A copper-colored metallic luster glaze, its preparation method, and a ceramic product

Abstract

The present invention discloses a copper-colored metallic luster glaze, a preparation method thereof, and a ceramic product. The composition of the copper-colored metallic luster glaze includes a solid content and water; wherein, the solid content by weight percentage includes: nepheline syenite 40-60%, lead-free and non-toxic boron frit 15-30%, light calcium carbonate 5-15%, kaolin 3-8%, zinc oxide 0.5-3%, manganese oxide 5-15%, tin oxide 1-8%, vanadium pentoxide 1-8%, copper oxide 1-5%, nickel oxide 0.5-3%, red lead 5-20%. The metallic luster glaze of the present invention adopts a formula composition, with simple raw materials, no need for additional separate firing, simple process, stable quality, low processing cost, greatly improving the productivity and being easy for mass production.

Description

Technical Field

[0001] The present invention relates to the technical field of metallic luster glazes, and particularly to a copper-colored metallic luster glaze, a preparation method thereof, and a ceramic product. Background Art

[0002] Metallic luster glazes are one of the components of ceramic art glazes. They have matte, semi-matte, and glossy glaze surfaces, and the colors are yellow, silver-white, copper-color, etc., similar to the tones presented by metallic materials in nature. They are decorative glazes that are not very common in ceramic art glazes, and the fired products of their glazes are also one of the favorite collection works of people. Among them, the glaze with the appearance properties similar to metallic copper is called a copper-colored metallic luster glaze.

[0003] Chinese Patent CN107698153A discloses a copper-like luster ceramic glaze, which is composed of the following components: potassium sodium feldspar, white glass, boric acid powder, ocher, potassium nitrate, glaze fruit, green glass, tin crystal material, copper oxide; the preparation steps are as follows: A. Add the above raw materials into a crusher and crush them to 300 mesh - 320 mesh to obtain mixed particles; B. Stir the mixed particles evenly, melt them at 1350°C - 1500°C, and keep them warm for 2h - 4h; C. Quench them into frit in water at a temperature of 15°C - 18°C, and then perform ultrasonic vibration for 5min - 8min to obtain the copper-like luster ceramic glaze. This method has complex raw materials, and adopts secondary processing for firing (glaze preparation + glaze layer formation), with complex processes, easy to cause unstable quality, and high processing costs. Summary of the Invention

[0004] The purpose of the present invention is to overcome the above technical deficiencies, and propose a copper-colored metallic luster glaze, a preparation method thereof, and a ceramic product, so as to solve the technical problems in the prior art that the raw materials of the copper-colored metallic luster glaze are complex, and the formation of the copper-colored metallic luster glaze requires an additional separate firing process, with complex processes, easy to cause unstable quality, and high processing costs.

[0005] In the first aspect, the present invention provides a copper-colored metallic luster glaze, including a solid content and water; wherein, the solid content is calculated by weight percentage and includes: nepheline syenite 40 - 60%, lead-free and non-toxic boron frit 15 - 30%, light calcium carbonate 5 - 15%, kaolin 3 - 8%, zinc oxide 0.5 - 3%, manganese oxide 5 - 15%, tin oxide 1 - 8%, vanadium pentoxide 1 - 8%, copper oxide 1 - 5%, nickel oxide 0.5 - 3%, red lead 5 - 20%.

[0006] In the second aspect, the present invention provides a preparation method of a copper-colored metallic luster glaze, including the following steps:

[0007] Weigh the materials according to the above formula, and crush and process them in a ball mill until the fineness of the glaze slurry leaving the mill is 0.3 - 0.5% of the residue on a ten thousand-hole sieve;

[0008] The above glaze slurry is continuously stirred and homogenized, and then passed through a 80-100 mesh sieve to obtain a copper-colored metallic luster glaze.

[0009] In a third aspect, the present invention provides a ceramic product, which is obtained by applying the copper-colored metallic luster glaze provided in the first aspect of the present invention to a bisque body, followed by drying and firing in an oxidizing atmosphere.

[0010] Compared with the prior art, the beneficial effects of the present invention include:

[0011] The present invention uses silicate mineral materials as the main raw materials, adds some color-forming oxides and auxiliary color-forming materials, and manufactures a copper-colored metallic luster glaze through a special processing technology; after applying it to a bisque body, it is fired under specific temperature conditions in an oxidizing atmosphere firing condition to obtain a ceramic product with metallic luster and metallic color display; the metallic luster glaze of the present invention adopts a formula composition, with simple raw materials, no need for additional separate firing, simple process, stable quality, low processing cost, greatly improving the productivity, and being easy for mass production. Detailed Embodiments

[0012] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention.

