CN109111243B - Method for spraying composite copper powder on surface of ceramic artwork - Google Patents
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- CN109111243B CN109111243B CN201811098191.4A CN201811098191A CN109111243B CN 109111243 B CN109111243 B CN 109111243B CN 201811098191 A CN201811098191 A CN 201811098191A CN 109111243 B CN109111243 B CN 109111243B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5144—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the metals of the iron group
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Abstract
The invention discloses a method for spraying composite copper powder on the surface of a ceramic artwork, which comprises the following operation steps: (1) reacting aluminum powder, gadolinium powder and isopropanol to obtain gadolinium-aluminum double metal alkoxide; (2) calcining gadolinium-aluminum bimetallic alkoxide to obtain gadolinium-aluminum composite oxide powder; (3) uniformly mixing zinc oxide, vanadium oxide, ethylene diamine tetraacetic acid, behenamide and deionized water, washing and drying a product to obtain zinc pyrovanadate hollow microsphere powder; (4) mixing brass powder, iron powder, zirconium nitride, gadolinium-aluminum composite oxide powder and zinc pyrovanadate hollow microsphere powder to prepare composite copper powder; (5) and spraying the prepared composite copper powder on the surface of the cleaned ceramic artwork by adopting flame spraying equipment. The coating prepared on the surface of the ceramic artwork has bright color, high glossiness, smooth surface and high hardness, and particularly has high bonding strength with the surface of the ceramic, so that the coating is not easy to fall off.
Description
Technical Field
The invention belongs to the technical field of surface treatment of ceramic artware, and particularly relates to a method for spraying composite copper powder on the surface of the ceramic artware.
Background
The ceramic is originated from China, is a scientific and technical result of Chinese workers, and forms very typical technical and artistic characteristics of each era. The ceramic is originally produced to meet the daily life needs of people, and with the development of times, the ceramic technology is continuously developed and improved, and finally, the ceramic is developed into an artwork. The ceramic artwork is the earliest artistic form in the human civilization history, is the simplest and simplest art and has incomparable mystery and abstract properties. From the ceramic artwork we can see the cultural connotation of an era and national ethnic spirits. The ceramic artware is popular in ancient times, is a symbol of nobility and luxury, meets the requirements of daily life, and is developed into an art ornament with extremely strong ornamental value. The ceramic artwork is an art variety which can be enjoyed, played, used and invested and collected. The ceramic artware forms modern unique ceramic culture with exquisite decoration beauty, fantasy artistic conception, individual beauty of ceramic art and unique material beauty, is popular with the masses of people, and gradually becomes the first choice for investment collection of modern people. The brass is sprayed on the surface of the ceramic product which is not glazed and is fired, so that the ceramic product has the process characteristics of the ceramic product and has the muddy texture of the cast copper figure, and the brass and the cast copper figure are organically combined, so that the quality of the ceramic product can be greatly improved. However, in the prior art, the coating prepared on the surface of the ceramic craft has low bonding strength, low surface hardness and easy damage.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for spraying composite copper powder on the surface of a ceramic artwork.
The invention is realized by the following technical scheme.
A method for spraying composite copper powder on the surface of a ceramic artwork comprises the following operation steps:
(1) adding 36-44 parts of aluminum powder and 10-15 parts of gadolinium powder into an activation solution, after activation treatment, centrifuging, cleaning and drying precipitates, then adding the precipitates into 380-420 parts of isopropanol, adding 0.4-0.8 part of mercury chloride, mixing and stirring uniformly, heating to 70-75 ℃ for reflux extraction for 4-5 hours, and evaporating to remove unreacted isopropanol to obtain gadolinium aluminum bimetallic alkoxide, wherein the activation solution is prepared from the following components in parts by weight: 14-18 parts of sodium methallyl sulfonate, 5-9 parts of sodium molybdate dihydrate, 1-3 parts of citric acid, 2-4 parts of N-octyl diamino ethyl glycine hydrochloride and 500 parts of water 450-containing agents;
(2) calcining gadolinium-aluminum bimetallic alkoxide to obtain gadolinium-aluminum composite oxide powder;
(3) uniformly mixing 14-19 parts of zinc oxide, 28-33 parts of vanadium oxide, 1-5 parts of ethylene diamine tetraacetic acid, 4-8 parts of behenamide and 600 parts of 550-ion water in parts by weight, heating the mixture to 165-ion 175 ℃, carrying out hydrothermal heat preservation reaction for 6-8 hours, washing and drying the product to obtain pyro-vanadic acid zinc hollow microsphere powder;
(4) adding 44-50 parts by weight of brass powder, 8-12 parts by weight of iron powder, 1-3 parts by weight of zirconium nitride, 7-10 parts by weight of gadolinium-aluminum composite oxide powder and 5-10 parts by weight of zinc pyrovanadate hollow microsphere powder into a ball mill, carrying out ball milling treatment, adopting polyvinyl alcohol for agglomeration, drying and crushing to obtain composite copper powder;
(5) and spraying the prepared composite copper powder on the surface of the cleaned ceramic artwork by adopting flame spraying equipment, wherein the thickness of the coating is 0.5-0.7mm, and then, polishing and flattening by adopting a grinding wheel to obtain a finished product.
