CN110370848B - Method for sintering transparent enamel on surface of copper wire and copper tire for manufacturing cloisonne enamel - Google Patents
Method for sintering transparent enamel on surface of copper wire and copper tire for manufacturing cloisonne enamel Download PDFInfo
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- CN110370848B CN110370848B CN201910663655.XA CN201910663655A CN110370848B CN 110370848 B CN110370848 B CN 110370848B CN 201910663655 A CN201910663655 A CN 201910663655A CN 110370848 B CN110370848 B CN 110370848B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
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Abstract
The invention discloses a method for sintering transparent enamel on the surfaces of copper blanks and copper wires for manufacturing cloisonne enamel, which is characterized in that two technical measures are added on the basis of the prior art, firstly, the surfaces of the copper blanks are respectively cleaned and passivated before the enamel is sintered, and the measures effectively remove residual organic matters on the surfaces of the copper blanks and avoid the generation of trace carbon on the surfaces in the process of sintering the enamel. And secondly, sintering under the protection of inert gas to avoid the formation of an oxide layer on the surface of the copper tire. The two technical measures are simple, convenient and effective, the transparent bottom enamel can be obtained on the surface of the copper tire, and the technical effect is similar to that of the gold and silver tire. In addition, the technical measure has low requirement on supporting facilities, is easy to implement and has little accretion production cost. The method has the advantages of standard process, reasonable path, strong operability and stable quality of the obtained product, and is particularly suitable for batch production.
Description
Technical Field
The invention belongs to a technical scheme in the technical field of handicraft manufacturing, and particularly relates to a manufacturing method of external enamel of cloisonne enamel ornaments, in particular to a method for sintering transparent enamel on copper blanks and copper wire surfaces for manufacturing cloisonne.
Background
The cloisonne ornaments are one of the unique traditional handicraft articles in China, and the production technology integrating art, material science, chemical engineering and mechanical technology has higher technological content, so the manufacturing method of the cloisonne ornaments belongs to the national protected non-material cultural heritage. The core technology for manufacturing cloisonne ornaments is mainly embodied in glaze preparation and sintering processes. In reality, it is known to those skilled in the art that the quality of the obtained products varies greatly by applying the same glaze and sintering process to different types of tires. For example, a visually pleasing transparent enamel is readily available on gold or silver bodies, whereas an opaque enamel is obtained on copper bodies. It is well known that the honeysuckle embryo is expensive and is not a commodity which can be consumed by the public. In reality, the green tire for manufacturing cloisonne ornaments is preferably made of copper. Under the conditions of the prior art, the enamel sintered on the copper blank has the biggest defect of non-transparency, and transparent enamel cannot be obtained even if high-quality glaze is selected. The reason for this is that the surface layer of the copper body is easily oxidized during sintering, and a black oxide layer is formed at the joint of the glaze and the copper body. The objective black oxide layer becomes a background layer of the transparent enamel, and a shielding effect is naturally formed in the structure, so that shading and metallic luster of patterns engraved on the surface of the built-in copper tire cannot be normally penetrated out, and the enamel layer at the bottom layer is inevitably dull and dull, so that the visual effect of the external enamel of the cloisonne ornament is greatly reduced.
Disclosure of Invention
The invention mainly aims at the defect that a black oxide layer is easily generated at the joint of a copper blank and a copper blank in the process of sintering a ground glaze material in the prior art, and provides a method for sintering transparent enamel on the surfaces of the copper blank and the copper wire for manufacturing cloisonne.
The invention achieves the technical aim through the following technical scheme.
