CN101736342A - Method for plating metal on surface of flower - Google Patents
Method for plating metal on surface of flower Download PDFInfo
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- CN101736342A CN101736342A CN201010013612A CN201010013612A CN101736342A CN 101736342 A CN101736342 A CN 101736342A CN 201010013612 A CN201010013612 A CN 201010013612A CN 201010013612 A CN201010013612 A CN 201010013612A CN 101736342 A CN101736342 A CN 101736342A
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Abstract
The invention relates to a method for plating a metal on the surface of a flower. The method comprises the following processes: cleaning the flower, coarsening the cleaned flower, applying polymethacrylate to the surface of the coarsened flower, plasticizing the flower of which the surface is applied with the polymethacrylate, ammonolyzing the plasticized flower, adsorbing copper and reducing; electroplating copper on the flower, and plating the metal on the electroplated flower; and solution of polymethacrylate used in the step for applying the polymethacrylate on the surface of the flower is prepared by stirring and heating 0.03 mass part of zaodiisobutyronitrile and 50 mass parts of polymethacrylate to 80 DEG C, preserving the heat and performing reaction until the system viscosity is between 600 and 1,600 MPa, adding 0.3 mass part of stearic acid, and cooling the mixture in an ice bath to obtain the solution of polymethacrylate. The method avoids using noble metals such as Ag and the like, is beneficial to uniform coating after surface plasticization and prevents factors such as burrs on petals and the like from affecting the coating. The method has the advantages of more convenient process and lower cost.
Description
Technical field
The present invention relates to the electroplating technology field, concretely, relate to a kind of method of flowers plating metal on surface.
Background technology
Chinese patent is announced CN1212425C number and CN1157502C number, all disclose a kind of method at the flowers plating metal on surface, concrete technology is: clean → roughening treatment → sensitization processing → activation treatment → reduction processing → electroless copper → electro-coppering → metallizing.
The product that comes out according to this explained hereafter has had sale on market, majority is gold-plated and silver-colored on tough and tensile on the spot vein and flower, the coating of vein is comparatively even, and it is extremely inhomogeneous as the coating of flowers jagged on the petals such as rose, there is thicker coating at the petal edge, major cause is jagged on the petals of these flowers, and copper electroplating layer is difficult to form coating comparatively uniformly, the metallizing process after being unfavorable for behind the electroless copper.And this method adopts your valency metal such as Ag, and production cost is higher.
Therefore, be necessary to study a kind of method of novel flower plating metal on surface, to solve the problems of the technologies described above.
Summary of the invention
The method that the purpose of this invention is to provide a kind of flowers plating metal on surface, this method do not adopt your valency metal such as Ag with reduce production costs and coating even.
To achieve these goals, the operation of a kind of flowers surface gold-plating of the present invention method is:
1) clean: at 30-50 ℃ 40-60 minute clean carried out on the flowers surface with suds, take out with clear water and soaked 30 minutes, put into volumetric concentration then and be 75% alcohol and soaked 30 minutes;
2) roughening treatment: cleaned flowers were handled 5 minutes with the coarsening solution room temperature;
3) surface applies the processing of polymethyl methyl esters: with the flowers 0.5-1h after the polymethyl methyl ester solution immersion roughening treatment of preformulation;
4) plasticizing: the surface is applied flowers behind the polymethyl methyl esters 50-80 ℃ of plasticizing 5 hours;
5) ammonia is separated: the hydrazine hydrate solution that to put into 50-80 ℃ of mass concentration be 20-80% of the flowers after the plasticizing was soaked 5-10 hour;
6) absorbing copper-reduction is handled: ammonia is separated flowers later put into 30g/L copper-bath immersion 0.5 hour, put into mass concentration after drying again and be 20% hydrazine hydrate solution and soak 0.5h, above process repeats 3 to 5 times, till the even reddish black coating of surface coverage one deck;
7) electro-coppering: use the acidic copper-plating of bright aqueous solution at 20-40 ℃ to the flowers after the step 6) processing, 0.5-1.5A/dm
2The cathode current density condition under the acidic copper-plating of bright that carried out 20-30 minute handle;
8) metallizing: be that 4.8-5.6, cathode current density are 0.05-0.1A/dm with acid electroplating Jinsui River solution at 20-30 ℃, pH value at last
2Conditionality carry out the acid electroplating gold;
Described polymethyl methyl ester solution is prepared according to following method:
By mass parts, 0.03 part of Diisopropyl azodicarboxylate and 50 parts of methyl-propyl olefin(e) acid methyl esters are heated with stirring to 80 ℃, insulation reaction adds 0.3 part of stearic acid again to system viscosity 600mPa-1600mPa, and the ice bath cooling promptly gets the polymethyl methyl ester solution.
