CN105648486A - Preparation method of electroplating liquid of mercapto carboxylic acid metal complex and surface treatment method thereof - Google Patents
Preparation method of electroplating liquid of mercapto carboxylic acid metal complex and surface treatment method thereof Download PDFInfo
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- CN105648486A CN105648486A CN201510848297.1A CN201510848297A CN105648486A CN 105648486 A CN105648486 A CN 105648486A CN 201510848297 A CN201510848297 A CN 201510848297A CN 105648486 A CN105648486 A CN 105648486A
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- C—CHEMISTRY; METALLURGY
- 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
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Abstract
The invention relates to a method for preparing electroplating liquid of a mercapto carboxylic acid metal complex. The method comprises the following steps that (i) a mercapto carboxylic acid compound dissolves in first solvent to form a mercapto carboxylic acid compound solution; (ii) a metallic compound dissolves in second solvent to form a metallic compound solution; (iii) the mercapto carboxylic acid compound solution and the metallic compound solution are mixed, so that a mercapto carboxylic acid metal complex solution is obtained; (iv) ammonium citrate is added to the mercapto carboxylic acid metal complex solution; and (v) the pH value of the solution obtained in the step (iv) is adjusted to range from 6.5 to 7.0. When the electroplating liquid of the mercapto carboxylic acid metal complex is used for conducting cyanide-free gold plating treatment, the good gold plating effect can be achieved.
Description
Technical field
The present invention relates to compou nd synthesis and field of surface treatment, particularly relate to mercaptan carboxylic acid's metal complex, especially the preparation method of the electroplate liquid of mercaptan carboxylic acid's gold potassium compound, this electroplate liquid can be used for surface treatment.
Background technology
Prussiate has extremely high complex ability, and itself and zinc, cadmium, copper, silver, gold etc. can generate complex compound, and the prussiate electroplate liquid excellent performance being made up of cyano complex. At present, in the process for treating surface utilizing metal to carry out, prussiate is still widely used as excellent complexing agent. Especially, in craft of gilding, prussiate Gold-plating technique is mostly still adopted. Such as, in prussiate craft of gilding, it is possible to use potassium cyanide (KCN), as main complexing agent, generates potassium auric cyanide (K [Au (CN) with gold salt complexing2]). In electroplating process, potassium auric cyanide ionizes in the electrolytic solution, and generation is reduced and precipitated out gold on negative electrode:
K[Au(CN)2]==K++[Au(CN)2]2
[Au(CN)2]-+ e==Au+2CN-
Potassium cyanide, outside generating gold potassium cyanide complex salt (that is, potassium auric cyanide) with gold, also needs to maintain a certain amount of free potassuim cyanide in gold plating solution. In electroplate liquid, the effect of free potassuim cyanide is stable electrical plating liquid, it is to increase cathodic polarization makes coating fine uniform, promotes anode dissolution, it is to increase electroplate liquid conductive capability, etc.
Primary product in the gold-plated process of prussiate is potassium cyanaurite and potassium auric cyanide. After gold-plated completing, gold is deposited on plating piece prussiate and is then released process as refuse. Owing to prussiate is the chemical substance of a kind of severe toxicity, these prussiates can bring serious safety and pollution problem. Therefore, prussiate plating has been listed in superseded class technique and has listed " industry restructuring guidance list " (electroplate gold and silver, copper base alloy and give copper facing bottoming technique, postpone eliminating) in. But up to the present, due to its there is bath stability, the advantage such as anti-impurity ability is strong, coating is fine and close and excellent property, plating liquid is cheap, prussiate is still in the electroplating technology such as silver, gold the complexing agent being widely used.
In order to solve potential safety and the pollution problem that prussiate brings, prussiate carries out gold-plated technology to replace to have attempted adopting sulfurous acid gold salt and citric acid gold salt in prior art. But, the coating obtained in these technology often with problems such as the groove liquid life-span are short and plating piece color and luster is uneven, affects gold-plated effect.