The improvement of the method for sintering transparent enamel on the surfaces of copper tire and copper wire for manufacturing cloisonne enamel is as follows: the method comprises the following steps: 1.1, placing the selected copper tire with engraved pattern and shading on the surface into a weak alkaline degreasing agent for soaking for at least 10min, fishing out after chemical degreasing, and brushing a soft copper wire as a mechanical cleaning surface layer; 1.2, cleaning the copper tire at least twice by using clean water, draining, and drying for at least 15min at the temperature of 40-50 ℃;
1.3 wire inlay operation according to the design pattern;
1.4 the wires arranged in place are stuck to the outer wall of the copper tire by using an adhesive;
1.5, uniformly spraying seaweed glue at the joint of the wire inlay and the copper matrix, and spraying the soldering flux on the seaweed glue;
1.6, feeding the copper tire subjected to wire inlaying treatment into a furnace, and heating at the furnace temperature of 930-950 ℃ for 2-5 min to fuse the wires with the outer wall of the copper tire;
1.7 taking out the copper tire from the furnace, and cooling to normal temperature under natural conditions;
1.8 polishing residual soldering flux on the surface of the welding wire on the copper tire;
1.9, then, placing the copper tire with the surface used as the welding wire into an acid solution to soak for at least 5 hours;
1.10 fishing out the copper tire, and mechanically removing impurities by using a soft copper wire brush;
1.11, cleaning the surface of the copper tire at least twice by using clear water, draining, and drying for at least 15min at the temperature of 40-50 ℃;
1.12 soaking the cleaned copper tire in a passivation solution for 30-60 seconds;
taking out at 1.13 times, cleaning the surface of the copper tire at least twice by using clear water, and drying for at least 15min at 40-50 ℃ after draining;
1.14 preparing a bottom glaze material, adding the selected copper white transparent glaze material into an agate grinding bowl, adding deionized water for grinding for 4-6 min, rinsing with the deionized water until no white slurry exists, filtering water, putting the cleaned copper white transparent glaze material into a glassware, sending the glassware into a drying oven at 90-110 ℃ for at least drying for 2h, and then still putting the glassware in the drying oven for later use;
1.15 spraying seaweed glue on the outer wall of the passivated copper tire to be used as enamel;
1.16 selecting a 100-120-mesh sieve, and screening the dried copper white transparent glaze at the position where the seaweed glue is sprayed on the outer wall of the copper tire, wherein the natural stacking thickness is 1.2-1.8 mm;
1.17 spraying seaweed glue on the screened copper white transparent enamel raw material, and then sending the copper white transparent enamel raw material into a drying oven at 50-60 ℃ for at least 1 h;
1.18, sending the copper blank treated in the previous step into an enamel furnace for sintering, and sintering the middle-sole glaze into transparent enamel at the furnace temperature of 780-790 ℃ before heating after vacuumizing a hearth and injecting inert gas;
1.19 taking out the cloisonne semi-finished product from the enamel furnace, brushing and coating the oxidized black skin generated at the part which is not covered by the ground glaze material by using a soft copper wire after natural cooling, and finishing the processing of manufacturing the bottom transparent enamel on the surface of the copper base.
As a further improvement scheme, the adhesive is in the form of glue and is prepared by blending natural bletilla striata ground powder and deionized water, wherein the content of the bletilla striata ground powder is 40% -60%, and the balance is the deionized water.
As a further improvement scheme, the soldering flux is prepared from red copper welding flux and borax, wherein the weight ratio of the red copper welding flux to the borax is 1: 1.3 to 1.7.
As a further improvement scheme, the seaweed glue is prepared by blending seaweed glue and deionized water, wherein the weight ratio of the seaweed glue to the deionized water is 1: 8 to 12.
As a further improvement scheme, the acid solution contains 72-78% of phosphoric acid, 12-18% of nitric acid and 8-12% of glacial acetic acid by mass percentage.
As a further improvement scheme, the passivation solution is prepared by adding 135-165 g of potassium dichromate solution into 8-12% of dilute sulfuric acid/L and mixing.
As a further improvement, the inert gas comprises nitrogen and argon.
Compared with the prior art, the invention has the following positive effects:
1. the cleaning and passivating procedures are added before enamel is sintered on the surface of the copper tire, so that the method is simple and convenient, the requirement on matched facilities is low, the implementation is easy, and the accretion production cost is low;
2. in order to improve the quality of the bottom enamel sintered on the surface of the copper blank and strictly control the sintering temperature and environment, the sintering method under the clean environment effectively avoids the generation of a black oxide layer on the junction surface of the copper blank and the enamel, and ensures that the whole body of the sintered bottom enamel is transparent;
3. because the enamel at the bottom layer is transparent, the pattern shading engraved on the surface of the built-in copper tire and the copper luster are naturally refracted outwards, the cloisonne product shows more pearly luster.
