Jun kiln celadon glaze and method for preparing celadon by using glaze

Abstract

The invention relates to Jun kiln celadon glaze and a method for preparing celadon by adopting the glaze, molybdenum tailings are used as a coloring agent of the Jun kiln celadon glaze and are combined with basic glaze to prepare a mixed glaze raw material, and the Jun kiln celadon is prepared by glazing and firing. According to the Jun kiln celadon glaze and the method for preparing celadon, the firing cost of Jun kiln celadon is greatly reduced, the glaze surface can present stable cyan by firing in a reducing atmosphere, and the environmental pollution is reduced. In addition, waste molybdenum tailings in Koelreuteria and Sichuan near Liuzhou of Jun kiln origin are adopted as raw materials, and the method has the double advantages of being low in raw material cost and low in transportation cost. The glaze can be widely applied to domestic porcelain, building porcelain, art porcelain and the like, and has a relatively good industrial large-scale production application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic material preparation, and in particular to a Jun kiln celadon glaze and a method for preparing celadon by using the glaze. Background Art

[0002] Jun kiln celadon porcelain is a kind of porcelain made by applying iron as a coloring agent to the body of the green glaze, which is fired in a reducing flame at high temperature. Throughout the ages, the color of celadon porcelain is often affected by the characteristics of regional raw materials, formula composition and process conditions, and it is difficult to grasp. On the one hand, the glaze, which is the core raw material for the production of Jun porcelain, is a non-renewable mineral resource. Local high-quality glazes are already facing depletion. While purchasing raw materials to fill the shortage of demand, it also affects the quality and characteristics of Jun porcelain. There is an urgent need to find low-cost raw materials to improve the competitiveness of Jun kiln products. On the other hand, many years of large-scale molybdenum mining development have also resulted in a huge amount of tailings and solid waste accumulated in mining in Henan Province, which urgently needs to be developed and utilized. Molybdenum tailings often contain Fe2O3, which has the conditions to become a coloring agent for Jun kiln celadon glaze.

[0003] In order to prepare Jun kiln celadon glaze at low cost, the current common practice is to directly add industrial Fe2O3 into the glaze. Although it is relatively simple, some colorants contain toxic substances such as lead and cadmium, and harmful substances will be dissolved after firing at 800℃-1300℃. Long-term use will cause harm to human health. Summary of the invention

[0004] The purpose of the present invention is to solve the above problems and to provide a Jun kiln celadon glaze and a method for firing Jun kiln celadon glaze using the glaze.

[0005] The technical solution of the present invention is: A Jun kiln celadon glaze, comprising a basic glaze and a colorant, wherein the basic glaze, calculated by weight, comprises 30~39 parts of orthoclase, 6~14 parts of calcite, 10~14 parts of quartz, 9 parts of white feldspar, 6~16 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, 1 part of tin oxide, The colorant is molybdenum tailings, which is calculated by weight and accounts for 15-20% of the total mass of the basic glaze. The basic glaze and the colorant are evenly mixed to obtain a mixed glaze.

[0006] Jun Kiln is located in Yuzhou, Henan Province. Nearby Luanchuan, Henan Province is a molybdenum mine. The molybdenum tailings from Luanchuan are used nearby. On the one hand, the amount of molybdenum tailings from Luanchuan is large, which can achieve a stable supply. On the other hand, the two places are close to each other, which is convenient for transportation and can save the cost of obtaining materials.

[0007] Preferably, the base glaze contains, calculated by weight, 39 parts of orthoclase, 14 parts of calcite, 14 parts of quartz, 9 parts of white feldspar, 16 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide.

[0008] Preferably, the base glaze contains, calculated by weight, 33 parts of orthoclase, 12 parts of calcite, 10 parts of quartz, 9 parts of white feldspar, 12 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide.

[0009] Preferably, the base glaze contains, calculated by weight, 30 parts of orthoclase, 6 parts of calcite, 12 parts of quartz, 9 parts of white feldspar, 6 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide.