To achieve these goals, a kind of flowers surface gold-plating of the present invention method can also adopt following operation to be:
1) clean: at 30-50 ℃ 40-60 minute clean carried out on the flowers surface with suds, take out with clear water and soaked 30 minutes, put into volumetric concentration then and be 75% alcohol and soaked 30 minutes;
2) roughening treatment: cleaned flowers were handled 5 minutes with the coarsening solution room temperature;
3) surface applies the processing of polymethyl methyl esters: with the flowers 0.5-1h after the polymethyl methyl ester solution immersion roughening treatment of preformulation;
4) plasticizing: the surface is applied flowers behind the polymethyl methyl esters 50-80 ℃ of plasticizing 5 hours;
5) ammonia is separated: the hydrazine hydrate solution that to put into 50-80 ℃ of mass concentration be 20-80% of the flowers after the plasticizing was soaked 5-10 hour;
6) absorbing copper-reduction is handled: ammonia is separated flowers later put into 30g/L copper-bath immersion 0.5 hour, put into mass concentration after drying again and be 20% hydrazine hydrate solution and soak 0.5h, above process repeats 3 to 5 times, till the even reddish black coating of surface coverage one deck;
7) electro-coppering: use the acidic copper-plating of bright aqueous solution at 20-40 ℃ to the flowers after the step 6) processing, 0.5-1.5A/dm
2The cathode current density condition under the acidic copper-plating of bright that carried out 20-30 minute handle;
8) non-cyanide imitating gold electroplating: use the Cyanida free imitative electrogilding solution that configures at 30 ℃, pH value 8.5-8.8, cathode current density 1.0A/dm
2, it is non-cyanide imitating gold electroplating under 20 times/minute the condition that negative electrode moves;
9) Passivation Treatment: with the passivating solution passivation 1h in the time of 25 ℃ for preparing;
10) smear protective membrane: under 60 ℃, smeared protective membrane 30 minutes with the protective layer liquid that configures;
Described polymethyl methyl ester solution is prepared according to following method:
By mass parts, 0.03 part of Diisopropyl azodicarboxylate and 50 parts of methyl-propyl olefin(e) acid methyl esters are heated with stirring to 80 ℃, insulation reaction adds 0.3 part of stearic acid again to system viscosity 600mPa-1600mPa, and the ice bath cooling promptly gets the polymethyl methyl ester solution.
Compared with prior art, the present invention has the following advantages: this method avoids using your valency metal such as Ag, help after the surface plasticizing coating evenly, avoided of the influence of factor such as burr on the petal to coating, this kind method course of processing is more convenient, cost is lower; Some quality softish leaves can not only make coating even with this invention, also have moulding effect.
Embodiment
The specific embodiment preferable below in conjunction with the present invention is described in further detail the present invention.
Embodiment 1
The concrete steps of the method for flowers plating metal on surface of the present invention are as follows:
1) clean: at 30 ℃ 60 minutes clean are carried out on the flowers surface with suds, take out with clear water and soaked 30 minutes, put into volumetric concentration then and be 75% alcohol and soaked 30 minutes;
2) roughening treatment: cleaned flowers were handled 5 minutes with preparation coarsening solution room temperature;
3) surface applies polymethyl methyl esters (PMMA) processing: with the flowers 0.5h after the polymethyl methyl ester solution immersion roughening treatment of preformulation;
4) plasticizing: the surface is applied flowers behind the polymethyl methyl esters 50 ℃ of plasticizings 5 hours;
5) ammonia is separated: it is that 80% hydrazine hydrate solution soaked 10 hours that the flowers after the plasticizing are put into 50 ℃ mass concentration;
6) absorbing copper-reduction is handled: ammonia is separated flowers later put into 30g/L copper-bath immersion 0.5 hour, put into mass concentration after drying again and be 20% hydrazine hydrate solution and soak 0.5h, above process repeats 3 to 5 times, till the even reddish black coating of surface coverage one deck;
7) electro-coppering: use the acidic copper-plating of bright aqueous solution at 20 ℃ to the flowers after the step 6) processing, 0.5A/dm
2The cathode current density condition under the acidic copper-plating of bright that carried out 30 minutes handle;
8) metallizing: be that 4.8-5.6, cathode current density are 0.05A/dm with acid electroplating Jinsui River solution at 20 ℃, pH value at last
2Conditionality carry out the acid electroplating gold, finish gold-plated operation carried out on the flowers surface.