Detailed Description
The present invention will be further described with reference to the following examples.
The method for sintering transparent enamel on the surfaces of copper blanks and copper wires for manufacturing cloisonne enamel is implemented according to the following steps:
1.1 selecting a copper tire with engraved pattern shading on the surface according to the cloisonne ornaments to be manufactured, placing the copper tire into a weak alkaline degreasing agent for soaking for at least 10min, fishing out after chemical degreasing, and using a soft copper wire brush for mechanically cleaning a surface layer;
1.2, cleaning the copper tire with clear water for three times, draining, then sending the copper tire into a low-temperature oven, and drying for 20min at the temperature of 45 +/-2 ℃;
1.3 wire inlay operation according to the design pattern;
1.4 wire inlay arranged in place is adhered to the outer wall of a copper tire by using an adhesive, the adhesive used in the embodiment is in a glue shape and is prepared by blending natural bletilla striata milled powder and deionized water, wherein the milled powder comprises 60% of bletilla striata milled powder and 40% of deionized water by mass percent;
1.5 inlaying the silk and copper child junction evenly spraying marine alga glue, the scaling powder is spilt on the marine alga glue, and the marine alga glue that this embodiment used is harmonious by marine alga glue and deionized water and is formed, and the weight ratio of marine alga glue and deionized water is 1: 10; the scaling powder is prepared by mixing commercial red copper welding flux and borax, and the proportion of the red copper welding flux to the borax is 1: 1.5;
1.6, feeding the copper tire subjected to wire inlay treatment into a furnace, and heating at the furnace temperature of 940 +/-5 ℃ for 3min to fuse the wire inlay with the outer wall of the copper tire;
1.7 taking out the copper tire from the furnace, and cooling to normal temperature under natural conditions;
1.8 polishing residual soldering flux on the surface of the welding wire on the copper tire;
1.9 soaking the copper base with the surface used as the welding wire in an acid solution for 6 hours, wherein the acid solution used in the embodiment contains 75% of phosphoric acid, 15% of nitric acid and 10% of glacial acetic acid;
1.10 fishing out the copper tire, and mechanically removing impurities by using a soft copper wire brush;
1.11, cleaning the surface of the copper tire for three times by using clear water, draining, and drying for 20min at the temperature of 45 +/-2 ℃;
1.12 soaking the cleaned copper tire in a passivation solution for 40-45S, wherein the passivation solution used in the embodiment is prepared by adding 150g of potassium dichromate solution into 10% dilute sulfuric acid/L and mixing;
taking out at 1.13 times, cleaning the surface of the copper tire with clear water for three times, and drying for 20min at the temperature of 45 +/-2 ℃ after draining;
1.14 preparing a bottom glaze material, adding the selected copper white transparent glaze material into an agate grinding bowl, adding deionized water for grinding for 5min, rinsing with the deionized water until no white slurry exists, filtering water, putting the cleaned enamel raw material into a glassware, namely, putting the glassware into an oven, drying for 2h at the temperature of 100 ℃, and then still putting the enamel raw material into the oven for later use;
1.15 spraying seaweed glue on the outer wall of the passivated copper tire to be used as enamel;
1.16 selecting a 100-mesh sieve, and screening the dried copper white transparent glaze material at the position where the seaweed glue is sprayed on the outer wall of the copper tire, wherein the natural stacking thickness is 1.5 +/-0.1 mm;
1.17 spraying seaweed glue on the screened copper white transparent glaze, and then sending the copper white transparent glaze into a drying oven at 55 +/-2 ℃ for at least 1 h;
1.18 sending the copper blank processed in the previous step into an enamel furnace for sintering, before heating, after vacuumizing a hearth and injecting inert gas, sintering the copper blank into transparent enamel at the furnace temperature of 785 +/-3 ℃, wherein the inert gas used in the embodiment is nitrogen;
1.19 taking out the cloisonne semi-finished product from the enamel furnace, brushing and coating the oxidized black skin generated at the part which is not covered by the ground glaze material by using a soft copper wire after natural cooling, and finishing the processing of manufacturing the bottom transparent enamel on the surface of the copper base.
