CN114686941A - Sulfite cyanide-free gold plating electrolyte for reducing gold loss and hard gold electroforming method - Google Patents
Sulfite cyanide-free gold plating electrolyte for reducing gold loss and hard gold electroforming method Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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- C25D3/48—Electroplating: Baths therefor from solutions of gold
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- C25D1/00—Electroforming
Abstract
The invention belongs to the technical field of chemistry and materials, and discloses a sulfite cyanide-free gold plating electrolyte for reducing gold loss and a hard gold electroforming method, wherein the 3D hard gold electroforming method comprises the following steps: and (3) carrying out double-pulse electrodeposition electroforming by adopting multi-complex sulfite cyanide-free gold plating electrolyte and a double-pulse power supply to obtain the 3D hard gold. The invention adopts a multi-complex system to reconstruct a formula, and is matched with a novel double-pulse power supply to achieve the effects of improving the yield of electroformed gold and reducing the gold loss. According to the invention, a multi-complexing system and a double-pulse power supply are adopted for electroforming gold, so that a product with a smoother and smoother surface, high repeated engraving property and high yield can be obtained, the gold loss is reduced from 2% to 0.5% through comprehensive measurement, 600 ten thousand yuan can be saved in each ton of 3D hard gold products, and the profit of a factory can be improved by 6%. The sulfite cyanide-free gold-plating electrolyte provided by the invention is odorless, can improve the product percent of pass and reduce the gold loss.
Description
Technical Field
The invention belongs to the technical field of chemistry and materials, and particularly relates to a sulfite cyanide-free gold plating electrolyte for reducing gold loss and a 3D hard gold electroforming method.
Background
At present, the production technologies of hard pure gold electroforming process, electroforming K gold, 3D hard gold process and the like are generally applied to the jewelry industry. The core of these techniques is the process of making a metal article by electrochemical deposition of metal on a cathode mandrel followed by stripping to separate the metal from the mandrel.
The power supply adopted by the existing electroforming technology for producing the 3D hard gold is basically a direct current power supply, the controllability is poor, and the uniformity of the thickness of an electroforming layer is difficult to ensure. In the existing electroforming solution formula, due to the instability of the plating solution, sulfite ions in the solution are easily oxidized by oxygen generated by the anode or oxygen in the air, so that granular gold is separated out, which is a great reason for gold loss in the electroforming process. The direct current power supply is matched with the existing electroforming liquid formula, the electroforming period and electroforming time are long, the electroforming effect (including brightness, precision and the like) is not ideal enough, the rejection rate of products is about 20%, gold loss is 2%, energy waste and electroforming efficiency have a very large improvement space.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) the existing electrolyte for producing 3D hard gold has poor water solubility and stability, and is easy to cause abnormal precipitation of gold particles in the electroforming process to cause gold loss;
(2) the existing 3D hard gold electroforming method has long electroforming period, high cost and large gold consumption in the production and processing processes; meanwhile, the electroforming effect is not ideal, the indexes of hardness, brightness, purity and the like of the obtained product are unstable, the rejection rate is high, and a plurality of bad phenomena such as pits, pinholes, water marks and the like are easy to generate on the surface of the electroforming layer.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a sulfite cyanide-free gold plating electrolyte for reducing gold loss and a 3D hard gold electroforming method.
The electrolyte for cyanide-free gold plating of sulfite is composed of 0.5-20 g/L of gold in the form of a sulfite complex, 0.5-200 g/L of free sulfite, 0-150 g/L of buffer salt complex, 0.01-10g/L of wetting agent, 0.1-1000 mg/L of hardness agent, 0.1-1000 mg/L of stabilizer and 0.1-1000 mg/L of brightener according to the mass volume ratio.
Further, the buffer salt complex consists of a supporting electrolyte and a buffer salt in the form of an alkali metal phosphate, borate or citrate and a complexing agent.
Further, the complexing agent includes alcohols, alkyls, pyridines or other forms of complexing agents.
Further, the alcohol complexing agent is: polyethylene glycol.
Further, the wetting agent is a surfactant; the brightener is an organic sulfonate of alkyl or aryl.