[0010] A method for preparing celadon using the above-mentioned Jun kiln celadon glaze comprises the following steps: a. Preparation of mixed glaze Weigh various raw materials of the basic glaze by weight, and obtain the total weight of the basic glaze after summing up. Calculate the required weight of the molybdenum tailings according to the percentage of the molybdenum tailings relative to the total weight of the basic glaze, and weigh them. All the above raw materials (including the raw materials of the basic glaze and the raw materials of the colorant, the molybdenum tailings) are fully mixed to obtain a mixed glaze; b. Preparation of glaze slurry The mixed glaze is wet ball-milled to obtain glaze slurry. c. Glazing Apply the glaze slurry evenly on the ceramic body. d. Firing After the glazed body is dried, it is fired in a kiln to produce celadon.

[0011] Preferably, in step b, the glaze slurry is wet-milled to a fineness of 250 mesh, and the sieve residue after ball milling is less than 0.5%; then the specific gravity of the glaze slurry is adjusted to 1.60-1.70 g / cm 3 The method for adjusting the specific gravity of the glaze slurry is the commonly used method of diluting with water, or the method of removing the upper clear water after clarification. This is the conventional process for making Jun porcelain, so I will not describe it in detail.

[0012] Preferably, in step d, the sintering is carried out in a kiln under a reducing atmosphere to a sintering temperature of 1280°C, and the temperature control process in the kiln includes: d1. The heating rate in the temperature range from room temperature to 300°C is 5°C / min; d2. The heating rate in the temperature range of 300℃~900℃ is 3℃ / min; d3. The heating rate in the temperature range from 900℃ to firing temperature is 1.5℃ / min; d4. After reaching the firing temperature, do not keep warm and let it cool naturally to room temperature in the furnace. Then turn off the fire and let it cool naturally.

[0013] Preferably, the rotation speed of the ball milling in step b is 300-350 r / min, and the mass ratio of material: ball: water is 1:2:0.75.

[0014] Preferably, the glazing thickness in step c is 1.5 mm to 2 mm.

[0015] Preferably, the kiln in step d is a shuttle natural gas kiln.

[0016] The Jun kiln celadon glaze of the present invention and the method for preparing celadon using the glaze use molybdenum tailings as the colorant of the Jun kiln celadon glaze, combine with the base glaze, and form a mixed glaze, and after glazing and firing, Jun kiln celadon is made. The Jun kiln celadon glaze and the method for preparing celadon not only greatly reduce the cost of firing Jun kiln celadon, directly reduce the environmental pollution caused by molybdenum tailings slag, but also indirectly reduce the environmental mining pollution caused by using other mineral colorants. In addition, the present invention uses the abandoned molybdenum tailings in Luanchuan near Yuzhou, the origin of Jun kiln, as raw materials, and has the dual advantages of low raw material cost and low transportation cost. The glaze can be widely used in daily-use porcelain, architectural porcelain and artistic porcelain, etc., and has a good industrial-scale production application prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a picture of the Jun porcelain fired when the amount of molybdenum tailings added in Example 4 is 15% of the total mass of the base glaze. Figure 2 for Figure 1 The microstructure of the glaze surface after being etched by hydrofluoric acid solution under a scanning electron microscope; Figure 3 This is a picture of the Jun porcelain fired when the amount of molybdenum tailings added in Example 4 is 0% of the total mass of the base glaze. Figure 4 This is a picture of the fired Jun porcelain when the amount of molybdenum tailings added in Example 4 is 5% of the total mass of the base glaze. Figure 5 This is a picture of the fired Jun porcelain when the amount of molybdenum tailings added in Example 4 is 10% of the total mass of the base glaze. Figure 6 This is a picture of the Jun porcelain fired when the amount of molybdenum tailings added in Example 4 is 20% of the total mass of the base glaze. DETAILED DESCRIPTION

[0018] Embodiment 1: A Jun kiln celadon glaze contains a base glaze and a colorant. The base glaze contains, by weight, 39 parts of orthoclase, 14 parts of calcite, 14 parts of quartz, 9 parts of white feldspar, 16 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide. The colorant is molybdenum tailings, which is calculated by weight and accounts for 15% of the total mass of the base glaze. The base glaze and the colorant are mixed to obtain a mixed glaze.