If the pattern of the cloisonne ornaments to be manufactured is multicolor, corresponding surface enamel raw materials can be selected according to different colors, and then the process is carried out according to 1.14 to 1.19, so that the cloisonne ornaments with the multicolor transparent enamel patterns are obtained on the basis of the bottom transparent enamel.
The invention is mainly to improve the transparency of the bottom enamel sintered on the surface of the copper blank, and two technical measures are added on the basis of the prior art, firstly, the surface of the copper blank is respectively cleaned and passivated before the enamel is sintered, and the measures effectively remove the residual organic matters on the surface of the copper blank and avoid the generation of trace carbon on the surface in the enamel sintering process. And secondly, sintering the copper tire under the protection of inert gas to avoid an oxide layer from being generated on the surface of the copper tire. The two measures are simple and effective, transparent bottom enamel can be obtained on the surface of the copper tire, and the technical effect is similar to that of a gold or silver tire. In addition, the technical measure has low requirement on matched design, is easy to implement and has little increased production cost.
Claims (7)
1. A method for sintering transparent enamel on the surfaces of copper tire and copper wire for manufacturing cloisonne enamel is characterized by comprising the following steps: the method comprises the following steps:
1.1, placing the selected copper tire with engraved pattern and shading on the surface into a weak alkaline degreasing agent for soaking for at least 10min, fishing out after chemical degreasing, and brushing a soft copper wire as a mechanical cleaning surface layer;
1.2, cleaning the copper tire at least twice by using clean water, draining, and drying for at least 15min at the temperature of 40-50 ℃;
1.3 wire inlay operation according to the design pattern;
1.4 the wires arranged in place are stuck to the outer wall of the copper tire by using an adhesive;
1.5, uniformly spraying seaweed glue at the joint of the wire inlay and the copper matrix, and spraying the soldering flux on the seaweed glue;
1.6, feeding the copper tire subjected to wire inlaying treatment into a furnace, and heating at the furnace temperature of 930-950 ℃ for 2-5 min to fuse the wires with the outer wall of the copper tire;
1.7 taking out the copper tire from the furnace, and cooling to normal temperature under natural conditions;
1.8 polishing residual soldering flux on the surface of the welding wire on the copper tire;
1.9, then, placing the copper tire with the surface used as the welding wire into an acid solution to soak for at least 5 hours;
1.10 fishing out the copper tire, and mechanically removing impurities by using a soft copper wire brush;
1.11, cleaning the surface of the copper tire at least twice by using clear water, draining, and drying for at least 15min at the temperature of 40-50 ℃;
1.12 soaking the cleaned copper tire in a passivation solution for 30-60 seconds;
taking out at 1.13 times, cleaning the surface of the copper tire at least twice by using clear water, and drying for at least 15min at 40-50 ℃ after draining;
1.14 preparing a bottom glaze material, adding the selected copper white transparent glaze material into an agate grinding bowl, adding deionized water for grinding for 4-6 min, rinsing with the deionized water until no white slurry exists, filtering water, putting the cleaned copper white transparent glaze material into a glassware, sending the glassware into a drying oven at 90-110 ℃ for at least drying for 2h, and then still putting the glassware in the drying oven for later use;
1.15 spraying seaweed glue on the outer wall of the passivated copper tire to be used as enamel;
1.16 selecting a 100-120-mesh sieve, and screening the dried copper white transparent glaze at the position where the seaweed glue is sprayed on the outer wall of the copper tire, wherein the natural stacking thickness is 1.2-1.8 mm;
1.17 spraying seaweed glue on the screened copper white transparent glaze, and then sending the copper white transparent glaze into a drying oven at 50-60 ℃ for at least 1 h;
1.18, sending the copper blank treated in the previous step into an enamel furnace for sintering, and sintering the middle-sole glaze into transparent enamel at the furnace temperature of 780-790 ℃ before heating after vacuumizing a hearth and injecting inert gas;
1.19 taking out the cloisonne semi-finished product from the enamel furnace, naturally cooling, and brushing off oxidized black skin generated at the part which is not covered by the ground glaze by using a soft copper wire to finish the processing of manufacturing the bottom transparent enamel on the surface of the copper base.