[0013] In a first aspect, the present invention provides a copper-colored metallic luster glaze, the raw materials of which include solid content and water; wherein, the solid content is calculated by weight percentage and includes: nepheline syenite 40-60%, lead-free and non-toxic boron frit 15-30%, light calcium carbonate 5-15%, kaolin 3-8%, zinc oxide 0.5-3%, manganese oxide 5-15%, tin oxide 1-8%, vanadium pentoxide 1-8%, copper oxide 1-5%, nickel oxide 0.5-3%, red lead 5-20%.

[0014] The mechanism of the present invention is as follows: The base materials of the copper-colored metallic luster glaze of the present invention are nepheline syenite, light calcium carbonate, kaolin, lead-free and non-toxic boron frit, and red lead, which form a medium-temperature base glaze; it is fired with the body once, and the firing temperature is 1220-1250 °C, saving energy consumption and having low cost. The auxiliary color-forming materials are tin oxide, zinc oxide, and red lead; the color-forming oxides are manganese oxide, vanadium pentoxide, copper oxide, and nickel oxide. The color-forming oxides penetrate each other at high temperature and undergo chemical reactions to produce molten color changes. These color changes must occur under the condition that there are auxiliary color-forming materials. The substances after the reaction are evenly dissolved in the vitreous body of the base glaze, and a copper-metal luster glaze surface is formed on the surface of the ceramic product after cooling.

[0015] In this embodiment, the solid content is by weight percentage and includes: nepheline syenite 40 - 55%, lead-free and non-toxic boron frit 15 - 30%, light calcium carbonate 5 - 10%, kaolin 3 - 5%, zinc oxide 0.5 - 2%, manganese oxide 5 - 7%, tin oxide 1 - 3%, vanadium pentoxide 1 - 2%, copper oxide 1 - 2%, nickel oxide 0.5 - 1%, red lead 5 - 10%.

[0016] In this embodiment, the water content of the copper-colored metallic luster glaze is 30% - 40%.

[0017] In a second aspect, the present invention provides a method for preparing a copper-colored metallic luster glaze, comprising the following steps:

[0018] S101. Weigh materials according to the above formula and crush and process them in a ball mill until the fineness of the glaze slurry leaving the mill is 0.3 - 0.5% of the residue on a ten-thousand-hole sieve; wherein, the mass ratio of the medium material in the mill: balls: water is 1:(1.5 - 2):(0.5 - 0.7), further 1:(1.5 - 2):0.6; the ball milling time is 48 - 72 hours; the specific gravity of the glaze slurry is 1.55 - 1.65 g / cm 3 .

[0019] S102. Continuously stir and homogenize the glaze slurry, and then pass it through an 80 - 100 mesh sieve to obtain a copper-colored metallic luster glaze; wherein, the homogenization time is 1 - 2 months, and the specific gravity of the copper-colored metallic luster glaze is 1.55 - 1.65 g / m 3 , and the viscosity flow rate is 40 - 45 seconds.

[0020] In a third aspect, the present invention provides a ceramic product, which is obtained by applying the copper-colored metallic luster glaze provided in the first aspect of the present invention to a bisque body, followed by drying and firing in an oxidizing atmosphere.

[0021] In this embodiment, the glaze is applied to the bisque body by dipping, pouring, or spraying.

[0022] In this embodiment, the thickness of the glaze layer is 1 - 2 mm. Within this range, the phenomenon of glaze running can be avoided, and the glaze surface has good wear resistance and corrosion resistance.

[0023] In this embodiment, the glazed body is dried to a water content of less than 1%. If the water content is too high, the glaze surface will have no metallic luster. The present invention does not limit the drying temperature, and those skilled in the art can select according to the actual situation. For example, it can be dried at 80 - 100 °C or dried naturally.

[0024] In this embodiment, during the firing process, the maximum firing temperature is 1220 - 1250 °C, the high-fire holding time is 30 - 60 minutes, the firing cycle is 10 - 12 hours, and the volume content of oxygen in the oxidizing atmosphere is controlled at 3 - 5%. Under this firing regime, it is beneficial for the color-forming oxides to react completely with the assistance of the auxiliary color-forming oxides, and finally a copper-colored metallic luster glaze with stable quality is formed. It can be seen that in addition to the glaze formulation, the firing regime (including the oxygen content in the oxidizing atmosphere, firing temperature, and time) is the key technology for controlling the high-quality stability of the copper-colored metallic luster glaze.