Embodiment 2
The concrete steps of the method for flowers plating metal on surface of the present invention are as follows:
1) clean: at 40 ℃ 55 minutes clean are carried out on the flowers surface with suds, take out with clear water and soaked 30 minutes, put into volumetric concentration then and be 75% alcohol and soaked 30 minutes;
2) roughening treatment: cleaned flowers were handled 5 minutes with preparation coarsening solution room temperature;
3) surface applies polymethyl methyl esters (PMMA) processing: with the flowers 0.8h after the polymethyl methyl ester solution immersion roughening treatment of preformulation;
4) plasticizing: the surface is applied flowers behind the polymethyl methyl esters 60 ℃ of plasticizings 5 hours;
5) ammonia is separated: it is that 50% hydrazine hydrate solution soaked 7 hours that the flowers after the plasticizing are put into 65 ℃ of mass concentrations;
6) absorbing copper-reduction is handled: ammonia is separated flowers later put into 30g/L copper-bath immersion 0.5 hour, put into mass concentration after drying again and be 20% hydrazine hydrate solution and soak 0.5h, above process repeats 3 to 5 times, till the even reddish black coating of surface coverage one deck;
7) electro-coppering: use the acidic copper-plating of bright aqueous solution at 32 ℃ to the flowers after the step 6) processing, 1.0A/dm
2The cathode current density condition under the acidic copper-plating of bright that carried out 24 minutes handle;
8) metallizing: be that 4.8-5.6, cathode current density are 0.08A/dm with acid electroplating Jinsui River solution at 26 ℃, pH value at last
2Conditionality carry out the acid electroplating gold, finish gold-plated operation carried out on the flowers surface.
Embodiment 3
The concrete steps of the method for flowers plating metal on surface of the present invention are as follows:
1) clean: at 50 ℃ 40 minutes clean are carried out on the flowers surface with suds, take out with clear water and soaked 30 minutes, put into volumetric concentration then and be 75% alcohol and soaked 30 minutes;
2) roughening treatment: cleaned flowers were handled 5 minutes with preparation coarsening solution room temperature;
3) surface applies polymethyl methyl esters (PMMA) processing: with the flowers 1h after the polymethyl methyl ester solution immersion roughening treatment of preformulation;
4) plasticizing: the surface is applied flowers behind the polymethyl methyl esters 80 ℃ of plasticizings 5 hours;
5) ammonia is separated: it is that the broad liquid of 20% hydrazine hydrate soaked 5 hours that the flowers after the plasticizing are put into 80 ℃ of mass concentrations;
6) absorbing copper-reduction is handled: ammonia is separated flowers later put into 30g/L copper-bath immersion 0.5 hour, put into mass concentration after drying again and be 20% hydrazine hydrate solution and soak 0.5h, above process repeats 3 to 5 times, till the even reddish black coating of surface coverage one deck;
7) electro-coppering: use the acidic copper-plating of bright aqueous solution at 40 ℃ to the flowers after the step 6) processing, 1.5A/dm
2The cathode current density condition under the acidic copper-plating of bright that carried out 30 minutes handle;
8) metallizing: be that 4.8-5.6, cathode current density are 0.1A/dm with acid electroplating Jinsui River solution at 30 ℃, pH value at last
2Conditionality carry out the acid electroplating gold, finish gold-plated operation carried out on the flowers surface.
The prescription of the employed aqueous solution is as follows respectively in the foregoing description:
1, coarsening solution is prepared by following recipe ratio:
Chromium is done 50g/L,
Vitriol oil 200ml/L.