2. The method for sintering transparent enamel on the surface of copper tyre and copper wire for manufacturing cloisonne according to claim 1, characterized in that: the adhesive is in the shape of glue and is prepared by blending natural bletilla striata milled powder and deionized water, wherein the content of the bletilla striata milled powder is 40-60% by mass, and the balance is the deionized water.
3. The method for sintering transparent enamel on the surface of copper tyre and copper wire for manufacturing cloisonne according to claim 1, characterized in that: the soldering flux is prepared from red copper welding flux and borax, wherein the weight ratio of the red copper welding flux to the borax is 1: 1.3 to 1.7.
4. The method for sintering transparent enamel on the surface of copper tyre and copper wire for manufacturing cloisonne according to claim 1, characterized in that: the seaweed glue is prepared by mixing seaweed glue and deionized water, wherein the weight ratio of the seaweed glue to the deionized water is 1: 8 to 12.
5. The method for sintering transparent enamel on the surface of copper tyre and copper wire for manufacturing cloisonne according to claim 1, characterized in that: the acid solution contains 72-78% of phosphoric acid, 12-18% of nitric acid and 8-12% of glacial acetic acid by mass percentage.
6. The method for sintering transparent enamel on the surface of copper tyre and copper wire for manufacturing cloisonne according to claim 1, characterized in that: the passivation solution is prepared by adding 135-165 g of potassium dichromate solution into 8-12% of dilute sulfuric acid/L and mixing.
7. The method for sintering transparent enamel on the surface of copper tyre and copper wire for manufacturing cloisonne according to claim 1, characterized in that: the inert gas includes nitrogen and argon.
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| CN115323376B (en) * | 2022-08-10 | 2023-08-01 | 上海海事大学 | Enamel processing method using copper-clad oxide layer |
| CN115716381B (en) * | 2022-12-08 | 2024-04-09 | 深圳市宝瑞莱珠宝首饰有限公司 | Gold and enamel combined processing technology for improving ornament strength |
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| GB165200A (en) * | 1920-03-22 | 1921-06-22 | Charles Elwin Leheup | An improved method of producing decorative surfaces on india-rubber goods |
| GB2050944A (en) * | 1979-05-23 | 1981-01-14 | Ramsden & Co Ltd C E | Decorating method |
| JPS58185771A (en) * | 1983-01-18 | 1983-10-29 | Daiei:Kk | Formation of cloisonne on tool for table use |
| CN86105688A (en) * | 1986-07-29 | 1988-02-10 | 谢天生 | Metal handicraft and preparation method thereof |
| CN1045369A (en) * | 1989-03-06 | 1990-09-19 | 齐向春 | Cloisonne ' products and manufacture method |
| FR2889485B1 (en) * | 2005-08-02 | 2007-10-05 | Lotoise Evaporation Soc Par Ac | PROCESS FOR DECORATING A TRANSPARENT OR TRANSLUCENT CONTAINER |
| CN102002695B (en) * | 2010-12-20 | 2013-01-30 | 江西理工大学 | Brass surface passivation solution and passivation method |
| CN103624863B (en) * | 2013-12-05 | 2016-09-21 | 赵爱民 | Welding agent in the gold tire melting welding cloisonne ' products that wires inlay and the manufacture method of cloisonne ' products |
| CN105087997B (en) * | 2015-08-07 | 2019-07-23 | 广州番禺职业技术学院 | A kind of red billon and preparation method thereof for firing temperature resistant transparent enamel |
| CN105063409B (en) * | 2015-08-17 | 2017-01-11 | 广州番禺职业技术学院 | Silver alloy and method for preparing high-temperature transparent enamel decorating silver jewelry by using silver alloy |
| CN106240217A (en) * | 2016-08-26 | 2016-12-21 | 河南梦祥纯银制品有限公司 | A kind of thread weaving enamel silverware and preparation method thereof |
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