Specifically, in the step (1), the temperature at the time of the evaporation treatment is 88 to 92 ℃.
Specifically, in the step (2), the temperature during the calcination treatment is 1100-1200 ℃, and the calcination treatment time is 2-3 hours.
Specifically, in the step (4), the polyvinyl alcohol agglomeration treatment specifically comprises: adding polyvinyl alcohol into water with the weight 5 times of that of the polyvinyl alcohol to obtain a polyvinyl alcohol solution, then adding the polyvinyl alcohol solution with the weight 1.5 times of that of the ball-milled material, and mixing and stirring uniformly.
Specifically, in the step (4), the temperature of the drying treatment was 80 ℃, the time of the drying treatment was 5 hours, and the average particle size of the composite copper powder after the pulverization treatment was 500 mesh.
Specifically, in the step (5), during the flame spraying treatment, the spraying distance is 150-200mm, the powder feeding amount of the flame spray gun is 50-70g/min, compressed air is used as the protective gas, and the pressure of the protective gas is 0.3 MPa.
According to the technical scheme, the beneficial effects of the invention are as follows:
the coating prepared on the surface of the ceramic artwork has bright color, high glossiness, smooth surface and high hardness, and particularly has high bonding strength with the surface of the ceramic, so that the coating is not easy to fall off. After the gadolinium-aluminum composite oxide powder prepared in the step (2) is thermally sprayed, the coating has a typical layered structure, the phenomenon that the composite copper powder is sintered and grows up in the thermal spraying process can be effectively inhibited, so that the coating layers are uniformly spread and smaller, the compactness and the surface hardness of the coating are greatly improved, and meanwhile, the gadolinium-aluminum composite oxide powder has excellent optical performance and can effectively improve the glossiness of the coating; the addition of the zinc pyrovanadate hollow microsphere powder can effectively absorb oxidizing substances in the coating, prevent the coating from being oxidized by the oxidizing substances in the environment, and further cause the phenomenon of dull color, and meanwhile, the zinc pyrovanadate hollow microsphere powder can also effectively improve the melting effect of the composite copper powder, effectively reduce the number of particles which are not melted, and further effectively improve the bonding strength of the coating on the surface of the ceramic; the crystal structure of the zirconium nitride can effectively improve the color of the coating, effectively reduce the interface cracks between layers in the coating and avoid the phenomenon of cracks on the surface of the coating.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
Example 1
A method for spraying composite copper powder on the surface of a ceramic artwork comprises the following operation steps:
(1) adding 36 parts by weight of aluminum powder and 10 parts by weight of gadolinium powder into an activation solution, after activation treatment, centrifuging, cleaning and drying a precipitate, then adding the precipitate into 380 parts by weight of isopropanol, then adding 0.4 part of mercury chloride into the isopropanol, mixing and stirring uniformly, heating to 70 ℃, refluxing and extracting for 4 hours, evaporating to remove unreacted isopropanol to obtain gadolinium-aluminum double metal alkoxide, wherein the activation solution is prepared from the following components in parts by weight: 14 parts of sodium methallyl sulfonate, 5 parts of sodium molybdate dihydrate, 1 part of citric acid, 2 parts of N-octyl diamino ethyl glycine hydrochloride and 450 parts of water;
(2) calcining gadolinium-aluminum bimetallic alkoxide to obtain gadolinium-aluminum composite oxide powder;
(3) uniformly mixing 14 parts of zinc oxide, 28 parts of vanadium oxide, 1 part of ethylenediamine tetraacetic acid, 4 parts of behenamide and 550 parts of deionized water in parts by weight, heating the mixture to 165 ℃, carrying out hydrothermal heat preservation reaction for 6 hours, washing and drying the product to obtain zinc pyrovanadate hollow microsphere powder;
(4) adding 44 parts of brass powder, 8 parts of iron powder, 1 part of zirconium nitride, 7 parts of gadolinium-aluminum composite oxide powder and 5 parts of zinc pyrovanadate hollow microsphere powder into a ball mill, performing ball milling treatment, agglomerating by using polyvinyl alcohol, drying and crushing to obtain composite copper powder;
(5) and spraying the prepared composite copper powder on the surface of the cleaned ceramic artwork by adopting flame spraying equipment, wherein the thickness of the coating is 0.5mm, and then, polishing and flattening by adopting a grinding wheel to obtain a finished product.