[0019] Embodiment 2: A Jun kiln celadon glaze contains a base glaze and a colorant. The base glaze contains, by weight, 33 parts of orthoclase, 12 parts of calcite, 10 parts of quartz, 9 parts of white feldspar, 12 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide. The colorant is molybdenum tailings, which is calculated by weight and accounts for 18% of the total mass of the base glaze. The base glaze and the colorant are mixed to obtain a mixed glaze.

[0020] Embodiment 3: A Jun kiln celadon glaze contains a base glaze and a colorant. The base glaze contains, by weight, 30 parts of chalcite, 6 parts of calcite, 12 parts of quartz, 9 parts of white feldspar, 6 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide. The colorant is molybdenum tailings, which is calculated by weight and accounts for 20% of the total mass of the base glaze. The base glaze and the colorant are mixed to obtain a mixed glaze.

[0021] The Jun kiln celadon glazes of the above-mentioned embodiments 1 to 3 use molybdenum tailings as a colorant, which not only greatly reduces the cost of firing Jun kiln celadon, directly reduces the environmental pollution caused by molybdenum tailings slag, but also indirectly reduces the environmental mining pollution caused by the use of other mineral colorants. In addition, the present invention uses the abandoned molybdenum tailings in Luanchuan near Yuzhou, the origin of Jun kiln, as raw materials, which has the dual advantages of low raw material cost and low transportation cost. The glaze can be widely used in daily-use porcelain, architectural porcelain and artistic porcelain, etc., and has a good prospect for industrial-scale production and application.

[0022] Embodiment 4: A method for preparing celadon using the Jun kiln celadon glaze in Embodiment 1, comprising the following steps: a. Preparation of mixed glaze Weigh various raw materials of the basic glaze by weight, and obtain the total weight of the basic glaze after summing up. The required weight of the molybdenum tailings is converted according to the percentage of the molybdenum tailings relative to the total weight of the basic glaze, and weighed. All the above raw materials are fully mixed to obtain a mixed glaze; b. Preparation of glaze slurry The mixed glaze is wet ball-milled to obtain a glaze slurry, and then the glaze slurry specific gravity is adjusted to 1.65 g / cm 3;Wherein, the fineness of the glaze slurry is 250 mesh by wet ball milling in step b, and the sieve residue after ball milling is less than 0.5%. The speed of ball milling in step b is 300r / min, the ball milling time is 40 min, and the mass ratio of material: ball: water is 1:2:0.75.

[0023] c. Glazing The glaze slurry is evenly applied on the ceramic body, and the glazing thickness in step c is 1.6 mm.

[0024] d. Firing After the glazed body is dried, it is fired in a kiln to produce celadon.

[0025] In step d, the sintering is carried out in a reducing atmosphere in a kiln to a firing temperature of 1280°C, and the temperature control process in the kiln includes: d1. The heating rate in the temperature range from room temperature to 300°C is 5°C / min; d2. The heating rate in the temperature range of 300℃~900℃ is 3℃ / min; d3. The heating rate in the temperature range from 900℃ to firing temperature is 1.5℃ / min; d4. After reaching the firing temperature, do not keep warm and let it cool naturally to room temperature in the furnace.

[0026] The kiln in step d is a shuttle natural gas kiln.

[0027] In order to compare the influence of molybdenum tailings on the color of celadon after firing, the inventor took the raw material ratio of Example 4 as a benchmark, kept the basic glaze ratio unchanged, adjusted the proportion of different molybdenum tailings added, obtained mixed glazes respectively, and then fired and compared them respectively, and set color parameters for comparison; No. W0 represents the ratio of the mixed glaze in which the molybdenum tailings account for 0% of the total weight of the basic glaze, No. W5 represents the ratio of the mixed glaze in which the molybdenum tailings account for 5% of the total weight of the basic glaze, ... No. W20 represents the ratio of the mixed glaze in which the molybdenum tailings account for 20% of the total weight of the basic glaze.

