CN116217080A - Copper-colored metallic luster glaze, preparation method thereof and ceramic product - Google Patents
Copper-colored metallic luster glaze, preparation method thereof and ceramic product Download PDFInfo
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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Abstract
The invention discloses a copper-colored metallic luster glaze, a preparation method thereof and a ceramic product. The copper-colored metallic luster glaze comprises solid components and water; wherein, the solid parts comprise the following components in percentage by weight: 40-60% of nepheline orthoclase, 15-30% of lead-free nontoxic boron frit, 5-15% of light calcium carbonate, 3-8% of kaolin, 0.5-3% of zinc oxide, 5-15% of manganese oxide, 1-8% of tin oxide, 1-8% of vanadium pentoxide, 1-5% of copper oxide, 0.5-3% of nickel oxide and 5-20% of red lead. The metallic luster glaze disclosed by the invention is composed of a formula, is simple in raw materials, does not need additional independent sintering, is simple in process, stable in quality and low in processing cost, greatly improves the productivity, and is easy for mass production.
Description
Technical Field
The invention relates to the technical field of metallic luster glaze, in particular to a copper-colored metallic luster glaze, a preparation method thereof and a ceramic product.
Background
The metallic luster glaze is one of the components in the ceramic artistic glaze. The glaze has matte, semi-matte and glossy glaze gloss, and the color tone of the glaze is yellow, silvery white, copper and other similar metal materials in nature, so that the glaze is a decoration glaze which is not too much seen in ceramic art glaze, and the glaze firing product is also one of favorite collection works. Among them, a glaze having appearance properties similar to metallic copper is called a bronze metallic luster glaze.
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, glazed fruit, green glass, tin crystal material and copper oxide; the preparation method comprises the following steps: A. adding the raw materials into a pulverizer, and pulverizing to 300-320 meshes to obtain mixed particles; B. uniformly stirring the mixed particles, melting at 1350-1500 ℃, and preserving the heat for 2-4 hours; C. putting into water with the temperature of 15-18 ℃ to quench into a frit, and then vibrating for 5-8 min by ultrasonic wave to obtain the copper-imitating luster ceramic glaze. The method has the advantages of complex raw materials, adoption of secondary processing firing (glaze preparation and glaze layer formation), complex process, easy quality instability and high processing cost.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a copper-colored metallic luster glaze, a preparation method thereof and a ceramic product, which solve the technical problems that the raw materials of the copper-colored metallic luster glaze are complex, the copper-colored metallic luster glaze is formed by an additional independent sintering process, the process is complex, the quality is easy to be unstable and the processing cost is high in the prior art.
In a first aspect, the present invention provides a copper-colored metallic luster glaze comprising solid components and water; wherein, the solid parts comprise the following components in percentage by weight: 40-60% of nepheline orthoclase, 15-30% of lead-free nontoxic boron frit, 5-15% of light calcium carbonate, 3-8% of kaolin, 0.5-3% of zinc oxide, 5-15% of manganese oxide, 1-8% of tin oxide, 1-8% of vanadium pentoxide, 1-5% of copper oxide, 0.5-3% of nickel oxide and 5-20% of red lead.
In a second aspect, the present invention provides a method for preparing a copper-colored metallic luster glaze, comprising the steps of:
weighing materials according to the formula, and crushing in a ball mill until the fineness of the glaze slip is tens of thousands Kong Shaiyu 0.3-0.5%;
the glaze slip is continuously stirred and homogenized, and then is sieved by a 80-100 mesh sieve, so that the copper-colored metallic luster glaze is obtained.
In a third aspect, the present invention provides a ceramic article obtained by applying the copper-colored metallic luster glaze material provided in the first aspect of the present invention to a biscuit firing blank, followed by drying and firing under an oxidizing atmosphere.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes silicate mineral materials as main materials, adds some coloring oxides and auxiliary coloring materials, and prepares the copper-colored metallic luster glaze through a special processing technology; after the ceramic is applied to a biscuit firing blank, firing the biscuit under the condition of oxidizing atmosphere firing by adopting a specific temperature system to obtain a ceramic product with metallic luster and metallic color; the metallic luster glaze disclosed by the invention is composed of a formula, is simple in raw materials, does not need additional independent sintering, is simple in process, stable in quality and low in processing cost, greatly improves the productivity, and is easy for mass production.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In a first aspect, the invention provides a copper-colored metallic luster glaze, which comprises the following raw materials in parts by solid and water; wherein, the solid parts comprise the following components in percentage by weight: 40-60% of nepheline orthoclase, 15-30% of lead-free nontoxic boron frit, 5-15% of light calcium carbonate, 3-8% of kaolin, 0.5-3% of zinc oxide, 5-15% of manganese oxide, 1-8% of tin oxide, 1-8% of vanadium pentoxide, 1-5% of copper oxide, 0.5-3% of nickel oxide and 5-20% of red lead.