Specifically, in the step (1), the temperature at the time of the evaporation treatment was 88 ℃.
Specifically, in the step (2), the temperature at the time of the calcination treatment was 1100 ℃, and the calcination treatment time was 2 hours.
Specifically, in the step (4), the polyvinyl alcohol agglomeration treatment specifically comprises: adding polyvinyl alcohol into water with the weight 5 times of that of the polyvinyl alcohol to obtain a polyvinyl alcohol solution, then adding the polyvinyl alcohol solution with the weight 1.5 times of that of the ball-milled material, and mixing and stirring uniformly.
Specifically, in the step (4), the temperature of the drying treatment was 80 ℃, the time of the drying treatment was 5 hours, and the average particle size of the composite copper powder after the pulverization treatment was 500 mesh.
Specifically, in the step (5), during the flame spraying treatment, the spraying distance is 150mm, the powder feeding amount of the flame spray gun is 50g/min, compressed air is used as protective gas, and the pressure of the protective gas is 0.3 MPa.
Example 2
A method for spraying composite copper powder on the surface of a ceramic artwork comprises the following operation steps:
(1) adding 40 parts by weight of aluminum powder and 13 parts by weight of gadolinium powder into an activation solution, after activation treatment, centrifuging, cleaning and drying a precipitate, then adding the precipitate into 400 parts by weight of isopropanol, then adding 0.6 part by weight of mercury chloride into the isopropanol, mixing and stirring uniformly, heating to 73 ℃, carrying out reflux extraction for 4.5 hours, and evaporating to remove unreacted isopropanol to obtain gadolinium-aluminum double metal alkoxide, wherein the activation solution is prepared from the following components in parts by weight: 16 parts of sodium methallyl sulfonate, 7 parts of sodium molybdate dihydrate, 2 parts of citric acid, 3 parts of N-octyl diamino ethyl glycine hydrochloride and 480 parts of water;
(2) calcining gadolinium-aluminum bimetallic alkoxide to obtain gadolinium-aluminum composite oxide powder;
(3) uniformly mixing 16 parts of zinc oxide, 30 parts of vanadium oxide, 3 parts of ethylene diamine tetraacetic acid, 6 parts of behenamide and 580 parts of deionized water in parts by weight, heating the mixture to 170 ℃, carrying out hydrothermal heat preservation reaction for 7 hours, washing and drying the product to obtain zinc pyrovanadate hollow microsphere powder;
(4) adding 46 parts of brass powder, 10 parts of iron powder, 2 parts of zirconium nitride, 9 parts of gadolinium-aluminum composite oxide powder and 8 parts of zinc pyrovanadate hollow microsphere powder into a ball mill, performing ball milling treatment, agglomerating by using polyvinyl alcohol, drying and crushing to obtain composite copper powder;
(5) and spraying the prepared composite copper powder on the surface of the cleaned ceramic artwork by adopting flame spraying equipment, wherein the thickness of the coating is 0.6mm, and then, polishing and flattening by adopting a grinding wheel to obtain a finished product.
Specifically, in the step (1), the temperature at the time of the evaporation treatment is 90 ℃.