2, polymethyl methyl ester solution preparation:
By mass parts, 0.03 part of Diisopropyl azodicarboxylate and 50 parts of methyl-propyl olefin(e) acid methyl esters are heated with stirring to 80 ℃, insulation reaction adds 0.3 part of stearic acid again to system viscosity 600mPa-1600mPa, and the ice bath cooling promptly gets the polymethyl methyl ester solution.
3, the acidic copper-plating of bright aqueous solution is prepared by following recipe ratio:
Copper sulfate 200g/L,
Sulfuric acid 30g/L,
Chlorion 50mol/L,
2-mercaptan 20mL/L.
4, the acid gold-plated aqueous solution is prepared by following recipe ratio:
Potassium auric chloride 8g/L,
Ammonium citrate 120g/L,
Citric acid 75g/L,
Antimonypotassium tartrate 0.3g/L.
The step that metallizing step among the present invention also can adopt non-cyanide imitating gold electroplating, Passivation Treatment and smear protective membrane, concrete steps are as follows:
A) non-cyanide imitating gold electroplating: use the Cyanida free imitative electrogilding solution that configures at 30 ℃, pH value 8.5-8.8, cathode current density 1.0A/dm
2, it is non-cyanide imitating gold electroplating under 20 times/minute the condition that negative electrode moves;
B) Passivation Treatment: with the passivating solution passivation 1h in the time of 25 ℃ for preparing;
C) smear protective membrane: under 60 ℃, smeared protective membrane 30 minutes with the protective layer liquid that configures.
Above-mentioned Cyanida free imitative electrogilding solution is prepared by following recipe ratio:
Cupric sulfate pentahydrate 45g/L,
Sulfate dihydrate zinc 15g/L,
Stannous chloride dihydrate 5g/L,
Potassium pyrophosphate 320g/L,
Seignette salt 35g/L,
Tripotassium Citrate 20g/L,
Nitrilotriacetic acid(NTA) 25g/L.
The above-mentioned passivation aqueous solution is prepared by following recipe ratio:
K
2CrO
7 40g/L，
Transfer PH 3 with acetic acid.
Above-mentioned protective layer liquid is prepared by following recipe ratio:
1 part of 115 acrylic varnish,
2 parts of ring ethyl ketones.
Before the material surface metallizing, generally need carry out roughening treatment to material surface, help the even of metal plating.Physical method is wherein arranged as polishing and chemical process such as acid corrosion.Because the special petal part of flowers quality softness is carried out comparatively difficulty of physics coarsening process to it; And petal surface is generally adhered to wax layer and villous, and this part is guaranteeing also to be difficult to removal with chemical process under the complete prerequisite of petal, and wherein fine hair has the greatest impact to coating.Tapetum is under situation about not eliminating, and chemical plating can not be formed homogeneous coating by the fine hair disjunction, is unfavorable for later plating.And electroplating process is relevant with current density, and is fast in the big metal deposition of local current density that specific surface area is big, slow in the little metal deposition of local current density that specific surface area is little.Because petal edge specific surface area is big, the metal preferential deposition, along with deposit thickness increases, resistance reduces, and electric current can increase, and current density can constantly increase along with electroplating process like this, so can cause the thin situation of the petal edge thick central authorities of coating.The present invention applies synthetic glass on the flowers surface method essence is the tapetum that covers petal surface with perspex layer, makes the surface become smooth.Because synthetic glass is the polymethyl methyl esters, be uniform-distribution with ester group on the microcosmic face, by carrying out with hydrazine hydrate after ammonia separates, ester group becomes hydrazide group, and hydrazides is a good metal-chelating group, the easy adsorbing metal ions of perspex layer after process ammonia is separated, metal ion is reduced into metal simple-substance under reducing atmosphere, and even metal is adsorbed with to be beneficial to and electroplates the coating that forms fine and close homogeneous like this.