[0025] In this embodiment, the firing process is carried out in an electric kiln. The present invention can be carried out under the oxidizing atmosphere firing conditions of a general electric kiln, and the formed copper-colored metallic luster glaze has stable quality, which is beneficial for popularization.

[0026] In this embodiment, the method for preparing the biscuit-fired body includes the following steps:

[0027] S201. Weigh raw materials according to the formula of 25 - 30 parts of kaolin, 20 - 25 parts of feldspar, 20 - 30 parts of quartz, and 10 - 15 parts of clay, add water and crush and process in a ball mill until the fineness of the slip leaving the mill is 3 - 5% of the residue on a 10,000-hole sieve; among them, the mass ratio of the material in the mill: balls: water is 1:(1.5 - 2):(0.6 - 0.8), further 1:(1.5 - 2):0.7; the ball milling time is 20 - 24 hours; the specific gravity of the slip is 1.5 - 1.6 g / cm 3 .

[0028] S202. Dehydrate the slip until the water content is 25 - 30%, and then homogenize and age the mud cake for 1 - 2 months. During this process, through homogenization and aging, the water in the mud cake can be made uniform and the sodium humate can be alcoholized, enhancing the plasticity of the blank material.

[0029] S203. Knead the homogenized and aged mud cake in a vacuum pug mill to discharge the air in the mud cake, make the water content uniform, and the structure dense, further improving the plasticity; among them, the vacuum degree of the vacuum pug mill is 90 - 98%, and the number of kneading times is 2 - 3 times; the water content of the blank mud after kneading is 20 - 22%.

[0030] S204. According to the different shapes of the greenware, different forming processes are used for forming. After drying, dehydration and sizing, and fine trimming, it is dried again until the water content is less than 1%. Among them, the forming processes include rolling mechanical pressing, manual throwing, grouting and other processes, and the present invention does not limit this; since the green body contains a certain amount of moisture and still has a certain plasticity and is prone to soft collapse, it is necessary to dry and dehydrate and size it. The present invention does not limit the temperature of drying, dehydration and sizing, and those skilled in the art can choose according to the actual situation. For example, it can be dried at a temperature of 60-80°C or dried naturally; after drying, dehydration and sizing, the surface of the green body is rough and uneven and the size is inaccurate. It is necessary to finely trim the surface of the green body with a knife and sandpaper, and use a brush to dip water to make the surface of the green body smooth and the size accurate; the present invention does not limit the temperature of the second drying, and those skilled in the art can choose according to the actual situation. For example, it can be dried at a temperature of 80-100°C or dried naturally.

[0031] S205. The dried green body is fired to obtain a bisque body. In order to improve the mechanical strength of the green body, it is necessary to fire the dried green body to evaporate the mechanical crystallization water, carbonize the organic matter, decompose some carbonate and sulfate substances, and transform the quartz crystal form. The bisque body has a certain mechanical strength, reducing the breakage rate in subsequent processes and improving the finished product quality. Among them, the firing temperature is 750-800°C and the firing time is 6-8 hours.

[0032] In the following embodiments of the present invention, unless otherwise specified, the preparation method of the bisque body includes the following steps:

[0033] (1) Take 30 parts of kaolin, 25 parts of feldspar, 30 parts of quartz, and 15 parts of clay. Weigh the materials accurately according to the above formula, and crush and process them in a ball mill according to the mass ratio of material in the mill: balls: water = 1:2:0.7. The ball milling time is 20 hours, the fineness of the slurry leaving the mill is 4% of the residue on a 10,000-hole sieve, and the specific gravity of the slurry is 1.54 g / cm 3 ;

[0034] (2) Continuously stir the slurry in the storage slurry tank to prevent the slurry from settling, and then pump it to a filter press with a slurry pump to press and dehydrate it into a mud cake with a water content of 25%. Then, drag the mud cake to the mud storage for homogenization and aging for 1 month;

[0035] (3) Repeatedly knead the homogenized and aged mud cake in a vacuum kneading machine (vacuum degree 95%) 3 times, and the water content of the kneaded mud is 20%.

[0036] (4) Use the rolling mechanical pressing process for forming, and dry and dehydrate and size it naturally. Then, finely trim the surface of the green body with a knife and sandpaper, and use a brush to dip water to make the surface of the green body smooth and the size accurate. Then, dry the finely trimmed green body naturally until the water content is less than 1%;

[0037] (5) Bake the dried green body in a kiln at 800 °C for 6 hours to obtain a bisque-fired body.