Further, the hardness agent is arsenic, tin, antimony, tellurium, cobalt or titanium and other metal compounds.
Another object of the present invention is to provide a 3D hard gold electroforming method using the electrolyte for cyanide-free gold plating with sulfite, the 3D hard gold electroforming method comprising:
and (3) carrying out double-pulse electrodeposition electroforming by adopting multi-complex sulfite cyanide-free gold plating electrolyte and a double-pulse power supply to obtain the 3D hard gold.
Further, the 3D hard gold electroforming method comprises the following steps:
preparing multi-complex sulfite cyanide-free gold-plating electrolyte;
and step two, electroforming gold by using a double-pulse electrodeposition method by taking the platinum titanium mesh subjected to surface treatment as an anode and the copper blank subjected to surface treatment as a cathode.
Further, the double pulse electrodeposition comprises:
the forward current density is 0.1-2A/dm2The reverse current density is 0.01-0.1A/dm2The positive duty ratio is 50% -90%, and the negative duty ratioThe duty ratio of the forward direction is 40% -60%, the forward direction period is 4-5 ms, and the reverse direction period is 1-2 ms.
Further, the electrodeposition time is 10 hours, the stirring speed is 60-80 r/min, and the temperature is 50 ℃.
The invention also aims to provide a 3D hard gold product prepared by the 3D hard gold electroforming method.
In combination with the technical solutions and the technical problems to be solved, please analyze the advantages and positive effects of the technical solutions to be protected in the present invention from the following aspects:
first, aiming at the technical problems existing in the prior art and the difficulty in solving the problems, the technical problems to be solved by the technical scheme of the present invention are closely combined with results, data and the like in the research and development process, and some creative technical effects are brought after the problems are solved. The specific description is as follows:
the electrolyte formula is improved by adding additives such as brightening agent, hardness agent, stabilizing agent and the like and a plurality of complexing agents for matching use; the direct current power supply is changed into the double-pulse power supply, the double-pulse power supply is matched with the novel electrolyte, the deposition rate of gold is improved, the cathode polarization is improved, the current efficiency is improved, the concentration polarization is reduced, the rate of cathode hydrogen evolution reaction is reduced, a gold casting layer with high brightness, stable hardness and purity and a smooth and flat surface is obtained on a base material, the production qualified rate can be greatly improved, and the gold loss is greatly reduced from 2% to 0.5%.
The invention provides a sulfite cyanide-free gold-plating electrolyte, which contains 0.5-20 g/L of gold in the form of a sulfite complex, 0.5-200 g/L of free sulfite, 0-150 g/L of supporting electrolyte, buffer salt in the form of alkali metal phosphate, borate or citrate, complexing agents in the forms of alcohols, alkyls, pyridines and the like, optional wetting agents, stabilizing agents and brightening agents, the stability of the electrolyte exceeds a relative extension period, the thickness of the electrolyte can reach 0.18mm in ten hours, and the current density is 0.1-1.5A/dm2No smell, high qualified rate and low gold lossAnd (4) consuming.
The plating solution of the invention contains 1-200g/L of free sulfur-containing compound or alkali metal salt, and the amount of the free sulfur-containing compound or alkali metal salt exceeds the stoichiometric proportion of corresponding gold complex. In addition, the plating solution contains 0.01-10g/L of surfactant as wetting agent, 0.1-1000 mg/L of metal compounds of arsenic, tin, antimony, tellurium, cobalt or titanium and the like as hardness agent and brightening agent, and organic sulfonate of alkyl or aryl as main brightening agent. The bath has a pH of about 7-11 and the sulfur-containing compounds used in the bath according to the invention exhibit good water solubility and high stability without noticeable odor.
The invention adopts a multi-complex system to reconstruct a formula, and is matched with a novel double-pulse power supply to achieve the effects of improving the yield of electroformed gold and reducing the gold loss.
Secondly, considering the technical solution as a whole or from the perspective of products, the technical effects and advantages of the technical solution to be protected by the present invention are specifically described as follows:
according to the invention, a multi-complexing system and a double-pulse power supply are adopted for electroforming gold, so that a product with a smoother and smoother surface, high repeated engraving property and high yield can be obtained, the gold loss is reduced from 2% to 0.5% through comprehensive measurement, 600 ten thousand yuan can be saved in each ton of 3D hard gold products, and the profit of a factory can be improved by 6%.