Summary of the invention
It is an object of the invention to provide a kind of method preparing mercaptan carboxylic acid's metal complex electroplate liquid.This mercaptan carboxylic acid's metal complex electroplate liquid can be used for the plating of metal. The method preparing mercaptan carboxylic acid's metal complex electroplate liquid of the present invention comprises the following steps:
(i) by mercaptan carboxylic acid's compound dissolution in the first solvent, to form mercaptan carboxylic acid's compound solution;
(ii) metallic compound is dissolved in the 2nd solvent, to form metal compound solution;
(iii) mercaptan carboxylic acid's compound solution is mixed with metal compound solution, obtain mercaptan carboxylic acid's metal complex solution;
(iv) in described mercaptan carboxylic acid's metal complex solution, add the ammonium citrate of 20-40g/L; And
(v) by the pH regulator of gained solution in step (iv) to 6.5-7.0.
In certain embodiments of the present invention, the concentration of mercaptan carboxylic acid's solution is 0.5-350g/L, it is preferable that 0.5-300g/L, it is preferable that 10-200g/L, it is more preferable to 10-100g/L; The concentration of metallic compound is 0.1-300g/L, it is preferable that 1-300g/L, it is preferable that 20-300g/L, it is more preferable to 20-30g/L.
In certain embodiments of the present invention, one or more in this mercaptan carboxylic acid's compound selected from mercapto gluconic acid, mercaptan carboxylic acid, wherein said sulfhydryl compound is one or more in Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, mercaptobutyric acid, mercaptoundecylic acid, mercaptohexanoic acid, mercaptosuccinic acid and dimercaptosuccinic acid.
In certain embodiments of the present invention, this mercaptan carboxylic acid's metal complex is mercaptan carboxylic acid's gold potassium or thiocarboxylic acid gold potassium.
In one embodiment of the invention, this metallic compound is selected from the compound of gold and silver, tin, zinc or copper. In the preferred embodiment of the present invention, described metallic compound is gold perchloride.
In certain embodiments of the present invention, the first solvent and the 2nd solvent be selected from water, methyl alcohol, ethanol, glycerol, acetone, butanone, benzene, chloroform, methylene dichloride one or more.
In one embodiment of the invention, described metal compound solution is joined in mercaptan carboxylic acid's compound solution. And in the preferred embodiment of the present invention, metal compound solution is added drop-wise in sulfhydryl compound solution.
In one embodiment of the invention, step (iii) is at 20-70 DEG C, it is preferable that carry out in the temperature range of 20-50 DEG C.
In one embodiment of the invention, in step (v), the pH of electroplate liquid is regulated with potassium hydroxide or ammoniacal liquor.
In certain embodiments of the present invention, described plating liquid also comprises ancillary compound (such as stablizer). The stablizer being suitable in the present invention is ammonium citrate. The effect of stablizer is the extension slot liquid life-span.
In one embodiment of the invention, described electroplate liquid also comprises vitriol for the hardness increasing coating. In certain embodiments of the present invention, this vitriol is rose vitriol or single nickel salt, and based on the volume of described electroplate liquid, the consumption of described vitriol is 0.1-0.5 grams per liter. Vitriol adds according to the practical use of coating, and along with the increase of hardness, coating can become crisp. Those skilled in the art can determine whether according to the practical use of coating according to the content of present disclosure to need to add vitriol.
Present invention also offers the method utilizing the electroplate liquid of the present invention to carry out surface treatment, the method comprises: (i) will treat that coating surface and anode soak in electroplate liquid; (ii) 0.5-1A/dm is applied3Galvanic current, control electroplate liquid temperature range be 30-60 DEG C;(iii) time continuing the 30-60 second completes plating, thus treats that plating forms metal plating on the surface described. Realistic executing in mode one, described surface treatment method also comprises the pH regulator of electroplate liquid by pH value regulator to the step of 7.2-10.0.
As described above, the present inventor finds, when using mercaptan carboxylic acid's metal complex electroplate liquid of the present invention to carry out cyanogen-less gold process, solves potential safety and pollution problem that prussiate brings. And the problem such as the coating obtained avoids that the prior art middle slot liquid life-span is short and plating piece color and luster is uneven, obtain good gold-plated effect.