[0038] Example 1

[0039] (1) Weigh 40 parts of nepheline syenite, 20 parts of lead-free and non-toxic boron frit, 10 parts of light calcium carbonate, 3 parts of kaolin, 2 parts of zinc oxide, 7 parts of manganese oxide, 3 parts of tin oxide, 2 parts of vanadium pentoxide, 2 parts of copper oxide, 1 part of nickel oxide, and 10 parts of red lead. Crush and process them in a ball mill according to the mass ratio of medium material in the mill: balls: water = 1:1.5:0.6. The ball milling time is 48 hours. The fineness of the glaze slurry discharged from the mill is 0.4% residue on a ten-thousand-hole sieve, and the specific gravity is 1.58 g / cm 3 ;

[0040] (2) Continuously stir and homogenize the glaze slurry in the tank for one month. Then, pump the homogenized glaze slurry in the tank into the glazing working bucket, and pass it through a 100-mesh sieve. The specific gravity of the glaze slurry is 1.57 g / m 3 , and the viscosity flow rate is 40 seconds;

[0041] (3) Apply the glaze slurry onto the bisque-fired body with a glaze layer thickness of 2 mm, and naturally dry the glazed body until the water content is less than 1%;

[0042] (4) Fire the glazed body in an electric kiln under an oxidizing atmosphere. Control the volume content of oxygen in the oxidizing atmosphere at 5%. The maximum firing temperature is 1230 °C, the high-fire holding time is 45 minutes, the firing cycle is 12 hours, and finally cool it naturally to room temperature to obtain a ceramic product with a copper-colored metallic luster glaze on the surface.

[0043] Example 2

[0044] (1) Weigh 48 parts of nepheline syenite, 30 parts of lead-free and non-toxic boron frit, 5 parts of light calcium carbonate, 3 parts of kaolin, 0.5 parts of zinc oxide, 5 parts of manganese oxide, 1 part of tin oxide, 1 part of vanadium pentoxide, 1 part of copper oxide, 0.5 parts of nickel oxide, and 5 parts of red lead. Crush and process them in a ball mill according to the mass ratio of medium material in the mill: balls: water = 1:2:0.6. The ball milling time is 48 hours. The fineness of the glaze slurry discharged from the mill is 0.3% residue on a ten-thousand-hole sieve, and the specific gravity is 1.61 g / cm 3 ;

[0045] (2) Continuously stir and homogenize the glaze slurry in the tank for one month. Then, pump the homogenized glaze slurry in the tank into the glazing working bucket, and pass it through a 100-mesh sieve. The specific gravity of the glaze slurry is 1.62 g / m 3 , and the viscosity flow rate is 42 seconds;

[0046] (3) Apply the glaze slurry onto the bisque-fired body with a glaze layer thickness of 1.5 mm, and naturally dry the glazed body until the water content is less than 1%;

[0047] (4) The glazed blank is fired in an electric kiln under an oxidizing atmosphere. The volume content of oxygen in the oxidizing atmosphere is controlled at 3%, the maximum firing temperature is 1250 °C, the high-fire holding time is 60 minutes, the firing cycle is 10 hours, and finally it is naturally cooled to room temperature to obtain a ceramic product with a copper-colored metallic luster glaze on its surface.

[0048] Example 3

[0049] (1) Weigh 53 parts of nepheline syenite, 15 parts of lead-free non-toxic boron frit, 5 parts of light calcium carbonate, 5 parts of kaolin, 1 part of zinc oxide, 5 parts of manganese oxide, 2 parts of tin oxide, 2 parts of vanadium pentoxide, 1 part of copper oxide, 1 part of nickel oxide, and 10 parts of red lead. Crush and process them in a ball mill according to the mass ratio of medium grinding material: ball: water = 1:2:0.6. The ball milling time is 48 hours. The fineness of the milled glaze slurry is 0.4% of the residue on a ten-thousand-hole sieve, and the specific gravity is 1.55 g / cm 3 ;

[0050] (2) Continuously stir and homogenize the glaze slurry in the tank for one month. Then, pump the homogenized glaze slurry in the tank into the glazing working bucket, and pass it through a 100-mesh sieve. The specific gravity of the glaze slurry is 1.54 g / m 3 , and the viscosity flow rate is 40 seconds;

[0051] (3) Apply the glaze slurry to the bisque-fired body, with the glaze layer thickness being 2 mm, and naturally dry the glazed blank until the water content is below 1%;

[0052] (4) The glazed blank is fired in an electric kiln under an oxidizing atmosphere. The volume content of oxygen in the oxidizing atmosphere is controlled at 4%, the maximum firing temperature is 1220 °C, the high-fire holding time is 30 minutes, the firing cycle is 12 hours, and finally it is naturally cooled to room temperature to obtain a ceramic product with a copper-colored metallic luster glaze on its surface.

