CN103320820B - Acid bright copper plating electroplating technology - Google Patents
Acid bright copper plating electroplating technology Download PDFInfo
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- CN103320820B CN103320820B CN201310241056.1A CN201310241056A CN103320820B CN 103320820 B CN103320820 B CN 103320820B CN 201310241056 A CN201310241056 A CN 201310241056A CN 103320820 B CN103320820 B CN 103320820B
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Abstract
The present invention relates to a kind of acid bright copper plating electroplating technology, comprise the steps such as the preparation of copper plating solution, workpiece pre-treatment and acid bright copper plating.Adopt present invention process on metal base surface, the copper coating of several mm thick can be plated continuously, do not need to electroplate several times; Well, the machines such as car, milling, stretching, outer throwing that can bear add external force for plating cast copper and basal body binding force; Bath stability is good, surface uniform.
Description
Technical field
The invention belongs to electroplating technology field, be specifically related to a kind of acid bright copper plating electroplating technology.
Background technology
Acid copper-plating has current efficiency high (close to 100%), and composition is simple, can obtain the coating of entire bright, good toughness after adding brightening agent, is the most superior plating of current Surface flat, bright property.The price of metallic copper is far below metallic nickel in addition, therefore, is widely used in China.
It is well known that, the chlorion of finite concentration scope must be contained in acid copper plating solution.But it is very delicate on the impact of sour copper.Prove according to theoretical investigation, when chloride ion content is on the low side, chlorion forms surface complex electronic configuration in cathodic area and copper mainly exists with dsp2 hydridization form, and complex ion stability is excessively strong, and causes cathodic polarization value to increase, activation energy needed for bivalent cupric ion reduction raises, be unfavorable for cupric step-by-step reduction, cupric reacts directly to zerovalent copper, occurs that Surface flat is poor, coarse, the dendritic coating of coating, pin hole, the phenomenon such as even to burn.When chlorine ion concentration is too high, the electronic configuration of cathodic area surface complex mainly exists with sp3d2 type form, and cathodic polarization is too small, causes the luminance brightness of copper coating to decline, and low current density district walks variation.
At present, adopt common electroplating technology, metallic matrix plate the layers of copper of several mm thick, mainly there is following problem:
1, when coating exceedes certain thickness, in the unit time, thickness of coating increase is too slow, and the time is longer, needs to be divided into repeatedly to carry out;
2, layers of copper and metallic matrix bonding force poor, work-ing life is short, and later process needs to add man-hour, coating and Matrix separation;
3, plating solution is unstable, and coating surface there will be copper gold-plating, and outward appearance is very coarse, causes difficulty to later process processing.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of acid bright copper plating electroplating technology, and this technique overcomes coating surface unfairness, has the defect of hot tearing, and the coating of this technique plating is even, bright, and bonding force is good, and solidity to corrosion is stronger.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of acid bright copper plating electroplating technology, comprise the preparation of copper plating solution, workpiece pre-treatment and acid bright copper plating, these technique concrete steps are as follows:
(1) preparation of copper plating solution
Copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 360 ~ 440kg, and sulfuric acid is 120 ~ 180kg, and gac is 4 ~ 6kg, hydrochloric acid 100 ~ 180g, and brightening agent A is 12 ~ 16L and brightening agent B is 1.2 ~ 2L;
Specific configuration method is as follows:
A. under stirring, by copper plating solution proportioning raw materials by 2 m
3deionized water injects 3 m
3pre-groove in;
B. under stirring, in step a, add 120 ~ 180kg sulfuric acid, to control in pre-groove solution temperature between 33 ~ 37 DEG C;
C. under stirring, in step b, add 360 ~ 440kg copper sulfate, be stirred to till dissolving completely;
D. under stirring, in step c, be sprinkled into 4 ~ 6kg gac equably, stop after stirring 1 ~ 2 h, filter after solution clarification in pre-groove, filtrate is proceeded to 6 m
3plating tank in;
E. under stirring, in the filtrate in steps d plating tank, add 100 ~ 180g hydrochloric acid, regulate chloride ion content;
F. under stirring, add 12 ~ 16L brightening agent A and 1.2 ~ 2L brightening agent B in step e, stop after stirring 2 ~ 3 h, the solution obtained is copper plating solution; Described brightening agent A is hydrogen peroxide;
Described brightening agent B is mixed with by 2-mercaptobenzimidazole, sodium polydithio-dipropyl sulfonate, polyoxyethylene glycol, ethylene thiourea, sodium lauryl sulphate, hydrochloric acid and deionized water and forms, wherein, 2-mercaptobenzimidazole 0.0003 ~ 0.001g/L, sodium polydithio-dipropyl sulfonate 0.015 ~ 0.02 g/L, polyoxyethylene glycol 0.05 ~ 0.1 g/L, ethylene thiourea 0.0003 ~ 0.0008 g/L, sodium lauryl sulphate 0.05 ~ 0.1 g/L and hydrochloric acid 0.02 ~ 0.08 g/L;
(2) workpiece pre-treatment: adopt conventional alkaline copper plating technique to carry out copper pre-plating to workpiece;
(3) acid bright copper plating: put into the plating tank containing copper plating solution at the workpiece of copper pre-plating, carry out acid bright copper plating at workpiece surface to shunt workpiece simultaneously, copper plating solution temperature controls between 31 ~ 37 DEG C, and cathode current density is 1.5 ~ 6A/dm
2, anodic current density 0.5 ~ 2.5A/dm
2, electroplating time is 55 ~ 65 h.
