parts of water;

[0038] The raw materials of the color display layer, by weight, include the following components: 35 parts of albite, 10 parts of quartz, 15 parts of topaz coloring agent, 10 parts of epidote crystal nucleating agent, 5 parts of calcined zinc oxide, 6 parts of clay, and 45 parts of water;

[0039] The raw materials of the transition layer, by weight, include the following components: 40 parts of albite, 10 parts of quartz, 5 parts of topaz coloring agent, 3 parts of epidote crystal nucleating agent, 8 parts of calcined zinc oxide, 5 parts of clay, and 50 parts of water. The raw materials of the topaz coloring agent, by weight, include the following components: 50 parts of topaz powder and 15 parts of ilmenite. The raw material of the epidote crystal nucleating agent is epidote powder.

[0040] Specific implementation two:

[0041] The raw materials of the spray painting slurry of the painted layer, by weight, include the following components: 30 parts of inorganic pigment, 15 parts of fusant, 8 parts of binder, and 18 parts of solvent;

[0042] The raw materials of the green body, by weight, include the following components: 60 parts of kaolin, 25 parts of quartz, 20 parts of potassium feldspar, 8 parts of topaz coarse powder, and 4 parts of epidote fine powder;

[0043] The raw materials of the transparent glaze layer, by weight, include the following components: 60 parts of feldspar, 30 parts of quartz, 20 parts of borax, and 55 parts of water;

[0044] The raw materials of the color display layer, by weight, include the following components: 38 parts of albite, 13 parts of quartz, 20 parts of topaz coloring agent, 13 parts of epidote crystal nucleating agent, 8 parts of calcined zinc oxide, 8 parts of clay, and 55 parts of water;

[0045] The raw materials of the transition layer, by weight, include the following components: 45 parts of albite, 13 parts of quartz, 8 parts of topaz coloring agent, 5 parts of epidote crystal nucleating agent, 10 parts of calcined zinc oxide, 7 parts of clay, and 60 parts of water. The raw materials of the topaz coloring agent, by weight, include the following components: 50 parts of topaz powder and 20 parts of ilmenite. The raw material of the epidote crystal nucleating agent is epidote powder.

[0046] Specific implementation three:

[0047] The raw materials of the spray painting slurry of the painted layer, by weight, include the following components: 24 parts of inorganic pigment, 12 parts of fusant, 7 parts of binder, and 16 parts of solvent;

[0048] The raw materials of the green body, by weight, include the following components: 55 parts of kaolin, 22 parts of quartz, 17 parts of potassium feldspar, 6 parts of topaz coarse powder, and 3.5 parts of epidote fine powder;

[0049] The raw materials of the transparent glaze layer, by weight, include the following components: 55 parts of feldspar, 27 parts of quartz, 17 parts of borax, and 52 parts of water;

[0050] The raw materials of the color display layer, by weight, include the following components: 36 parts of albite, 12 parts of quartz, 17 parts of topazolite colorant, 12 parts of epidote crystal nucleating agent, 6 parts of calcined zinc oxide, 7 parts of clay, and 50 parts of water;

[0051] The raw materials of the transition layer, by weight, include the following components: 42 parts of albite, 11 parts of quartz, 6 parts of topazolite colorant, 4 parts of epidote crystal nucleating agent, 7 parts of calcined zinc oxide, 6 parts of clay, and 55 parts of water. The raw materials of the topazolite colorant, by weight, include the following components: 50 parts of topazolite powder and 17 parts of ilmenite. The raw material of the epidote crystal nucleating agent is epidote powder.

[0052] The spraying and preparation process of the above high-temperature underglaze color porcelain includes the following steps:

[0053] Step a, forming the green body and drying and biscuit-firing it; after mixing the raw materials of the green body, ball-milling for 8 h, through vacuum pugging with a vacuum degree of -0.095 MPa, forming by slip casting or die pressing, drying to a moisture content of ≤2%, and biscuit-firing to 850 °C at a heating rate of 5 °C / min and holding for 1 h.

[0054] Step b, spraying underglaze color on the surface of the green body;

[0055] Step c, glazing the surface of the green body;

[0056] Step d, firing in the kiln for glazing.

[0057] In step b, the spraying process includes the following steps: 1. Designing the pattern: Designing the pattern according to requirements and drawing the required color image by computer; 2. Making the spraying template: Converting the designed pattern into a spraying template for subsequent spraying operations; 3. Preparing the spraying slurry: Mixing the components in the above formula evenly to make the spraying slurry for underglaze color; 4. Spraying: Spraying the special spraying slurry according to the pattern requirements to form the required colors and textures on the surface of the porcelain; 5. Drying treatment: Drying the sprayed porcelain to remove the excess moisture.

[0058] In step c, the color display layer, the transition layer, and the transparent glaze layer are sprayed in sequence. First, use a spray gun with an air pressure of 0.3 MPa, spray the color display layer evenly at a distance of 20 cm from the green body, with a thickness controlled at 0.8 - 1.0 mm, and dry for 1 h; then adjust the air pressure of the spray gun to 0.2 MPa, spray the transition layer obliquely at an angle of 45°, with a thickness of 0.5 - 0.7 mm, and dry for 2 h. Finally, apply the transparent glaze by dipping or pouring, with a glaze layer thickness of 0.3 - 0.5 mm, and dry for 2 h;

[0059] In step d, the firing curve is as follows:

[0060] Raise the temperature from room temperature to 600°C at a rate of 3°C / min, and maintain an oxidizing atmosphere.