Third, as an inventive supplementary proof of the claims of the present invention, there are also presented several important aspects:
(1) the expected income and commercial value after the technical scheme of the invention is converted are as follows:
according to the invention, a multi-complexing system and a double-pulse power supply are adopted for electroforming gold, so that a product with a smoother and smoother surface, high repeated engraving property and high yield can be obtained, the gold loss is reduced from 2% to 0.5% through comprehensive measurement, 600 ten thousand yuan can be saved in each ton of 3D hard gold products, and the profit of a factory can be improved by 6%.
(2) The technical scheme of the invention solves the technical problem that people are eagerly to solve but can not be successfully solved all the time:
the main defects of the current electroforming technology are that the production period is long, the cost is high, the indexes of the product such as hardness, brightness and purity are unstable, the product is mostly scrapped in actual production, a plurality of adverse phenomena such as pits, pinholes and water marks are easy to generate on the surface of an electroforming layer, and the time and the cost of manual treatment in the subsequent process are prolonged. The invention greatly improves the problems of the current electroforming technology on the basis.
On one hand, the electroforming period is greatly shortened, the electroforming period required by the current electroforming technology is shortened from 16-24h to 10h, the effective stability of the electroforming solution is enhanced by shortening the electroforming time, so that the gold loss is reduced, the consumption of energy sources such as electric energy and the like is greatly saved, and the electroforming efficiency is improved.
On the other hand, the method of combining the multi-complex system electroforming liquid and the double-pulse power supply is used for electroforming gold, compared with a common casting, the obtained casting is higher in precision and brightness, smooth and delicate in surface, the product rejection rate is reduced, the product qualification rate is improved, and therefore the gold loss caused by manual polishing in the subsequent processing process can be reduced.
Drawings
Fig. 1 is a flowchart of a 3D hard gold electroforming method according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
First, an embodiment is explained. This section is an explanatory embodiment expanding on the claims so as to fully understand how the present invention is embodied by those skilled in the art.
The multi-complex sulfite cyanide-free gold plating electrolyte provided by the embodiment of the invention comprises 0.5-20 g/L of gold in a sulfite complex form, 0.5-200 g/L of free sulfite, 0-150 g/L of buffer salt compound, 0.01-10g/L of wetting agent, 0.1-1000 mg/L of hardness agent, 0.1-1000 mg/L of stabilizer and 0.1-1000 mg/L of brightener according to the mass volume ratio.
The buffer salt complex consists of a supporting electrolyte and a buffer salt in the form of an alkali metal phosphate, borate or citrate and a complexing agent.
The complexing agent provided by the embodiment of the invention comprises alcohols, alkyls, pyridines or other forms of complexing agents.
The alcohol complexing agent provided by the embodiment of the invention is as follows: polyethylene glycol.
The wetting agent provided by the embodiment of the invention is a surfactant.
The brightener provided by the embodiment of the invention is organic sulfonate of alkyl or aryl.
The hardness agent provided by the embodiment of the invention is arsenic, tin, antimony, tellurium, cobalt or titanium and other metal compounds.
The 3D hard gold electroforming method provided by the embodiment of the invention comprises the following steps:
and (3) carrying out double-pulse electrodeposition electroforming by adopting multi-complex sulfite cyanide-free gold plating electrolyte and a double-pulse power supply to obtain the 3D hard gold.
As shown in fig. 1, the 3D hard gold electroforming method provided by the embodiment of the present invention includes the following steps:
s101, preparing multi-complex sulfite cyanide-free gold plating electrolyte;
s102, electroforming gold by using a double-pulse electrodeposition method by using a platinum titanium mesh subjected to surface treatment as an anode and a copper blank subjected to surface treatment as a cathode.
The double-pulse electrodeposition provided by the embodiment of the invention comprises the following steps:
the forward current density is 0.1-2A/dm2The reverse current density is 0.01-0.1A/dm2The forward duty ratio is 50-90%, the reverse duty ratio is 40-60%, the forward period is 4-5 ms, and the reverse period is 1-2 ms.