[0028] See the table below. When the firing temperature is 1280℃, the test results of Jun porcelain products fired with different mixed glaze ratios are as follows: serial number Molybdenum tailings / base glaze (wt.%) Product images W0 0 43.05 -2.60 5.52 Figure 3 W5 5 51.22 -2.78 7.28 Figure 4 W10 10 47.71 -3.74 7.15 Figure 5 W15 15 7.48 -2.65 1.64 Figure 1 W20 20 7.11 -2.29 2.41 Figure 6 in the above table L *Indicates brightness: a *Indicates a range from red to green; b *Indicates a range from blue to yellow.

[0029] L *The value range is 0 to 100. L *When the value is 100, it means the glaze is 50% white; a *and b *The range is from -120 to +120. when a * When the value is -120, it means the glaze is green. a *When the value increases gradually to +120, it means the glaze is red; when b * When the value is -120, it means the glaze is blue. b *When the value gradually increases to +120, it means that the glaze surface turns yellow.

[0030] From the table above, we can see that in the reducing atmosphere at 1280℃, the mixed glaze No. W15 produced a better glaze effect on the Jun kiln celadon. For the specific glaze effect of Jun porcelain, please refer to Figure 1 , it can be seen that the color is stable and the glaze has no defects. The microstructure diagram under a scanning electron microscope after being corroded by hydrofluoric acid solution is shown in Figure 2 It can be seen that the celadon glaze prepared by the present invention has a phase-separated structure at the microscopic level and has the conditions for structural coloration. Figure 6 The glaze effect can also meet the color parameters of celadon.

[0031] Embodiment 5: A method for preparing celadon using the Jun kiln celadon glaze in Embodiment 2, comprising the following steps: a. Preparation of mixed glaze Weigh various raw materials of the basic glaze by weight, and obtain the total weight of the basic glaze after summing up. The required weight of the molybdenum tailings is converted according to the percentage of the molybdenum tailings relative to the total weight of the basic glaze, and weighed. All the above raw materials are fully mixed to obtain a mixed glaze; b. Preparation of glaze slurry The mixed glaze is wet ball-milled to obtain a glaze slurry, and then the glaze slurry specific gravity is adjusted to 1.70 g / cm 3 ;Wherein, the fineness of the glaze slurry is 250 mesh by wet ball milling in step b, and the sieve residue after ball milling is less than 0.5%. The speed of ball milling in step b is 320r / min, the ball milling time is 35min, and the mass ratio of material: ball: water is 1:2:0.75.

[0032] c. Glazing The glaze slurry is evenly applied on the ceramic body, and the glazing thickness in step c is 2 mm.

[0033] d. Firing After the glazed body is dried, it is fired in a kiln to produce celadon.

[0034] In step d, the sintering is carried out in a reducing atmosphere in a kiln to a firing temperature of 1280°C, and the temperature control process in the kiln includes: d1. The heating rate in the temperature range from room temperature to 300°C is 5°C / min; d2. The heating rate in the temperature range of 300℃~900℃ is 3℃ / min; d3. The heating rate in the temperature range from 900℃ to firing temperature is 1.5℃ / min; d4. After reaching the firing temperature, do not keep warm and let it cool naturally to room temperature in the furnace.

[0035] The kiln in step d is a shuttle natural gas kiln.

[0036] Embodiment 6: A method for preparing celadon using the Jun kiln celadon glaze in Embodiment 3, comprising the following steps: a. Preparation of mixed glaze Weigh various raw materials of the basic glaze by weight, and obtain the total weight of the basic glaze after summing up. The required weight of the molybdenum tailings is converted according to the percentage of the molybdenum tailings relative to the total weight of the basic glaze, and weighed. All the above raw materials are fully mixed to obtain a mixed glaze; b. Preparation of glaze slurry The mixed glaze is wet ball-milled to obtain a glaze slurry, and then the glaze slurry specific gravity is adjusted to 1.60 g / cm 3 ;Wherein, the fineness of the glaze slurry is 250 mesh by wet ball milling in step b, and the sieve residue after ball milling is less than 0.5%. The speed of ball milling in step b is 350r / min, the ball milling time is 30 min, and the mass ratio of material: ball: water is 1:2:0.75.