Claims (10)
1. a flowers method for plating metal on surface is characterized in that, the operation of this flowers surface gold-plating method is:
1) clean: at 30-50 ℃ 40-60 minute clean carried out on the flowers surface with suds, take out with clear water and soaked 30 minutes, put into volumetric concentration then and be 75% alcohol and soaked 30 minutes;
2) roughening treatment: cleaned flowers were handled 5 minutes with the coarsening solution room temperature;
3) surface applies the processing of polymethyl methyl esters: with the flowers 0.5-1h after the polymethyl methyl ester solution immersion roughening treatment of preformulation;
4) plasticizing: the surface is applied flowers behind the polymethyl methyl esters 50-80 ℃ of plasticizing 5 hours;
5) ammonia is separated: the hydrazine hydrate solution that to put into 50-80 ℃ of mass concentration be 20-80% of the flowers after the plasticizing was soaked 5-10 hour;
6) absorbing copper-reduction is handled: ammonia is separated flowers later put into 30g/L copper-bath immersion 0.5 hour, put into mass concentration after drying again and be 20% hydrazine hydrate solution and soak 0.5h, above process repeats 3 to 5 times, till the even reddish black coating of surface coverage one deck;
7) electro-coppering: use the acidic copper-plating of bright aqueous solution at 20-40 ℃ to the flowers after the step 6) processing, 0.5-1.5A/dm
2The cathode current density condition under the acidic copper-plating of bright that carried out 20-30 minute handle;
8) metallizing: be that 4.8-5.6, cathode current density are 0.05-0.1A/dm with acid electroplating Jinsui River solution at 20-30 ℃, pH value at last
2Conditionality carry out the acid electroplating gold;
Described polymethyl methyl ester solution is prepared according to following method:
By mass parts, 0.03 part of Diisopropyl azodicarboxylate and 50 parts of methyl-propyl olefin(e) acid methyl esters are heated with stirring to 80 ℃, insulation reaction adds 0.3 part of stearic acid again to system viscosity 600mPa-1600mPa, and the ice bath cooling promptly gets the polymethyl methyl ester solution.
2. flowers method for plating metal on surface as claimed in claim 1, its spy just is that described coarsening solution is prepared by following recipe ratio:
Chromium is done 50g/L,
Vitriol oil 200ml/L.
3. flowers method for plating metal on surface as claimed in claim 1, its spy just is that the described acidic copper-plating of bright aqueous solution is prepared by following recipe ratio:
Copper sulfate 200g/L,
Sulfuric acid 30g/L,
Chlorion 50mol/L,
2-mercaptan 20mL/L.
4. flowers method for plating metal on surface as claimed in claim 1, its spy just is that the gold-plated aqueous solution of described acidity is prepared by following recipe ratio:
Potassium auric chloride 8g/L,
Ammonium citrate 120g/L,
Citric acid 75g/L,
Antimonypotassium tartrate 0.3g/L.
5. a flowers method for plating metal on surface is characterized in that, the operation of this flowers surface gold-plating method is:
1) clean: at 30-50 ℃ 40-60 minute clean carried out on the flowers surface with suds, take out with clear water and soaked 30 minutes, put into volumetric concentration then and be 75% alcohol and soaked 30 minutes;
2) roughening treatment: cleaned flowers were handled 5 minutes with the coarsening solution room temperature;
3) surface applies the processing of polymethyl methyl esters: with the flowers 0.5-1h after the polymethyl methyl ester solution immersion roughening treatment of preformulation;
4) plasticizing: the surface is applied flowers behind the polymethyl methyl esters 50-80 ℃ of plasticizing 5 hours;
5) ammonia is separated: the hydrazine hydrate solution that to put into 50-80 ℃ of mass concentration be 20-80% of the flowers after the plasticizing was soaked 5-10 hour;
6) absorbing copper-reduction is handled: ammonia is separated flowers later put into 30g/L copper-bath immersion 0.5 hour, put into mass concentration after drying again and be 20% hydrazine hydrate solution and soak 0.5h, above process repeats 3 to 5 times, till the even reddish black coating of surface coverage one deck;
7) electro-coppering: use the acidic copper-plating of bright aqueous solution at 20-40 ℃ to the flowers after the step 6) processing, 0.5-1.5A/dm
2The cathode current density condition under the acidic copper-plating of bright that carried out 20-30 minute handle;
8) non-cyanide imitating gold electroplating: use the Cyanida free imitative electrogilding solution that configures at 30 ℃, pH value 8.5-8.8, cathode current density 1.0A/dm
2, it is non-cyanide imitating gold electroplating under 20 times/minute the condition that negative electrode moves;
9) Passivation Treatment: with the passivating solution passivation 1h in the time of 25 ℃ for preparing;
10) smear protective membrane: under 60 ℃, smeared protective membrane 30 minutes with the protective layer liquid that configures;
Described polymethyl methyl ester solution is prepared according to following method:
By mass parts, 0.03 part of Diisopropyl azodicarboxylate and 50 parts of methyl-propyl olefin(e) acid methyl esters are heated with stirring to 80 ℃, insulation reaction adds 0.3 part of stearic acid again to system viscosity 600mPa-1600mPa, and the ice bath cooling promptly gets the polymethyl methyl ester solution.