In described step (1), copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 380 ~ 420kg, and sulfuric acid is 140 ~ 170kg, and gac is 5 ~ 6kg, hydrochloric acid 120 ~ 160g, and brightening agent A is 13 ~ 15L and brightening agent B is 1.5 ~ 1.8L.
In described step (1), copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 390 ~ 400kg, and sulfuric acid is 150 ~ 160kg, and gac is 5 ~ 5.5kg, hydrochloric acid 140 ~ 150g, and brightening agent A is 14 ~ 14.5L and brightening agent B is 1.6 ~ 1.7L.
Shunting adopted part flow arrangement to workpiece in described step (3) is specifically the wire of closed circle in plating piece hanger one side mounting lower end, and it is vertical just to workpiece that described closed circle is positioned at workpiece lower end.
Copper material selected by described wire.
the present invention has positive beneficial effect:
1., compared with common copper-plating technique, Technology Bright Acidic plating cast copper can plate the copper coating of several mm thick continuously on metal base surface, does not need to electroplate several times; Well, the machines such as car, milling, stretching, outer throwing that can bear add external force for plating cast copper and basal body binding force; Bath stability is good, surface uniform.
2. the method carries out pre-treatment to workpiece, the steps such as acid bright copper plating by adopting conventional alkaline copper plating technique, can obtain the layers of copper that light is level and smooth.Wherein acidic copper-plating of bright liquid is that add brightening agent A in the plating solution and brightening agent B gained coating is even, bright, bonding force is good, and solidity to corrosion is stronger with copper sulfate and sulfuric acid for main component.
3. the present invention is by shunting in pretreated workpiece Technology Bright Acidic electroplating process, and workpiece surface can be made smooth, and coating is even.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but do not limit content of the present invention.
Embodiment 1: a kind of acid bright copper plating electroplating technology, comprises the preparation of copper plating solution, workpiece pre-treatment and acid bright copper plating, and these technique concrete steps are as follows:
(1) preparation of copper plating solution
Copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 400kg, and sulfuric acid is 160kg, and gac is 5kg, hydrochloric acid 150g, and brightening agent A is 15L and brightening agent B is 1.6L;
Specific configuration method is as follows:
A. under stirring, by copper plating solution proportioning raw materials by 2 m
3deionized water injects 3 m
3pre-groove in;
B. under stirring, in step a, add 160kg sulfuric acid, to control in pre-groove solution temperature at 33 DEG C;
C. under stirring, in step b, add 400kg copper sulfate, be stirred to till dissolving completely;
D. under stirring, in step c, be sprinkled into 5kg gac equably, stop after stirring 2 h, filter after solution clarification in pre-groove, filtrate is proceeded to 6 m
3plating tank in;
E. under stirring, in the filtrate in steps d plating tank, add 150g hydrochloric acid, regulate chloride ion content;
F., under stirring, in step e, add 15L brightening agent A and 1.6L brightening agent B, stop after stirring 2.5 h, the solution obtained is copper plating solution; Described brightening agent A is hydrogen peroxide;
Described brightening agent B is mixed with by 2-mercaptobenzimidazole, sodium polydithio-dipropyl sulfonate, polyoxyethylene glycol, ethylene thiourea, sodium lauryl sulphate, hydrochloric acid and deionized water and forms, wherein, 2-mercaptobenzimidazole 0.0006g/L, sodium polydithio-dipropyl sulfonate 0.02 g/L, polyoxyethylene glycol 0.05g/L, ethylene thiourea 0.0005 g/L, sodium lauryl sulphate 0.07 g/L and hydrochloric acid 0.06 g/L;
(2) workpiece pre-treatment: adopt conventional alkaline copper plating technique to carry out copper pre-plating to workpiece;
(3) acid bright copper plating: put into the plating tank containing copper plating solution at the workpiece of copper pre-plating, carry out acid bright copper plating at workpiece surface to shunt workpiece simultaneously, it is specifically the copper conductor of closed circle in plating piece hanger one side mounting lower end that workpiece carries out shunting adopted part flow arrangement, it is vertical just to workpiece that described closed circle is positioned at workpiece lower end, copper plating solution temperature controls at 33 DEG C, and cathode current density is 1.5A/dm
2, anodic current density 0.5A/dm
2, electroplating time is 60 h.