Accompanying drawing explanation
The Figure of description of the part forming the application is used to provide a further understanding of the present invention, and the schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention. In the accompanying drawings:
Fig. 1 utilizes the electroplate liquid according to one embodiment of the present invention to carry out the gold-plated rear edges of boards Gold plated Layer SEM0M gold face obtained.
Fig. 2 utilizes the electroplate liquid according to one embodiment of the present invention to carry out the gold-plated rear edges of boards Gold plated Layer SEM45 gold face obtained.
Fig. 3 utilizes the electroplate liquid according to one embodiment of the present invention to carry out the gold-plated rear heat radiation district Gold plated Layer SEM0M gold face obtained.
Fig. 4 utilizes the electroplate liquid according to one embodiment of the present invention to carry out the gold-plated rear heat radiation district Gold plated Layer SEM45 gold face obtained.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually. Below with reference to the accompanying drawings and come the present invention is described in detail in conjunction with the embodiments. Unless otherwise expressly defined, the technician of this area should think that the technical term of chemistry used during full text herein describes have the usual implication used in this area.
Definition
As used herein, term " mercaptan carboxylic acid's compound " refers to the carboxylic acid compound comprising sulfydryl (-SH), include but not limited to, sulfydryl gluconic acid or sulfydryl alkanoic acid etc., such as, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, mercaptobutyric acid, mercaptoundecylic acid, mercaptohexanoic acid, mercaptosuccinic acid and dimercaptosuccinic acid etc., and other can produce the compound of mercaptan acid by other modes such as hydrolysis.
As used herein, term " mercaptan carboxylic acid's metal complex " refers to compound complexing action occurring and generate between mercaptan carboxylic acid's compound and metal. " mercaptan carboxylic acid's metal complex " is dissolved in water usually.
As used herein, term " mercaptan carboxylic acid's metal complex " refers to the compound comprising between mercaptan carboxylic acid's compound and metal and complexing action occurring and generate. " mercaptan carboxylic acid's metal complex " is dissolved in water usually, is insoluble to methyl alcohol, ether, ethanol etc.
Method
The method preparing mercaptan carboxylic acid's metal complex electroplate liquid of the present invention comprises the following steps:
(i) by mercaptan carboxylic acid's compound dissolution in the first solvent, to form mercaptan carboxylic acid's compound solution;
(ii) metallic compound is dissolved in the 2nd solvent, to form metal compound solution;
(iii) mercaptan carboxylic acid's compound solution is mixed with metal compound solution, obtain mercaptan carboxylic acid's metal complex solution;
(iv) in described mercaptan carboxylic acid's metal complex solution, add the ammonium citrate of 20-40g/L;
(v) by the pH regulator of gained solution in step (iv) to 6.5-7.0..
In some embodiments, the concentration of mercaptan carboxylic acid's solution is 0.5-350g/L, it is preferable that 0.5-300g/L, it is preferable that 10-200g/L, it is more preferable to 10-100g/L; The concentration of metallic compound is 0.1-300g/L, it is preferable that 1-300g/L, it is preferable that 20-300g/L, it is more preferable to 20-30g/L. For gold-plated, those skilled in the art control the gold content in electroplate liquid according to the content of present disclosure. Such as, if the gold content in electroplate liquid higher (as being greater than 20g/L), then required electroplating time is shorter, but obtained coating relatively loosen and planeness poor; If the gold content in electroplate liquid is lower, then required electroplating time is long, but the more even densification of the coating obtained, planeness and luminance brightness are better. Usually, the gold content in electroplate liquid (in gold, g/L) is advisable for 1-30g/L, it is preferable that 4-20g/L.
In certain embodiments of the present invention, one or more in this sulfhydryl compound selected from mercapto gluconic acid or sulfydryl alkanoic acid, wherein said sulfhydryl compound is one or more in Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, mercaptobutyric acid, mercaptoundecylic acid, mercaptohexanoic acid, mercaptosuccinic acid and dimercaptosuccinic acid.
In certain embodiments of the present invention, this mercaptan carboxylic acid's metal complex is mercaptan carboxylic acid's gold potassium or thiocarboxylic acid gold potassium.
In one embodiment of the invention, this metallic compound is selected from the compound of gold and silver, tin, zinc or copper. In the preferred embodiment of the present invention, described metallic compound is gold perchloride.