6. flowers method for plating metal on surface as claimed in claim 5, its spy just is that described coarsening solution is prepared by following recipe ratio:
Chromium is done 50g/L,
Vitriol oil 200ml/L.
7. flowers method for plating metal on surface as claimed in claim 5, its spy just is that the described acidic copper-plating of bright aqueous solution is prepared by following recipe ratio:
Copper sulfate 200g/L,
Sulfuric acid 30g/L,
Chlorion 50mol/L,
2-mercaptan 20ml/L.
8. flowers method for plating metal on surface as claimed in claim 5, its spy just is that the gold-plated aqueous solution of described acidity is prepared by following recipe ratio:
Potassium auric chloride 8g/L,
Ammonium citrate 120g/L,
Citric acid 75g/L,
Antimonypotassium tartrate 0.3g/L.
9. flowers method for plating metal on surface as claimed in claim 5, its spy just is that described Cyanida free imitative electrogilding solution is prepared by following recipe ratio:
Cupric sulfate pentahydrate 45g/L,
Sulfate dihydrate zinc 15g/L,
Stannous chloride dihydrate 5g/L,
Potassium pyrophosphate 320g/L,
Seignette salt 35g/L,
Tripotassium Citrate 20g/L,
Nitrilotriacetic acid(NTA) 25g/L.
10. flowers method for plating metal on surface as claimed in claim 5, its spy just is that the described passivation aqueous solution is prepared by following recipe ratio:
K
2CrO
7 40g/L，
Transfer PH 3 with acetic acid;
Described protective layer liquid is prepared by following recipe ratio:
1 part of 115 acrylic varnish,
2 parts of ring ethyl ketones.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100136126A CN101736342B (en) | 2010-01-19 | 2010-01-19 | Method for plating metal on surface of flower |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100136126A CN101736342B (en) | 2010-01-19 | 2010-01-19 | Method for plating metal on surface of flower |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101736342A true CN101736342A (en) | 2010-06-16 |
| CN101736342B CN101736342B (en) | 2012-05-09 |
Family
ID=42460361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010100136126A Expired - Fee Related CN101736342B (en) | 2010-01-19 | 2010-01-19 | Method for plating metal on surface of flower |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757193A (en) * | 2016-11-24 | 2017-05-31 | 中国地质大学（武汉） | A kind of method without cyanogen acid bright copper plating of leaf |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157502C (en) * | 2000-08-24 | 2004-07-14 | 韩巍 | Gold electroplatic method for flowers |
| CN1524978A (en) * | 2003-02-26 | 2004-09-01 | 夏红元 | Electroplating method for flowers and tree leaves |
| CN1212425C (en) * | 2003-04-01 | 2005-07-27 | 中国地质大学（武汉） | Non-cyanide gold imitation electro plating method of flowers and plants |
| CN200987382Y (en) * | 2006-01-19 | 2007-12-12 | 宏江科技有限公司 | Plant flower surface electroplating structure |
| CN101361603B (en) * | 2008-10-14 | 2013-01-02 | 深圳市金龙珠宝首饰有限公司 | Living rose gold-plating production technique flow |
-
2010
- 2010-01-19 CN CN2010100136126A patent/CN101736342B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757193A (en) * | 2016-11-24 | 2017-05-31 | 中国地质大学（武汉） | A kind of method without cyanogen acid bright copper plating of leaf |
| CN106757193B (en) * | 2016-11-24 | 2018-07-13 | 中国地质大学（武汉） | A kind of method without cyanogen acid bright copper plating of leaf |
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| Publication number | Publication date |
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| CN101736342B (en) | 2012-05-09 |
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