[0037] c. Glazing The glaze slurry is evenly applied on the ceramic body, and the glazing thickness in step c is 1.5 mm.

[0038] d. Firing After the glazed body is dried, it is fired in a kiln to produce celadon.

[0039] In step d, the sintering is carried out in a reducing atmosphere in a kiln to a firing temperature of 1280°C, and the temperature control process in the kiln includes: d1. The heating rate in the temperature range from room temperature to 300°C is 5°C / min; d2. The heating rate in the temperature range of 300℃~900℃ is 3℃ / min; d3. The heating rate in the temperature range from 900℃ to firing temperature is 1.5℃ / min; d4. After reaching the firing temperature, do not keep warm and let it cool naturally to room temperature in the furnace.

[0040] The kiln in step d is a shuttle natural gas kiln.

Claims

1. A Jun kiln celadon glaze, comprising a base glaze and a colorant, The base glaze contains 30~39 parts of orthoclase, 6~14 parts of calcite, 10~14 parts of quartz, 9 parts of white feldspar, 6~16 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, 1 part of tin oxide, The colorant is molybdenum tailings, which is calculated by weight and accounts for 15-20% of the total mass of the basic glaze. The basic glaze and the colorant are evenly mixed to obtain a mixed glaze.

2. The Jun kiln celadon glaze according to claim 1, characterized in that: The The base glaze contains 39 parts of orthoclase, 14 parts of calcite, 14 parts of quartz, 9 parts of white feldspar, 16 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide.

3. The Jun kiln celadon glaze according to claim 1, characterized in that: The The base glaze contains 33 parts of orthoclase, 12 parts of calcite, 10 parts of quartz, 9 parts of white feldspar, 12 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide.

4. The Jun kiln celadon glaze according to claim 1, characterized in that: The The base glaze contains 30 parts of orthoclase, 6 parts of calcite, 12 parts of quartz, 9 parts of white feldspar, 6 parts of this medicine, 2 parts of talc, 5 parts of zinc oxide, and 1 part of tin oxide.

5. A method for preparing celadon using the Jun kiln celadon glaze according to any one of claims 1 to 4, comprising the following steps: a. Preparation of mixed glaze Weigh various raw materials of the basic glaze by weight, and obtain the total weight of the basic glaze after summing up. Calculate the required weight of the molybdenum tailings according to the percentage of the molybdenum tailings relative to the total weight of the basic glaze, and weigh them. After fully mixing all the above raw materials, a mixed glaze is obtained; b. Preparation of glaze slurry The mixed glaze is wet ball-milled to obtain glaze slurry. c. Glazing Apply the glaze slurry evenly on the ceramic body. d. Firing After the glazed body is dried, it is fired in a kiln to produce celadon.

6. The method for preparing celadon using Jun kiln celadon glaze according to claim 5, characterized in that: In step b, the glaze slurry is wet-milled to a fineness of 250 mesh, and the sieve residue after ball milling is less than 0.5%; then the specific gravity of the glaze slurry is adjusted to 1.60-1.70 g / cm 3 .

7. The method for preparing celadon using Jun kiln celadon glaze according to claim 5, characterized in that: In step d, the sintering is carried out in a reducing atmosphere in a kiln to a firing temperature of 1280°C, and the temperature control process in the kiln includes: d1. The heating rate in the temperature range from room temperature to 300°C is 5°C / min; d2. The heating rate in the temperature range of 300℃~900℃ is 3℃ / min; d3. The heating rate in the temperature range from 900℃ to firing temperature is 1.5℃ / min; d4. After reaching the firing temperature, do not keep warm and let it cool naturally to room temperature in the furnace.

8. The method for preparing celadon using Jun kiln celadon glaze according to claim 5, characterized in that: The rotation speed of the ball milling in step b is 300-350 r / min, and the mass ratio of material: ball: water is 1:2:0.

75.

9. The method for preparing celadon using Jun kiln celadon glaze according to claim 5, characterized in that: The glazing thickness in step c is 1.5 mm to 2 mm.

10. The method for preparing celadon using Jun kiln celadon glaze according to claim 5, characterized in that: The kiln in step d is a shuttle natural gas kiln.

Images