[0053] Compared with the prior art, the beneficial effects of the present invention also include:

[0054] (1) The ceramic decorated with the copper-colored metallic luster glaze of the present invention has a matte or semi-matte luster, shows a copper metallic luster color, and is simple and elegant, with an antique charm.

[0055] (2) The process of the present invention is simple, the operation is safe, the quality is stable, the artistic effect of the product glaze is good, and it is easy to produce in batches.

[0056] The specific embodiments of the present invention described above do not constitute a limitation to the protection scope of the present invention. Any other corresponding changes and deformations made according to the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for preparing a ceramic product, characterized in that, It includes the following steps: Weigh the raw materials of the copper-colored metallic luster glaze, crush and process them in a ball mill until the fineness of the glaze slurry leaving the mill is 0.3% - 0.5% of the residue on a ten-thousand-hole sieve. Continuously stir and homogenize the glaze slurry, and then pass it through an 80 - 100 mesh sieve to obtain the copper-colored metallic luster glaze. Apply the copper-colored metallic luster glaze to the biscuit body, and then dry it to a water content of less than 1% and fire it in an oxidizing atmosphere to obtain the ceramic product. Among them, The raw materials of the copper-colored metallic luster glaze include solid content and water. The solid content, by weight percentage, includes: nepheline syenite 40% - 60%, lead-free non-toxic boron frit 15% - 30%, light calcium carbonate 5% - 15%, kaolin 3% - 8%, zinc oxide 0.5% - 3%, manganese oxide 5% - 15%, tin oxide 1% - 8%, vanadium pentoxide 1% - 8%, copper oxide 1% - 5%, nickel oxide 0.5% - 3%, red lead 5% - 20%. During the firing process, the maximum firing temperature is 1220 - 1250 °C, the high-fire holding time is 30 - 60 minutes, the firing cycle is 10 - 12 hours, and the volume content of oxygen in the oxidizing atmosphere is controlled at 3% - 5%.

2. The preparation method of the ceramic product according to claim 1, characterized in that, The solid content, by weight percentage, includes: nepheline syenite 40% - 55%, lead-free non-toxic boron frit 15% - 30%, light calcium carbonate 5% - 10%, kaolin 3% - 5%, zinc oxide 0.5% - 2%, manganese oxide 5% - 7%, tin oxide 1% - 3%, vanadium pentoxide 1% - 2%, copper oxide 1% - 2%, nickel oxide 0.5% - 1%, red lead 5% - 10%.

3. The preparation method of the ceramic product according to claim 1, characterized in that, The water content of the copper-colored metallic luster glaze is 30% - 40%.

4. The preparation method of the ceramic product according to claim 1, characterized in that, During the preparation process of the copper-colored metallic luster glaze, the mass ratio of the material, balls, and water in the ball mill is 1:(1.5 - 2):(0.5 - 0.7), the ball milling time is 48 - 72 hours, and the homogenization time is 1 - 2 months.

5. The method for preparing the ceramic article according to claim 1, wherein, The thickness of the glaze layer is 1 - 2 mm.

6. The preparation method of the ceramic product according to claim 1, characterized in that, The preparation method of the biscuit body includes the following steps: Weigh the raw materials according to the formula of 25 - 30 parts of kaolin, 20 - 25 parts of feldspar, 20 - 30 parts of quartz, and 10 - 15 parts of clay, add water and crush and process them in a ball mill until the fineness of the blank slurry leaving the mill is 3% - 5% of the residue on a ten-thousand-hole sieve. Dehydrate the blank slurry to a water content of 25% - 30%, and then homogenize and age the mud cake for 1 - 2 months. Knead the homogenized and aged mud cake in a vacuum pug mill until the water content of the blank mud is 20% - 22%. According to the different shapes of the blank products, use different forming processes to form, after drying, dehydrating, shaping, and precision trimming, dry it again to a water content of less than 1%. Fire the dried blank body to obtain the biscuit body. Among them, the firing temperature is 750 - 800 °C, and the firing time is 6 - 8 hours.

7. A ceramic product, characterized in that, It is obtained by the preparation method of the ceramic product according to any one of claims 1 - 6.