The electro-deposition time provided by the embodiment of the invention is 10h, the stirring speed is 60-80 r/min, and the temperature is 50 ℃.
The technical solution of the present invention is further described with reference to the following specific embodiments.
The embodiment of the invention provides a 3D hard gold electroforming method for reducing gold loss, which is characterized in that additives such as a brightener, a hardness agent, a stabilizer and the like and a plurality of complexing agents are added to be matched for use on the basis of not changing the basic composition of the existing sulfite electrolyte, so that the electrolyte formula is improved; on the basis of not changing the existing process flow, a direct current power supply is changed into a double-pulse power supply, 16 groups of orthogonal experiments with five factors and four levels are designed according to the characteristics of multiple and complex parameters of the double-pulse power supply through orthogonal design experiments, and a group of optimal power supply parameters are screened to be matched with the novel electrolyte, so that a whole set of novel process for improving the deposition rate of gold, improving the cathode polarization, improving the current efficiency, reducing the concentration polarization and reducing the cathode hydrogen evolution reaction is achieved, finally, a gold casting layer with high brightness, stable hardness and purity and smooth surface is obtained on a base material, the production qualification rate can be greatly improved, and the gold loss is greatly reduced from 2% to 0.5%.
The embodiment of the invention provides a sulfite cyanide-free gold plating electrolyte, which contains 0.5-20 g/L of gold in the form of a sulfite complex, 0.5-200 g/L of free sulfite, 0-150 g/L of supporting electrolyte and a complexing agent in the form of alkali metal phosphate, borate or citrate, alcohol, alkyl, pyridine and the like. Optionally wetting agent, stabilizer and brightener, the stability of the composition exceeds a relatively prolonged period, the electroforming thickness can reach 0.18mm in ten hours, and the current density is 0.1-1.5A/dm2Has no smell, can improve the product percent of pass and reduce the gold loss.
The plating solution of the embodiment of the invention contains 1-200g/L of free sulfur-containing compound or alkali metal salt, and the amount of the free sulfur-containing compound or alkali metal salt exceeds the stoichiometric ratio of the corresponding gold complex. In addition, the plating solution contains 0.01-10g/L of surfactant as wetting agent, 0.1-1000 mg/L of metal compounds of arsenic, tin, antimony, tellurium, cobalt or titanium and the like as hardness agent and brightening agent, and organic sulfonate of alkyl or aryl as main brightening agent. The bath has a pH of about 7-11 and the sulfur-containing compounds used in the bath according to the invention exhibit good water solubility and high stability without noticeable odor.
Aiming at the existing electrolyte formula, the production process is further improved by adopting a double-pulse electroplating technology. Designing a corresponding orthogonal experiment table according to the previous experiment work and the related analysisThe best matching degree of the double-pulse parameters and the existing electrolyte is discussed. Respectively using forward current density of 0.1-2.0A/dm2The designed orthogonal test is a five-factor four-level test, namely L16(45), and 16 groups of tests are total. Taking a platinum titanium mesh subjected to surface treatment as an anode, taking a copper blank subjected to surface treatment as a cathode, and electroforming gold by adopting a double-pulse electrodeposition process, wherein the electrodeposition time is 10h, and the stirring speed is as follows: 60-80 r/min, temperature: at 50 ℃.
Cleaning the electroformed product, drying the electroformed product, observing whether the surface of the electroformed product has a large area of bright areas or not by naked eyes, and then placing the electroformed product on a flat tabletop to observe the surface condition, edges and corners and pits of the casting, thereby judging the stress in the plating layer and the electroplating effect. Through comprehensive comparison of brightness and surface conditions, the optimal dipulse power supply parameter corresponding to the first-level bright, smooth and fine casting on the lower surface of the existing plating solution is determined, namely the dipulse power supply parameter and the solution reach the optimal matching degree, and the dipulse power supply parameter range at the moment is as follows: the forward current density is 0.1-2A/dm2Reverse current density: 0.01 to 0.1A/dm2The forward duty ratio: 50% -90%, reverse duty cycle: 40% -60%, forward cycle 4-5 ms, reverse cycle 1-2 ms.