Specifically, in the step (2), the temperature at the time of the calcination treatment was 1150 ℃, and the calcination treatment time was 2.5 hours.
Specifically, in the step (4), the polyvinyl alcohol agglomeration treatment specifically comprises: adding polyvinyl alcohol into water with the weight 5 times of that of the polyvinyl alcohol to obtain a polyvinyl alcohol solution, then adding the polyvinyl alcohol solution with the weight 1.5 times of that of the ball-milled material, and mixing and stirring uniformly.
Specifically, in the step (4), the temperature of the drying treatment was 80 ℃, the time of the drying treatment was 5 hours, and the average particle size of the composite copper powder after the pulverization treatment was 500 mesh.
Specifically, in the step (5), during the flame spraying treatment, the spraying distance is 180mm, the powder feeding amount of the flame spray gun is 60g/min, compressed air is used as protective gas, and the pressure of the protective gas is 0.3 MPa.
Example 3
A method for spraying composite copper powder on the surface of a ceramic artwork comprises the following operation steps:
(1) adding 44 parts by weight of aluminum powder and 15 parts by weight of gadolinium powder into an activation solution, after activation treatment, centrifuging, cleaning and drying a precipitate, then adding the precipitate into 420 parts by weight of isopropanol, then adding 0.8 part by weight of mercury chloride into the isopropanol, mixing and stirring uniformly, heating to 75 ℃, refluxing and extracting for 5 hours, and evaporating to remove unreacted isopropanol to obtain gadolinium-aluminum double metal alkoxide, wherein the activation solution is prepared from the following components in parts by weight: 18 parts of sodium methallyl sulfonate, 9 parts of sodium molybdate dihydrate, 3 parts of citric acid, 4 parts of N-octyl diamino ethyl glycine hydrochloride and 500 parts of water;
(2) calcining gadolinium-aluminum bimetallic alkoxide to obtain gadolinium-aluminum composite oxide powder;
(3) uniformly mixing 19 parts of zinc oxide, 33 parts of vanadium oxide, 5 parts of ethylene diamine tetraacetic acid, 8 parts of behenamide and 600 parts of deionized water in parts by weight, heating the mixture to 175 ℃, carrying out hydrothermal heat preservation reaction for 8 hours, washing and drying the product to obtain zinc pyrovanadate hollow microsphere powder;
(4) adding 50 parts by weight of brass powder, 12 parts by weight of iron powder, 3 parts by weight of zirconium nitride, 10 parts by weight of gadolinium-aluminum composite oxide powder and 10 parts by weight of zinc pyrovanadate hollow microsphere powder into a ball mill, performing agglomeration by using polyvinyl alcohol after ball milling treatment, and crushing after drying to obtain composite copper powder;
(5) and spraying the prepared composite copper powder on the surface of the cleaned ceramic artwork by adopting flame spraying equipment, wherein the thickness of the coating is 0.7mm, and then, polishing and flattening by adopting a grinding wheel to obtain a finished product.
Specifically, in the step (1), the temperature at the time of the evaporation treatment was 92 ℃.
Specifically, in the step (2), the temperature at the time of the calcination treatment was 1200 ℃ and the calcination treatment time was 3 hours.
Specifically, in the step (4), the polyvinyl alcohol agglomeration treatment specifically comprises: adding polyvinyl alcohol into water with the weight 5 times of that of the polyvinyl alcohol to obtain a polyvinyl alcohol solution, then adding the polyvinyl alcohol solution with the weight 1.5 times of that of the ball-milled material, and mixing and stirring uniformly.
Specifically, in the step (4), the temperature of the drying treatment was 80 ℃, the time of the drying treatment was 5 hours, and the average particle size of the composite copper powder after the pulverization treatment was 500 mesh.
Specifically, in the step (5), during the flame spraying treatment, the spraying distance is 200mm, the powder feeding amount of the flame spray gun is 70g/min, compressed air is used as protective gas, and the pressure of the protective gas is 0.3 MPa.
Comparative example 1
In step (4), zirconium nitride was not added, and the remaining operation steps were exactly the same as in example 1.
Comparative example 2
In the step (4), no gadolinium-aluminum composite oxide powder was added, and the remaining operation steps were exactly the same as in example 2.