[0061] Raise the temperature from 600°C to 1000°C at a rate of 5°C / min, with an oxygen content ≥ 5%.

[0062] Raise the temperature from 1000°C to 1280°C at a rate of 4°C / min, introduce CO with a concentration of 3%-5%, and maintain a reducing atmosphere.

[0063] Keep the temperature at 1280°C for 40 min; promote the diffusion of the double-layer glaze and the crystallization of astrophyllite.

[0064] Cool the furnace at a rate of 10°C / min. After cooling to 800°C, open the kiln and rapidly cool to room temperature.

[0065] The above are only several specific embodiments of the present invention, but the design concept of the present invention is not limited thereto. Any non-substantive modification of the present invention using this concept shall fall within the scope of infringement of the protection scope of the present invention.

Claims

1. High-temperature underglaze colored porcelain, characterized in that: It includes a green body, on which a painted layer and a transparent glaze layer are successively provided from bottom to top. The raw materials of the spray-painting slurry of the painted layer, by weight, include the following components: 20-30 parts of inorganic pigment, 10-15 parts of fusant, 5-8 parts of binder, and 15-18 parts of solvent.

2. The underglaze colored porcelain at high temperature according to claim 1, characterized in that: The inorganic pigment is one or more of iron oxide red and cobalt oxide blue. The fusant is low-melting glass powder. The binder is selected from polymer. The solvent is organic solvent.

3. The underglaze colored porcelain at high temperature according to claim 1, characterized in that: The raw materials of the green body, by weight, include the following components: 50-60 parts of kaolin, 20-25 parts of quartz, 15-20 parts of potassium feldspar, 4-8 parts of grossularite coarse powder, and 3-4 parts of astrophyllite fine powder.

4. The underglaze colored porcelain at high temperature according to claim 1, characterized in that: The raw materials of the transparent glaze layer, by weight, include the following components: 50-60 parts of feldspar, 25-30 parts of quartz, 15-20 parts of borax, and 50-55 parts of water.

5. The underglaze colored porcelain at high temperature according to claim 1, wherein: A color-developing layer and a transition layer are further provided between the painted layer and the glaze layer from bottom to top.

6. The underglaze colored porcelain at high temperature according to claim 5, wherein: The raw materials of the color-developing layer, by weight, include the following components: 35-38 parts of albite, 10-13 parts of quartz, 15-20 parts of grossularite colorant, 10-13 parts of astrophyllite crystal nucleating agent, 5-8 parts of calcined zinc oxide, 6-8 parts of clay, and 45-55 parts of water.

7. The underglaze colored porcelain at high temperature according to claim 5, characterized in that: The raw materials of the transition layer, by weight, include the following components: 40-45 parts of albite, 10-13 parts of quartz, 5-8 parts of grossularite colorant, 3-5 parts of astrophyllite crystal nucleating agent, 8-10 parts of calcined zinc oxide, 5-7 parts of clay, and 50-60 parts of water. The raw materials of the grossularite colorant, by weight, include the following components: 50 parts of grossularite powder, and 15-20 parts of ilmenite. The raw material of the astrophyllite crystal nucleating agent is astrophyllite powder.

8. The spraying and preparation process of the high-temperature underglaze color porcelain according to any one of claims 1-7, characterized in that, It includes the following steps: Step a: Mold the green body and dry and biscuit it. Step b: Spray underglaze color on the surface of the green body. Step c: Glaze the surface of the green body. Step d: Fire it in a kiln for glazing.

9. The spraying and preparation process of high-temperature underglaze colored porcelain according to claim 8, characterized in that: In step b, the spray-painting process includes the following steps: (1) Design the pattern: Design the pattern according to requirements and draw the required color image by computer. (2) Make the spray-painting template: Convert the designed pattern into a spray-painting template for subsequent spray-painting operations. (3) Prepare the spray-painting slurry: Mix the components in the above formula evenly to make the spray-painting slurry for underglaze color. (4) Spray-paint: Spray the special spray-painting slurry according to the pattern requirements so that the required colors and textures are formed on the surface of the porcelain. (5) Drying treatment: Dry the spray-painted porcelain to remove excess moisture.

10. The spraying and preparation process of the high-temperature underglaze colored porcelain according to claim 8, characterized in that: In step c, spray the color-developing layer, the transition layer and the transparent glaze layer in sequence. First, use a spray gun with an air pressure of 0.3 MPa to evenly spray the color-developing layer at a distance of 20 cm from the green body, with the thickness controlled at 0.8-1.0 mm and dried for 1 h. Then adjust the air pressure of the spray gun to 0.2 MPa and spray the transition layer obliquely at an angle of 45°, with the thickness of 0.5-0.7 mm and dried for 2 h. Finally, apply the transparent glaze by dipping method or pouring method, with the thickness of the glaze layer of 0.3-0.5 mm and dried for 2 h. In step d, the firing curve is as follows: Heat from room temperature to 600°C at a rate of 3°C / min while maintaining an oxidizing atmosphere; Heat from 600°C to 1000°C at a rate of 5°C / min with an oxygen content ≥ 5%; Heat from 1000°C to 1280°C at a rate of 4°C / min while introducing CO with a concentration of 3% - 5% to maintain a reducing atmosphere; Hold at 1280°C for 40 min; Cool in the furnace at a rate of 10°C / min. After cooling to 800°C, quickly cool to room temperature by opening the kiln.