In certain embodiments of the present invention, the first solvent and the 2nd solvent be selected from water, methyl alcohol, ethanol, glycerol, acetone, butanone, benzene, chloroform, methylene dichloride one or more.
The object joined by metal compound solution in described mercaptan carboxylic acid's compound solution is to make the gold ion in metal compound solution can complexing abundant with mercaptan carboxylic acid's salt. In one embodiment of the invention, described metal compound solution is joined in mercaptan carboxylic acid's compound solution. And in the preferred embodiment of the present invention, metal compound solution is added drop-wise in sulfhydryl compound solution. Therefore, in preparation process, gold perchloride dropwise is dripped in mercaptan carboxylic acid's salts solution, make gold ion completely by mercaptan carboxylic acid's salt complexing.
In one embodiment of the invention, step (iii) is at 20-70 DEG C, it is preferable that carry out in the temperature range of 20-50 DEG C.
In one embodiment of the invention, described electroplate liquid also comprises vitriol for the hardness increasing coating. In certain embodiments of the present invention, described vitriol is rose vitriol or single nickel salt, and based on the volume of described electroplate liquid, the consumption of described vitriol is 0.1-0.5 grams per liter.
In certain embodiments of the present invention, described plating liquid also comprises ancillary compound (such as stablizer). The stablizer being suitable in the present invention is ammonium citrate. The effect of stablizer is the extension slot liquid life-span.
Present invention also offers the method utilizing the electroplate liquid of the present invention to carry out surface treatment, the method comprises: (i) will treat that coating surface and anode soak in electroplate liquid; (ii) 0.5-1A/dm is applied3Galvanic current, control electroplate liquid temperature range be 30-60 DEG C; (iii) time continuing the 30-60 second completes plating, thus treats that plating forms metal plating on the surface described.In reaction process, the carboxyl generation complexing in gold ion and sulfhydryl compound, produces mercaptan carboxylic acid's gold salt, and reaction product be mercaptan carboxylic acid's gold salt or thiocarboxylic acid gold salt, such as mercaptan carboxylic acid's gold potassium or the golden potassium of thiocarboxylic acid.
In electroplating process, when applicable potassium hydroxide or ammoniacal liquor regulate pH, potassium can be deposited on anode with gold or discharge ammonia, thus the pH value making groove liquid reduces gradually, now can utilize pH value regulator by the pH regulator of groove liquid to 7.2-10.0. The pH value regulator used in the present invention is ammonium hydroxide, volatile salt, citric acid, potassium hydroxide, salt of wormwood, Tripotassium Citrate, tartrate and/or potassium hydroxide, it is preferable that ammonium hydroxide and tartrate, but is not limited to this. It is understood by those skilled in the art that pH adjusting agent conventional in field of electroplating all can be used in the present invention.
The method of the present invention can be used for utilizing the surface treatment of various metals compound, such as gold (Au), silver (Ag), tin (Sn), zinc (Zn) or copper (Cu) etc. In some preferred implementations of the present invention, the method for the present invention is especially suitable for gold-plated. In some especially preferred enforcement modes, this metallic compound is gold perchloride (AuCl3)��
Accompanying drawing 1-4 respectively illustrates 1000 times, 3000 times and 5000 times of amplification electron microphotographs that the electroplate liquid utilized according to one embodiment of the present invention carries out the gold-plated golden face with heat radiation district Gold plated Layer of the gold-plated rear edges of boards obtained. Can find out from Fig. 1-4, utilize the electroplate liquid of one embodiment of the present invention to carry out the gold-plated rear layer gold obtained even, fine and close and smooth.
Following examples are only make for the object illustrated, instead of limit the scope of the invention by any way.
Embodiment 1:
At room temperature, in an inert atmosphere, 1 gram of Thiovanic acid is dissolved in 50mL water (weight percent is 200g/L), obtains the Thiovanic acid aqueous solution of 50 milliliters. 0.6 gram of gold perchloride (AuCl3) is dissolved in 20mL water (weight percent is 300g/L), under the temperature condition of about 45 DEG C, the gold perchloride aqueous solution is dropwise joined in the Thiovanic acid aqueous solution. Keep this temperature and continue to stir 12 hours, so that complex reaction fully carries out. In the mercaptan carboxylic acid's metal complex solution generated, add 1 gram of ammonium citrate as stablizer, by ammonium hydroxide or tartrate adjust ph to 6.5, namely can be used for gold-plated.