The copper coating of copper coating workpiece to appearance obtained by this technique is polished, without peeling; Then workpiece is carried out quick sawing, copper coating is followed between workpiece without peeling; Finally, workpiece is carried out quick cutter milling, find that copper coating has stripping not yet with workpiece; Copper coating is good with the bonding force of workpiece.
Embodiment 2: a kind of acid bright copper plating electroplating technology, comprises the preparation of copper plating solution, workpiece pre-treatment and acid bright copper plating, and these technique concrete steps are as follows:
(1) preparation of copper plating solution
Copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 360kg, and sulfuric acid is 180kg, and gac is 6kg, hydrochloric acid 120g, and brightening agent A is 14L and brightening agent B is 1.5L;
Specific configuration method is as follows:
A. under stirring, by copper plating solution proportioning raw materials by 2 m
3deionized water injects 3 m
3pre-groove in;
B. under stirring, in step a, add 180kg sulfuric acid, to control in pre-groove solution temperature at 35 DEG C;
C. under stirring, in step b, add 360kg copper sulfate, be stirred to till dissolving completely;
D. under stirring, in step c, be sprinkled into 6kg gac equably, stop after stirring 2 h, filter after solution clarification in pre-groove, filtrate is proceeded to 6 m
3plating tank in;
E. under stirring, in the filtrate in steps d plating tank, add 120g hydrochloric acid, regulate chloride ion content;
F. under stirring, add 14L brightening agent A and 1.5L brightening agent B in step e, stir, stop after 3 h, the solution obtained is copper plating solution; Described brightening agent A is hydrogen peroxide;
Described brightening agent B is mixed with by 2-mercaptobenzimidazole, sodium polydithio-dipropyl sulfonate, polyoxyethylene glycol, ethylene thiourea, sodium lauryl sulphate, hydrochloric acid and deionized water and forms, wherein, 2-mercaptobenzimidazole 0.0003g/L, sodium polydithio-dipropyl sulfonate 0.02 g/L, polyoxyethylene glycol 0.08 g/L, ethylene thiourea 0.0007g/L, sodium lauryl sulphate 0.06 g/L and hydrochloric acid 0.04g/L;
(2) workpiece pre-treatment: adopt conventional alkaline copper plating technique to carry out copper pre-plating to workpiece;
(3) acid bright copper plating: put into the plating tank containing copper plating solution at the workpiece of copper pre-plating, carry out acid bright copper plating at workpiece surface to shunt workpiece simultaneously, it is specifically the copper conductor of closed circle in plating piece hanger one side mounting lower end that workpiece carries out shunting adopted part flow arrangement, it is vertical just to workpiece that described closed circle is positioned at workpiece lower end, copper plating solution temperature controls at 35 DEG C, and cathode current density is 3A/dm
2, anodic current density 1.5A/dm
2, electroplating time is 62 h.
The copper coating of copper coating workpiece to appearance obtained by this technique is polished, without peeling; Then workpiece is carried out quick sawing, copper coating is followed between workpiece without peeling; Finally, workpiece is carried out quick cutter milling, find that copper coating has stripping not yet with workpiece; Copper coating is good with the bonding force of workpiece.