The mechanism of the invention is as follows: the basic materials of the glaze material with copper-colored metallic luster are nepheline orthoclase, light calcium carbonate, kaolin, lead-free nontoxic boron frit and red lead, which form medium-temperature basic glaze; and the material is sintered with the green body at 1220-1250 ℃ once, so that the energy consumption is saved and the cost is low. The auxiliary coloring material is tin oxide, zinc oxide and red lead; the colored oxide is manganese oxide, vanadium pentoxide, copper oxide or nickel oxide. The chromogenic oxide interpenetrates at high temperatures and chemically reacts to produce a molten hue change. These color shade changes must occur in the presence of auxiliary color-forming materials. After the reaction, the substances are uniformly melted in the glass body of the basic glaze, and after cooling, the surface of the ceramic product is provided with a glaze surface with copper metal luster.
In this embodiment, the solid parts include, in weight percent: 40-55% of nepheline orthoclase, 15-30% of lead-free nontoxic boron frit, 5-10% of light calcium carbonate, 3-5% of kaolin, 0.5-2% of zinc oxide, 5-7% of manganese oxide, 1-3% of tin oxide, 1-2% of vanadium pentoxide, 1-2% of copper oxide, 0.5-1% of nickel oxide and 5-10% of red lead.
In this embodiment, the water content of the glaze material with copper-colored metallic luster is 30% -40%.
In a second aspect, the present invention provides a method for preparing a copper-colored metallic luster glaze, comprising the steps of:
s101, weighing materials according to the formula, and crushing in a ball mill until the fineness of the glaze slip is tens of thousands Kong Shaiyu 0.3.3-0.5%; wherein, mill the intermediate material: ball: the mass ratio of water is 1: (1.5-2): (0.5-0.7), further 1: (1.5-2): 0.6; ball milling time is 48-72 hours; the specific gravity of the glaze slip is 1.55-1.65 g/cm 3 。
S102, continuously stirring and homogenizing the glaze slip, and then sieving the glaze slip with a 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 The viscosity flow rate is 40-45 seconds.
In a third aspect, the present invention provides a ceramic article obtained by applying the copper-colored metallic luster glaze material provided in the first aspect of the present invention to a biscuit firing blank, followed by drying and firing under an oxidizing atmosphere.
In the embodiment, glaze is applied to the biscuit firing blank by adopting a glazing mode of dipping, spraying and spraying.
In this embodiment, the thickness of the glaze layer is 1-2mm. In this range, the occurrence of the glazing phenomenon can be avoided, and the glaze has excellent wear resistance and corrosion resistance.
In this embodiment, the glaze is dried to a moisture content of 1% or less. If the water content is too high, the glaze will have no metallic luster. The drying temperature is not limited in the present invention, and one skilled in the art may select according to the actual situation, and for example, drying at 80-100 ℃ or natural drying may be performed.
In the embodiment, in the sintering process, the highest sintering temperature is 1220-1250 ℃, the high-fire heat preservation time is 30-60 minutes, the sintering period is 10-12 hours, and the volume content of oxygen in the oxidizing atmosphere is controlled to be 3-5%. Under the firing system, the colored oxide is favorable to complete reaction under the assistance of the auxiliary colored oxide, and finally the copper colored metallic luster glaze with stable quality is formed. Therefore, except the glaze formula, the firing system (comprising the oxygen content of the oxidizing atmosphere, the firing temperature and the firing time) is a key technology for controlling the high-quality stability of the copper-colored metallic luster glaze.
In this embodiment, the firing process is performed in an electric kiln. The method can be carried out under the firing condition of the oxidizing atmosphere of a common electric kiln, and the formed copper-colored metallic luster enamel is stable in quantity and is favorable for popularization.