Example 2 the following formulation was used:
| substance(s) | Content (g/L) |
| Sodium gold sulfite | 8 |
| Sodium sulfite | 80 |
| Citric acid sodium salt | 50 |
| Dipotassium hydrogen phosphate | 40 |
| Polyethylene glycol | 30 |
| EDTA-2Na | 2 |
| Sodium selenite | 0.1 |
| Pyridine compound | 0.08 |
| Saccharin | 2 |
| Potassium perfluorobutylsulfonate | 0.05 |
The simultaneous dipulse parameters were selected as follows:
| parameter(s) | Numerical value |
| Forward current density | 0.4A/dm2 |
| Forward duty cycle | 70％ |
| Reverse duty cycle | 40％ |
| Forward period | 6ms |
| Reverse period | 2ms |
Electroforming for 10h to obtain the 3D hard gold product.
Example 3 the following formulation was used:
| substance(s) | Content (g/L) |
| Sodium gold sulfite | 8 |
| Sodium sulfite | 100 |
| Citric acid sodium salt | 60 |
| Dipotassium hydrogen phosphate | 45 |
| Polyethylene glycol | 30 |
| EDTA-2Na | 1 |
| Sodium selenite | 0.1 |
| Pyridine compound | 0.1 |
| Saccharin | 1.5 |
| Potassium perfluorobutylsulfonate | 0.05 |
The simultaneous dipulse parameters were selected as follows:
| parameter(s) | Numerical value |
| Forward current density | 0.35A/dm2 |
| Forward duty cycle | 80％ |
| Reverse duty cycle | 60％ |
| Forward period | 6ms |
| Reverse period | 2ms |
Electroforming for 10h to obtain the 3D hard gold product.
Example 4 the following formulation was used:
the simultaneous dipulse parameters were selected as follows:
| parameter(s) | Numerical value |
| Forward current density | 0.4A/dm2 |
| Forward duty cycle | 70％ |
| Reverse duty cycle | 50％ |
| Forward period | 4ms |
| Reverse period | 2ms |
Electroforming for 10h to obtain the 3D hard gold product.
And II, application embodiment. In order to prove the creativity and the technical value of the technical scheme of the invention, the part is the application example of the technical scheme of the claims on specific products or related technologies.
The application embodiment of the invention provides application of a 3D hard gold electroforming method in a prepared 3D hard gold product, which comprises the following steps:
(1) 50g of anhydrous sodium sulfite and 20g of dipotassium hydrogen phosphate which are weighed are placed in a beaker, and a proper amount of deionized water is added and stirred to be pasty.
(2) 0.5g of EDTA-2Na was weighed into a beaker and stirred well.
(3) And (4) transferring a proper amount of the prepared gold sodium sulfite solution into a beaker, and stirring until the solid in the solution is completely dissolved.
(4) 0.1g of sodium tellurate, 0.1g of pyridine sulfonic acid, 0.5g of saccharin and 1g of sodium dibutylnaphthalene sulfonate are mixed with warm water at about 50 ℃, fully dissolved and cooled, and then poured into the beaker.
(5) The solution pH was adjusted to the appropriate value with 20% sodium hydroxide solution and made up to 500ml with deionized water.
(6) The solution was filtered and stored in a sealed manner to obtain the final electrocasting solution used in the experiment.
The gold cyanide-free electroforming solution is adopted for electroforming, a double-pulse power supply is adopted, and the electroforming time is 10 hours. A bright and smooth surface and golden and bright color cast can be obtained, the thickness of the coating is measured, the gradual surface flatness and accuracy are analyzed, the electroforming solution is recovered and the gold loss rate is calculated as shown in table 1.
TABLE 1 application example parameters
From table 1, in the application example of electroforming gold, the electroforming method provided by the invention can obtain a casting with excellent surface flatness under the premise of greatly shortening the electroplating time, and the gold loss rate can be controlled to be about 0.5%.
And thirdly, evidence of relevant effects of the embodiment. The embodiment of the invention achieves some positive effects in the process of research and development or use, and has great advantages compared with the prior art, and the following contents are described by combining data, diagrams and the like in the test process.