Embodiment 3: a kind of acid bright copper plating electroplating technology, comprises the preparation of copper plating solution, workpiece pre-treatment and acid bright copper plating, and these technique concrete steps are as follows:
(1) preparation of copper plating solution
Copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 420kg, and sulfuric acid is 160kg, and gac is 5kg, hydrochloric acid 130g, and brightening agent A is 16L and brightening agent B is 1.8L;
Specific configuration method is as follows:
A. under stirring, by copper plating solution proportioning raw materials by 2 m
3deionized water injects 3 m
3pre-groove in;
B. under stirring, in step a, add 160kg sulfuric acid, to control in pre-groove solution temperature at 36 DEG C;
C. under stirring, in step b, add 420kg copper sulfate, be stirred to till dissolving completely;
D. under stirring, in step c, be sprinkled into 5kg gac equably, stop after stirring 2 h, filter after solution clarification in pre-groove, filtrate is proceeded to 6 m
3plating tank in;
E. under stirring, in the filtrate in steps d plating tank, add 130g hydrochloric acid, regulate chloride ion content;
F. under stirring, add 16L brightening agent A and 1.8L brightening agent B in step e, stop after stirring 2 ~ 3 h, the solution obtained is copper plating solution; Described brightening agent A is hydrogen peroxide;
Described brightening agent B is mixed with by 2-mercaptobenzimidazole, sodium polydithio-dipropyl sulfonate, polyoxyethylene glycol, ethylene thiourea, sodium lauryl sulphate, hydrochloric acid and deionized water and forms, wherein, 2-mercaptobenzimidazole 0.001g/L, sodium polydithio-dipropyl sulfonate 0.015 g/L, polyoxyethylene glycol 0.08g/L, ethylene thiourea 0.0007g/L, sodium lauryl sulphate 0.08 g/L and hydrochloric acid 0.05g/L;
(2) workpiece pre-treatment: adopt conventional alkaline copper plating technique to carry out copper pre-plating to workpiece;
(3) acid bright copper plating: put into the plating tank containing copper plating solution at the workpiece of copper pre-plating, carry out acid bright copper plating at workpiece surface to shunt workpiece simultaneously, it is specifically the copper conductor of closed circle in plating piece hanger one side mounting lower end that workpiece carries out shunting adopted part flow arrangement, it is vertical just to workpiece that described closed circle is positioned at workpiece lower end, copper plating solution temperature controls at 36 DEG C, and cathode current density is 5A/dm
2, anodic current density 2.5A/dm
2, electroplating time is 55h.
The copper coating of copper coating workpiece to appearance obtained by this technique is polished, without peeling; Then workpiece is carried out quick sawing, copper coating is followed between workpiece without peeling; Finally, workpiece is carried out quick cutter milling, find that copper coating has stripping not yet with workpiece; Copper coating is good with the bonding force of workpiece.
Embodiment 4: a kind of acid bright copper plating electroplating technology, comprises the preparation of copper plating solution, workpiece pre-treatment and acid bright copper plating, and these technique concrete steps are as follows:
(1) preparation of copper plating solution
Copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 360kg, and sulfuric acid is 120kg, and gac is 6kg, hydrochloric acid 120g, and brightening agent A is 12L and brightening agent B is 1.2L;
Specific configuration method is as follows:
A. under stirring, by copper plating solution proportioning raw materials by 2 m
3deionized water injects 3 m
3pre-groove in;
B. under stirring, in step a, add 120kg sulfuric acid, to control in pre-groove solution temperature between 33 DEG C;
C. under stirring, in step b, add 360kg copper sulfate, be stirred to till dissolving completely;
D. under stirring, in step c, be sprinkled into 6kg gac equably, stop after stirring 1.5h, filter after solution clarification in pre-groove, filtrate is proceeded to 6 m
3plating tank in;
E. under stirring, in the filtrate in steps d plating tank, add 120g hydrochloric acid, regulate chloride ion content;
F., under stirring, in step e, add 12 brightening agent A and 1.2 brightening agent B, stop after stirring 2.5 h, the solution obtained is copper plating solution; Described brightening agent A is hydrogen peroxide;
Described brightening agent B is mixed with by 2-mercaptobenzimidazole, sodium polydithio-dipropyl sulfonate, polyoxyethylene glycol, ethylene thiourea, sodium lauryl sulphate, hydrochloric acid and deionized water and forms, wherein, 2-mercaptobenzimidazole 0.001g/L, sodium polydithio-dipropyl sulfonate 0.015 g/L, polyoxyethylene glycol 0.09 g/L, ethylene thiourea 0.0005 g/L, sodium lauryl sulphate 0.05g/L and hydrochloric acid 0.04g/L;
(2) workpiece pre-treatment: adopt conventional alkaline copper plating technique to carry out copper pre-plating to workpiece;
(3) acid bright copper plating: put into the plating tank containing copper plating solution at the workpiece of copper pre-plating, carry out acid bright copper plating at workpiece surface to shunt workpiece simultaneously, it is specifically the copper conductor of closed circle in plating piece hanger one side mounting lower end that workpiece carries out shunting adopted part flow arrangement, it is vertical just to workpiece that described closed circle is positioned at workpiece lower end, copper plating solution temperature controls between 31 ~ 37 DEG C, and cathode current density is 5A/dm
2, anodic current density 2.5A/dm
2, electroplating time is 63 h.