Comparative example 3
In the step (4), no zinc pyrovanadate hollow microsphere powder is added, and the rest of the operation steps are completely the same as those in the example 3.
The ceramic artware is prepared by the methods of the examples and the comparative examples respectively, and then the surface coating of the ceramic artware is tested for various properties, and the test results are shown in table 1:
TABLE 1 ceramic artwork Performance testing
As can be seen from table 1, the ceramic artwork prepared by the embodiment has excellent compactness of the surface coating, high surface hardness of the coating, and high bonding strength on the ceramic surface, and effectively improves the quality of the ceramic artwork.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (6)
1. The method for spraying the composite copper powder on the surface of the ceramic artwork is characterized by comprising the following operation steps of:
(1) adding 36-44 parts of aluminum powder and 10-15 parts of gadolinium powder into an activation solution, after activation treatment, centrifuging, cleaning and drying precipitates, then adding the precipitates into 380-420 parts of isopropanol, adding 0.4-0.8 part of mercury chloride, mixing and stirring uniformly, heating to 70-75 ℃ for reflux extraction for 4-5 hours, and evaporating to remove unreacted isopropanol to obtain gadolinium aluminum bimetallic alkoxide, wherein the activation solution is prepared from the following components in parts by weight: 14-18 parts of sodium methallyl sulfonate, 5-9 parts of sodium molybdate dihydrate, 1-3 parts of citric acid, 2-4 parts of N-octyl diamino ethyl glycine hydrochloride and 500 parts of water 450-containing agents;
(2) calcining gadolinium-aluminum bimetallic alkoxide to obtain gadolinium-aluminum composite oxide powder;
(3) uniformly mixing 14-19 parts of zinc oxide, 28-33 parts of vanadium oxide, 1-5 parts of ethylene diamine tetraacetic acid, 4-8 parts of behenamide and 600 parts of 550-ion water in parts by weight, heating the mixture to 165-ion 175 ℃, carrying out hydrothermal heat preservation reaction for 6-8 hours, washing and drying the product to obtain pyro-vanadic acid zinc hollow microsphere powder;
(4) adding 44-50 parts by weight of brass powder, 8-12 parts by weight of iron powder, 1-3 parts by weight of zirconium nitride, 7-10 parts by weight of gadolinium-aluminum composite oxide powder and 5-10 parts by weight of zinc pyrovanadate hollow microsphere powder into a ball mill, carrying out ball milling treatment, adopting polyvinyl alcohol for agglomeration, drying and crushing to obtain composite copper powder;
(5) and spraying the prepared composite copper powder on the surface of the cleaned ceramic artwork by adopting flame spraying equipment, wherein the thickness of the coating is 0.5-0.7mm, and then, polishing and flattening by adopting a grinding wheel to obtain a finished product.
2. The method for spraying the composite copper powder on the surface of the ceramic artwork according to claim 1, wherein the temperature during the evaporation treatment in the step (1) is 88-92 ℃.
3. The method for spraying the composite copper powder on the surface of the ceramic artwork as claimed in claim 1, wherein in the step (2), the temperature for the calcination treatment is 1100-1200 ℃, and the calcination treatment time is 2-3 hours.
4. The method for spraying the composite copper powder on the surface of the ceramic artwork according to claim 1, wherein in the step (4), the specific operation of the polyvinyl alcohol agglomeration treatment is as follows: adding polyvinyl alcohol into water with the weight 5 times of that of the polyvinyl alcohol to obtain a polyvinyl alcohol solution, then adding the polyvinyl alcohol solution with the weight 1.5 times of that of the ball-milled material, and mixing and stirring uniformly.
5. The method for spraying the composite copper powder on the surface of the ceramic artwork according to claim 1, wherein in the step (4), the drying temperature is 80 ℃, the drying time is 5 hours, and the composite copper powder has an average particle size of 500 meshes after the crushing treatment.
6. The method for spraying the composite copper powder on the surface of the ceramic artwork as claimed in claim 1, wherein in the step (5), during the flame spraying treatment, the spraying distance is 150-200mm, the powder delivery amount of the flame spray gun is 50-70g/min, compressed air is used as protective gas, and the pressure of the protective gas is 0.3 MPa.
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