In this embodiment, the preparation method of the biscuit firing blank includes the following steps:
s201, weighing raw materials according to a formula of 25-30 parts of kaolin, 20-25 parts of feldspar, 20-30 parts of quartz and 10-15 parts of clay, adding water, and then crushing in a ball mill until the fineness of the slurry is tens of thousands Kong Shaiyu-5%; wherein, grind the internal material: ball: the mass ratio of water is 1: (1.5-2): (0.6-0.8), further 1: (1.5-2): 0.7; ball milling time is 20-24 hours; the specific gravity of the green stock is 1.5-1.6 g/cm 3 。
S202, dehydrating the blank slurry until the water content is 25-30%, and homogenizing and ageing the mud cake for 1-2 months. In the process, the water content in the mud cake can be uniform and the sodium humate alcoholized through homogenization and aging, so that the plasticity of the blank is enhanced.
S203, pugging the homogenized and stale mud cake in a vacuum pugging machine to discharge air in the mud cake, and ensuring uniform water content and compact structure, thereby further improving the plasticity; wherein the vacuum degree of the vacuum pugging machine is 90-98%, and the pugging times are 2-3 times; the content of mud in the blank is 20-22% after pugging.
S204, forming by adopting different forming processes according to different shapes of the blank, drying, dehydrating, shaping and finishing, and drying again until the water content is below 1%. Wherein, the molding process is rolling mechanical pressing, manual blank drawing, grouting and other processes, and the invention is not limited to the processes; because the green body contains a certain moisture, the green body still has a certain plasticity and is easy to generate a soft couch, the soft couch needs to be dried, dehydrated and shaped, the temperature of the drying, dehydrating and shaped is not limited, and the temperature can be selected by a person skilled in the art by himself in practical situations, for example, the soft couch can be dried or naturally dried at the temperature of 60-80 ℃; after drying, dehydration and shaping, the surface of the green body is rough and uneven, the size is inaccurate, the surface of the green body is subjected to finishing by a knife and sand paper, and the surface of the green body is smooth by dipping water by a brush, so that the size is accurate; the temperature of the re-drying is not limited in the present invention, and the person skilled in the art can choose it by himself in practice, for example, it can be dried at 80-100℃or naturally dried.
And S205, sintering the dried green body to obtain a biscuit firing green body. In order to improve the mechanical strength of the green body, the dried green body needs to be sintered, so that the green body is evaporated, mechanical crystallization moisture is carried out, organic substances are carbonized, partial carbonate and sulfate substances are decomposed, a quartz crystal form is converted, the biscuit firing green body has certain mechanical strength, the breakage rate is reduced in the subsequent working procedure, and the quality of a finished product is improved. Wherein the sintering temperature is 750-800 ℃ and the sintering time is 6-8 hours.
In the following examples of the present invention, the preparation method of the biscuit firing blank comprises the following steps, if not specified:
(1) 30 parts of kaolin, 25 parts of feldspar, 30 parts of quartz and 15 parts of clay are taken, the materials are accurately weighed according to the formula, and the materials are ground according to the following formula: ball: water = 1:2:0.7 in a ball mill for 20 hours, wherein the grinding fineness of the slurry is tens of thousands Kong Shaiyu percent and the specific gravity of the slurry is 1.54 g/cm 3 ；
(2) Continuously stirring the blank slurry in a slurry storage pool to prevent the blank slurry from precipitating, pumping the blank slurry into a filter press by a slurry pump, pressing and dehydrating to obtain a mud cake with the water content of 25%, and dragging the mud cake into a mud warehouse to be homogenized and aged for 1 month;
(3) Repeatedly pugging the homogenized and stale mud cake in a vacuum pugging machine (the vacuum degree is 95%) for 3 times, wherein the mud content of the mud blank after pugging is 20%.
(4) Adopting a rolling mechanical pressing process to form, naturally drying, dehydrating and shaping, then finishing the surface of the green body by a knife and sand paper, dipping water by a hairbrush to make the surface of the green body smooth, ensuring the size to be accurate, and naturally drying the finished green body to the water content of below 1%;
(5) And (3) firing the dried green body in a kiln for 6 hours at 800 ℃ to obtain a biscuit firing green body.