The copper coating of copper coating workpiece to appearance obtained by this technique is polished, without peeling; Then workpiece is carried out quick sawing, copper coating is followed between workpiece without peeling; Finally, workpiece is carried out quick cutter milling, find that copper coating has stripping not yet with workpiece; Copper coating is good with the bonding force of workpiece.
Claims (4)
1. an acid bright copper plating electroplating technology, comprises the preparation of copper plating solution, workpiece pre-treatment and acid bright copper plating, it is characterized in that: these technique concrete steps are as follows:
(1) preparation of copper plating solution
Copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 360 ~ 440kg, and sulfuric acid is 120 ~ 180kg, and gac is 4 ~ 6kg, hydrochloric acid 100 ~ 180g, and brightening agent A is 12 ~ 16L and brightening agent B is 1.2 ~ 2L;
Specific configuration method is as follows:
A. under stirring, by copper plating solution proportioning raw materials by 2 m
3deionized water injects 3 m
3pre-groove in;
B. under stirring, in step a, add 120 ~ 180kg sulfuric acid, to control in pre-groove solution temperature between 33 ~ 37 DEG C;
C. under stirring, in step b, add 360 ~ 440kg copper sulfate, be stirred to till dissolving completely;
D. under stirring, in step c, be sprinkled into 4 ~ 6kg gac equably, stop after stirring 1 ~ 2 h, filter after solution clarification in pre-groove, filtrate is proceeded to 6 m
3plating tank in;
E. under stirring, in the filtrate in steps d plating tank, add 100 ~ 180g hydrochloric acid, regulate chloride ion content;
F. under stirring, add 12 ~ 16L brightening agent A and 1.2 ~ 2L brightening agent B in step e, stop after stirring 2 ~ 3 h, the solution obtained is copper plating solution; Described brightening agent A is hydrogen peroxide;
Described brightening agent B is mixed with by 2-mercaptobenzimidazole, sodium polydithio-dipropyl sulfonate, polyoxyethylene glycol, ethylene thiourea, sodium lauryl sulphate, hydrochloric acid and deionized water and forms, wherein, 2-mercaptobenzimidazole 0.0003 ~ 0.001g/L, sodium polydithio-dipropyl sulfonate 0.015 ~ 0.02 g/L, polyoxyethylene glycol 0.05 ~ 0.1 g/L, ethylene thiourea 0.0003 ~ 0.0008 g/L, sodium lauryl sulphate 0.05 ~ 0.1 g/L and hydrochloric acid 0.02 ~ 0.08 g/L;
(2) workpiece pre-treatment: adopt conventional alkaline copper plating technique to carry out copper pre-plating to workpiece;
(3) acid bright copper plating: put into the plating tank containing copper plating solution at the workpiece of copper pre-plating, carry out acid bright copper plating at workpiece surface to shunt workpiece simultaneously, copper plating solution temperature controls between 31 ~ 37 DEG C, and cathode current density is 1.5 ~ 6A/dm
2, anodic current density 0.5 ~ 2.5A/dm
2, electroplating time is 55 ~ 65 h; Described shunts workpiece, and the part flow arrangement adopted is specifically the wire of closed circle in plating piece hanger one side mounting lower end, and it is vertical just to workpiece that described closed circle is positioned at workpiece lower end.
2. acid bright copper plating electroplating technology according to claim 1, is characterized in that: in described step (1), copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 380 ~ 420kg, and sulfuric acid is 140 ~ 170kg, and gac is 5 ~ 6kg, hydrochloric acid 120 ~ 160g, and brightening agent A is 13 ~ 15L and brightening agent B is 1.5 ~ 1.8L.