Embodiment 2-7:
As shown in table 1, prepare the electroplate liquid of embodiment 2-7 in the way of similar to embodiment 1, other mercaptan carboxylic acids described in the application (such as Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, mercaptobutyric acid, mercaptoundecylic acid, mercaptohexanoic acid, mercaptosuccinic acid and dimercaptosuccinic acid etc., but be not limited to this) wherein can be used to replace Thiovanic acid. The concentration (in gold) of mercaptan carboxylic acid's gold potassium is monitored by method well known in the art, such as, monitored the content of gold by weighting method; Or the concentration (in gold) of mercaptan carboxylic acid's gold potassium converts by the amount of the gold perchloride used. Gold content in gold perchloride is about 48%-50%. Those skilled in the art can convert according to the gold content in gold perchloride and obtain the concentration (in gold) of mercaptan carboxylic acid's gold potassium, repeat no more herein.
Table 1 electroplate liquid forms
As shown above with mentioned above, obtained electroplate liquid likely has relatively large pH scope, now needs to use ammonium hydroxide or tartrate by the pH regulator of electroplate liquid to the scope (such as pH6.5-7.0) of slightly acidic.Such as, when the pH of electroplate liquid is reduced to slant acidity, ammonium hydroxide (NH can be utilized4OH) regulate the pH value of electroplate liquid to the scope being about pH6.5-7.0. When the pH value of electroplate liquid is meta-alkalescence, then available tartrate or citric acid are by pH regulator extremely about pH6.5-7.0.
Electro-plating method and coating properties evaluations:
Utilizing the electroplate liquid of the present invention to electroplate at circuit board surface, anode adopts titanium platinum plating net (application for organizing the Olympic Games metallic substance company limited), and control size of current is at 0.5-1 ampere/cubic decimeter (A/dm3), control electroplating temperature, at 30-60 DEG C, belongs to gold at electroplating gold on surface of circuit board. Electroplating time is 30 seconds-60 seconds. The character of plating condition and gained coating is as shown in table 2.
In electroplating process, the pH of electroplate liquid can change in time, now needs the pH to electroplate liquid again to regulate. Usually, along with the deposition of gold, the pH of groove liquid can change. In order to the duration of service of extension slot liquid, its pH need to be regulated, make in the scope that pH remains on pH7.2-10.0, such as, potassium hydroxide or ammoniacal liquor can be used to carry out the pH of regulating tank liquid. When using potassium hydroxide or ammoniacal liquor to regulate pH, potassium can be deposited on anode with gold or discharge ammonia, thus the pH value making groove liquid reduces gradually. The embodiment of the application uses ammoniacal liquor, because compared to solid-state potassium hydroxide, the use of ammoniacal liquor is convenient.
Table 2 electroplates condition and coating character
Can finding out from above-described embodiment, embodiment 1-7 all obtains the coating with good colour and outward appearance, and hardness is higher, has good wear resistance, is more applicable for the coating of outer device. Not using vitriol in embodiment 8-10, gained coating light color is golden yellow, but hardness is lower than embodiment 1-7. Those skilled in the art can determine whether according to the practical use of coating according to the content of present disclosure to need to add vitriol. Can find out from above-described embodiment, when using mercaptan carboxylic acid's metal complex electroplate liquid of the present invention to carry out cyanogen-less gold process, solve potential safety and pollution problem that prussiate brings. The coating obtained avoids that the prior art middle slot liquid life-span is short and the problem such as plating piece color and luster is uneven, obtains good gold-plated effect.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations. Within the spirit and principles in the present invention all, any amendment of doing, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (16)
1., for the preparation of a method for mercaptan carboxylic acid's metal complex electroplate liquid, described method comprises:
I (), by mercaptan carboxylic acid's compound dissolution in the first solvent, to form mercaptan carboxylic acid's compound solution, the concentration of described mercaptan carboxylic acid's solution is 0.5-350g/L;
(ii) being dissolved in by metallic compound in the 2nd solvent, to form metal compound solution, the concentration of wherein said metallic compound is 0.1-300g/L;
(iii) mercaptan carboxylic acid's compound solution is mixed with metal compound solution, obtain mercaptan carboxylic acid's metal complex solution;
(iv) in described mercaptan carboxylic acid's metal complex solution, add the ammonium citrate of 20-40g/L; And
(v) by the pH regulator of gained solution in step (iv) to 6.5-7.0.