Example 1
(1) 40 parts of nepheline orthoclase, 20 parts of lead-free nontoxic 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 are weighed, and the following materials are ground: ball: water = 1:1.5: pulverizing 0.6 in ball mill for 48 hr to obtain ground glaze slurry with fineness of ten thousand Kong Shaiyu 0.4.4% and specific gravity of 1.58 g/cm 3 ；
(2) Stirring and homogenizing the glaze slurry in a tank for one month, pumping the homogenized glaze slurry in the tank into a glazing working barrel, sieving with 100 mesh sieve, and the specific gravity of the glaze slurry is 1.57 g/m 3 Viscosity flow rate 40 seconds;
(3) Applying the glaze slurry to the biscuit firing blank, wherein the thickness of the glaze layer is 2mm, and naturally drying the glaze blank until the water content is less than 1%;
(4) And (3) sintering the glaze blank in an electric kiln under an oxidizing atmosphere, wherein the volume content of oxygen in the oxidizing atmosphere is controlled to be 5%, the highest sintering temperature is 1230 ℃, the high-fire heat preservation time is 45 minutes, the sintering period is 12 hours, and finally, naturally cooling to room temperature to obtain the ceramic product with the copper-colored metallic luster glaze decorated on the surface.
Example 2
(1) 48 parts of nepheline orthoclase, 30 parts of lead-free nontoxic boron frit, 5 parts of light calcium carbonate, 3 parts of kaolin, 0.5 part 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 part of nickel oxide and 5 parts of red lead are weighed, and the following materials are ground: ball: water = 1:2: pulverizing 0.6 in ball mill for 48 hr to obtain ground glaze slurry with fineness of ten thousand Kong Shaiyu 0.3.3% and specific gravity of 1.61 g/cm 3 ；
(2) Stirring and homogenizing the glaze slurry in a tank for one month, pumping the homogenized glaze slurry in the tank into a glazing working barrel, sieving with 100 mesh sieve, and the specific gravity of the glaze slurry is 1.62 g/m 3 Viscosity flow rate 42 seconds;
(3) Applying the glaze slurry to the biscuit firing blank, wherein the thickness of the glaze layer is 1.5mm, and naturally drying the glaze blank until the water content is less than 1%;
(4) And (3) sintering the glaze blank in an electric kiln under an oxidizing atmosphere, wherein the volume content of oxygen in the oxidizing atmosphere is controlled to be 3%, the highest sintering temperature is 1250 ℃, the high-fire heat preservation time is 60 minutes, the sintering period is 10 hours, and finally, naturally cooling to room temperature to obtain the ceramic product with the copper-colored metallic luster glaze decorated on the surface.
Example 3
(1) 53 parts of nepheline orthoclase, 15 parts of lead-free nontoxic 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 are weighed, and the following materials are ground: ball: water = 1:2: pulverizing 0.6 in ball mill for 48 hr to obtain ground glaze slurry with fineness of ten thousand Kong Shaiyu 0.4.4% and specific gravity of 1.55 g/cm 3 ；
(2) Stirring and homogenizing the glaze slurry in a tank for one month, pumping the homogenized glaze slurry in the tank into a glazing working barrel, sieving with 100 mesh sieve, and the specific gravity of the glaze slurry is 1.54 g/m 3 Viscosity flow rate 40 seconds;
(3) Applying the glaze slurry to the biscuit firing blank, wherein the thickness of the glaze layer is 2mm, and naturally drying the glaze blank until the water content is less than 1%;
(4) And (3) sintering the glaze blank in an electric kiln under an oxidizing atmosphere, wherein the volume content of oxygen in the oxidizing atmosphere is controlled to be 4%, the highest sintering temperature is 1220 ℃, the high-fire heat preservation time is 30 minutes, the sintering period is 12 hours, and finally, naturally cooling to room temperature to obtain the ceramic product with the copper-colored metallic luster glaze decorated on the surface.
Compared with the prior art, the invention has the beneficial effects that:
(1) The glaze decoration craft ceramic with copper luster presents matte and semi-matte luster, presents copper luster and ancient color, and is simple and elegant.