3. acid bright copper plating electroplating technology according to claim 1, is characterized in that: in described step (1), copper plating solution proportioning raw materials is with 2 m
3deionized water be benchmark, copper sulfate is 390 ~ 400kg, and sulfuric acid is 150 ~ 160kg, and gac is 5 ~ 5.5kg, hydrochloric acid 140 ~ 150g, and brightening agent A is 14 ~ 14.5L and brightening agent B is 1.6 ~ 1.7L.
4. acid bright copper plating electroplating technology according to claim 1, is characterized in that: copper material selected by described wire.
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|---|---|---|---|
| CN201310241056.1A CN103320820B (en) | 2013-06-18 | 2013-06-18 | Acid bright copper plating electroplating technology |
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|---|---|---|---|
| CN201310241056.1A CN103320820B (en) | 2013-06-18 | 2013-06-18 | Acid bright copper plating electroplating technology |
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| CN103320820B true CN103320820B (en) | 2015-08-19 |
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| CN103469260A (en) * | 2013-09-27 | 2013-12-25 | 昆山纯柏精密五金有限公司 | Acid copper plating method of hardware |
| CN103911635B (en) * | 2014-03-21 | 2016-02-24 | 复旦大学 | A kind of copper electroplating solution |
| CN103866358B (en) * | 2014-03-24 | 2016-07-13 | 无锡宝顺不锈钢有限公司 | Rustless steel copper coating |
| CN103981553A (en) * | 2014-05-27 | 2014-08-13 | 深圳市欧比纳科技有限公司 | High-temperature-resistant copper sulfate brightener and application method thereof |
| CN104264194A (en) * | 2014-10-13 | 2015-01-07 | 无锡长辉机电科技有限公司 | Preparation method of acid copper plating bath |
| CN105220186A (en) * | 2015-11-03 | 2016-01-06 | 江苏梦得电镀化学品有限公司 | A kind of high bright levelling dye-type acid plating solution electroplating technology |
| CN105921706B (en) * | 2016-05-19 | 2018-03-20 | 西峡龙成特种材料有限公司 | A kind of online restorative procedure of continuous casting crystallizer copper plate |
| CN106367782B (en) * | 2016-08-26 | 2018-12-14 | 湖北吉和昌化工科技有限公司 | Electroplate liquid of subacidity system electroplating bright copper and preparation method thereof and electroplating technology |
| CN106480479B (en) * | 2016-10-12 | 2019-02-15 | 东莞华威铜箔科技有限公司 | Preparation method, product and its application of flexible additive for electrolytic copper foil |
| CN109706488A (en) * | 2017-10-26 | 2019-05-03 | 丹阳市金长汽车部件有限公司 | A kind of copper facing bright plating liquid |
| CN109023447A (en) * | 2018-08-27 | 2018-12-18 | 江苏澳光电子有限公司 | A kind of preparation method of high-intensity and high-tenacity layered nano-structure copper |
| CN110284163B (en) * | 2019-07-31 | 2020-08-04 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN110373687A (en) * | 2019-08-30 | 2019-10-25 | 广州皓悦新材料科技有限公司 | A kind of pulse plating photo etching and preparation method thereof plating high aspect ratio through-hole and blind hole |
| CN111088509A (en) * | 2020-01-17 | 2020-05-01 | 浙江金欣新材料科技股份有限公司 | Acidic copper plating additive and preparation method thereof |
| CN111593376A (en) * | 2020-06-15 | 2020-08-28 | 深圳市缤纷珠宝开发有限公司 | Method for electrodepositing bright copper |
| CN111793810A (en) * | 2020-07-22 | 2020-10-20 | 六安市金安区宝德龙科技创新有限公司 | Slightly-acidic brightening agent for bright copper plating of plating solution and preparation method thereof |
| CN114561674B (en) * | 2022-03-25 | 2023-03-31 | 江阴纳力新材料科技有限公司 | Plastic film brush copper plating process |
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| CN1469940A (en) * | 2000-10-10 | 2004-01-21 | 日本利罗纳尔株式会社 | Copper electroplating using insoluble anode |
| CN201180164Y (en) * | 2008-03-26 | 2009-01-14 | 嘉兴敏惠汽车零部件有限公司 | Electroplating rack |
| CN101928940A (en) * | 2009-06-22 | 2010-12-29 | 尼尔金属(苏州)有限公司 | Process method of plating copper on aluminum and aluminum alloy substrate |
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