The designed orthogonal test is a four-factor level of five factors, namely L16(45), with the forward current density of 0.1-2.0A/dm 2, the forward duty ratio of 20-80%, the reverse duty ratio of 20-80%, the forward period of 4-10 ms and the reverse period of 1-4 ms, and has 16 groups of tests in total.
(1) Purity analysis of gold castings
TABLE 216 sets of purity data for orthogonal test castings
The gold purity of the electroformed layer is detected by an X-fluorescence noble metal detector, and the purity meets the requirements of national standard for sufficient gold in sixteen groups of experiments.
(2) Hardness analysis of gold castings
Table 316 sets of orthogonal hardness data
The vickers hardness of the orthogonal experimental casting is tested by a microhardness tester, and the result is shown in the table above, so that the overall hardness is relatively balanced, and the hardness required by the post-processing can be achieved.
(3) Surface flatness analysis
The gold casting layer obtained by adding the electroforming stabilizer has a very flat and smooth surface and meets the production requirements.
(4) Different formulas and different contents of stabilizers are adopted to realize the implementation effect of the electroforming experiment:
no defective products appear in 200 electroformed experimental products, the surface of a hard gold casting layer reaches first-grade mirror surface brightness, the color is bright golden, the Vickers hardness is 125HV, the gold content is 99.99 percent, and the production requirements are met.
No defective products appear in 200 electroformed experimental products, the surface of the hard gold casting layer reaches first-level mirror surface brightness, the color is bright golden, the Vickers hardness is 125HV, and the gold content is 99.99 percent, thereby meeting the production requirements.
And thirdly, in 200 electroformed experimental products, defective products do not appear, the surface of the hard gold casting layer reaches first-grade mirror surface brightness, the color is bright golden, the Vickers hardness is 120HV, the gold content is 99.98%, and the production requirements are met.
It should be noted that embodiments of the present invention can be realized in hardware, software, or a combination of software and hardware. The hardware portion may be implemented using dedicated logic; the software portions may be stored in a memory and executed by a suitable instruction execution system, such as a microprocessor or specially designed hardware. Those skilled in the art will appreciate that the apparatus and methods described above may be implemented using computer executable instructions and/or embodied in processor control code, such code being provided on a carrier medium such as a disk, CD-or DVD-ROM, programmable memory such as read only memory (firmware), or a data carrier such as an optical or electronic signal carrier, for example. The apparatus and its modules of the present invention may be implemented by hardware circuits such as very large scale integrated circuits or gate arrays, semiconductors such as logic chips, transistors, or programmable hardware devices such as field programmable gate arrays, programmable logic devices, etc., or by software executed by various types of processors, or by a combination of hardware circuits and software, e.g., firmware.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The electrolyte for cyanide-free gold plating of the sulfite is characterized by comprising 0.5-20 g/L of gold in a sulfite complex form, 0.5-200 g/L of free sulfite, 0-150 g/L of buffer salt compound, 0.01-10g/L of wetting agent, 0.1-1000 mg/L of hardness agent, 0.1-1000 mg/L of stabilizer and 0.1-1000 mg/L of brightener according to the mass volume ratio.
2. The sulfite cyanide-free gold-plating electrolyte according to claim 1 wherein the buffer salt complex is comprised of a supporting electrolyte and a buffer salt in the form of an alkali metal phosphate, borate or citrate and a complexing agent.
3. The sulfite cyanide-free gold-plating electrolyte according to claim 2, wherein the complexing agent comprises an alcohol-based complexing agent, an alkyl-based complexing agent, a pyridine-based complexing agent;
the alcohol complexing agent is: polyethylene glycol.
4. The sulfite cyanide-free gold-plating electrolyte according to claim 1, wherein the wetting agent is a surfactant;
the brightener is an organic sulfonate of alkyl or aryl.
5. The sulfite cyanide-free gold-plating electrolyte according to claim 1, wherein the hardness agent is arsenic, tin, antimony, tellurium, cobalt, titanium or a metal compound.