2. method according to claim 1, it is characterized in that, described mercaptan carboxylic acid's compound selected from mercapto gluconic acid or sulfydryl alkanoic acid, wherein said sulfhydryl compound is one or more in Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, mercaptobutyric acid, mercaptoundecylic acid, mercaptohexanoic acid, mercaptosuccinic acid and dimercaptosuccinic acid.
3. method according to claim 2, it is characterised in that, described mercaptan carboxylic acid's metal complex is mercaptan carboxylic acid's gold potassium or thiocarboxylic acid gold potassium.
4. method according to claim 1, it is characterised in that, the concentration of described mercaptan carboxylic acid's solution is 0.5-300g/L, it is preferable that 10-200g/L, it is more preferable to 10-100g/L; The concentration of described metallic compound is 1-300g/L, it is preferable that 20-300g/L, it is more preferable to 20-30g/L.
5. method according to claim 1, it is characterised in that, described metallic compound is selected from the compound of gold and silver, tin, zinc or copper.
6. method according to claim 5, it is characterised in that, described metallic compound is gold perchloride.
7. method according to claim 1, it is characterised in that, described first solvent and the 2nd solvent be selected from water, methyl alcohol, ethanol, glycerol, acetone, butanone, benzene, chloroform, methylene dichloride one or more.
8. method according to claim 1, it is characterised in that, described metal compound solution is joined in mercaptan carboxylic acid's compound solution.
9. method according to claim 8, it is characterised in that, metal compound solution is added drop-wise in sulfhydryl compound solution.
10. method according to claim 1, it is characterised in that, described step (iii) carries out in the temperature range of 20-70 DEG C.
11. methods according to claim 1, it is characterised in that, step (v) regulates the pH of electroplate liquid with potassium hydroxide or ammoniacal liquor.
12. methods according to claim 1, it is characterised in that, described electroplate liquid also comprises vitriol for the hardness increasing coating.
13. methods according to claim 1, it is characterised in that, described vitriol is rose vitriol or single nickel salt, and based on the volume of described electroplate liquid, the consumption of described vitriol is 0.1-0.5 grams per liter.
14. utilize the electroplate liquid according to any one of claim 1-13 to carry out the method for surface treatment, and described method comprises:
I () will treat that coating surface and anode soak in electroplate liquid;
(ii) 0.5-1A/dm is applied3Galvanic current, control electroplate liquid temperature range be 30-60 DEG C; With
(iii) time continuing the 30-60 second completes plating, thus treats that plating forms metal plating on the surface described.
15. methods according to claim 14, it is characterised in that, by pH adjusting agent, the pH value regulator of electroplate liquid is adjusted to 7.2-10.0, it is preferable that pH8.0.
16. methods according to claim 15, it is characterised in that, described pH value regulator is potassium hydroxide, salt of wormwood, Tripotassium Citrate, ammonium hydroxide, volatile salt, citric acid and/or tartrate.
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| CN106757201A (en) * | 2016-12-29 | 2017-05-31 | 三门峡恒生科技研发有限公司 | It is a kind of without cyanogen faintly acid electroplate liquid, and preparation method thereof and application method |
| CN106757201B (en) * | 2016-12-29 | 2019-01-15 | 三门峡恒生科技研发有限公司 | A kind of no cyanogen faintly acid electroplate liquid, and preparation method thereof and application method |
| CN115197412A (en) * | 2021-04-09 | 2022-10-18 | 本田技研工业株式会社 | Functionalized metals, their synthesis and their use |
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| CN105646305A (en) | 2016-06-08 |
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