(2) The invention has simple process, safe operation, stable quality, good artistic effect of the glaze surface of the product and easy mass production.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. The copper-colored metallic luster glaze is characterized in that the raw materials comprise solid matters and water; wherein, the solid parts comprise the following components in percentage by weight: 40-60% of nepheline orthoclase, 15-30% of lead-free nontoxic boron frit, 5-15% of light calcium carbonate, 3-8% of kaolin, 0.5-3% of zinc oxide, 5-15% of manganese oxide, 1-8% of tin oxide, 1-8% of vanadium pentoxide, 1-5% of copper oxide, 0.5-3% of nickel oxide and 5-20% of red lead.
2. The bronze metallic luster glaze according to claim 1, wherein said solid parts by weight comprises: 40-55% of nepheline orthoclase, 15-30% of lead-free nontoxic boron frit, 5-10% of light calcium carbonate, 3-5% of kaolin, 0.5-2% of zinc oxide, 5-7% of manganese oxide, 1-3% of tin oxide, 1-2% of vanadium pentoxide, 1-2% of copper oxide, 0.5-1% of nickel oxide and 5-10% of red lead.
3. The bronze glaze according to claim 1, wherein the moisture content of the bronze glaze is 30% to 40%.
4. A method for producing the bronze metallic luster glaze according to any one of claims 1 to 3, comprising the steps of:
weighing materials according to the formula of the copper-colored metallic luster glaze material according to any one of claims 1-3, and crushing the materials in a ball mill until the fineness of the glaze slurry is tens of thousands Kong Shaiyu 0.3-0.5%;
and continuously stirring and homogenizing the glaze slip, and then sieving the glaze slip with a 80-100 mesh sieve to obtain the copper-colored metallic luster glaze.
5. The method for producing a copper-based metal luster glaze according to claim 4, wherein during the production of the copper-based metal luster glaze, the following grinding materials are used: ball: the mass ratio of water is 1: (1.5-2): (0.5-0.7), ball milling time is 48-72 hours, and homogenization time is 1-2 months.
6. A ceramic article, characterized in that it is obtained by applying the bronze metallic luster glaze according to any one of claims 1 to 3 to a biscuit firing blank, followed by drying and firing under an oxidizing atmosphere.
7. The ceramic article of claim 6, wherein the glaze layer has a thickness of 1-2mm.
8. The ceramic article of claim 6, wherein the glaze is dried to a moisture content of less than 1%.
9. The ceramic article according to claim 6, wherein during firing, the maximum firing temperature is 1220-1250 ℃, the high fire holding time is 30-60 minutes, the firing period is 10-12 hours, and the volume content of oxygen in the oxidizing atmosphere is controlled to be 3-5%.
10. The ceramic article of claim 6, wherein the method of making a bisque fired body comprises the steps of:
weighing raw materials according to a formula of 25-30 parts of kaolin, 20-25 parts of feldspar, 20-30 parts of quartz and 10-15 parts of clay, adding water, and then crushing in a ball mill until the grinding fineness of the blank slurry is tens of thousands Kong Shaiyu-5%;
dehydrating the blank slurry until the water content is 25-30%, homogenizing and ageing the mud cake for 1-2 months;
pugging the homogenized and stale mud cake in a vacuum pugging machine until the mud content is 20-22%;
according to different shapes of the blank, different molding processes are adopted for molding, and after drying, dehydration, shaping and finishing, the blank is dried again until the water content is below 1%;
firing the dried green body to obtain a biscuit firing green body; wherein the sintering temperature is 750-800 ℃ and the sintering time is 6-8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310283976.3A CN116217080A (en) | 2023-03-22 | 2023-03-22 | Copper-colored metallic luster glaze, preparation method thereof and ceramic product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202310283976.3A CN116217080A (en) | 2023-03-22 | 2023-03-22 | Copper-colored metallic luster glaze, preparation method thereof and ceramic product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535248A (en) * | 2023-05-23 | 2023-08-04 | 广东天弼陶瓷有限公司 | Polished glazed hole stone brick with metallic luster and strong third dimension and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535248A (en) * | 2023-05-23 | 2023-08-04 | 广东天弼陶瓷有限公司 | Polished glazed hole stone brick with metallic luster and strong third dimension and preparation method thereof |
| CN116535248B (en) * | 2023-05-23 | 2024-07-19 | 广东天弼陶瓷有限公司 | Polished glazed hole stone brick with metallic luster and strong third dimension and preparation method thereof |
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