6. A 3D hard gold electroforming method using the sulfite cyanide-free gold plating electrolyte of any of claims 1 to 5, wherein said 3D hard gold electroforming method comprises: and (3) carrying out double-pulse electrodeposition electroforming by adopting multi-complex sulfite cyanide-free gold plating electrolyte and a double-pulse power supply to obtain the 3D hard gold.
7. The 3D hard gold electroforming process according to claim 6 wherein said 3D hard gold electroforming process comprises the steps of:
preparing multi-complex sulfite cyanide-free gold-plating electrolyte;
and step two, electroforming gold by using a double-pulse electrodeposition method by taking the platinum titanium mesh subjected to surface treatment as an anode and the copper blank subjected to surface treatment as a cathode.
8. The 3D hard gold electroforming process according to claim 7 wherein said double pulse electrodeposition comprises: the forward current density is 0.1-2A/dm2The reverse current density is 0.01-0.1A/dm2The forward duty ratio is 50-90%, the reverse duty ratio is 40-60%, the forward period is 4-5 ms, and the reverse period is 1-2 ms.
9. The 3D hard gold electroforming method according to claim 7 wherein the electrodeposition time is 10 hours, the stirring rate is 60 to 80r/min, and the temperature is 50 ℃.
10. A 3D hard gold article produced by the 3D hard gold electroforming process according to any of claims 6 to 9.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806053A (en) * | 2012-11-12 | 2014-05-21 | 无锡三洲冷轧硅钢有限公司 | Dual-pulse gold plating process |
| CN104357883A (en) * | 2014-11-20 | 2015-02-18 | 中国地质大学（武汉） | Cyanide-free electroforming gold solution and gold electroforming method |
| CN104451790A (en) * | 2014-12-11 | 2015-03-25 | 重庆材料研究院有限公司 | Cyanide-free gold plating electroplate liquid for refractory metal wires |
| WO2015131796A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海新技术有限公司 | Cyanide-free electroplating solution and use therefor |
| CN105112953A (en) * | 2015-09-17 | 2015-12-02 | 深圳市瑞世兴科技有限公司 | Cyanide-free gold plating solution |
| CN109913912A (en) * | 2019-04-02 | 2019-06-21 | 深圳市昊扬电铸技术开发有限公司 | A kind of electroforming solution for gold without cyanogen electroforming process |
| CN111364074A (en) * | 2020-02-21 | 2020-07-03 | 厦门大学 | Preparation method of composite coordination low-concentration monovalent gold cyanide-free gold-plating electroplating solution |
| CN113862736A (en) * | 2021-10-22 | 2021-12-31 | 深圳市潮尊珠宝首饰有限公司 | Electrogilding liquid for cyanide-free sulfite system and application thereof |
-
2022
- 2022-03-28 CN CN202210311273.2A patent/CN114686941A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806053A (en) * | 2012-11-12 | 2014-05-21 | 无锡三洲冷轧硅钢有限公司 | Dual-pulse gold plating process |
| WO2015131796A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海新技术有限公司 | Cyanide-free electroplating solution and use therefor |
| CN104357883A (en) * | 2014-11-20 | 2015-02-18 | 中国地质大学（武汉） | Cyanide-free electroforming gold solution and gold electroforming method |
| CN104451790A (en) * | 2014-12-11 | 2015-03-25 | 重庆材料研究院有限公司 | Cyanide-free gold plating electroplate liquid for refractory metal wires |
| CN105112953A (en) * | 2015-09-17 | 2015-12-02 | 深圳市瑞世兴科技有限公司 | Cyanide-free gold plating solution |
| CN109913912A (en) * | 2019-04-02 | 2019-06-21 | 深圳市昊扬电铸技术开发有限公司 | A kind of electroforming solution for gold without cyanogen electroforming process |
| CN111364074A (en) * | 2020-02-21 | 2020-07-03 | 厦门大学 | Preparation method of composite coordination low-concentration monovalent gold cyanide-free gold-plating electroplating solution |
| CN113862736A (en) * | 2021-10-22 | 2021-12-31 | 深圳市潮尊珠宝首饰有限公司 | Electrogilding liquid for cyanide-free sulfite system and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 方景礼, 国防工业出版社 * |
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